JP2012136558A - Method of reducing metal adhesion of thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of preventing the generation of contaminants due to burning when continuous molding is performed, by having flame retardance and reducing the sticking of a resin to metals such as a screw and cylinder of a molding machine during a molding process.SOLUTION: A resin composition comprises 0.01-5 pts.wt of (B) a release agent (component B) based on 100 pts.wt of (A) a thermoplastic resin (component A). In a method, an ester of dipentaerythritol and 13-35C saturated aliphatic carboxylic acid is used as the component B, thereby reducing metal adhesion.

Description

  The present invention relates to a method for reducing the adhesiveness of a resin to a metal such as a screw or cylinder of a molding machine. More specifically, in (A) a resin composition containing 0.01 to 5 parts by weight of a release agent (B component) with respect to 100 parts by weight of a thermoplastic resin (A component), dipenta is used as the B component. The present invention relates to a method for reducing the adhesiveness of a resin to a metal such as a molding machine screw or a cylinder by using an ester of erythritol and a saturated aliphatic carboxylic acid having 13 to 35 carbon atoms.

  Thermoplastic resins, especially aromatic polycarbonate resins, or polymer alloys of aromatic polycarbonate resins and graft copolymers typified by ABS resins have excellent moldability and high impact properties. It is used in a wide range of applications such as electronic equipment and automobiles. Particularly in housings for office equipment such as laser beam printers, copiers, notebook computers and projectors, and electrical and electronic equipment, there is a strong demand for high impact properties and excellent moldability. Such aromatic polycarbonate resins and graft copolymers The polymer alloy which consists of becomes mainstream. However, since these compositions have high adhesiveness to metals in the molten state, there is a problem that the resin easily adheres to the screw or the cylinder during the molding process, and burnt foreign substances are likely to be generated during long-term continuous molding. As a method for solving these problems, it is conceivable to add a release agent or the like into the resin. Document 1 describes a resin composition in which a specific aliphatic ester is added to an alloy material of a graft polymer obtained by graft polymerization of an aromatic polycarbonate resin and a vinyl monomer. Although it has been disclosed that the occurrence of burnt foreign matter is small even in long-term continuous molding and has low metal adhesion, no mention is made of esters of dipentaerythritol and saturated aliphatic carboxylic acids.

  Document 2 shows that an ester compound of pentaerythritol and a saturated aliphatic carboxylic acid is used as a release agent in a flame retardant resin composition based on a polycarbonate resin and a styrene resin. However, with this composition, although the mold releasability between the molded resin composition and the mold can be reduced, it is insufficient to reduce the adhesion to the metal in a molten state in a cylinder or the like. Document 3 discloses a resin composition in which a halogenated epoxy flame retardant having an epoxy group and a basic inorganic compound are blended with a styrene-based thermoplastic resin, but dipentaerythritol and saturated aliphatic carboxylic acid There is no mention of esters. Document 4 describes a composition comprising an aromatic polycarbonate resin containing an effective release amount of an ester of pentaerythritol and an improved release property of an ester of dipentaerythritol. However, with this composition, although the mold releasability between the molded resin composition and the mold can be reduced, it is insufficient to reduce the adhesion to the metal in a molten state in a cylinder or the like.

JP-A-8-259793 Japanese Patent No. 3662420 Japanese Patent Laid-Open No. 9-255842 Japanese Patent Laid-Open No. 11-152403

  The object of the present invention is to provide a method of suppressing the generation of burnt foreign matter in long-term continuous molding by having flame retardancy and reducing the adhesion of resin to a metal such as a screw or cylinder of a molding machine in the molding process. Is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have found that a thermoplastic resin, particularly an aromatic polycarbonate resin or a graft copolymer represented by an aromatic polycarbonate resin and an ABS resin, has dipentaerythritol and carbon number. By blending an ester with a saturated aliphatic carboxylic acid of 13 to 35, the adhesion of the resin to a metal such as a screw or cylinder of a molding machine is reduced in the molding process, and the occurrence of burnt foreign matter in long-term continuous molding is reduced. The inventors have found that it can be suppressed, and have completed the present invention.

  According to the present invention, in (1) (A) a resin composition containing 0.01 to 5 parts by weight of a release agent (B component) with respect to 100 parts by weight of a thermoplastic resin (A component), By using an ester of dipentaerythritol and a saturated aliphatic carboxylic acid having 13 to 35 carbon atoms as the B component, a method for reducing metal tackiness is provided.

