SPECIFICATION
METAL/RESIN COMPOSITE STRUCTURE
5 TECHNICAL FIELD
[OOOl]
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 .
BACKGROUND ART
10 [00021
Resins are used as a s u b s t i t u t e for metals from a viewpoint of
l i g h t weight of various components. However, a l l metal components
may be d i f f i c u l t t o be substituted with r e s i n s . I n such a case, a
metalmoldedbodyanda resinmoldedbodymaybe bondedandintegrated
15 soastomanufactureanericompositecomponent. Horsiever, atechnology
of bonding and integrating a metal molded body and a resin molded
body a t high bonding strengthbyanindustrialLyadvantageousmethod
has not implemented yet.
[0003]
20 In recent .yea-rs, as a technology of bonding and integrating a
metal molded body and a resin molded body, a technology of bonding
engineering p l a s t i c s including a polar group having a f f i n i t y w i t h
ametalmember, t o a surfaceofthemetalmemberwhere fineconcavities
and convexities are formed has been proposed (for example, Patent
25 Documents 1 to 5 ) .
[00041
For example, Patent Documents 1 to 3 disclose a technology of
performing a dipping treatment with respect to an aluminum alloy in
an aqueous hydrazine solution, forming concave portions having a
diameter of 30 nm to 300 nm on the surface thereof, and bonding a
polybutylene terephthalate resin ( h e r e i n a f t e r , r e f e r r e d to as "PBT")
5 or a polyphenylene s u l f i d e r e s i n (hereinafter, referred to as 'PPS")
t o the surface subjected t o the treatment.
[00051
PatentDocument4 discloses atechnologyofperformingananodic
oxidation treatment with respect to an aluminum material using an
10 e l e c t r o l y t i c bath of phosphoric a c i d o r sodium hydroxide, forming
an anodized coating film having concave portions having a diameter
e q u a l t o o r g r e a t e r t h a n 2 5 n m o n t h e surfaceofthealuminummaterial,
and bonding engineering p l a s t i c s to the surface subjected t o the
treatment.
15 [0006]
Patent Document 5 discloses a technology of forming f i n e
concavities and convexities or holes in an aluminum alloy with a
s p e c i f i c etchingagentandinjectinga polyamide 6 resin, a polyamide
6 resin, and PPS t o the holes for bonding.
20 [0007]
In recent years, a metal/resin composite s t r u c t u r e i n which
metals and engineering p l a s t i c s a r e bonded t o each other has been
obtained by the technologies described above. However, when
r e a l i z i n g t h e technologies, higher bonding 'strength is required
25 between metals and resins.
[00081
In Patent Documents 1 to 5, engineering p l a s t i c s including a
polar group are used as resin members. Meanwhile, in a case of
applying the technologies described above regarding a non-polar
polyolefin resin not having a f f i n i t y with a metal member, an
acid-modified polyolefin resin i n which a polar group is introduced
5 t o a polyolefin resin may be used (Patent Document 6 ) .
[0009]
However, i n order to bond the resin described above and a metal
member, it is n e c e s s a r y t h a t t h e resinismaintainedinameltedstate
and t h e r e s i n and the metal member come into contact with each other
10 a t high pressure for a long t i m e , and in general, the bonding is
performedbyalaminatingmethodorapressingmethodbymeltextrusion.
However, i n a case of the laminating method or the pressing method,
a degree of freedom of an applicable shape is low. In addition, the
acid-modified polyolefin resin attaches to portions other than a
15 desired portion for bonding, and accordingly, performance or
appearance ofametalmembermaynotbe exhibiteddependingon a shape
o f a component.
RELATED DOCUMENTS
PATENT DOCUMENTS
20 [00101
[Patent Document 11 Japanese Unexamined Patent PublicationNo.
2004-216425
[Patent Document21 Japanese Unexamined Patent Publication No.
2009-6721
25 [Patent Document 31 Pamphlet of International Publication No.
W02003/064150
[Patent Document 41 Pamphlet of International Publication No.
W02004/055248
[PatentDocument51 Japanese Unexamined Patent Publication No.
2013-52611
[Patent Document 61 Japanese Unexamined Patent Publication No.
5 2002-3805
SUMMARY OF THE INVENTION
[00111
The invention is made in consideration of these circumstances
10 a n d a n o b j e c t t h e r e o f i s t o p r o v i d e a m e t a l / r e s i n composite s t r u c t u r e
in which a 'metal member and a resin member can be d i r e c t l y bond t o
eachotherandbondingstrengthbetrieenthemetalmemberandthe r e s i n
member is excellent.
[0012]
15 The inventors have performed various studies regarding a
technology, represented by technologies disclosed in Patent
Documents 1 t o 5, of directlybonding a resinmember formedof a r e s i n
composition including a non-polar resin which is represented by a
polyolefin resin and does not have a f f i n i t y with a metal member, t o
20 a metal member having a metal surface subjected t o a roughening
treatment. However, even when the metal member subjected to a
roughening treatment and a resin member formed of a non-polar r e s i n
are bonded t o each other, bonding strength is l o w , and accordingly,
aninterfacebetr~eenthemetalmemberandtheresinmemberis separated
25 and it is d i f f i c u l t t o forma composite structure havinghighbonding
strength.
[00131
Accordingly, the inventionparticularlyprovides ametal/resin
composite structure in which a resin member and a metal member can
be directly bonded to each other without receiving an effect of
denaturation ofthe resin andhas excellent bonding strength between
5 the metal member and the resin member, even in a case of using a resin
composition containing a non-polar resin which is represented by a
polyolefin resin and does not have affinity with the metal member,
as the resin member.
10 [0014]
The inventors have performed research in order to solve the
above-mentionedproblerns. As a result, theinventors have foundthat
a metal/resin composite structure having excellent bonding strength
between a resin member and a metal member is obtained by directly
15 bonding a metal member having a concavo-convex shape having two or
more different types of characteristics and a resin member to each
other, and the invention has been completed.
[0015]
That is, the invention relates to the following [I] to [ 7 ] .
20 [I] A-~netal/resinc omposite structure,
in which the metal/resin composite structure is formed by
bonding a metal member and a resin member to each other, and
aconcavo-convexshapesatisfyingthefollowingcharacteristics
(i) and (ii) is formed on a bonding surface of the metal member to
25 be bonded to the resin member.
(i) A mean width of the profile elements (RSm) is equal to or
greater than 150 pm and equal to or less than 1500 pm and a maximum
height roughness (Rz) is equal to or greater than 170 pm and equal
to or smaller than 800 pm
(ii) A mean width of the profile elements (RSm) is equal to or
greaterthan 100 nmandequalto or smallerthan10000 nmandamaximum
5 height roughness (Rz) is equal to or greater than 100 nm and equal
to or smaller than 10000 nm
[21 The metal/resin composite structure according to [I],
in which an ultrafine concavo-convex shape having a diameter
equal to or greater than 5 nm and equal to or smaller than 100 nm
10 and a depth equal to or greater than 10 nm and equal to or smaller
than 500 nm is formed on the surface of the metal member.
[ 3 ] Themetal/resincomposite structureaccordingto [I] or 121,
in which the concavo-convex shape satisfying characteristics
(ii) is formedonthe concavo-convexshapesatisfyingcharacteristics
15 (i).
[41 The metal/resin composite structure according to any one
of [ll to 131,
inwhichthemetalmemberis formedofametalmaterialcontaining
one kind or two or more kinds of metal selected from iron, stainless
20 steel, alutn?num, an aluminum alloy, magnesium, a magnesium alloy,
copper, a copper alloy, titanium, and a titanium alloy.
[51 The metal/resin composite structure according to any one
of [ll to [dl,
in which the resin member is formed of a resin composition
25 containing an (A) thermoplastic resin.
[6] The metal/resin composite structure according to [5],
in which the (A) thermoplastic resin is a polyolefin resin.
[7] Themetal/resincornpositestructureaccordingto [5] or [6],
in which the resin composition contains a (B) filling material
and the content of the (B) filling material is equal to or greater
than 1 part by mass and equal to or smaller than 100 parts by mass
5 with respect to 100 parts by mass of the (A) thermoplastic resin.
