FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
&
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
[See section 10, Rule 13]
THERMOPLASTIC RESIN COMPOSITION, MOLDED ARTICLE, AND
PRODUCT
MITSUBISHI ELECTRIC CORPORATION, A CORPORATION ORGANISED AND
EXISTING UNDER THE LAWS OF JAPAN, WHOSE ADDRESS IS 7-3,
MARUNOUCHI 2-CHOME, CHIYODA-KU, TOKYO 100-8310, JAPAN
THE FOLLOWING SPECIFICATION PARTICULARLY DESCRIBES THE
INVENTION AND THE MANNER IN WHICH IT IS TO BE PERFORMED.

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DESCRIPTION
TITLE OF INVENTION
Thermoplastic Resin Composition, Molded Article, and Product
5 TECHNICAL FIELD
[0001] The present disclosure relates to thermoplastic resin compositions, molded
articles, and products.
BACKGROUND ART
[0002] Thermoplastic molded articles have been used under a variety of environments
10 in a variety of applications such as inner parts of home appliance products and OA
apparatuses, housings, parts for vehicles, and sundry goods because thermoplastic
resins are lighter than metals and easier to process than metals.
[0003] Their usage environment and usage method may cause powdery dust fouling
made of sand dust, dust, soot, oily smoke, or the like to adhere to these thermoplastic
15 resin molded articles. Adhesion of powdery dust fouling to the molded articles results
in bad appearances thereof, and may reduce the performance of the products.
[0004] Thus, to suppress adhesion of powdery dust fouling, attempts to impart
antistatic performance to thermoplastic resin molded articles using an antistatic agent
have been made.
20 [0005] For example, a method of imparting antistatic performance to a molded article
by causing an antistatic agent to adhere to the surface of the molded article through
spraying, immersion, or application thereof is known. However, the method of
causing the antistatic agent to adhere to the surface of the molded article has problems
such that most of antistatic agents are made of a water-soluble surfactant and are
25 removed by wiping, washing or the like, resulting in loss of antistatic effects of the
antistatic agents.
[0006] On the other hand, another method (kneading method) of imparting antistatic
performance to a thermoplastic resin molded article by compounding an antistatic agent
as an additive with a thermoplastic resin is known. This kneading method has been
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recently receiving attention because of its long-lasting high antistatic effects.
[0007] A variety of compounds are known as antistatic agents used in the kneading
method. For example, PTL 1 (Japanese Patent Laying-Open No. 2011-256293)
discloses fatty acid amide compounds of aminoethylethanolamine. PTL 2 (Japanese
5 Patent Application Laying-Open No. 58-118838) and PTL 3 (Japanese Patent
Application Laying-Open No. 3-290464) disclose polyether ester amide. PTL 4
(Japanese Patent Application Laying-Open No. 2001-278985), PTL 5 (WO
2014/115745), and PTL 6 (WO 2014/148454) each disclose a block copolymer
including an olefin block and a hydrophilic polymer block, and the like. PTLs 5 and 6
10 also disclose a polyether ester polymer-type antistatic agent.
[0008] To be noted, PTL 1 discloses use of an alkali metal compound or an alkaline
earth metal compound (such as calcium stearate) in combination to enhance the
antistatic effects of the fatty acid amide compounds of aminoethylethanolamine.
Moreover, PTL 4 discloses use of an alkali metal compound, such as lithium chloride,
15 potassium acetate, or sodium dodecylbenzenesulfonate, in combination to enhance the
antistatic effects of the block copolymer including an olefin block and a hydrophilic
polymer block. PTLs 5 and 6 disclose compounding of an alkali metal compound
such as potassium acetate or sodium dodecylbenzenesulfonate with a polyether ester
polymer-type antistatic agent.
20 CITATION LIST
PATENT LITERATURE
[0009] PTL 1: Japanese Patent Application Laying-Open No. 2011-256293
PTL 2: Japanese Patent Application Laying-Open No. 58-118838
PTL 3: Japanese Patent Application Laying-Open No. 3-290464
25 PTL 4: Japanese Patent Application Laying-Open No. 2001-278985
PTL 5: WO 2014/115745
PTL 6: WO 2014/148454
SUMMARY OF INVENTION
TECHNICAL PROBLEM
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[0010] However, it is found that the antistatic agents above all demonstrate some
effects of suppressing adhesion of hydrophilic powdery dust fouling made of sand dust,
dust or the like, but they hardly demonstrate the effects of suppressing adhesion of
hydrophobic powdery dust fouling made of soot, oily smoke, or the like. In other
5 words, any resin composition which hardly allow adhesion of both hydrophilic
powdery dust fouling and hydrophobic powdery dust fouling has not been provided.
[0011] Accordingly, an object of the present disclosure is to suppress adhesion of both
hydrophilic powdery dust fouling and hydrophobic powdery dust fouling to a molded
article comprising a thermoplastic resin composition.
10 SOLUTION TO PROBLEM
[0012] A thermoplastic resin composition comprising: a thermoplastic resin (A)
selected from the group consisting of an aromatic polycarbonate resin (A1), a styrenebased resin (A2), an aromatic polyester resin (A3), a polyphenylene ether resin (A4), a
methacrylic resin (A5), a polyarylene sulfide resin (A6), an olefin resin (A7), a
15 polyamide resin (A8), and a mixture thereof;
a hydrophilic copolymer (B) having a polyoxyethylene chain; and
a fatty acid metal salt (C) represented by the following formula (1):
[0013] M(OH)y(R-COO)x ... (1)
wherein R is an alkyl group or alkenyl group having 6 to 40 carbon atoms; M is at least
20 one metal element selected from the group consisting of aluminum, zinc, calcium,
magnesium, lithium, and barium; and x and y each independently represent an integer
of 0 or more, and satisfy the relation represented by x + y = [valency of M].
ADVANTAGEOUS EFFECTS OF INVENTION
[0014] In the present disclosure, adhesion of both hydrophilic powdery dust fouling
25 hydrophobic powdery dust fouling to a molded article comprising a thermoplastic resin
composition can be suppressed by compounding the hydrophilic copolymer (B) and the
fatty acid metal salt (C) with the thermoplastic resin (A).
BRIEF DESCRIPTION OF DRAWINGS
[0015] FIG. 1 is a cross-sectional schematic view showing one example of a molded
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article according to Embodiment 2.
FIG. 2 is a schematic graph showing the compositional distribution in the depth
direction of one example of the molded article according to Embodiment 2.
FIG. 3 is a conceptual diagram illustrating a thermoplastic resin composition
5 according to an embodiment.
FIG. 4 is a conceptual diagram illustrating a thermoplastic resin composition
according to an embodiment.
FIG. 5 is a cross-sectional schematic view showing one example of an air
conditioner according to Embodiment 3.
10 FIG. 6 is a conceptual diagram illustrating a thermoplastic resin composition
according to an embodiment.
DESCRIPTION OF EMBODIMENTS
[0016] Embodiments according to the present disclosure will now be described. In
the drawings, dimensional relations such as the length, the width, the thickness, the
15 depth, and the like are appropriately changed for clarifying and simplifying the
drawings, and do not represent actual dimensional relations.
[0017] Embodiment 1.
The thermoplastic resin composition according to the present embodiment
comprises:
20 a thermoplastic resin (A) selected from the group consisting of an aromatic
polycarbonate resin (A1), a styrene-based resin (A2), an aromatic polyester resin (A3),
a polyphenylene ether resin (A4), a methacrylic resin (A5), a polyarylene sulfide resin
(A6), an olefin resin (A7), a polyamide resin (A8), and a mixture thereof;
a hydrophilic copolymer (B) having a polyoxyethylene chain; and
25 a fatty acid metal salt (C).
[0018] The molded article comprising the thermoplastic resin composition according to
the present embodiment provides a remarkable anti-contamination effect of suppressing
adhesion of both hydrophilic powdery dust fouling and hydrophobic powdery dust
fouling. Such a remarkable anti-contamination effect is provided by a thermoplastic
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resin composition containing all the components (A) to (C), and is difficult to obtain
using only the component (A), only the component (B), only the component (C), only
the components (A) and (B), only the components (A) and (C), or only the components
(B) and (C).
5 [0019] The molded article comprising the thermoplastic resin composition according to
the present embodiment can further have mechanical strength such as impact resistance.
[0020]
The thermoplastic resin (A) is selected from the group consisting of an aromatic
polycarbonate resin (A1), a styrene-based resin (A2), an aromatic polyester resin (A3),
10 a polyphenylene ether resin (A4), a methacrylic resin (A5), a polyarylene sulfide resin
(A6), an olefin resin (A7), a polyamide resin (A8), and a mixture thereof.
[0021] Examples of the mixture, that is, the mixture of at least two resins selected from
the aromatic polycarbonate resin (A1), the styrene-based resin (A2), the aromatic
polyester resin (A3), the polyphenylene ether resin (A4), the methacrylic resin (A5), the
15 polyarylene sulfide resin (A6), the olefin resin (A7), and the polyamide resin (A8)
include, but should not be limited to, combinations of the aromatic polycarbonate resin
(A1) with the styrene-based resin (A2), the aromatic polycarbonate resin (A1) with the
aromatic polyester resin (A3), the aromatic polycarbonate resin (A1) with the olefin
resin (A7), the aromatic polycarbonate resin (A1) with the methacrylic resin (A5), the
20 styrene-based resin (A2) with the aromatic polyester resin (A3), the styrene-based resin
(A2) with the methacrylic resin (A5), the styrene-based resin (A2) with the olefin resin
(A7), the styrene-based resin (A2) with the polyamide resin (A8), the polyphenylene
ether resin (A4) with the olefin resin (A7), the methacrylic resin (A5) with the olefin
resin (A7), and the olefin resin (A7) with the polyamide resin (A8).
25 [0022] (Aromatic polycarbonate resin (A1))
The aromatic polycarbonate resin (A1) is prepared usually by reacting a
dihydroxy compound with a carbonate precursor through interface polycondensation or
melt transesterification, or by polymerizing a carbonate prepolymer through solid phase
transesterification, or by polymerizing a cyclic carbonate compound through ring-
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opening polymerization.
[0023] The dihydroxy component used there may be any dihydroxy component of an
aromatic polycarbonate usually used, and may be bisphenols or aliphatic diols.
[0024] Examples of the bisphenols include 4,4'-dihydroxybiphenyl, bis(4-
5 hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-
phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-
methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-
bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane,
2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-
10 bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-
dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,
1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-
hydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-
hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-
15 hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxy-3,3'-
dimethyldiphenylether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-
dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-
dimethyldiphenyl sulfoxide, 4,4'-hydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy20 3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-
(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-
hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5,2,1,02,6]decane, and
4,4'-(1,3-adamantanediyl)diphenol, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.
[0025] Examples of the aliphatic diols include 2,2-bis-(4-hydroxycyclohexyl)-propane,
25 1,1,4-tetradecanediol, octaethylene glycol, 1,1,6-hexadecanediol, 4,4'-bis(2-
hydroxyethoxy)biphenyl, bis{(2-hydroxyethoxy)phenyl}methane, 1,1-bis{(2-
hydroxyethoxy)phenyl}ethane, 1,1-bis{(2-hydroxyethoxy)phenyl}-1-phenylethane,
2,2-bis{(2-hydroxyethoxy)phenyl}propane, 2,2-bis{(2-hydroxyethoxy)-3-
methylphenyl}propane, 1,1-bis{(2-hydroxyethoxy)phenyl}-3,3,5-trimethylcyclohexane,
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2,2-bis{4-(2-hydroxyethoxy)-3,3'-biphenyl}propane, 2,2-bis{(2-hydroxyethoxy)-3-
isopropylphenyl}propane, 2,2-bis{3-t-butyl-4-(2-hydroxyethoxy)phenyl}propane, 2,2-
bis{(2-hydroxyethoxy)phenyl}butane, 2,2-bis{(2-hydroxyethoxy)phenyl}-4-
methylpentane, 2,2-bis{(2-hydroxyethoxy)phenyl}octane, 1,1-bis{(2-
5 hydroxyethoxy)phenyl}decane, 2,2-bis{3-bromo-4-(2-hydroxyethoxy)phenyl}propane,
2,2-bis{3,5-dimethyl-4-(2-hydroxyethoxy)phenyl}propane, 2,2-bis{3-cyclohexyl-4-(2-
hydroxyethoxyphenylpropane, 1,1-bis{3-cyclohexyl-4-(2-
hydroxyethoxy)phenyl}cyclohexane, bis{(2-hydroxyethoxy)phenyl}diphenylmethane,
9,9-bis{(2-hydroxyethoxy)phenyl}fluorene, 9,9-bis{4-(2-hydroxyethoxy)-3-
10 methylphenyl}fluorene, 1,1-bis{(2-hydroxyethoxy)phenyl}cyclohexane, 1,1-bis{(2-
hydroxyethoxy)phenyl}cyclopentane, 4,4'-bis(2-hydroxyethoxy)diphenylether, 4,4'-
bis(2-hydroxyethoxy)-3,3'-dimethyldiphenylether, 1,3-bis[2-{(2-
hydroxyethoxy)phenyl}propyl]benzene, 1,4-bis[2-{(2-
hydroxyethoxy)phenyl}propyl]benzene, 1,4-bis{(2-
15 hydroxyethoxy)phenyl}cyclohexane, 1,3-bis{(2-hydroxyethoxy)phenyl}cyclohexane,
4,8-bis{(2-hydroxyethoxy)phenyl}tricyclo[5,2,1,02,6]decane, 1,3-bis{(2-
hydroxyethoxy)phenyl}-5,7-dimethyladamantane, 3,9-bis(2-hydroxy-1,1-
dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, 1,4:3,6-dianhydro-D-sorbitol
(isosorbide), 1,4:3,6-dianhydro-D-mannitol (isomannide), and 1,4:3,6-dianhydro-L20 iditol (isoidide).
[0026] Among these, preferred are aromatic bisphenols. Among these, preferred are
1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-
bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-
bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-
25 dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-
(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene,
and particularly preferred are 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-
hydroxyphenyl)cyclohexane, 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-
methylphenyl)fluorene. Among these, most suitable is 2,2-bis(4-
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hydroxyphenyl)propane having high strength and high durability. These may be used
alone or in combination.
[0027] The aromatic polycarbonate resin (A1) may be a branched polycarbonate resin
prepared by using the dihydroxy compound in combination with a branching agent.
5 [0028] Examples of polyfunctional aromatic compounds having three or more
functionalities and used in the branched polycarbonate resin include phloroglucin,
phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2,2,4,6-trimethyl2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-
hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-
10 hydroxy-5-methylbenzyl)-4-methylphenol, and 4-{4-[1,1-bis(4-
hydroxyphenyl)ethyl]benzene}-,-dimethylbenzylphenol, tetra(4-
hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-
dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenone
tetracarboxylic acid, and acid chlorides thereof. Among these, preferred are 1,1,1-
15 tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, and
particularly preferred is 1,1,1-tris(4-hydroxyphenyl)ethane.
[0029] These aromatic polycarbonate resins are produced by a standard known per se
reaction method of producing an aromatic polycarbonate resin, for example, a method
of reacting an aromatic dihydroxy component with a carbonate precursor substance
20 such as phosgene or a carbonic diester. The basic method of the production method
will be simply described.
[0030] In a reaction using phosgene as a carbonate precursor substance, usually the
reaction is performed in the presence of an acid bonding agent and a solvent. The acid
bonding agent to be used is an alkali metal hydroxide such as sodium hydroxide or
25 potassium hydroxide or an amine compound such as pyridine, for example. The
solvent to be used is a halogenated hydrocarbon such as methylene chloride or
chlorobenzene, for example. To promote the reaction, for example, a catalyst such as
a tertiary amine or a quaternary ammonium salt can also be used. At this time, the
reaction temperature is usually 0 to 40C, the reaction time is several minutes to 5
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hours.
