WO2021010366A1

WO2021010366A1 - Polycarbonate resin composition

Info

Publication number: WO2021010366A1
Application number: PCT/JP2020/027189
Authority: WO
Inventors: 晃司廣瀬
Original assignee: 三菱エンジニアリングプラスチックス株式会社
Priority date: 2019-07-17
Filing date: 2020-07-13
Publication date: 2021-01-21
Also published as: JPWO2021010366A1; CN114127190A; JP7500566B2; KR20220035876A; TW202110996A; TWI849182B

Abstract

A polycarbonate resin composition which, in relation to 100 parts by mass of a polycarbonate resin (A), contains 1-50 parts by mass of a filler (B) having an average particle diameter of 0.1-10 μm, characterised in that, when a filler having an average particle diameter exceeding 10 μm is contained, the contained amount thereof is less than 10 mass% in the resin composition, and the contained amount, when containing a phosphorus flame retardant, is 2% or less in the resin composition.

Description

Polycarbonate resin composition

The present invention relates to a polycarbonate resin composition and an optical module, and more particularly to a polycarbonate resin composition and an optical module which are excellent in rigidity and impact resistance, exhibit low anisotropy, and are also excellent in moisture and heat resistance.

Polycarbonate resin has excellent mechanical properties and is widely used as an engineering plastic, and depending on the field of application, various strengthening agents and additives may be added for the purpose of improving the properties, especially the mechanical properties. It has been broken. In fields where high mechanical strength and rigidity are required, fibrous reinforcing materials such as glass fibers are used. However, although the resin composition obtained by blending the glass fiber with the polycarbonate resin has excellent mechanical strength and rigidity, it has a drawback that anisotropy of the molding shrinkage rate occurs due to the orientation of the fiber.

In recent years, for example, in imaging or optical equipment equipped with a lens such as a camera, optical modules such as a lens barrel tubular body (lens barrel) have been made into a resin in order to reduce the weight and cost. Materials reinforced with fiberglass are also used. In the lens barrel, sufficient rigidity and high dimensional accuracy are required for the material of the lens barrel so that the optical axis of the optical system does not shift during focusing or zoom driving.

Dimensional accuracy is also improved by using glass fibers having a specific cross-sectional shape.
Patent Document 1 proposes an aromatic polycarbonate resin composition having improved mechanical strength and flame retardancy, which comprises a polycarbonate resin, a flat cross-sectional glass fiber having a specific cross-sectional shape, and a phosphoric acid ester flame retardant. In the example, a polycarbonate resin composition in which flat cross-section glass fiber and glass flakes having a thickness of 5 μm are blended in a specific amount ratio and further contains a phosphate ester flame retardant and polytetrafluoroethylene is described. The anisotropy is not sufficiently satisfactory, and since a phosphorus-based flame retardant is used, the impact strength and heat resistance are likely to decrease due to the plasticization of the polycarbonate resin. The heat resistance and anisotropy were insufficient and unsatisfactory.

In addition, since the lens barrel or the like is required to have uniformity (roundness) in the circumferential direction when it is formed into a tubular shape, the resin material needs to have low anisotropy, and the resin material and aluminum, magnesium, etc. Since it is composited with a metal (or alloy), it is necessary to prevent the optical axis from shifting due to the difference in thermal expansion even at a wide operating environment temperature, and the resin material is required to have a linear expansion coefficient close to those of these metals. On the other hand, in optical modules such as those used for camera modules of mobile devices such as smartphones, the lens and lens barrel are integrated due to their structure, and the resin material of the lens barrel expands linearly to prevent optical axis deviation. It is required to match the coefficient with the lens. Since most of the lenses of such optical modules are made of resins such as polycarbonate, it is desirable that the coefficient of linear expansion be close to those resins in this application. As described above, in lens barrel applications, there is a demand for a material system in which the coefficient of linear expansion can be controlled by a device.

Japanese Patent No. 5021918

The present invention has been made in view of the above circumstances, and an object (problem) thereof is to provide a polycarbonate resin composition and an optical module having excellent rigidity and impact resistance and further exhibiting low anisotropy.

The inventor of the present invention improves rigidity and low anisotropy by blending a polycarbonate resin with a fine filler having a specific average particle size, and at that time, a filler having a large average particle diameter of 10 μm or more. It was found that it is better not to add more than a specific amount of or phosphorus-based flame retardants.
Furthermore, by combining an olefin / maleic anhydride copolymer, an elastomer, and a fluororesin in a specific amount ratio, the impact strength is dramatically improved, and the characteristics of high rigidity and high impact resistance are exhibited. Moreover, it has been found that it exhibits low anisotropy, and further, deterioration of the polycarbonate resin is suppressed and excellent in moisture and heat resistance, and the present invention has been completed.
The present invention relates to the following polycarbonate resin compositions, molded articles, and optical modules.

[1] A polycarbonate resin composition containing 1 to 50 parts by mass of a filler (B) having an average particle size of 0.1 to 10 μm with respect to 100 parts by mass of the polycarbonate resin (A), wherein the average particle size is 10 μm. When the filler exceeds the content, the content is less than 10% by mass in the resin composition, and when the phosphorus-based flame retardant is contained, the content is 2% or less in the resin composition. Polycarbonate resin composition.
[2] Further, with respect to 100 parts by mass of the polycarbonate resin (A), 0.1 to 5 parts by mass of the olefin / maleic anhydride copolymer (C), 1 to 25 parts by mass of the elastomer (D), and a fluororesin ( E) Containing 0.05 to 10 parts by mass,
The polycarbonate resin composition according to the above [1], wherein the ratio (D) / (E) of the contents of the elastomer (D) and the fluororesin (E) is more than 1 and 250 or less.
[3] The polycarbonate resin composition according to the above [2], wherein the ratio (B) / (E) of the contents of the filler (B) and the fluororesin (E) is more than 1 and 500 or less.
[4] The polycarbonate resin composition according to any one of the above [1] to [3], wherein the filler (B) is a plate-shaped filler.
[5] The filler (B) is a plate-shaped filler, and is at least one selected from talc, mica, glass flakes, montmorillonite, hydrotalcite, sericite, kaolin, alumina, clay, and graphite. The polycarbonate resin composition according to any one of 1] to [4].
[6] The polycarbonate resin composition according to any one of the above [1] to [5], wherein the filler (B) is talc.
[7] The polycarbonate resin composition according to any one of the above [2] to [6], wherein the elastomer (D) is a core / shell type elastomer.
[8] The polycarbonate resin composition according to any one of the above [2] to [7], wherein the elastomer (D) is a core / shell type elastomer of a butadiene rubber core.
[9] The polycarbonate resin composition according to any one of the above [1] to [8], wherein the notched Charpy impact strength measured based on ISO179 is 20 kJ / m ² or more.
[10] Any of the above [1] to [9] in which the notched Charpy impact strength after treatment for 100 hours under the conditions of a temperature of 85 ° C. and a relative humidity of 85% measured based on ISO179 is 10 kJ / m ² or more. The polycarbonate resin composition according to the above.
[11] The polycarbonate resin composition according to any one of the above [1] to [10], wherein the deflection temperature under load measured based on the ISO75 A method is 120 ° C. or higher.
[12] A molded product made of the polycarbonate resin composition according to any one of the above [1] to [11].
[13] An optical module including the molded product according to the above [12].

