WO2020158293A1

WO2020158293A1 - Molding material comprising carbon fiber-reinforced polycarbonate resin composition

Info

Publication number: WO2020158293A1
Application number: PCT/JP2019/051381
Authority: WO
Inventors: 角田　敦; 国飛華
Original assignee: 帝人株式会社
Priority date: 2019-01-30
Filing date: 2019-12-27
Publication date: 2020-08-06
Also published as: JPWO2020158293A1; TWI830851B; CN113383035B; TW202037649A; JP7116198B2; CN113383035A

Abstract

The present invention provides a molding material comprising a carbon fiber-reinforced polycarbonate resin composition, said molding material having superior flame retardancy, external appearance, strength, and colorability.　In this molding material, 50-2,000 parts by weight of a polycarbonate resin composition is adhered to a readily impregnable carbon fiber bundle that comprises 100 parts by weight of carbon fibers and 3-15 parts by weight of one or more types of impregnation aid. The molding material is characterized in that the polycarbonate resin composition includes (C) 10-20 parts by weight of a bromine-based flame retardant (C component), (D) 0.01-2 parts by weight of a fluorine-including drip prevention agent (D component), and (E) 0.05-2 parts by weight of a full ester (E component) of a polyvalent alcohol and an aliphatic carboxylic acid, per 100 parts by weight of a resin component that consists of (A) 1-100wt% of an aromatic polycarbonate resin (A component) and (B) 0-99wt% of a polycarbonate-polydiorganosiloxane copolymer resin (B component).

Description

Molding material comprising carbon fiber reinforced polycarbonate resin composition

The present invention relates to a molding material made of a carbon fiber reinforced polycarbonate resin composition. More specifically, it relates to a molding material comprising a carbon fiber reinforced polycarbonate resin composition excellent in flame retardancy, appearance, strength and colorability.

A composite material in which a resin is reinforced with carbon fiber is known as a means for obtaining a resin material having high strength and suppressed brittle fracture. In particular, a composite material in which a thermoplastic resin is reinforced with carbon fibers as a matrix resin (also referred to as a carbon fiber reinforced thermoplastic resin, and may be abbreviated as CFRTP hereinafter) has excellent workability and recyclability as a molding material. And is expected to be applied to various fields. On the other hand, as CFRTP is expected to be used in various applications, the demand for flame retardancy to ensure safety is increasing. In addition to the flame retardancy and the higher surface appearance than before, due to the complexity of the shape of the molded product in recent years, the thinning of the molded product thickness, and the improvement of the required level for the appearance of the molded product by omitting the painting process. In some cases, good colorability is required.

Against this background, a resin composition composed of a polycarbonate resin reinforced with an inorganic filler and a halogenated carbonate compound has been proposed (Patent Document 1), but the expected improvement in strength was not obtained and was obtained. The product made of the resin composition had poor carbon fiber dispersion and the appearance was not satisfactory. A molding material composed of a polycarbonate resin attached to a carbon fiber bundle containing a specific compound has been proposed as a material satisfying strength and appearance (Patent Document 2), but it is flame retardant depending on the specific compound used. Was insufficient and the coloring property was poor. As a material having excellent strength, flame retardancy, and appearance, a method for producing a molding material in which a carbon fiber bundle preliminarily impregnated with a phosphate ester flame retardant and a thermoplastic resin is impregnated with a polycarbonate resin is disclosed. (Patent Document 3) However, it does not have flame retardancy capable of coping with the recent thinning, and further improvement has been demanded. As described above, a molding material excellent in flame retardancy, appearance, strength and colorability has not been obtained so far.

Japanese Patent No. 4588154 WO2013/137246 JP, 2014-159559, A

An object of the present invention is to solve the above problems and to provide a molding material comprising a carbon fiber reinforced polycarbonate resin composition excellent in flame retardancy, strength, appearance and colorability.

The present inventors have conducted extensive studies to solve the above problems, and a polycarbonate resin composition in which a brominated flame retardant, a fluorine-containing anti-dripping agent, and a full ester of a polyhydric alcohol and an aliphatic carboxylic acid are added to the polycarbonate resin. It was found that a molding material excellent in flame retardancy, appearance, strength and colorability can be obtained by adhering the resin to carbon fiber, and thus the present invention has been accomplished.

That is, according to the present invention, (1) an easily impregnable carbon fiber bundle comprising 100 parts by weight of carbon fiber and 3 to 15 parts by weight of one or more impregnating aids, and 50 to 2,000 parts by weight of a polycarbonate resin. A molding material having the composition adhered, wherein the polycarbonate resin composition comprises (A) 1 to 100% by weight of an aromatic polycarbonate resin (component A) and (B) a polycarbonate-polydiorganosiloxane copolymer resin (component B). ) 10 to 20 parts by weight of (C) brominated flame retardant (C component) and (D) 0.01 to 2 of fluorine-containing anti-dripping agent (D component) per 100 parts by weight of resin component consisting of 0 to 99% by weight. There is provided a molding material, characterized in that it contains 0.05 to 2 parts by weight and (E) a full ester of a polyhydric alcohol and an aliphatic carboxylic acid (E component).

One of the more preferred embodiments of the present invention is characterized in that the (2) impregnation aid comprises one or more aliphatic hydroxycarboxylic acid type polyesters satisfying the following formulas (1) and (2). It is the molding material according to configuration (1).

Viscosity of the impregnation aid at 300° C.≦10 Pa·s (1)
2≦(Tg ₀ −Tg ₁ )/D (2)
[Wherein D is the proportion (% by weight) of the impregnating aid in the resin composition comprising the polycarbonate resin and the impregnating aid, and Tg ₁ is the resin composition obtained by adding the impregnating aid to the polycarbonate resin in this proportion. Glass transition temperature (° C.) and Tg ₀ represent the glass transition temperature (° C.) of the polycarbonate resin. ]
One of the more preferred embodiments of the present invention is (3) wherein the aliphatic hydroxycarboxylic acid type polyester has a weight average molecular weight of 3,000 to 50,000, ε-caprolactone, δ-caprolactone, β-propiolactone, γ. One selected from the group consisting of homopolymers of butyrolactone, δ-valerolactone, γ-valerolactone, enanthlactone and copolymers of two or more of these monomers having a weight average molecular weight of 3,000 to 50,000 It is a molding material as described in the above constitution (2), which is the above compound.

One of the more preferred embodiments of the present invention is characterized in that (4) the component (A) and the component (B) contain 1 to 10 parts by weight of an adhesion improver (F component) per 100 parts by weight. The molding material according to any one of the above configurations (1) to (3).

According to one of the more preferred embodiments of the present invention, (5) E component is an aliphatic carboxylic acid containing a palmitic acid component and a stearic acid component, and its peak area in gas chromatography-mass spectrometry (GC/MS method) In, the sum of the area of the palmitic acid component (Sp) and the area of the stearic acid component (Ss) is 80% or more in the total aliphatic carboxylic acid component, and the area ratio (Ss/Sp) of both is 1.3 to 30. Any of the above constitutions (1) to (4), characterized in that it is a full ester of a polyhydric alcohol having an acid value of 0.1 to 20 and an aliphatic carboxylic acid The molding material as described in 1 above.

One of the more preferred embodiments of the present invention is the above-mentioned constitution (1), wherein (6) the E component is a full ester of a polyhydric alcohol whose polyhydric alcohol is pentaerythritol and an aliphatic carboxylic acid. The molding material according to any one of to (5).

One of the more preferred embodiments of the present invention is that (7) F component is at least one organic compound selected from the group consisting of glycidyl methacrylate, bisphenol A type epoxy resin, polyarylate and styrene-maleic acid resin. The molding material as described in any one of the above-mentioned constitutions (4) to (6).

One of the more preferred embodiments of the present invention is (8) a pellet having a core-sheath structure having an easily impregnable carbon fiber bundle as a core component and a polycarbonate resin composition as a sheath component (1) )-(7) The molding material according to any one of items.

One of the more preferred embodiments of the present invention is (9) the molding material described in the above configuration (8), wherein the length of the pellet in the longitudinal direction is 3 to 10 mm.

One of the more preferable embodiments of the present invention is (10) a molded body made of the molding material according to any one of the above configurations (1) to (9).

(11) The carbon fiber derived from the easily impregnable carbon fiber bundle is dispersed in an average fiber length of 0.3 mm or more (10). ).

One of the more preferred embodiments of the present invention is (12) the molded article according to the above configuration (10), in which the molded article is an OA/electrical electronic interior/exterior member.

One of the more preferable embodiments of the present invention is (13) the molded article according to the above configuration (10) in which the molded article is an automobile member.

Molded articles obtained from the molding material comprising the carbon fiber reinforced polycarbonate resin composition of the present invention are excellent in strength, flame retardancy, appearance and colorability, and therefore, OA/electrical electronic interior/exterior parts, home electrification It is useful for products, automobile parts, infrastructure related parts, housing related parts, etc., and the industrial effect produced by it is exceptional.

Hereinafter, the present invention will be specifically described.
(A component: polycarbonate resin)
The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid-state transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Typical examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, and 2,2-bis(4-hydroxyphenyl). ) Propane (commonly called bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)- 1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl) Pentane, 4,4'-(p-phenylenediisopropylidene)diphenol, 4,4'-(m-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. To be A preferred dihydric phenol is bis(4-hydroxyphenyl)alkane, and among them, bisphenol A is particularly preferred from the viewpoint of impact resistance and is widely used.

In the present invention, in addition to bisphenol A-based polycarbonate which is a general-purpose polycarbonate, it is possible to use a special polycarbonate produced by using other dihydric phenols as the A component.

For example, 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxy) as a part or all of the dihydric phenol component. (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 a dimension due to water absorption. It is suitable for applications in which changes and morphological stability are particularly demanding. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more, based on the total amount of the dihydric phenol components constituting the polycarbonate.

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

These special polycarbonates may be used alone or in admixture of two or more kinds. Further, these can be used as a mixture with a commonly used bisphenol A type polycarbonate.

The production method and characteristics of these special polycarbonates are described in detail, for example, in 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 and a Tg (glass transition temperature) within the following ranges by adjusting the copolymerization composition and the like have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where morphological stability is required.
(I) a polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and a Tg of 120 to 180° C., or (ii) a Tg of 160 to 250° C., A polycarbonate having a temperature of 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 of polycarbonate is a value obtained by measuring the water content after dipping it in water at 23° C. for 24 hours in accordance with ISO62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Further, Tg (glass transition temperature) is a value obtained by a differential scanning calorimeter (DSC) measurement according to JIS K7121.

Carbonyl halide, carbonic acid diester or haloformate is used as the carbonate precursor, and specific examples thereof include phosgene, diphenyl carbonate or dihaloformate of dihydric phenol.

In producing an aromatic polycarbonate resin by an interfacial polymerization method of the dihydric phenol and the carbonate precursor, a catalyst, an end terminating agent, and an antioxidant for preventing the dihydric phenol from being oxidized, if necessary. Etc. may be used. The aromatic polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher functional polyfunctional aromatic compound, and a polyester obtained by copolymerizing an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. It includes a carbonate resin, a copolycarbonate resin obtained by copolymerizing a difunctional alcohol (including an alicyclic group), and a polyester carbonate resin obtained by copolymerizing such a difunctional carboxylic acid and a difunctional alcohol. Further, it may be a mixture of two or more kinds of the obtained aromatic polycarbonate resins.

The branched polycarbonate resin can impart anti-drip performance to the polycarbonate resin composition of the present invention. Examples of trifunctional or higher-functional polyfunctional aromatic compounds used for the branched polycarbonate resin include phloroglucin, phlorogluside, or 4,6-dimethyl-2,4,6-tris(4-hydrodiphenyl)heptene-2,2. ,4,6-Trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl) Ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[ 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol and other trisphenols, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, Examples thereof include 4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among which 1,1,1-tris(4-hydroxy) Phenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferable, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferable.