181 The metal/resin composite structure according to [2],
in which the concavo-convex shape satisfying the
characteristics (i) is formed on the surface of the metal member by
performing a blast treatment with respect to the metal member, the
10 concavo-convex shape satisfying the characteristics (ii) is further
formed on the surface of the metal member by performing a chemical
etching method of dipping the metal member in at least one kind of
anaqueous solution selected fromanaqueous solution of aninorganic
base and an aqueous solution of an inorganic acid, and the ultrafine
15 concavo-convex shape is further formed on the surface of the metal
member by dipping the metal member in an aqueous solution containing
one or more kinds selected from hydrazine hydrate, ammonia, and a
water-soluble amine compound.
[0016]
2 0 According to the invention, it is possible to obtain a
metal/resin composite structure having excellent bonding strength
between a metal member and a resin member.
[0017]
Particularly, in the invention, it is possible to obtain a
25 metal/resin composite structure in which the metal member and the
resin member are bonded to each other with high strength, even in
a case where the resin member is formed of a resin composition
containing a non-polar resin which is represented by a polyolefin
resin and does not have affinity with the metal member. This
technologyr.~adsi fficult to obtain in the technologies ofthe related
art.
5
BRIEF DESCRIPTION OF THE DRAWINGS
[0018l
The above-described object and other objects, features, and
advantages will become more apparent by preferred embodiments
10 described below and the following accompanying drawings.
[0019]
FIG. 1 is an outline view schematically showing an example of
a structure of a metal/resin composite structure according to an
embodiment.
15 FIG. 2 is a configuration diagram schematically showing an
example of a process of manufacturing the metal/resin composite
structure according to the embodiment.
FIG. 3isadiagramshowing electronmicroscope images ((a) shows
250 magnifications, (b) shows 100000 magnifications, and (c) shorqs
20 300000 magnificatidns) of a surface of a metal member manufactured
in Preparation Example 1.
FIG. 4 isadiagramshorvingelectronmicroscopeimages ((a) shows
250 magnifications, (b) shows 100000 magnifications, and (c) shows
300000 magnifications) of a surface of a metal member manufactured
25 in Preparation Example 4.
FIG. 5isadiagramshowingelectronmicroscope images ((a) shows
100000 magnifications and (b) shorsrs 300000 magnifications) of a
s u r f a c e o f a metal member manufactured i n Preparation Example 5.
FIG. 6 i s adiagramshob~inganelectronmicroscopeimage (100000
magnifications) of a bonding surface r e s i n s i d e of a m e t a l / r e s i n
composite s t r u c t u r e manufactured i n Example 1.
5 FIG. 7 is a diagramshowing an electronmicroscope image (100000
magnifications) of a bonding s u r f a c e r e s i n s i d e of a m e t a l / r e s i n
composite s t r u c t u r e manufactured i n Comparative Example 1.
DESCRIPTION OF EMBODIMENTS
10 [0020]
Hereinafter, embodimentsoftheinventionr~illbedescribedwith
reference t o t h e drawings. In a l l drawings, t h e same r e f e r e n c e
numerals are used f o r t h e same c o n s t i t u e n t elements and t h e
d e s c r i p t i o n t h e r e o f w i l l n o t b e repeated. Aterm'to"betweennumbers
15 i n t h i s document means an expression "equal t o o r more than a number
and equal to o r less than a number", i f not otherwise s p e c i f i e d .
FIG. 1 is an o u t l i n e view schematically showing an example of
a s t r u c t u r e of a m e t a l / r e s i n composite s t r u c t u r e 106 according t o
20 t h e embodiment.
A metal member 103 and a r e s i n member 105 a r e bonded t o each
o t h e r inthemetal/resincomposite s t r u c t u r e 106 a n d t h e m e t a l / r e s i n
composite s t r u c t u r e 106 is obtained by bonding t h e metal member 103
and t h e r e s i n member 105 t o each o t h e r .
25 100221
A bonding s u r f a c e 104 of t h e m e t a l member 103 t o be bonded t o
t h e r e s i n member 105 has a concavo-convex shape s a t i s f y i n g
c h a r a c t e r i s t i c s (i) and (ii) described belov~.
(i) A mean width of the p r o f i l e elements (RSm) is equal t o or
g r e a t e r t h a n 1 5 0 p m a n d e q u a l t o or s m a l l e r t h a n 1 5 0 0 pmand a maximum
height roughness (Rz) is equal t o o r g r e a t e r than 170 pm and equal
5 t o o r smaller than 800 pm.
(ii) A mean width of the p r o f i l e elements (RSm) is equal t o or
g r e a t e r t h a n 1 0 0 n m a n d e q u a l t o o r smallerthanlOOO0 nmandamaximum
height roughness (Rz) is equal t o o r g r e a t e r than 100 nm and equal
t o o r s m a l l e r t h a n 10000 nm.
10 [00231
H e r e i n a f t e r , each c o n s t i t u e n t element configuring t h e
m e t a l / r e s i n composite s t r u c t u r e 106 according t o t h e embodiment and
apreparingmethodthereof, and f e a t u r e s ofthemetal/resincomposite
s t r u c t u r e 106 w i l l be described.
15 [0024]

[Kind of Metal of Metal Member]
In t h e embodiment, a s kindofmetalconfiguringthemetalmember
103, ametalmaterialcontainingone k i n d o r t w o o r m o r e kinds s e l e c t e d
20 from i r o n , s t a i n l e s s steel, aluminum, an aluminum a l l o y , magnesium,
a magnesium a l l o y , copper, a copper a l l o y , titanium, and a t i t a n i u m
a l l o y is d e s i r a b l e . Among these, i r o n , s t a i n l e s s steel, an aluminum
a l l o y , a magnesium a l l o y , a copper a l l o y , and a t i t a n i u m a l l o y are
p r e f e r a b l e a n d s t a i n l e s s steel, analuminumalloy, amagnesiumalloy,
25 and a copper a l l o y a r e more p r e f e r a b l e a s kinds of m e t a l s c o n f i g u r i n g
t h e m e t a l member 103.
Among these, aluminum (simple substance o f aluminum) and an
aluminum alloy are preferable and an aluminum alloy is more preferable,
from a viewpoint of light weight and high strength.
Asanaluminurnalloy, alloynumbers 1050, 1100, 2014, 2024, 3003,
5052, and 7075 based on JIS A4000 are preferably used.
5 [00251
The shape of the metal member 103 is not particularly limited
as long as it is a shape which can be bonded to the resin member 105,
and a flat plate shape, a curved plate shape, a stick shape, a tubular
shape, or a lump shape can be used, for example. The metal member
10 may be a structure formed of a combination of the shapes described
above.
The shape of a bonding surface 104 to be bonded to the resin
member 105 is not particularly limited and may be a flat surface or
a curved surface.
15 [00261
[Surface Shape of Metal Member]
The metal member 103 configuring the metal/resin composite
structure 106 according tothe embodiment has a concavo-convex shape
having two or more different types of characteristics, on a side of
20 the bonding surface 104 to be bonded to the resin member 105.
[0027]
The characteristics are represented by a mean width of the
profile elements (RSm) and a maximum height roughness (Rz) and a
surface 110 of the metal member 103 has at least a mean width of the
25 profile elements (RSm) and a maximum height roughness (Rz) which are
in ranges shown in (i) and (ii) described below. The mean width of
the profile elements (RSm) and the maximum height roughness (Rz) are
measured by a method based on JIS B 0633-2001.
(i) A mean width of t h e p r o f i l e elements (RSm) is equal t o or
g r e a t e r t h a n 150 pm and equal t o o r s m a l l e r t h a n 1500 pmand a maximum
height roughness (Rz) is equal t o o r g r e a t e r than 170 pm and equal
5 t o o r smaller than 800 pm
(ii) A mean width of t h e p r o f i l e elements (RSm) is equal t o o r
g r e a t e r t h a n 1 0 0 nmandequaltoorsmallerthan 10000 nmandamaximum
height roughness (Rz) is equal t o o r g r e a t e r than 100 nm and equal
t o o r smaller than 10000 nm
10 Hereinafter, the ranges of (i) and (ii) as t h e c h a r a c t e r i s t i c s
oftheconcavo-convexshapeandamethodofformingtheconcavo-convex
shape w i l l be described.