[14] A notched Charpy made of a resin composition containing 1 to 50 parts by mass of a filler (B) having an average particle size of 0.1 to 10 μm with respect to 100 parts by mass of the polycarbonate resin (A), and measured based on ISO179. An optical module including a molded body having an impact strength of 20 kJ / m ² or more.
[15] The resin composition further contains 0.1 to 5 parts by mass of the olefin / maleic anhydride copolymer (C) and 1 to 25 parts by mass of the elastomer (D) with respect to 100 parts by mass of the polycarbonate resin (A). , And 0.05 to 10 parts by mass of the fluororesin (E), and the ratio (D) / (E) of the contents of the elastomer (D) and the fluororesin (E) is more than 1 and 250 or less. The optical module according to the above [14].
[16] The optical module according to the above [15], wherein when the resin composition contains a filler having an average particle size of more than 10 μm, the content thereof is less than 10% by mass in the resin composition.
[17] The optical module according to the above [15] or [16], wherein the ratio (B) / (E) of the content of the filler (B) to the fluororesin (E) is more than 1 and 500 or less.
[18] The optical module according to any one of the above [14] to [17], wherein the filler (B) is talc.
[19] The optical module according to any one of [15] to [18] above, wherein the elastomer (D) is a core / shell type elastomer.
[20] The optical module according to any one of [15] to [19] above, wherein the elastomer (D) is a core / shell type elastomer of a butadiene rubber core.
[21] The resin composition has a notched Charpy impact strength of 10 kJ / m ² or more after 100 hours of treatment under the conditions of a temperature of 85 ° C. and a relative humidity of 85%, as measured based on ISO179. 20] The optical module according to any one of.
[22] The optical module according to any one of [14] to [21] above, wherein the resin composition has a deflection temperature under load measured based on the ISO75 A method of 120 ° C. or higher.

The polycarbonate resin composition of the present invention is excellent in rigidity and impact resistance, exhibits low anisotropy, and is also excellent in moisture and heat resistance.
In the present invention, by blending a fine filler (B) having an average particle size of 0.1 to 10 μm, rigidity and low anisotropy are improved, and optical performance is deteriorated even when used in an optical module or the like. Can be suppressed. Then, preferably, the olefin / maleic anhydride copolymer (C) is blended to suppress the resin deterioration of the polycarbonate resin due to the filler (B), the impact resistance is further improved by the elastomer (D), and further. The compounding of the fluororesin (E) acts like a surfactant to improve the impact resistance, and can exhibit rigidity, impact resistance, low anisotropy, and moist heat resistance.
The optical module of the present invention is an optical module containing a molded body made of the above polycarbonate resin composition, and is excellent in rigidity, impact resistance and low anisotropy, so that it does not deform and has extremely good dimensional accuracy. It is effective as a high-performance optical module that does not break even if dropped.

Hereinafter, the polycarbonate resin composition of the present invention, each component used in the resin composition constituting the optical module, and the like will be described in detail.
In addition, in this specification, when the range is expressed by sandwiching the value before and after the value by using “～”, it means the range including the value before and after the value.

[Polycarbonate resin (A)]
The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the formula:-[-O-X-OC (= O)-]-. In the formula, X is generally a hydrocarbon, but X with a heteroatom or a heterobond introduced may be used to impart various properties.
Further, the polycarbonate resin can be classified into an aromatic polycarbonate resin in which the carbon directly bonded to the carbonic acid bond is an aromatic carbon and an aliphatic polycarbonate resin in which the carbon is an aliphatic carbon, and any of them can be used. Of these, aromatic polycarbonate resins are preferable from the viewpoints of heat resistance, mechanical properties, electrical properties, and the like.

The specific type of the polycarbonate resin is not limited, and examples thereof include a polycarbonate polymer obtained by reacting a dihydroxy compound with a carbonate precursor. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Alternatively, a method of reacting carbon dioxide with cyclic ether using carbon dioxide as a carbonate precursor may be used. Further, the polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a copolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, as the copolymer, various copolymer forms such as a random copolymer and a block copolymer can be selected. Usually, such a polycarbonate polymer becomes a thermoplastic resin.

Among the 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, 1 , 7-Dihydroxynaphthalene, 2,7-dihydroxynaphthalene and other 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) Dihydroxydiaryl 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 (ie, bisphenol C),
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,
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,
Cardo-structure-containing bisphenols such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

4,4'-Dihydroxydiphenylsulfide,
Dihydroxydiarylsulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide;

Dihydroxydiarylsulfoxides such as 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide;

4,4'-Dihydroxydiphenylsulfone,
Dihydroxydiaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone;
And so on.

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are particularly preferable, and 2,2-bis (4-hydroxyphenyl) propane (particularly from the viewpoint of impact resistance and heat resistance). That is, bisphenol A) and 2,2-bis (3-methyl-4-hydroxyphenyl) propane (that is, bisphenol C) are preferable.
As the aromatic dihydroxy compound, one type may be used, or two or more types may be used in any combination and ratio.

Further, to give an example of a monomer which is a raw material of an aliphatic polycarbonate resin,
Ethan-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 diols, butane-1,4-diols, pentane-1,5-diols, hexane-1,6-diols and decane-1,10-diols;

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 (that is, diethylene glycol), triethylene glycol, propylene glycol, and spiroglycol;

1,2-Benzene dimethanol, 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- Aralkyldiols such as bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2-hydroxyethyl) ether;

1,2-Epoxide ethane (ie, ethylene oxide), 1,2-epoxide propane (ie, propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxide cyclohexane, 1-methyl Cyclic ethers such as -1,2-epoxycyclohexane, 2,3-epoxide norbornane, and 1,3-epoxide propane; and the like.

Among the monomers used as raw materials for polycarbonate resins, carbonyl halides, carbonate esters, etc. are used as examples of carbonate precursors. As the carbonate precursor, one kind may be used, or two or more kinds may be used in any combination and ratio.

Specific examples of the carbonyl halide include phosgene; a bischloroformate of a dihydroxy compound, a haloformate of a monochloroformate of a dihydroxy compound, and the like.

Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditril carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate of dihydroxy compound, monocarbonate of dihydroxy compound, and cyclic carbonate. Examples thereof include carbonates of dihydroxy compounds such as.

The method for producing the polycarbonate resin is not particularly limited, and any method can be adopted. 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.

A preferred example of the polycarbonate resin is a polycarbonate resin in which bisphenol A or bisphenol A is used in combination with another aromatic dihydroxy compound, or bisphenol C or bisphenol C is used in combination with another aromatic dihydroxy compound (particularly bisphenol A). Examples thereof include a polycarbonate resin obtained from the above, and a blend of these resins.

