JP2015164993A - Polycarbonate resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition and a molded article which have high thermal conductivity and excellent mechanical characteristics such as shock resistance, tensile characteristics and bending characteristics, high fluidity and highly reduced molding shrinkage, and excellent self-tap strength.SOLUTION: A polycarbonate resin composition comprises 10 to 100 parts by mass of carbon fiber, and 10 to 100 parts by mass of glass fiber, based on 100 parts by mass of a polycarbonate resin. The polycarbonate resin composition has the following characteristics: (i) a molding shrinkage factor is 0.15% or less in a resin flow direction (MD direction), and is 0.35% or less in a direction orthogonal to the MD direction (TD direction) during molding; (ii) a coefficient of linear expansion (measured in accordance with ISO 11359-2) is 2×10/°C or less in the MD direction; (iii) a volume resistivity (measured in accordance with IEC 60093) is 1×10Ω m or less; and (iv) a surface resistivity (measured in accordance with IEC 60093) is 1×10Ω or less.

Description

  The present invention relates to a polycarbonate resin composition and a molded article, and more specifically, it has excellent thermal properties such as high thermal conductivity and impact resistance, tensile properties and bending properties, and further has high fluidity and a highly reduced molding shrinkage. In addition, the present invention relates to a polycarbonate resin composition and a molded article excellent in self-tap strength.

  Polycarbonate resin is excellent in impact resistance, heat resistance, electrical insulation, dimensional stability, etc., and has a good balance of these characteristics. Therefore, electrical and electronic equipment parts, OA equipment parts, precision equipment parts, vehicle parts Widely used in such fields.

  However, since the polycarbonate resin has a high electric resistivity and is easily charged, it may cause various troubles due to static electricity. Moreover, in the above-mentioned field, most devices are equipped with components that generate heat. However, in recent years, there has been a strong demand for higher functionality and higher speed of devices. On the other hand, the amount of heat generated from the internal elements of the device tends to increase as the power consumption per component increases due to high-speed processing and large capacity. In situations where heat dissipation is not sufficient, there is concern about thermal damage to internal elements and problems that cause local high temperatures on the surface of parts (housing) that hold the elements. There is a need for a polycarbonate resin material that is one and exhibits higher thermal conductivity.

  As a method of imparting thermal conductivity to a polycarbonate resin material, a method of blending various thermal conductive fillers is known, and Patent Documents 1 to 6 show polycarbonate resin compositions having good thermal conductivity. ing. However, these polycarbonate resin compositions can exhibit good thermal conductivity, but have the disadvantage that the impact resistance is deteriorated, and the thermal conductivity is excellent, and the impact resistance. In addition, an excellent polycarbonate resin composition is desired.

In addition, there are remarkable trends in the reduction in size and weight of electrical and electronic equipment and precision equipment. For example, parts (outer shell parts and housings) for holding internal elements and the like are extremely thin. Such parts are required not only to have fluidity but also to have a material that has both higher rigidity and superior dimensional accuracy than conventional ones.
Especially for electronic equipment parts and precision equipment parts, such as camera parts, especially parts for holding image processing elements in digital cameras (frames, housings), etc., high dimensional accuracy, high rigidity and fluidity There is a strong demand for a polycarbonate resin material that has excellent properties, high thermal conductivity for heat dissipation, and high self-tap strength.

JP 2007-16093 A JP 2007-238917 A JP 2008-127554 A JP 2008-163270 A JP 2009-161582 A JP 2011-16936 A

  In view of the above, an object (issue) of the present invention is excellent in mechanical properties such as high thermal conductivity, impact resistance, tensile properties and bending properties, and further has high fluidity, a highly reduced molding shrinkage rate, and self The object is to provide a polycarbonate resin composition and a molded article excellent in tap strength.

As a result of intensive studies to achieve the above-mentioned problems, the inventor is a polycarbonate resin composition containing carbon fibers and glass fibers in specific amounts, respectively, and has a specific molding shrinkage rate and linear expansion coefficient. The present inventors have found that a polycarbonate resin composition having a volume resistivity and a surface resistivity solves the above problems, and has completed the present invention.
The present invention provides the following polycarbonate resin composition and molded article.

[1] A polycarbonate resin composition containing 10 to 100 parts by mass of carbon fiber and 10 to 100 parts by mass of glass fiber with respect to 100 parts by mass of polycarbonate resin,
(I) Mold shrinkage is 0.15% or less in the resin flow direction during molding (hereinafter “MD direction”) and 0.35% or less in the direction perpendicular to the MD direction (hereinafter “TD direction”). ,
(Ii) the coefficient of linear expansion (measured in accordance with ISO 11359-2) is 2 × 10 ⁻⁵ / ° C. or less in the MD direction;
(Iii) Volume resistivity (measured according to IEC 60093) is 1 × 10 ¹⁰ Ω · m or less, and (iv) Surface resistivity (measured according to IEC 60093) is 1 × 10 ¹⁰ Ω or less. [2] The polycarbonate resin composition according to [1], wherein the mass ratio of carbon fiber to glass fiber (carbon fiber / glass fiber) is 1.0 or more.
[3] The polycarbonate resin composition according to [1] or [2], further containing 0.1 to 3 parts by mass of carbon black with respect to 100 parts by mass of the polycarbonate resin.
[4] The polycarbonate resin composition according to any one of [1] to [3], wherein the self-tap breaking torque is 0.3 N · m or more when the catch rate is 34%.
[5] A molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [4].
[6] The molded product according to [5], which is a camera component.

