SPECIFICATION
METAL-RESIN COMPOSITE STRUCTURE AND METAL MEMBER
5 TECHNICAL FIELD
[ O O O l ]
The present invention r e l a t e s t o a metal-resin composite
s t r u c t u r e and a metal member.
BACKGROUND ART
10 [0002]
Fromtheviewpointof reducingtheweightofvarious components,
a resin is used as a s u b s t i t u t e of metal. However, there are many
cases where it is d i f f i c u l t t o s u b s t i t u t e a l l the metal components
r i i t h a resin. I n t h i s case, atechnique ofintegrallybondingametal
15 moldedarticleandaresinmoldedarticletoeachothertomanufacture
a new composite component is considered. However, a technique of
i n t e g r a l l y bonding a metal molded a r t i c l e and a r e s i n molded a r t i c l e
t o each other using an i n d u s t r i a l l y advantageous method with high
bond strength has not been put i n t o practice.
20 [0003]
Recently, as a technique of i n t e g r a l l y bonding a metal molded
a r t i c l e and a r e s i n molded a r t i c l e t o each other, a technique of
bondingametalmemberonwhichafineconcavo-convexportionis formed
t o an engineering p l a s t i c having a polar group which has a f f i n i t y
25 t o the metal member is considered (for example, Patent Documents 1
t o 5 ) .
[0004]
For example, Patent Documents 1 to 3 disclose techniques of
dipping an aluminum alloy in an aqueous hydrazine solution t o form
a concave portion having a diameter of 30 nm t o 300 nm on a surface
of the aluminum alloy, and then bonding a polybutylene terephthalate
5 r e s i n (hereinafter referred t o as "PBT") or a polyphenylene s u l f i d e
r e s i n (hereinafter referred t o as "PPS") t o t h e t r e a t e d surface.
[00051
In addition, Patent Document 4 discloses a technique of
anodizing an aluminum raw material in an e l e c t r o l y t i c bath of
10 phosphoric acid or sodium hydroxide t o form an anodic oxidation
coating having a concave portion with a diameter of greater than or
equal t o 25 nm on a surface of the aluminum raw material, and bonding
an engineering p l a s t i c t o the t r e a t e d surface.
[00061
15 Further, Patent Document 5 discloses a technique of forming a
f i n e concavo-convex portion or a hole on an aluminum alloy using a
s p e c i f i c e t c h a n t , andtheninjectingandbondingapolyamide 6 resin,
a polyamide 66 resin, or PPS t o the hole.
[0007 I
2 0 In Patent Documents 1 t o 5, anengineeringplastichavingapolar
group is used as a r e s i n member. On the other hand, regarding a
non-polar polyolefin r e s i n not having a f f i n i t y t o a metal member,
examples of a case t o which the above-described technique is applied
include an acid-modified polyolefin resin in which a polar group is
25 introduced i n t o a polyolefin resin (Patent Document 6 ) . However,
in order t o bond t h e r e s i n and a metal member t o each other, it is
necessary t h a t the metal member and t h e r e s i n be i n contact with each
other under high pressure for a long period of time in a state where
the resin is melted, and the bonding is performed using a lamination
method by melt extrusion, a press method, or the like. However, a
lamination method, a press method, or the like has a low degree of
5 freedom for the applicable shape and has a problem in that the
performance and appearance of a metal member cannot be utilized
dependingonthe shape ofthememberwhenthe acid-modifiedpolyolefin
resin is bondedto aportion ofthemember other than a bondingtarget
area.
10 [0008]
In addition, in the related art, an oil-based coating material
is used as a coating material of a metal member used for home
electronics, construction materials, or automobiles. However,
recently, the use of a water-based coating material has increased
15 instead of the oil-based coating material from the viewpoints of
reduction in environmental pollution, occupational health, and
safety. As a coating component (resin component) contained in these
water-based coating materials, for example, an epoxy resin, an
acrylic resin, a polyester resin, or a polyurethane resin is used.
20 [0009]
Examples of the coating component in the related art include
an water-based dispersion composition (Patent Document 7) that is
obtained by a reaction of an ethylene-unsaturated carboxylic acid
copolymer and an epoxy compound; a water-based rust preventive
25 coating composition (Patent Document 8) that includes a vinyl-based
copolymer having a hydrolyzable silylgroup and an aminimide group,
an uncured epoxy resin, and a rust preventive pigment; a water-based
resin composition (Patent Document 9) in which a modifier component
containing at least one compound of a diketone compound, a keto ester
compound, a ketimine compound, and a benzotriazole compound, a
bisphenol type epoxy resin, and a phosphate compound are used; and
5 a water-dispersible urethane compound (Patent Document 10) that
contains a dicarboxylic acid dihydrazide compound.
[OOlO]
However, even when a water-based coating material containing
the above-described resin composition is used, coating adhesion to
10 a metal surface is not sufficiently satisfactory.
RELATED DOCUMENT
PATENT DOCUMENT
[OOll]
[Patent Document 11 Japanese Unexamined Patent PublicationNo.
15 2004-216425
[Patent Document21 Japanese Unexamined Patent PublicationNo.
2009-6721
[Patent Document 31 Pamphlet of International Publication No.
WO 2003/064150
20 [Patent Document 41 Pamphlet of International Publication No.
WO 2004/055248
[Patent Document51 Japaneseunexamined Patent PublicationNo.
2013-52671
[Patent Document 61 Japanese Unexamined Patent PublicationNo.
25 2002-3805
[Patent Document 71 Japanese Unexamined Patent PublicationNo.
2002-241670
[PatentDocument8] Japanese Unexamined Patent PublicationNo.
H06-41471
[Patent Document 91 Japanese Unexamined Patent PublicationNo.
2003-2950
5 [Patent DocumentlO] JapaneseUnexaminedPatent PublicationNo.
2003-226728
DISCLOSURE OF THE INVENTION
[0012]
10 According t o investigation by the present inventors, it was
clarifiedthatthebondstrengthofametal-resincomposite s t r u c t u r e
obtained using any one of the methods disclosed in Patent Documents
1 t o 1 0 i s n o t s u f f i c i e n t l y s a t i s f a c t o r y . I n p a r t i c u l a r , forexample,
whenanon-polarthermoplasticresinsuchasapolyolefinresinhaving
15 low a f f i n i t y t o a metal member, a thermoplastic resin having a high
melting point which is a so-called super engineering p l a s t i c , a
thermoplastic r e s i n having a glass t r a n s i t i o n temperature of higher
thanorequalto140°C, anamorphous thermoplasticresin, o r a c o a t i n g
filmformedofawater-basedcoatingmaterialisusedas aresinmember,
20 the bond strength of the metal-resin composite structure
d e t e r i o r a t e s .
[0013]
The present invention has been made i n consideration of the
above-described circumstances, and an object thereof is t o provide
25 a metal-resin composite s t r u c t u r e in which a metal member and a resin
member formed of a thermoplastic r e s i n composition can be d i r e c t l y
bonded t o each other without deterioration or the l i k e of the resin,
and the bond strength between the metal member and t h e r e s i n member
is excellent.
[00141
In addition, another object of the present invention is t o
5 provide a metal-resin composite s t r u c t u r e i n which coating adhesion
t o a metal surface is s i g n i f i c a n t l y improved. S t i l l another object
of the present invention is t o provide a metal-resin composite
s t r u c t u r e i n which coating adhesion is high even when a resin coating
film formed on a metal surface is formed of a water-based coating
10 material.
[00151
Thepresent inventors haveinvestigateda configuration inwhich
a ten point average roughness (Rz) of a surface of a metal member
is adjusted i n order t o improve the bond strength between the metal
15 memberandaresinmemberformedofathermoplasticresincomposition.
However, it was c l a r i f i e d t h a t , with only the configuration of
adjusting a ten point average roughness (Rz) of a surface of a metal
member, the bond strengthbetween themetal member anda resinmember
cannot be s u f f i c i e n t l y improved.
20 Therefore, the present inventors have investigated more
thoroughlyondesigncriteria forimprovingthebondstrengthbetween
a metal member and a resin member formed of a thermoplastic resin
composition. As a r e s u l t , t h e present inventors have found t h a t a
materialratiooftheroughnessprofile (Rmr) ofametalmembersurface
25 is e f f e c t i v e as one of the design c r i t e r i a , thereby completing the
present invention.
[0016]
That is, according t o the present invention, a metal-resin
composite s t r u c t u r e and a metal member described below are provided.
[0017]
[I1
5 Ametal-resin composite structure which is obtained by bonding
a metal member and a r e s i n member formed of a thermoplastic resin
composition t o each other,
i n which regarding s i x l i n e a r portions i n t o t a l on a surface
of the metal member including three a r b i t r a r y l i n e a r portions which
10 areparalleltoeachotherandanotherthreearbitrarylinearportions
whichareperpendiculartothe formerthreelinearportions, asurface
roughness measured according t o JIS B0601 (corresponding
i n t e r n a t i o n a l standard: 1504287) s a t i s f i e s the following
requirements (1) and (2) a t the same t i m e :
(1) material r a t i o of the roughness p r o f i l e (Rmr) of one or more
l i n e a r portions a t a cutting level of 20% and an evaluation length
of 4 mrn are lower than or equal t o 30%; and
(2) tenpointaverageroughnesses (Rz) o f a l l t h e l i n e a r p o r t i o n s
a t an evaluation length of 4 mm are greater than 2 pm.
[21
The metal-resin composite structure according t o [I],
inwhichregardingthe s i x l i n e a r p o r t i o n s i n t o t a l o n t h e s u r f a c e
of the metal member including three a r b i t r a r y l i n e a r portions rihich
areparalleltoeachotherandanotherthreearbitrarylinearportions
25 which are perpendicular t o the former three l i n e a r portions, the
surface roughness measured according to JIS B0601 (corresponding
i n t e r n a t i o n a l standard: IS04287) further s a t i s f i e s the following
requirement (3) :
(3) material r a t i o of the roughness p r o f i l e (Rmr) of one or more
l i n e a r portions a t a cutting level of 40% and an evaluation length
of 4 nun are lower than or equal t o 60%.
5 [31
The metal-resin composite s t r u c t u r e according t o [I] or [2],
inrihichregardingthesixlinearportionsintotalonthe surface
of the metal member including t h r e e a r b i t r a r y l i n e a r portions which
areparalleltoeachotherandanotherthreearbitrarylinearportions
10 which are perpendicular t o the former three l i n e a r portions, t h e t e n
point average roughnesses (Rz) of a l l t h e l i n e a r portions are greater
than 5 pm.
[41
The metal-resin composite s t r u c t u r e according t o [3],
15 inwhi~hregardingthesixlinearportionsintotalonthesurface
of the metal member including three a r b i t r a r y l i n e a r portions which
areparalleltoeachotherandanotherthreearbitrarylinearportions
which are perpendicular t o the former three l i n e a r portions, t h e t e n
point average roughnesses (Rz) of a l l the l i n e a r p o r t i o n s are greater
20 than or equal t o 15 pm.
[51
The metal-resin composite s t r u c t u r e according t o any one of [I]
t o [ d l ,
i n w h i c h r e g a r d i n g t h e s i x l i n e a r p o r t i o n s i n t o t a l o n t h e s u r f a c e
25 of the metal member including three a r b i t r a r y l i n e a r portions which
areparalleltoeachotherandanotherthreearbitrarylinearportions
which are perpendicular t o the former three l i n e a r portions, the
surface roughness measured according to JIS B0601 (corresponding
i n t e r n a t i o n a l standard: IS04287) f u r t h e r s a t i s f i e s the following
requirement ( 4 ) :
( 4 ) mean width of the p r o f i l e elements (RSm) of a l l t h e l i n e a r
5 portions are greater than 10 pm and l e s s than 300 vm.
[ G I
The metal-resin composite s t r u c t u r e according to any one of [ I ]
t o [51,
i n which the surface of the metal member is roughened,
10 the roughening is performed using an acidic etchant i n a f i n a l
step of the roughening process of the metal member, and
t h e a c i d i c e t c h a n t c o n t a i n s a t l e a s t e i t h e r f e r r i c i o n s o r c u p r i c
ions and an acid.
[ T I
15 The metal-resin composite s t r u c t u r e according t o [6],
inwhich themetalmember is washedby ultrasonic cleaning a f t e r
the roughening process.
181
The metal-resin composite s t r u c t u r e according t o any one of [I]
20 t o [71,
inrihichthemetalmemberisformedofametalmaterialcontaining
one or two ormoremetals selected fromaluminumand aluminumalloys.
[91
The metal-resin composite s t r u c t u r e according t o any one of [ I ]
25 t o [8],
i n which the thermoplastic r e s i n composition contains one or
two or more thermoplastic resins selected from polyolefin resins,
polyester resins, and polyamide resins.
[lo]
The metal-resin composite structure according to any one of [I]
to [81,
5 in which the thermoplastic resin composition contains one or
two ormore thermoplastic resins selected frompolycarbonate resins,
polyether ether ketone resins, polyether ketone resins, polyimide
resins, and polyether sulfone resins all of which have a glass
transition temperature of higher than or equal to 140°C.
10 [Ill
The metal-resin composite structure according to any one of [I]
to [81,
in which the thermoplastic resin composition contains one or
trio ormore amorphous thermoplastic resins selected frompolystyrene
15 resins, polyacrylonitrile resins, styrene-acrylonitrile copolymer
resins, acrylonitrile-butadiene-styrene copolymer resins,
polymethyl methacrylate resins, and polycarbonate resins.
[ 12 I
The metal-resin composite structure according to any one of [I]
20 to [Ill,
in which the resin member is a coating film.
1131
The metal-resin composite structure according to [12],
in which the coating film is obtained by coating the surface
25 of the metal member with a water-based coating material.
[I41
Ametalmemberrihichisusedtobebondedtoa resinmember formed
of a thermoplastic r e s i n composition,
i n which regarding s i x l i n e a r portions i n t o t a l on a surface
of the metal member including three a r b i t r a r y l i n e a r portions which
a r e p a r a l l e l t o e a c h o t h e r a n d a n o t h e r t h r e e a r b i t r a r y l i n e a r p o r t i o n s
5 whichareperpendiculartothe formerthreelinearportions, a s u r f a c e
roughness measured according t o JIS 80601 (corresponding
i n t e r n a t i o n a l standard: IS04287) s a t i s f i e s the following
requirements (1) and (2) a t the same time:
(1) material r a t i o of the roughness p r o f i l e (Rmr) of one or more
10 l i n e a r portions a t a c u t t i n g l e v e l of 20% and an evaluation length
of 4 mm are lower than or equal t o 30%; and
(2) tenpoint average roughnesses (Rz) o f a l l t h e l i n e a r p o r t i o n s
a t an evaluation length of 4 mm are greater than 2 pm.
[I51
15 The metal member according t o [ 1 4 ] ,
inwhichregardingthesixlinearportionsintotalonthesurface
of the metal member including three a r b i t r a r y l i n e a r portions which
areparalleltoeachotherandanotherthreearbitrarylinearportions
which are perpendicular t o the former three l i n e a r portions, the
20 surface roughness measured according to JIS B0601 (corresponding
i n t e r n a t i o n a l standard: 1504287) further s a t i s f i e s the following
requirement (3) :
(3) material r a t i o of the roughness p r o f i l e (Rmr) of one or more
l i n e a r portions a t a cutting level of 40% and an evaluation length
25 of 4 mm are lower than or equal t o 60%.
[I61
The metal member according t o [14] or [15],
inwhichregardingthesixlinearportionsintotalonthesurface
of the metal member including three a r b i t r a r y l i n e a r portions which
areparalleltoeachotherandanotherthreearbitrarylinearportions
which are perpendicular t o the former three l i n e a r portions, the ten
5 point average roughnesses (Rz) of a l l the l i n e a r portions are greater
than 5 pm.
[I71
The metal member according t o [16],
inwhichregardingthe s i x l i n e a r p o r t i o n s i n t o t a l o n t h e surface
10 of the metal member including three a r b i t r a r y l i n e a r portions which
areparalleltoeachotherandanotherthreearbitrarylinearportions
which are perpendicular t o the former three l i n e a r portions, t h e t e n
point average roughnesses (Rz) of a l l the l i n e a r p o r t i o n s a r e greater
than or equal t o 15 pm.
15 [I81
The metal member according to any one of [ 1 4 ] t o [ 1 7 ] ,
i n w h i c h r e g a r d i n g t h e s i x l i n e a r p o r t i o n s i n t o t a l o n t h e surface
of the metal member including three a r b i t r a r y l i n e a r portions which
areparalleltoeachotherandanotherthreearbitrarylinearportions
20 which are perpendicular t o the former three l i n e a r portions, the
surface roughness measured according to JIS B0601 (corresponding
i n t e r n a t i o n a l standard: IS04287) further s a t i s f i e s the following
requirement ( 4 ) :
( 4 ) mean width of the p r o f i l e elements (RSm) of a l l the l i n e a r
25 portions are greater than 10 pm and l e s s than 300 pm.
[I91
The metal member according t o any one of [ 1 4 ] t o [ 1 8 ] ,
inwhichthemetalmember is formedofametalmaterialcontaining
one or two or moremetals selected fromaluminumand aluminumalloys.
[0018]
According t o the present invention, a metal-resin composite
5 s t r u c t u r e in which the bond strength between a metal member and a
resinmember formedofathermoplasticresincomposition is excellent
can be provided.
[0019]
In addition, according t o the present invention, a metal-resin
10 composite s t r u c t u r e in which a r e s i n coating film formed on a surface
of a metal member is strongly bonded to the metal member surface can
be provided. Further, even when the coating film is formed of a
water-based coating material, due t o its high coating adhesion, the
metal-resin composite s t r u c t u r e according t o the present invention
15 is excellent from the viewpoints of reduction i n environmental
pollution, occupational health, and safety.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020]
Theabove-describedobjectsandotherobjects, c h a r a c t e r i s t i c s ,
20 andadvantageous e f f e c t s ~ i i l l b e c l e a r l y d e s c r i b e d u s i n g a p r e f e r a b l e
embodiment described below and the accompanying drawings below.