[0031] A transesterification reaction using a carbonic diester as the carbonate precursor
substance is performed by a method of stirring the aromatic dihydroxy component and
a carbonic diester with heating under an inert gas atmosphere to distill away the
5 generated alcohol or phenols. Although the reaction temperature varies according to
the boiling point of the generated alcohol or phenols, the reaction temperature is
usually in the range of 120 to 300C. The reaction is completed while the generated
alcohol or phenols are distilled away under reduced pressure from the initial stage of
the reaction. To promote the reaction, a catalyst usually used in the transesterification
10 reaction can also be used.
[0032] Examples of the carbonic diester used in the transesterification reaction include
diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, dimethyl carbonate,
diethyl carbonate, and dibutyl carbonate. Among these, particularly preferred is
diphenyl carbonate.
15 [0033] In the present disclosure, a terminal terminator can be used in the
polymerization reaction. The terminal terminator is used to control the molecular
weight. The resulting aromatic polycarbonate resin has capped terminals, and thus
higher thermal stability than those not having capped terminals. Examples of the
terminal terminator include monofunctional phenols represented by the following
20 formulae (2) to (4):
[0034] [Chemical Formula 1]
(Formula 2)
[0035] [In formula (2), A is a hydrogen atom, an alkyl group having 1 to 9 carbon
atoms, an alkylphenyl group (the alkyl moiety has 1 to 9 carbon atoms), a phenyl group,
25 or a phenylalkyl group (the alkyl moiety has 1 to 9 carbon atoms), and r is an integer of
1 to 5 (preferably 1 to 3)].
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[0036] [Chemical Formula 2]
(Formula 3)
[0037] [Chemical Formula 3]
(Formula 4)
5 [0038] [In formulae (3) and (4), X is -R-O-, -R-CO-O-, or -R-O-CO-, where R
represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10
(preferably 1 to 5) carbon atoms and n represents an integer of 10 to 50.]
Specific examples of the monofunctional phenols represented by the general
formula (2) include phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p10 cumylphenol, 2-phenylphenol, 4-phenylphenol, and isooctylphenol.
[0039] The monofunctional phenols represented by the general formulae (3) and (4) are
phenols having a long-chain alkyl group or an aliphatic ester group as a substituent. If
the terminals of the aromatic polycarbonate resin are capped using these, these not only
function as a terminal terminator or a molecular weight modifier, but also improve the
15 melt fluidity of the resin to facilitate molding process thereof. In addition, these have
an effect of reducing the water absorption rate of the resin. For these reasons, these
phenols are preferably used.
[0040] The substituted phenols represented by the general formula (3) are those where
n is10 to 30, particularly preferably those where n is 10 to 26. Specific examples
20 thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol,
octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol.
[0041] The substituted phenols represented by the general formula (4) are suitably
compounds where X is -R-CO-O- and R is a single bond, those where n is 10 to 30,
particularly suitably those where n is 10 to 26. Specific examples thereof include
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decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate,
hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate, and
triacontyl hydroxybenzoate.
[0042] Among these monofunctional phenols, preferred are the monofunctional
5 phenols represented by the general formula (2), more preferred are alkyl- or
phenylalkyl substituted phenols, and particularly preferred is p-tert-butylphenol, pcumylphenol, or 2-phenylphenol.
[0043] These monofunctional phenol terminal terminators are desirably introduced into
at least 5 mol%, preferably at least 10 mol% of the total terminals of the resulting
10 aromatic polycarbonate resin. These terminal terminators may be used alone or in
combination in the form of a mixture.
[0044] The aromatic polycarbonate resin (A1) may be a polyester carbonate prepared
by copolymerizing an aromatic dicarboxylic acid, such as terephthalic acid, isophthalic
acid, naphthalene dicarboxylic acid, or a derivative thereof, in the range not impairing
15 the gist of the present disclosure.
[0045] The aromatic polycarbonate resin (A1) can have any viscosity average
molecular weight without limitation. To be noted, a viscosity average molecular
weight of less than 10000 reduces strength and the like and a viscosity average
molecular weight of more than 50000 reduces molding processing properties. Thus,
20 the viscosity average molecular weight is in the range of preferably 10000 to 50000,
more preferably 12000 to 30000, still more preferably 15000 to 28000. The viscosity
average molecular weight in the present disclosure is determined as follows: first, the
specific viscosity to be calculated from the following expression is determined using an
Ostwald viscometer from a solution of 0.7 g of the aromatic polycarbonate resin
25 dissolved in 100 mL of methylene chloride at 20C, and the determined specific
viscosity is substituted into another expression below to determine the viscosity
average molecular weight Mv:
[0046] Specific viscosity (SP) = (t - t0)/t0
wherein t0 is the dropping time (in seconds) of methylene chloride, and t is the
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dropping time (in seconds) of the sample solution,
SP/c = [] + 0.45  []
2c, where [] is the limiting viscosity,
[] = 1.23  10-4 Mv0.83, and
c = 0.7.
5 The total chlorine content in the aromatic polycarbonate resin (A1) is preferably
0 to 200 ppm, more preferably 0 to 150 ppm. A total chlorine content of more than
200 ppm in the aromatic polycarbonate resin is not preferable because of reduced hue
and thermal stability.
[0047] (Styrene-based resin (A2))
10 Examples of the main component for the styrene-based resin (A2) according to
the present embodiment include polystyrene resins (PSs), impact-resistant polystyrene
resins (HIPSs), copolymers (MSs) of alkyl (meth)acrylate monomers with aromatic
vinyl monomers, copolymers (ASs) of vinyl cyanide compounds with aromatic vinyl
compounds, copolymers (ABSs) of vinyl cyanide compounds containing a diene rubber
15 component with aromatic vinyl compounds, copolymers (AESs) of vinyl cyanide
compounds containing an ethylene--olefin rubber component with aromatic vinyl
compounds, copolymers (ASAs) of vinyl cyanide compounds containing an acrylic
rubber component with aromatic vinyl compounds, copolymers (MBSs) of alkyl
(meth)acrylate monomers containing a diene rubber component with aromatic vinyl
20 compounds, copolymers (MABSs) of alkyl (meth)acrylate monomers containing a
diene rubber component with vinyl cyanide compounds and aromatic vinyl compounds,
and copolymer (MASs) of alkyl (meth)acrylate monomers containing an acrylic rubber
component with aromatic vinyl compounds.
[0048] The main component indicates a component having the largest mass. The
25 content of the main component in the styrene-based resin (A2) is preferably 90% by
mass or more, more preferably 95% by mass or more.
[0049] The styrene-based resin (A2) may be a resin which is prepared in the presence
of a catalyst such as a metallocene catalyst during production and has high
stereoregularity, such as syndiotactic polystyrene. Alternatively, the styrene-based
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resin (A2) may be a polymer, a copolymer, and a block copolymer prepared by a
method such as anionic living polymerization or radical living polymerization and
having a narrow molecular weight distribution, and a polymer and a copolymer having
high stereoregularity.
5 [0050] The polystyrene resin (PS) is a polymer prepared by polymerizing at least one
aromatic vinyl compound by a polymerization method such as solution polymerization,
bulk polymerization, suspension polymerization, or bulk-suspension polymerization.
Examples of preferred aromatic vinyl compounds include styrene, alkylstyrenes such as
-methylstyrene, methylstyrene, ethylstyrene, isopropylstyrene, and tertiary10 butylstyrene, phenylstyrene, vinylstyrene, chlorostyrene, bromostyrene, fluorostyrene,
chloromethylstyrene, methoxystyrene, and ethoxystyrene. These can be used alone or
in combination. Among these, particularly preferred aromatic vinyl compounds are
styrene, p-methylstyrene, m-methylstyrene, p-tertiary-butylstyrene, p-chlorostyrene, mchlorostyrene, and p-fluorostyrene, and particularly preferred is styrene.
15 [0051] The polystyrene resin (PS) can have any molecular weight without limitation.
The mass average molecular weight measured against polystyrene standards by gel
permeation chromatography (GPC) at 135C using trichlorobenzene as a solvent is
preferably 100,000 or more, more preferably 150,000 or more. The molecular weight
distribution can have any broadness.
20 [0052] The impact-resistant polystyrene resin (HIPS) is a polymer prepared by
dispersing a rubber-like polymer made of, for example, butadiene rubber in the form of
particles in a matrix made of an aromatic vinyl polymer such as PS. HIPS can be
prepared, for example, by dissolving a rubber-like polymer in a mixed solution of an
aromatic vinyl monomer and an inert solvent, and performing bulk polymerization,
25 suspension polymerization, or solution polymerization with stirring. Alternatively,
HIPS may be a mixture of a polymer prepared by dissolving a rubber-like polymer in a
mixed solution of an aromatic vinyl monomer and an inert solvent with another
aromatic vinyl polymer separately prepared, for example.
[0053] Although the matrix moiety made of the aromatic vinyl polymer in HIPS is not
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particularly limited, the mass average molecular weight measured against polystyrene
standards by gel permeation chromatography (GPC) at 135C using trichlorobenzene as
a solvent is preferably 100,000 or more, more preferably 150,000 or more. Although
not particularly limited, generally the average particle diameter of the rubber-like
5 polymer is appropriately 0.4 to 6.0 m.
[0054] Styrene and derivatives thereof (such as o-methylstyrene, m-methylstyrene, pmethylstyrene, and 2,4-dimethylstyrene) can be used as the aromatic vinyl monomer,
and styrene is most suitable. These monomers can be used in combination.
[0055] Polybutadiene, polyisoprene, a styrene-butadiene copolymer, or the like can be
10 used as the rubber-like polymer. Examples of the polybutadiene include high cispolybutadienes having a large cis-bond content and low cis-polybutadienes having a
small cis-bond content.
[0056] Among these, preferably used is a polybutadiene containing 70% by mass or
more of a high cis-polybutadiene rubber in 100% by mass of the rubber-like polymer,
15 the high cis-polybutadiene rubber containing 90 mol% or more of a cis-1,4-bond.
[0057] Specifically, it is preferred that 70% by mass or more of the high cispolybutadiene rubber be contained in 100% by mass of the rubber-like polymer present
in the rubber-modified styrene resin in any case of a rubber-modified styrene resin
prepared using a high cis-polybutadiene rubber alone, a rubber-modified styrene resin
20 prepared using a mixture of a high cis-polybutadiene rubber and a low cispolybutadiene rubber, or a mixture of a rubber-modified styrene resin prepared using a
high cis-polybutadiene rubber and a rubber-modified styrene resin prepared using a low
cis-polybutadiene rubber. Here, the high cis-polybutadiene rubber indicates a
polybutadiene rubber containing the cis-1,4-bond in the proportion of 90 mol% or more,
25 for example. The low cis-polybutadiene rubber indicates a polybutadiene rubber
containing the 1,4-cis-bond in the proportion of 10 to 40 mol%, for example.
[0058] In the copolymer (MS) of an alkyl (meth)acrylate monomer and an aromatic
vinyl monomer, the alkyl (meth)acrylate monomer is at least one monomer selected
from methyl (meth)acrylate and phenyl (meth)acrylate, for example. In particular, use
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of methyl (meth)acrylate is preferred. The expression "(meth)acrylate" encompasses
both methacrylate and acrylate.
[0059] As the aromatic vinyl monomer, for example, styrene, -methylstyrene, omethylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert5 butylstyrene, vinylnaphthalene, methoxystyrene can be used, and particularly styrene is
preferred. These can be used alone or in combination.
[0060] Although the compositional ratio of the mass average molecular weight of the
MS and methyl (meth)acrylate/styrene are not particularly limited, the mass average
molecular weight is preferably 80000 to 300000, more preferably 100000 to 200000,
10 and the compositional ratio of methyl (meth)acrylate/styrene is preferably 80/20 to
40/60, more preferably 70/30 to 50/50.
[0061] In the copolymer (AS) of a vinyl cyanide compound and an aromatic vinyl
compound, particularly acrylonitrile can be preferably used as the vinyl cyanide
compound. Styrene and -methylstyrene can be preferably used as the aromatic vinyl
15 compound.
[0062] For the proportions of the components in the AS where the total is 100% by
mass, the proportion of the vinyl cyanide compound is preferably 5 to 50% by mass,
more preferably 15 to 35% by mass, and the proportion of the aromatic vinyl
compound is preferably 95 to 50% by mass, more preferably 85 to 65% by mass.
20 [0063] Furthermore, other copolymerizable vinyl compounds described above may be
mixed with these vinyl compounds. In this case, the proportion of the other vinyl
compounds contained is preferably 15% by mass or less in the AS.
[0064] Although the AS may be produced by any method of bulk polymerization,
suspension polymerization, emulsion polymerization, and the like, the AS is preferably
25 produced by bulk polymerization. The copolymerization method may be any one of
one-stage copolymerization and multi-stage copolymerization.
[0065] The AS has a reduced viscosity of preferably 0.2 to 1.0 dL/g (20 to 100 mL/g),
more preferably 0.3 to 0.5 dL/g (30 to 50 mL/g). A reduced viscosity of less than 0.2
dL/g (20 mL/g) reduces the impact while a reduced viscosity of more than 1.0 dL/g
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(100 mL/g) reduces processability.
[0066] The reduced viscosity is measured as follows: A solution prepared by precisely
weighing 0.25 g of a copolymer (AS) prepared by copolymerizing a vinyl cyanide
compound and an aromatic vinyl compound, and dissolving the AS in 50 mL of
5 dimethylformamide over 2 hours is measured under an environment at 30C using an
Ubbelohde viscometer. In the viscometer used, the flow time of the solvent is 20 to
100 seconds. The reduced viscosity is determined from the flow time of the solvent in
seconds (t0) and the flow time of the solution in seconds (t) using the following
expression:
10 [0067] reduced viscosity (sp/C) = {(t/t0) - 1}/0.5
The copolymer (ABS) of a vinyl cyanide compound containing a diene rubber
component with an aromatic vinyl compound, the copolymer (AES) of a vinyl cyanide
compound containing an ethylene--olefin rubber component with an aromatic vinyl
compound, the copolymer (ASA) of a vinyl cyanide compound containing an acrylic
15 rubber component with an aromatic vinyl compound, the copolymer (MBS) of an alkyl
(meth)acrylate monomer containing a diene rubber component with an aromatic vinyl
compound, the copolymer (MABS) of an alkyl (meth)acrylate monomer containing a
diene rubber component with a vinyl cyanide compound and an aromatic vinyl
compound, and the copolymer (MAS) of an alkyl (meth)acrylate monomer containing
20 an acrylic rubber component with an aromatic vinyl compound are thermoplastic
copolymers.
[0068] In the present embodiment, the proportions of a variety of rubber components
contained in ABS, AES, ASA, MBS, MABS, and MAS each are preferably 5 to 80%
by mass, more preferably 8 to 50% by mass, particularly preferably 10 to 30% by mass.
25 [0069] Acrylonitrile can be particularly preferably used as the vinyl cyanide compound
grafted to the rubber component. Styrene and -methylstyrene can be particularly
preferably used as the aromatic vinyl compound grafted to the rubber component.
[0070] Furthermore, methyl (meth)acrylate and ethyl (meth)acrylate can be particularly
preferably used as the alkyl (meth)acrylate monomer.
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[0071] The proportion of the component grafted to the rubber component is preferably
20 to 95% by mass, more preferably 50 to 90% by mass relative to 100% by mass of
the styrene-based resin (A2). Furthermore, maleic anhydride, N-substituted
maleimide, or the like can be mixed and used as part of the component grafted to the
5 rubber component, and the proportion of the content thereof is preferably 15% by mass
or less in the styrene-based resin (A2).
[0072] The rubber component is present in the form of particles in ABS, AES, ASA,
MBS, MABS, and MAS. The rubber component has a particle diameter of preferably
0.1 to 5.0 m, more preferably 0.15 to 1.5 m, particularly preferably 0.2 to 0.8 m.
