WO2023281602A1

WO2023281602A1 - Thermoplastic resin composition, molded article and product

Info

Publication number: WO2023281602A1
Application number: PCT/JP2021/025355
Authority: WO
Inventors: 怜司森岡
Original assignee: 三菱電機株式会社
Priority date: 2021-07-05
Filing date: 2021-07-05
Publication date: 2023-01-12
Also published as: JPWO2023281602A1

Abstract

A thermoplastic resin composition which contains: a thermoplastic resin (A) that is selected from the group consisting of an aromatic polycarbonate resin (A1), a styrene 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 of these resins; a hydrophilic copolymer (B) that has an oxyethylene group; and a fatty acid metal salt (C) that is represented by formula (1). With respect to this thermoplastic resin composition, the hydrophilic copolymer (B) is obtained by bonding a plurality of alternating copolymers (a) of a polyester (a1) and a hydrophilic polymer (a2) having an oxyethylene group to each other by the intermediary of an ester bond with at least one compound that is selected from the group consisting of a polyhydric alcohol compound (b1) having three or more hydroxyl groups, an epoxy compound (b2) having two or more epoxy groups, and a polycarboxylic acid compound (b3). (1): M(OH)y(R-COO)x (In formula (1), R represents an alkyl group having 6 to 40 carbon atoms or an alkenyl group; M represents at least one metal element that is selected from the group consisting of aluminum, zinc, calcium, magnesium, lithium and barium; and each of x and y independently represents an integer of 0 or more, while satisfying the relational expression (x + y) = (valence of M).)

Description

Thermoplastic resin compositions, moldings and products

The present disclosure relates to thermoplastic resin compositions, molded articles and products.

Thermoplastic resins are lighter than metals and easier to process. used below.

Depending on the environment and method of use, dust, dirt, soot, oil smoke, and other dust stains may adhere to these thermoplastic resin molded products. When dust stains adhere to the molded product, the appearance of the molded product becomes unsightly, and there is a possibility that the performance of the product may be deteriorated.

Therefore, in order to suppress the adhesion of dust stains, attempts have been made to impart antistatic performance to thermoplastic resin molded articles using antistatic agents.

For example, there is a known method of imparting antistatic performance to a molded product by spraying, immersing, or coating an antistatic agent onto the surface of the molded product. However, in the method of attaching an antistatic agent to the surface of a molded product, most of the antistatic agent is a water-soluble surfactant, and the antistatic agent is removed by wiping, washing, etc., and the antistatic effect is lost. There's a problem.

On the other hand, there is also known a method (kneading method) of imparting antistatic performance to a thermoplastic resin molded product by adding an antistatic agent as an additive to the thermoplastic resin. This kneading method has been attracting attention in recent years because of its long-lasting antistatic effect.

Various compounds are known as antistatic agents used in the kneading method. For example, Patent Document 1 (JP-A-2011-256293) discloses a fatty acid amide compound of aminoethylethanolamine. Patent Document 2 (JP-A-58-118838) and Patent Document 3 (JP-A-3-290464) disclose polyetheresteramides. Patent Document 4 (Japanese Patent Laid-Open No. 2001-278985), Patent Document 5 (International Publication No. 2014/115745) and Patent Document 6 (International Publication No. 2014/148454) disclose an olefin block and a hydrophilic polymer block In addition, Patent Documents 5 and 6 disclose a polyether ester polymer type antistatic agent.

Patent Document 1 discloses the combined use of an alkali metal compound, an alkaline earth metal compound (for example, calcium stearate), etc. in order to improve the antistatic effect of the fatty acid amide compound of aminoethylethanolamine. there is Further, in Patent Document 4, in order to improve the antistatic effect of a block copolymer consisting of an olefin block and a hydrophilic polymer block, an alkali metal compound such as lithium chloride, potassium acetate, and sodium dodecylbenzenesulfonate is used in combination. It is disclosed to Further, Patent Documents 5 and 6 disclose the blending of an alkali metal compound such as potassium acetate or sodium dodecylbenzenesulfonate with a polyether ester polymer type antistatic agent.

However, although all of the antistatic agents described above are effective in suppressing adhesion of hydrophilic dust stains such as dust and dirt to some extent, they are not effective in suppressing adhesion of hydrophobic dust stains such as soot and oily smoke. was largely unrecognized. Therefore, Patent Document 7 (International Publication No. 2021/006192) discloses a resin composition to which both hydrophilic dust stains and hydrophobic dust stains are less likely to adhere.

JP 2011-256293 A JP-A-58-118838 JP-A-3-290464 Japanese Unexamined Patent Application Publication No. 2001-278985 WO2014/115745 WO2014/148454 WO2021/006192

However, in the resin composition of Patent Document 7, B1 (olefin skeleton. Melting point: about 130 to 140 ° C.) and B2 (polyamide skeleton. Melting point: about 130 to 140 ° C.) specifically disclosed as a hydrophilic copolymer (B) having a polyoxyethylene chain : about 195-200°C) is not suitable for low-temperature processes because of its high melting point. In addition, processing may become difficult, or the time required for processing, kneading, etc. may become longer. In addition, it may cause decomposition of other materials.

Therefore, an object of the present disclosure is to use a material with a lower melting point than conventional materials to provide a resin composition to which both hydrophilic dust stains and hydrophobic dust stains are less likely to adhere.

As a result of investigation, the present inventors found that such a hydrophilic copolymer (B) is disclosed in International Publication No. 2021/006192 (Patent Document 7) "A hydrophilic polymer having a polyolefin and a polyoxyethylene chain. Even when using a hydrophilic copolymer having a lower melting point than the hydrophilic copolymer "(B1) and "polyether ester amide" (B2) in which is repeatedly and alternately bonded, hydrophilic dust stains and hydrophobic dust stains are used. and can provide a resin composition that is difficult to adhere to.

The thermoplastic resin composition of the present disclosure is
Aromatic polycarbonate resin (A1), styrene resin (A2), aromatic polyester resin (A3), polyphenylene ether resin (A4), methacrylic resin (A5), polyarylene sulfide resin (A6), olefin resin (A7 ), a polyamide resin (A8), and a thermoplastic resin (A) selected from the group consisting of mixtures thereof;
a hydrophilic copolymer (B) having an oxyethylene group;
and a fatty acid metal salt (C) represented by the following formula (1).

M(OH)y(R-COO)x (1)

(In formula (1), R is an alkyl group or alkenyl group having 6 to 40 carbon atoms. M is at least one metal selected from the group consisting of aluminum, zinc, calcium, magnesium, lithium and barium. is an element, x and y are each independent integers of 0 or more and satisfy the relationship x + y = [valence of M].)
The hydrophilic copolymer (B) is a polyhydric alcohol compound (b1 ), an epoxy compound (b2) having two or more epoxy groups, and at least one selected from the group consisting of a polycarboxylic acid compound (b3) via an ester bond.

According to the present disclosure, by blending the hydrophilic copolymer (B) and the fatty acid metal salt (C) with the thermoplastic resin (A), hydrophilicity to the molded article containing the thermoplastic resin composition Adhesion of both dust stains and hydrophobic dust stains can be suppressed. Therefore, by using a material having a lower melting point than conventional materials, it is possible to provide a resin composition to which both hydrophilic dust stains and hydrophobic dust stains are less likely to adhere.

FIG. 5 is a schematic cross-sectional view showing an example of a molded product according to Embodiment 2; 6 is a schematic graph showing composition distribution in the depth direction for an example of a molded article according to Embodiment 2. FIG. BRIEF DESCRIPTION OF THE DRAWINGS It is a conceptual diagram for demonstrating the thermoplastic resin composition which concerns on embodiment. BRIEF DESCRIPTION OF THE DRAWINGS It is a conceptual diagram for demonstrating the thermoplastic resin composition which concerns on embodiment. FIG. 10 is a schematic cross-sectional view showing an example of an air conditioner according to Embodiment 3; BRIEF DESCRIPTION OF THE DRAWINGS It is a conceptual diagram for demonstrating the thermoplastic resin composition which concerns on embodiment.

An embodiment of the present disclosure will be described below. In the drawings, dimensional relationships such as length, width, thickness, and depth are changed as appropriate for clarity and simplification of the drawings, and do not represent actual dimensional relationships.

Embodiment 1.
The thermoplastic resin composition of the present embodiment is
Aromatic polycarbonate resin (A1), styrene resin (A2), aromatic polyester resin (A3), polyphenylene ether resin (A4), methacrylic resin (A5), polyarylene sulfide resin (A6), olefin resin (A7 ), a polyamide resin (A8), and a thermoplastic resin (A) selected from the group consisting of mixtures thereof;
a hydrophilic copolymer (B) having an oxyethylene group;
and a fatty acid metal salt (C).

A molded article containing the thermoplastic resin composition of the present embodiment exhibits a remarkable antifouling effect that adhesion of both hydrophilic dust stains and hydrophobic dust stains is suppressed. This effect is exhibited by a thermoplastic resin composition containing all of the above components (A) to (C), and only component (A), only component (B), only component (C), and and (B) alone, components (A) and (C) alone, or components (B) and (C) alone, it is difficult to obtain such a remarkable antifouling effect.

Furthermore, as the hydrophilic copolymer (B), a plurality of alternating copolymers (a) of the polyester (a1), the hydrophilic polymer (a2) having an oxyethylene group, and (a) are repeatedly and alternately bonded, An ester bond with at least one selected from the group consisting of a polyhydric alcohol compound (b1) having 3 or more hydroxyl groups, an epoxy compound (b2) having 2 or more epoxy groups, and a polycarboxylic acid compound (b3). A hydrophilic copolymer formed by binding via is used.

As a result, a material with a lower melting point than conventionally used as the hydrophilic copolymer (B) can be used to suppress a resin composition to which both hydrophilic dust stains and hydrophobic dust stains are difficult to adhere.

A molded article containing the thermoplastic resin composition of the present embodiment can also have better mechanical strength such as impact resistance.

<Thermoplastic resin (A)>
The thermoplastic resin (A) includes aromatic polycarbonate resin (A1), styrene resin (A2), aromatic polyester resin (A3), polyphenylene ether resin (A4), methacrylic resin (A5), polyarylene sulfide resin ( A6), olefinic resins (A7), polyamide resins (A8), and mixtures thereof.

A mixture of the above, that is, aromatic polycarbonate resin (A1), styrene resin (A2), aromatic polyester resin (A3), polyphenylene ether resin (A4), methacrylic resin (A5), polyarylene sulfide resin (A6) , the olefin resin (A7), and the polyamide resin (A8) are not particularly limited, but for example, the aromatic polycarbonate resin (A1) and Styrene resin (A2), aromatic polycarbonate resin (A1) and aromatic polyester resin (A3), aromatic polycarbonate resin (A1) and olefin resin (A7), aromatic polycarbonate resin (A1) and methacrylic resin (A5 ), styrene resin (A2) and aromatic polyester resin (A3), styrene resin (A2) and methacrylic resin (A5), styrene resin (A2) and olefin resin (A7), styrene resin (A2) and polyamide resin (A8), polyphenylene ether resin (A4) and olefin resin (A7), methacrylic resin (A5) and olefin resin (A7), olefin resin (A7) and polyamide resin (A8), etc. can be mentioned.

The melting point of the thermoplastic resin (A) is, for example, 150-270°C, preferably 160-230°C.

(Aromatic polycarbonate resin (A1))
The aromatic polycarbonate resin (A1) is usually obtained by reacting a dihydroxy compound and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or by polymerizing a carbonate prepolymer by a solid phase transesterification method. or obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.

The dihydroxy component used here may be one that is usually used as a dihydroxy component for aromatic polycarbonates, and may be bisphenols or aliphatic diols.

Examples of bisphenols include 4,4′-dihydroxybiphenyl, bis(4-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-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-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 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′-diphenyl-4,4′-sulfonyldiphenol, 4,4′-dihydroxy-3, 3′-diphenyldiphenylsulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenylsulfide, 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, 4,4′-(1,3-adamantane diyl)diphenol 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane and the like.

Examples of aliphatic diols include 2,2-bis-(4-hydroxycyclohexyl)-propane, 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, 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-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-methylphenyl}fluorene, 1,1-bis{(2- hydroxyethoxy)phenyl}cyclohexane, 1,1-bis{(2-hydroxyethoxy)phenyl}cyclopentane, 4,4'-bis(2-hydroxyethoxy)diphenyl ether, 4,4'-bis(2- hydroxyethoxy)-3,3′-dimethyldiphenyl ether, 1,3-bis[2-{(2-hydroxyethoxy)phenyl}propyl]benzene, 1,4-bis[2-{(2-hydroxyethoxy)phenyl}propyl]benzene, 1,4-bis{(2-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), 1,4:3,6-dianhydro-L-iditol (isoidide) and the like.

Among these, aromatic bisphenols are preferred, and among them 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'-sulfonyl Diphenol, 2,2'-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 are preferred, especially 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl ) cyclohexane, 4,4′-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferred. Among them, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used alone or in combination of two or more.

The aromatic polycarbonate resin (A1) may be a branched polycarbonate resin obtained by using a branching agent in combination with the above dihydroxy compound.

Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucine, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2,2 ,4,6-trimethyl-2,4,6-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-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[ trisphenols such as 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, 4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, acid chlorides thereof, and the like. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris (4-Hydroxyphenyl)ethane is preferred.

These aromatic polycarbonate resins are produced by reaction means known per se for producing ordinary aromatic polycarbonate resins, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. Basic means of the manufacturing method will be briefly described.

For reactions using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine. Halogenated hydrocarbons such as methylene chloride and chlorobenzene are used as the solvent. A catalyst such as a tertiary amine or a quaternary ammonium salt may also be used to accelerate the reaction. At that time, the reaction temperature is usually 0 to 40° C., and the reaction time is several minutes to 5 hours.

The transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by stirring the aromatic dihydroxy component with the carbonic acid diester while heating in an inert gas atmosphere, and distilling off the alcohol or phenol that is produced. Although the reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, it is usually in the range of 120 to 300°C. The reaction is completed under reduced pressure from the initial stage while the alcohol or phenols produced are distilled off. Also, a catalyst commonly used for transesterification can be used to accelerate the reaction.

Examples of carbonic acid diesters used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among these, diphenyl carbonate is particularly preferred.

In the present disclosure, a terminal terminator can be used in the polymerization reaction. A terminal terminator is used for molecular weight control, and the obtained aromatic polycarbonate resin is end-capped, so that it has excellent thermal stability as compared to other resins. Monofunctional phenols represented by the following formulas (2) to (4) can be shown as such a terminal terminator.

[In the 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, or a phenylalkyl group (the alkyl moiety has 1 to 9) and r is an integer of 1 to 5 (preferably 1 to 3)].

[In formulas (3) and (4), X is -R-O-, -R-CO-O- or -R-O-CO-, where R is a single bond or (preferably 1-5) represents a divalent aliphatic hydrocarbon group, n represents an integer of 10-50. ]
Specific examples of monofunctional phenols represented by the formula (2) include phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenylphenol. , isooctylphenol and the like.

Further, the monofunctional phenols represented by the above formulas (3) to (4) are phenols having a long-chain alkyl group or an aliphatic ester group as a substituent. When these are used to block the ends of the aromatic polycarbonate resin, they not only function as a terminal terminating agent or a molecular weight modifier, but also improve the melt flowability of the resin and facilitate molding. These phenols are preferably used because they have the effect of lowering the water absorption rate of .

As the substituted phenols of the above formula (3), those having n of 10 to 30, particularly 10 to 26 are preferred, and specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol and octadecylphenol. , eicosylphenol, docosylphenol, triacontylphenol and the like.

As the substituted phenols of the above formula (4), compounds in which X is -R-CO-O- and R is a single bond are suitable, and n is 10 to 30, particularly 10 to 26. is preferred. Specific examples include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

Among these monofunctional phenols, monofunctional phenols represented by the above formula (2) are preferred, and alkyl-substituted or phenylalkyl-substituted phenols are more preferred, such as p-tert-butylphenol and p-cumylphenol. or 2-phenylphenol is particularly preferred.

These monofunctional phenolic terminal terminating agents are desirably introduced into at least 5 mol %, preferably at least 10 mol % of all terminals of the obtained aromatic polycarbonate resin. may be used alone or in combination of two or more.

The aromatic polycarbonate resin (A1) may be a polyester carbonate obtained by copolymerizing an aromatic dicarboxylic acid, such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or a derivative thereof, within the scope of the present disclosure.

The viscosity average molecular weight of the aromatic polycarbonate resin (A1) is not limited. However, if the viscosity-average molecular weight is less than 10,000, the strength, etc. will be reduced, and if it exceeds 50,000, the moldability will be reduced. A range of 15,000 to 28,000 is more preferred. In addition, the viscosity average molecular weight referred to in the present disclosure is obtained by first using an Ostwald viscometer from a solution in which 0.7 g of an aromatic polycarbonate resin is dissolved in 100 mL of methylene chloride at 20 ° C. to obtain the specific viscosity calculated by the following formula. The obtained specific viscosity is inserted into the following equation to obtain the viscosity average molecular weight Mv.

Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
η _SP /c=[η]+0.45×[η] ^2c (where [η] is the intrinsic viscosity)
[η]=1.23×10 ⁻⁴ Mv ^0.83
c=0.7
The aromatic polycarbonate resin (A1) preferably has a total chlorine content of 0 to 200 ppm, more preferably 0 to 150 ppm. If the total chlorine content in the aromatic polycarbonate resin exceeds 200 ppm, the hue and heat stability will deteriorate, which is not preferred.