The molecular weight of the polycarbonate resin (A) is preferably in the range of 16,000 to 50,000, more preferably 18,000 or more, still more preferably 20,000 or more, still more preferably 45,000 or less, still more preferably 45,000 or less, in terms of viscosity average molecular weight (Mv). Is 40,000, particularly preferably 38,000 or less. If the viscosity average molecular weight is smaller than 16000, the impact resistance of the molded product is likely to decrease and cracks may occur, which is not preferable. If the viscosity average molecular weight is larger than 50,000, the fluidity deteriorates and the moldability becomes a problem. It is not preferable because it is easy.
The polycarbonate resin (A) may be used by mixing two or more types of polycarbonate resins having different viscosity average molecular weights. In this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned suitable range is mixed. You may.

In the present invention, the viscosity average molecular weight [Mv] of the polycarbonate resin is the ultimate viscosity [η] (unit: dl / g) at a temperature of 25 ° C. using a Ubbelohde viscometer using methylene chloride as a solvent. , Schnell's viscosity formula, ie
η = 1.23 × 10 ^-4 Mv It means a value calculated from ^0.83 . The ultimate viscosity [η] is a value calculated by the following formula by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

Further, in the present invention, for example, for the purpose of further enhancing flame retardancy and impact resistance, a polycarbonate resin is used as a copolymer with an oligomer or polymer having a siloxane structure; thermal oxidation stability and flame retardancy. A copolymer with a monomer, oligomer or polymer having a phosphorus atom for the purpose of further improving; a copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; A copolymer mainly composed of a polycarbonate resin such as a copolymer with an oligomer or a polymer having an olefin-based structure such as polystyrene; a copolymer with a polyester resin oligomer or a polymer for the purpose of improving chemical resistance; It may be configured as a polymer.

Further, the polycarbonate resin may contain a polycarbonate oligomer in order to improve the appearance and fluidity of the molded product. The viscosity average molecular weight (Mv) of this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and usually 9500 or less, preferably 9000 or less. When the polycarbonate oligomer is contained, the content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less, based on 100 parts by mass of the polycarbonate resin (A). The lower limit is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and particularly preferably 3 parts by mass or more.

Further, the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin recycled from a used product (so-called material recycled polycarbonate resin).
However, the regenerated polycarbonate resin is preferably 80% by mass or less, and more preferably 50% by mass or less of the polycarbonate resin (A). Since the regenerated polycarbonate resin is likely to be deteriorated by heat deterioration, aging deterioration, etc., if such a polycarbonate resin is used in a larger amount than the above range, the hue and mechanical properties can be deteriorated. Because it has sexual characteristics.

[Filler (B)]
As the filler (B), a filler having an average particle size of 0.1 to 10 μm is used. The average particle size of the filler (B) is preferably 9 μm or less, more preferably 8 μm or less, 7 μm or less, 6 μm or less, 5 μm or less, 4 μm or less, and particularly preferably 3 μm or less, particularly 2.5 μm or less.
Further, it is preferably 0.12 μm or more, more preferably 0.15 μm or more, 0.18 μm or more, and particularly preferably 0.2 μm or more, particularly 0.25 μm or more.

The average particle size of the filler (B) is a D ₅₀ average particle size determined by laser diffraction.

The filler (B) is preferably an inorganic filler, more preferably a plate-shaped filler, specifically talc, mica, glass flakes, montmorillonite, hydrotalc stone, sericite, kaolin, alumina, clay, graphite and the like. Is preferable, one type may be used alone, or two or more types may be mixed and used.
Of these, talc and mica are preferred.

[talc]
The polycarbonate resin composition of the present invention preferably contains talc as the filler (B). By containing talc together with each component described later, the resin composition can be made to have lower anisotropy and low linear expansion, and the rigidity can be further improved.

As is well known, talc is a hydrous magnesium silicate having a layered structure.
As the talc, one having an average particle size of 0.1 to 10 μm is used. The average particle size is preferably 0.3 to 8 μm, more preferably 0.7 to 5 μm. The thermal stability of the resin composition tends to be further improved by setting the average particle size to 0.1 μm or more, and the appearance and rigidity of the molded product of the resin composition are further improved by setting the average particle size to less than 10 μm. To do.

It is also preferable that the talc is surface-treated in order to enhance the affinity with the polycarbonate resin (A). Specific examples of the surface treatment agent include alcohols such as trimethylolethane, trimethylolpropane, and pentaerythritol, alkanolamines such as triethylamine, and organic silicone compounds such as organopolysiloxane. , Higher fatty acids such as stearic acid, fatty acid metal salts such as calcium stearate and magnesium stearate, hydrocarbon lubricants such as polyethylene wax and liquid paraffin, basic amino acids such as lysine and arginine, polyglycerin and derivatives thereof, and silanes. At least one selected from coupling agents such as coupling agents, titanate-based coupling agents, and aluminum-based coupling agents can be mentioned.

Further, the talc is preferably in the form of granules granulated using a binder from the viewpoint of surface appearance and thermal stability when contained in the resin composition. The bulk density of the granular talc is preferably 0.4 to 1.5 g / ml.

The preferable content of the filler (B) is 1 to 50 parts by mass with respect to 100 parts by mass of the polycarbonate resin fat (A). Within such a range, low-line expansion and sufficient mechanical properties can be obtained. If the content of the filler (B) is less than 1 part by mass, low linear expansion cannot be achieved and the rigidity is insufficient, and if it exceeds 50 parts by mass, the production stability is lowered and the toughness is also lowered. To do. The content of the filler is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, preferably 45 parts by mass or less, more preferably 40 parts by mass or less, and further 35 parts by mass or less, particularly 30 parts by mass. Part or less is preferable.

The polycarbonate resin composition of the present invention is characterized in that, when a filler having an average particle size of more than 10 μm is contained, the content thereof is less than 10% by mass in the resin composition.
Here, as the filler having an average particle size of more than 10 μm (hereinafter, also referred to as a filler (BX)), a filler of the same type as the filler (B) used and having an average particle diameter of more than 10 μm is used. It may be blended, or it may be a filler different from the filler used (B) and having an average particle size of more than 10 μm. The filler (BX) is not contained, or when it is contained, the content is less than 10% by mass in the resin composition.

As an example of the filler (BX) different from the filler (B), for example, a whisker-like filler such as potassium titanate or aluminum borate, a fibrous filler such as carbon fiber or glass fiber, or the like is preferable. It can be illustrated. In the present invention, when the filler (BX) is whisker-shaped, needle-shaped, fibrous, or the like, the average fiber length of the filler (BX) is applied.