[0028]
< C h a r a c t e r i s t i c s (i)>
15 A concavo-convex shape having a mean width of t h e p r o f i l e
elements (RSm) which is equal t o o r g r e a t e r than 150 pm and equal
t o o r smaller than 1500 pm, p r e f e r a b l y equal t o o r g r e a t e r than 175
pm and equal t o or s m a l l e r t h a n 1300 pm, and more p r e f e r a b l y equal
t o o r g r e a t e r than 600 pm and equal t o o r s m a l l e r t h a n 1000 pm and
20 a maximum keiglrt roughness (Rz) which is equal t o o r g r e a t e r than
170 pm and equal t o o r smaller than 800 pm, p r e f e r a b l y equal t o o r
g r e a t e r than 200 pm and equal t o o r smaller than 600 pm, and more
p r e f e r a b l y equal t o o r g r e a t e r than 300 pm and equal t o o r s m a l l e r
than 500 pm is formed on t h e metal member 103 configuring t h e
25 m e t a l / r e s i n composite s t r u c t u r e 106 according t o t h e embodiment on
t h e bonding surface 104 side t o be bonded t o t h e r e s i n member 105.
100291
As a method of forming the concavo-convex shape, a physical
treatment, for example, a b l a s t treatment or knurling is performed
with respect t o the surface 110 of the metal member 103, and a b l a s t
treatment is preferably performed.
5 [00301
Herein, a s t h e b l a s t treatment, there is a shot b l a s t treatment
of projecting a blast material using a c e n t r i f u g a l f o r c e of a bladed
wheel which is called an impeller and an a i r b l a s t treatment of
projectingablastmaterialbycompressedairusinganaircompressor,
10 and both treatments can apply the s p e c i f i c concavo-convex shape to
the surface 110 of the metal member 103. The adjustment of the mean
width of the p r o f i l e elements (RSm) and the maximum height roughness
(Rz) can be achieved by adjusting a rotation r a t e of the impeller,
i n a c a s e o f t h e shot b l a s t treatment, andcanbeachievedbyadjusting
15 i n j e c t i o n pressure of compressed a i r , i n a case of the a i r b l a s t
treatment.
[00311
In the a i r b l a s t treatment, injection pressure of a b l a s t
material is higher than t h a t in the shot b l a s t treatment, and
20 accordingly, it is possible t o form a more uniform concavo-convex
shape. Therefore, the a i r b l a s t treatment is preferable as a method
of the b l a s t treatment.
[0032]
Examples o f t h e blast material includematerials such as s i l i c a
25 sand, alumina, aluminum-cut wires, s t e e l g r i t , and s t e e l shot, and
each can be used according t o each purpose. Regarding bonding with
r e s i n s , s i l i c a sand is preferably used from viewpoints of a higher
anchor effect, cost, and efficiency.
[00331

A concavo-convex shape having a mean width of the profile
5 elements (RSm) b~hich is equal to or greater than 100 nm and equal
to or smaller than 10000 nm, preferably equal to or greater than 300
nm and equal to or smaller than 5000 nm, and more preferably equal
to or greater than 600 nm and equal to or smaller than 1000 nm and
a maximum height roughness (Rz) which is equal to or greater than
10 100 nm and equal to or smaller than 10000 nm, preferably equal to
or greater than 150 nm and equal to or smaller than 400 nm, and more
preferably equal to or greater than 200 nm and equal to or smaller
than 300 nm is formed on the metal member 103 configuring the
metal/resin composite structure 106 according to the embodiment on
15 the bonding surface 104 side to be bonded to the resin member 105.
[0034]
The concavo-convex shape may be further formed on the surface
110wheretheconcavo-convexshapehavingthemeanwidthoftheprofile
elements (RSm) and the maximum height roughness (Rz) shown in the
20 characteristics (i) is formed.
I00351
As a method of forming the concavo-convex shape, a method such
as a chemical etching method of dipping metal in an erosion aqueous
solution or an erosion suspension or an anodic oxidation method is '
25 used. These methods can be selectively used depending on the kind
of metal used for the metal member 103 or the concavo-convex shape
to be formed in the ranges of the mean width of the profile elements
(RSm) and the maximum height roughness (Rz) . Among these methods,
a chemical etching method of dipping metal i n an aqueous solution
of an inorganic base such as NaOH and/or an aqueous solution of an
inorganic acid such as HC1 or HN03 as an erosion agent is preferably
5 used.
[0036]

In the metal member 103 configuring the metal/resin composite
s t r u c t u r e 106 according to the embodiment on the bonding surface 104
10 side to be bonded t o the r e s i n member 105, u l t r a f i n e pores may be
formed according t o the method such as a method of dipping metal in
an erosion aqueous solution or an erosion suspension or an anodic
oxidation method which is performed when forming the concavo-convex
shape having the mean width of the p r o f i l e elements (RSm) and the
15 maximumheight roughness (Rz) according t o t h e c h a r a c t e r i s t i c s (ii),
or u l t r a f i n e pores may be positively formed by dipping metal in an
aqueous solutionof oneormorekinds selectedfromhydrazinehydrate,
ammonia, and a water-soluble amine compound disclosed i n Pamphlet
of International Publication No. W02009/31632, for example, a f t e r
20 forming the.eoncavo-convex shape having c h a r a c t e r i s t i c s (ii).
LOO371
A diameter of the u l t r a f i n e pores is equal t o or greater than
5nmandequaltoorsmallerthan100 nm, preferablyequaltoorgreater
than 10 nm and equal t o or smaller than 70 nm, and more preferably
25 equal to or greater than 15 nm and equal t o or smaller than 50 nm.
A depth of the hole is equal t o or greater than 10 nm and equal t o
or smaller than 500 nm, preferably equal to or greater than 15 nm
and equal t o or smaller than 300 nm, and more preferably equal to
o r g r e a t e r than 20 nm and equal t o or smaller than 70 nm.
The diameter of the u l t r a f i n e pores and the depth of hole can
be measured as follows.
5 F i r s t , regarding the diameter, the surface 110 of the metal
member 103 is imaged using a scanning electron microscope (SEM) . 50
u l t r a f i n e pores are a r b i t r a r y selected from the observation image
and diameters thereof are measured. A l l diameters are added and
divided by 50, and a r e s u l t is s e t as the diameter of the u l t r a f i n e
10 pores.
Next, regardingthedepthof hole, across s e c t i o n o f t h e v i c i n i t y
of the surface of the metal member 103 is imaged using a transmission
electron microscope (TEM). 10 portions for the depths of the hole
formed by the u l t r a f i n e pores are a r b i t r a r i l y selected and depths
15 oftheholearemeasured. Alldepths oftheholeareaddedanddivided
by 10 and a r e s u l t is s e t a s t h e depth of the hole of the u l t r a f i n e
pores.
[0038]
When t h e u l t r a f i n e pores are present on the surface 110 of the
20 metal member 103, a resin composition configuring t h e r e s i n member
105 which w i l l be described l a t e r can e n t e r t h e holes and a physical
resistingpower (anchor e f f e c t ) is exhibitedbetweenthemetalmember
103andtheresinmember 105, andaccordingly, i t i s p o s s i b l e t o e x p e c t
impro'vement of bonding strength.
25 [0039]
In the embodiment, a method of forming the concavo-convex shape
having the c h a r a c t e r i s t i c s (i) by performing the physical treatment
such as the blast treatment with respect to the surface 110 of the
metal member 103, forming the concavo-convex shape having the
c h a r a c t e r i s t i c s (ii) by performing the chemical etching method of
dipping metal i n an aqueous solution of an inorganic base and/or an
5 aqueous solution of an inorganic acid, and forming a u l t r a f i n e
concavo-convex shapeusinganaqueous solution containingone ormore
kinds selected from hydrazine hydrate, ammonia, and a water-soluble
amine compound is preferably used.