  One of the preferred embodiments of the present invention is that (2) the thermoplastic resin (component A) is a polycarbonate resin (component A-1), a styrene resin (component A-2) and a polyester resin (component A-3). The metal of the said structure (1) which is at least 1 sort (s) of thermoplastic resin chosen from the group which consists of, and A-1 component is 50 weight% or more among the total 100 weight% of A-1 component-A-3 component This is a method for reducing the adhesiveness.

  One of the preferred embodiments of the present invention is that (3) the resin composition is 0.01 to 25 parts by weight of (C) a flame retardant (C component) and (D) an inorganic filler with respect to 100 parts by weight of the A component. (D component) 1 to 60 parts by weight, and (E) fluorine-containing anti-dripping agent (E component) is a method for reducing the metal adhesiveness of the above constitution (1) or (2) containing 0 to 2 parts by weight. .

  One of the preferred embodiments of the present invention is (4) a method for reducing the metal adhesiveness of the above-mentioned constitution (3), wherein the C component is an organophosphate compound.

  One of the preferred embodiments of the present invention is that (5) D component is (D-1) mica (D-1 component), (D-2) talc (D-2 component), (D-3) At least one inorganic filler selected from the group consisting of lastite (D-3 component), (D-4) glass fiber (D-4 component), and (D-5) glass flake (D-5 component). This is a method for reducing the metal adhesiveness of the above constitution (3) or (4).

  One of the preferred embodiments of the present invention is (6) a method for reducing the metal adhesiveness of the above constitutions (3) to (5), wherein the E component has a fibril forming ability.

Details of the present invention will be described below.
(Component A: thermoplastic resin)
The thermoplastic resin used as the component A in the present invention is not basically limited. Polyolefin resins such as polyethylene resin, polypropylene resin, poly-4-methylpentene-1, and cyclic polyolefin resin, polystyrene resin , HIPS resin, MS resin, ABS resin, AS resin, AES resin, ASA resin, MBS resin, MAS resin, hydrogenated polystyrene resin, styrene resin such as SMA resin, acrylic resin such as polymethyl methacrylate, modified polyphenylene oxide Resins, polyamide resins, polycarbonate resins, polyphenylene ether resins, PET resins, PBT resins and other polyester resins, polyarylate resins, styrene thermoplastic elastomers, olefinic thermoplastic elastomers, polyesters Ether-based elastomers, polyamide-based elastomers, and include thermoplastic elastomers such as acrylic elastomers. Among these, more preferred are polycarbonate resins, styrene resins, polyester resins, and mixtures of two or more thereof. Particularly suitable are polycarbonate resin (A-1 component) and at least one thermoplastic resin selected from the group consisting of styrene resin (A-2 component) and polyester resin (A-3 component). And a thermoplastic resin in which the A-1 component is 50% by weight or more of the total 100% by weight of the A-1 component to the A-3 component.

[Polycarbonate resin]
The polycarbonate resin may be various polycarbonate resins having a high heat resistance or a low water absorption, which are polymerized using other dihydric phenols, in addition to the commonly used bisphenol A type polycarbonate. 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.

[Styrene resin]
Styrene resins include homopolymers or copolymers of styrene derivatives such as styrene, α-methylstyrene, and p-methylstyrene, and copolymers of these monomers with vinyl monomers such as acrylonitrile and methyl methacrylate. Is mentioned. 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, acrylonitrile / styrene copolymer (AS resin) and acrylonitrile / butadiene / styrene copolymer (ABS resin) are preferable from the viewpoint of affinity with the polycarbonate resin. 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. 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
If the reduced viscosity is less than 0.2 dl / g, the impact is lowered, and if 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 50 to 90% 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 a free vinyl cyanide compound and aromatic vinyl compound is preferably a reduced viscosity (30 ° C.) determined by the above-described method of 0.2 to 1.0 dl / g. 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.

[Polyester resin]
The polyester resin is a polymer or copolymer obtained by a condensation reaction mainly comprising an aromatic dicarboxylic acid or a reactive derivative thereof and a diol or an ester derivative thereof.

  As the aromatic dicarboxylic acid here, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenyl ether Dicarboxylic acid, 4,4′-biphenylmethane dicarboxylic acid, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid Aromatic dicarboxylic acids such as acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-terphenylene dicarboxylic acid, 2,5-pyridinedicarboxylic acid are preferably used, In particular, terephthalic acid and 2,6-naphthalenedicarboxylic acid can be preferably used.

