WO2020009076A1 - Polycarbonate resin composition - Google Patents

Abstract

Provided is a polycarbonate resin composition having excellent mechanical properties, chemical resistance, anti-fouling properties, and outward appearance. The polycarbonate resin composition is characterized by comprising, per 100 parts by weight of the total of (A) a polycarbonate-polydiorganosiloxane copolymer resin (A component) and (B) a polyester resin (B component), (C) 3-15 parts by weight of a graft copolymer (C component) having a core-shell structure in which at least one unit selected from the group consisting of aromatic alkenyl compound monomer units and alkyl (meth)acrylate compound monomer units is graft polymerized to a compositerubber comprising a component which includes a polyorganosiloxane rubber and an alkyl (meth) acrylate rubber, and (D) 0.5-6 parts by weight of an anti-fouling adhesive (D component).

Description

Polycarbonate resin composition

The present disclosure relates to a polycarbonate resin composition and a molded product thereof. More specifically, the present disclosure relates to a composite rubber comprising a polycarbonate resin and a polyester resin, a component containing a polyorganosiloxane rubber and an alkyl (meth) acrylate rubber, and an aromatic alkenyl compound monomer unit and an alkyl (meth) ) Mechanical properties and chemical resistance by adding a graft copolymer having a core-shell structure in which at least one unit selected from the group consisting of acrylate compound monomer units is graft-polymerized, and an antifouling agent. The present invention relates to a polycarbonate resin composition having improved antifouling properties and appearance. The present disclosure further relates to flame-retardant polycarbonate resin compositions that have improved flame retardancy and thermal stability in addition to mechanical properties, chemical resistance, stain resistance, and appearance.

Aromatic polycarbonate resins are widely used industrially because of their excellent mechanical and thermal properties. However, the aromatic polycarbonate resin is a non-crystalline resin, and therefore has a drawback of poor chemical resistance. For this reason, alloying with various polymers has been studied. Among them, an aromatic polycarbonate is alloyed with a polyester resin represented by polyethylene terephthalate resin or polybutylene terephthalate resin (see Patent Document 1). Resin's weakness in chemical resistance has been improved, and due to its well-balanced properties, its use is being studied not only in the fields of automobiles and electrical and electronic equipment, but also in the field of housing equipment and infrastructure. .

So far, examples have been reported in which a Si copolymerized PC is applied (see Patent Document 2) and an example in which a Si-based rubber is applied (see Patent Documents 3 and 4) to improve the impact strength particularly at low temperatures. ing. Further, examples have been reported in which a siloxane compound such as silicone oil or dialkyl silicone is added for the purpose of flow reforming and further improvement of chemical resistance (see Patent Documents 5, 6, and 7).

要求 Further, the demand for flame retardancy is increasing for applications such as electric and electronic equipment, and various flame retardant resin compositions have been proposed. For example, there is a method in which a halogen-based flame retardant and an antimony compound are used in combination with a polycarbonate resin and a polyester-based resin (see Patent Document 8). However, thermal stability is significantly reduced due to the catalytic action of the antimony compound. Further, there is a method in which a boron compound (see Patent Document 9), red phosphorus (see Patent Document 10), and a phosphoric ester (see Patent Document 11) are used as flame retardants.

JP 2012-36323 A JP-A-2-43255 JP-A 1-261454 JP 2008-88334 A JP-A-2004-162014 JP-A-1-272661 JP 2005-133807 A JP-A-2005-081327 JP 2000-001610 A JP 2000-136297 A JP-A-08-012864

In recent years, high chemical resistance and prevention of resin have been used in order to make it possible to use products comfortably even in environments where the products are easily contaminated, mainly for outdoor and water-use (bathrooms, toilets, kitchens, etc.) applications. Dirtyness is being required. However, conventional reports have not focused on antifouling properties, and at present have provided a polycarbonate resin composition having both mechanical properties, chemical resistance, antifouling properties and appearance that can satisfy market requirements. Not in.

In view of the above, an object of the present disclosure is to provide a polycarbonate resin composition that satisfies mechanical properties, chemical resistance, antifouling properties, and appearance at a high level.

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a polycarbonate resin composition having a polycarbonate-polydiorganosiloxane copolymer resin and a polyester-based resin has an antifouling agent and a specific composite rubber. It has been found that the above problem can be solved by further having a graft copolymer having a core-shell structure in which a specific monomer unit is grafted.

That is, the present inventor has found that the above object is achieved by the following polycarbonate resin composition.
<Aspect 1>
(A) Polycarbonate-polydiorganosiloxane copolymer resin (A component) and (B) 100% by weight of polyester resin (B component) in total
(C) a composite rubber comprising a component containing a polyorganosiloxane rubber and an alkyl (meth) acrylate rubber, wherein at least one selected from the group consisting of an aromatic alkenyl compound monomer unit and an alkyl (meth) acrylate compound monomer unit; 3 to 15 parts by weight of a graft copolymer having a core-shell structure in which one type of unit is graft-polymerized (component C), and 0.5 to 6 parts by weight of (D) an antifouling agent (component D) A polycarbonate resin composition comprising:
<Aspect 2>
(E) 5 to 35 parts by weight of a halogen-based flame retardant (component E), and (F) 0.5 to 5 parts by weight of a phosphorus-based flame retardant (component F) having a structure represented by the following formula (1). Parts by weight,
The polycarbonate resin composition according to aspect 1, further comprising:

(In the formula, X ₁ and X ₂ are the same or different and are each an aromatic substituted alkyl group represented by the following general formula (I).)

(Wherein, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, Ar is a phenyl group, a naphthyl group or an anthryl group, n represents an integer of 1 to 3, Ar can be attached to any carbon atom of AL.)
<Aspect 3>
3. The polycarbonate resin composition according to aspect 1 or 2, wherein the content of the component B is 20 to 70 parts by weight based on 100 parts by weight of the total of the component A and the component B.
<Aspect 4>
The polycarbonate resin composition according to any one of aspects 1 to 3, wherein the component B contains at least one of a polyethylene terephthalate resin and a polybutylene terephthalate resin.
<Aspect 5>
The polycarbonate resin composition according to any one of aspects 1 to 4, wherein the component D is a silicone gum having a molecular weight of 100,000 or more.
<Aspect 6>
The polycarbonate resin composition according to any one of aspects 1 to 5, wherein the component D is a polyorganosiloxane-grafted polyolefin resin.
<Aspect 7>
The polycarbonate resin composition according to any one of aspects 1 to 6, wherein the proportion of the polyorganosiloxane rubber component in the composite rubber of the component C is 15% or more.
<Aspect 8>
8. The method according to any one of aspects 1 to 7, wherein (G) an anti-drip agent (component G) is contained in an amount of 0.05 to 2 parts by weight based on 100 parts by weight in total of the component A and the component B. Polycarbonate resin composition.
<Aspect 9>
The polycarbonate resin composition according to aspect 8, wherein the G component is a fluoropolymer having fibril-forming ability.

Since the polycarbonate resin composition of the present disclosure satisfies mechanical properties, chemical resistance, antifouling properties, and appearance at a high level, it is not limited to outdoors / indoors, but also for housing facilities, building materials, living materials, It is widely useful in infrastructure equipment applications, automotive applications, OA / EE applications, outdoor equipment applications, and other various fields. Therefore, the industrial effects of the invention according to the present disclosure are extremely large.

Hereinafter, details of the invention according to the present disclosure will be described.

≪Polycarbonate resin composition≫
Polycarbonate resin composition according to the present disclosure,
(A) a polycarbonate-polydiorganosiloxane copolymer resin (component A) and (B) a polyester resin (component B),
And for the total 100 parts by weight of the component A and the component B
(C) a composite rubber comprising a component containing a polyorganosiloxane rubber and an alkyl (meth) acrylate rubber, wherein at least one selected from the group consisting of an aromatic alkenyl compound monomer unit and an alkyl (meth) acrylate compound monomer unit; 3 to 15 parts by weight of a graft copolymer having a core-shell structure in which one type of unit is graft-polymerized (component C), and 0.5 to 6 parts by weight of (D) an antifouling agent (component D) Includes parts.

According to the resin composition of the present invention, excellent properties in stain resistance are obtained in addition to mechanical properties, chemical resistance and appearance. The mechanism by which such an effect is obtained is not necessarily clear, but the following mechanism is conceivable: That is, although not intended to be limited by theory, (A) polycarbonate-polydiorganosiloxane copolymer resin (component A) The polydiorganosiloxane appearing on the surface of the resin and the organosiloxane rubber component appearing on the surface of the copolymer (C) in the graft copolymer (C) are (D) an antifouling agent It is considered that the antifouling property is improved by the siloxane portion together with the (D component).

Further, according to the composition of the present disclosure, mechanical properties and antifouling properties are obtained by using (B) a polyester resin (B component) in addition to (A) a polycarbonate-polydiorganosiloxane copolymer resin (A component). It is believed that in addition to properties and appearance, excellent properties are also provided in chemical resistance.

(Component A: polycarbonate-polydiorganosiloxane copolymer resin)
The resin composition of the present disclosure contains a polycarbonate-polydiorganosiloxane copolymer resin as the component A.

(4) When a polycarbonate resin containing no polydiorganosiloxane is used as the component A, impact resistance, stain resistance and chemical resistance are not improved.

The polycarbonate-polydiorganosiloxane copolymer resin (component A) used in the present disclosure includes a polycarbonate block represented by the following general formula (2) and a polydiorganosiloxane block represented by the following general formula (4). Is preferred.

[(In the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and 6 carbon atoms. A cycloalkyl group having 20 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, carbon Represents an aralkyl group having 7 to 20 atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; E and f may each be an integer from 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (3). That.)

[In the above general formula (3), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, wherein R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a halogen atom, a C 1 to C 18 atom; An alkyl group, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, Aryl group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and Represents a group selected from the group consisting of a carboxyl group, and when there are plural groups, they may be the same or different; g is an integer of 1 to 10; h is an integer of 4 to 7; ]

[In the above general formula (4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substituted group having 6 to 12 carbon atoms. Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number. And q is 0 or a natural number, and p + q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

The polycarbonate-polydiorganosiloxane copolymer resin (component A) used in the present disclosure is preferably a dihydric phenol represented by the following general formula (5) and a hydroxyaryl terminal represented by the following general formula (6). It can be prepared by copolymerizing a polydiorganosiloxane.

[(In the general formula (5), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and 6 carbon atoms. A cycloalkyl group having 20 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, carbon Represents an aralkyl group having 7 to 20 atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; E and f may each be an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the above general formula (3). That.)

[In the above general formula (6), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substituted group having 6 to 12 carbon atoms. Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number. And q is 0 or a natural number, and p + q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

Examples of the dihydric phenol (I) represented by the general formula (5) include, for example, 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1 -Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3′-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropyl) Phenyl) propane, 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2 -Bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) ) Fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4 '-Dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyl Phenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4 '-Dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'- Dihydroxy-3,3'-diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydr Loxyphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1 , 3-adamantanediyl) diphenol and 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane.

Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-sulfonyldiphenol, 2,2′-dimethyl- 4,4'-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis} 2- (4-Hydroxyphenyl) propyl} benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis ( - hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane, which has excellent strength and good durability, is most preferable. These may be used alone or in combination of two or more.

As the hydroxyaryl-terminated polydiorganosiloxane represented by the general formula (6), for example, the following compounds are preferably used.

The hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol or 2-methoxy-4-allylphenol. Can be easily produced by subjecting a polysiloxane chain terminal having a degree of polymerization to a hydrosilylation reaction. Among them, (2-allylphenol) -terminated polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferred, and (2-allylphenol) -terminated polydimethylsiloxane and (2-methoxy-4) are particularly preferred. (-Allylphenol) terminal polydimethylsiloxane is preferred. The hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw / Mn) of 3 or less. Such molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, still more preferably 2 or less, in order to exhibit more excellent low outgassing property and low-temperature impact property during high-temperature molding. When it is within such a preferable range, the amount of outgas generated during high-temperature molding may be suppressed, and the low-temperature impact resistance may be excellent.

た め Further, in order to realize high impact resistance, the degree of polymerization (p + q) of diorganosiloxane of hydroxyaryl-terminated polydiorganosiloxane (II) is suitably from 10 to 300. Such a diorganosiloxane polymerization degree (p + q) is preferably from 10 to 200, more preferably from 12 to 150, and still more preferably from 14 to 100. In such a preferable range, when the degree of polymerization (p + q) is sufficiently large, the impact resistance characteristic of the polycarbonate-polydiorganosiloxane copolymer is effectively exhibited, and the degree of polymerization (p + q) is not too large. , Good appearance.

The content of the polydiorganosiloxane in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in the component A is preferably from 0.1% by weight to 50% by weight. The content of the polydiorganosiloxane component is more preferably 0.5% by weight to 30% by weight, and still more preferably 1% by weight to 20% by weight. Above the lower limit of such a preferred range, excellent impact resistance and flame retardancy are obtained, and below the upper limit of such a preferred range, a stable appearance that is less affected by molding conditions is likely to be obtained. Such polydiorganosiloxane polymerization degree and polydiorganosiloxane content can be calculated by ¹ H-NMR measurement.

に お い て In the present disclosure, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.

In addition, a comonomer other than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) may be used in an amount of 10% by weight based on the total weight of the copolymer within a range not to hinder the invention according to the present disclosure. The following ranges can be used together.

In the present disclosure, a mixed solution containing an oligomer having a terminal chloroformate group is prepared by reacting a dihydric phenol (I) with a carbonate-forming compound in a mixed solution of an organic solvent insoluble in water and an aqueous alkali solution in advance. I do.

In producing the oligomer of the dihydric phenol (I), the whole amount of the dihydric phenol (I) used in the method of the present disclosure may be converted into an oligomer at a time, or a part of the oligomer may be used as a post-addition monomer in the subsequent interface. You may add as a reaction raw material to a polycondensation reaction. The post-addition monomer is added in order to promptly advance the subsequent polycondensation reaction, and it is not necessary to add the monomer when unnecessary.

方式 The system for the oligomer formation reaction is not particularly limited, but a system which is usually carried out in a solvent in the presence of an acid binder is preferred.

使用 The proportion of the carbonate-forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. When a gaseous carbonate-forming compound such as phosgene is used, a method of blowing the compound into the reaction system can be suitably employed.

