JP7311356B2 - Polycarbonate resin composition - Google Patents

Description

The present invention provides a resin composition comprising a component comprising a polycarbonate resin and a liquid crystal polyester resin in a specific ratio, a flame retardant, an anti-drip agent, glass fiber and/or carbon fiber, a phenoxy resin and/or epoxy resin, and a phosphorus stabilizer. and molded articles made thereof. More particularly, the present invention relates to a polycarbonate resin composition which is excellent in high tensile strength, dimensional accuracy and flame retardancy, and which is particularly suitable for thin-walled molded articles requiring strength.

Polycarbonate resin is a resin excellent in heat resistance, impact resistance, dimensional stability, etc., and is widely used in the fields of electric/electronic parts, mechanical parts, automobile parts, OA equipment parts, and the like. In recent years, products have become more high-performance, lighter, thinner, shorter, and smaller. Therefore, even when thin-walled products are designed for resin materials, it is necessary to have high strength and thin-walled flame-retardant properties that can maintain the safety of products. is strongly desired.

Conventionally, in order to improve mechanical properties such as tensile strength of polycarbonate resin, a method of mixing phosphorus-based additives and polyethylene wax together with glass fiber (see Patent Document 1), or adhesion of fibrous filler and resin Although a method of adding a modifier (see Patent Document 2) has been used, sufficient properties cannot be obtained when the thickness of the molded product is thin.

Further, many methods have been proposed for simultaneously improving rigidity and fluidity by blending a polymer exhibiting liquid crystallinity with a thermoplastic resin and fiberizing the liquid crystal polymer in the composition. Also in aromatic polycarbonate resins, many attempts have been made to blend liquid crystalline polymers, and examples of blending fibrous inorganic reinforcing materials to further increase rigidity have been reported (see Patent Documents 3 and 4). . Also, as shown below, attempts have already been made to add a phosphorus-based flame retardant or a metal salt-based flame retardant to impart flame retardancy (see Patent Documents 5 to 8).

Patent Document 5 describes a resin composition comprising a polycarbonate resin, a liquid crystal polymer, a flame retardant (including a phosphorus-based flame retardant), and polytetrafluoroethylene, but discloses the use of a fibrous inorganic reinforcing material. Therefore, it cannot be said that the method for solving such technical problems is sufficiently disclosed.

Patent Document 6 describes a resin composition comprising a polycarbonate resin, a liquid crystal polymer, a metal salt-based flame retardant, and a fibrous inorganic reinforcing material, but does not disclose the use of polytetrafluoroethylene, nor is it implemented. Since the flame-retardant effect shown in the examples is V-2 in UL Standard-94, it cannot be said to sufficiently disclose a method for solving such a technical problem.

Patent Documents 7 and 8 disclose polycarbonate resin, liquid crystal polymer, flame retardant (including phosphorus-based flame retardant), and polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene and organic polymer particles. Although a resin composition is described, it has not yet achieved both strength and non-halogen flame retardancy. In addition, these techniques do not disclose the use of a liquid crystal polymer and a fibrous inorganic reinforcing material to improve the tensile strength of thin-walled molded products, and cannot be said to disclose a sufficient solution to such technical problems. .

JP-A-57-94039 JP 2009-292953 A JP-A-07-258531 JP 2012-188578 A JP-A-07-331051 JP-A-2003-82219 JP 2003-113314 A JP 2008-163315 A

SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide a polycarbonate resin composition which is excellent in tensile strength, dimensional accuracy and flame retardancy, and which is particularly suitable for thin-walled molded articles requiring strength.

As a result of intensive studies to solve the above problems, the present inventors have found that a component consisting of a polycarbonate resin and a liquid crystal polyester resin in a specific ratio, a flame retardant, an anti-drip agent, glass fibers and / or carbon fibers, a phenoxy resin and / Alternatively, the inventors have found that a polycarbonate resin composition excellent in tensile strength, dimensional accuracy and flame retardancy can be obtained by blending an epoxy resin and a phosphorus-based stabilizer, thereby completing the present invention.

According to the present invention, the above problem is solved by adding (C) a flame retardant (C component) to 100 parts by weight of a component consisting of (A) a polycarbonate resin (component A) and (B) a liquid crystal polyester resin (component B). .01 to 40 parts by weight, (D) anti-drip agent (component D) 0.1 to 3 parts by weight, (E) glass fiber and/or carbon fiber (component E) 25 to 150 parts by weight, (F) phenoxy resin ( A)/(B)] is achieved with a polycarbonate resin composition having a ratio of 98/2 to 60/40.

The details of the present invention will be described below.
(A component: polycarbonate resin)
The polycarbonate resin used as component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of reaction methods 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 dihydric phenols used herein include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 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-phenylenediisopropylidene)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. be done. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, of which bisphenol A is particularly preferred from the standpoint of impact resistance and is widely used.

In the present invention, in addition to bisphenol A-based polycarbonates, which are general-purpose polycarbonates, special polycarbonates produced using other dihydric phenols can be used as component A.

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. Suitable for applications with particularly stringent demands on change and morphological stability. These dihydric phenols other than BPA are preferably used in an amount of 5 mol % or more, particularly 10 mol % or more, of the total dihydric phenol components constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that component A constituting the resin composition is the following copolymerized polycarbonate (1) to (3). be.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, still more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF is 20 to 80 mol % (more preferably 25 to 60 mol %, still more preferably 35 to 55 mol %).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, still 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 %, still more preferably 15 to 40 mol %).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, still more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis - A copolymerized polycarbonate in which the TMC is 20-80 mol% (more preferably 25-60 mol%, still more preferably 35-55 mol%).

These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be used by mixing with a widely used bisphenol A type polycarbonate.

The manufacturing 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.

Among the various polycarbonates described above, those having a water absorption rate and Tg (glass transition temperature) within the following range by adjusting the copolymer composition etc. have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage properties after molding, it is particularly suitable in fields where shape stability is required.
(i) a polycarbonate having a water absorption of 0.05-0.15%, preferably 0.06-0.13% and a Tg of 120-180°C, or (ii) a Tg of 160-250°C, A polycarbonate having a temperature of preferably 170 to 230° C. and a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

Here, the water absorption rate of polycarbonate is a value obtained by measuring the water content after immersing a disk-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm in water at 23 ° C. for 24 hours in accordance with ISO62-1980. be. Further, Tg (glass transition temperature) is a value determined by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.

Carbonate precursors include carbonyl halides, diesters of carbonic acid and haloformates, and specific examples include phosgene, diphenyl carbonate and dihaloformates of dihydric phenols.

In producing the aromatic polycarbonate resin by interfacial polymerization of the dihydric phenol and the carbonate precursor, if necessary, a catalyst, a terminal terminator, and an antioxidant for preventing oxidation of the dihydric phenol. etc. may be used. In addition, the aromatic polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, a polyester obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid It includes carbonate resins, copolymerized polycarbonate resins copolymerized with difunctional alcohols (including alicyclic alcohols), and polyester carbonate resins copolymerized with such difunctional carboxylic acids and difunctional alcohols. Moreover, the mixture which mixed 2 or more types of 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 trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucine, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)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-[ trisphenols such as 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, 4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among others, 1,1,1-tris(4-hydroxy Phenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

Structural units derived from a polyfunctional aromatic compound in the branched polycarbonate are preferably 0.01 to 1 mol %, more preferably 0.05 to 0.9 mol %, still more preferably 0.05 to 0.8 mol %.

In addition, particularly in the case of the melt transesterification method, branched structural units may occur as a side reaction. It is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, still more preferably 0.01 to 0.8 mol %. The ratio of such branched structures can be calculated by 1H-NMR measurement.

Aliphatic bifunctional carboxylic acids are preferably α,ω-dicarboxylic acids. Examples of aliphatic bifunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid, and cyclohexanedicarboxylic acid. Alicyclic dicarboxylic acids such as are preferably exemplified. Alicyclic diols are more suitable as bifunctional alcohols, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

Reaction formats such as the interfacial polymerization method, the melt transesterification method, the carbonate prepolymer solid-phase transesterification method, and the ring-opening polymerization method of a cyclic carbonate compound, which are methods for producing polycarbonate resins, can be found in various literatures and patent publications. It is a known method.

In producing the polycarbonate resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate 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 , particularly preferably 1.7×10 ⁴ to 2.1×10 ⁴ . Polycarbonate resins having a viscosity-average molecular weight of less than 1×10 ⁴ may not provide good mechanical properties, especially high tensile strength. On the other hand, a resin composition obtained from an aromatic polycarbonate resin having a viscosity-average molecular weight exceeding 5×10 ⁴ may be inferior in versatility due to poor fluidity during injection molding.