[00401
10 [Preparing Method of Metal Member]
In the embodiment, a concavo-convex shape having two or more
d i f f e r e n t types ofcharacteristicswhichis formedinthemetalmember
103 on the bonding surface 104 side to be bonded t o the resin member
105 can be formed by a method of applying respective c h a r a c t e r i s t i c s
15 (i) and (ii) described above. As described above, when forming the
concavo-convex shape, f i r s t , the concavo-convex shape is formed by
the method of applying the c h a r a c t e r i s t i c s (i) and then, the
concavo-convex shape is formed by the method of applying the
c h a r a c t e r i s t i c s (ii). Ifthemethodsofapplyingthecharacteristics
20 (i) and (ii) are performed in the reversed order, the concavo-convex
shape which is previously formedandis r e l a t i v e l y finemaybe broken
by the l a t t e r process, and the desired shape may not be formed.
[00411
Accordingly, in the embodiment, as described above, the method
25 of applying the c h a r a c t e r i s t i c s (ii) is performed with respect t o
themetalmember 103 a f t e r t h e m e t h o d o f a p p l y i n g t h e c h a r a c t e r i s t i c s
(i),a nd therefore, t h e r e l a t i v e l y smaller concavo-convex shape is
formed in the r e l a t i v e l y large concavo-convex shape. Thus, rihen
performing bonding with the resin member 105 which w i l l be described
l a t e r , a higher anchor e f f e c t is exhibited compared t o technologies
o f t h e r e l a t e d a r t , a n d a s a r e s u l t , itispossibletoincreasebonding
5 strength between the metal member 103 and t h e r e s i n member 105.
(00421
It is preferable that the metal member 103 is subjected t o the
treatments performed by the methods described above, a f t e r working
the metal i n the predetermined shape described above by p l a s t i c
10 working such a s c u t t i n g or pressing or removing working such as
punching, cutting, polishing, or electro-dischargemachining. That
is, metal which is worked in a necessary shape by various working
methods is preferably used. Regarding the metal member 103 worked
i n a necessary shape, it is preferable t h a t a surface t o be bonded
15 t o t h e r e s i n member 105 which w i l l be described l a t e r is not oxidized
or hydroxylated, and rihen it is clear t h a t r u s t which is an oxidized
coating film is present in the surface 110 which is l e f t i n a natural
s t a t e for a long time, the rust is preferably removed by polishing
or a chemical treatment.
20 [0043]
A primer layer may be formed on the surface 110 of the metal
member 103 subjected t o the treatment performed by the method
describedabove. Intheembodiment, whenthespecificconcavo-convex
shape is formed in the surface 110 of the metal member 103 by the
25 method described above, the bonding between the metal member 103 and
t h e r e s i n member 105 which w i l l be described l a t e r is performed with
high strength. However, when acquiring stronger bonding strength,
a primer layer can be formed. P a r t i c u l a r l y , when t h e r e s i n member
105 is formed of a r e s i n composition containing a polyolefin r e s i n ,
a primer layer is formed on the surface 110 of the metal member 103,
and accordingly, it is p o s s i b l e t o obtain t h e m e t a l / r e s i n composite
5 s t r u c t u r e 106 having higher bonding s t r e n g t h .
[0044]
Amaterial f o r configuring the primer l a y e r is not p a r t i c u l a r l y
l i m i t e d , andisgenerallyformedofaprimerresinmaterialcontaining
r e s i n components. The primer r e s i n m a t e r i a l is not p a r t i c u l a r l y
10 l i m i t e d and a well-known m a t e r i a l can be used. S p e c i f i c a l l y ,
well-known polyolefin primer, epoxy primer, o r urethane primer can
be used. The forming method of the primer l a y e r is not p a r t i c u l a r l y
l i m i t e d , and t h e primer l a y e r can be formed by applying a s o l u t i o n
of t h e primer r e s i n m a t e r i a l o r an emulsion of t h e primer r e s i n
15 m a t e r i a l t o the metal member 103 subjected t o t h e s u r f a c e treatment.
As a s o l v e n t used when using a s o l u t i o n , toluene, methyl e t h y l ketone
(MEK), ordimethylformamide (DMF) i s u s e d . Asamediumforemulsion,
an a l i p h a t i c hydrocarbon medium or water is used.
loo451
20
The r e s i n member 105 configuring t h e m e t a l / r e s i n composite
s t r u c t u r e 106 according t o t h e embodiment is formed of a r e s i n
composition containing a (A) thermoplastic r e s i n and, i f necessary,
a (B) f i l l i n g m a t e r i a l . The resincomposition f u r t h e r c o n t a i n s o t h e r
25 compounding agents, i f necessary. For convenience, even when t h e
r e s i n member 105 is formed of only t h e (A) thermoplastic r e s i n , it
is still s t a t e d t h a t t h e r e s i n member 105 is formed of a r e s i n
composition.
[00461
Hereinafter, the (A) thermoplastic resin, the (B) filling
material, and other compounding agents will be described and a
5 preparing method of the resin composition will be described.
[(A) thermoplastic resin]
Examples of the (A) thermoplastic resin as a raw material of
the resinmember105 ofthe embodiment include a polyamide resin such
as polyamide 6, polyamide 66, an aromatic polyamide resin; a
10 polyolefin resin such as a polyethylene resin or a polypropylene
resin; a polyester resin such as a polyethylene terephthalate resin
or a polybutylene terephthalate resin; an amorphous resin such as
anacrylonitrile-butadiene-styrenecopolyn~erresina,p olycarbonate
resin, or a polymethylmethacrylate resin; a polyphenylene sulfide
15 resin, a polyphenylene ether resin, a polyether ether ketone resin,
a polyimide resin, or a combination of two or more kinds thereof.
Amongthese, apolyamide resin, apolyolefinresin, anamorphous
resin, a polyester resin, an acrylonitrile-butadiene-styrene
copolymer resin, a polycarbonate resin, and a polyphenylene sulfide
20 resin are preferably used. A polyamide resin, a polyolefin resin,
a polyester resin, an acrylonitrile-butadiene-styrene copolymer
resin, a polycarbonate resin, and a polyphenylene sulfide resin are
more preferably used. Regardinga polyolefin resin, apolypropylene
resin is preferably used. The (A) thermoplastic resins described
25 above may be used alone or a combination of two or more kinds thereof
may be used.
[0047]
As the polyolefin resin, a polymer obtained by polymerizing
olefin can be used without particular limitation.
As olefin configuringthepolyolefinresin, ethylene, a-olefin,
or cyclic olefin is used.
5 100481
As thea-olefin, linearorbrancheda-olefinhaving3to30carbon
atoms or preferably 3to 20 carbonatoms is used. More specifically,
examples thereof include propylene, 1-butene, 1-pentene,
3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,
10 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, and 1-eicosene.
[00491
As the cyclic olefin, cyclic olefin having 3 to 30 carbon atoms
is used and the number of carbon atoms is preferably 3 to 20. More
15 specifically, examples thereof include cyclopentene, cycloheptene,
norbornene, 5-methyl-2-norbornene, tetracyclododecene,
2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- octa
tetrahydronaphthalene.
[0050]
20 Prefer;Tble examples of olefin configuring the polyolefin resin
include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene,
1-hexene, 4-methyl-1-pentene, and3-methyl-1-pentene. Among these,
ethylene, propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene are
morepreferablyusedandethyleneorpropyleneisevenmorepreferably
25 used.
[0051]
The polyolefin resinmaybe obtainedbypolymerizingthe olefin
alone or may be obtained by combining two or more kinds with each
other and performing a random copolymerization, a block
copolymerization, or a graft copolymerization.
100521
5 The polyolefin may have a linear or branched structure.
[0053]
In the embodiment, when the resin member 105 is formed of the
resin composition containing the (A) thermoplastic resin described
above, the bonding with the metal member 103 is solidly performed.