  Aromatic dicarboxylic acids may be used as a mixture of two or more. In addition, if the amount is small, it is also possible to use a mixture of one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanediic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc. together with the dicarboxylic acid. .

  Examples of the diol that is a component of the aromatic polyester of the present invention include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, 2-methyl-1, Contains aromatic diols such as 2,2-bis (β-hydroxyethoxyphenyl) propane, aliphatic diols such as 3-propanediol, diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol Diols and the like, and mixtures thereof. 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.

  The aromatic polyester of the present invention can be branched by introducing a small amount of a branching agent. Although there is no restriction | limiting in the kind of branching agent, A trimesic acid, a trimellitic acid, a trimethylol ethane, a trimethylol propane, a pentaerythritol, etc. are mentioned.

  Specific aromatic polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1, In addition to 2-bis (phenoxy) ethane-4,4′-dicarboxylate, and the like, copolymer polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, and the like can be given. Among these, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and a mixture thereof having a good balance of mechanical properties and the like can be preferably used.

  Further, the terminal group structure of the obtained aromatic polyester resin is not particularly limited, and may be a case where the ratio of one of the hydroxyl groups and the carboxyl group in the terminal group is large in addition to the case where the ratio is almost the same. . Moreover, those terminal groups may be sealed by reacting a compound having reactivity with such terminal groups.

  About the manufacturing method of such an aromatic polyester resin, the dicarboxylic acid component and the diol component are polymerized while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., as a by-product, according to a conventional method. It is carried out by discharging water or lower alcohol out of the system. For example, germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, and the like. More specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. Can be illustrated.

  Further, in the present invention, compounds such as manganese, zinc, calcium and magnesium used in the transesterification reaction, which is a known prior stage of polycondensation, can be used in combination, and phosphoric acid or phosphorous after completion of the transesterification reaction. Such a catalyst can be deactivated and polycondensed with an acid compound or the like.

  The molecular weight of the aromatic polyester resin is not particularly limited, but the intrinsic viscosity measured at 25 ° C. using o-chlorophenol as a solvent is 0.4 to 1.2, preferably 0.65 to 1.15.

(B component: ester of dipentaerythritol and saturated aliphatic carboxylic acid having 13 to 35 carbon atoms)
The B component in the present invention is an ester of dipentaerythritol and a saturated aliphatic carboxylic acid having 13 to 35 carbon atoms.

  The manufacturing method of said specific ester compound is not specifically limited, Dipentaerythritol and a C13-35 saturated aliphatic carboxylic acid can be manufactured using conventionally well-known various methods. it can. In addition, in order to satisfy the specific conditions of the present invention, a slight excess of saturated fat is required rather than complete reaction of a theoretical equivalent of aliphatic polyhydric alcohol and saturated aliphatic carboxylic acid over a sufficient time. It is preferable to react with the group carboxylic acid and finish the reaction at a relatively early stage.

  Examples of the reaction catalyst include organic tin compounds such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, calcium oxide, barium oxide, magnesium oxide, zinc oxide, sodium carbonate, potassium carbonate, and 2-ethylhexyltin. Is mentioned.

(Saturated aliphatic carboxylic acid)
Examples of the saturated aliphatic carboxylic acid having 13 to 35 carbon atoms include adipic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearin). Acid), nonadecanoic acid, icosanoic acid, docosanoic acid and the like. The saturated aliphatic carboxylic acid preferably has 14 to 32 carbon atoms, more preferably 15 to 30 carbon atoms. When carbon number is smaller than 13, the effect which reduces adhesiveness with a metal is hardly exhibited. On the other hand, when the carbon number is larger than 35, ester polymerization with dipentaerythritol is difficult, and purification of the mold release agent is difficult. Even if it can be polymerized, the effect of reducing the adhesiveness with the metal is excessively large, and the problem that the resin bites into the screw in the molding or extrusion process becomes worse. In addition, when several saturated aliphatic carboxylic acid is used, those carbon number uses those weighted average values. In particular, stearic acid and adipic acid are preferred.

