JP6193624B2 - Resin composition - Google Patents

Description

  The present invention relates to a polyarylene sulfide-containing resin composition, which relates to a resin composition that significantly suppresses the occurrence of burrs during molding while maintaining the excellent characteristics of the polyarylene sulfide resin.

  Polyarylene sulfide resin is an engineering plastic that is excellent in chemical resistance, heat resistance, mechanical properties, and the like. For this reason, polyarylene sulfide resins are widely used as electrical and electronic parts, vehicle parts, aircraft parts, and residential equipment parts. However, polyarylene sulfide resins have a problem that burrs are generated during molding. As means for solving this problem, Patent Documents 1 and 2 disclose a method for suppressing the generation of burrs using a silane coupling agent or alkoxysilane. In this method, there is an effect of suppressing the generation of burrs. However, when the suppression effect is to be sufficiently exerted, it is necessary to increase the amount of the additive, and the characteristics of the polyarylene sulfide resin may be reduced, or during the molding process. Problems such as generation of gas occur. Patent Document 3 discloses a method for suppressing the generation of burrs by introducing a branched structure into the structure of the polyarylene sulfide resin. However, the high burr suppression effect of the present invention cannot be achieved only by improving the structure of the polyarylene sulfide resin. Patent Document 4 discloses a method of suppressing the generation of burrs by using a polycarbonate resin containing a polyorganosiloxane component. However, the effect was not satisfactory.

JP 2007-186672 A JP 2007-77246 A WO06 / 068161 JP-A-8-81630

  An object of the present invention is to provide a polyarylene sulfide-containing resin composition, which maintains the excellent characteristics of the polyarylene sulfide resin and significantly suppresses the occurrence of burrs during molding. is there.

  As a result of intensive studies, the inventor has included a polycarbonate resin having a branched structure with respect to the polyarylene sulfide resin, thereby maintaining the excellent characteristics of the polyarylene sulfide resin and at the time of molding processing. The inventors have found that it is possible to greatly suppress the occurrence and have arrived at the present invention.

Specifically, the above object is achieved by a resin composition comprising (1) 99 to 10 parts by weight of a polyarylene sulfide resin (component A) and 1 to 90 parts by weight of a polycarbonate resin (component B) having a branched structure. .
One of the preferred embodiments of the present invention is (2) the resin composition of the above constitution (1) containing 5 to 400 parts by weight of a filler (component C) with respect to 100 parts by weight of the total of component A and component B. It is a thing.
One of the suitable aspects of the present invention is the resin composition having the above constitution (1) or (2), wherein (3) the branching ratio of the B component is 0.25 to 1.6 mol%.
One of the preferred embodiments of the present invention is (4) a molded product obtained by molding the resin composition of any one of the above-mentioned configurations (1) to (3).

Details of the present invention will be described below.
(Component A: polyarylene sulfide resin)
As the polyarylene sulfide resin used as the component A of the present invention, any polyarylene sulfide resin may be used as long as it belongs to the category called polyarylene sulfide.
The polyarylene sulfide resin has, for example, p-phenylene sulfide unit, m-phenylene sulfide unit, o-phenylene sulfide unit, phenylene sulfide sulfone unit, phenylene sulfide ketone unit, phenylene sulfide ether unit, diphenylene sulfide unit as structural units. , A substituent-containing phenylene sulfide unit, a branched structure-containing phenylene sulfide unit, and the like. Among them, those containing a p-phenylene sulfide unit of 70 mol% or more, particularly 90 mol% or more. Furthermore, poly (p-phenylene sulfide) is more preferable.

