JP2017125140A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in impact resistance, chemical resistance, and flame retardancy.SOLUTION: The polycarbonate resin composition contains, based on (A) 100 pts.wt. of a polycarbonate resin (component A) comprising 0-100 pts.wt. of an aromatic polycarbonate resin (component A1) and 0-100 pts.wt. of a polycarbonate-polydiorganosiloxane copolymer resin (component A2), (B) 10-80 pts.wt. of a polyarylene sulfide resin (component B) having at its terminal a functional group reactive with at least one group selected from the group consisting of a glycidyl group and an epoxy group, (C) 1-15 pts.wt. of an impact modifier (component C) having at least one group selected from the group consisting of a glycidyl group and an epoxy group, and (D) 0.005-1 pt.wt. of a metal salt-based compound (component D).SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition excellent in impact resistance, chemical resistance and flame retardancy. More specifically, the present invention relates to a polycarbonate resin composition containing polycarbonate and polyarylene sulfide as main components, containing an impact modifier and a metal salt compound, and excellent in impact resistance, chemical resistance and flame retardancy.

  Since polycarbonate resin has excellent impact resistance, it is widely used as an engineering plastic in various fields such as OA equipment field and automobile field. However, since the polycarbonate resin is an amorphous resin, it has a difficulty in chemical resistance. On the other hand, polyarylene sulfide resins have excellent properties such as chemical resistance and flame retardancy, and are widely used in various fields such as electronic parts and automobiles. However, the polyarylene sulfide resin is brittle and has a difficulty in impact resistance.

  In order to improve the chemical resistance of the polycarbonate resin and the impact resistance of the polyarylene sulfide resin, a resin composition obtained by melt blending a polycarbonate resin and a polyarylene sulfide resin has been proposed (see Patent Document 1). However, simply blending the polycarbonate resin and the polyarylene sulfide resin results in poor compatibility with each other, and particularly, the impact resistance is greatly reduced, and the practical application is poor. Therefore, in order to enhance the compatibility between the polycarbonate resin and the polyarylene sulfide resin, a method using a terminal carboxylated polyarylene sulfide resin (see Patent Document 2), or a thermoplastic resin containing an epoxy group or a glycidyl group as a compatibilizing agent. A method of adding an elastomer (see Patent Documents 3 to 5) has been proposed. However, in any resin composition, the compatibility between the polycarbonate resin and the polyarylene sulfide resin is still insufficient, so that the impact resistance is lowered, and the polyarylene sulfide is characterized by adding a large amount of a compatibilizing agent. However, the present situation is that a polycarbonate resin composition satisfying a high level of impact resistance, chemical resistance and flame retardancy has not been obtained so far.

JP-A 51-59952 Japanese Patent No. 2707714 JP 59-155461 A JP-A-4-18447 JP 7-316313 A

  An object of the present invention is to provide a polycarbonate resin composition excellent in impact resistance, chemical resistance and flame retardancy, and a resin molded product obtained therefrom.

  As a result of intensive studies, the inventor added a metal salt compound to a resin composition comprising a polycarbonate resin, a polyarylene sulfide resin containing a reactive functional group, and an impact modifier containing a reactive functional group. As a result, it was found that a polycarbonate resin composition satisfying impact resistance, chemical resistance and flame retardancy at a high level can be obtained, and the present invention has been achieved.

Specifically, the above-mentioned problems are solved by (1) a polycarbonate resin comprising (A) an aromatic polycarbonate resin (A1 component) 0 to 100 parts by weight and a polycarbonate-polydiorganosiloxane copolymer resin (A2 component) 0 to 100 parts by weight. (A component) Polyarylene sulfide resin (B component) 10-80 which has a terminal functional group that reacts with at least one group selected from the group consisting of (B) glycidyl group and epoxy group with respect to 100 parts by weight Parts by weight, (C) 1-15 parts by weight of impact modifier (C component) containing at least one group selected from the group consisting of glycidyl group and epoxy group, and (D) metal salt compound (D component) It is achieved by a polycarbonate resin composition characterized by containing 0.005 to 1 part by weight.
One preferred embodiment of the present invention, (2) B component, polyarylene having an absorption peak derived from carboxyl groups between ^{1600cm -1 ~1800cm} -1 at FT-IR spectrum of FT-IR spectroscopy 2. The polycarbonate resin composition according to Configuration 1, wherein the polycarbonate resin composition is a sulfide resin.
One preferred embodiment of the present invention is as follows. (3) The polycarbonate resin composition according to the above constitution 1 or 2, wherein the component A comprises 0 to 90 parts by weight of the component A1 and 10 to 100 parts by weight of the component A2. It is a thing.

Details of the present invention will be described below.
(A component: polycarbonate resin)
The polycarbonate resin used as the component A of the present invention is a polycarbonate resin comprising 0 to 100 parts by weight of an aromatic polycarbonate resin (component A1) and 0 to 100 parts by weight of a polycarbonate-polydiorganosiloxane copolymer resin (component A2). The A1 component is preferably 0 to 90 parts by weight and the A2 component is preferably 10 to 100 parts by weight.

(A1 component: aromatic polycarbonate resin)
The aromatic polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol and 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 called 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-phenylenediisopropyl Pyridene) 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) Examples include fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance, and is widely used.

In the present invention, in addition to bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, it is possible to use a special polycarbonate produced using other dihydric phenols as the A component.
For example, as part or all of the dihydric phenol component, 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 sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape 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, it is particularly preferable that the A1 component constituting the resin composition is the following (1) to (3) copolymer polycarbonate. is there.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Is 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis -Copolymer polycarbonate in which TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).