The polycarbonate-based resin may be obtained by mixing resins having a viscosity-average molecular weight outside the above range. In particular, a polycarbonate-based 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-assisted molding and foam molding, which are sometimes used when molding reinforced resin materials into structural members. Such improvement in moldability is even better than that of the branched polycarbonate. In a more preferred embodiment, component A is a polycarbonate resin (Component A-1-1) having a viscosity average molecular weight of 7×10 ⁴ to 3×10 ⁵ and an aromatic component having a viscosity average molecular weight of 1×10 ⁴ to 3×10 ⁴ Polycarbonate resin (A-1 component) ( ^hereinafter referred to ^as "high molecular weight component Polycarbonate-based resin") can also be used.

In such a high-molecular-weight component-containing polycarbonate resin (component A-1), the molecular weight of component A-1-1 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 , particularly preferably 1×10 ⁵ to 1.6×10 ⁵ . The molecular weight of component A-1-2 is preferably 1×10 ⁴ to 2.5×10 ⁴ , more preferably 1.1×10 ⁴ to 2.4×10 ⁴ , 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 (component A-1) can be obtained by mixing the components A-1-1 and A-1-2 in various proportions and adjusting the mixture to satisfy a predetermined molecular weight range. can. Preferably, in 100% by weight of A-1 component, A-1-1 component is 2 to 40% by weight, more preferably A-1-1 component is 3 to 30% by weight, still more preferably The content of component A-1-1 is 4 to 20% by weight, and the content of component A-1-1 is particularly preferably 5 to 20% by weight.

In addition, as a method for preparing the A-1 component, (1) a method in which the A-1-1 component and the A-1-2 component are polymerized independently and then mixed, and (2) JP-A-5-306336. Using a method for producing an aromatic polycarbonate resin showing multiple polymer peaks in a molecular weight distribution chart by GPC method in the same system, represented by the method shown in JP-A-2003-120002, such an aromatic polycarbonate resin is produced by the A- of the present invention. A method of manufacturing to satisfy the conditions of one component, and (3) an aromatic polycarbonate resin obtained by such a manufacturing method (manufacturing method of (2)), separately manufactured A-1-1 component and / or A method of mixing with the A-1-2 component can be mentioned.

The viscosity-average molecular weight referred to in the present invention is obtained by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of polycarbonate in 100 ml of methylene chloride at 20° C. to determine the specific viscosity (η _SP ) calculated by the following formula.
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
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

Calculation of the viscosity-average molecular weight of the polycarbonate-based resin is performed in the following manner. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble matter in the composition. Such soluble matter is collected by celite filtration. The solvent in the resulting solution is then removed. After removing the solvent, the solid is sufficiently dried to obtain a solid of the component soluble in methylene chloride. From a solution obtained by dissolving 0.7 g of this solid in 100 ml of methylene chloride, the specific viscosity at 20° C. is obtained 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.

A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate-based resin (component A). A polycarbonate-polydiorganosiloxane copolymer resin is a dihydric phenol deriving a structural unit represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane deriving a structural unit represented by the following general formula (3). is a copolymer resin prepared by copolymerizing the

[In the above general formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, cycloalkyl group having 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, aryloxy group having 6 to 14 carbon atoms, carbon atom represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon 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 are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula (2). ]

[In the above 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, a carbon 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; R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, a halogen atom, or a an alkyl group having 1 to 10 carbon atoms, 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, and 6 carbon atoms. an aryl group of up to 14, an aryloxy group of 6 to 10 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an aralkyloxy group of 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group represents a group selected from the group consisting of; when there are more than one, they may be the same or different; g is an integer of 1-10; h is an integer of 4-7; ]

[In the 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 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, 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 from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

Examples of the dihydric phenol (I) from which the structural unit represented by the general formula (1) is derived 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-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxy phenyl) 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′-dimethyldiphenyl 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-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxy phenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4′-(1,3-adamantanediyl)diphenol, 1,3-bis (4-hydroxyphenyl)-5,7-dimethyladamantane and the like. Among others, 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(4-hydroxyphenyl)cyclohexane (BPZ), 4,4′- Sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferred. Among them, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used alone or in combination of two or more.

As the hydroxyaryl-terminated polydiorganosiloxane from which the structural unit represented by the general formula (3) is derived, for example, the following compounds are preferably used.

Hydroxyaryl-terminated polydiorganosiloxane (II) is selected from phenols having olefinically unsaturated carbon-carbon bonds, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol. It is easily produced by subjecting the end of a polysiloxane chain 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, (2-methoxy-4 -allylphenol) terminated polydimethylsiloxane is preferred. The hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw/Mn) of 3 or less. The molecular weight distribution (Mw/Mn) is more preferably 2.5 or less, still more preferably 2 or less, in order to achieve even better low-outgassing properties and low-temperature impact resistance during high-temperature molding. If the upper limit of the preferred range is exceeded, a large amount of outgas is generated during high-temperature molding, and the low-temperature impact resistance may be poor.

Moreover, the diorganosiloxane polymerization degree (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300 in order to achieve high impact resistance. Such a diorganosiloxane polymerization degree (p+q) is preferably 10-200, more preferably 12-150, still more preferably 14-100. Below the lower limit of the preferred range, impact resistance characteristic of the polycarbonate-polydiorganosiloxane copolymer is not effectively exhibited, and above the upper limit of the preferred range, poor appearance appears.

The polydiorganosiloxane content in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used as component A is preferably 0.1 to 50% by weight. The content of such polydiorganosiloxane component is more preferably 0.5 to 30% by weight, more preferably 1 to 20% 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 less susceptible to molding conditions is likely to be obtained. Such polydiorganosiloxane polymerization degree and polydiorganosiloxane content can be calculated by 1H-NMR measurement.

In the present invention, only one type of hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more types may be used.

In addition, other comonomers than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) are added in an amount of 10% by weight or less based on the total weight of the copolymer, as long as they do not interfere with the present invention. They can also be used in combination.

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

In producing the oligomer of dihydric phenol (I), the whole amount of dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at one time, or part of it may be used as a post-addition monomer to form an interface in the latter stage. It may be added as a reaction raw material to the polycondensation reaction. The post-addition monomer is added in order to facilitate the subsequent polycondensation reaction, and it is not necessary to add it unless necessary.

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

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

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. The ratio of the acid binder to be used may also be appropriately determined in consideration of the stoichiometric ratio (equivalents) of the reaction in the same manner as described above. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of the acid binder with respect to the number of moles of the dihydric phenol (I) used to form the oligomer (usually 1 mol corresponds to 2 equivalents). .

As the solvent, a solvent inert to various reactions, such as those used in the production of known polycarbonates, may be used singly or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene, and the like. In particular, halogenated hydrocarbon solvents such as methylene chloride are preferably used.

The reaction pressure for oligomer production is not particularly limited and may be normal pressure, increased pressure 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. In many cases, heat is generated with polymerization, so water cooling or ice cooling is desirable. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours. The pH range of the oligomer-forming reaction is the same as the well-known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

In the present invention, after obtaining a mixed solution containing an oligomer of dihydric phenol (I) having a terminal chloroformate group, the mixed solution is stirred until the molecular weight distribution (Mw/Mn) is 3 or less. A highly purified hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (4) is added to the dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation. A polycarbonate-polydiorganosiloxane copolymer is thus obtained.

(In general formula (4) above, 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 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, 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 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

In carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate in consideration of the stoichiometric ratio (equivalents) 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, if a portion of the hydroxyaryl-terminated polydiorganosiloxane (II) used or, as noted above, the dihydric phenol (I) is added to this reaction step as a post-add monomer, two of the post-add monomers It is preferable to use 2 equivalents or more of the alkali with respect to the total number of moles of the phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mol corresponds to 2 equivalents).

Interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixture.

Terminal terminator or molecular weight modifier is usually used in such polymerization reaction. Examples of terminal terminating agents include compounds having a monovalent phenolic hydroxyl group, such as usual phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, long-chain alkylphenols and aliphatic carboxylic acids. Examples include chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of all dihydric phenol compounds used, and it is of course possible to use two or more kinds of compounds together. be.

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

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

A branching agent can be used in combination with the above dihydric phenolic compound to form a branched polycarbonate-polydiorganosiloxane. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucine, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl ) 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, trisphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxy phenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among others, 1,1,1 -tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred. . The ratio of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol %, more preferably 0.005 to 0, based on the total amount of the aromatic polycarbonate-polydiorganosiloxane copolymer resin. 0.9 mol %, more preferably 0.01 to 0.8 mol %, particularly preferably 0.05 to 0.4 mol %. Incidentally, such a branched structure amount can be calculated by 1H-NMR measurement.