  The method for producing the polyarylene sulfide resin is not particularly limited, and can be produced, for example, by a method in which an alkali metal sulfide and a dihaloaromatic compound are reacted in a generally known polymerization solvent. Examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and a mixture thereof, and these may be used in the form of hydrate. These alkali metal sulfides are obtained by reacting an alkali metal hydrosulfide with an alkali metal base and can be prepared in situ prior to addition of the dihaloaromatic compound into the polymerization system, or outside the system. The prepared one can be used. Examples of the dihaloaromatic compound include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 1-chloro-4-bromobenzene. 4,4′-dichlorodiphenyl sulfone, 4,4′-dichlorodiphenyl ether, 4,4′-dichlorobenzophenone, 4,4′-dichlorodiphenyl, and the like. The charging ratio of the alkali metal sulfide and the dihaloaromatic compound is preferably in the range of alkali metal sulfide / dihaloaromatic compound (molar ratio) = 1.00 / 0.90 to 1.10.

  As the polymerization solvent, a polar solvent is preferable, and an organic amide which is aprotic and stable to alkali at high temperature is particularly preferable. Examples of the organic amide include N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoramide, N-methyl-ε-caprolactam, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, dimethyl sulfoxide, sulfolane, tetramethylurea, and mixtures thereof. Further, the polymerization solvent is preferably used in an amount of 150 to 3500% by weight, particularly preferably 250 to 1500% by weight, based on the polymer produced by polymerization. The polymerization is preferably carried out at 200 to 300 ° C., particularly 220 to 280 ° C. for 0.5 to 30 hours, particularly 1 to 15 hours with stirring.

  Further, the polyarylene sulfide resin may be linear or treated at high temperature in the presence of oxygen and cross-linked, or a slight cross-linked or branched structure by adding a small amount of trihalo or higher polyhalo compound. May be used, or may be heat-treated in a non-oxidizing inert gas such as nitrogen, or may be a mixture of these structures.

  For other production methods for producing polyarylene sulfide resins, US Pat. Nos. 4,746,758 and 4,786,713 describe compositions and methods for production. The manufacturing method is a method in which a diiodoaryl compound and solid sulfur are directly heated and polymerized without a polar solvent instead of using a dichloride compound and a sulfide.

  The manufacturing method includes an iodination step and a polymerization step. In the iodination step, aryl compounds are reacted with iodine to obtain a diiodoaryl compound, and in the subsequent polymerization step, the diiodoaryl compound is polymerized with solid sulfur using a nitro compound catalyst to obtain a PAS resin. To manufacture. Iodine is generated in a gaseous state in this step, and this is recovered and used again in the iodination step. Essentially iodine is a catalyst.

(B component: polycarbonate resin having a branched structure)
The polycarbonate resin having a branched structure used as the B component of the present invention is a polycarbonate resin (B-1 component) having a branched structure, or a B-1 component and a linear polycarbonate resin (B-2 component). Either of the mixtures may be used. The branching ratio as the whole B component is preferably 0.25 to 1.6 mol%, more preferably 0.3 to 1.2 mol%, and still more preferably 0.5 to 1.1 mol%. In addition, you may include the aromatic polycarbonate resin which has a branched structure in which a branch rate remove | deviates from the range of 0.25-1.6 mol% in a part of component. Both the case where the branching ratio is less than 0.25 mol% and the case where it exceeds 1.6 mol% is not preferable because the burr suppressing effect is small.

The viscosity average molecular weight of the component B of the present invention is preferably in the range of 1.0 × 10 ^{4 to} 5.0 × 10 ⁴ , more preferably in the range of 1.6 × 10 ^{4 to} 3.0 × 10 ⁴ . The range of 8 × 10 ^{4 to} 2.8 × 10 ⁴ is even more preferable, and the range of 1.9 × 10 ^{4 to} 2.6 × 10 ⁴ is most preferable. If the molecular weight exceeds 5.0 × 10 ⁴ , the melt tension may be too high and the moldability may be inferior, and if the molecular weight is less than 1.0 × 10 ⁴ , the burr suppressing effect is hardly exhibited. Further, the polycarbonate resin having a branched structure used as the component B of the present invention may be mixed with one or more polycarbonate resins having a branched structure so that the molecular weight satisfies the above-mentioned preferable molecular weight range. . In this case, it is naturally possible to mix a polycarbonate resin having a branched structure whose viscosity average molecular weight is outside the above preferred molecular weight range.