10 Particularly, among these, when the resin member 105 is formed of
the resincompositioncontainingapolyolefinresin, it wasdifficult
to perform the bonding using a metal member after performing metal
surface roughening treatment performed in the related art, but in
the embodiment, the bonding strength with the metal mernber.103 is
15 dramatically improved, even with the resin member 105 formed of the
resin composition containing the polyolefin resin, and accordingly,
a utility value in industries is extremely high. Therefore, it is
preferable that a polyolefin resin is selected as the (A)
thermoplastic resin.
20 100541
A melt flow rate (MFR) or density of the (A) thermoplastic resin
can be suitably selected andused depending on performance acquired
forthemetal/resincompositestructure106. Forexample, whenusing
a polypropylene resin is used as the (A) thermoplastic resin, an MFR
25 of a polypropylene resin measured under conditions of 230°C and a
load of 2.16 kg based on ASTM Dl238 is preferably equal to or greater
than 0.1 9/10 min and equal to or smaller than 800 9/10 min, more
preferablyequaltoorgreaterthan 0.5g/10minandequalto or smaller
than 100 g/10 min, and even more preferably equal to or greater than
1 . 0 g/10 min and equal to or smaller than 20 g/l0 min.
When using a polyamide resin such as polyamide 6 or polyamide
5 6 6 a s t h e (A) thermoplastic resin, anMFRofthepolyamideresinunder
conditions of 260°C and a load of 2.16 kg is preferably equal to or
greater than 1 g/10 min and equal t o or smaller than 200 9/10 min,
more preferably equal t o or greater than 1 g/10 min and equal t o or
smallerthan150 g/lOmin, andevenmorepreferablyequaltoorgreater
10 than 1 g/10 min and equal t o or smaller than 100 g/10 min.
[00551
[ ( B ) F i l l i n g Material]
The resin composition configuring the resin member 105 of the
embodiment may f u r t h e r contain the (B) f i l i n g material according to
15 the necessary purpose, i n addition t o the (A) thermoplastic resin
which is set a s a compulsory component.
roo561
A s the (B) f i l i n g material, one kind or two or more kinds can
be selected from a group consisting of glass f i b e r s , carbon f i b e r s ,
20 carbonparticles, clay, t a l c , s i l i c a , minerals, andcellulose f i b e r s ,
forexample. Amongthese, one kindortwoormore kindsarepreferably
selected from glass f i b e r s , carbon f i b e r s , t a l c , and minerals.
[00571
The shape of the (B) f i l i n g material may be any shape such as
25 a fibrous shape, a p a r t i c l e shape or a p l a t e shape.
[0058l
When the resin composition contains the (B) f i l i n g material,
the content thereof is preferably equal t o or greater than 1 part
bymass a n d e q u a l t o o r smallerthanlOOpartsbymass, more preferably
equal t o or greater than 5 parts by mass and equal t o or smaller than
90 p a r t s by mass, and p a r t i c u l a r l y preferably equal to or greater
5 than 10 parts by mass and equal t o or smaller than 80 p a r t s by mass,
with respect to 100 parts by mass of the (A) thermoplastic resin.
roo591
The (B) f i l i n g material causes an e f f e c t of decreasing and
controlling a coefficient of l i n e a r expansion of t h e r e s i n member
10 105, in addition to an e f f e c t of increasing r i g i d i t y of t h e r e s i n
member105. Particularly, inacaseofacompositeofthemetalmember
103 and the resin member 105 of the embodiment, a temperature
dependability of a shape s t a b i l i t y of each of the metal member 103
and the resin member 105 is largely d i f f e r e n t from each other i n many
15 cases, and accordingly, the composite may be d i s t o r t e d when a great
change occurs in temperature. This d i s t o r t i o n canbe decreasedwhen
the r e s i n member 105 contains the (B) f i l i n g material. In addition,
it is possible to prevent a decrease i n toughness by s e t t i n g the
content of the (B) f i l i n g material in the range described above.
20 [0060]
[Other Compounding Agents]
In the embodiment, compounding agents may be contained i n the
r e s i n member 105 for applying each function.
[0061]
25 Examplesofthecompoundingagents includeathermalstabilizer,
an antioxidant, a pigment, a weathering agent, a flame retardant,
a p l a s t i c i z e r , a dispersing agent, a lubricant, a release agent, and
an antistatic agent.
LO0621
[Preparation of Resin Composition]
The resin composition can be obtained by mixing or melting and
5 mixing the (A) thermoplastic resin, and if necessary (B) filling
material and other compounding agents using a mixing device such as
a Banbury mixer, a single screw extruder, a twin-screw extruder, or
a high-speed twin-screw extruder.
100631
10
The metal/resin composite structure 106 according to the
embodiment is configuredc1iththemetalmember103andtheresinmember
105.
[0064]
15 More specifically, the resin composition configuringthe resin
member 105 enters the specific concavo-convex shape portion having
two or more different types of characteristics which is formed in
the surface 110 of the metal member 103, the metal and the resin are
bonded to each other, and a metal-resin interface is formed, and
20 accordingly, the metal/resin composite structure 106 of the
embodiment is obtained.
[0065]
In the embodiment, it is not clear why high bonding strength
with the resin member 105 is exhibited by forming the specific
25 concavo-convex shape having two or more different types of
characteristics describedaboveinthesurface110ofthemetalmember
103, but the reason may be that the concavo-convex shape and the
u l t r a f i n e holes exhibit a vent e f f e c t based on t h e c h a r a c t e r i s t i c s
(ii) and a i r releasing occurs. That is, it is assumed t h a t , i n a
case of only the concavo-convex shape based on the c h a r a c t e r i s t i c s
(i),w hen the resin composition configuring the resin member is
5 attempted t o be bonded to the metal member based on a manufacturing
methodofthemetal/resincomposite s t r u c t u r e r ~ h i c h w i l l b e d e s c r i b e d
l a t e r , the r e s i n composition hardly enters deep portions of the
concave portions d u e t o t h e presence of a n a i r layerbetweenthemetal
member and t h e r e s i n member. However, by combining the
10 concavo-convex shape and t h e u l t r a f i n e pores based on the
c h a r a c t e r i s t i c s (ii) with the concavo-convex shape based on the
c h a r a c t e r i s t i c s (i), a i r e n t e r s t h e concavo-convex shape and the
u l t r a f i n e pores based on the c h a r a c t e r i s t i c s (ii) and the r e s i n
composition can enter deep portions of the concave portions based
15 on the c h a r a c t e r i s t i c s (i). With such a circumference, the metal
member103 and the resinmember 105 may exhibit highbonding strength
by applying the c h a r a c t e r i s t i c s (i) and (ii) t o the surface 110 of
the metal member 103.
[0066]
20
A manufacturing method of the metal/resin composite s t r u c t u r e
106oftheembodimentisnotparticularlylimited, andthemetal/resin
composite s t r u c t u r e is obtained by bonding the resin composition t o
themetalmember103 havingthecharacteristics describedaboverihile
25 molding the resin composition so as to have a desired shape of the
r e s i n member 105.
[0067]
As a molding method of the resin member 105, a resin molding
method such as injection molding, extrusion molding, heat press
molding, compression molding, transfer molding, cast molding, laser
welding molding, reaction injection molding (RIM molding), LIM
5 molding, spray forming, or the like.
[0068]
Amongthese, injectionmolding is preferable, and specifically,
it is preferable that the metal member 103 is inserted into a cavity
portion of an injection molding die and the resin member is
10 manufactured by an injection molding method of injecting the resin
composition to the die. Specifically, the method includes the
following steps (1) to ( 3 ) .
(1) A step of preparing the resin composition
(2) A step of installing the metal member 103 in a die for
15 injection molding,
(3) A step of performing injection molding of the resin
compositioninthediesothattheresincompositioncomesintocontact
with at least a part of the metal member 103
Hereinafter, each step will be described.
20 [00691
As described above, in the (1) step of preparing the resin
composition, the resin composition can be obtained by mixing or
melting and mixing the (A) thermoplastic resin, and if necessary (B)
filling material and other compounding agents using a mixing device
25 such as a Banbury mixer, a single screw extruder, a twin-screw extruder,
or a high-speed twin-screw extruder.
[0070]
Next, an injection molding method performed by steps ( 2 ) and
(3) w i l l be described.