(Styrene resin (A2))
Main components of the styrene-based resin (A2) of the present embodiment include, for example, polystyrene resin (PS), high-impact polystyrene resin (HIPS), alkyl (meth)acrylate monomer and aromatic vinyl monomer. (MS), a copolymer of a vinyl cyanide compound and an aromatic vinyl compound (AS), a copolymer of a vinyl cyanide compound containing a diene rubber component and an aromatic vinyl compound (ABS) , a copolymer of a vinyl cyanide compound and an aromatic vinyl compound containing an ethylene-α-olefin rubber component (AES), a copolymer of a vinyl cyanide compound and an aromatic vinyl compound containing an acrylic rubber component (ASA), A copolymer (MBS) of an alkyl (meth)acrylate monomer containing a diene rubber component and an aromatic vinyl compound, an alkyl (meth)acrylate monomer containing a diene rubber component, a vinyl cyanide compound, and an aromatic A copolymer with a vinyl compound (MABS), a copolymer of an alkyl (meth)acrylate monomer containing an acrylic rubber component and an aromatic vinyl compound (MAS), and the like can be mentioned.

The main component is the component with the largest mass, and the content of the main component in the styrene resin (A2) is preferably 90% by mass or more, more preferably 95% by mass or more.

The styrene-based resin (A2) may be a resin having high stereoregularity such as syndiotactic polystyrene obtained by using a catalyst such as a metallocene catalyst during its production. The styrene-based resin (A2) is a polymer, copolymer, or block copolymer with a narrow molecular weight distribution obtained by a method such as anionic living polymerization or radical living polymerization, and a polymer with high stereoregularity. and copolymers.

A polystyrene resin (PS) is a polymer obtained by polymerizing at least one aromatic vinyl compound by a polymerization method such as solution polymerization, bulk polymerization, suspension polymerization, or bulk-suspension polymerization. Preferred aromatic vinyl compounds include, for example, styrene, alkylstyrenes such as α-methylstyrene, methylstyrene, ethylstyrene, isopropylstyrene, tert-butylstyrene, phenylstyrene, vinylstyrene, chlorostyrene, bromostyrene, fluorostyrene, chloromethylstyrene, methoxystyrene, ethoxystyrene and the like. These can be used alone or in combination of two or more. Particularly preferred aromatic vinyl compounds among these are styrene, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, p-chlorostyrene, m-chlorostyrene and p-fluorostyrene, especially styrene. preferable.

The molecular weight of the polystyrene resin (PS) is not particularly limited, but the weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) at 135° C. using trichlorobenzene as a solvent is preferably 100, 000 or more, more preferably 150,000 or more. The width of the molecular weight distribution is not limited.

A high-impact polystyrene resin (HIPS) is a polymer in which a rubber-like polymer made of butadiene rubber or the like is dispersed in the form of particles in a matrix made of an aromatic vinyl polymer such as PS. HIPS can be obtained, for example, by dissolving a rubber-like polymer in a mixture of an aromatic vinyl monomer and an inert solvent, stirring the mixture, and performing bulk polymerization, suspension polymerization, solution polymerization, or the like. HIPS is, for example, a mixture obtained by mixing a polymer obtained by dissolving a rubber-like polymer in a mixture of an aromatic vinyl monomer and an inert solvent, and an aromatic vinyl polymer obtained separately. There may be.

In HIPS, the matrix portion composed of the aromatic vinyl polymer is not particularly limited, but using trichlorobenzene as a solvent at 135° C., the mass average molecular weight in terms of polystyrene as measured by GPC (gel permeation chromatography) is It is preferably 100,000 or more, more preferably 150,000 or more. Also, the average particle size of the rubber-like polymer is not particularly limited, but generally 0.4 to 6.0 μm is appropriate.

As the above aromatic vinyl monomer, styrene and its derivatives (eg, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, etc.) can be used, but styrene is the most preferred. preferred. Two or more of these monomers may be used in combination.

Polybutadiene, polyisoprene, styrene-butadiene copolymer, and the like can be used as the above rubber-like polymer. Examples of polybutadiene include high-cis polybutadiene having a high cis-bond content and low-cis polybutadiene having a low cis-bond content.

Among these, polybutadiene containing 70% by mass or more of high-cis polybutadiene rubber having 90 mol% or more of cis-1,4 bonds in 100% by mass of the rubber-like polymer is preferably used.

Specifically, a rubber-modified styrene resin obtained by using high-cis polybutadiene rubber alone, a rubber-modified styrene resin obtained by using a mixture of high-cis polybutadiene rubber and low-cis polybutadiene rubber, or high-cis polybutadiene rubber. 100 mass of the rubber-like polymer present in the rubber-modified styrenic resin in both the rubber-modified styrenic resin obtained using %, the high-cis polybutadiene rubber is preferably contained in an amount of 70% by mass or more. Here, the high-cis polybutadiene rubber means, for example, a polybutadiene rubber containing 90 mol % or more of cis-1,4 bonds. Low-cis polybutadiene rubber means, for example, polybutadiene rubber having a 1,4-cis bond content of 10 to 40 mol %.

In the copolymer (MS) of the alkyl (meth)acrylate monomer and the aromatic vinyl monomer, the alkyl (meth)acrylate monomer is selected from, for example, methyl (meth)acrylate and phenyl (meth)acrylate is at least one monomer that is In particular, it is preferable to use methyl (meth)acrylate. In addition, the notation of "(meth)acrylate" means including both methacrylate and acrylate.

Examples of aromatic vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, and the like. can be used, and styrene is particularly preferred. These can be used alone or in combination of two or more.

The mass average molecular weight of MS and the composition ratio of methyl (meth) acrylate/styrene are not particularly limited, but the mass average molecular weight is preferably 80,000 to 300,000, more preferably 100,000 to 200,000, and methyl (meth) acrylate. /styrene composition ratio is preferably 80/20 to 40/60, more preferably 70/30 to 50/50.

In the copolymer (AS) of a vinyl cyanide compound and an aromatic vinyl compound, acrylonitrile can be preferably used as the vinyl cyanide compound. Styrene and α-methylstyrene are preferably used as the aromatic vinyl compound.

As for the ratio of each component in AS, when the whole is 100% by mass, the ratio of the vinyl cyanide compound is preferably 5 to 50% by mass, more preferably 15 to 35% by mass, and the aromatic vinyl compound is preferably 95 to 50 mass %, more preferably 85 to 65 mass %.

Further, these vinyl compounds may be mixed with other copolymerizable vinyl compounds. In this case, the content of other vinyl compounds is preferably 15% by mass or less in AS.

The AS may be produced by any method such as bulk polymerization, suspension polymerization, or emulsion polymerization, but is preferably produced by bulk polymerization. Further, the method of copolymerization may be either one-step copolymerization or multi-step copolymerization.

The reduced viscosity of AS is preferably 0.2-1.0 dL/g (20-100 mL/g), more preferably 0.3-0.5 dL/g (30-50 mL/g). If the reduced viscosity is less than 0.2 dL/g (20 mL/g), the impact will be reduced, and if it exceeds 1.0 dL/g (100 mL/g), the workability will be poor.

The reduced viscosity was obtained by precisely weighing 0.25 g of a copolymer (AS) obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound and dissolving it in 50 mL of dimethylformamide over 2 hours. was measured in an environment of 30°C using A viscometer with a solvent flowing time of 20 to 100 seconds is used. The reduced viscosity is obtained by the following equation from the number of seconds (t ₀ ) of the solvent flowing down and the number of seconds (t) of the solution flowing down.

Reduced viscosity (η _sp /C) = {(t/t ₀ )-1}/0.5
In addition, a copolymer of a vinyl cyanide compound and an aromatic vinyl compound containing a diene rubber component (ABS), a copolymer of a vinyl cyanide compound and an aromatic vinyl compound containing an ethylene-α-olefin rubber component (AES ), a copolymer of a vinyl cyanide compound and an aromatic vinyl compound containing an acrylic rubber component (ASA), a copolymer of an alkyl (meth)acrylate monomer containing a diene rubber component and an aromatic vinyl compound ( MBS), a copolymer of an alkyl (meth)acrylate monomer containing a diene rubber component, a vinyl cyanide compound and an aromatic vinyl compound (MABS), and an alkyl (meth)acrylate monomer containing an acrylic rubber component Copolymers of solids and aromatic vinyl compounds (MAS) are thermoplastic copolymers.

In the present embodiment, the ratio of various rubber components contained in ABS, AES, ASA, MBS, MABS and MAS is preferably 5 to 80% by mass, more preferably 8 to 50% by mass, and particularly preferably 10 to 50% by mass. 30% by mass.

Acrylonitrile is particularly preferably used as the vinyl cyanide compound grafted onto the rubber component. Styrene and α-methylstyrene are particularly preferred as the aromatic vinyl compound to be grafted onto the rubber component.

Furthermore, methyl (meth)acrylate and ethyl (meth)acrylate can be preferably used as alkyl (meth)acrylate monomers.

The ratio of the component grafted to the rubber component is preferably 20-95% by mass, more preferably 50-90% by mass, relative to 100% by mass of the styrene resin (A2). Furthermore, maleic anhydride, N-substituted maleimide, etc. can be mixed and used for some of the components grafted to the rubber component, and the content of these components is 15% by mass or less in the styrene resin (A2). is preferred.

The rubber component exists in the form of particles in ABS, AES, ASA, MBS, MABS and MAS. The particle size of the rubber component is preferably 0.1-5.0 μm, more preferably 0.15-1.5 μm, and particularly preferably 0.2-0.8 μm. Here, the particle size distribution of the rubber component may be a single distribution, or may have two or more peaks. Further, in terms of the morphology of the particle size of the rubber component, the rubber particles may form a single phase, or may have a salami structure by containing an occluded phase around the rubber particles.

ABS, AES, ASA, MBS, MABS and MAS may contain free polymer components (aromatic vinyl compounds, etc.) generated during polymerization.

The reduced viscosity of ABS, AES, ASA, MBS, MABS and MAS (reduced viscosity at 30° C. determined by the method described above) 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).

In addition, the ratio of the aromatic vinyl compound or the like grafted to the rubber component (graft ratio) is preferably 20 to 200% by mass, more preferably 20 to 70% by mass, relative to the rubber component.

ABS, AES, ASA, MBS, MABS and MAS may be produced by any of bulk polymerization, suspension polymerization and emulsion polymerization. In particular, ABS is preferably produced by bulk polymerization. Typical bulk polymerization methods include, for example, a continuous bulk polymerization method (so-called Toray method) described in Kagaku Kogaku, Vol. 48, No. 6, p. 415 (1984); 1989) (so-called Mitsui Toatsu method).

In the present embodiment, ABS, AES, ASA, MBS, MABS and MAS can all be suitably used as the styrenic resin (A2). Also, the copolymerization may be carried out in one step or in multiple steps. Further, the ABS, AES, ASA, MBS, MABS and MAS obtained by such a production method are blended with a vinyl compound polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide component. A resin can also be preferably used as the styrene resin (A2).

For AS, ABS, AES, ASA, MBS, MABS and MAS, it is preferable that the content of alkali (earth) metals is low from the viewpoint of good thermal stability and hydrolysis resistance. The alkali (earth) metal content in the styrenic resin (A2) is preferably less than 100 ppm, more preferably less than 80 ppm, even more preferably less than 50 ppm, particularly preferably less than 10 ppm. Thus, the bulk polymerization method is preferably used also from the viewpoint of reducing the content of alkali (earth) metals.

In relation to such good thermal stability and hydrolysis resistance, when an emulsifier is used in AS, ABS, etc., the emulsifier is preferably a sulfonate, more preferably an alkylsulfonate. Also, when a coagulant is used, the coagulant is preferably sulfuric acid or an alkaline earth metal salt of sulfuric acid.

Rubber components contained in ABS, AES, ASA, MBS, MABS and MAS include polybutadiene, polyisoprene, diene copolymers, copolymers of ethylene and α-olefins, and mixtures of ethylene and unsaturated carboxylic acid esters. copolymers, copolymers of ethylene and aliphatic vinyl (eg, ethylene-vinyl acetate copolymers), non-conjugated diene terpolymers of ethylene and propylene, acrylic rubbers, silicone rubbers, and the like.

Examples of diene-based copolymers include random copolymers and block copolymers of styrene-butadiene, acrylonitrile-butadiene copolymers, and copolymers of (meth)acrylic acid alkyl esters and butadiene.

Copolymers of ethylene and α-olefins include, for example, ethylene-propylene random copolymers and block copolymers, ethylene-butene random copolymers and block copolymers, and the like.

Examples of copolymers of ethylene and unsaturated carboxylic acid esters include ethylene-methacrylate copolymers and ethylene-butyl acrylate copolymers.

Examples of non-conjugated diene terpolymers of ethylene and propylene include ethylene-propylene-hexadiene copolymers.

Examples of acrylic rubbers include polybutyl acrylate, poly(2-ethylhexyl acrylate), copolymers of butyl acrylate and 2-ethylhexyl acrylate, and the like.

Examples of silicone-based rubbers include polyorganosiloxane rubber, and IPN rubber composed of a polyorganosiloxane rubber component and a polyalkyl (meth)acrylate rubber component (that is, a structure in which the two rubber components are intertwined so that they cannot be separated). rubber), IPN type rubber consisting of a polyorganosiloxane rubber component and a polyisobutylene rubber component, and the like.

The rubber component is preferably selected from the group consisting of polydiene rubber (such as polybutadiene), acrylic rubber, and ethylene-propylene rubber. The glass transition temperature of the rubber component, for example, is typically −10° C. to −20° C. for acrylic rubber, −50° C. to −58° C. for ethylene-propylene rubber, and about -100°C.

The rubber component content in ABS, AES, ASA, MBS, MABS and MAS used in the present embodiment is preferably 4% by mass to 25% by mass. The content of the rubber component can be adjusted, for example, by adjusting the amount of the rubber component during copolymerization. Further, for example, by mixing an aromatic vinyl copolymer containing a rubber component and an aromatic vinyl polymer or copolymer not containing a rubber component, it is also possible to adjust the content of the rubber component. be.

(Aromatic polyester resin (A3))
The aromatic polyester resin (A3) is a polymer or copolymer obtained by a condensation reaction of aromatic dicarboxylic acid or its reactive derivative and diol or its ester derivative as main components.

The aromatic dicarboxylic acids referred to herein include, for example, 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'-biphenylisopropylidenedicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4 aromatic dicarboxylic acids such as '-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4'-p-terphenylenedicarboxylic acid, and 2,5-pyridinedicarboxylic acid; be done. Also included are diphenylmethane dicarboxylic acid, diphenyl ether dicarboxylic acid, and β-hydroxyethoxybenzoic acid. In particular, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferably used. Aromatic dicarboxylic acids may be used in combination of two or more. If the amount is small, it is also possible to mix and use one or more kinds of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanedioic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid together with the dicarboxylic acid. .

Examples of diols include 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. and the like.

and alicyclic diols such as 1,4-cyclohexanedimethanol. Also included are diols containing aromatic rings such as 2,2-bis(β-hydroxyethoxyphenyl)propane, and mixtures thereof. Furthermore, if the amount is small, one or more long-chain diols having a molecular weight of 400 to 6000, ie, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. may be copolymerized.

Also, the aromatic polyester resin (A3) can be branched by introducing a small amount of a branching agent. Although the type of branching agent is not limited, it includes trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane, pentaerythritol and the like.

As the aromatic polyester resin (A3), polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1 , 2-bis(phenoxy)ethane-4,4′-dicarboxylate and the like. Copolymer polyester resins such as polyethylene isophthalate/terephthalate and polybutylene terephthalate/isophthalate are also included. Among these, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and mixtures thereof, which have well-balanced mechanical properties, can be preferably used.

In addition, the terminal group structure of the aromatic polyester resin (A3) is not particularly limited, and the ratio of the hydroxyl group and the carboxyl group in the terminal group may be approximately the same amount, or the ratio of one may be greater. . Moreover, the terminal groups may be blocked by, for example, reacting a compound having reactivity with such terminal groups.

The method for producing the alkylene glycol ester of aromatic dicarboxylic acid and/or its low polymer is not limited, but usually aromatic dicarboxylic acid or its ester-forming derivative and alkylene glycol or its ester It is produced by reacting a forming derivative with heat. For example, an ethylene glycol ester of terephthalic acid and/or a low polymer thereof used as a raw material for polyethylene terephthalate is obtained by direct esterification reaction of terephthalic acid and ethylene glycol, or by a lower alkyl ester of terephthalic acid and ethylene glycol. or by addition reaction of ethylene oxide to terephthalic acid.

In addition, the alkylene glycol ester of the aromatic dicarboxylic acid and / or the low polymer thereof, other dicarboxylic acid ester copolymerizable therewith, as an additional component, the effect of the method of the present disclosure is substantially It may be contained in an amount within a range that does not cause damage. Specifically, other dicarboxylic acid esters may be contained in an amount within the range of 10 mol % or less, preferably 5 mol % or less based on the total molar amount of acid components.

The copolymerizable additional component is selected from an ester of an acid component and a glycol component, or an anhydride thereof. Acid components include aliphatic and alicyclic dicarboxylic acids such as adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, and hydroxycarboxylic acids such as β-hydroxyethoxybenzoic acid and p-oxybenzoic acid. etc. 1 type or more are mentioned.

Examples of glycol components include aliphatic, alicyclic and aromatic diol compounds such as alkylene glycol having 2 or more carbon atoms, 1,4-cyclohexanedimethanol, neopentyl glycol, bisphenol A and bisphenol S, and Polyoxyalkylene glycols may be mentioned. The postscript component ester may be used alone, or two or more thereof may be used in combination. However, the copolymerization amount is preferably within the above range.

