JP2013014684A - Thermoplastic resin composition for supercritical foam molding with excellent characteristics for die corrosivity - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for supercritical foam molding excellent characteristics for die corrosivity, and also excellent in mechanical strengths, flowability, and mold releasability.SOLUTION: The thermoplastic resin composition for foam molding contains 0.05-2 pts.wt. of (B) a non-ester releasing agent (B component) based on 100 pts.wt. of (A) a thermoplastic resin (A component).

Description

  In the molding process of a foamed resin composition by physical foaming using a supercritical fluid, the present invention is excellent in mold corrosiveness by containing a specific additive in a specific ratio, and has a mechanical strength that a conventional resin has, The present invention relates to a resin composition for supercritical foam molding that is also excellent in fluidity and releasability.

  In recent years, for plastic materials used in office machines such as laser beam printers, copiers, and projectors, electrical and electronic equipment such as personal computers, information communication equipment and cameras, automobile parts such as automobiles and railway vehicles, etc. Various properties such as mechanical strength, fluidity, flame retardancy, and dimensional accuracy are required depending on the application. In recent years, regardless of the field or application, environmentally friendly designs have been made that focus on reducing fuel consumption by reducing the amount of resin used, or improving fuel efficiency by reducing weight in vehicle parts applications. As part of this, manufacturing methods that reduce the weight and reduce the amount of resin used, such as thin wall design, hollow molding, and foam molding, have been adopted.

  However, even in resin compositions in which mold corrosion problems do not occur in conventional processing methods such as injection molding, such manufacturing methods, particularly foam molding, more specifically, supercritical fluid is added to molten resin. By adopting a foam molding method using a physical foaming method for foaming, there has been a problem of mold corrosion.

  Patent Document 1 discloses a resin composition having thermal stability at the time of residence and mold corrosion characteristics by setting the amount of alkali metal salt, alkaline earth metal salt and chlorine in ABS to a specific amount or less. In Patent Document 2, a rubber-reinforced styrene resin containing a bromine-based compound as a flame retardant is subjected to injection molding in a state in which a pressurized gas of atmospheric pressure or higher is applied to a mold cavity so that corrosive gaseous substances are contained in the resin. Discloses an injection molding method for preventing mold corrosion. Patent Document 3 discloses a flame retardant having reduced metal corrosivity by containing no halogen element in the molecular structure of the flame retardant, and by making the contents of chlorine, bromine and phenols in the resin composition total amount below a specific amount. A functional resin composition is disclosed. Patent Documents 4 and 5 disclose flame retardant thermoplastic resin compositions in which specific amounts of higher fatty acids and partial esters of polyhydric alcohols or epoxy compounds are added for the purpose of preventing mold corrosion caused by brominated flame retardants. ing. However, in Patent Documents 2 to 4, there is no specific description regarding foam molding, but only a description regarding mold corrosion prevention regarding a general injection molding method. Although a method for preventing mold corrosion by keeping the inside of the mold in a pressurized state and keeping the corrosive gas in the molten resin has been described, the results of studies on the resin composition are not shown. Further, in the foam molding referred to in the present application, even in a resin composition that does not take mold corrosion prevention measures as described in Patent Documents 2 to 4, in a period of use in which a mold corrosion problem does not normally occur, There is a problem that mold corrosion occurs due to foam molding of the resin composition. In other words, there has been room for improvement since sufficient investigation has not been made on prevention of mold corrosion in foam molding.

Japanese Patent Laid-Open No. 06-263962 Japanese Examined Patent Publication No. 58-042823 Japanese Patent Laid-Open No. 10-045945 Japanese Patent Laid-Open No. 09-227787 JP 09-272757 A

  An object of the present invention is to provide a resin composition for supercritical foam molding that is excellent in mold corrosiveness and excellent in mechanical strength, fluidity, and releasability.

  As a result of intensive studies, the present inventor has found that the above-described problems can be solved by containing a specific release agent at a specific ratio. The present invention has been completed by further study.

According to the present invention, the above-mentioned problems include (1) (A) thermoplastic resin (component A) 100 parts by weight, and (B) non-ester release agent (component B) 0.05 to 2 parts by weight. This is achieved by the thermoplastic resin composition for supercritical foam molding.
One of the preferred embodiments of the present invention is the thermoplastic resin composition for supercritical foam molding of the above constitution (1), wherein (2) B component is a polyolefin-based mold release agent.
One of the preferred embodiments of the present invention is (3) oxidation-modified polyethylene in which the component B has a molecular weight of 2,000 to 6,000 and an acid value of 0.1 to 3.0 mg / KOH. It is a thermoplastic resin composition for supercritical foam molding of said structure (2).
One of the preferred embodiments of the present invention is that (4) the A component is an aromatic polycarbonate resin (A-1 component), a styrene resin (A-2 component), and a polyphenylene ether resin (A-3 component). The thermoplastic resin composition for supercritical foam molding according to any one of the above constitutions (1) to (3), which is at least one thermoplastic resin selected from the group consisting of:
One of the preferred embodiments of the present invention is any one of the above constitutions (1) to (4) containing (C) 2 to 30 parts by weight of a flame retardant (C component) with respect to 100 parts by weight of the A component. This is a thermoplastic resin composition for supercritical foam molding.
One preferred embodiment of the present invention is the above (6) containing 0.05 to 5 parts by weight of a fluorine-containing anti-dripping agent (D component) having a fibril-forming ability with respect to 100 parts by weight of the A component. It is a thermoplastic resin composition for supercritical foam molding in any one of constitutions (1) to (5).
One of the preferred embodiments of the present invention is (7) the thermoplastic resin composition for supercritical foam molding according to any one of the above constitutions (1) to (6), wherein the supercritical fluid is nitrogen.
One of the preferred embodiments of the present invention is a foam-molded article comprising (8) the supercritical foam-molding thermoplastic resin composition of any one of the above constitutions (1) to (7).
One of the preferred embodiments of the present invention is (9) foam molding of the above configuration (8), which is a part used in office machines, household appliances, electrical and electronic equipment, and vehicles having a weight reduction rate of 3% or more. It is a product.

Details of the present invention will be described below.
<About component A>
The thermoplastic resin of the component A used in the present invention is not basically limited, and a thermoplastic resin conventionally used for office machines, household appliances, electrical and electronic equipment, and vehicle parts is preferably used. . Examples of the thermoplastic resin include polyolefin resins such as polyethylene resin, polypropylene resin, poly-4-methylpentene-1, and cyclic polyolefin resin, PS resin, HIPS resin, MS resin, ABS resin, AS resin, and AES resin. , ASA resin, MBS resin, MAS resin, hydrogenated polystyrene resin, styrene resin such as SMA resin, acrylic resin such as polymethyl methacrylate, polyphenylene resin such as PPE resin and PPS resin, polyamide resin, polycarbonate resin, polyphenylene Ether resins, PET resins, polyester resins such as PBT resins and aliphatic polyesters, thermoplastic resins such as polyarylate resins, styrene thermoplastic elastomers, olefin thermoplastic elastomers, poly Ester-based elastomers include polyamide elastomer.

  A more preferred thermoplastic resin of the present invention is selected from the group consisting of an aromatic polycarbonate resin (A-1 component), a styrene resin (A-2 component), and a polyphenylene ether resin (A-3 component). At least one thermoplastic resin. Among them, a thermoplastic resin comprising an A-1 component and an A-2 component, and a total of 100 parts by weight of the A-1 component and the A-2 component, the A-1 component is 50 parts by weight or more, or A-2 The thermoplastic resin which consists of a component and an A-3 component and whose A-3 component of a total of 100 weight part of A-2 component and A-3 component is 30 weight part or more is preferable.