These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.
The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition, etc. have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(I) polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C, or (ii) Tg of 160 to 250 ° C, Polycarbonate which is preferably 170 to 230 ° C. and has a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.
As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing the aromatic polycarbonate resin by the interfacial polymerization method using the dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The aromatic polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, a polyester copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. Carbonate resin, copolymer polycarbonate resin copolymerized with bifunctional alcohol (including alicyclic), and polyester carbonate resin copolymerized with such bifunctional carboxylic acid and bifunctional alcohol are included. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.

  The branched polycarbonate resin can impart anti-drip performance and the like to the resin composition of the present invention. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) 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- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

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

In particular, 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 100% by mole in total with the structural unit derived from dihydric phenol. The content is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and still more preferably 0.01 to 0.8 mol%. The ratio of the branched structure can be calculated by ¹ H-NMR measurement.

  The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other straight-chain saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

  Reaction formats such as interfacial polymerization, melt transesterification, carbonate prepolymer solid phase transesterification, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate-based resin of the present invention, are various documents and patent publications. This is a well-known method.

In producing the resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate-based resin is not particularly limited, but is preferably 1 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1.4 × 10. ^{4 to} 3 × 10 ⁴ , more preferably 1.4 × 10 ^{4 to} 2.4 × 10 ⁴ .
With a polycarbonate resin having a viscosity average molecular weight of less than 1 × 10 ⁴ , good mechanical properties cannot be obtained. On the other hand, a resin composition obtained from an aromatic polycarbonate resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ is inferior in versatility in that it is inferior in fluidity during injection molding.

In addition, the said polycarbonate-type resin may be obtained by mixing that whose viscosity average molecular weight is outside the said range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above range (5 × 10 ⁴ ) improves the entropy elasticity of the resin. As a result, good moldability is exhibited in gas assist molding and foam molding which may be used when molding a resin material into a structural member. Such improvement in moldability is even better than that of the branched polycarbonate. As a more preferred embodiment, the A1 component has a viscosity average molecular weight of 7 × 10 ^{4 to} 3 × 10 ⁵ polycarbonate resin A1-1-1-1 component), and the viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ Polycarbonate resin (A1-1-1 component) consisting of an aromatic polycarbonate resin (A1-1-1-2 component) and having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3.5 × 10 ⁴ (below) , Sometimes referred to as “high molecular weight component-containing polycarbonate resin”).

In such a high molecular weight component-containing polycarbonate resin (A1-1-1 component), the molecular weight of the A1-1-1-1 component is preferably 7 × 10 ⁴ to 2 × 10 ⁵ , more preferably 8 × 10 ⁴ to 2. × 10 ⁵ , more preferably 1 × 10 ⁵ to 2 × 10 ⁵ , and particularly preferably 1 × 10 ^{5 to} 1.6 × 10 ⁵ . The molecular weight of the A-1-1-2 component is preferably 1 × 10 ^{4 to} 2.5 × 10 ⁴ , more preferably 1.1 × 10 ^{4 to} 2.4 × 10 ⁴ , and still more preferably 1.2 ×. 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 resin (A1-1-1 component) is a mixture of the A1-1-1-1 component and the A1-1-1-2 component at various ratios so as to satisfy a predetermined molecular weight range. It can be obtained by adjusting. Preferably, the amount of A1-1-1-1 component is 2 to 40% by weight in 100% by weight of A1-1-1 component, and more preferably 3 to 30% by weight of A1-1-1-1 component. More preferably, the A1-1-1-1 component is 4 to 20% by weight, and particularly preferably the A1-1-1-1 component is 5 to 20% by weight.

  Moreover, as a preparation method of A1-1-1 component, (1) The method of polymerizing A1-1-1-1 component and A1-1-1-2 component each independently, and mixing these, (2 ) A method for producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method represented by the method disclosed in Japanese Patent Application Laid-Open No. 5-306336 in the same system. And (3) an aromatic polycarbonate resin obtained by the production method (production method (2)), and separately produced A1. Examples thereof include a method of mixing the 1-1-1 component and / or the A1-1-1-2 component.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C. with a specific viscosity (η _SP ) calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  In addition, calculation of the viscosity average molecular weight of polycarbonate-type resin in the transparent flame-retardant resin composition of this invention is performed in the following way. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

(A2 component: polycarbonate-polydiorganosiloxane copolymer resin)
The polycarbonate-polydiorganosiloxane copolymer resin used as the A2 component of the present invention comprises a dihydric phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3). A copolymer resin prepared by copolymerization is preferred.

[In General Formula (1), R ¹ and R ² are each independently a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a cyclohexane having 6 to 20 carbon atoms. Alkyl group, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl group having 3 to 14 carbon atoms, aryloxy group having 3 to 14 carbon atoms, 7 to 7 carbon atoms Represents a group selected from the group consisting of 20 aralkyl groups, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and when there are plural groups, they may be the same or different. Well, e and f are each 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 following general formula (2). ]

[In the general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. Alkyl groups, alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 carbon atoms. -14 aryl group, aryloxy 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 It represents a group selected from the group consisting of carboxyl groups, and when there are a plurality thereof, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7. ]

[In General Formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution 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 Q is 0 or a natural number, and p + q is a natural number of 10-60. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

  Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1 -Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropyl) Phenyl) propane, 2,2-bis (3-tert-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'-dimethyldi Enyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4 '-Dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'- Dihydroxy-3,3′-diphenyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydro Xylphenyl) 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, and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-biphenyl. (4-hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

  As the hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (3), 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, 2-methoxy-4-allylphenol. It is easily produced by hydrosilylation reaction at the end of a polysiloxane chain having a degree of polymerization of. Of these, (2-allylphenol) -terminated polydiorganosiloxane, (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferred, and (2-allylphenol) -terminated polydimethylsiloxane and (2-methoxy-) are particularly preferred. 4-Allylphenol) -terminated polydimethylsiloxane is preferred.