酸 As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof are used. Similarly to the above, the ratio of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder relative to the number of moles of the dihydric phenol (I) used for the formation of the oligomer (1 mole usually corresponds to 2 equivalents). .

は As the solvent, a solvent inert to various reactions such as those used in the production of known polycarbonates may be used alone or as a mixed solvent. Representative examples include, for example, hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Particularly, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

The reaction pressure for oligomer formation is not particularly limited and may be normal pressure, increased pressure, or reduced pressure, but it is generally advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of −20 ° C. to 50 ° C., and in many cases, heat is generated during the polymerization. The reaction time depends on other conditions and cannot be specified unconditionally, but is usually 0.2 to 10 hours. The pH range of the oligomer formation reaction is the same as known interface reaction conditions, and the pH is always adjusted to 10 or more.

In the present disclosure, after obtaining a mixed solution containing an oligomer of dihydric phenol (I) having a terminal chloroformate group in this way, while stirring the mixed solution, the molecular weight distribution (Mw / Mn) is 3 Hydroxyaryl-terminated polydiorganosiloxane (II) represented by the above general formula (6) highly purified to the following is added to the mixed solution, and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are interfacially polycondensed. Thereby, a polycarbonate-polydiorganosiloxane copolymer is obtained.

In performing the interfacial polycondensation reaction, an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalent) of the reaction. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when a part of the hydroxyaryl-terminated polydiorganosiloxane (II) used or the dihydric phenol (I) is added as a post-addition monomer to the reaction step as described above, the post-addition It is preferable to use 2 equivalents or an excess amount of alkali with respect to the total number of moles of the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (normally 1 mole corresponds to 2 equivalents).

The polycondensation of the oligomer of the dihydric phenol (I) with the hydroxyaryl-terminated polydiorganosiloxane (II) by the interfacial polycondensation reaction is carried out by vigorously stirring the mixture.

末端 In such a polymerization reaction, a terminal terminator or a molecular weight regulator is usually used. Examples of the terminal stopper include compounds having a monovalent phenolic hydroxyl group. In addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long-chain alkylphenols, aliphatic carboxylic acids Examples thereof include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, and alkyl ether phenol. The amount of use is in the range of 100 mol to 0.5 mol, preferably 50 mol to 2 mol, based on 100 mol of all the dihydric phenol compounds used. Naturally, two or more compounds can be used in combination. It is possible.

触媒 A catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added to promote the polycondensation reaction.

反 応 The reaction time of such a polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

A branching agent can be used in combination with the above-mentioned dihydric phenol compound to obtain a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher-functional polyfunctional aromatic compound used in the branched polycarbonate-polydiorganosiloxane copolymer resin include phloroglucin, phloroglucid, and 4,6-dimethyl-2,4,6-tris (4-hydrodiphenyl). ) Heptene-2,2,4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol Lisphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone Examples thereof include tetracarboxylic acids and acid chlorides thereof. Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are exemplified. Preferred is 1,1,1-tris (4-hydroxyphenyl) ethane. The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 mol% to 1 mol%, more preferably 0.005 mol%, based on the total amount of the aromatic polycarbonate-polydiorganosiloxane copolymer resin. It is from mol% to 0.9 mol%, more preferably from 0.01 mol% to 0.8 mol%, particularly preferably from 0.05 mol% to 0.4 mol%. It should be noted that such a branched structure amount can be calculated by ¹ H-NMR measurement.

The reaction pressure can be any of reduced pressure, normal pressure and pressurized pressure, but usually, it can be suitably performed at normal pressure or about the self-pressure of the reaction system. The reaction temperature is selected from the range of −20 ° C. to 50 ° C., and in many cases, heat is generated during the polymerization. Since the reaction time varies depending on other conditions such as the reaction temperature, the reaction time cannot be unconditionally specified, but is usually 0.5 to 10 hours.

In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is subjected to appropriate physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to obtain the desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity [η _SP / c].

(4) The obtained reaction product (crude product) can be subjected to various post-treatments such as a known separation and purification method, and recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purity).

平均 The average size (average domain size) of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded product is preferably in the range of 1 nm to 40 nm. Such average size is more preferably from 1 nm to 30 nm, even more preferably from 5 nm to 25 nm. In such a preferable range, the impact resistance and the flame retardancy may be sufficiently exhibited by the average domain size being sufficiently large, and the impact resistance is stabilized by the average domain size not being too large. May be demonstrated. Thereby, a polycarbonate resin composition having particularly excellent impact resistance and appearance is provided.

The average domain size of the polydiorganosiloxane domain of the polycarbonate-polydiorganosiloxane copolymer resin molded article according to the present disclosure was evaluated by a small angle X-ray scattering method (SAXS). The small-angle X-ray scattering method is a method of measuring diffuse scattering / diffraction occurring in a small-angle region within a scattering angle (2θ) <10 °. In the small-angle X-ray scattering method, when there is a region having a size of about 1 nm to 100 nm and different electron densities in a substance, diffuse scattering of X-rays is measured by the electron density difference. The particle diameter of the object to be measured is determined based on the scattering angle and the scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregated structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, diffuse scattering of X-rays occurs due to a difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity (I) at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10 ° is measured, the small-angle X-ray scattering profile is measured, and the polydiorganosiloxane domain is a spherical domain, and the particle size distribution varies. Is assumed, the simulation is performed using commercially available analysis software from the temporary particle size and the temporary particle size distribution model to determine the average size of the polydiorganosiloxane domain. According to the small-angle X-ray scattering method, it is possible to measure the average size of polydiorganosiloxane domains dispersed in a matrix of a polycarbonate polymer accurately, simply, and with good reproducibility, which cannot be accurately measured by observation with a transmission electron microscope. it can. The average domain size means the number average of individual domain sizes.

The term “average domain size” used in connection with the present disclosure refers to a measured value obtained by measuring a 1.0-mm-thick portion of a three-stage plate manufactured by the method described in the example by such a small-angle X-ray scattering method. Show. In addition, the analysis was performed using an isolated particle model without considering the interaction between particles (inter-particle interference).

The viscosity-average molecular weight (M) of the polycarbonate-polydiorganosiloxane copolymer resin is not particularly limited, but is preferably 1.8 × 10 ⁴ to 4.0 × 10 ⁴ , more preferably 2.0 × 10 ⁴ . It is 3.5 × 10 ⁴ , more preferably 2.2 × 10 ⁴ to 3.0 × 10 ⁴ . With a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight of 1.8 × 10 ⁴ or more, good mechanical properties may be obtained, and a sufficient melt viscosity difference from the polyolefin resin is ensured. , Appearance and tape peeling resistance may be good. On the other hand, a resin composition obtained from a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight of 4.0 × 10 ⁴ or less may have excellent versatility in terms of excellent fluidity during injection molding.

The polycarbonate-polydiorganosiloxane copolymer resin may be obtained by mixing resins having a viscosity average molecular weight outside the above range. In particular, a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight exceeding the above range (5 × 10 ⁴ ) has improved entropic elasticity of the resin. As a result, good moldability is exhibited in gas assist molding and foam molding that are sometimes used when molding a reinforced resin material into a structural member. More preferable embodiments include a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight of 7 × 10 ⁴ to 3 × 10 ⁵ (component A-1-1-1), and a viscosity average molecular weight of 1 × 10 ⁴ to 3 ×. 10 ⁴ polycarbonate - consists polydiorganosiloxane copolymer resin (a-1-1-2 component), a viscosity-average molecular weight of 1.6 × ¹⁰ 4 ~ 3.5 × 10 polycarbonate of ⁴ - polydiorganosiloxane copolymer A polymer resin (A-1-1 component) (hereinafter sometimes referred to as a “polycarbonate-polydiorganosiloxane copolymer resin containing a high molecular weight component”) may also be used.

In such a polycarbonate-polydiorganosiloxane copolymer resin containing a high molecular weight component (component A-1-1), the molecular weight of component A-1-1-1 is preferably from 7 × 10 ⁴ to 2 × 10 ⁵ , and more preferably from 8 × 10 ⁴ to 2 × 10 ^5. × 10 ⁴ to 2 × 10 ⁵ , more preferably 1 × 10 ⁵ to 2 × 10 ⁵ , particularly preferably 1 × 10 ⁵ to 1.6 × 10 ⁵ . The molecular weight of the component A-1-1-2 is preferably from 1 × 10 ⁴ to 2.5 × 10 ⁴ , more preferably from 1.1 × 10 ⁴ to 2.4 × 10 ⁴ , and even more preferably 1.2 × 10 ⁴ . It is 10 ⁴ to 2.4 × 10 ⁴ , particularly preferably 1.2 × 10 ⁴ to 2.3 × 10 ⁴ .

The high molecular weight component-containing polycarbonate-polydiorganosiloxane copolymer resin (A-1-1 component) is obtained by mixing the above-mentioned A-1-1-1 component and the A-1-1-2 component in various ratios, and preparing a mixture having a predetermined molecular weight. It can be obtained by adjusting to satisfy the range. Preferably, the amount of the A-1-1-1 component is 2% by weight to 40% by weight in 100% by weight of the A-1-1 component, and more preferably, the amount of the A-1-1-1 component is 3% by weight. %, More preferably 4% to 20% by weight of the A-1-1-1 component, and particularly preferably 5% to 20% by weight of the A-1-1-1 component. .

The method for preparing the A-1-1 component is as follows:
(1) A method of independently polymerizing the A-1-1-1 component and the A-1-1-2 component and mixing them,
(2) A method of producing an aromatic polycarbonate resin having a plurality of polymer peaks in a molecular weight distribution chart by the GPC method, which is represented by the method disclosed in JP-A-5-306336, in the same system, A method for producing a polycarbonate resin so as to satisfy the conditions of the component A-1-1 of the present disclosure; and (3) an aromatic polycarbonate resin obtained by the production method (the production method of (2)), And a method of mixing the A-1-1-1 component and / or A-1-1-2 component.

First, the viscosity average molecular weight referred to in the present disclosure is a specific viscosity (η _SP ) calculated from the following equation, which is determined by calculating the Ostwald viscosity from a solution obtained by dissolving 0.7 g of a polycarbonate-polydiorganosiloxane copolymer resin in 100 ml of methylene chloride at 20 ° C. Using the total
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is the number of seconds of falling methylene chloride, t is the number of seconds of falling of the sample solution]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight M is calculated by the following equation.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10−4M ^0.83
c = 0.7

The calculation of the viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin in the polycarbonate resin composition of the present disclosure is performed in the following manner. That is, the composition is mixed with 20 to 30 times the weight of methylene chloride to dissolve soluble components in the composition. The soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after the removal of the solvent is sufficiently dried to obtain a solid component that is soluble in methylene chloride. From a solution in which 0.7 g of the solid is dissolved in 100 ml of methylene chloride, the specific viscosity at 20 ° C. is determined in the same manner as above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as above.

(Component B: polyester resin)
The polyester resin used as the component B of the present disclosure is a polymer or copolymer obtained by a condensation reaction containing an aromatic dicarboxylic acid or a reactive derivative thereof and a diol or an ester derivative thereof as main components.

The aromatic dicarboxylic acids referred to herein include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and 4,4′-biphenyl ether Dicarboxylic acid, 4,4'-biphenylmethanedicarboxylic acid, 4,4'-biphenylsulfonedicarboxylic acid, 4,4'-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid Acids, aromatic dicarboxylic acids such as 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4'-p-terphenylenedicarboxylic acid, 2,5-pyridine dicarboxylic acid, diphenylmethane dicarboxylic acid, diphenyl ether Dicarboxylic acid and β-hydroxyethoxy ammonium Those selected from incense acid are preferably used, in particular terephthalic acid, 2,6-naphthalenedicarboxylic acid can be preferably used. Two or more aromatic dicarboxylic acids may be used as a mixture. 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 dodecane diacid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid together with the dicarboxylic acid. .

The diol which is a component of the polyester resin of the present disclosure includes ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, 2-methyl-1, Contains aromatic rings such as 2,2-bis (β-hydroxyethoxyphenyl) propane and the like, aliphatic diols such as 3-propanediol, diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol and the like. Diols and mixtures thereof. If the amount is further small, 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 or the like may be copolymerized.

ポ リ エ ス テ ル Further, the polyester resin of the present disclosure can be branched by introducing a small amount of a branching agent. The type of the branching agent is not limited, and examples thereof include trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane, and pentaerythritol.

Specific polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polyethylene-1,2. Other than -bis (phenoxy) ethane-4,4'-dicarboxylate and the like, copolymerized polyester resins such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate and the like can be mentioned. Of these, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and mixtures thereof, which are well balanced in mechanical properties and the like, can be preferably used.

The structure of the terminal group of the obtained polyester resin is not particularly limited, and may be a case where the ratio of the hydroxyl group and the carboxyl group in the terminal group is substantially equal to each other, or one of the ratios is large. Further, the terminal group may be sealed by reacting a compound having reactivity with the terminal group.

Regarding the method for producing such a polyester resin, according to a conventional method, in the presence of a polymerization catalyst containing titanium, germanium, antimony, etc., the dicarboxylic acid component and the diol component are polymerized while heating, and water or This is performed by discharging the lower alcohol out of the system. For example, examples of the germanium-based polymerization catalyst include oxides, hydroxides, halides, alcoholates, and phenolates of germanium, and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, and the like. Can be exemplified.

Preferred examples of the polymerization catalyst for the organic titanium compound include titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitate, and a reaction product of tetrabutyl titanate and trimellitic anhydride. Can be mentioned. Further, when produced using a specific titanium-based catalyst other than the above, a polyester-based resin having more excellent thermal stability can be obtained, so that it is more preferably used.

The above specific titanium-based catalyst contains a reaction product of the following titanium compound component (A) and phosphorus compound component (B).

The titanium compound component (A) includes a titanium compound (1) represented by the following general formula (I), and a titanium compound (1) and an aromatic polycarboxylic acid represented by the following general formula (II) or an anhydride thereof. And at least one titanium compound component selected from the group consisting of the titanium compounds (2) obtained by reacting the titanium compound with the compound.

