JP2013133350A - Polycarbonate resin composition and molded article comprising the same - Google Patents

Abstract

Disclosed are a polycarbonate resin composition and a molded article that are excellent in mechanical properties such as impact resistance, excellent in total light transmittance, light diffusibility, and dispersibility, and also excellent in moldability and flame retardancy.
SOLUTION: For 100 parts by mass of polycarbonate resin (A), (i) the average particle diameter is 1 to 4 μm, (ii) the proportion of particles having a particle diameter of 1 μm or more and less than 2 μm, and the particle diameter is 2 μm or more and less than 3 μm. The ratio of the particles and the ratio of the particles having a particle size of 3 μm or more are each in the range of 20 to 40%, and (iii) the acrylic resin fine particles (B) substantially not containing particles having a particle size of 10 μm or more. According to the polycarbonate resin composition characterized by containing 0.1 to 5 parts by mass and an aryl group-containing polysilane (C) of 0.05 parts by mass or more and less than 0.3 parts by mass.
[Selection figure] None

Description

  The present invention relates to a polycarbonate resin composition and a molded article comprising the same, and more specifically, without impairing mechanical properties such as the excellent impact resistance of the polycarbonate resin, the total light transmittance, light diffusibility, dispersity, and initial hue. The present invention relates to a polycarbonate resin composition excellent in moldability, flame retardancy, and heat discoloration and a molded article comprising the same.

  Polycarbonate resin has a wide range of uses as a thermoplastic resin with excellent impact resistance, heat resistance, and transparency, and is lighter and more productive than inorganic glass, providing light diffusibility. By doing so, it can be suitably used for applications that require light diffusibility, such as lighting covers, lighting signs, transmissive screens, various displays, and light diffusion sheets for liquid crystal display devices.

  Addition of inorganic compounds such as glass, silica, and aluminum hydroxide has been proposed to impart light diffusibility to polycarbonate resin, but the thermal stability during molding and extrusion is low, impact strength, etc. There is a drawback that the mechanical strength is greatly lowered. As a light diffusing polycarbonate resin improved in such a drawback, for example, Patent Document 1 discloses that the refractive index is larger than that of the polycarbonate resin and the weight average particle size is 0.5 to 0.5. A light diffusing polycarbonate resin to which polymethyl methacrylate fine particles in the range of 100 μm are added is disclosed. However, in this method, the haze is not sufficient and the practicality is inferior.

In Patent Document 2, high transmittance made of polycarbonate resin having a total light transmittance of 85% or more and a diffuse transmittance of 10 to 30%, in which fine particles having a particle size of 50 μm or less and an average particle size of 5 to 20 μm are blended. Although a light diffusion plate is disclosed, the light diffusibility is low and the practicality is inferior.
Patent Document 3 discloses a polycarbonate resin composition to which calcium carbonate, titanium oxide and polyorganohydrogensiloxane are added as a resin composition having excellent light transmittance and light diffusibility. It was not satisfactory in terms of impact resistance, and the total light transmittance was not sufficient.

  Further, Patent Document 4 discloses a light diffusing plate for a direct backlight of a polycarbonate resin formed from a composition in which transparent fine particles having an average particle diameter of 1 to 30 μm and a fluorescent brightening agent are blended. Since the brightness is improved by using a brightening agent, the thermal stability is insufficient, and it is easy to cause discoloration during molding and extrusion, and discoloration during recycling. .

Japanese Patent Laid-Open No. 03-143950 Japanese Patent Laid-Open No. 05-257002 JP 2000-169695 A JP 2004-029091 A

In recent years, specs of diffusible polycarbonate resin compositions for optical applications are becoming more and more demanding, and there is a demand for polycarbonate resin compositions having excellent balance of transmittance, diffusivity, and dispersibility.
Furthermore, in recent years, the development of lighting fixtures typified by LED lighting has progressed, and the demand for LED lighting equipment has increased. In addition to the above-mentioned transmittance, diffusivity, and dispersion degree, it has excellent moldability and impact strength and is flame retardant. There is a strong demand for polycarbonate resin materials that are excellent in properties, initial hue, and heat discoloration.
In view of the above-mentioned problems of the prior art, the object of the present invention is excellent in total light transmittance, light diffusibility, dispersity, and moldability without impairing mechanical properties such as impact resistance of the polycarbonate resin itself. An object of the present invention is to provide a polycarbonate resin composition excellent in flame retardancy, initial hue and heat discoloration, and a molded product comprising the same.

  As a result of intensive studies in order to achieve the above-mentioned problems, the present inventor has blended polycarbonate resin with a specific average particle size of acrylic resin-based fine particles and a specific particle size distribution among them. In addition, when each aryl group-containing polysilane compound is blended in a specific amount with a polycarbonate resin, it has excellent mechanical properties such as impact resistance, total light transmittance, light diffusivity, dispersibility, moldability, and difficulty. The inventors have found that a polycarbonate resin composition having excellent flammability, initial hue, and heat discoloration can be obtained, and have completed the present invention.

  That is, according to 1st invention of this invention, the average particle diameter measured on the number basis in the range of 0.4-12 micrometers in diameter by (i) Coulter counter method is 1 with respect to 100 mass parts of polycarbonate resin (A). (Ii) a ratio of particles having a particle diameter of 1 μm or more and less than 2 μm, a ratio of particles having a particle diameter of 2 μm or more and less than 3 μm, and a ratio of particles having a particle diameter of 3 μm or more are in the range of 20 to 40%, respectively. And (iii) 0.1-5 parts by mass of acrylic resin-based fine particles (B) having substantially no particle size of 10 μm or more, and 0.05 parts by mass of the aryl group-containing polysilane compound (C) A polycarbonate resin composition characterized by containing at least part and less than 0.3 part by weight is provided.

  According to the second invention of the present invention, in the first invention, the acrylic resin-based fine particles (B) are 90 to 99% by mass of the non-crosslinkable acrylic monomer (B1) and the crosslinkable monomer (B2) 10 to 10. There is provided a polycarbonate resin composition characterized in that it is a copolymer fine particle from 1% by mass.

  According to a third aspect of the present invention, there is provided a polycarbonate resin composition according to the first or second aspect, wherein the acrylic resin-based fine particles (B) are polymethyl methacrylate-based fine particles. Is done.

  According to the fourth aspect of the present invention, in any one of the first to third aspects, the aryl group-containing polysilane compound (C) is a structural unit represented by the following formulas (1) to (3): A polycarbonate resin composition having at least one structural unit is provided.

[式（１）〜（３）中、Ｒ^１、Ｒ^２及びＲ^３は、一価炭化水素基、水素原子、シリル基から選ばれる少なくとも１種を表し、それぞれの繰り返し単位において同一であっても異なっていてもよい。但し、Ｒ^１、Ｒ^２及びＲ^３は、少なくとも１つ以上のアリール基を含有する。ｘ、ｙ、ｚは０又は整数を表し、ｘ＋ｙ＋ｚ≧２を満たす。ａ、ｂ、ｃは、０または１を表す。]

[In the formulas (1) to (3), R ¹ , R ² and R ³ represent at least one selected from a monovalent hydrocarbon group, a hydrogen atom and a silyl group, and are the same in each repeating unit. May be different. However, R ¹ , R ² and R ³ contain at least one aryl group. x, y, z represents 0 or an integer, and satisfies x + y + z ≧ 2. a, b and c each represents 0 or 1; ]

  According to a fifth aspect of the present invention, there is provided a polycarbonate resin composition characterized in that in any one of the first to fourth aspects, the aryl group is a phenyl group.

  According to the sixth invention of the present invention, in any one of the first to fifth inventions, the aryl group-containing polysilane compound (C) is a cyclic aryl group-containing silane represented by the following formula (4). A polycarbonate resin composition is provided.