  According to the polycarbonate resin composition of the present invention, it has high thermal conductivity and excellent mechanical properties such as impact resistance, tensile properties and bending properties, and further has a high fluidity, a highly reduced molding shrinkage rate and a self-tap strength. It is possible to provide a polycarbonate resin composition and a molded article excellent in the above.

It is the schematic of the spiral long resin molded object created by the measurement of the spiral flow length in an Example.

Hereinafter, although an embodiment, an example thing, etc. are shown and explained in detail about the present invention, the present invention is limited to an embodiment, an example, etc. shown below and is not interpreted.
In the present specification, unless otherwise specified, “to” is used in a sense that includes numerical values described before and after it as a lower limit value and an upper limit value.

[Overview]
The polycarbonate resin composition of the present invention is a polycarbonate resin composition containing 10 to 100 parts by mass of carbon fibers and 10 to 100 parts by mass of glass fibers with respect to 100 parts by mass of the polycarbonate resin,
(I) Mold shrinkage is 0.15% or less in the MD direction, 0.35% or less in the TD direction,
(Ii) the coefficient of linear expansion (measured in accordance with ISO 11359-2) is 2 × 10 ⁻⁵ / ° C. or less in the MD direction;
(Iii) Volume resistivity (measured according to IEC 60093) is 1 × 10 ¹⁰ Ω · m or less, and (iv) Surface resistivity (measured according to IEC 60093) is 1 × 10 ¹⁰ Ω or less. It is characterized by that.

[Polycarbonate resin]
There is no restriction | limiting in the kind of polycarbonate resin used in this invention, A polycarbonate resin may use 1 type and may use 2 or more types together by arbitrary combinations and arbitrary ratios.
The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the formula: — [— O—X—O—C (═O) —] —.
In the formula, X is generally a hydrocarbon, but for imparting various properties, X into which a hetero atom or a hetero bond is introduced may be used.
The polycarbonate resin can be classified into an aromatic polycarbonate resin in which carbon directly bonded to a carbonic acid bond is aromatic carbon and an aliphatic polycarbonate resin in which aliphatic carbon is aliphatic carbon, either of which can be used. Of these, aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.

  Although there is no restriction | limiting in the specific kind of polycarbonate resin, For example, the polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. The polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

  Among monomers used as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include:

Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl;

2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

2,2′-dihydroxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxy diaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,1-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

9,9-bis (4-hydroxyphenyl) fluorene,
Cardio structure-containing bisphenols such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

4,4′-dihydroxydiphenyl sulfide,
Dihydroxydiaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide;

Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

4,4′-dihydroxydiphenyl sulfone,
Dihydroxydiaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone;
Etc.

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are particularly preferable, and 2,2-bis (4-hydroxyphenyl) propane (especially from the viewpoint of impact resistance and heat resistance). That is, bisphenol A) is preferred.
In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

In addition, examples of monomers that are raw materials for aliphatic polycarbonate resins
Ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3- Alkanediols such as diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol;

  Cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4- (2-hydroxyethyl) cyclohexanol, 2,2,4, Cycloalkanediols such as 4-tetramethyl-cyclobutane-1,3-diol;

  Glycols such as ethylene glycol, 2,2'-oxydiethanol (ie, diethylene glycol), triethylene glycol, propylene glycol, spiro glycol and the like;

  1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-hydroxyethoxy) benzene, 2,3-bis (hydroxymethyl) naphthalene, 1,6-bis (hydroxyethoxy) naphthalene, 4,4′-biphenyldimethanol, 4,4′-biphenyldiethanol, 1,4- Aralkyl diols such as bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2-hydroxyethyl) ether;

  1,2-epoxyethane (ie ethylene oxide), 1,2-epoxypropane (ie propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl And cyclic ethers such as -1,2-epoxycyclohexane, 2,3-epoxynorbornane, and 1,3-epoxypropane;

  Among the monomers used as the raw material for the polycarbonate resin, carbonyl halides, carbonate esters and the like are used as examples of the carbonate precursor. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.

  Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as

-Manufacturing method of polycarbonate resin The manufacturing method of polycarbonate resin is not specifically limited, Arbitrary methods are employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
Hereinafter, a particularly preferable one of these methods will be described in detail.

.. Interfacial polymerization method First, the case where a polycarbonate resin is produced by the interfacial polymerization method will be described.
In the interfacial polymerization method, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher. Polycarbonate resin is obtained by interfacial polymerization in the presence. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

  The dihydroxy compound and the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and a method using phosgene is particularly called a phosgene method.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, among which sodium hydroxide and water Potassium oxide is preferred. In addition, 1 type may be used for an alkali compound and it may use 2 or more types together by arbitrary combinations and a ratio.

  Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Among these, it is preferable that the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Formula tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Pyridine; guanine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the molecular weight regulator include aromatic phenols having a monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like. Of these, aromatic phenols are preferred. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-hydroxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction.
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

-Melt transesterification method Next, the case where a polycarbonate resin is manufactured by the melt transesterification method is demonstrated.
In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable. In addition, carbonic acid diester may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin is obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound, and above all, 1.01 mol or more is used. It is more preferable. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In the polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, a polycarbonate resin in which the amount of terminal hydroxyl groups is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic diester and the aromatic dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing by a batch type, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily. However, considering the stability of the polycarbonate resin and the like, the melt polycondensation reaction is preferably carried out continuously.