When terephthalic acid and/or dimethyl terephthalate is used as a starting material, recovered dimethyl terephthalate obtained by depolymerizing polyalkylene terephthalate or recovered terephthalic acid obtained by hydrolyzing it is used. , 70 mass % or more can also be used based on the mass of all acid components constituting the polyester. In this case, the target polyalkylene terephthalate is preferably polyethylene terephthalate, particularly recovered PET bottles, recovered fiber products, recovered polyester film products, and polymer scraps generated in the manufacturing process of these products. is preferable from the viewpoint of effective utilization of resources.

Here, the method for depolymerizing the recovered polyalkylene terephthalate to obtain dimethyl terephthalate is not particularly limited, and any conventionally known method can be employed. For example, after depolymerizing the recovered polyalkylene terephthalate with ethylene glycol, the depolymerized product is subjected to a transesterification reaction with a lower alcohol, such as methanol, and the reaction mixture is purified to recover lower alkyl esters of terephthalic acid. A polyester resin can be obtained by subjecting this to transesterification with alkylene glycol and polycondensing the obtained phthalic acid/alkylene glycol ester.

Also, the method for recovering terephthalic acid from the recovered dimethyl terephthalate is not particularly limited, and any conventional method may be used. For example, after recovering dimethyl terephthalate from the reaction mixture obtained by the transesterification reaction by recrystallization and/or distillation, it can be hydrolyzed by heating with water under high temperature and high pressure to recover terephthalic acid. . Among the impurities contained in the terephthalic acid obtained by this method, the total content of 4-carboxybenzaldehyde, p-toluic acid, benzoic acid and dimethyl hydroxyterephthalate is preferably 1 ppm or less. Also, the content of monomethyl terephthalate is preferably in the range of 1 to 5000 ppm.

A polyester resin can be produced by subjecting terephthalic acid recovered by the above-described method to direct esterification reaction with alkylene glycol and polycondensing the resulting ester.

There are no particular restrictions on the production reaction conditions for the aromatic polyester resin (A3). In general, the polycondensation reaction is preferably carried out at a temperature of 230 to 320° C. under normal pressure, under reduced pressure (0.1 Pa to 0.1 MPa), or a combination of these conditions for 15 to 300 minutes. .

In the aromatic polyester resin (A3), if necessary, a reaction stabilizer such as trimethyl phosphate may be added to the reaction system at any stage in polyester production. Furthermore, if necessary, one or more of antioxidants, ultraviolet absorbers, flame retardants, fluorescent whitening agents, matting agents, color conditioning agents, antifoaming agents, and other additives may be added to the reaction system. In particular, the polyester resin preferably contains an antioxidant containing at least one hindered phenol compound. The content thereof is preferably 1% by mass or less with respect to the mass of the polyester resin. If the content exceeds 1% by mass, the heat deterioration of the antioxidant itself may cause the inconvenience of deteriorating the quality of the obtained product.

Hindered phenol compounds include, for example, pentaerythritol-tetraextract [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3- tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane and the like. It is also preferable to use these hindered phenol-based antioxidants and thioether-based secondary antioxidants in combination.

The method of adding the hindered phenolic antioxidant to the polyester resin is not particularly limited, but preferably at any stage after the completion of the transesterification reaction or the esterification reaction until the completion of the polymerization reaction. added.

Although there are no restrictions on the intrinsic viscosity of the aromatic polyester resin (A3), it is preferably in the range of 0.30 to 1.5. When the intrinsic viscosity is within this range, melt molding is easy and the strength of the molding obtained therefrom is high. A more preferable range of the intrinsic viscosity is 0.40 to 1.2, and particularly preferably 0.50 to 1.0. The intrinsic viscosity of the aromatic polyester resin is measured by dissolving the aromatic polyester resin in orthochlorophenol and measuring at a temperature of 35°C. Polyester resins obtained by solid-phase polycondensation are generally used for bottles and the like in many cases, and often have an intrinsic viscosity of 0.70 to 0.90.

It is preferable that the content of the cyclic trimer of the ester of the aromatic dicarboxylic acid and alkylene glycol is 0.5% by mass or less and the content of acetaldehyde is 5 ppm or less.

The cyclic trimer includes alkylene terephthalate (e.g., ethylene terephthalate, trimethylene terephthalate, tetramethylene terephthalate, hexamethylene terephthalate, etc.) and alkylene naphthalate (e.g., ethylene naphthalate, trimethylene naphthalate, tetramethylene naphthalate). , hexamethylene naphthalate, etc.).

(Polyphenylene ether resin (A4))
The polyphenylene ether-based resin (A4) may be a mixed resin in which a polystyrene-based resin is mixed in advance with a polyphenylene ether resin, or may consist of a polyphenylene ether resin alone.

Examples of polyphenylene ether resins include homopolymers having a repeating unit structure represented by the following formula (5) and copolymers having a repeating unit structure represented by the following formula (5).

In the above formula (5), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, a selected from the group consisting of secondary alkyl groups, phenyl groups, haloalkyl groups, aminoalkyl groups, hydrocarbonoxy groups, and halohydrocarbonoxy groups in which at least two carbon atoms separate the halogen and oxygen atoms; is a monovalent group that

From the viewpoint of fluidity, toughness and chemical resistance during processing, the above polyphenylene ether resin uses a chloroform solution with a concentration of 0.5 g / dL at 30 ° C. The reduced viscosity was measured with an Ubbelohde viscosity tube. is preferably 0.15 to 2.0 dL/g, more preferably 0.20 to 1.0 dL/g, still more preferably 0.30 to 0.70 dL/g.

Examples of the polyphenylene ether resin include, but are not limited to, poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), homopolymers such as poly(2,6-dichloro-1,4-phenylene ether), 2,6-dimethylphenol and others and copolymers with phenols (eg, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol). Among them, poly(2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and Copolymers with 2,3,6-trimethylphenol are preferred, and poly(2,6-dimethyl-1,4-phenylene ether) is more preferred.

A polyphenylene ether resin can be produced by a known method. The method for producing the polyphenylene ether resin is not limited to the following, but for example, using a cuprous salt and amine complex by Hay described in US Pat. No. 3,306,874 as a catalyst, 2,6- A method of oxidative polymerization of xylenol, US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. Examples include the method described in Japanese Patent Application Laid-Open No. 63-152628.

Examples of polystyrene-based resins that are preliminarily contained in the polyphenylene ether-based resin (A4) include atactic polystyrene, rubber-reinforced polystyrene (high-impact polystyrene, HIPS), and styrene-acrylonitrile copolymers having a styrene content of 50% by mass or more ( AS), ABS resin in which the styrene-acrylonitrile copolymer is reinforced with rubber, etc., and atactic polystyrene and/or high impact polystyrene are preferred.

The above polystyrene-based resins may be used singly or in combination of two or more.

The polyphenylene ether-based resin (A4) is composed of a polyphenylene ether resin and a polystyrene-based resin, and the mass ratio of the polyphenylene ether resin and the polystyrene-based resin is 97/3 to 5/95. Polyphenylene ether-based resin (A4) is preferably used. The mass ratio of the polyphenylene ether resin and the polystyrene resin is more preferably 90/10 to 10/90, more preferably 80/20 to 10/90, from the viewpoint of better fluidity.

(Methacrylic resin (A5))
The methacrylic resin (A5) used in the present disclosure is substantially a copolymer of alkyl methacrylate and alkyl acrylate, and other aromatic vinyl monomer-free, as long as the object of the present disclosure is not impaired. Vinyl monomers can be copolymerized.

The methacrylic resin contains, for example, 30 to 100% by mass of alkyl methacrylate, 0 to 70% by mass of acrylic acid ester, and 0 other vinyl monomers that do not contain copolymerizable aromatic vinyl monomers. It is a polymer obtained by polymerization of monomers containing up to 49% by mass. Further, when the methacrylic resin is a copolymer of alkyl methacrylate and alkyl acrylate, the mass ratio of alkyl methacrylate and alkyl acrylate is based on the total 100 mass% of alkyl methacrylate and alkyl acrylate. As, the alkyl methacrylate is preferably 40 to 90% by mass, more preferably 10 to 60% by mass, and the alkyl methacrylate is preferably 50 to 85% by mass, more preferably 50 to 15% by mass. %.

The alkyl methacrylate may have an alkyl group having about 1 to 8 carbon atoms, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, and the like. Among them, methyl methacrylate is preferred. Two or more of these alkyl methacrylates may be used as necessary.

The alkyl acrylate may have an alkyl group with about 1 to 8 carbon atoms, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and the like. Among them, methyl acrylate and n-butyl acrylate are preferred. If necessary, two or more of these alkyl acrylates may be used. In that case, n-butyl acrylate is used as the main component, and one or more alkyl acrylates other than n-butyl acrylate are used. More preferably, n-butyl acrylate and methyl acrylate are used, and n-butyl acrylate is the main component. Here, n-butyl acrylate is the main component means that the mass ratio of n-butyl acrylate exceeds 50% by mass based on the total 100% by mass of two or more alkyl acrylates. .

Alkyl methacrylates, alkyl acrylates, and other monomers that do not contain aromatic vinyl monomers are, for example, monofunctional monomers, i.e., have one polymerizable carbon-carbon double bond in the molecule. It may be a compound or a polyfunctional monomer, ie, a compound having at least two polymerizable carbon-carbon double bonds in the molecule.

Examples of this monofunctional monomer include alkenyl cyanides such as acrylonitrile and methacrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide.

Examples of polyfunctional monomers include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, and trimethylolpropane triacrylate, allyl acrylate, allyl methacrylate, and cinnamon. Examples include alkenyl esters of unsaturated carboxylic acids such as allyl acid, and polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate and triallyl isocyanurate. Two or more of these monomers other than alkyl methacrylate, alkyl acrylate, and aromatic vinyl may be used, if necessary.

One type of methacrylic resin may be used, or two or more types may be used. The two or more types of methacrylic resins may differ in the type of the monomers constituting the methacrylic resin, or the types of the monomers may be the same, but the mass ratio of each monomer may be different. may be

The method of polymerizing the methacrylic resin is not particularly limited, and ordinary bulk polymerization, suspension polymerization, emulsion polymerization, and the like can be used.

In addition, a so-called high-impact methacrylic resin in which rubber particles are preliminarily compounded can also be used as the methacrylic resin. Generally, these high-impact methacrylic resins contain 5 to 40% by mass of rubber component.

The rubber component to be blended is not particularly limited, but is preferably one having a refractive index close to that of methacrylic resin, such as a diene-based graft copolymer containing butadiene or the like as a main component, or an acrylic ester/methacrylic ester. Examples include a rubber-like polymer having a core-shell type graft structure and a rubber-like polymer grafted to an enlarged particle.

The MFR value (230°C, 3.8 kg load) of the methacrylic resin (B) is preferably 5 to 25 g/10 minutes, more preferably 10 to 20 g/10 minutes.

(Polyarylene sulfide resin (A6))
The polyarylene sulfide resin (A6) has a resin structure in which a repeating unit is a structure in which arylene and sulfur atoms are bonded. A polyarylene sulfide resin contains a repeating unit represented by the following formula (6).

In the above formula (6), Ar is substituted or unsubstituted arylene.
Examples of the arylene include, but are not particularly limited to, phenylene, naphthylene, biphenylene, terphenylene, and the like.

When Ar has a substituent, the substituent is not particularly limited, but 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 group groups; alkoxy groups such as methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutyloxy group, sec-butyloxy group and tert-butyloxy group; nitro group; amino group; cyano group and the like.

The above Ar may have a single substituent or may have two or more substituents. When it has two or more substituents, the substituents may be the same or different.

Among the polyarylene sulfide resins described above, polyphenylene sulfide resins (PPS resins) in which Ar is substituted or unsubstituted phenylene are preferred. The PPS resin contains at least one repeating unit represented by the following formulas (7) and (8).

In the above formulas (7) and (8), each R is independently an alkyl group 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 group. groups; alkoxy groups such as methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutyloxy group, sec-butyloxy group and tert-butyloxy group; nitro group; amino group; cyano group and the like.

Also, n is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0. Mechanical strength can become it high that n is 0.

Among the above, the PPS resin preferably contains a repeating unit represented by formula (7) from the viewpoint of heat resistance, crystallinity, and the like.

In addition, the PPS resin may contain a trifunctional structural unit represented by the following formula (9).

In formula (9) above, R is the same as in formulas (7) and (8) above.
Also, m is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

In addition, when the trifunctional structural unit represented by the above formula (9) is included, the content in the PPS resin is 0.001 to 3 mol% with respect to the total number of moles of all structural units. is preferred, and 0.01 to 1 mol % is more preferred.

Furthermore, the PPS resin may contain structural units represented by the following formulas (10) to (14).

In formulas (10) to (14) above, R and n are the same as in formula (7) above. Also, p is an integer of 0 to 6, preferably an integer of 0 to 3, more preferably 0 or 1, and still more preferably 0.

When structural units represented by the above formulas (10) to (14) are included, the content in the PPS resin is 10 mol% or less with respect to all structural units from the viewpoint of mechanical strength. It is preferably 5 mol % or less, more preferably 3 mol % or less. At this time, when two or more structural units represented by the above formulas (10) to (14) are included, the total content is preferably the above content.

The polyarylene sulfide resins described above may be used alone or in combination of two or more.

The polyarylene sulfide resin may be linear or branched. In one embodiment, the branched type can be obtained by heating a linear type PAS resin in the presence of oxygen.

The weight average molecular weight of the polyarylene sulfide resin is preferably 25,000 to 80,000, more preferably 25,000 to 50,000. A weight-average molecular weight of 25,000 or more is preferable because the strength of the material can be maintained. On the other hand, a weight average molecular weight of 80,000 or less is preferable from the viewpoint of moldability.

In addition, in this specification, the value of "weight average molecular weight" shall adopt the value measured by the gel permeation chromatography method. Under the present circumstances, the measurement conditions of the said gel permeation chromatography are as follows. That is, using a high-speed GPC HLC-8220 (manufactured by Tosoh Corporation) and a column (TSK-GELGMHX L x 2), 200 mL of a solution of 5 mg of a sample dissolved in 10 g of tetrahydrofuran (THF) was injected into the apparatus, and the flow rate was : 1 mL/min (THF), constant temperature bath temperature: 40°C, measured with a differential refraction (RI) detector.

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, and even more preferably 60 to 200 Pa·s. A melt viscosity of 2 Pa·s or more is preferable because the strength of the material can be maintained. On the other hand, a melt viscosity of 1000 Pa·s or less is preferable from the viewpoint of moldability.

The non-Newtonian index of the polyarylene sulfide resin is preferably 0.90 to 2.00, more preferably 0.90 to 1.50, even more preferably 0.95 to 1.20. . A non-Newtonian exponent of 0.90 or more is preferable because the strength of the material can be maintained. On the other hand, a non-Newtonian index of 2.00 or less is preferable from the viewpoint of moldability.

The method for producing the polyarylene sulfide resin described above can be produced by a known method. For example, (1) a method of polymerizing a dihalogenoaromatic compound in the presence of sulfur and sodium carbonate, if necessary, by adding a polyhalogenoaromatic compound or other copolymerization components, and (2) a sulfidating agent in a polar solvent. (3) adding p-chlorothiophenol and, if necessary, other copolymerization components. is added to cause self-condensation.

Among these methods, method (2) is versatile and preferable. During the reaction, an alkali metal salt of a carboxylic acid or a sulfonic acid, or an alkali hydroxide may be added in order to adjust the degree of polymerization.

Among the methods of (2) above,
(a) introducing a hydrous sulfidating agent into a heated mixture containing an organic polar solvent and a dihalogenoaromatic compound at a rate such that water can be removed from the reaction mixture, and is optionally added with a polyhalogenoaromatic compound for reaction, and by controlling the amount of water in the reaction system within the range of 0.02 to 0.5 mol per 1 mol of the organic polar solvent. , a method for producing a PAS resin (see JP-A-07-228699), or
(b) a solid alkali metal sulfide and, in the presence of an aprotic polar organic solvent, a dihalogenoaromatic compound and, if necessary, a polyhalogenoaromatic compound or other copolymerization components are added to form an alkali metal hydrosulfide and an organic The acid alkali metal salt is 0.01 to 0.9 mol of the organic acid alkali metal salt per 1 mol of the sulfur source, and the amount of water in the reaction system is 0.02 mol per 1 mol of the aprotic polar organic solvent. Method of reacting while controlling the range of (see International Publication No. 2010/058713)
is particularly preferred.

The dihalogeno aromatic compound is not particularly limited, but examples include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-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'-dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide, and Compounds having an alkyl group having 1 to 18 carbon atoms in the aromatic ring of each of the above compounds can be mentioned. The above dihalogeno aromatic compounds may be used alone or in combination of two or more.

The polyhalogenoaromatic compound is not particularly limited, but 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5-tetrahalobenzene, Benzene, 1,2,4,5-tetrahalobenzene, 1,4,6-trihalonaphthalene and the like. The polyhalogeno aromatic compounds described above may be used alone or in combination of two or more.

The halogen atom contained in each of the above compounds is preferably a chlorine atom or a bromine atom.