[式（４）中、Ｒ^４及びＲ^５は、一価炭化水素基、水素原子、シリル基から選ばれる少なくとも１種を表し、それぞれの繰り返し単位において同一であっても異なっていてもよい。但し、Ｒ^４及びＲ^５は、少なくとも１つ以上のアリール基を含有する。ｍは４〜１２を表す。]

[In Formula (4), R ⁴ and R ⁵ represent at least one selected from a monovalent hydrocarbon group, a hydrogen atom, and a silyl group, and may be the same or different in each repeating unit. However, R ⁴ and R ⁵ contain at least one or more aryl groups. m represents 4-12. ]

According to the seventh invention of the present invention, in the sixth invention, in the aryl group-containing polysilane of the formula (4), R ⁴ and R ⁵ are both phenyl groups, and d and e are both 0. A polycarbonate resin composition is provided.

  According to an eighth aspect of the present invention, the polycarbonate resin composition according to any one of the first to seventh aspects, wherein the aryl group-containing polysilane compound (C) is decaphenylcyclopentasilane. Is provided.

  According to the ninth invention of the present invention, in the first invention, the polycarbonate resin (A) contains 20% by mass or more of a polycarbonate resin having a structural viscosity index N of 1.2 or more. A resin composition is provided.

  According to a tenth aspect of the present invention, in any one of the first to ninth aspects, the organic sulfonic acid metal salt (D) is further added in an amount of 0.01 to 100 parts by mass of the polycarbonate resin (A). A polycarbonate resin composition containing ˜1 part by mass is provided.

  According to the eleventh aspect of the present invention, in the tenth aspect, the organic sulfonic acid metal salt (D) is an organic sulfonic acid alkali metal salt or an alkaline earth metal salt. A composition is provided.

  According to a twelfth aspect of the present invention, in the tenth or eleventh aspect, the organic sulfonic acid metal salt (D) is a perfluoroalkanesulfonic acid alkali metal salt. Things are provided.

  According to the thirteenth aspect of the present invention, in any one of the first to twelfth aspects, 0.001 to 1 part by mass of the fluororesin (E) is further added to 100 parts by mass of the polycarbonate resin (A). A polycarbonate resin composition characterized by containing is provided.

  According to the fourteenth aspect of the present invention, in any one of the first to thirteenth aspects, the ultraviolet absorbent (F) is further added in an amount of 0.05 to 1 mass with respect to 100 parts by mass of the polycarbonate resin (A). The polycarbonate resin composition characterized by containing a part is provided.

  According to the fifteenth aspect of the present invention, in any one of the first to fourteenth aspects, a molded product obtained from the polycarbonate resin composition is provided.

According to a sixteenth aspect of the present invention, there is provided the molded product according to the fifteenth aspect, wherein the molded product is a lighting cover, a light diffusion plate or a sheet.

  According to the polycarbonate resin composition of the present invention and a molded product comprising the same, it has excellent mechanical properties such as impact resistance, excellent total light transmittance, light diffusibility, and dispersibility, and moldability, flame retardancy, and initial hue. In addition, a polycarbonate resin composition having excellent heat discoloration resistance and a molded product comprising the same can be obtained.

Hereinafter, the present invention will be described in more detail.
[1. Overview]
The polycarbonate resin composition of the present invention has an average particle diameter of 1 to 4 μm measured on a number basis in a range of 0.4 to 12 μm in diameter by (i) Coulter counter method with respect to 100 parts by mass of the polycarbonate resin (A). (Ii) The ratio of particles having a particle diameter of 1 μm or more and less than 2 μm, the ratio of particles having a particle diameter of 2 μm or more and less than 3 μm, and the ratio of particles having a particle diameter of 3 μm or more are in the range of 20 to 40%, And (iii) 0.1 to 5 parts by mass of acrylic resin-based fine particles (B) having substantially no particle size of 10 μm or more, and poly (dimethylsiloxane) having a kinematic viscosity of 1 to 120 centistokes It contains 0.05 to 3 parts by mass of poly (diphenylsiloxane) copolymer (C).

[2. Polycarbonate resin (A)]
Examples of the polycarbonate resin (A) used in the present invention include aromatic polycarbonate resins, aliphatic polycarbonate resins, and aromatic-aliphatic polycarbonate resins. Preferred are aromatic polycarbonate resins. Specifically, A thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid is used.

  Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane, 2,2 -Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxy- 3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-methoxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4 -Hydroxy-3- (1-methylethyl) phenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propyl Bread, 2,2-bis (4-hydroxy-3- (1-methylpropyl) phenyl) propane, 2,2-bis (4-hydroxy-3-cyclohexylphenyl) propane, 2,2-bis (4-hydroxy) -3-phenylphenyl) propane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane Bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1 -Bis (4-hydroxy-3- (1-methylethyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy) 3-tert-butylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexane, 1, 1-bis (4-hydroxy-3-phenylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3, 5- Dimethylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylethyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-tert-butyl) Phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) -1-pheny Ruethane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) -1-phenylethane, 1,1-bis ( 4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 4,4 ′-(1,3-phenylenediisopropylidene) bisphenol, 4,4 ′-(1,4-pheny Range isopropylidene) bisphenol, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxy Phenyl ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) Sulfoxide, bis (4-hydroxyphenyl) sulfone, 4,4′-dihydroxybiphenyl, 1,1-bis (4-hydroxyphenyl) -3,3-5-trimethylcyclohexane, 1,1-bis (4-hydroxy-) 6-methyl-3-tert-butylphenyl) butane, hydroquinone, resorcinol, and the like.

Examples of the aliphatic dihydroxy compound include tricyclo [5.2.1.0 ^2,6 ] decanedimethanol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,5-norbornanedimethanol, 2, 6-norbornanedimethanol, trans-2,6-decalindimethanol, 1,4-cyclohexanediol, 2,2,4,4, -tetramethylcyclopropanediol, 1,4-butanediol, 1,5-pentane Diol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1, Examples thereof include 11-undecanediol and 1,12-dodecanediol.

  Further, as a part of the dihydroxy compound, when a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the dihydroxy compound, or a polymer or oligomer having a siloxane structure and containing both terminal phenolic OH groups is used, flame retardancy A highly polycarbonate resin can be obtained.

  Preferred examples of the polycarbonate resin (A) used in the present invention include 2,2-bis (4-hydroxyphenyl) propane as a dihydroxy compound, or 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy. The polycarbonate resin which used the compound together is mentioned. In the present invention, two or more polycarbonate resins may be used in combination as the component (A).

  The molecular weight of the polycarbonate resin used in the present invention is not limited, but it is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, preferably 10,000 to 40,000. Preferably it is 14,000-32,000. When the viscosity average molecular weight is within this range, a molded product having good moldability and high mechanical strength can be obtained. The most preferred molecular weight range of the polycarbonate resin is 16,000 to 30,000.

  The production method of the polycarbonate resin (A) is not particularly limited, and a polycarbonate resin produced by any of the phosgene method (interfacial polymerization method) and the melting method (transesterification method) can be used. Moreover, it is also preferable to use the polycarbonate resin which performed the post-process which adjusts the amount of terminal OH groups to the polycarbonate resin manufactured by the melting method.

The polycarbonate resin (A) in the present invention preferably contains a certain percentage or more of a polycarbonate resin having a structural viscosity index N in a predetermined range.
The structural viscosity index N is an index for evaluating the flow characteristics of a melt as described in detail in the document “Rheology for chemists” (Chemical Doujin, 1982, pp. 15-16). . Usually, the melting characteristics of polycarbonate resin can be expressed by the formula: γ = a · σ ^N. In the above formula, γ: shear rate, a: constant, σ: stress, N: structural viscosity index.