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

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

The α,ω-dicarboxylic acid is preferable as the aliphatic bifunctional carboxylic acid. Examples of the aliphatic difunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as An alicyclic diol is more preferable as the bifunctional alcohol, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

The reaction modes such as the interfacial polymerization method, the melt transesterification method, the carbonate prepolymer solid phase transesterification method, and the ring-opening polymerization method of the cyclic carbonate compound, which are the production methods of the aromatic polycarbonate resin of the present invention, include various documents and patents. This method is well known in the bulletins.

The viscosity average molecular weight as referred to in the present invention is obtained by first using a Ostwald viscometer to calculate a specific viscosity (η _SP ) calculated by the following equation from a solution prepared by dissolving 0.7 g of polycarbonate in 100 ml of methylene chloride at 20° C.
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[T ₀ is the number of seconds of methylene chloride drop, t is the number of seconds of drop of the sample solution]
The viscosity average molecular weight M is calculated from the determined specific viscosity (ηSP) by the following mathematical 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
The viscosity average molecular weight of the aromatic polycarbonate resin in the polycarbonate resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. The soluble matter is collected by Celite filtration. After that, the solvent in the obtained solution is removed. After removing the solvent, the solid is sufficiently dried to obtain a solid of a component soluble in methylene chloride. A specific viscosity at 20° C. is obtained from a solution prepared by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as above.

The content of the component A is 1 to 100% by weight, preferably 30 to 100% by weight, and more preferably 50 to 95% by weight, based on 100% by weight of the resin component consisting of the components A and B. When the content of the component A is less than 1% by weight, the colorability is poor.
(Component B: Polycarbonate-polydiorganosiloxane copolymer resin)
The resin composition of the present invention may contain a polycarbonate-polydiorganosiloxane copolymer resin as the B component. The polycarbonate-polydiorganosiloxane copolymer resin used in the present invention is a dihydric phenol deriving a structural unit represented by the following general formula (1) and a hydroxy deriving a structural unit represented by the following general formula (3). A copolymer resin prepared by copolymerizing an aryl-terminated polydiorganosiloxane is preferable.

[In the 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, and 6 to 6 carbon atoms. 20 cycloalkyl group, C 6-20 cycloalkoxy group, C 2-10 alkenyl group, C 6-14 aryl group, C 6-14 aryloxy group, 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, and when there are a plurality of groups, they may be the same or different. E and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2). )

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

[In 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 substituent having 6 to 12 carbon atoms. Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number. And q is 0 or a natural number, and p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]
Examples of the dihydric phenol (I) for deriving the constitutional unit represented by the general formula (1) include, for example, 4,4′-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane and 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′-dihydroxydiphenylether 4,4'-dihydroxy-3,3'-dimethyldiphenylether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 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'-diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 1,3-bis{2- (4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4 -Bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4, 4'-(1,3-adamantanediyl)diphenol, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane and the like can be mentioned.

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

As the hydroxyaryl-terminated polydiorganosiloxane for deriving the constitutional unit represented by the general formula (3), for example, the compounds shown below are preferably used.

The hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol. It can be easily produced by subjecting a terminal of a polysiloxane chain having a polymerization degree of 1 to a hydrosilylation reaction. Among them, (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane are preferable, and particularly (2-allylphenol)-terminated polydimethylsiloxane and (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 exhibit more excellent low outgassing properties and low temperature impact properties during high temperature molding. If the amount exceeds the upper limit of the preferable range, the amount of outgas generated during high temperature molding may be large and the low temperature impact resistance may be poor.

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

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

In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.

Further, within a range not hindering the present invention, other comonomer other than the above dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) is added in an amount of 10% by weight or less based on the total weight of the copolymer. It can also be used together.

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

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

The method of this oligomer formation reaction is not particularly limited, but usually a method performed in a solvent in the presence of an acid binder is suitable.

The proportion of the carbonic acid ester forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Further, when a gaseous carbonic acid ester-forming compound such as phosgene is used, a method of blowing it into the reaction system can be suitably adopted.

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

As the solvent, solvents that are inert to various reactions such as those used in the production of known polycarbonates may be used alone 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. Particularly, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

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

According to the present invention, a mixed solution containing an oligomer of a dihydric phenol (I) having a terminal chloroformate group is thus obtained, and then the mixed solution is stirred to have a molecular weight distribution (Mw/Mn) of 3 or less. The 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. Thus, a polycarbonate-polydiorganosiloxane copolymer is obtained.

(In the general formula (4), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substituent having 6 to 12 carbon atoms. Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number. , Q is 0 or a natural number, 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 appropriately added in consideration of the stoichiometric ratio (equivalent amount) of the reaction. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) to be used or a part of the dihydric phenol (I) as described above is added as a post-added monomer to this reaction step, the amount of the post-added component It is preferable to use 2 equivalents or an excess of alkali with respect to the total number of moles of the polyhydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

The polycondensation by the interfacial polycondensation reaction of the dihydric phenol (I) oligomer and the hydroxyaryl-terminated polydiorganosiloxane (II) is performed by vigorously stirring the above mixed solution.

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

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

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

A branching agent can be used in combination with the above dihydric phenol compound to give a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher-functional polyfunctional aromatic compound used in the branched polycarbonate-polydiorganosiloxane copolymer resin include phloroglucin, phlorogluside, or 4,6-dimethyl-2,4,6-tris(4-hydrodiphenyl). ) Heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris (4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol and other trisphenols, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxy) Examples thereof include phenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among which 1,1,1 -Tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferable, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferable. .. The proportion 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. 0.99 mol%, more preferably 0.01 to 0.8 mol%, particularly preferably 0.05 to 0.4 mol%. The amount of the branched structure can be calculated by 1H-NMR measurement.

The reaction pressure may be any of reduced pressure, normal pressure, and increased pressure, but normally, it can be suitably carried out at normal pressure or the self pressure of the reaction system. The reaction temperature is selected from the range of −20 to 50° C., and in many cases, heat is generated with the polymerization, so water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as the reaction temperature and therefore cannot be specified unconditionally, 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, crosslinking treatment, partial decomposition treatment, etc.) to achieve the desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity [η _SP /c].

The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purification degree) by subjecting it to various post-treatments such as a known separation and purification method. ‥

The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded product is preferably in the range of 1 to 40 nm. The average size is more preferably 1 to 30 nm, further preferably 5 to 25 nm. Below the lower limit of this preferred range, impact resistance and flame retardancy may not be fully exhibited, and above the upper limit of this preferred range, impact resistance may not be exhibited stably. This provides a polycarbonate resin composition excellent in strength and appearance.

The average domain size of the polydiorganosiloxane domains of the polycarbonate-polydiorganosiloxane copolymer resin molded article of the present invention was evaluated by the small angle X-ray scattering method (Small Angle X-ray Scattering: SAXS). The small-angle X-ray scattering method is a method for measuring diffuse scattering/diffraction occurring in a small-angle region within a scattering angle (2θ)<10°. In this small-angle X-ray scattering method, when there are regions with different electron densities of about 1 to 100 nm in the substance, diffuse scattering of X-rays is measured due to the difference in electron density. The particle size of the measurement target is obtained based on the scattering angle and the scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregate structure in which polydiorganosiloxane domains are dispersed in a matrix of a polycarbonate polymer, diffuse scattering of X-rays occurs due to a difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domain. The small-angle X-ray scattering profile was measured by measuring the scattering intensity I at each scattering angle (2θ) in the scattering angle (2θ) range of less than 10°, and the polydiorganosiloxane domain was a spherical domain, and the particle size distribution was uneven. Assuming that there exists, a simulation is performed using a commercially available analysis software from the temporary particle size and the temporary particle size distribution model, and the average size of the polydiorganosiloxane domain is obtained. According to the small angle X-ray scattering method, the average size of polydiorganosiloxane domains dispersed in a matrix of a polycarbonate polymer, which cannot be accurately measured by observation with a transmission electron microscope, can be measured accurately, simply, and with good reproducibility. it can. The average domain size means the number average of individual domain sizes.

The term "average domain size" used in connection with the present invention means a measurement value obtained by measuring a 1.0 mm thickness portion of a three-stage plate produced by the method described in Examples by such a small angle X-ray scattering method. Show. In addition, the analysis was performed using an isolated particle model that does not consider the interaction between particles (interference between particles).

The viscosity average molecular weight (M) of the polycarbonate-polydiorganosiloxane copolymer resin is not particularly limited, but is preferably 1.8×10 ⁴ to 4.0×10 ⁴ , and more preferably 2.0×10 ⁴ to It is 3.5×10 ⁴ , and more preferably 2.2×10 ⁴ to 3.0×10 ⁴ . A polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight of less than 1.8×10 ⁴ may not be able to obtain good mechanical properties. On the other hand, a resin composition obtained from a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight of more than 4.0×10 ⁴ may be inferior in versatility because it is inferior in fluidity during injection molding.

The polycarbonate-polydiorganosiloxane copolymer resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, the polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight exceeding the above range (5×10 ⁴ ) improves the entropy elasticity of the resin. As a result, good moldability is exhibited in gas assist molding and foam molding, which are sometimes used when molding a reinforced resin material into a structural member. More preferred embodiments include a polycarbonate-polydiorganosiloxane copolymer resin (B-1-1 component) having a viscosity average molecular weight of 7×10 ⁴ to 3×10 ⁵ , and a viscosity average molecular weight of 1×10 ⁴ to 3×10 ^4. Polycarbonate-polydiorganosiloxane copolymer resin (B-1-2 component) having a viscosity average molecular weight of 1.6×10 ⁴ to 3.5×10 ⁴ (B-1-2). -1 component) (hereinafter, may be referred to as "polycarbonate-polydiorganosiloxane copolymer resin containing high molecular weight component").

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

The polycarbonate-polydiorganosiloxane copolymer resin (B-1 component) containing a high molecular weight component is prepared by mixing the above-mentioned B-1-1 component and B-1-2 component in various ratios to satisfy a predetermined molecular weight range. You can get it. The B-1-1 component is preferably 2 to 40% by weight in 100% by weight of the B-1 component, more preferably 3 to 30% by weight, and further preferably the B-1-1 component is 3 to 30% by weight. The B-1-1 component is 4 to 20% by weight, and particularly preferably the B-1-1 component is 5 to 20% by weight.

As the method for preparing the B-1 component, (1) a method in which the B-1-1 component and the B-1-2 component are independently polymerized and mixed, and (2) JP-A-5-306336. A method of producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by the GPC method in the same system, as represented by the method disclosed in Japanese Patent Publication No. A method for producing so as to satisfy the condition of one component, and (3) an aromatic polycarbonate resin obtained by the production method (production method of (2)), and a separately produced B-1-1 component and/or Examples thereof include a method of mixing with the component B-1-2.

The viscosity average molecular weight referred to in the present invention is the Ostwald viscosity calculated from a solution prepared by dissolving 0.7 g of a polycarbonate-polydiorganosiloxane copolymer resin in 100 ml of methylene chloride at a specific viscosity (η _SP ) calculated by the following formula at 20° C. Using a total,
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[T ₀ is the number of seconds of methylene chloride drop, t is the number of seconds of drop of the sample solution]
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
The calculation of the viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin in the polycarbonate resin composition of the present invention is carried out as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. The soluble matter is collected by Celite filtration. After that, the solvent in the obtained solution is removed. After removing the solvent, the solid is sufficiently dried to obtain a solid of a component soluble in methylene chloride. A specific viscosity at 20° C. is obtained from a solution prepared by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as above.
(C component: brominated flame retardant)
The resin composition of the present invention contains a brominated flame retardant as the C component. As the brominated flame retardant, brominated polycarbonate (including oligomer) is particularly suitable. Brominated polycarbonate has excellent heat resistance and can significantly improve flame retardancy. In the brominated polycarbonate used in the present invention, the structural unit represented by the following formula (5) is preferably at least 60 mol% of all structural units, more preferably at least 80 mol%, and particularly preferably substantially the following. It is a brominated polycarbonate compound comprising a structural unit represented by the formula (5).

In the formula (5), X is a bromine atom, R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or —SO ₂ —.