[0021]
FIG. 1 is an external view schematically showing a s t r u c t u r a l
example of a metal-resin composite s t r u c t u r e according t o an
25 embodiment of the present invention.
FIG. 2 is a configuration diagram schematically shovring an
example o f a p r o c e s s ofpreparingthemetal-resincomposite s t r u c t u r e
according t o the embodiment of the present invention.
FIG. 3 is a schematic diagram showing measurement positions
which are s i x l i n e a r portions i n t o t a l on a surface of a metal member
accofdingtotheembodimentincludingthree a r b i t r a r y l i n e a r p o r t i o n s
5 which a r e p a r a l l e l t o each other and another three a r b i t r a r y l i n e a r
portions whichare perpendiculartothe formerthreelinearportions.
FIG. 4 is a schematic diagram showing measurement positions
which are s i x l i n e a r portions i n t o t a l on a surface of an aluminum
p l a t e , which is obtainedineachpreparationexample, includingthree
10 arbitrarylinearportionswhichareparalleltoeachotherandanother
threearbitrarylinearportionswhichareperpendiculartothe former
three l i n e a r portions.
FIG. 5 i s adiagramshowingasurfaceroughness c u r v e o f a s u r f a c e
of an aluminum p l a t e obtained in Preparation Example 1A.
15 FIG. 6 is an electron micrograph showing an enlarged view of
the surface of the aluminum p l a t e obtained i n Preparation Example
1A.
FIG. 7 isadiagramshowingasurfaceroughnesscurveofasurface
of an aluminum p l a t e obtained in Preparation Example 2A.
2 0 FIG. 8 is an electron micrograph showing an enlarged view of
the surface of the aluminum p l a t e obtained i n Preparation Example
2A.
FIG. 9isadiagramshowinga surfaceroughnesscurveofasurface
of an aluminum p l a t e obtained in Preparation Example 3A.
25 FIG. 10 is an electron micrograph showing an enlarged view of
the surface of the aluminum p l a t e obtained i n Preparation Example
3A.
FIG. 11 is a conceptual diagram schematically showing the
definition of a maximum length of filler particles.
FIG. 12 is an electron micrograph showing an enlarged view of
a surface of an aluminum plate obtained in Preparation Example 1B.
5 FIG. 13 is an electron micrograph showing an enlarged view of
a surface of an aluminum plate obtained in Preparation Example 2B.
FIG. 14 is an electron micrograph showing an enlarged view of
a surface of an aluminum plate obtained in Preparation Example 4B.
FIG. 15 is an electron micrograph showing an enlarged view of
10 a surface of an aluminum plate obtained in Preparation Example 6B.
FIG. 16 is an electron micrograph showing an enlarged view of
a surface of an aluminum plate obtained in Preparation Example 7D.
DESCRIPTION OF EMBODIMENTS
15 [0022]
Hereinafter, an embodiment of the present invention will be
described using the drawings. In all the drawings, the same
components are represented by the same reference numerals, and the
description thereof will not be repeated. "To" between numerical
20 values in the specification represents "greater than or equal to and
less than or equal to".
[00231
[Metal-Resin Composite Structure]
First, a metal-resin composite structure 106 according to the
25 embodiment will be described.
FIG. 1 is an external view schematically showing a structural
example of the metal-resin composite structure 106 according to the
embodiment of the present invention. In the metal-resin composite
structure 106, a metal member 103 and a resin member 105 formed of
a thermoplastic resin composition (P) are bonded to each other, and
the metal-resin composite structure 106 can be obtained by bonding
5 the metal member 103 and the resin member 105 to each other.
In the embodiment, when the resin member 105 is a coating film,
themetal-resin composite structure 106 is also calleda coatedmetal
member.
[0024]
10 Regarding six linear portions in total on a surface 110 of the
metal member including three arbitrary linear portions which are
parallel to each other and another three arbitrary linear portions
v ~ h i c h a r e p e r p e n d i c u l a r t o t h ef ormerthreelinearportions, asurface
roughness measured according to JIS B0601 (corresponding
15 international standard: 1504287) satisfies the following
requirements (1) and (2) at the same time:
(1) material ratio of the roughness profile (Rmr) of one or more
linear portions at a cutting level of 20% and an evaluation length
of 4 mm are lower than or equal to 30%; and
20 (2) tenpoint average roughnesses (Rz) ofallthe linearportions
at an evaluation length of 4 mm are greater than 2 pm.
The resin member 105 is formed of the thermoplastic resin
composition (P) containing a thermoplastic resin (A) as a resin
component.
25 [0025]
In the metal-resin composite structure 106 according to the
embodiment, the thermoplastic resincomposition (P) constitutingthe
resin member 105 infiltrates into a concavo-convex portion formed
on the surface 110 of the metal member. As a result, metal is bonded
to the resin, and the metal-resin composite structure is formed.
[00261
5 On the surface 110 of the metal member 103, the concavo-convex
portion suitable for improving the bond strength between the metal
member 103 and the resin member 105 is formed. Therefore, the
adhesion between the metal member 103 and the resin member 105 can
be secured without using an adhesive.
10 Specifically, it is considered that, by the thermoplastic resin
composition (P) infiltrating into the concavo-convex portion of the
surface 110 of the metal member which satisfies the requirements (1)
and (2) at the same time, a physical resistance force (anchor effect)
is efficiently exhibited between the metal member 103 and the resin
15 member 105, and the metal member 103 and the resin member 105 formed
of the thermoplastic resin composition (P) which are usually
difficult to bond can be strongly bonded to each other.
[00271
The metal-resin composite structure 106 obtained as above can
20 also prevent infiltration of moisture or humidity into an interface
between the metal member 103 and the resin member 105. That is, air
tightness and water tightness of the adhesion interface of the
metal-resin composite structure 106 can be improved.
Hereinafter, eachmemberconstitutingthemetal-resincomposite
25 structure 106 will be described.
[00281

Hereinafter, the metal member 103 according to the embodiment
w i l l be described.
Regarding six l i n e a r portions i n t o t a l on a surface 110 of the
metal member including three a r b i t r a r y l i n e a r portions which are
5 p a r a l l e l t o each other and another three a r b i t r a r y l i n e a r portions
whichareperpendiculartothe formerthreelinearportions, a s u r f a c e
roughness measured according t o JIS B0601 (corresponding
i n t e r n a t i o n a l standard: IS04287) s a t i s f i e s the following
requirements (1) and (2) a t the same time:
(1) material r a t i o of the roughness p r o f i l e (Rmr) of one or more
l i n e a r portions a t a cutting level of 20% and an evaluation length
of 4 mm are lower than or equal t o 30%; and
(2) tenpointaverageroughnesses (Rz) of a l l t h e l i n e a r p o r t i o n s
a t an evaluation length of 4 mm are greater than 2 pm.
15 [0029]
FIG. 3 is a schematic diagram showing measurement positions
which are the s i x l i n e a r portions i n t o t a l on the surface 110 of the
metal member including three a r b i t r a r y l i n e a r portions which are
p a r a l l e l t o each other and another three a r b i t r a r y l i n e a r portions
20 which are perpendicular t o the former three l i n e a r portions.
As the above-described s i x l i n e a r portions, for example, s i x
l i n e a r portions B1 to B6 shown i n FIG. 3 can be selected. F i r s t ,
as a reference line, the center l i n e B1 which passes through a c e n t e r
portion A of a bonding portion surface 104 of the metal member 103
25 is selected. Next, the l i n e s B2 and B3 p a r a l l e l t o the center l i n e
Blare selected. Next, the center l i n e B4 p e r p e n d i c u l a r t o t h e c e n t e r
l i n e B1 is selected, and the l i n e s B5 and B6 perpendicular t o the
center l i n e B l a n d p a r a l l e l t o t h e center l i n e B4 are selected. Here,
v e r t i c a l distances D l to D4 between the respective l i n e s are, for
example, 2 mm t o 5 mm.
Usually, n o t o n l y t h e bondingportion surface 104 o f t h e surface
5 110 of the metal member but the e n t i r e portion of the surface 110
of the metal member is roughened. Therefore, for example, as shown
in FIG. 4, on the same surface of the bonding portion surface 104
of the metal member 103, six l i n e a r portions may be selected from
p o s i t i o n s o t h e r than the bonding portion surface 1 0 4 .
10 [0030]
The reason why the metal-resin composite structure 106 having
an excellent bond strength can be obtained when the requirements (1)
and (2) are s a t i s f i e d is not n e c e s s a r i l y c l e a r , but is considered
to be t h a t the bonding portion surface 104 of the metal member 103
15 has a s t r u c t u r e i n which the anchor e f f e c t between the metal member
103 and t h e r e s i n member 105 can be e f f i c i e n t l y exhibited.
Thepresentinventorshaveinvestigatedaconfigurationinwhich
a ten point average roughness (Rz) of a surface of a metal member
is adjusted i n order to improve the bond strength between the metal
20 memberandaresinmemberformedofathermoplasticresincomposition.
However, it was c l a r i f i e d t h a t , with only the configuration of
adjusting a ten point average roughness (Rz) of a surface of a metal
member, the bondstrengthbetweenthemetalmemberanda resinmember
cannot be s u f f i c i e n t l y improved.
25 Here, the present inventors thought t h a t the c r i t e r i o n m a t e r i a l
r a t i o o f t h e p r o f i l e is e f f i c i e n t a s a n i n d e x i n d i c a t i n g t h e sharpness
of the concavo-convex portion of the metal member surface. A low
material ratio of the profile represents high sharpness of the
concavo-convex portion of the metal member surface, and a high
material ratio of the profile represents low sharpness of the
concavo-convex portion of the metal member surface.
5 Therefore, as one of the design criteria for improving the bond
strength between a metal member and a resin member formed of a
thermoplastic resin composition, the present inventors have focused
on the material ratio of the profile of a roughness curve of a metal
member surface and have investigatedmore thoroughly. As a result,
10 the present inventors have found that, by adjusting a material ratio
of the profile of a metal member surface to be lower than or equal
to a specific value, the anchor effect between the metal member 103
and the resin member 105 can be efficiently exhibited, and thus the
metal-resincomposite structure 106havinganexcellentbondstrength
15 can be realized, thereby completing the present invention.
[0031]
From the viewpoint of further improving the bond strength
between the metal member 103 and the resin member 105, regarding the
six linear portions in total on the surface 110 of the metal member
20 includingthree arbitrarylinearportions which are parallel to each
other and another three arbitrary linear portions which are
perpendicular to the former three linear portions, the surface
roughness measured according to JIS B0601 (corresponding
international standard: 1504287) preferably further satisfies one
25 or more requirements and more preferably further satisfies the
requirement (1C) among the following requirements (1A) to (1C) . The
requirement (1C) is the same as the above-described requirement (3).
(1A) materialratiooftheroughnessprofile (Rmr) o f p r e f e r a b l y
two or more l i n e a r portions, more preferably three or more l i n e a r
portions, and most preferably the s i x l i n e a r portions a t a cutting
l e v e l of 20% and an evaluation length of 4 mm are lower than or equal
5 t o 30%.
(1B) materialratiooftheroughnessprofile (Rmr) of preferably
one or more l i n e a r portions, more preferably two or more l i n e a r
portions, still more preferably three or more l i n e a r portions, and
most preferably the s i x l i n e a r portions a t a c u t t i n g l e v e l of 20%
10 and an evaluation length of 4 mm are lower than or equal t o 20%.
(1C) material r a t i o o f t h e roughnessprofile (Rmr) ofpreferably
one or more l i n e a r portions, more preferably two or more l i n e a r
portions, s t i l l more preferably three or more l i n e a r portions, and
most preferably the s i x l i n e a r portions a t a c u t t i n g l e v e l of 40%
15 and an evaluation length of 4 mm are lower than or equal t o 60%.
[00321
In addition, from the viewpoint of f u r t h e r improving the bond
strength between the metal member 103 and t h e r e s i n member 105, when
measured according t o JIS B0601 (corresponding i n t e r n a t i o n a l
20 standard: IS04287), an average value of material r a t i o of the
roughness p r o f i l e (Rmr) on the surface 110 of the metal member 103
a t a c u t t i n g l e v e l o f 2 0 % andanevaluationlengthof 4mrnispreferably
higher than or equal t o 0.1% and l e s s than or equal to 40%, more
preferably higher than or equal to 0.5% and l e s s than or equal to
25 30%, s t i l l more preferably higher than or equal t o 1% and l e s s than
or equal t o 20%, and most preferably higher than or equal t o 2% and
l e s s than or equal t o 15%.
As the average value of the material ratio of the roughness
profile (Rmr), an average value of material ratio of the roughness
profile (Rmr) of the above-described six arbitrary linear portions
can be adopted.
5 [0033]
The respective material ratio of the roughness profile (Rmr)
of the surface 110 of the metal member according to the embodiment
can be controlled by appropriately adjusting conditions of the
roughening on the surface of the metal member 103.
10 In the embodiment, for example, particularly, the kind and
concentration of an etchant, the temperature and time of the
roughening, and the timing of etching can be used as factors for
controlling the respective material ratio of the roughness profile
(Rmr).
15 [0034]
From the viewpoint of further improving the bond strength
between the metal member 103 and the resin member 105, regarding the
six linear portions in total on the surface 110 of the metal member
includingthree arbitrary linear portions which are parallel to each
20 other and another three arbitrary linear portions which are
perpendicular to the former three linear portions, the surface
roughness measured according to JIS B0601 (corresponding
international standard: 1504287) preferably further satisfies the
following requirement (2A):
25 (2A) ten point average roughnesses (Rz) of all the linear
portions at an evaluation length of 4 mm are preferably greater than
5 pm, more preferably greater than or equal to 10 pm, and still more
preferably greater than or equal t o 15 pm.
[0035]
From the viewpoint of f u r t h e r improving the bond strength
between the metal member 103 and the resin member 105, an average
5 value of ten point average roughnesses (Rz) on the surface 110 of
the metal member is preferably greater than 2 pm and l e s s than or
equal t o 50 pm, more preferably greater than 5 pm and l e s s than or
equal t o 45 pm, still more preferably greater than or equal to 10
p m a n d l e s s t h a n o r e q u a l t o 40pm, andparticularlypreferablygreater
10 than or equal t o 15 pm and l e s s than or equal t o 30 pm.
As the average value of the ten point average roughnesses (Rz) ,
an average value of ten point average roughnesses (Rz) of the
above-described s i x a r b i t r a r y l i n e a r portions can be adopted.
[0036]
15 From the viewpoint of f u r t h e r improving the bond strength
between the metal member 103 and t h e r e s i n member 105, regarding the
s i x l i n e a r portions i n t o t a l on the surface 110 of the metal member
includingthree a r b i t r a r y l i n e a r p o r t i o n s which a r e p a r a l l e l t o each
other and another three a r b i t r a r y l i n e a r portions which are
20 perpendicular to the former three l i n e a r portions, the surface
roughness measured according t o JIS B0601 (corresponding
i n t e r n a t i o n a l standard: IS04287) preferably further s a t i s f i e s the
following requirement ( 4 ) :
( 4 ) mean width of the p r o f i l e elements (RSm) of a l l t h e l i n e a r
25 portionsaregreaterthan10pmandlessthan300pmandmorepreferably
greater than or equal to 20 pm and less than or equal t o 200 pm.
[0037]
From the viewpoint of further improving the bond strength
between the metal member 103 and the resin member 105, an average
value of mean width of the profile elements (RSm) on the surface 110
of the metal member is preferably greater than 10 pm and less than
5 300 pm and more preferably greater than or equal to 20 pm and less
than or equal to 200 pm.
As the average value of the mean width of the profile elements
(RSm), an average value of mean width of the profile elements (RSm)
ofthe above-described six arbitrarylinearportions canbe adopted.
10 [0038]
The ten point average roughnesses (Rz) and the mean width of
the profile elements (RSm) of the surface 110 of the metal member
according to the embodiment can be controlled by appropriately
adjustingconditions oftherougheningonthe surface110 ofthemetal
15 member.
In the embodiment, for example, particularly, the temperature
andtimeoftherougheningandtheetchingamountcanbeusedas factors
for controlling the ten point average roughnesses (Rz) and the mean
width of the profile elements (RSm).
20 [0039]
A metal material constituting the metal member 103 is not
particularly limited, and examples thereof include iron, stainless
steel, aluminum, aluminum alloys, magnesium, magnesium alloys,
copper, and copper alloys. These metal materials may be used alone
25 or in a combination of two or more kinds. Among these, from the
viewpoints of reducing weight and obtaining high strength, aluminum
(aluminum alone) and aluminum alloys are preferable, and aluminum
alloys are more preferable.
As the aluminumalloys, for example, Alloy No. 1050, 1100, 2014,
2024, 3003, 5052, and 7075 which are defined according t o JIS H4000
are preferably used.
5 [0040]
The shape of the metal member 103 is not p a r t i c u l a r l y limited
as long as the metal member 103 can be bonded t o t h e r e s i n member
105, and examples thereof include a f l a t shape, a curved shape, a
rodshape, acylindricalshape, andanagglomerateshape. Inaddition,
10 a structure having a combination of the above-described shapes may
be adopted.
In addition, the shape of the bonding portion surface 104 which
is bonded t o t h e r e s i n member 105 is not p a r t i c u l a r l y limited, and
examples thereof include a f l a t shape and a curved shape.
15 [0041]
It i s preferable t h a t themetalmember103 be formedofthemetal
material which is roughenedas describedbelow a f t e r being processed
i n t o a predetermined shape by thickness reduction processing such
as p l a s t i c working by machining or pressing, punching, cutting,
20 polishing, or e l e c t r i c discharge machining. In short, it is
preferable t h a t the metal member 103 be processed into a necessary
shape using various processing methods.
[0042]
(Roughening Method of Metal Member Surface)
25 Next, a roughening method of the surface of the metal member
103 w i l l be described.