10 Here, the distribution of the particle diameter of the rubber component may be a
monodistribution, or may have two or more peaks. In the morphology of the particle
diameter of the rubber component, rubber particles may form a single phase, or rubber
particles and an occlude phase contained therearound may form a salami-like structure.
[0073] ABS, AES, ASA, MBS, MABS, and MAS may contain a free polymer
15 component (such as an aromatic vinyl compound) generated during polymerization.
[0074] The reduced viscosity (the reduced viscosity previously determined at 30C by
the method described above) of ABS, AES, ASA, MBS, MABS, and MAS is
preferably 0.2 to 1.0 dL/g (20 to 100 mL/g), more preferably 0.3 to 0.7 dL/g (30 to 70
mL/g).
20 [0075] The proportion (grafting rate) of the aromatic vinyl compound or the like
grafted to the rubber component is preferably 20 to 200% by mass, more preferably 20
to 70% by mass relative to the rubber component.
[0076] ABS, AES, ASA, MBS, MABS, and MAS may be produced by any one method
of bulk polymerization, suspension polymerization, and emulsion polymerization. In
25 particular, preferred ABS is those produced by bulk polymerization. Examples of
representative bulk polymerization methods include continuous bulk polymerization
(the so-called Toray method) described in Kagakukougyou (1984), Vol. 48, No. 6, p.
415, and continuous bulk polymerization (the so-called Mitsui Toatsu method)
described in Kagakukougyou (1989), Vol. 53, No. 6, p. 423.
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[0077] In the present embodiment, ABS, AES, ASA, MBS, MABS, and MAS all can
be suitably used as the styrene-based resin (A2). In the copolymerization method,
copolymerization may be performed at one stage or at several stages. Moreover,
resins prepared by blending the ABS, AES, ASA, MBS, MABS, and MAS prepared by
5 such a method with a vinyl compound polymer prepared by separately copolymerizing
an aromatic vinyl compound and a vinyl cyanide component and the like can also be
preferably used as the styrene-based resin (A2).
[0078] A small content of an alkali (earth) metal in AS, ABS, AES, ASA, MBS,
MABS, and MAS is preferred from the viewpoint of favorable thermal stability and
10 hydrolysis resistance. The content of the alkali (earth) metal in the styrene-based
resin (A2) is preferably less than 100 ppm, more preferably less than 80 ppm, more
preferably less than 50 ppm, particularly preferably less than 10 ppm. Thus, bulk
polymerization is suitably used to reduce the content of the alkali (earth) metal.
[0079] In association with such favorable thermal stability and hydrolysis resistance, if
15 an emulsifier is used in AS and ABS, the emulsifier is suitably sulfonates, more
suitably alkyl sulfonates. If a solidifying agent is used, the solidifying agent is
suitably sulfuric acid or an alkaline earth metal salt of sulfuric acid.
[0080] Examples of the rubber component contained in ABS, AES, ASA, MBS,
MABS, and MAS include polybutadiene, polyisoprene, diene copolymers, copolymers
20 of ethylene and -olefins, copolymers of ethylene and unsaturated carboxylic acid
esters, copolymers of ethylene and aliphatic vinyls (such as ethylene-vinyl acetate
copolymer), non-conjugated diene terpolymers of ethylene and propylene, acrylic
rubbers, and silicone rubbers.
[0081] Examples of the diene copolymers include random copolymers of styrene25 butadiene and block copolymers thereof, acrylonitrile-butadiene copolymers, and
copolymers of alkyl (meth)acrylate esters and butadiene.
[0082] Examples of the copolymers of ethylene and -olefins include ethylenepropylene random copolymers and block copolymers, and ethylene-butene random
copolymers and block copolymers.
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[0083] Examples of the copolymers of ethylene and unsaturated carboxylic acid esters
include ethylene-methacrylate copolymers and ethylene-butyl acrylate copolymers.
[0084] Examples of the non-conjugated diene terpolymers of ethylene and propylene
include ethylene-propylene-hexadiene copolymers.
5 [0085] Examples of the acrylic rubbers include polybutyl acrylate, poly(2-ethylhexyl
acrylate), and copolymers of butyl acrylate and 2-ethylhexyl acrylate.
[0086] Examples of the silicone rubbers include polyorganosiloxane rubber, IPN-type
rubbers (i.e., rubbers having a structure composed of two rubber components mutually
entangled not to separate from each other) made of a polyorganosiloxane rubber
10 component and a polyalkyl (meth)acrylate rubber component, and IPN-type rubbers
made of a polyorganosiloxane rubber component and a polyisobutylene rubber
component.
[0087] The rubber component is preferably selected from the group consisting of
polydiene rubbers (such as polybutadiene), acrylic rubbers, and ethylene-propylene
15 rubbers. For the glass transition temperature of the rubber component, for example,
that of acrylic rubber is typically -10C to -20C, that of the ethylene-propylene rubber
is typically -50C to -58C, and that of the butadiene rubber is typically about -100C.
[0088] The content of the rubber component in the ABS, AES, ASA, MBS, MABS,
and MAS used in the present embodiment is preferably 4% by mass to 25% by mass.
20 The content of the rubber component can be adjusted by controlling the amount of the
rubber component during copolymerization, for example. Alternatively, the content
of the rubber component can also be adjusted by mixing an aromatic vinyl copolymer
containing the rubber component with an aromatic vinyl polymer or copolymer not
containing the rubber component, for example.
25 [0089] (Aromatic polyester resin (A3))
The aromatic polyester resin (A3) is a polymer or copolymer prepared by a
condensation reaction in which an aromatic dicarboxylic acid or a reactive derivative
thereof and a diol or an ester derivative thereof are used as main components.
[0090] Examples of the aromatic dicarboxylic acid mentioned here include aromatic
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dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-
naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-
biphenyldicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 4,4'-
biphenylmethanedicarboxylic acid, 4,4'-biphenylsulfonedicarboxylic acid, 4,4'-
5 biphenylisopropylidenedicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic
acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4'-pterphenylenedicarboxylic acid, and 2,5-pyridinedicarboxylic acid. Examples thereof
also include diphenylmethanedicarboxylic acid, diphenyletherdicarboxylic acid, and -
hydroxyethoxybenzoic acid. In particular, terephthalic acid and 2,6-
10 naphthalenedicarboxylic acid can be preferably used. These aromatic dicarboxylic
acids may be used in combination in the form of a mixture. To be noted, a small
amount of one or more of an aliphatic dicarboxylic acid such as adipic acid, azelaic
acid, sebacic acid, or dodecane diacid, an alicyclic dicarboxylic acid such as
cyclohexanedicarboxylic acid, or the like can be mixed and used with the dicarboxylic
15 acid.
[0091] Examples of the diol include aliphatic diols such as ethylene glycol, propylene
glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol,
hexamethylene glycol, decamethylene glycol, 2-methyl-1,3-propanediol, diethylene
glycol, and triethylene glycol.
20 [0092] Examples thereof also include alicyclic diols such as 1,4-
cyclohexanedimethanol. Examples thereof include diols having an aromatic ring,
such as 2,2-bis(-hydroxyethoxyphenyl)propane, and mixtures thereof. Furthermore,
a small amount of a long-chain diol having a molecular weight of 400 to 6000, that is,
one or more of polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene
25 glycol, and the like may be copolymerized.
[0093] The aromatic polyester resin (A3) can be branched by introducing a small
amount of a branching agent. Any branching agent can be used, and examples thereof
include trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane, and
pentaerythritol.
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[0094] Examples of the aromatic polyester resin (A3) include polyethylene
terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate (PBT),
polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate
(PBN), and polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate. Examples
5 thereof also include copolymerized polyester resins such as polyethylene
isophthalate/terephthalate and polybutylene terephthalate/isophthalate. Among these,
polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and
polybutylene naphthalate having well-balanced mechanical properties and mixtures
thereof can be preferably used.
10 [0095] The terminal group structure of the aromatic polyester resin (A3) is not
particularly limited. The proportions of the hydroxyl group and the carboxyl group in
the terminal group may be substantially equal, or the proportion of one of them may be
higher. A compound reactive with such a terminal group may be reacted to cap the
terminal group.
15 [0096] Although an alkylene glycol ester of an aromatic dicarboxylic acid and/or a low
polymer thereof can be produced by any production method, the alkylene glycol ester
of an aromatic dicarboxylic acid and/or a low polymer thereof is usually produced by
reacting an aromatic dicarboxylic acid or an ester formable derivative thereof with an
alkylene glycol or an ester formable derivative thereof under heating. For example, an
20 ethylene glycol ester of terephthalic acid and/or a low polymer thereof used as a raw
material for polyethylene terephthalate is produced by a direct esterification reaction of
terephthalic acid with ethylene glycol, by a transesterification reaction of a lower alkyl
ester of terephthalic acid with ethylene glycol, or by an addition reaction of ethylene
oxide to terephthalic acid.
25 [0097] The alkylene glycol ester of an aromatic dicarboxylic acid and/or a low polymer
thereof may contain another dicarboxylic acid ester copolymerizable therewith as an
additional component in the range not substantially impairing the effect of the method
according to the present disclosure. Specifically, another dicarboxylic acid ester may
be contained in the range of 10 mol% or less, preferably 5 mol% or less relative to the
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total molar amount of the acid components.
[0098] The additional copolymerizable component is selected from the group
consisting of esters of acid components and glycol components and anhydrides thereof.
Examples of the acid components include one or more of aliphatic and alicyclic
5 dicarboxylic acids such as adipic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic
acid, and hydroxycarboxylic acids such as -hydroxyethoxybenzoic acid and poxybenzoic acid.
[0099] Examples of the glycol components include alkylene glycols having two or
more carbon atoms, aliphatic, alicyclic, and aromatic diol compounds such as 1,4-
10 cyclohexanedimethanol, neopentyl glycol, bisphenol A, and bisphenol S, and
polyoxyalkylene glycol. These component esters may be used alone or in
combination. The copolymerization amount thereof is preferably within the range
specified above.
[0100] If terephthalic acid and/or dimethyl terephthalate is used as a starting raw
15 material, a recovered dimethyl terephthalate prepared by depolymerization of
polyalkylene terephthalate or a recovered terephthalic acid prepared by hydrolysis
thereof can be used in an amount of 70% by mass or more relative to the mass of the
total acid components which form polyester. In this case, the target polyalkylene
terephthalate is preferably polyethylene terephthalate. In particular, use of recovered
20 PET bottles, recovered fiber products, recovered polyester film products, and further
polymer wastes generated in the production process of the products as raw material
sources for production of polyester is preferred from the viewpoint of effective
utilization of resources.
[0101] Here, the method of depolymerizing the recovered polyalkylene terephthalate to
25 yield dimethyl terephthalate is not particularly limited, and any conventionally known
method can be used. For example, the recovered polyalkylene terephthalate is
depolymerizing in the presence of ethylene glycol, and the depolymerized product is
fed to a transesterification reaction with a lower alcohol, such as methanol. This
reaction mixture is refined to recover a lower alkyl ester of terephthalic acid, which is
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fed to a transesterification reaction with alkylene glycol. Th resulting phthalic
acid/alkylene glycol ester is polycondensed. Thereby, a polyester resin can be yielded.
[0102] The method of recovering terephthalic acid from the recovered dimethyl
terephthalate is not particularly limited, and any conventional method can be used.
5 For example, dimethyl terephthalate is recovered from the reaction mixture obtained by
a transesterification reaction by recrystallization and/or distillation, and is hydrolyzed
by heating with water at a high temperature under pressure to recover terephthalic acid.
In impurities contained in the terephthalic acid yielded by the method, the total content
of 4-carboxybenzaldehyde, paratoluic acid, benzoic acid, and hydroxydimethyl
10 terephthalate is preferably 1 ppm or less. The content of monomethyl terephthalate is
preferably in the range of 1 to 5000 ppm.
[0103] The terephthalic acid recovered by the above method is subjected to a direct
esterification reaction with alkylene glycol, and the resulting ester is polycondensed.
Thereby, a polyester resin can be produced.
15 [0104] The production reaction condition for the aromatic polyester resin (A3) is also
not particularly limited. Usually, the polycondensation reaction is preferably
performed for 15 to 300 minutes under a temperature of 230 to 320C or under normal
pressure or reduced pressure (0.1 Pa to 0.1 MPa) or under a combined condition thereof.
[0105] In the aromatic polyester resin (A3), an optional reaction stabilizer, such as
20 trimethyl phosphate, may be added to the reaction system at any stage of the production
of polyester. Furthermore, one or more of an antioxidant, an ultraviolet absorbing
agent, a flame retardant, fluorescent brightener, a matting agent, a color adjuster, an
antifoaming agent, and other additives may be compounded with the reaction system as
needed. In particular, the polyester resin preferably contains an antioxidant containing
25 at least one hindered phenol compound. The content is preferably 1% by mass or less
relative to the mass of the polyester resin. If the content exceeds 1% by mass, it may
cause a problem that the quality of the resulting product is reduced by thermal
degradation of the antioxidant itself.
[0106] Examples of the hindered phenol compound include pentaerythritol-tetrakis[3-
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(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 3,9-bis{2-[3-(3-tert-butyl-4-
hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-
tetraoxaspiro[5,5]undecane. Combinations of these hindered phenol-based
antioxidants with thioether secondary antioxidants are preferably used.
5 [0107] Although the method of adding the hindered phenol-based antioxidant to the
polyester resin is not particularly limited, the hindered phenol-based antioxidant is
preferably added after the end of the transesterification reaction or the esterification
reaction or at any stage before the polymerization reaction is completed.
[0108] Although not limited, the aromatic polyester resin (A3) preferably has an
10 intrinsic viscosity in the range of 0.30 to 1.5. An intrinsic viscosity within this range
facilitates melt molding and results in high strength of the molded article prepared
therefrom. A more preferred range of the intrinsic viscosity is 0.40 to 1.2, particularly
preferably 0.50 to 1.0. The intrinsic viscosity of the aromatic polyester resin is
measured by dissolving an aromatic polyester resin in orthochlorophenol and
15 measuring the solution at a temperature of 35C. To be noted, usually the polyester
resin yielded by solid phase polycondensation is often used in bottles and the like, and
often has an intrinsic viscosity of 0.70 to 0.90.
[0109] Preferably, the content of a cyclic trimer of the ester of the aromatic
dicarboxylic acid and the alkylene glycol above is 0.5% by mass or less and the content
20 of acetaldehyde is 5 ppm or less.
[0110] The cyclic trimer includes alkylene terephthalates (such as ethylene
terephthalate, trimethylene terephthalate, tetramethylene terephthalate, and
hexamethylene terephthalate) and alkylene naphthalates (such as ethylene naphthalate,
trimethylene naphthalate, tetramethylene naphthalate, and hexamethylene naphthalate).
25 [0111] (Polyphenylene ether resin (A4))
The polyphenylene ether resin (A4) may be a mixed resin of a polyphenylene
ether resin premixed with a polystyrene resin, or may be composed of only a
polyphenylene ether resin.
[0112] Examples of the polyphenylene ether resin include a homopolymer having a
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repeating unit structure represented by the following formula (5) and a copolymer
having a repeating unit structure represented by the following formula (5):
[0113] [Chemical Formula 4]
(Formula 5)
[0114] In the formula (5), R1
, R2
, R3
, and R4 5 each independently are a monovalent
group selected from the group consisting of a hydrogen atom, halogen atoms, primary
alkyl groups having 1 to 7 carbon atoms, secondary alkyl groups having 1 to 7 carbon
atoms, a phenyl group, haloalkyl groups, aminoalkyl groups, hydrocarbonoxy groups,
and halohydrocarbonoxy groups having at least two carbon atoms which separate a
10 halogen atom from an oxygen atom.