Further, in the formula (5), R is preferably a methylene group, an ethylene group, an isopropylidene group or —SO ₂ —, and particularly preferably an isopropylidene group.

The brominated polycarbonate has few residual chloroformate group terminals, and the terminal chlorine amount is preferably 0.3 ppm or less, more preferably 0.2 ppm or less. The amount of such terminal chlorine was obtained by dissolving the sample in methylene chloride, adding 4-(p-nitrobenzyl)pyridine, and reacting with terminal chlorine (terminal chloroformate). This was analyzed by an ultraviolet-visible spectrophotometer (U, Hitachi, Ltd.). -3200) to measure and obtain. When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the flame-retardant polycarbonate resin composition may be better, and molding at higher temperatures becomes possible, and as a result, the resin composition having better molding processability can be obtained. Things may be provided.

Further, it is preferable that the brominated polycarbonate has few remaining hydroxyl groups. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, and more preferably 0.0003 mol or less, relative to 1 mol of the structural unit of the brominated polycarbonate. The amount of terminal hydroxyl groups can be determined by dissolving the sample in deuterated chloroform and measuring by ¹ H-NMR method. With such an amount of terminal hydroxyl groups, the thermal stability of the flame-retardant polycarbonate resin composition may be further improved.

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

The content of the component C is 10 to 20 parts by weight, preferably 12 to 20 parts by weight, and more preferably 12 to 18 parts by weight, based on 100 parts by weight of the total of the components A and B. If the content of the C component is less than 10 parts by weight, flame retardancy is not exhibited, and if it exceeds 20 parts by weight, the appearance is deteriorated.
(Component D: Fluorine-containing anti-dripping agent)
The resin composition of the present invention contains a fluorine-containing anti-dripping agent as the D component. By containing this fluorine-containing anti-dripping agent, good flame retardancy can be achieved without impairing the physical properties of the molded product.

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

The molecular weight of PTFE capable of forming fibrils is extremely high, and PTFE tends to bind to each other by an external action such as shearing force to become fibrous. 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. In addition to the solid form, such PTFE may be in the form of an aqueous dispersion. Further, PTFE having such fibril-forming ability improves dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there.

Examples of commercially available PTFE capable of forming fibrils include Teflon (registered trademark) 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., and Polyflon MPA FA500 and F-201L manufactured by Daikin Industries, Ltd. Commercially available aqueous dispersions of PTFE include Fluon AD-1, AD-936 manufactured by Asahi IC Polymers Co., Ltd., Fluon D-1 and D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro. Typical examples thereof include Teflon (registered trademark) 30J manufactured by Chemical Co., Ltd.

The mixed form of PTFE is (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and coprecipitated to obtain a coaggregation mixture (JP-A-60-258263, Japanese Unexamined Patent Publication (Kokai) No. 63-154744), (2) A method of mixing an aqueous dispersion of PTFE with dried organic polymer particles (Japanese Unexamined Patent Publication No. 4-272957) (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (JP-A 06-220210, JP-A 08-188653, etc.). Described method), (4) a method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of PTFE (method described in JP-A-9-95583), and (5) PTFE A method in which an aqueous dispersion and an organic polymer dispersion are uniformly mixed, and then a vinyl-based monomer is further polymerized in the mixed dispersion to obtain a mixture (method described in JP-A No. 11-29679). What was obtained by can be used. Commercially available products of these mixed forms of PTFE include METHYBRENE A3800 (trade name) manufactured by Mitsubishi Chemical Corporation.

The proportion of PTFE in the mixed form is preferably 1 to 60% by weight and more preferably 5 to 55% by weight in 100% by weight of the PTFE mixture. When the proportion of PTFE is in such a range, good dispersibility of PTFE can be achieved. The ratio of the component D represents the net amount of the fluorine-containing anti-dripping agent, and in the case of PTFE in the mixed form, the net amount of PTFE.

The content of the component D is 0.01 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, and more preferably 0.2 to 1 with respect to 100 parts by weight of the total of the components A and B. Parts by weight. If the content of component D exceeds the above range and is too small, flame retardancy becomes insufficient. On the other hand, when the content of the component D exceeds the above range and is too large, not only the PTFE is deposited on the surface of the molded article and the appearance is deteriorated, but also the cost of the resin composition is increased.

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

The acrylic monomer used in the organic polymer used in the polytetrafluoroethylene-based mixture of the present invention contains an optionally substituted (meth)acrylate derivative. Specifically, the acrylic monomer is substituted with at least one group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, and a glycidyl group. (Meth)acrylate derivatives, 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) Examples thereof include acrylates, maleimides which may be substituted with an alkyl group having 1 to 6 carbon atoms, or aryl groups, for example, maleimides, N-methyl-maleimides and N-phenyl-maleimides, maleic acid, phthalic acid and itaconic acid. However, it is not limited to these. The acrylic monomers may be used alone or in admixture of two or more. Among these, (meth)acrylonitrile is preferable.

The amount of the acrylic monomer-derived unit contained in the organic polymer used in the coating layer is preferably 8 to 11 parts by weight, more preferably 8 to 10 parts by weight, based on 100 parts by weight of the styrene-based monomer-derived unit. Parts, more preferably 8 to 9 parts by weight. If the amount of 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 product may be deteriorated.

The polytetrafluoroethylene-based mixture of the present invention preferably has a residual water content of 0.5% by weight or less, more preferably 0.2 to 0.4% by weight, still more preferably 0.1 to 0. It is 3% by weight. If the residual water content is more than 0.5% by weight, flame retardancy may be adversely affected.

In the manufacturing process of 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. Is external to the branched polytetrafluoroethylene. Further, after the step of forming the coating layer, the residual water content is dried to 0.5% by weight or less, preferably 0.2 to 0.4% by weight, more preferably 0.1 to 0.3% by weight. It is preferable to include a step. The drying step can be performed using a method known in the art, for example, a hot air drying method or a vacuum drying method.

The initiator used in the polytetrafluoroethylene-based mixture of the present invention can be used without limitation as long as it is used in 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 can 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 kind/amount of the monomer, and is 0.15 to 0. It is preferable to use 25 parts by weight.

The polytetrafluoroethylene-based mixture of the present invention was manufactured 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 put into a reactor, and then acrylic monomer and styrene were added while 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, water was removed by centrifugation for 30 minutes in a centrifuge to obtain a pasty product. Then, the product paste was dried in a hot air dryer at 80 to 100° C. for 8 hours. Then, the dried product was pulverized to obtain a polytetrafluoroethylene-based mixture of the present invention.

The suspension polymerization method does not require a polymerization step by emulsion dispersion in the emulsion polymerization method exemplified in Japanese Patent No. 3469391, and thus does not require an emulsifier and an electrolyte salt for coagulating and precipitating a latex after polymerization. Further, in the polytetrafluoroethylene mixture produced by the emulsion polymerization method, since the emulsifier and the electrolyte salt in the mixture easily mix and become difficult to remove, the emulsifier, the sodium metal ion derived from the electrolyte salt, and the potassium metal ion are reduced. It's difficult. Since the polytetrafluoroethylene-based mixture used in the present invention is produced by the suspension polymerization method, it is possible to reduce sodium metal ions and potassium metal ions in the mixture because such emulsifiers and electrolyte salts are not used. The heat stability and hydrolysis resistance can be improved.

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

The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. When the contained polytetrafluoroethylene is not branched polytetrafluoroethylene, the effect of preventing dripping becomes insufficient when the amount of polytetrafluoroethylene added is small. The branched polytetrafluoroethylene is particulate and preferably has a particle diameter of 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, and still more preferably 0.3 to 0.4 μm. When the particle size is smaller than 0.1 μm, the surface appearance of the molded product is excellent, but it is difficult to commercially obtain polytetrafluoroethylene having a particle size smaller than 0.1 μm. If the particle size is larger than 0.6 μm, the surface appearance of the molded product may be deteriorated. 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 , and generally has a high molecular weight. Fluoroethylene is more preferable in terms of stability. Either powder or dispersion form can be used.

The content of branched polytetrafluoroethylene in the coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, still more preferably 47 to 100 parts by weight based on the total weight of the coated branched PTFE. It is 53 parts by weight, particularly preferably 48 to 52 parts by weight, most preferably 49 to 51 parts by weight. When the proportion of the branched polytetrafluoroethylene is within such a range, good dispersibility of the branched polytetrafluoroethylene can be achieved.
(Component E: full ester of polyhydric alcohol and aliphatic carboxylic acid)
The E component used in the present invention is a full ester of a polyhydric alcohol and an aliphatic carboxylic acid (fatty acid full ester). When another ester is used as the E component, good colorability cannot be obtained. The aliphatic carboxylic acid contains a palmitic acid component and a stearic acid component, and in the peak area in the gas chromatograph-mass spectrometry (GC/MS method), the area of the palmitic acid component (Sp) and the area of the stearic acid component ( It is preferable that the total of Ss) and the total aliphatic carboxylic acid component is 80% or more and the area ratio (Ss/Sp) of both is 1.3 to 30.

The full ester in the present invention does not necessarily have an esterification rate of 100%, and may be 80% or more, preferably 85% or more.

The pyrolysis methylation method is used as the GC/MS method in the present invention. That is, a fatty acid full ester as a sample is reacted with methylammonium hydroxide as a reaction reagent on a pyrofil to decompose the fatty acid full ester and produce a methyl ester derivative of a fatty acid, and a GC/MS measurement is performed on the derivative. It is a thing. From such measurement, the total ratio of Ss and Sp in the total aliphatic carboxylic acid component and their area ratio (Ss/Sp) are calculated. Therefore, the peak area of each component is based on each methyl ester derivative.

The upper limit of the area ratio (Ss/Sp) is more preferably 10, more preferably 4, and particularly preferably 2. If the area ratio is less than 1.3, good colorability may not be obtained, and if it exceeds 30, strength may be reduced.

In the composition of the present invention, the fatty acid full ester contained preferably contains the palmitic acid component and the stearic acid component in the specific ratios as described above, and the aspect thereof may be any, for example, the following aspect: Can be mentioned.
Aspect (i): Resin composition obtained by blending one type of fatty acid full ester satisfying the above area ratio (Ss/Sp) in a polycarbonate resin. Aspect (ii): The above area ratio (Ss/Sp) Resin composition in which two or more fatty acid full esters are blended in a polycarbonate resin so as to satisfy the requirements. The production of fatty acid full esters is not particularly limited, and polyhydric alcohols and aliphatic carboxylic acids are conventionally known. It is possible by various methods. Examples of the reaction catalyst include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, calcium oxide, barium oxide, magnesium oxide, zinc oxide, sodium carbonate, potassium carbonate, and organotin compounds such as 2-ethylhexyltin. Are listed.

Further, examples of the production method of the fatty acid full ester satisfying the above area ratio (Ss/Sp) of the invention include the following.
Aspect (1): A full ester is obtained by reacting stearic acid having a purity of about 100% with a polyhydric alcohol. Similarly, palmitic acid and polyhydric alcohol are reacted to obtain a full ester. These are blended with the polycarbonate resin so that the above area ratio (Ss/Sp) is satisfied in the composition of the present invention as in the above aspect (ii).
Aspect (2): A full ester is obtained by reacting an aliphatic carboxylic acid containing both stearic acid and palmitic acid with a polyhydric alcohol. Two or more kinds of these are combined as in the above embodiment (ii) and blended in a polycarbonate resin so as to satisfy the above area ratio (Ss/Sp) conditions in the composition.
Aspect (3): A full-ester is obtained by reacting an aliphatic carboxylic acid containing stearic acid and palmitic acid with a polyhydric alcohol in a composition ratio that satisfies the above area ratio (Ss/Sp) conditions. The resin composition of the present invention is obtained by blending the full ester with a polycarbonate resin.

The aspect (3) is particularly preferable among the above. This is because such an aspect is simple in the production of the composition and is highly uniform because it is produced as an integral compound.

