KR20120092129A

KR20120092129A - Polycarbonate resin composition

Info

Publication number: KR20120092129A
Application number: KR1020127012532A
Authority: KR
Inventors: 노리타다 다케우치; 세이이치 젬바
Original assignee: 이데미쓰 고산 가부시키가이샤
Priority date: 2009-11-20
Filing date: 2010-11-11
Publication date: 2012-08-20
Also published as: WO2011062105A1; JP5654744B2; TWI490269B; JP2011105914A; TW201124469A; CN102612542A

Abstract

The present invention relates to 100 parts by mass of an aromatic polycarbonate resin containing (A) a polycarbonate-polyorganosiloxane copolymer. 100 parts by mass, (C) polytetrafluoroethylene 1? 10 parts by mass and (D) an organic alkali metal salt and / or an organic alkaline earth metal salt of 0.05? A polycarbonate resin composition excellent in flame retardancy (particularly thin flame retardancy), thermal conductivity, and impact properties without using a chlorine flame retardant, bromine flame retardant, and phosphorus flame retardant, which is blended in 1 part by mass, and a molded article comprising the same.

Description

Polycarbonate resin composition {POLYCARBONATE RESIN COMPOSITION}

The present invention relates to a polycarbonate resin composition and a molded article made of the resin composition, wherein the polycarbonate resin composition has excellent flame retardancy (particularly thin flame retardancy), thermal conductivity, and impact properties without using a chlorine flame retardant, bromine flame retardant, and phosphorus flame retardant. It is related with the molded object which consists of it.

In product development in the field of electric and electronics, we focus on heat dissipation measures with high pixel size and high speed processing in digital cameras and digital video cameras, miniaturization of projectors, high speed processing in PCs and mobile devices, and LED lighting of various light sources. Is laid.

The countermeasure for constituting a heat dissipation circuit with a metal part is also taken, but since the heat dissipation circuit becomes complicated in a miniaturized device, it is excellent in thermal conductivity, which can integrate the resin casing and the heat dissipation circuit, and also has excellent mechanical strength as a casing. Material is required.

Moreover, in a small electronic device, thickness reduction is also requested | required also in a casing and a chassis, and also flame-retardance in a thin molded object is also requested | required with it.

Polycarbonate resins are widely used in casings of electronic devices. In order to flame-retard molded articles made of polycarbonate resin compositions, it is known to add halogen flame retardants such as chlorine flame retardants and bromine flame retardants. However, in recent years, in view of the safety and the impact on the environment during disposal and incineration, a flame retardant method using a halogen-free flame retardant has been required in the market. As such a non-halogen flame retardant, it is necessary to mix | blend an organic phosphorus flame retardant, especially an organic phosphate ester compound with a polycarbonate resin composition, and to comprise a comparatively large amount of a phosphate ester compound in order to flame-retard. Since the polycarbonate resin has a high molding temperature and a high melt viscosity, the molding temperature tends to be high. For this reason, although a phosphate ester compound generally contributes to a flame retardance, it may not necessarily be sufficient in the molding environment and molded article appearance, such as mold corrosion and gas generation at the time of shaping | molding process.

Therefore, it is required to find a polycarbonate resin composition which is excellent in thermal conductivity while achieving flame retardancy (particularly thin flame retardancy) in a required molded body without using halogen flame retardants such as chlorine flame retardants and bromine flame retardants or phosphorus flame retardants. have.

It is known to mix | blend graphite as a means of providing the said heat dissipation property to a thermoplastic resin (refer patent document 1, patent document 2). Although patent document 1 mix | blends specific graphite with a thermoplastic resin, it is disclosed that the thermoplastic resin composition which has little metal corrosiveness and is excellent in thermal conductivity is obtained, In order to improve flame retardance, organic halogen, such as a halogenated carbonate oligomer and a halogenated epoxy compound, is disclosed. It is described that it is preferable to use a flame retardant or a phosphate ester flame retardant, and does not disclose the technique which does not use a chlorine flame retardant, a bromine flame retardant, and a phosphorus flame retardant.

In addition, Patent Document 2 relates to a heat dissipation casing in which a heating element is housed. There is no description of flame retardancy required for casings such as electronic devices, and as an additive to be blended as necessary, a flame retardant such as an organic bromine flame retardant or a phosphorus flame retardant is used. Although it discloses, it does not disclose the technique which does not actively use a chlorine flame retardant, a bromine flame retardant, and a phosphorus flame retardant, and since it does not add a flame retardant and an anti-drip agent in the Example, it is thought that it does not have sufficient flame retardance.

Moreover, the polycarbonate resin composition which mix | blended graphite and mix | blended the flame retardant in order to provide antistatic property and electroconductivity to polycarbonate resin is known (refer patent document 3, patent document 4). Patent Document 3 discloses an aromatic polycarbonate resin composition containing a specific silicone compound in a compound composed of an aromatic polycarbonate resin and graphite, and has been evaluated for flame retardancy along with antistatic properties, but is required for casings such as electronic devices. There is no description of the technical content that sufficient flame retardancy is obtained by thinning about 1.5 mm. In addition, Patent Literature 4 discloses a flame retardant resin composition comprising a polycarbonate resin, graphite, and an organic alkali sulfonic acid (sat) metal salt as a technique that does not actively use a chlorine flame retardant, a bromine flame retardant, and a phosphorus flame retardant. Only evaluation in the molded object of thickness 2.5mm is made | formed, and similar to patent document 3, sufficient flame retardance is not obtained by the thickness of about 1.5 mm required for casings, such as an electronic device.