[00711
F i r s t , a d i e forinjectionmoldingisprepared, thedieisopened,
5 and the metal member 103 is i n s t a l l e d in a part of t h e d i e .
Next, the die is closed, the resin composition obtained in the
step (1) is injected i n t o t h e d i e and s o l i d i f i e d so t h a t a t l e a s t
a part of the resin composition comes i n t o contact with the surface
where the concave shape of the metal member 103 is formed. After
10 t h a t , t h e die is opened and separated, and accordingly, the
metal/resin composite structure 106 can be obtained.
COO721
Theinjectionmoldingperformedbythe steps (1) t o ( 3 ) described
aboveandinjection foamingmoldingorrapidheatcyclemolding (RHCM,
15 heating and cooling molding) of rapidly heating and cooling the die
may be used i n combination.
As a method of the injection foaming molding, a method of adding
a chemical foaming agent to the resin, a method of d i r e c t l y i n j e c t i n g
nitrogen gas or carbon dioxide gas t o a cylinder part of an injection
20 molding device, or a MuCell injection foaming molding method of
i n j e c t i n g nitrogen gas or carbon dioxide gas t o a cylinder part of
an i n j e c t i o n molding device in a s u p e r c r i t i c a l s t a t e is used.
[0073]
It is possible t o obtain the metal/resin compdsite s t r u c t u r e
25 106 i n which the resin member 105 is a foam body by any method. With
any method, counter pressure can be used or core back can be used
depending on a shape of a molded product as a controlling method of
the die.
The rapid heat cycle molding can be performed by connecting a
rapid heating and cooling device to a die. The rapid heating and
cooling device may use a generally used system. A heating method
5 may be any one method or a combination of a plurality of methods from
a steam method, a pressurized hot water method, a hot water method,
a heat oil method, an electric heater method, and an electromagnetic
induction heating type.
[0074]
10 A cooling method may be any one method or a combination of a
cold water method and a cold oil method. It is desired that the
injection molding die is heated to a temperature equal. to or higher
thanlOO°Candequalto or lowerthan 250°C, and the injectionmolding
die is cooled after completing injection of the resin composition,
15 for example, as conditions of the rapid heat cycle molding method.
A temperature for heating the die has different preferred ranges
depending on the (A) thermoplastic resin configuring the resin
composition, and when the (A) thermoplastic resin is a crystalline
resin and a resin having a melting point lower than 200°C, the
20 temperature thereof is preferably equal to or higher than 100°C and
equal to or lower than 150°C, and when the (A) thermoplastic resin
is a crystalline resin and a resin having a melting point equal to
or higher than 200°C, the temperature thereof is preferably equal
to or higher than 140°C and equal to or lower than 250°C. When the
25 (A) thermoplastic resin is an amorphous resin, the temperature
thereof is desirably equal to or higher than 100°C and equal to or
lower than 180°C.
[0075]

The metal/resin composite structure 106 of the embodiment has
high productivity and a high degree of freedom of shape controlling,
5 andaccordingly, themetal/resin composite s t r u c t u r e canbe used for
various purposes.
[0076]
Examples thereof include s t r u c t u r a l components for a car,
car-mounted components, a housing of an electronic device, a housing
10 of household e l e c t r i c appliances, s t r u c t u r a l components, mechanical
components, various automobile components, components for an
electronicdevice, thepurpose forhouseholdgoods suchas f u r n i t u r e ,
or kitchenware, medical equipment, components of construction
materials, other s t r u c t u r a l components or e x t e r i o r components.
15 [00771
More s p e c i f i c a l l y , examples thereof include the following
components which are designed so t h a t a portion having i n s u f f i c i e n t
strength j u s t with the resin is supportedbythemetal. Invehicles,
an instrument panel, a console box, door knobs, door t r i m , a s h i f t
20 lever, pedals, a glove box, a bumper, a hood, fenders, a trunk, doors,
a roof, a p i l l a r , seats, a radiator, an o i l pan, a steering wheel,
an ECU box, and e l e c t r i c a l parts are used. In construction or
household goods, glass window frames, handrails, curtain r a i l , a
chest of drawers, and drawer, closet, a bookshelf, a desk, and a chair
25 are used. A connector, a relay, and gears are used as precise
e l e c t r o n i c components. A transport container, a suitcase, and a
trunk are used as transportation containers.
[0078]
Various consumer electronics can also be used. Household
appliances suchas a r e f r i g e r a t o r , awashingmachine, a vacuumcleaner,
amicrowave oven, a n a i r conditioner, lightingequipment, a n e l e c t r i c
5 k e t t l e , a TV, a clock, a ventilating fan, a projector, and speakers,
andelectronicinformationdevices suchasacomputer, amobilephone,
a smart phone, a d i g i t a l camera, a t a b l e t PC, a portable music player,
a portable game machine, a charger, and a battery are used.
[0079]
10 For other uses, toys, sports equipment, shoes, sandals, bags,
tableware such as forks, knifes, spoons, and dishes, stationery such
as a b a l l pen or a mechanical pencil, a f i l e , and a binder, cookware
such as a pan or a pot, a k e t t l e , a spatula, a ladle, a perforated
l a d l e , a whisk, and a tong, components for lithium i o n secondary
15 battery, and a robot are used.
[00801
Hereinabove, the usage of the metal/resin composite s t r u c t u r e
106 of the invention has been described, but these are examples of
the use a p p l i c a t i o n o f t h e inventionandvarious other configurations
20 can be used.
[00811
Hereinabove,theembodimentsoftheinventionhasbeendescribed,
b u t t h e s e are merely examples of the invention and various other
configurations can be used.
25 [Examples]
[0082]
Hereinafter, the embodiments o f t h e invention w i l l be described
with referencetoExamplesbutthe embodiment is not l i m i t e d t h e r e t o .
100831
FIGS. 1 and 2 a r e used as common diagrams of each example.
FIG. 1 is an o u t l i n e view schematically showing an example of
5 a s t r u c t u r e o f t h e m e t a l / r e s i n composite s t r u c t u r e 106 including t h e
m e t a l member 103 and t h e r e s i n member 105.
FIG. 2 is a configuration diagram schematically showing an
example of a process o f manufacturing t h e m e t a l / r e s i n composite
s t r u c t u r e 106 including the metal member 103 and t h e r e s i n member
10 105. S p e c i f i c a l l y , t h e drawing schematically shows a process o f
i n s t a l l i n g t h e metal member 103 which is worked i n a predetermined
shape and includes t h e surface 110 where a s u r f a c e treatment area
(bondingsurface104) havingafineconcavo-convex s u r f a c e is formed,
i n a d i e 102 f o r i n j e c t i o n molding, i n j e c t i n g t h e r e s i n composition
15 by an i n j e c t i o n molding device 101 through a gate/runner 107, and
manufacturing t h e metal/resin composite s t r u c t u r e 106 which is
integratedwiththemetalmember103 inwhich the f i n e concavo-convex
s u r f a c e is formed.
[0084]
20 (Metal Surface Analysis)
The mean width of t h e p r o f i l e elements (RSm) and the maximum
height roughness (Rz) of t h e c h a r a c t e r i s t i c s (i) were measured by
a laser microscope (VK-XI00 manufactured by KEYENCE).
[0085]
25 In a d d i t i o n , t h e mean width of t h e p r o f i l e elements (RSm) and
t h e maximum height roughness (Rz) of t h e c h a r a c t e r i s t i c s (ii) were
measured by a scanning probe microscope (SPM-9700 manufactured by
Shimadzu Corporation).
[0086]
(Evaluation Method and Determination of Bonding Strength)
The measurement was performed using a tensile strength tester
5 'model 1323 (manufactured by Aikoh Engineering Co., Ltd.)" and
attaching a dedicated jig to the tensile strength tester, under
conditions of room temperature (23OC), a distance between chucks of
60 mm, and a tensile rate of 10 mm/min. A breaking weight (N) was
dividedbyanareaofthemetal/resinbondedportiontoobtainbonding
10 strength (MPa).