  The diorganosiloxane polymerization degree (p + q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is a natural number of 10-60. If it exceeds 60, the incorporation of polydiorganosiloxane units in the polycarbonate becomes uneven and the proportion of polydiorganosiloxane units in the polymer molecule increases, resulting in a polycarbonate containing the unit and a polycarbonate not containing it. It becomes easy and mutual compatibility falls easily. As a result, the dispersion of the polydiorganosiloxane domain becomes non-uniform, the transparency is lost, the appearance defect is liable to occur, and sufficient flame retardancy cannot be obtained. The degree of diorganosiloxane polymerization (p + q) is preferably 12 to 58, more preferably 15 to 55, and still more preferably 20 to 50. Below the lower limit of this range, sufficient flame retardancy cannot be obtained, the polydiorganosiloxane domain diameter is small, and sufficient impact resistance is not exhibited. In the present invention, the polydiorganosiloxane domain means a domain mainly composed of polydiorganosiloxane dispersed in a polycarbonate matrix and may contain other components. As described above, the polydiorganosiloxane domain is not necessarily composed of a single component because the structure is formed by phase separation from the polycarbonate polycarbonate.

The polydiorganosiloxane content in the total weight of the copolymer resin is preferably 0.5 to 30% by weight. The polydiorganosiloxane component content is more preferably 0.7 to 20% by weight, still more preferably 1 to 10% by weight. Above the lower limit of the preferred range, the impact resistance and flame retardancy are excellent, and below the upper limit of the preferred range, a stable appearance that is hardly affected by the molding conditions is easily obtained. Such polydiorganosiloxane polymerization degree and polydiorganosiloxane content can be calculated by ¹ H-NMR measurement.

  In this invention, hydroxyaryl terminal polydiorganosiloxane (II) may use only 1 type, and may use 2 or more types. Further, within the range not hindering the production method of the present invention, other comonomer other than the dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) is 10% by weight or less based on the total weight of the copolymer. It can also be used in combination in the range.

  In the present invention, a chloroformate-forming compound such as divalent phenol (I) and phosgene or chloroformate of divalent phenol (I) in a mixed solution of an organic solvent insoluble in water and an aqueous alkaline solution in advance. To prepare a mixed solution of a chloroformate compound containing a chloroformate of dihydric phenol (I) and / or a carbonate oligomer of dihydric phenol (I) having a terminal chloroformate group. As the chloroformate-forming compound, phosgene is preferred.

In producing the chloroformate compound from the dihydric phenol (I), the whole amount of the dihydric phenol (I) used in the production method of the present invention may be converted to the chloroformate compound at one time, or a part thereof may be used. A post-added monomer may be added as a reaction raw material to a subsequent interfacial polycondensation reaction. The post-added monomer is added to allow the subsequent polycondensation reaction to proceed rapidly, and it is not necessary to add it when it is not necessary.
The method for this chloroformate compound formation reaction is not particularly limited, but usually a method of carrying out in a solvent in the presence of an acid binder is preferred. Furthermore, if desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added, and it is preferable to add them.

The use ratio of the chloroformate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using the phosgene which is a suitable chloroformate formation compound, the method of blowing gasified phosgene into a reaction system can be employ | adopted suitably.
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. Is used.
The use ratio of the acid binder may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction as described above. Specifically, 2 equivalents or slightly more than 2 equivalents per mole of dihydric phenol (I) used for forming the chloroformate compound of dihydric phenol (I) (usually 1 mole corresponds to 2 equivalents). It is preferable to use an acid binder.

  As said solvent, what is necessary is just to use a solvent inert to various reaction, such as what is used for manufacture of a well-known polycarbonate, individually or as a mixed solvent. Representative examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

  The molar ratio of the organic solvent insoluble in water is preferably 8 moles or more, more preferably 10 moles or more, still more preferably 12 moles or more, particularly preferably 14 moles or more, per mole of dihydric phenol (I). The upper limit is not particularly limited, but 50 mol or less is sufficient from the viewpoint of the size and cost of the apparatus. By setting the molar ratio of the organic solvent to the dihydric phenol (I) within such a range, it becomes easier to control the average size and normalized dispersion of the polydiorganosiloxane domain to appropriate values.

The pressure in the formation reaction of the chloroformate compound is not particularly limited and may be any of normal pressure, pressurization, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50 ° C, and in many cases, heat is generated with the reaction, so it is desirable to cool with water or ice. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours.
As the pH range in the formation reaction of the chloroformate compound, known interfacial reaction conditions can be used, and the pH is usually adjusted to 10 or more.

  In the present invention, after preparing a mixed solution of the chloroformate of the dihydric phenol (I) and the chloroformate compound containing the carbonate oligomer of the dihydric phenol (I) having a terminal chloroformate group in this way, While stirring the mixed solution, the hydroxyaryl-terminated polydiorganosiloxane (II) represented by the formula (4) is added in an amount of 0.01 mol per 1 mol of the dihydric phenol (I) charged in preparing the mixed solution. The polycarbonate-polydiorganosiloxane copolymer resin is obtained by adding the hydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound by interfacial polycondensation.

[In General Formula (4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution 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 Q is 0 or a natural number, and p + q is a natural number of 10-60. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

  The polycarbonate-polydiorganosiloxane copolymer resin of the present invention can be made into a branched polycarbonate copolymer by using a branching agent in combination with the above dihydric phenol compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) 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- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

The branched polycarbonate copolymer is produced by a branching agent used in the interfacial polycondensation reaction after completion of the production reaction, even if the branched solution is contained in the mixed solution during the production reaction of the chloroformate compound. May be added. The proportion of the carbonate constituent unit derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol% in the total amount of carbonate constituent units constituting the copolymer. Especially preferably, it is 0.05-1.0 mol%. Such a branched structure amount can be calculated by ¹ H-NMR measurement.

  The pressure in the system in the polycondensation reaction can be any of reduced pressure, normal pressure, or increased pressure, but can usually be suitably performed at normal pressure or about the pressure of the reaction system. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be generally specified, but it is usually performed in 0.5 to 10 hours.