The surface o f the metal member 103 according t o the embodiment
can be formed by, for example, roughening using an etchant.
Here, the roughening on the surface of the metal member using
an etchant is performed using t h e r e l a t e d technique. However, in
the embodiment, the f a c t o r s such as the kind and concentration of
5 anetchant, the temperatureandtimeofthe roughening, andthe timing
of etching are highly controlled. In order t o obtain the bonding
portionsurface104 ofthemetalmember103accordingtotheembodiment,
it is important to highly c o n t r o l t h e s e f a c t o r s .
Hereinafter, an example of the roughening method of the metal
10 member surface according t o the embodiment w i l l be described.
However, the rougheningmethod o f t h e metal member surface according
t o the embodiment is not limited t o the following examples.
[0043]
(1) Pre-Treatment Process
F i r s t , it is preferable t h a t a thick f i l m such as an oxide f i l m
or a hydroxide not be formed on a surface of the metal member 103
which is bonded t o t h e r e s i n member 105. In order t o remove such
a t h i c k film, beforebeingtreatedusinganetchant, the surface layer
may be polished by mechanical polishing such as sand blasting, shot
20 blasting, grinding or barrel finishing or by chemicalpolishing. In
addition, when the surface of the metal member 103 which i s bonded
t o the resin member 105 is s i g n i f i c a n t l y contaminated by machine o i l
or the like, it is preferable t h a t t h i s surface be t r e a t e d using an
aqueous alkaline solution such as an aqueous sodium hydroxide
25 s o l u t i o n o r an aqueous potassiumhydroxide solution or be degreased.
[0044]
(2) Surface-Roughening Process
As a surface-roughening method of the metal member according
t o the embodiment, it is preferable t h a t a treatment using an acidic
etchant described below be performed a t a s p e c i f i c timing.
Specifically, it is preferable t h a t the treatment using an acidic
5 etchant be performed i n a f i n a l step of the surface-roughening
process.
[00451
As the etchant used for the surface-roughening of the metal
member which is formed of the metal material containing aluminum,
10 PatentDocument5 describedabove d i s c l o s e s a configuration of using
an a l k a l i n e etchant, a configuration of using an a l k a l i n e etchant
and an acidic etchant in combination, and a configuration of
roughening a metal surface using an acidic etchant and then washing
t h e t r e a t e d surface with an alkaline solution.
15 The alkaline etchant is moderately reactive t o the metal member
and thus is preferably used from the viewpoint of workability.
However, according to the investigation by the present inventors,
it was c l a r i f i e d t h a t , when the alkaline etchant is used, due t o its
moderate r e a c t i v i t y , the roughening degree of the metal member
20 surface is weak, and it is d i f f i c u l t to form a deep concavo-convex
portion. Inaddition, i t w a s c l a r i f i e d t h a t , whenanalkalineetchant
or an alkaline solution is used i n combination a f t e r the treatment
usinganacidicetchant, adeepconcavo-convexportionwhichis formed
using the acidic etchant is smoothened by the alkaline etchant or
25 the alkaline solution.
Accordingly, in a metal member which is t r e a t e d using the
a l k a l i n e etchant, or i n a metal member which is obtained by using
the alkaline etchant or the alkaline solution in a f i n a l step of the
etching process, it is considered t h a t it is d i f f i c u l t t o maintain
ahighbondstrengthbetweenthemetalmemberandaresinmemberformed
of a thermoplastic resin composition.
5 [0046]
Examples o f a rougheningmethodusingthe a c i d i c e t c h a n t i n c l u d e
treatment methods using dipping or spraying. The treatment
temperatureispreferably2O0Cto4O0C,thetreatmenttimeis5 seconds
to350 seconds, andfromtheviewpointoffurtheruniformlyroughening
10 themetalmembersurface, ismorepreferably20 secondsto 300 seconds
and p a r t i c u l a r l y preferably 50 seconds t o 300 seconds.
[0047]
Due t o the roughening using t h e a c i d i c etchant, the surface of
the metal member 103 is roughened i n a concavo-convex shape. When
15 being calculated from the mass, s p e c i f i c gravity, and surface area
of the dissolved metal member 103, the etching amount (dissolved
amount) of the metal member 103 in the thickness direction i n the
case of using the acidic etchant is preferably 0.1 pm t o 500 pm, more
preferably 5 pm t o 500 pm, and still more preferably 5 pm t o 100 pm.
20 When the etching amount is greater than or equal t o the lower l i m i t ,
the bond strength between the metal member 103 and the resin member
105 can be f u r t h e r improved. In addition, when the etching amount
is l e s s than or equal t o the upper l i m i t , the treatment cost can be
reduced. The etching amount can be adjusted by the treatment
25 temperature, the treatment time, and the l i k e .
[00481
In the embodiment, when the metal member is roughened using the
acidic etchant, the entire surface of the metal member surface may
be roughened, or only a surface of the metal member which is bonded
to the resin member 105 may be partially roughened.
[0049]
5 (3) Post-Treatment Process
In the embodiment, it is preferable that washing and drying be
performed after the surface-roughening treatment. Awashingmethod
is not particularly limited, but it is preferable that dipping or
washing with flowing water for a predetermined amount of time be
10 performed.
[0050]
Further, as the post-treatment process, it is preferable that
ultrasonic cleaning be performed to remove smut and the like formed
by the treatment using the acidic etchant. Ultrasonic cleaning
15 conditions are not particularly limited as long as the formed smut
and the like can be removed under the conditions. However, water
is preferably used as a solvent to be used, and the treatment time
is preferably 1 minute to 20 minutes.
[00511
(Acidic Etchant)
In the embodiment, as the etchant used for the roughening of
the metal member surface, a specific acidic etchant described below
is preferably used. It is considered that, by performing the
treatment using the specific etchant, a concavo-convex portion
25 suitable for improving the adhesion between the metal member and the
resin member containing the thermoplastic resin (A) is formed on the
surface of the metal member, and due to this anchor effect, the bond
strength between the metal member 103 and the resin member 105 is
improved.
[0052]
In p a r t i c u l a r , it is preferable t h a t an a c i d i c etchant capable
5 offormingadeeperconcavo-convexportiononthemetalmembersurface
be used from the viewpoints of: improving the bond strength between
the metal member and a r e s i n member, which is not l i k e l y t o be bonded
tothemetalmemberwithanordinarytreatment, includingapolyolefin
resin, a thermoplastic resin having a glass t r a n s i t i o n temperature
10 o f h i g h e r t h a n o r e q u a l t o 1 4 0 ° C , or anamorphous thermoplastic resin;
andimprovingthebondstrengthbetweenthemetalmemberandacoating
film formed of a water-based coating material which is not l i k e l y
t o be bonded t o the metal member with an ordinary treatment.
[0053]
Hereinafter, components of the acidic etchant which can be used
i n the embodiment w i l l be described.
[0054]
T h e a c i d i c e t c h a n t c o n t a i n s a t l e a s t e i t h e r f e r r i c i o n s o r c u p r i c
ions and an acid, and may optionally further contain manganese ions
20 and various additives.
[00551
.Ferric Ions
The f e r r i c ions are a component t h a t oxidizes the metal member
and can be contained i n t h e a c i d i c etchant by mixing a f e r r i c ion
25 source with t h e a c i d i c etchant. Examples of the f e r r i c ion source
include f e r r i c n i t r a t e , f e r r i c s u l f a t e , and f e r r i c chloride. Among
the f e r r i c ion sources, f e r r i c chloride is preferably used fromthe
viewpoint of high s o l u b i l i t y and low c o s t .
[0056]
In t h e embodiment, t h e content of t h e ferric ions i n t h e a c i d i c
e t c h a n t is p r e f e r a b l y 0.01 mass% t o 20 mass%, more p r e f e r a b l y 0 . 1
5 mass% t o 12 mass%, s t i l l more p r e f e r a b l y 0.5 mass% t o 7 mass%, even
s t i l l m o r e p r e f e r a b l y l m a s s % t o 6mass%, andparticularlypreferably
1 mass% t o 5 mass%. When t h e content of t h e ferric ions is g r e a t e r
than o r equal t o t h e lower l i m i t , a decrease i n t h e roughening rate
( d i s s o l v i n g r a t e ) ofthemetalmember c a n b e prevented. On t h e other
10 hand, when t h e content of t h e ferric ions is less than o r equal t o
t h e u p p e r l i m i t , t h e rougheningratecanbeappropriatelymaintained.
Therefore, uniform roughening which is more s u i t a b l e f o r improving
t h e bond s t r e n g t h between t h e metal member 103 and t h e r e s i n member
105 can be performed.
15 [0057]
.Cupric Ions
The c u p r i c i o n s a r e a component t h a t o x i d i z e s t h e metal member
and can b e c o n t a i n e d i n t h e a c i d i c e t c h a n t by mixing a cupric ion
source with t h e a c i d i c e t c h a n t . Examples of t h e cupric ion source
20 include cupric s u l f a t e , cupric chloride, c u p r i c n i t r a t e , and cupric
hydroxide. Among the cupric ion sources, c u p r i c s u l f a t e o r cupric
c h l o r i d e is p r e f e r a b l y used from t h e viewpoint o f high s o l u b i l i t y
and low c o s t .
[0058]
25 In t h e embodiment, t h e content of t h e c u p r i c i o n s i n the a c i d i c
e t c h a n t is p r e f e r a b l y 0.001 mass% t o 10 mass%, more p r e f e r a b l y 0.01
mass% t o 7 mass%, s t i l l more p r e f e r a b l y 0.05 mass% t o 1 mass%, yet
s t i l l more preferably 0.1 mass% t o 0.8 mass%, even yet s t i l l more
preferably 0.15mass% t o 0.7 mass%, andparticularlypreferably 0.15
mass% t o 0 . 4 mass%. When the content of the cupric ions is greater
than or equal to the lower l i m i t , a decrease i n the roughening r a t e
5 (dissolving r a t e ) ofthemetalmember canbe prevented. On the other
hand, when the content of the cupric ions is l e s s than or equal to
theupper l i m i t , the rougheningrate canbeappropriatelymaintained.
Therefore, uniform roughening which is more s u i t a b l e f o r improving
the bond strength between the metal member 103 and t h e r e s i n member
10 105 can be performed.
[0059]
The acidic etchant may contain e i t h e r or both of the f e r r i c ions
and the cupric ions, but it is preferable t h a t the a c i d i c etchant
contain both the f e r r i c ions and the cupric ions. By t h e a c i d i c
15 etchant containing the f e r r i c ions and the cupric ions, an excellent
roughening shape which is more s u i t a b l e f o r improving the bond
strength between the metal member 103 and t h e r e s i n member 105 can
be e a s i l y obtained.
[0060]
20 When the acidic etchant contains both the f e r r i c ions and the
cupric ions, it is preferable t h a t the respective contents of the
f e r r i c ions and the cupric ions be in the above-described ranges.
In addition, the t o t a l content of the f e r r i c ions and the cupric ions
i n the acidic etchant is preferably 0.011 mass% t o 20 mass%, more
25 preferably 0.1 mass% t o 15 mass%, still more preferably 0.5 mass%
t o 10 mass%, and p a r t i c u l a r l y preferably 1 mass% t o 5 mass%.
[0061]
.Manganese Ions
In order to uniformly roughen the metal member surface without
unevenness, the acidic etchant may contain manganese ions. The
manganese ions can be contained i n the acidic etchant by mixing a
5 manganese ion source with the acidic etchant. Examples of the
manganese ion source include manganese s u l f a t e , manganese chloride,
manganeseacetate, manganese fluoride, andmanganesenitrate. Among
the manganese ion sources, manganese n i t r a t e or manganese chloride
is preferably used from the viewpoints of low cost and the l i k e .
10 [0062]
Intheembodiment,thecontentofthemanganeseionsintheacidic
etchant is preferably 0 mass% t o 1 mass% and more preferably 0 mass%
t o 0.5 mass%. The present inventors v e r i f i e d t h a t , in a case where
the thermoplastic resin (A) constituting t h e r e s i n member 105 was
15 a polyolefin resin, even when the content of the manganese ions was
0 mass%, a s u f f i c i e n t bond strength was exhibited. That is, when
a polyolefin resin is used as the thermoplastic resin (A), it is
preferable t h a t the content of the manganese ions be 0 mass%. On
the other hand, when a thermoplastic r e s i n other than a polyolefin
20 resin is used, the manganese ions are appropriately used i n a content
of the above-described upper l i m i t or l e s s .
[0063]
Acid
The above-describedacidis acomponentthatdissolvesthemetal
25 oxidized by the f e r r i c ions and/or the cupric i o n s . Examples of the
acid include inorganic acids such as hydrochloric acid, hydrobromic
acid, s u l f u r i c acid, n i t r i c acid, phosphoric acid, perchloric acid,
and sulfamic acid; and organic acids such as sulfonic acid and
carboxylicacid. Examplesofthecarboxylicacidinclude formicacid,
a c e t i c acid, citric acid, oxalic acid, and malic acid. One kind or
two or more kinds of the acids can be mixed with t h e a c i d i c etchant.
5 Among the inorganic acids, s u l f u r i c acid is preferably used from the
viewpointofsubstantiallynoodoremissionandlowcost. Inaddition,
among the organic acids, carboxylic acid is preferably used from the
viewpoint of the uniformity of the roughening shape.
[0064]
10 In the embodiment, the content of the acid in t h e a c i d i c etchant
is preferably 0.1 mass% t o 50 mass%, more preferably 0.5 mass% t o
50 mass%, s t i l l more preferably 1 mass% t o 50 mass%, yet still more
p r e f e r a b l y l m a s s % t o 30mass%, even yetstillmorepreferablylmass%
to 25 mass%, and p a r t i c u l a r l y preferably 2 mass% t o 18 mass%. When
15 the content of the acid is greater than or equal t o the lower l i m i t ,
a decrease i n the roughening r a t e (dissolving r a t e ) of the metal can
be prevented. On the other hand, when the content of the acid is
l e s s than or equal to the upper l i m i t , c r y s t a l p r e c i p i t a t i o n of a
metal s a l t a t a decreased liquid temperature can be prevented, and
20 workability can be improved.
[0065]
.Other Components
To the acidic etchant which can be used in the embodiment, a
surfactant for preventing unevenness in roughening caused by a
25 surfacecontaminantsuchasa fingerprintmaybeadded, andoptionally
other additivesmayalsobe added. Examples o f t h e additives include
h a l i d e i o n sources which are added t o form a deep concavo-convex
portion, for example, sodium chloride, potassium chloride, sodium
bromide, and potassium bromide. Other examples of the additives
include thio compounds which are added to increase the roughening
rate, for example, thiosulfate ions and thiourea; azoles which are
5 added to obtain a more uniform roughening shape, for example,
imidazole, triazole, and tetrazole; and a pH adjuster which is added
to controla roughening reaction. When these other embodiments are
added, the total content thereof in the acidic etchant is preferably
0 . 0 1 mass% to 10 mass%.
10 [OD661
The acidic etchant according to the embodiment can be easily
prepared by dissolving the above-described respective components in
ion exchange water or the like.
[0067]

Hereinafter, the resin member 105 according to the embodiment
will be described.
The resin member 105 is formed of the thermoplastic resin
composition ( P ) . The thermoplastic resin composition (P) contains
20 the thermoplastic resin (A) as the resin component and optionally
further contains a filler (B). Further, the thermoplastic resin
composition ( P ) optionally furthercontains othercompoundingagents
For convenience of description, the resin member 105 being formed
of only the thermoplastic resin (A) is described as the resin member
25 105 being formed of the thermoplastic resin composition (P).
[0068]
(Thermoplastic Resin (A) )
The thermoplastic resin (A) is not particularly limited, and
examples thereof include polyolefin resins, polymethacrylic resins
such as polymethyl methacrylate resin, polyacrylic resins such as
polymethyl acrylate resin, polystyrene resins, polyvinyl
5 alcohol-polyvinylchloridecopolymerresins, polyvinylacetalresins,
polyvinyl butyral resins, polyvinyl formal resins, polymethyl
pentene resins, maleic anhydride-styrene copolymer resins,
polycarbonate resins, polyphenyleneetherresins, aromaticpolyether
ketones such as polyether ether ketone resins and polyether ketone
10 resins, polyester resins, polyamide resins, polyamide imide resins,
polyimide resins, polyether imide resins, styrene elastomers,
polyolefin elastomers, polyurethane elastomers, polyester
elastomers, polyamide elastomers, ionomers, amino polyacrylamide
resins, isobutylene-maleic anhydride copolymers, ABS, ACS, AES, AS,
15 ASA,MBS, ethylene-vinylchloridecopolymers, ethylene-vinylacetate
copolymers, ethylene-vinyl acetate-vinyl chloride graft polymers,
ethylene-vinyl alcohol copolymers, chlorinated polyvinyl chloride
resins, chlorinated polyethylene resins, chlorinated polypropylene
resins, carboxyl vinyl polymers, ketone resins, amorphous
20 copolyester resins, norbornene resins, fluoroplastics,
polytetrafluoroethylene resins, fluorinated ethylene polypropylene
resins, PFA, polychlorofluoroethylene
resins,ethylene-tetrafluoroethylene copolymers, polyvinylidene
fluoride resins, polyvinyl fluoride resins, polyarylate resins,
25 thermoplastic polyimide resins, polyvinylidene chloride resins,
polyvinyl chloride resins, polyvinyl acetate resins, polysulfone
resins, poly-para-methylstyrene resins, polyallylamine resins,
polyvinyl ether resins, polyphenylene oxide resins, polyphenylene
sulfide (PPS) resins, polymethylpentene resins, oligoesteracrylates,
xylene resins, maleic acid resins, polyhydroxybutyrate resins,
polysulfone resins, polylacticacidresins, polyglutamicacidresins,
5 polycaprolactone resins, polyether sulfone resins,
polyacrylonitrile resins, and styrene-acrylonitrile copolymer
resins. These thermoplastic resins may be used alone or in a
combination of two or more kinds.