The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure, but usually normal pressure or the self-pressure of the reaction system is suitable. The reaction temperature is selected from the range of −20 to 50° C. In many cases, heat is generated with polymerization, so water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as the reaction temperature and cannot be generally defined, but is usually 0.5 to 10 hours.

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

The resulting reaction product (crude product) is subjected to various post-treatments such as known separation and purification methods, and can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin of desired purity (purity). The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molding is preferably in the range of 1 to 40 nm. Such average size is more preferably 1-30 nm, more preferably 5-25 nm. Below the lower limit of the preferred range, sufficient impact resistance and flame retardancy may not be exhibited, and above the upper limit of the preferred range, impact resistance may not be exhibited stably.

The average domain size and normalized dispersion of the polydiorganosiloxane domains of the polycarbonate-polydiorganosiloxane copolymer resin molded article in the present invention were evaluated by small angle X-ray scattering (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 this small-angle X-ray scattering method, if there are regions with different electron densities on the order of 1 to 100 nm in a substance, diffuse scattering of X-rays is measured from the difference in electron densities. Based on this scattering angle and scattering intensity, the particle diameter of the object to be measured is obtained. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregate structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, diffuse scattering of X-rays occurs due to the electron density difference between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I at each scattering angle (2θ) in the range of less than 10° scattering angle (2θ) is measured to measure the small-angle X-ray scattering profile, and the polydiorganosiloxane domain is a spherical domain and the particle size distribution varies. Assuming the presence of , the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domains are obtained by performing a simulation using commercially available analysis software from the provisional particle size and the provisional particle size distribution model. The small-angle X-ray scattering method enables accurate, simple, and reproducible analysis of the average size and particle size distribution of polydiorganosiloxane domains dispersed in a polycarbonate polymer matrix, which cannot be accurately measured by transmission electron microscopy. can be measured. Average domain size means the number average of individual domain sizes. The normalized dispersion means a parameter obtained by normalizing the spread of the particle size distribution by the average size. Specifically, it is a value obtained by normalizing the polydiorganosiloxane domain size distribution by 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 refer to measurement of a 1.0 mm thick portion of a three-tiered plate produced by the method described in Examples by the small-angle X-ray scattering method. Measured values obtained by In addition, the analysis was performed using an isolated particle model that does not consider the interaction between particles (interference between particles).

(B component: liquid crystal polyester resin)
The liquid crystalline polyester resin used as component B in the present invention is a thermotropic liquid crystalline polyester resin, and has the property that polymer molecular chains are aligned in a certain direction in a molten state. The form of such arrangement may be nematic, smectic, cholesteric or discotic, or may exhibit two or more forms. Further, the structure of the liquid crystalline polyester resin may be any of main chain type, side chain type, rigid main chain bent side chain type, etc., but the main chain type liquid crystalline polyester resin is preferred.

The morphology of the alignment state, that is, the nature of the anisotropic melt phase can be confirmed by a conventional polarization inspection method using crossed polarizers. More specifically, confirmation of the anisotropic molten phase can be carried out by using a Leitz polarizing microscope and observing the molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. The polymers of the present invention are optically anisotropic and transmit polarized light even in the molten quiescent state when examined between crossed polarizers.

The heat resistance of the liquid crystalline polyester resin may be within any range, but it is suitable that it melts at a portion close to the processing temperature of the polycarbonate resin to form a liquid crystal phase. A liquid crystalline polyester having a deflection temperature under load (ISO75-1/2 under load of 1.8 Mpa) of 150 to 280°C, preferably 150 to 250°C is more suitable. Such liquid crystalline polyesters belong to the so-called type II heat-resistant class. When it has such heat resistance, it is excellent in moldability as compared with Type I, which has higher heat resistance, and it achieves better flame retardancy than Type III, which has lower heat resistance.

The liquid crystalline polyester resin used in the present invention preferably contains a polyester unit and a polyesteramide unit, and is preferably an aromatic polyester resin or an aromatic polyesteramide resin. A liquid crystalline polyester resin partially contained in is also a preferred example.

Particularly preferably, wholly aromatic polyester resins and wholly aromatic polyester amides having as unit constituents derived from one or more compounds selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines and aromatic diamines Resin. More specifically, 1) a liquid crystalline polyester resin synthesized from one or more compounds selected mainly from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, 2) mainly a) aromatic hydroxycarboxylic acids and one or more compounds selected from the group consisting of derivatives thereof, b) one or more compounds selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof, and c) Liquid crystalline polyester resins synthesized from one or more compounds selected from the group consisting of aromatic diols, alicyclic diols, aliphatic diols and their derivatives, 3) mainly a) aromatic hydroxycarboxylic acids and their derivatives one or more compounds selected from the group consisting of b) one or more compounds selected from the group consisting of aromatic hydroxylamines, aromatic diamines and derivatives thereof, and c) aromatic dicarboxylic acids , a liquid crystal polyesteramide resin synthesized from one or more compounds selected from the group consisting of alicyclic dicarboxylic acids and derivatives thereof; 4) mainly selected from the group consisting of a) aromatic hydroxycarboxylic acids and derivatives thereof; b) one or more compounds selected from the group consisting of aromatic hydroxylamines, aromatic diamines and derivatives thereof, c) aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof, and d) one or more compounds selected from the group consisting of aromatic diols, alicyclic diols, aliphatic diols and derivatives thereof. 1) Liquid crystalline polyester resins synthesized from one or more compounds selected mainly from the group consisting of aromatic hydroxycarboxylic acids and their derivatives are preferred.

Furthermore, a molecular weight modifier may be used in combination with the above constituents, if necessary.

Preferable examples of specific compounds used for synthesizing the liquid crystalline polyester resin used in the polycarbonate resin composition of the present invention are 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene and 6 -Naphthalene compounds such as hydroxy-2-naphthoic acid, 4,4'-diphenyldicarboxylic acid, biphenyl compounds such as 4,4'-dihydroxybiphenyl, p-hydroxybenzoic acid, terephthalic acid, hydroquinone, p-aminophenol and p - para-substituted benzene compounds such as phenylenediamine and their nucleus-substituted benzene compounds (where the substituent is selected from chlorine, bromine, methyl, phenyl and 1-phenylethyl), isophthalic acid, meta-substituted benzene such as resorcinol compounds and compounds represented by the following general formulas (5), (6) or (7). Among them, p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are particularly preferred, and a liquid crystalline polyester resin obtained by mixing the two is preferred. The ratio of the former is preferably 90 to 50 mol %, more preferably 80 to 65 mol %, and the latter is preferably 10 to 50 mol %, more preferably 20 to 35 mol %.

(where X is a group selected from the group consisting of alkylene groups and alkylidene groups having 1 to 4 carbon atoms, -O-, -SO-, -SO ₂ -, -S-, and -CO-, and Y is A group selected from the group consisting of -(CH ₂ )n- (n = 1 to 4) and -O(CH ₂ )nO- (n = 1 to 4).)

In the liquid crystalline polyester resin used in the present invention, in addition to the constituent components described above, polyalkylene terephthalate-derived units that do not partially exhibit an anisotropic melting phase may be present in the same molecular chain. In this case, the alkylene group has 2 to 4 carbon atoms.

The basic method for producing the liquid crystalline polyester resin used in the present invention is not particularly limited, and can be produced according to a known polycondensation method for liquid crystalline polyester resins. The above liquid crystalline polyester resin also has a logarithmic viscosity ( IV value).

Due to the characteristics described above, the liquid crystalline polyester resin forms fine fibrils during injection molding, retains its shape during the cooling and solidification process, and exerts a reinforcing effect on the matrix. Therefore, it is possible to impart tensile strength by the liquid crystal polyester resin. The reduction in the viscosity of the resin composition due to the liquid crystal polyester resin also has the effect of reducing the injection speed and resin pressure.

The weight ratio [(A)/(B)] of (A) aromatic polycarbonate resin and (B) liquid crystal polyester resin used in the present invention is 98/2 to 60/40, preferably 95/5 to 80/20, more preferably in the range of 95/5 to 85/15. If the proportion of the liquid crystalline polyester resin exceeds this range, the tensile strength and flame retardancy are lowered. If the ratio is smaller than this range, the effect of improving the tensile strength by blending the liquid crystal polyester resin cannot be obtained.