Explain the aliphatic carboxylic acid used in the above aspect (3). As well known, aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from various vegetable fats and animal fats and oils. Since these oils and fats are ester compounds containing various aliphatic carboxylic acids as their components, the stearic acid produced usually contains a large amount of other aliphatic carboxylic acid components such as palmitic acid. Therefore, in order to produce the aliphatic carboxylic acid used in the aspect (3) of the present invention, stearic acid and palmitic acid are used to prepare an aliphatic carboxylic acid satisfying the conditions of the above area ratio (Ss/Sp). It is necessary to use, and it is appropriate to use a fat and oil suitable for the conditions as a raw material of the aliphatic carboxylic acid. It is possible to mix two or more kinds of the above-mentioned aliphatic carboxylic acids so as to have a predetermined composition condition, but it is more preferable to satisfy the predetermined composition condition from one kind of raw material.

Palm oil is widely used as a raw material for aliphatic carboxylic acids because of its production cost advantage. However, in the present invention, it is not appropriate to use such an aliphatic carboxylic acid derived from palm oil in the above aspect (3). Examples of fats and oils as a raw material for the aliphatic carboxylic acid include animal fats and oils such as beef tallow and lard, and linseed oil, safflower oil, sunflower oil, soybean oil, corn oil, peanut oil, cottonseed oil, sesame oil, olive oil, and the like. The vegetable oils and fats of the above can be mentioned. Among the above, animal fats and oils are preferable, and beef tallow is more preferable, because they contain more stearic acid. Further, among beef tallow, oleostearine containing a large amount of saturated components such as stearic acid and palmitic acid is preferable.

On the other hand, the polyhydric alcohol used preferably has 3 to 32 carbon atoms. Specific examples of the polyhydric alcohol include glycerin, diglycerin, polyglycerin (for example, decaglycerin, etc.), pentaerythritol, dipentaerythritol, diethylene glycol, propylene glycol and the like, among which pentaerythritol is preferable.

Explain the acid value, hydroxyl value, iodine value of fatty acid full ester, and 5% weight loss temperature in TGA (thermogravimetric analysis) measurement.

The acid value of the fatty acid full ester is preferably low from the viewpoint of suppressing the strength reduction, while it is preferably relatively high from the viewpoint of improving the coloring property. The acid value of the fatty acid full ester is preferably in the range of 0.1 to 20, more preferably in the range of 2 to 18, and even more preferably in the range of 5 to 15. If the oxidation is less than 0.1, good colorability may not be obtained, and if it exceeds 2, strength may be reduced. Here, the acid value is the mg number of potassium hydroxide required to neutralize free fatty acids and the like contained in 1 g of the sample, and can be determined by the method specified in JIS K0070. Although the relationship between the acid value and the reduction of the releasing force is not clear in the above, it is considered that the unreacted free carboxylic acid is likely to migrate to the surface during molding.

The hydroxyl value of the fatty acid full ester is preferably low from the viewpoint of suppressing strength reduction and improving colorability, while too low is not preferable because the manufacturing time increases and the cost increases. The hydroxyl value of the fatty acid full ester is preferably in the range of 0.1 to 40, more preferably in the range of 1 to 30, and even more preferably in the range of 2 to 20. Here, the hydroxyl value is the number of mg of potassium hydroxide required to neutralize the acetic acid bound to the hydroxyl group when 1 g of the sample is acetylated, and can be determined by the method specified in JIS K0070. ..

Io The iodine value of the fatty acid full ester is preferably low from the viewpoint of suppressing the reduction in strength. The iodine value of the fatty acid full ester is preferably 10 or less, more preferably 1 or less. The iodine value is an amount obtained by converting the amount of halogen bound when 100 g of a sample is reacted with halogen into the g number of iodine, and can be obtained by the method specified in JIS K0070.

The 5% weight loss temperature in TGA (thermogravimetric analysis) measurement of fatty acid full ester is preferably moderately low from the viewpoint of improving the colorability, and is preferably high from the viewpoint of suppressing strength reduction. The 5% weight loss temperature of the fatty acid full ester is preferably in the range of 250 to 400°C, more preferably in the range of 280 to 360°C, further preferably in the range of 300 to 350°C, particularly preferably in the range of 310 to 340°C. The 5% weight loss temperature is determined by the TGA measuring device under the measurement condition that the temperature is raised from 23° C. in a nitrogen gas atmosphere to 600° C. at a heating rate of 20° C./min. Although the relationship between the 5% weight loss temperature and the reduction of the mold release force is not clear in the above, those having a weight loss temperature in the above range have high volatility components such as unreacted free carboxylic acid. It is considered that this is due to the fact that the above components are contained in an appropriate amount and such components easily migrate to the surface during molding.

The content of the E component is 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight, and more preferably 0.2 to 0. 0, based on 100 parts by weight of the total of the A component and the B component. 8 parts by weight. When the amount of polyvalent fatty acid ester is less than 0.05 parts by weight, the appearance is not sufficiently improved, and when it is used in excess of 2 parts by weight, the flame retardancy of the molded product is lowered.
(F component: adhesion improver)
The adhesion improver used as the F component of the present invention is a compound that improves the adhesion between the resin composition and the carbon fiber. Among them, an organic compound having at least one functional group selected from the group consisting of an epoxy group, a carboxylic acid group and an acid anhydride group in one molecule is preferably used.

In the present invention, in order to remarkably exhibit the strength improving effect which is the effect of the present invention, the above organic compound may be contained. When the resin composition of the present invention is blended with the above-mentioned organic compound, it becomes possible to strengthen the adhesiveness between the resin composition and the carbon fiber, whereby the strength improving effect is remarkably exhibited.

The epoxy group-containing compound is not particularly limited as long as it is an organic compound containing an epoxy group, and examples thereof include a phenoxy resin and an epoxy resin.

Examples of the phenoxy resin include phenoxy resins represented by the following general formula (6).

(In the formula, X is at least one group selected from the group consisting of groups represented by the following general formula (7), Y is a residue of a compound that reacts with a hydrogen atom or a hydroxyl group, and n is an integer of 0 or more. .)

(In the formula, Ph represents a phenyl group.)
Examples of the epoxy resin include epoxy resins represented by the following general formula (8).

(In the formula, X and n are the same as those in the general formula (6).)
In the general formula (6), examples of the compound that reacts with a hydroxyl group include a compound having an ester, a carbonate, an epoxy group, a carboxylic acid anhydride, an acid halide, a compound having an isocyanate group, and the like. In particular, an intramolecular ester is preferable, and examples thereof include caprolactone. In the phenoxy resin represented by the general formula (6), the compound in which Y is a hydrogen atom can be easily produced from divalent phenols and epichlorohydrin. A compound in which Y is a residue of a compound that reacts with a hydroxyl group can be easily produced by mixing a phenoxy resin produced from a divalent phenol and epichlorohydrin with a compound that reacts with the hydroxyl group under heating. You can

The epoxy resin represented by the above general formula (7) can be easily produced from divalent 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 and 4,4′-dihydroxy. Biphenyl or the like is used.

Commercially available products can also be used as the phenoxy resin and the epoxy resin. Commercially available phenoxy resins (bisphenol A type) include PKHB (InChem, Mw=13,700), PKHH (InChem, Mw=29,000), PKFE (InChem, Mw=36,800). ), YP-50 (manufactured by Tohto Kasei Co., Ltd., Mw=43,500) and the like. Commercial products of epoxy resin (bisphenol A type) include EPICLON HM-101 (manufactured by Dainippon Ink and Chemicals, Inc., Mw=48,000), jER1256 (manufactured by Mitsubishi Chemical Corporation, Mw=26,600), etc. Are listed.

The weight average molecular weight of the phenoxy resin and the epoxy resin is not particularly limited, but is usually 5,000 to 100,000, preferably 8,000 to 80,000, more preferably 10,000 to 50,000. is there. When the weight average molecular weight is in the range of 5,000 to 100,000, the mechanical properties are particularly good.

Also, as an organic compound containing an epoxy group, a polymer of a vinyl unit containing a glycidyl group can be mentioned. Specific examples of the glycidyl group-containing vinyl unit include glycidyl methacrylate, glycidyl itaconate, diglycidyl itaconate, allyl glycidyl ether, styrene-4-glycidyl ether, and 4-glycidyl styrene, which have impact resistance and strength improving effects. Glycidyl methacrylate is most preferably used because of its large size.

The carboxylic acid group-containing compound is not particularly limited as long as it is an organic compound containing a carboxylic acid group, but from the viewpoint of compatibility with the component A, aromatic polyesters such as polybutylene terephthalate, polyethylene terephthalate and polyarylate. A resin is preferable, and polybutylene terephthalate is most preferably used because it is excellent in impact resistance and fluidity.

As the aromatic polybutylene terephthalate resin and the aromatic polyethylene terephthalate resin which are preferably used in the present invention, of the dicarboxylic acid component and the diol component forming the polyester, 70 mol% or more of 100 mol% of the dicarboxylic acid component is aromatic. An aromatic polyester resin that is a dicarboxylic acid is preferable, more preferably 90 mol% or more, and most preferably 99 mol% or more is an aromatic polyester resin that is an aromatic dicarboxylic acid. Examples of this dicarboxylic acid include terephthalic acid, isophthalic acid, adipic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbenedicarboxylic acid and 4,4-biphenyldicarboxylic acid. Acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4- Examples thereof include diphenoxyethanedicarboxylic acid, 5-Nasulfoisophthalic acid, ethylene-bis-p-benzoic acid and the like. These dicarboxylic acids can be used alone or in admixture of two or more. The aromatic polyester resin of the present invention can be copolymerized with an aliphatic dicarboxylic acid component of less than 30 mol% in addition to the above aromatic dicarboxylic acid. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Examples of the diol component of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2. 4,4-Tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3 Examples thereof include cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis(2-hydroxyethyl ether) and the like. These may be used alone or in combination of two or more. The dihydric phenol content in the diol component is preferably 30 mol% or less.

Regarding the method for producing the aromatic polybutylene terephthalate resin and the aromatic polyethylene terephthalate resin used in the present invention, according to a conventional method, in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., dicarboxylic acid while heating. It is carried out by polymerizing the component and the diol component and discharging the by-produced water or lower alcohol out of the system. For example, examples of the germanium-based polymerization catalyst include germanium oxide, hydroxide, halide, alcoholate, phenolate, and the like, and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, and the like. Can be illustrated. Further, in the present invention, compounds such as manganese, zinc, calcium and magnesium used in the transesterification reaction which is a prior stage of polycondensation which is conventionally known can be used in combination, and phosphoric acid or phosphorus after the transesterification reaction is completed. It is also possible to deactivate such a catalyst with an acid compound or the like for polycondensation. Furthermore, the method for producing the aromatic polybutylene terephthalate resin and the aromatic polyethylene terephthalate resin can be either batch type or continuous polymerization type.

The molecular weight of the aromatic polybutylene terephthalate resin and the aromatic polyethylene terephthalate resin of the present invention is not particularly limited, but the intrinsic viscosity measured at 25° C. with o-chlorophenol as a solvent is 0.4 to 1.5. It is preferably 0.5 to 1.2, and particularly preferably 0.5 to 1.2.

The amount of terminal carboxyl groups of the aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin used in the present invention is preferably 5 to 75 eq/ton, more preferably 5 to 70 eq/ton, and further preferably 7 to 65 eq/ton. Is.

The aromatic polyarylate resin preferably used in the present invention is obtained from an aromatic dicarboxylic acid or its derivative and a dihydric phenol or its derivative. The aromatic dicarboxylic acid used for preparing the polyarylate may be any one as long as it reacts with the dihydric phenol to give a satisfactory polymer, and one kind or a mixture of two or more kinds is used.

Favorable aromatic dicarboxylic acid components include terephthalic acid and isophthalic acid. It may also be a mixture of these.

Specific examples of the dihydric phenol component include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane and 2,2-bis(4- Hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'- Dihydroxydiphenylmethane, 2,2'-bis(4hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4, 4'-dihydroxydiphenyl, hydroquinone and the like can be mentioned. Although these dihydric phenol components are para-substituted, other isomers may be used, and ethylene glycol, propylene glycol, neopentyl glycol and the like may be used in combination with the dihydric phenol component.