The post-treatment method of the reaction mixture containing the polyarylene sulfide resin obtained by the polymerization step is not particularly limited, but for example,
(1) After the completion of the polymerization reaction, the reaction mixture is left as it is, or after adding an acid or base, the solvent is distilled off under reduced pressure or normal pressure, and then the solid after the solvent is distilled off is treated with water, the reaction solvent (or , an organic solvent having a similar solubility to the low-molecular-weight polymer), washing once or twice with a solvent such as acetone, methyl ethyl ketone, alcohols, etc., followed by neutralization, washing with water, filtering and drying,
(2) After completion of the polymerization reaction, solvents such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons (soluble in the polymerization solvent used) are added to the reaction mixture. and a solvent which is a poor solvent for at least polyarylene sulfide) is added as a precipitant to precipitate solid products such as polyarylene sulfide and inorganic salts, which are separated by filtration, washed and dried. ,
(3) After completion of the polymerization reaction, a reaction solvent (or an organic solvent having a solubility equivalent to that of the low-molecular-weight polymer) is added to the reaction mixture and stirred, followed by filtration to remove the low-molecular-weight polymer. a method of washing once or twice or more with a solvent such as acetone, methyl ethyl ketone or alcohols, followed by neutralization, washing with water, filtration and drying;
(4) After completion of the polymerization reaction, a method of adding water to the reaction mixture, washing with water, filtering, and if necessary, acid-treating by adding an acid at the time of washing with water, followed by drying;
(5) A method of filtering the reaction mixture after completion of the polymerization reaction, washing with a reaction solvent once or twice or more if necessary, further washing with water, filtering and drying, and the like.

In the post-treatment methods exemplified in (1) to (5) above, the drying of the polyarylene sulfide resin may be carried out in a vacuum or in the air, using an inert solvent such as nitrogen. It may be carried out in a gas atmosphere.

(Olefin resin (A7))
The olefinic resin (A) is a synthetic resin obtained by polymerizing or copolymerizing an olefinic monomer having a radically polymerizable double bond.

The olefinic monomer is not particularly limited, and examples thereof include α-olefins and conjugated dienes. Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene and the like. Examples of conjugated dienes include butadiene and isoprene. The olefinic monomers may be used alone or in combination of two or more.

The olefinic resin (A7) is not particularly limited, and examples thereof include homopolymers of ethylene, copolymers of ethylene and α-olefins other than ethylene, homopolymers of propylene, and propylene and α-olefins other than propylene. copolymers, homopolymers of butene, and homopolymers or copolymers of conjugated dienes such as butadiene and isoprene. The olefin resin (A7) is preferably a propylene homopolymer or a copolymer of propylene and an α-olefin other than propylene.

When the olefin-based resin (A7) is a copolymer of propylene and other monomers (polypropylene-based copolymer), α-olefins for copolymerization other than propylene include linear α-olefins, branched α-olefins and the like can be preferably used. Linear olefins include, for example, ethylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1 and the like. Branched α-olefins include, for example, 2-methylpropene-1,3-methylpentene-1,4-methylpentene-1,5-methylhexene-1,4-methylhexene-1,4,4-dimethyl pentene-1 and the like. These α-olefins for copolymerization may be used alone or in combination of two or more.

The blending amount of these α-olefins for copolymerization (copolymerization components) in the olefin resin (A) is preferably 30% by mass or less, more preferably 20% by mass or less. When these are copolymerized, the form of the copolymer is not particularly limited, and may be, for example, random type, block type, graft type, or a mixture thereof. Polypropylene copolymers (copolymers of propylene and other monomers) may be any of commonly used random copolymers, block copolymers, and the like. Preferred examples of polypropylene copolymers include propylene-ethylene copolymers, propylene-butene-1 copolymers and propylene-ethylene-butene-1 copolymers.

As the olefin resin (A7), for example, the above-mentioned polypropylene polymer (polymer of propylene monomer), polypropylene copolymer, etc. may be added with an acid anhydride group, a carboxyl group, a hydroxyl group, an amino group and A functional group-containing olefinic resin into which at least one functional group selected from the group consisting of isocyanate groups has been introduced can also be used.

(Polyamide resin (A8))
Polyamide resin (A8) is a thermoplastic polymer having an amide bond, the main constituents of which are amino acids, lactams, diamines and dicarboxylic acids or their amide-forming derivatives. A polycondensate obtained by condensing a diamine and a dicarboxylic acid or its acyl active substance can be used. Polymers obtained by polycondensation of aminocarboxylic acids, lactams or amino acids can also be used. Copolymers of these can also be used.

Diamines include aliphatic diamines and aromatic diamines.
Examples of aliphatic diamines include tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methyl Nonamethylenediamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethyl cyclohexane, 3,8-bis(aminomethyl)tricyclodecane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, aminoethylpiperazine and the like.

Examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,6-naphthalenediamine, 4,4′-diphenyldiamine, 3,4′-diphenyldiamine, 4,4′-diaminodiphenyl ether, 3 , 4'-diaminodiphenyl ether, 4,4' sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2-bis(4-aminophenyl ) propane and the like.

Examples of dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, diglycolic acid and the like.

Specifically, polyamide resins include, for example, polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610 ), polyhexamethylenedodecanamide (nylon 612), polyundecamethyleneadipamide (nylon 116), polyundecaneamide (nylon 11), polydodecanamide (nylon 12). In addition, polytrimethylhexamethylene terephthalamide, polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalate/isophthalamide (nylon 6T/6I), polybis(4-aminocyclohexyl)methandodedecamide (nylon PACM12), polybis ( 3-methyl-4-aminocyclohexyl)methandodedecamide (nylon dimethyl PACM12), polymetaxylylene adipamide (nylon MXD6), polyundecamethylene terephthalamide (nylon 11T), polyundecamethylene hexahydroterephthalamide (nylon 11T(H)), and aliphatic-aromatic polyamides such as these copolyamides. Copolymers and mixtures thereof, poly(p-phenylene terephthalamide), poly(p-phenylene terephthalamide-co-isophthalamide) and the like are also included.

<Hydrophilic copolymer (B)>
The hydrophilic copolymer (B) has oxyethylene groups (preferably polyoxyethylene chains). Since the oxyethylene group functions as a hydrophilic segment, the presence of the oxyethylene group exhibits antistatic performance and exhibits the effect of suppressing adhesion of hydrophilic dust stains.

Hydrophilic copolymer having an oxyethylene group (B), when mixed with the thermoplastic resin (A), compared to other hydrophilic polymers and antistatic agents, tends to gather on the surface of the molded article containing the thermoplastic resin composition. There is a feature. That is, the hydrophilic copolymer (B) having an oxyethylene group is present in a large amount on the surface of the molded article without being buried inside, compared to other hydrophilic polymers and antistatic agents. Therefore, the antifouling effect is efficiently exhibited with respect to the added amount of the hydrophilic copolymer (B) having an oxyethylene group. Therefore, the amount of hydrophilic copolymer (B) required to obtain equivalent antifouling performance may be less than that of other hydrophilic polymers.

In the present embodiment, as such a hydrophilic copolymer (B), a plurality of alternating copolymers (a) of a polyester (a1) and a hydrophilic polymer (a2) having an oxyethylene group have three hydroxyl groups. polyhydric alcohol compound (b1) having one or more epoxy groups, epoxy compound (b2) having two or more epoxy groups, and at least one selected from the group consisting of polycarboxylic acid compound (b3) via an ester bond. A conjugated hydrophilic copolymer is used.

This hydrophilic copolymer (B) has a melting point of about 90 to 100° C., and is disclosed in International Publication No. 2021/006192 (Patent Document 7). The melting point is lower than that of the alternately bonded hydrophilic copolymer” (B1) (melting point: about 135° C.) and “polyether ester amide” (B2) (melting point: about 195-200° C.).

By using such a hydrophilic copolymer (B) having a lower melting point than conventional ones, the thermoplastic resin composition according to the present embodiment can be produced by a low-temperature process and is easy to process. In addition, even when the processing time, kneading time, etc. are relatively short, the hydrophilic copolymer (B) is easily dispersed in the thermoplastic resin composition. In addition, the materials constituting the thermoplastic resin composition (especially materials other than the hydrophilic copolymer (B)) are difficult to decompose. These effects are effects that cannot be obtained when B1 or B2 disclosed in WO2021/006192 (Patent Document 7) is used.

[Alternating copolymer (a)]
The alternating copolymer (a) is a copolymer in which the polyester (a1) and the hydrophilic polymer (a2) having an oxyethylene group are repeatedly and alternately bonded via ester bonds. In other words, the alternating copolymer (a) is a copolymer having alternating multiple blocks derived from the polyester (a1) and multiple blocks derived from the hydrophilic polymer (a2) having an oxyethylene group. is.

The terminal of the alternating copolymer (a) may be a block derived from the polyester (a1) or a block derived from the hydrophilic polymer (a2). When the terminal of the alternating copolymer (a) is a block derived from the polyester (a1), the terminal has a carboxyl group. When the terminal of the alternating copolymer (a) is a block derived from the hydrophilic polymer (a2), the terminal has a hydroxyl group. The terminal functional groups of the alternating copolymer (a) may be the same or different.

The alternating copolymer (a) is represented, for example, by the following formula (15) or formula (16). The alternating copolymer (a) represented by formula (15) has carboxyl groups at both ends. The alternating copolymer (a) represented by formula (16) has hydroxyl groups at both ends. The alternating copolymer (a) preferably has carboxyl groups at both ends as shown in formula (15).

In the above formulas (15) and (16), "a1" represents the residue from which the carboxyl group of the polyester (a1) was removed, and "a2" represents the hydrophilic polymer (a2) from which the hydroxyl group of the diol was removed. represents a residue. n is a natural number, preferably an integer of 1-10, more preferably an integer of 1-7, and most preferably an integer of 1-5.

[Polyester (a1)]
The polyester (a1) is not particularly limited as long as it is a polyester having carboxyl groups at both ends. and the residue other than the hydroxyl group of are repeatedly and alternately bonded via an ester bond.

In the above formula (17), X represents the residue of the dicarboxylic acid from which the carboxyl group has been removed, and Y represents the residue of the diol from which the hydroxyl group has been removed. n is preferably an integer of 1-50, more preferably an integer of 5-40, still more preferably an integer of 10-30.

The polyester (a1) represented by the above formula (17) can be obtained, for example, by subjecting a dicarboxylic acid and a diol to a polycondensation reaction.

(Dicarboxylic acid)
Dicarboxylic acids include aliphatic dicarboxylic acids and aromatic dicarboxylic acids, and may be mixtures of aliphatic and aromatic dicarboxylic acids.

Aliphatic dicarboxylic acids preferably include aliphatic dicarboxylic acids having 2 to 20 carbon atoms, such as oxalic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 2,5-furandicarboxylic acid, itaconic acid, 1,10-decanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, maleic acid, fumaric acid and the like. Among these aliphatic dicarboxylic acids, dicarboxylic acids having 4 to 16 carbon atoms are preferable, and dicarboxylic acids having 6 to 12 carbon atoms are more preferable, from the viewpoint of melting point and heat resistance.

The aromatic dicarboxylic acid may be a derivative of aromatic dicarboxylic acid (eg, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.). Also, the aromatic dicarboxylic acid and its derivative may be a mixture of two or more.

Aromatic dicarboxylic acids preferably include aromatic dicarboxylic acids having 8 to 20 carbon atoms, such as terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutarate. acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate, 3-sulfoisophthalic acid Potassium etc. are mentioned.

The dicarboxylic acid used in obtaining the polyester (a1) by polycondensation reaction may be a derivative of dicarboxylic acid (eg, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.). In this case, after the reaction between the dicarboxylic acid derivative and the diol, the resulting polyester may be treated with carboxyl groups at both ends. It may be used in the reaction for obtaining the following alternating copolymer (a) without such treatment. Dicarboxylic acids (including derivatives thereof) may be a mixture of two or more.

(diol)
The diol is not particularly limited as long as it is a compound having two hydroxyl groups, and examples thereof include aliphatic diols and aromatic group-containing diols. Also, the diol may be a mixture of two or more.

Examples of aliphatic diols include 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol and 1,3-butanediol. , 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl- 1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentane diol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9- nonanediol, 1,10-decanediol, 1,12-octadecanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1,2-, 1,3- or 1,4-cyclohexanediol, cyclododecanediol , dimer diol, isosorbide, hydrogenated dimer diol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol and the like. Among these aliphatic diols, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A are preferable from the viewpoint of dust adhesion suppression effect.

In addition, since the polyester represented by the above formula (17) having carboxyl groups at both ends is preferably hydrophobic, hydrophilic polyethylene glycol is not preferable among the aliphatic diols. However, when used together with a hydrophobic diol other than polyethylene glycol, hydrophilic polyethylene glycol can also be used.

Examples of aromatic group-containing diols include bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, 1,4-benzenedimethanol, ethylene oxide adducts of bisphenol A, Propylene oxide adducts of bisphenol A, 1,4-bis(2-hydroxyethoxy)benzene, resorcinol, and polyhydroxyethyl adducts of mononuclear dihydric phenol compounds (pyrocatechol, etc.). Among these aromatic group-containing diols, an ethylene oxide adduct of bisphenol A and 1,4-bis(β-hydroxyethoxy)benzene are preferred.

The polyester (a1) can be obtained, for example, by subjecting the dicarboxylic acid or its derivative and the diol to a polycondensation reaction.

When obtaining a polyester (a1) having carboxyl groups at both ends, it is preferable to use an excess amount of dicarboxylic acid or its derivative relative to the diol, and the molar ratio of the dicarboxylic acid or its derivative to the diol is preferably 2 or more. preferable.

A catalyst that accelerates the esterification reaction may be used during the polycondensation reaction for obtaining the polyester (a1). As the catalyst, conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate and zinc acetate can be used. In the polycondensation reaction for obtaining the polyester (a1), an antioxidant such as a phenolic antioxidant may be added to the reaction system in order to suppress oxidation of the product.

The polyester (a1) having a carboxyl group at both ends forms an ester bond by reacting with a hydrophilic polymer (a2) having a hydroxyl group at both ends, as long as it can form an alternating copolymer (a). , is not particularly limited. The carboxyl groups at both ends of the polyester (a1) may be protected or modified, and may be in the form of a precursor.

[Hydrophilic polymer (a2) having an oxyethylene group]
The hydrophilic polymer (a2) having oxyethylene groups is a hydrophilic polymer having oxyethylene groups (preferably polyoxyethylene chains). Also, the hydrophilic polymer (a2) has hydroxyl groups at both ends.

The hydrophilic polymer (a2) has one or more groups (oxyethylene groups) represented by the following formula (18), preferably a plurality of groups (oxyethylene groups) represented by the formula (18). The hydrophilic polymer (a2) is more preferably polyethylene glycol (having a polyoxyethylene chain) represented by the following formula (19).

In the above formula (19), m represents an integer of 5-250. m is preferably 20 to 150 from the viewpoint of heat resistance and dust adhesion suppression effect.

Polymers having hydroxyl groups at both ends and having one or more groups represented by the formula (18) include, for example, polyethylene glycol obtained by addition reaction of ethylene oxide, and ethylene oxide and other alkylene oxides ( Examples thereof include polyethers obtained by addition reaction with at least one of propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide. This polyether may be a random copolymer or a block copolymer.

Another example of the compound having hydroxyl groups at both ends and having one or more groups represented by the above formula (18) is a compound having a structure in which ethylene oxide is added to an active hydrogen atom-containing compound, and One of ethylene oxide and other alkylene oxides (e.g., propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide, 1,3-butylene oxide, etc.) as active hydrogen atom-containing compounds A compound having a structure in which at least one species is added can be mentioned. Addition in these compounds may be either random addition or block addition.

Examples of active hydrogen atom-containing compounds include glycols, dihydric phenols, primary monoamines, secondary diamines and dicarboxylic acids.

Examples of glycols include aliphatic glycols having 2 to 20 carbon atoms, alicyclic glycols having 5 to 12 carbon atoms, and araliphatic glycols having 8 to 26 carbon atoms.

Examples of aliphatic glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3- Hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecane diol, 1,20-eicosanediol, diethylene glycol, triethylene glycol, thiodiethylene glycol and the like.

Alicyclic glycols include, for example, 1-hydroxymethyl-1-cyclobutanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1-methyl-3,4-cyclohexanediol. , 2-hydroxymethylcyclohexanol, 4-hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol, 1,1′-dihydroxy-1,1′-dicyclohexyl and the like.

Examples of aromatic glycols include dihydroxymethylbenzene, 1,4-bis(β-hydroxyethoxy)benzene, 2-phenyl-1,3-propanediol, 2-phenyl-1,4-butanediol, 2-benzyl-1, 3-propanediol, triphenylethylene glycol, tetraphenylethylene glycol, benzopinacol and the like.

As dihydric phenols, phenols having 6 to 30 carbon atoms can be used. Examples thereof include alkyl (having 1 to 10 carbon atoms) and halogen-substituted products thereof.

Primary monoamines include aliphatic primary monoamines having 1 to 20 carbon atoms, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, s-butylamine, isobutylamine, n- pentylamine, isopentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-octadecylamine, n-icosylamine and the like.

Secondary diamines include aliphatic secondary diamines having 4 to 18 carbon atoms, heterocyclic secondary diamines having 4 to 13 carbon atoms, alicyclic secondary diamines having 6 to 14 carbon atoms, and the number of carbon atoms. Examples include aromatic secondary diamines having 8 to 14 carbon atoms, secondary alkanol diamines having 3 to 22 carbon atoms, and the like.

Examples of aliphatic secondary diamines include N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N'-dibutylethylenediamine, N,N'-dimethylpropylenediamine, N,N'-diethylpropylenediamine, N,N'-dibutylpropylenediamine, N,N'-dimethyltetramethylenediamine, N,N'-diethyltetramethylenediamine, N,N'-dibutyltetramethylenediamine, N,N'-dimethylhexamethylenediamine, N , N'-diethylhexamethylenediamine, N,N'-dibutylhexamethylenediamine, N,N'-dimethyldecamethylenediamine, N,N'-diethyldecamethylenediamine, N,N'-dibutyldecamethylenediamine, etc. mentioned.