[0115] From the viewpoint of fluidity, toughness, and resistance against chemicals
during processing, the reduced viscosity of the polyphenylene ether resin, which is
measured using a 0.5 g/dL chloroform solution under a condition at 30C with an
Ubbelohde viscosity tube, is preferably 0.15 to 2.0 dL/g, more preferably 0.20 to 1.0
15 dL/g, still more preferably 0.30 to 0.70 dL/g.
[0116] Examples of the polyphenylene ether resin include, but should not be limited to,
homopolymers such as poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), and poly(2,6-
dichloro-1,4-phenylene ether); and copolymers of copolymers of 2,6-dimethylphenol
20 and other phenols (such as 2,3,6-trimethylphenol and 2-methyl-6-butylphenol).
Among these, preferred are poly(2,6-dimethyl-1,4-phenylene ether) and a copolymer of
2,6-dimethylphenol and 2,3,6-trimethylphenol, and more preferred is poly(2,6-
dimethyl-1,4-phenylene ether) from the viewpoint of the balance between the
toughness and the rigidity of the resulting resin composition and availability of raw
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materials.
[0117] The polyphenylene ether resin can be produced by a known method.
Examples of the method of producing the polyphenylene ether resin include, but should
not be limited to, the method according to Hay described in the specification of U.S.
5 Patent No. 3306874 in which 2,6-xylenol is subjected to oxidation polymerization in
the presence of a complex of a cuprous salt and amine as a catalyst; and methods
described in the specifications of U.S. Patent Nos. 3306875, 3257357, and 3257358;
and those described in Japanese Patent Publication No. 52-17880, and Japanese Patent
Application Laying-Open Nos. 50-51197 and 63-152628.
10 [0118] Examples of the polystyrene resin preliminarily contained in the polyphenylene
ether resin (A4) include atactic polystyrenes, rubber-reinforced polystyrenes (high
impact polystyrenes, HIPSs), styrene-acrylonitrile copolymers (ASs) having 50% by
mass or more of styrene content, and ABS resins prepared by reinforcing the styreneacrylonitrile copolymer with rubber. Atactic polystyrenes and/or high impact
15 polystyrenes are preferred.
[0119] These polystyrene resins may be used alone or in combination.
[0120] Preferably, the polyphenylene ether resin (A4) to be used is a polyphenylene
ether resin (A4) comprising a polyphenylene ether resin and a polystyrene resin and
having a mass proportion of the polyphenylene ether resin to the polystyrene resin of
20 97/3 to 5/95. The mass proportion of the polyphenylene ether resin to the polystyrene
resin is more preferably 90/10 to 10/90, still more preferably 80/20 to 10/90 from the
viewpoint of higher fluidity.
[0121] (Methacrylic resin (A5))
The methacrylic resin (A5) used in the present disclosure is substantially a
25 copolymer with alkyl methacrylate or alkyl acrylate, and another vinyl monomer not
containing an aromatic vinyl monomer can be copolymerized in the range not
impairing the object of the present disclosure.
[0122] The methacrylic resin is a polymer prepared by polymerizing a monomer
comprising 30 to 100% by mass of alkyl methacrylate, 0 to 70% by mass of an acrylate
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ester, and 0 to 49% by mass of another vinyl monomer which is copolymerizable with
these and does not contain an aromatic vinyl monomer. If the methacrylic resin is a
copolymer of an alkyl methacrylate and an alkyl acrylate, for the mass proportion of the
alkyl methacrylate to the alkyl acrylate, the mass proportion of the alkyl methacrylate is
5 preferably 40 to 90% by mass, more preferably 10 to 60% by mass, and that of the
alkyl methacrylate is preferably 50 to 85% by mass, more preferably 50 to 15% by
mass relative to 100% by mass of the total of the alkyl methacrylate and the alkyl
acrylate.
[0123] The alkyl methacrylate may have an alkyl group having about 1 to 8 carbon
10 atoms. Examples thereof include methyl methacrylate, ethyl methacrylate, n-butyl
methacrylate, t-butyl methacrylate, and 2-ethylhexyl methacrylate. Among these,
methyl methacrylate is preferred. These alkyl methacrylates may be used in
combination as needed.
[0124] The alkyl acrylate may have an alkyl group having about 1 to 8 carbon atoms.
15 Examples thereof include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl
acrylate, and 2-ethylhexyl acrylate. Among these, methyl acrylate and n-butyl
acrylate are preferred. These alkyl acrylates may be used in combination as needed.
In this case, it is preferred that n-butyl acrylate be used as a main component and one or
more alkyl acrylates other than n-butyl acrylate be used, and it is more preferred that n20 butyl acrylate and methyl acrylate be used and n-butyl acrylate be the main component.
Here, the expression "n-butyl acrylate is the main component" indicates that the mass
proportion of n-butyl acrylate is more than 50% by mass relative to 100% by mass of
the total of two or more alkyl acrylates.
[0125] Another monomer not including alkyl methacrylate, alkyl acrylate, and the
25 aromatic vinyl monomer may be a monofunctional monomer, i.e., a compound having
one polymerizable carbon-carbon double bond in the molecule, or may be a
polyfunctional monomer, i.e., a compound having at least two polymerizable carboncarbon double bonds in the molecule.
[0126] Examples of the monofunctional monomer include cyanated alkenyls such as
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acrylonitriles and methacrylonitriles, acrylic acid, methacrylic acid, maleic anhydride,
and N-substituted maleimide.
[0127] Examples of the polyfunctional monomer include polyunsaturated carboxylic
acid esters of polyhydric alcohols, such as ethylene glycol dimethacrylate, butanediol
5 dimethacrylate, and trimethylolpropane triacrylate; alkenyl esters of unsaturated
carboxylic acids, such as allyl acrylates, allyl methacrylates, and allyl cinnamates; and
polyalkenyl esters of polybasic acid, such as diallyl phthalates, diallyl maleates, triallyl
cyanurate, and triallyl isocyanurate. These monomers other than alkyl methacrylate,
alkyl acrylate, and aromatic vinyls may be used in combination as needed.
10 [0128] One or two or more of the methacrylic resins may be used. In the two or more
methacrylic resins, the methacrylic resins may be composed of different monomers, or
may be composed of the same monomer in different mass proportions of the monomer.
[0129] The method of polymerizing the methacrylic resin is not particularly limited,
and the methacrylic resin can be polymerized by a standard method such as bulk
15 polymerization, suspension polymerization, or emulsion polymerization.
[0130] The methacrylic resin to be used can also be a so-called high impact
methacrylic resin to which rubber particles are preliminarily compounded. Generally,
these high impact methacrylic resins contain 5 to 40% by mass of a rubber component.
[0131] Although not particularly limited, the compounded rubber component suitably
20 has a refractive index close to that of the methacrylic resin. Examples thereof include
diene graft copolymers containing butadiene as the main component, rubber-like
polymers having a core-shell type graft structure and containing an acrylate ester/a
methacrylate ester as the main component, and rubber-like polymers grafted to
enlarged particles.
25 [0132] The methacrylic resin (B) has an MFR value (230C, load: 3.8 kg) of preferably
5 to 25 g/10 min, more preferably 10 to 20 g/10 min.
[0133] (Polyarylene sulfide resin (A6))
The polyarylene sulfide resin (A6) has a resin structure composed of a repeating
unit having a structure in which arylene is bonded to a sulfur atom. The polyarylene
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sulfide resin includes the repeating unit represented by the following formula (6):
[0134] [Chemical Formula 5]
(Formula 6)
[0135] In the above formula (6), Ar is a substituted or non-substituted arylene.
5 Examples of the arylene include, but should not be limited to, phenylene, naphthylene,
biphenylene, and terphenylene.
[0136] If Ar has a substituent, examples of the substituent include, but should not be
limited to, alkyl groups such as a methyl group, an ethyl group, a propyl group, an
isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl
10 group; alkoxy groups such as a methoxy group, an ethoxy group, a propyloxy group, an
isopropyloxy group, a butoxy group, an isobutyloxy group, a sec-butyloxy group, and a
tert-butyloxy group; a nitro group; an amino group; and a cyano group.
[0137] Ar may have a single substituent, or may have two or more substituents. If Ar
has two or more substituents, the substituents may be the same or different.
15 [0138] Among these polyarylene sulfide resins described above, preferred is a
polyphenylene sulfide resin (PPS resin) where Ar is a substituted or non-substituted
phenylene. The PPS resin includes at least one of the repeating units represented by
the following formulae (7) and (8):
[0139] [Chemical Formula 6]
20 (Formula 7)
(Formula 8)
[0140] In the above formulae (7) and (8), examples of R each independently include
alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group,
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a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group; alkoxy
groups such as a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy
group, a butoxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy
group; a nitro group; an amino group; and a cyano group.
5 [0141] n is an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1, still more
preferably 0. If n is 0, mechanical strength can be enhanced.
[0142] Among those described above, the PPS resin preferably includes the repeating
unit represented by the formula (7) from the viewpoint of heat resistance, crystallinity,
and the like.
10 [0143] The PPS resin may include a trifunctional structural unit represented by the
following formula (9):
[0144] [Chemical Formula 7]
(Formula 9)
[0145] In the above formula (9), R is the same as that in the above formulae (7) and (8).
15 m is an integer of 0 to 3, preferably 0 to 2, more preferably 0 or 1, still more preferably
0.
[0146] If the PPS resin includes the trifunctional structural unit represented by the
above formula (9), the content of the PPS resin is preferably 0.001 to 3 mol%, more
preferably 0.01 to 1 mol% relative to the total molar amount of all the structural units.
20 [0147] Furthermore, the PPS resin may include structural units represented by the
following formulae (10) to (14):
[0148] [Chemical Formula 8]
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(Formula 10)
(Formula 11)
(Formula 12)
[0149] [Chemical Formula 9]
5 (Formula 13)
[0150] [Chemical Formula 10]
(Formula 14)
[0151] In the above formulae (10) to (14), R and n are the same as those in the above
formula (7) and the like. p is an integer of 0 to 6, preferably 0 to 3, more preferably 0
10 or 1, still more preferably 0.
[0152] If the PPS resin includes the structural units represented by the above formulae
(10) to (14), the content of the PPS resin is preferably 10 mol% or less, more preferably
5 mol% or less, still more preferably 3 mol% or less relative to the total structural units
from the viewpoint of mechanical strength and the like. At this time, if the PPS resin
15 includes two or more of the structural units represented by the above formulae (10) to
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(14), it is preferred that the total fall within the range of the content specified above.
[0153] These polyarylene sulfide resins described above may be used alone or in
combination.
[0154] The polyarylene sulfide resin may be linear or may be branched. In an
5 embodiment, a branched polyarylene sulfide resin can be obtained by heating a linear
PAS resin in the presence of oxygen.
[0155] The polyarylene sulfide resin has a weight average molecular weight of
preferably 25000 to 80000, more preferably 25000 to 50000. A weight average
molecular weight of 25000 or more is preferred because material strength can be
10 retained. On the other hand, a weight average molecular weight of 80000 or less is
preferred from the viewpoint of molding properties.
[0156] In this specification, the value of the "weight average molecular weight" to be
used is a value measured by gel permeation chromatography. At this time, the
conditions for measurement by gel permeation chromatography are specified as follows.
15 Namely, using a high performance GPC HLC-8220 (manufactured by Tosoh
Corporation) and columns (TSK-GELGMHX L  2), 200 mL of a solution prepared by
dissolving 5 mg of a sample in 10 g of tetrahydrofuran (THF) is injected into the
apparatus to measure the weight average molecular weight at a flow rate of 1 mL/min
(THF) and a thermostat temperature of 40C with a reflective index (RI) detector.
20 [0157] The melt viscosity of the polyarylene sulfide resin measured at 300C is
preferably 2 to 1000 Pas, more preferably 10 to 500 Pas, still more preferably 60 to
200 Pas. A melt viscosity of 2 Pas or more is preferred because material strength can
be retained. On the other hand, a melt viscosity of 1000 Pas or less is preferred from
the viewpoint of molding properties.
25 [0158] The non-Newtonian index of the polyarylene sulfide resin is preferably 0.90 to
2.00, more preferably 0.90 to 1.50, still more preferably 0.95 to 1.20. A nonNewtonian index value of 0.90 or more is preferred because material strength can be
retained. On the other hand, a non-Newtonian index of 2.00 or less is preferred from
the viewpoint of molding properties.
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[0159] The polyarylene sulfide resin can be produced by a known method. Examples
thereof include (1) a method of polymerizing a dihalogenoaromatic compound in the
presence of sulfur and sodium carbonate with a polyhalogenoaromatic compound or
other copolymerization components added as needed, (2) a method of polymerizing a
5 dihalogenoaromatic compound in a polar solvent in the presence of a sulfidating agent
with a polyhalogenoaromatic compound or other copolymerization components added
as needed, and (3) a method of self-condensing p-chlorothiophenol with other
copolymerization components added as needed.
[0160] Among these methods, the method (2) is versatile and preferred. In the
10 reaction, an alkali metal salt of carboxylic acid or sulfonic acid may be added or an
alkali hydroxide may be added to control the degree of polymerization.
[0161] In the method (2) above, particularly preferred is
(a) a method of introducing a hydrous sulfidating agent to a mixture of a heated organic
polar solvent and a dihalogenoaromatic compound at a rate such that water can be
15 removed from the reaction mixture, reacting the dihalogenoaromatic compound and the
sulfidating agent in the organic polar solvent with a polyhalogenoaromatic compound
added as needed, and controlling the water content in the reaction system to the range
of 0.02 to 0.5 mol relative to 1 mol of the organic polar solvent to produce a PAS resin
(see Japanese Patent Application Laying-Open No. 07-228699), or
20 (b) a method of reacting a dihalogenoaromatic compound with an alkali metal
hydrosulfide and an alkali metal salt of an organic acid in the presence of a solid alkali
metal sulfide and an aprotic polar organic solvent with a polyhalogenoaromatic
compound and other copolymerization components added as needed, while the alkali
metal salt of an organic acid is being controlled to 0.01 to 0.9 mol relative to 1 mol of a
25 sulfur source and the water content in the reaction system is being controlled in the
range of 0.02 mol relative to 1 mol of the aprotic polar organic solvent (see WO
2010/058713).
[0162] Examples of the dihalogenoaromatic compound include, but should not be
limited to, p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-
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dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-
dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-
dihalonitrobenzene, 2,4-dihaloanisole, p,p'-dihalodiphenylether, 4,4'-
dihalobenzophenone, 4,4'-dihalodiphenylsulfone, 4,4'-dihalodiphenyl sulfoxide, 4,4'-
5 dihalodiphenyl sulfide, and those compounds whose aromatic rings have an alkyl group
having 1 to 18 carbon atoms. These dihalogenoaromatic compounds may be used
alone or in combination.
[0163] Examples of the polyhalogenoaromatic compound include, but should not be
limited to, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5-
10 tetrahalobenzene, 1,2,4,5-tetrahalobenzene, and 1,4,6-trihhalonaphthalene. These
polyhalogenoaromatic compounds may be used alone or in combination.
[0164] The halogen atom contained in each compound is preferably a chlorine or
bromine atom.