Among the above, preferable polyarylate resins include those in which the aromatic dicarboxylic acid component is terephthalic acid and isophthalic acid and the dihydric phenol component is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). To be The ratio of terephthalic acid to isophthalic acid is preferably terephthalic acid/isophthalic acid=9/1 to 1/9 (molar ratio), and particularly preferably 7/3 to 3/7 in terms of melt processability and performance balance.

Other representative polyarylate resins include those in which the aromatic dicarboxylic acid component is terephthalic acid and the dihydric phenol component is bisphenol A and hydroquinone. The ratio of such bisphenol A and hydroquinone is preferably bisphenol A/hydroquinone=50/50 to 70/30 (molar ratio), more preferably 55/45 to 70/30, and further preferably 60/40 to 70/30. ..

The viscosity average molecular weight of the polyarylate resin in the present invention is preferably in the range of about 7,000 to 100,000 from the viewpoint of physical properties and extrusion processability. For the polyarylate resin, either of the interfacial polycondensation method and the transesterification reaction method can be selected. As the acid anhydride group-containing compound, as a maleic acid resin, a marquise series (maleic acid resin, manufactured by Arakawa Chemical Co., Ltd.), an alaster series (styrene-maleic acid resin, manufactured by Arakawa Chemical Co., Ltd.), an isovan series ( Isobutylene-maleic anhydride block copolymer, manufactured by Kuraray Co., Ltd., and the like, and styrene-maleic acid resin is most preferably used from the viewpoint of compatibility with the component A.

The content of the component F is preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the resin composition including the components A and B. When the content of the F component is less than 1 part by weight, a resin composition having excellent strength may not be obtained. Further, if it exceeds 10 parts by weight, flame retardancy may decrease.
[Easily impregnable carbon fiber bundle]
The easily impregnable carbon fiber bundle in the present invention means a polycarbonate resin composition (preferably a plasticized polycarbonate resin composition, by containing 3 to 15 parts by weight of an impregnation aid with respect to 100 parts by weight of carbon fibers. ) Is easily impregnated with the carbon fiber bundle.

The impregnation aid preferably satisfies the following formulas (1) and (2).
Viscosity at 300°C ≤ 10 Pa·s (1)
2≦(Tg ₀ −Tg ₁ )/D (2)
[Wherein D is the proportion (% by weight) of the impregnating aid in the resin composition comprising the polycarbonate resin and the impregnating aid, and Tg ₁ is the resin composition obtained by adding the impregnating aid to the polycarbonate resin in this proportion. Glass transition temperature (° C.) and Tg ₀ represent the glass transition temperature (° C.) of the polycarbonate resin. ]
The easily impregnable carbon fiber bundle may be any carbon fiber bundle containing an impregnation aid in a predetermined amount with respect to the carbon fiber, a method for producing the same, and a form in which the carbon fiber and the impregnation aid are contained. It doesn't matter. The impregnation aid used in the present invention preferably satisfies the above formula (1), which has a low viscosity state at 300° C. which is a typical processing temperature of a general-purpose polycarbonate, and This means that viscosity measurement as a liquid at 300° C. is possible. The viscosity of the impregnation aid at 300° C. is preferably 8 Pa·s or less, and more preferably 6 Pa·s or less. If the viscosity at 300° C. exceeds 10 Pa·s, the dispersibility of the carbon fiber in the resin may be impaired during molding, and a good appearance may not be obtained.

Regarding the above formula (1), a rotary viscometer is suitable as a method for measuring the viscosity of the impregnation aid as a liquid. Specifically, a method of measuring with a parallel plate with a high temperature tank can be exemplified.

Further, the impregnation aid preferably satisfies the above formula (2). In the above formula (2), the impregnation aid does not have to have (Tg ₀ −Tg ₁ )/D of 2 or more in the entire range of the compounding amount of 3 to 15 parts by weight per 100 parts by weight of the polycarbonate. It may be 2 or more in a part of the blending amount range. When (Tg ₀ −Tg ₁ )/D is 2 or more, it has an effect of promoting impregnation, and (Tg ₀ −Tg ₁ )/D is more preferably 3 or more. When (Tg ₀ −Tg ₁ )/D is less than 2, the impregnation aid is in a state not compatibilized with the polycarbonate, and therefore, it is presumed that the Tg of the polycarbonate is measured almost as it is. Even if an impregnation aid having a (Tg ₀ −Tg ₁ )/D of less than 2 is added to a carbon fiber bundle and a polycarbonate is adhered to the bundle, the effect of promoting impregnation by the impregnation aid is extremely low. In the obtained molded product, carbon fiber may be poorly dispersed.

Regarding the above formula (2), as a method for measuring the glass transition temperature of the polycarbonate resin or the resin composition of the polycarbonate resin and the impregnation aid, a method by differential scanning calorimetry (DSC) and the like can be mentioned.

The easily impregnable carbon fiber bundle used in the present invention may contain plural kinds of impregnation aids, and the impregnation aid used in the present invention is selected from the group consisting of aliphatic hydroxycarboxylic acid-based polyesters. It is preferable that it is one or more of These aliphatic hydroxycarboxylic acid type polyesters used as the impregnation aid will be described later in detail. The amount of the impregnation aid attached to the easily impregnable carbon fiber bundle is 3 to 15 parts by weight, preferably 5 to 12 parts by weight, more preferably 6 to 10 parts by weight, based on 100 parts by weight of the carbon fibers. When the amount is less than 3 parts by weight, the impregnability of the polycarbonate resin into the carbon fibers is insufficient, so that the appearance and colorability of the resulting molded article are deteriorated, and when the amount is more than 15 parts by weight, the impregnability is excellent, but the matrix resin When the glass transition temperature of a polycarbonate resin is lowered, the flame retardancy of the obtained molded article is lowered.

As a typical production method of the easily impregnable carbon fiber bundle, a general-purpose carbon fiber bundle is impregnated by one or more kinds selected from the group selected from a dipping method, a spray method, a roller transfer method, a slit coater method and the like. A method of incorporating an auxiliary is exemplified. In these methods, when the carbon fiber bundle contains an impregnation auxiliary agent, the impregnation auxiliary agent mainly adheres to the surface of the carbon fiber bundle, and a part of the impregnation auxiliary agent also penetrates into the inside of the carbon fiber bundle. Seem.

The form of the impregnation aid in the production of the easily impregnable carbon fiber bundle can be handled as an aqueous emulsion, an organic solvent diluted solution, or a heated viscous or molten liquid. A preferred combination of the production method and the form of the impregnation aid is a dipping method or a roller transfer method in the case of an aqueous emulsion, but a drying step under an atmosphere of 100° C. or higher is required to sufficiently dry the water. Becomes Further, in the case of the heated viscous liquid, a general coating method such as a slit coater method is possible, and it is possible to apply an appropriate amount to the carbon fiber bundle and then apply it uniformly with a smoothing roll or the like.

In order to obtain a molded product in which carbon fibers are homogeneously dispersed in polycarbonate by molding using the molding material of the present invention, it is preferable that the impregnation aid is attached to the carbon fiber bundle as uniformly as possible. As a method of more uniformly adhering the impregnation aid to the carbon fiber bundle, a method of attaching the impregnation aid to the carbon fiber bundle by the above method and then heat-treating again at a temperature at which the viscosity of these impregnation aids is sufficiently lowered Is exemplified. Further, for the heat treatment, for example, hot air, a hot plate, a roller, an infrared heater or the like can be used, and a roller is preferably used.
[Carbon fiber]
The carbon fiber contained in the molding material of the present invention may be any carbon fiber such as polyacrylonitrile (PAN) type, petroleum/petroleum pitch type, rayon type and lignin type. In particular, PAN-based carbon fiber made from PAN is preferable because it has excellent productivity and mechanical properties on a factory scale.

As carbon fibers, those having an average diameter of 5 to 10 μm can be preferably used. A general carbon fiber is a carbon fiber filament in which 1,000 to 50,000 single fibers form a fiber bundle. The carbon fiber bundle in the present invention includes such general carbon fiber filaments, but the carbon fiber filaments are further superposed and combined into a yarn, or the combined yarn is twisted to form a twisted yarn. Is also included. As the carbon fibers contained in the molding material of the present invention, those having an oxygen-containing functional group introduced on the surface by a surface treatment are also preferable in order to enhance the adhesiveness between the carbon fibers and the polycarbonate.

Further, as described above, when the easily impregnable carbon fiber bundle is made by including the impregnation aid in the carbon fiber bundle, the carbon fiber bundle is stabilized in order to stabilize the step of uniformly attaching the impregnation aid to the carbon fiber bundle. It is preferable that it is treated with a converging agent for imparting converging property. As the sizing agent, those known for producing carbon fiber filaments can be used. Further, as the carbon fiber bundle, even if the oil agent used for improving the slipperiness during production remains, it can be used without problems in the present invention. In addition, hereinafter, the term "surface treatment agent" may be used in the sense of a superordinate concept including the impregnation aid and the other treatment agents such as the above-mentioned sizing agent.
[Aliphatic Hydroxycarboxylic Acid Polyester]
In the present invention, the aliphatic hydroxycarboxylic acid-based polyester that can be used as the impregnation aid is a polyester composed of an aliphatic hydroxycarboxylic acid residue, and may be a single-polymerized polyester composed of a single aliphatic hydroxycarboxylic acid residue. It may be a copolyester containing certain aliphatic hydroxycarboxylic acid residues. Further, the aliphatic hydroxycarboxylic acid-based polyester is a residue other than the aliphatic hydroxycarboxylic acid residue, such as a diol residue or a dicarboxylic acid, in an amount of less than 50 mol% of the residues constituting the polymer. A copolyester containing an acid residue or the like may be used, but a homopolymer to which no copolymerization component is intentionally added is preferable because it is easily available.

The weight average molecular weight of the aliphatic hydroxycarboxylic acid type polyester used in the present invention is preferably 3,000 to 50,000. When the weight average molecular weight is in the range of 3,000 to 50,000, the affinity with the polycarbonate resin is good and the emulsification is easy. The range is more preferably 5,000 to 20,000, further preferably 8,000 to 15,000. As a method for measuring the weight average molecular weight, a known method such as a high temperature GPC method can be used.

The aliphatic hydroxycarboxylic acid-based polyester is not particularly limited, but each homopolymer of ε-caprolactone, δ-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, and enanthlactone, And a copolymer of two or more kinds of these monomers, and ε-caprolactone, δ-caprolactone, β-propiolactone, γ-butyrolactone, δ-valero having a weight average molecular weight of 3,000 to 50,000 are preferable. One or more selected from the group consisting of homopolymers of lactone, γ-valerolactone, and enanthlactone, and copolymers of two or more kinds of these monomers having a weight average molecular weight of 3,000 to 50,000. Is more preferable. Particularly preferred are homopolymers of ε-caprolactone or δ-caprolactone having a weight average molecular weight of 3,000 to 50,000. In the present invention, when referring to a lactone polymer, not only a polymer obtained by ring-opening polymerization of a lactone but also an aliphatic hydroxycarboxylic acid or a derivative thereof which is an equivalent of the lactone is used as a raw material. Polymers of similar structure are also included.
[Molding material]
In the molding material of the present invention, the polycarbonate resin composition adheres to the easily impregnable carbon fiber bundle in an amount of 50 to 2,000 parts by weight per 100 parts by weight of the carbon fiber contained in the easily impregnable carbon fiber bundle. The amount is preferably 66 to 1,900 parts by weight, more preferably 100 to 1,800 parts by weight. If the amount of adhesion is less than 50 parts by weight, the predetermined shape of the molding material cannot be obtained, and if it exceeds 2,000 parts by weight, good strength cannot be obtained. The shape of the molding material of the present invention is not particularly limited, and examples thereof include a columnar shape, a plate shape, a granular shape, a lump shape, a thread shape (string shape), a net shape, and the like, and a plurality of molding materials having different shapes may be used for molding. It is possible.