  Saturated aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats (such as beef tallow and pork fat), vegetable fats (such as palm oil), and mineral oils (brown coal). Therefore, since the saturated aliphatic carboxylic acid referred to here is a natural product, it is usually supplied industrially as a mixture containing other carboxylic acid components having different carbon numbers. In the production of the ester compound of the present invention, it is produced from such natural fats and oils and is in the form of a mixture containing other carboxylic acid components. For example, in the case of stearic acid, it is generally a mixture of stearic acid and palmitic acid. is there.

  Content of an ester compound (B component) is 0.01-5 weight part with respect to 100 weight part of A component, Preferably it is 0.05-4 weight part, More preferably, it is 0.08-3 weight part. When the ester compound exceeds the above range and is too small, the adhesiveness of the resin to a metal such as a molding machine screw or cylinder is not reduced. On the other hand, when there are too many ester compounds exceeding the said range, a thermal stability deterioration, a flame retardance fall, etc. generate | occur | produce.

(C component: flame retardant)
The resin composition of the present invention can contain a flame retardant as the C component. As such a flame retardant (C component), an organic halogen flame retardant and an organic phosphate compound are preferable, and an organic phosphate compound is more preferable.

  Examples of the organic halogen flame retardant include halogenated carbonate oligomer, halogenated epoxy compound, halogenated polystyrene, halogenated triazine compound, halogenated diphenylalkane compound, halogenated indane compound, and halogenated aromatic phthalimide compound. Among these, halogenated carbonate oligomers and halogenated epoxy compounds are preferred because of their excellent compatibility with polycarbonate and their good heat resistance and thermal stability.

  On the other hand, 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 (I) 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.

Another suitable example of the C component is a metal salt flame retardant. Such metal salt flame retardants include organic sulfonate alkali or alkaline earth metal salts.
The content of the flame retardant (component C) is preferably 0.01 to 25 parts by weight, more preferably 1 to 22 parts by weight, and more preferably 2 to 20 parts by weight with respect to 100 parts by weight of the component A. 3 to 18 parts by weight is most preferable.
When the amount of the flame retardant is too much less than the above range, it is difficult to obtain good flame retardancy. When the amount of the flame retardant exceeds the above range, the composition may be deteriorated in heat resistance and physical properties.

(D component: inorganic filler)
The resin composition of the present invention can contain an inorganic filler as the D component. Representative inorganic fillers for component D include reinforcing fillers formulated for the purpose of improving the rigidity and strength of flame retardant resin compositions, and inorganic pigments formulated for the purpose of coloring thermoplastic resin compositions, etc. Illustratively. Glass fiber, glass flake, glass bead, glass balloon, carbon fiber, carbon flake, carbon bead, talc, clay, kaolin, wollastonite, mica, calcium carbonate, various inorganic whiskers, metal fiber, metal flake , Metal coated glass fibers, metal coated glass flakes, and metal coated carbon fibers. Among them, at least one selected from mica, talc, kaolin, wollastonite, glass fiber and glass flakes is preferable, and at least one selected from plate-shaped mica, talc, kaolin and glass flakes from the viewpoint of dimensional accuracy. Is more preferable. Further, mica and talc are particularly suitable. On the other hand, typical examples of the inorganic filler blended as the colorant include titanium dioxide, zinc oxide, zinc sulfide, and iron oxide, and titanium dioxide is most preferably used.

Furthermore, D component consists of mica (D-1 component), talc (D-2 component), wollastonite (D-3 component), glass fiber (D-4 component), and glass flake (D-5 component). It is preferably at least one inorganic filler selected from the group. Furthermore, the amount of D-1 component added is D1 parts by weight, the amount of D-2 component added is D2 parts by weight, the amount of D-3 component added is D3 parts by weight, the amount of D-4 component added is D4 parts by weight, The amount of D-5 component added is D5 parts by weight, the molding shrinkage in the flow direction of the molded product molded from the resin composition is α%, the molding shrinkage in the vertical direction is β%, and the linear expansion coefficient in the flow direction. Is γ (× 10 ⁻⁵ / ° C.) and the linear expansion coefficient in the vertical direction is δ (× 10 ⁻⁵ / ° C.), it is preferable to satisfy the conditions of the following formulas (1) to (5).
D1 + D2 + D5> D3 + D4 (1)
α / β> 0.65 (2)
γ / δ> 0.70 (3)
0.4 <α + β <1 (4)
3.0 <γ + δ <10 (5)

Of the above formulas (1) to (5), formulas (2) to (5) are represented by α / β> 0.70 (2 ′).
γ / δ> 0.75 (3 ′)
0.55 <α + β <0.85 (4 ′)
6.0 <γ + δ <10 (5 ′)
It is more preferable to satisfy the above, and by setting the content within these ranges, a resin composition with less warpage and excellent dimensional accuracy can be obtained.