Japanese Unexamined Patent Publication No. 2007-31611 Japanese Laid-Open Patent Publication No. 2008-31358 Japanese Unexamined Patent Publication No. 2007-126499 Japanese Laid-Open Patent Publication No. 2006-273931

The present invention is excellent in flame retardancy (thickness 1.2 to 1.0 mm, hereinafter referred to as "thin flame retardance") in a thin molded article without using a chlorine flame retardant, bromine flame retardant, and phosphorus flame retardant, and excellent in impact properties having high thermal conductivity. It is an object to provide a resin composition and a molded article.

As a result of intensive studies, the inventors have found that aromatic polycarbonate resins, graphite, polytetrafluoroethylene, and organic alkali metal salts and / or organic alkaline earth metal salts containing polycarbonate-polyorganosiloxane copolymers in specific proportions. By blending, it was found that a polycarbonate resin composition excellent in thin flame retardancy and further excellent in thermal conductivity and impact characteristics was obtained and completed the present invention.

That is, the present invention,

(1) To (A) 100 parts by mass of the aromatic polycarbonate resin containing the polycarbonate-polyorganosiloxane copolymer, (B) graphite 30? 100 parts by mass, (C) polytetrafluoroethylene 1? 10 parts by mass and (D) an organic alkali metal salt and / or an organic alkaline earth metal salt of 0.05? Polycarbonate resin composition which mix | blends 1 mass part,

(2) Content of polyorganosiloxane in (A) is 1? The polycarbonate resin composition as described in said (1) which is 6 mass%,

(3) The polycarbonate resin composition according to the above (1) or (2), wherein the polyorganosiloxane of the aromatic polycarbonate-polyorganosiloxane copolymer is polydimethylsiloxane,

(4) Said (1) whose graphite is natural graphite? The polycarbonate resin composition according to any one of (3),

(5) Said (1) whose graphite is artificial graphite? The polycarbonate resin composition according to any one of (3),

(6) The above (1), wherein the organic alkali metal salt and / or organic alkaline earth metal salt is at least one member selected from organic sulfonic acid alkali metal salts, organic sulfonic acid alkaline earth metal salts, polystyrene sulfonic acid alkali metal salts and polystyrene sulfonic acid alkaline earth metal salts. The polycarbonate resin composition according to any one of (5),

(7) above (1)? A molded article made of the polycarbonate resin composition according to any one of (6),

(8) The molded article according to the above (7), which is a component for an electric and electronic device,

(9) The molded article according to the above (7), which is a casing for an electric and electronic device,

(10) The molded article according to (7), which is a chassis for electrical and electronic equipment.

To provide.

According to the present invention, the polycarbonate is excellent in thin flame retardancy, impact characteristics, and thermal conductivity without inhibiting the inherent mechanical properties of the polycarbonate, and the decrease in molecular weight at the time of granulation is suppressed to increase the strength of the product. A maintainable resin composition can be obtained.

Hereinafter, the present invention will be described in detail.

The polycarbonate resin (hereinafter may be abbreviated as "PC resin") of the present invention is composed of (A) aromatic polycarbonate resin, (B) graphite, (C) polytetrafluoroethylene, and (D) organic A polycarbonate resin composition having an alkali metal salt and / or an organic alkaline earth metal salt as an essential component.

As (A) aromatic polycarbonate resin in this invention, the aromatic containing (A-1) polycarbonate polyorganosiloxane copolymer (Hereinafter, abbreviate as "PC-POS copolymer".) Polycarbonate resin is used.

Specifically, (A-1) PC-POS copolymer alone or (A-2) aromatic polycarbonate resin (hereinafter referred to as "generic PC resin") produced by reaction of a dihydric phenol and a carbonate precursor May be abbreviated). The content of the PC-POS copolymer is 10? Aromatic polycarbonate resin which is 100 mass% is used preferably.

General PC resin which is (A-2) component in (A) component does not have a restriction | limiting in particular in the manufacturing method, The thing manufactured by the conventional various methods can be used. For example, interfacial polycondensation of divalent phenol and carbonate precursors produced by solution method (interface polycondensation method) or melting method (ester exchange method), i.e., divalent phenol and phosgene in the presence of end terminators In the presence of a legal method or a terminal terminator, the thing manufactured by making it react by transesterification methods, such as a bivalent phenol and diphenyl carbonate, can be used.

Various examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane and 1,1-bis (4-hydroxy). Phenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4- Hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide and bis (4-hydroxyphenyl) ketone Can be. In addition, hydroquinone, resorcin, catechol, etc. can be mentioned. Although these may be used independently, respectively and may be used in combination of 2 or more type, Among these, it is preferable that it is a bis (hydroxyphenyl) alkane type, and bisphenol A is especially preferable.

On the other hand, as a carbonate precursor, they are carbonyl halide, carbonyl ester, haloformate, etc., specifically, phosgene, the dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate, etc.

Moreover, this general PC resin may have a branched structure, and as a branching agent, 1,1,1-tris (4-hydroxyphenyl) ethane, (alpha), (alpha), (alpha)-tris (4-hydroxyphenyl) ) -1,3,5-triisopropylbenzene, phloroglucine, trimellitic acid and isatinbis (o-cresol).

In the present invention, the viscosity average molecular weight of the general PC resin used as the component (A-2) is usually 10,000? 50,000, preferably 13,000? 35,000, more preferably 15,000? 20,000.

This viscosity average molecular weight (Mv) measures the viscosity of the methylene chloride solution in 20 degreeC using a ubelide-type viscometer, and calculates an intrinsic viscosity [(eta)] from this, and calculates it by following Formula.