The method of forming the molding material of the present invention by attaching the polycarbonate resin composition to the easily impregnable carbon fiber bundle, a method of coating the surface of the easily impregnable carbon fiber bundle with a polycarbonate resin composition in a molten state, A method of casting a melted polycarbonate resin composition using a T-die or the like after stacking the easily impregnable carbon fiber bundles, and laminating the easily impregnated carbon fiber bundles into a film-like polycarbonate resin composition resin A method of laminating and laminating, a method of spraying a powdery polycarbonate resin composition after aligning the easily impregnable carbon fiber bundle, and the like. Instead of the easily impregnable carbon fiber bundles arranged in a continuous manner, an aggregate of easily impregnable fiber bundles cut into a predetermined length can be used in the same manner.

The molding material of the present invention preferably has a core-sheath structure having an easily impregnable carbon fiber bundle as a core component and a polycarbonate resin composition as a sheath component, and particularly, for the molding material of the present invention, for injection molding. As the one, the easily impregnable carbon fiber bundle is obtained by cutting a strand coated with the polycarbonate resin composition around the strand with a strand cutter, the easily impregnable carbon fiber bundle as a core component, a polycarbonate resin composition. A pellet having a core-sheath structure having a sheath component is more preferable, and a pellet having a longitudinal length of about 3 to 10 mm (hereinafter, also referred to as a core-sheath pellet) is more preferable. The diameter of the core-sheath pellet is not particularly limited, but is preferably 1/10 or more and 2 times or less the pellet length, and more preferably 1/4 or more of the pellet length and equal to or less than the pellet length.
(Other ingredients)
Various additives may be added to the polycarbonate resin composition of the present invention within a range that does not impair the effects of the present invention. Examples of such additives include phosphorus-based heat stabilizers, phenol-based heat stabilizers, sulfur-containing antioxidants, release agents, ultraviolet absorbers, hindered amine-based light stabilizers, compatibilizers, flame retardants, dyes and pigments, and the like. To be Hereinafter, these additives will be specifically described.
(Phosphorus heat stabilizer)
As the phosphorus-based stabilizer used in the present invention, any of a phosphite compound, a phosphonite compound and a phosphate compound can be used.

A variety of phosphite compounds can be used. Specific examples include phosphite compounds represented by the following general formula (9), phosphite compounds represented by the following general formula (10), and phosphite compounds represented by the following general formula (11).

[Wherein R ³¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a halo or alkylthio (alkyl group) thereof. Represents a C1 to C30) or hydroxy substituent, and three R ^{31 s} may be the same or different from each other, and a cyclic structure may be selected by being derived from a dihydric phenol. ]

[Wherein R ³² and R ³³ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkylaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, and an alkyl group having 4 to 20 carbon atoms] A cycloalkyl group and a 2-(4-oxyphenyl)propyl-substituted aryl group having 15 to 25 carbon atoms are shown. The cycloalkyl group and the aryl group can be selected from those not substituted with an alkyl group and those substituted with an alkyl group. ]

[Wherein R ³⁴ and R ³⁵ are alkyl groups having 12 to 15 carbon atoms]. It should be noted that R ³⁴ and R ³⁵ can be selected whether they are the same as or different from each other. ]
Examples of the phosphonite compound include a phosphonite compound represented by the following general formula (12) and a phosphonite compound represented by the following general formula (13).

[Wherein Ar ¹ and Ar ² represent an aryl group or an alkylaryl group having 6 to 20 carbon atoms or a 2-(4-oxyphenyl)propyl-substituted aryl group having 15 to 25 carbon atoms, and four Ar ¹ are Either the same or different from each other can be selected. Alternatively, the ^two Ar ² can be selected to be the same or different from each other. ]
Preferred specific examples of the phosphite compound represented by the general formula (9) include diphenylisooctylphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, diphenylmono. (Tridecyl)phosphite, phenyldiisodecylphosphite, and phenyldi(tridecyl)phosphite.

Preferred specific examples of the phosphite compound represented by the general formula (10) include distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2 ,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like are preferable, and distearyl pentaerythritol diphosphite is preferable, Examples thereof include bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite. Such phosphite compounds can be used alone or in combination of two or more.

A preferred specific example of the phosphite compound represented by the general formula (11) is 4,4'-isopropylidenediphenol tetratridecyl phosphite.

Specific preferred examples of the phosphonite compound represented by the general formula (12) include tetrakis(2,4-di-iso-propylphenyl)-4,4′-biphenylenediphosphonite and tetrakis(2,4-di). -N-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert) -Butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, tetrakis(2,6-di-iso-propyl) Phenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,6-di-n-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3 , 3'-biphenylenediphosphonite and the like, tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite is preferable, and tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonite is more preferable. preferable. The tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite is preferably a mixture of two or more kinds, specifically, tetrakis(2,4-di-tert-butylphenyl)-4,4. '-Biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite and tetrakis(2,4-di-tert-butylphenyl)-3,3' -One or two or more kinds of biphenylenediphosphonite can be used in combination, but a mixture of these three kinds is preferable.

Preferred specific examples of the phosphonite compound represented by the above general formula (13) include bis(2,4-di-iso-propylphenyl)-4-phenyl-phenylphosphonite and bis(2,4-di-n). -Butylphenyl)-3-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3 -Phenyl-phenylphosphonite bis(2,6-di-iso-propylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphonite, Examples thereof include bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite. Di-tert-butylphenyl)-phenyl-phenylphosphonite is preferred, and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite is more preferred. The bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite is preferably a mixture of two or more kinds, specifically, bis(2,4-di-tert-butylphenyl)-4- One or two of phenyl-phenylphosphonite and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite can be used in combination, but preferably two of these are used. It is a mixture. In the case of a mixture of two kinds, the mixing ratio by weight is preferably in the range of 5:1 to 4, more preferably in the range of 5:2 to 3.

On the other hand, as the phosphate compound, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl. Phosphate, diisopropyl phosphate and the like can be mentioned, with preference given to trimethyl phosphate.

Among the phosphorus-containing heat stabilizers, more preferable compounds include compounds represented by the following general formulas (14) and (15).

[In the formula, R ³⁶ and R ³⁷ each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. ]

[Wherein R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or aralkyl. R ⁴⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴⁶ represents a hydrogen atom or a methyl group. ]
In formula (14), R ³⁶ and R ³⁷ are preferably alkyl groups having 1 to 12 carbon atoms, and more preferably alkyl groups having 1 to 8 carbon atoms. Specific examples of the compound represented by the formula (14) include tris(dimethylphenyl)phosphite, tris(diethylphenyl)phosphite, tris(di-iso-propylphenyl)phosphite, tris(di-n-butyl). Phenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl) Examples of the phosphite include tris(2,6-di-tert-butylphenyl)phosphite.

Specific examples of the compound represented by the formula (15) include phosphite derived from 2,2′-methylenebis(4,6-di-tert-butylphenol) and 2,6-di-tert-butylphenol, 2 , 2'-methylenebis(4,6-di-tert-butylphenol) and a phosphite derived from phenol, especially from 2,2'-methylenebis(4,6-di-tert-butylphenol) and phenol. Derived phosphites are preferred.

The content of the phosphorus-based heat stabilizer is preferably 0.001 to 3.0 parts by weight, more preferably 0.01 to 2.0 parts by weight, based on 100 parts by weight of the total of the components A and B, and It is preferably 0.05 to 1.0 part by weight. If the content of the phosphorus-based heat stabilizer is less than 0.001 part by weight, the mechanical properties may not be sufficiently exhibited, and if it exceeds 3.0 parts by weight, the mechanical properties may not be sufficiently exhibited.
(Phenolic heat stabilizer)
The phenol-based stabilizer used in the present invention generally includes hindered phenols, semi-hindered phenols, and less hindered phenol compounds, but particularly from the viewpoint of applying a heat-stable formulation to polypropylene-based resins. A hindered phenol compound is more preferably used. Specific examples of such hindered phenol compounds include vitamin E, n-octadecyl-β-(4′-hydroxy-3′,5′-di-tert-butylfel)propionate, 2-tert-butyl-6. -(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-ethyl-6-tert) -Butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6- α-methyl-benzyl-p-cresol)2,2′-ethylidene-bis(4,6-di-tert-butylphenol), 2,2′-butylidene-bis(4-methyl-6-tert-butylphenol), 4,4′-butylidene bis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6- Hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, bis[2-tert-butyl-4-methyl 6-(3-tert-butyl-5-methyl-2 -Hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2, 4,8,10-Tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol) ), 2,2′-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4′-di-thiobis(2,2) 6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,4-bis(n-octylthio)-6-(4 -Hydroxy-3',5'-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide ), N,N′-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert) -Butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl) -4-Hydroxyphenyl)isocyanurate, Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6 -Dimethylbenzyl) isocyanurate, 1,3,5-tris2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3', 5′-di-tert-butyl-4-hydroxyphenyl)propionate]methane and the like can be mentioned, and preferably used.

More preferably, n-octadecyl-β-(4′-hydroxy-3′,5′-di-tert-butylfel)propionate, 2-tert-butyl-6-(3′-tert-butyl-5′-methyl) -2'-hydroxybenzyl)-4-methylphenyl acrylate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,- Dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, and tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane And n-octadecyl-β-(4′-hydroxy-3′,5′-di-tert-butylfel)propionate is more preferable.
(Sulfur-containing antioxidant)
A sulfur-containing antioxidant can also be used as an antioxidant in the polycarbonate resin composition of the present invention. In particular, it is suitable when the resin composition is used for rotational molding or compression molding. Specific examples of the sulfur-containing antioxidant include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodipropionic acid ester. , Distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, pentaerythritol tetra(β-laurylthiopropionate) ester, bis[2-methyl-4 -(3-laurylthiopropionyloxy)-5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis(2-naphthol), etc. be able to. More preferably, pentaerythritol tetra(β-laurylthiopropionate) ester can be mentioned.

The phosphorus-based stabilizer, the phenol-based stabilizer, and the sulfur-containing antioxidant listed above can be used alone or in combination of two or more kinds. The content of the phenolic stabilizer and the sulfur-containing antioxidant is preferably 0.0001 to 1 part by weight based on 100 parts by weight of the total of the component A and the component B. The amount is more preferably 0.0005 to 0.5 part by weight, still more preferably 0.001 to 0.2 part by weight.
(UV absorber)
The polycarbonate resin composition of the present invention may contain an ultraviolet absorber. Examples of benzophenone-based compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy- 5-Sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2 ,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl) ) Methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like are exemplified.

In the benzotriazole type, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3, 5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3 ,3-Tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2- Hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5) -Tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'- Methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2-hydroxy-3-(3,4,4) 5,6-Tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, and vinyl monomer copolymerizable with 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and the monomer 2-hydroxyphenyl-2H, such as a copolymer with 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer Examples thereof include polymers having a benzotriazole skeleton.

In the hydroxyphenyl triazine type, for example, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5 -Triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl -1,3,5-triazin-2-yl)-5-propyloxyphenol and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol It is illustrated. Furthermore, the phenyl group of the above exemplified compounds such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol is 2,4-dimethyl. A compound having a phenyl group is exemplified.

In the cyclic imino ester system, for example, 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazine -4-one), 2,2′-(2,6-naphthalene)bis(3,1-benzoxazin-4-one) and the like.

In the case of cyanoacrylates, for example, 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy ] Methyl)propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene and the like are exemplified.

Further, the above-mentioned UV absorber has a structure of a monomer compound capable of radical polymerization, whereby the UV-absorbing monomer and/or the light-stable monomer having a hindered amine structure and an alkyl (meth)acrylate are used. It may be a polymer type ultraviolet absorber obtained by copolymerizing with a monomer such as. Preferred examples of the ultraviolet absorbing monomer include compounds having a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester. It

Among the above, a benzotriazole type and a hydroxyphenyl triazine type are preferable in terms of ultraviolet absorption ability, and a cyclic iminoester type and a cyanoacrylate type are preferable in terms of heat resistance and hue (transparency). The above UV absorbers may be used alone or as a mixture of two or more kinds.