[Wherein, in the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 2 to 10 carbon atoms, k represents an integer of 1 to 3, When k is 2 or 3, two or three R ² and R ³ may be the same or different from each other. ]

[In the formula (II), m represents an integer of 2 to 4.] ]

The phosphorus compound component (B) is a phosphorus compound component comprising at least one phosphorus compound (3) represented by the following general formula (III).

[Wherein, in the formula (III), R ⁵ represents an unsubstituted or substituted aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. ]

(4) The polyester resin produced by using the above-mentioned specific titanium-based catalyst has better heat stability and wet heat resistance than the case where germanium, antimony and other titanium-based catalysts are used. When the above specific titanium-based catalyst is used, the quality is stable even when the amount of additives such as a hue stabilizer and a heat stabilizer during the production is smaller than when other catalysts are used. Since the decomposition of the additive under a thermal environment or a moist heat environment is reduced, it is presumed that the additive has excellent thermal stability and moist heat resistance.

In the reaction product of the titanium compound component (A) and the phosphorus compound component (B), the molar amount (mTi) of the titanium compound component (A) in terms of titanium atoms and the molar amount in terms of phosphorus atoms of the phosphorus compound component (B) The molar ratio of reaction with (mP) (mTi / mP) is preferably in the range of 1/3 to 1/1, and more preferably in the range of 1/2 to 1/1.

The titanium atom converted molar amount of the titanium compound component (A) is the product of the product of the molar amount of each titanium compound contained in the titanium compound component (A) and the number of titanium atoms contained in one molecule of the titanium compound. It is a total value, and the molar amount of phosphorus compound component (B) in terms of phosphorus atom is the molar amount of each phosphorus compound contained in phosphorus compound component (B) and the phosphorus atom contained in one molecule of the phosphorus compound. This is the total value of the product with the number. However, since the phosphorus compound represented by the formula (III) contains one phosphorus atom per molecule, the molar amount of the phosphorus compound in terms of phosphorus atom is equal to the molar amount of the phosphorus compound.

When the reaction molar ratio (mTi / mP) is 1/1 or less, that is, when the amount of the titanium compound component (A) is not too large, the polyester-based resin obtained using the obtained catalyst has good properties. Color tone (b value is not too high), and the heat resistance may be good. In addition, when the reaction molar ratio (mTi / mP) is 1/3 or more, that is, when the amount of the titanium compound component (A) is not too small, the catalyst activity of the obtained catalyst with respect to the polyester formation reaction is reduced. May be enough.

Examples of the titanium compound (1) represented by the general formula (I) used in the titanium compound component (A) include titanium such as titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetrapropoxide, and titanium tetraethoxide. Tetraalkoxides, and alkyl titanates such as octaalkyltrititanates and hexaalkyldititanates can be mentioned. Among them, titanium having good reactivity with the phosphorus compound component used in the present disclosure is exemplified. It is preferable to use tetraalkoxides, and it is more preferable to use titanium tetrabutoxide.

チ タ ン The titanium compound (2) used for the titanium compound component (A) is obtained by reacting the titanium compound (1) with the aromatic polycarboxylic acid represented by the general formula (II) or an anhydride thereof. The aromatic polycarboxylic acid of the general formula (II) and its anhydride are preferably selected from the group consisting of phthalic acid, trimellitic acid, hemmellitic acid, pyromellitic acid and anhydrides thereof. In particular, it is more preferable to use trimellitic anhydride having good reactivity with the titanium compound (1) and high affinity with the polyester of the obtained polycondensation catalyst.

The reaction between the titanium compound (1) and the aromatic polycarboxylic acid of the general formula (II) or the anhydride thereof is performed by mixing the aromatic polycarboxylic acid or the anhydride with a solvent and partially or entirely mixing the solvent. Is dissolved in a solvent, the titanium compound (1) is added dropwise to the mixture, and the mixture is heated at a temperature of 0 ° C. to 200 ° C. for 30 minutes or more, preferably at a temperature of 30 ° C. to 150 ° C. for 40 minutes to 90 minutes. Done by The reaction pressure at this time is not particularly limited, and normal pressure is sufficient. The catalyst can be appropriately selected from those capable of dissolving a required amount of the compound of the formula (II) or a part or all of its anhydride, and is preferably ethanol, ethylene glycol, trimethylene. Glycol, tetramethylene glycol, benzene, xylene and the like.

反 応 The reaction molar ratio of the titanium compound (1) to the compound represented by the formula (II) or its anhydride is not limited. However, when the proportion of the titanium compound (1) is not too high, the color tone of the obtained polyester resin becomes good, and a decrease in the softening point can be prevented. Conversely, if the proportion of the titanium compound (1) is not too low, the polycondensation reaction can proceed favorably. For this reason, the reaction molar ratio of the titanium compound (1) to the compound of the formula (II) or its anhydride is preferably controlled within the range of 2/1 to 2/5. The reaction product obtained by this reaction may be directly used for the reaction with the above-mentioned phosphorus compound (3), or the product may be recrystallized using a solvent composed of acetone, methyl alcohol and / or ethyl acetate. After the purification, this may be reacted with the phosphorus compound (3).

In the phosphorus compound (3) of the general formula (III) used for the phosphorus compound component (B), an aryl group having 6 to 20 carbon atoms represented by R ⁵ or 1 to 20 carbon atoms The alkyl group may be unsubstituted or substituted with one or more substituents. The substituent includes, for example, a carboxyl group, an alkyl group, a hydroxyl group and an amino group.

Examples of the phosphorus compound (3) of the general formula (III) include monomethyl phosphate, monoethyl phosphate, monotrimethyl phosphate, mono-n-butyl phosphate, monohexyl phosphate, monoheptyl phosphate, monooctyl phosphate, monononyl phosphate, Monodecyl phosphate, monododecyl phosphate, monolauryl phosphate, monooleyl phosphate, monotetradecyl phosphate, monophenyl phosphate, monobenzyl phosphate, mono (4-dodecyl) phenyl phosphate, mono (4-methylphenyl) phosphate, mono (4 -Ethylphenyl) phosphate, mono (4-propylphenyl) phosphate, mono (4-dodecylphenyl) phosphate, monotolylphosphate Monoalkyl phosphates and monoaryl phosphates such as monoxylyl phosphate, monoxylyl phosphate, monobiphenyl phosphate, mononaphthyl phosphate, and monoanthryl phosphate, which may be used alone or in combination of two or more. The above mixture may be used, for example, as a mixture of a monoalkyl phosphate and a monoaryl phosphate. However, when the above phosphorus compound is used as a mixture of two or more, the proportion of the monoalkyl phosphate preferably accounts for 50% or more, more preferably 90% or more, and particularly preferably 100%. It is more preferable that

In order to prepare a catalyst from the titanium compound component (A) and the phosphorus compound component (B), for example, a phosphorus compound component (B) comprising at least one phosphorus compound (3) of the formula (III) and a solvent are used. After mixing, part or all of the phosphorus compound component (B) is dissolved in a solvent, and the titanium compound component (A) is added dropwise to the mixture, and the reaction system is usually set to preferably 50 ° C to 200 ° C, more preferably 50 ° C to 200 ° C. Is carried out at a temperature of 70 ° C. to 150 ° C., preferably for 1 minute to 4 hours, more preferably 30 minutes to 2 hours. In this reaction, the reaction pressure is not particularly limited, and may be any of under pressure (0.1 MPa to 0.5 MPa), under normal pressure, or under reduced pressure (0.001 MPa to 0.1 MPa). It is usually performed under normal pressure.

The solvent for the phosphorus compound component (B) of the formula (III) used in the catalyst preparation reaction is not particularly limited as long as at least a part of the phosphorus compound component (B) can be dissolved. A solvent composed of at least one selected from glycol, trimethylene glycol, tetramethylene glycol, benzene, xylene and the like is preferably used. In particular, it is preferable to use the same compound as the glycol component constituting the polyester finally obtained as the solvent.

The reaction product of the titanium compound component (A) and the phosphorus compound component (B) is separated from the reaction system by means such as centrifugal sedimentation or filtration, and then purified without purification. The separated reaction product may be used as a catalyst for resin production, or the separated reaction product may be purified by recrystallization with a recrystallization agent such as acetone, methyl alcohol and / or water. The product may be used as a catalyst. Further, the reaction product-containing reaction mixture may be used as it is as a catalyst-containing mixture without separating the reaction product from the reaction system.

As a titanium-based catalyst, a titanium compound component (A) comprising at least one kind of a titanium compound (1) of the above formula (I) (where k represents 1), that is, a titanium tetraalkoxide; Preferably, a reaction product of at least one phosphorus compound with the phosphorus compound component (B) is used as a catalyst.
Further, a compound represented by the following general formula (IV) is preferably used as a titanium-based catalyst.

[In the above formula, R ⁶ and R ⁷ each independently represent an alkyl group having 2 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.]

The catalyst containing the titanium / phosphorus compound represented by the formula (IV) has high catalytic activity, and the polyester resin produced by using the catalyst has a good color tone (low b value), and It has a sufficiently low content of acetaldehyde, residual metal and cyclic trimer of an ester of an aromatic dicarboxylic acid and an alkylene glycol, and has practically sufficient polymer performance.

In the titanium-based catalyst, the titanium / phosphorus compound represented by the general formula (IV) is preferably contained in an amount of 50% by weight or more, more preferably 70% by weight or more.

The amount of the titanium-based catalyst to be used is preferably such that the molar amount of titanium in terms of titanium atoms is 2 to 40 milli% with respect to the total amount of aromatic dicarboxylic acid contained in the polymerization starting material. More preferably, it is 5 to 35 mm%, even more preferably 10 to 30 mm%. When the content is 2 milli% or more, the effect of promoting the catalyst for the polycondensation reaction of the polymerization starting material is sufficient, the polyester production efficiency is sufficient, and a polyester resin having a desired degree of polymerization can be obtained. There are cases. When the content is 40 mm% or less, the color tone (b value) of the obtained polyester-based resin becomes good, yellowing is suppressed, and its practicality can be ensured.

The method for producing the alkylene glycol ester of an aromatic dicarboxylic acid and / or a low polymer thereof is not limited, but usually, an aromatic dicarboxylic acid or an ester-forming derivative thereof and an alkylene glycol or an ester-forming derivative thereof are heated and heated. It is produced by reacting. For example, an ethylene glycol ester of terephthalic acid and / or a low polymer thereof used as a raw material of polyethylene terephthalate is obtained by directly subjecting terephthalic acid and ethylene glycol to an esterification reaction, or a lower alkyl ester of terephthalic acid and ethylene glycol. It is produced by a transesterification reaction or an addition reaction of terephthalic acid with ethylene oxide. The alkylene glycol ester of the aromatic dicarboxylic acid and / or the low polymer thereof may contain another dicarboxylic acid ester copolymerizable therewith as an additional component, thereby substantially impairing the effect of the method of the present disclosure. It may be contained in an amount within the range not present, specifically, 10 mol% or less, preferably 5 mol% or less based on the total molar amount of the acid component.

Said copolymerizable additional components are preferably as acid components, for example aliphatic and cycloaliphatic dicarboxylic acids such as adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, and hydroxycarboxylic acids, for example, at least one kind of β-hydroxyethoxybenzoic acid, p-oxybenzoic acid and the like, and as a glycol component, for example, an alkylene glycol having 2 or more constituent carbon atoms, 1,4-cyclohexanedimethanol, neopentyl glycol, bisphenol A And esters of at least one of aliphatic, alicyclic, and aromatic diol compounds such as bisphenol S and polyoxyalkylene glycol, or anhydrides thereof. The above-mentioned additional component esters may be used alone or in combination of two or more. However, the copolymerization amount is preferably within the above range.

In the case where terephthalic acid and / or dimethyl terephthalate is used as a starting material, the recovered dimethyl terephthalate obtained by depolymerizing polyalkylene terephthalate or the recovered terephthalic acid obtained by hydrolyzing the same is converted into a polyester. It can be used in an amount of 70% by weight or more based on the weight of all the constituent acid components. In this case, the target polyalkylene terephthalate is preferably polyethylene terephthalate, and in particular, recovered PET bottles, recovered fiber products, recovered polyester film products, and polymer waste generated in the manufacturing process of these products. It is preferable to use as a raw material source for polyester production from the viewpoint of effective utilization of resources.

Here, the method for depolymerizing the recovered polyalkylene terephthalate to obtain dimethyl terephthalate is not particularly limited, and any conventionally known method can be employed. For example, after the recovered polyalkylene terephthalate is depolymerized using ethylene glycol, the depolymerized product is subjected to a transesterification reaction with a lower alcohol, for example, methanol, and the reaction mixture is purified to recover a lower alkyl ester of terephthalic acid. Then, this is subjected to a transesterification reaction with an alkylene glycol, and the obtained phthalic acid / alkylene glycol ester is polycondensed to obtain a polyester resin. The method for recovering terephthalic acid from the recovered dimethyl terephthalate is not particularly limited, and any of the conventional methods may be used. For example, dimethyl terephthalate is recovered from a reaction mixture obtained by a transesterification reaction by a recrystallization method and / or a distillation method, and then heated with water at high temperature and high pressure to hydrolyze to recover terephthalic acid. Among the impurities contained in terephthalic acid obtained by this method, the total content of 4-carboxybenzaldehyde, paratoluic acid, benzoic acid and dimethyl hydroxyterephthalate is preferably 1 ppm or less. Further, the content of monomethyl terephthalate is preferably in the range of 1 ppm to 5000 ppm. A polyester resin can be produced by directly esterifying the terephthalic acid recovered by the above-described method with an alkylene glycol and subjecting the resulting ester to polycondensation.

In the polyester resin used in the present disclosure, the catalyst is added to the polymerization starting material at any stage before the start of the polycondensation reaction of the aromatic dicarboxylic acid alkylene glycol ester and / or its low polymer. The addition method is not limited. For example, an aromatic dicarboxylic acid alkylene glycol ester may be prepared, and a polycondensation reaction may be started by adding a catalyst solution or slurry to the reaction system, or the aromatic dicarboxylic acid alkylene glycol ester may be used as a starting material. A catalyst solution or slurry may be added to the reaction system together with the starting materials during the preparation, or after the preparation thereof.