In some cases, the obtained polycarbonate copolymer is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [η _SP / C] can also be obtained as a polycarbonate copolymer.
The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purity) after various post-treatments such as a known separation and purification method.

The viscosity-average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin is preferably in the range of 5.0 × 10 ^{3 to} 5.0 × 10 ⁴ . The viscosity average molecular weight is more preferably 1.0 × 10 ^{4 to} 4.0 × 10 ⁴ , further preferably 1.5 × 10 ^{4 to} 3.5 × 10 ⁴ , and particularly preferably 1.7 × 10 ⁴ to 2. .5 × 10 ⁴ . When the viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin is less than 5.0 × 10 ³ , practical mechanical strength is difficult to obtain in many fields, and when it exceeds 5.0 × 10 ⁴ , the melt viscosity is It is high and generally requires a high molding temperature, so it tends to cause problems such as thermal degradation of the resin.

  The average size of the polydiorganosiloxane domain in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 40 nm. The average size is more preferably 2 to 30 nm, still more preferably 5 to 25 nm. If it is less than the lower limit of such a suitable range, the impact resistance and flame retardancy are not sufficiently exhibited, and if it exceeds the upper limit of such a suitable range, the impact resistance may not be stably exhibited. As a result, a polycarbonate resin composition excellent in both impact resistance and flame retardancy is provided.

  Furthermore, even if the average size of the polydiorganosiloxane domain is in a suitable range, if its normalized dispersion exceeds 40%, good and stable transparency may not be exhibited. The normalized dispersion of the polydiorganosiloxane domain size is preferably 40% or less, more preferably 30% or less, still more preferably 25% or less, and most preferably 20% or less. The lower limit of such normalized dispersion is practically preferably 7% or more, more preferably 10% or more. Providing a polycarbonate-polydiorganosiloxane copolymer-containing resin excellent in both transparency, impact resistance, and flame retardancy, and its molded article, by having such an appropriate average domain size and its normalized dispersion Is done.

  The average domain size and normalized dispersion of the polydiorganosiloxane domain of the polycarbonate-polydiorganosiloxane copolymer resin molded article in the present invention were evaluated by the Small Angle X-ray Scattering (SAXS) method. The small-angle X-ray scattering method is a method for measuring diffuse scattering / diffraction generated in a small-angle region within a scattering angle (2θ) <10 °. In this small-angle X-ray scattering method, if there are regions with different electron densities of about 1 to 100 nm in the substance, the X-ray diffuse scattering is measured by the difference in electron density. The particle diameter of the measurement object is obtained based on the scattering angle and the scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregate structure in which a polydiorganosiloxane domain is dispersed in a polycarbonate polymer matrix, X-ray diffuse scattering occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domain. 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, the polydiorganosiloxane domain is a spherical domain, and the particle size distribution varies. Assuming that there is a particle size, a simulation is performed using a commercially available analysis software from the temporary particle size and the temporary particle size distribution model to obtain the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domain. According to the small-angle X-ray scattering method, the average size and particle size distribution of the polydiorganosiloxane domain dispersed in the polycarbonate polymer matrix, which cannot be accurately measured by observation with a transmission electron microscope, can be accurately, simply, and reproducibly reproduced. Can be measured. The average domain size means the number average of individual domain sizes. Normalized dispersion means a parameter in which the spread of the particle size distribution is normalized by the average size. Specifically, it is a value obtained by normalizing the dispersion of the polydiorganosiloxane domain size with the average domain size, and is represented by the following formula (1).

  In the above formula (1), δ is the standard deviation of the polydiorganosiloxane domain size, and Dav is the average domain size.

  The terms “average domain size” and “normalized dispersion” used in connection with the present invention are the measurement of the 1.0 mm thickness of the three-stage plate produced by the method described in the Examples by the small angle X-ray scattering method. The measured values obtained by In addition, the analysis was performed using an isolated particle model that does not take into account the interparticle interaction (interparticle interference).

The content of the polydiorganosiloxane derived from the polycarbonate-polydiorganosiloxane copolymer resin in the resin composition of the present invention is preferably 0.5 to 8.4% by weight. More preferably, it is 0.8-7.0 weight%, More preferably, it is 1.0-6.0 weight%, Most preferably, it is 1.2-5.5 weight%. When the amount is less than 0.5% by weight, sufficient impact resistance and flame retardancy are not exhibited. When the amount exceeds 8.4% by weight, flame retardancy may not be exhibited. The polydiorganosiloxane content in the composition was calculated from the PDMS amount contained in the polycarbonate-polydiorganosiloxane copolymer resin (PC-PDMS copolymer resin) by the following formula.
PDMS amount in composition (% by weight) = {(PDMS amount in PC-PDMS copolymer resin) / (weight of entire composition)} × 100

(B component: polyarylene sulfide resin)
The polyarylene sulfide resin used as the component B of the present invention is a polyarylene sulfide resin having a functional group at the terminal that reacts with at least one group selected from the group consisting of a glycidyl group and an epoxy group, particularly a carboxyl group. Polyarylene sulfide resins having the following are preferred. The polyarylene sulfide resin exhibits excellent compatibility with other polymer materials (especially olefin copolymers having reactive functional groups) and fillers, and therefore has excellent impact resistance when used. A composition can be obtained. Incidentally, presence and concentration of the carboxyl group can be confirmed by an absorption peak derived from carboxyl groups between ^{1600cm -1 ~1800cm} -1 Nite FT-IR spectrum of FT-IR spectroscopy.