In addition, the viscosity average molecular weight as used in the field of this invention calculates | requires first using the Ostwald viscometer from the solution which melt | dissolved 0.7 g of polycarbonate resins in 20 ml of methylene chloride with the specific viscosity computed by following Formula,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The obtained specific viscosity is inserted by the following equation to determine the viscosity average molecular weight M.
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

The total N (nitrogen) amount in the B component resin of the present invention is preferably 0 to 7 ppm, more preferably 0 to 5 ppm. The total N (nitrogen) content in the resin can be measured using a TN-10 type trace nitrogen analyzer (chemiluminescence method) manufactured by Mitsubishi Chemical Corporation.
The total Cl (chlorine) amount is preferably 0 to 200 ppm, more preferably 0 to 150 ppm. If the total N amount exceeds 7 ppm or the total Cl amount exceeds 200 ppm, the thermal stability deteriorates, which is not preferable.
The polycarbonate resin having a branched structure as the B-1 component of the present invention can be obtained by an interfacial polymerization reaction method performed in the presence of an organic solvent using a dihydric phenol, a branching agent, a monohydric phenol and phosgene.

  Representative examples of the dihydric phenol used to obtain the polycarbonate resin having a branched structure of the present invention are 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), hydroquinone, resorcinol, 4, 4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1, 1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2 , 2-bis (4-hydroxyphenyl) pentane, 4,4 ′-(p-phenylenediisopropylidene) diph Nord, 4,4 ′-(m-phenylenediisopropylidene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) ) Sulfide, bis (4-hydroxyphenyl) sulfoxide and the like. These may be used alone or in combination of two or more. Of these, 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A is preferable.

  A typical example of a trivalent or higher-valent phenol (branching agent) used for the production of a polycarbonate resin having a branched structure which is the B-1 component of the present invention is 1,1,1-tris (4-hydroxyphenyl). Ethane, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 1,3 5-tri (4-hydroxyphenyl) benzene, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, tetra (4-hydroxyphenyl) methane, trisphenol, bis (2,4 -Dihydroxylphenyl) ketone, phloroglucin, phloroglucid, isantine bisphenol, 1,4-bis (4,4-dihydroxytriphenylmethyl) ben Emissions, trimellitic acid, pyromellitic acid, and the like. These may be used alone or in combination of two or more. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane is preferable.

  The monohydric phenol (end terminator) used in the production of the polycarbonate resin having a branched structure which is the B-1 component of the present invention may have any structure and is not particularly limited. For example, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, 4-hydroxybenzophenone, phenol and the like can be mentioned. These may be used alone or in combination of two or more. Of these, p-tert-butylphenol is preferable.

  That is, the polycarbonate resin having a branched structure which is the B-1 component of the present invention has a structure in which the branched structure portion is derived from 1,1,1-tris (4-hydroxyphenyl) ethane. The removed linear structure portion is preferably a structure derived from bisphenol A, and the terminal is preferably a structure derived from p-tert-butylphenol.

The polycarbonate resin having a branched structure of the present invention is preferably produced by the following method.
That is, phosgene was blown into an alkaline aqueous solution in which a dihydric phenol compound and a branching agent were dissolved in the presence of an organic solvent to obtain a polycarbonate oligomer. It is the method characterized by making it superpose | polymerize.

  Further, as a reaction catalyst for promoting the reaction, for example, tertiary amine such as triethylamine, tributylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compound, quaternary phosphonium A catalyst such as a compound can also be used. The reaction catalyst is preferably 0.002 mol% or less, more preferably 0.001 mol% or less, based on the dihydric phenol compound. In particular, the above reaction is preferably carried out without a catalyst. When it exceeds 0.002 mol%, the melt tension becomes too high with respect to the amount of the branching agent, or a gel is formed. In addition, the catalyst reacts with the chloroformate group to increase the number of thermally unstable urethane bonds, and the remaining catalyst increases the total N content in the polycarbonate resin having a branched structure, resulting in impact resistance, Since transparency and heat resistance are lowered, it is not preferable. Therefore, it is particularly preferable to carry out the above reaction without a catalyst. At that time, the reaction temperature is usually preferably 0 to 40 ° C, more preferably 15 to 38 ° C. The reaction time is about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9.0 or more, more preferably 11.0 to 13.8.