  In the above formula, when N = 1, Newtonian fluidity is shown, and the non-Newtonian fluidity increases as the value of N increases. That is, the flow characteristics of the melt are evaluated by the magnitude of the structural viscosity index N. In general, a polycarbonate resin having a large structural viscosity index N tends to have a high melt viscosity in a low shear region. For this reason, when a polycarbonate resin having a large structural viscosity index N is mixed with another polycarbonate resin, dripping at the time of combustion of the obtained polycarbonate resin composition can be suppressed, and flame retardancy can be improved. However, in order to maintain the moldability of the obtained polycarbonate resin composition in a favorable range, the structural viscosity index N of the polycarbonate resin is preferably not excessively large.

Therefore, the polycarbonate resin (A) in the polycarbonate resin composition of the present invention has a structural viscosity index N of preferably 1.2 or more, more preferably 1.25 or more, and further preferably 1.28 or more. Usually, it is preferable to contain a certain proportion or more of a polycarbonate resin of 1.8 or less, preferably 1.7 or less, preferably an aromatic polycarbonate resin.
Thus, the high structural viscosity index N means that the polycarbonate resin has a branched chain. By containing the polycarbonate resin having a high structural viscosity index N in this way, the polycarbonate resin composition is dripped at the time of combustion. Can be suppressed and flame retardancy can be improved.

The structural viscosity index N can also be expressed by Log η _a = [(1-N) / N] × Log γ + C, which is derived from the above equation, as described in, for example, JP-A-2005-232442. Is possible. In the above formula, N: structural viscosity index, γ: shear rate, C: constant, η _a : apparent viscosity. As can be seen from this equation, the N value can also be evaluated from γ and ηa in _a low shear region in which the viscosity behavior is greatly different. For example, the N value can be determined from η _a at γ = 12.16 sec ⁻¹ and γ = 24.32 sec ⁻¹ .

  An aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more is obtained by a melting method (transesterification method) as described in JP-A-8-259687 and JP-A-8-245782, for example. When reacting an aromatic dihydroxy compound and a carbonic acid diester, an aromatic polycarbonate resin having a high structural viscosity index and excellent hydrolytic stability can be obtained without adding a branching agent by selecting catalyst conditions or production conditions. be able to.

An aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more can also be produced by a method using a branching agent when produced by a phosgene method or a melting method (a transesterification method) according to a conventional method. .
Specific examples of the branching agent include phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tris (4-hydroxy). Phenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenylheptene-3,1,3,5-tris (4-hydroxyphenyl) ethane and the like, and 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol, 5,7-dichloroisatin bisphenol, 5-bromoisatin bisphenol and the like.
The amount used is in the range of 0.01 to 10 mol%, particularly preferably in the range of 0.1 to 3 mol%, based on the aromatic dihydroxy compound.

  The molecular weight of the aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more is a viscosity average molecular weight in the range of 16,000 to 30,000 converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent. Is preferred.

In the polycarbonate resin composition of the present invention, the polycarbonate resin (A) is the above-described polycarbonate resin having the structural viscosity index N in a predetermined range (hereinafter, this polycarbonate resin may be referred to as “predetermined N polycarbonate resin”). In the polycarbonate resin, it is desirable to contain 20% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more. By combining with the predetermined N polycarbonate resin in this way, the torque during extrusion is not increased more than necessary, so that the productivity is hardly lowered, and the polycarbonate resin is hardly colored due to shear heat generation.
In addition, there is no restriction | limiting in the upper limit of content of predetermined N polycarbonate resin in polycarbonate resin, Usually, it is 100 mass% or less, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less.
Moreover, 1 type may be used for predetermined N polycarbonate resin, and it may use 2 or more types together by arbitrary combinations and a ratio.

  Further, the polycarbonate resin (A) may contain a polycarbonate resin having a structural viscosity index N outside the above predetermined range in addition to the above predetermined N polycarbonate resin. Although there is no restriction | limiting in the kind, A linear polycarbonate resin is preferable especially. By combining the predetermined N polycarbonate resin and the linear polycarbonate resin, there is an advantage that it is easy to balance the flame retardancy (anti-dripping property) and moldability (fluidity) of the obtained polycarbonate resin composition. From this viewpoint, it is particularly preferable that the polycarbonate resin (A) is composed of a predetermined N polycarbonate resin and a linear polycarbonate resin. In addition, the structural viscosity index N of this linear polycarbonate resin is usually about 1-1.15.

  When the polycarbonate resin (A) contains a linear polycarbonate resin, the proportion of the linear polycarbonate resin in the polycarbonate resin is usually 80% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less. Moreover, it is more than 0 mass% normally, Preferably it is 10 mass% or more, More preferably, it is 15 mass% or more. By setting the content of the linear polycarbonate resin in the polycarbonate resin within the above range, it is easy to obtain good dispersibility of the additive, and there is an advantage that a polycarbonate resin excellent in flame retardancy and moldability is easily obtained. It is done.

  The polycarbonate resin (A) is not limited to an embodiment including only one type of polycarbonate resin, and includes an embodiment including a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. It may be used in the sense) or may be used in combination with an alloy (mixture) of a polycarbonate resin and another thermoplastic resin. 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.

  In addition, the polycarbonate resin (A) 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 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 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 (A) 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, more preferably 50% by mass or less, among the polycarbonate resins contained in the polycarbonate resin composition of the present invention. 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.

[3. Acrylic resin-based fine particles (B)]
The polycarbonate resin composition of the present invention contains 0.1 to 5 parts by mass of acrylic resin-based fine particles (B) satisfying specific particle sizes and particle size distributions (i) to (iii) below.
(I) The average particle diameter measured on a number basis in the range of 0.4 to 12 μm in diameter by the Coulter counter method is 1 to 4 μm,
(Ii) The ratio of particles having a particle diameter of 1 μm or more and less than 2 μm, the ratio of particles having a particle diameter of 2 μm or more and less than 3 μm, and the ratio of particles having a particle diameter of 3 μm or more are in the range of 20 to 40%, respectively ( iii) substantially does not contain particles having a particle size of 10 μm or more.
By blending such acrylic resin-based fine particles in such an amount, it is possible to achieve the excellent light diffusibility and light transmittance of the polycarbonate resin composition of the present invention.

  As the acrylic resin-based fine particles (B), any polymer or copolymer using an acrylic monomer that satisfies the above characteristics (i) to (iii) can be used. Examples of the polymer include polymethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polycyclohexyl methacrylate, and copolymers thereof.

Particularly preferred as the acrylic resin resin fine particles (B) used in the present invention is an acrylic resin produced by a non-crosslinkable acrylic monomer (B1) and a crosslinkable monomer (B2), preferably by suspension polymerization. System fine particles.
As the non-crosslinkable acrylic monomer, an acrylic monomer alone or a combination of acrylic monomers is used. As acrylic monomers, acrylic acid esters such as methyl acrylate, n-butyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl-hexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate Preferred examples thereof include methacrylic acid esters, and these can be used alone or in combination of two or more. Of these, methyl methacrylate is preferably used.
The monomer may be added with a monomer copolymerizable with a (meth) acrylic acid ester monomer. Examples of such a monomer include styrene, α-methylstyrene, Examples thereof include monomers having a vinyl group such as vinyl acetate.

  On the other hand, as the crosslinkable monomer, a compound having two or more unsaturated bonds in the molecule is preferably used. For example, trimethylolpropane tri (meth) acrylate, allyl methacrylate, triallyl cyanurate, triallyl isocyanate, ethylene glycol dimethacrylate, propylene glycol diallyl ether, divinylbenzene, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, etc. Can be mentioned. Of these, trimethylolpropane tri (meth) acrylate is preferable.