[0087]
(Surface Treatment of Metal)
[Preparation Example 1 1
A commercially available A5052 aluminum alloy plate having a
15 thickness of 1.6 mm was cut into a rectangular piece having a size
of 18 mm x 45 mm, and a concavo-convex shape having Rsm of 900 prn
and Rz of 400 pm GJaS prepared on the plate surface by an air nozzle
type blast treatment using silica sand (No. 5 A manufactured by Ube
Sand Industries, Ltd. ) and an air blast device (injection pressure
20 of compressed air: 5.25 kg/cm2) which is ACR-1 manufactured by ATSUCHI
TEKKO CO., LTD. Next, the surface treatment was performed based on
a method of an experimental example 1 disclosed in Pamphlet of
International Publication No. W02009/31632 and a metal member was
obtained.
25 [0088]
When observing the metal member using a scanning type probe
microscope (SPM-9700 manufactured by Shimadzu Corporation) with a
field of vision of 4 pm, a concavo-convex shape having RSm of 800
nm and RZ of 240 nm was formed in the concavo-convex surface which
is formed by the blast treatment. In addition, when observing the
metal member using a scanning electron microscope (JSM-6701F
5 manufactured by JEOL) with 300000 magnifications, ultrafine pores
having a depth of approximately 20 nm were formed on the surface of
the metal member. The images are shown in FIG. 3.
[0089]
[Preparation Example 21
10 A commercially available A5052 aluminum alloy plate having a
thickness of 1.6 mm was cut into a rectangular piece having a size
of 18 mm x 45 mi, and a concavo-convex shape having Rsm of 200 vm
and Rz of 250 pm was prepared on the plate surface by an air nozzle
type blast treatment using silica sand (No. 5 A manufactured by Ube
15 Sand Industries, Ltd.) and an air blast device (injection pressure
of compressed air: 3.25 kg/cm2) which is ACR-1 manufactured by ATSUCHI
TEKKO CO., LTD. Next, the surface treatment was performed based on
a method of an experimental example 1 disclosed in Pamphlet of
International Publication No. W02009/31632 and a metal member was
20 obtained.
[0090]
When observing the metal member using a scanning type probe
microscope (SPM-9700 manufactured by Shimadzu Corporation) with a
field of vision of 4 pm, a concavo-convex shape having RSm of 800
25 nm and RZ of 240 nm was formed in the concavo-convex surface which
is formed by the blast treatment. In addition, when observing the
metal member using a scanning electron microscope (JSM-6701F
manufactured by JEOL) with 300000 magnifications, ultrafine pores
having a depth of approximately 20 nm were formed on the surface of
the metal member. [00911
[Preparation Example 31
5 A commercially available A5052 aluminum alloy plate having a
thickness of 1.6 mrn was cut into a rectangular piece having a size
of 18 mrn x 45 mm, and a concavo-convex shape having Rsm of 900 pm
and Rz of 400 pm was prepared on the plate surface by an air nozzle
type blast treatment using silica sand (No. 5 A manufactured by Ube
10 Sand Industries, Ltd.) and an air blast device (injection pressure
of compressedair: 5.25 kg/cm2) whichisACR-1manufacturedbyATSUCHI
TEKKO CO., LTD. Next, the surface treatment was performed by
partially changing (without performing dipping in an aqueous
hydrazine solution) a method of an experimental example 1 disclosed
15 in Pamphlet of International PublicationNo. W02009/31632 andametal
member was obtained.
100921
When observing the metal member using a scanning type probe
microscope (SPM-9700 manufactured by Shimadzu Corporation) with a
20 field of vision of 4 pm, a concavo-convex shape having RSm of 800
nm and RZ of 240 nm was formed in the concavo-convex surface which
is formed by the blast treatment. In addition, the metal member xias
observed using a scanning electron nlicroscope (JSM-6701F
manufacturedby JEOL) with 300000magnifications andultrafine pores
25 observed in Preparation Example 1 were not observed.
[0093]
[Preparation Example 41
A commercially available A5052 aluminum alloy plate having a
thickness of 1.6 mm was cut into a rectangular piece having a size
of 18 mm x 45 mm, a concavo-convex shape having Rsm of 900 pm and
Rz of 400 pm was prepared on the plate surface by an air nozzle type
5 blast treatment using silica sand (No. 5 A manufactured by Ube Sand
Industries, Ltd.) and an air blast device (injection pressure of
compressed air: 5.25 kg/cm2) which is ACR-1 manufactured by ATSUCHI
TEKKO CO., LTD, and a metal member was obtained.
[0094]
10 The metal member was observed using a scanning electron
microscope (JSM-6701F manufactured by JEOL) with 300000
magnifications, butthe concavo-convex shape and the ultrafine pores
observed in Preparation Example 1 were not observed. The images are
shown in FIG. 4.
15 [0095]
[Preparation Example 51
A commercially available A5052 aluminum alloy plate having a
thickness of 1.6 mm was cut into a rectangular piece having a size
of 18 mmx 45mm, the surfacetreatmentwasperformedbasedonamethod
20 of an experimental example 1 disclosed in Pamphlet of International
PublicationNo. W02009/31632, withoutperformingtheblasttreatment,
and a metal member was obtained.
[0096]
When observing the metal member using a scanning type probe
25 microscope (SPM-9700 manufactured by Shimadzu Corporation) with a
field of vision of 4 pm, a concavo-convex shape having RSm of 800
nm and RZ of 240 nm was formed. In addition, when observing the metal
member using a scanning electron microscope (JSM-6701Fmanufactured
by JEOL) with 300000 magnifications, ultrafine pores having a depth
of approximately 20 nm were formed in the concavo-convex surface.
The images are shown in FIG. 5.
5 f00971
[Preparation Example 61
A commercially available A5052 aluminum alloy plate having a
thickness of 1.6 mm was cut into a rectangular piece having a size
of 18 mm x 45 mm, and a concavo-convex shape having Rsm of 120 pm
10 and Rz of 150 pm was prepared on the plate surface by an air nozzle
type blast treatment using silica sand (No. 6 A manufactured by Ube
Sand Industries, Ltd.) and an air blast device (injection pressure
ofcompressedair: 3.25 kg/cm2) whichisACR-1manufacturedbyATSUCHI
TEKKO CO., LTD. Next, the surface treatment was performed based on
15 a method of an experimental example 1 disclosed in Pamphlet of
International Publication No. W02009/31632 and a metal member was
obtained.
[0098]
When observing the metal member using a scanning type probe
20 microscope (SPM-9700 manufactured by Shimadzu Corporation) with a
field of vision of 4 pm, a concavo-convex shape having RSm of 800
nm and RZ of 240 nm was formed in the concavo-convex surface which
is formed by the blast treatment. In addition, when observing the
metal member using a scanning electron microscope (JSM-6701F
25 manufactured by JEOL) with 300000 magnifications, ultrafine pores
havingadepthofapproximately20nmwere formedintheconcavo-convex
surface.
[0099]
[Example 11
A small dumbbell metal insert die 102 was mounted on JSW J85AD
manufactured by the Japan Steel Works, LTD. and the aluminum piece
5 (metal member 103) prepared in Preparation Example 1 was installed
inthedie102. Then, theinjectionmoldingofglass fiber-reinforced
polypropylene (80 parts by weight of V7100 manufactured by Prime
Polymer Co., Ltd., polypropylene (MFR (230°C load of 2.16 kg): 18
g/10 min) and 20 parts by weight of glass fiber), as the resin
10 composition, was performed in the die 102 under conditions of a
cylinder temperature of 250°C, a die temperature of l2O0C, an
injection rate of 25 mm/sec, holding pressure of 80 MPa, and holding
timeof10 seconds, andametal/resincompositestructurerias obtained
An evaluation result of bonding strength is shown in Table 1.
15 [0100]
[Example 21
A metal/resin composite structure was obtained by the same
method as in Example 1, except for changing the aluminum piece used
to a piece prepared in Preparation Example 2. An evaluation result
20 of bonding strength is shown in Table 1.
[ 01011
[Example 31
A metal/resin composite structure was obtained by the same
method as in Example 1, except for changing the aluminum piece used
25 to a piece prepared in Preparation Example 3. An evaluation result
of bonding strength is shown in Table 1.