  There is no particular limitation on the method of emulsifying the monohydric phenols after adding the above-mentioned interfacial polymerization reaction, but examples include a method of stirring with a stirrer or a method of adding an alkaline aqueous solution. There are simple stirring devices such as paddles, propellers, turbines or chi-type blades, high-speed stirrers such as homogenizers, mixers and homomixers, static mixers, colloid mills, orifice mixers, flow jet mixers, ultrasonic emulsifiers and the like. Of these, homomixers, static mixers and the like are preferably used in the polymerization without catalyst.

  Next, the polycarbonate resin organic solvent solution having the branched structure can be washed, granulated, and dried to obtain the polycarbonate resin (powder) having the branched structure of the present invention. Further, the powder is melt extruded and pelletized to obtain a polycarbonate resin (pellet) having a branched structure of the present invention. Cleaning, granulation, drying and the like are not particularly limited, and known methods can be employed.

  In order to reduce the total Cl content in the polycarbonate resin having a branched structure, dichloromethane (methylene chloride), dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, dichloroethylene, chlorobenzene, used as a solvent during the reaction, It is necessary to remove chlorinated hydrocarbon solvents such as dichlorobenzene. For example, it is possible to sufficiently dry the polycarbonate resin powder and pellets having a branched structure.

  The polycarbonate resin having a branched structure of the present invention is preferably substantially free of halogen atoms. The phrase “substantially free of halogen atoms” means that the molecule does not contain halogen-substituted dihydric phenols, etc., and a trace amount of solvent (halogenated hydrocarbon) remaining in the above aromatic polycarbonate production method or carbonate precursor Not even the body.

  B-2 component linear aromatic polycarbonate resin is usually obtained by reacting dihydric phenol and carbonate precursor by interfacial polycondensation method or melt transesterification method. It is obtained by polymerizing by an exchange method or polymerized by a ring-opening polymerization method of a cyclic carbonate compound.

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl). Phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A) ), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(3 -Isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 2 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4- Bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4- Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4 -Hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α'-bis ( -Hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3- Bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ester, etc., and these can be used alone or in admixture of two or more.

  Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3 -Methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) A homopolymer or copolymer obtained from at least one bisphenol selected from the group consisting of 3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene In particular, a homopolymer of bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl Copolymers of rucyclohexane and bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane or α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used. Is done. Among these, 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A is more preferable.

As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like. Of these, phosgene or diphenyl carbonate is industrially advantageous.
In producing polycarbonate resin by reacting the above dihydric phenol and carbonate precursor by interfacial polycondensation method or melt transesterification method, catalyst, terminal terminator, dihydric phenol antioxidant, etc., as necessary May be used. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

  The reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and phosgene, and is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butylphosphonium bromide, a quaternary ammonium compound or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more. In this polymerization reaction, a terminal stopper (monohydric phenol) is usually used. Monofunctional phenols can be used as such end terminators. Monofunctional phenols are generally used as end terminators for molecular weight control. Such monofunctional phenols are generally phenols or lower alkyl-substituted phenols, which are represented by the following formula (1). Functional phenols can be indicated.

(In the formula, A is a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3.)

Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.
In addition, as other monofunctional phenols, phenols or benzoic acid chlorides having a long chain alkyl group or an aliphatic polyester group as a substituent, or long chain alkyl carboxylic acid chlorides can also be shown. Of these, phenols having a long-chain alkyl group represented by the following formulas (2) and (3) as substituents are preferably used.

Wherein X is —R—O—, —R—CO—O— or —R—O—CO—, wherein R is a single bond or a carbon number of 1 to 10, preferably 1 to 5; A valent aliphatic hydrocarbon group, and n represents an integer of 10 to 50.)