[OD691
10 Among these, as the thermoplastic resin (A), one or two or more
thermoplastic resins selected from polyolefin resins, polyester
resins, and polyamide resins are preferably used fromthe viewpoint
of more efficiently obtaining the effect of improving the bond
strength between the metal member 103 and the resin member 105.
15 [0070]
As the polyolefin resins, polymers obtained by polymerization
of olefins can be used without any particular limitation.
Examples of the olefins constituting the polyolefin resins
include ethylene, a-olefins, and cyclic olefins.
20 [0071]
Examples ofthe a-olefins include linear or branched a-olefins
having 3 to 30 carbon atoms, preferably, 3 to 20 carbon atoms. More
specific examples of the a-olefins include propylene, 1-butene,
1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,
25 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, and 1-eicosene.
[0072]
Examples of the cyclic olefins include cyclic olefins having
3to 30 carbonatoms, preferably, 3to 20 carbonatoms. More specific
examples of the cyclic olefins include cyclopentene, cycloheptene,
norbornene, 5-methyl-2-norbornene, tetracyclododecene, and
5 2-methyl-l,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalen
e.
(00731
Preferable examples ofthe olefins constituting the polyolefin
resins include ethylene, propylene, 1-butene, 1-pentene,
10 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and
3-methyl-1-pentene. Among these, ethylene, propylene, 1-butene,
1-hexene, or 4-methyl-1-pentene are more preferable, and ethylene
or propylene is still more preferable.
[0074]
15 The polyolefin resins may be obtained by polymerization of one
kind of the above-described olefins, or may be obtained by random
copolymerization, blockcopolymerization, or graft copolymerization
of two or more kinds of the above-described olefins.
[00751
20 In addition, as the polyolefin resins, those having a linear
or branched structure may be used.
[0076]
Examples of the polyester resins include polylactic acid,
polyglycolic acid, polycaprolactone, aliphatic polyester such as
25 polyethylene succinate, polyethylene terephthalate, polyethylene
naphthalate, polybutylene terephthalate (PBT), and
polycyclohexylenedimethylene terephthalate (PCT) .
[0077]
Examples of the polyamide resins include aliphatic polyamides
by ring opening polymerization such as PA6 and PA12; polyamides by
polycondensation polymerization such as PA66, PA46, PA610, PA612,
5 andPA11; semi-aromaticpolyamides suchasMXD6, PAGT, PAgT, PA6T/66,
PA6T/6, amorphous PA; and fully aromatic polyamides such as
poly(p-phenylene terephthalamide), poly(m-phenylene
terephthalamide), and poly(m-phenylene isophthalamide) and amide
elastomers.
10 [0078]
In addition, as the thermoplastic resin (A) , one or two or more
thermoplastic resins selected from thermoplastic resins having a
glass transition temperature of higher than or equal to 140°C and
amorphousthermoplasticresinsarepreferablyusedfromtheviewpoint
15 of more efficiently obtaining the effect of improving the bond
strength between the metal member 103 and the resin member 105.
[0079]
Examples of the thermoplastic resins having a glass transition
temperature of higher than or equal to 140°C include one or two or
20 more thermoplastic resins selected from polycarbonate resins;
aromatic polyether ketones such as polyether ether ketone resins and
polyether ketone resins; polyimide resins; and polyether sulfone
resins.
[0080]
25 Examples of the amorphous thermoplastic resins include one or
two ormore amorphous thermoplastic resins selected frompolystyrene
resins, polyacrylonitrile resins, styrene-acrylonitrile copolymer
resins, acrylonitrile-butadiene-styrene copolymer resins (ABS
r e s i n s ) , polymethylmethacrylate resins, and polycarbonate r e s i n s .
[00811
Inordertopromoteinfiltrationintotheconcavo-convexportion
5 of the surface of the metal member 103, it is preferable t h a t the
thermoplastic r e s i n (A) have high f l u i d i t y . Therefore, in the
embodiment, MFR of the thermoplastic r e s i n (A) which is measured
according to ASTM Dl238 under a condition of a load of 2.16 kg is
preferably 10 9/10 min t o 200 9/10 min. MFR can be measured a t a
10 temperaturerihichis determineddependingoneach resin, for example,
a t 230°C in the case of a propylene polymer and a t 190°C in the case
of an ethylene polymer.
[0082]
The resinmember105 accordingtothe embodimentmaybeacoating
15 film. Forthe coating film, various commercially available coating
materials can be used.
[0083]
The kinds of the coating materials can be broadly c l a s s i f i e d
into an oil-based coatingmaterialandav~ater-basedc oatingmaterial.
20 Examples o f t h e oil-based coatingmaterial include coatingmaterials
in which a resin such as an a c r y l i c resin, a polyolefin resin, a
polyurethane resin, anepoxyresin, aphenolresin, a p o l y e s t e r r e s i n ,
or an alkyd resin is dissolved in an organic solvent. Examples of
thewater-basedcoatingmaterialincludea coatingmaterialsinwhich
25 a resin such as an a c r y l i c resin, an a c r y l i c s i l i c o n resin, a
polyolefin resin, a s i l i c o n resin, a polyurethane resin, an epoxy
resin, a phenol resin, a polyester resin, an alkyd resin, or a
biodegradable resin is suspended in water.
[0084]
The coating film may be formed of either the oil-based coating
material or the water-based coating material. Since a deep
5 concavo-convex portion is formed on the surface-roughened metal
member 103, a coating resin infiltrates into the concave portion,
and a coating film is formed. Therefore, the adhesion of the coating
film with metal is high, and it can be expected that the coating film
isnotlikelytobepeeledoff. Intheembodiment, asdescribedabove,
10 a deep concavo-convex portion is formed on the surface-roughened
metal member 103. Therefore, in particular, as in the case of the
water-based coating material, even when a coating resin is suspended
in water and the respectivemolecules ofthe coating resin formlarge
agglomerates based on the surface tension, the coating resin can
15 infiltrate into the concave portion during coating. Accordingly,
the metal-resin composite structure 106 according to the embodiment
is excellent from the viewpoint that a coating film having high
adhesion can be formed even when the water-based coating material,
with which a coating film having high adhesion is not likely to be
20 formed on the metal member surface in the related art, is used.
[0085]
(Filler (B))
The thermoplastic resin composition (P) may further contain the
filler (B) from the viewpoints of adjusting a difference in linear
25 expansion coefficient between the metal member 103 and the resin
member 105 and improving a mechanical strength of the resin member
105.
[0086]
As the f i l l e r ( B ) , for example, one or two or more kinds can
be selected from the group consisting of glass f i b e r , carbon fiber,
carbon p a r t i c l e s , clay, t a l c , s i l i c a , mineral, and cellulose f i b e r .
5 Amongthese, oneor twoormore kinds selectedfromglass f i b e r , carbon
f i b e r , t a l c , and mineral are preferably used.
[0087]
The shape of the f i l l e r (B) is not p a r t i c u l a r l y limited and may
be any shape, for example, fibrous, p a r t i c u l a t e , or p l a t e - l i k e .
10 [0088]
It is preferable t h a t the f i l l e r (B) contain 5%to100%of f i l l e r
p a r t i c l e s having a maximum length of longer than or equal t o 10 nm
and shorter than or equal t o 600 pm by number f r a c t i o n . The maximum
length is more preferably longer than or equal t o 30 nm and shorter
15 than or equal t o 550 pmand s t i l l m o r e preferablylongerthan or equal
t o 50 nm and shorter than or equal t o 500 pm. In addition, the number
f r a c t i o n of the f i l l e r (B) p a r t i c l e s having a maximum length in the
above-described range is preferably 10% t o 100% andmore preferably
20% t o 100%.
20 [0089]
When the maximum length of the f i l l e r (B) p a r t i c l e s is within
the above-described range, the f i l l e r (B) can e a s i l y functions i n
the thermoplastic resin (A) which is melted during the molding of
the thermoplastic resin composition (P). Therefore, during the
25 preparation of the metal-resin composite s t r u c t u r e 106 described
below, the f i l l e r (B) can be made t o be present i n the v i c i n i t y of
the metal member surface a t a c e r t a i n r a t i o . Therefore, the resin
which i n t e r a c t s with the f i l l e r (B) i n f i l t r a t e s i n t o the
concavo-convexportion ofthemetalmember surface as describedabove
and thus can obtain a stronger bond strength.
[0090]
5 In addition, when the number f r a c t i o n is within the
above-described range, a s u f f i c i e n t number of the f i l l e r (B)
p a r t i c l e s arepresent i n t h e thermoplastic resin composition (P) such
t h a t the f i l l e r (B) can a c t with the concavo-convex portion of the
surface of the metal member 103.
10 [0091]
In order to obtain the length of the filler (B) p a r t i c l e s , a
member formed of the thermoplastic r e s i n composition (P) is removed
from the obtained metal-resin composite s t r u c t u r e 106, the
thermoplastic resin composition (P) is heated i n an oven so as to
15 be completely carbonized, and then the f i l l e r (B) remaining a f t e r
the removal of the carbonized r e s i n is measured with a scanning
electronmicroscope. Here, a s i n d i c a t e d b y L 1 t o L3 i n the schematic
drawing of FIG. 11, the maximum length of the f i l l e r (B) p a r t i c l e s
r e f e r s t o : t h e maximum length L1 among the lengths of three sides
20 in the case of a rectangular shape; the longer length L2 among the
long-axis diameter length of a circle or the height of a cylinder
i n the case of a cylindrical shape; and the length L3 of the longest
diameter among the long axis diameter lengths of a l l the
cross-sections in the case of a sphere or a spheroid.
25 [0092]
Inordertoobtainthenumber f r a c t i o n o f t h e f i l l e r (B) p a r t i c l e s ,
the number of a l l the filler (B) p a r t i c l e s i n the electronmicrograph
used to measure the lengths of the filler (B) particle is counted,
andthenumberof filler (B) particlescontainedintheabove-describe
range is calculated.
[00931
5 As the filler (B), one kind or two or more kinds thereof may
be used. When trio or more kinds of fillers are used, the maximum
lengths of all the kinds ofthe filler (B) particles are collectively
obtained using the above-described method.
[0094]
10 The filler (B) particles may have a maximum length of greater
than 600 pm before being kneaded with the thermoplastic resin (A)
or may be cut and pulverized during kneading and molding such that
the maximum length is within the above-described range.
[0095]
15 Whenthethermoplasticresincomposition (P) containsthe filler
(B), the content of the filler (B) is preferably 1 part by mass to
100 parts by mass, more preferably 5 parts by mass to 90 parts by
mass, and particularly preferably 10 parts by mass to 80 parts by
mass riith respect to 100 parts by mass of the thermoplastic resin
20 (A).
[0096]
The filler (B) has an effect of controlling the linear expansion
coefficient of the resin member 105 as well as an effect of improving
the stiffness of the resin member 105. In particular, in the case
25 of a composite of the metal member 103 and the resin member 105
according to the embodiment, there is a large difference in the
temperature dependences of shape stability between the metal member
103 and the resin member 105 in many cases. Therefore, when a
temperature change is large, strain is likely to be generated in the
composite. By the resin member 105 containing the filler (B), this
strain can be reduced. In addition, by controlling the content of
5 the filler (B) to be within the above-described range, a decrease
in toughness can be suppressed.
[0097]
(Other Compounding Agents)
The thermoplastic resin composition (P) may contain other
10 compounding agents in order to impart various functions thereto.
[0098]
Examples of the compounding agent include a heat stabilizer,
an antioxidant, a pigment, a weather-resistant agent, a flame
retardant, aplasticizer, adispersant, alubricant, areleaseagent,
15 and an antistatic agent.
[0099]
(Method of Preparing Thermoplastic Resin Composition (P))
A method of preparing the thermoplastic resin composition (P)
is not particularly limited, and the thermoplastic resin composition
20 can be prepared using a generally well-known method. For example,
the following method may be used. First, the thermoplastic resin
(A), optionally the filler (B), and further optionally the other
compounding agents are mixed or melt-mixed with each other using a
mixing machine such as a Banbury mixer, a single screw extruder, a
25 twinscrewextruder, orahighspeedtr.rinscreriextruder. Asaresult,
the thermoplastic resin composition (P) is obtained.
[OlOO]
[Method of Preparing Metal-Resin Composite Structure]
Next, amethodof preparingthemetal-resin composite structure
106 according to the embodiment will be described.
~ h e m e t h o d o f ~ r e ~ a r i n ~ t h e m e t a l - rceosmipno site structure 106
5 is not particularly limited, and can be obtained by bonding the
thermoplastic resin composition (P) to the surface-roughened metal
member 103 while molding the thermoplastic resin composition (P) to
obtain a desired shape of the resin member 105.
[ OlOl]
10 Examples of a molding method of the resin member 105 include
resin molding methods such as injection molding, extrusion molding,
hot press molding, compression molding, transfer molding, cast
molding, laser welding molding, reaction injection molding (RIM
molding), liquid injectionmolding (LIMmolding), and spray forming.
15 [0102]
In addition, when a composite is formed of a metal
member-thermoplastic resin composition coating in which a coating
of the thermoplastic resin composition (P) is formed on the metal
member 103, a method of dissolving or dispersing the thermoplastic
20 resin composition (P) in a solvent to prepare a resin vanish and
coating the metal member 103 with this resin vanish or various other
coatingmethods canbe adopted. Examples ofthe other coatingmethod
include baking coating, electrodeposition coating, electrostatic
coating, powder coating, and ultraviolet curable coating.
25 [0103]
Among these, an injection molding method is preferably used as
the method of preparing the metal-resin composite structure 106.
Specifically, it is preferable that the metal-resin composite
structure 106 be prepared using an injection molding method of
inserting the metal member 103 into a cavity of an injection mold
and injecting the thermoplastic resin composition (P) into the mold.
5 Specifically, a method including the following processes (i) to (iii)
is preferable:
(i) a process of preparing the thermoplastic resin composition
( p ) ;
(ii) a process of installing the metal member 103 into an
10 injection mold; and
(iii) aprocessofinjectingthethermoplasticresincomposition
(P) into the mold so as to come into contact with at least a part
of the metal member 103 to thereby form the resin member 105.
Hereinafter, the respective processes will be described.
15 [01041
Inthe step (i) ofpreparingthethermoplasticresincomposition
( P ) , the above-describedmethodofpreparingthethermoplastic resin
composition (P) is used. For example, the thermoplastic resin (A),
optionally the filler (B), and further optionally the other
20 compounding agents are mixed or melt-mixed with each other using a
mixing machine such as a Banbury mixer, a single screw extruder, a
twinscrewextruder, orahighspeedtwinscrewextruder. Asaresult,
the thermoplastic resin composition (P) can be obtained.
[0105]
25 Next, the injection molding method in the processes (ii) and
(iii) will be described.
[01061
F i r s t , aninjectionmoldingmoldisprepared, themoldisopened,
and the metal member 103 is i n s t a l l e d i n t o a part of the mold. Next,
the mold is closed, the thermoplastic r e s i n composition (P) obtained
in the process (i) is injected i n t o the mold such t h a t a t l e a s t a
5 part of the thermoplastic r e s i n composition (P) comes i n t o contact
with a surface of the metal member 103 on which a concave portion
is formed, and the injected thermoplastic resin composition (P) is
s o l i d i f i e d . Next, the metal-resin composite s t r u c t u r e 106 can be
obtained by opening and releasing the mold.
10 [0107]
In addition, along with the injection molding including the
processes (i) t o (iii), i n j e c t i o n foam molding or rapid heat cycle
molding (RHCM, Heat and Cool Molding) of rapidly heating and cooling
a mold may be used in combination.
Examples of a method of the injection foam molding include a
method of adding a chemical foaming agent t o a resin; a method of
d i r e c t l y i n j e c t i n g n i t r o g e n g a s or carbondioxide gas i n t o a cylinder
portion of an injection molding machine; and a MuCell i n j e c t i o n
foaming molding method of i n j e c t i n g nitrogen gas or carbon dioxide
20 gas i n t h e s u p e r c r i t i c a l s t a t e i n t o a cylinderportionof an i n j e c t i o n
molding machine. In any of the methods, a metal-resin composite
s t r u c t u r e i n which a r e s i n member is a foam body can be obtained.
In addition, i n any of the methods, as a method of controlling the
mold, a method using counter pressure may be used, or a method using
25 core backmay a l s o b e useddepending on the shape of a m o l d e d a r t i c l e .
The rapid heat cycle molding can be performed by connecting the
mold t o a rapid heating and cooling device. The rapid heating and
cooling device may be a commonly-used type. As a heating method,
one of methods using steam, pressurized hot water, hot water, an
electric heater, and electromagnetic induction heating or a
combination of plural methods thereof may be used. As a cooling
5 method, one of methods using cold water and cold oil or a combination
thereof may be used. As rapid heat cycle molding conditions, for
example, it is preferable that an injection mold be heated at a
temperature of higher than or equal to 100°C and lower than or equal
to 250°C, and the injection mold be cooled after the injection of
10 the thermoplastic resin composition (P) . A preferable range of the
moldheatingtemperaturevaries depending on the thermoplastic resin
(A) constituting the thermoplastic resin composition (P). When a
crystalline resin having a melting point of lower than 200°C is used,
the mold heating temperature is preferably higher than or equal to
1 5 100°C and lower than or equal to 150°C. When a crystalline resin
having a melting point of higher than or equal to 200°C is used, the
mold heating temperature is preferably higher than or equal to 14OoC
and lower than or equal to 250°C. When an amorphous resin is used,
the mold heating temperature is preferably higher than or equal to
20 50°C and lower than or equal to 250°C and more preferably higher than
or equal to 100°C and lower than or equal to 180°C.
[0108]
Next, a method of forming the coating film on the metal member
103 will be described.
25 As the method of forming the coating film on the metal member
103, a method of forming a coating film which is used in the related
art can be used without any limitation.
[01091
For example, the surface of the metal member 103 can coated with
the above-described various coating materials using a method, for
example, spray coating such as air spraying or airless spraying, dip
5 coating, brush coating, roller coating, or coater coating.