[Polycarbonate resin]
The polycarbonate resin used in the present invention may be various polycarbonate resins that are polymerized using other dihydric phenols in addition to the commonly used bisphenol A-type polycarbonate and that have high heat resistance or low water absorption. Good. The polycarbonate resin may be produced by any production method, and in the case of interfacial polycondensation, a terminal stopper of a monohydric phenol is usually used. The polycarbonate resin may also be a branched polycarbonate resin obtained by polymerizing trifunctional phenols, and further a copolymer obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a divalent aliphatic or alicyclic alcohol. Polycarbonate may be used. The viscosity average molecular weight of the polycarbonate resin is preferably 1.3 × 10 ^{4 to} 4.0 × 10 ⁴ , more preferably 1.5 × 10 ^{4 to} 3.8 × 10 ⁴ . The viscosity average molecular weight (M) of the aromatic polycarbonate resin is obtained by inserting the specific viscosity (ηsp) obtained at 20 ° C. from a solution of 0.7 g of the polycarbonate resin in 100 ml of methylene chloride into the following equation. Details of the polycarbonate resin are described in JP-A No. 2002-129003.
η _sp /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

As specific examples of various polycarbonate resins polymerized using other dihydric phenols and having high heat resistance or low water absorption, the following can be suitably exemplified.
(1) In 100 mol% of the dihydric phenol component constituting the polycarbonate, 4,4 '-(m-phenylenediisopropylidene) diphenol (hereinafter abbreviated as "BPM") component is 20 to 80 mol% (more preferable) 40 to 75 mol%, more preferably 45 to 65 mol%), and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as "BCF") component is 20 to 20 mol. Copolycarbonate which is 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the bisphenol A component is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%), And a BCF component in an amount of 5 to 90 mol% (more preferably 10 to 50 mol%, and still more preferably 15 to 40 mol%).
(3) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and The 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane component is 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%). Copolycarbonate. These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used. The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing. Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

  As the polycarbonate resin, not only a virgin raw material but also a polycarbonate regenerated from a used product can be used. Examples of the used products include containers represented by water bottles, optical disks, automobile headlamps, and the like.

[Styrene resin]
Examples of the styrenic resin used in the present invention include homopolymers or copolymers of styrene derivatives such as styrene, α-methylstyrene, and p-methylstyrene, these monomers and vinyl such as acrylonitrile and methyl methacrylate. Examples thereof include a copolymer with a monomer. Furthermore, diene rubbers such as polybutadiene, ethylene / propylene rubber, acrylic rubber, and composites that have a structure in which the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are intertwined so that they cannot be separated. Examples of the rubber (hereinafter referred to as IPN type rubber) include styrene and / or styrene derivatives, or those obtained by graft polymerization of styrene and / or styrene derivatives and other vinyl monomers. Examples of such styrene resins include polystyrene, styrene / butadiene / styrene copolymer (SBS), hydrogenated styrene / butadiene / styrene copolymer (hydrogenated SBS), hydrogenated styrene / isoprene / styrene copolymer (water). SIS), impact polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), methyl Methacrylate / acrylonitrile / butadiene / styrene copolymer (MABS resin), acrylonitrile / acrylic rubber / styrene copolymer (AAS resin), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES resin) and styrene / IP Resins such as type rubber copolymer or mixtures thereof.

  Such a styrenic thermoplastic resin may have a high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst at the time of production. Further, in some cases, polymers and copolymers having a narrow molecular weight distribution, block copolymers, polymers with high stereoregularity, and copolymers obtained by methods such as anion living polymerization and radical living polymerization are used. It is also possible. For the purpose of improving the compatibility with the polycarbonate resin, it is possible to copolymerize a compound having a functional group such as maleic anhydride or N-substituted maleimide with the styrenic resin.

Among these, when used in combination with polycarbonate, which is the main resin suitably used in the present invention, from the viewpoint of affinity with the polycarbonate resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / Styrene copolymer (ABS resin) is preferred. It is also possible to use a mixture of two or more styrene resins. The AS resin used in the present invention is a thermoplastic copolymer obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound. Examples of such vinyl cyanide compounds include those described above, and acrylonitrile is particularly preferred. As the aromatic vinyl compound, those described above can be used as well, but styrene and α-methylstyrene are preferably used. The proportion of each component in the AS resin is preferably 5 to 50% by weight of vinyl cyanide compound, more preferably 15 to 35% by weight, and preferably 95% of aromatic vinyl compound when the total is 100% by weight. -50% by weight, more preferably 85-65% by weight. Furthermore, the above-mentioned other copolymerizable vinyl compounds can be used by mixing with these vinyl compounds, and the content ratio thereof is preferably 15% by weight or less in the AS resin component. Moreover, conventionally well-known various things can be used for the initiator, chain transfer agent, etc. which are used by reaction as needed. Such an AS resin may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization, but is preferably bulk polymerization. The copolymerization method may be either one-stage copolymerization or multistage copolymerization. Further, the reduced viscosity of the AS resin is preferably 0.2 to 1.0 dl / g, more preferably 0.3 to 0.5 dl / g. The reduced viscosity is a value obtained by precisely weighing 0.25 g of AS resin and measuring a solution obtained by dissolving in 50 ml of dimethylformamide over 2 hours in an environment of 30 ° C. using an Ubbelohde viscometer. A viscometer having a solvent flow time of 20 to 100 seconds is used. The reduced viscosity is determined from the following formula from the solvent flow down seconds (t ₀ ) and the solution flow down seconds (t).
Reduced viscosity (η _sp / C) = {(t / t ₀ ) −1} /0.5
When the reduced viscosity is less than 0.2 dl / g, the impact is lowered, and when it exceeds 1.0 dl / g, the fluidity may be deteriorated.

  The ABS resin used in the present invention is a mixture of a thermoplastic graft copolymer obtained by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound to a diene rubber component, and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. It is. As the diene rubber component forming this ABS resin, for example, rubber having a glass transition temperature of −30 ° C. or less such as polybutadiene, polyisoprene and styrene-butadiene copolymer is used, and the proportion thereof is 100% by weight of the ABS resin component. The content is preferably 5 to 80% by weight, more preferably 8 to 50% by weight, and particularly preferably 10 to 30% by weight. Examples of the vinyl cyanide compound grafted onto the diene rubber component include those described above, and acrylonitrile is particularly preferably used. As the aromatic vinyl compound grafted onto the diene rubber component, those described above can be used as well, and styrene and α-methylstyrene are particularly preferably used. The ratio of the component grafted to the diene rubber component is preferably 95 to 20% by weight, particularly preferably 90 to 50% by weight, based on 100% by weight of the ABS resin component. Furthermore, it is preferable that the vinyl cyanide compound is 5 to 50% by weight and the aromatic vinyl compound is 95 to 50% by weight with respect to 100% by weight of the total amount of the vinyl cyanide compound and the aromatic vinyl compound. Further, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide and the like can be mixed and used for some of the components grafted to the diene rubber component, and the content ratio thereof is in the ABS resin component. What is 15 weight% or less is preferable. Furthermore, conventionally well-known various things can be used for the initiator, chain transfer agent, emulsifier, etc. which are used by reaction as needed.

  In the ABS resin of the present invention, the rubber particle diameter is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, and particularly preferably 0.3 to 1.5 μm. As the distribution of the rubber particle diameter, either a single distribution or a rubber particle having two or more peaks can be used, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles.

In addition, it is well known that the ABS resin contains a vinyl cyanide compound and an aromatic vinyl compound that are not grafted to the diene rubber component, and the ABS resin of the present invention is free of the occurrence of such polymerization. The polymer component may be contained. The reduced viscosity of the copolymer comprising such free vinyl cyanide compound and aromatic vinyl compound is preferably 0.2 to 1.0 dl / g in reduced viscosity (30 ° C.) determined by the method described above. Preferably it is 0.3-0.7 dl / g.
The ratio of the grafted vinyl cyanide compound and aromatic vinyl compound is preferably 20 to 200%, more preferably 20 to 70% in terms of graft ratio (% by weight) with respect to the diene rubber component. is there.

  Such an ABS resin may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization, but is preferably bulk polymerization. In the case of bulk polymerization, an alkali metal salt derived from an emulsifier and the like is substantially not contained, and thus the thermal stability of the polycarbonate resin composition can be kept better. Further, the copolymerization may be carried out in one step or in multiple steps. Moreover, what blended the vinyl compound polymer obtained by copolymerizing an aromatic vinyl compound and a vinyl cyanide component separately to the ABS resin obtained by this manufacturing method can also be used preferably.