  As the substituted phenols of the formula (2), those having n of 10 to 30, particularly 10 to 26 are preferable. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eico. Examples include silphenol, docosylphenol, and triacontylphenol.

  Further, as the substituted phenols of the formula (3), those in which X is —R—CO—O— and R is a single bond are suitable, and those in which n is 10 to 30, particularly 10 to 26 are suitable. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Moreover, you may use a terminal terminator individually or in mixture of 2 or more types.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the alcohol or phenol produced by mixing the dihydric phenol and the carbonate ester with heating in the presence of an inert gas. Is carried out by distilling the water. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system is evacuated to about 1.33 × 10 ^{3 to} 13.3 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

  Examples of the carbonate ester include esters such as an optionally substituted aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among them, diphenyl carbonate is preferable.

A polymerization catalyst can be used to increase the polymerization rate. Examples of such polymerization catalyst include sodium hydroxide, potassium hydroxide, sodium salt of dihydric phenol, alkali metal compounds such as potassium salt, calcium hydroxide, Alkaline earth metal compounds such as barium hydroxide and magnesium hydroxide, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine, alkoxides of alkali metals and alkaline earth metals, alkali metals And organic earth salts of alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds manganese compounds, H Emission compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. A catalyst may be used independently and may be used in combination of 2 or more type. The amount of these polymerization catalysts used is preferably in the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻³ equivalent, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalent, relative to 1 mol of dihydric phenol as a raw material. Chosen by

  In the polymerization reaction, in order to reduce phenolic end groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate, bis ( Compounds such as phenylphenyl) carbonate, chlorophenylphenyl carbonate, bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate and ethoxycarbonylphenylphenyl carbonate can be added. Of these, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate and 2-ethoxycarbonylphenyl phenyl carbonate are preferable, and 2-methoxycarbonylphenyl phenyl carbonate is particularly preferably used.

  Furthermore, it is preferable to use a deactivator that neutralizes the activity of the catalyst in the polymerization reaction. Specific examples of the deactivator include, for example, benzene sulfonic acid, p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, p-toluene sulfone. Sulfonic acid esters such as methyl acid, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate; trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene , Methyl acrylate-sulfonated styrene copolymer, dodecylbenzenesulfonate-2-phenyl-2-propyl, dodecylbenzenesulfonate-2-phenyl-2-butyl, octylsulfonate tetrabutylphospho Salts, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, tetradecylbenzenesulfonate tetra Octyl phosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl dimethyl ammonium methyl sulfate, tetramethyl ammonium hexyl sulfate Over DOO, decyl trimethyl ammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds can be used in combination.

  Among the quenching agents, those of phosphonium salt or ammonium salt type are preferred. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably 0 with respect to the polycarbonate resin after polymerization. 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

In addition, even if the polycarbonate-polyorganosiloxane copolymer which copolymerized the polyorganosiloxane unit is used as B component in this invention, the expression of a burr | flash suppression effect is inadequate. That is, the component B does not include a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units.
Content of B component is 1-90 weight part in the total 100 weight part of A component and B component, 5-80 weight part is preferable, 5-50 weight part is more preferable, 5-20 weight part Is more preferable. If the content of component B is less than 1 part by weight, the effect of suppressing burr is small, and if it exceeds 90 parts by weight, the chemical resistance is poor.

(C component: filler)
In the present invention, a filler can be further contained. The material is not particularly limited, and fillers such as fibrous, plate-like, powdery, and granular can be used. Specifically, for example, fibrous fillers such as glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone koji fiber, metal fiber, wollastonite, selenium Sites, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, etc., swellable layered silicates such as montmorillonite, synthetic mica, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide Non-fibers such as metal compounds such as carbonates, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and silica Shaped fillers, these are May be empty, it is also possible to further combination of these fillers 2 or more.