ポ リ エ ス テ ル There is no particular limitation on the reaction conditions for producing the polyester resin used in the present disclosure. Generally, the polycondensation reaction is carried out at a temperature of 230 ° C. to 320 ° C. under normal pressure or reduced pressure (0.1 Pa to 0.1 MPa), or a combination of these conditions, for 15 minutes to 300 minutes. Is preferred.

In the polyester resin used in the present disclosure, a reaction stabilizer, for example, trimethyl phosphate may be added to the reaction system as needed at any stage in the production of the polyester resin. One or more of an additive, an ultraviolet absorber, a flame retardant, a fluorescent whitening agent, a matting agent, a coloring agent, an antifoaming agent, and other additives may be blended. In particular, it is preferable that the polyester resin contains an antioxidant containing at least one kind of hindered phenol compound, but the content is 1% by weight or less based on the weight of the polyester resin. Is preferred. When the content is 1% by weight or less, the quality of the obtained product can be ensured by preventing thermal degradation of the antioxidant itself.

The hindered phenol compound for an antioxidant used in the polyester resin used in the present disclosure is pentaerythritol-tetraextract [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3, 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5 , 5] undecane, etc., and it is also preferable to use these hindered phenol-based antioxidants in combination with thioether-based secondary antioxidants. The method for adding the hindered phenolic antioxidant to the polyester resin is not particularly limited, but is preferably an arbitrary step from completion of the transesterification reaction or esterification reaction to completion of the polymerization reaction. Is added.

Further, in order to finely adjust the color tone of the obtained polyester resin, an organic blue pigment such as an azo-based, triphenylmethane-based, quinoline-based, anthraquinone-based, phthalocyanine-based, etc. And a tinting agent consisting of one or more inorganic blue pigments. In the production method of the present disclosure, it is needless to say that it is not necessary to use an inorganic blue pigment containing cobalt or the like which lowers the melting heat stability of the polyester-based resin as a coloring agent. Therefore, the polyester resin used in the present disclosure does not substantially contain cobalt.

ポ リ エ ス テ ル The polyester resin used in the present disclosure preferably contains 0.001 ppm to 100 ppm of the above-mentioned catalyst-derived titanium element. The content is more preferably from 0.001 ppm to 50 ppm, further preferably from 1 ppm to 50 ppm. When the content of the titanium element is more than 100 ppm, thermal stability and wet heat resistance may be deteriorated. When the content is less than 0.001 ppm, the residual amount of the catalyst of the polyester resin to be used is significantly lower. This means that good mechanical strength, thermal stability and wet heat stability characteristic of the present composition may not be obtained.

に お い て In the polyester resin used in the present disclosure, it is usually preferable that the L value obtained by a Hunter type color difference meter is 80.0 or more and the b value is in the range of −2.0 to 5.0. If the L value of the polyester-based resin is less than 80.0, the whiteness of the obtained polyester-based resin will be low, and a high-whiteness molded product that can be practically used may not be obtained. When the b value is less than -2.0, the resulting polyester resin has a small yellowish tint, but has a bluish tint. When the b value exceeds 5.0, the resulting polyester resin has a yellow tint. , It may not be possible to produce a practically useful molded product. The L value of the polyester resin obtained by the method of the present disclosure is more preferably 82 or more, particularly preferably 83 or more, and the b value is more preferably in the range of -1.0 to 4.5, and particularly preferably 0. 0.0 to 4.0.

固有 The intrinsic viscosity of the polyester resin obtained according to the present disclosure is preferably 0.4 to 1.5. A more preferable range of the intrinsic viscosity is 0.45 to 1.4, and further preferably 0.50 to 1.3. If the intrinsic viscosity of the polyester resin is 0.4 or more, sufficient impact characteristics and chemical resistance may be obtained. If the intrinsic viscosity is 1.5 or less, fluidity during injection molding is secured. Thus, appearance defects such as flow marks and coloring defects can be prevented from occurring. The intrinsic viscosity of the polyester resin is measured at a temperature of 35 ° C. by dissolving the polyester resin in orthochlorophenol. The polyester-based resin obtained by solid-phase polycondensation is often used for general bottles and the like, and is therefore contained in the polyester-based resin and has an intrinsic viscosity of 0.70 to 0.90. Preferably, the content of the cyclic trimer of the ester of the aromatic dicarboxylic acid and the alkylene glycol is 0.5 wt% or less, and the content of acetaldehyde is 5 ppm or less. The cyclic trimers include alkylene terephthalates such as ethylene terephthalate, trimethylene terephthalate, tetramethylene terephthalate, and hexamethylene terephthalate, and alkylene naphthalates such as ethylene naphthalate, trimethylene naphthalate, tetramethylene naphthalate, and hexamethylene. Methylene naphthalate and the like.

Further, in the present disclosure, a compound such as manganese, zinc, calcium, and magnesium used in a transesterification reaction that is a former stage of a conventionally known polycondensation can be used in combination, and phosphoric acid or phosphorus phosphite is used after the transesterification reaction is completed. It is also possible to deactivate such a catalyst with an acid compound or the like for polycondensation.

The method for producing the polyester resin can be any of a batch method and a continuous polymerization method.

The content of the component B is preferably 20 to 70 parts by weight, more preferably 30 to 70 parts by weight, and more preferably 35 to 65 parts by weight based on 100 parts by weight of the total of the components A and B. More preferably, it is particularly preferably 40 to 60 parts by weight. When the content of the B component is too small, the chemical resistance may not be exhibited, and when the content of the B component is too large, good mechanical properties, flame retardancy and antifouling properties are reduced. There is.

(Component C: a composite rubber comprising a component containing a polyorganosiloxane rubber and an alkyl (meth) acrylate rubber, selected from the group consisting of an aromatic alkenyl compound monomer unit and an alkyl (meth) acrylate compound monomer unit Graft copolymer having a core-shell structure in which at least one unit is graft-polymerized)
The resin composition according to the present disclosure is characterized in that a compound rubber containing a polyorganosiloxane rubber and an alkyl (meth) acrylate rubber as a C component is added to an aromatic alkenyl compound monomer unit and an alkyl (meth) acrylate compound At least one selected from the group consisting of body units also contains a graft copolymer having a core-shell structure in which units are graft-polymerized.

The rubber component of the component C is a composite rubber component comprising a component containing a polyorganosiloxane rubber and an alkyl (meth) acrylate rubber. The composite rubber refers to a rubber obtained by copolymerizing two types of rubber components or a rubber obtained by polymerizing so as to have an IPN structure entangled with each other so as to be inseparable. In addition, from the viewpoint of antifouling properties, the proportion of the polyorganosiloxane rubber in the rubber component is preferably 10% or more, and more preferably 15% or more. The upper limit of the proportion of the polyorganosiloxane rubber in the rubber component is not particularly limited, but is preferably 95% or less, 90% or less, 80% or less, or 70% or less. In the core-shell type graft polymer, the core has a weight average particle diameter of preferably 0.05 μm to 0.8 μm, more preferably 0.1 μm to 0.6 μm, and still more preferably 0.15 μm to 0.5 μm. When the thickness is in the range of 0.05 μm to 0.8 μm, better impact resistance may be achieved, which is preferable.

芳香 Examples of the aromatic alkenyl compound to be graft-polymerized on the shell of the core-shell type graft polymer include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene. Examples of the alkyl (meth) acrylate compound include acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, and methacrylic acid. Methacrylic esters such as cyclohexyl and octyl methacrylate can be mentioned.

Graft polymerizing at least one unit selected from the group consisting of an aromatic alkenyl compound monomer unit and an alkyl (meth) acrylate compound monomer unit onto the composite rubber from the viewpoint of affinity with the aromatic polycarbonate resin. Thereby, the good impact resistance of the aromatic polycarbonate resin is more effectively exhibited, and as a result, the impact resistance of the resin composition is improved.

An elastic polymer containing a composite rubber comprising a component containing a polyorganosiloxane rubber and an alkyl (meth) acrylate rubber is produced by any one of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. The copolymerization method may be a single-stage graft or a multi-stage graft. Further, it may be a mixture with a copolymer of only a graft component which is by-produced during the production. Examples of the polymerization method include a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-step swelling polymerization method. In the suspension polymerization method, a method in which an aqueous phase and a monomer phase are separately held, and both are accurately supplied to a continuous disperser, and the particle diameter is controlled by the number of revolutions of the disperser. In the method, a method of supplying a monomer phase into an aqueous liquid having a dispersing ability by passing it through a small-diameter orifice having a diameter of several to several tens of μm or a porous filter to control the particle size may be employed. In the case of a core-shell type graft polymer, the reaction may be performed in one stage or in multiple stages for both the core and the shell.

Such polymers are commercially available and can be easily obtained. For example, Mitsubishi Chemical Corporation's Methrene S-2501, S-2030, SX-005, whose core component is a silicone-acrylic composite rubber and whose shell component is methyl methacrylate as a main component, or shell component is acrylonitrile and styrene, manufactured by Mitsubishi Chemical Corporation. Examples thereof include those commercially available under the trade names SRK-200A and SX-200R, which are the main components.

When a graft copolymer other than the above graft copolymer is used as the C component, chemical resistance and antifouling properties are not exhibited.

The content of the component C is 3 parts by weight to 15 parts by weight, preferably 4 parts by weight to 12 parts by weight, more preferably 5 parts by weight to 10 parts by weight based on 100 parts by weight of the total of the components A and B. Department. The addition of the C component further improves impact resistance, chemical resistance, and antifouling properties. When the amount is 15 parts by weight or less, a good appearance is secured.

(D component: antifouling agent)
The resin composition of the present disclosure contains, as a D component, an antifouling agent. Specific examples of the antifouling agent of the present disclosure include silicone oil, silicone gum, silicone resin fine particles, polyolefin, silicone-modified polyolefin, wax and the like. From the viewpoint, silicone gum and silicone-modified polyolefin are particularly desirable.

シ リ コ ー ン The silicone gum used in the present disclosure is preferably a gum-like polyorganosiloxane having a molecular weight of 100,000 or more. Polyorganosiloxane is a polymer substance in which an organic group is added to a structure in which a silicon atom is bonded to another silicon atom via an oxygen atom. The skeleton of the polyorganosiloxane may be linear, branched, cyclic, or a mixture thereof.

Examples of the structure of polyorganosiloxane include polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, aralkyl-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, alkyl-modified polydimethylsiloxane, higher fatty acid-modified polydimethylsiloxane, and fluoropolysiloxane. Examples include alkyl-modified polydimethylsiloxane, amino-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, carbinol-modified polydimethylsiloxane, carboxyl-modified polydimethylsiloxane, phenol-modified polydimethylsiloxane, and silanol-modified polydimethylsiloxane. These may be used alone or in combination of two or more. Of these, polydimethylsiloxane is most preferably used in view of the balance between performance and cost.

こ と When the molecular weight is 100,000 or more, very high viscosity can be obtained. From the viewpoint of improving the handleability, a master batch product diluted with a thermoplastic resin is preferably used. Such masterbatch products are commercially available and can be easily obtained. For example, trade names of MB50-315 which is a 50% masterbatch product of Toray Dow Corning Co., Ltd., BY27-001 which is a masterbatch product of 50% polypropylene, and BY27-009 which is a 50% masterbatch product of a polyester elastomer. Commercially available ones can be mentioned.

シ リ コ ー ン In the present disclosure, a silicone-modified polyolefin can also be used. The silicone-modified polyolefin is obtained by chemically bonding a polyorganosiloxane to a polyolefin resin. Examples of the silicone-modified polyolefin include a polyorganosiloxane-grafted polyolefin resin. The polyolefin resin is a synthetic resin obtained by polymerizing or copolymerizing an olefin monomer having a radical polymerizable double bond. The olefin-based monomer is not particularly limited, and examples thereof include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 4-methyl-1-pentene. Examples include olefins and conjugated dienes such as butadiene and isoprene. The olefin monomers may be used alone or in combination of two or more. The polyolefin resin is not particularly limited, and examples thereof include a homopolymer of ethylene, a copolymer of ethylene and an α-olefin other than ethylene, a homopolymer of propylene, and a copolymer of propylene and an α-olefin other than propylene. Polymers, butene homopolymers, conjugated diene homopolymers or copolymers such as butadiene and isoprene, and the like. Preferred are propylene homopolymers and copolymers of propylene and α-olefins other than propylene. . More preferably, it is a homopolymer of propylene. The polyolefin resins may be used alone or in combination of two or more. In the present disclosure, a polypropylene-based resin is more preferably used from the viewpoint of versatility and rigidity.

The skeleton of the polyorganosiloxane may be linear, branched, cyclic, or a mixture thereof. Examples of the structure of polyorganosiloxane include polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, aralkyl-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, alkyl-modified polydimethylsiloxane, higher fatty acid-modified polydimethylsiloxane, and fluoropolysiloxane. Examples include alkyl-modified polydimethylsiloxane, amino-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, carbinol-modified polydimethylsiloxane, carboxyl-modified polydimethylsiloxane, phenol-modified polydimethylsiloxane, and silanol-modified polydimethylsiloxane. These may be used alone or in combination of two or more. Of these, polydimethylsiloxane is most preferably used in view of the balance between performance and cost. Such polymers are commercially available and can be easily obtained. For example, those commercially available under the trade names BY27-201 and BY27-201C, which are polyorganosiloxane-grafted polypropylene manufactured by Toray Dow Corning Co., Ltd., may be mentioned.

The content of the component D is 0.5 to 6.0 parts by weight, preferably 1.0 to 5.0 parts by weight, based on 100 parts by weight of the total of the components A and B. Preferably it is 1.5 to 4.0 parts by weight. When the component D is 0.5 parts by weight or more, antifouling properties are exhibited. When the content of the D component is 4.0 parts by weight or less, appearance defects such as bleed-out do not occur. When the above-mentioned master batch product is used, the content of the D component indicates the amount of the antifouling agent included in the master batch product.

<< Flame-retardant polycarbonate resin composition >>
In one embodiment of the present disclosure, the polycarbonate resin composition further comprises the following flame retardant:
(E) a halogen-based flame retardant (component E), and (F) a phosphorus-based flame retardant having a structure represented by the following formula (1) (component F)

(In the formula, X ₁ and X ₂ are the same or different and are an aromatic substituted alkyl group represented by the following general formula (I).)