  The polyarylene sulfide resin has, for example, p-phenylene sulfide unit, m-phenylene sulfide unit, o-phenylene sulfide unit, phenylene sulfide sulfone unit, phenylene sulfide ketone unit, phenylene sulfide ether unit, diphenylene sulfide unit as structural units. , A substituent-containing phenylene sulfide unit, a branched structure-containing phenylene sulfide unit, and the like. Among them, those containing a p-phenylene sulfide unit of 70 mol% or more, particularly 90 mol% or more. Furthermore, poly (p-phenylene sulfide) is more preferable.

  The method for introducing the reactive functional group into the polyarylene sulfide resin is not particularly limited, and polymerization is performed by a known method, but a polymerization terminator having one or more groups on the conjugated aromatic ring skeleton. The method of using is mentioned. Examples of the conjugated aromatic ring skeleton used in the polymerization terminator include diphenyl disulfide, monoiodobenzene, thiophenol, 2,2′-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, and N-cyclohexyl-2-benzo. Examples include thiazolylsulfenamide, 2- (morpholinothio) benzothiazole, N, N′-dicyclohexyl-1,3-benzothiazole-2-sulfenamide.

As a suitable polymerization method of the method for producing a polyarylene sulfide resin having a carboxyl group terminal group structure, a step of polymerizing a reactant containing a diiodo aromatic compound and a sulfur element, while proceeding through the polymerization reaction step, And a production method in which a compound having a group is added and the terminal group of the polyarylene sulfide main chain is substituted with a carboxyl group. A typical example used in the compound having a carboxyl group is at least one selected from the group consisting of 2-iodobenzoic acid, 3-iodobenzoic acid, 4-iodobenzoic acid, and 2,2′-dithiobenzoic acid. Species are mentioned. The compound having a carboxyl group may be added in an amount of about 0.0001 to 5 parts by weight based on 100 parts by weight of the diiodo aromatic compound.
Content of B component is 10-80 weight part with respect to 100 weight part of A component, Preferably it is 10-70 weight part, More preferably, it is 20-60 weight part. If the B component is less than 10 parts by weight, the flame retardancy and chemical resistance are lowered, and if it exceeds 80 parts by weight, the impact resistance is lowered.

(C component: impact modifier)
The impact modifier used as component C in the present invention is an impact modifier containing at least one group selected from the group consisting of glycidyl groups and epoxy groups. When the impact modifier contains the above group, the impact resistance is further improved. As the impact modifier, an olefin copolymer is preferably used. Specifically, an olefin copolymer mainly composed of an α-olefin and an alkyl ester of an α, β-unsaturated carboxylic acid is preferably used. Among them, a copolymer of an α-olefin and an α, β-unsaturated carboxylic acid glycidyl ester is preferable. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and the like. Among these, ethylene is preferably used. Two or more kinds of these α-olefins can be used. Next, examples of the glycidyl ester of α, β-unsaturated carboxylic acid include acrylic acid glycidyl ester, methacrylic acid glycidyl ester, ethacrylic acid glycidyl ester, and the like. These copolymers further include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, and alkyl esters thereof, acrylonitrile, styrene. Etc. may be copolymerized. Examples of commercially available products of such olefin copolymers include Bond First E and Bond First 7M manufactured by Sumitomo Chemical Co., Ltd.
Content of C component is 1-15 weight part with respect to 100 weight part of A component, Preferably it is 1-10 weight part, More preferably, it is 1-5 weight part. When the content of component C is less than 1 part by weight, impact resistance and chemical resistance are lowered, and when it exceeds 15 parts by weight, flame retardancy is lowered.

(D component: metal salt compound)
As the organic metal salt-based flame retardant used as the D component of the present invention, various organic metal salts conventionally used for flame-retarding polycarbonate resins can be used. (Earth) metal salt, alkali (earth) metal salt of aromatic imide, alkali (earth) metal salt of sulfate ester, and alkali (earth) metal salt of phosphoric acid partial ester. (Here, the notation of alkali (earth) metal salt is used to include both alkali metal salts and alkaline earth metal salts). These are not only used alone but also used in combination of two or more. It is also possible to do. The metal constituting the organic alkali (earth) metal salt is an alkali metal or an alkaline earth metal, and more preferably an alkali metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, and barium, and lithium, sodium, and potassium are particularly preferable.

Examples of the alkali (earth) metal salt of the organic sulfonic acid include an alkali (earth) metal salt of an aliphatic sulfonic acid and an alkali (earth) metal salt of an aromatic sulfonic acid.
Preferred examples of the alkali (earth) metal salt of the aliphatic sulfonic acid include an alkali (earth) metal salt of an alkyl sulfonate, and a part of the alkyl group of the alkali (earth) metal salt of the alkyl sulfonate is a fluorine atom. And alkali (earth) metal salts of sulfonates substituted with, and alkali (earth) metal salts of perfluoroalkyl sulfonates, and these can be used alone or in combination of two or more.

  Preferred examples of the alkali (earth) metal salt of alkyl sulfonate include methane sulfonate, ethane sulfonate, propane sulfonate, butane sulfonate, methyl butane sulfonate, hexane sulfonate, heptane sulfone. Examples thereof include acid salts and octane sulfonates, and these can be used alone or in combination of two or more. In addition, a metal salt in which a part of the alkyl group is substituted with a fluorine atom can also be mentioned.

  On the other hand, preferred examples of alkali (earth) metal salts of perfluoroalkyl sulfonate include perfluoromethane sulfonate, perfluoroethane sulfonate, perfluoropropane sulfonate, perfluorobutane sulfonate, perfluoro Examples include methylbutane sulfonate, perfluorohexane sulfonate, perfluoroheptane sulfonate, and perfluorooctane sulfonate, and those having 1 to 8 carbon atoms are particularly preferable. These can be used alone or in combination of two or more.