  The content of the inorganic filler (component D) is preferably 1 to 60 parts by weight, more preferably 2 to 50 parts by weight, and further preferably 5 to 40 parts by weight with respect to 100 parts by weight of the component A. If the inorganic filler is too small beyond the above range, the mechanical strength and dimensional accuracy required for the mechanical part may not be obtained. On the other hand, when there are too many inorganic fillers exceeding the said range, a moldability may be remarkably impaired.

(E component: fluorine-containing anti-dripping agent)
The resin composition of the present invention preferably contains a fluorine-containing anti-dripping agent (E component). By including this fluorine-containing anti-dripping agent (E component), good flame retardancy can be achieved without impairing the physical properties of the molded product.

  The fluorine-containing anti-dripping agent for component E is preferably 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 1 million to 10 million, more preferably 2 million to 9 million in 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 “Metametabrene 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 E 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 the fluorine-containing anti-dripping agent (component E) is preferably 0 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight, still more preferably 0.1 to 100 parts by weight of the component A. 1 part by weight. If the fluorine-containing anti-dripping agent exceeds the above range and is too small, flame retardancy may be insufficient. On the other hand, when the amount of the fluorine-containing anti-dripping agent exceeds the above range, PTFE may be deposited on the surface of the molded product and the appearance may be deteriorated, leading to an increase in the cost of the resin composition.

(About other ingredients)
In the flame retardant resin composition of the present invention, in addition to exhibiting the effects of the present invention, a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a release agent other than the component B, a foaming agent, Dyeing pigments and the like can also be blended.

  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 0.002 to 0.3 part by weight with respect to 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 blending amount of the antioxidant is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, and 0.002 to 0.3 part by weight with respect to 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 more preferably 0.002 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 0.002 to 0.3 part by weight with respect to 100 parts by weight of the component A. Further preferred.

  Examples of the mold release agent other than the component B include olefin wax, silicone oil, organopolysiloxane, higher fatty acid ester of monohydric or polyhydric alcohol, paraffin wax, beeswax and the like. The amount of the release agent is preferably 0.005 to 2 parts by weight with respect to 100 parts by weight of component A.

<Method to reduce adhesion to metal>
As a mixing method of each component in the method of the present invention, the above-mentioned components are mixed simultaneously or in any order by a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, or extruder. Is mentioned. Preferably, melt kneading with a twin-screw extruder is preferred, and in that case, it is preferred that component D is fed into the other melt-mixed component from the second feed port by 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 3.3 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 3.5 mm.

The composition prepared by the method of the present invention can be easily molded by a known method such as injection molding, extrusion molding, compression molding, or rotational molding, and injection molding is particularly preferable.
In such injection molding, not only a normal molding method but also injection compression molding, injection press molding, gas assist injection molding, and foam molding (including a method of injecting a supercritical fluid) in order to satisfy characteristics required for products. , Insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.

  By using the method of reducing the adhesiveness of the resin to the metal of the present invention, while having good flame retardancy, the adhesion of the resin to the screw or cylinder of the molding machine in the molding process is suppressed, and long-term In the continuous molding, the generation of burnt foreign matter is small and the yield during mass production is improved, so that it is widely useful in OA applications and other various fields. Therefore, the industrial effect exhibited by the present invention is extremely great.

  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 following examples further illustrate the present invention. Unless otherwise specified, parts in the examples are parts by weight, and% is% by weight. Evaluation was carried out by the following method.

(Evaluation)
(I) Flame retardance Using the test piece prepared by the following method, a combustion test was performed at thicknesses of 1.5 mm, 1.6 mm and 2.0 mm in accordance with UL standard 94. The flame retardance rank is preferably V-0 for thicknesses of 1.5 mm and 1.6 mm, and 5 VB class for 2.0 mm.