(Wherein, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, Ar is a phenyl group, a naphthyl group or an anthryl group, n represents an integer of 1 to 3, Ar can be attached to any carbon atom of AL.).

用途 In applications such as electric and electronic equipment, the demand for flame retardancy is increasing, and various flame retardant resin compositions have been proposed. However, none of the proposals has provided a flame-retardant polycarbonate resin composition having both mechanical properties, appearance, flame retardancy, chemical resistance, antifouling property, and thermal stability.

The polycarbonate resin composition according to the embodiment of the present disclosure further includes the above-mentioned components E and F as a flame retardant, so that the polycarbonate resin composition has excellent mechanical properties, chemical resistance, antifouling properties, and appearance. Satisfies flame retardancy and thermal stability at a high level. Therefore, the present invention is widely and particularly useful not only in outdoor / indoor use, but also in various applications such as housing equipment, building materials, living materials, infrastructure equipment, automobiles, OA / EE, outdoor equipment, and the like.

(E component: halogen-based flame retardant)
The resin composition according to one embodiment of the present disclosure contains a halogen-based flame retardant as the E component. As the halogen-based flame retardant, brominated polycarbonate (including oligomer) is particularly preferred. Brominated polycarbonate is excellent in heat resistance and can greatly improve flame retardancy. In the brominated polycarbonate used in the present disclosure, the structural unit represented by the following formula (7) is preferably at least 60 mol%, more preferably at least 80 mol% of all the structural units, and particularly preferably substantially the following. It is a brominated polycarbonate compound comprising a structural unit represented by the formula (7).

In the formula (7), X is a bromine atom, R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or —SO ₂ —.
In the formula (7), R preferably represents a methylene group, an ethylene group, an isopropylidene group, —SO ₂ —, and particularly preferably an isopropylidene group.

(4) The brominated polycarbonate has few residual chloroformate group terminals, and the amount of terminal chlorine is preferably 0.3 ppm or less, more preferably 0.2 ppm or less. The amount of terminal chlorine can be determined by dissolving a sample in methylene chloride, adding 4- (p-nitrobenzyl) pyridine and reacting with terminal chlorine (terminal chloroformate), and using an ultraviolet-visible spectrophotometer (manufactured by Hitachi, Ltd.). -3200). When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the polycarbonate resin composition becomes better, and molding at a higher temperature becomes possible. As a result, a resin composition having more excellent moldability is provided.

Further, the brominated polycarbonate preferably has a small number of remaining hydroxyl group terminals. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, more preferably 0.0003 mol or less, per 1 mol of the structural unit of the brominated polycarbonate. The amount of terminal hydroxyl groups can be determined by dissolving a sample in deuterated chloroform and measuring by ¹ H-NMR method. Such an amount of terminal hydroxyl groups is preferable because the thermal stability of the polycarbonate resin composition is further improved.

(4) The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the brominated polycarbonate is calculated according to the above-mentioned specific viscosity calculation formula used in calculating the viscosity average molecular weight of the polycarbonate resin as the component A of the present disclosure.

The content of the component E is 5 parts by weight to 35 parts by weight, preferably 8 parts by weight to 30 parts by weight, more preferably 10 parts by weight to 25 parts by weight based on 100 parts by weight of the total of the components A and B. It is. When the content of the E component is 5 parts by weight or more, flame retardancy may be exhibited, and when the content is 35 parts by weight or less, good mechanical properties, appearance, and chemical resistance may be secured.

ハ ロ ゲ ン Although a halogen-based flame retardant can generally further increase the flame retardancy of a resin composition when used in combination with an antimony oxide compound, it is not desirable in the present disclosure because thermal stability is significantly reduced.

(F component: phosphorus-based flame retardant)
The phosphorus-based flame retardant of the present disclosure is an organic phosphorus compound represented by the following general formula (1).

In the above formula (1), X ₁ and X ₂ are the same or different and represent an aromatic-substituted alkyl group represented by the following general formula (I).

ＡＬ In the above formula (I), AL is a branched or straight-chain aliphatic hydrocarbon group having 1 to 5, preferably 1 or 2 carbon atoms. Specifically, AL is preferably an alkyl group represented by the following formula (8). Ar is a phenyl group, a naphthyl group or an anthryl group, of which a phenyl group is preferable. n represents an integer of 1 to 3, preferably 1 or 2. Ar can be attached to any carbon of AL.

The organophosphorus flame retardant represented by the above formula (1) exhibits an extremely excellent flame retardant effect on an aromatic polyester resin.
The organophosphorous flame retardant is represented by the general formula (1), and the most preferred representative compound is at least one compound selected from the group consisting of the following formulas (Ba) to (Bd). is there. One or more of these compounds can be used.

Of these formulas (Ba) to (Bd), the Ba component represented by the formula (Ba) or the Bc component represented by the formula (Bc) has a flame-retardant effect or It is suitable in terms of ease of synthesis and the like. In addition, when a phosphorus-based flame retardant other than the phosphorus-based flame retardant is used, the flame retardancy does not appear if the amount is within the range of the present disclosure.

合成 The method for synthesizing the organic phosphorus-based flame retardant in the present disclosure may be synthesized by a known method, and may be manufactured by a method other than the method described below.

The organic phosphorus-based flame retardant is obtained, for example, by reacting pentaerythritol with phosphorus trichloride, subsequently treating the oxidized reactant with an alkali metal compound such as sodium methoxide, and then reacting with aralkyl halide. Further, it can also be obtained by a method of reacting aralkylphosphonic dichloride with pentaerythritol or a method of reacting aralkyl alcohol with a compound obtained by reacting pentaerythritol with phosphorus trichloride and then performing Arbuzov transition at a high temperature. . The latter reaction is disclosed in, for example, US Pat. No. 3,141,032, JP-A-54-157156 and JP-A-53-39698.

Although a specific synthesis method is described below, this synthesis method is merely for explanation, and the organophosphorus flame retardant used in the present disclosure includes not only these synthesis methods but also modifications and other synthesis methods. It may be synthesized. A more specific synthesis method will be described in Preparation Example 1 described later.
(I) the organic phosphorus compound of (Ba);
The reaction product obtained by reacting pentaerythritol with phosphorus trichloride and then oxidizing with tert-butanol can be obtained by treating with sodium methoxide and reacting with benzyl bromide.
(Ii) the organic phosphorus compound of (Bb);
The reaction product obtained by reacting pentaerythritol with phosphorus trichloride and subsequently oxidizing with tert-butanol can be obtained by treating with sodium methoxide and reacting with 1-bromoethylbenzene.
(Iii) the organic phosphorus compound of (Bc);
The reaction product obtained by reacting pentaerythritol with phosphorus trichloride and subsequently oxidizing with tert-butanol can be obtained by treating with sodium methoxide and reacting with 2-bromoethylbenzene.
(Iv) the organic phosphorus compound of (Bd);
It can be obtained by reacting pentaerythritol with diphenylmethylphosphonic acid dichloride.

酸 The acid value of the organophosphorus flame retardant is preferably 0.7 mgKOH / g or less, more preferably 0.5 mgKOH / g or less. By using an organic phosphorus-based flame retardant having an acid value in this range, the polyester resin hardly decomposes and the thermal stability becomes good, so that a composition having good processability is obtained. Most preferably, the organic phosphorus-based flame retardant has an acid value of 0.4 mgKOH / g or less. Here, the acid value means the amount (mg) of KOH required to neutralize the acid component in 1 g of the sample. When the acid value is 0.7 mgKOH / g or less, good thermal stability is ensured and workability may be excellent, which is preferable.

Furthermore, as the organophosphorus flame retardant, those having an HPLC purity of preferably 90% or more, more preferably 95% or more are used. Such a high-purity product is preferable because of its excellent flame retardancy and hue. Here, the HPLC purity of the F component can be measured effectively by using the following method. The column used was Develosil {ODS-7} 300 mm × 4 mmφ manufactured by Nomura Chemical Co., Ltd., and the column temperature was 40 ° C. As a solvent, a mixed solution of acetonitrile and water 6: 4 (volume ratio) was used, and 5 μl was injected. The detector used was UV-260 nm. The method of removing impurities in the F component is not particularly limited, but a method of performing repulp washing with a solvent such as water or methanol (washing with a solvent and repeating filtration several times) is most effective, It is also advantageous in terms of cost.

The content of the component F is 0.5 to 5 parts by weight, preferably 0.8 to 4 parts by weight, more preferably 1 part by weight, based on 100 parts by weight of the total of the components A and B. Parts to 3 parts by weight. When the content of the F component is 0.5 parts by weight or more, flame retardancy is exhibited, and when the content is 5 parts by weight or less, good mechanical properties, appearance, and chemical resistance may be ensured. is there.

(G component: anti-drip agent)
The resin composition of the present disclosure may contain an anti-drip agent as a G component. By containing this anti-drip agent, good flame retardancy can be achieved without impairing the physical properties of the molded article.

Examples of the anti-drip agent of the G component include a fluorine-containing polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene and tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer). Polymers, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable.

PTFE having a fibril-forming ability has a very high molecular weight, and has a tendency to combine with each other by an external action such as shearing force to form a fibrous form. Its molecular weight is 1,000,000 to 10,000,000, more preferably 2,000,000 to 9,000,000, in number average molecular weight determined from the standard specific gravity. As the PTFE, not only a solid form but also an aqueous dispersion form can be used. In addition, PTFE having such fibril-forming ability can use a PTFE mixture in a mixed form with another resin in order to improve the dispersibility in the resin and to obtain better flame retardancy and mechanical properties. is there.

Examples of commercially available PTFE having such a fibril-forming ability include Teflon (registered trademark) 6J of DuPont-Mitsui Fluorochemicals Co., Ltd., and Polyflon MPA FA500 and F-201L of Daikin Industries, Ltd. Commercially available PTFE aqueous dispersions include Fluon AD-1, AD-936 manufactured by Asahi ICI Fluoropolymers Co., Ltd., Fluon D-1 and D-2 manufactured by Daikin Industries, Ltd., and DuPont Mitsui Teflon (registered trademark) 30J manufactured by Chemical Co., Ltd. can be mentioned as a representative.

As the 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 coaggregated mixture (JP-A-60-258263, JP-A-63-154744). Gazettes),
(2) a method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (a method described in JP-A-4-272957);
(3) A method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer particle solution and simultaneously removing the respective media from the mixture (described in JP-A-06-220210 and JP-A-08-188655). Method),
(4) a method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of PTFE (method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer. After the combined dispersion is uniformly mixed, a vinyl monomer is further polymerized in the mixed dispersion, and then the mixture is obtained by a method of obtaining a mixture (a method described in JP-A-11-29679). Can be used.
Examples of commercially available PTFE in these mixed forms include “METABLEN A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

割 合 The proportion of PTFE in the mixed form is preferably 1% by weight to 60% by weight, more preferably 5% by weight to 55% by weight, based on 100% by weight of the PTFE mixture. When the proportion of PTFE is in such a range, good dispersibility of PTFE can be achieved. Note that the ratio of the G component indicates the net amount of the anti-drip agent, and in the case of PTFE in a mixed form, indicates the net amount of PTFE.

The content of the component G is preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1.5 parts by weight, based on 100 parts by weight of the total of the components A and B. Preferably it is 0.2 to 1 part by weight. If the amount of the anti-drip agent is less than the above range, the flame retardancy may be insufficient. On the other hand, if the amount of the anti-drip agent is too large, exceeding the above range, not only may PTFE precipitate on the surface of the molded article, resulting in poor appearance, but also leads to an increase in the cost of the resin composition, which is not preferable.

The styrene-based monomer used in the organic polymer used in the polytetrafluoroethylene-based mixture of the present disclosure includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and halogen. Styrene which may be substituted with one or more groups selected from the group consisting of, for example, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethyl-styrene, para-tert-butylstyrene , Methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, vinylnaphthalene, but are not limited thereto. The styrene monomers may be used alone or in combination of two or more.

ア ク リ ル The acrylic monomer used in the organic polymer used in the polytetrafluoroethylene-based mixture of the present disclosure includes a (meth) acrylate derivative that may be substituted. Specifically, the acrylic monomer is substituted with at least one group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, and a glycidyl group. (Meth) acrylate derivatives that may be used, such as (meth) acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and glycidyl (meth) acrylate; Alkyl having 1 to 6 carbon atoms , Or maleimide which may be substituted by an aryl group, for example, maleimide, N- methyl - maleimide and N- phenyl - maleimide, maleic acid, phthalic acid and itaconic acid are exemplified, but are not limited thereto. The acrylic monomers may be used alone or in combination of two or more. Among these, (meth) acrylonitrile is preferred.

The amount of the acrylic monomer-derived unit contained in the organic polymer used for the coating layer is preferably 8 parts by weight to 11 parts by weight, more preferably 8 parts by weight, based on 100 parts by weight of the styrene-based monomer-derived unit. Parts to 10 parts by weight, more preferably 8 to 9 parts by weight. When the unit derived from the acrylic monomer is at least 8 parts by weight, the coating strength may be ensured, and when it is at most 11 parts by weight, a good surface appearance of the molded article can be ensured.

The polytetrafluoroethylene-based mixture of the present disclosure preferably has a residual moisture content of 0.5% by weight or less, more preferably 0.2% to 0.4% by weight, and still more preferably 0.1% by weight. % To 0.3% by weight. When the residual water content is 0.5% by weight or less, adverse effects on flame retardancy can be avoided.

In the manufacturing process of the polytetrafluoroethylene-based mixture of the present disclosure, a coating layer containing at least one monomer selected from the group consisting of a styrene-based monomer and an acrylic monomer in the presence of an initiator. Is formed outside the branched polytetrafluoroethylene. Further, the residual moisture content after the step of forming the coating layer is 0.5% by weight or less, preferably 0.2% by weight to 0.4% by weight, more preferably 0.1% by weight to 0.3% by weight. It is preferable to include a drying step. The drying step can be performed using a method known in the art, for example, a hot air drying method or a vacuum drying method.