The acrylic resin fine particles (B) can be produced by suspension polymerization of the non-crosslinkable acrylic monomer (B1) and the crosslinkable monomer (B2). For example, the polymerization can be carried out by suspending both monomers using polyvinyl alcohol as a dispersant, followed by filtration, washing, sieving and drying. The proportions of both monomers used are preferably 90 to 99% by mass of the non-crosslinkable acrylic monomer (B1) and 10 to 1% by mass of the crosslinkable monomer (B2).
If the amount of the crosslinkable monomer is too small, the dispersibility of the obtained bead-shaped crosslinked acrylic resin in the polycarbonate resin is poor, and conversely, if the blending ratio of the crosslinkable monomer (B2) is large, an acrylic resin type Since the fine particles (B) become too hard and impact strength decreases, it is not preferable.

  As described above, the acrylic resin-based fine particles (B) are (i) those having an average particle size of 1 to 4 μm, and (ii) the proportion of particles having a particle size of 1 μm or more and less than 2 μm, and the particle size is The ratio of particles having a particle diameter of 2 μm or more and less than 3 μm and the ratio of particles having a particle diameter of 3 μm or more are in the range of 20 to 40%, respectively, and (iii) those having substantially no particles having a particle diameter of 10 μm or more are used. It is characterized by doing. As the acrylic resin-based fine particles (B), those having an average particle size of 1 to 4 μm, which is smaller than that of the average particle size of 6 to 10 μm, which has been conventionally used until now, are used. Contrary to conventional common sense that the dispersion is said to be good, it is characterized by using a broad particle size distribution as described above.

In the present invention, the particle size and particle size distribution are measured on a number basis by the Coulter counter method. In the Cole Counter method, an electrolyte in which sample particles are suspended is passed through pores (apertures), and changes in voltage pulses generated in proportion to the volume of the particles at that time are read to quantify the particle diameter. In addition, the volume distribution histogram of the sample particles can be obtained by measuring the voltage pulse height one by one. Such particle size or particle size distribution measurement by the call counter method is most frequently used as a particle size distribution measuring apparatus.
In the present invention, the particle diameter measurement of the acrylic resin-based fine particles (B) eliminates the influence of extremely small fine particles and extremely large maximal particles, and obtains highly reliable and highly reproducible data. It is defined by measuring in a range of ˜12 μm. The average particle diameter is an average particle diameter based on the number.
In addition, the average particle diameter in this invention says D50 measured with a laser diffraction type particle size distribution measuring apparatus, and measured using Shimadzu Corporation "laser diffraction type particle size distribution measuring apparatus SALD-2100".

  The acrylic resin-based fine particles (B) used in the present invention have an average particle diameter of 1 to 4 μm, and if the average particle diameter is not within this range, the light diffusivity and the degree of dispersion are reduced. The average particle size is preferably 1 to 3 μm, more preferably 1.5 to 3 μm.

  In addition, the acrylic resin-based fine particles (B) may be referred to as a “number reference frequency” in which the ratio of particles in the range of 1 μm or more and less than 2 μm (%, the total number in the range of 0.4 to 12 μm in diameter is 100%. ) Is 20 to 40%, the proportion of particles having a particle size of 2 μm or more and less than 3 μm is 20 to 40%, and the proportion of particles having a particle size of 3 μm or more is 20 to 40%. You need to be in range. Thus, by making the number standard frequency in each particle size into the range of 20 to 40%, the light diffusion effect and the transmittance can be further improved, and the impact resistance can be improved.

Furthermore, the acrylic resin-based fine particles (B) are characterized by containing substantially no particles having a particle size of 10 μm or more, preferably 8 μm or more. When the particle size contains 10 μm or more, impact resistance, which is a particularly necessary characteristic for a lighting member, is lowered.
In addition, “substantially does not contain” in “substantially does not contain particles having a particle diameter of 10 μm or more” includes, of course, the case where particles having a prescribed particle diameter are not included, and the particle diameter is 10 μm. It means that the amount of the above particles is 1% by number or less, preferably 0.5% by number or less, particularly 0.1% by number or less with respect to the total number of the acrylic resin fine particles (B).

  The content of the acrylic resin-based fine particles (B) needs to be 0.1 to 5 parts by mass, preferably 0.1 to 2 parts by mass, more preferably 100 parts by mass of the polycarbonate resin (A). Is 0.3 to 1.5 parts by mass. When the usage rate of the acrylic resin fine particles (B) is less than 0.1 parts by mass, the effect of improving the transmittance and light diffusibility of the polycarbonate resin cannot be sufficiently obtained, and the usage rate exceeds 5 parts by mass. Is not preferable because the impact resistance and the like of the polycarbonate resin tend to decrease.

  Then, the average particle size is 1 to 4 μm, the number reference frequency in each particle size range is 20 to 40%, and the material substantially not containing 10 μm or more is 0.1 to 0.1%. By blending 5 parts by mass, polycarbonate resin composition with excellent mechanical properties such as impact resistance, improved total light transmittance, light diffusibility, dispersibility, excellent moldability, and easy flame resistance. It can be a thing.

A method for producing acrylic resin-based fine particles having such a particle size is known and is not particularly limited, but is directly polymerized and produced as particles by an emulsion polymerization method or a suspension polymerization method. It is also preferable to do. When the acrylic resin-based fine particles are produced directly by polymerization, the particle diameter can be controlled by the polymerization conditions. For example, a polymer having a broad distribution can be obtained by using a homogenizer so that the particle diameter is a predetermined one and the particle diameter distribution is not loaded with an excessive shearing force.
In addition, the acrylic resin obtained in the solid state is pulverized by a pulverizer such as a jet airflow pulverizer, mechanical collision pulverizer, roll mill, hammer mill, impeller breaker, etc. The particle size of the particles may be controlled by being introduced into a classification device such as a device for classification.
Moreover, it can also select and use from the various acrylic resin particle | grains known commercially.

[4. Aryl group-containing polysilane (C)]
The polycarbonate resin composition of the present invention contains an aryl group-containing polysilane. Thus, the flame retardance of the polycarbonate resin composition of the present invention can be remarkably improved by containing the aryl group-containing polysilane simultaneously with the metal salt compound described above. Although the details of the reason for the synergistic effect of the remarkable flame retardancy improvement with this metal salt compound are not known, the catalytic action of the metal salt compound partially cleaves the Si-Si bond of polysilane at the temperature during combustion. This can be attributed to the efficient formation of a composite of polycarbonate resin and polysilane.
Moreover, when the aryl group is contained, the heat resistance of the polysilane itself is increased, and the compatibility and dispersibility in the polycarbonate resin are improved, whereby a polycarbonate resin composition having excellent transparency and impact resistance can be obtained. Conceivable.
The component (C) does not have a Si—O—Si structure in the molecule, unlike the polyorganosiloxane particles (B) (hereinafter also referred to as the component (B)).

The aryl group-containing polysilane is not particularly limited as long as it is a polymer containing an aryl group as an essential substituent in the molecule and having a Si—Si bond, and any of linear, branched, cyclic or network-like Although it may take a form, it usually has at least one structural unit among the structural units represented by the above formulas (1) to (3).

As such an aryl group-containing polysilane, for example, a linear or cyclic aryl group-containing polysilane composed of a structural unit represented by the above formula (1), a structure represented by the above formula (2) or (3) A branched or network-like aryl group-containing polysilane composed of units, a combination of structural units represented by the above formulas (1) to (3), for example, formula (1) and formula (2), formula (1) and formula ( 3), an aryl group-containing polysilane composed of the formula (2), the formula (3), and the formulas (1) to (3). Of these, linear aryl group-containing polysilanes and cyclic aryl group-containing polysilanes are preferred because they tend to be excellent in dispersibility in polycarbonate resins, and in particular, cyclic aryl group-containing polysilanes tend to have high dispersibility in polycarbonate resins. Therefore, it is preferable.

Specific examples of the cyclic aryl group-containing polysilane having the structural unit represented by the formula (1) as described above can also be represented by the formula (4).