[0165] Examples of the method of post-treating the resulting reaction mixture yielded
15 in the polymerization step and containing the polyarylene sulfide resin include, but
should not be limited to:
(1) a method of distilling away the solvent under reduced pressure or normal pressure
from the reaction mixture after the end of the polymerization reaction with or without
adding an acid or a base, and then washing the solid product after the distillation of the
20 solvent one time or two or more times with water, the reaction solvent (or an organic
solvent having similar solubility to the low molecular polymer), or a solvent such as
acetone, methyl ethyl ketone, or an alcohol, followed by neutralization, washing with
water, filtration, and drying;
(2) a method of adding a solvent (a solvent which is soluble to the polymerization
25 solvent used and is a poor solvent to at least polyarylene sulfide), such as water,
acetone, methyl ethyl ketone, an alcohol, an ether, a halogenated hydrocarbon, an
aromatic hydrocarbon, or an aliphatic hydrocarbon as a sedimentation agent to the
reaction mixture after the end of the polymerization reaction to sediment solid products
such as polyarylene sulfide and an inorganic salt, followed by filtration, washing, and
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drying;
(3) a method of adding the reaction solvent (or an organic solvent having similar
solubility to the low molecular polymer) to the reaction mixture after the end of the
polymerization reaction, stirring the reaction mixture, filtering the reaction mixture to
5 remove the low molecular weight polymer, and washing the product with a solvent
such as water, acetone, methyl ethyl ketone, or an alcohol one time or two or more
times, followed by neutralization, washing with water, filtration, and drying;
(4) a method of adding water to the reaction mixture after the end of the polymerization
reaction to wash the product with water, filtering the product, and optionally adding an
10 acid during washing with water to perform an acid treatment, and drying the product;
and
(5) a method of filtering the reaction mixture after the end of the polymerization
reaction, and optionally washing the product with the reaction solvent one time or two
or more times, followed by washing with water, filtration, and drying.
15 [0166] In the post-treatment methods exemplified in (1) to (5) above, the polyarylene
sulfide resin may be dried in vacuum, in the air, or in an inert gas atmosphere of
nitrogen or the like.
[0167] (Olefin resin (A7))
The olefin resin (A) is a synthetic resin prepared by polymerizing or
20 copolymerizing an olefin monomer having a radically polymerizable double bond.
[0168] Examples of the olefin monomer include, but should not be limited to, -olefins
and conjugated dienes. Examples of the -olefins include ethylene, propylene, 1-
butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 4-methyl-1-pentene. Examples
of the conjugated dienes include butadiene and isoprene. These olefin monomers may
25 be used alone or in combination.
[0169] Examples of the olefin resin (A7) include, but should not be limited to,
homopolymers of ethylene, copolymers of ethylene with -olefins other than ethylene,
homopolymers of propylene, copolymers of propylene with -olefins other than
propylene, homopolymers of butene, and homopolymers or copolymers of conjugated
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dienes such as butadiene and isoprene. The olefin resin (A7) is preferably a
homopolymer of propylene or a copolymer of propylene with an -olefin other than
propylene.
[0170] If the olefin resin (A7) is a copolymer (polypropylene copolymer) of a
5 propylene and another monomer, linear -olefins and branched -olefins can be
suitably used as the -olefin for copolymerization other than propylene. Examples of
the linear olefins include ethylene, butene-1, pentene-1, hexene-1, heptene-1, and
octene-1. Examples of the branched -olefins include 2-methylpropene-1, 3-
methylpentene-1, 4-methylpentene-1, 5-methylhexene-1, 4-methylhexene-1, and 4,4-
10 dimethylpentene-1. These -olefins for copolymerization may be used alone or in
combination.
[0171] The compounding amount of these -olefins (copolymerization components)
for copolymerization in the olefin resin (A) is preferably 30% by mass or less, more
preferably 20% by mass or less. The form of the copolymer prepared through
15 copolymerization of these is not particularly limited, and may be any one of random,
block, and graft types and mixed types of these, for example. The polypropylene
copolymer (copolymer of propylene and another monomer) may be any one of a
random copolymer and block copolymer usually used. Preferred examples of the
polypropylene copolymer include propylene-ethylene copolymers, propylene-butene-1
20 copolymers, and propylene-ethylene-butene-1 copolymers.
[0172] The olefin resin (A7) to be used can also be a functional group-containing olefin
resin prepared by introducing at least one functional group to the polypropylene
polymer (polymer of a propylene monomer), the polypropylene copolymer, or the like,
the functional group being selected from the group consisting of acid anhydride groups,
25 a carboxyl group, a hydroxyl group, an amino group, and an isocyanate group.
[0173] (Polyamide resin (A8))
The polyamide resin (A8) is a thermoplastic polymer having an amido bond,
which polymer is made of amino acid, lactam, diamine, and dicarboxylic acid or an
amide formable derivative thereof as the main constitutional raw material. A
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polycondensate prepared by condensing a diamine and a dicarboxylic acid or an acyl
active form thereof can be used. A polymer prepared by polycondensing
aminocarboxylic acid, lactam, or amino acid can also be used. These copolymers
thereof can also be used.
5 [0174] Examples of the diamine include aliphatic diamines and aromatic diamines.
Examples of the aliphatic diamines include tetramethylenediamine,
hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-
trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-
methylnanomethylenediamine, 2,4-dimethyloctamethylenediamine,
10 metaxylylenediamine, paraxylylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1-
amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3,8-
bis(aminomethyl)tricyclodecane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-
aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane,
bis(aminopropyl)piperazine, and aminoethylpiperazine.
15 [0175] Examples of the aromatic diamines include p-phenylenediamine, mphenylenediamine, 2,6-naphthalenediamine, 4,4'-diphenyldiamine, 3,4'-
diphenyldiamine, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 4,4'-sulfone,
3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylketone, 3,4'-diaminodiphenylketone,
and 2,2-bis(4-aminophenyl)propane.
20 [0176] Examples of the dicarboxylic acid include adipic acid, suberic acid, azelaic acid,
sebacic acid, dodecanoic acid, terephthalic acid, isophthalic acid, naphthalene
dicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-
methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid,
hexahydroisophthalic acid, and diglycolic acid.
25 [0177] Specifically, examples of the polyamide resin include aliphatic polyamides such
as polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46),
polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610),
polyhexamethylene dodecamide (nylon 612), polyundecamethyleneadipamide (nylon
116), polyundecaneamide (nylon 11), and polydodecaneamide (nylon 12). Examples
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thereof also include aliphatic-aromatic polyamides such as polytrimethylhexamethylene
terephthalamide, polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene
terephthal/isophthalamide (nylon 6T/6I), polybis(4-aminocyclohexyl)methane
dodecamide (nylon PACM12), polybis(3-methyl-4-aminocyclohexyl)methane
5 dodecamide (nylondimethyl PACM12), polymethxylylene adipamide (nylon MXD6),
polyundecamethylene terephthalamide (nylon 11T), polyundecamethylene hexahydro
terephthalamide (nylon 11T(H)), and copolymerized polyamides thereof. Examples
thereof also include copolymers and mixtures thereof, and poly(p-phenylene
terephthalamide), and poly(p-phenylene terephthalamide-co-isophthalamide).
10 [0178]
The hydrophilic copolymer (B) has a polyoxyethylene chain. Because the
polyoxyethylene chain functions as a hydrophilic segment, a hydrophilic copolymer (B)
having a polyoxyethylene chain demonstrates antistatic performance and an effect of
suppressing adhesion of hydrophilic powdery dust fouling.
15 [0179] Examples of the hydrophilic copolymer (B) include a hydrophilic copolymer
(B1) composed of a polyolefin repeatedly and alternately bonded to a hydrophilic
polymer having the polyoxyethylene chain; and polyether ester amide (B2).
[0180] The hydrophilic copolymer (B) preferably contains at least one of the
hydrophilic copolymer (B1) and the polyether ester amide (B2). In other words, the
20 hydrophilic copolymer (B1) and the polyether ester amide (B2) are each a copolymer
alternately having a plurality of blocks derived from polyolefin or polyamide and a
plurality of blocks derived from the hydrophilic polymer having the polyoxyethylene
chain. Use of at least one of the hydrophilic copolymer (B1) and the polyether ester
amide (B2) further enhances the anti-contamination effect of the thermoplastic resin
25 composition (molded article).
[0181] Compared to other hydrophilic polymers and the antistatic agent, the
hydrophilic copolymer (B) having a polyoxyethylene chain (the hydrophilic copolymer
(B1) and the polyether ester amide (B2) in particular) when mixed with the
thermoplastic resin (A) is likely to reside on the surface of a molded article comprising
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the thermoplastic resin composition. In other words, compared to other hydrophilic
polymers and the antistatic agent, a larger amount of the hydrophilic copolymer (B)
having a polyoxyethylene chain is present on the surface thereof without buried inside
the molded article. Thus, the anti-contamination effect is efficiently demonstrated
5 with respect to the amount of the added hydrophilic copolymer (B) having a
polyoxyethylene chain. For this reason, the hydrophilic copolymer (B) needed to
provide similar anti-fouling performance is added in an amount smaller than those of
other hydrophilic polymers.
[0182] The hydrophilic copolymer (B1) composed of a polyolefin repeatedly and
10 alternately bonded to the hydrophilic polymer having a polyoxyethylene chain can be
prepared by a method of modifying polypropylene or polyethylene with an acid, and
reacting this with polyalkylene glycol, for example, as described in Japanese Patent
Application Laying-Open Nos. 2001-278985 and 2003-48990.
[0183] The polyether ester amide is a block copolymer having a polyoxyethylene chain
15 as a hydrophilic segment, and can be prepared by the methods described in Japanese
Patent Application Laying-Open Nos.49-8472 and 6-287547.
[0184] The mass average molecular weight of the polyoxyethylene chain is preferably
1000 to 15000 from the viewpoint of heat resistance and reactivity with the polyolefin
chain.
20 [0185] Because the hydrophilic copolymer (B) according to the present embodiment is
dispersed in the thermoplastic resin composition to demonstrate the effect of
suppressing adhesion of hydrophilic powdery dust fouling, usually a lower surface
resistance value of the hydrophilic copolymer (B) itself is preferred. The surface
resistance value of the hydrophilic copolymer (B) is preferably 1  104
to 1  1010 ,
more preferably 1  104
to 1  107 25 .
[0186] For the purpose of enhancing the effect of suppressing adhesion of hydrophilic
powdery dust fouling, the thermoplastic resin composition may further contain an
antistatic agent other than the hydrophilic polymer described above. Examples of
other antistatic agents include surfactants (such as anionic surfactants, cationic
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surfactants, nonionic surfactants, and amphoteric surfactants), and ionic liquids.
[0187] The hydrophilic copolymer (B) having a polyoxyethylene chain also has
another special effect.
[0188] To obtain amphoteric (hydrophilic and hydrophobic) anti-fouling properties,
5 both of the hydrophilic copolymer (B) and a fatty acid metal salt (C) described later are
needed. The fatty acid metal salt (C) has a smaller molecular weight than that of the
hydrophilic copolymer (B) and is less entangled with the thermoplastic resin (A) than
the hydrophilic copolymer (B) is, and thus may drop from the surface of the molded
article or may be degraded. However, if a large amount of the hydrophilic copolymer
10 (B) is present on the surface of the molded article, the hydrophilic group of the fatty
acid metal salt (C) adheres to the hydrophilic group of the hydrophilic copolymer (B)
whose antistatic effect prevents adhesion of hydrophilic powdery dust fouling, thereby
enabling the fatty acid metal salt (C) to be stably present on the surface thereof without
dropping therefrom.
15 [0189] Because the fatty acid metal salt (C) has a non-polar hydrophobic group, i.e., R
located opposite to the hydrophilic group of the fatty acid metal salt (C), a new effect
not provided only by the hydrophilic copolymer (B), that is, a high effect of
suppressing adhesion of hydrophobic powdery dust fouling is provided.
[0190] In other words, both the hydrophilic copolymer (B) having a polyoxyethylene
20 chain and the fatty acid metal salt (C) are present on the surface of the molded article to
demonstrate the synergetic effect, thereby demonstrating a high effect of suppressing
both types of powdery dust fouling (anti-fouling properties).
[0191]
The fatty acid metal salt (C) is a compound represented by the following
25 formula (1):
[0192] M(OH)y(R-COO)x ... (1)
wherein R is an alkyl group or alkenyl group having 6 to 40 carbon atoms; M is at least
one metal element selected from the group consisting of aluminum, zinc, calcium,
magnesium, lithium, and barium; x and y each independently represent an integer of 0
668881: 9200500
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or more, and satisfy the relation represented by x + y = [valency of M].
The effect of suppressing adhesion of hydrophilic powdery dust fouling is
provided even if only the hydrophilic polymer and the antistatic agent are used as
additives. However, such use results in a low effect of suppressing adhesion of
5 hydrophobic powdery dust fouling, and a reduction in adhesion amount of hydrophobic
powdery dust fouling in Comparative Examples described later is no more than a half.
For this reason, a novel measures is required.
[0193] Although silicone oil, a fluorinated resin such as PTFE, and hydrophobic silica
such as fumed silica are known as additives which usually provide a water-repellant or
10 oil-repellant effect, any one of the additives does not provide the effect of suppressing
adhesion of hydrophobic powdery dust fouling. This is because these additives, when
added to the resin, are buried inside the resin and do not reside on the surface thereof.
The problem can be solved by compounding the fatty acid metal salt (C) with the
thermoplastic resin (A) and the hydrophilic copolymer (B), the fatty acid metal salt
15 being a material which can be present on the surface of the resin in a high concentration
and has hydrophobicity and water and oil repellency.
[0194] The fatty acid metal salt used in the present embodiment is a fatty acid metal
salt represented by the formula (1):
M(OH)y(R-COO)x ... (1)
20 wherein R is an alkyl group or alkenyl group having 6 to 40 carbon atoms; M is at least
one metal element selected from the group consisting of aluminum, zinc, calcium,
magnesium, lithium, and barium; x and y each independently represent an integer of 0
or more, and satisfy the relation represented by x + y = [valency of M].
In the formula (1), R has 6 to 40 carbon atoms, preferably 11 to 27 carbon
25 atoms, still more preferably 15 to 20 carbon atoms. If R has less than 6 carbon atoms
or more than 40 carbon atoms, these cases are not preferred because the effect of
preventing adhesion of powdery dust is reduced. R is an alkyl group or an alkenyl
group, and is preferably an alkyl group.
[0195] Generally, if the material has a contact angle to water larger than that to
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petroleum and mineral oil, it is considered that the material has water and oil
repellency; and if the material has a contact angle to water larger than 90 degrees, it is
considered that the material has hydrophobicity. The fatty acid metal salt (C) is such
a material.
5 [0196] (Metal element M)
In the formula (1), M is at least one metal element selected from the group
consisting of aluminum, zinc, calcium, magnesium, lithium, and barium.
[0197] M is preferably at least one metal element selected from the group consisting of
aluminum and zinc. In this case, the thermoplastic resin composition can demonstrate
10 higher anti-fouling performance. M is more preferably aluminum. In this case, the
thermoplastic resin composition can demonstrate still higher anti-fouling performance.
[0198] With reference to FIG. 3, compared to M having a large ionic radius ((b1) and
(b2) of FIG. 3), M having a small ionic radius ((a1) and (a2) of FIG. 3) allows the nonpolar group (hydrophobic group) of the fatty acid metal salt to be more densely
15 arranged on the surface of the molded article comprising the thermoplastic resin
composition. As the hydrophobic group is denser, the effect of suppressing adhesion
of hydrophobic powdery dust fouling is more significantly enhanced. The ionic radius
of M is 54 for aluminum, 74 for zinc, 100 for calcium, and 135 for barium, and
aluminum has the largest ionic radius and zinc has the second largest ionic radius.
20 Thus, to enhance the anti-contamination effect, aluminum is the most optimal and zinc
is preferred as the metal element M.
[0199] (Fatty acid)
Examples of the fatty acid which forms the fatty acid metal salt (C) according to
the present embodiment include caproic acid, capric acid, lauric acid, palmitic acid,
25 stearic acid, behenic acid, lignoceric acid, montanic acid, oleic acid, and linoleic acid.
The fatty acid is preferably a long-chain fatty acid (fatty acid having 12 or more carbon
atoms) such as stearic acid, behenic acid, or montanic acid. In particular, stearic acid
is more preferred for production because of its availability and inexpensiveness.