(Ii) Adhesiveness of resin to screw 3 kg of the study material was extruded under the conditions of a cylinder temperature of 250 ° C. and a screw rotation speed of 120 rpm using a single-screw extruder VSK30 manufactured by Nakatani Machinery Co., Ltd. Thereafter, 200 g of polyethylene was extruded, screwed out, and the amount of resin adhered to the screw was visually evaluated.
○: Adhesion amount is small △: Adhesion amount is slightly high ×: Adhesion amount is large

(Iii) Long-term continuous moldability A square plate having a width of 150 mm, a length of 150 mm, and a thickness of 3 mm was molded by injection molding. The evaluation was carried out using the number of square plates in which 500 shots were discarded and 100 consecutive shots were formed and burnt foreign matter was observed. The square plate was formed using a mold cavity having a fan gate with a width of 30 mm and a thickness of 2 mm. The molding conditions of the square plate are as follows. That is, injection molding machine: Toshiba Machine Industry Co., Ltd. EC-160Nii, cylinder temperature: 250 ° C., mold temperature: 70 ° C., filling time: 0.8 seconds, holding pressure: 80 MPa, holding pressure time: 10 seconds, And the cooling time was 30 seconds.
Number of burnt foreign matter generated during 100 consecutive shots ○: 0 to 5 sheets Δ: 6 to 10 sheets ×: 11 sheets or more

(Iv) Thermal stability Evaluation is the same as long-term thermal stability except that 500 shots are discarded and 100 shots are continuously formed and the number of square plates in which silver is observed is implemented. Evaluation was carried out by the method.
Number of silver generated during 100 consecutive shots ○: Less than 5 shots △: 5-10 shots x: Over 10 shots

[Examples 1-12, Comparative Examples 1-9]
Of the components listed in Tables 1 and 2, A, B, E, and other components, excluding the flame retardant (C component) and inorganic filler (D component), were mixed in a V-type blender. A mixture was made. Using a bent type twin screw extruder with a screw diameter of 30 mm [Nippon Steel Works TEX-30XSST], the mixture mixed with a V-type blender was added from the first inlet at the end, and an inorganic filler (component D) ) From the second supply port in the middle of the cylinder using a side feeder to supply a predetermined ratio with a measuring instrument, while the flame retardant (C component) is heated to 80 ° C. Using Fuji Techno Industry Co., Ltd. HYM-JS-08), supply to the extruder from the middle of the cylinder (between the first supply port and the second supply port) to a predetermined ratio, and use a vacuum pump In a vacuum of 3 kPa, the mixture was melt extruded at a cylinder temperature of 270 ° C. and pelletized. The obtained pellets were dried with a hot air circulating dryer at 100 ° C. for 6 hours. Unless otherwise specified in the description of the evaluation items, the cylinder temperature was measured with an injection molding machine [EC160Nii manufactured by Toshiba Machine Industries Co., Ltd.]. Test pieces for evaluation were prepared at 260 ° C. and a mold temperature of 70 ° C., and the evaluation was performed by the above evaluation method. The results are shown in Tables 1 and 2.