[Η] = 1.23 × 10 ^-5 Mv ^0.83

In the aromatic polycarbonate resin of the said (A) component, (A-1) PC-POS copolymer consists of a polycarbonate part and a polyorganosiloxane part, For example, the polycarbonate which comprises the polycarbonate part manufactured previously Polyorgano which has reactive groups, such as an o-allylphenol residue, a p-hydroxy styrene residue, an eugenol residue, in the terminal which comprises an oligomer (henceforth a PC oligomer), and a polyorganosiloxane part (segment). The siloxane is dissolved in a solvent such as methylene chloride, chlorobenzene, chloroform, and a caustic aqueous alkali solution of dihydric phenol is added, and a tertiary amine (such as triethylamine) or a quaternary ammonium salt (trimethylbenzyl ammonium chloride) is used as a catalyst. Etc.) can be produced by interfacial polycondensation reaction in the presence of a terminal terminator.

The PC oligomer used for manufacture of this PC-POS copolymer is made to react the above-mentioned dihydric phenol and carbonate precursors, such as phosgene, in solvents, such as methylene chloride, or a dihydric phenol and a carbonate compound, for example For example, it can be easily manufactured by reacting a carbonate precursor such as diphenyl carbonate.

Examples of the carbonate ester compound include diaryl carbonates such as diphenyl carbonate, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

The PC oligomer provided for manufacture of a PC-POS copolymer may be a homo oligomer using the 1 type of dihydric phenol mentioned above, and may be a co oligomer using 2 or more types. Moreover, the thermoplastic random branched oligomer obtained by using a polyfunctional aromatic compound together with the said bivalent phenol may be sufficient.

In that case, as a branching agent (polyfunctional aromatic compound), 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ', α'-tris (4-hydroxyphenyl) -1,3 , 5-triisopropylbenzene, 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4′-hydroxyphenyl) ethyl] benzene , Phloroglucin, trimellitic acid, isatinbis (o-cresol) and the like can be used.

This PC-POS copolymer is Unexamined-Japanese-Patent No. 3-292359, Unexamined-Japanese-Patent No. 4-202465, Unexamined-Japanese-Patent No. 8-81620, and Unexamined-Japanese-Patent No. 8-302178, for example. And JP-A-10-7897.

As said PC-POS copolymer, the degree of polymerization of a polycarbonate part is 3? 100 degree, the degree of polymerization of the polyorganosiloxane portion is 2? It is preferably used that is about 500

In addition, content in the whole (A) component of the polyorganosiloxane part in the said PC-POS copolymer is 1 from a viewpoint of the flame retardance provision effect, impact resistance provision effect, and economical balance with respect to the PC resin composition obtained, etc. ? It is preferable to set it as 6 mass%.

In addition, the viscosity average molecular weight (Mv) of the said PC-POS copolymer is 5,000? 100,000, preferably 10,000? 30,000, particularly preferably 12,000? 30,000. Here, these viscosity average molecular weights (Mv) can be calculated | required similarly to the said general PC resin.

As a polyorganosiloxane part in the said PC-POS copolymer, the segment which consists of polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, etc. is preferable, and a polydimethylsiloxane segment is especially preferable.

The use ratio of the (A-1) PC-POS copolymer and the general PC resin which is (A-2) component in (A) component is the whole (A) component of the polyorganosiloxane part in the said PC-POS copolymer Content in 1 is? The raw material molecular weight (viscosity average molecular weight) as the whole component (A) was 17,000? In the range of 30,000, preferably 18,000? It is desirable to adjust to 26,000.

For example, when using the PC-POS copolymer which has the polyorganosiloxane part of the high content exceeding 6 mass% with respect to content of a polyorganosiloxane part, it is low by using a large amount of general PC resin, and In the case of using a PC-POS copolymer, the content in the whole component is reduced by using no general PC resin or by using a small amount of general PC resin. It can adjust to 6 mass%.

Usually, the (A-1) PC-POS copolymer in the component (A) is 10? It is used within the range of 100 mass%. As for the ratio of a PC-POS copolymer, the impact strength of a molded object is easy to obtain many, and the molecular weight fall at the time of granulation is suppressed.

As a molecular weight regulator used as a molecular terminal group in the aromatic PC resin of the said (A) component, what is necessary is just what is normally used for superposition | polymerization of a polycarbonate, and various monovalent phenols can be used. Specifically, phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, bromophenol, tribromophenol, nonylphenol, etc. are mentioned, for example.

In the PC resin composition of the present invention, in addition to the aromatic PC resin and the PC-POS copolymer, esters such as bifunctional carboxylic acids such as terephthalic acid, or ester-forming derivatives thereof, within the range in which the object of the present invention is not impaired. Copolymerization resin, such as polyester-polycarbonate resin obtained by superposing | polymerizing polycarbonate in presence of a precursor, or other polycarbonate resin can be contained suitably.

(B) Graphite is mix | blended with the polycarbonate resin composition of this invention mainly in order to provide thermal conductivity.

As the graphite used in the present invention, both natural graphite and various artificial graphites can be used. As natural graphite, any of earthy graphite, impression graphite (Vein Graphite also called block graphite), and flaky graphite (Flake Graphite) can be used. In the natural graphite exemplified above, flaky graphite can be preferably used. By application of natural graphite, higher thermal conductivity and high modulus of elasticity can be obtained.