Heterocyclic secondary diamines include, for example, piperazine and 1-aminopiperidine.

Examples of alicyclic secondary diamines include N,N'-dimethyl-1,2-cyclobutanediamine, N,N'-diethyl-1,2-cyclobutanediamine, N,N'-dibutyl-1,2- Cyclobutanediamine, N,N'-dimethyl-1,4-cyclohexanediamine, N,N'-diethyl-1,4-cyclohexanediamine, N,N'-dibutyl-1,4-cyclohexanediamine, N,N'- dimethyl-1,3-cyclohexanediamine, N,N'-diethyl-1,3-cyclohexanediamine, N,N'-dibutyl-1,3-cyclohexanediamine and the like.

Examples of aromatic secondary diamines include N,N'-dimethyl-phenylenediamine, N,N'-dimethyl-xylylenediamine, N,N'-dimethyl-diphenylmethanediamine, and N,N'-dimethyl-diphenyletherdiamine. , N,N-dimethyl-benzidine, N,N'-dimethyl-1,4-naphthalenediamine, and the like.

Examples of secondary alkanol diamines include N-methyldiethanolamine, N-octyldiethanolamine, N-stearyldiethanolamine, N-methyldipropanolamine and the like.

Dicarboxylic acids include dicarboxylic acids having 2 to 20 carbon atoms. Examples of dicarboxylic acids having 2 to 20 carbon atoms include aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alicyclic dicarboxylic acids.

Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid, β-methylglutaric acid, ethylsuccinic acid, isopropylmalonic acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, icosanedicarboxylic acid and the like.

Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2 ,2′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate, potassium 3-sulfoisophthalate and the like.

Alicyclic dicarboxylic acids include, for example, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid. acid, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, dicyclohexyl-4,4-dicarboxylic acid and the like.

One of these active hydrogen atom-containing compounds may be used, or a mixture of two or more of these active hydrogen atom-containing compounds may be used.

The hydrophilic polymer (a2) used to obtain the alternating copolymer (a) can form an ester bond by reacting with the polyester (a1) component to form the alternating copolymer (a). Any compound may be used, and hydroxyl groups at both ends of the hydrophilic polymer (a2) may be protected or modified, and may be in the form of a precursor.

The alternating copolymer (a) can be obtained by subjecting a polyester (a1) having carboxyl groups at both ends and a hydrophilic polymer (a2) having hydroxyl groups at both ends to a polycondensation reaction.

Incidentally, the polyester (a1) and the hydrophilic polymer (a2), if it has a structure in which the ester bond formed by the carboxyl group and the hydroxyl group are repeatedly and alternately bonded, the above-mentioned specific It is not necessary to synthesize the alternating copolymer (a) from the polyester (a1) and the above specific hydrophilic polymer (a2).

Both ends of the alternating copolymer (a) are either carboxyl groups or hydroxyl groups depending on the ratio of the amounts of the polyester (a1) and the hydrophilic polymer (a2) used during polymerization.

For example, if the reaction ratio of the polyester (a1) and the hydrophilic polymer (a2) is adjusted so that the amount of the polyester (a1) is 2 mol parts per 1 mol part of the hydrophilic polymer (a2). , an alternating copolymer (a) having carboxyl groups at both ends can be obtained. Further, if the reaction ratio of the polyester (a1) and the hydrophilic polymer (a2) is adjusted so that the amount of the hydrophilic polymer (a2) is 2 mol parts with respect to 1 mol part of the polyester (a1), , an alternating copolymer (c2) having hydroxyl groups at both ends can be obtained.

After completion of the synthesis reaction of the polyester (a1), a polycondensation reaction of the polyester (a1) and the hydrophilic polymer (a2) for obtaining the alternating copolymer (a) is carried out without isolating the polyester (a1). may be performed.

A catalyst that promotes the esterification reaction may be used during the polycondensation reaction for obtaining the alternating copolymer (a). As the catalyst, conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate and zinc acetate can be used. Moreover, in the polycondensation reaction for obtaining the alternating copolymer (a), an antioxidant such as a phenolic antioxidant may be added to the reaction system in order to suppress oxidation of the product.

[Compounds (b1) to (b3)]
Hydrophilic copolymer (B) is an alternating copolymer (a), polyhydric alcohol compound (b1) having 3 or more hydroxyl groups, epoxy compound (b2) having 2 or more epoxy groups, polycarboxylic acid compound (b3) ) is a copolymer formed by bonding via an ester bond with one selected from the group consisting of

In the present embodiment, the polyester (a1) has carboxyl groups at both ends. Moreover, the hydrophilic polymer (a2) having an oxyethylene group has hydroxyl groups at both ends. The alternating copolymer (a) is obtained by ester bonding between the carboxyl groups of the polyester (a1) and the hydroxyl groups of the hydrophilic polymer (a2).

Specifically, for example, when both ends of the alternating copolymer (a) are carboxyl groups, a plurality of alternating copolymers (a) may contain a polyhydric alcohol compound (b1) or two epoxy groups. A hydrophilic copolymer (B) can be obtained by bonding via an ester bond with at least one of the epoxy compounds (b2) having the above.

Further, when both ends of the alternating copolymer (a) are hydroxyl groups, a plurality of alternating copolymers (a) are bonded via an ester bond with the polycarboxylic acid compound (b3), resulting in hydrophilicity. A copolymer (B) is obtained.

Derived from the number of alternating copolymers (a) per hydrophilic copolymer (B) used to obtain the hydrophilic copolymer (B) (i.e., the alternating copolymer (a) contained in the hydrophilic copolymer (B) is preferably 1 to 50 mol parts, more preferably 1 to 30 mol parts, and still more preferably 1 to 50 mol parts per 1 mol part of the hydrophilic copolymer (B). 10 mole parts.

The hydrophilic copolymer (B) may further contain ester bonds formed by carboxyl groups other than both ends of the polyester (a1) and the polyhydric alcohol compound (b1) or the epoxy compound (b2). Also, it may contain an ester bond formed by a hydroxyl group other than both ends of the hydrophilic polymer (a2) and the polycarboxylic acid (b3).

(b1) Polyhydric alcohol compound having 3 or more hydroxyl groups The polyhydric alcohol compound (b1) is not particularly limited as long as it is a compound having 3 or more hydroxyl groups. Examples include glycerin and 1,2,3-butanetriol. , 1,2,4-butanetriol, 2-methyl-1,2,3-propanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 1,3,5-pentanetriol, 2,3,4-pentanetriol, 2-methyl-2,3,4-butanetriol, trimethylolethane, 2,3,4-hexanetriol, 2-ethyl-1,2,3-butanetriol, trimethylol Propane, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, triethanolamine, triisopropanolamine, 1,3,5-tris(2-hydroxyethyl ) trihydric alcohols such as isocyanurates;
Pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexanetetrol , diglycerin, ditrimethylolpropane, sorbitan, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, etc. alcohol;
pentahydric alcohols such as adonitol, arabitol, xylitol, triglycerin;
Hexavalent alcohols such as dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose and allose;
tripentaerythritol and polypentaerythritol;

Two or more of such polyhydric alcohol compounds (b1) may be used.
(b2) Epoxy compound The epoxy compound (b2) is not particularly limited as long as it is a compound having two or more epoxy groups. a polyglycidyl ether compound of;
Dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(orthocresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis(orthocresol), tetrabromobisphenol A, 1,3-bis(4- hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl) Polyglydyl ether compounds of polynuclear polyhydric phenol compounds such as ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak, and terpenephenol;
Polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct;
Maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyrroic acid homopolymers or copolymers of glycidyl esters and glycidyl methacrylates of aliphatic, aromatic or alicyclic polybasic acids such as mellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid and endomethylenetetrahydrophthalic acid;
epoxy compounds having a glycidylamino group such as N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, and diglycidylorthotoluidine;
vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis(3 epoxidized products of cyclic olefin compounds such as ,4-epoxy-6-methylcyclohexylmethyl)adipate;
Epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer; heterocyclic compounds such as triglycidyl isocyanurate; epoxidized soybean oil and the like.

In addition, these epoxy compounds are internally cross-linked with a prepolymer of terminal isocyanate, or polyvalent active hydrogen compounds (polyhydric phenols, polyamines, carbonyl group-containing compounds, polyphosphate esters, etc.) are used to increase the molecular weight. It may be Two or more kinds of such epoxy compounds (b2) may be used.

(b3) Polycarboxylic acid compound Examples of the polycarboxylic acid compound (b3) include carboxylic acids having 3 or more carboxyl groups, and carboxylic acids having 2 or more carboxyl groups and 1 or more hydroxyl groups. Carboxylic acids having 3 or more carboxyl groups are preferred from the viewpoint of the effect of suppressing adhesion of dust. Polycarboxylic acid compound (b3) may be a mixture thereof.

Carboxylic acids having 3 or more carboxyl groups may be derivatives thereof (eg, acid anhydrides, alkyl esters, alkali metal salts, acid halides, etc.). Carboxylic acids having 3 or more carboxyl groups and derivatives thereof may be a mixture of two or more.

Carboxylic acids having 3 or more carboxyl groups include, for example, aconitic acid, 1,2,3-propanetricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, 3-butene-1,2,3 -tricarboxylic acid, trimellitic acid, pyromellitic acid, mellitic acid, cyclohexanetricarboxylic acid, naphthalene-1,2,5-tricarboxylic acid, naphthalene-2,6,7-tricarboxylic acid, 1,3,5-pentanetricarboxylic acid , trimesic acid, 3,3′,4-diphenyltricarboxylic acid, benzophenone-3,3′,4-tricarboxylic acid, diphenylsulfone-3,3′,4-tricarboxylic acid, diphenyl ether-3,3′,4-tricarboxylic acid acid, diphenyl-2,2',3,3'-tetracarboxylic acid, benzophenone-2,2',3,3'-tetracarboxylic acid, diphenylsulfone-2,2',3,3'-tetracarboxylic acid , diphenyl-2,2′,3,3′-tetracarboxylic acid, benzophenone-2,2′,3,3′-tetracarboxylic acid, diphenylsulfone-2,2′,3,3′-tetracarboxylic acid, diphenyl ether-2,2',3,3'-tetracarboxylic acid and the like. Furthermore, acid-modified polyethylene wax having 3 or more carboxyl groups, polyacrylic acid, and the like can also be used.

Carboxylic acids having two or more carboxyl groups and one or more hydroxyl groups may be derivatives thereof (eg, acid anhydrides, alkyl esters, alkali metal salts, acid halides, etc.). The carboxylic acid having two or more carboxyl groups and one or more hydroxyl groups and derivatives thereof may be a mixture of two or more.

Examples of carboxylic acids having two or more carboxyl groups and one or more hydroxyl groups include tartaric acid, malic acid, citric acid, isocitric acid, citramaric acid, and tartronic acid.

The total amount of hydroxyl groups in the polyhydric alcohol compound (b1) used to obtain the alternating copolymer (a) (not the number of hydroxyl groups per polyhydric alcohol compound (b1). The same shall apply hereinafter.), or epoxy The total amount of epoxy groups of the compound (b2) is preferably 0.1 to 4.0 equivalents, more preferably 0.5 to 3.0 equivalents, relative to the total amount of carboxyl groups of the alternating copolymer (a) to be reacted therewith. more preferred.

Further, the total amount of carboxyl groups of the polycarboxylic acid (b3) used to obtain the alternating copolymer (a) is 0.1 to 0.1 with respect to the total amount of hydroxyl groups of the alternating copolymer (a) to be reacted therewith. 4.0 equivalents are preferred, and 0.5 to 3.0 equivalents are more preferred.

The reaction for obtaining the alternating copolymer (a) may be carried out in various solvents or in a molten state.

After completion of the reaction (synthesis reaction) for obtaining the alternating copolymer (a), without isolating the alternating copolymer (a), the polyhydric alcohol compound (b1), the epoxy compound (b2) or , the polycarboxylic acid (b3) may be added, and the reaction for obtaining the hydrophilic copolymer (B) may be performed as it is. In that case, the carboxyl groups of the unreacted polyester (a1) used excessively when synthesizing the alternating copolymer (a), the hydroxyl groups of some of the polyhydric alcohol compounds (b1), or the epoxy compound ( It may react with the epoxy group of b2) to form an ester bond. In addition, the hydroxyl groups of the unreacted hydrophilic polymer (a2) used excessively when synthesizing the alternating copolymer (a) react with some carboxyl groups of the polycarboxylic acid (b3) to form an ester bond. may be formed.

Hydrophilic copolymer (B) has a structure in which alternating copolymer (a) and polyhydric alcohol compound (b1), epoxy compound (b2) or polycarboxylic acid (b3) are bonded via ester bonds. If so, it is necessary to synthesize from the above specific alternating copolymer (a) and the above specific polyhydric alcohol compound (b1), epoxy compound (b2), or polycarboxylic acid (b3). no.

In the hydrophilic copolymer (B), the polystyrene-equivalent number average molecular weight of the block derived from the polyester (a1) is preferably 800 to 8000, more preferably 1000 to 6000, still more preferably 2000 to 4000. .

In the hydrophilic copolymer (B), the polystyrene-equivalent number average molecular weight of the block derived from the hydrophilic polymer (a2) is preferably 400 to 6000, more preferably 1000 to 5000, still more preferably 2000 to 4000. is.

In the hydrophilic copolymer (B), the polystyrene-equivalent number-average molecular weight of the blocks derived from the alternating copolymer (a) is preferably 5,000 to 25,000, more preferably 7,000 to 17,000, and more preferably 9,000. ~13000.

Since the hydrophilic copolymer (B) of the present embodiment exhibits a hydrophilic effect of suppressing adhesion of dust stains by being dispersed in the thermoplastic resin composition, the surface resistance value of the hydrophilic copolymer (B) itself is As low as possible is usually preferred. The surface resistance value of the hydrophilic copolymer (B) is preferably 1×10 ⁴ to 1×10 ¹⁰ Ω, more preferably 1×10 ⁴ to 1×10 ⁷ Ω.

The thermoplastic resin composition may further contain an antistatic agent other than the hydrophilic polymer described above for the purpose of improving the effect of suppressing the adhesion of hydrophilic dust stains. Other antistatic agents include, for example, surfactants (anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc.), ionic liquids, and the like.

In addition, the hydrophilic copolymer (B) having an oxyethylene group also has another special effect.

In order to obtain amphoteric (hydrophilic and hydrophobic) antifouling properties, both the hydrophilic copolymer (B) and the fatty acid metal salt (C) described later are necessary, but the fatty acid metal salt (C) is hydrophilic. Since it has a lower molecular weight than the copolymer (B) and is less entangled with the thermoplastic resin (A), it may fall off from the surface of the molded product or deteriorate. However, a large amount of the hydrophilic copolymer (B) exists on the surface of the molded product, and the hydrophilic group of the hydrophilic copolymer (B), which prevents the adhesion of hydrophilic dust stains due to its antistatic effect, contains the fatty acid metal salt (C). By attaching a hydrophilic group, the fatty acid metal salt (C) can stably exist on the surface without falling off.

On the opposite side of the hydrophilic group of the fatty acid metal salt (C), there is R, which is a non-polar hydrophobic group of the fatty acid metal salt (C), so the hydrophilic copolymer ( A new effect that cannot be obtained by B) alone can be obtained.

In other words, both the hydrophilic copolymer (B) having an oxyethylene group and the fatty acid metal salt (C) are present on the surface of the molded article, and exhibit a synergistic effect with each other, resulting in a high effect of suppressing adhesion of amphoteric dust stains. (antifouling property) is exhibited.

<Fatty acid metal salt (C)>
Fatty acid metal salt (C) is a compound represented by the following formula (1).

M(OH)y(R-COO)x (1)

(In formula (1), R is an alkyl group or alkenyl group having 6 to 40 carbon atoms. M is at least one metal selected from the group consisting of aluminum, zinc, calcium, magnesium, lithium and barium. is an element, x and y are each independent integers of 0 or more and satisfy the relationship x + y = [valence of M].)
Only by using the above hydrophilic polymer or antistatic agent as an additive, the effect of suppressing adhesion of hydrophilic dust stains can be obtained, but on the other hand, the effect of suppressing adhesion of hydrophobic dust stains is low. In this case, the amount of adhesion of hydrophobic dust contaminants is not even less than half, so a new means is required.

Additives that generally provide water and oil repellency include silicone oil, fluororesins such as PTFE, and hydrophobic silica such as fumed silica. The effect of suppressing adhesion of dirt was not obtained either. This is because when added to the resin, the additive is buried inside the resin and does not come out to the surface. A fatty acid metal salt (C) is compounded with a thermoplastic resin (A) and a hydrophilic copolymer (B) as a material that can be present at a high concentration on the surface and has hydrophobicity and water and oil repellency. can solve the problem.

The fatty acid metal salt used in this embodiment is a fatty acid metal salt represented by formula (1).

M(OH)y(R-COO)x (1)

(In formula (1), R is an alkyl group or alkenyl group having 6 to 40 carbon atoms. M is at least one metal selected from the group consisting of aluminum, zinc, calcium, magnesium, lithium and barium. is an element, x and y are each independent integers of 0 or more and satisfy the relationship x + y = [valence of M].)
In formula (1), R has 6 to 40 carbon atoms, preferably 11 to 27 carbon atoms, more preferably 15 to 20 carbon atoms. If the number of carbon atoms in R is less than 6, or if the number of carbon atoms in R is more than 40, the effect of preventing adhesion of dust is reduced, which is undesirable. Also, R is an alkyl group or an alkenyl group, preferably an alkyl group.