  In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, 1 type may be used for a catalyst deactivator and it may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

-Other matters concerning polycarbonate resin The molecular weight of the polycarbonate resin may be appropriately selected and determined, but is usually 10,000 or more, preferably 16000 or more, more preferably 17000 or more, more preferably 18000 or more in terms of viscosity average molecular weight [Mv]. Moreover, it is 40000 or less normally, Preferably it is 30000 or less.

The viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

  The terminal hydroxyl group concentration of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability and color tone of polycarbonate resin can be improved more. In addition, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly for polycarbonate resins produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of a resin composition can be improved more.

  In addition, the unit of a terminal hydroxyl group density | concentration represents the mass of the terminal hydroxyl group with respect to the mass of polycarbonate resin in ppm. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

  The polycarbonate resin is a polycarbonate resin alone (the polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin, and is used in a sense including an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights, for example. .), Or an alloy (mixture) of a polycarbonate resin and another thermoplastic resin may be used in combination. Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; A copolymer with an oligomer or polymer having an olefin structure; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Good.

  Further, in order to improve the appearance of the molded product and improve the fluidity, the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and is usually 9500 or less, preferably 9000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated polycarbonate resin is preferably 80% by mass or less of the polycarbonate resin, and more preferably 50% by mass or less. Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.

[Carbon fiber]
As the carbon fiber, any of pitch-based, PAN-based (polyacrylonitrile-based), rayon-based and the like can be used, but pitch-based carbon fiber is preferable from the viewpoint of impact resistance and thermal conductivity.
The average fiber diameter of the carbon fibers is preferably 20 μm or less, and most preferably in the range of 5 to 8 μm from the balance of fluidity, impact resistance, dimensional stability, and appearance. If the average fiber diameter exceeds 20 μm, the balance between dimensional stability and impact resistance is lowered, which is not preferable.
Moreover, it is preferable from the point of balance of impact resistance, dimensional stability, thermal conductivity, and external appearance that the average fiber length in the composition is in the range of 0.1 to 2 mm.

The carbon fiber is preferably subjected to a surface treatment, and the tensile strength and bending strength as the resin composition are improved. Any commonly used surface treating agent can be used, and examples thereof include epoxy sizing agents, urethane sizing agents, epoxy-urentane sizing agents, polyamide sizing agents, and olefin sizing agents. Among these, epoxy-based, polyamide-based, and urethane-based materials are preferable because of their good dispersibility with respect to the polycarbonate resin.
The amount of the surface treatment agent is preferably in the range of 0.5 to 15 parts by mass and more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the carbon fiber.

  Content of the carbon fiber in the polycarbonate resin composition of this invention is 10-100 mass parts with respect to 100 mass parts of polycarbonate resin. When the carbon fiber content is less than 10 parts by mass, the thermal conductivity is insufficient, and when it exceeds 100 parts by mass, the impact resistance and fluidity are insufficient. The carbon fiber content is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and preferably 80 parts by mass or less, more preferably 65 parts by mass or less.

[Glass fiber]
The polycarbonate resin composition of the present invention contains glass fibers.
As the glass fiber used in the present invention, as long as it is usually used for a thermoplastic resin, an A glass, an E glass, an alkali-resistant glass composition containing a zirconia component, a chopped strand, a roving glass, a thermoplastic resin. Any known glass fiber can be used regardless of the form of the glass fiber at the time of blending the (long fiber) masterbatch and the like. Especially, as a glass fiber used for this invention, an alkali free glass (E glass) is preferable from the objective of improving the thermal stability of the polycarbonate resin composition of this invention.

The number average fiber length of the glass fibers is preferably 1 mm or more and 10 mm or less, more preferably 1.5 to 6 mm, and further preferably 2 to 5 mm.
When the number average fiber length exceeds 10 mm, the glass fibers are likely to fall off from the surface of the molded product, and the productivity tends to be lowered. If the number average fiber length is less than 1 mm, the glass fiber has a small aspect ratio, and therefore mechanical strength is likely to be insufficiently improved.
In addition, the number average fiber length is an image analysis from an image obtained by observing 2,000 glass fibers of filler residue collected by processing such as high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical using an optical microscope. It is a value calculated by the device. Further, when calculating such a value, the fiber diameter is used as a guide and the length is less than that.

  The diameter of the glass fiber is preferably 3 μm or more and 20 μm or less. These can be produced by pulverizing glass fiber strands using, for example, a hammer mill or a ball mill according to any conventionally known method. When the diameter of the glass fiber is less than 3 μm, the improvement of the mechanical strength is similarly insufficient, and when it exceeds 20 μm, the appearance tends to deteriorate. The diameter of the glass fiber is more preferably 5 μm or more and 15 μm or less, and further preferably 6 μm or more and 14 μm or less.

  The glass fiber used in the present invention can be subjected to surface treatment with a silane coupling agent such as aminosilane or epoxysilane for the purpose of improving the adhesion to the polycarbonate resin.

Moreover, it is preferable to use a glass fiber that is usually a bundle of many of these fibers as a chopped strand (chopped glass fiber) cut into a predetermined length. At this time, the glass fiber should contain a sizing agent. Is preferred. In addition to the advantage of increasing the production stability of the polycarbonate resin composition of the present invention by blending the sizing agent, good mechanical properties can be obtained.
The sizing agent is not particularly limited, and examples thereof include urethane-based, epoxy-based, acrylic-based sizing agents. Among them, as the glass fiber sizing agent used in the present invention, urethane-based and epoxy-based sizing agents are more preferable, and epoxy-based sizing agents are more preferable.