開始 The initiator used in the polytetrafluoroethylene-based mixture of the present disclosure can be used without any limitation as long as it is used for the polymerization reaction of styrene-based and / or acrylic-based monomers. Examples of the initiator include, but are not limited to, cumyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, hydrogen peroxide, and potassium peroxide. In the polytetrafluoroethylene-based mixture of the present disclosure, one or more of the above initiators can be used depending on reaction conditions. The amount of the initiator is freely selected within the range used in consideration of the amount of polytetrafluoroethylene and the type / amount of the monomer, and is from 0.15 parts by weight based on the total amount of the composition. It is preferred to use 0.25 parts by weight.

ポ リ The polytetrafluoroethylene-based mixture of the present disclosure was produced by a suspension polymerization method according to the following procedure.

First, water and a branched polytetrafluoroethylene dispersion (solid concentration: 60%, polytetrafluoroethylene particle size: 0.15 to 0.3 μm) are put into a reactor, and then, an acrylic monomer and styrene are stirred while stirring. Cumene hydroperoxide was added as a monomer and a water-soluble initiator, and the mixture was reacted at 80 ° C. to 90 ° C. for 9 hours. After completion of the reaction, water was removed by centrifuging for 30 minutes using a centrifuge to obtain a paste-like product. Thereafter, the product paste was dried with a hot air drier at 80 ° C. to 100 ° C. for 8 hours. Thereafter, the dried product was pulverized to obtain a polytetrafluoroethylene-based mixture of the present disclosure.

懸 濁 Since such a suspension polymerization method does not require a polymerization step by emulsification dispersion in the emulsion polymerization method exemplified in Japanese Patent No. 3469391, it does not require an emulsifier and electrolyte salts for coagulating and precipitating a latex after polymerization. In addition, in the polytetrafluoroethylene mixture produced by the emulsion polymerization method, the emulsifier and the electrolyte salts in the mixture are easily mixed and difficult to remove, so that such emulsifier, sodium metal ions and potassium metal ions derived from the electrolyte salts are reduced. It is difficult. Since the polytetrafluoroethylene-based mixture used in the present disclosure is manufactured by a suspension polymerization method, such an emulsifier and a sodium metal ion and a potassium metal ion in the mixture can be reduced since no electrolyte salt is used. To improve heat stability and hydrolysis resistance.

被覆 Also, in the present disclosure, coated branched PTFE can be used as an anti-drip agent. The coated branched PTFE is a polytetrafluoroethylene-based mixture composed of branched polytetrafluoroethylene particles and an organic polymer, and an organic polymer, preferably a styrene-based monomer, is provided outside the branched polytetrafluoroethylene. It has a coating layer made of a polymer containing units and / or units derived from an acrylic monomer. The coating layer is formed on the surface of the branched polytetrafluoroethylene. The coating layer preferably contains a copolymer of a styrene monomer and an acrylic monomer.

The polytetrafluoroethylene contained in the coated branched PTFE is a branched polytetrafluoroethylene. When the contained polytetrafluoroethylene is not a branched polytetrafluoroethylene, the effect of preventing dripping when the addition of polytetrafluoroethylene is small is insufficient. The branched polytetrafluoroethylene is in the form of particles, and preferably has a particle diameter of 0.1 μm to 0.6 μm, more preferably 0.3 μm to 0.5 μm, and still more preferably 0.3 μm to 0.4 μm. When the particle diameter is smaller than 0.1 μm, the surface appearance of the molded article is excellent, but it is difficult to commercially obtain polytetrafluoroethylene having a particle diameter smaller than 0.1 μm. When the particle diameter is 0.6 μm or less, good surface appearance of the molded product may be secured. The number average molecular weight of the polytetrafluoroethylene used in the present disclosure is preferably 1 × 10 ⁴ to 1 × 10 ⁷ , more preferably 2 × 10 ⁶ to 9 × 10 ⁶ , and generally polytetrafluoroethylene having a high molecular weight. Fluoroethylene is more preferred in terms of stability. Either in powder or dispersion form can be used.

The content of the branched polytetrafluoroethylene in the coated branched PTFE is preferably 20 parts by weight to 60 parts by weight, more preferably 40 parts by weight to 55 parts by weight, based on 100 parts by weight of the total weight of the coated branched PTFE. It is preferably from 47 to 53 parts by weight, particularly preferably from 48 to 52 parts by weight, most preferably from 49 to 51 parts by weight. When the proportion of the branched polytetrafluoroethylene is in such a range, good dispersibility of the branched polytetrafluoroethylene can be achieved.

(Other additives)
(I) Phosphorus-based stabilizer Examples of the phosphorus-based stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.

Specifically, examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, and dioctyl monophenyl. Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethyl phenyl) phosphite, tris (di-iso-propyl phenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, di Teaarylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and the like.

Further phosphite compounds which react with dihydric phenols and have a cyclic structure can also be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butyl) Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.

Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, and dioctyl phosphate. Examples thereof include diisopropyl phosphate, and preferred are triphenyl phosphate and trimethyl phosphate.

Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediene Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite , Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4- -Tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, Bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, and tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -Phenyl-phenylphosphonite is more preferred. Such a phosphonite compound can be used in combination with the phosphite compound having an aryl group in which two or more alkyl groups are substituted, and is thus preferable.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

Examples of the tertiary phosphine include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, and tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

The above-mentioned phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus-based stabilizers, a phosphonite compound or a phosphite compound represented by the following general formula (9) is preferable.

(In the formula (9), R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different.)

As described above, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferred as the phosphonite compound, and the stabilizer containing phosphonite as a main component is Sandostab @ P-EPQ (trademark, manufactured by Clariant). ) And Irgafos @ P-EPQ (trademark, manufactured by CIBA SPECTIALTY CHEMICALS), and both can be used.

In the above formula (9), more preferred phosphite compounds include distearylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6-diphosphite). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

Distearyl pentaerythritol diphosphite is commercially available as ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Co., Ltd.), and any of them can be used. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is manufactured by ADK STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes), and Ultranox. P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgaofos 126 and 126FF (trademark, manufactured by CIBA SPECTIALTY CHEMICALS) are commercially available. Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available as ADK STAB PEP-36 (trademark, manufactured by Asahi Denka Kogyo KK) and can be easily used. Bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite is available from ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo KK) and Doverphos @ S-9228 (trademark). , Dover @ Chemical Co., Ltd.), and any of them can be used.

The above phosphorus-based stabilizers can be used alone or in combination of two or more. The content of the phosphorus-based stabilizer is preferably from 0.01 to 1.0 part by weight, more preferably from 0.03 to 0 parts by weight, based on 100 parts by weight of the total of the component A and the component B. 0.8 parts by weight, more preferably 0.05 to 0.5 parts by weight. When the content is 0.01 part by weight or more, the effect of suppressing thermal decomposition during processing is exhibited, and good mechanical properties may be ensured. Even when the content is 1.0 part by weight or less, Good mechanical properties may be ensured.

(Ii) Phenolic stabilizer The resin composition of the present disclosure may contain a phenol stabilizer. Phenolic stabilizers generally include hindered phenols, semi-hindered phenols, and re-hindered phenol compounds, but hindered phenol compounds are more preferable in terms of applying a heat-stable formulation to a polypropylene resin. Used for Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyr alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl -6-tert-butylphenol), 4,4'-methylenebis (2.6 Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2 ′ -Ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert) -Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediolbis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl6- (3-tert-butyl) 5-Methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -Dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 ′ -Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodie Lenbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Cyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3- tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2 {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [Methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy -5-methylbenzyl) benzene, and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate. Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferably used, and as a material excellent in suppressing a decrease in mechanical properties due to thermal decomposition during processing, represented by the following formula (10): (3,3 ', 3'',5,5', 5 '' -Hexa-tert-butyl-a, a ', a''-(mesitylene-2,4,6-triyl) tri-p-cresol and 1,3,5 represented by the following formula (11) -Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is more preferably used.

The above phenolic stabilizers can be used alone or in combination of two or more. The content of the phenol stabilizer is preferably 0.05 to 1.0 part by weight, more preferably 0.07 to 0 parts by weight, based on 100 parts by weight of the total of the component A and the component B. 0.8 parts by weight, more preferably 0.1 to 0.5 parts by weight. When the content is 0.05 parts by weight or more, the effect of suppressing thermal decomposition during processing is exhibited, and good mechanical properties may be ensured. Even when the content is 1.0 parts by weight or less, Good mechanical properties may be ensured.

It is preferable that one of the phosphorus-based stabilizer and the phenol-based stabilizer is blended, and the combination of these is more preferred. When used in combination, 0.01 to 0.5 parts by weight of a phosphorus-based stabilizer and 0.01 to 0.5 parts by weight of a phenol-based stabilizer, based on 100 parts by weight of the total of the components A and B. Preferably, an agent is blended.

(Iii) Ultraviolet absorber The polycarbonate resin composition of the present disclosure can contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, Hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4 ′ -Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4- Hydroxy-2-methoxyphenyl) Examples include methane, 2-hydroxy-4-n-dodecyloxybensophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

In the benzotriazole type, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3 , 3-Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2- Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3, -Di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine- 4-one), 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacrylic Roxyethylphenyl) -2H-benzotriazole and a copolymerizable vinyl monomer. 2-hydroxyphenyl-2H-benzotriazole skeleton such as a copolymer or a copolymer of 2- (2'-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with the monomer. And the like.

Hydroxyphenyl triazines include, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5 -Triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl -1,3,5-triazin-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol Is exemplified. Furthermore, the phenyl group of the above exemplified compound such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl A compound having a phenyl group is exemplified.

In the case of cyclic iminoesters, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazin-4-one) And 2,2′-p, p′-diphenylenebis (3,1-benzoxazin-4-one).

In the cyanoacrylate system, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenylacryloyl) oxy ] Methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorber and / or the light-stable monomer can be combined with a monomer such as alkyl (meth) acrylate. It may be a polymer type ultraviolet absorber obtained by copolymerization with a body. Preferred examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in an ester substituent of a (meth) acrylate. You.

中 で も Among the above compounds, in the present disclosure, a compound represented by any of the following formulas (12), (13) and (14) is more preferably used.

The above ultraviolet absorbers can be used alone or in combination of two or more.
The content of the ultraviolet absorbent is preferably from 0.1 to 2 parts by weight, more preferably from 0.12 to 1.5 parts by weight, based on 100 parts by weight of the total of the component A and the component B. Parts, more preferably 0.15 parts by weight to 1 part by weight. When the content of the ultraviolet absorber is 0.1 part by weight or more, sufficient light resistance may be exhibited, and when the content is 2 parts by weight or less, poor appearance or physical property deterioration due to gas generation may occur. It is preferable because it can be avoided.

(Iv) Hindered amine light stabilizer The polycarbonate resin composition of the present disclosure may contain a hindered amine light stabilizer. The hindered amine light stabilizer is generally called HALS (Hindered Amine Light Stabilizer) and is a compound having a 2,2,6,6-tetramethylpiperidine skeleton in its structure. For example, 4-acetoxy-2,2,6 , 6-Tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2, 2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2, 2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6- Tramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarbamoyloxy) -2,2,6 , 6-Tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, bis (2 , 2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6,6-tetramethyl-4-) Piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl) 4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) carbonate, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) oxalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, bis (1,2,2,6,6-pentamethyl-4) -Piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) terephthalate, N, N'- Bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, 1,2-bis (2,2,6,6-tetramethyl-4-piperid Loxy) ethane, α, α'-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyltolylene -2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl-4 -Piperidyl) -benzene-1,3,5-tricarboxylate, N, N ', N ", N'"-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2 , 6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine.N, N ' -Bis (2,2,6,6-tetramethyl-4-pi Peridyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1,1,3,3-tetra Methylbutyl) amino-1,3,5-triazine-2,4-diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene} (2,2,6,6- Tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2) 6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4- Tricarboxylate 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl ) Propionyloxy] 2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, and condensates with β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.

Hindered amine light stabilizers are broadly classified according to the bonding partner of the nitrogen atom in the piperidine skeleton, such as NH (hydrogen is bonded to a nitrogen atom), NR (alkyl group (R) is bonded to a nitrogen atom), There are three types of N-OR type (alkoxy group (OR) is bonded to the nitrogen atom), but when applied to a polycarbonate resin, from the viewpoint of basicity of the hindered amine-based light stabilizer, NR having low basicity is used. And N-OR type are more preferably used.

中 で も Among the above compounds, in the present disclosure, compounds represented by the following formulas (15) and (16) are more preferably used.

The hindered amine light stabilizers can be used alone or in combination of two or more. The content of the hindered amine light stabilizer is preferably from 0 to 1 part by weight, more preferably from 0.05 to 1 part by weight, based on 100 parts by weight of the total of the component A and the component B. It is more preferably from 0.08 to 0.7 parts by weight, particularly preferably from 0.1 to 0.5 parts by weight. When the content of the hindered amine-based light stabilizer is 1 part by weight or less, poor appearance due to gas generation and deterioration in physical properties due to decomposition of the polycarbonate resin may be avoided, which is preferable. When the amount is 0.05 parts by weight or more, sufficient light resistance may be exhibited.

(V) Release Agent The polycarbonate resin composition of the present disclosure preferably further contains a release agent for the purpose of improving productivity during molding and reducing distortion of a molded product. Known release agents can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin-based waxes (polyethylene wax, 1-alkene polymer, etc .; those modified with a functional group-containing compound such as acid modification can also be used), silicone compounds, fluorine compounds ( Fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax, and the like. Among them, preferred release agents include fatty acid esters. Such a fatty acid ester is an ester of an aliphatic alcohol and an aliphatic carboxylic acid. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Further, the carbon number of the alcohol is in the range of 3 to 32, more preferably 5 to 30. Examples of such a monohydric alcohol include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol. Such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, mannitol and the like. Polyhydric alcohols are more preferred in the fatty acid esters of the present disclosure.

On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as icosanoic acid, and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and setrenic acid. . Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred. Particularly preferred are stearic acid and palmitic acid.

The above-mentioned aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats and fats such as tallow and lard and vegetable fats and fats such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components having different numbers of carbon atoms. Accordingly, in the production of the fatty acid ester of the present disclosure, an aliphatic carboxylic acid, particularly stearic acid or palmitic acid, which is produced from such natural fats and oils and is in the form of a mixture containing other carboxylic acid components, is preferably used.