When the filler (BX) is contained, the proportion in the polycarbonate resin composition is less than 10% by mass, preferably less than 0% by mass or less than 10% by mass, more preferably 0% by mass or in the resin composition. It is less than 7% by mass, 0% by mass or less than 5% by mass, 0% by mass or less than 3% by mass. When the content ratio of the filler (BX) exceeds the above upper limit value, problems such as deterioration of the optical performance of the lens unit of the optical module occur.

[Olefin / maleic anhydride copolymer (C)]
By containing the olefin / maleic anhydride copolymer (C) together with the above-mentioned and the following components, the direct contact between the polycarbonate resin and the filler (B) is hindered, and the thermal stability and mechanical characteristics of the resin composition are impaired. Can be improved, and impact resistance can be further improved.

As the olefin / maleic anhydride copolymer (C), an olefin / maleic anhydride copolymer and / or a maleic anhydride-modified olefin polymer is preferable.

The olefin / maleic anhydride copolymer is a copolymer of maleic anhydride and α-olefin, a copolymer of a conjugated diene-based monomer, and a copolymer of a conjugated diene / aromatic vinyl-based monomer. And so on.

As the α-olefin, α-olefins having 2 to 10 carbon atoms such as ethylene, propylene, butene-1, penten-1, hexene-1, 4-methylpentene-1, octene-1, 1-decene and the like are preferably mentioned. These may be used alone or in combination of two or more. Among these, ethylene, propylene, butene-1, hexene-1, and octene-1 are more preferable, and a combination of ethylene with propylene, butene-1, hexene-1, or octene-1 is particularly preferable.

Conjugated diene-based monomers include conjugates of 1,3-butadiene, isoprene (ie, 2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Diene monomers can be used alone or in combination of two or more. As these, those in which a part or all of the unsaturated bonds existing in the polymer are reduced by hydrogenation can also be preferably used.
Examples of the aromatic vinyl-based monomer include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene and the like, and among them, styrene can be preferably used.

As the α-olefin / maleic anhydride copolymer, maleic anhydride-ethylene-propylene copolymer and maleic anhydride-ethylene-butene-1 copolymer are particularly preferable.

Examples of the olefin-based polymer in the maleic anhydride-modified olefin polymer include homopolymers of α-olefins such as ethylene, propylene, butene-1, penten-1, hexene-1, 4-methylpentene-1, and octene-1. Alternatively, ethylene-based copolymers, conjugated diene-based polymers (monopolymers or copolymers of diolefin-based monomers), conjugated diene / aromatic vinyl hydrocarbon-based copolymers, non-conjugated diene, etc. can be mentioned. , These can be used by mixing two or more kinds.

Examples of the homopolymer referred to here include polyethylene, polypropylene, polybutene and the like. As the polyethylene, those having any molecular structure such as LDPE, LLDPE and HDPE can be preferably used.
Further, the ethylene-based copolymer refers to a copolymer of ethylene and another monomer and a multiple copolymer. In the ethylene-based copolymer, the copolymerization amount of ethylene is preferably 50 to 99 mol%. The other monomer copolymerized with ethylene can be selected from α-olefins having 3 or more carbon atoms, non-conjugated diene, vinyl acetate and the like.
Examples of the α-olefin having 3 or more carbon atoms include propylene, butene-1, penten-1, 3-methylpentene-1, octene-1, and propylene and butene-1 can be preferably used.

Among these ethylene-based copolymers, a copolymer of ethylene and an α-olefin having 3 or more carbon atoms is preferable, and specifically, an ethylene-propylene copolymer, an ethylene-butene-1 copolymer and the like are used. Particularly preferred.

Non-conjugated dienes include 5-methyriden-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-. Norbornene compounds such as crotyl-2-norbornene, 5- (2-methyl-2-butenyl) -2-norbornene, 5- (2-ethyl-2-butenyl) -2-norbornene, 5-methyl-5-vinylnorbornene , Dicyclopentadiene, methyltetrahydroinden, 4,7,8,9-tetrahydroinden, 1,5-cyclooctadiene, 1,4-hexadiene, isoprene, 6-methyl-1,5-heptadiene, 11-tridecadien, etc. 5-Methylidene-2-norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene, 1,4-hexadien and the like are preferable.

As the conjugated diene polymer, a single amount of conjugated diene such as 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Examples thereof include homopolymers and copolymers of the compound. Those in which some or all of the unsaturated bonds present in these polymers are reduced by hydrogenation can also be preferably used.

Furthermore, a copolymer of a conjugated diene and an aromatic vinyl hydrocarbon can also be used. For example, block copolymers or random copolymers having various ratios of conjugated diene to aromatic vinyl hydrocarbons include the above-mentioned monomers as examples of the conjugated diene constituting the block copolymers or random copolymers. 3-butadiene and isoprene are preferable. Examples of aromatic vinyl hydrocarbons include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene and the like, and among them, styrene can be preferably used. Further, it is also preferable to use a conjugated diene / aromatic vinyl hydrocarbon-based copolymer in which a part or all of unsaturated bonds other than the aromatic ring is reduced by hydrogenation. Preferred examples include a styrene-butadiene-styrene block copolymer and a copolymer obtained by partially adding a styrene-butadiene-styrene block copolymer.

Preferred examples of the olefin-based polymer described above include an ethylene / propylene copolymer, an ethylene / butene-1 copolymer, and a copolymer obtained by partially hydrolyzing a styrene / butadiene / styrene block copolymer. It can be mentioned, and an ethylene / propylene copolymer is particularly preferable.

The maleic anhydride-modified olefin polymer is obtained by graft-modifying maleic anhydride to the olefin-based polymer. A known method can be used for the method of graft modification. For example, an extruder can be used to mix and react a predetermined amount of unsaturated carboxylic acids with a molten olefin polymer.
The amount of maleic anhydride to be graft-reacted is usually in the range of 0.005 to 25% by mass, preferably 0.01 to 20% by mass, based on 100% by mass of the maleic anhydride-modified olefin polymer.

The preferable content of the olefin / maleic anhydride copolymer (C) is 0.1 to 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin fat (A). Within such a range, deterioration of the polycarbonate resin can be suppressed, impact resistance is high, and mold contamination due to generated gas is reduced. If the content of the copolymer (C) is less than 0.1 parts by mass, the impact resistance of the molded product is lowered, and if it exceeds 5 parts by mass, the rigidity of the molded product is lowered, and it is generated during molding. Mold contamination caused by gas increases. The content of the copolymer (C) is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, preferably 4.5 parts by mass or less, and more preferably 4 parts by mass or less. Further, 3.5 parts by mass or less, particularly 3 parts by mass or less, particularly 2.5 parts by mass or less, particularly 2 parts by mass or less is preferable.

[Elastomer (D)]
By containing the elastomer (D) in combination with each of the above components and the fluororesin (E), the impact resistance of the resin composition can be improved, and the elastomer (D) and the fluororesin (E) can be improved. By setting the content ratio (D) / (E) of (D) / (E) to more than 1 to 250, the impact strength is dramatically improved, and a polycarbonate resin composition having high rigidity and high impact resistance can be obtained. ..