[Polyphenylene ether resin]
The polyphenylene ether resin used in the present invention is a polymer or copolymer of a nucleus-substituted phenol having a phenylene ether structure (hereinafter sometimes simply referred to as a PPE polymer). Typical examples of the polymer of the nucleus-substituted phenol having a phenylene ether structure include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl-1,4-phenylene) ether. Poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1) , 4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl) -6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, and the like. Of these, poly (2,6-dimethyl-1,4-phenylene) ether is particularly preferred. Representative examples of the copolymer of a nucleus-substituted phenol having a phenylene ether structure include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and o-cresol, Or a copolymer of 2,6-dimethylphenol with 2,3,6-trimethylphenol and o-cresol. The method for producing the above PPE polymer is not particularly limited. For example, according to the method described in US Pat. No. 4,788,277 (Japanese Patent Application No. 62-77570), in the presence of dibutylamine. In addition, 2,6-xylenol can be produced by oxidative coupling polymerization. Various molecular weights and molecular weight distributions of polyphenylene ether can be used. The molecular weight is 0.5 g / dl chloroform solution, and the reduced viscosity at 30 ° C. is in the range of 0.20 to 0.70 dl / g. The range of 0.30 to 0.55 dl / g is more preferable. In addition, the polyphenylene ether of the present invention includes, as a partial structure, other various phenylene ether units that have been proposed to exist in the polyphenylene ether as long as the gist of the present invention is not contradicted. It doesn't matter. Examples of those proposed to coexist in a small amount include 2- (dialkylaminomethyl) -6-methylphenylene ether described in Japanese Patent Application Nos. 63-12698 and 63-301222. Unit, 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit, and the like. Also included are those in which a small amount of diphenoquinone or the like is bonded to the main chain of polyphenylene ether.

[Polyester resin]
The polyester-based resin used in the present invention includes both aliphatic polyester resins and aromatic polyester resins. Examples of the aliphatic polyester resin include polyester polymers and copolymers formed from aliphatic hydroxycarboxylic acids such as lactic acid and ε-caprolactone. The aromatic polyester resin is a polyester polymer formed from an aromatic dicarboxylic acid and a diol and a polyester polymer formed from a hydroxy aromatic carboxylic acid, and a polyalkylene terephthalate (a copolymer of another aromatic dicarboxylic acid). ), Polyalkylene naphthalates (including copolymers of other aromatic dicarboxylic acids), and fully aromatic polyesters such as polymers of dihydric phenols and aromatic dicarboxylic acids and polymers of hydroxy aromatic carboxylic acids Resins are exemplified and any of them can be used. The aromatic polyester resin refers to a polyester resin containing an aromatic dicarboxylic acid component in an amount of preferably 80 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more in 100 mol% of the dicarboxylic acid component. The diol component of the aromatic polyester resin contains an aliphatic diol or an alicyclic diol preferably in an amount of 80 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more in 100 mol%. Polyester resin. Here, the dicarboxylic acid component indicates a structural unit derived from a dicarboxylic acid of an aromatic polyester resin or an ester-forming derivative thereof, and the diol component is derived from a diol of an aromatic polyester resin or an ester-forming derivative thereof. Indicates the structural unit to perform.

  Polycaprolactone can be produced by, for example, ring-opening polymerization of caprolactone in the presence of a catalyst such as an acid, a base, or an organometallic compound. Moreover, the terminal of polycaprolactone may be subjected to terminal treatment such as esterification or etherification. The molecular weight of polycaprolactone is not particularly limited, but is preferably 300 to 40,000, more preferably 400 to 30,000, still more preferably 400 to 15,000, and more preferably 500 to 12,000 in terms of number average molecular weight. Is particularly preferred. Such a preferred molecular weight polycaprolactone has both good thermal stability and flow modification effect.

  As the polyester resin formed from an aliphatic hydroxycarboxylic acid, a copolymer of polylactic acid and / or lactic acid and other hydroxycarboxylic acid is suitable. Polylactic acid is synthesized by ring-opening polymerization from a cyclic dimer of lactic acid, usually called lactide, and its production method is disclosed in USP 1,995,970, USP 2,362,511, USP 2,683,136. Copolymers of lactic acid and other hydroxycarboxylic acids are usually synthesized by ring-opening polymerization from a cyclic ester intermediate of lactide and hydroxycarboxylic acid, and their production methods are disclosed in USP 3,635,956 and USP 3,797,499. Has been. In the case of producing a lactic acid resin by direct dehydration polycondensation without using ring-opening polymerization, lactic acids and other hydroxycarboxylic acids as necessary are preferably azeotroped in the presence of an organic solvent, particularly a phenyl ether solvent. A lactic acid resin having a degree of polymerization suitable for the present invention is obtained by polymerizing by a method of dehydrating condensation and, particularly preferably, removing water from a solvent distilled by azeotropic distillation to return it to a substantially anhydrous solvent. Is obtained. L- and D-lactic acid, a mixture thereof, or lactide, which is a dimer of lactic acid, can be used as the starting lactic acid. Other hydroxycarboxylic acids that can be used in combination with lactic acids include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, and 6-hydroxycaproic acid. A cyclic ester intermediate of carboxylic acid, for example, glycolide, which is a dimer of glycolic acid, or ε-caprolactone, which is a cyclic ester of 6-hydroxycaproic acid, can also be used.

  The following are illustrated as an example of the aromatic dicarboxylic acid which comprises aromatic polyester resin. In the following specific examples of the dicarboxylic acid component and the diol component, “component” is abbreviated. That is, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6 -Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5- Examples thereof include Na sulfoisophthalic acid and ethylene-bis-p-benzoic acid. These dicarboxylic acids can be used alone or in admixture of two or more. Of these, terephthalic acid and 2,6-naphthalenedicarboxylic acid can be preferably used.

  Other copolymerizable dicarboxylic acids include aliphatic and alicyclic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Mention may be made of acids. Aromatic dicarboxylic acids and copolymerizable dicarboxylic acids can be used alone or in admixture of two or more.

Examples of the diol component of the aromatic polyester resin include ethylene glycol, 1,4-butanediol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- Or aliphatic diols such as cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, and decamethylene glycol; Alicyclic diols such as 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and cyclohexanediol, and dihydric phenols such as p-xylenediol and bisphenol A. If the amount is even smaller, one or more long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and the like may be copolymerized. These diol components can be used alone or in combination of two or more.
These can be used alone or in admixture of two or more. In addition, when dihydric phenol is included as a copolymerization component, it is preferable that the dihydric phenol in a diol component is 30 mol% or less.

  Specific aromatic polyester resins include polyethylene terephthalate resin (PET), cyclohexanedimethanol copolymerized PET, polypropylene terephthalate resin, polybutylene terephthalate resin (PBT), polyhexylene terephthalate resin, polyethylene naphthalate resin (PEN), Polybutylene naphthalate resin (PBN), polyethylene-1,2-bis (phenoxy) ethane-4,4′-dicarboxylate resin, polyethylene isophthalate / terephthalate copolymer, polybutylene terephthalate / isophthalate copolymer, Examples include polyethylene naphthalate / terephthalate copolymer and polybutylene naphthalate / terephthalate copolymer. Among them, polyethylene terephthalate resin, polybutylene Terephthalate resin is preferably used.

In PET, ethylene glycol is generally used as the diol and terephthalic acid is used as the aromatic dicarboxylic acid. However, the PET in the present invention may contain a dicarboxylic acid component other than the terephthalic acid component as a copolymer component.
Examples of such other dicarboxylic acid components include isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid. Acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane Examples thereof include structural units derived from dicarboxylic acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid and the like. These dicarboxylic acid components can be used alone or in admixture of two or more. The dicarboxylic acid component other than the terephthalic acid component is preferably 30 mol% or less, more preferably 20 mol% or less, when the total amount of the dicarboxylic acid component is 100 mol%.