In the above formulas (1) to (4), the substituent represented by R1, R2, R3, R4 and R5 represents at least one selected from a monovalent hydrocarbon group, a hydrogen atom and a silyl group. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, an aralkyl group, and the like. Among them, an alkyl group and an aryl group are preferable, and an aryl group is particularly preferable. Preferably, a phenyl group is more preferable.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group. An alkyl group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, and hexyl group is preferable. The group is particularly preferred.

Examples of the cycloalkyl group include cycloalkyl groups having 5 to 14 carbon atoms such as a cyclopentyl group and a cyclohexyl group. Among them, a cycloalkyl group having 5 to 8 carbon atoms is preferable.

Examples of the alkenyl group include alkenyl groups having 2 to 8 carbon atoms such as vinyl group and allyl group. Examples of the cycloalkenyl group include cycloalkenyl groups having 5 to 12 carbon atoms such as cyclopentyl group and cyclohexyl group. Is mentioned.

As an alkynyl group, aryls, such as C2-C8 alkynyl groups, such as an ethynyl group and a propynyl group, an ethynylbenzene group, etc. are mentioned, for example.

Examples of the aryl group include aryl groups having 6 to 20 carbon atoms such as a phenyl group, a methylphenyl (that is, tolyl) group, a dimethylphenyl (that is, xylyl) group, a naphthyl group, and a biphenyl group. An aryl group having 6 to 10 carbon atoms is preferred, and a phenyl group is particularly preferred.

Examples of the aralkyl group include aralkyl groups having 6 to 20 carbon atoms such as a benzyl group, a phenethyl group, and a phenylpropyl group. Among them, an aralkyl group having 6 to 10 carbon atoms is preferable, and a benzyl group is particularly preferable.

Examples of the silyl group include silyl groups having 1 to 10 silicon atoms such as a silyl group, a disilanyl group, and a trisilanyl group. Among them, a silyl group having 1 to 6 silicon atoms is preferable. In the case of the silyl group, at least one of the hydrogen atoms may be substituted with a functional group such as an alkyl group, an aryl group, or an alkoxy group.

The polymerization degree of the aryl group-containing polysilane, that is, the sum of x, y and z in the structural units (1) to (3) is usually 2 or more, preferably 3 or more, more preferably 4 or more, and usually 500 or less, Preferably it is 300 or less, More preferably, it is 100 or less. When the sum of x, y and z is less than 2, since it is a polysilane monomer, that is, a polysilane monomer, the heat resistance is extremely reduced, and when it is a polycarbonate resin composition, it is easy to gasify (volatilize), This is not preferable because it tends to cause mold contamination, mechanical properties and flame retardancy. Further, those exceeding 500 are extremely difficult in production, and the dispersibility into the polycarbonate resin is extremely lowered.

The degree of polymerization of the cyclic aryl group-containing polysilane in formula (4), that is, m is usually 4 or more, preferably 5 or more, usually 12 or less, preferably 10 or less, more preferably 8 or less, and particularly preferably m. = 5. When m is 3 or less, it is difficult to produce due to chemical structure, and when m is greater than 12, it is also difficult to produce.

In the formulas (1) to (3), a, b, c, d and e represent 0 or 1. When a, b, c, d and e are 0, the aryl group-containing polysilane is an organic functional group as an alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, aralkyl group, hydrogen atom , A, b, c, d and e are 1, when polysilane is an organic functional group, an alkoxy group, a cycloalkyloxy group, an alkenyloxy group, a cycloalkenyloxy group, It means having an alkynyloxy group, an aryloxy group, an aralkyloxy group, and a hydroxyl group. From the viewpoint of the heat resistance of the aryl group-containing polysilane, a, b, c, d, and e are preferably 0. However, in order to improve the affinity with the resin, intentionally or by oxidation action or the like It may be 1 unintentionally.

When the aryl group-containing polysilane has an acyclic structure (linear, branched, or network), the terminal substituent is usually a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, or a silyl group.

Examples of such aryl group-containing polysilanes include polyalkylaryl silanes such as polymethylphenylsilane and methylphenylsilane-phenylhexylsilane copolymers; polydiarylsilanes such as polydiphenylsilane; dimethylsilane-methylphenylsilane copolymers. , Dimethylsilane-phenylhexylsilane copolymer, dialkylsilane-alkylarylsilane copolymer such as dimethylsilane-methylnaphthylsilane copolymer; linear or branched, network-like, aryl group-containing polysilane such as ,
And cyclic aryl group-containing polysilanes such as cyclic alkylarylsilanes such as methylphenylcyclosilane, cyclic arylsilanes such as diphenylcyclosilane;
Details of such an aryl group-containing polysilane are described in, for example, R.A. D. Miller, J.M. Michl; Chemical Review, 89, 1359 (1989); Matsumoto; Japan Journal of Physics, Vol. 37, p. 5425 (1998).

The aryl group-containing polysilane according to the present invention is preferably a cyclic aryl group-containing polysilane, and more preferably a cyclic arylsilane. Specific examples of such cyclic arylsilanes include octaphenylcyclotetrasilane, decaphenylcyclopentasilane, dodecaphenylcyclohexasilane, and the like, and decaphenylcyclopentasilane is particularly preferable.
By selecting such a cyclic aryl group-containing polysilane, the compatibility and dispersibility in the polycarbonate resin are remarkably improved, and a polycarbonate resin composition having excellent flame retardancy, transparency, hue and impact resistance can be obtained. There is a tendency.

The molecular weight of the aryl group-containing polysilane according to the present invention is a number average molecular weight [Mn] of usually 300 or more, preferably 350 or more, more preferably 400 or more, and usually 200000 or less, preferably 50000 or less, more preferably 10000. Hereinafter, it is more preferably 5000 or less, and most preferably 2000 or less. When the number average molecular weight is less than 300, the heat resistance of polysilane is lowered, the flame retardancy of the polycarbonate resin composition is lowered, and mold contamination at the time of molding processing may be induced, which is not preferable. Those exceeding 200,000 are also not preferable because the dispersibility and compatibility in the polycarbonate resin are extremely lowered, and there is a risk of lowering mechanical properties and flame retardancy.

In addition, the number average molecular weight [Mn] of the aryl group-containing polysilane is a value obtained by measurement with a gel permeation chromatography (GPC) using tetrahydrofuran as a solvent at a temperature of 40 ° C. and a polystyrene conversion value. is there

The method for producing an aryl group-containing polysilane according to the present invention is not particularly limited as long as it is a known method, and may be appropriately selected and used. For example, a silicon-containing monomer having a specific structural unit is used as a raw material, magnesium Dehalogenation condensation polymerization of halosilanes using magnesium as a reducing agent (magnesium reduction method), dehalogenation condensation polymerization of halosilanes in the presence of antkari metal (capping method), and dehalogenation condensation polymerization of halosilanes by electrode reduction Method, method of dehalogenating polycondensation of halosilanes by electrode reduction, method of dehydrogenating polycondensation of hydrazine in the presence of a metal catalyst, method of anionic polymerization of disilene crosslinked with biphenyl, etc., ring opening of cyclic silanes Examples of these production methods include aliquots obtained by polymerization. The purity of the Le group-containing polysilane, molecular weight distribution, a point easily controlled impurity content such as of sodium, chlorine and the like, magnesium reduction method from the viewpoint industrial merit is great in terms of production cost and safety are particularly preferred. Note that silanol groups may be generated by adding water to the obtained aryl group-containing polysilane.

The content of the aryl group-containing polysilane in the polycarbonate resin composition of the present invention needs to be 0.05 parts by mass or more, preferably 0.075 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). Part or more, more preferably 0.1 part by weight or more, and the upper limit thereof is less than 0.3 part by weight, preferably 0.25 part by weight or less, more preferably 0.2 part by weight or less.
When the content of the aryl group-containing polysilane is the above content, the polycarbonate resin composition of the present invention is excellent in optical balance, excellent in flame retardancy, and further has high fluidity, releasability, impact resistance, It can have initial hue and heat discoloration.
In addition, an aryl group containing polysilane can be used individually or in combination of 2 or more types.