Artificial graphite is a method of artificially aligning micro graphite crystals in an irregular arrangement by heat treating amorphous carbon, and includes, in addition to artificial graphite used in general carbon materials, kishi graphite, decomposed graphite, pyrolytic graphite, and the like. Artificial graphite used for general carbon materials is usually produced by graphitization treatment using petroleum coke or coal-based pitch coke as a main raw material.

Such artificial graphite has lower elasticity and thermal conductivity than natural graphite, but has an advantage of being able to improve high weld strength.

The compounding quantity of (B) component is 30 to 30 mass parts of above-mentioned (A) component. It is necessary to set it as the range of 100 mass parts, Preferably it is 30? It is in the range of 70 parts by mass. If the blending amount is less than 30 parts by mass, sufficient thermal conductivity is hardly obtained, and if it exceeds 100 parts by mass, there is a problem that the impact strength tends to be lowered.

In the present invention, the particle size of the graphite has a cumulative diameter of 30% to 50%. The thing of 180 micrometers can be used preferably. The fixed carbon amount of the graphite is preferably 80% by weight or more, more preferably 90% by weight or more, even more preferably 98% by weight or more. Moreover, the volatile matter of graphite becomes like this. Preferably it is 3 weight% or less, More preferably, it is 1.5 weight% or less, More preferably, it is 1 weight% or less.

In order to increase the affinity with the thermoplastic resin as long as the surface of the graphite is not impaired the properties of the composition of the present invention, the surface treatment, for example, epoxy treatment, urethane treatment, silane coupling treatment, oxidation treatment, etc. You may carry out.

(C) polytetrafluoroethylene (PTFE) is mix | blended with the polycarbonate resin composition of this invention in order to improve thin flame retardance. This (C) component gives the resin composition of this invention a melt dripping prevention effect, and expresses the outstanding thin flame retardance.

It is preferable that (C) component has fibril formation ability. Here, "fibrill formation ability" refers to showing the tendency which resins couple | bond together and become fibrous by external action, such as a shear force. As (C) component of this invention, a polytetrafluoroethylene, a tetrafluoroethylene-type copolymer (for example, tetrafluoroethylene / hexafluoropropylene copolymer etc.) etc. are mentioned, for example. . Among these, polytetrafluoroethylene is preferable.

PTFE having fibril forming ability has a very high molecular weight and is a number average molecular weight determined from standard specific gravity, and is usually 500,000 or more, preferably 500,000? 15 million, more preferably 1 million? 10 million. Specifically, tetrafluoroethylene is used in an aqueous solvent in the presence of sodium, potassium or ammonium peroxy disulfide, Under pressure of 700 kPa, temperature 0? About 200 ° C, preferably 20? It can obtain by superposing | polymerizing at 100 degreeC.

In addition to the solid form, it is also possible to use an aqueous dispersion form, and those classified as Type 3 according to ASTM standards may be used. As a commercial item classified into this type 3, For example, "Teflon 6-J" [brand name, Mitsui Dupont Floro Chemical Co., Ltd. product], "Polyflon D-1", and "Polyflon F-103" [ Brand name, Daikin Industries Co., Ltd.] etc. are mentioned. Moreover, other than type 3, "Algoflon F5" (brand name, the product made by Solvay Solesis Co., Ltd.), and "polyflon MPAFA-100" (brand name, Daikin Industries Co., Ltd. product) etc. are mentioned.

The PTFE may be used alone or in combination of two or more thereof.

(C) The compounding quantity of polytetrafluoroethylene (PTFE) is 1-1 with respect to 100 mass parts of (A) aromatic polycarbonate resin mentioned above. 10 parts by mass, preferably 1.5? 9 parts by mass. If the compounding quantity is less than 1 mass part, the dripping prevention effect will disappear, and if it exceeds 10 mass parts, impact characteristic will fall.

The compounding quantity is 1? Although 1.5 mass parts has an effect as an anti dripping agent, when it mixes exceeding 1.5 mass parts, it can exhibit not only an anti dripping agent but also the effect of improving impact strength and mold release property, and the mold release effect at the time of shaping | molding also becomes favorable.

In order to further improve the thin flame retardance of the polycarbonate resin composition of the present invention, (D) an organic alkali metal salt and / or an organic alkaline earth metal salt are blended.

(D) Various examples of the organic alkali metal salt and / or organic alkaline earth metal salt include organic acids having at least one carbon atom, or alkali metal salts and organic alkaline earth metal salts of organic acid esters.

Here, an organic acid or organic acid ester is organic sulfonic acid, organic carboxylic acid, etc. On the other hand, alkali metals are lithium, sodium, potassium, cesium and the like, and alkaline earth metals are magnesium, calcium, strontium, barium, and the like. Among them, salts of sodium and potassium are preferably used. The salt of the organic acid may be substituted with halogen such as fluorine, chlorine and bromine. An alkali metal salt and an organic alkaline earth metal salt can be used individually by 1 type or in combination of 2 or more types.

Of the various organic alkali metal salts and organic alkaline earth metal salts, for example, in the case of organic sulfonic acid, alkali metal salts and alkaline earth metal salts of perfluoroalkanesulfonic acid represented by the following general formula (1) are preferably used.

(C _e F _{2e + 1} SO ₃ ) _f M (1)

In the formula, e is 1? The integer of 10 is shown, M represents alkali metals, such as lithium, sodium, potassium, and cesium, and alkaline-earth metals, such as magnesium, calcium, strontium, and barium, f represents the valence of M.

As these compounds, what is described, for example in Unexamined-Japanese-Patent No. 47-40445 corresponds to this.