  Furthermore, the PET of the present invention can be copolymerized with an aliphatic dicarboxylic acid component of less than 30 mol% in addition to the aromatic dicarboxylic acid component. Specific examples of the component include structural units derived from adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like.

  The PET of the present invention may contain a diol component other than the ethylene glycol component as a copolymer component. Examples of other diol components include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or -2,2,4,4. -Tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedi Examples include structural units derived from methanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether), and the like. These can be used alone or in admixture of two or more.

Further, polyethylene terephthalate obtained by slightly copolymerizing a polyethylene glycol component can be used as the diol component. The molecular weight of the polyethylene glycol component is preferably in the range of 150 to 6,000.
The composition ratio of the polyethylene glycol component is preferably 5% by weight or less, more preferably 3% by weight or less, and still more preferably 2% by weight or less in 100% by weight of the diol component. On the other hand, the lower limit is preferably 0.5% by weight or more, and more preferably 1% by weight or more.

Furthermore, in PET, as a side reaction product at the time of polymerization, about 100 mol% of the diol component contains about 0.5 mol% or more of a diethylene glycol component, but the diethylene glycol component is preferably 6 mol% or less, 5 mol% or less is still more preferable.
In the PET of the present invention, a terephthalic acid component and isophthalic acid in a polyethylene terephthalate / isophthalate copolymer (hereinafter sometimes referred to as TA / IA copolymer) in which a part of the terephthalic acid component is an isophthalic acid component. The proportion of the component is preferably 70 to 99.9 mol%, more preferably 75 to 99 mol%, still more preferably 80 to 99 mol% of the terephthalic acid component when the total dicarboxylic acid component is 100 mol%. is there. The isophthalic acid component is preferably 0.1 to 30 mol%, more preferably 1 to 25 mol%, and still more preferably 1 to 20 mol%.

  Further, in this TA / IA copolymer, the aromatic dicarboxylic acid component such as naphthalenedicarboxylic acid other than the terephthalic acid component and isophthalic acid component is preferably 10 mol% or less, more preferably 5 mol% or less, and adipine. It is possible to copolymerize the aliphatic dicarboxylic acid component such as an acid, preferably 5 mol% or less, more preferably 3 mol% or less, but consisting only of a terephthalic acid component and an isophthalic acid component as the dicarboxylic acid component Is most preferred. Further, the ethylene glycol component alone is most preferable as the diol component in the TA / IA copolymer, but a diol component other than ethylene glycol can be copolymerized.

  In the PET of the present invention, an ethylene glycol component and neopentyl in a polyethylene / neopentyl terephthalate copolymer (hereinafter sometimes referred to as EG / NPG copolymer) in which a part of the ethylene glycol component is a neopentyl glycol component in the PET of the present invention. The proportion of the glycol component is preferably from 90 to 99 mol%, more preferably from 95 to 99 mol%, still more preferably from 97 to 99 mol%, when the total diol component is 100 mol%. Further, the neopentyl glycol component is preferably 1 to 10 mol%, more preferably 1 to 8 mol%, and further preferably 1 to 5 mol%. It is also possible to copolymerize diol components other than ethylene glycol and neopentyl glycol.

  In the EG / NPG copolymer, the aromatic dicarboxylic acid component such as isophthalic acid and naphthalenedicarboxylic acid other than the terephthalic acid component is preferably 10 mol% or less, more preferably 5 mol% or less, and adipic acid or the like. The above aliphatic dicarboxylic acid component can be copolymerized preferably in an amount of 5 mol% or less, more preferably 3 mol% or less, and most preferably the dicarboxylic acid component is a terephthalic acid component alone. It is also possible to copolymerize an aliphatic dicarboxylic acid component.

  Regarding the method for producing PET used in the present invention, in accordance with a conventional method, in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., a compound that induces a dicarboxylic acid component while heating and the diol component are derived. This is carried out by polymerizing the resulting compound and discharging by-product water or lower alcohol out of the system. As the polycondensation catalyst, a germanium-based polymerization catalyst is preferable, and examples thereof include germanium oxides, hydroxides, halides, alcoholates, phenolates, and the like. More specifically, germanium dioxide, germanium hydroxide, Examples include germanium tetrachloride and tetramethoxygermanium. Other examples include insoluble catalysts such as antimony trioxide. In particular, PET using a germanium polymerization catalyst is suitable for the purpose of the present invention, particularly chemical resistance and heat stability.

  Further, in the present invention, compounds such as manganese, zinc, calcium, magnesium, etc., which are used in a transesterification reaction that is a prior stage of a conventionally known polycondensation, can be used in combination, and phosphoric acid or phosphorous after completion of the transesterification Such a catalyst can be deactivated and polycondensed with an acid compound or the like. The production method of PET can be either batch type or continuous polymerization type.

  The IV value of PET used in the present invention is preferably 0.45 to 0.57 dl / g, more preferably 0.47 to 0.55 dl / g, and still more preferably 0.49 to 0.52 dl / g. When the IV value is high, the fluidity is lowered, and there is a problem that the effect of improving the chemical resistance is hardly exhibited. On the other hand, when the IV value is too low, the strength is greatly reduced and the thermal stability of the resin composition is lowered due to the large amount of the terminal group of PET. In addition, the production of PET with a low IV value has a problem that pelletization is difficult because the threat is crushed.

The IV value of PET is a logarithmic viscosity value (IV value) measured at 25 ° C. in o-chlorophenol unless otherwise specified. That is, 1.2 g of PET is dissolved in 15 cm ³ of o-chlorophenol by heating and then cooled and calculated from the solution viscosity measured at 25 ° C. The density of the PET obtained after the polycondensation reaction step is preferably 1.35~1.41g / cm ^3, more preferably 1.37~1.39g / cm ^3. In the present invention, the density of PET is measured at a temperature of 23 ° C. by a density gradient tube method using a calcium nitrate solution in accordance with D method of JISK7112.

  The amount of terminal carboxyl groups of PET used in the present invention is preferably 20 to 35 eq / ton, more preferably 22 to 30 eq / ton, and even more preferably 23 to 28 eq / ton or less.

  The more preferable PET of the present invention satisfies that the content of dioxyethylene terephthalate units is in the range of 1.0 to 5.0 mol% (preferably 1.0 to 2.5 mol%). In this way, the PET obtained from the final polycondensation reactor is usually formed into granules (chips) by a melt extrusion molding method. Such granular PET usually has an average particle diameter of 2 to 5 mm (preferably 2.2 to 4 mm). As the PET of the present invention, it is preferable to use the granular PET that has undergone the liquid phase polycondensation step as it is.

  As the PET resin, not only virgin raw materials but also PET recycled from used products can be used. Particularly suitable PET can be used effectively because it is consumed in large quantities and its regeneration system has been established. Examples of the used products include containers represented by PET bottles and blisters, various films, and fibers.

  The PBT of the present invention is a resin obtained by polycondensation reaction from terephthalic acid or a derivative thereof and 1,4-butanediol or a derivative thereof, but other than dicarboxylic acid and / or 1,4-butanediol. In which the alkylene glycol component is copolymerized. The alkylene glycol component other than 1,4-butanediol is preferably 20 mol% or less in 100 mol% of the alkylene glycol component.

  The terminal group structure of PBT is preferably such that the ratio of terminal hydroxyl group content (meq / kg) / terminal carboxyl group content (meq / kg) is 1 or more and the terminal hydroxyl group content is preferably 10 meq / kg or more. The ratio of terminal hydroxyl group content (meq / kg) / terminal carboxyl group content (meq / kg) is 1.2 or more and the terminal hydroxyl group content is 15 meq / kg or more, more preferably the terminal hydroxyl group content. The ratio of (meq / kg) / terminal carboxyl group content (meq / kg) is 1.3 or more and the terminal hydroxyl group content is 20 meq / kg or more.

  On the other hand, the upper limit of the ratio of terminal hydroxyl group content (meq / kg) / terminal carboxyl group content (meq / kg) is preferably 300 or less, more preferably 100 or less. Moreover, as an upper limit of terminal hydroxyl group content, 150 meq / kg or less is preferable, More preferably, it is 100 meq / kg or less.