[5. Organic sulfonic acid metal salt (D)]
In the resin composition of the present invention, it is preferable to use an organic sulfonic acid metal salt (D).
The types of metals possessed by organic sulfonic acid metal salts include alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs); magnesium (Mg), calcium (Ca ), Alkaline earth metals such as strontium (Sr), barium (Ba); and aluminum (Al), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), Zinc (Zn), zirconium (Zr), molybdenum (Mo), etc. are mentioned.
Among these, alkali metals or alkaline earth metals are preferable. Promotes the formation of a carbonized layer during the combustion of polycarbonate resin, further enhances flame retardancy, and maintains good properties such as impact resistance and other mechanical properties, heat resistance, and electrical properties of polycarbonate resin it can.
Of the alkali metals or alkaline earth metals, alkali metals are more preferred, sodium, potassium, cesium or lithium are more preferred, sodium, potassium and cesium are more preferred, and sodium and potassium are particularly preferred.

  Examples of preferred organic sulfonic acid metal salts (D) include organic sulfonic acid lithium (Li) salts, organic sulfonic acid sodium (Na) salts, organic sulfonic acid potassium (K) salts, and organic sulfonic acid rubidium (Rb) salts. , Organic sulfonic acid cesium (Cs) salt, organic sulfonic acid magnesium (Mg) salt, organic sulfonic acid calcium (Ca) salt, organic sulfonic acid strontium (Sr) salt, organic sulfonic acid barium (Ba) salt, and the like. . Among these, organic sulfonic acid alkali metal salts such as organic sulfonic acid sodium (Na) salt, organic sulfonic acid potassium (K) salt compound, and organic sulfonic acid cesium (Cs) salt compound are particularly preferable.

  Among the organic sulfonic acid metal salts (D), preferred are a fluorine-containing aliphatic sulfonic acid metal salt, a fluorine-containing aliphatic sulfonic acid imide metal salt, an aromatic sulfonic acid metal salt, and an aromatic sulfonamide. Metal salts are mentioned.

  Among them, specific examples of preferable ones include potassium nonafluorobutanesulfonate, lithium nonafluorobutanesulfonate, sodium nonafluorobutanesulfonate, cesium nonafluorobutanesulfonate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, Containing at least one C—F bond in the molecule, such as potassium trifluoromethanesulfonate, potassium pentafluoroethanesulfonate, potassium heptafluoropropanesulfonate, potassium decafluoro-4- (pentafluoroethyl) cyclohexanesulfonate; Alkali metal salts of fluoroaliphatic sulfonic acids;

  At least one C—F in the molecule, such as magnesium nonafluorobutanesulfonate, calcium nonafluorobutanesulfonate, barium nonafluorobutanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, barium trifluoromethanesulfonate, etc. An alkaline earth metal salt of a fluorine-containing aliphatic sulfonic acid having a bond;

  Disodium difluoromethane disulfonate, dipotassium difluoromethane disulfonate, sodium tetrafluoroethane disulfonate, dipotassium tetrafluoroethane disulfonate, dipotassium hexafluoropropane disulfonate, dipotassium hexafluoroisopropane disulfonate, disodium octafluorobutane disulfonate, A metal salt of a fluorinated aliphatic sulfonic acid, such as an alkali metal salt of a fluorinated aliphatic disulfonic acid having at least one C—F bond in the molecule, such as dipotassium octafluorobutanedisulfonate;

  Bis (perfluoropropanesulfonyl) imide lithium, bis (perfluoropropanesulfonyl) imide sodium, bis (perfluoropropanesulfonyl) imide potassium, bis (perfluorobutanesulfonyl) imide lithium, bis (perfluorobutanesulfonyl) imide sodium, In the molecule, such as potassium bis (perfluorobutanesulfonyl) imide, potassium trifluoromethane (pentafluoroethane) sulfonylimide, sodium trifluoromethane (nonafluorobutane) sulfonylimide, potassium trifluoromethane (nonafluorobutane) sulfonylimide, trifluoromethane, etc. An alkali metal salt of a fluorine-containing aliphatic disulfonic imide having at least one C—F bond;

  Cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide lithium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide sodium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide potassium An alkali metal salt of a cyclic fluorinated aliphatic sulfonimide having at least one C—F bond in the molecule; a metal salt of a fluorinated aliphatic sulfonic imide, such as

  Diphenylsulfone-3,3′-disulfonate dipotassium, diphenylsulfone-3-sulfonate potassium, sodium benzenesulfonate, sodium (poly) styrenesulfonate, sodium paratoluenesulfonate, sodium (branched) dodecylbenzenesulfonate, tri Sodium chlorobenzenesulfonate, potassium benzenesulfonate, potassium styrenesulfonate, potassium (poly) styrenesulfonate, potassium paratoluenesulfonate, potassium (branched) dodecylbenzenesulfonate, potassium trichlorobenzenesulfonate, cesium benzenesulfonate, ( Poly) cesium styrene sulfonate, cesium p-toluenesulfonate, cesium (branched) dodecylbenzene sulfonate, cesium trichlorobenzene sulfonate Etc., alkali metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule;

  Magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, magnesium (branched) dodecylbenzenesulfonate, calcium (branched) calcium dodecylbenzenesulfonate in the molecule An alkaline earth metal salt of an aromatic sulfonic acid having an aromatic group of: an aromatic sulfonic acid metal salt, etc.

  Sodium salt of saccharin, potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfimide, potassium salt of N- (N′-benzylaminocarbonyl) sulfanilimide, potassium of N- (phenylcarboxyl) -sulfanilimide Examples thereof include metal salts of aromatic sulfonamides such as alkali metal salts of aromatic sulfonamides having at least one aromatic group in the molecule, such as salts.

  Among the above-mentioned examples, fluorine-containing aliphatic sulfonic acid metal salts are preferable. As the fluorine-containing aliphatic sulfonic acid metal salt, an alkali metal salt of fluorine-containing aliphatic sulfonic acid having at least one C—F bond in the molecule is more preferable, and an alkali metal salt of perfluoroalkanesulfonic acid is particularly preferable. Specifically, potassium nonafluorobutanesulfonate is preferred.

  In addition, 1 type may be used for organic sulfonic acid metal salt (D), and it may use 2 or more types together by arbitrary combinations and a ratio.

The average particle diameter of the organic sulfonic acid metal salt (D) is not particularly limited, and it is usually sufficient to use an organic sulfonic acid metal salt in the range of 1 μm to 500 μm. In particular, transparency can be achieved by setting the average particle diameter to 20 to 200 μm. It is preferable because it tends to improve. By setting it within this range, it is considered that the dispersibility of the organic sulfonic acid metal salt in the polycarbonate resin is improved and the aggregation property is suppressed. From such a viewpoint, the average particle diameter is preferably 25 to 150 μm, more preferably 30 to 100 μm.
The average particle diameter was measured in the range of 0.1 to 10,000 μm using a Microtrac MT3300 laser diffraction scattering type particle size distribution measuring device manufactured by Nikkiso Co., Ltd. under a dispersion pressure of 200 kPa, and the cumulative frequency was 50%. Represents the volume average particle diameter (D50).

  The content of the organic sulfonic acid metal salt (D) is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and still more preferably 0.03 with respect to 100 parts by mass of the polycarbonate resin (A). The upper limit thereof is preferably 1 part by mass or less, more preferably 0.75 part by mass or less, still more preferably 0.5 part by mass or less, particularly preferably 0.5 part by mass or more. 0.3 parts by mass or less. If the content is too small, the flame retardancy of the obtained polycarbonate resin composition may be insufficient. On the other hand, if the content is too large, the thermal stability of the polycarbonate resin is deteriorated, and the appearance of the molded product is poor. There is a possibility that the mechanical strength is reduced.