  Although there is no restriction | limiting in particular also about the cut length of a chopped strand (chopped glass fiber), Usually, 1-10 mm, Preferably it is 1.5-6 mm, More preferably, it is 2-5 mm.

The glass fiber used in the present invention preferably has a substantially circular cross section. Specifically, the cross section of the fiber cross section (major axis / minor axis) is 1 to 1.5, and the cross section is substantially circular. It is preferable that the glass fiber. The flatness is preferably 1 to 1.4, more preferably 1 to 1.2, and particularly preferably 1 to 1.1.
The flatness value is calculated from an image obtained by observing, with an optical microscope, 2000 glass fibers of a filler residue collected by high temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical. Is an average value calculated by.

  Moreover, it is also preferable that the glass fiber used for this invention is a flat cross-section glass fiber with a flat fiber cross section. As the flat cross-section glass fiber, the average value of the major axis of the fiber cross section is preferably 10 to 50 μm, and the average value of the ratio of the major axis to the minor axis (major axis / minor axis) is preferably 1.5 to 8. Is mentioned. By using such a flat cross-section glass fiber, the fluidity, rigidity, low warpage, impact resistance, and anisotropy of the polycarbonate resin composition of the present invention can be effectively increased.

The average value of the major axis of the fiber cross section of the flat cross-section glass fiber is preferably 10 to 50 μm, more preferably 12 to 40 μm, still more preferably 15 to 35 μm, and particularly preferably 18 to 30 μm.
Further, the average value of the ratio of the major axis to the minor axis (major axis / minor axis) of the flat cross-section glass fiber is preferably 1.5 to 8, more preferably 1.6 to 7, and further preferably 1.7 to. 6, particularly preferably 1.8-5. By using a flat cross-section glass fiber having an average value of the major axis and minor axis ratio (major axis / minor axis) in such a range, the fluidity, low warpage, and impact resistance of the polycarbonate resin composition of the present invention are used. , The anisotropy can be further increased.

Moreover, the ratio (aspect ratio) of the average fiber length and the average fiber diameter of the flat cross-section glass fiber is preferably 2 to 120, more preferably 2.5 to 70, and further preferably 3 to 50. When the ratio of the average fiber length to the average fiber diameter (aspect ratio) of the flat cross-section glass fiber is less than 2, the mechanical strength tends to decrease. Conversely, when it exceeds 120, warp and anisotropy are present. In addition to the increase, the appearance of the molded product tends to deteriorate significantly.
The average fiber length of such flat cross-section glass fibers refers to the number average fiber diameter when the flat cross-sectional shape is converted to a true circle of the same area. The average fiber length refers to the number average fiber length in the polycarbonate resin composition of the present invention. The number average fiber length is a value calculated by an image analysis device from an image obtained by observing a filler residue collected by high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical with an optical microscope. It is. Further, when calculating such a value, the fiber diameter is used as a guide and the length is less than that.

  Content of the glass fiber in the polycarbonate resin composition of this invention is 10-100 mass parts with respect to 100 mass parts of polycarbonate resin. If the glass fiber content is less than 10 parts by mass, the elastic modulus and strength are insufficient, while if it exceeds 100 parts by mass, the impact resistance and fluidity become insufficient. The glass fiber content is preferably 11 parts by mass or more, more preferably 12 parts by mass or more, preferably 80 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, particularly preferably. Is 40 parts by mass or less.

The mass ratio of the carbon fiber and glass fiber content in the polycarbonate resin composition of the present invention is preferably carbon fiber / glass fiber, and is preferably 1.0 or more, more preferably 1.1 or more, and even more preferably 1. .2 or more, particularly preferably 1.25 or more, preferably 4.0 or less, more preferably 3.5 or less, still more preferably 3.0 or less, and particularly preferably 2.8 or less. By setting the mass ratio of the carbon fiber and glass fiber content within the above range, it is possible to improve the properties such as thermal conductivity, elastic modulus, strength, impact resistance, and fluidity during molding in a well-balanced manner.
Further, the total content of carbon fiber and glass fiber is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, further preferably 40 parts by mass or more, preferably 100 parts by mass of the polycarbonate resin. 150 parts by mass or less, more preferably 125 parts by mass or less, and still more preferably 100 parts by mass or less.

[Carbon black]
The polycarbonate resin composition of the present invention preferably contains carbon black. There is no restriction | limiting in the kind, raw material seed | species, and manufacturing method as carbon black, Any of furnace black, channel black, acetylene black, ketjen black, etc. can be used. The number average particle diameter is not particularly limited, but is preferably about 5 to 60 nm. By containing carbon black having a number average particle diameter in such a range, it becomes easy to obtain a composition in which blisters hardly occur at high temperatures.

Nitrogen adsorption specific surface area of the carbon black ^{(unit: m} 2 / g) is preferably usually less than 1000 m ² / g, is preferably Among them 50 to 400 m ² / g. By making the nitrogen adsorption specific surface area less than 1000 m ² / g, the flowability of the polycarbonate resin composition of the present invention and the appearance of the molded product tend to be improved, which is preferable. The nitrogen adsorption specific surface area can be measured according to JIS K6217.

The DBP (dibutyl phthalate) absorption amount of carbon black ^is preferably less than 300 cm 3/100 g, is preferably Among them 30~200cm ³ / 100g. The DBP absorption amount by less than 300 cm ^3/100 g, preferably tends to increase the appearance of fluidity and a molded article of the polycarbonate resin composition of the present invention.
Incidentally, DBP absorption ^(unit: cm 3 / 100g) can be measured according to JIS K6217. The carbon black used in the present invention is not particularly limited with respect to its pH, but it is usually 2 to 10, preferably 3 to 9, and more preferably 4 to 8.