[0102]
[Comparative Example 11
A metal/resin composite structure was obtained by the same
method as in Example 1, except for changing the aluminum piece used
to a piece prepared in Preparation Example 4. An evaluation result
5 of bonding strength is shown in Table 1.
[0103]
[Comparative Example 21
A metal/resin composite structure was obtained by the same
method as in Example 1, except for changing the aluminum piece used
10 to a piece prepared in Preparation Example 5.
An evaluation result of bonding strength is shown in Table 1.
[0104]
[Comparative Example 31
A metal/resin composite structure v7as obtained by the same
15 method as in Example 1, except for changing the aluminum piece used
to a piece prepared in Preparation Example 6. An evaluation result
of bonding strength is shown in Table 1.
RSm: mean width of the profile elements
Rz: maximum height roughness
Table 1
corn. EX. 1 Corn. EX. 2 Corn. EX. 3
Preparing method

ultrafine concavities
and convexities
Bonding
strength
-
MPa
Observed
18
Observed
13
None
14
None
9
Observed
0
Onserved
10
[0106]
The aluminum piece used in Example 1 s a t i s f i e d RSm and Rz s e t
by t h e b l a s t treatment performed for the c h a r a c t e r i s t i c s (i) and RSm
and Rz s e t by the etching performed for the c h a r a c t e r i s t i c s (ii) i n
5 therangesdescribedabove, andultrafineconcavitiesandconvexities
formed i n the concavo-convex surface were present, and accordingly,
the aluminum piece having extremely high bonding strength with the
r e s i n member was obtained. When a metal side of the metal/resin
composite structure was dissolved i n 5% of a n i t r i c acid aqueous
10 solution and a surface s t r u c t u r e of a resin side was observed using
a scanningelectronmicroscope (JSM-6701Fmanufactured by JEOL) with
100000 magnifications, u l t r a f i n e convex shape having a height of
approximately20 nmwas observedanditrgas foundthat theresinmember
e n t e r e d t h e u l t r a f i n e pores formedinthe s u r f a c e ofthemetalmember.
15 The image is shorm in FIG. 6.
[01071
Meanwhile, in Comparative Example 1, the aluminum piece has RSm
of 900 pm and Rz of 400 pm s e t by the b l a s t treatment performed f o r
the c h a r a c t e r i s t i c s (i) and s a t i s f i e s the ranges described above,
20 buttheetchingforapplyingthecharacteristics (ii) isnotperformed,
and accordingly, the features of the invention are not s a t i s f i e d .
I n Comparative Example 2, the aluminum piece has RSm of 800 nm
and Rz of 240 nm s e t by the etching performed f o r t h e c h a r a c t e r i s t i c s
(ii) and s a t i s f i e s the ranges described above, and u l t r a f i n e
25 concavitiesandconvexities formedintheconcavo-convex surfacewere
present, but the blast treatment for applying the c h a r a c t e r i s t i c s
(i) is not performed, and accordingly, the features of the invention
are not s a t i s f i e d .
A metal side of the metal/resin composite structure of
Comparative Example 1 was dissolved in 5% of a n i t r i c acid aqueous
solution and a surface s t r u c t u r e of a r e s i n side was observed using
5 a scanning electronmicroscope (JSM-6701Fmanufacturedby JEOL) with
100000 magnifications. However, the u l t r a f i n e convex shape i n the
order of nanometer was not observed. The image is shown i n FIG. 7.
In Comparative Example 2, the metal member and the r e s i n member
are separatedfromeach other immediately a f t e r injectionmonolithic
10 molding, and accordingly, the observation of the surface s t r u c t u r e
of the r e s i n side of the metal/resin composite structure was not
performed. However, it is considered t h a t the resin member does not
e n t e r t h e u l t r a f ine pores formed on the surface of the metal member.
Accordingly, in Comparative Examples 1 and 2, bonding strength with
15 the r e s i n member is also low.
In Comparative Example 3, it is attempted t o increase a bonding
area with the resin member by forming the concavo-convex shape which
is d i f f e r e n t l y o r d e r e d t o b e formedonthe surface ofthemetalmember
i n order t o improve the bonding strength with the resin member, but
20 desired e f f e c t s were not obtained. The reason thereof is because
RSmandRz set by t h e b l a s t treatment and the features o f t h e invention
are not s a t i s f i e d .
[01081
P r i o r i t y is claimed on Japanese Patent Application No.
25 2013-190607, f i l e d September 13, 2013, the e n t i r e content of which
is incorporated herein by reference
CLAIMS
1. A metal/resin composite structure,
r ~ h e r e i n t h e m e t a l / r e s i n c o m p o s i t e s t r u c t u r e i sfo rmedbybonding
5 a metal member and a resin member t o each other, and
aconcavo-convexshapesatisfyingthe followingcharacteristics
(i) and (ii) is formed on a bonding surface of the metal member t o
be bonded t o the r e s i n member.
(i) A mean width of the p r o f i l e elements (RSm) is equal to or
10 greater than 150 pm and equal to or smaller than 1500 pm and a maximum
height roughness (Rz) is equal t o or greater than 170 pm and equal
t o or smaller than 800 vm
(ii) A mean width of t h e p r o f i l e elements (RSm) is equal t o or
greaterthan100 nmandequalto or smallerthan1OOOO nmandamaximum
15 height roughness (Rz) is equal t o or greater than 100 nm and equal
t o or smaller than 10000 nm
2. The metal/resin composite structure according to claim 1,
wherein an u l t r a f i n e concavo-convex shape having a diameter
20 equal to or greater than 5 nm and equal to or smaller than 100 nm
and a depth equal to or greater than 10 nm,and equal to or smaller
than 500 nm is formed on the surface of the metal member.
3. The metal/resin composite structure according to claim 1 or 2,
25 wherein the concavo-convex shape s a t i s f y i n g c h a r a c t e r i s t i c s
(ii)i s formedontheconcavo-convexshape satisfying c h a r a c t e r i s t i c s
(i).
4 . Themetal/resincomposite structureaccording to any oneof claims
1 t o 3,
r.rhereinthemetalmemberis formedofametalmaterialcontaining
5 one kind or two or more kinds of metal selected from iron, s t a i n l e s s
s t e e l , aluminum, an aluminum alloy, magnesium, a magnesium alloy,
copper, a copper alloy, titanium, and a titanium alloy.
5. Themetal/resincomposite structure accordingto any one of claims
10 1 t o 4 ,
wherein the resin member is formed of a resin composition
containing an (A) thermoplastic resin.
6. The metal/resin composite s t r u c t u r e according to claim 5,
15 wherein the (A) thermoplastic resin is a polyolefin r e s i n .
7 . The metal/resin composite structure according to claim 5 or 6,
wherein the resin composition contains a (8) f i l l i n g material
and the content of the (B) f i l l i n g material is equal t o or greater
20 than 1 p a r t by mass and equal to or smaller than 100 parts by mass
with respect to 100 p a r t s by mass of the (A) thermoplastic r e s i n .
8. The metal/resin composite structure according t o claim 2,
whereintheconcavo-convexshape satisfying t h e c h a r a c t e r i s t i c s
25 (i) is formed on the surface ofthemetalmember by performing a b l a s t
treatment with respect t o the metal member, the concavo-convex shape
s a t i s f y i n g t h e c h a r a c t e r i s t i c s (ii) is f u r t h e r formed on t h e s u r f a c e
ofthemetalmemberbyperforminga chemical etchingmethodof d i p p i n g
t h e metal member i n a t l e a s t one kind of an aqueous s o l u t i o n s e l e c t e d
froman aqueous s o l u t i o n of an i n o r g a n i c b a s e andan aqueous s o l u t i o n
o f a n inorganic acid, and t h e u l t r a f i n e concavo-convex shape is
5 f u r t h e r formedon t h e s u r f a c e ofthemetalmemberby dipping t h e m e t a l
member i n an aqueous s o l u t i o n containing one o r more kinds s e l e c t e d
fromhydrazinehydrate, ammonia, a n d a w a t e r - s o l u b l e amine compound.