In general, if the contact angle with water is higher than that of petroleum or mineral oil, it is said to have water and oil repellency, and if the contact angle with water is higher than 90 degrees, it is said to be hydrophobic. Fatty acid metal salt (C) corresponds to this.

The melting point of the fatty acid metal salt (C) is, for example, 130-180°C, preferably 140-170°C, more preferably 150-160°C.

(Metal element M)
In formula (1), M is at least one metal element selected from the group consisting of aluminum, zinc, calcium, magnesium, lithium and barium.

M is preferably at least one metal element selected from aluminum and zinc. In this case, the thermoplastic resin composition can exhibit higher antifouling performance. Moreover, M is more preferably aluminum. In this case, the thermoplastic resin composition can exhibit even higher antifouling performance.

Referring to FIG. 3, when the ionic radius of M is small (FIGS. 3A1 and 3A2), the thermal This is because the nonpolar groups (hydrophobic groups) of the fatty acid metal salt can be densely arranged on the surface of the molded product containing the plastic resin composition. As the hydrophobic groups become denser, the effect of suppressing adhesion of hydrophobic dust stains increases. The ionic radii of M are respectively 54 for aluminum, 74 for zinc, 100 for calcium and 135 for barium, with aluminum being the smallest followed by zinc. Therefore, in order to enhance the antifouling effect, the metal element M is most preferably aluminum, followed by zinc.

(fatty acid)
Examples of fatty acids constituting the fatty acid metal salt (C) of the present embodiment include caproic acid, capric acid, lauric acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, montanic acid, oleic acid, and linoleic acid. is mentioned. Fatty acids are preferably long-chain fatty acids (fatty acids having 12 or more carbon atoms) such as stearic acid, behenic acid, and montanic acid. In particular, stearic acid is more preferable for production because it is readily available and inexpensive.

Examples of fatty acid metal salts (C) include zinc stearate, zinc 12-hydroxystearate, zinc laurate, zinc oleate, zinc 2-ethylhexanoate, aluminum tristearate, (dihydroxy)aluminum monostearate, (Hydroxy)aluminum distearate, aluminum 12-hydroxystearate, aluminum laurate, aluminum oleate, aluminum 2-ethylhexanoate and the like. The fatty acid metal salt (C) is preferably zinc stearate, aluminum tristearate, (dihydroxy)aluminum monostearate, and (hydroxy)aluminum distearate, more preferably (hydroxy)aluminum distearate. be. The fatty acid metal salt (C) may be used singly or in combination of two or more.

Aluminum stearate, zinc stearate, calcium stearate, and barium stearate are characterized by smoothness, high water repellency, and low surface free energy (about 21.2 mN/m). A material with a low surface free energy has a stable surface condition, such as a fluororesin (surface free energy: about 21.5 mN/m), so dirt does not adhere easily. By forming a layer of aluminum stearate with low surface free energy on the surface of a molded article containing a thermoplastic resin composition, the effect of preventing the adhesion of hydrophobic dust stains such as carbon black, soot and oil smoke is exhibited. In addition, since the surface free energy is lowered, it becomes difficult for hydrophilic dust stains such as dust, sand, and soil to adhere. Therefore, in addition to the static elimination effect of the hydrophilic copolymer (B) blended in the thermoplastic resin composition, antifouling properties against hydrophobic dust stains and hydrophilic dust stains are improved.

(Valence)
In formula (1), x and y are independent integers of 0 or more and satisfy the relationship x+y=[valence of M].

When the valence of M is 1, y is 0, but when the valence of M is 2 or more, y is 0 or an integer of 1 or more. When the valence of M is 3 or more, y is preferably 1. In this case, the thermoplastic resin composition can exhibit higher antifouling performance.

As an example, aluminum stearate, which is a long-chain fatty acid salt of aluminum in which the valence of M is 3, will be described.

Examples of aluminum stearate include mono-type aluminum monostearate [Al(C ₁₇ H ₃₅ COO)(OH) ₂ ] containing one stearic acid, di-type aluminum distearate [Al(C ₁₇ H ₃₅ COO) ₂ (OH)], and the tri-type aluminum tristearate [Al(C ₁₇ H ₃₅ COO) ₃ ], which contains three stearic acids.

Referring to FIG. 4, aluminum tristearate has a large amount of non-polar groups, so it is difficult to migrate to the surface of the molded product (FIG. 4(a)). to a mixture with aluminum monostearate or aluminum distearate. Therefore, aluminum distearate easily migrates to the surface of the molded product (Fig. 4(b)), and has a higher amphoteric dust suppression effect than aluminum tristearate. Even when the valence of M is more than 3, similarly, a ditype fatty acid metal salt having a smaller number of fatty acids than a tritype has a higher amphoteric dust suppression effect.

On the other hand, aluminum monostearate has a smaller number of non-polar groups (hydrophobic groups) R than aluminum distearate when the number of aluminum atoms is the same (Fig. 4(c)). Therefore, aluminum distearate has a higher amphoteric dust control effect than aluminum monostearate.

When the vicinity of the surface of the molded article was actually measured using time-of-flight secondary ion mass spectrometry (TOF-SIMS), C ₁₈ H ₃₅ O ₂ ^- derived from stearic acid was detected as secondary ions. Since the detection depth of TOF-SIMS is generally 1 to 2 nm, it was confirmed that stearic acid was present on the outermost surface of the molded article.

The secondary ionic strength ratio of C ₁₈ H ₃₅ O ₂ ^— to the ionic strength of C ₂ H ^— , which is the main peak during polystyrene analysis, was 0.341 in the case of the molded article using aluminum distearate. , which was 2 to 4 times more than the molded article using aluminum monostearate (0.0687) and the molded article using aluminum tristearate (0.172). Therefore, a molded product using aluminum distearate where y=1 has many non-polar groups (hydrophobic groups) on the surface, and is most likely to exhibit the dust suppressing effect.

For the same reason as in the case where the valence of M is 3 or more, when the valence of M is 2, the ditype fatty acid metal salt suppresses amphoteric dust more than the monotype fatty acid metal salt. Highly effective. Therefore, when the valence of M is 2, y is preferably 0 (x is 2).

<Content of each component>
In the thermoplastic resin composition of the present embodiment, the amount of the hydrophilic copolymer (B) is preferably 1 to 20 parts by mass, more preferably 1 part by mass with respect to 100 parts by mass of the thermoplastic resin (A). ~17 parts by mass.

The amount of the fatty acid metal salt (C) to be blended is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, based on 100 parts by mass of the thermoplastic resin (A).

The thermoplastic resin composition of the present embodiment is particularly composed of 100 parts by mass of thermoplastic resin (A), 1 to 20 parts by mass of hydrophilic copolymer (B), and 0.5 to 10 parts by mass of fatty acid metal salt (C) It is preferable to contain the part and

The fatty acid metal salt (C) is generally added to the thermoplastic resin composition at a content of 0.5% by mass or less (especially about 0.1%) as a lubricant, mold release agent, etc. for improving moldability. Although there are cases, by blending more than 0.5% by mass of the fatty acid metal salt (C), both the hydrophilic copolymer (B) and the fatty acid metal salt (C) are present at high concentrations on the surface of the molded article. The effect of making it exist is exhibited, and the amphoteric antifouling effect is further improved.

When the amount of the hydrophilic copolymer (B) exceeds 20 parts by mass, the mechanical strength such as elastic modulus is lowered, and when it is less than 1 part by mass, the effect of suppressing adhesion of dust is reduced. become.

When the amount of the fatty acid metal salt (C) is more than 10 parts by mass, the heat resistance and impact resistance are lowered. will be available.

As described above, the fatty acid metal salt (C) is generally used for a purpose different from the purpose of the present embodiment, which is to suppress adhesion of both hydrophilic and hydrophobic dust stains. There is something. It is used, for example, as a lubricant, molding modifier, release agent, antifogging agent, etc., as disclosed in JP-A-2004-168055, JP-A-2003-183529, and the like. In this case, the blending amount of the fatty acid metal salt (C) is less than 0.5 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). Furthermore, it is 0.1 parts by mass or less for use in general manufacturing industries. Further, the effect of the fatty acid metal salt (C) on dust adhesion suppression has not been known so far.

In the present embodiment, the amount of fatty acid metal salt ( It has been found that only by sufficiently increasing the amount of C) can a remarkable effect of suppressing adhesion to amphoteric dust stains be obtained. Therefore, the amount of the fatty acid metal salt (C) to be blended is preferably 0.5 parts by mass or more, more preferably 1 to 8 parts by mass, per 100 parts by mass of the thermoplastic resin (A). In this case, a good dust suppression effect equal to or better than that obtained by applying a dust suppression coating to the surface of the molded product can be obtained. An example in which 1 part by mass or more of fatty acid metal salt (C) is blended with 100 parts by mass of thermoplastic resin for the purpose of dust suppression has not been known so far.

A new effect of suppressing adhesion of hydrophobic dust stains is obtained by R, which is a non-polar hydrophobic group facing the air of the fatty acid metal salt. By adding 0.5% by mass or more of the fatty acid metal salt (C) to the thermoplastic resin (A), many hydrophobic groups can be densely arranged on the surface of the molded article containing the thermoplastic resin composition. It is possible to increase the effect of suppressing the adhesion of hydrophobic dust stains.

As will be described later, the antistatic effect of the hydrophilic copolymer (B) having an oxyethylene group enhances the effect of suppressing adhesion of hydrophilic dust stains, and the addition of the fatty acid metal salt (C) together reduces hydrophobic dust. The effect of suppressing the adhesion of dirt is enhanced, and a new effect that is strong against amphoteric dirt can be obtained.

<Optional component>
The thermoplastic resin composition of the present embodiment includes optional components such as heat stabilizers, ultraviolet absorbers, light stabilizers, antibacterial agents, antifungal agents, inorganic Ingredients such as fillers may also be included.

(Heat stabilizer)
The thermoplastic resin composition of the present embodiment may contain a thermal stabilizer in order to improve thermal stability during production.

As the heat stabilizer, it is preferable to use a phosphorus stabilizer and/or a hindered phenol antioxidant, and it is more preferable to use them together.

The amount of the phosphorus-based stabilizer and/or the hindered phenol-based antioxidant added to the thermoplastic resin composition of the present embodiment is not particularly limited.

Since the effect of improving thermal stability is effectively obtained and the blending amount of each of the above essential components is not affected, it is preferably 0.01 to 1 with respect to 100 parts by mass of the thermoplastic resin composition. parts by mass, more preferably 0.01 to 0.6 parts by mass.

Phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, esters thereof, phosphonite compounds, and tertiary phosphines.

Phosphites (phosphite compounds) include triphenylphosphite, tris(nonylphenyl)phosphite, tridecylphosphite, distearylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl ) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}penta Erythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like.

As the phosphite (phosphite compound), in addition to the above, those that react with dihydric phenols and have a cyclic structure can also be used.

For example, 2,2′-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2′-methylenebis(4,6-di-tert- butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite and 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite.

Phosphate esters (phosphate compounds) include triphenyl phosphate and trimethyl phosphate.

Phosphonite compounds include tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, and the like.

The phosphonite compound is preferable because it can be used in combination with the above phosphite compound having an aryl group substituted with two or more alkyl groups.

Phosphonate esters (phosphonate compounds) include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

Tertiary phosphines include triphenylphosphine and the like.
Among the above phosphorus-based stabilizers, phosphonite compounds or phosphite compounds represented by the following formula (20) are preferable.

(In formula (20), 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-tert-butylphenyl)-biphenylene diphosphonite.

More preferred phosphite compounds among the formula (15) are distearylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di- tert-butyl-4-methylphenyl)pentaerythritol diphosphite and bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite.

Hindered phenol compounds include tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-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 and the like.

The thermoplastic resin composition of the present embodiment can optionally contain other thermal stabilizers than the phosphorus stabilizer and the hindered phenol antioxidant.

The other heat stabilizer is preferably used in combination with at least one of the phosphorus stabilizer and the hindered phenol antioxidant, and particularly preferably in combination with both.

Other heat stabilizers include lactone stabilizers represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (details of this stabilizer See Japanese Patent Application Laid-Open No. 7-233160).

Regarding the above lactone-based stabilizer, Irganox HP-136 (registered trademark, manufactured by CIBA SPECIALTY CHEMICALS) and the like are commercially available.

Irganox HP-2921 (registered trademark, manufactured by CIBA Specialty Chemicals) and the like are commercially available as a stabilizer obtained by mixing the lactone stabilizer, phosphite compound, and hindered phenol compound.

The amount of the lactone stabilizer added is preferably 0.0005 to 0.05 parts by mass, more preferably 0.001 to 0.03 parts by mass, based on 100 parts by mass of the thermoplastic resin composition.

Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. be done.

The addition amount of the stabilizer other than the phosphorus stabilizer and/or the hindered phenol antioxidant in the thermoplastic resin composition of the present embodiment is not particularly limited, and is On the other hand, it is preferably 0.0005 to 0.1 parts by mass, more preferably 0.001 to 0.08 parts by mass, and particularly preferably 0.001 to 0.05 parts by mass.

(Ultraviolet absorber)
The thermoplastic resin composition of this embodiment may contain an ultraviolet absorber. Since the thermoplastic resin composition of the present embodiment may be inferior in weather resistance due to the influence of the rubber component and the like, it is effective to add an ultraviolet absorber to improve the weather resistance.

Examples of the ultraviolet absorber of the present embodiment include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a hydroxyphenyltriazine-based ultraviolet absorber, a cyclic imino ester-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber. An ultraviolet absorber etc. are mentioned.

Benzophenone-based UV absorbers include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy -4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'- Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy -2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Benzotriazole-based UV absorbers include, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2 -hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2′-methylenebis[4-( 1,1,3,3-tetramethylbutyl)-6-(2H-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-tert-amylphenyl)benzotriazole, 2-( 2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2′-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis(1,3-benzoxazin-4-one), 2-[2-hydroxy-3-( 3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole and the like. Other benzotriazole-based UV absorbers are exemplified by polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton. Polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton include, for example, 2-(2′-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and a vinyl-based monomer copolymerizable therewith. and a copolymer of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer.

Examples of hydroxyphenyltriazine-based UV absorbers 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-triazin-2-yl)-5- butyloxyphenol and the like. Furthermore, the phenyl group of the above-exemplified compounds such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol is 2, A compound substituted with a 4-dimethylphenyl group is exemplified.

Cyclic iminoester-based UV absorbers include, for example, 2,2′-p-phenylenebis(3,1-benzoxazin-4-one), 2,2′-(4,4′-diphenylene)bis( 3,1-benzoxazin-4-one), 2,2′-(2,6-naphthalene)bis(3,1-benzoxazin-4-one), and the like.

Examples of cyanoacrylate ultraviolet absorbers include 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3, 3-diphenylacryloyl)oxy]methyl)propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene, and the like.

Furthermore, the UV absorber is a polymer-type UV-absorbing agent obtained by copolymerizing a UV-absorbing monomer and/or a photostable monomer having a hindered amine structure with a monomer such as an alkyl (meth)acrylate. It may be an agent. As the UV-absorbing monomer, a (meth)acrylic acid ester is preferably a compound containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent. exemplified.

Among the above, benzotriazole-based and hydroxyphenyltriazine-based UV absorbers are preferred in terms of UV absorption capacity, and cyclic iminoester-based and cyanoacrylate-based UV absorbers are preferred in terms of heat resistance and hue (transparency). is preferred. The ultraviolet absorbers may be used singly or as a mixture of two or more.

The content of the ultraviolet absorber is preferably 0.01 to 2 parts by mass, more preferably 0.02 to 2 parts by mass, and still more preferably 0.03 to 1 part by mass, based on 100 parts by mass of the thermoplastic resin composition. parts, particularly preferably 0.05 to 0.5 parts by mass.

(light stabilizer)
The thermoplastic resin composition of this embodiment may contain a light stabilizer. Since the thermoplastic resin composition of the present embodiment may cause yellowing in the dark, it is effective to add a light stabilizer to prevent such deterioration.

Hindered amine light stabilizers (HALS) can be suitably used as such light stabilizers. HALS are, for example, compounds represented by the following formulas (21) to (24), and combinations of two or more of these compounds.

In formulas (21)-(24), R ₁ -R ₃ are independent substituents.
Examples of the substituents include hydrogen, ether groups, ester groups, amine groups, amide groups, alkyl groups, alkenyl groups, alkynyl groups, aralkyl groups, cycloalkyl groups, and aryl groups.

These substituents may contain functional groups. Such functional groups include, for example, alcohols, ketones, anhydrides, imines, siloxanes, ethers, carboxyl groups, aldehydes, esters, amides, imides, amines, nitriles, ethers, urethanes, and combinations thereof.

Hindered amine light stabilizers (HALS) are preferably compounds derived from substituted piperidine compounds, more preferably compounds derived from alkyl-substituted piperidyl, piperidinyl or piperazinone compounds, and substituted alkoxypiperidinyl compounds.