  Of these, the alkali metal salt of perfluoroalkylsulfonic acid is most preferable. Among these alkali metals, rubidium and cesium are suitable when the demand for flame retardancy is higher, but these are not versatile and difficult to purify, resulting in disadvantages in terms of cost. There is. On the other hand, although it is advantageous in terms of cost, lithium and sodium may be disadvantageous in terms of flame retardancy. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

  Specific examples of alkali metal perfluoroalkyl sulfonates include potassium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethane sulfonate, perfluoro Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonate Cesium, cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perf Oro hexane sulfonate rubidium, and these may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  The aromatic sulfonic acid used in the aromatic (earth) metal salt of aromatic sulfonate includes monomeric or polymeric aromatic sulfide sulfonic acid, aromatic carboxylic acid and ester sulfonic acid, monomeric or polymeric sulfonic acid. Aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid, Examples include at least one acid selected from the group consisting of sulfonic acids of aromatic sulfoxides and condensates of methylene type bonds of aromatic sulfonic acids, and these are used alone or in combination of two or more. be able to.

Monomer or polymer aromatic sulfite alkali (earth) metal salts of aromatic sulfides are described in JP-A-50-98539, for example, disodium diphenyl sulfide-4,4′-disulfonate. And dipotassium diphenyl sulfide-4,4′-disulfonate.
Examples of sulfonic acid alkali (earth) metal salts of aromatic carboxylic acids and esters are described in JP-A No. 50-98540, for example, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, polyethylene terephthalate. And polysodium acid polysulfonate.

  Monomeric or polymeric aromatic ether sulfonate alkali (earth) metal salts are described in JP-A-50-98542, for example, 1-methoxynaphthalene-4-sulfonate calcium, 4- Disodium dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate, polysodium poly (1,3-phenylene oxide) polysulfonate, polysodium poly (1,4-phenylene oxide) polysulfonate And poly (2,6-diphenylphenylene oxide) polypotassium polysulfonate, poly (2-fluoro-6-butylphenylene oxide) lithium polysulfonate, and the like.

Examples of alkali (earth) metal sulfonates of aromatic sulfonates are described in JP-A No. 50-98544, and examples thereof include potassium sulfonate of benzene sulfonate.
Monomeric or polymeric aromatic (earth) metal sulfonates are described in JP-A No. 50-98546, for example, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, Examples include dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, and calcium biphenyl-3,3′-disulfonate.

Monomeric or polymeric aromatic sulfonesulfonic acid alkali (earth) metal salts are described in JP-A-52-54746, for example, sodium diphenylsulfone-3-sulfonate, diphenylsulfone-3- Examples include potassium sulfonate, dipotassium diphenyl-3,3′-disulfonate, dipotassium diphenylsulfone-3,4′-disulfonate, and the like.
Examples of alkali sulfonate alkali (earth) metal salts of aromatic ketones are described in JP-A No. 50-98547, for example, α, α, α-trifluoroacetophenone-4-sulfonic acid sodium salt, benzophenone-3 , 3'-disulfonic acid dipotassium.

Heterocyclic sulfonic acid alkali (earth) metal salts are described in JP-A-50-116542, for example, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate. Thiophene-2,5-disulfonate calcium, sodium benzothiophenesulfonate, and the like.
Examples of the alkali (earth) metal sulfonate of aromatic sulfoxide are described in JP-A-52-54745, and examples thereof include potassium diphenyl sulfoxide-4-sulfonate.
Examples of the condensate obtained by methylene bond of alkali (earth) metal salt of aromatic sulfonate include formalin condensate of sodium naphthalene sulfonate and formalin condensate of sodium anthracene sulfonate.

  Examples of the alkali (earth) metal salt of the sulfate ester include, in particular, alkali (earth) metal salts of sulfate esters of monovalent and / or polyhydric alcohols. Alcohol sulfates include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate, and lauric acid monoglyceride. And sulfuric acid ester of palmitic acid monoglyceride, stearic acid monoglyceride sulfate and the like. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

  Specific examples of the alkali (earth) metal salt of the phosphoric acid partial ester include bis (2,6-dibromo-4-cumylphenyl) phosphoric acid, bis (4-cumylphenyl) phosphoric acid, and bis (2,4,6). Alkali (earth) such as bis (2,4-dibromophenyl) phosphoric acid, bis (4-bromophenyl) phosphoric acid, diphenylphosphoric acid, bis (4-tert-butylphenyl) phosphoric acid ) Metal salts can be mentioned.

  Examples of the alkali (earth) metal salt of the aromatic imide include saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonamide (in other words, di (p-toluenesulfone) imide), N- (N Examples include '-benzylaminocarbonyl) sulfanilimide, and alkali (earth) metal salts such as N- (phenylcarboxyl) sulfanilimide and bis (diphenylphosphoric acid) imide.

  Among these, preferable components are selected from the group consisting of alkali (earth) metal salts of perfluoroalkyl sulfonates, alkali (earth) metal aromatic sulfonates, and alkali (earth) metal salts of aromatic imides. One or more of the following compounds, among which potassium perfluorobutane sulfonate, sodium perfluorobutane sulfonate, diphenyl sulfone sulfonate, di (p-toluene sulfone) imide potassium salt, and di ( One or more compounds selected from the group consisting of sodium salts of p-toluenesulfone) imide are more preferred. Most preferred is potassium perfluorobutane sulfonate.

  Content of D component is 0.005-1 weight part with respect to 100 weight part of A component, Preferably it is 0.01-0.7 weight part, More preferably, it is 0.01-0.5 weight part. . If the content of component D is less than 0.005 parts by weight, the flame-retardant effect is insufficient and the impact resistance is not improved. If the content of the D component exceeds 1 part by weight, the resin decomposes during molding and flame retardancy and chemical resistance are reduced.

(Other ingredients)
The resin composition in the present invention can contain an elastomer component other than the C component within a range not impairing the effects of the present invention. Suitable elastomer components include core-shells such as acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), and silicone-acrylic composite rubber-based graft copolymer. Examples of the graft copolymer resin include thermoplastic elastomers such as silicone-based thermoplastic elastomers, olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers.