In the said General formula (1), as perfluoro alkanesulfonic acid, a perfluoro methane sulfonic acid, a perfluoroethane sulfonic acid, a perfluoro propane sulfonic acid, a perfluoro butane sulfonic acid, a perfluoromethyl butane sulfonic acid, for example , Perfluorohexane sulfonic acid, perfluoroheptanesulfonic acid, perfluorooctane sulfonic acid, and the like. In particular, these potassium salts are used preferably. In addition, paratoluenesulfonic acid and 2, 5- dichlorobenzene sulfonic acid; 2,4,5-trichlorobenzene sulfonic acid; Diphenylsulfone-3-sulfonic acid; Diphenylsulfone-3,3'- disulfonic acid; Alkali metal salts of organic sulfonic acids, such as naphthalene trisulfonic acid, etc. are mentioned.

Moreover, as organic carboxylic acid, for example, perfluoro formic acid, perfluoromethane carboxylic acid, perfluoroethane carboxylic acid, perfluoro propane carboxylic acid, perfluorobutane carboxylic acid, purple Luoromethylbutanecarboxylic acid, perfluorohexanecarboxylic acid, perfluoroheptancarboxylic acid, perfluorooctanecarboxylic acid, etc. are mentioned, The alkali metal salt of these organic carboxylic acids is used.

Next, as an alkali metal salt and / or alkaline earth metal salt of polystyrene sulfonic acid which can be used for (D) component, the sulfonic acid base containing aromatic vinyl resin represented by following General formula (2) can be used.

[Formula 1]

In the formula (2), Z ¹ is a sulfonic acid base, Z ² is a hydrogen atom or a C 1? 10 hydrocarbon groups are shown. g is 1? Is an integer of 5. h represents a mole fraction and 0 <h≤1.

Here, the sulfonic acid base is an alkali metal salt and / or alkaline earth metal salt of sulfonic acid, and examples of the metal include sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium.

Wherein, Z ² represents a hydrogen atom or a C 1? It is a hydrocarbon group of 10, Preferably it is a hydrogen atom or a methyl group. And g is 1? It is an integer of 5, and h is a relationship of 0 <h <= 1. That is, the sulfonic acid base (Z ¹ ) may be all substituted with or partially substituted with the aromatic ring.

In order to further enhance the flame retardant effect of the polycarbonate resin composition of the present invention, the substitution ratio of the sulfonic acid base is determined in consideration of the content of the sulfonic acid base-containing aromatic vinyl resin, and the like. 100% substitution is used.

In addition, in the alkali metal salt and / or alkaline earth metal salt of polystyrene sulfonic acid, the sulfonic acid base-containing aromatic vinyl resin is not limited to the polystyrene resin of the general formula (2), but is air of another monomer copolymerizable with the styrene monomer. It may be a coalescence.

Here, as a manufacturing method of a sulfonic acid base containing aromatic vinyl resin, (I) the method of superposing | polymerizing or copolymerizing the aromatic vinyl monomer which has the said sulfonic acid group etc., or another monomer copolymerizable with these, (II) aromatic vinyl polymer Or a copolymer of an aromatic vinyl monomer and another copolymerizable monomer, or a mixture of these polymers and sulfonated to neutralize an alkali metal compound and / or an alkaline earth metal compound.

For example, in the method (II), a polystyrene sulfone oxide is produced by adding a mixed solution of concentrated sulfuric acid and acetic anhydride to a 1,2-dichloroethane solution of a polystyrene resin and heating the mixture. Subsequently, potassium polystyrene sulfonate salt or sodium salt can be obtained by neutralizing with sulfonic acid group and sugar molar amount of potassium hydroxide or sodium hydroxide.

The weight average molecular weight of the sulfonic acid base-containing aromatic vinyl resin used in the present invention is 1,000? About 300,000, preferably 2,000? 200,000 or so. In addition, a weight average molecular weight can be measured by GPC method.

The said (D) organic alkali metal salt and / or organic alkaline-earth metal salt may be used 1 type, or may be used in combination of 2 or more type. Moreover, the content is 0.05? With respect to 100 mass parts of (A) aromatic polycarbonate resin. 1 part by mass, preferably 0.1? 0.9 parts by weight. If the said content is less than 0.05 mass part, it will be difficult to achieve target thin flame retardance, and when it exceeds 1 mass part, there exists a problem that thermal stability falls.

In the polycarbonate resin composition of the present invention, for the purpose of moldability, impact resistance, appearance improvement, weather resistance improvement and rigidity improvement, the above-mentioned (A)? A phenol type, phosphorus type | system | group, and sulfur type (E) antioxidant and (F) mold release agent can be contained in the component which consists of (D).

(E) Regarding the compounding amount of the antioxidant, in the phosphorus antioxidant, 0.001? 0.5 mass part is preferable. If it is 0.001 mass part or more, the thermal stability in an assembly process and a molding process can be maintained, but below 0.5 mass part does not produce molecular weight fall well. Moreover, in a phenolic antioxidant, 0.001? Addition of 0.5 mass part is preferable, and impact strength tends to improve.

(F) The mold release agent is not particularly limited as long as it can be blended with a polycarbonate resin to improve mold release properties during molding. In particular, mold release properties excellent in organic compounds such as beeswax, glycerin monostearate, glycerin tristearate, pentaerythritol monostearate, pentaerythritol tristearate, pentaerythritol tetrastearate, montan ester wax, and carboxylic acid esters It is used preferably.