Hindered amine light stabilizers include, but are not limited to, 2,2,6,6-tetramethyl-4-piperidone; 2,2,6,6-tetramethyl-4-piperidinol; -(1,2,2,6,6-pentamethylpiperidyl)-(3′,5′-di-t-butyl-4′-hydroxybenzyl)butylmalonate; di-(2,2,6,6) -tetramethyl-4-piperidyl) sebacate; N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and oligomers of succinic acid; cyanuric acid and N,N-di(2, Oligomers of 2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine; bis-(2,2,6,6-tetramethyl-4-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-butanetetracarboxylate; N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexane-1,6-diamine; N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; 2,2′-[(2,2,6,6-tetramethyl-piperidinyl)-imino]-bis-[ethanol]; Poly((6-morpholine-S-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidinyl)-iminohexamethylene-(2,2,6,6-tetramethyl- 4-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-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro(4 .5) Decane-2,4-dione; polymethylpropyl-3-oxy-[4(2,2,6,6-tetramethyl)-piperidinyl]siloxane; 1,2,3,4-butane-tetracarboxylic acid-1,2,3-tris(1,2,2,6,6-pentamethyl-4-piperidinyl)-4-tridecyl ester; α-methylstyrene-N-(2,2,6,6-tetra Methyl-4-piperidinyl)maleimide and N-steary Copolymer with lumaleimide; 1,2,3,4-butanetetracarboxylic acid-β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3 ,9-diethanol and 1,2,2,6,6-pentamethyl-4-piperidinyl ester; 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol and β,β,β',β'-tetramethyl-polymer with 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester; D-glucitol, 1,3: 2,4-bis-o-(2,2,6,6-tetramethyl-4-piperidinylidene)-; 7-oxa-3,20-diazadispiro [5.1.11.2 ]-Heneicosan-21-one-2,2,4,4-tetramethyl-20-(oxiranylmethyl) oligomers; propanedioic acid, [(4-methoxyphenyl)methylene]-, bis(1,2 ,2,6,6-pentamethyl-4-piperidinyl) ester; formamide, N,N′-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl); 3,5-triazine-2,4,6-triamine, N,N'''-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl- 4-piperidinyl)amino]-1,3,5-triazin-2-yl]imino]-3,1-propanediyl]]-bis[N′,N″-dibutyl-N′,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)-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) ester; 1,5-dioxaspiro(5.5)undecane 3,3-dicarboxylic acid, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester; N-2,2,6,6-tetramethyl-4-piperidinyl-N-amino-oxamide; 4-acryloyloxy-1,2,2,6,6-pentamethyl-4-piperidine; 1,5,8,1 2-tetrakis[2′,4′-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)-pyrrolidine-2 ,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); 1,1′, 1″-(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethanediyl)tris(3,3,4,5,5-tetramethylpiperazinone) etc.

The amount of the hindered amine light stabilizer (HALS) added is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, still more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the thermoplastic resin composition. It is 1 to 1 part by mass.

(Antibacterial agent)
The thermoplastic resin composition of this embodiment may contain an antibacterial agent. The antibacterial agent is not particularly limited. Inorganic antibacterial agents carried on soil, activated carbon, zirconium phosphate, hydroxyapatite, magnesium oxide, magnesium perchlorate, glass and the like can be mentioned. Zinc oxide is preferred as the antimicrobial metal.

Zinc oxide is not particularly limited and may be commercially available. For example, metallic zinc is heated to vaporize and burned in air, or zinc sulfate or zinc nitrate is heated. It may be prepared by As zinc oxide, for example, various shapes such as fibrous, plate-like, particulate, and tetrapod-like can be used. The zinc oxide used in this embodiment may be surface-treated with silicon oxide, silicone oil, an organic silicon compound, an organic titanium compound, or the like.

Examples of commercially available zinc oxide include "Type 1 zinc oxide", "Type 2 zinc oxide", and "Type 3 zinc oxide" classified by JIS K-1410, and pharmacopoeia stipulated in the Japanese Pharmacopoeia. Zinc oxide and anisotropic (columnar, plate-like, tetrapod-like) zinc oxide (zinc oxide having shape anisotropy) prepared through a hydrothermal synthesis process can be mentioned. Among these zinc oxides, particulate zinc oxide having an average particle diameter of 50 to 200 nm is preferred, and particulate zinc oxide having an average particle diameter of 100 to 150 nm is particularly preferred. The average particle size referred to here is the particle size at which the cumulative mass distribution is 50% in the particle size distribution obtained by measuring with a laser diffraction/scattering particle size distribution analyzer.

The amount of zinc oxide compounded is preferably 0.01 to 1 part by mass, more preferably 0.05 to 0.5 part by mass, and still more preferably 0.1 to 0 part by mass with respect to 100 parts by mass of the thermoplastic resin composition. .3 parts by mass.

(Inorganic filler)
The thermoplastic resin composition of the present embodiment may contain an inorganic filler as a reinforcing filler for the purpose of imparting rigidity and improving strength.

Examples of inorganic fillers include talc, wollastonite, mica, clay, montmontlilonite, smectite, kaolin, calcium carbonate, glass fibers, glass beads, glass balloons, glass milled fibers, glass flakes, carbon fibers, and 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, Various whiskers such as graphite, potassium titanate whisker, aluminum borate whisker, and basic magnesium sulfate are included. Among them, silicate-based fillers such as talc, wollastonite, mica, glass fiber, and glass milled fiber are preferably used. Among them, talc, wollastonite and mica are particularly preferred.

When an inorganic filler is blended, the thermoplastic resin composition of the present embodiment contains an additive containing an acidic group such as a carboxylic anhydride group or a sulfonic acid group in order to improve the wettability of the inorganic filler. can include

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 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition. 10 parts by mass. If the amount is less than 0.1 parts by mass, the reinforcing effect of the filler will not be obtained, and if it exceeds 30 parts by mass, the impact strength will be significantly lowered, which is not preferable.

(other optional ingredients)
Dyes for coloring, pigments, antifoaming agents, plasticizers, lubricants, release agents, flame retardants, and the like can be given as other optional components that can be used in the present embodiment. Furthermore, thermoplastic resins other than the thermoplastic resin (A) and the hydrophilic copolymer (B) can be blended within a range that does not impair the purpose of the present embodiment.

As such a thermoplastic resin, a general-purpose thermoplastic resin used in home appliances and OA equipment can be used.

Examples of such thermoplastic resins include:
Olefin resins, polyolefin resins (high density polyethylene, low density polyethylene, polypropylene, etc.), cyclic olefin resins, and polyester resins (polylactic acid, polyethylene terephthalate, polybutylene terephthalate, etc.),
polystyrene (PS resin), acrylonitrile butadiene styrene (ABS resin), and acrylonitrile styrene (AS resin), which are styrene resins;
ASA resin obtained by polymerizing acrylic rubber instead of butadiene in ABS resin,
AES resin obtained by polymerizing ethylene-based rubber instead of butadiene in ABS resin,
Examples include methyl methacrylate butadiene styrene (MBS resin).

Examples of other general-purpose resins include polyvinyl chloride-based resins (polyvinyl chloride, polyvinylidene chloride, etc.), polymethyl methacrylate-based resins, polyvinyl alcohol, polyethylene terephthalate (PET resin), and polybutylene terephthalate (PBT resin). .

Examples of engineering plastics that are particularly strong and have enhanced functions such as heat resistance include polycarbonate resins (BPA type polycarbonate, aliphatic polycarbonate, etc.), polyamide resins, polyphenylene ether resins (PPE resins), Examples include polyoxymethylene resins (polyacetal, etc.), polyphenylene sulfide resins, polyetherimide resins, aromatic polyetherketone resins, polysulfone resins, and polyamideimide resins.

These resins may be used singly or in combination as raw materials for the thermoplastic resin composition of the present embodiment. A plurality of resins are, for example, polymer alloys such as PC/ABS and PC/AS. Such polymer alloys have the features of both polycarbonate (PC resin) and styrene resins (ABS resin, AS resin, etc.) It is used in a wide range of fields such as household goods.

Since the fatty acid metal salt (C) has a lower molecular weight than the thermoplastic resin (A) or the hydrophilic copolymer (B) having an oxyethylene group (preferably a polyoxyethylene chain), any resin can be used as a raw material. However, since the fatty acid metal salt (C) is likely to be exposed on the surface of the molded article, various resins can be blended into the thermoplastic resin composition.

It should be noted that, referring to FIG. 6, the fatty acid metal salt (C) and the hydrophilic copolymer (B) have different melt viscosities during molding. During molding, the thermoplastic resin (A) injected into the mold first hardens, then the hydrophilic copolymer (B) hardens, and then the fatty acid metal salt (C) with a low molecular weight hardens. That is, the hydrophilic copolymer (B) and the fatty acid metal salt (C) have slower solidification speeds than the thermoplastic resin (A), and tend to be exposed on the surface of the molded product. As described above, the hydrophilic copolymer (B) and the fatty acid metal salt (C) can be blended in the thermoplastic resin (A) because they have different melt viscosities during molding than the thermoplastic resin (A).

On the other hand, for example, a resin raw material with a high melting point (for example, about 320°C or higher) and extremely high polarity is difficult to disperse, so it is difficult to obtain the desired dust suppression effect. In other words, the hydrophilic copolymer (B) and the fatty acid metal salt (C) are more likely to gather near the surface layer of the molded article than the thermoplastic resin (A), so that the dust suppressing effect is likely to be exhibited.

Furthermore, the polar group of the low-molecular-weight fatty acid metal salt (C) has an affinity with the hydrophilic copolymer (B) having an oxyethylene group. Therefore, by attaching the hydrophilic copolymer (B) to the fatty acid metal salt (C), the hydrophilic copolymer (B) and the fatty acid metal salt (C) are prevented from being detached, and a large amount of can exist in Therefore, the effect of suppressing the adhesion of both hydrophilic and hydrophobic dust stains is likely to be exhibited.

<Production of thermoplastic resin composition>
Any method is employed for the production of the thermoplastic resin composition of the present embodiment. For example, a thermoplastic resin (A), a hydrophilic copolymer (B), a fatty acid metal salt (C) and optionally other additives are combined with a premixing means such as a V-blender, a Henschel mixer, a mechanochemical apparatus, an extrusion mixer, etc. After sufficiently mixing using, the pre-mixture is granulated with an extrusion granulator, briquetting machine, etc. as necessary, and then melt-kneaded with a melt-kneader typified by a vented twin-screw extruder. , and then pelletizing with a pelletizer.

In addition, there is a method of supplying each component independently to a melt kneader represented by a vented twin-screw extruder, or a method of premixing a part of each component and then supplying the rest of the components independently to a melt kneader. There are also methods of As a method of pre-mixing a part of each component, for example, after pre-mixing the components other than the thermoplastic resin (A), it is mixed with the thermoplastic resin (A), or a method of directly supplying to the extruder. mentioned.

As the extruder, one having a vent that can deaerate moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed from the vent for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to install a screen in front of the die portion of the extruder to remove foreign matters and the like mixed in the extruded raw material to remove the foreign matters from the resin composition. Such screens include wire meshes, screen changers, sintered metal plates (such as disk filters), and the like.

Examples of the melt-kneader include a Banbury mixer, a kneading roll, a single-screw extruder, and a multi-screw extruder with three or more screws, in addition to the twin-screw extruder.

The thermoplastic resin composition extruded as described above is directly cut and pelletized, or is pelletized by forming strands and then cutting the strands with a pelletizer. The shape of the pellet is preferably cylindrical. The diameter of such a cylinder is preferably 1-5 mm, more preferably 1.5-4 mm, still more preferably 2-3.3 mm. On the other hand, the length of the cylinder is preferably 1-30 mm, more preferably 2-5 mm, and even more preferably 2.5-3.5 mm.

Various products can be produced from the thermoplastic resin composition of the present embodiment by injection-molding the pellets produced as described above to obtain molded articles. In such injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including a method of injecting supercritical fluid), insert molding, in-mold coating molding, heat insulation Mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding can be mentioned. For molding, either cold runner method or hot runner method can be selected.

Also, the thermoplastic resin composition of the present embodiment can be used in the form of various profile extrudates, sheets, films, etc. by extrusion molding. In addition, the inflation method, calender method, casting method, and the like can be used for forming sheets and films. Furthermore, it is possible to form a heat-shrinkable tube by applying a stretching operation. The thermoplastic resin composition of the present embodiment can also be formed into a molded product by rotational molding, blow molding, or the like.

Embodiment 2.
A molded article according to the present embodiment is made of the above thermoplastic resin composition. In the molded article according to the present embodiment, the effect of suppressing adhesion of both hydrophilic dust stains and hydrophobic dust stains is exhibited by using the above thermoplastic resin composition.

In the molded article according to the present embodiment, the concentration (content in the thermoplastic resin composition) of the fatty acid metal salt (C) in the vicinity of the surface of the molded article (a portion from the surface to a certain depth) is is preferably higher than the concentration of the fatty acid metal salt (C) in the interior of (a portion deeper than a certain depth from the surface). Specifically, for example, the concentration of the fatty acid metal salt (C) in a portion within 10 nm from the surface of the molded article is higher than the concentration of the fatty acid metal salt (C) in a portion deeper than 10 nm from the surface of the molded article. preferable.

The term "surface of the molded article" as used herein means at least a part of the surface of the molded article, and does not need to be the entire surface of the molded article. It may be the surface.

Such a difference in the concentration of the fatty acid metal salt (C) in the depth direction of the molded product, for example, while scraping the surface of the molded product with Ar ions, the molded product in the state of being scraped to each depth. It can be confirmed by performing elemental analysis of the metal element M (measurement of the area ratio of the metal element M) on the surface using X-ray photoelectron spectroscopy (XPS) (see FIG. 2).

For example, as shown in FIG. 1, the concentration of fatty acid metal salt (C) (area ratio of metal element M) at each depth is measured within 10 nm from the surface of the molded product (measurement depth A). and find the highest concentration among them. On the other hand, the concentration of the fatty acid metal salt (C) is measured at a depth (L/2: measurement depth B) half the thickness L of the molded product indicated by the dotted line in FIG. By comparing the measured values of these concentrations, it is possible to confirm the difference in concentration of the fatty acid metal salt (C) in the depth direction of the molded product.

For example, in a sample (specimen) of a molded article having an antifouling effect on amphiphiles, which will be described later in Examples, the concentration of the fatty acid metal salt (C) in a portion within 10 nm from the surface is greater than 10 nm from the surface of the molded article. It was more than twice the concentration of the fatty acid metal salt (C) in the deep part. In a specific example, the concentration of the fatty acid metal salt (C) in a portion within 10 nm from the surface is 3.2% by mass at maximum, and the concentration of the fatty acid metal salt (C) in a portion deeper than 10 nm from the surface of the molded article is The concentration was about 0.3% to 0.6% by weight, the former being about 5-10 times higher than the latter.

In the fatty acid metal salt (C), the R portion is a non-polar group and the remaining portion is a polar group. It is believed that during molding, the polar groups are attached to the mold and the fatty acid metal salt (C) is aligned with the non-polar groups directed toward the inside of the thermoplastic resin composition. Furthermore, after molding, other fatty acid metal salt (C) melted inside the thermoplastic resin composition migrates to the surface.

In addition, since the fatty acid metal salt (C) has low compatibility with the thermoplastic resin, when it is blended in an amount equal to or greater than the critical solubility (concentration), it diffuses to the surface of the thermoplastic resin composition (molded article). . In the vicinity of the surface of the thermoplastic resin composition, a plurality of fatty acid metal salts (C) are bonded with their polar groups, and arranged with the hydrophobic group R, which is a non-polar group, facing the outside (air side) of the molded product. Conceivable.

Therefore, in the vicinity of the surface of the molded article, the concentration of the fatty acid metal salt (C) in the thermoplastic resin composition is higher than in the interior of the molded article, and the surface of the molded article to which dust stains adhere can be effectively treated. Energy reduction and water and oil repellency effects can be obtained. As a result, unlike the case where the fatty acid metal salt (C) is used as a general application such as a lubricant or a mold release agent, a new effect of suppressing adhesion of hydrophobic dust stains on the surface of the molded product is obtained. can get.

In the case of molding a molded product into an arbitrary shape after liquefying the resin material once, the component ratio of the thermoplastic resin composition according to Embodiment 1 should be the same at the stage of liquefaction. the above effect can be obtained. For example, it is possible for the thermoplastic resin composition of the present embodiment to contain the optional components described in the first embodiment at the stage of liquefying the resin material.

Embodiment 3.
A product according to the present embodiment includes the molded product described above. That is, the above-mentioned molded product is used, for example, as resin parts (internal parts, housings, etc.) of products such as home electric appliances and OA equipment. In the product of the present embodiment, by including the molded product described above, the effect of improving cleanliness and reducing the frequency of maintenance can be achieved.

Products include, for example, personal computers, notebook computers, CRT displays, printers, mobile terminals, mobile phones, copiers, fax machines, recording media (CD, CD-ROM, DVD, PD, FDD, etc.) drives, parabolic antennas, and power tools. , VTR, TV, iron, hair dryer, rice cooker, microwave oven, audio equipment, audio equipment (audio, laser disc (registered trademark), compact disc, etc.), lighting equipment (LED), remote control, ventilation fan, range hood, refrigerator , air conditioners (air conditioners, dehumidifiers, humidifiers, etc.), air purifiers, vacuum cleaners, rice cookers, cooking heaters, bath products, washroom products, jet towels, fans, typewriters, word processors, automobiles, vehicles Equipment (car navigation, car stereo, etc.), miscellaneous goods, and the like.

In addition, for example, if the above molded products are applied to resin parts such as air conditioners, doors, display devices, insulators, mirrors, measuring instruments, and operation parts of various devices, adhesion of dust dirt is reduced and cleanliness is improved. can be improved and maintenance frequency can be reduced. In particular, the molded article is useful as a resin part of a product that cannot be maintained for a long period of time by a user or a trader.