[01101
[Use of Metal-Resin Composite Structure]
The metal-resin composite structure 106 according to the
embodiment is applicabletovarious uses due to its high productivity
10 and high degree of freedom for shape control.
Further, the metal-resin composite structure 106 according to
the embodiment exhibits air tightness and water tightness and thus
can be preferably used according to the properties.
[Olll]
15 Examples ofthe uses ofthemetal-resin composite structure 106
include structural components for vehicles, components mounted in
vehicles, casesofelectronicapparatuses, casesofhomeelectronics,
structuralcomponents, mechanicalcomponents, various components for
vehicles, components for electronic apparatuses, furniture,
20 household components such as kitchenware, medical equipment,
components of construction materials, and other structural
components and exterior components.
[01121
More specifically, the following components are used, which are
25 designed such that metal supports a portion in which the strength
is insufficient with only a resin. Examples of components for
vehicles include an instrument panel, a console box, a door knob,
a door trim, a shift lever, pedals, a glove box, a bumper, a hood,
a fender, a trunk, a door, a roof, a pillar, a seat sheet, a radiator,
anoil pan, a steeringriheel, anECUbox, andan electrical component.
Inaddition, examples of constructionmaterials andfurnitureinclude
5 a glass window frame, a handrail, a curtain rail, a chest of drawers,
a drawer, a closet, a bookshelf, a desk, and a chair. In addition,
examples of high-precisionelectroniccomponentsinclude a connector,
a relay, and a gear. In addition, examples of shipping casks include
a shipping container, a suitcase, and a trunk.
10 [0113]
Inaddition, themetal-resincomposite structure 106 canbeused
for components in which the high thermal conductivity of the metal
member 103 and the insulating property of the thermoplastic resin
(A) are combined to optimally design heat management, for example,
15 can be used for various home electronics. Specific examples of the
home electronics include home electronics such as a refrigerator,
a washing machine, a vacuum cleaner, a microwave oven, an air
conditioner, an lighting device, an electric water heater, a
television, a timepiece, a ventilating fan, a projector, and a
20 speaker; and electronic information devices such as a personal
computer, a mobile phone, a smartphone, a digital camera, a tablet
PC, a mobile music player, a mobile game machine, a charger, and a
battery.
[01141
25 Regarding these components, the surface area thereof increases
by roughening the surface of the metal member 103. Therefore, the
contact area between the metal member 103 and the resin member 105
increases, and the heat resistance at a contact interface can be
reduced.
[0115]
Examples of other uses of the metal-resin composite structure
5 106includetoys, sports goods, shoes, sandals, bags, dinnerware such
as a fork, a knife, a spoon, or a dish, stationery goods such as a
ball-point pen, a mechanical pencil, a file, or a binder, cookware
such as a frying pan, a pot, a kettle, a spatula, a ladle, a perforated
ladle, a whisk, or tongs, components for lithium ion secondary
10 batteries, and robots.
[0116]
Hereinabove, the uses of the metal-resin composite structure
according to the present invention have been described. However,
these uses are merely exemplary, and the present invention is
15 applicable to uses other than the above-described examples.
[0117]
Hereinabove, the embodiment of the present invention has been
described. However, the embodimentismerelyexemplary, andvarious
configurations other than the above-described configurations can be
20 adopted.
[Examples]
[0118]
Hereinafter, the embodiment will be described in detail with
reference to Examples and Comparative Examples. The embodiment is
25 not limited to the description of these examples.
[0119]
FIGS. 1 and 2 are used as drawings common to the respective
examples.
FIG. 1 is an external view schematically showing a structural
exampleofthemetal-resincompositestructure106ofthemetalmember
103 and the resin member 105.
5 FIG. 2 is a configuration diagram schematically showing an
example ofaprocess ofpreparingthemetal-resincomposite structure
106usingthemetalmember103 andtheresinmember105. Specifically,
the metal member 103, which is processed into a predetermined shape
and has a surface on which the bonding portion surface
10 (surface-roughened region) 104 having a fine concavo-convex portion
is formed, is installed into an injection mold 102; and the
thermoplasticresincomposition (P) i s i n j e c t e d t h r o u g h a g a t e - r u n n e r
107 using an injection molding machine 101 and is integrated with
themetalmember103onwhichthefineconcavo-convexportionis formed,
15 thereby preparing the metal-resin composite structure 106. These
processes are schematically shown in FIG. 2.
[0120]
(Material Ratio of the Roughness Profile (Rmr), Ten Point
Average Roughness (Rz) , and Mean Width of the Profile Elements (RSm)
20 on Metal Member Surface)
Regarding the surface roughness which was measured according
to JIS B0601 (corresponding international standard: 1504287) using
a surface roughness measuring device "SURFCOM 1400D (manufactured
by Tokyo Seimitsu Co., Ltd.)", a material ratio of the roughness
25 profile (Rmr) , a ten point average roughness (Rz) , and a mean width
ofthe profile elements (RSm) weremeasured. Measurement conditions
were as follows.
-Stylus t i p radius: 5 pm
.Reference length: 0.8 mm
.Evaluation length: 4 mrn
.Measurement speed: 0.06 mm/sec
5 The measurement was performed on s i x l i n e a r portions i n t o t a l
on a surface of a metal member including three a r b i t r a r y l i n e a r
portions ~ihichwereparalleltoeachotherandanotherthreea r b i t r a r y
l i n e a r portions which were perpendicular t o the former three l i n e a r
portions ( r e f e r t o FIG. 4 ) . In Examples and Comparative Examples,
10 theentireportionofthesurfaceofthemetalmember103wasroughened.
Therefore, it can be understood t h a t , even when a material r a t i o of
the roughness p r o f i l e (Rmr) , a ten point average roughness (Rz) , and
a mean width of t h e p r o f i l e elements (RSm) are measured regarding
the bonding portion surface 104 of the metal-resin composite
15 structure106, thesameevaluationresultsasthoseofthemeasurement
positions shown i n FIG. 4 can be obtained.
[0121]
(Evaluation Method of Bond Strength and Pass-Fail
Determination)
20 Using a t e n s i l e strength t e s t e r (Model 1323 (manufactured by
Aikoh Engineering Co., Ltd. ) ) t o which a j i g dedicated t o the t e n s i l e
strength test was i n s t a l l e d , t h e measurement was performed a t room
temperature (23°C) under conditions of a distance between chucks of
60 mm and a t e n s i l e speed of 10 mm/min. The bond strength (MPa) was
25 obtainedbydividingabreakingload (N) b y t h e a r e a o f t h e m e t a l - r e s i n
bonded portion.
[0122]
(Adhesion Test of Metal Member and Coating Film)
Using an applicator, an aluminum plate (dimension: 70x150~1t )
of Alloy No. 5052 defined in JIS H4000 was coated with a water-based
coating material such that the thickness of a dried coating film was
5 40 pm, and the aluminum plate was dried. Next, an end portion and
a back surface were also coated with the same water-based coating
material. This coated metal member was dried for one day in an
atmosphere of 20°C and 55% RH.
[0123]
10 The adhesion of the coated metal member obtained as above was
measured according to JIS K 5600-5-6 (cross-cut method). Swelling
was evaluated for adhesion based on the following criteria.
[0124]
[Evaluation of Adhesion of Coating Film]
0: The cut edge was completely smooth, and there was no peeling
in any lattice cell.
1: The coating film at the intersection of cuts. The cross-cut
portion affected did not clearly exceed 5%.
2: A small amount of peeling of the coating film was observed
20 along the cut edge and/or the intersection point of cuts. The
cross-cut portion affected was greater than 5% but did not exceed
15%.
3: A large amount of peeling of the coating film was observed
partiallyandcompletelyalongtheedgeof cuts, and/orvariousparts
25 of the lattice cell were partially or completely peeled. The
cross-cut portion affected was greater than 15% but did not exceed
35%.
4: A large amount of peeling of the coating film was observed
partiallyandcompletelyalongtheedge of cuts, and/or several parts
of the lattice cell were partially or completely peeled. The
cross-cut portion affected was greater than 35% but did not exceed
5 65%.
5: The degree of peeling was greater than Grade 4.
[0125]
(Surface-Roughening A of Metal Member)
[Preparation Example 1Al
10 (Surface-Roughening Using Acidic Etchant 1A)
An aluminum plate (thickness: 1.6 mm) of Alloy No. 5052 defined
in JIS H4000 was cut into a length of 45 mm and a width of 18 mm.
This aluminum plate was etched by being dipped in an acidic etchant
1A (30'~) having a composition shown in Table 1A for 40 seconds and
15 being shaken. Next, the aluminum plate was washed with flowing water
by ultrasonic cleaning (in water, 1 minute) and then was dried. As
a result, a surface-treated metal member was obtained.
The surface roughness of the obtained surface-treated metal
member was measured using a surface roughness measuring device
20 "SURFCOM 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)". In
addition, regarding six linear portions, material ratio of the
roughness profile (Rmr) at cutting levels of lo%, 20%, 30%, 40%, 50%,
60%, 70%, and 80%, ten point average roughnesses (Rz) and mean width
of the profile elements (RSm) were obtained. Among these, Table 2A
25 shows: Rmr (20%) values a t a c u t t i n g l e v e l o f 2 0 % ; t h e n u m b e r o f l i n e a r
portions in which the Rmr (20%) is lower than or equal to 30%; Rmr
(40%) values at a cutting level of 40%; the number of linear portions
in which the Rmr (40%) is lower than or equal to 60%; Rz values and
mean width of the profile elements (RSm) of the six linear portions;
and an etching ratio obtained from mass ratios of the metal member
before and after etching. In addition, FIG. 5 shows a surface
5 roughness curve obtained from the above measurement.
The surface of the surface-treated metal member was observed
using a scanning electron microscope (manufactured by JEOL Ltd.,
Model No. JSM-6701F) at a magnification of 5000 times. FIG. 6 shows
a micrograph.
10 [01261
[Preparation Example 2A]
(Surface-Roughening Using Acidic Etchant 2A)
A surface-treated metal member was obtained by performing the
same treatment as that of Preparation Example lA, except that the
15 aluminum plate was etched for 80 seconds using an acidic etchant 2A
instead of the acidic etchant 1A shown in Table 1A.
Table 2AshowsRmr, Rz, RSm, andanetchingratiooftheobtained
surface-treated metal member. In addition, FIG. 7 shows a surface
roughness curve obtained from the above measurement.
20 The surface of the surface-treated metal member was observed
using a scanning electron microscope (manufactured by JEOL Ltd.,
Model No. JSM-6701F) at a magnification of 5000 times. FIG. 8 shows
a micrograph.
[0127]
25 [Preparation Example 3A]
(Treatment Using Alkaline Solution After Surface-Roughening
Using Acidic Etchant 1A)
An aluminum p l a t e (thickness: 1.6 mm) of Alloy No. 5052 defined
i n JIS H4000 was cut into a length of 45 mm and a width of 18 mm.
This aluminum p l a t e was etched by being dipped in an acidic etchant
1A (30°C) having a composition shown i n Table 1A for 40 seconds and
5 being shaken. Next, the aluminum was riashed with flowing water (1
minute). Next, t h e t r e a t e d aluminum p l a t e was dipped i n an aqueous
solution (25°C) of 5 mass% of sodium hydroxide, was shaken for 30
seconds, andrias washedwithwater. Next, thetreatedaluminumplate
was dipped i n an aqueous solution (25°C) of 35 mass% of n i t r i c acid,
10 was shaken for 30 seconds, was washed (1 minute) with flowing water,
and was dried. As a r e s u l t , a surface-treated metal member was
obtained.
Table 2Ashows Rmr, Rz, RSm, andanetching r a t i o o f t h e o b t a i n e d
surface-treated metal member. In addition, FIG. 9 shows a surface
15 roughness curve obtained from the above measurement.
The surface of the surface-treated metal member was observed
using a scanning electron microscope (manufactured by JEOL Ltd.,
Model No. JSM-6701F) a t a magnification of 5000 times. FIG. 10 shoris
a micrograph.
20 [01281
[Preparation Example 4A]
(Surface-Roughening Using Acidic Etchant 3A)
A surface-treated metal member was obtained by performing the
same treatment as t h a t of Preparation Example lA, except t h a t the
25 aluminum p l a t e was etched for 160 seconds using an acidic etchant
3A instead of the acidic etchant 1A shown i n Table 1A.
Table 2Ashows Rmr, Rz, RSm, andanetching r a t i o o f t h e obtained
surface-treated metal member.
[0129]
[Preparation Example 5A]
(Surface-Roughening Using Acidic Etchant 3A)
5 A surface-treated metal member was obtained by performing the
same treatment as that of Preparation Example lA, except that the
aluminum plate was etched for 80 seconds using an acidic etchant 3A
instead of the acidic etchant 1A shown in Table 1A.
Table 2Ashows Rmr, Rz, RSm, andanetching ratiooftheobtained
10 surface-treated metal member.
[0130]
[Preparation Example 6A]
(Surface-Roughening Using Acidic Etchant 3A)
A surface-treated metal member was obtained by performing the
15 same treatment as that of Preparation Example lA, except that the
aluminum plate was etched for 40 seconds using an acidic etchant 3A
instead of the acidic etchant 1A shown in Table 1A.
Table 2A shows an etching ratio of the obtained surface-treated
metal member.
20 [0131]
[Preparation Example 7A]
(Surface-Roughening Using Acidic Etchant 4A)
A surface-treated metal member was obtained by performing the
same treatment as that of Preparation Example lA, except that the
25 aluminum plate was etched for 320 seconds using an acidic etchant
4A instead of the acidic etchant 1A shown in Table 1A.
Table 2Ashows an etching ratio ofthe obtainedsurface-treated
metal member.
[0132]
[Preparation Example 8A]
(Surface-Roughening Using Acidic Etchant 4A)
5 A surface-treated metal member was obtained by performing the
same treatment as that of Preparation Example lA, except that the
aluminum plate was etched for 160 seconds using an acidic etchant
4A instead of the acidic etchant 1A shown in Table 1A.
Table 2A shows an etching ratio of the obtained surface-treated
10 metal member.
[0133]
[Preparation Example 9A]
(Surface-Roughening Using Acidic Etchant 4A)
A surface-treated metal member was obtained by performing the
15 same treatment as that of Preparation Example lA, except that the
alumlnum plate was etched for 80 seconds using an acidic etchant 4A
instead of the acidic etchant 1A shown in Table 1A.
Table 2Ashows an etching ratio ofthe obtained surface-treated
metal member.
20 [0134]
[Preparation Example 10A]
(Surface-Roughening Using Acidic Etchant 4A)
A surface-treated metal member was obtained by performing the
same treatment as that of Preparation Example lA, except that the
25 aluminum plate was etched for 40 seconds using an acidic etchant 4A
instead of the acidic etchant 1A shown in Table 1A.
Table 2A shows an etching ratio of the obtained surface-treated
metal member.
[01351
[Example lA]
The small dumbbell-shaped metal insert mold 102 was mounted on
5 J85AD11OHmanufacturedbyTheJapanSteelWorksLtd., andthealuminum
plate (metal member 103) prepared in Preparation Example 1A was
installed into the mold 102. Next, as the thermoplastic resin
composition (P), glass fiber reinforced polypropylene (V7100
manufactured by Prime Polymer Co., Ltd.; 80 parts by mass of
10 polypropylene (MFR (230°C, load: 2.16 kg) : 18 g/10 min) and 20 parts
bymass of glass fiber) wasinjectedintothemold102 underconditions
of a cylinder temperature of 250°C, a mold temperature of 12OoC, an
injection rate of 25 rnm/sec, a holding pressure of 80 MPa, and a
pressure holding time of 10 seconds. As a result, a metal-resin
15 composite structure 106 was obtained. Table 3A shows the evaluation
results of the bond strength.
[0136]
[Example 2A]
A metal-resin composite structure 106 was obtained using the
20 same method as that of Example lA, except that the aluminum plate
prepared in Preparation Example 2A was installed instead of the
aluminum plate prepared in Preparation Example 1A. Table 3A shows
the evaluation results of the bond strength.
[0137]
2 5 [Example 3A]
A metal-resin composite structure 106 was obtained using the
same method as that of Example lA, except that the aluminum plate
prepared in Preparation Example 4A was installed instead of the
aluminum plate prepared in Preparation Example 1A. Table 3A shows
the evaluation results of the bond strength.
[0138]
5 [Example 4A]
A metal-resin composite structure 106 was obtained using the
same method as that of Example lA, except that the aluminum plate
prepared in Preparation Example 5A was installed instead of the
aluminum plate prepared in Preparation Example 1A. Table 3A shows
10 the evaluation results of the bond strength.
[0139]
[Example 5A]
A metal-resin composite structure 106 was obtained using the
same method as that of Example lA, except that the aluminum plate
15 prepared in Preparation Example 7A was installed instead of the
aluminum plate prepared in Preparation Example 1A. Table 3A shows
the evaluation results of the bond strength.
[0140]
[Comparative Example lA]
20 A metal-resin composite structure 106 was obtained using the
same method as that of Example lA, except that the aluminum plate
prepared in Preparation Example 3A was installed instead of the
aluminum plate prepared in Preparation Example 1A. Table 3A shows
the evaluation results of the bond strength.
25 [0141]
[Comparative Example 2A]
A metal-resin composite structure 106 tias obtained using the
same method as that of Example lA, except that the aluminum plate
prepared in Preparation Example 6A was installed instead of the
aluminum plate prepared in Preparation Example 1A. Table 3A shows
the evaluation results of the bond strength.
5 [01421
[Comparative Example 3Al
A metal-resin composite structure 106 was obtained using the
same method as that of Example lA, except that the aluminum plate
prepared in Preparation Example 8A was installed instead of the
10 aluminum plate prepared in Preparation Example 1A. Table 3A shows
the evaluation results of the bond strength.