[0200] Examples of the fatty acid metal salt (C) include zinc stearate, zinc 12-
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hydroxystearate, zinc laurate, zinc oleate, zinc 2-ethylhexanoate, aluminum tristearate,
(dihydroxy)aluminum monostearate, (hydroxy)aluminum distearate, aluminum 12-
hydroxystearate, aluminum laurate, aluminum oleate, and aluminum 2-ethylhexanoate.
The fatty acid metal salt (C) is preferably zinc stearate, aluminum tristearate,
5 (dihydroxy)aluminum monostearate, and (hydroxy)aluminum distearate, more
preferably (hydroxy)aluminum distearate. These fatty acid metal salts (C) may be
used alone or in combination.
[0201] As the features, aluminum stearate, zinc stearate, calcium stearate, and barium
stearate have smoothness, high water repellency, and low surface free energy (about
10 21.2 mN/m). The material having low surface free energy, such as a fluorinated resin
(surface free energy: about 21.5 mN/m), has a stable surface state. For this reason,
fouling hardly adheres thereto. The effect of preventing hydrophobic powdery dust
fouling, such as carbon black, soot, and oily smoke, is demonstrated by formation of a
layer of aluminum stearate having low surface free energy on the surface of the molded
15 article comprising the thermoplastic resin composition. Low surface free energy
results in prevention of adhesion of hydrophilic powdery dust fouling, such as dust,
sand, and clay. Accordingly, in addition to the static elimination effect of the
hydrophilic copolymer (B) compounded in the thermoplastic resin composition, the
anti-fouling properties of hydrophobic powdery dust fouling and hydrophilic powdery
20 dust fouling are further enhanced.
[0202] (Valency)
In the formula (1), x and y each independently represent an integer of 0 or more,
and satisfy the relation represented by x + y = [valency of M].
[0203] If the valency of M is 1, y is 0. If the valency of M is 2 or more, y is an
25 integer of 0 or 1 or more. If the valency of M is 3 or more, y is preferably 1. In this
case, the thermoplastic resin composition can demonstrate much higher anti-fouling
performance.
[0204] As one example, aluminum stearate will be described, which is a long-chain
fatty acid salt of aluminum where the valency of M is 3.
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[0205] Aluminum stearate includes aluminum monostearate [Al(C17H35COO)(OH)2]
containing one stearic acid (mono-type), aluminum distearate [Al(C17H35COO)2(OH)]
containing two stearic acids (di-type, and aluminum tristearate [Al(C17H35COO)3]
containing three stearic acids (tri-type).
5 [0206] With reference to FIG. 4, aluminum tristearate hardly migrates to the surface of
the molded article ((a) of FIG. 4) due to a large amount of the non-polar group.
Furthermore, aluminum tristearate is an unstable substance and thus is readily
hydrolyzed by the water content in the air to form a mixture with aluminum
monostearate or aluminum distearate. Thus, aluminum distearate more readily
10 migrates to the surface of the molded article ((b) of FIG. 4) and has a higher effect of
suppressing both types of powdery dust than aluminum tristearate. If the valency of
M is more than 3, similarly, the effect of suppressing both types of powdery dust by the
di-type fatty acid metal salt having a smaller number of fatty acids is higher than that
by the tri-type fatty acid metal salt.
15 [0207] On the other hand, aluminum monostearate has a smaller number of non-polar
groups (hydrophobic groups) for R than that of aluminum distearate where the number
of aluminum atoms is identical ((c) of FIG. 4). Accordingly, aluminum distearate has
a higher effect of suppressing both types of powdery dust than that of aluminum
monostearate.
20 [0208] In the actual measurement near the surface of the molded article using a timeof-flight secondary ion mass spectrometer (TOF-SIMS), C18H35O2
-
derived from stearic
acid was detected as secondary ions. Because the detection depth for TOF-SIMS is
usually 1 to 2 nm, it was verified that stearic acid is present on the outermost surface of
the molded article.
[0209] The secondary ion intensity ratio of C18H35O2
-
, where the ion intensity of C2H
- 25
as the main peak during analysis of polystyrene is used as a reference, was 0.341 in the
molded article containing aluminum distearate, which was 2- to 4-fold or higher than
that (0.0687) of the molded article containing aluminum monostearate and that (0.172)
of the molded article containing aluminum tristearate. Accordingly, in the molded
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article containing aluminum distearate (where y = 1), a large amount of the non-polar
group (hydrophobic group) is present on the surface thereof, and the effect of
suppressing powdery dust is most readily demonstrated.
[0210] For the same reason as that for the above case where the valency of M is 3 or
5 more, the effect of suppressing both types of powdery dust by the di-type fatty acid
metal salt is higher than that by the mono-type fatty acid metal salt also if the valency
of M is 2. Thus, if the valency of M is 2, y is preferably 0 (where x is 2).
[0211]
In the thermoplastic resin composition according to the present embodiment, the
10 compounding amount of the hydrophilic copolymer (B) is preferably 1 to 20 parts by
mass, more preferably 1 to 17 parts by mass relative to 100 parts by mass of the
thermoplastic resin (A).
[0212] The compounding amount of the fatty acid metal salt (C) is preferably 0.5 to 10
parts by mass, more preferably 1 to 8 parts by mass relative to 100 parts by mass of the
15 thermoplastic resin (A).
[0213] In particular, the thermoplastic resin composition according to the present
embodiment preferably comprises 100 parts by mass of the thermoplastic resin (A), 1
to 20 parts by mass of the hydrophilic copolymer (B), and 0.5 to 10 parts by mass of
the fatty acid metal salt (C).
20 [0214] Although the fatty acid metal salt (C) is usually compounded with the
thermoplastic resin composition in an amount of 0.5% by mass or less (particularly,
about 0.1%) as a lubricant, a mold release agent, or the like for improving molding
properties, by compounding the fatty acid metal salt (C) in an amount of more than
0.5% by mass, the action of causing both the hydrophilic copolymer (B) and the fatty
25 acid metal salt (C) on the surface of the molded article in high concentrations is
demonstrated, and further amphoteric anti-contamination effect is enhanced.
[0215] If the compounding amount of the hydrophilic copolymer (B) is more than 20
parts by mass, mechanical strength such as elastic modulus reduces. If the
compounding amount is less than 1 part by mass, a reduction in the effect of
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suppressing adhesion of powdery dust is observed.
[0216] If the compounding amount of the fatty acid metal salt (C) is more than 10 parts
by mass, the heat resistance and the impact resistance reduce. If the compounding
amount is less than 0.5 parts by mass, a reduction in the effect of suppressing adhesion
5 of powdery dust is observed.
[0217] As described above, usually the fatty acid metal salt (C) is used for a purpose
different from that of the present embodiment, i.e., suppressing both types of powdery
dust fouling of hydrophilic powdery dust fouling and hydrophobic powdery dust
fouling in some cases. As disclosed in Japanese Patent Application Laying-Open Nos.
10 2004-168055 and 2003-183529, for example, the fatty acid metal salt (C) is used as a
lubricant, a molding improver, a mold release agent, an anti-fogging agent, or the like.
In this case, the compounding amount of the fatty acid metal salt (C) is less than 0.5
parts by mass relative to 100 parts by mass of the thermoplastic resin (A).
Furthermore, the compounding amount of the fatty acid metal salt (C) is 0.1 parts by
15 mass or less in standard usage related to the production industry. The effect of
suppressing adhesion of powdery dust by the fatty acid metal salt (C) has not been
known yet.
[0218] In the present embodiment, the followings have been found: To obtain the effect
of suppressing adhesion of both hydrophilic powdery dust fouling and hydrophobic
20 powdery dust fouling for the purpose completely different from that of the conventional
usage, the fatty acid metal salt (C) is used in a compounding amount sufficiently larger
than that usually used, and such a sufficiently large compounding amount thereof
provides a remarkable effect of suppressing adhesion of both types of powdery dust
fouling. Accordingly, the compounding amount of the fatty acid metal salt (C) is
25 preferably 0.5 parts by mass or more, more preferably 1 to 8 parts by mass relative to
100 parts by mass of the thermoplastic resin (A). In this case, the resulting effect of
suppressing powdery dust is equal to or higher than that in the case where the coating
for suppressing powdery dust is applied to the surface of the molded article. Such an
example in which 1 part by mass or more of the fatty acid metal salt (C) is compounded
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relative to 100 parts by mass if the thermoplastic resin for the purpose of suppressing
powdery dust has not been known yet.
[0219] The new effect of suppressing adhesion of hydrophobic powdery dust fouling is
provided by R, which is a non-polar hydrophobic group of the fatty acid metal salt
5 directed to the air. By adding the fatty acid metal salt (C) in an amount of 0.5% by
mass or more relative to the thermoplastic resin (A), a large amount of hydrophobic
groups can be densely disposed on the surface of the molded article comprising the
thermoplastic resin composition to enhance the effect of suppressing adhesion of
hydrophobic powdery dust fouling.
10 [0220] As described later, the effect of suppressing adhesion of hydrophilic powdery
dust fouling is enhanced by the antistatic effect of the hydrophilic copolymer (B)
having a polyoxyethylene chain, and the effect of suppressing adhesion of hydrophobic
powdery dust fouling is enhanced by compounding the fatty acid metal salt (C) in
combination, thus providing a new high effect on both types of fouling.
15 [0221]
The thermoplastic resin composition according to the present embodiment may
contain optional components such as a heat stabilizer, an ultraviolet absorbing agent, a
photostabilizer, an antibacterial agent, an antifungal agent, and an inorganic filler in the
ranges not impairing the object of the present embodiment.
20 [0222] (Heat stabilizer)
The thermoplastic resin composition according to the present embodiment may
contain a heat stabilizer to improve the thermal stability during production.
[0223] The heat stabilizer to be used is preferably a phosphorus-based stabilizer and/or
a hindered phenol-based antioxidant, more preferably a combination thereof.
25 [0224] The phosphorus-based stabilizer and/or the hindered phenol-based antioxidant
can be added to the thermoplastic resin composition according to the present
embodiment in any amount.
[0225] The amount thereof to be added is preferably 0.01 to 1 part by mass, more
preferably 0.01 to 0.6 parts by mass relative to 100 parts by mass of the thermoplastic
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resin composition because the effect of improving thermal stability is effectively
obtained and the compounding amounts of the essential components described above
are not affected.
[0226] Examples of the phosphorus-based stabilizer include phosphorous acid,
5 phosphoric acid, phosphonous acid, phosphonic acid, esters thereof, phosphonite
compounds, and tertiary phosphines.
[0227] Examples of the phosphorous acid esters (phosphite compounds) include
triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite,
distearylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol
10 diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis{2,4-
bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite, phenyl bisphenol A
pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, and
dicyclohexylpentaerythritol diphosphite.
[0228] In addition to those listed above, those which are reactive with divalent phenols
15 and have a cyclic structure can also be used as the phosphorous acid esters (phosphite
compounds).
[0229] Examples thereof include 2,2'-methylene bis(4,6-di-tert-butylphenyl)(2,4-ditert-butylphenyl) phosphite, 2,2'-methylene bis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-
methylphenyl) phosphite, and 2,2-methylene bis(4,6-di-tert-butylphenyl)octyl
20 phosphite.
[0230] Examples of the phosphoric acid esters (phosphate compounds) include
triphenyl phosphate and trimethyl phosphate.
[0231] Examples of the phosphonite compounds include tetrakis(di-tert-butylphenyl)-
biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenyl phosphonite.
25 [0232] These phosphonite compounds can be used in combination with the phosphite
compounds having aryl groups which substitute two or more alkyl groups can be used,
and such use in combination is preferred.
[0233] Examples of the phosphonic acid esters (phosphonate compounds) include
dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl
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benzenephosphonate.
[0234] Examples of the tertiary phosphines include triphenyl phosphine.
Among these phosphorus-based stabilizers, preferred are phosphonite compounds or
phosphite compounds represented by the following general formula (15):
5 [0235] [Chemical Formula 11]
(Formula 15)
[0236] (In the formula (15), R and R' represent an alkyl group having 6 to 30 carbon
atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different).
As described above, the phosphonite compound is preferably tetrakis(2,4-di-tert10 butylphenyl)-biphenylene diphosphonite.
[0237] Among these, more suitable phosphite compounds represented by the above
formula (15) are distearylpentaerythritol diphosphite, bis(2,4-di-tertbutylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-
methylphenyl)pentaerythritol diphosphite, and bis{2,4-bis(1-methyl-1-
15 phenylethyl)phenyl}pentaerythritol diphosphite.
[0238] Examples of the hindered phenol compound include tetrakis[methylene-3-(3-
tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tertbutyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-
methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane.
20 [0239] The thermoplastic resin composition according to the present embodiment can
contain a different heat stabilizer other than the phosphorus-based stabilizer and the
hindered phenol-based antioxidant.
[0240] The different heat stabilizer is preferably used in combination with at least one
of the phosphorus-based stabilizer and the hindered phenol-based antioxidant, and is
25 particularly preferably used in combination with both thereof.
[0241] Examples of the different heat stabilizer include lactone-based stabilizers (see
Japanese Patent Application Laying-Open No. 7-233160 for the details of this
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stabilizer) such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and
o-xylene.
[0242] For the lactone-based stabilizers, Irganox HP-136 (registered trademark,
manufactured by CIBA SPECIALTY CHEMICALS) and the like are commercially
5 available.
[0243] As a mixed stabilizer of the lactone-based stabilizer, the phosphite compound,
and the hindered phenol compound, Irganox HP-2921 (registered trademark,
manufactured by CIBA SPECIALTY CHEMICALS) and the like are commercially
available.
10 [0244] The amount of lactone-based stabilizer to be added is preferably 0.0005 to 0.05
parts by mass, more preferably 0.001 to 0.03 parts by mass relative to 100 parts by
mass of the thermoplastic resin composition.
[0245] Examples of other different stabilizers include sulfur-containing stabilizers such
as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis (3-
15 laurylthiopropionate), and glycerol-3-stearylthiopropionate.
[0246] The different stabilizers other than the phosphorus-based stabilizer and/or the
hindered phenol-based antioxidant can be added to the thermoplastic resin composition
according to the present embodiment in any amount, and the amount thereof to be
added is preferably 0.0005 to 0.1 parts by mass, more preferably 0.001 to 0.08 parts by
20 mass, particularly preferably 0.001 to 0.05 parts by mass relative to 100 parts by mass
of the thermoplastic resin composition.
[0247] (Ultraviolet absorbing agent)
The thermoplastic resin composition according to the present embodiment may
contain an ultraviolet absorbing agent. Because the weatherability of the
25 thermoplastic resin composition according to the present embodiment may be reduced
due to influences from the rubber component or the like in some cases, compounding of
the ultraviolet absorbing agent is effective in improving the weatherability.
[0248] Examples of the ultraviolet absorbing agent according to the present
embodiment include benzophenone-based ultraviolet absorbing agents, benzotriazole-
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based ultraviolet absorbing agents, hydroxyphenyltriazine-based ultraviolet absorbing
agents, cyclic iminoester-based ultraviolet absorbing agents, and cyanoacrylate-based
ultraviolet absorbing agents.
[0249] Examples of the benzophenone-based ultraviolet absorbing agents include 2,4-
5 dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-
sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridelatebenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-
dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium
10 sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-
hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-
carboxybenzophenone.
[0250] Examples of the benzotriazole-based ultraviolet absorbing agents include 2-(2-
hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole,
15 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-
methylphenyl)-5-chlorobenzotriazole, 2,2'-methylene bis[4-(1,1,3,3-tetramethylbutyl)-
6-(2 H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole,
2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tertamylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-
20 hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole,
2,2'-methylene bis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylene bis(1,3-
benzooxazin-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-
methylphenyl]benzotriazole. Examples of other benzotriazole-based ultraviolet
absorbing agents include polymers having a 2-hydroxyphenyl-2H-benzotriazole
25 skeleton. Examples of the polymers having a 2-hydroxyphenyl-2H-benzotriazole
skeleton include copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2Hbenzotriazole and vinyl monomers copolymerizable with the monomer, and
copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and vinyl
monomers copolymerizable with the monomer.