The elastomer used in the present invention is preferably a graft copolymer obtained by graft-copolymerizing a rubber component with a copolymerizable monomer component. The method for producing the graft copolymer may be any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like, and the copolymerization method may be a one-step graft or a multi-step graft.

As the rubber component, the glass transition temperature is usually 0 ° C. or lower, particularly preferably −20 ° C. or lower, and further preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate and 2-ethylhexyl acrylate copolymer, and polyorganosiloxane rubber. IPN (Interpentrating Polymer Network) type composite rubber composed of silicone rubber, butadiene-acrylic composite rubber, polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber, etc. Examples thereof include ethylene-α-olefin rubber, ethylene-acrylic rubber, and fluororubber. These may be used alone or in combination of two or more.
Among these, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber, and styrene-butadiene rubber are preferable from the viewpoint of mechanical properties and surface appearance. ..

Specific examples of the rubber component and the monomer component that can be graft-copolymerized include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and glycidyl (meth) acrylate. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and their anhydrides. Examples include compounds (eg, maleic anhydride, etc.). One of these monomer components may be used alone, or two or more thereof may be used in combination. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable, and (meth) acrylic acid ester is more preferable, from the viewpoint of mechanical properties and surface appearance. It is a compound. Specific examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and octyl (meth) acrylate. be able to.

The graft copolymer obtained by copolymerizing the rubber component is preferably a core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from an IPN type composite rubber composed of polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, polyorganosiloxane rubber and polyalkylacrylate rubber is used as a core layer, and around it. A core / shell type graft copolymer composed of a shell layer formed by copolymerizing a (meth) acrylic acid ester is particularly preferable. Among the core / shell type graft copolymers, those containing 40% by mass or more of the rubber component are preferable, and those containing 60% by mass or more are more preferable. Further, the (meth) acrylic acid preferably contains 10% by mass or more.

Among the above, the elastomer (D) is preferably a core / shell type elastomer, and among them, a core / shell type elastomer having a silicone / acrylic composite type, an acrylic rubber, or a butadiene type rubber as a core is preferable, and a butadiene type is particularly preferable. A core / shell type elastomer with a rubber core is preferable.

The core / shell type in the present invention does not necessarily mean that the core layer and the shell layer can be clearly distinguished, and the purpose is to broadly include a compound obtained by graft-polymerizing a rubber component around the core portion. Is.

Preferred specific examples of these core / shell type graft copolymers are methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Combined (MB), Methyl Methacrylate-Acrylic Rubber Copolymer (MA), Methyl Methacrylate-Acrylic Rubber-Styline Copolymer (MAS), Methyl Methacrylate-Acrylic-butadiene Rubber Copolymer, Methyl Methacrylate-Acrylic-butadiene Rubber- Examples thereof include styrene copolymers, methyl methacrylate- (acrylic silicone IPN rubber) copolymers, silicone-acrylic composite rubbers containing polyorganosiloxane and polyalkyl (meth) acrylate, and polyorganosiloxane and polyalkyl (meth). ) Silicone-acrylic composite rubber containing acrylate and methyl methacrylate-butadiene copolymer (MB) are particularly preferred. Such a rubbery polymer may be used alone or in combination of two or more.

The preferable content of the elastomer (D) is 1 to 25 parts by mass, more preferably 2 parts by mass or more, still more preferably 2.5 parts by mass or more, and particularly preferably 2.5 parts by mass or more, based on 100 parts by mass of the polycarbonate resin (A). It is 3 parts by mass or more, more preferably 20 parts by mass or less, further preferably 18 parts by mass or less, and particularly preferably 15 parts by mass or less.
Only one type of elastomer (D) may be contained, or two or more types may be contained. When two or more types are included, the total amount is within the above range.

[Fluororesin (E)]
By containing the fluororesin together with the above-mentioned components, the fluororesin acts like a surfactant to improve the impact resistance, and the mechanical properties of the resin composition can be further improved. It is possible to improve the drip prevention property at the time of combustion and further improve the flame retardancy. By setting the ratio (D) / (E) of the contents of the elastomer (D) and the fluororesin (E) to preferably more than 1 to 250, the impact strength is dramatically improved, and high rigidity and high rigidity are achieved. Impact resistance can be exhibited.

As the fluoroolefin resin, a fluoroolefin resin is preferable. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, and specific examples thereof include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, and the like. Of these, tetrafluoroethylene resin is preferable.
Further, as the fluororesin, those having a fibril-forming ability are preferable, and specific examples thereof include fluoroolefin resins having a fibril-forming ability. By having the ability to form fibrils, the impact resistance and flexural modulus are remarkably improved, and the drip prevention property at the time of combustion tends to be improved.

Further, as the fluororesin, an organic polymer-coated fluoroolefin resin can also be preferably used. By using the organic polymer-coated fluoroolefin resin, the dispersibility is improved, the surface appearance of the molded product is improved, and foreign substances on the surface can be suppressed.
The organic polymer-coated fluoroolefin resin can be produced by various known methods. For example, (1) a polyfluoroethylene particle aqueous dispersion and an organic polymer particle aqueous dispersion are mixed and coagulated or spray-dried into powder. Method of producing by embodying, (2) Method of polymerizing the monomers constituting the organic polymer in the presence of an aqueous dispersion of polyfluoroethylene particles, and then powdering by coagulation or spray drying. 3) In a dispersion obtained by mixing an aqueous dispersion of polyfluoroethylene particles and an aqueous dispersion of organic polymer particles, a monomer having an ethylenically unsaturated bond is emulsion-polymerized and then coagulated or spray-dried into powder. Examples thereof include a method of polymerizing and manufacturing.

As the monomer for producing the organic polymer that coats the fluoroolefin resin, one having a high affinity with the polycarbonate resin is preferable from the viewpoint of dispersibility when blended with the polycarbonate resin, and it is an aromatic vinyl type. More preferably, a monomer, a (meth) acrylic acid ester-based monomer, and a vinyl cyanide-based monomer.

One type of the fluororesin (E) may be used, or two or more types may be used in any combination and in any ratio.

The preferable content of the fluororesin (E) is 0.05 to 10 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), and the upper limit thereof is preferably 8 parts by mass or less, more preferably 5 parts by mass or less. Further, it is preferably 3 parts by mass or less, particularly 2 parts by mass or less.
By setting the content of the fluororesin (E) to 0.05 parts by mass or more, a sufficient effect of improving mechanical properties can be obtained, and by setting the content to 10 parts by mass or less, the fluoropolymer-containing molded product obtained by molding the resin composition. Appearance defects due to poor dispersion of the resin are unlikely to occur, and high mechanical strength can be maintained.