[0143]
[Comparative Example 4A]
A metal-resin composite structure 106 was obtained using the
15 same method as that of Example lA, except that the aluminum plate
prepared in Preparation Example 9A was installed instead of the
aluminum plate prepared in Preparation Example 1A. Table 3A shoris
the evaluation results of the bond strength.
[0144]
20 [Comparative Example 5A]
A metal-resin composite structure 106 rias obtained using the
same method as that of Example lA, except that the aluminum plate
prepared in Preparation Example 10A was installed instead of the
aluminum plate prepared in Preparation Example 1A. Table 3A shows
25 the evaluation results of the bond strength.
[0145]
[Table lA]
Table 1A
Component
S u l f u r i c Acid
F e r r i c Chloride
Cupric Chloride
Manganese Sulfate
(Monohydrate)
Ion Exchange
W ; l t e r
Mixing Amount
Acidic
Etchant 1A
8.2 rut%
15" wt%
(pe3+: 5.4
wt-%.l
0.2 v1t% (cuZ+:
0.1 w t % )
Not Contained
Balance
0.4 W t % (cuZ+:
0.2 v ~ t % )
0.7 r.rt% (~n'+:
0.2 w t % )
Balance
Acidic Etchant
2A
8.2 w t %
7.8 wt% (pe3+:
2.7 w t % )
0.1 w t % (cuZ+:
0.05 w t % )
Not Contained
Balance
0.4 wt% (cuZ+:
0.2 w t % )
Not Contained
Balance
Acidic Etchant
3A
4 . 1 w t %
3.9 v l t % ( ~ e ~ ' :
1.35 v r t % )
Acidic Etchant
4A
2.05 ut%
1.95 v l t % (pe3':
0.68 w t % )
[ T a b l e 2A]
T a b l e 2A
66
In the above table, ND represents "Not Measured".
[0147]
[Table 3A]
Table 3A
Comoonent
[0148]
InExamplelA, as showninFIG. 5, aconcavo-convexportionhaving
a sharp angle was formed on the surface of the metal member t r e a t e d
i n Preparation Example lA, and it is considered t h a t , by t h e r e s i n
member 105 being inserted i n t o the concavo-convex portion, the
obtained metal-resin composite s t r u c t u r e 106 obtained a high bond
strength.
InExample2A, asshowninFIG. 7, aconcavo-convexportionhaving
a sharper angle than t h a t of FIG. 5 was formed on the surface of the
metal member t r e a t e d i n Preparation Example 2A, and it i s considered
t h a t , by t h e r e s i n member being inserted i n t o t h e concavo-convex
portion, the obtained metal-resin composite s t r u c t u r e 106 obtained
a high bond strength.
On the other hand, i n Comparative Example l A , as shown i n FIG.
9, a concavo-convex portion having a s u f f i c i e n t s i z e was not formed
on the surface of the metal member treated in Preparation Example
3A, and the obtained metal-resin composite structure 106 obtained
a low bond strength.
[0149]
5 (Surface-Roughening B of Metal Member)
[Preparation Example lB]
(Surface-Roughening Using Acidic Etchant B)
An aluminum plate (thickness : 1.6 mm) of Alloy No. 5052 defined
in JIS H4000 was cut into a length of 45 mm and a riidth of 18 mm.
10 This aluminum plate was etched in an etching amount shown in Table
3B by being dipped in an acidic etchant B (30°C) having a composition
shown in Table 1B and being shaken. Next, the aluminum plate was
washedwith flowingriater (lminute) and thenwas dried. As a result,
a surface-treated metal member was obtained. The etching amount was
15 calculated from a mass difference of the aluminum component before
and after the etching, the specific gravity of aluminum, and the
surface area ofthe aluminumplate, andwas controlledby the etching
time. The same shall be applied to the "etching amount" described
below.
20 [01501
The surface of the surface-treated metal member was observed
using a scanning electron microscope (manufactured by JEOL Ltd.,
Model No. JSM-6701F) at a magnification of 5000 times. FIG. 12 shows
a micrograph.
25 [0151]
[Preparation Example 2B]
(Ultrasonic Cleaning After Surface-Roughening Using Acidic
Etchant B)
A surface-treated metal member was obtained by performing the
same treatment as that of Preparation Example 1B, except that the
aluminumplate was washedby ultrasonic cleaning (inwater, lminute)
5 after being etched using the acidic etchant B.
[01521
The surface of the surface-treated metal member was observed
using a scanning electron microscope (manufactured by JEOL Ltd.,
Model No. JSM-6701F) at a magnification of 5000 times. FIG. 13 shows
10 a micrograph.
[0153]
[Preparation Example 3B]
(Surface-Roughening Using Acidic Etchant B After Treatment
Using Alkaline Etchant)
15 An aluminum plate (thickness: 1.6 mm) of Alloy No. 5052 defined
in JIS H4000 was cut into a length of 45 mm and a width of 18 mm.
This aluminum plate was dipped in an alkaline etchant (35°C) having
a composition shown in Table 2B, was shaken for 1 minute, and was
washed (I minute) with flowing water. Next, this aluminum plate was
20 etched in an etching amount shown in Table 3B by being dipped in an
acidic etchant B (30°C) having a composition shown in Table 1B and
being shaken. Next, the aluminumplatewas washedwith flowingwater
(1 minute) and then was dried. As a result, a surface-treated metal
member was obtained. The etching amount shown in Table 3B is the
25 sum of the etching amount by the alkaline etchant and the etching
amount by the acidic etchant B.
[0154]
[Preparation Example 4B]
(Surface-Roughening Using Alkaline Etchant)
An aluminum p l a t e (thickness: 1.6 mm) of Alloy No. 5052 defined
i n JIS H4000 was cut i n t o a length of 45 mm and a width of 18 mm.
5 This aluminum p l a t e was etched in an etching amount shown i n Table
3Bbybeing dippedinan alkaline etchant (35'C) havinga composition
shown i n Table 2B and being shaken. After being washed (I minute)
with flowingwater, thetreatedaluminumplatewasdippedinanaqueous
solution (25°C) of 15 mass% of n i t r i c acid, was shaken for 60 seconds,
10 was washed (lminute) with flowingwater, andwas dried. As a r e s u l t ,
a surface-treated metal member was obtained.
[01551
The surface of the surface-treated metal member was observed
using a scanning electron microscope (manufactured by JEOL Ltd.,
15 Model No. JSM-6701F) a t a magnification of 5000 times. FIG. 14 shows
a micrograph.
[0156]
[Preparation Example 5B]
(Surface-Roughening Using Alkaline Etchant After Treatment
20 Using Acidic Etchant B)
An aluminum p l a t e (thickness: 1.6 mm) of Alloy No. 5052 defined
i n JIS H4000 was cut i n t o a length of 45 mm and a width of 18 mm.
This aluminum p l a t e was dipped i n t h e a c i d i c etchant B (30°C) having
a composition shown i n Table l B , was shaken for 1 minute, and was
25 washed (1 minute) with flowing water. Next, t h i s aluminum p l a t e was
etched i n an etching amount shown i n Table 3B by being dipped i n an
alkaline etchant (35'C) having a composition shown i n Table 2B and
being shaken. Next, the aluminumplate wasviashedwith flowingwater
(I minute) and then was dried. As a r e s u l t , a surface-treated metal
member was obtained. The etching amount shown i n Table 3B is the
sum of the etching amount by t h e a c i d i c etchant B and the etching
5 amount by the alkaline etchant.
[0157]
[Preparation Example 6B]
(Treatment Using Alkaline Solution After Surface-Roughening
Using Acidic Etchant B)
10 An aluminum p l a t e (thickness: 2 mm) of Alloy No. 5052 defined
i n JIS H4000 tias cut i n t o a length of 110 mm and a width of 25 mm.
This aluminum plate was etched i n an etching amount shown i n Table
3B by being dipped in an acidic etchant B (30°C) having a composition
shown i n Table 1B and being shaken. Next, the aluminum p l a t e was
15 washed (I minute) with flowing water. Next, the t r e a t e d aluminum
p l a t e was dipped in an aqueous solution (25'C) of 5 mass% of sodium
hydroxide, was shakenfor30 seconds, andr.raswashedwithwater. Next,
t h e t r e a t e d aluminum p l a t e was dipped in an aqueous solution (25°C)
of 35 mass% of n i t r i c acid, was shaken for 30 seconds, was washed
20 (I minute) with flowing water, and vias dried. As a r e s u l t , a
surface-treated metal member was obtained.
[01581
The surface of the surface-treated metal member was observed
using a scanning electron microscope (manufactured by JEOL Ltd.,
25 Model No. JSM-6701F) a t a magnification of 5000 times. FIG. 15 shows
a micrograph.
[0159]
[Example lB]
The small dumbbell-shaped metal insert mold 102 was mounted on
J85ADl10HmanufacturedbyTheJapanSteelWorksLtd., andthealuminum
plate (metal member 103) prepared in Preparation Example 1B bras
5 installed into the mold 102. Next, as the thermoplastic resin
composition (P), glass fiber reinforced polypropylene (V7100
manufactured by Prime Polymer Co., Ltd.; 80 parts by mass of
polypropylene (MFR (230°C, load: 2.16 kg) : 18 9/10 min) and 20 parts
bymassofglass fiber) wasinjectedintothemold102 underconditions
10 of a cylinder temperature of 250°C, a mold temperature of 120°C, an
injection rate of 25 rnrn/sec, a holding pressure of 80 MPa, and a
pressure holding time of 10 seconds. As a result, a metal-resin
composite structure 106 was obtained. Table 4B shows the evaluation
results of the bond strength.
15 [01601
[Example 2B]
A metal-resin composite structure 106 was obtained using the
same method as that of Example lB, except that the aluminum plate
prepared in Preparation Example 2B was installed instead of the
20 aluminum plate prepared in Preparation Example 1B. Table 4B shows
the evaluation results of the bond strength.
[0161]
[Example 3B]
A metal-resin composite structure 106 was obtained using the
25 same method as that of Example lB, except that, as the thermoplastic
resincomposition (P), glass fiberreinforcedpolypropylene (L-2040P
manufactured by Prime Polymer Co., Ltd.; 80 parts by mass of
polypropylene (MFR (230°C, load: 2.16 kg) : 20 g/10 min) and 20 parts
bymass of glass fiber) wasusedinsteadoftheglass fiber reinforced
polypropylene (V7100 manufactured by Prime Polymer Co., Ltd.; 80
parts by mass of polypropylene (MFR (230°C, load: 2.16 kg) : 18 g/10
5 min) and 20 parts by mass of glass fiber). Table 4B shows the
evaluation results of the bond strength.
[0162]
[Example 4B]
A metal-resin composite structure 106 was obtained using the
10 same method as that of Example lB, except that, as the thermoplastic
resin composition (P), homopolypropylene (J105G manufactured by
Prime Polymer Co., Ltd., (MFR (23OoC, load: 2.16 kg) : 9 9/10 min) )
was used instead of the glass fiber reinforced polypropylene (V7100
manufactured by Prime Polymer Co., Ltd.; 80 parts by mass of
15 polypropylene (MFR (230°C, load: 2.16 kg) : 18 9/10 min) and 20 parts
by mass of glass fiber). Table 4B shows the evaluation results of
the bond strength.
[0163]
[Example 5B]
20 A metal-resin composite structure 106 was obtained using the
same method as that of Example 1B, except that the aluminum plate
prepared in Preparation Example 38 was installed instead of the
aluminum plate prepared in Preparation Example 1B. Table 4B shows
the evaluation results of the bond strength.
25 [0164]
[Comparative Example lB]
A metal-resin composite structure 106 was obtained using the
same method as that of Example lB, except that the aluminum plate
prepared in Preparation Example 4B was installed instead of the
aluminum plate prepared in Preparation Example 1B. Table 4B shows
the evaluation results of the bond strength.
[Comparative Example 2B]
A metal-resin composite structure 106 was obtained using the
same method as that of Example lB, except that the aluminum plate
prepared in Preparation Example 5B was installed instead of the
10 aluminum plate prepared in Preparation Example 1B. Table 4B shows
the evaluation results of the bond strength.
[Comparative Example 3B]
A metal-resin composite structure 106 was obtained using the
15 same method as that of Example lB, except that the aluminum plate
prepared in Preparation Example 6B was installed instead of the
aluminum plate prepared in Preparation Example 1B. Table 4B shows
the evaluation results of the bond strength.
20 [Table 1B]
Table 1B
Acidic Etchant B
Component
Sulfuric Acid
Ferric Chloride
Cupric Chloride
Manganese Sulfate (Monohydrate)
Ion Exchanqe Water
Mixing Amount
8.2 wt%
15.6 wt%
(Ferric Ions: 5.37 wt%)
0.4 wt%
(Cupric Ions: 0.19 wt%)
0.7 wt%
(Manganese Ions: 0.23 wt%)
Balance
[0168]
[Table 2B]
Table 2B
Alkaline Etchant
I Zinc Nitrate I (Zinc Ions: 4.32 wt%, Nitrate
Component
Sodium Hydroxide
Mixing Amount
16.8 wt%
(Hydroxide Ions: 7.14 wt%)
12.5 wt%
[Table 3B]
Sodium Thiosulfate
Ion Exchange Water
Table 3B
Ions: 8.18 wt%)
1.0 wt%
(Thiosulfate Ions: 0.71 wt%)
Balance
Preparation Example 1B
Preparation Example 2B
Preparation Example 38
Preparation Example 4B
Acidic Etchant B
+ Washing vlith Water
Acidic Etchant B
+ Ultrasonic Cleaning
Alkaline Etchant
Preparation Example 5B
2 0
2 0 - Acidic Etchant B
+ Washing with Water
Alkaline Etchant
+ Washing r.rithi qater
Acidic Etchant B
6B
15
4
1 Acidic Etchant B I
+- Alkaline Etchant Washing with Water
2 0
+- Aqueous Sodium Hydroxide Solution Aqueous Nitric Acid Solution
+ Washing with Plater
20
[0170]
[Table 4B]
Table 4B
[0171]
In Example lB, as shown in FIG. 12, a concavo-convex portion
having a sharp angle was formed on the surface of the metal member
103 treated in Preparation Example lB, and it is considered that,
bytheresinmember105beinginsertedintotheconcavo-convexportion,
the obtainedmetal-resincomposite s t r u c t u r e 1 0 6 o b t a i n e d a h i g h b o n d
strength.
[0172]
In Example 28, the metal member 103 treated in Preparation
Example 1B was further washed by ultrasonic cleaning (in water, one
minute) in Preparation Example 2B. Due to the above treatment, smut
and the like formed on the metal surface can be removed. Therefore,
as shown in FIG. 13, a concavo-convex portion having a sharp angle
was formedonthe surfaceofthemetalmember103, a n d i t is considered
t h a t , by t h e r e s i n member 105 being inserted into the concavo-convex
portion, the obtained metal-resin composite s t r u c t u r e 106 obtained
a high bond strength.
5 [0173]
In Example 3B, t h e g l a s s f i b e r reinforced polypropylene
(L-2040P) havingarelativelylongglass f i b e r lengthwas usedinstead
o f t h e glass f i b e r reinforced polypropylene (V-7100) usedin Example
l B , but a high bond strength was obtained as in the case of Example
10 1B.
[01741
In addition, in Example 4B, the homopolypropylene (J105G) was
used instead of the glass f i b e r reinforced polypropylene (V-7100)
used i n Example l B , but a high bond strength was obtained as i n the
15 case of Example 1B.
[0175]
InExample5B, the samemethodasthatofExample1Bwasperformed
using the metal member 103 obtained i n Preparation Example 3B which
was surface-roughenedusingthe acidic etchantB a f t e r being t r e a t e d
20 using the alkaline etchant, but the obtained metal-resin composite
s t r u c t u r e 106 obtained as a high bond strength as the bond strength
in Example 1B.
[0176]
On the other hand, i n Comparative Example l B , as shown i n FIG.
25 1 4 , a concavo-convex portion having a s u f f i c i e n t s i z e was not formed
on the surface of the metal member t r e a t e d in Preparation Example
48, and the obtained metal-resin composite structure 106 obtained
a low bond strength.
[01771
In Comparative Example 2B, the metal member, which was t r e a t e d
with the alkaline etchant a f t e r being e t c h e d u s i n g t h e a c i d i c etchant
5 B in Preparation Example 5B, was used. In Comparative Example 3B,
themetalmember, whichwastreatedusingtheaqueous sodiumhydroxide
solutionandtheaqueousnitricacidsolutionafterbeingetchedusing
the acidic etchant B i n Preparation Example 6B, was used. It is
assumed t h a t , as shown in FIG. 12, a concavo-convex portion having
10 a sharp angle was formed on the surface of the metal member due t o
the treatment using the acidic etchant B. However, it is considered
t h a t the concavo-convex portion deteriorated due t o the treatment
usingthealkalineetchantorsodiumhydroxide, andalov~bondstrength
was obtained. FIG. 15 shows the shape of the metal surface of
15 Comparative Example 3B which was t r e a t e d i n Preparation Example 6B.
[0178]
[Example l C ]
The small dumbbell-shaped metal i n s e r t mold 102 was mounted on
J85ADllOHmanufacturedbyTheJapanSteelWorksLtd., andthealuminum
20 plate (metal member 103) prepared i n Preparation Example 1B was
i n s t a l l e d i n t o the mold 102. Next, as the thermoplastic resin
composition ( P ) , apolyetherimide r e s i n (1100FmanufacturedbySaudi
Basic Industries Corporation, Tg=217"C) was injected i n t o the mold
102 under conditions of a cylinder temperature of 40OoC, a mold
25 temperature of 170°C, an injection r a t e of 25 mm/sec, a holding
pressure of 180 MPa, and a pressure holding time of 10 seconds. As
a r e s u l t , ametal-resin composite s t r u c t u r e 106was obtained. Table
1C shows the evaluation results of the bond strength.
[0179]
[Example 2C]
A metal-resin composite structure 106 was obtained using the
5 same method as that of Example lC, except that the aluminum plate
prepared in Preparation Example 2B was installed instead of the
aluminum plate prepared in Preparation Example 1B. Table 1C shows
the evaluation results of the bond strength.