[6. Fluoropolymer (E)]
The polycarbonate resin composition of the present invention preferably contains 0.001 to 1 part by mass of the fluororesin (E) with respect to 100 parts by mass of the polycarbonate resin (A). By containing the fluororesin in this manner, the melting characteristics of the polycarbonate resin composition can be improved, and specifically, the dripping prevention property at the time of combustion can be improved.

  If the content of the fluororesin is less than 0.001 part by mass, the effect of improving the flame retardancy by the fluororesin tends to be insufficient, and if it exceeds 1 part by mass, the appearance of the molded product molded from the polycarbonate resin composition is poor. There is a tendency for mechanical strength to decrease. The lower limit of the content is more preferably 0.05 parts by mass or more, still more preferably 0.075 parts by mass or more, particularly preferably 0.1 parts by mass or more, and the upper limit of the content is more preferably 0. .75 parts by mass or less, more preferably 0.5 parts by mass or less, and particularly preferably 0.45 parts by mass or less.

Of these, fluoroolefin resins are preferred as the fluororesin. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, and specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, Of these, tetrafluoroethylene resin is preferred.
Moreover, as this fluororesin, what has a fibril formation ability is preferable, and specifically, the fluoro olefin resin which has a fibril formation ability is mentioned. Thus, it has the tendency to improve dripping prevention property at the time of combustion by having fibril formation ability.

  Examples of the fluoroolefin resin having fibril-forming ability include “Teflon (registered trademark) 6J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Polyflon (registered trademark) F201L” and “Polyflon (registered trademark) F103 manufactured by Daikin Chemical Industries "," Polyflon (registered trademark) FA500 "and the like. Furthermore, as commercially available products of aqueous dispersions of fluoroolefin resins, for example, “Teflon (registered trademark) 30J”, “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Fluon ( Registered trademark) D-1 "and the like.

  Furthermore, an organic polymer-coated fluoroolefin resin can also be suitably used. By using the organic polymer-coated fluoroolefin resin, the dispersibility is improved, the surface appearance of the molded product is improved, and the surface foreign matter 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 powdered by coagulation or spray drying. (2) A method of polymerizing a monomer constituting an organic polymer in the presence of an aqueous dispersion of polyfluoroethylene particles, and then pulverizing or producing the powder by solidification or spray drying. 3) After emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing an aqueous dispersion of polyfluoroethylene particles and an aqueous dispersion of organic polymer particles, a powder is obtained by coagulation or spray drying. And the like, and the like.

The organic polymer for coating the fluoroolefin resin is not particularly limited, and specific examples of monomers for producing such an organic polymer include styrene, α-methylstyrene, p. -Methylstyrene, o-methylstyrene, tert-butylstyrene, o-ethylstyrene, p-chlorostyrene, o-chlorostyrene, 2,4-dichlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4- Aromatic vinyl monomers such as dimethylstyrene;
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, (Meth) acrylic acid ester monomers such as tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate;

Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile;
Α, β-unsaturated carboxylic acids such as maleic anhydride; maleimide monomers such as N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide;
Glycidyl group-containing monomers such as glycidyl methacrylate;
Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate;
Olefinic monomers such as ethylene, propylene, isobutylene;
Examples thereof include diene monomers such as butadiene, isoprene and dimethylbutadiene. In addition, these monomers can be used individually or in mixture of 2 or more types.

  Among them, as a monomer for producing an organic polymer that coats a fluoroolefin resin, those having high affinity with the polycarbonate resin are preferable from the viewpoint of dispersibility when blended with the polycarbonate resin, and aromatic monomers are preferable. A vinyl monomer, a (meth) acrylic acid ester monomer, and a vinyl cyanide monomer are more preferable.

  The content ratio of the fluoroolefin resin in the organic polymer-coated fluoroolefin resin is usually 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and particularly preferably 45% by mass or more. Usually, it is 95 mass% or less, Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, Most preferably, it is 75 mass% or less. It is preferable that the content ratio of the fluoroolefin resin in the organic polymer-coated fluoroolefin resin is in the above-described range because the balance between the flame retardancy and the appearance of the molded product tends to be excellent.

As such an organic polymer-coated fluoroolefin resin, specifically, “Metabrene (registered trademark) A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex (registered trademark) 449” manufactured by GE Specialty Chemical Co., Ltd., PIC Company "Poly TS AD001" manufactured by the company etc. are mentioned.
In addition, 1 type may contain fluororesin and 2 or more types may contain it by arbitrary combinations and a ratio.

[7. UV absorber (F)]
It is also preferable to mix | blend a ultraviolet absorber (F) with the resin composition of this invention. Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; organics such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, and hindered amine compounds. Examples include ultraviolet absorbers. Of these, organic ultraviolet absorbers are preferred, and benzotriazole compounds are more preferred. By selecting the organic ultraviolet absorber, the polycarbonate resin composition of the present invention has good transparency and mechanical properties.

  Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like, among others, 2- (2′- Hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] And 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferable.

  Specific examples of such benzotriazole compounds include “Seesorb 701”, “Seesorb 702”, “Seesorb 703”, “Seesorb 704”, and “Seesorb 705” manufactured by Sipro Kasei Co., Ltd. (trade names, the same applies hereinafter). , “Seasorb 709”, “Biosorb 520”, “Biosorb 580”, “Biosorb 582”, “Biosorb 583” manufactured by Kyodo Yakuhin Co., Ltd. “UV5411”, “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, manufactured by Adeka Corporation, “Tinuvin P”, “Cinuvin 234” manufactured by Ciba Specialty Chemicals , "Tinubin 326", "Tinubin 327", "Tinubin 328 Etc. The.

  The content of the ultraviolet absorber is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and usually 1 part by mass or less, preferably 100 parts by mass of the polycarbonate resin (A). Is 0.7 parts by mass or less. If the content of the UV absorber is below the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and if the content of the UV absorber exceeds the upper limit of the above range, the mold Debogit etc. may occur and cause mold contamination. In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

[8. Other additives]
The polycarbonate resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Such additives include heat stabilizers, antioxidants, release agents, dyes and pigments, fluorescent brighteners, antistatic agents, antifogging agents, lubricants, antiblocking agents, fluidity improvers, plasticizers, A dispersing agent, an antibacterial agent, etc. are mentioned.

-Heat stabilizer As a heat stabilizer, a phosphorus compound is mentioned, for example. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Examples thereof include phosphates of Group 1 or Group 10 metals such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.

  Among them, triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl diphenyl phosphite, Dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) ) Organic phosphites such as octyl phosphite are preferred.

  The content of the heat stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, based on 100 parts by mass of the polycarbonate resin. It is not more than part by mass, preferably not more than 0.7 part by mass, more preferably not more than 0.5 part by mass. If the amount of the heat stabilizer is too small, the heat stabilization effect may be insufficient. If the amount of the heat stabilizer is too large, the effect may reach a peak and may not be economical.

-Antioxidant As an antioxidant, a hindered phenolic antioxidant is mentioned, for example. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesi Tylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

  Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable.

  The content of the antioxidant is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 0.5 part by mass with respect to 100 parts by mass of the polycarbonate resin. Or less. When the content of the antioxidant is less than or equal to the lower limit of the range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the range, There is a possibility that the effect reaches its peak and is not economical.

-Release agent 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 15,000, and polysiloxane silicone oils. It is done.

  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, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic or alicyclic saturated monohydric alcohol or aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable.

  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.

  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 15,000 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.

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 5,000 or less.