  Carbon black can be used alone or in combination of two or more. Furthermore, carbon black can be granulated using a binder, and can also be used in a masterbatch that is melt-kneaded at a high concentration in another resin. By using the melt-kneaded master batch, the handling property during extrusion and the dispersibility improvement in the resin composition can be achieved. Examples of the resin include polystyrene resin, polycarbonate resin, acrylic resin, and the like.

  The preferable content of carbon black is 0.5 to 5 parts by mass, more preferably 0.8 parts by mass or more, still more preferably 1 part by mass or more, with respect to 100 parts by mass of the polycarbonate resin. Preferably it is 4 mass parts or less, More preferably, it is 3 mass parts or less.

[Release agent]
Moreover, it is preferable that the polycarbonate resin composition of this invention contains a mold release agent. Preferable examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, polysiloxane silicone oils, and the like.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the term “aliphatic” is used as a term including alicyclic compounds.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine and comprise one ester may each be used 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized.

Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5000 or less.
The aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

  In addition, 1 type may contain the release agent mentioned above, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass or less with respect to 100 parts by mass of the polycarbonate resin. It is. When the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the range, hydrolysis resistance And mold contamination during injection molding may occur.

[Flame retardants]
The polycarbonate resin composition of the present invention preferably contains a flame retardant. Examples of the flame retardant include halogen-based, phosphorus-based, silicone-based, nitrogen-based, metal salt-based flame retardant, and the like, and any known amount can be blended in a necessary amount, for example, condensed phosphate ester, Phosphazene, silicone compounds, sulfonic acid metal salts, polytetrafluoroethylene and the like are preferably used. By using these alone or in combination of two or more kinds, a polycarbonate resin composition having desired flame retardancy can be obtained.

  When the flame retardant is a sulfonic acid metal salt, a silicone compound, or polytetrafluoroethylene, the content of the flame retardant is preferably 0.01 parts by mass or more, more preferably 0.00 parts by mass with respect to 100 parts by mass of the polycarbonate resin. The upper limit is preferably 5 parts by mass or less, more preferably 2 parts by mass or less. When the flame retardant is a condensed phosphate ester or phosphazene, it is preferably 1 part by mass or more, more preferably 5 parts by mass or more, with respect to 100 parts by mass of the polycarbonate resin, and the upper limit thereof is preferably 30 parts by mass or less. More preferably, it is 15 parts by mass or less. When the flame retardant content is less than the lower limit of the above range, it is difficult to obtain an effect of improving flame retardancy, and when it exceeds the upper limit, mechanical strength, heat and humidity resistance, thermal stability, etc. may be reduced. is there. 1 type may be contained for a flame retardant and 2 or more types may be contained by arbitrary combinations and a ratio.

[Other ingredients]
The polycarbonate resin composition of the present invention may contain other components other than the above, if necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resins and various resin additives other than those described above. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

Other resins Examples of the other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin;
Polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin), acrylonitrile-butadiene-styrene copolymer ( Styrene resins such as ABS resin); polyolefin resins such as polyethylene resins and polypropylene resins; polyamide resins; polyimide resins; polyether imide resins; polyurethane resins; polyphenylene ether resins;
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.
When other resins are contained, it is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and more preferably 20 parts by mass or less, in a total of 100 parts by mass of the polycarbonate resin and other resins. More preferably.

Resin additives Examples of resin additives include heat stabilizers, antioxidants, UV absorbers, dyes and pigments, antistatic agents, antifogging agents, lubricants, antiblocking agents, plasticizers, dispersants, antibacterial agents, etc. Is mentioned. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.

[Production Method of Polycarbonate Resin Composition]
There is no limitation on the production method of the polycarbonate resin composition of the present invention, and a wide variety of production methods of known polycarbonate resin compositions can be adopted. Polycarbonate resin, carbon fiber, glass fiber, and other components blended as necessary Are mixed in advance using various mixers such as a tumbler or Henschel mixer, and then melt-kneaded with a mixer such as a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. Can be mentioned. When using a twin-screw kneading extruder, the carbon fibers and / or glass fibers are preferably side fed.
The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

[Characteristics of polycarbonate resin composition]
The polycarbonate resin composition of the present invention must satisfy the following characteristics.
(I) Mold shrinkage is 0.15% or less in the MD direction, 0.35% or less in the TD direction,
(Ii) the coefficient of linear expansion (measured in accordance with ISO 11359-2) is 2 × 10 ⁻⁵ / ° C. or less in the MD direction;
(Iii) Volume resistivity (measured in accordance with IEC 60093) is 1 × 10 ¹⁰ Ω · m or less,
(Iv) Surface resistivity (measured in accordance with IEC 60093) is 1 × 10 ¹⁰ Ω or less

  The polycarbonate resin composition of the present invention needs to have a molding shrinkage of 0.15% or less in the MD direction and 0.35% or less in the TD direction. It is possible to improve the dimensional stability. The mold shrinkage is preferably 0.13% or less, more preferably 0.12% or less, particularly 0.11% or less, preferably 0.03% or more in the MD direction, preferably 0.03% or more, preferably TD direction. 0.30% or less, more preferably 0.28% or less, still more preferably 0.26% or less, particularly 0.25% or less, preferably 0.10% or more, more preferably 0. .12% or more, more preferably 0.14% or more, and particularly preferably 0.15% or more. If the molding shrinkage ratio exceeds 0.15% in the MD direction and exceeds 0.35% in the TD direction, the dimensional stability at the time of molding is lowered, which is not preferable.