These are, for example, "Beeswax Golden Brand" manufactured by Mickey Chemical Industries, Ltd., "Rikemal S-100A", "Rikemal SL-900" and "Rikesta EW-440A" manufactured by Ricken Vitamin Co., Ltd., Kogu "Roxyol VPG861" by Nice Japan, "Licowax E" by Client Japan, and "Roxyol EP-32" by Kogunis Japan. The amount of the compound is 0.001? 2 mass parts is preferable.

Moreover, you may contain the additive component compatible with other synthetic resin, an elastomer, and a thermoplastic resin as needed. Examples of the additive include an antistatic agent, a polyamide polyether block copolymer (permanent antistatic performance), a benzotriazole-based or benzophenone-based ultraviolet absorber, a hindered amine-based light stabilizer (weather agent), a plasticizer, an antibacterial agent, and a commercialization. Agents and colorants (dyes, pigments) and the like.

There is no restriction | limiting in particular if the compounding quantity of arbitrary components is a range in which the characteristic of the polycarbonate resin composition of this invention is maintained.

Next, the manufacturing method of the polycarbonate resin composition of this invention is demonstrated.

The polycarbonate resin composition of this invention is each said component (A)? It is obtained by mix | blending and mixing (D) in the said ratio and the various arbitrary components used further as needed in an appropriate ratio.

The compounding and kneading is premixed with an apparatus commonly used, for example, a ribbon blender, a drum tumbler, or the like, and using a Henschel mixer, Banbury mixer, single screw extruder, twin screw extruder, multi screw extruder, conical It can be carried out by the method. The heating temperature at the time of kneading is normally 240? It is suitably selected in the range of 320 degreeC. As this melt-kneading molding, use of an extrusion molding machine, particularly a vented extrusion molding machine, is preferable.

Incidentally, other components other than the polycarbonate resin may be added in advance as melt kneading, that is, as a master batch, with the polycarbonate resin or another thermoplastic resin.

The polycarbonate resin composition of the present invention can produce various molded bodies by injection molding method, injection compression molding method, extrusion molding method, blow molding method, press molding method, vacuum molding method and foam molding method using the melt kneading molding machine or the obtained pellet as a raw material. Can be. In particular, the obtained pellets can be preferably used for production of injection molded bodies by injection molding and injection compression molding.

The molded object which consists of a polycarbonate resin composition of this invention is, for example,

(1) Parts for electric and electronic devices such as televisions, radio cassettes, video cameras, video tape recorders, audio players, DVD players, air conditioners, mobile phones, displays, computers, registers, electronic desk calculators, copiers, printers, facsimiles,

(2) the casing for electrical and electronic equipment described in 1 above;

(3) the chassis for electrical and electronic equipment according to 1 above;

Etc., it can be used preferably.

Example

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not restrict | limited at all by these.

A performance evaluation method and the raw material used are shown next.

[Performance evaluation method]

(1) viscosity average molecular weight

The intrinsic viscosity [η] of the methylene chloride solution at 20 ° C. was measured with an ubelode viscous tube and calculated from the following relational expression (Schnell's equation).

[Η] ^{= 1.23 × 10 -5 × Mv 0} .83

In addition, the pellet molecular weight melt | dissolved the pellet sample for evaluation in methylene chloride, isolate | dissolved insoluble content, and measured the molecular weight of the extracted polycarbonate resin.

(2) flame retardant

The vertical combustion test was done using the test piece (length 127mm, width 12.7mm, thickness 1.2mm) produced according to UL specification 94. Based on the test result, it evaluated by the grade of UL94 V-0, V-1, or V-2, and set it as V-2out that does not reach V-2.

In addition, UL standard 94 is a method of evaluating a flame retardance from the residual flame time after flame-burning a burner flame for 10 second to the test piece of the predetermined magnitude | size maintained perpendicularly | vertically.

(3) thermal conductivity

It measured by the hot-disk method using the thermal conductivity measuring apparatus "TPA-501" (made by Kyoto Electronics Industry Co., Ltd.).

(4) density

It measured based on JISK7112: 0.

(5) bending characteristics

Modulus of elasticity; It measured according to ASTMD790.

Bending strength; It measured according to ASTMD790.

(6) impact characteristics

Izod impact strength with notches (IZOD)

Using the test piece (length 12.7mm, width 63mm, height 3.2mm) produced by the injection molding machine, impact strength was measured at 23 degreeC of measurement temperature based on ASTM specification D-256.

[Use raw materials]

(A) Aromatic Polycarbonate Resin

A-1 (1); Polycarbonate-polydimethylsiloxane copolymer [made by Idemitsu Koyama Co., Ltd .; "FC1700"; Viscosity average molecular weight = 17,800, degree of polymerization of polydimethylsiloxane (PDMS) part = 40, PDMS content = 3.5 mass%]

A-1 (2); Polycarbonate-polydimethylsiloxane copolymer obtained by the following Preparation Example 1 [viscosity average molecular weight = 17,300, polymerization degree of polydimethylsiloxane (PDMS) part = 90, PDMS content = 6.6 mass%]

Preparation Example 1

(Polycarbonate oligomer synthesis step)

To the bisphenol A (BPA) dissolved later in 5.6 mass% sodium hydroxide solution was added 2,000 ppm of sodium itionate, to which BPA was dissolved so as to have a BPA concentration of 13.5 mass%, to prepare an aqueous sodium hydroxide solution of BPA. .

At a flow rate of 40 liters / hr of sodium hydroxide aqueous solution of this BPA and 15 liters / hr of methylene chloride, phosgene was continuously passed through a tubular reactor having an inner diameter of 6 mm and a pipe length of 30 m at a flow rate of 4.0 kg / hr. The tubular reactor had a jacket portion, and the cooling water was passed through the jacket to maintain the temperature of the reaction solution below 40 ° C.