(Component C: flame retardant)
Various compounds known as flame retardants for flame-retardant polycarbonate resins may be blended with the flame retardant of the C component. Incorporation of such compounds provides improved flame retardancy, but also provides, depending on the properties of each compound, improved antistatic properties, fluidity, stiffness, and thermal stability, for example. Such flame retardants include (i) organophosphorus flame retardants (e.g., monophosphate compounds, phosphate oligomeric compounds, phosphonate oligomeric compounds, phosphonitrile oligomeric compounds, phosphonic acid amide compounds, etc.), (ii) organometallic salt flame retardants. Retardants (e.g., organic sulfonate alkali (earth) metal salts, borate metal salt-based flame retardants, stannate metal salt-based flame retardants, etc.), (iii) silicone-based flame retardants composed of silicone compounds, (iv) alkali sulfonates Organic metal salts other than (earth) metal salts and the like can be mentioned, and among them, organic phosphorous flame retardants are preferred.

(i) Organic Phosphorus Flame Retardant As the organic phosphorus flame retardant of the present invention, phosphate compounds, particularly aryl phosphate compounds are suitable. This is because such phosphate compounds are generally excellent in hue. Phosphate compounds have a plasticizing effect, and are therefore advantageous in that they can enhance the moldability of the resin composition of the present invention. It should be noted that the phosphate compound as the organophosphorus flame retardant referred to herein is preferably a phosphate compound having a molecular weight of 300 or more. If the molecular weight is less than 300, the difference between the boiling point of the phosphate compound and the combustion temperature of the resin composition increases, and the phosphate compound may volatilize more during combustion, resulting in a lower effect as a flame retardant, which is preferable. do not have. As such a phosphate compound, various phosphate compounds conventionally known as flame retardants can be used, and more preferably, one or more phosphate compounds represented by the following general formula (8) can be mentioned.

(X in formula (8) is hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone and A dihydric phenol residue derived from a dihydroxy compound selected from the group consisting of bis(4-hydroxyphenyl) sulfides, where n is an integer from 0 to 5, or in the case of a mixture of n different phosphate esters is their average value, and R ¹ , R ² , R ³ and R ⁴ are each independently derived from an aryl group selected from the group consisting of phenol, cresol, xylenol, isopropylphenol, butylphenol and p-cumylphenol. is a monohydric phenol residue.)

The phosphate compound of general formula (8) above may be a mixture of compounds having different n numbers, and in such mixtures, the average n number is preferably 0.5 to 1.5, more preferably 0.5 to 1.5. 8 to 1.2, more preferably 0.95 to 1.15, particularly preferably 1 to 1.14.

Suitable specific examples of the dihydric phenol from which X in the general formula (8) is derived are resorcinol, bisphenol A and dihydroxydiphenyl, with resorcinol and bisphenol A being preferred.

Preferable specific examples of the monohydric phenol from which R ¹ , R ² , R ³ and R ⁴ in the general formula (8) are derived are phenol, cresol, xylenol and 2,6-dimethylphenol. is phenol, and 2,6-dimethylphenol.

Specific examples of the phosphate compound of the general formula (8) include monophosphate compounds such as triphenyl phosphate and tri(2,6-xylyl)phosphate, and resorcinol bisdi(2,6-xylyl)phosphate). phosphate oligomers based on 4,4-dihydroxydiphenyl bis(diphenyl phosphate), and phosphate ester oligomers based on bisphenol A bis(diphenyl phosphate), among which resorcinol bis di(2,6 Phosphate oligomers based on 4,4-dihydroxydiphenylbis(diphenylphosphate), and phosphate oligomers based on bisphenol A bis(diphenylphosphate) are preferred.

The content of the organic phosphorus flame retardant is 0.01 to 40 parts by weight, preferably 3 to 20 parts by weight, and more preferably 4 to 10 parts by weight with respect to the total of 100 parts by weight of the components A and B. . If it exceeds this range, the extrusion workability will be insufficient. On the other hand, if it is less than this range, the flame retardancy is insufficient and the tensile strength also decreases.

(ii) Organic Metal Salt Flame Retardant The organic metal salt compound in the present invention is preferably an organic sulfonic acid alkali (earth) metal salt having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms. The organic sulfonic acid alkali (earth) metal salts include fluorine-substituted alkyl sulfones such as metal salts of perfluoroalkyl sulfonic acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and alkali metals or alkaline earth metals. Included are metal salts of acids and metal salts of aromatic sulfonic acids having 7 to 50, preferably 7 to 40 carbon atoms and alkali metal or alkaline earth metal salts.

Alkali metals constituting the metal salt of the present invention include lithium, sodium, potassium, rubidium and cesium, and alkaline earth metals include beryllium, magnesium, calcium, strontium and barium. Alkali metals are more preferred. Among such alkali metals, rubidium and cesium, which have larger ionic radii, are suitable when the demand for transparency is higher. It may be disadvantageous. On the other hand, metals with smaller ionic radii, such as lithium and sodium, may be disadvantageous in terms of flame retardancy. Although the alkali metal in the alkali metal sulfonate can be properly used in consideration of these factors, the potassium sulfonate is most preferable because of its well-balanced properties in all respects. Such potassium salts and alkali metal sulfonate salts of other alkali metals can also be used in combination.

Specific examples of perfluoroalkylsulfonic acid alkali metal salts include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, perfluoro Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonic acid Cesium, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, rubidium perfluorohexanesulfonate, and the like can be mentioned, and these can be used alone or in combination of two or more. The perfluoroalkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Among these, potassium perfluorobutanesulfonate is particularly preferred.

The alkali (earth) metal salt of perfluoroalkylsulfonate, which is an alkali metal, usually contains not a small amount of fluoride ions (F-). Since the presence of such fluoride ions can be a factor in deteriorating flame retardancy, it is preferable to reduce them as much as possible. The proportion of such fluoride ions can be measured by ion chromatography. The content of fluoride ions is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. In addition, it is preferable that the concentration is 0.2 ppm or more in terms of production efficiency. Such an alkali (earth) metal perfluoroalkylsulfonate having a reduced amount of fluoride ions is produced by a known production method and is contained in raw materials for producing a fluorine-containing organic metal salt. A method of reducing the amount of fluoride ions, a method of removing hydrogen fluoride and the like obtained by the reaction by gas generated during the reaction or by heating, and a purification method such as recrystallization and reprecipitation for the production of fluorine-containing organometallic salts. can be produced by a method of reducing the amount of fluoride ions using In particular, alkali (earth) metal salts of perfluoroalkylsulfonic acid are relatively soluble in water. It is preferable to use water that satisfies the above, dissolve at a temperature higher than room temperature, wash, then cool and recrystallize.

Specific examples of the alkali (earth) metal aromatic sulfonate include disodium diphenylsulfide-4,4′-disulfonate, dipotassium diphenylsulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, poly(2,6-dimethylphenylene oxide) polysodium polysulfonate , poly(1,3-phenylene oxide) polysodium polysulfonate, poly(1,4-phenylene oxide) polysodium polysulfonate, poly(2,6-diphenylphenylene oxide) polypotassium polysulfonate, poly(2-fluoro- 6-Butylphenylene oxide) lithium polysulfonate, potassium benzenesulfonate sulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, biphenyl -3,3'-calcium disulfonate, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, diphenylsulfone-3,4'-disulfonic acid dipotassium α,α,α-trifluoroacetophenone-4-sulfonate sodium, benzophenone-3,3′-dipotassium sulfonate, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate , calcium thiophene-2,5-disulfonate, sodium benzothiophene sulfonate, potassium diphenyl sulfoxide-4-sulfonate, formalin condensate of sodium naphthalene sulfonate, and formalin condensate of sodium anthracene sulfonate. can be done. Of these alkali (earth) metal salts of aromatic sulfonates, potassium salts are particularly preferred. Among these alkali (earth) metal salts of aromatic sulfonates, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3'-disulfonate are preferred, and mixtures thereof (the former and the latter weight ratio of 15/85 to 30/70).

Preferred examples of organic metal salts other than alkali (earth) metal sulfonates include alkali (earth) metal salts of sulfate esters and alkali (earth) metal salts of aromatic sulfonamides. As alkali (earth) metal salts of sulfate esters, mention may be made in particular of alkali (earth) metal salts of sulfate esters of monohydric and/or polyhydric alcohols, such monohydric and/or polyhydric alcohols Sulfuric acid esters include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono-, di-, tri-, tetra-sulfate, lauric acid monoglyceride sulfate esters, palmitate monoglyceride sulfates, stearate monoglyceride sulfates, and the like. The alkali (earth) metal salts of these sulfate esters are preferably alkali (earth) metal salts of lauryl sulfate.

Alkali (earth) metal salts of aromatic sulfonamides include, for example, saccharin, N-(p-tolylsulfonyl)-p-toluenesulfimide, N-(N'-benzylaminocarbonyl)sulfanilimide, and N-( and alkali (earth) metal salts of phenylcarboxyl)sulfanilimide.