  Various methods can be used for the production method, but the following are preferable. The production method is more preferably a continuous polymerization type. This is because the quality stability is high and the cost is advantageous. Further, an organic titanium compound is preferably used as the polymerization catalyst. This is because there is a tendency that the influence on the transesterification reaction when mixed with the polycarbonate resin is small. Furthermore, in order to produce PBT having a ratio of terminal hydroxyl group content (meq / kg) / terminal carboxyl group content (meq / kg) of 1 or more, there can be mentioned methods such as solution polymerization and solid phase polymerization. More preferably, solid phase polymerization is advantageous.

  Preferred examples of such organic titanium compounds include titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitic acid, a reaction product of tetrabutyl titanate and trimellitic anhydride, and the like. be able to. The amount of the organic titanium compound used is preferably such that the titanium atom is 3 to 12 mg atomic% with respect to the acid component constituting the polybutylene terephthalate.

[Liquid crystal polyester resin]
The liquid crystal polyester resin used in the present invention is a thermotropic liquid crystal polyester resin and has a property that polymer molecular chains are aligned in a certain direction in a molten state. The arrangement state may be any of nematic, smectic, cholesteric, and discotic, and may exhibit two or more forms. Furthermore, the structure of the liquid crystal polyester resin may be any structure such as a main chain type, a side chain type, and a rigid main chain bent side chain type, but a main chain type liquid crystal polyester resin is preferred.
The form of the arrangement state, that is, the property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage at a magnification of 40 times in a nitrogen atmosphere. When inspected between crossed polarizers, the polymer of the present invention transmits polarized light and exhibits optical anisotropy even in a molten stationary state.

  Further, the heat resistance of the liquid crystal polyester resin may be in any range, but it is appropriate that the liquid crystal polyester resin melts at a portion close to the processing temperature of the polycarbonate resin to form a liquid crystal phase. In this respect, it is more preferable that the deflection temperature under load of the liquid crystalline polyester is 150 to 280 ° C, preferably 180 to 250 ° C. Such liquid crystal polyesters belong to the so-called heat resistant category II. In the case of such heat resistance, excellent moldability is achieved as compared with type I having higher heat resistance, and good flame retardancy is achieved as compared with type III having lower heat resistance.

  The liquid crystal polyester resin used in the present invention contains a polyester unit and a polyesteramide unit, preferably an aromatic polyester resin and an aromatic polyesteramide resin, and the aromatic polyester unit and the aromatic polyesteramide unit are in the same molecular chain. A liquid crystal polyester resin partially contained in is also a preferred example.

Particularly preferred are wholly aromatic polyester resins and wholly aromatic polyester amides having unit constituents derived from one or more compounds selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines and aromatic diamines. Resin. More specifically,
1) a liquid crystal polyester resin synthesized mainly from one or more of aromatic hydroxycarboxylic acids and derivatives thereof,
2) Mainly a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, b) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof, and c) aromatic diols , A liquid crystal polyester resin synthesized from at least one or more of alicyclic diol, aliphatic diol and derivatives thereof,
3) Mainly a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof, and c) aromatic dicarboxylic acids, A liquid crystal polyesteramide resin synthesized from one or more of alicyclic dicarboxylic acids and derivatives thereof,
4) Mainly a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof, c) aromatic dicarboxylic acids and fats A liquid crystal polyester amide resin synthesized from one or more of a cyclic dicarboxylic acid and a derivative thereof; and d) at least one or more of an aromatic diol, an alicyclic diol, an aliphatic diol and a derivative thereof. 1) Liquid crystalline polyester resins synthesized mainly from one or more of aromatic hydroxycarboxylic acids and derivatives thereof are preferred.
Furthermore, you may use a molecular weight modifier together with said structural component as needed.

  Preferred examples of specific compounds used for the synthesis of the liquid crystalline polyester resin of the present invention include 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 6-hydroxy-2-naphthoic acid and the like. Na-phthalene compounds, biphenyl compounds such as 4,4′-diphenyldicarboxylic acid and 4,4′-dihydroxybiphenyl, para-position substitution such as p-hydroxybenzoic acid, terephthalic acid, hydroquinone, p-aminophenol and p-phenylenediamine Benzene compounds and their nuclear substituted benzene compounds (substituents are selected from chlorine, bromine, methyl, phenyl, 1-phenylethyl), meta-substituted benzene compounds such as isophthalic acid and resorcin, and the following general formula (1 ), (2) or (3)Among these, p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are particularly preferable, and a liquid crystal polyester resin obtained by mixing both is preferable. As for the ratio of both, the range of 90-50 mol% is preferable for the former, The range of 80-65 mol% is more preferable, The range of 10-50 mol% is preferable for the latter, The range of 20-35 mol% is more preferable.

（但し、Ｘは炭素数１〜４のアルキレン基およびアルキリデン基、−Ｏ−、−ＳＯ−、−ＳＯ_２−、−Ｓ−、並びに−ＣＯ−よりなる群より選ばれる基であり、Ｙは−（ＣＨ_２）_ｎ−（ｎ＝１〜４）、および−Ｏ（ＣＨ_２）_ｎＯ−（ｎ＝１〜４）よりなる群より選ばれる基である。）

(However, X is a group selected from the group consisting of an alkylene group having 1 to 4 carbon atoms and an alkylidene group, —O—, —SO—, —SO ₂ —, —S—, and —CO—, and Y is It is a group selected from the group consisting of — (CH ₂ ) _n — (n = 1 to 4) and —O (CH ₂ ) _n O— (n = 1 to 4).

  The liquid crystal polyester resin used in the present invention may contain a polyalkylene terephthalate-derived unit that does not partially exhibit an anisotropic molten phase in the same molecular chain in addition to the above-described constituent components. In this case, the alkyl group preferably has 2 to 4 carbon atoms.

  The basic production method of the liquid crystal polyester resin used in the present invention is not particularly limited, and can be produced according to a known polycondensation method of liquid crystal polyester resin. The liquid crystalline polyester resin also has a logarithmic viscosity of at least about 2.0 dl / g, such as about 2.0-10.0 dl / g when dissolved in pentafluorophenol at 60% at a concentration of 0.1% by weight ( IV values) are generally indicated.

<About B component>
The non-ester release agent of component B used in the present invention is not basically limited as long as the main component is a non-ester compound, and conventionally, office machines, household appliances, electrical and electronic equipment Of the release agents that are preferably used for thermoplastic resins used in vehicle parts, the release agents are those other than the ester release agents composed of higher aliphatic ester waxes of monohydric or polyhydric alcohols. Examples of the mold release agent include polyolefin wax, silicone oil, polyorganosiloxane, metal soap, paraffin wax, beeswax and the like. The reason why a non-ester release agent is preferable is as follows. In other words, the supercritical fluid has the property of uniformly compatibilizing the resin components and making the contained chemical species easy to cause reactions such as hydrolysis and cross-linking reactions. Among them, a large amount of long-chain carboxylic acid as a raw material is generated due to dissociation of the ester bond of the ester release agent due to a minute amount of water, which is discharged from the resin during or immediately after injection. Entrained when the supercritical gas injected into the molten resin is discharged through a minute gap generated in any mold such as an air vent or ejector pin section, nesting section, or parting surface provided in the mold It is presumed that corrosion occurs due to adhesion to the mold. Alternatively, even if the decomposition of the ester release agent by the supercritical fluid described above is not promoted, the decomposition product of the ester release agent retained in the resin in general injection molding is a supercritical gas molded product. It is presumed that it accompanies the mold as it is discharged to the outside and leads to mold corrosion.