The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, and further preferably 0.03 with respect to 100 parts by weight as the total of the components A and B. To 1 part by weight, more preferably 0.05 to 0.5 part by weight.
(Hindered amine light stabilizer)
The polycarbonate resin composition of the present invention may contain a hindered amine light stabilizer. The hindered amine light stabilizer is generally called HALS (Hindered Amine Light Stabilizer) and is a compound having a 2,2,6,6-tetramethylpiperidine skeleton in its structure, for example, 4-acetoxy-2,2,6. ,6-Tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(phenylacetoxy)-2, 2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2, 2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2, 2,6,6-tetramethylpiperidine, 4-(ethylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(cyclohexylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(phenylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl)carbonate, bis(2,2,6,6-tetra Methyl-4-piperidyl)oxalate, bis(2,2,6,6-tetramethyl-4-piperidyl)malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2 2,6,6-tetramethyl-4-piperidyl)adipate, bis(2,2,6,6-tetramethyl-4-piperidyl)terephthalate, bis(1,2,2,6,6-pentamethyl-4-) Piperidyl)carbonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)oxalate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)malonate, bis(1,2,2 2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis(1,2,2,6,6-pentamethyl-4- Piperidyl) terephthalate, N,N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, 1,2-bis(2,2,6,6-tetra Methyl-4-pi Peridyloxy)ethane, α,α'-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-p-xylene, bis(2,2,6,6-tetramethyl-4-piperidyltolylene -2,4-dicarbamate, bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene-1,6-dicarbamate, tris(2,2,6,6-tetramethyl-4) -Piperidyl)-benzene-1,3,5-tricarboxylate, N,N',N",N'"-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2) ,6,6-Tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine·1,3,5-triazine·N,N′ -Polycondensation product of bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine , Poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4- Piperidyl)imino}hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl)imino}], tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3 ,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tris(2,2,6,6- Tetramethyl-4-piperidyl)-benzene-1,3,4-tricarboxylate, 1-[2-{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy}butyl]- 4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid 1,2,2,6,6-Pentamethyl-4-piperidinol and β,β,β',β'-Tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5) Undecane] and a condensate with diethanol.

Hindered amine light stabilizers are roughly classified into NH type (hydrogen is bonded to nitrogen atom), NR type (alkyl group (R) is bonded to nitrogen atom) according to the bonding partner of nitrogen atom in piperidine skeleton, There are three types of N-OR type (alkoxy group (OR) is bonded to nitrogen atom), but when applied to a polycarbonate resin, it is a low basic type NR from the viewpoint of the basicity of the hindered amine light stabilizer. Type and N-OR type are more preferable. The hindered amine light stabilizers can be used alone or in combination of two or more kinds.

The content of the hindered amine light stabilizer is preferably 0 to 1 part by weight, more preferably 0.05 to 1 part by weight, still more preferably 0, based on 100 parts by weight of the total of the components A and B. 0.08 to 0.7 part by weight, particularly preferably 0.1 to 0.5 part by weight. If the content of the hindered amine-based light stabilizer is more than 1 part by weight, the appearance may be deteriorated due to gas generation and the physical properties may be deteriorated due to decomposition of the polycarbonate resin, which is not preferable. If it is less than 0.05 part by weight, sufficient light resistance may not be exhibited.
(Dye and pigment)
The polycarbonate resin composition of the present invention can further contain various dyes and pigments to provide molded articles exhibiting various design properties. By blending a fluorescent whitening agent or a fluorescent dye that emits light other than that, it is possible to impart a better design effect by utilizing the emission color. Further, it is possible to provide a fiber-reinforced polypropylene resin composition which is colored with an extremely small amount of dye and pigment and has a vivid color-forming property.

Examples of the fluorescent dye (including a fluorescent whitening agent) used in the present invention include coumarin fluorescent dye, benzopyran fluorescent dye, perylene fluorescent dye, anthraquinone fluorescent dye, thioindigo fluorescent dye, xanthene fluorescent dye. , Xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes, which have good heat resistance and little deterioration during molding of a polycarbonate resin, are preferable.

As the dye other than the bluing agent and the fluorescent dye, perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as dark blue, perinone dyes, quinoline dyes, quinacridone. Examples thereof include dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Further, the resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. As the metallic pigment, those having a metal coating or a metal oxide coating on various plate-like fillers are suitable.

The content of the above dye/pigment is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of the total of the components A and B.
(Other resins)
In the polycarbonate resin composition of the present invention, other resins may be used in a small proportion within the range in which the effects of the present invention are exhibited.

Examples of such other resins include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyolefin resins other than polypropylene resins, polymethacrylate resins, phenolic resins. Resins such as epoxy resin can be used.
(Other filling materials)
In the polycarbonate resin composition of the present invention, other fillers may be used in a small proportion within the range in which the effects of the present invention are exhibited.

Such other fillers include potassium whisker titanate, zinc oxide whiskers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, fibrous fillers such as metal fibers, wollastonite, sericite, kaolin, Silicates such as mica, clay, bentonite, asbestos, talc and alumina silicate, swelling layered silicates such as montmorillonite and synthetic mica, metal compounds such as alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide and iron oxide , Carbonates such as calcium carbonate, magnesium carbonate, dolomite, sulfates such as calcium sulfate and barium sulfate, non-fibrous fillers such as glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and silica. Can be mentioned.
(Other additives)
The polycarbonate resin composition of the present invention may contain a small proportion of additives known per se in order to impart various functions to the molded article and improve the characteristics. The amounts of these additives to be added are usual amounts unless the object of the present invention is impaired. Such additives include sliding agents (for example, PTFE particles), fluorescent dyes, inorganic fluorescent substances (for example, fluorescent substances having aluminate as a mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents. , Photocatalyst type antifouling agents (for example, fine particle titanium oxide, fine particle zinc oxide), radical generators, infrared absorbers (heat ray absorbers), and photochromic agents.
[Molded body and manufacturing method thereof]
By molding the molding material of the present invention in the existing thermoplastic resin molding process without performing a treatment for impregnating the reinforcing fiber with the thermoplastic resin in an independent step as in the prior art, In a molding material, a polycarbonate resin composition is impregnated into a carbon fiber bundle that is easily impregnated, melts and flows while unraveling the carbon fiber bundle, and spreads in the mold, so that a molded body with good physical properties can be obtained. is there.

That is, in the present application, the invention of a molded article made of the above-described molding material of the present invention, and the molding material being present in the mold at a temperature of the plasticizing temperature of the polycarbonate resin composition or higher. In the molding material, the polycarbonate resin composition is impregnated into the easily impregnable carbon fiber bundle, and the carbon fiber bundle of the easily impregnable carbon fiber bundle is released and molded, and then cooled. The invention of a method for producing a molded article is also included.

In the method for producing a molded body of the present invention, "to disperse and disperse the carbon fiber bundle of the easily impregnable carbon fiber bundle" means that the carbon fiber bundle is as large as the carbon fiber does not become a lump in the molded body. It means that it is defibrated and dispersed, and it is excellent even if you do not completely loosen the carbon fiber bundles such as carbon fiber filaments to each of the constituent thousands of tens of thousands of carbon fiber single yarns. A molded product having excellent physical properties and appearance can be obtained.

In the production of the molded article of the present invention, the above molding material can be used in various forms suitable for the molding method adopted. For example, in the case of molding by injection molding, a strand in which a polycarbonate resin composition is coated around an easily impregnable carbon fiber bundle is used as a pellet-shaped molding material obtained by cutting the strand with a strand cutter into a length of about 3 to 10 mm. be able to.

Also, press molding is effective for obtaining a large plate-shaped molded product. When performing press molding, a plate-shaped molding material obtained by laminating a polycarbonate resin composition and a bundle of easily impregnable carbon fibers, which is heated to a plasticizing temperature of the polycarbonate resin composition or higher, It is also possible to perform molding under a predetermined press pressure after installation in. Depending on the shape and the like, a method of molding using a preform body obtained by previously heating and pressing the molding material according to the present invention is also effective.

When a molding is obtained using the molding material of the present invention without adding other molding materials or additives, the molding material and the carbon fiber content of the molding and the proportion thereof That is, the composition based on mass is naturally the same. Therefore, the amount of the carbon fiber or the polycarbonate resin composition contained in the molded product of the present invention and the preferable range thereof are as described above for the molding material.

When the molding material of the present invention is used for molding without adding other molding materials or additives, the carbon fiber content of either one of the molding material or the obtained molded body ( The rate) can be measured and this can be regarded as the content (rate) of the other carbon fiber. Further, even when the molding material of the present invention is molded by adding other molding materials, additives, etc., the calculation is performed based on the addition amount thereof, and the molding material or molded article of the present invention The carbon fiber content (rate) of the other can be determined from the carbon fiber content (rate) of either one.

A conventional carbon fiber reinforced thermoplastic resin molded product is a pellet or the like in which the thermoplastic resin and the carbon fiber are melt-kneaded by a twin-screw extruder or the like in order to make the carbon fiber uniformly dispersed in the thermoplastic resin. It is obtained by molding as a material. However, in this method, since the carbon fiber is crushed in the extruder due to the high shearing and kneading, and the length of the carbon fiber in the obtained molded product becomes less than 0.3 mm, the physical property reinforcing effect of the fiber is obtained. Will decrease. On the other hand, since the molded body of the molding material of the present invention has excellent impregnation properties of the polycarbonate resin composition into the carbon fiber bundle, it is not necessary to knead the carbon fiber bundle and the molten resin with high shear. Therefore, the carbon fibers remain in the obtained molded product for a long time, and the mechanical strength is excellent.

The molded product of the present invention is preferably a molded product in which carbon fibers in which the easily impregnable carbon fiber bundles are unwound are dispersed with an average fiber length of 0.3 mm or more, more preferably the carbon fiber. Are dispersed with an average fiber length of 0.4 mm or more. In the molded product of the present invention, there is no particular upper limit on the average fiber length of the remaining carbon fibers, and it depends on the application and the molding method employed. For example, for a molded product obtained by injection molding using a strand coated with a polycarbonate resin composition around a bundle of easily impregnable carbon fibers as a molding material in the form of pellets, a mean fiber of carbon fibers The length is generally about 10 mm or less, and a carbon fiber bundle impregnated with a thermoplastic resin having a higher degree is more likely to be broken during injection molding. Therefore, the average fiber length is often 2 mm or less.

Furthermore, the molded product of the present invention is preferably one in which the relationship of the following formula (C) is established in a tensile test piece having an ISO527 standard wall thickness of 4 mm.

Carbon fiber content (% by weight)×3+90<tensile strength (MPa) (C)
The fact that the above formula (C) is satisfied means that in the molded product of the carbon fiber reinforced thermoplastic resin, the tensile strength of the molded product is extremely high as compared with the carbon fiber content, and it is extremely preferable in terms of cost and performance. ..

The present invention, which is considered to be the best by the present inventors, is a compilation of preferable ranges of the above-mentioned requirements. Of course, the present invention is not limited to these forms.