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[0251] Examples of the hydroxyphenyltriazine-based ultraviolet absorbing agents
include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-
triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol,
2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-
5 triazin-2-yl)-5-butyloxyphenol. Furthermore, examples thereof include compounds
listed above and having a 2,4-dimethylphenyl group which substitutes the phenyl group,
such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol.
[0252] Examples of the cyclic imino ester-based ultraviolet absorbing agents include
2,2'-p-phenylene bis(3,1-benzooxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-
10 benzooxazin-4-one), and 2,2'-(2,6-naphthalene)bis(3,1-benzooxazin-4-one).
[0253] Examples of the cyanoacrylate-based ultraviolet absorbing agents include1,3-
bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-
diphenylacryloyl)oxy]methyl)propane, and 1,3-bis-[(2-cyano-3,3-
diphenylacryloyl)oxy]benzene.
15 [0254] Furthermore, the ultraviolet absorbing agent may be a polymer-type ultraviolet
absorbing agent prepared by copolymerizing an ultraviolet light absorbable monomer
and/or a photostable monomer having a hindered amine structure with a monomer such
as alkyl (meth)acrylate. Examples of the ultraviolet light absorbable monomer
suitably include compounds which are (meth)acrylate esters and contain a
20 benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino
ester skeleton, and a cyanoacrylate skeleton in the substituents of the esters.
[0255] Among these, preferred are benzotriazole-based and hydroxyphenyltriazinebased ultraviolet absorbing agents from the viewpoint of ultraviolet light absorbability,
and preferred are cyclic imino ester-based and cyanoacrylate-based ultraviolet
25 absorbing agents from the viewpoint of heat resistance and hue (transparency). These
ultraviolet absorbing agents may be used alone or in the form of a mixture thereof.
[0256] The content of the ultraviolet absorbing agent is preferably 0.01 to 2 parts by
mass, more preferably 0.02 to 2 parts by mass, still more preferably 0.03 to 1 part by
mass, particularly preferably 0.05 to 0.5 parts by mass relative to 100 parts by mass of
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the thermoplastic resin composition.
[0257] (Photostabilizer)
The thermoplastic resin composition according to the present embodiment may
contain a photostabilizer. Compounding of a photostabilizer is effective to prevent
5 degradation because the thermoplastic resin composition according to the present
embodiment may cause yellowing in the dark.
[0258] Hindered amine photostabilizers (HALSs) can be suitably used as such a
photostabilizer. The HALSs include compounds represented by the following
formulae (16) to (19) or combinations of thereof:
10 [0259] [Chemical Formula 12]
(Formula 16)
[0260] [Chemical Formula 13]
(Formula 17)
[0261] [Chemical Formula 14]
15 (Formula 18)
[0262] [Chemical Formula 15]
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(Formula 19)
[0263] In the formulae (16) to (19), R1 to R3 are independent substituents.
Examples of the substituents include hydrogen, an ether group, an ester group, an
amine group, an amide group, an alkyl group, an alkenyl group, an alkynyl group, an
5 aralkyl group, a cycloalkyl group, and an aryl group.
[0264] These substituents may have a functional group. Examples of the functional
group include alcohols, ketones, anhydrides, imines, siloxanes, ethers, a carboxyl group,
aldehydes, esters, amides, imides, amines, nitriles, ethers, urethanes, and combinations
thereof.
10 [0265] The hindered amine photostabilizers (HALSs) are preferably compounds
derived from substituted piperidine compounds, more preferably compounds derived
from alkyl-substituted piperidyl, piperidinyl, or piperazinone compounds and
substituted alkoxypiperidinyl compounds.
[0266] Examples of the hindered amine photostabilizers include, but should not be
15 limited to, 2,2,6,6-tetramethyl-4-piperidone; 2,2,6,6-tetramethyl-4-piperidinol; bis-
(1,2,2,6,6-pentamethylpiperidyl)-(3',5'-di-t-butyl-4'-hydroxybenzyl)butyl malonate; di-
(2,2,6,6-tetramethyl-4-piperidyl) sebacate; oligomers of N-(2-hydroxyethyl)-2,2,6,6-
tetramethyl-4-piperidinol and succinic acid; oligomers of cyanuric acid and N,Ndi(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine; bis-(2,2,6,6-tetramethyl-4-
20 piperidinyl) succinate; bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate; bis-
(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate; tetrakis-(2,2,6,6-tetramethyl-4-
piperidyl)-1,2,3,4-butane tetracarboxylate; N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-
hexane-1,6-diamine; N-butyl-2,2,6,6-tetramethyl-4-piperidineamine; 2,2'-[(2,2,6,6-
tetramethyl-piperidinyl)-imino]-bis-[ethanol]; poly((6-morpholine-S-triazine-2,4-
25 diyl)(2,2,6,6-tetramethyl-4-piperidinyl)-iminohexamethylene-(2,2,6,6-tetramethyl-4-
668881: 9200500
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piperidinyl)-imino); 5-(2,2,6,6-tetramethyl-4-piperidinyl)-2-cyclo-undecyl-oxazole);
1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetramethyl-piperazinone); 8-acetyl-3-dodecyl7,7,9,9-tetramethyl-1,3,8-triazaspiro(4.5)decane-2,4-dione; polymethyl propyl-3-oxy-
[4(2,2,6,6-tetramethyl)-piperidinyl]siloxane; 1,2,3,4-butane-tetracarboxylic acid-1,2,3-
5 tris(1,2,2,6,6-pentamethyl-4-piperidinyl)-4-tridecyl esters; copolymers of -
methylstyrene-N-(2,2,6,6-tetramethyl-4-piperidinyl)maleimide and Nstearylmaleimide; copolymers of 1,2,3,4-butanetetracarboxylic acid-,,', '-
tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol and 1,2,2,6,6-
pentamethyl-4-piperidinyl esters; 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol
10 and 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl esters and
,,', '-tetramethyl-polymer; D-glucitol, 1,3:2,4-bis-o-(2,2,6,6-tetramethyl-4-
piperidinylidene)-; oligomers of 7-oxa-3,20-diazadispiro[5.1.11.2]-heneicosan-21-one2,2,4,4-tetramethyl-20-(oxiranylmethyl); propanedioic acid and [(4-
methoxyphenyl)methylene]-,bis(1,2,2,6,6-pentamethyl-4-piperidinyl) esters;
15 formamide and N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl; 1,3,5-
triazine-2,4,6-triamine, N,N'''-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl4-piperidinyl)amino]-1,3,5-triazin-2-yl]imino]-3,1-propanediyl]]-bis[N',N''-dibutylN',N''-bis(1,2,2,6,6-pentamethyl-4-piperidinyl); poly[[6-[(1,1,3,33-
tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)-
20 imino]-1,6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidinyl)imino]]; 1,5-
dioxaspiro(5.5)undecane 3,3-dicarboxylic acid, bis(2,2,6,6-tetramethyl-4-piperidinyl)
esters; 1,5-dioxaspiro(5.5)undecane 3,3-dicarboxylate, bis(1,2,2,6,6-pentamethyl-4-
piperidinyl) esters; N-2,2,6,6-tetramethyl-4-piperidinyl-N-amino-oxamide; 4-
acryloyloxy-1,2,2,6,6-pentamethyl-4-piperidine; 1,5,8,12-tetrakis[2',4'-
25 bis(1'',2'',2'',6'',6''-pentamethyl-4''-piperidinyl(butyl)amino)-1',3',5'-triazin-6'-yl]-
1,5,8,12-tetraazadodecane; 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidine2,5-dione; 1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetra-methyl-piperazinone); 1,1'1''-
(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethanediyl)tris(3,3,5,5-
tetramethylpiperazinone); and 1,1',1''-(1,3,5-triazine-2,4,6-trilytris((cyclohexylimino)-
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2,1-ethanediyl)tris(3,3,4,5,5-tetramethylpiperazinone).
[0267] The amount of the hindered amine photostabilizer (HALS) to be added is
preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, still more
preferably 0.1 to 1 part by mass relative to 100 parts by mass of the thermoplastic resin
5 composition.
[0268] (Antibacterial agent)
The thermoplastic resin composition according to the present embodiment may
contain an antibacterial agent. Examples of the antibacterial agent include, but should
not be limited to, inorganic antibacterial agents of antibacterial metals, such as zinc
10 oxide, silver, copper, and zinc carried on crystalline aluminosilicic acid salts,
amorphous aluminosilicic acid salts, silica gel, active alumina, diatomite, activated
carbon, zirconium phosphate, hydroxy apatite, magnesium oxide, magnesium
perchlorate, and glass. A preferred antibacterial metal is zinc oxide.
[0269] Zinc oxide is not particularly limited, and may be a commercially available
15 product. For example, zinc oxide may be a product prepared by vaporizing a metal
zinc by heating and burning it in the air or a product prepared by heating zinc sulfate or
zinc nitrate. Those having a variety of shapes such as fibrous, platy, particulate, and
tetrapodic zinc oxides can be used. The zinc oxide used in the present embodiment
may be surface treated with silicon oxide, silicone oil, an organic silicon compound, or
20 an organic titanium compound.
[0270] Examples of the commercially available zinc oxides include "Class 1 zinc
oxide", "Class 2 zinc oxide", and "Class 3 zinc oxide" classified by JIS K-1410,
pharmaceutical zinc oxides specified in The Japanese Pharmacopoeia, and anisotropic
(columnar, platy, and tetrapodic) zinc oxides (zinc oxides having shape anisotropy)
25 prepared through a hydrothermal preparation step. Among these zinc oxides,
particulate zinc oxides having an average particle diameter of 50 to 200 nm,
particularly 100 to 150 nm are preferred. The average particle diameter mentioned
here indicates a particle diameter whose integrated mass distribution is 50% in the
particle diameter distribution obtained from the measurement with a laser
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diffraction/scattering particle diameter distribution analyzer.
[0271] The compounding amount of the zinc oxide is preferably 0.01 to 1 part by mass,
more preferably 0.05 to 0.5 parts by mass, still more preferably 0.1 to 0.3 parts by mass
relative to 100 parts by mass of the thermoplastic resin composition.
5 [0272] (Inorganic filler)
The thermoplastic resin composition according to the present embodiment may
contain an inorganic filler as a reinforcing filler to impart rigidity and enhance strength.
[0273] Examples of the inorganic filler include talc, wollastonite, mica, clay,
montmorillonite, smectite, kaolin, calcium carbonate, glass fibers, glass beads, glass
10 balloons, glass milled fibers, glass flakes, carbon fibers, carbon flakes, carbon beads,
carbon milled fibers, metal flakes, metal fibers, metal-coated glass fibers, metal-coated
carbon fibers, metal-coated glass flakes, silica, ceramic particles, ceramic fibers,
ceramic balloons, aramid particles, aramid fibers, polyarylate fibers, graphite, and a
variety of whiskers such as potassium titanate whiskers, aluminum borate whiskers, and
15 basic magnesium sulfate. Among these, silicate fillers such as talc, wollastonite, mica,
glass fibers, and glass milled fibers are preferably used. Among these, particularly
preferred are talc, wollastonite, and mica.
[0274] If the inorganic filler is compounded, the thermoplastic resin composition
according to the present embodiment can contain an additive having an acidic group
20 such as a carboxylic anhydride group or a sulfonate group to enhance the wettability of
the inorganic filler.
[0275] The content of the inorganic filler in the present embodiment is preferably 0.1
to 30 parts by mass, more preferably 0.5 to 20 parts by mass, still more preferably 1 to
10 parts by mass relative to 100 parts by mass of the thermoplastic resin composition.
25 If the compounding amount is less than 0.1 parts by mass, the reinforcement effect by
the filler is not provided. If the compounding amount is more than 30 parts by mass,
impact strength significantly reduces, and this is not preferred.
[0276] (Other optional components)
Examples of other optional components usable in the present embodiment
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include dyes and pigments for coloring, an antifoaming agent, a plasticizer, a lubricant,
a mold release agent, and a flame retardant. Furthermore, a thermoplastic resin other
than the thermoplastic resin (A) and the hydrophilic copolymer (B) can be compounded
in the range not imparting the object of the present embodiment.
5 [0277] Such a thermoplastic resin to be used can be thermoplastic resins used as
general-purpose resins in home appliances and OA apparatuses.
[0278] Examples of such thermoplastic resins include:
olefin resins, such as polyolefin resins (such as high density polyethylene, low
density polyethylene, and polypropylene), cyclic olefin resins, and polyester resins
10 (such as polylactic acid, polyethylene terephthalate, and polybutylene terephthalate),
styrene-based resins, such as polystyrene (PS resins), acrylonitrile butadiene
styrene (ABS resins), and acrylonitrile styrene (AS resins),
ASA resins prepared by polymerizing the ABS resins in which butadiene is
substituted by acrylic rubber,
15 AES resins prepared by polymerizing the ABS resins in which butadiene is
substituted by ethylene rubber, and
methyl methacrylate butadiene styrene (MBS resins).
[0279] Examples of other general-purpose resins include polyvinyl chloride resins
(such as polyvinyl chloride and polyvinylidene chloride), polymethyl methacrylate
20 resins, polyvinyl alcohol, polyethylene terephthalate (PET resins), and polybutylene
terephthalate (PBT resins).
[0280] Examples of engineering plastics having particularly high strength and
reinforced functions such as heat resistance include polycarbonate resins (BPA-type
polycarbonate and aliphatic polycarbonate), polyamide resins, polyphenylene ether
25 resins (PPE resins), polyoxymethylene resins (such as polyacetal), polyphenylene
sulfide resins, polyether imide resins, aromatic polyether ketone resins, polysulfone
resins, and polyamidimide resins.
[0281] As the raw material(s) for the thermoplastic resin composition according to the
present embodiment, these resins may be used alone or a plurality of resins thereof may
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be used in combination. The plurality of resins indicates a polymer alloy such as
PC/ABS or PC/AS. Such a polymer alloy has both characteristics of polycarbonate
(the PC resin) and those of the styrene-based resin (such as the ABS resin or the AS
resin), and is used in broad fields such as electrical and electronic related applications,
5 OA apparatuses, lighting apparatuses, precision instruments, automobile parts, and
housewares.
[0282] Because the fatty acid metal salt (C) has a molecular weight lower than those of
the thermoplastic resin (A) and the hydrophilic copolymer (B) having a
polyoxyethylene chain, even if any one of the resins is used as the raw material, the
10 fatty acid metal salt (C) is likely to be exposed from the surface of the molded article.
Thus, a variety of resins can be compounded with the thermoplastic resin composition.
[0283] With reference to FIG. 6, the melt viscosity during molding of the fatty acid
metal salt (C) and that of the hydrophilic copolymer (B) are different from each other.
During molding, the thermoplastic resin (A) injected into a metal mold is first solidified,
15 the hydrophilic copolymer (B) is then solidified, and thereafter the fatty acid metal salt
(C) having a low molecular weight is solidified. In other words, because the
solidifying rates of the hydrophilic copolymer (B) and the fatty acid metal salt (C) are
lower than that of the thermoplastic resin (A), the hydrophilic copolymer (B) and the
fatty acid metal salt are likely to be exposed from the surface of the molded article.
20 Because the hydrophilic copolymer (B) and the fatty acid metal salt (C) have a melt
viscosity during molding different from that of the thermoplastic resin (A) as described
above, the hydrophilic copolymer (B) and the fatty acid metal salt (C) can be
compounded with the thermoplastic resin (A).