  The mold release agent suitably used in the present invention is preferably a polyolefin-type mold release agent from the viewpoint of mold release, thermal stability, combustibility and the like conventionally required in addition to the mold corrosivity. Further, in order to improve the miscibility with the resin to be used, oxidation-modified polyethylene having a carboxyl group or an epoxy group introduced by grafting with an acid compound such as air oxidation or maleic anhydride is more preferably used. The The molecular weight is preferably 2,000 to 6,000, more preferably 2,500 to 5,000, and still more preferably 3,000 to 5,000. When the molecular weight is less than 2,000, appearance defects such as silver streaks may occur on the surface of the resin molded product due to decomposition gas generated due to insufficient heat resistance of the release agent. When exceeding, it may be inferior to releasability, and it is not preferable. Furthermore, the acid value is preferably 0.1 to 3.0 mg / KOH, more preferably 0.3 to 2.5 mg / KOH, and 0.5 to 2.0 mg / KOH. Further preferred. When the acid value is less than 0.1 mg / KOH, bleed-out may occur due to poor affinity with the resin. On the other hand, when it exceeds 3.0 mg / KOH, the thermal stability of the resin composition is impaired. This is not preferable because it may occur.

  Content of B component is 0.05-2 weight part with respect to 100 weight part of A component, It is preferable that it is 0.1-1.5 weight part, It is 0.2-1.0 weight part Is more preferable. When the component B is too small, the sufficient release property is difficult to obtain. When the component B is too large, the appearance is poor, which is not industrially useful.

<About component C>
The resin composition of the present invention preferably contains a flame retardant as the C component.
Such flame retardants are not particularly limited, and flame retardants for resins such as halogen flame retardants, phosphorus flame retardants, salt flame retardants, and silicon flame retardants can be used. A phosphorus-based flame retardant having an excellent balance between flame retardancy and flame retardancy, particularly an organic phosphate compound is preferred.
Preferred examples of the organic phosphate compound include phosphate esters, phosphonate esters, and phosphazene oligomers. Further, as the phosphate ester, a compound represented by the following formula (4) is suitable.

[式中、Ｘは、ハイドロキノン、レゾルシノール、ビス（４−ヒドロキシジフェニル）メタン、ビスフェノールＡ、ジヒドロキシジフェニル、ジヒドロキシナフタレン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）ケトン、およびビス（４−ヒドロキシフェニル）サルファイドからなる群より選ばれる化合物から誘導される二価の基である。ｎは０〜５の整数であり、ｎ数の異なるリン酸エステルの混合物の場合は０〜５の平均値である。Ｒ^１１、Ｒ^１２、Ｒ^１３、およびＲ^１４はそれぞれ独立して１個以上のハロゲン原子で置換したもしくは置換していないフェノール、クレゾール、キシレノール、イソプロピルフェノール、ブチルフェノール、およびｐ−クミルフェノールからなる群より選ばれる化合物より誘導される一価の基である。]

[Wherein X is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, and bis ( It is a divalent group derived from a compound selected from the group consisting of 4-hydroxyphenyl) sulfide. n is an integer of 0 to 5, and is an average value of 0 to 5 in the case of a mixture of phosphate esters having different n numbers. R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ each independently comprise phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol substituted or unsubstituted with one or more halogen atoms. It is a monovalent group derived from a compound selected from the group. ]

More preferably, X in the above formula is a divalent group derived from a compound selected from the group consisting of hydroquinone, resorcinol, bisphenol A, and dihydroxydiphenyl, and R ¹¹ , R ¹² , R ¹³ , And R ¹⁴ are each independently a monovalent group derived from a compound selected from the group consisting of phenol, cresol, and xylenol, which are substituted or more preferably substituted with one or more halogen atoms; A compound containing as a main component a component in which n is an integer of 1 to 3 can be mentioned.
The content of component C is preferably 2 to 30 parts by weight, more preferably 3 to 25 parts by weight, even more preferably 4 to 20 parts by weight with respect to 100 parts by weight of component A. If the amount of the flame retardant exceeds the above range, the composition may be deteriorated in heat resistance and physical properties. Conversely, if the amount is too small, the desired flame retardancy may not be obtained.

<About D component>
It is preferable that the resin composition of this invention contains the fluorine-containing dripping inhibitor which has a fibril formation ability as D component. By containing this fluorine-containing anti-drip agent, good flame retardancy can be achieved without impairing the physical properties of the molded product.

  Examples of the fluorine-containing anti-drip agent include a fluorine-containing polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene and tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer). For example, partially fluorinated polymers as disclosed in US Pat. No. 4,379,910, and polycarbonate resins produced from fluorinated diphenols. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable. PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded to each other by an external action such as shearing force to form a fiber. The molecular weight is preferably 1 million to 10 million, more preferably 2 million to 9 million in terms of the number average molecular weight determined from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there. Examples of commercially available PTFE having such fibril forming ability include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., and Polyflon MPAFA500 and F-201L from Daikin Industries, Ltd. Commercially available PTFE aqueous dispersions include Asahi IC Fluoropolymers' full-on AD-1, AD-936, Daikin Kogyo's full-on D-1 and D-2, Mitsui Dupont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical Corporation. As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (Japanese Patent Application Laid-Open No. 60-258263; (Method described in JP-A-63-154744), (2) A method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957), (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and each medium is simultaneously removed from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.) And (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method in which an aqueous dispersion of TFE and an organic polymer dispersion are uniformly mixed, and a vinyl monomer is further polymerized in the mixture dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Examples of commercially available PTFE in a mixed form include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals. As a ratio of PTFE in the mixed form, 1 to 60% by weight of PTFE is preferable in 100% by weight of the PTFE mixture, and more preferably 5 to 55% by weight. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved. In addition, the ratio of the said D component shows the quantity of a net fluorine-containing dripping inhibitor, and in the case of mixed form PTFE, it shows a net PTFE quantity.

  The content of component D is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 1 part by weight, with respect to 100 parts by weight of component A. If the fluorine-containing anti-dripping agent exceeds the above range, PTFE will be deposited on the surface of the molded product, resulting in poor appearance, leading to an increase in the cost of the resin composition, and conversely if too little. In some cases, the dripping prevention effect is not sufficiently exhibited.

<About other ingredients>
The resin composition of the present invention is blended with a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a foaming agent, a dye / pigment, a flame retardant aid and the like as long as the effects of the present invention are exhibited. You can also

  Examples of the heat stabilizer include phosphorus-based heat stabilizers such as phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples thereof include triphenyl phosphite, trisnonylphenyl phosphite. , Tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite , Monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylene bis (4 6-di- phosphite compounds such as ert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tributyl phosphate, trimethyl Phosphate compounds such as phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, Furthermore, tetrakis (2,4-di-tert-butylphenyl) -4,4 ′ is another phosphorus-based heat stabilizer. Biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenedi Examples thereof include phosphonite compounds such as phosphonite and bis (2,4-di-tert-butylphenyl) -4-biphenylenephosphonite. Among these, trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) Phosphite, triphenyl phosphate, trimethyl phosphate, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4- Biphenylene phosphonite is preferred. These heat stabilizers may be used alone or in admixture of two or more. The blending amount of the heat stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, and 0.001 to 0.3 part by weight based on 100 parts by weight of the component A. Further preferred.

  Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], penta Erythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3 , 5-trimethyl-2,4,6-tris (3,5-di-t-butyl 4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxy- Benzylphosphonate-diethyl ester, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphosphinic acid tetrakis (2,4-di-t-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) Undecane etc. are mentioned. These antioxidants may be used alone or in admixture of two or more. The amount of the antioxidant is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, and 0.001 to 0.3 part by weight based on 100 parts by weight of the component A. Further preferred.

  Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers represented by 2,2′-dihydroxy-4-methoxybenzophenone, and, for example, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5. -Chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethyl Butyl) -6- (2H-benzotriazol-2-yl) phenol], 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole and 2- (3 , 5-Di-tert-amyl-2-hydroxyphenyl) benzotriazole-based UV absorption represented by benzotriazole Agents are exemplified. Further, hindered amine light stabilizers typified by bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and the like Can also be used. These ultraviolet absorbers and light stabilizers may be used alone or in admixture of two or more. The blending amount of the ultraviolet absorber and the light stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, and 0.001 to 0. More preferred is 3 parts by weight.