[0180]
10 [Example 3C]
A metal-resin composite structure 106 was obtained using the
same method as that of Example lC, except that, as the thermoplastic
resin composition (P), a glass fiber reinforced polyimide resin
(JGH3030 manufactured by Mitsui Chemicals Inc.; 70 parts by weight
15 of polyimide resin having Tg of 250°c and 30 parts by mass of glass
fiber) was used instead of the polyether imide resin (1100F
manufacturedby Saudi Basic Industries Corporation). Table 1C shows
the evaluation results of the bond strength.
[0181]
20 [Example 4C]
A metal-resin composite structure 106 was obtained using the
same method as that of Example lC, except that, as the thermoplastic
resin composition (P), a polyether sulfone resin (4101GL20
manufactured by Sumitomo Chemical Co., Ltd., ~g=225O~w)as used
25 instead of the polyether imide resin (1100F manufactured by Saudi
BasicIndustriesCorporation). Table1Cshowstheevaluationresults
of the bond strength.
[0182]
[Example 5C]
A metal-resin composite structure 106 was obtained using the
same method as that of Example lC, except that, as the thermoplastic
5 resin composition (P), a glass fiber reinforced polycarbonate resin
(GN3630H manufactured by Teijin Ltd., Tg of a resin portion=150°C)
was used instead of the polyether imide resin (1100F manufactured
by Saudi Basic Industries Corporation). Table 1C shows the
evaluation results of the bond strength.
10 [0183]
[Example 6C]
A metal-resin composite structure 106 was obtained using the
same method as that of Example lC, except that the aluminum plate
prepared in Preparation Example 3B was installed instead of the
15 aluminum plate prepared in Preparation Example 1B. Table 1C shows
the evaluation results of the bond strength.
101841
[Comparative Example lC]
A metal-resin composite structure 106 was obtained using the
20 same method as that of Example lC, except that the aluminum prepared
in Preparation Example 4Bwas installedinsteadofthe aluminumplate
prepared in Preparation Example 1B. Table 1C shows the evaluation
results of the bond strength.
[01851
25 [Comparative Example 2C]
A metal-resin composite structure was obtained using the same
methodas that of Example lC, except that the aluminumplate prepared
in Preparation Example 5Bwas installed insteadofthe aluminumplate
prepared in Preparation Example 1B. Table 1C shows the evaluation
results of the bond strength.
[0186]
5 [Comparative Example 3C]
A metal-resin composite structure 106 was obtained using the
same method as that of Example lC, except that the aluminum plate
prepared in Preparation Example 6B was installed instead of the
aluminum plate prepared in Preparation Example 1B. Table 1C shows
10 the evaluation results of the bond strength.
[0187]
[Table lC]
Table 1C
I llOOF (L.lanufacture, Example 1C I Polyether Imide Resin I Basic - ' '
1,laior Component
Bond
Product Name I Etching ?,lethod I Strenqth I
I I ' by Saudi
nou us cries
loration)
Example 2C
Example 3C
Examole 4C
Examole 5C
Examole 6C
[0188]
15 In Example lC, as shown in FIG. 12, a concavo-convex portion
having a sharp angle was formed on the surface of the metal member
103 treated in Preparation Example lB, and it is considered that,
Preparation
Example 1B
Comparative
Examole 1C
Comparative
Examole 2C
Example 3C
[I.SP~-I
11
Polyether Imide Resin
Glass Fiber Reinforced
Polyimide Resin
Polyether Sulfone Resin
Glass Fiber Reinforced
Polycarhonate Resin
Polyether Imide Resin
Polyether Imide Resin
Polyether Imide Resin
Polyether Imide Resin
coq
1100k' (Manuracrurea ny saual Preparation
Basic Industries I Example 48
llOOF (1.lanufacturel
Basic - ' '
corg
llOOF (1.lanufactured by Saudi
Basic Industries Preparation
Orr....d .-> Example 6B
llOOF (1.lanufactured by Saudi
Basic Industries
Corporation)
JGH3030 (1.lanufactured by
1,fitsui Chemicals Inc. I
4101GL20 (1,lanufactured by
sumitomo Chemical Co., Ltd.)
GN3630H (Manufactured by
Teijin Ltd.)
llOOF (1,lanufactured by Saudi
Basic Industries
Cornornti on)
Preparation
ExallQle 2B
Preparation
Example 1B
Preparation
Example 18
Preparation
Exawle 18
Preparation
Example 38
10
17
12
15
10
bytheresinmember105beinginsertedintotheconcavo-convexportion,
the obtainedmetal-resincomposite structure106 obtainedahighbond
strength.
[0189]
5 In Example 2C, the metal member t r e a t e d in Preparation Example
1B was f u r t h e r washed by ultrasonic cleaning (in water, one minute)
in Preparation Example 2B. Due to the above treatment, smut and the
l i k e formed on the metal surface can be removed. Therefore, as shown
in FIG. 13, a concavo-convex portion having a sharp angle tias formed
10 on the surface of the metal member 103, and it is considered t h a t ,
bytheresinmember105beinginsertedintotheconcavo-convexportion,
the obtained metal-resin composite s t r u c t u r e 106 exhibited a high
bond strength.
[0190]
In Example 3C, t h e g l a s s f i b e r reinforced polyimide r e s i n
(JGH3030) was used instead of the polyether imide resin (1100F) used
in Example l C , but a high bond strength tias obtained as in the case
of Example 1C.
[0191]
20 In addition, in Example 4C, the polyether sulfone r e s i n
(4101GL20) was used instead of the polyether imide resin (11OOF) used
in Example l C , but a high bond strength was obtained as in the case
of Example 1C.
In addition, in Example 5C, the glass f i b e r reinforced
25 polycarbonateresin (GN3630H) wasusedinsteadofthepolyetherimide
resin (1100F) usedinExample l C , butahighbondstrengthwasobtained
as i n the case of Example 1C.
[0192]
InExample 6C,thesamemethodasthatofExample1Cwasperformed
using the metal member 103 obtained i n Preparation Example 3B which
was surface-roughened u s i n g t h e a c i d i c etchant B a f t e r being t r e a t e d
5 using the a l k a l i n e etchant, but the obtained metal-resin composite
s t r u c t u r e 106 obtained as a high bond strength as the bond strength
in Example 1C.
[0193]
On the other hand, in Comparative Example l C , as shown in FIG.
10 1 4 , a concavo-convex portion having a s u f f i c i e n t s i z e was not formed
on the surface ofthemetalmember 103 t r e a t e d i n Preparation Example
4B, and the obtained metal-resin composite s t r u c t u r e 106 obtained
a low bond strength.
[0194]
In Comparative Example 2C, the metal member, which was t r e a t e d
with the alkaline etchant a f t e r being etchedusingthe acidic etchant
B i n Preparation Example 5B, was used. In Comparative Example 3C,
themetalmember, whichwastreatedusingtheaqueous sodiumhydroxide
solutionandtheaqueousnitricacidsolutionafterbeingetchedusing
20 the acidic etchant B i n Preparation Example 6B, was used. It is
assumed t h a t , as shown i n FIG. 12, a concavo-convex portion having
a sharp angle was formed on the surface of the metal member due t o
the treatment using the acidic etchant B. However, it is considered
t h a t the concavo-convex portion deteriorated due t o the treatment
25 usingthealkalineetchantorsodiumhydroxide, andalowbondstrength
was obtained. FIG. 15 shows the shape of the metal surface of
Comparative Example 3C which was t r e a t e d i n Preparation Example 68.
[0195]
(Surface-Roughening D of Metal Member)
[Preparation Example ID]
(Surface-Roughening Using Acidic Etchant B)
5 An aluminum plate (thickness: 1 mm) of Alloy No. 5052 defined
in JIS H4000 was cut into a length of 150 mm and a width of 75 mm.
This aluminum plate was etched in an etching amount shown in Table
1D by being dipped in an acidic etchant B (30°C) having a composition
shown in Table 1B and being shaken. Next, the aluminum plate was
10 washed with flowing water (1 minute) and then was dried. As a result,
a surface-treatedmetalmember was obtained. The etching amount was
calculated from a mass difference of the aluminum component before
and after the etching, the specific gravity of aluminum, and the
surface area ofthe aluminumplate, andwas controlledby the etching
15 time. The same shall be applied to the "etching amount" described
below.
[01961
[Preparation Example 2D]
(Ultrasonic Cleaning After Surface-Roughening Using Acidic
20 Etchant B)
A surface-treated metal member was obtained by performing the
same treatment as that of Preparation Example ID, except that the
aluminumplate was washedby ultrasonic cleaning (inriater, lminute)
after being etched using the acidic etchant B.
25 [0197]
[Preparation Example 3D]
(Surface-Roughening Using Acidic Etchant B After Treatment
Using Alkaline Etchant)
An aluminum p l a t e (thickness: 1 mm) of Alloy No. 5052 defined
in JIS H4000 was cut i n t o a length of 150 mm and a width of 75 rnm.
This aluminum plate was dipped in an alkaline etchant (35OC) having
5 a composition shown i n Table 2B, was shaken for 1 minute, and was
washed (I minute) with flowing water. Next, t h i s aluminum plate was
etched i n an etching amount shown i n Table 1 D by being dipped in an
a c i d i c etchant B (30°C) having a composition shown in Table 1 B and
being shaken. Next, the aluminumplate was washedwith flowing water
10 (1 minute) and then was dried. As a r e s u l t , a surface-treated metal
member was obtained. The etching amount shown i n Table I D i s the
sum of the etching amount by the alkaline etchant and the etching
amount by the acidic etchant B.
[0198]
[Preparation Example 4D]
(Surface-Roughening Using Alkaline Etchant)
An aluminum p l a t e (thickness: 1 mm) of Alloy No. 5052 defined
i n JIS H4000 was cut i n t o a length of 150 mm and a width of 75 mm.
This aluminum plate was etched i n an etching amount shown in Table
20 1Dbybeingdippedin an alkaline etchant (35'C) having a composition
shown i n Table 2B and being shaken. After being washed (1 minute)
with flowingwater,thetreatedaluminumplatewasdippedinanaqueous
solution (25'C) of 15 mass% of n i t r i c acid, was shaken for 60 seconds,
was washed (lminute) with flowingwater, andwas dried. A s a r e s u l t ,
25 a surface-treated metal member was obtained.
[0199]
[Preparation Example 5D]
(Surface-Roughening Using Alkaline Etchant After Treatment
Using Acidic Etchant B)
An aluminum plate (thickness: 1 mm) of Alloy No. 5052 defined
in JIS H4000 rias cut into a length of 150 mm and a width of 75 mm.
5 This aluminum plate was dipped in the acidic etchant B (30°C) having
a composition shown in Table lB, was shaken for 1 minute, and was
washed (1 minute) with flowing water. Next, this aluminum plate was
etched in an etching amount shown in Table ID by being dipped in an
alkaline etchant (35'C) having a composition shown in Table 2B and
10 being shaken. Next, the aluminumplatewas washedriith flowingwater
(I minute) and then was dried. As a result, a surface-treated metal
member was obtained. The etching amount shown in Table 1D is the
sum of the etching amount by the acidic etchant B and the etching
amount by the alkaline etchant.
15 [0200]
[Preparation Example 6Dl
(Treatment Using Alkaline Solution After Surface-Roughening
Using Acidic Etchant B)
An aluminum plate (thickness: 1 mm) of Alloy No. 5052 defined
20 in JIS H4000 was cut into a length of 150 mm and a width of 75 mm.
This aluminum plate was etched in an etching amount shown in Table
ID by being dipped in an acidic etchant B (30°C) having a composition
shown in Table 1B and being shaken. Next, the aluminum plate was
washed (1 minute) with flowing water. Next, the treated aluminum
25 plate was dipped in an aqueous solution (25°C) of 5 mass% of sodium
hydroxide, was shaken for 30 seconds, andwasriashedwithwater. Next,
the treated aluminum plate was dipped in an aqueous solution (25°C)
of 35 mass% of nitric acid, was shaken for 30 seconds, was washed
(1 minute) with flowing water, and was dried. As a result, a
surface-treated metal member was obtained.
[0201]
5 [Preparation Example 7D]
(Treatment describe din Example 1of Japanese Unexamined Patent
Publication No. 2005-119005)
A commercially available aluminum degreasing agent "NE-6
(manufactured by Meltex Inc.)" was dissolved in water at a
10 concentration of 15%, and the temperature thereof was controlled to
75°C. The aluminum plate was dipped in an aluminum degreasing bath
containingthis aqueous solution for 5 minutes and washedwith water,
and then was dipped in an aqueous solution of 1% of hydrochloric acid
at 40°C for 1 minute and washed with water. Next, the aluminum plate
15 was dipped in a bath containing an aqueous solution of 1% of sodium
hydroxide at 40°C for 1 minute and washed with water. Next, the
aluminum plate was dipped in a bath containing an aqueous solution
of 1% of hydrochloric acid at 40°C for 1 minute and washed with water,
was dipped in a first hydrazine treatment bath containing an aqueous
20 solution of 2.5% of hydrazine monohydrate at 60°C for 1 minute, and
was dippedin a secondhydrazinetreatmentbath containing an aqueous
solution of 0.5% of hydrazine monohydrate at 40°C for 0.5 minute and
washed with water. The aluminum plate was dried with warm air at
40°C for 15 minutes and at 60°C for 5 minutes. As a result, a
25 surface-treated metal member was obtained.
[0202]
The surface of the surface-treated metal member was observed
using a scanning electron microscope (manufactured by JEOL Ltd.,
Model No. JSM-6701F) at a magnification of 100000 times. FIG. 16
sho~is a micrograph.
[02031
5 [Example ID]
Using an applicator, the aluminumplate prepared in Preparation
Example 1D was coated with a water-based coating material such that
the thickness of a dried coating film was 40 pm, and the aluminum
plate was dried in an oven at 120°C. As a result, a coated metal
10 member rias obtained. As the coating material, a water-dispersible
polyolefin (CHEMIPEARL (trade name) S300, manufactured by Mitsui
Chemicals Inc.) was used. Table 2D shows the evaluation results of
the adhesion.
[0204]
[Example 2D]
Acoatedmetalmember was obtainedusingthe samemethod as that
of Example ID, except that the aluminumplate prepared in Preparation
Example 2D was installed instead of the aluminum plate prepared in
Preparation Example ID. Table 2D shows the evaluation results of
20 the adhesion.
[0205]
[Example 3D]
A coated metal member was obtained using the same method as that
of Example ID, except that, as the coating material, a
25 water-dispersible polyolefin (CHEMIPEARL (trade name) M200,
manufacturedby Mitsui Chemicals Inc.; lowdensitypolyethylene) was
used instead ofthe water-dispersible polyolefin (CHEMIPEARL (trade
name) 5300, manufactured by Mitsui Chemicals Inc. ; ionomer) . Table
2D shows the evaluation r e s u l t s of the adhesion.
[0206]
[Example 4D]
5 A coated metal member was obtained using the same method as t h a t
of Example I D , except t h a t , as the coating material, a
water-dispersible polyolefin (CHEMIPEARL (trade name) W310,
manufactured by Mitsui Chemicals Inc.; low molecular weight
polyethylene) was used instead of the water-dispersible polyolefin
10 (CHEMIPEARL (tradename) 5300, manufacturedbyMitsuiChemicals Inc.;
ionomer). Table 2D shows the evaluation r e s u l t s of the adhesion.
[0207]
[Example 5D]
A coated metal member pias obtained using the same method as t h a t
15 of ExamplelD, except t h a t the aluminumplate prepared in Preparation
Example 3D tias i n s t a l l e d instead of the aluminum plate prepared in
Preparation Example I D . Table 2D shows the evaluation r e s u l t s of
the adhesion.
[0208]
20 [Comparative Example I D ]
An aluminum p l a t e (thickness: 1 mm) of Alloy No. 5052 defined
i n JIS H4000 was cut i n t o a length of 150 mm and a width of 75 mm.
Usingan applicator, the aluminumplatewas coatedwitha water-based
coating material such t h a t the thickness of a dried coating film was
25 40 pm, and the aluminum p l a t e was dried in an oven a t 120°C. As a
r e s u l t , a coatedmetalmemberwas obtained. As the coatingmaterial,
a water-dispersible polyolefin (CHEMIPEARL (trade name) S300,
manufactured by Mitsui Chemicals Inc.; ionomer) rias used. Table 2D
shows the evaluation r e s u l t s of the adhesion.
[0209]
[Comparative Example 2Dl
5 A coated metal member pias obtained using the same method as t h a t
of Example I D , except t h a t the aluminumplate prepared i n Preparation
Example 4D was i n s t a l l e d instead of the aluminum p l a t e prepared i n
Preparation Example I D . Table 2D shows the evaluation r e s u l t s of
the adhesion.
10 [0210]
[Comparative Example 3D]
Acoatedmetalmemberwas obtainedusingthe samemethod as t h a t
of Example I D , except t h a t the aluminumplate preparedin Preparation
Example 5D was i n s t a l l e d instead of the aluminum p l a t e prepared in
15 Preparation Example I D . Table 2D shows the evaluation r e s u l t s of
the adhesion.
[02111
[Comparative Example 4D]
A coatedmetalmember was obtainedusingthe same method as t h a t
20 of Example I D , except t h a t the aluminumplate prepared i n Preparation
Example 6D rias i n s t a l l e d instead of the aluminum p l a t e prepared in
Preparation Example I D . Table 2D shoris the evaluation r e s u l t s of
the adhesion.
[02121
25 [Comparative Example 5Dl
A coated metal member was obtained using the same method as that
of Example I D , except t h a t the aluminumplate preparedin Preparation
Example 7D was installed instead of the aluminum plate prepared in
Preparation Example ID. Table 2D shows the evaluation results of
the adhesion.