  Here, the molding shrinkage ratio is a flat plate test having a thickness of 3 mm and 100 mm × 100 mm obtained by molding in a molding cycle of cylinder temperature: 300 ° C., mold temperature 100 ° C., holding pressure 10 seconds, and cooling time 20 seconds. Using a piece, measure the distance between marks on the surface of the test piece at intervals of 70 mm in the MD direction and TD direction, respectively, using a high-precision CCD laser displacement meter three-dimensional dimension measuring device, The molding shrinkage was calculated from the ratio to the actual dimensions.

  In order to make the mold shrinkage 0.15% or less in the MD direction and 0.3% or less in the TD direction, the total amount of inorganic filler components such as carbon fibers and glass fibers added to 100 parts by mass of the polycarbonate resin, It becomes possible by setting it to 30 parts by mass or more.

The linear expansion coefficient of the polycarbonate resin composition of the present invention needs to be 2 × 10 ⁻⁵ / ° C. or less in the MD direction, preferably 1.8 × 10 ⁻⁵ / ° C. or less, more preferably 1 It is 6 × 10 ⁻⁵ / ° C. or less, more preferably 1.4 × 10 ⁻⁵ / ° C. or less. When the linear expansion coefficient exceeds 2 × 10 ⁻⁵ / ° C., dimensional stability is not sufficient due to large thermal expansion.

  Here, the linear expansion coefficient was measured in accordance with ISO 11359-2 by cutting a 4 mm × 4 mm × 4 mm cubic test piece from the center of the ISO multipurpose test piece and measuring the MD direction and the TD direction. . The measurement was performed using TMA / SS6100 manufactured by SII Nanotechnology Inc., and an average linear expansion coefficient of 10 ° C to 110 ° C was calculated at a heating rate of 5 ° C / min.

  The method for making the linear expansion coefficient as described above is not particularly limited. For example, with respect to 100 parts by mass of the polycarbonate resin, the total addition amount of inorganic filler components such as carbon fibers and glass fibers is 30 parts by mass or more. Can be mentioned.

The volume resistivity of the polycarbonate resin composition of the present invention is required to be 1 × 10 ¹⁰ Ω · m or less. The volume resistivity is preferably 0.8 × 10 ¹⁰ Ω · m or less, more preferably 0.6 × 10 ¹⁰ Ω · m or less, and further preferably 0.4 × 10 ¹⁰ Ω · m or less. Further, it is preferably 1 × 10 ⁵ Ω · m or more, and more preferably 5 × 10 ⁵ Ω · m or more.
By exhibiting such volume resistivity, antistatic performance is exhibited, and there is an effect of suppressing adverse effects due to charging (dust adsorption, damage to electronic equipment due to discharge, danger of fire and explosion, etc.).

  The volume resistivity is measured according to IEC 60093.

The surface resistivity of the polycarbonate resin composition of the present invention needs to be 1 × 10 ¹⁰ Ω or less. The surface resistivity is preferably 0.8 × 10 ¹⁰ Ω or less, more preferably 0.6 × 10 ¹⁰ Ω or less, still more preferably 0.4 × 10 ¹⁰ Ω or less, and preferably 1 × 10 ⁵ Ω or more, more preferably 5 × 10 ⁵ Ω or more.
By exhibiting such surface resistivity, antistatic performance is exhibited, and there is an effect of suppressing adverse effects due to charging (such as dust adsorption, breakage of electronic equipment due to discharge, danger of fire and explosion).

  The surface resistivity is measured according to IEC 60093.

  In order to obtain a polycarbonate resin composition having a volume resistivity and a surface resistivity in the above range, it is possible to adjust the content of a conductive compound such as carbon fiber, and when the content ratio of the conductive compound is too small. The effect of improving the volume resistivity and the surface resistivity is insufficient, and if it is too much, it is disadvantageous in terms of cost and physical properties, and the preferred ranges of the volume resistivity and the surface resistivity are deviated.

  Moreover, in order to make all of (i) molding shrinkage, (ii) linear expansion coefficient, (iii) volume resistivity, and (iv) surface resistivity into said range, it adjusts combining said method. Specifically, for example, it can be achieved by adjusting the amount of each raw material component so as to have a composition ratio as shown in each example and uniformly dispersing it.

Furthermore, the polycarbonate resin composition of the present invention preferably has a self-tap breaking torque of 0.3 N · m or more when the catching rate is 34%. It can be screwed directly to the body. The self-tap breaking torque is more preferably 0.4 N · m or more, and more preferably 0.5 N · m or more.
In order to set the self-tap breaking torque within the above range, it is possible to optimize the amount and shape of the filler component added.

  The self-tap breaking torque is obtained by drying the pellets of the polycarbonate resin composition at 100 ° C. for 5 hours, and then using an injection molding machine (“J55-60H” manufactured by Nippon Steel Works) with a cylinder set temperature of 290 to 310 ° C., At a mold temperature of 100 ° C., an outer diameter of 7.63 mm, an inner diameter of 2.61 mm, a height of 10 mm, an outer diameter of 7.33 mm, an inner diameter of 2.44 mm, and a height of 10 mm are formed on a plate-shaped portion of 70 mm × 45 mm × 3 mm. A self-tapping test boss hole test piece in which a boss hole is formed is injection-molded, and a screw (M3 × 6 P type thread diameter 3) with a catch rate of 34% is obtained in the two boss holes of the obtained test piece. .02 mm, screw valley diameter 2.17 mm) is screwed with a torque screwdriver, the torque that leads to breakage due to cracking of the boss hole is measured, and measured as self-tap breaking torque.