  Examples of the antistatic agent include polyether ester amide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, maleic anhydride monoglyceride, maleic anhydride diglyceride and the like. These antistatic agents may be used alone or in admixture of two or more. The blending amount of the antistatic agent is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, and 0.001 to 0.3 part by weight based on 100 parts by weight of the component A. Is more preferable.

<Manufacture of resin composition>
The resin composition of the present invention can be produced by mixing the above-mentioned components simultaneously or in any order with a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, or extruder. . Preferably, melt kneading with a twin-screw extruder is preferred, and if necessary, it is preferable to supply an optional component into the other melt-mixed component from the second supply port using a side feeder or the like.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Although the shape of the obtained pellet can take general shapes, such as a cylinder, a prism, and a spherical shape, it is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.5 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 4 mm.

  The resin composition thus obtained has a check ring (hereinafter referred to as an intermediate ring) in the middle part of the screw, a supercritical gas inlet between the three-point tip set and the intermediate ring, and supercritical gas generation and external equipment. In an injection molding machine equipped with an injection device, pellets are introduced from the hopper port, heated and melted in the conveying zone and compression zone of the molding machine screw, and then a dedicated gas injection port provided in the heating cylinder in the measuring zone part Supercritical foam molding is performed by introducing a supercritical gas of nitrogen or carbon dioxide. In such supercritical foam molding, by adopting injection compression molding, injection press molding, and core back molding as necessary on the mold control side, not only the injection amount of the supercritical gas but also the foaming ratio can be set. It is possible to control. As the mold runner, either the cold runner method or the hot runner method can be selected, but the latter hot runner method is preferable in terms of easy control of the expansion ratio. Furthermore, as the nozzle of the molding machine, both an open nozzle and a shut-off valve can be used, but the latter shut-off valve is more preferable in consideration of molding stability.

Further, the molded article of the present invention can be subjected to various surface treatments. As the surface treatment, various surface treatments such as a hard coat, a water / oil repellent coat, a hydrophilic coat, an antistatic coat, an ultraviolet absorption coat, an infrared absorption coat, and metalizing (evaporation) can be performed. Examples of the surface treatment method include liquid deposition, vapor deposition, thermal spraying, and plating. As the vapor deposition method, either a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method.
Moreover, in order to give the external appearance of the molded product of the present invention, various insert moldings are possible, and examples include film insert molding and in-mold molding.

  The present invention is a supercritical foam molding that is excellent in mold corrosiveness and mechanical strength, fluidity, and releasability possessed by conventional resins in the molding processing of foam moldings by physical foaming using a supercritical fluid. In particular, the composition is excellent in mold corrosiveness, and is therefore effective for cost reduction in production, and its industrial effect is exceptional.

It is a front view which shows the shape of the U-shaped metal mold | die for corrosion evaluation of metal mold | die used in the Example, and the nest | insert for corrosion evaluation. The resin injected from the direct gate flows separately to the left and right, joins at the final filling position, and only the gas component is released from the gas vent to the outside of the mold. It is a replaceable type corrosion evaluation insert inserted in the product part final filling position of the mold corrosion evaluation mold used in the examples, and has a shape that matches the channel thickness of the U-shaped molded product. It is a replaceable type corrosion evaluation insert inserted in the gas vent position of the mold corrosion evaluation mold used in the examples, and has a shape that matches the gas vent depth. [4-A] is a front view showing the shape of a cup-shaped molded product for release force evaluation used in Examples. [4-B] is a side view showing the shape of a cup-shaped molded product for release force evaluation used in Examples. [4-C] is a rear view showing the shape of a cup-shaped molded product for releasing force evaluation used in Examples. [5-A] shows an outline of the mold structure used in the release force evaluation. The state which filled the resin in the metal mold cavity is shown. [5-B] indicates a state where the mold is cooled and opened after the filling of [5-A]. At this point, the molded product is in close contact with the movable mold. In [5-C], after the mold opening in [5-B], the protruding pin is pushed out by advancing the protruding rod, and the molded product is released. The force at the time of ejection is detected by a load cell in contact with the ejection pin.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

  The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The following items were evaluated.

(I) Mold corrosiveness Showa Carbonic Co., Ltd. Supercritical gas injection device SII-TRJ-10 (used gas: nitrogen) equipped with Nippon Steel Works Co., Ltd. injection molding machine J140AD-110H, and FIGS. Using the mold corrosion evaluation mold and the corrosion evaluation nest shown in FIG. 3 and continuously forming 10,000 shots at the cylinder temperature and mold temperature shown in Tables 1 and 2, reference numeral 2 in FIG. The corrosion evaluation inserts shown in No. 5 and No. 5 were extracted from the mold, and the occurrence of rust after the inserts were treated for 24 hours in a constant temperature and humidity chamber at a set temperature of 50 ° C. and a humidity of 75% was visually determined. Evaluation was performed as follows.
◎: No particular change ○: Slight corrosion or spear deposits are observed. (Less than 10% of nested surface area)
Δ: Corrosion is observed. (10% to less than 30% of nesting surface area)
X: Corrosion is noticeable. (More than 30% of the nesting surface area)
(If judgment is difficult, judgments such as ◎ to ○ are possible.)
In the foam molding, supercritical nitrogen is injected from the supercritical gas injection device from the injection port provided in the molding machine cylinder, and the mixture that is uniformly mixed with the heat-melted resin composition is injected into the cavity. In general molding, the same apparatus was used under the conditions for injection injection, and the evaluation was performed without supercritical gas injection.

(Ii) Lightweight ratio Specific gravity of a molded product molded in the above corrosion test and a molded product molded under the condition that supercritical gas is not injected in the above corrosion test using MIRAGE's electronic hydrometer MD-200S (trade name) Was measured and calculated by the following formula.
Weight reduction rate (%) = 100 × {(specific molded product specific gravity) − (foamed molded product specific gravity)} / (general molded product specific gravity)

(Iii) Flexural modulus The flexural modulus was measured according to ISO178. The shape of the test piece was 80 mm long × 10 mm wide × 4 mm thick. The molding was general molding.

(Iv) Impact strength Notched Charpy impact strength was measured according to ISO79. The shape of the test piece was 80 mm long × 10 mm wide × 4 mm thick. The molding was general molding.

(V) Releasability The mold release load when the cup-shaped molded product shown in FIG. 4 was ejected by an ejector pin and released was measured. The release load was measured by installing a load cell on the ejector plate and pushing the ejector pin while the tip of the load cell was in contact with the root of the ejector pin. With this configuration, the stress applied to the load cell at the time of ejection was measured, and the maximum value of the stress was taken as the release load. In the table, as the release load, the cup-shaped molded product is continuously formed into 40 shots, the release load is stabilized, and then the release is measured at each shot when 20 continuous shots are formed. The average value of the mold load is shown. The molding conditions for the cup-shaped molded product are as follows. That is, injection molding machine: Toshiba Machine EC-160NII, cylinder temperature, mold temperature, filling time: 4 seconds, holding pressure: 50 MPa, holding pressure: 10 seconds, and cooling time described in Tables 1 and 2. It was 40 seconds. Under such conditions, a good molded product was obtained.

(Vi) Surface appearance In the cup-shaped molded product molded in the above-described mold release evaluation, the occurrence of appearance defects such as silver streak (silver strip) and peeling is visually determined for 20 shots of the release load measurement target. did. Evaluation was performed as follows. From the viewpoint of stability, it is necessary that it is ◯ or Δ.
○: Appearance defect in 20 shots is 2 shots or less △: Appearance defect in 20 shots 3-5 shots ×: Appearance defect in 20 shots 6 shots or more

[Examples 1 to 13, Comparative Examples 1 to 13]
Of the components listed in Table 1 and Table 2, components A to D excluding components that can be independently supplied or can be stably extruded by independently supplying (for example, pellet-shaped components such as ABS resin), and other components The ingredients were mixed in a V-type blender to make a mixture. Using a bent type twin screw extruder with a screw diameter of 30 mm [Nippon Steel Works TEX-30XSST], a mixture mixed in a V-type blender, components that can be supplied independently, or can be stably extruded by supplying independently Ingredients and other optional ingredients are supplied from the first input port at the end to a predetermined ratio using a meter, and melt extrusion is performed at a cylinder temperature of 270 ° C. under a vacuum of 3 kPa using a vacuum pump. And pelletized. However, when the C component is C-1, a liquid injection device (HYM-JS-08, manufactured by Fuji Techno Industry Co., Ltd.) is used while being heated to 80 ° C. (first supply port and second supply port) To the extruder at a predetermined ratio. The obtained pellets were dried by a hot air circulation dryer, and then evaluated by the above evaluation method. In addition, the test piece was created with the injection molding machine (general injection molding machine) [EC160Nii by Toshiba Machine Industry Co., Ltd.]. The results are shown in Tables 1 and 2.