The content of the organometallic salt-based flame retardant is 0.01 to 40 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.05 to 100 parts by weight, based on the total of 100 parts by weight of component A and component B. 5 parts by weight. If it exceeds this range, the flame retardancy is lowered and the cost is increased. On the other hand, if it is smaller than this range, flame retardancy is insufficient.

(iii) Silicone Flame Retardant The silicone compound used as the silicone flame retardant of the present invention improves flame retardancy through a chemical reaction during combustion. As the compound, various compounds that have been proposed as flame retardants for aromatic polycarbonate resins can be used. The silicone compound imparts a flame-retardant effect to the polycarbonate resin by forming a structure by combining with itself or by combining with a component derived from the resin during combustion, or by a reduction reaction during the formation of the structure. It is considered. Therefore, it preferably contains a group that is highly active in such reactions, and more specifically, it preferably contains a predetermined amount of at least one group selected from alkoxy groups and hydrogen (that is, Si—H groups). preferable. The content ratio of such groups (alkoxy group, Si—H group) is preferably in the range of 0.1 to 1.2 mol/100 g, more preferably in the range of 0.12 to 1 mol/100 g, and more preferably 0.15 to 0.15 mol/100 g. A range of 6 mol/100 g is more preferred. Such a ratio can be obtained by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkaline decomposition method. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group is particularly preferable.

Generally, the structure of a silicone compound is constructed by arbitrarily combining the four types of siloxane units shown below. That is, M units: ( _CH3 )3SiO1 _{/ 2} , H( _CH3 ) _{2SiO1/ 2} , _H2 ( _CH3 )SiO1 _/2 , ( _CH3 ) ₂ ( _CH2 =CH) _{SiO1 /2 ,} ( _CH3 ) ₂ ( _C6H5 )SiO1 _/ 2, ( _CH3 )( _C6H5 )( _CH2 =CH)SiO1 _{/ 2} , and other monofunctional siloxane units, D units: (CH ₃ ) ₂ SiO, H(CH ₃ ) SiO, H ₂ SiO, H(C ₆ H ₅ ) SiO, (CH ₃ )(CH ₂ =CH) SiO, (C ₆ H5) ₂ SiO, etc. siloxane unit, T unit: ( _CH3 )SiO3 _/2 , ( _C3H7 )SiO3 _{/ 2} , HSiO3 _/2 , ( _CH2 =CH)SiO3 _{/2 , (C6H5 )} SiO Trifunctional siloxane units such as _3/2 , Q units: tetrafunctional siloxane units represented by SiO ₂ .

Specifically, the structures of silicone compounds used in silicone-based flame retardants include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq. Among these, preferred structures of the silicone compounds are MmDn, MmTp, MmDnTp and MmDnQq, and more preferred structures are MmDn or MmDnTp.

Here, the coefficients m, n, p, and q in the formula are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . The average degree of polymerization is preferably in the range of 3-150, more preferably in the range of 3-80, still more preferably in the range of 3-60, and most preferably in the range of 4-40. It comes to be excellent in flame retardance, so that it is such a suitable range. Furthermore, as described later, silicone compounds containing a predetermined amount of aromatic groups are excellent in transparency and hue. As a result, good reflected light can be obtained.

When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with that coefficient can be two or more siloxane units having different bonding hydrogen atoms and organic residues. .

The silicone compound may be linear or branched. Also, the organic residue that bonds to the silicon atom preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such organic residues include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and decyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, and aralkyl groups such as tolyl groups. More preferably, it is an alkyl group, alkenyl group or aryl group having 1 to 8 carbon atoms. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group and propyl group is particularly preferred.

Furthermore, the silicone compound used as the silicone-based flame retardant preferably contains an aryl group. On the other hand, silane compounds and siloxane compounds used as organic surface treatment agents for titanium dioxide pigments are clearly distinguished from silicone-based flame retardants in their preferred aspects in that they exhibit favorable effects when they do not contain aryl groups. . A more preferable silicone-based flame retardant is a silicone containing 10 to 70% by weight (more preferably 15 to 60% by weight) of an aromatic group represented by the following general formula (9) (amount of aromatic group). is a compound.

(In formula (9), each X independently represents an OH group and a monovalent organic residue having 1 to 20 carbon atoms. n represents an integer of 0 to 5. Furthermore, in formula (9), n is 2. In each of the above cases, different types of X can be taken.)
Silicone compounds used as silicone flame retardants may contain reactive groups other than the Si—H groups and alkoxy groups. Examples of such reactive groups include amino groups, carboxyl groups, epoxy groups, vinyl groups, mercapto groups, and methacryloxy groups.

Preferred examples of silicone compounds having an Si—H group include silicone compounds containing at least one or more structural units represented by the following general formulas (10) and (11).

(In formulas (10) and (11), Z ¹ to Z ³ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (12). α1 to α3 each independently represent 0 or 1. m1 represents an integer of 0 or 1. Further, in the formula (10), when m1 is 2 or more, each repeating unit may be a plurality of different repeating units. can be taken.)

(In formula (12), Z ⁴ to Z ⁸ each independently represent a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms, α4 to α8 each independently represent 0 or 1, m2 is 0 Alternatively, it represents an integer of 1 or more.In addition, in formula (12), when m2 is 2 or more, the repeating unit can be a plurality of mutually different repeating units.)
In the silicone compound used for the silicone flame retardant, examples of the silicone compound having an alkoxy group include at least one compound selected from compounds represented by general formulas (13) and (14).

(In formula (13), β ¹ represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms. ^{γ 1} , γ ² , γ ³ , γ ⁴ , γ ⁵ and γ ⁶ represent alkyl and cycloalkyl groups having 1 to 6 carbon atoms and aryl and aralkyl groups having 6 to 12 carbon atoms, at least one of which is aryl or an aralkyl group, and δ ¹ , δ ² and δ ³ each represent an alkoxy group having 1 to 4 carbon atoms.)

(In formula (14), β ² and β ³ represent a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group and an aralkyl group having 6 to 12 carbon atoms. γ ⁷ , γ ⁸ , γ ⁹ , γ ¹⁰ , γ ¹¹ , γ ¹² , γ ¹³ and γ ¹⁴ are alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and cycloalkyl groups having 6 to 12 carbon atoms. represents an aryl group and an aralkyl group, at least one of which is an aryl group or an aralkyl group, and δ ⁴ , δ ⁵ , δ ⁶ and δ ⁷ represent an alkoxy group having 1 to 4 carbon atoms.)
The amount of the silicone-based flame retardant compounded is 0.01 to 40 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, per 100 parts by weight of the total amount of components A and B. be. If it exceeds this range, the flame retardancy is lowered and the cost is increased. On the other hand, if it is smaller than this range, flame retardancy is insufficient.

(D component: anti-drip agent)
Anti-dripping agents used as component D in the present invention include fluorine-containing polymers having fibril-forming ability. hexafluoropropylene copolymers, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, and polycarbonate resins made from fluorinated diphenols. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

PTFE having fibril-forming ability has an extremely high molecular weight, and exhibits a tendency to bond PTFE to become fibrous by an external action such as a shearing force. Its molecular weight is 1,000,000 to 10,000,000, more preferably 2,000,000 to 9,000,000 in terms of number average molecular weight determined from standard specific gravity. Such PTFE can be used not only in a solid form but also in an aqueous dispersion form. In addition, PTFE having such fibril-forming ability improves its dispersibility in resin, and it is also possible to use a PTFE mixture in which it is mixed with other resins in order to obtain good flame retardancy and mechanical properties. be.

Examples of commercially available PTFE having fibril-forming ability include Teflon (registered trademark) 6-J manufactured by Mitsui Chemours Fluoro Products Co., Ltd., Polyflon MPA FA500H and F-201 manufactured by Daikin Industries, Ltd., and the like. can. Commercially available PTFE aqueous dispersions include Fluon D series manufactured by Daikin Industries, Ltd., and Teflon (registered trademark) 31-JR manufactured by Mitsui Chemours Fluoro Products Co., Ltd., and the like.

(1) A method of mixing an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer to co-precipitate to obtain a co-aggregated mixture (JP-A-60-258263, JP-A-60-258263; (2) a method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957); (3) A method of uniformly mixing an aqueous dispersion of PTFE and a solution of organic polymer particles and simultaneously removing the respective media from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.). (4) a method of polymerizing a monomer that forms an organic polymer in an aqueous dispersion of PTFE (the method described in JP-A-9-95583); and (5) an aqueous dispersion of PTFE. After uniformly mixing the dispersion and the organic polymer dispersion, a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained (method described in JP-A-11-29679, etc.). You can use what you get. Examples of commercially available PTFE in mixed form include "METABLEN A3800" (trade name) and "METABLEN A3750" available from Mitsubishi Chemical Corporation.