[Molding]
The pellets obtained by pelletizing the above-described polycarbonate resin composition are molded into various molded products by various molding methods. Further, the resin melt-kneaded by an extruder can be directly molded into a molded product without going through the pellets.
The shape of the molded product is not particularly limited and can be appropriately selected according to the use and purpose of the molded product. For example, a plate shape, a plate shape, a rod shape, a sheet shape, a film shape, a cylindrical shape, an annular shape, Examples include a circular shape, an elliptical shape, a polygonal shape, an irregular shape, a hollow shape, a frame shape, a box shape, and a panel shape.

  The method for molding the molded body is not particularly limited, and a conventionally known molding method can be employed.For example, an injection molding method, an injection compression molding method, an extrusion molding method, a profile extrusion method, a transfer molding method, a hollow molding method, Gas assisted hollow molding method, blow molding method, extrusion blow molding, IMC (in-mold coating molding) molding method, rotational molding method, multilayer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method And a pressure molding method.

  The polycarbonate resin composition of the present invention is a resin material excellent in mechanical properties such as high thermal conductivity and impact resistance, tensile properties and bending properties, and further in high fluidity, high dimensional accuracy and self-tap strength. Therefore, a molded product obtained by molding this is suitable for various electronic and electrical devices, personal computers, cameras, various precision devices, parts and casings of various portable terminals, and the like. In particular, as camera parts, lens barrels, camera housings, and various parts for digital cameras and digital video cameras, for example, elements and parts such as solid-state image sensors, photo sensors, A / D conversion elements, imagers, etc. It is useful as a component (frame body, frame) that holds the element, and by efficiently releasing the heat generated when executing a large amount of optical signal processing at high speed, deformation of the element and component is prevented, and high S / This is preferable because a clear image with an N ratio can be realized.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
Each raw material component used in the following Examples and Comparative Examples is as shown in Table 1 below.

(Examples 1-6)
Using a twin screw extruder (“TEX30HSST” manufactured by Nippon Steel Co., Ltd.), using each component described in Table 1 above at a cylinder temperature of 280 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 20 kg / hr, the finished composition is Adjustments were made so that the proportions shown in Table 2 below (all expressed in parts by mass) were obtained, thereby obtaining pellets of the polycarbonate resin composition.
Under the present circumstances, after carbon fiber and glass fiber other than each component were uniformly mixed with the tumbler mixer, it was fed to the extruder from the barrel of the upstream part of the extruder. On the other hand, the carbon fiber and glass fiber used together are side-fed from the vicinity of the exit of the extruder as much as possible so that the fiber length is not broken as much as possible. Using a kneading screw and a 0.5D reverse feed kneading screw, the mixture was kneaded to obtain pellets of a polycarbonate resin composition.

[Manufacture of ISO multipurpose test pieces]
After drying the pellet obtained above at 100 ° C. for 5 hours, using an injection molding machine (“J55-60H” manufactured by Nippon Steel Works), cylinder set temperature 270-290 ° C., mold temperature 100 ° C., injection time Injection molding was performed under conditions of 2 seconds and a molding cycle of 40 seconds, and an ISO multipurpose test piece (4 mm thick) was injection molded.

[Evaluation of tensile properties]
Using the above-mentioned ISO multipurpose test piece (4 mm thickness), in accordance with ISO standard 527-1 and ISO527-2, tensile modulus (unit: MPa), breaking point strength (unit: MPa), breaking point nominal strain (unit) :%).

[Evaluation of bending properties]
Based on ISO178, the bending elastic modulus (unit: MPa) and bending stress (unit: MPa) were measured at 23 ° C. using the ISO multipurpose test piece (4 mm thickness).

[Evaluation of impact resistance: Charpy impact value (unit: kJ / m ² )]
The obtained ISO multipurpose test piece (4 mm thick) was used, and a test piece with a notch was also prepared by cutting. Using the obtained test piece, in accordance with ISO 179, notched and notched Charpy impact strength (unit: kJ / m ² ) was measured under the condition of 23 ° C.

[Evaluation of heat resistance: deflection temperature under load (unit: ° C)]
Using the ISO multipurpose test piece (4 mm thickness) obtained above, the measurement was performed in accordance with ISO 75-1 & 2 under the condition (Method A) under a load of 1.80 MPa.

[Measurement of thermal conductivity (unit: W / m · K)]
The ISO multipurpose test piece (4 mm) obtained above was cut into a slice of 0.15 to 0.5 mm thickness, and this was used as a sample. Temperature phase thermal analyzer “ai-Phase Mobile1” manufactured by I-Phase Co., Ltd. Was measured for the MD direction and the thickness direction.

[Self-tap breaking torque (unit: N · m)]
After drying the pellet obtained above at 100 ° C. for 5 hours, using an injection molding machine (“J55-60H” manufactured by Nippon Steel Works) at a cylinder set temperature of 290 to 310 ° C. and a mold temperature of 100 ° C., Self-tapping in which a boss hole of outer diameter 7.63 mm x inner diameter 2.61 mm x height 10 mm, outer diameter 7.33 mm x inner diameter 2.44 mm x height 10 mm is formed on a plate-like portion of 70 mm x 45 mm x 3 mm Test boss hole specimens were injection molded.
Screw the screw (M3 × 6 P type, thread diameter 3.02mm, thread valley diameter 2.17mm) to a hook ratio of 34% into the two boss holes of the obtained test piece with a torque screwdriver. Torque to break due to hole cracking was measured and used as self-tap breaking torque.