[0284] In contrast, for example, a resin raw material having a high melting point (e.g.,
25 about 320C or more) and a significantly high polarity is difficult to disperse; thus, a
desired effect of suppressing powdery dust is difficult to obtain. In other words,
because the hydrophilic copolymer (B) and the fatty acid metal salt (C) are more likely
to reside near the surface layer of the molded article than the thermoplastic resin (A) is,
the effect of suppressing powdery dust is more readily demonstrated.
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[0285] Furthermore, the polar group of the fatty acid metal salt (C) having a low
molecular weight and the hydrophilic copolymer (B) having a polyoxyethylene chain
have compatibility. For this reason, adhesion of the hydrophilic copolymer (B) to the
fatty acid metal salt (C) can prevent detachment of the hydrophilic copolymer (B) and
5 the fatty acid metal salt (C), causing a large amount of the hydrophilic copolymer (B)
and a large amount of the fatty acid metal salt (C) to be present near the surface layer of
the molded article. Thus, the effect of suppressing adhesion is likely to be
demonstrated to both hydrophilic powdery dust fouling and hydrophobic powdery dust
fouling.
10 [0286]
The thermoplastic resin composition according to the present embodiment can
be produced by any method. Examples thereof include a method of sufficiently
mixing the thermoplastic resin (A), the hydrophilic copolymer (B), the fatty acid metal
salt (C), and other optional additives with preliminary mixing means such as a V-type
15 blender, a Henschel mixer, a mechanochemical apparatus, or an extrusion mixer,
optionally granulating the preliminary mixture with an extrusion granulator or a
briquetting machine, then melt kneading the kneaded product with a melt kneader such
as a vent-type twin screw extruder, and subsequently pelletizing the product with a
pelletizer.
20 [0287] Other examples thereof include a method of feeding the components each
independently to a melt kneader such as a vent-type twin screw extruder, and a method
of preliminarily mixing part of the components, and then feeding the mixture to a melt
kneader independently from the remainings of the components. Examples of the
method of preliminarily mixing part of the components include a method of
25 preliminarily mixing the components other than the thermoplastic resin (A) and
thereafter mixing the mixture with the thermoplastic resin (A) or directly feeding the
mixture to an extruder.
[0288] As the extruder, those having a vent through which the water content in the raw
materials and a volatile gas generated from the melt kneaded resin are discharged can
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be preferably used. A vacuum pump is preferably disposed to efficiently discharge
the water content and the volatile gas generated from the vent to the outside of the
extruder. In addition, a screen for removing foreign substances mixed in the extruded
raw material can be disposed in a zone upstream of an extruder die to remove foreign
5 substances from the resin composition. Examples of such a screen include metallic
meshes, screen changers, and sintered metal plates (such as disk filters).
[0289] Examples of the melt kneader include a twin screw extruder, a Banbury mixer, a
kneading roll, a single screw extruder, and a multi-screw extruders having 3 or more
screws.
10 [0290] The thermoplastic resin composition extruded as above are pelletized by
directly cutting the extruded thermoplastic resin composition, or is pelletized by
forming strands and then cutting the strands with a pelletizer. The shape of the pellet
is suitably columnar. The diameter of the column is preferably 1 to 5 mm, more
preferably 1.5 to 4 mm, still more preferably 2 to 3.3 mm. On the other hand, the
15 length of the column is preferably 1 to 30 mm, more preferably 2 to 5 mm, still more
preferably 2.5 to 3.5 mm.
[0291] Usually the thermoplastic resin composition according to the present
embodiment can be produced into a variety of products by obtaining a molded article
through injection molding of the pellets thereof. Examples of such injection molding
20 include not only a standard molding method but also injection compression molding,
injection press molding, gas assist injection molding, foaming molding (including a
method of injecting a supercritical fluid), insert molding, inmold coating molding, heatinsulating mold molding, rapid heating/cooling mold molding, two-color molding,
sandwich molding, and ultra-high speed injection molding. Any one of cold runner
25 molding and hot runner molding can be selected.
[0292] Moreover, by extrusion molding, the thermoplastic resin composition according
to the present embodiment can also be used in a variety of forms, such as various
extrusion molded products, sheets, and films. The thermoplastic resin composition
according to the present embodiment can also be molded into sheets and films thereof
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by inflation, calendering, or casting. Furthermore, the thermoplastic resin
composition according to the present embodiment can also be molded into a thermally
shrunk tube by performing a drawing operation thereon. The thermoplastic resin
composition according to the present embodiment can also be formed into molded
5 articles by rotational molding or blow molding.
[0293] Embodiment 2.
The molded article according to the present embodiment comprises the
thermoplastic resin composition described above. The molded article according to the
present embodiment comprising the thermoplastic resin composition provides an effect
10 of suppressing adhesion of both hydrophilic powdery dust fouling and hydrophobic
powdery dust fouling.
[0294] In the molded article according to the present embodiment, the concentration
(content in the thermoplastic resin composition) of the fatty acid metal salt (C) near the
surface of the molded article (in a portion ranging from the surface to a predetermined
15 depth) is preferably higher than that of the fatty acid metal salt (C) inside the molded
article (in a portion deeper than the predetermined depth from the surface).
Specifically, for example, the concentration of the fatty acid metal salt (C) in a portion
ranging from the surface of the molded article to a depth of 10 nm deeper from the
surface is preferably higher than that of the fatty acid metal salt (C) in a portion deeper
20 than the depth of 10 nm deeper from the surface.
[0295] The term "surface of the molded article" used here indicates at least part of the
surface of the molded article, and does not need to be the entire surface of the molded
article and may be part of the surface of the molded article.
[0296] Such a difference in the concentration of the fatty acid metal salt (C) in the
25 depth direction of the molded article can be verified, for example, by scraping the
surface of the molded article with Ar ions to depths and performing elemental analysis
of the metal element M (measurement of the area ratio of the metal element M) on the
surface of the molded article scraped to each of the depths by X-ray photoemission
spectroscopy (XPS) (see FIG. 2).
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[0297] For example, as shown in FIG. 1, the concentrations of the fatty acid metal salt
(C) (area ratios of the metal element M) at the respective depths are measured in a
portion located within 10 nm from the surface of the molded article (measurement
depth A) to determine the highest concentration among them. On the other hand, the
5 concentration of the fatty acid metal salt (C) is measured at a depth corresponding to a
half of the thickness L of the molded article (L/2: measurement depth B) shown by the
dotted line in FIG. 1. By comparing these measured values of the concentration, the
difference in the concentration of the fatty acid metal salt (C) in the depth direction of
the molded article can be verified.
10 [0298] For example, in the sample (test piece) of the molded article having an
amphoteric anti-contamination effect described later in Examples, the concentration of
the fatty acid metal salt (C) in the portion located within 10 nm from the surface was
two or more times the concentration of the fatty acid metal salt (C) in the portion
deeper than the portion located within 10 nm from the surface of the molded article.
15 In one specific example, the concentration of the fatty acid metal salt (C) in the portion
located within 10 nm from the surface was 3.2% by mass at the maximum, and the
concentration of the fatty acid metal salt (C) in the portion deeper than the portion
located within 10 nm from the surface of the molded article was about 0.3% by mass to
0.6% by mass. The former was about 5 to 10 times the latter.
20 [0299] In the fatty acid metal salt (C), R is a non-polar group and the residue is a polar
group. It is considered that during molding, the polar group adheres to the metal mold,
and thus the fatty acid metal salt (C) is aligned in the state where the non-polar group is
directed to the inside of the thermoplastic resin composition. Furthermore, after
molding, the fatty acid metal salt (C) melted inside the thermoplastic resin composition
25 migrates to the surfaces thereof.
[0300] Due to low miscibility with the thermoplastic resin, the fatty acid metal salt (C)
is diffused to the surface of the thermoplastic resin composition (molded article) if
compounded in an amount equal to or above critical solubility (concentration). It is
considered that near the surfaces of the thermoplastic resin composition, a plurality of
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fatty acid metal salts (C) are bonded with their polar groups, and are aligned such that
the hydrophobic groups Rs as the non-polar group are directed toward the outside (the
air side) of the molded article.
[0301] Accordingly, the concentration of the fatty acid metal salt (C) in the
5 thermoplastic resin composition near the surface of the molded article is higher than
that inside the molded article, thus efficiently reducing the surface energy and
providing a water and oil repellant effect on the surface of the molded article to which
powdery dust fouling adheres. As a result, unlike the cases where the fatty acid metal
salt (C) is used in standard applications such as a lubricant, a mold release agent, and
10 the like, a novel effect of suppressing adhesion of hydrophobic powdery dust fouling
on the surface of the molded article is obtained.
[0302] If a resin material after subjected to liquefaction once is molded into any shape
to mold a molded article, the above effect can be obtained by providing the component
proportion of the thermoplastic resin composition according to Embodiment 1 at the
15 stage of liquefaction. For example, at the stage where the resin material is liquefied,
the thermoplastic resin composition according to the present embodiment can also
contain optional components described in Embodiment 1.
[0303] Embodiment 3.
The product according to the present embodiment includes the molded article
20 described above. In other words, the molded article is used as resin parts (such as
inner parts and housings) for products such as home appliances and OA apparatuses,
for example. The product according to the present embodiment including the molded
article above provides effects of improving cleanliness and reducing the frequency of
maintenance.
25 [0304] Examples of the product include personal computers, laptop personal computers,
CRT displays, printers, mobile terminals, mobile phones, copiers, fax machines, drivers
for recording media (such as CDs, CD-ROMs, DVDs, PDs, and FDDs), parabola
antennas, electric tools, VTRs, television sets, irons, hair dryers, rice cookers,
microwave ovens, acoustic instruments, sound instruments (such as audio, laser disks
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(registered trademark), and compact disks), lighting apparatuses (LED), remote
controllers, vent fans, range hoods, refrigerators, air conditioners (such as air
conditioners, dehumidifiers, and humidifiers), air purifiers, cleaners, rice cookers,
cooking heaters, bath goods, lavatory goods, jet towels, electric fans, typewriters, word
5 processors, automobiles, apparatuses for automobiles (such as car navigators and car
stereo systems), and sundry goods.
[0305] For example, if the molded article is used in resin parts for air conditioners,
doors, display apparatuses, insulators, mirrors, measurement instruments, and
operational units of a variety of apparatuses, adhesion of powdery dust fouling can be
10 reduced to improve cleanliness and reduce the frequency of maintenance. In
particular, the molded article is useful as resin parts for products which cannot be
maintained for a long time by users or vendors.
[0306] The molded article according to the present embodiment comprising the
thermoplastic resin composition above can be used in products including resin parts,
15 and can be used in the applications above but also in broader applications.
[0307] Because the anti-contamination effect is simply obtained only by molding, the
molded article according to the present embodiment comprising the thermoplastic resin
composition above has an advantage over paintings and coatings having an anticontamination effect such that the number of complex steps such as movement of the
20 molded article and application work is significantly smaller. For this reason, the
molded article comprising the thermoplastic resin composition above is suitable for
mass production of products and has extremely high utility. Moreover, the molded
article comprising the thermoplastic resin composition above is suitable for mass
production of products and has extremely high utility because the molded article
25 comprising the thermoplastic resin composition above has an advantage over paintings
and coatings having an anti-contamination effect such that it is more readily used as an
outer member without caring about uneven coating of the surface, rainbow patterns,
and the gloss level.
[0308] FIG. 5 is a cross-sectional schematic view showing an air conditioner according
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to the present embodiment. As shown in FIG. 5, a body case 10 of the indoor
equipment of the air conditioner is formed in a shape horizontally long and
approximately cuboidal. An air suction port 11 is disposed on the top surface. An
air discharge port 12 is disposed in a lower portion of the front surface. A prefilter 17
5 is disposed from a side downstream of air suction port 11 to the front surface side of
body case 10. A front surface panel 14 is disposed to cover the front surface of body
case 10.
[0309] A fan 13 for discharging indoor air, which is suctioned from air suction port 11,
from air discharge port 12 is disposed inside body case 10. A heat exchanger 22 is
10 disposed upstream of fan 13, and a wind path 21 is present downstream of fan 13.
The air passes through wind path 21. A drain pan 18 is disposed under heat exchanger
22.
[0310] Although not illustrated, a fan motor which drives fan 13, a controller which
controls the operation of the air conditioner, and the like are disposed inside body case
15 10.
[0311] Vertical wind directing plates 15 and 16 adjust the discharge angle of the air
discharged from air discharge port 12 in the vertical direction. A horizontal wind
directing plate 19 adjusts the discharge angle of the air discharged from air discharge
port 12 in the vertical direction. A support shaft is disposed at one end of vertical
20 wind directing plates 15 and 16, and is supported by a bearing disposed on the side wall
of air discharge port 12 to be freely swung and attachable/detachable. There are three
cases for horizontal wind directing plate 19, i.e., it is fixed, the direction thereof can be
manually set, or it is driven by a motor to be automatically swung in the horizontal
direction.
25 [0312] After fan 13 is driven, the indoor air is suctioned from air suction port 11,
passes through prefilter 17, heat exchanger 22, fan 13, wind path 21, air discharge port
12, horizontal wind directing plate 19, and vertical wind directing plates 15 and 16 in
this order, and is discharged into the room. Together with the air, hydrophilic
powdery dust fouling such as dust and sand fiber and hydrophobic powdery dust

We Claim :
1. A thermoplastic resin composition comprising:
a thermoplastic resin (A) selected from the group consisting of an aromatic
5 polycarbonate resin (A1), a styrene-based resin (A2), an aromatic polyester resin (A3),
a polyphenylene ether resin (A4), a methacrylic resin (A5), a polyarylene sulfide resin
(A6), an olefin resin (A7), a polyamide resin (A8), and mixtures thereof;
a hydrophilic copolymer (B) having a polyoxyethylene chain; and
a fatty acid metal salt (C) represented by the following formula (1):
10 M(OH)y(R-COO)x ... (1)
wherein R is an alkyl group or alkenyl group having 6 to 40 carbon atoms; M is at least
one metal element selected from the group consisting of aluminum, zinc, calcium,
magnesium, lithium, and barium; and x and y each independently represent an integer
of 0 or more, and satisfy the relation represented by x + y = [valency of M].
15
2. The thermoplastic resin composition according to claim 1, comprising 100
parts by mass of the thermoplastic resin (A), 1 to 20 parts by mass of the hydrophilic
copolymer (B), and 0.5 to 10 parts by mass of the fatty acid metal salt (C).
20 3. The thermoplastic resin composition according to claim 1 or 2, wherein in
the formula (1), M is at least one metal element selected from aluminum and zinc.
4. The thermoplastic resin composition according to claim 3, wherein in the
formula (1), M is aluminum.
25
5. The thermoplastic resin composition according to any one of claims 1 to 4,
wherein in the formula (1), the valency of M is 3 or more, and y is 1.
6. The thermoplastic resin composition according to any one of claims 1 to 5,
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wherein the styrene-based resin (A2) is selected from the group consisting of PS resins,
HIPS resins, MS resins, ABS resins, AS resins, AES resins, ASA resins, MBS resins,
MABS resins, MAS resins, and mixtures thereof.
5 7. The thermoplastic resin composition according to any one of claims 1 to 6,
wherein the aromatic polyester resin (A3) is selected from the group consisting of
polybutylene terephthalate resins, polyethylene terephthalate resins, and mixtures
thereof.
10 8. The thermoplastic resin composition according to any one of claims 1 to 7,
wherein the hydrophilic copolymer (B) is a hydrophilic copolymer (B1) composed of a
polyolefin repeatedly and alternately bonded to a hydrophilic polymer having a
polyoxyethylene chain, or a polyether ester amide (B2).
15 9. A molded article comprising the thermoplastic resin composition according
to any one of claims 1 to 8.
10. The molded article according to claim 9, wherein the concentration of the
fatty acid metal salt (C) in a portion ranging from a surface of the molded article to a
20 predetermined depth is higher than the concentration of the fatty acid metal salt (C) in a
portion deeper than the predetermined depth.
11. A product comprising the molded article according to claim 9 or 10.