脂肪酸 The fatty acid ester of the present disclosure may be either a partial ester or a whole ester (full ester). However, a partial ester is more preferably a full ester since the hydroxyl value is usually high and the resin is easily decomposed at a high temperature. The acid value of the fatty acid ester of the present disclosure is preferably 20 or less, more preferably 4 to 20, and still more preferably 4 to 12, from the viewpoint of thermal stability. Incidentally, the acid value can take substantially zero. Further, the hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Further, the iodine value is preferably 10 or less. Incidentally, the iodine value can take substantially zero. These characteristics can be obtained by a method specified in JIS K 0070.

The content of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and still more preferably 100 parts by weight of the total of the component A and the component B. Is 0.05 to 0.5 parts by weight. Within such a range, the polycarbonate resin composition has good release properties and roll release properties. In particular, such an amount of the fatty acid ester provides a polycarbonate resin composition having a good releasing property and a good roll releasing property without impairing a good hue.

(Vi) Dye and pigment The polycarbonate resin composition of the present disclosure can further provide a molded article containing various dyes and pigments and exhibiting various design properties. By blending a fluorescent whitening agent or a fluorescent dye that emits other light, a better design effect utilizing the emitted color can be provided. It is also possible to provide a polycarbonate resin composition which is colored by a trace amount of dye and pigment and has vivid coloration.

Examples of the fluorescent dye (including a fluorescent whitening agent) used in the present disclosure include, for example, a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Of these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes, which have good heat resistance and are less likely to deteriorate during molding of the polycarbonate resin, are preferred.

As the dyes other than the bluing agent and the fluorescent dye, perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as navy blue, perinone dyes, quinoline dyes, quinacridone Dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Further, the resin composition of the present disclosure can also obtain a better metallic color by blending a metallic pigment. As the metallic pigment, those having a metal coating or a metal oxide coating on various plate-like fillers are preferable.

The content of the dye / pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of the total of the component A and the component B. .

(Vii) Other heat stabilizers The polycarbonate resin composition of the present disclosure may also contain other heat stabilizers other than the above-mentioned phosphorus-based stabilizer and phenol-based stabilizer. Such other heat stabilizers are preferably used in combination with any one of these stabilizers and antioxidants, and particularly preferably used in combination with both. Such other heat stabilizers include, for example, lactone stabilizers represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one with o-xylene (such stabilizers) The details are described in JP-A-7-233160). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compound can be used. Further, stabilizers obtained by mixing the compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. Such premixed stabilizers can also be utilized in the present disclosure. The compounding amount of the lactone stabilizer is preferably 0.0005 to 0.05 part by weight, more preferably 0.001 to 0.03 part by weight, based on 100 parts by weight of the total of the component A and the component B. Department.

Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Is exemplified. Such a stabilizer is particularly effective when the resin composition is applied to rotational molding. The amount of the sulfur-containing stabilizer to be added is preferably 0.001 part by weight to 0.1 part by weight, more preferably 0.01 part by weight to 0.1 part by weight, based on 100 parts by weight of the total of the component A and the component B. 08 parts by weight.

(Viii) Filler In the polycarbonate resin composition of the present disclosure, various fillers can be blended as a reinforcing filler within a range in which the effects of the present disclosure are exhibited. For example, calcium carbonate, glass fiber, glass beads, glass balloon, glass milled fiber, glass flake, carbon fiber, carbon flake, carbon beads, carbon milled fiber, graphite, vapor grown ultrafine carbon fiber (fiber diameter 0.1 μm Less than), carbon nanotubes (fiber diameter less than 0.1 μm, hollow), fullerene, metal flake, metal fiber, metal-coated glass fiber, metal-coated carbon fiber, metal-coated glass flake, silica, metal oxide particles, Examples include metal oxide fibers, metal oxide balloons, and various whiskers (such as potassium titanate whiskers, aluminum borate whiskers, and basic magnesium sulfate). These reinforcing fillers may be used alone or in combination of two or more. The content of these fillers is preferably from 0.1 to 60 parts by weight, more preferably from 0.5 to 50 parts by weight, based on 100 parts by weight of the total of the component A and the component B.

(Ix) High-reflection white pigment The polycarbonate resin composition of the present disclosure can be mixed with a high-reflection white pigment to impart a light reflection effect. Examples of such white pigments include titanium oxide, zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, calcined kaolin and the like, and in particular, titanium oxide is publicly used. As the titanium oxide to be used, titanium oxide having an average particle diameter of 0.1 to 5.0 μm, which is surface-treated with an organic substance, is preferable. (In the present disclosure, the titanium oxide component of the titanium oxide pigment is described as “TiO ₂ ”, and the entire pigment including the surface treatment agent is described as “titanium oxide.”) TiO ₂ has a crystal form of anatase type or rutile type. Any of these may be used, and they may be used as a mixture if necessary. The rutile type is more preferable in terms of initial mechanical properties and long-term weather resistance. The rutile-type crystal may contain an anatase-type crystal. Further, as the method for producing TiO ₂ , those produced by various methods such as a sulfuric acid method and a chlorine method can be used, but the chlorine method is more preferable. Further, the titanium oxide of the present disclosure is not particularly limited in its shape, but is preferably in the form of particles. Titanium oxide is generally used for various coloring purposes, and the average particle diameter of titanium oxide used as the white pigment of the present disclosure is preferably 0.10 μm to 5.0 μm, and more preferably 0.15 μm to 2.0 μm. 0 μm is more preferred, and 0.18 μm to 1.5 μm is even more preferred. When the average particle size is 0.10 μm or more, poor appearance such as silver may be avoided even in the case of high filling, and when the average particle size is 5.0 μm or less, a good appearance is obtained. And mechanical characteristics may be ensured. The average particle diameter is calculated from the number average of individual single particle diameters measured by electron microscope observation.

チ タ ン The titanium oxide used in the present disclosure is preferably surface-treated with an organic compound. When using titanium oxide that has not been subjected to organic treatment, the appearance is deteriorated due to yellowing, and the reflectance of the molded article is significantly reduced, so that sufficient solar reflectance may not be obtained. May not be suitable for As such a surface treating agent, various treating agents such as polyol-based, amine-based, and silicone-based can be used. Examples of the polyol-based surface treatment agent include pentaerythritol, trimethylolethane, and trimethylolpropane, and examples of the amine-based surface treatment agent include triethanolamine acetate and trimethylolamine acetate. Examples of the silicone-based surface treatment agent include alkyl chlorosilane (such as trimethylchlorosilane), alkylalkoxysilane (such as methyltrimethoxysilane), and hydrogenpolysiloxane. Examples of the hydrogen polysiloxane include an alkyl hydrogen polysiloxane and an alkylphenyl hydrogen polysiloxane. As such an alkyl group, a methyl group and an ethyl group are preferable. The titanium oxide surface-treated with such an alkylalkoxysilane and / or hydrogenpolysiloxane gives the resin composition of the present disclosure better light reflectivity. The amount of the organic compound used for the surface treatment is preferably from 0.05 to 5 parts by weight, more preferably from 0.5 to 3 parts by weight, and still more preferably from 1.5 to 3 parts by weight, per 100 parts by weight of titanium oxide. The range is from 2.5 parts by weight to 2.5 parts by weight. When the surface treatment amount is 0.05 parts by weight or more, sufficient thermal stability may be obtained, and when the surface treatment amount is 5 parts by weight or less, it is preferable because molding defects such as silver can be avoided. . It is preferable that the surface treatment agent of the organic compound is previously formed on titanium oxide (more preferably, titanium oxide coated with another metal oxide). However, a method in which the surface treatment agent is separately added when the raw materials of the resin composition are melt-kneaded, and the surface treatment of titanium oxide is performed in the melt-kneading step may be employed.

The content of the white pigment for high light reflection is preferably from 0.1 to 10 parts by weight, and more preferably from 0.15 to 7.5 parts by weight, based on 100 parts by weight of the total of the component A and the component B. Parts by weight, more preferably 0.15 parts by weight to 5 parts by weight. When the content of the high-reflection white pigment is 0.1 part by weight or more, a sufficient white appearance or light-shielding property may be obtained. When the content is 10 parts by weight or less, molding of silver or the like is performed. This is preferable because defects and remarkable reduction in physical properties can be avoided. In addition, two or more kinds of white pigments for high light reflection can be used in combination.

(X) Other Resins and Elastomers In the resin composition of the present disclosure, a small proportion of other resins and graft polymers other than the D component may be used as long as the effects of the present disclosure are exhibited.

As such other resins, for example, styrene resins such as ABS, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenol resins, Examples of the resin include an epoxy resin.

エ ラ ス ト マ ー Also, examples of the elastomer include isobutylene / isoprene rubber, ethylene / propylene rubber, styrene-based elastomer, acrylic-based elastomer, polyester-based elastomer, and polyamide-based elastomer.

(Xi) Polycarbonate resin other than A component In the resin composition of the present disclosure, a small amount of a polycarbonate resin other than the A component may be used as long as the effects of the present disclosure are exhibited.

ポ リ カ ー ボ ネ ー ト A polycarbonate resin other than the polycarbonate-polydiorganosiloxane copolymer resin (component A) used in the present disclosure is generally obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly known as bisphenol A), 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) diphenol, 4,4'-(m-phenylenediiso (Ropylidene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes. Among them, bisphenol A is particularly preferred from the viewpoint of impact resistance, and is widely used.

In the present disclosure, besides bisphenol A-based polycarbonate which is a general-purpose polycarbonate, a special polycarbonate produced by using other dihydric phenols can be used as the component A.

For example, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter may be abbreviated as “BCF”) has a dimension due to water absorption. It is particularly suitable for applications where the requirements for change and morphological stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, a polycarbonate resin other than the component A constituting the resin composition is copolymerized with any of the following (1) to (3): Particularly preferred is polycarbonate:
(1) 20 mol% to 80 mol% (more preferably 40 mol% to 75 mol%, more preferably 45 mol% to 65 mol%) of BPM in 100 mol% of the dihydric phenol component constituting the polycarbonate. ), And having a BCF of 20 mol% to 80 mol% (more preferably 25 mol% to 60 mol%, and still more preferably 35 mol% to 55 mol%). BPA is 10 mol% to 95 mol% (more preferably 50 mol% to 90 mol%, more preferably 60 mol% to 85 mol%) in 100 mol% of the dihydric phenol component, and BCF Is from 5 mol% to 90 mol% (more preferably from 10 mol% to 50 mol%, and still more preferably from 15 mol% to 40 mol%). BPM is 20 mol% to 80 mol% (more preferably 40 mol% to 75 mol%, still more preferably 45 mol% to 65 mol%) in 100 mol% of the dihydric phenol component, and Bis- A copolymerized polycarbonate having a TMC of 20 mol% to 80 mol% (more preferably 25 mol% to 60 mol%, and still more preferably 35 mol% to 55 mol%).

These special polycarbonates may be used alone or as a mixture of two or more. These can also be used by mixing with a commonly used bisphenol A type polycarbonate.

The production methods and properties 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.

Among the above-mentioned various polycarbonates, those whose water absorption and Tg (glass transition temperature) are adjusted to the following ranges by adjusting the copolymer composition and the like have good hydrolysis resistance of the polymer itself, and Since it is extremely excellent in low warpage after molding, it is particularly suitable in the field where form stability is required.
(I) a polycarbonate having a water absorption of 0.05% to 0.15%, preferably 0.06% to 0.13% and a Tg of 120% to 180 ° C, or (ii) a Tg of 160 ° C To 250 ° C., preferably 170 ° C. to 230 ° C., and a water absorption of 0.10% to 0.30%, preferably 0.13% to 0.30%, more preferably 0.14% to 0.30%. Polycarbonate that is 27%.

Here, the water absorption of the polycarbonate is a value obtained by measuring a water content after immersing in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disk-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Further, Tg (glass transition temperature) is a value determined by a differential scanning calorimeter (DSC) measurement based on JIS K7121.

As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate or dihaloformate of dihydric phenol.

In producing the aromatic polycarbonate resin by the interfacial polymerization method of the dihydric phenol and the carbonate precursor, if necessary, a catalyst, a terminal stopper, an antioxidant to prevent oxidation of the dihydric phenol. May be used. Further, the aromatic polycarbonate resin of the present disclosure is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester obtained by copolymerizing an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. Includes carbonate resins, copolymerized polycarbonate resins copolymerized with a difunctional alcohol (including alicyclic), and polyester carbonate resins copolymerized with such a difunctional carboxylic acid and a difunctional alcohol. Further, a mixture of two or more of the obtained aromatic polycarbonate resins may be used.

A branched polycarbonate resin can impart drip prevention performance and the like to the resin composition of the present disclosure. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin include phloroglucin, phloroglucid, and 4,6-dimethyl-2,4,6-tris (4-hydrodiphenyl) heptene-2,2. , 4,6-Trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol Roxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Chloride and the like, among which 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane is particularly preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is preferably 100 mol% of the total of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound, and is preferably It is 0.01 mol% to 1 mol%, more preferably 0.05 mol% to 0.9 mol%, and still more preferably 0.05 mol% to 0.8 mol%.

In addition, particularly in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction, and the amount of the branched structural unit is preferably in a total of 100 mol% with the structural unit derived from dihydric phenol. It is preferably 0.001 mol% to 1 mol%, more preferably 0.005 mol% to 0.9 mol%, and still more preferably 0.01 mol% to 0.8 mol%. It should be noted that the ratio of such a branched structure can be calculated by ¹ H-NMR measurement.

Α The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decandioic acid), dodecandioic acid, tetradecandioic acid, icosandioic acid, and cyclohexanedicarboxylic acid. And alicyclic dicarboxylic acids. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

Reaction methods such as an interfacial polymerization method, a melt transesterification method, a carbonate prepolymer solid-phase transesterification method, and a ring-opening polymerization method of a cyclic carbonate compound, which are production methods of the polycarbonate resin of the present disclosure, are disclosed in various literatures and patent publications. This is a well-known method.

(Xi) Other additives In addition, the polycarbonate resin composition of the present disclosure may contain a small amount of additives known per se for imparting various functions to a molded article and improving properties. These additives are in a usual amount unless the purpose of the present disclosure is impaired.