The ratio of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, based on 100% by weight of the PTFE mixture. Good dispersibility of PTFE can be achieved when the proportion of PTFE is in this range.

As the organic polymer used in the polytetrafluoroethylene-based mixture, the styrene-based monomer is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and halogen. styrenes optionally substituted with one or more groups, such as ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethyl-styrene, para-tert-butylstyrene, methoxystyrene, fluorostyrene, Examples include, but are not limited to, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, vinylnaphthalene. The styrenic monomers may be used alone or in combination of two or more.

Acrylic monomers used as organic polymers used in polytetrafluoroethylene-based mixtures include optionally substituted (meth)acrylate derivatives. Specifically, the acrylic monomer is substituted with one or more groups 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 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 Examples include maleimides optionally substituted by acrylates, alkyl groups having 1 to 6 carbon atoms, or aryl groups, such as maleimide, N-methyl-maleimide and N-phenyl-maleimide, maleic acid, phthalic acid and itaconic acid. but not limited to these. 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 units contained in the organic polymer is preferably 8 to 11 parts by weight, more preferably 8 to 10 parts by weight, and still more preferably 100 parts by weight of the styrene-based monomer-derived units. 8 to 9 parts by weight. If the acrylic monomer-derived unit is less than 8 parts by weight, the coating strength may be lowered, and if it is more than 11 parts by weight, the surface appearance of the molded article may be deteriorated.

The polytetrafluoroethylene-based mixture of the present invention 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 to 0.4% by weight. 3% by weight. If the residual water content is more than 0.5% by weight, it may adversely affect flame retardancy.

In the process for producing the polytetrafluoroethylene-based mixture of the present invention, a coating layer containing one or more monomers selected from the group consisting of styrene-based monomers and acrylic monomers in the presence of an initiator outside the branched polytetrafluoroethylene. Further, after the step of forming the coating layer, drying is performed so that the remaining moisture content is 0.5 wt% or less, preferably 0.2 to 0.4 wt%, more preferably 0.1 to 0.3 wt%. It preferably includes steps. The drying step can be performed using methods known in the art such as, for example, hot air drying or vacuum drying methods.

The initiator used for the polytetrafluoroethylene-based mixture of the present invention can be used without 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. One or more of the above initiators may be used in the polytetrafluoroethylene-based mixture of the present invention, depending on the 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 0.15 to 0.15 based on the amount of the total composition. It is preferred to use 25 parts by weight.

The polytetrafluoroethylene-based mixture of the present invention was produced by the suspension polymerization method according to the following procedure.

First, water and branched polytetrafluoroethylene dispersion (solid concentration: 60%, polytetrafluoroethylene particle size: 0.15 to 0.3 μm) were placed in a reactor, and then acrylic monomers and styrene were mixed with stirring. Cumene hydroperoxide was added as a monomer and a water-soluble initiator, and the reaction was carried out at 80 to 90° C. for 9 hours. After completion of the reaction, centrifugation was performed for 30 minutes in a centrifuge to remove moisture and obtain a paste-like product. After that, the product paste was dried in a hot air dryer at 80 to 100° C. for 8 hours. Thereafter, the dried product was pulverized to obtain the polytetrafluoroethylene-based mixture of the present invention.

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, and thus does not require an emulsifier and electrolytic salts for coagulating and precipitating latex after polymerization. In addition, in a polytetrafluoroethylene mixture produced by an emulsion polymerization method, the emulsifier and electrolyte salts in the mixture are easily mixed and difficult to remove, so sodium metal ions and potassium metal ions derived from such emulsifiers and electrolyte salts are reduced. It is difficult. Since the polytetrafluoroethylene-based mixture (component B) used in the present invention is produced by a suspension polymerization method, such emulsifiers and electrolyte salts are not used, so sodium metal ions and potassium metal ions in the mixture can be reduced, and thermal stability and hydrolysis resistance can be improved.

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

The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. If the contained polytetrafluoroethylene is not branched polytetrafluoroethylene, the anti-dripping effect will be insufficient when the amount of polytetrafluoroethylene added is small. The branched polytetrafluoroethylene is particulate and preferably has a particle size of 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, still more preferably 0.3 to 0.4 μm. When the particle size is smaller than 0.1 μm, the surface appearance of molded articles is excellent, but it is difficult to commercially obtain polytetrafluoroethylene having a particle size smaller than 0.1 μm. Also, if the particle size is larger than 0.6 μm, the surface appearance of the molded product may deteriorate. The polytetrafluoroethylene used in the present invention preferably has a number average molecular weight of 1×10 ⁴ to 1×10 ⁷ , more preferably 2×10 ⁶ to 9×10 ⁶ . Fluoroethylene is more preferred in terms of stability. Either powder or dispersion form can be used.

The content of the branched polytetrafluoroethylene in the coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, and still more preferably 47 to 60 parts by weight with respect to 100 parts by weight of the total weight of the coated branched PTFE. 53 parts by weight, particularly preferably 48 to 52 parts by weight, most preferably 49 to 51 parts by weight. When the proportion of branched polytetrafluoroethylene is within this range, good dispersibility of branched polytetrafluoroethylene can be achieved.

The content of component D is 0.1 to 3 parts by weight, preferably 0.15 to 2 parts by weight, more preferably 0.5 to 1.5 parts by weight, with respect to the total 100 parts by weight of components A and B. Department. If it exceeds this range, the cost will increase and the extrusion processability will be insufficient. On the other hand, if it is less than this range, the flame retardancy will be insufficient and the tensile strength will also decrease. The ratio of component D indicates the net amount of anti-dripping agent, and in the case of mixed PTFE, indicates the net amount of PTFE.

(E component: glass fiber and/or carbon fiber)
The glass fiber used as the component E in the present invention is a glass fiber having a round cross section, an average value of the major diameter of the long cross section of the fiber of 10 to 50 μm, and an average value of the ratio of the major diameter to the minor diameter (long diameter / minor diameter). Flat cross-section glass fibers and glass milled fibers having a diameter of 1.5 to 8 are preferable examples, but in particular, the average value of the major diameter of the fiber long cross section is 10 to 50 μm, and the ratio of the major diameter to the minor diameter (long diameter/short diameter) is 10 to 50 μm. A flat cross-section glass fiber having an average value of 1.5 to 8 is more preferable in terms of tensile strength and dimensional accuracy. The average value of the fiber length cross section of the flat cross-section glass fiber is preferably 15 to 40 μm, more preferably 15 to 35 μm. Also, the average value of the ratio of the major axis to the minor axis (major axis/minor axis) is preferably 2-6, more preferably 2-5. The flat cross-sectional shape includes not only flat but also non-circular cross-sectional shapes such as elliptical, cocoon-shaped, trefoil, or similar shapes. Among them, improvement in mechanical strength and low anisotropy Therefore, a flat shape is preferable.

The glass composition of the glass fiber is not particularly limited, and various glass compositions represented by A glass, C glass, E glass, and the like are applied. Such glass fibers may contain components such as TiO ₂ , SO ₃ and P ₂ O ₅ as necessary. Among these, E glass (alkali-free glass) is more preferable. Such glass fibers are preferably surface-treated with a known surface treatment agent such as a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like, from the viewpoint of improving mechanical strength. In addition, it is preferable to use olefin-based resin, styrene-based resin, acrylic-based resin, polyester-based resin, epoxy-based resin, urethane-based resin, or the like for convergence treatment. Especially preferred. The amount of the sizing agent attached to the sizing-treated glass fibers is preferably 0.1 to 3% by weight, more preferably 0.2 to 1% by weight, based on 100% by weight of the glass fibers.

Examples of carbon fibers used as the E component in the present invention include carbon fibers such as metal-coated carbon fibers, carbon milled fibers, vapor-grown carbon fibers, and carbon nanotubes. Carbon nanotubes have a fiber diameter of 0.003 to 0.1 μm and may be single-walled, double-walled or multi-walled, with multi-walled (so-called MWCNT) being preferred. Among these, carbon fiber is preferable in terms of excellent mechanical strength.

Any of cellulose-based, polyacrylonitrile-based, and pitch-based carbon fibers can be used as the carbon fiber. Alternatively, it can be obtained by spinning or molding a raw material composition consisting of a solvent and a polymer of aromatic sulfonic acids or their salts or a methyle type bond, followed by carbonization or the like, and spinning without an infusibilization step. It is also possible to use the Furthermore, general-purpose type, medium modulus type, and high modulus type can all be used. Among these, a polyacrylonitrile-based high elastic modulus type is particularly preferable.