[Ratio of content of each component]
In the polycarbonate resin composition of the present invention, the ratio (D) / (E) of the contents of the elastomer (D) and the fluororesin (E) is preferably more than 1 to 250, but more preferably 2 or more. Yes, more preferably 200 or less, further 150 or less, and particularly preferably 100 or less.
The ratio (B) / (E) of the content of the filler (B) to the fluororesin (E) is preferably more than 1 to 500, preferably from the viewpoint of exhibiting impact resistance, and more preferably 400 or less. Further, it is 300 or less, particularly preferably 250 or less.
The ratio (D) / (C) of the contents of the elastomer (D) and the olefin / maleic anhydride copolymer (C) is preferably 0.2 to 250 from the viewpoint of exhibiting impact resistance, and more preferably. Is more than 1, more preferably 200 or less, further 100 or less, particularly 50 or less, particularly 30 or less, and particularly preferably 10 or less.
The ratio (C) / (E) of the content of the olefin / maleic anhydride copolymer (C) to the fluororesin (E) is preferably 0.1 to 50 from the viewpoint of exhibiting impact resistance. It is more preferably 0.5 or more, more preferably 30 or less, further 20 or less, and particularly preferably 15 or less.

[Flame retardants]
The polycarbonate resin composition also preferably contains a flame retardant. The preferable content is 0.01 to 30 parts by mass, and more preferably 0.03 to 20 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A).
Examples of the flame retardant include an organic metal salt-based flame retardant, a siloxane-based flame retardant, a phosphorus-based flame retardant, a boron-based flame retardant, a nitrogen-based flame retardant, a halogen-based flame retardant, and the like. Salt flame retardants are preferred.

As the organometallic salt compound, an organosulfonic acid metal salt is particularly preferable.
The metal of the metal salt compound is preferably an alkali metal or an alkaline earth metal, and is an alkali such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs). Metals: Alkaline earth metals such as magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Of these, sodium, potassium, and cesium are particularly preferable.

Examples of organic sulfonic acid metal salts include organic sulfonic acid lithium salt, organic sulfonic acid sodium salt, organic sulfonic acid potassium salt, organic sulfonic acid rubidium salt, organic sulfonic acid cesium salt, organic sulfonic acid magnesium salt, and organic sulfonic acid. Calcium salt, organic sulfonic acid strontium salt, organic sulfonic acid barium salt and the like can be mentioned. Of these, organic sulfonic acid alkali metal salts such as organic sulfonic acid sodium salt, organic sulfonic acid potassium salt, and organic sulfonic acid cesium salt are particularly preferable.

Among the organic sulfonic acid metal salt compounds, a preferable example is a metal salt of a fluoroaliphatic sulfonic acid or an aromatic sulfonic acid. Specific examples of the preferred ones include at least one CF bond in the molecule, such as potassium perfluorobutane sulfonate, lithium perfluorobutane sulfonate, sodium perfluorobutane sulfonate, cesium perfluoro butane sulfonate, and the like. Alkali metal salt of fluoroaliphatic sulfonic acid having; magnesium perfluorobutane sulfonate, calcium perfluorobutane sulfonate, barium perfluorobutane sulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, barium trifluoromethanesulfonate Alkaline earth metal salt of fluoroaliphatic sulfonic acid having at least one CF bond in the molecule; etc .;

Diphenylsulfon-3,3'-dipotassium disulfonate, potassium diphenylsulfon-3-sulfonate, sodium benzenesulfonate, sodium (poly) styrene sulfonate, sodium paratoluenesulfonate, (branched) sodium dodecylbenzenesulfonate, tri Sodium chlorobenzene sulfonate, potassium benzene sulfonate, potassium styrene sulfonate, potassium (poly) styrene sulfonate, potassium paratoluene sulfonate, (branched) potassium dodecylbenzene sulfonate, potassium trichlorobenzene sulfonate, cesium benzene sulfonate, ( Alkali metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule, such as cesium styrene sulfonate, cesium paratoluene sulfonate, cesium dodecylbenzene sulfonate, cesium trichlorobenzene sulfonate, etc. At least one in the molecule, such as magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, (branched) magnesium dodecylbenzenesulfonate, (branched) calcium dodecylbenzenesulfonate, etc. Alkaline earth metal salts of aromatic sulfonic acids having a species of aromatic group; and the like, aromatic sulfonic acid metal salts and the like.

Among the above-mentioned examples, an alkali metal salt of a fluorine-containing aliphatic sulfonic acid and an alkali metal salt of an aromatic sulfonic acid are more preferable, and an alkali metal salt of a fluorine-containing aliphatic sulfonic acid is particularly preferable, and perfluoroalkane sulfonic acid is particularly preferable. The alkali metal salt of the above is more preferable, and specifically, potassium perfluorobutanesulfonate and the like are preferable.
In addition, one kind of metal salt compound may be used, or two or more kinds may be used in any combination and ratio.

When the organic metal salt flame retardant is contained, the content is preferably 0.01 to 1.5 parts by mass, more preferably 0.02 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A). It is more preferably 0.03 parts by mass or more, more preferably 1 part by mass or less, further preferably 0.5 parts by mass or less, and particularly preferably 0.3 parts by mass or less, and particularly preferably 0.15 parts by mass or less. ..

[Colorant]
The polycarbonate resin composition also preferably contains a colorant.
Examples of dyeing pigments as colorants include inorganic pigments, organic pigments, and organic dyes.

As inorganic pigments, for example, sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as Prussian blue; titanium oxide, zinc flower, petals, chromium oxide, iron black, titanium yellow, zinc-iron. Oxide pigments such as brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black, copper-iron black; chrome acid pigments such as chrome yellow and molybdate orange; ferrussian such as navy blue Examples include system pigments.
Further, as organic pigments and organic dyes as colorants, for example, phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, and quinacridone. , Dioxazine-based, isoindolinone-based, quinophthalone-based condensed polycyclic dyes; quinoline-based, anthraquinone-based, heterocyclic, methyl-based dyes and the like can be mentioned.
Among these, carbon black, titanium oxide, cyanine-based, quinoline-based, anthraquinone-based, phthalocyanine-based dyes and the like are preferable from the viewpoint of thermal stability. The dyeing pigment may contain one type or two or more types in any combination and ratio.

Further, the dyeing pigment may be master-batched with polystyrene-based resin, polycarbonate-based resin, or acrylic-based resin for the purpose of improving handleability at the time of extrusion and improving dispersibility in the resin composition. Good.

The amount of the colorant contained is, for example, 5 parts by mass or less, preferably 4.8 parts by mass or less, and more preferably 4.5 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A). If the content of the colorant is too large, the impact resistance may not be sufficient.

[Additives, etc.]
The polycarbonate resin composition can contain additives other than those described above, such as stabilizers, mold release agents, fluorescent whitening agents, antistatic agents, plasticizers, and compatibilizers. These additives or other resins may be used alone or in combination of two or more.

Further, the polycarbonate resin composition may contain a resin other than the polycarbonate resin (A), the olefin / maleic anhydride copolymer (C), and the elastomer (D). Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyphenylene. Examples thereof include ether resin; polyphenylene sulfide resin; polysulfone resin and the like. As the other resin, one type may be contained, or two or more types may be contained in any combination and ratio.
However, when a resin other than the polycarbonate resin (A) is contained, the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the polycarbonate resin (A). Further, it is preferably 5 parts by mass or less, particularly preferably 3 parts by mass or less.