In addition, these fillers are pretreated with an organic onium ion in the case of coupling agents such as isocyanate compounds, organosilane compounds, organic titanate compounds, organoborane compounds, and epoxy compounds, and swellable layered silicates. The use is preferable in terms of obtaining a higher mechanical strength.
It is preferable that content of C component is 5-400 weight part with respect to a total of 100 weight part of A component and B component. More preferably, it is 10-200 weight part, Most preferably, it is 20-150 weight part. If the content of component C is less than 5 parts by weight, rigidity and heat resistance are inferior, and if it exceeds 400 parts by weight, molding processability may be deteriorated.

  The resin composition of the present invention can contain a conductive filler as a filler in order to impart conductivity. The material is not particularly limited, but the conductive filler is not particularly limited as long as it is a conductive filler usually used for conductive resin, and specific examples thereof include metal powder, metal flakes, and metal ribbons. , Metal fiber, metal oxide, inorganic filler coated with a conductive substance, carbon powder, graphite, carbon fiber, carbon flake, scaly carbon, and the like.

Specific examples of metal species of metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.
Specific examples of the metal species of the metal fiber include iron, copper, stainless steel, aluminum, and brass.
Such metal powders, metal flakes, metal ribbons, and metal fibers may be surface-treated with a surface treatment agent such as titanate, aluminum, or silane.
Specific examples of the metal oxide include SnO ₂ (antimony dope), In ₂ O ₃ (antimony dope), ZnO (aluminum dope), etc., and these include the surface of titanate, aluminum, and silane coupling agents. Surface treatment may be performed with a treating agent.

Specific examples of the conductive material in the inorganic filler coated with the conductive material include aluminum, nickel, silver, carbon, SnO ₂ (antimony doped), and In ₂ O ₃ (antimony doped). Examples of the inorganic filler to be coated include mica, glass beads, glass fiber, carbon fiber, potassium titanate whisker, barium sulfate, zinc oxide, titanium oxide, aluminum borate whisker, zinc oxide whisker, titanic acid whisker, carbonized. Examples include silicon whiskers. Examples of the coating method include vacuum deposition, sputtering, electroless plating, and baking. These may be subjected to a surface treatment with a surface treatment agent such as a titanate, aluminum or silane coupling agent.

  Carbon powders are classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disc black, etc., depending on the raw materials and production method. The carbon powder that can be used in the present invention is not particularly limited in its raw material and production method, but acetylene black and furnace black are particularly preferably used.

(Other ingredients)
In the resin composition in the present invention, other components within the range not impairing the effects of the present invention, such as antioxidants and heat stabilizers (hindered phenol-based, hydroquinone-based, phosphite-based and substituted products thereof), Weathering agent (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), mold release agent and lubricant (montanic acid and its metal salt, its ester, its half ester, stearyl alcohol, stearamide, various bisamides, bisamides Urea and polyethylene wax), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate, N -Butylbenzenesulfonamide, etc.), electrification Stopper (alkyl sulfate type anionic antistatic agent, quaternary ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc.), difficult Flame retardant (eg, red phosphorus, phosphate ester, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin or Combinations of these brominated flame retardants and antimony trioxide, etc.) and other polymers can be added.

(Manufacture of resin composition)
The resin composition of the present invention can be produced by mixing the above 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.

(About molded products)
A molded product using the resin composition of the present invention can be obtained by molding the pellets produced as described above. Preferably, it is obtained by injection molding or extrusion molding. In injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, and heat insulation gold Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, multicolor molding, sandwich molding, and ultrahigh-speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding. In extrusion molding, various shaped extrusion molded products, sheets, films and the like are obtained. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can also be formed into a molded product by rotational molding, blow molding or the like.

  Since the resin composition of the present invention is a resin composition in which the occurrence of burrs during molding is greatly suppressed while maintaining the excellent properties of polyarylene sulfide resin, the industrial effect is extremely large. .

  Examples of the present invention and comparative examples will be described below, but the present invention is not limited to these examples.