  In the resin composition in this invention, another thermoplastic resin can be included in the range which does not impair the effect of this invention. Other thermoplastic resins include, for example, general-purpose plastics represented by polyethylene resin, polypropylene resin, polyalkylmethacrylate resin, polyphenylene ether resin, polyacetal resin, aromatic polyester resin, liquid crystalline polyester resin, polyamide resin, cyclic resin Engineering plastics represented by polyolefin resin, polyarylate resin (amorphous polyarylate, liquid crystalline polyarylate), polytetrafluoroethylene, polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, etc. What is called super engineering plastics can be mentioned.

  In the resin composition of the present invention, an antioxidant, a heat stabilizer (hindered phenol-based, hydroquinone-based, phosphite-based and substituted products thereof), weathering agent (resorcinol, etc.) within a range not impairing the effects of the present invention. , Salicylates, benzotriazoles, benzophenones, hindered amines, etc., release agents and lubricants (montanic acid and its metal salts, its esters, their half esters, stearyl alcohol, stearamide, various bisamides, bisureas and polyethylene waxes) Etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (eg, nigrosine), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfone) Amides), antistatic agents (alkyl) Sulfate type anionic antistatic agent, quaternary ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc.), difficulty other than D component Flame retardant (eg, red phosphorus, phosphate ester, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin or Combinations of these brominated flame retardants and antimony trioxide, etc.) and other polymers can be added.

(Manufacture of resin composition)
Arbitrary methods are employ | adopted in order to manufacture the thermoplastic resin composition of this invention. For example, the components A to D and optionally other additives are sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical apparatus, an extrusion mixer, and then extruded granulated as necessary. There is a method of granulating such a premixed mixture using a vessel or a briquetting machine, then melt-kneading with a melt-kneader represented by a vent type twin screw extruder, and then pelletizing with a pelletizer.

  In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of the method of premixing a part of each component include a method of premixing components other than the component A in advance and then mixing the components with the thermoplastic resin of the component A or supplying them directly to the extruder.

  As a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are mixed to produce a master batch of the additive diluted with the powder. A method using a master batch can be mentioned. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.

As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. 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, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

(Manufacture of molded products)
The resin composition of the present invention can be produced by injection molding. In such injection molding, other molding techniques such as film insert decorative molding, injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting supercritical fluid), and ultra-high speed injection molding are used. Can be used. In addition, either a cold runner method or a hot runner method can be selected for molding.

  The resin composition of the present invention is a polycarbonate resin that satisfies a high level of impact resistance, chemical resistance, and flame retardancy, and can be widely applied to the electrical and electronic equipment, OA equipment, automobile fields, etc. The effect is extremely large.

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

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

(Evaluation of thermoplastic resin composition)
(I) Charpy impact strength According to ISO 179, the Charpy impact strength with a notch was measured (test condition 23 ° C.) using an ISO bending test piece prepared by the following method.

(Ii) Flame retardance Based on the UL94 standard, the maximum combustion seconds and UL94 rank were evaluated at a thickness of 2.0 mm. In addition, the test piece was shape | molded by the cylinder temperature of 280 degreeC and the metal mold temperature of 60 degreeC with the injection molding machine (Nissei Plastic Industry Co., Ltd. NEX50).

(Iii) Chemical resistance After applying 0.7% strain by the three-point bending test method using the ISO tensile test piece obtained by the following method, impregnated with Magiclin (manufactured by Kao Corporation) The cloth was put on and allowed to stand at 23 ° C. for 96 hours. The evaluation was performed according to the following criteria.
○: No change in appearance is observed Δ: Fine cracks are observed ×: Large cracks are observed that lead to breakage When the above chemical resistance test evaluation results are ○ and Δ, The chemical resistance test was further performed by changing the strain amount to 1.0%. Those with a rating of ○ at a strain amount of 0.7% have excellent chemical resistance, and those with a rating of ○ at a strain amount of 1.0% have very good chemical resistance. .

[Examples 1-11, Comparative Examples 1-10]
The mixture which consists of a component except the polyarylene sulfide resin of B component with the composition shown in Table 1 and Table 2 was supplied from the 1st supply port of the extruder. Such a mixture was obtained by mixing with a V-type blender. The B component polyarylene sulfide resin was supplied from the second supply port using a side feeder. Extrusion is performed by using a vent type twin screw extruder (Nippon Steel Works TEX30α-38.5BW-3V) with a diameter of 30 mmφ and melt kneading at a screw speed of 200 rpm, a discharge rate of 25 kg / h, and a vent vacuum of 3 kPa. Pellets were obtained. In addition, about extrusion temperature, it implemented at 300 degreeC from the 1st supply port to the die part. Part of the obtained pellets was dried in a hot air circulating dryer at 90-100 ° C. for 6 hours, and then evaluated for evaluation at a cylinder temperature of 280 ° C. and a mold temperature of 60 ° C. using an injection molding machine. A piece (ISO tensile test piece (conforming to ISO527-1 and ISO527-2), an ISO bending test piece (conforming to ISO179)) and a UL test piece were molded.