In addition, the following were used as a raw material.
(A component)
A-1: Aromatic polycarbonate resin [Terit Kasei Co., Ltd. Panlite L-1225WP (trade name), aromatic polycarbonate resin powder having a viscosity average molecular weight of 22,500 made from bisphenol A and phosgene by a conventional method]
A-2-1: ABS resin [manufactured by Nippon A & L Co., Ltd., Clarastic SXH-330 (trade name), butadiene rubber component about 17.5% by weight, average rubber particle size 400 nm, according to ISO 1133 at 220 ° C. under 10 kg load measured MVR is 53cm ^3/10 minutes]
A-2-2: MBS resin [Rohm & Haas Paraloid EXL2638 (trade name)]
A-2-3: Silicon acrylic resin [S2001 (trade name) manufactured by Mitsubishi Rayon Co., Ltd.]
A-2-4: PS resin [High impact polystyrene H9152 (trade name) manufactured by PS Japan Co., Ltd.]
A-3: PPE resin ["PPE" manufactured by GEM]
(B component)
B-1: Oxidation-modified polyethylene wax [High wax 405MP (trade name) manufactured by Mitsui Chemicals, Inc., density 960 kg / m ³ measured according to JIS K7112, acid value 1 mg KOH / measured according to JIS K5902 g, molecular weight 4000 measured by viscosity method)]
B-2: Low density polyethylene wax [High wax 420P (trade name) manufactured by Mitsui Chemicals, Inc., density 930 kg / m ³ measured according to JIS K7112, acid value 0 mg KOH / g measured according to JIS K5902 , Molecular weight 4000 measured by viscosity method]
(Releasing agents other than B component)
R-1: Ester compound mainly composed of ester compound of glycerin and aliphatic carboxylic acid mainly composed of stearin [SL900 (trade name) manufactured by Riken Vitamin Co., Ltd.]
R-2: Ester compound mainly composed of an ester compound of glycol and an aliphatic carboxylic acid mainly composed of stearin [EP237 (trade name) manufactured by Emery Oleochemical Co., Ltd.]
(C component)
C-1: Phosphate ester mainly composed of bisphenol A bis (diphenyl phosphate) [manufactured by Daihachi Chemical Industry Co., Ltd .: CR-741 (trade name)]
C-2: Resorcinol bis (dixylenyl phosphate) [manufactured by Daihachi Chemical Industry Co., Ltd .: PX200 (trade name)]
(D component)
D-1: Polytetrafluoroethylene having a fibril forming ability [Daikin Industries, Ltd .: Polyflon MPAFA500 (trade name)]
D-2: Polytetrafluoroethylene-based mixture (mixture of polytetrafluoroethylene and acrylic copolymer produced by an emulsion polymerization method) [Mitsubishi Rayon Co., Ltd .: A3700 (trade name) Polytetra Fluoroethylene content 50% by weight, potassium metal ions 16ppm or more)]
(Other ingredients)
E-1: Carbon Black Master [Koshigaya Kasei Co., Ltd. ROYALBLACK 961S (trade name) carbon black 50 wt%, PS resin 50 wt%]
E-2: Phenol heat stabilizer [Ciba Specialty Chemicals K. K. Made; IRGANOX 1076 (trade name)]

  As is apparent from the above table, the resin composition of the present invention is excellent in mold corrosiveness in foam molding by blending a specific amount of a specific release agent, and has a mechanical strength and a release level equivalent to those of conventional products. Resin compositions suitable for resin moldings for office machines, household electrical appliances, electrical and electronic equipment, and vehicles were obtained. In addition, when there were too few B components, it was inferior to mold release property, and conversely, when too large, the product external appearance was impaired.

1 U-shaped mold for mold corrosion evaluation (width 20mm, flow path thickness 2mm, material: NAK80)
2 Nest for product surface mold corrosion evaluation (diameter 20mm, flow path thickness 2mm with flange, material: S50C)
3 Direct gate (diameter 7mm)
4 Gas vent (width 20mm, depth 0.03mm)
5 Gas vent part mold corrosion evaluation insert (diameter 20mm, gas vent depth 0.03mm, with flange, material: S50C)
6 Center sectional line of the nesting portion of the mold base AA ′ 2 (showing the section of FIG. 2)
Center sectional line of the nesting portion of BB ′ 5 (showing the section of FIG. 3)
21 Cup-shaped molded product body 22 Distance from the axis of symmetry (26) (15mm)
23 to 24 24 height (20mm)
25 Cup upper surface end face (Corner R: 2.5mm)
26 Axis of symmetry 27 Internal hole (radius 1mm)
28 Z pin protrusion (radius 7.5mm from the central axis to the outer periphery)
29 Bottom of the cup (corner part R: 5mm)
30 thickness (4mm)
31 Distance from the central axis (34) to the inner bottom hole (27) central axis (13mm)
32 Distance from the central axis (34) to the outer edge of the cup bottom (36) (26mm)
33 Distance from central axis (34) to cup upper surface edge (25) outer edge (30mm)
34 Cup center shaft 35 Sprue (outer radius 6 mm, tip radius 3 mm, length 39 mm)
36 Cup bottom part 37 Cup bottom part thickness (4mm)
38 Cup outer peripheral thickness (2.5mm, all outer peripheral parts are the same)
39 Cup outer peripheral wall 41 Fixed side mold 42 Molded product 43 Extrusion pin (tip Z pin)
44 load cell

Claims (10)

  (A) A thermoplastic resin composition for supercritical foam molding containing 0.05 to 2 parts by weight of (B) a non-ester release agent (component B) with respect to 100 parts by weight of a thermoplastic resin (component A).   The thermoplastic resin composition for supercritical foam molding according to claim 1, wherein the component B is a polyolefin-based release agent.   The thermoplastic resin composition for supercritical foam molding according to claim 2, wherein the component B is an oxidized modified polyethylene having a molecular weight of 2,000 to 6,000 and an acid value of 0.1 to 3.0 mg / KOH. object.   The A component is at least one thermoplastic resin selected from the group consisting of an aromatic polycarbonate resin (A-1 component), a styrene resin (A-2 component), and a polyphenylene ether resin (A-3 component). The thermoplastic resin composition for supercritical foam molding according to any one of claims 1 to 3.   The thermoplastic resin composition for supercritical foam molding according to any one of claims 1 to 4, comprising 2 to 30 parts by weight of (C) a flame retardant (C component) with respect to 100 parts by weight of the A component.   The supercritical of any one of Claims 1-5 which contain 0.05-5 weight part of fluorine-containing anti-dripping agents (D component) which have the fibril formation ability with respect to 100 weight part of A component. A thermoplastic resin composition for foam molding.   The thermoplastic resin composition for supercritical foam molding according to any one of claims 1 to 6, wherein the supercritical fluid is nitrogen.   A foam molded article comprising the thermoplastic resin composition for supercritical foam molding according to any one of claims 1 to 7.   The foam molded article according to claim 8, which is a part used in office machines, household appliances, electrical and electronic equipment, and vehicles having a weight reduction rate of 3% or more.   As a resin composition, a thermoplastic resin composition containing 0.05 to 2 parts by weight of (B) a non-ester release agent (component B) with respect to 100 parts by weight of (A) thermoplastic resin (component A) A method to prevent die corrosion in supercritical foam molding.

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