In addition, the following were used as a raw material.
(Component A) Thermoplastic resin A-1: Aromatic polycarbonate resin [Aromatic polycarbonate resin powder having a viscosity average molecular weight of 21,300 made from bisphenol A and phosgene by a conventional method, “Panlite L, manufactured by Teijin Chemicals Ltd.” -1225WS "(trade name)
A-2-1: 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 content: 17.5% by weight ]
A-2-2: ABS resin [“CHT” (trade name) manufactured by Daiichi Koryo Co., Ltd., weight average molecular weight in terms of standard polystyrene by GPC measurement: 60000, butadiene content: 58% by weight]
A-2-3: Acrylonitrile-styrene copolymer [“HF5670” (trade name) manufactured by Daiichi Koryo Co., Ltd., weight average molecular weight in terms of standard polystyrene by GPC measurement: 95000, acrylonitrile content: 28.5 wt% , Styrene content: 71.5% by weight]
B-1: Dipentaerythritol full-stearate adipic acid ["EW-100" (trade name) manufactured by Riken Vitamin Co., Ltd.] (carbon number of saturated aliphatic carboxylic acid: 17)
B-2: Dipentaerythritol full monarate adipate (carbon number of saturated aliphatic carboxylic acid: 32)
B-3 (for comparison): ester compound of pentaerythritol and saturated aliphatic carboxylic acid (mainly stearic acid) ["EW-400" (trade name) manufactured by Riken Vitamin Co., Ltd.] (saturated aliphatic Carbon number of carboxylic acid: 17)
B-4 (for comparison): Ester compound composed mainly of ester compound of glycerin and saturated aliphatic carboxylic acid (mainly stearic acid) [“SL-900” (trade name) manufactured by Riken Vitamin Co., Ltd.] ] (Carbon number of saturated aliphatic carboxylic acid: 17)
B-5 (for comparison): adipate dipentaerythritol laurate (carbon number of saturated aliphatic carboxylic acid: 11)
C-1: Phosphate ester mainly composed of bisphenol A bis (diphenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd .: CR-741 (trade name))
(Component D) Inorganic filler D-1-1: Mascobite mica having an average particle size of about 35 μm pulverized by a dry pulverization method (manufactured by Kinsei Matech Co., Ltd .: KDM200 (trade name))
D-1-2: Muscobite mica having an average particle size of about 250 μm pulverized by a dry pulverization method (manufactured by Hayashi Kasei Co., Ltd .: MC40 (trade name))
D-2: Talc (Hayashi Kasei Co., Ltd .; HST0.8 (trade name))
D-3: Wollastonite having a fiber diameter of 5 μm (manufactured by Shimizu Kogyo Co., Ltd., H-1250F (trade name))
D-4-1: Fiber diameter: 13 μm, cut length: 3 mm, aminosilane treatment-epoxy / urethane-based converged glass fiber, treatment agent adhesion amount: about 1.0%, bulk density: 0.80 g / cm ³ glass fiber (Nittobo Co., Ltd .: 3PE937 (trade name))
D-4-2: Fiber diameter: 13 μm, cut length: 40 μm, aminosilane-treated surface treatment and epoxy / urethane sizing agent (manufactured by Nitto Boseki Co., Ltd .: PFE-301 (trade name))
(E component) PTFE
E-1: Polytetrafluoroethylene having fibril-forming ability (manufactured by Daikin Industries, Ltd .: Polyflon MPAFA500 (trade name))
E-2: Polytetrafluoroethylene-based mixture. A mixture of polytetrafluoroethylene and an acrylic copolymer produced by an emulsion polymerization method (polytetrafluoroethylene content 50% by weight, potassium metal ion 16 ppm or more) (Daikin Industries, Ltd .: A3700 (trade name) )
(Other ingredients)
F-1: Carbon Black Master (ROYALBLACK904S (trade name) manufactured by Koshigaya Kasei Co., Ltd. 40% by weight of carbon black, 60% by weight of PS resin)
F-2: Olefin wax by copolymerization of α-olefin and maleic anhydride (manufactured by Mitsubishi Chemical Corporation; Diacarna 30M (trade name))
F-3: Phenolic heat stabilizer (Ciba Specialty Chemicals KK; IRGANOX 1076 (trade name))

  As is clear from the above table, by containing a specific ester compound in a specific ratio as in the method of the present invention, the adhesiveness of the resin to the molding machine screw is reduced, and the occurrence of burnt foreign matter in long-term continuous molding is suppressed. It was done.

Claims (6)

  (A) In a resin composition containing 0.01 to 5 parts by weight of a release agent (component B) with respect to 100 parts by weight of a thermoplastic resin (component A), dipentaerythritol and carbon number as component B A method for reducing metal tackiness by using an ester with a saturated aliphatic carboxylic acid having a value of 13 to 35.   From the group which A component consists of (A-1) polycarbonate resin (A-1 component), (A-2) styrene-type resin (A-2 component), and (A-3) polyester-type resin (A-3 component). 2. The metal adhesiveness according to claim 1, wherein the metal adhesiveness is at least one kind of thermoplastic resin selected, and the A-1 component is 50% by weight or more out of a total of 100 wt% of the A-1 component to the A-3 component. How to reduce.   The resin composition comprises (C) flame retardant (C component) 0.01 to 25 parts by weight, (D) inorganic filler (D component) 1 to 60 parts by weight, and (E) with respect to 100 parts by weight of component A. The method for reducing metal adhesiveness according to claim 1 or 2, comprising 0 to 2 parts by weight of a fluorine-containing anti-dripping agent (component F).   The method for reducing metal adhesion according to claim 3, wherein the component C is an organophosphate compound.   D component is (D-1) mica (D-1 component), (D-2) talc (D-2 component), (D-3) wollastonite (D-3 component), (D-4) The metal tackiness according to claim 3 or 4, which is at least one inorganic filler selected from the group consisting of glass fiber (D-4 component) and (D-5) glass flake (D-5 component). How to reduce.   The method for reducing metal adhesiveness according to any one of claims 3 to 5, wherein the E component has a fibril-forming ability.