Next, Examples and Comparative Examples of the present invention will be described in detail, but the present invention is not limited thereto. Each measurement item in the examples was measured by the following method.
(I) Evaluation of molding material
1) Surface appearance
The surface appearance of the molding material obtained by the following method was observed, and lumps and bubbles of a fibrous substance having a diameter of 3 mm or more, which were generated due to insufficient impregnation of the carbon fiber bundle with polycarbonate, were confirmed on the surface. Those that did not exist were rated as ○ (good), lumps of fibrous material were not confirmed, but those where air bubbles were confirmed were rated as Δ (somewhat good), and those where lumps of fibrous material were confirmed were marked as × (bad). ..
2) Bending elastic modulus A bending test piece was prepared from the molding material obtained by the following method using an injection molding machine, and the bending elastic modulus was measured according to ISO178.
3) Colorability The molding material obtained by the following method was injection-molded using an injection molding machine under the conditions of a cylinder temperature of 300° C. and a mold temperature of 80° C. to obtain a molded body (width 50 mm, length 90 mm, A thickness of 2 mm) was obtained. The appearance color tone of the obtained molded body was visually confirmed. Further, the L* value of the reflected light of the obtained molded body was measured by using a spectrocolorimeter (model name “U4100”, manufactured by Hitachi High-Technologies Corporation) in accordance with ISO 11664-4, using a C light source and a visual field. It was calculated from tristimulus values X, Y and Z measured by reflection measurement under the condition of an angle of 2°. For the reflection measurement, an integrating sphere was used, and the specular reflection component and the diffuse reflection component were integrated and received. The obtained L* value of 30 or less was judged to be good in colorability.
4) Flame retardance The molding material obtained by the following method is dried at 120° C. for 6 hours with a hot air circulation dryer, and the cylinder temperature is 280° C. by an injection molding machine [TOSHIBA MACHINE CO., Ltd. IS150EN-5Y]. A test piece for flame retardancy evaluation was molded at a mold temperature of 80°C. A vertical burning test of UL standard 94 was performed with a thickness of 0.7 mm to evaluate the grade. In addition, when the judgment fails to satisfy any of the criteria of V-0, V-1, and V-2, it is indicated as "notV".
[Production Examples 1-18, Examples 1-15, Comparative Example 1-11]
A mixture having the composition shown in Table 1 and composed of all components was supplied from the first supply port of the extruder. Such a mixture was obtained by mixing with a V-type blender. For the extrusion, a bent type twin-screw extruder with a diameter of 30 mm (TEX30α-38.5BW-3V, Japan Steel Works, Ltd.) was used, and the melt was kneaded at a screw rotation speed of 230 rpm, a discharge rate of 25 kg/h and a vent vacuum degree of 3 kPa. Pellets were obtained. The extrusion temperature was 280° C. from the first supply port to the die. Next, the easily impregnable carbon fiber bundle was coated with a resin composition composed of the above-mentioned pellets melted at 280° C. using a wire-cover crosshead die having an outlet diameter of 3 mm, and this was cut into a length of 6 mm, A molding material as shown in Tables 2 and 3 having a diameter of 3.2 mm and a length of 6 mm, which is a core-sheath type pellet suitable for injection molding, was obtained.

The components represented by symbols in Tables 1 to 3 are as follows.
[Use composition]
In the examples, the following components were used.
(A component)
A-1: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 25,100 made from bisphenol A and phosgene by a conventional method, Panlite L-1250WQ (product name) manufactured by Teijin Ltd.)
A-2: Aromatic polycarbonate resin (polycarbonate resin powder having 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 Ltd.)
(B component)
B-1: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 24,000, PDMS amount 8.4%, PDMS degree of polymerization 37, Panlite W-0111 (trade name) manufactured by Teijin Ltd.)
B-2: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,50, PDMS amount 8.4%, PDMS degree of polymerization 37, Panlite W-00528 trade name manufactured by Teijin Ltd.)
(C component)
C-1: Brominated flame retardant (brominated carbonate oligomer having bisphenol A skeleton, FG-8500 (product name) manufactured by Teijin Ltd.)
C-2: Brominated flame retardant (brominated carbonate oligomer having bisphenol A skeleton, FG-7000 (product name) manufactured by Teijin Ltd.)
(D component)
D-1: Coated PTFE (polytetrafluoroethylene coated with styrene-acrylonitrile copolymer (polytetrafluoroethylene content 50% by weight), SN3307PF (trade name) manufactured by Shine polymer)
D-2: Polytetrafluoroethylene capable of forming fibrils (Polyflon FA500H (trade name) manufactured by Daikin Industries, Ltd.)
(E component)
E-1: The total area of the stearic acid component (Ss) and the area of the palmitic acid component (Sp) in the GC/MS method was 94% in the total aliphatic carboxylic acid component, and their area ratio (Ss/Sp ) Is 1.44, a full ester of pentaerythritol and an aliphatic carboxylic acid (manufactured by Riken Vitamin Co., Ltd.: Riquester EW-400 (trade name), acid value: 9, hydroxyl value: 6, iodine value: 0) ., and TGA 5% weight loss temperature: 322° C., the aliphatic carboxylic acid is made from animal fats and oils.)
E-2: Full ester of pentaerythritol and aliphatic carboxylic acid in which the total of Ss and Sp is 91% in the total aliphatic carboxylic acid component, and their area ratio (Ss/Sp) is 1.11. (Manufactured by Cognis Japan KK: Roxyol VPG-861 (trade name), acid value: 1, hydroxyl value: 7, iodine value: 0, and TGA 5% weight loss temperature: 390° C., the aliphatic carboxylic acid is vegetable Oil and fat as raw material.)
E-3: Ratio of higher alcohol fatty acid ester (ester of monoalcohol having 10 to 20 carbon atoms and fatty acid having 10 to 20 carbon atoms) and triglyceride (ester of glycerin and fatty acid having 10 to 20 carbon atoms) is 30 : 70 (weight ratio) mixture (Rikemar SL-900 (trade name) manufactured by Riken Vitamin Co., Ltd.)
E-4: Low molecular weight polyethylene (high wax HW405MP (trade name) manufactured by Mitsui Chemicals, Inc.)
(F component)
F-1: Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation jER1256 (trade name), Mw=26,600)
(Other ingredients)
P-1: Phosphorus flame retardant (resorcinol bis(di-2,6-xylyl phosphate), PX-200 (product name) manufactured by Daihachi Chemical Industry Co., Ltd.)
TMP: trimethyl phosphate CB: 30 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: Crystall N352 (trade name)) , 0.2 part by weight of montanic acid ester wax (manufactured by Clariant Japan Co., Ltd.: Ricorb WE-1 powder (trade name)) and 66.8 parts by weight of bisphenol A type polycarbonate resin (manufactured by Teijin Chemicals Ltd.: CM Carbon black master pellets produced by melt mixing 100 parts by weight of four components of -1000 (trade name) and viscosity average molecular weight of 16,000 using a twin-screw extruder.
(Easily impregnated carbon fiber bundle)
CF-1: Polycaprolactone which is an aliphatic hydroxycarboxylic acid type polyester (PLACCEL (registered trademark) H1P molecular weight 10000 manufactured by Daicel Chemical Industries, Ltd.) was used as an impregnation aid, and this was made into an emulsion liquid having a nonvolatile content of 12% by weight. After passing a PAN-based carbon fiber filament (corresponding to STS40 24K manufactured by Toho Tenax Co., Ltd., fiber diameter 7.0 μm, number of filaments 24000, tensile strength 4000 MPa) as a carbon fiber bundle, the excessively adhered solution was removed by a nip roll, After that, it was passed through a hot air drying oven heated to 180° C. for 2 minutes to be dried. The easily impregnated carbon fiber bundle obtained by the above treatment is placed along two metal rolls having a diameter of 60 mm heated to 200° C., and the heat treatment is performed again, so that the impregnation auxiliary agent is evenly attached to the carbon fiber bundle. It was set as the impregnable carbon fiber bundle. The content of the polycaprolactone impregnation aid in this easily impregnable carbon fiber bundle was 5% by weight (5.3 parts by weight per 100 parts by weight of carbon fiber).
CF-2: The same operation as in CF-1 was performed, except that the carbon fiber filaments were treated as an emulsion liquid having a nonvolatile content of 25% by weight as the emulsified solution of polycaprolactone as the impregnation aid. The content of the polycaprolactone impregnation aid in this easily impregnable carbon fiber bundle was 10% by weight (11.1 parts by weight per 100 parts by weight of carbon fiber).
CF-3: The same operation as in CF-1 was carried out, except that the carbon fiber filament was treated as an emulsion liquid having a nonvolatile content of 5% by weight as an emulsified solution of polycaprolactone as an impregnation aid. The content of polycaprolactone in this easily impregnable carbon fiber bundle was 1.9% by weight (2 parts by weight per 100 parts by weight of carbon fiber).
CF-4: The same operation as that for CF-1 was performed except that the carbon fiber filament was treated as an emulsion liquid having a nonvolatile content of 35% by weight as an emulsified solution of polycaprolactone as an impregnation aid. The content of the polycaprolactone impregnation aid in this easily impregnable carbon fiber bundle was 14.5% by weight (17 parts by weight per 100 parts by weight of carbon fiber).

From Tables 2 and 3, it can be seen that the compounding material of the present invention can provide a molding material excellent in flame retardancy, appearance, strength and colorability.

Claims

A molding material in which 50 to 2,000 parts by weight of a polycarbonate resin composition is adhered to an easily impregnated carbon fiber bundle consisting of 100 parts by weight of carbon fiber and 3 to 15 parts by weight of one or more impregnating aids. Wherein the polycarbonate resin composition comprises (A) 1 to 100% by weight of an aromatic polycarbonate resin (component A) and (B) 0 to 99% by weight of a polycarbonate-polydiorganosiloxane copolymer resin (component B). With respect to 100 parts by weight, (C) brominated flame retardant (C component) 10 to 20 parts by weight, (D) fluorine-containing anti-dripping agent (D component) 0.01 to 2 parts by weight, and (E) polyhydric alcohol A molding material containing 0.05 to 2 parts by weight of a full ester (E component) with an aliphatic carboxylic acid.
The molding material according to claim 1, wherein the impregnation aid is made of one or more aliphatic hydroxycarboxylic acid-based polyesters satisfying the following formulas (1) and (2).
Viscosity of the impregnation aid at 300° C.≦10 Pa·s (1)
2≦(Tg 0 −Tg 1 )/D (2)
[Wherein D is the proportion (% by weight) of the impregnating aid in the resin composition comprising the polycarbonate resin and the impregnating aid, and Tg 1 is the resin composition obtained by adding the impregnating aid to the polycarbonate resin in this proportion. Glass transition temperature (° C.) and Tg 0 represent the glass transition temperature (° C.) of the polycarbonate resin. ]
Aliphatic hydroxycarboxylic acid polyester having a weight average molecular weight of 3,000 to 50,000, ε-caprolactone, δ-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, and enanthate. The one or more compounds selected from the group consisting of homopolymers of lactones and copolymers of these two or more monomers having a weight average molecular weight of 3,000 to 50,000. Molding material.
4. The adhesive composition according to claim 1, wherein 1 to 10 parts by weight of the (F) adhesion improver (F component) is contained in 100 parts by weight of the total of the A component and the B component. Molding material.
The E component is an aliphatic carboxylic acid containing a palmitic acid component and a stearic acid component, and the area of the palmitic acid component (Sp) and the stearic acid component of the peak area in the gas chromatograph-mass spectrometry (GC/MS method) An aliphatic carboxylic acid having a total area (Ss) of 80% or more in the total aliphatic carboxylic acid component and an area ratio (Ss/Sp) of both of them of 1.3 to 30, and having an acid value of 0. 5. The molding material according to any one of claims 1 to 4, which is a full ester of a polyhydric alcohol having 1 to 20 and an aliphatic carboxylic acid.
The molding material according to any one of claims 1 to 5, wherein the E component is a full ester of a polyhydric alcohol whose polyhydric alcohol is pentaerythritol and an aliphatic carboxylic acid.
The F component is at least one organic compound selected from the group consisting of glycidyl methacrylate, bisphenol A type epoxy resin, polyarylate and styrene-maleic acid resin, according to any one of claims 4 to 6. The molding material described.
The molding material according to any one of claims 1 to 7, which is a pellet having a core-sheath structure having an easily impregnable carbon fiber bundle as a core component and a polycarbonate resin composition as a sheath component.
The molding material according to claim 8, wherein the length of the pellet in the longitudinal direction is 3 to 10 mm.
A molded body made of the molding material according to any one of claims 1 to 9.
The molded product according to claim 10, wherein the carbon fibers derived from the easily impregnable carbon fiber bundle are dispersed with an average fiber length of 0.3 mm or more.
The molded product according to claim 10, which is an interior/exterior member for OA/electrical and electronic equipment.
The molded product according to claim 10, which is a member for automobiles.