In addition, each component of the symbol description in Table 1 and Table 2 is as follows.
<A1 component>
A1: Linear polycarbonate resin powder having a viscosity average molecular weight of 22,400 (manufactured by Teijin Limited; Panlite L-1225WP (trade name))
<A2 component>
A2: Polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight of 19,800 obtained by the following production method

[Production method]
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 21591 g of ion-exchanged water and 3673 g of 48.5% aqueous sodium hydroxide, 3880 g of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), and hydro After dissolving 7.6 g of sulfite, 14565 g of methylene chloride (14 mol relative to 1 mol of dihydroxy compound (I)) was added, and 1900 g of phosgene was blown in at 22-30 ° C. for 60 minutes with stirring. Next, a solution obtained by dissolving 1131 g of 48.5% sodium hydroxide aqueous solution and 105 g of p-tert-butylphenol in 800 g of methylene chloride was added, and the polydiorganosiloxane compound represented by the following formula (5) (in the formula: The rate at which dihydroxyaryl-terminated polydiorganosiloxane (II) is 0.0008 mol / min per mol of dihydric phenol (I) in a solution of 430 g of average repeat number p = about 37) dissolved in 1600 g of methylene chloride Was added to obtain an emulsified state and then vigorously stirred again. Under such stirring, 4.3 g of triethylamine was added while the reaction solution was at 26 ° C., and stirring was continued for 45 minutes at a temperature of 26 to 31 ° C. to complete the reaction. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and poured into a kneader filled with warm water when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water. Then, methylene chloride was evaporated while stirring to obtain a polycarbonate-polydiorganosiloxane copolymer resin powder. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation dryer to obtain a polycarbonate-polydiorganosiloxane copolymer resin powder.

<B component>
B-1: Polyphenylene sulfide resin obtained by the following production method [Production method]
A reaction product containing 5130 g of paradiiodobenzene and 450 g of sulfur and 4 g of mercaptobenzothiazole as a reaction initiator is heated to 180 ° C. to completely melt and mix, then the temperature is raised to 220 ° C. and the pressure is set to 350 Torr. The pressure dropped. The resulting mixture was subjected to a polymerization reaction while gradually changing the temperature and pressure so that the final temperature and pressure were 300 ° C. and 1 Torr or less, respectively. When the polymerization reaction has progressed 80% (the degree of progress of the polymerization reaction was confirmed by the method of relative ratio by viscosity ((current viscosity / target viscosity) × 100%)), 25 g of mercaptobenzothiazole was added as a polymerization terminator And reacted. After 1 hour, 51 g of 4-iodobenzoic acid was added and reacted in a nitrogen atmosphere for 10 minutes. After gradually raising the degree of vacuum to 0.5 Torr or less and further reacting for 1 hour, the reaction was terminated. Was produced at the end of the main chain. The resulting polyarylene sulfide resin showed a peak derived from carboxyl groups between ^{1600cm -1 ~1800cm} -1 at FT-IR spectrum of FT-IR spectroscopy.

B-2: Polyphenylene sulfide resin obtained by the following production method [Production method]
To 300.00 g of paradiiodobenzene and 27.00 g of sulfur, 0.60 g of diphenyl disulfide was added as a polymerization terminator and heated to 180 ° C. to completely melt and mix them, and then the temperature was raised to 220 ° C. The pressure was reduced to 200 Torr. The resulting mixture was subjected to a polymerization reaction for 8 hours while gradually changing the temperature and pressure so that the final temperature and pressure were 320 ° C. and 1 Torr, respectively, to produce a polyphenylene sulfide resin. The obtained polyarylene sulfide resin is a polyarylene sulfide resin having no terminal functional group that reacts with at least one group selected from the group consisting of a glycidyl group and an epoxy group.

<C component>
C-1: Glycidyl group-containing impact modifier (Bond First 7M (trade name) manufactured by Sumitomo Chemical Co., Ltd.)
C-2: Glycidyl group-containing impact modifier (Sumitomo Chemical Co., Ltd. Bond First 2B (trade name))
C-3: Epoxy group-containing impact modifier (Mitsubrene S-2200 (trade name), Mitsubishi Rayon Co., Ltd.)
C-4: Impact modifier containing no glycidyl group or epoxy group (Kane ACE M-701 (trade name) manufactured by Kaneka Corporation)

<D component>
D-1: Perfluorobutanesulfonic acid potassium salt (Dai Nippon Ink Co., Ltd. MegaFuck F-114P (trade name))
D-2: Potassium diphenylsulfone sulfonate (KSS (trade name) manufactured by Arichem)

  From the above table, the aromatic polycarbonate resin of the present invention, the polycarbonate-polydiorganosiloxane copolymer resin, the polyphenylene sulfide resin having a terminal functional group that reacts with at least one group selected from the group consisting of a glycidyl group and an epoxy group, glycidyl The resin composition comprising an impact modifier having at least one group selected from the group consisting of a group and an epoxy group and a metal salt compound satisfies a high level of impact resistance, chemical resistance and flame retardancy. I understand that.

Claims (6)

  (A) To 100 parts by weight of polycarbonate resin (component A) consisting of 0 to 100 parts by weight of aromatic polycarbonate resin (component A1) and polycarbonate-polydiorganosiloxane copolymer resin (component A2) (100 parts by weight) B) From 10 to 80 parts by weight of a polyarylene sulfide resin (component B) having a functional group that reacts with at least one group selected from the group consisting of a glycidyl group and an epoxy group, and (C) from a glycidyl group and an epoxy group 1 to 15 parts by weight of an impact modifier (C component) having at least one group selected from the group consisting of: 0.005 to 1 part by weight of (D) a metal salt compound (D component) A polycarbonate resin composition. B component, according to claim 1, characterized in that the polyarylene sulfide resin having an absorption peak derived from carboxyl groups between ^{1600cm -1 ~1800cm} -1 at FT-IR spectrum of FT-IR spectroscopy Polycarbonate resin composition.   The polycarbonate resin composition according to claim 1 or 2, wherein the component A comprises 0 to 90 parts by weight of the A1 component and 10 to 100 parts by weight of the A2 component.   The polycarbonate resin composition according to any one of claims 1 to 3, wherein the component D is an organic alkali metal salt and / or an organic alkaline earth metal salt.   The D component is selected from the group consisting of alkali (earth) metal salts of perfluoroalkyl sulfonates, alkali (earth) metal aromatic sulfonates, and alkali (earth) metal salts of aromatic imides The polycarbonate resin composition according to claim 4, wherein the polycarbonate resin composition is an organic alkali (earth) metal salt.   A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 5.