[Manufacturing of Polycarbonate Resin Composition]
There is no limitation on the method for producing the polycarbonate resin composition, and a known method for producing the polycarbonate resin composition can be widely adopted, and the above-mentioned essential components and other components to be blended as needed can be used, for example, a tumbler or a Henschel mixer. After mixing in advance using various mixers such as, there is a method of melt-kneading with a mixer such as a Banbury mixer, a roll, a brabender, a single-screw kneading extruder, a twin-screw kneading extruder, and a kneader. The temperature of melt-kneading is not particularly limited, but is usually in the range of 260 to 320 ° C.

The polycarbonate resin composition of the present invention can produce various molded products by molding pellets obtained by pelletizing the above-mentioned polycarbonate resin composition by various molding methods. Further, the resin melt-kneaded by an extruder can be directly molded into a molded product without passing through pellets.

The polycarbonate resin composition has a notched Charpy impact strength measured based on ISO179, preferably 20 kJ / m ² or more, more preferably 25 kJ / m ² or more, preferably 100 kJ / m ² or less, more preferably 80 kJ /. It is m ² or less.
Further, the polycarbonate resin composition of the present invention has a flexural modulus measured based on ISO178, preferably 2500 MPa or more, more preferably 2800 MPa or more, and preferably 5000 MPa or less.

The polycarbonate resin composition has excellent moisture and heat resistance, and the notched Charpy impact strength after treatment for 100 hours under the conditions of a temperature of 85 ° C. and a relative humidity of 85% measured based on ISO179 is preferably 10 kJ / m ² or more, more preferably. Is 15 kJ / m ² or more.

The polycarbonate resin composition has excellent heat resistance, and the deflection temperature under load DTUL measured based on the ISO75A method is preferably 120 ° C. or higher, more preferably 121 ° C. or higher, further preferably 122 ° C. or higher, and particularly preferably 123 ° C. That is all.

The polycarbonate resin composition has a linear expansion coefficient ratio in the MD direction and the TD direction measured based on ISO 11359-2, that is, anisotropy (MD / TD), preferably 0.92 or more, more preferably 0. It is 94 or more, preferably 1.08 or less, and more preferably 1.06 or less. By lowering the anisotropy in this way, it is possible to prevent roundness and deviation of the optical axis due to the difference in thermal expansion even in a wide operating environment temperature.

The molded product obtained from the polycarbonate resin composition of the present invention is excellent in impact resistance and flexural modulus, and exhibits low anisotropy.
Therefore, its applications include, for example, housing parts such as cameras, telescopes, microscopes, projection exposure devices, optical measuring devices, lens barrels, mobile phone cameras, smartphone cameras, tablet cameras, in-vehicle cameras, and actions. Cameras, notebook PC cameras, drive recorders, surveillance cameras, small camera mounts for drones, housing parts and mechanical parts, car collision prevention sensors, back monitor sensors, vehicle speed sensors, temperature sensors, security sensors, games Sensor housings and mechanical parts such as motion sensors for machines, frame members and outer panel members for automobiles, bikes, bicycles, wheelchairs, etc., home TVs, personal computer displays, in-vehicle monitors, smartphones, head mount display panel members, etc. Mechanical parts, housings and mechanical parts of reading devices such as bar code readers and scanners, housings and mechanical parts such as air conditioners, air purifiers, compressors, wired / wireless LAN routers, WIFI receivers, WIFI storage, USB memory , Memory cards, card readers, housings and mechanical parts of information equipment such as data server storage equipment, optical equipment, semiconductor package substrates, manufacturing / processing equipment parts such as semiconductor manufacturing equipment, measuring equipment parts and the like are preferable.

In particular, the molded body obtained from the polycarbonate resin composition of the present invention can be suitably used for optical equipment parts, and is particularly suitable for an optical module, particularly an optical module having a lens holding portion, and particularly a camera including the molded body. It is suitably used for a module, for example, a lens barrel (Barrel) constituting a lens unit, a lens holder, a spacer, a stopper, and a camera module such as a sleeve, a pedestal, and a housing constituting an actuator unit.

The optical module of the present invention comprises a resin composition containing 1 to 50 parts by mass of a filler (B) having an average particle size of 0.1 to 10 μm with respect to 100 parts by mass of the polycarbonate resin (A), and is measured based on ISO179. It is characterized by including a molded body having a notched Charpy impact strength of 20 kJ / m ² or more.
The optical module of the present invention includes a molded body obtained by molding the above-mentioned polycarbonate resin composition as a constituent member thereof, and particularly supports a lens barrel (Barrel) constituting the lens unit, a lens holder, a spacer, a stopper, and the like. It is used for sleeves, pedestals, housings, etc. that make up members and actuator units. In particular, the optical module of the present invention is suitable for an imaging module mounted on various mobile terminals such as a mobile phone and a mobile personal computer, an LED light module, and the like.

The polycarbonate resin composition for molding the molded product included in the optical module of the present invention is as described above.

The molded body is a molded body having a high impact resistance made of a polycarbonate resin composition having a notched Charpy impact strength of 20 kJ / m ² or more measured based on ISO179, and is preferably measured based on ISO179. High moisture resistance with a notched Charpy impact strength of 10 kJ / m ² or more after 100 hours of treatment under the conditions of temperature 85 ° C and relative humidity 85%, and deflection temperature under load measured based on the ISO75 A method is 120 ° C or more. Since it has high heat resistance and is excellent in rigidity, impact resistance and low anisotropy, it is effective as a high-performance optical module that does not deform, has extremely good dimensional accuracy, and does not break even if dropped.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not construed as being limited to the following examples.

The raw materials used in the following examples and comparative examples are as shown in Table 1 below.

(Examples 1 to 11, Comparative Examples 1 to 11)
[Manufacturing of resin composition pellets]
Each of the above components was blended in the proportions shown in Table 2-3 (all by mass), uniformly mixed with a tumbler mixer, and then fed from a hopper to an extruder for melt-kneading.
As an extruder, a twin-screw extruder (TEX25αIII, L / D = 52.5) manufactured by Japan Steel Works, Ltd. was used, and melt extrusion was performed under the conditions of a screw rotation speed of 200 rpm, a cylinder temperature of 280 ° C., and a discharge rate of 25 kg / hr. The extruded strands were quenched in a water tank and pelleted using a pelletizer.

The pellets obtained by the above manufacturing method are dried at 120 ° C. for 5 hours, and then used by a NEX80 injection molding machine manufactured by Nissei Resin Industry Co., Ltd., a cylinder temperature of 280 ° C., a mold temperature of 100 ° C., and an injection speed of 30 mm / s. An ISO dumbbell test piece molded product having a thickness of 4 mm was molded under the condition of holding pressure of 90 MPa. Further, using the same model, a flat plate molded product having a length of 100 mm, a width of 100 mm, and a thickness of 2 mm was molded under the conditions of a cylinder temperature of 300 ° C., a mold temperature of 100 ° C., an injection speed of 100 mm / s, and a holding pressure of 80 MPa. ..