The reaction liquid from the tubular reactor was continuously introduced into a basal reactor with a baffle of internal volume 40 liters with a retracting vane, again with 2.8 liter / hr BPA aqueous sodium hydroxide solution, 25 mass% aqueous sodium hydroxide solution 0.07 The reaction was performed by adding 0.64 liter / hr of liter / hr, 17 liter / hr of water, and 1 mass% triethylamine aqueous solution. The reaction liquid overflowing from the bath type reactor was continuously taken out, the water phase was separated and removed, and the methylene chloride phase was collected.

Thus, the obtained polycarbonate oligomer was 318 g / L in concentration and 0.75 mol / L in chloroformate group concentration.

(Production Example 1 of Polycarbonate-Polydimethylsiloxane Copolymer)

Allylphenol terminal modified polydimethyl with a repeating number of 15 l of polycarbonate oligomer solution, 9.0 l of methylene chloride and 90 dimethylsiloxane units in a 50 l bath reactor equipped with a baffle, paddle stir blades and cooling jacket. 396 g of siloxane (PDMS) and 8.8 ml of triethylamine were injected, and 1389 g of a 6.4 mass% sodium hydroxide aqueous solution was added thereto under stirring to react the polycarbonate oligomer with allylphenol terminal-modified PDMS for 10 minutes.

To this polymerization solution, a methylene chloride solution of pt-butylphenol (PTBP) (140 g of PTBP dissolved in 2.0 l of methylene chloride) and an aqueous sodium hydroxide solution of BPA (NaOH 577 g and sodium ethionate 2.0 g 8.4 L of water) Was dissolved in an aqueous solution dissolved in BPA), and the polymerization reaction was carried out for 50 minutes.

10 l of methylene chloride was added for dilution and stirred for 10 minutes, then separated into an organic phase containing a polycarbonate-polydimethylsiloxane copolymer and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated.

The methylene chloride solution of the polycarbonate-polydimethylsiloxane copolymer thus obtained was sequentially washed with 15 vol% of 0.03 mol / L NaOH aqueous solution and 0.2 mol / L hydrochloric acid with respect to the solution, followed by electrical conductivity in the aqueous phase after washing. Washing was repeated with pure water until it became 0.01 μS / m or less.

The methylene chloride solution of the polycarbonate polydimethylsiloxane copolymer obtained by washing | cleaning was concentrated and pulverized, and the obtained flake was dried at 120 degreeC under reduced pressure.

PDMS residue amount (PDMS copolymerization amount) calculated | required by nuclear magnetic resonance (NMR) of the obtained polycarbonate polydimethylsiloxane copolymer was 6.6 mass%, the viscosity number measured based on ISO1628-4 (1999) is 46.7, the viscosity average Molecular weight Mv = 17,300.

A-1 (3); Polycarbonate-polydimethylsiloxane copolymer obtained by the following Production Example 2 [viscosity average molecular weight = 17,300, polymerization degree of polydimethylsiloxane (PDMS) part = 40, PDMS content = 10 mass%]

Production Example 2

(Production Example 2 of Polycarbonate-Polydimethylsiloxane Copolymer)

15 L polycarbonate oligomer solution used in the preparation of A-1 (2), 8.9 L methylene chloride, dimethylsilanooxy units in a 50 L bath reactor equipped with a baffle plate, paddle type stirring vanes and a cooling jacket. 670 g of allylphenol terminal-modified PDMS having a number of 40 and 8.8 ml of triethylamine were injected thereto, and 1389 g of a 6.4 mass% aqueous sodium hydroxide solution was added thereto under stirring to react the polycarbonate oligomer with allylphenol terminal-modified PDMS for 10 minutes. Was carried out.

To this polymerization solution, a methylene chloride solution of pt-butylphenol (PTBP) (137.9 g of PTBP dissolved in 2.0 l of methylene chloride) and an aqueous sodium hydroxide solution of BPA (NaOH 581 g and 2.3 g of sodium ionate) 8.5 L of water 1147 g of BPA dissolved in an aqueous solution dissolved therein) was added to conduct a polymerization reaction for 50 minutes. For dilution, 10 L of methylene chloride was added and stirred for 10 minutes, then separated into an organic phase containing polycarbonate and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated.

The methylene chloride solution of the polycarbonate thus obtained was washed sequentially with 15 vol.% 0.03 mol / l NaOH aqueous solution and 0.2 N hydrochloric acid with respect to the solution, and the electrical conductivity in the aqueous phase after washing was then 0.01 μS / m or less. Washing was repeated with pure water until. The methylene chloride solution of the polycarbonate obtained by washing | cleaning was concentrated and pulverized, and the obtained flake was dried at 120 degreeC under reduced pressure.

The quantity of PDMS residue calculated | required by NMR was 10.0 mass%, and the viscosity number measured based on ISO1628-4 (1999) was 46.6 and viscosity average molecular weight Mv = 17,300.

A-2 (1); Polycarbonate [Homopolycarbonate "Taflon FN1900A" manufactured from Idemitsu Koyama Co., Ltd., bisphenol A, viscosity average molecular weight = 19,500]

A-2 (2); Polycarbonate [Homopolycarbonate "Taflon FN2200A" manufactured from Idemitsu Kosan Co., Ltd. product, bisphenol A, viscosity average molecular weight = 21,500]

A-2 (3); Polycarbonate [Homopolycarbonate "Taflon FN2600A" manufactured from Idemitsu Kosan Co., Ltd. product and bisphenol A, viscosity average molecular weight = 26,000]

In addition, POS content in a table | surface: The polyorganosiloxane content (mass%) in (A) component is shown.