The molded article containing the above thermoplastic resin composition of the present embodiment can be applied as long as the product has a resin part, and can be widely applied without being limited to the uses described above.

In addition, since the antifouling effect can be easily obtained by molding alone, there is an advantage that there are overwhelmingly few complicated processes such as moving the molded product and coating work compared to painting or coating with an antifouling effect. Therefore, a molded article containing the above thermoplastic resin composition is suitable for mass production of products and has extremely high practicability. In addition, molded articles containing the above thermoplastic resin compositions can be applied as exterior members without worrying about surface unevenness, rainbow patterns, glossiness, etc., compared to antifouling paints and coatings. Since it has the advantage of being easy to use, it is suitable for mass production of products and has extremely high practicality.

FIG. 5 is a schematic cross-sectional view of the air conditioner according to this embodiment. As shown in FIG. 5, a main body case 10 of an indoor unit of an air conditioner is formed in a substantially oblong parallelepiped shape, and has an air inlet 11 on its upper surface and an air outlet 12 on its lower front surface. is provided. A pre-filter 17 is provided from the downstream side of the air suction port 11 to the front side of the body case 10 . A front panel 14 is provided to cover the front surface of the body case 10 .

A fan 13 is provided in the main body case 10 for sucking indoor air sucked from the air inlet 11 into the room from the air outlet 12 . A heat exchanger 22 is arranged on the upstream side of the fan 13 , and an air passage 21 is provided on the downstream side of the fan 13 , and air passes through the air passage 21 . A drain pan 18 is provided below the heat exchanger 22 .

Although not shown, the main body case 10 is provided with a fan motor for driving the fan 13, a control section for controlling the operation of the air conditioner, and the like.

The vertical

wind direction plates

15 and 16 adjust the blowing angle of the air blown from the air outlet 12 in the vertical direction. The left/right airflow direction plate 19 adjusts the blowing angle of the air blown out from the air outlet 12 in the left/right direction. Support shafts are provided at the ends of the vertical

wind direction plates

15 and 16, respectively, and are rotatably and detachably supported by bearings provided on the side walls of the air outlet 12, and the left and right wind direction plates 19 are fixed. There are cases where the direction can be set manually, and there are cases where it can be automatically rotated left and right by being driven by a motor.

When the fan 13 is driven, indoor air is sucked in through the air suction port 11, and the pre-filter 17, heat exchanger 22, fan 13, air passage 21, air outlet 12, left/right wind direction plate 19, and up/down

direction plates

15 and 16. Passing through in order, the wind is blown out into the room. Along with the air, hydrophilic dust stains such as dust, sand, and fibers, and hydrophobic dust stains such as oil smoke, soot, sebum, and tobacco come into contact with various air conditioner members along with the wind. The pre-filter 17, the heat exchanger 22, the fan 13, the air passage 21, the air outlet 12, the left and right wind direction plates 19, and the up and down

direction plates

15 and 16 are constantly being soiled. The sucked air also contacts the rear wall 20 facing the pre-filter 17 of the front panel 14, so that the rear wall 20 also continues to be soiled.

Styrene-based resin such as PS or ABS may be used as the constituent material of the front panel 14, the air outlet 12, the left/right wind direction plate 19, the up/down

direction plates

15 and 16, the air passage 21, and the rear wall 20. many. As a material for forming the frame of the pre-filter 17, an olefin resin such as polypropylene (PP) is often used. As a constituent material of the fan 13, an olefin resin such as PP or a styrene resin such as AS is often used.

A molded article containing the above thermoplastic resin composition can be suitably used for products that are constantly soiled, such as air conditioners.

As an effect of applying a molded product containing the above thermoplastic resin composition to an air conditioner, it is possible to reduce dirt on the parts, so it can be expected to improve cleanliness and reduce maintenance frequency. In addition, since there is no re-scattering of the dirt, discomfort caused when the odor caused by the dirt reaches with the wind is reduced. In addition, it is possible to suppress the growth of mold that feeds on adhering dirt. In addition, it is difficult to clean products such as air conditioners, which are installed high on the ceiling, and it is necessary for the user to use a stepladder or the like to clean them. can be lowered, which is particularly preferable for elderly people.

In addition, if dirt accumulates in the gaps of the fan 13 and fills the gaps, or if dirt accumulates on the surface of various air paths and narrows the air passage, the cooling and heating capacity will decrease due to the decrease in the air volume. However, by suppressing contamination by applying the above-mentioned molded product, it is possible to maintain the initial airflow at the time of purchase and suppress the increase in power consumption.

In addition, for example, vegetable trays in refrigerators often use styrene resins such as ABS and PS or olefin resins such as PP. Styrene-based resins such as ABS and PS or olefin-based resins such as PP are often used for dust boxes of vacuum cleaners. Sirocco fans of various ventilation fans and fans of electric fans often use olefin resins such as PP. In both cases, by reducing dirt, it is possible to reduce the trouble of maintenance.

<Evaluation method>
(1) Tensile strength Tensile strength (tensile yield strength) was measured according to ISO 527-1, 2. The measured value was compared with the tensile strength of the styrene resin (Component A) used alone, and evaluated based on the following criteria.

[Evaluation Criteria for Tensile Strength]
A: Retention rate is 95% or more, B: Retention rate is less than 95%, 90% or more, C: Retention rate is less than 90%, 85% or more, D: Less than 85% (2) Flexural modulus ISO 178, The flexural modulus was measured (specimen dimensions: length 80 mm×width 10 mm×thickness 4 mm). The measured value was compared with the flexural modulus of the styrene-based resin (Component A) and evaluated according to the following criteria.

[Evaluation Criteria for Flexural Modulus]
A: Retention rate is 95% or more, B: Retention rate is less than 95%, 90% or more, C: Retention rate is less than 90%, 85% or more, D: Less than 85% (3) Charpy impact strength According to ISO 179, Notched Charpy impact strength measurements were performed.
(4) Plane impact strength A square plate of 150 mm × 150 mm × 2 mm (thickness) was molded using an injection molding machine, and a high-speed plane impact test was performed at N = 5 to measure the plane impact strength (breaking energy). , N=5 were averaged. Also, the fracture mode was evaluated based on the following criteria.

[Evaluation Criteria for Fracture Mode]
A: ductile fracture, B: mixture of ductile fracture and brittle fracture (ductile fracture number > brittle fracture number), C: mixture of ductile fracture and brittle fracture (brittle fracture number > number of ductile fractures), D: brittle fracture In addition, the evaluation of the fracture mode indicates the mode in which the test piece does not break and scatter after the impact test, and the penetrating part of the shot center remains uniformly protruding. It was defined as ductile fracture, and brittle fracture when the test piece fractured in the shape of a striking core or a cradle, and the penetrating part remained flat and the end surface of the penetrating part showed a sharp state. The fracture morphology is preferably a ductile fracture morphology rather than a brittle fracture morphology.

As a tester, a high-speed surface impact tester Hydroshot HTM-1 (manufactured by Shimadzu Corporation) was used. The test conditions were as follows: impact speed of the striking core was 7 m/sec, a semi-circular tip with a radius of 6.35 mm was used, and the hole diameter of the cradle was 25.4 mm.
(5) Deflection temperature under load Deflection temperature under load was measured according to ISO 75-1 and 75-2. Note that the measurement load was 1.80 MPa.
(6) Evaluation of dust adhesion A square plate of 150 mm × 150 mm × 2 mm (thickness) was prepared and left in an environment of 23 ° C. and 50% humidity for one week, and then a dust adhesion test was performed on the square plate. bottom. Kanto loam (11 types of JIS test powder) was used for evaluation of hydrophilic dust adhesion, and carbon black (12 types of JIS test powder) was used for evaluation of hydrophobic dust adhesion.

Evaluation of dust adhesion is performed by blowing a certain amount (5 g) of dust on the surface of the molded product with air, and then observing the surface of the molded product at 100x with a digital microscope VHX-5000 manufactured by KEYENCE. The area ratio was determined and evaluated based on the following criteria.

[Evaluation Criteria for Dust Adhesion]
A: Dust adhesion area ratio is less than 3%, B: Dust adhesion area ratio is 3 to less than 6%, C: Dust adhesion area ratio is 6 to less than 9%, D: Dust adhesion area ratio is 9% or more <Example 1 to 20, Comparative Examples 1 to 20>
100 parts by mass of components A to C shown in Tables 1 to 8 (total amount of components A to C), release agent [Rikester EW400 (product name) manufactured by Riken Vitamin Co., Ltd.] 0.3 parts by mass, phosphorus heat Stabilizer [IRGAFOS168 (product name) manufactured by BASF] 0.1 parts by mass, phenolic heat stabilizer [manufactured by BASF; LA-57 (product name)] 0.2 parts by mass, and bend triazole-based ultraviolet absorber [SEESORB701 (product name) manufactured by Shipro Kasei Co., Ltd.] 0.1 parts by mass were mixed in a V-type blender, and the mixture was Obtained.

The resulting mixture was supplied from the first supply port of the extruder. The supply amount of the raw material (mixture) was precisely measured by a measuring instrument [CWF manufactured by Kubota Corporation]. For extruding the raw material, a vented twin-screw extruder with a diameter of 30 mm (Japan Steel Works, Ltd. TEX30α-38.5BW-3V) is used, the screw rotation speed is 200 rpm, the discharge rate is 20 kg / h, and the vent vacuum The raw materials were melt-kneaded under conditions of a viscosity of 3 kPa to obtain pellets of the thermoplastic resin composition. As for the extrusion temperature, the temperature from the first supply port to the die portion was set to the temperature shown in the table.

Some of the obtained pellets were dried with a hot air circulating dryer for 4 hours at the temperature shown in the table, and then molded into test pieces for evaluation using an injection molding machine (FANUC T-150D). Examples 1-20 and Comparative Examples 1-20). Basic conditions for injection molding were the cylinder temperature and mold temperature shown in the table, and the injection speed of 20 mm/s.

The components A to C shown in Tables 1 to 8 (symbolic components) are as follows.
[A component]
(PC: A1 component-1)
Aromatic polycarbonate resin [Panlite L-1225WX bisphenol A polycarbonate resin manufactured by Teijin Limited, viscosity average molecular weight = 19700]
(ABS: A2 component-1)
ABS resin [manufactured by Japan A&L Co., Ltd., Clarastic SXH-330 (trade name), weight average molecular weight in terms of standard polystyrene by GPC measurement: 90000, butadiene rubber component: about 17.5% by weight, weight average rubber particle diameter: 0 .40 μm]
(PET: A3 component-1)
Polyethylene terephthalate resin [Teijin Limited PET resin TR-8580H Ge-based catalyst used, IV = 0.83]
(PBT: A3 component-2)
Polybutylene terephthalate resin [DURANEX 500FP EF202X, IV=0.85, manufactured by Polyplastics Co., Ltd.])
(m-PPE: A4 component-1)
Modified polyphenylene ether resin [Polyphenylene ether obtained by oxidative polymerization of 2,6-xylenol (reduced viscosity measured at 30 ° C. in a chloroform solution with a concentration of 0.5 g / dL = 0.42 dL / g) and HIPS (PS Japan Co., Ltd. H8672) at a weight ratio of 40/60, using a vented twin-screw extruder with a diameter of 30 mm (Japan Steel Works, Ltd. TEX30α-38.5BW-3V), a cylinder temperature of 300 ° C., a screw Melt-kneaded at a rotation speed of 200 rpm, a discharge rate of 20 kg/h, and a vent vacuum degree of 3 kPa. ]
(PMMA: A5 component-1)
Polymethyl methacrylate resin [high-impact methacrylic resin: ACRYPET IRS204 manufactured by Mitsubishi Rayon Co., Ltd., acrylic resin composed of acrylic resin matrix component and acrylic rubber component, MFR = 13 g/10 min (230°C/3.8 kgf)]
(PPS: A6 component-1)
Polyphenylene sulfide resin [16.5 kg of sodium sulfide (containing 49% water of crystallization), 6.5 kg of sodium hydroxide, 5.2 kg of sodium acetate, and 22.0 kg of N-methyl-2-pyrrolidone were charged and dehydrated at 210°C. After that, 20.5 kg of 1,4-dichlorobenzene and 20.0 kg of N-methyl-2-pyrrolidone were added and reacted at 265° C. for 5 hours. Obtained by drying the reaction product after washing with water. The glass transition temperature was 90°C, the melting point was 280°C, and the number average molecular weight was 11,500. ]
(PA6: A8 component-1)
Polyamide 6 resin [Amilan CM1017 manufactured by Toray Industries, Inc., melting point = 225°C]
(PA66: A8 component-2)
Polyamide 66 resin [Amilan CM3001-N manufactured by Toray Industries, Inc., melting point = 260°C]
[B component]
Hydrophilic copolymer produced as follows (surface resistance: 8×10 ⁸ Ω)
(Production of component B)
1,4-cyclohexanedimethanol (544 g), adipic acid (558 g) and isophthalic acid (33 g) are polymerized in the presence of an antioxidant using a titanate-based catalyst at 210° C. under reduced pressure for 3 hours, A polyester having carboxyl groups at both ends was obtained.

The polyester (600 g) and polyethylene glycol (300 g) having hydroxyl groups at both ends are polymerized in the presence of an antioxidant using a zirconium catalyst at 210° C. under reduced pressure for 7 hours to form carboxyl groups at both ends. An alternating copolymer having

The obtained alternating copolymer (300 g) and trimethylolpropane (2.3 g) were polymerized at 240° C. under reduced pressure for 6 hours to convert the blocks derived from the alternating copolymer from trimethylolpropane. A hydrophilic copolymer (Component B: PEPO) having a structure formed by bonding via The obtained surface resistance value of the B component was 8×10 ⁸ Ω. Also, the melting point of the B component was about 90 to 100°C.

[Component C]
(StAl)
(Hydroxy) aluminum distearate [manufactured by NOF Corporation, aluminum stearate 600 (product name), metal content = 8.5 to 10.0%, free fatty acid = 12.0% or less, melting point: 150 to 160 ° C. ]
Tables 1 to 8 show the evaluation results of the above (1) to (6) for the obtained test pieces for evaluation (Examples 1 to 20 and Comparative Examples 1 to 20). However, not all of the above evaluations (1) to (6) were performed for all the examples and comparative examples.

From the evaluation results shown in Tables 1 to 8, a thermoplastic resin (A), a hydrophilic copolymer having an oxyethylene group (B), and a thermoplastic resin composition containing a fatty acid metal salt (C) were molded. It can be confirmed that in the examples, which are good products, an excellent adhesion suppressing effect (antifouling effect) is obtained against hydrophilic and hydrophobic dust stains.

Furthermore, it can be confirmed that good mechanical strength of the molded product can be obtained by adjusting the blending amount of each component.

In addition, when (hydroxy)aluminum distearate is used as the fatty acid metal salt (C) (that is, when the metal element M has a valence of 3 and a metal salt containing two fatty acids is used), Compared to the case of using zinc stearate, aluminum monostearate or aluminum tristearate, there is a tendency for the adhesion suppression effect (antifouling effect) to be superior to both hydrophilic dust stains and hydrophobic dust stains. .

The embodiments and examples disclosed this time should be considered illustrative in all respects and not restrictive. The scope of the present disclosure is indicated by the scope of claims rather than the above description, and is intended to include all changes within the meaning and scope of equivalence to the scope of claims.

10 main body case, 11 air inlet, 12 air outlet, 13 fan, 14 front panel, 15, 16 vertical wind direction plate, 17 pre-filter, 18 drain pan, 19 left and right wind direction plate, 20 rear wall, 21 air passage, 22 heat exchanger.

Claims

Aromatic polycarbonate resin (A1), styrene resin (A2), aromatic polyester resin (A3), polyphenylene ether resin (A4), methacrylic resin (A5), polyarylene sulfide resin (A6), olefin resin (A7 ), a polyamide resin (A8), and a thermoplastic resin (A) selected from the group consisting of mixtures thereof;
a hydrophilic copolymer (B) having an oxyethylene group;
and a fatty acid metal salt (C) represented by the following formula (1),
The hydrophilic copolymer (B) is a polyhydric alcohol compound (b1 ), an epoxy compound (b2) having two or more epoxy groups, and at least one selected from the group consisting of a polycarboxylic acid compound (b3) and a thermoplastic resin composition formed by bonding via an ester bond. thing.

M(OH)y(R-COO)x (1)

(In formula (1), R is an alkyl group or alkenyl group having 6 to 40 carbon atoms. M is at least one metal selected from the group consisting of aluminum, zinc, calcium, magnesium, lithium and barium. is an element, x and y are each independent integers of 0 or more and satisfy the relationship x + y = [valence of M].)
Claim 1, containing 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) The thermoplastic resin composition described.
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.
The thermoplastic resin composition according to claim 3, wherein M is aluminum in the formula (1).
The thermoplastic resin composition according to any one of claims 1 to 4, wherein in the formula (1), the valence of M is 3 or more and y is 1.
The styrene resin (A2) is selected from the group consisting of PS resin, HIPS resin, MS resin, ABS resin, AS resin, AES resin, ASA resin, MBS resin, MABS resin, MAS resin, and mixtures thereof , The thermoplastic resin composition according to any one of claims 1 to 5.
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 resin, polyethylene terephthalate resin, and mixtures thereof.
A molded article containing the thermoplastic resin composition according to any one of claims 1 to 7.
The concentration of the fatty acid metal salt (C) in a portion from the surface of the molded article to a certain depth is higher than the concentration of the fatty acid metal salt (C) in a portion deeper than a certain depth from the surface of the molded article. A molded article according to claim 8 .
A product comprising the molded article according to claim 8 or 9.