In addition, the surface of the carbon fiber is preferably oxidized for the purpose of enhancing adhesion to the matrix resin and improving mechanical strength. Although the oxidation treatment method is not particularly limited, for example, (1) a method of treating carbon fibers with an acid or alkali or a salt thereof, or an oxidizing gas; Preferable examples include a method of firing at a temperature of 700° C. or higher in the presence of an inert gas containing a compound, and (3) a method of subjecting carbon fibers to oxidation treatment followed by heat treatment in the presence of an inert gas.

A metal-coated carbon fiber is obtained by coating the surface of a carbon fiber with a metal layer. Examples of metals include silver, copper, nickel, and aluminum, and nickel is preferred from the viewpoint of corrosion resistance of the metal layer. Methods of metal coating include known methods such as plating and vapor deposition, among which plating is preferably used. Also in the case of such a metal-coated carbon fiber, the carbon fiber mentioned above can be used as the original carbon fiber. The thickness of the metal coating layer is preferably 0.1-1 μm, more preferably 0.15-0.5 μm. More preferably, it is 0.2 to 0.35 μm.

Such carbon fibers and metal-coated carbon fibers are preferably bundled with olefin-based resin, styrene-based resin, acrylic-based resin, polyester-based resin, epoxy-based resin, urethane-based resin, or the like. In particular, carbon fibers treated with urethane-based resins and epoxy-based resins are suitable in the present invention because of their excellent mechanical strength.

The content of component E is 25 to 150 parts by weight, preferably 30 to 140 parts by weight, and more preferably 40 to 120 parts by weight, per 100 parts by weight of components A and B combined. If the content of component E is less than 25 parts by weight, the improvement in tensile strength will be insufficient, and the mold shrinkage rate will increase, resulting in poor dimensional accuracy. On the other hand, if it exceeds 150 parts by weight, the strength and flame retardancy are lowered.

(F component: phenoxy resin and epoxy resin)
Examples of the phenoxy resin used as the F component in the present invention include phenoxy resins represented by the following general formula (15).

(Wherein, X is at least one group selected from the group consisting of groups represented by the following general formula (16), Y is a hydrogen atom or a residue of a compound that reacts with a hydroxyl group, n is an integer of 0 or more .)

(In the formula, Ph represents a phenyl group.)
In the general formula (16), examples of the compound that reacts with a hydroxyl group include esters, carbonates, compounds having an epoxy group, carboxylic acid anhydrides, acid halides, compounds having an isocyanate group, and the like. As, intramolecular esters are particularly preferable, and examples thereof include caprolactone and the like. A compound in which Y is a hydrogen atom in the phenoxy resin represented by the general formula (15) can be easily produced from dihydric phenols and epichlorohydrin. In addition, a compound in which Y is a residue of a compound that reacts with a hydroxyl group can be easily produced by mixing under heating a phenoxy resin produced from a dihydric phenol and epichlorohydrin and the compound that reacts with the hydroxyl group. can be done.

Examples of epoxy resins used as the F component in the present invention include epoxy resins represented by the following general formula (17).

(Wherein, X and n are the same as in formula (15).)
The epoxy resin represented by the general formula (17) can be easily produced from dihydric phenols and epichlorohydrin. Examples of dihydric phenols include bisphenol A type epoxy resins such as 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], 1,1-bis(4-hydroxyphenyl)ethane or 4,4'-dihydroxy Biphenyl and the like are used.

A commercial item can also be used as a phenoxy resin and an epoxy resin. Commercially available phenoxy resins (bisphenol A type) include PKHB (manufactured by Gabriel Phenoxies, Mw = 32,000), PKHH (manufactured by Gabriel Phenoxies, Mw = 52,000), PKFE (manufactured by Gabriel Phenoxies, Mw = 60,000) and the like. Commercially available epoxy resins (bisphenol A type) include jER1256 (manufactured by Mitsubishi Chemical Corporation, Mw=50,000).

Although the weight average molecular weight of the phenoxy resin and epoxy resin is not particularly limited, it is usually 5,000 to 100,000, preferably 8,000 to 80,000, more preferably 10,000 to 50,000. be. weight average molecular weight of 5,000 to 100,
000, the mechanical properties are particularly good.

The content of component F is 0.1 to 8 parts by weight, preferably 1 to 7 parts by weight, and more preferably 3 to 6 parts by weight, per 100 parts by weight of components A and B combined. If the content exceeds the above range and is too small, the tensile strength will be low. On the other hand, when the content exceeds the above range, the flame retardancy is deteriorated and the tensile strength is lowered.

(G component: phosphorus stabilizer)
In the present invention, in order to more effectively exhibit the effect of improving mechanical properties by fiberizing the liquid crystalline polyester resin of the component B during injection molding, it is efficient if the liquid crystalline polyester resin is previously microdispersed in the matrix phase. . Therefore, it is necessary to add a phosphorus-based stabilizer, which is the G component, as a dispersing aid for microdispersing the liquid crystalline polyester resin in the matrix phase. Phosphate compounds having a molecular weight of less than 300 are preferred as phosphorus-based stabilizers. If the molecular weight is 300 or more, the dispersion in the resin becomes poor, and the effect as a stabilizer may decrease. A specific example is trimethyl phosphate. Esters of phosphorous acid are also preferred, specifically tetrakis(2,4-di-t-butylphenyl)-4,4′-biphenylenephosphonite, bis(2,6-di-t-butyl-4 -methylphenyl)pentaerythritol-diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol-diphosphite, tris(2,4-di-t-butylphenyl)phosphite and the like. be. These phosphorus stabilizers may be added alone or in combination. The content of the G component is 0.01 to 3 parts by weight, preferably 0.01 to 1 part by weight, and 0.02 to 0.1 part by weight, based on 100 parts by weight of the total of the A component and the B component. is more preferred. If the content of the G component exceeds 3 parts by weight, a large amount of volatile gas is generated during extrusion processing, and mold deposits occur during molding even when pelletized. Moreover, it tends to be disadvantageous in terms of cost. If the amount is less than 0.01 parts by weight, the tensile strength peculiar to this composition is not exhibited.

(About other additives)
The resin composition of the present invention may further contain other thermoplastic resins (eg, polyarylate resins, fluororesins, polyester resins, etc.), antioxidants (eg, hinder Dophenol compounds, etc.), impact modifiers, UV absorbers, light stabilizers, release agents, lubricants, colorants, inorganic fillers (talc, mica, wollastonite, kaolin, etc.), etc. can.

Any method may be employed to produce the resin composition of the present invention. For example, a method of premixing each component and optionally other components, followed by melt-kneading and pelletizing can be mentioned. Means for premixing include a Nauta mixer, a V-type blender, a Henschel mixer, a mechanochemical device, an extrusion mixer, and the like. In the pre-mixing, granulation can be performed by an extrusion granulator, a briquetting machine, or the like. After pre-mixing, the mixture is melt-kneaded by a melt-kneader typified by a vented twin-screw extruder, and pelletized by a device such as a pelletizer. Other examples of the melt-kneader include a Banbury mixer, a kneading roll, a constant temperature stirring vessel and the like, but a vented twin-screw extruder is preferred. Alternatively, each component and, optionally, other components may be supplied independently to a melt-kneader typified by a twin-screw extruder without being premixed.

The polycarbonate resin composition of the present invention obtained as described above can be used to produce various products by injection molding the pellets produced as described above. Further, it is also possible to directly form sheets, films, profile extrusion moldings, direct blow moldings, and injection moldings from resins melted and kneaded in an extruder without going through pellets.

In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluid), insert molding, Molded articles can be obtained using injection molding methods such as in-mold coating molding, adiabatic molding, rapid heat and cool molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known. For molding, either cold runner method or hot runner method can be selected. Further, the polycarbonate resin composition of the present invention can also be molded into various profile extrudates and sheets by extrusion molding.

Examples of molded articles using the resin composition of the present invention include electric and electronic parts such as connectors, sockets, relay parts, coil bobbins, optical pickups, oscillators, printed wiring boards, and computer-related parts; IC trays and wafers. Components related to the semiconductor manufacturing process such as carriers; Computers, VTRs, TVs, irons, air conditioners, stereos, vacuum cleaners, refrigerators, rice cookers, lighting fixtures and other household electrical appliance components and housing materials; Lamp reflectors, lamp holders and other lighting fixtures Parts: Audio product parts such as compact discs, laser discs (registered trademark) and speakers; Ferrules for optical cables, telephone parts, facsimile parts, communication equipment parts such as modems; Copier related parts such as separation claws and heater holders; Machine parts such as fans, gears, gears, bearings, motor parts and cases; Automobile parts such as mechanical parts for automobiles, engine parts, parts in the engine room, electrical parts, interior parts; Cooking utensils; Heat insulation and soundproofing materials such as flooring and wall materials; Supporting materials such as beams and columns; Building materials such as roofing materials; Parts, marine facility parts, cleaning jigs, optical equipment parts, valves, pipes, nozzles, filters, membranes, medical equipment parts and medical materials, sensor parts, sanitary equipment, sporting goods, leisure goods etc.