[Evaluation of fluidity: spiral flow flow length (unit: mm)]
As an evaluation of fluidity, the spiral flow flow length (unit: mm) of the resin composition was evaluated using an injection molding machine (“J55-60H” manufactured by Nippon Steel Works). That is, after the pellets obtained above were dried at 120 ° C. for 4 hours or more, an injection pressure of 150 MPa, an injection speed of 60 mm / sec, a cylinder temperature of 280 ° C., 300 ° C. and 320 ° C., an injection time of 2 sec, The conditions were cooling 7 sec, mold temperature 100 ° C., suck back 2 mm.
Moreover, the shape of the evaluated resin molded product is a long resin molded product having a cross section of 1 mm in thickness and a width of 1.5 mm, and has a spiral shape. This spiral long resin molded product is shown in FIG. In FIG. 1, the central member represents the gate 1, and the size of the spiral long resin molded product is the distance between the centers of the long resin molded product (dimension h <b> 1 in the major axis direction) × (short axis Directional dimension h2) = 105 mm × 90 mm.
The spiral flow length indicates that the larger the value, the better the fluidity.

[Mold shrinkage (unit:%)]
After the pellets obtained above were dried at 80 ° C. for 5 hours, using an injection molding machine (“J85-60H” manufactured by Nippon Steel Works), cylinder temperature: 300 ° C., mold temperature 100 ° C., holding pressure A mark formed by molding with a molding cycle of 10 seconds and a cooling time of 20 seconds, with a thickness of 3 mm, 100 mm × 100 mm, and a test piece surface with 70 mm intervals in the MD and TD directions. The distance between them was measured by a non-contact method using a high-precision CCD laser displacement meter three-dimensional measuring device, and the molding shrinkage was calculated from the ratio to the actual dimensions of the mold.

[Linear expansion coefficient (unit: / ℃)]
The linear expansion coefficient was measured in accordance with ISO 11359-2 by cutting out a 4 mm × 4 mm × 4 mm cubic test piece from the center of the ISO multipurpose test piece and measuring the MD direction and the TD direction. The measurement was performed using TMA / SS6100 manufactured by SII Nanotechnology Inc., and an average linear expansion coefficient of 10 ° C to 110 ° C was calculated at a heating rate of 5 ° C / min.

[Volume resistivity (unit: Ω · m)]
A flat specimen having a thickness of 3 mm and 100 mm × 100 mm was measured with a resistivity meter (advantest R8340 digital ultrahigh resistance / microammeter and R12704 resiliency chamber) in accordance with IEC 60093. The measurement was performed on three test pieces, and the average value was taken as the volume resistivity.

[Surface resistivity (unit: Ω)]
A flat specimen having a thickness of 3 mm and 100 mm × 100 mm was measured with a resistivity meter (advantest R8340 digital ultrahigh resistance / microammeter and R12704 resiliency chamber) in accordance with IEC 60093. The measurement was performed on three test pieces, and the average value was defined as the surface resistivity.

(Comparative Examples 1-2)
A pellet of a polycarbonate resin composition was obtained in the same manner as in Example 1 except that the components described in Table 2 below were used in the mass ratio described in Table 2 without using carbon fiber and glass fiber in combination.
Various evaluations were performed in the same manner as in Example 1.

  The above evaluation results are shown in Table 2 below.

  According to the polycarbonate resin composition of the present invention, it has high thermal conductivity and excellent mechanical properties such as impact resistance, tensile properties and bending properties, and further has a high fluidity, a highly reduced molding shrinkage rate and a self-tap strength. Therefore, it is suitable for various electronic and electronic devices, personal computers, cameras, various precision devices, various portable terminal parts and housings. In particular, as a camera part, it can be particularly suitably used for a lens barrel, a camera casing, and various parts for a digital camera or a digital video camera, for example, and has very high industrial applicability.

Claims (6)

A polycarbonate resin composition containing 10 to 100 parts by mass of carbon fiber and 10 to 100 parts by mass of glass fiber with respect to 100 parts by mass of polycarbonate resin,
(I) Mold shrinkage is 0.15% or less in the resin flow direction (MD direction) during molding, 0.35% or less in the direction perpendicular to the MD direction (TD direction),
(Ii) the coefficient of linear expansion (measured in accordance with ISO 11359-2) is 2 × 10 ⁻⁵ / ° C. or less in the MD direction;
(Iii) Volume resistivity (measured according to IEC 60093) is 1 × 10 ¹⁰ Ω · m or less, and (iv) Surface resistivity (measured according to IEC 60093) is 1 × 10 ¹⁰ Ω or less. A polycarbonate resin composition characterized by that.   The polycarbonate resin composition according to claim 1, wherein a mass ratio of carbon fiber to glass fiber (carbon fiber / glass fiber) is 1.0 or more.   Furthermore, the polycarbonate resin composition of Claim 1 or 2 which contains 0.1-3 mass parts of carbon black with respect to 100 mass parts of polycarbonate resin.   The polycarbonate resin composition according to any one of claims 1 to 3, wherein the self-tap breaking torque is 0.3 N · m or more when the catch rate is 34%.   The molded product formed by shape | molding the polycarbonate resin composition of any one of Claims 1-4.   The molded article according to claim 5, which is a camera part.

Images