In Examples and Comparative Examples, each component shown in Table 1 is blended in the proportions shown in the table, using a vent type twin screw extruder (Nippon Steel Works TEX30XSST) with a diameter of 30 mmφ, from the first inlet at the screw root. Components other than A component, B component, and B component were supplied from a stirring blade type feeder provided on a measuring instrument (CWF manufactured by Kubota Corporation). On the other hand, the C component was supplied to the side feeder so as to have a predetermined ratio using a vibratory feeder provided on the measuring instrument, and supplied to the extruder through the feeder. Extrusion was performed at a temperature of 320 ° C. for both the cylinder and the die, and a strand was produced without using a vent suction with a screw rotation speed of 250 rpm and a discharge rate of 15 kg / hour, and then pelletized with a pelletizer.
This pellet was dried at 130 ° C. for 6 hours, and then tested for 1.5 mmt UL combustion at a molding temperature of 320 ° C., a mold temperature of 130 ° C., and an injection pressure of 70 MPa using an injection molding machine [T-150D manufactured by FANUC Co., Ltd.]. A piece was molded. A gas vent having a thickness of 200 μm and a width of 12 mm was provided in the final filling portion. Since Comparative Example 2 could not be molded under the above conditions, the test piece was molded at a mold temperature of 90 ° C.

[Bali evaluation]
The evaluation of burrs was carried out by measuring the length of burrs in the portion of the test piece that contacts the gas vent.
[Chemical resistance evaluation]
The said test piece was immersed in gasoline and the external appearance after 24 hours was observed. The case where there was no change in the appearance was marked with ◯, and the case where cracks were generated was marked with ×.

The evaluation results are shown in Table 1. In addition, each component of the symbol description in Table 1 is as follows.
<A component>
PPS 1: Polyphenylene sulfide resin obtained by the following production method [Production method]
A mixture of 30-0.0 g of para-diiobenzene (pDIB), 29.15 g of solid sulfur, and 1.48 g of 4-iodobiphenyl as a polymerization inhibitor was melted at 180 ° C. The molten mixture is heated at a temperature of 220 ° C. and a pressure of 350 Torr (46.7 kPa) for 1 hour, at a temperature of 230 ° C. and a pressure of 200 Torr (26.7 kPa) for 2 hours, at a temperature of 250 ° C. and a pressure of 120 Torr (16.0 kPa) for 1 hour. The pressure is reduced to 60 Torr (8.0 kPa) for 1 hour, the temperature is increased to 280 ° C. for 1 hour, the pressure is reduced to 10 Torr (1.3 kPa) for 1 hour, the temperature is 300 ° C. and the pressure is 1 Torr (0.13 kPa) or less. The polyphenylene sulfide resin was produced by polymerization reaction for 4 hours in total for 11 hours.
PPS 2: Polyphenylene sulfide resin (DIC-PPS MA-510, manufactured by DIC)
<B component>
Branched PC 1: Polycarbonate resin having a branched structure (manufactured by Teijin, branching ratio: 0.9 mol%, viscosity average molecular weight: 24,000)
Branched PC 2: Polycarbonate resin having a branched structure (manufactured by Teijin, branching rate: 0.3 mol%, viscosity average molecular weight: 24,000)
Branched PC 3: Polycarbonate resin having a branched structure (manufactured by Teijin, branching ratio: 1.5 mol%, viscosity average molecular weight: 24,000)
<Other than B component>
PC: Linear PC (manufactured by Teijin, viscosity average molecular weight 24000)
Si-PC: Siloxane copolymer PC (manufactured by Teijin, Si amount 4 wt%, viscosity average molecular weight 24000)
<Filler>
GF: Glass chopped strand (manufactured by Nittobo 3PE944)

Claims (4)

(A) polyarylene sulfide resin (A component) 99 to 10 parts by weight of (B) a polycarbonate resin (B component) having a branched structure of 1 to 90 Ri name than the weight part, and does not contain polyarylene ether resin composition.   The resin composition of Claim 1 which contains 5-400 weight part of (C) filler (C component) with respect to a total of 100 weight part of A component and B component.   The resin composition according to claim 1 or 2, wherein the B component has a branching ratio of 0.25 to 1.6 mol%.   The molded article formed by shape | molding the resin composition in any one of Claims 1-3.