[Measurement of flexural modulus]
Using the ISO dumbbell test piece (thickness 4 mm) obtained above, the flexural modulus (unit: MPa) was measured based on ISO178.

[Measurement of Charpy impact strength (notched) and evaluation of moisture resistance]
Using the ISO dumbbell piece (thickness 4 mm) obtained above, the notched Charpy strength (unit: kJ / m ² ) was measured based on ISO179.
Further, the ISO dumbbell piece (thickness 4 mm) obtained above was treated in a constant temperature and humidity chamber at a temperature of 85 ° C. and a relative humidity of 85% for 100 hours, and the notched Charpy impact strength (unit:: kJ / m ² )) was measured. The smaller the decrease in the Charpy impact strength value after the moist heat test treatment, the better the moist heat resistance.

[Measurement of heat resistance (deflection temperature under load, DTUL)]
Using the ISO dumbbell piece (thickness 4 mm) obtained above, the deflection temperature under load (DTUL, unit: ° C.) was measured under the condition of a load of 1.80 MPa based on the ISO75 A method.

[Measurement of anisotropy (MD / TD)]
A test piece was obtained by cutting out the central portion of the flat plate-shaped molded product obtained above into a length of 15 mm, a width of 10 mm, and a thickness of 2 mm in the MD / TD direction, respectively, and used for the measurement of anisotropy.
As a measuring device, TMA / SS6100 manufactured by Hitachi High-Tech Science Co., Ltd. is used, the length part of the test piece is targeted for measurement, the temperature is raised from -30 to + 120 ° C at a rate of 20 ° C / min, and the dimension with respect to the amount of temperature change. The coefficient of linear expansion (unit: / K) was calculated from the slope of the amount of change in.
In addition, the ratio of the coefficient of linear expansion between the MD direction and the TD direction calculated above, that is, the anisotropy (MD / TD) was calculated. The closer the MD / TD is to 1, the less anisotropy is.
The above evaluation results are shown in Table 2-Table 3 below.

Since the polycarbonate resin composition of the present invention is excellent in rigidity and impact resistance, exhibits low anisotropy, and is also excellent in moisture and heat resistance, it can be suitably used for various applications such as optical equipment parts, and the present invention. The optical module of is not deformed, has extremely high dimensional accuracy, and is effective as various high-performance optical modules that do not break even if dropped.

Claims

A filler containing 1 to 50 parts by mass of a filler (B) having an average particle size of 0.1 to 10 μm with respect to 100 parts by mass of the polycarbonate resin (A), and having an average particle size of more than 10 μm. The polycarbonate resin composition is characterized in that the content of the polycarbonate resin composition is less than 10% by mass in the resin composition and the content of the polycarbonate resin composition is 2% or less in the resin composition when the phosphorus-based flame retardant is contained. Stuff.
Further, with respect to 100 parts by mass of the polycarbonate resin (A), 0.1 to 5 parts by mass of the olefin / maleic anhydride copolymer (C), 1 to 25 parts by mass of the elastomer (D), and 0 parts of the fluororesin (E). Contains .05 to 10 parts by mass,
The polycarbonate resin composition according to claim 1, wherein the ratio (D) / (E) of the contents of the elastomer (D) and the fluororesin (E) is more than 1 and 250 or less.
The polycarbonate resin composition according to claim 2, wherein the ratio (B) / (E) of the contents of the filler (B) and the fluororesin (E) is more than 1 and 500 or less.
The polycarbonate resin composition according to any one of claims 1 to 3, wherein the filler (B) is a plate-shaped filler.
Claims 1 to 4 in which the filler (B) is a plate-shaped filler and is at least one selected from talc, mica, glass flakes, montmorillonite, hydrotalcite, sericite, kaolin, alumina, clay, and graphite. The polycarbonate resin composition according to any one of.
The polycarbonate resin composition according to any one of claims 1 to 5, wherein the filler (B) is talc.
The polycarbonate resin composition according to any one of claims 2 to 6, wherein the elastomer (D) is a core / shell type elastomer.
The polycarbonate resin composition according to any one of claims 2 to 7, wherein the elastomer (D) is a core / shell type elastomer of a butadiene rubber core.
The polycarbonate resin composition according to any one of claims 1 to 8, wherein the notched Charpy impact strength measured based on ISO179 is 20 kJ / m 2 or more.
The polycarbonate resin composition according to any one of claims 1 to 9, wherein the notched Charpy impact strength after treatment for 100 hours under the conditions of a temperature of 85 ° C. and a relative humidity of 85%, measured based on ISO179, is 10 kJ / m 2 or more. ..
The polycarbonate resin composition according to any one of claims 1 to 10, wherein the deflection temperature under load measured based on the ISO75 A method is 120 ° C. or higher.
A molded product made of the polycarbonate resin composition according to any one of claims 1 to 11.
An optical module including the molded product according to claim 12.
It is composed of a resin composition containing 1 to 50 parts by mass of a filler (B) having an average particle size of 0.1 to 10 μm with respect to 100 parts by mass of the polycarbonate resin (A), and has a notched Charpy impact strength measured based on ISO179. An optical module characterized by containing a molded body having a size of 20 kJ / m 2 or more.
The resin composition further contains 0.1 to 5 parts by mass of the olefin / maleic anhydride copolymer (C), 1 to 25 parts by mass of the elastomer (D), and 100 parts by mass of the polycarbonate resin (A). 14. Claim 14 which contains 0.05 to 10 parts by mass of the fluororesin (E) and the ratio (D) / (E) of the contents of the elastomer (D) and the fluororesin (E) is more than 1 and 250 or less. The optical module described in.
The optical module according to claim 15, wherein when the resin composition contains a filler having an average particle size of more than 10 μm, the content thereof is less than 10% by mass in the resin composition.
The optical module according to claim 15 or 16, wherein the ratio (B) / (E) of the contents of the filler (B) and the fluororesin (E) is more than 1 and 500 or less.
The optical module according to any one of claims 14 to 17, wherein the filler (B) is talc.
The optical module according to any one of claims 15 to 18, wherein the elastomer (D) is a core / shell type elastomer.
The optical module according to any one of claims 15 to 19, wherein the elastomer (D) is a core / shell type elastomer of a butadiene rubber core.
The resin composition according to any one of claims 14 to 20, wherein the notched Charpy impact strength after treatment for 100 hours under the conditions of a temperature of 85 ° C. and a relative humidity of 85% measured based on ISO179 is 10 kJ / m 2 or more. The optical module described.
The optical module according to any one of claims 14 to 21, wherein the resin composition has a deflection temperature under load measured based on the ISO75 A method of 120 ° C. or higher.