5 [Table ID]
Table 1D
Preparation Example
1 D
Preparation Example
Preparation Example
3 D
Preparation Example
Preparation Example
5 D
Preparation Example
6 D
Preparation Example
7D
dashing with Water
Acidic Etchant B
Etching Process
Acidic Etchant B
+Washing with Water
Acidic Etchant B
+Ultrasonic Cleaning
Alkaline Etchant
+Acidic Etchant B
+Washing with Water
Alkaline Etchant
Etching
Amount
[~lml
20
20
15
+Alkaline Etchant
+Washing with Water
Acidic Etchant B
+Aqueous Sodium Hydroxide
Solution
+Aqueous Nitric Acid Solution
+Washing with Water
Aqueous Hydrochloric Acid
Solution
+Aqueous Sodium Hydroxide
Solution
+Aqueous Hydrochloric Acid
Solution
+Aqueous Hydrazine Solution
+Aqueous Hydrazine Solution
+Washing with Water
20
20
0.05
[0214]
[Table 2D]
Table 2D
LfiiL'JI
Example ID I (Manufact
6Chemi . Example 2D I (Manufact
Chemi
I CHEMI
Example 3D I (Manufact
Chemi
Example 4D I (Manufact
Chemi
I CHEMI
'Example 5D I (Manufact
Chemi
I
Comparative (Manufact
Example 2D
Chemi
(Manufact
Comparative
CHEMI
Example 4D (Manufact
Comparative
Example 5D (Manufact
Cherni
LO2151
In Example ID, as shown in FIG. 12, a concavo-convex portion
having a sharp angle was formed on the surface of the metal member
103 treated i n Preparation Example ID, and it is considered t h a t ,
by the coating resin (resinmember 105) formedofthewater-dispersed
polyolefin being inserted i n t o the concavo-convex portion, the
obtained coated metal member obtained high adhesion.
LO2161
In Example 2D, the metal member t r e a t e d i n Preparation Example
I D was further riashed by ultrasonic cleaning (in riater, one minute)
in Preparation Example 2D. Due t o the above treatment, smut and the
l i k e formed on the metal surface can be removed. Therefore, as shown
i n FIG. 13, a concavo-convex portion having a sharp angle was formed
5 on the surface of the metal member 103, and it is considered t h a t ,
by the coating r e s i n formed of the water-dispersed polyolefin being
inserted i n t o the concavo-convex portion, the obtained coatedmetal
member obtained high adhesion.
[0217]
10 In Example 3D, the low density polyethylene (CHEMIPERAL M200
(trade name) manufactured by Mitsui Chemicals Inc.) having a large
p a r t i c l e sizewas usedinsteadoftheionomer (CHEMIPERAL S300 (trade
name) manufactured by Mitsui Chemicals Inc. ) used in Example I D , but
high adhesion was obtained as in the case of Example I D .
15 [0218]
In addition, in Example 4D, the low molecular weight
polyethylene (CHEMIPERAL W310 (trade name) manufactured by Mitsui
Chemicals Inc.) having a large p a r t i c l e s i z e was used instead of the
ionomer (CHEMIPERAL S300 (trade name) manufactured by Mitsui
20 Chemicals Inc.) used i n Example I D , but high adhesion was obtained
as i n the case of Example I D .
InExample5D,the samemethodasthatofExample1Dviasperformed
using the metal member 103 obtained in Preparation Example 3D which
pias surface-roughened usingthe acidic etchant B a f t e r being t r e a t e d
25 using the alkaline etchant, but the obtained coated metal member
obtained as high adhesion as the adhesion i n Example I D .
[0219]
On the other hand, i n Comparative Example ID, t h e r e s i n coating
formed of the water-dispersible polyolefin was formed without
performing the surface treatment. As a r e s u l t , somewhat high
adhesion was obtained but was not s u f f i c i e n t .
5 [0220]
Incomparative Example 2D, as shownin FIG. 12, a concavo-convex
portion having a s u f f i c i e n t s i z e was not formed on the surface of
the metalmembertreatedin Preparation Example 4D, and the obtained
coated metal member obtained low adhesion.
10 [0221]
In Comparative Example 3D, the metal member, which was t r e a t e d
with the alkaline etchant a f t e r being e t c h e d u s i n g t h e a c i d i c e t c h a n t
B i n Preparation Example 5D, was used. In Comparative Example 4D,
themetalmember, whichwastreatedusingtheaqueous sodiumhydroxide
15 solutionandtheaqueousnitricacidsolutionafterbeingetchedusing
t h e a c i d i c etchant B i n Preparation Example 6D, xias used. It is
assumed t h a t , as shown i n FIG. 12, a concavo-convex portion having
a sharp angle was formed on the surface of the metal member due t o
the treatment using t h e a c i d i c etchant B. However, it is considered
20 t h a t the concavo-convex portion deteriorated due t o the treatment
using the alkaline etchant or sodium hydroxide, and low adhesion was
obtained.
[0222]
InComparativeExample 5D, as shownin FIG. 16, aconcavo-convex
25 portion having a s u f f i c i e n t s i z e was not formed on the surface of
the metal member t r e a t e d i n Preparation Example 7D, and the obtained
coated metal member obtained low adhesion.
[0223]
As described above, in the metal-resin composite s t r u c t u r e 106
according t o t h e p r e s e n t invention, themetalmember103andthe resin
member 105 are integrated t o each other without being e a s i l y peeled
5 off, and a high bond strength can be obtained.
Themetal-resincomposite s t r u c t u r e 1 0 6 a c c o r d i n g t o t h e p r e s e n t
inventioncanbe r e a l i z e d i n v a r i o u s shapes usinga relativelysimple
method. Therefore, the contribution o f t h e present invention t o t h e
development of t h e i n d u s t r y is s i g n i f i c a n t .
10 [0224]
This application claims p r i o r i t y based on Japanese Unexamined
Patent ApplicationNo. 2013-149031, f i l e d o n July18, 2013, Japanese
Unexamined Patent Application No. 2013-166751, f i l e d on August 9,
2013, Japanese Unexamined Patent Application No. 2013-235731, f i l e d
15 on November 14, 2013, and Japanese Unexamined Patent Application No.
2014-138787, f i l e d on July 4, 2014, the e n t i r e contents of which are
incorporated herein by reference.
[0225]
The present invention includes the following aspects.
20 [ A l I
A metal-resin composite s t r u c t u r e obtained by bonding a metal
member, which is formed of a metal material containing aluminum and
is surface-roughened, and a r e s i n member, which is formed of a resin
composition containing a polyolefin resin, t o each other,
25 inwhichthe surface-rougheningofthemetalmemberisperformed
using an acidic etchant,
the surface-roughening using t h e a c i d i c etchant is performed
i n a f i n a l s t e p o f t h e surface-rougheningprocess ofthemetalmember,
and
t h e a c i d i c e t c h a n t c o n t a i n s a t l e a s t e i t h e r f e r r i c i o n s o r c u p r i c
ions and an acid.
5 [A2 I
The metal-resin composite s t r u c t u r e according t o [ A l l ,
i n which the metal member is washed by ultrasonic cleaning a f t e r
the surface-roughening process of the metal member.
[ B l l
1 0 A metal-resin composite s t r u c t u r e obtained by bonding a metal
member, which is formed of a metal material containing aluminum and
is surface-roughened, and a r e s i n member, which is formed of a resin
composition containing a thermoplastic r e s i n having a glass
transitiontemperatureofhigherthanorequalto1400C,toeachother,
15 inwhich the surface-rougheningofthemetalmemberis performed
using an acidic etchant,
the surface-roughening using t h e a c i d i c etchant is performed
i n a f i n a l s t e p o f t h e surface-rougheningprocess ofthemetalmember,
and
2 0 theacidicetchantcontains atleasteitherferricionsorcupric
ions and an acid.
[B21
A metal-resin composite s t r u c t u r e obtained by bonding a metal
member, which is formed of a metal material containing aluminum and
2 5 is surface-roughened, and a r e s i n member, which is formed of a resin
composition containing an amorphous thermoplastic resin, t o each
inwhichthe surface-rougheningofthemetalmemberisperformed
using an a c i d i c etchant,
the surface-roughening using the acidic etchant is performed
i n a f i n a l s t e p o f t h e surface-rougheningprocess ofthemetalmember,
5 and
t h e a c i d i c e t c h a n t c o n t a i n s a t l e a s t e i t h e r f e r r i c i o n s o r c u p r i c
ions and an acid.
[B31
The metal-resin composite s t r u c t u r e according t o [ B l ] or [B2],
inwhich themetalmember is riashedby ultrasonic cleaning a f t e r
the surface-roughening process of the metal member.
[B41
The metal-resin composite s t r u c t u r e according t o [B3],
inwhich themetalmember is washedby ultrasonic cleaning a f t e r
15 the surface-roughening process of the metal member.
LC11
A coated metal member obtained by forming a coating film on a
surface of a metal member which is formed of a metal material
containing aluminum and is surface-roughened,
20 inwhich the surface-rougheningofthemetalmemberisperformed
using an acidic etchant,
the surface-roughening using the acidic etchant is performed
i n a f i n a l s t e p o f t h e surface-rougheningprocess ofthemetalmember,
and
25 theacidicetchantcontains atleasteitherferricionsorcupric
ions and an acid.
[C21
Amethodofpreparingthe coatedmetalmember according t o [ C l ] ,
including
coatinga surface ofthemetalmemberriitha water-basedcoating
material t o form a coating film on the surface of the metal member.
5
CLAIMS
1. A metal-resin composite s t r u c t u r e which is obtained by bonding
a metal member and a r e s i n member formed of a thermoplastic resin
5 composition t o each other,
wherein regarding s i x l i n e a r portions i n t o t a l on a surface of
the metalmernberincludingthree a r b i t r a r y l i n e a r portions which are
p a r a l l e l t o each other and another three a r b i t r a r y l i n e a r portions
whichareperpendiculartotheformerthreelinearportions, asurface
10 roughness measured according t o JIS B0601 (corresponding
i n t e r n a t i o n a l standard: IS04287) s a t i s f i e s the following
requirements (1) and (2) a t the same t i m e :
(1) material r a t i o of the roughness p r o f i l e (Rmr) of one or more
l i n e a r portions a t a cutting level of 20% and an evaluation length
15 of 4 mm are lower than or equal to 30%; and
(2) tenpointaverageroughnesses (Rz) of a l l t h e l i n e a r p o r t i o n s
a t an evaluation length of 4 mm are greater than 2 pm.
2 . The metal.-resin composite s t r u c t u r e according t o claim 1,
20 whereinregardingthesixlinearportionsintotalonthesurface
of the metal member including three a r b i t r a r y l i n e a r portions which
areparalleltoeachotherandanotherthreearbitrarylinearportions
which are perpendicular t o the former three l i n e a r portions, the
surface roughness measured according t o JIS B0601 (corresponding
25 i n t e r n a t i o n a l standard: 1504287) f u r t h e r s a t i s f i e s the following
requirement (3) :
(3) material r a t i o of the roughness p r o f i l e (Rmr) of one or more
l i n e a r portions a t a cutting level of 40% and an evaluation length
of 4 mm are lower than or equal to 60%.
3. The metal-resin composite s t r u c t u r e according t o claim 1 or 2,
5 whereinregardingthesixlinearportionsintotalonthesurface
of the metal member including three a r b i t r a r y l i n e a r portions which
areparalleltoeachotherandanotherthreearbitrarylinearportions
which are perpendicular t o the former three l i n e a r portions, the ten
point average roughnesses (Rz) of a l l the l i n e a r portions a r e g r e a t e r
10 than 5 pm.
4 . The metal-resin composite s t r u c t u r e according t o claim 3,
whereinregardingthesixlinearportionsintotalonthesurface
of the metal member including three a r b i t r a r y l i n e a r portions which
15 areparalleltoeachotherandanotherthreearbitrarylinearportions
which are perpendicular t o the former three l i n e a r portions, the ten
point average roughnesses (Rz) of a l l t h e l i n e a r p o r t i o n s a r e g r e a t e r
than or equal t o 15 pm.
20 5. Themetal-resincompositestructureaccordingtoanyoneofclaims
1 t o 4,
whereinregardingthesixlinearportionsintotalonthesurface
of the metal member including three a r b i t r a r y l i n e a r portions which
areparalleltoeachotherandanotherthreearbitrarylinearportions
25 which are perpendicular t o the former three l i n e a r portions, the
surface roughness measured according t o JIS B0601 (corresponding
i n t e r n a t i o n a l standard: IS04287) further s a t i s f i e s the following
requirement ( 4 ) :
( 4 ) mean width of the p r o f i l e elements(RSm) of a l l the l i n e a r
portions are greater than 10 pm and l e s s than 300 pm.
5 6. Themetal-resincomposite s t r u c t u r e accordingtoanyoneofclaims
1 t o 5,
wherein the surface of the metal member is roughened,
the roughening is performed using an acidic etchant in a f i n a l
step of the roughening process of the metal member, and
10 theacidicetchantcontains atleasteitherferricionsorcupric
ions and an acid.
7. The metal-resin composite s t r u c t u r e according t o claim 6,
wherein the metal member is washed by ultrasonic cleaning a f t e r
15 the roughening process.
8. Themetal-resincomposite structureaccordingtoanyoneofclaims
1 t o 7,
wherein themetalmember is formedofametalmaterialcontaining
20 one or two or moremetals selected fromaluminumandaluminumalloys.
9. Themetal-resincompositestructureaccordingtoanyoneofclaims
1 t o 8,
wherein the thermoplastic r e s i n composition contains one or two
25 or more thermoplastic resins selected from polyolefin resins,
polyester resins, and polyamide resins.
10. The metal-resin composite structure according to any one of
claims 1 to 8,
wherein the thermoplastic resin composition contains one or two
or more thermoplastic resins selected from polycarbonate resins,
5 polyether ether ketone resins, polyether ketone resins, polyimide
resins, and polyether sulfone resins all of which have a glass
transition temperature of higher than or equal to 140°C.
11. The metal-resin composite structure according to any one of
10 claims 1 to 8,
wherein the thermoplastic resin composition contains one or two
or more amorphous thermoplastic resins selected from polystyrene
resins, polyacrylonitrile resins, styrene-acrylonitrile copolymer
resins, acrylonitrile-butadiene-styrene copolymer resins,
15 polymethyl methacrylate resins, and polycarbonate resins.
12. The metal-resin composite structure according to any one of
claims 1 to 11,
wherein the resin member is a coating film.
20
13. The metal-resin composite structure according to claim 12,
wherein the coating film is obtained by coating the surface of
the metal member with a water-based coating material.
25 14. Ametalmemberwhichis usedtobebondedtoa resinmember formed
of a thermoplastic resin composition,
wherein regarding six linear portions in total on a surface of
the metal member includingthree a r b i t r a r y l i n e a r portions which are
p a r a l l e l to each other and another three a r b i t r a r y l i n e a r portions
whichareperpendiculartothe formerthreelinearportions, a s u r f a c e
roughness measured according to JIS B0601 (corresponding
5 i n t e r n a t i o n a l standard: 1,504287) s a t i s f i e s the following
requirements (1) and (2) a t the same time:
(1) material r a t i o of the roughness p r o f i l e (Rmr) of one or more
l i n e a r portions a t a cutting level of 20% and an evaluation length
of 4 nun are lower than or equal to 30%; and
10 (2) tenpointaverageroughnesses (Rz) of a l l the l i n e a r p o r t i o n s
a t an evaluation length of 4 mm are greater than 2 pm.
15. The metal member according t o claim 14,
r v h e r e i n r e g a r d i n g t h e s i x l i n e a r p o r t i o n s i n t o t a l o n t h e s u r f a c e
15 of the metal member including three a r b i t r a r y l i n e a r portions which
areparalleltoeachotherandanotherthreearbitrarylinearportions
which are perpendicular t o the former three l i n e a r portions, the
surface roughness measured according to JIS B0601 (corresponding
i n t e r n a t i o n a l standard: 1504287) f u r t h e r s a t i s f i e s the following
20 requirement (3) :
(3) material r a t i o of the roughness p r o f i l e (Rmr) of one or more
l i n e a r portions a t a cutting level of 40% and an evaluation length
of 4 nun are lower than or equal t o 60%.
25 16. The metal member according to claim 1 4 or 15,
rihereinregardingthesixlinearportionsintotalonthesurface
of the metal member including three a r b i t r a r y l i n e a r portions rihich
I" L/
areparalleltoeachotherandanotherthreearbitrarylinearportions
which are perpendicular to the former t h r e e l i n e a r portions, the ten
point average roughnesses (Rz) of a l l the l i n e a r portions a r e g r e a t e r
than 5 pm.
5
17. The metal member according to claim 16,
-
whereinregardingthe s i x l i n e a r p o r t i o n s i n t o t a l onthe surface
of the metal member including three a r b i t r a r y l i n e a r portions which
a r e p a r a l l e l t o e a c h o t h e r a n d a n o t h e r t h r e e a r b i t r a r y l i n e a r p o r t i o n s
10 which are perpendicular to the former three l i n e a r portions, t h e t e n
point average roughnesses (Rz) of a l l t h e l i n e a r p o r t i o n s a r e greater
than or equal t o 15 pm.
18. The metal member according t o any one of claims 1 4 t o 17,
15 rihereinregardingthesixlinearportionsintotalonthesurface
of the metal member including three a r b i t r a r y l . - i n e a r portions which
areparalleltoeachotherandanotherthreearbitrarylinearportions
which are perpendicular t o the former three l i n e a r portions, the
surface roughness measured according t o JIS B0601 (corresponding
20 i n t e r n a t i o n a l standard: IS04287) f u r t h e r s a t i s f i e s the following
requirement ( 4 ) : -
( 4 ) mean width of the p r o f i l e elements (RSm) of a l l the l i n e a r
portions are greater than 10 pm and l e s s than 300 pm.
19. The metal member according t o any one of claims 1 4 t o 18,
rihereinthemetalmember is formedofametalmaterial containing
one or two or more metals selected from aluminum and aluminum alloys.