The polycarbonate resin composition of the present invention is excellent in tensile strength, dimensional accuracy and flame retardancy. Since these characteristics are not found in the prior art, the industrial effects of the present invention are extremely large.

The present inventors consider the best mode of the invention to be a summary of the preferred ranges of the above requirements, and representative examples thereof are described in the following examples, for example. Of course, the present invention is not limited to these forms.

The present invention will be further described with reference to the following examples. In addition, evaluation was implemented by the following method.
(Evaluation of polycarbonate resin composition)
(i) Tensile strength: Tensile strength was measured using a tensile test piece (dumbbell-shaped No. 3 according to JIS K6251: thickness 2 mm) obtained by the following method. (Tension speed: 5 mm/min, test temperature: 23°C)
(ii) Mold shrinkage rate: After leaving a square plate of width 50 mm × length 100 mm × thickness 2 mm obtained by the following method in an atmosphere of 23 ° C. and a relative humidity of 50% for 24 hours, the dimensions of the square plate are measured three-dimensionally. The molding shrinkage rate was calculated by measuring with a machine (manufactured by Mitutoyo Co., Ltd.). The molded article was molded using a mold cavity with a film gate at one longitudinal end. Therefore, the length direction is the machine direction, and the width direction is the direction perpendicular to the machine direction.
(iii) Flame retardancy: A V test (vertical burning test) at a thickness of 0.8 mm was carried out according to UL94 using a UL test piece obtained by the following method.
(iv) Extrusion processability: Stability during extrusion was evaluated according to the following criteria.
Strands are stable during extrusion. : O Strands during extrusion are somewhat unstable, but pelletization is possible. : △
Strands during extrusion are fairly unstable. Pelletization is difficult or there are many volatile gases. : ×

[Examples 1 to 12, Comparative Examples 1 to 12]
A mixture of components other than component E having the composition shown in Tables 1 and 2 was supplied from the first supply port of the extruder. Such a mixture was obtained by mixing in a V-blender. The E component was supplied using a side feeder from the second supply port. For extrusion, a vented twin-screw extruder (Japan Steel Works, Ltd. TEX30α-38.5BW-3V) with a diameter of 30 mm was used, and the screw rotation speed was 200 r.p.m. p. m. , a discharge rate of 25 kg/h and a vent vacuum degree of 3 kPa to obtain pellets. The extrusion temperature was 300° C. from the first supply port to the die.

A portion of the obtained pellets was dried at 120°C for 6 hours in a hot air circulating dryer, and then molded into a tensile test piece with a thickness of 2 mm at a cylinder temperature of 300°C and a mold temperature of 80°C using an injection molding machine. (JIS K6251 Dumbbell-shaped No. 3 type), test pieces for mold shrinkage measurement and UL test pieces were molded.

In addition, each component of symbol notation in Table 1 and Table 2 is as follows.
(A component)
A-1: Aromatic polycarbonate resin (Polycarbonate resin powder with a viscosity average molecular weight of 22,400 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WP (product name) manufactured by Teijin Limited)
A-2: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity average molecular weight of 19,700 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WX (product name) manufactured by Teijin Limited)
A-3: Aromatic polycarbonate resin (Polycarbonate resin powder with a viscosity average molecular weight of 16,000 made from bisphenol A and phosgene by a conventional method, Panlite CM-1000 (product name) manufactured by Teijin Limited)
A-4: PC-PDMS-1: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS content 4.2%, PDMS polymerization degree 37)
(B component)
B-1: liquid crystal polyester resin (liquid crystal polyester resin pellets containing repeating units derived from p-hydroxybenzoic acid and repeating units derived from 6-hydroxy-2-naphthoic acid, LAPEROS manufactured by Polyplastics Co., Ltd. A-950RX (product name)) Melting point = 275-285°C
(C component)
C-1: Phosphate ester containing resolnol [di(2,6-dimethylphenyl)phosphate] as a main component (PX-200 (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.)
C-2: Perfluorobutanesulfonic acid potassium salt (manufactured by DIC Corporation Megafac F-114P (trade name))
(D component)
D-1: anti-drip agent (polytetrafluoroethylene (manufactured by Daikin Industries, Ltd. Polyflon MPA FA-500H (trade name))
(E component)
E-1: Glass fiber: Flat cross-section chopped glass fiber (manufactured by Nitto Boseki Co., Ltd.: CSG 3PA-830 (trade name), major axis 28 μm, minor axis 7 μm, cut length 3 mm, epoxy sizing agent)
E-2: Glass fiber: Chopped glass fiber with circular cross section (manufactured by Nippon Electric Glass Co., Ltd.: T-120H (trade name), diameter: 10.5 μm, cut length: 3 mm, epoxy sizing agent)
E-3: Carbon fiber: PAN-based carbon fiber (HTC205 (trade name) manufactured by Teijin Limited, epoxy sizing agent 5.3 parts by weight, cut length 6 mm, fiber diameter 7 μm)
E-4: Glass fiber: Flat cross-section chopped glass fiber (manufactured by Nitto Boseki Co., Ltd.: CSG 3PL-830 (product name), major axis 20 μm, minor axis 10 μm, cut length 3 mm, epoxy sizing agent)
(F component)
F-1: Bisphenol A type phenoxy resin (PKHH (trade name) manufactured by Gabriel Phenoxies, weight average molecular weight 52,000)
F-2: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER-1256 (trade name), weight average molecular weight 50,000)
(G component)
G-1: Phosphorus-based stabilizer (trimethyl phosphate (TMP) manufactured by Daihachi Chemical Industry Co., Ltd.)
(other ingredients)
Talc: Victorilite TK-RC (manufactured by Katsumitsuyama Mining Co., Ltd.), talc with an average particle size (D50) of 4.7 μm measured by a laser diffraction/scattering method, with a bulk density of 0.7 to 0.8 g/cm Talc degassed and compressed to ³ , brightness: 92%, Ig. Loss (ignition loss ratio: compliant with JIS M8855): 5.83%, pH = 9.5)
Release agent: Licowax E powder (manufactured by Clariant Japan Co., Ltd., Montan acid ester wax)
Colorant: 40 parts by weight of carbon black (manufactured by Mitsubishi Chemical Corporation: carbon black MA-100 (trade name)), 3 parts by weight of white mineral oil (manufactured by Exxon Mobil: Primol N382 (trade name)), 0 2 parts by weight of Montan acid ester wax (manufactured by Clariant Japan Co., Ltd.: Licowax E powder (trade name)) and 56.8 parts by weight of bisphenol A type polycarbonate resin (manufactured by Teijin Limited: CM-1000 (trade name) Carbon black master pellets produced by melt mixing 100 parts by weight of four components (name) and viscosity-average molecular weight of 16,000) using a twin-screw extruder.

From Tables 1 and 2 above, it can be seen that the compounding of the present invention provides a polycarbonate resin composition having high tensile strength, less anisotropy in mold shrinkage, high dimensional accuracy, and excellent flame retardancy. .

Claims (5)

A group consisting of (C) an organic phosphorus flame retardant and an organic metal salt flame retardant per 100 parts by weight of a component consisting of (A) an aromatic polycarbonate resin (component A) and (B) a liquid crystal polyester resin (component B) At least one flame retardant (C component) selected from 0.01 to 40 parts by weight, (D) polytetrafluoroethylene (D component) 0.1 to 3 parts by weight, (E) glass fiber and / or carbon fiber (Component E) 25 to 150 parts by weight, (F) bisphenol A type phenoxy resin and/or bisphenol A type epoxy resin (Component F) 0.1 to 8 parts by weight, and (G) phosphate compound (Component G) 0.01 A polycarbonate resin composition containing up to 3 parts by weight and having a weight ratio [(A)/(B)] of component A to component B of 98/2 to 60/40. 2. The polycarbonate resin composition according to claim 1, wherein component A has a viscosity average molecular weight of 1.7×10 ⁴ to 2.1×10 ⁴ . 3. The polycarbonate resin composition according to claim 1, wherein component B is a liquid crystalline polyester resin containing repeating units derived from p-hydroxybenzoic acid and repeating units derived from 6-hydroxy-2-naphthoic acid. . Component E is a flat cross-section glass fiber having an average long diameter of 10 to 50 μm in cross section and an average ratio of long diameter to short diameter (long diameter/short diameter) of 1.5 to 8. 4. The polycarbonate resin composition according to any one of 3. A molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 4 .