Examples of such additives include a sliding agent (for example, PTFE particles), a coloring agent (for example, pigments and dyes such as carbon black), and a light diffusing agent (for example, acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, and calcium carbonate particles). , Fluorescent dyes, inorganic phosphors (for example, phosphors having an aluminate as a mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, and photocatalyst-based antifouling agents (for example, fine particle titanium oxide, fine particle oxidation) Zinc), a radical generator, an infrared absorber (heat ray absorber), and a photochromic agent.

(Production of polycarbonate resin composition)
An arbitrary method is employed for producing the polycarbonate resin composition of the present disclosure. For example, the components A to D or the components A to F excluding the component B and, optionally, other additives are sufficiently mixed by using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, and an extruder. After mixing, the premix is granulated by an extrusion granulator or briquetting machine as necessary, and then melt-kneaded by a melt kneader represented by a vented twin screw extruder, and then a pelletizer. To form pellets.

Alternatively, each component may be independently supplied to a melt kneader typified by a vented twin-screw extruder, or after a part of each component is premixed, supplied to the melt kneader independently of the remaining components. And the like. As a method of premixing a part of each component, for example, a method in which components other than the component A and the component B are preliminarily mixed and then mixed with the thermoplastic resin of the component A or directly supplied to an extruder can be mentioned.

As a method of pre-mixing, for example, in the case where a component having the form of powder as the A component is included, a master batch of an additive diluted with powder is produced by blending a part of the powder and an additive to be blended, and There is a method using a master batch. Furthermore, a method in which one component is independently supplied from the middle of the melt extruder may be used. When there is a liquid component to be compounded, a so-called liquid injection device or liquid addition device can be used for supply to the melt extruder.

As the extruder, a extruder having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump for efficiently discharging generated moisture and volatile gas from the vent to the outside of the extruder is preferably installed. It is also possible to install a screen for removing foreign matters and the like mixed in the extruded raw material in a zone in front of the die portion of the extruder to remove the foreign matters from the resin composition. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter) and the like.

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

樹脂 The resin extruded as described above is directly cut into pellets, or after the strands are formed, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust and the like during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, using various methods already proposed for polycarbonate resins for optical discs, narrowing of the shape distribution of pellets, reduction of miscuts, reduction of fine powder generated during transportation or transportation. In addition, air bubbles (vacuum air bubbles) generated inside the strands and pellets can be appropriately reduced. By these prescriptions, it is possible to increase the molding cycle and to reduce the occurrence rate of defects such as silver. The shape of the pellet may be a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder. The diameter of such a cylinder is preferably 1 mm to 5 mm, more preferably 1.5 mm to 4 mm, and still more preferably 2 mm to 3.3 mm. On the other hand, the length of the column is preferably 1 mm to 30 mm, more preferably 2 mm to 5 mm, and further preferably 2.5 mm to 3.5 mm.

(About a molded article comprising the resin composition of the present disclosure)
The resin composition of the present disclosure can be used to produce various products by injection molding the pellets obtained by the above-described method. In such injection molding, not only ordinary molding methods but also, as appropriate, injection compression molding, injection press molding, gas assist injection molding, foam molding (including injection by supercritical fluid), insert molding, A molded article can be obtained by using an injection molding method such as in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding. The advantages of these various molding methods are already widely known. For the molding, either a cold runner method or a hot runner method can be selected.

The resin composition of the present disclosure can also be used in the form of various shaped extruded products, sheets, films, etc. by extrusion. For forming a sheet or film, 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 performing a specific stretching operation. Further, the resin composition of the present disclosure can be formed into a molded product by rotational molding, blow molding, or the like.

Specific examples of molded articles in which the resin composition of the present disclosure is used include those suitable for application to living materials, housing equipment materials, building materials, interior goods, OA equipment and internal components of electric home appliances, housings, and the like. . These products include, for example, personal computers, notebook computers, CRT displays, printers, mobile terminals, mobile phones, copiers, faxes, recording media (CD, CD-ROM, DVD, PD, FDD, etc.) drives, parabolic antennas, Tools, VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, audio equipment such as audio, laser disks (registered trademark) and compact disks, lighting equipment, refrigerators, air conditioners, typewriters, word processors, suitcases And living equipment such as cleaning tools, bathrooms, toiletries, housing equipment such as vanities, and the like.Resin products formed from the polycarbonate resin composition of the present disclosure in various parts such as these housings. Can be used. Other resin products include vehicle parts such as deflector parts, car navigation parts, and car stereo parts.

形態 The mode for carrying out the invention according to the present disclosure is an aggregation of the preferred ranges of the above-described requirements. For example, representative examples are described in the following examples. Of course, the present disclosure is not limited to these modes.

発 明 The invention according to the present disclosure will be further described below with reference to examples. Unless otherwise specified, parts in Examples are parts by weight and% is% by weight. The evaluation was performed by the following method.

(Evaluation of polycarbonate resin composition)
(I) Charpy impact strength Notched Charpy impact strength was measured in accordance with ISO 179 using an ISO bending test piece obtained by the following method.
(Ii) Flame retardancy A V test was performed according to UL94 using the UL test piece obtained by the following method. The case where the judgment failed to satisfy any of the criteria of V-0, V-1, and V-2 was indicated as "notV".
(Iii) Chemical resistance After applying 1% strain by a three-point bending test method using an ISO tensile test piece obtained by the following method, magic phosphorus, bath magic phosphorus and toilet magic phosphorus (all, After a cloth impregnated with Kao Corporation) was impregnated and allowed to stand at 23 ° C. for 96 hours, the presence or absence of a change in appearance was confirmed. The evaluation was performed according to the following criteria.
：: No change in appearance is observed △: Fine cracks are observed X: Large cracks leading to breakage are observed (iv) Antifouling property (contact angle to water)
The contact angle of water on the surface of the sample plate (three-stage plate with holes) obtained by the following method was measured using a contact angle measuring machine GI-1000 (manufactured by Elma Corporation). The evaluation was performed as “対” when the contact angle with water was 100 ° or more, and “X” when the contact angle was less than 100 °.
(V) Thermal stability The amount of decrease in viscosity average molecular weight ΔMv between a test piece and a pellet obtained by molding after allowing to stay in a cylinder for 10 minutes under the same conditions as the following method is calculated based on the following equation. did.
Amount of decrease in viscosity average molecular weight ΔMv = (viscosity average molecular weight of pellet)-(viscosity average molecular weight of molded article after 10 minutes residence)
The evaluation was performed according to the following criteria.
：: ΔMv <3,000
Δ: 3,000 ≦ ΔMv <5,000
×: 5,000 ≦ ΔMv
(Vi) Appearance The appearance of a sample plate (three-step plate with holes) obtained by the following method was visually evaluated. The evaluation was performed according to the following criteria.
：: No noticeable appearance defect is observed near the gate. ×: Large flow mark or peeling occurs near the gate.

[Examples 1 to 33, Comparative Examples 1 to 11]
Mixtures having the compositions shown in Tables 1 to 3 and excluding the polyester resin as the B component were supplied from the first supply port of the extruder. The content of the D component in Examples 1 to 13, 15 to 29 and 31 to 33, and Comparative Examples 1 to 4, 6, 7, 10, and 11 was D-1 to D-3 shown in parentheses. (The numbers outside the parentheses indicate the amounts of master batches D-1 to D-3 having a concentration of 50%). Such a mixture was obtained by mixing with a V-type blender. The polyester resin of the component B was supplied from the second supply port using a side feeder. Extrusion was carried out using a vent-type twin screw extruder with a diameter of 30 mmφ (Nippon Steel Works TEX30α-38.5BW-3V) at a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a degree of vacuum of the vent of 3 kPa. A pellet was obtained. The extrusion temperature was 260 ° C. from the first supply port to the die. A part of the obtained pellets was dried at 80 ° C. for 6 hours by a hot air circulation type drier, and then, using an injection molding machine, a test piece for evaluation at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C. ( ISO tensile test piece (based on ISO527-1 and ISO527-2), ISO bending test piece (based on ISO178, ISO179, ISO75-1 and ISO75-2), UL test piece (width 13 mm x length 125 mm x thickness 1. 5 mm), and a sample plate (three-stage plate with holes)).

In addition, each component of the symbol notation in Tables 1-3 is as follows.

(A component)
A: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight: 25,000, PDMS amount: 8.4%, PDMS polymerization degree: 37, Panlite W-0111 manufactured by Teijin Limited)

(B component)
B-1: Polybutylene terephthalate resin (1100-211MD (product name) manufactured by Changchun Man-made Resin Co., Ltd., intrinsic viscosity: 0.965 dl / g)
B-2: Polybutylene terephthalate resin (1100-211XG (product name) manufactured by Changchun Manufactured Resins Co., Ltd., intrinsic viscosity: 1.26 dl / g)
B-3: Polyethylene terephthalate resin (TRN-8550FF (product name) manufactured by Teijin Limited, intrinsic viscosity: 0.77 dl / g)

(C component)
C-1: Silicone-based core-shell type graft polymer (graft copolymer having a core-shell structure in which a core is mainly composed of acryl-silicone composite rubber and a shell is mainly composed of methyl methacrylate, METABLEN S-2030 manufactured by Mitsubishi Rayon Co., Ltd. (product name))
C-2: Butadiene-based core-shell type graft polymer (graft copolymer having a core-shell structure in which a core is mainly composed of butadiene rubber and a shell is mainly composed of methyl methacrylate, Kaneace M-711 (product name) manufactured by Kaneka Corporation) )
C-3: Acrylic core-shell type graft polymer (graft copolymer having a core-shell structure having a core of butyl acrylate as a main component and a shell of methyl methacrylate as a main component, METABLEN W-600A manufactured by Mitsubishi Rayon Co., Ltd. (product name) ))

(D component)
D-1: Silicone gum PC master (ultra high molecular weight polydimethylsiloxane polycarbonate 50% masterbatch product, MB50-315 (product name) manufactured by Toray Dow Corning Co., Ltd.)
D-2: Silicone gum PEst master (Master batch product of 50% polyester elastomer of ultra-high molecular weight polydimethylsiloxane, BY27-009 (product name) manufactured by Toray Dow Corning Co., Ltd.)
D-3: Silicone gum PP master (50% polypropylene masterbatch of ultra-high molecular weight polydimethylsiloxane, BY27-001 (product name) manufactured by Toray Dow Corning Co., Ltd.)
D-4: Silicone-modified polypropylene (polymer obtained by graft-polymerizing polypropylene with polyorganosiloxane, BY27-201 (product name) manufactured by Toray Dow Corning Co., Ltd.)

(E component)
E: Brominated flame retardant (brominated carbonate oligomer having bisphenol A skeleton, FG-8500 (product name) manufactured by Teijin Limited)

(F component)
F-1: Phosphorus flame retardant (2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-dibenzyl-3,9-dioxide, FCX manufactured by Teijin Limited) -210 (product name))

(G component)
G-1: coated PTFE (polytetrafluoroethylene coated with a styrene-acrylonitrile copolymer (polytetrafluoroethylene content: 50% by weight), SN3307PF (trade name) manufactured by Shine Polymer)
G-2: coated PTFE (polytetrafluoroethylene coated with methyl methacrylate, butyl acrylate copolymer (polytetrafluoroethylene content: 50% by weight), METABLEN A3750 (trade name) manufactured by Mitsubishi Rayon Co., Ltd.)

(Other components)
PC: aromatic polycarbonate resin (polycarbonate resin powder having a viscosity-average molecular weight of 25,100, produced from bisphenol A and phosgene by a conventional method, Panlite L-1250WQ (product name) manufactured by Teijin Limited)
STB-1: Phenolic heat stabilizer (octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, molecular weight 531, Irganox 1330 (product name) manufactured by BASF Japan Ltd.)
STB-2: phosphorus-based heat stabilizer (tris (2,4-di-tert-butylphenyl) phosphite, Irgafos 168 (product name) manufactured by BASF Japan Ltd.)
STB-3: phosphorus-based heat stabilizer (trimethyl phosphate, TMP (product name) manufactured by Daihachi Chemical Industry Co., Ltd.)

Claims (9)

1. (A) Polycarbonate-polydiorganosiloxane copolymer resin (A component) and (B) 100% by weight of polyester resin (B component) in total
   (C) a composite rubber comprising a component containing a polyorganosiloxane rubber and an alkyl (meth) acrylate rubber, wherein at least one selected from the group consisting of an aromatic alkenyl compound monomer unit and an alkyl (meth) acrylate compound monomer unit; 3 to 15 parts by weight of a graft copolymer having a core-shell structure in which one type of unit is graft-polymerized (component C), and 0.5 to 6 parts by weight of (D) an antifouling agent (component D) A polycarbonate resin composition comprising:
2. (E) 5 to 35 parts by weight of a halogen-based flame retardant (component E), and (F) 0.5 to 5 parts by weight of a phosphorus-based flame retardant (component F) having a structure represented by the following formula (1). The polycarbonate resin composition according to claim 1, further comprising parts by weight.
   

   

   (In the formula, X ₁ and X ₂ are the same or different and are an aromatic substituted alkyl group represented by the following general formula (I).)
   

   

   (Wherein, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, Ar is a phenyl group, a naphthyl group or an anthryl group, n represents an integer of 1 to 3, Ar can be attached to any carbon atom of AL.)
3. 3. The polycarbonate resin composition according to claim 1, wherein the content of the component B is 20 to 70 parts by weight based on 100 parts by weight of the total of the component A and the component B.
4. 4. The polycarbonate resin composition according to claim 1, wherein the component B contains at least one of a polyethylene terephthalate resin and a polybutylene terephthalate resin.
5. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the component (D) is a silicone gum having a molecular weight of 100,000 or more.
6. The polycarbonate resin composition according to any one of claims 1 to 5, wherein the component (D) is a polyorganosiloxane-grafted polyolefin resin.
7. The polycarbonate resin composition according to any one of claims 1 to 6, wherein the proportion of the polyorganosiloxane rubber component in the composite rubber of the C component is 15% or more.
8. The method according to any one of claims 1 to 7, wherein (G) an anti-drip agent (G component) is contained in an amount of 0.05 to 2 parts by weight based on 100 parts by weight in total of the component A and the component B. The polycarbonate resin composition according to the above.
9. The polycarbonate resin composition according to claim 8, wherein the G component is a fluoropolymer having fibril-forming ability.