(B) graphite

B-1; Natural graphite ["CB-150" by Nippon Graphite Industry Co., Ltd .; Scaly, particle size distribution 63 μm or less 77? 87%, 106 micrometers or more and 5% or less, appearance density 0.2? 0.3 g / cm 3, 50% cumulative diameter 31? 48 micrometers, 98 mass% or more of fixed carbon, 1 mass% or less of ash, 1 mass% or less of volatile matter]

B-2; Artificial graphite ["PAG-420" by Nippon Graphite Industry Co., Ltd .; Indeterminate, 50% cumulative diameter 30? 40 µm (50 µm or more and 50% or less), appearance density 0.29? 0.37 g / cm 3, 99.4 mass% or more of fixed carbon, 0.3 mass% or less of ash, 0.3 mass% or less of volatile matter]

(C) polytetrafluoroethylene (PTFE)

C-1; PTFE [Solva Solesis, Inc., "Algoflon F5"; Algoflon F5 is agglomerated easily, so master batching with PC flakes (mixing ratio (mass) PC: PTFE = 90: 10 to 80:20) and then mixing]

(D) organic alkali (soil) metal salt

D-1; Perfluorobutane sulfonic acid salt [Mitsubishi Material, Ltd. product, "F-top KFBS"]

D-2; Sodium paratoluene sulfonate salt [manufactured by DAH DIING CHEMICAL INDUSTRY, product of purity 93%, impurities 3% by mass or less of sodium sulfate, 5% by mass or less of water]

(E) other additives antioxidant

E-1; Phosphorus antioxidant (diphenylisooctyl phosphite) [made by ADEKA Corporation, "adecastub C"]

E-2; Phenolic antioxidant (octadecyl-3- (3,5-di-t-butyl-hydroxyphenyl) propionate) [Ciba Japan Ltd. make, "Irganox 1076"]

(F) other additive release agents

F-1; Stearic acid monoglyceride [Liken vitamin Co., Ltd. product "rikemal S-100A"]

F-2; Pentaerythritol tetrastearate [rikenusuta Co., Ltd. production "Riquesta EW-440A"]

Example 1? 13, and comparative example 1? 7

Each component is mixed in the ratio shown in Table 1 and Table 2, and it supplies to the vent type biaxial extrusion molding machine (TEMBA make: TEM35), and has a barrel temperature of 300? 320 ℃, screw speed 200? 600 revolutions, discharge rate 10? It melt-kneaded at 30 kg / hr, and obtained the pellet sample for evaluation.

The viscosity average molecular weight was measured using this pellet sample for evaluation. Moreover, the test piece for each test was produced with the injection molding machine, and each test was implemented. The results are shown in Table 1 and Table 2.

The following was found from Table 1 and Table 2.

From Table 1, in Examples 1 to 13 satisfying all of the components (A) to (D) of the present invention, the thickness (1.2 mm) was excellent in flame retardancy, thermal conductivity, bending characteristics, and impact strength. The polycarbonate resin composition in which the molecular weight fall of the polycarbonate resin at the time of granulation is suppressed is obtained.

From Table 2, in the comparative example 1 which consists only of a homo polycarbonate resin, a thin flame retardance falls. In Comparative Example 2 with less graphite content of the component (B), thermal conductivity is lowered, and in Comparative Example 3 with too much component (B), the impact strength is lowered. In Comparative Example 4 with a small amount of PTFE in the component (C), the thin flame retardancy is lowered, and in Comparative Example 5 with too much component (C), the impact strength is lowered.

In Comparative Example 6 in which the metal salt content of the component (D) is low, thin flame retardancy decreases, and in Comparative Example 7 in which the component (D) is too large, the molecular weight decrease of the polycarbonate resin at the time of granulation is large.

Claims

(A) With respect to 100 mass parts of aromatic polycarbonate resin containing a polycarbonate polyorganosiloxane copolymer, (B) graphite 30? 100 parts by mass, (C) polytetrafluoroethylene 1? 10 parts by mass and (D) an organic alkali metal salt and / or an organic alkaline earth metal salt of 0.05? Polycarbonate resin composition which mix | blends 1 mass part.

The method of claim 1,
Content of polyorganosiloxane in (A) is 1? Polycarbonate resin composition which is 6 mass%.

The method according to claim 1 or 2,
The polycarbonate resin composition whose polyorganosiloxane of an aromatic polycarbonate polyorganosiloxane copolymer is polydimethylsiloxane.

The method according to any one of claims 1 to 3,
Polycarbonate resin composition in which graphite is natural graphite.

The method according to any one of claims 1 to 3,
Polycarbonate resin composition whose graphite is artificial graphite.

6. The method according to any one of claims 1 to 5,
(D) The polycarbonate resin composition wherein the organic alkali metal salt and / or the organic alkaline earth metal salt is at least one selected from organic sulfonic acid alkali metal salts, organic sulfonic acid alkaline earth metal salts, polystyrene sulfonic acid alkali metal salts and polystyrene sulfonic acid alkaline earth metal salts.

The molded object which consists of a polycarbonate resin composition in any one of Claims 1-6.

The method of claim 7, wherein
Molded product for electric and electronic devices.

The method of claim 7, wherein
Molded product which is a casing for electrical and electronic equipment.

The method of claim 7, wherein
Molded body that is a chassis for electrical and electronic equipment.