  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 not more than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

[9. Production method of polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely, polycarbonate resin (A), acrylic resin type microparticles | fine-particles (B), and aryl group containing polysilane (C) , And other ingredients to be blended as necessary, for example, using a mixer such as a tumbler, Henschel mixer, super mixer, ribbon blender, etc., and then premixed, then Banbury mixer, roll, Brabender, single screw kneading extrusion And a melt kneading method using a mixer such as a machine, a twin-screw kneading extruder, or a kneader. The temperature for melt kneading is not particularly limited, but is usually in the range of 220 to 360 ° C.

[10. Molding]
The polycarbonate resin composition of the present invention can be produced by molding pelletized pellets by various molding methods. Further, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion-molded product, a blow-molded product, an injection-molded product or the like without going through pellets.
Examples of molding methods include injection molding methods, ultra-high speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using heat insulating molds, and rapid heating molds. Molding method used, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding Law. A molding method using a hot runner method can also be used. There is no limitation on the shape, pattern, color, size, etc. of the molded product, and it may be set arbitrarily according to the application of the molded product.

  Preferred molded articles obtained by molding the composition of the present invention include various lighting covers, lighting signs, transmissive screens, various displays, light diffusing sheets and light diffusing plates for liquid crystal display devices, and particularly for liquid crystal display devices. The light diffusing sheet and the light diffusing plate can be suitably used particularly as a diffusing plate for large liquid crystal televisions.

  Examples of lighting covers include fluorescent lamps and incandescent light bulb covers and lamp shades, bathroom lights, chandeliers, stands, brackets, lanterns, ceiling lights, pendant lights, garage lights, eaves lights, gatepost lights, and porch lights. , Garden lights, entrance lights, step lights, stair lights, guide lights, crime prevention lights, downlights, base lights, electric signs, sign lights, and other vehicle lamps such as automobiles and motorcycles It can be suitably used for a cover or the like. In particular, it can be suitably used for a lighting fixture that uses a light source that emits less heat, such as an LED or organic EL.

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

(Examples 1-12, Comparative Examples 1-9)
[Polycarbonate resin (A)]
As the polycarbonate resin, polycarbonate resins (A1) to (A4) shown in Table 1 below were used.

[Acrylic resin fine particles (B)]
Acrylic resin-based particles (B1) to (B5) shown in Table 2 below were prepared.

[Aryl group-containing polysilane (C)]
(C-1) Aryl group-containing polysilane (cyclic polydiphenylsilane, manufactured by Osaka Gas Chemical Co., Ltd., trade name: Ogsol SI-30-10, decaphenylcyclopentasilane, number average molecular weight 550)
(C-2: for comparative example) Other polysilanes (polydimethylsilane, manufactured by Nippon Soda Co., Ltd., number average molecular weight 2000)

[Organic sulfonic acid metal salt (D), fluororesin (E), ultraviolet absorber (F) and other additive components]
As the organic sulfonic acid metal salt (D), the fluororesin (E), the ultraviolet absorber (F) and the release agent (G), those described in Table 3 below were used.

[Production of resin composition pellets]
The above-mentioned components (A) to (G) were blended in the proportions (mass%) described in Tables 5 to 8, mixed for 20 minutes with a tumbler, and then a twin shaft manufactured by Nippon Steel Works, Ltd. equipped with 1 vent. Supplied to an extruder (TEX30HSST), kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 290 ° C., the molten resin extruded in a strand is rapidly cooled in a water tank, and pelletized using a pelletizer To obtain pellets of the polycarbonate resin composition.

[Preparation of test piece]
After drying the pellets obtained by the above-described production method at 120 ° C. for 5 hours, using a SYCAP SG75M2 type injection molding machine manufactured by Sumitomo Heavy Industries, the cylinder temperature is 280 ° C., the mold temperature is 80 ° C., and the molding cycle is 45 Injection molding was performed under the conditions of seconds, and a three-stage plate (three-stage thickness of 3 mm-2 mm-1 mm) and an ISO multipurpose test piece (3 mm) were molded.
Using these test pieces, total light transmittance, diffusivity, dispersity, and impact resistance were evaluated.

  Similarly, after drying the pellets obtained by the above production method at 120 ° C. for 5 hours, using a SE100DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. Then, injection molding was performed under conditions of a molding cycle of 30 seconds, and three types of UL test specimens having a length of 125 mm, a width of 13 mm, and thicknesses of 1.5 mm, 1.2 mm and 1.0 mm were molded.

Each evaluation method is as follows.
[Flame retardance evaluation]
About the obtained test piece (1.5 mm, 1.2 mm, and 1.0 mm), the vertical combustion test based on UL94 was performed, and it was set as V-0, V-1, V-2 according to the reference | standard of the following Table 4, Those outside the standard were classified as NG.

[Total light transmittance]
In accordance with JIS K-7105, the above-mentioned flat test piece (1-2-3 mm three-stage thickness) was used as a test piece, and an NDH-2000 type turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd. was used, and the thickness was 1.0 mm. The total light transmittance (unit: “%”) was measured.

[Dispersity]
Using the above-mentioned flat test piece (1-2-3 mm three-stage thickness) as a test piece and using GP-5 GONIOPHOTOMETER made by MURAKAMI COLOR RESEARCH LABORATORY, incident light: 0 °, tilt angle: 0 °, light receiving range : Brightness of 1 mm thickness and 2 mm thickness was measured under the conditions of 0 ° to 90 °, light beam stop: 2.0, light receiving stop: 3.0, and the diffusivity (%) was determined by the following equation.
Diffusion rate (%) = {(20 ° luminance value + 70 ° luminance value) / (5 ° luminance value × 2)} × 100
Further, the angle at which the luminance is reduced by half with respect to the luminance of 0 ° was determined as the degree of dispersion (°). The higher the degree of dispersion, the higher the light diffusibility, and it is preferable because it has the effect of further diffusing the light from the light source, maintaining the illuminance in a wider range, and lowering the visibility of the light source.

[Shock resistance]
Based on ISO179, the ISO multipurpose test piece (3 mm thickness) produced above was notched, and the Charpy impact strength with notch (unit: kJ / m ² ) was measured at 23 ° C.

[Flow value]
As an evaluation of the fluidity and thermal stability of the resin composition, the flow value (Q value) of the pellets was evaluated by the method described in Appendix C of JIS K7210. The measurement was performed using a flow tester CFD500D manufactured by Shimadzu Corporation, using a die having a hole diameter of 1.0 mmφ and a length of 10 mm, a test temperature of 279 ° C., a test force of 160 kgf, and a remaining heat time of 420 seconds (× 0.01 cc / sec) was measured.

[Initial hue and heat discoloration]
The above-mentioned flat test piece (1-2-3 mm three-stage thickness) was used as a test piece, and the initial yellowness (initial YI) was measured using a measurement color difference meter (SE 6000 type) manufactured by Nippon Denshoku Industries Co., Ltd. .
Moreover, this flat test piece was exposed in a hot air circulating dryer for 200 hours in a 120 ° C. atmosphere to conduct a heat resistance test.
The test piece subjected to the heat resistance test was measured for yellowness by the above-described method, and the change in the color tone of the test piece after the exposure test with respect to the color tone of the test piece before the exposure test (YI after thermal aging) was measured.
Judgment criteria are as follows.
A: YI is less than 3 B: YI is 3 or more and less than 5 X: Evaluation results where YI is 5 or more are shown in Tables 5 to 8 below.

From Examples 1 to 12 shown in Tables 5 to 6, a polycarbonate resin composition containing a predetermined amount of acrylic resin fine particles (B1) satisfying the particle size and particle size distribution of the present invention and an aryl group-containing polysilane (C) is It can be seen that the film has excellent total light transmittance and dispersity, and is excellent in impact resistance, flame retardancy, initial hue and heat discoloration.
On the other hand, from Tables 7 to 8, it can be seen that Comparative Examples 1 to 4 not containing an aryl group-containing polysilane are inferior in heat discoloration (YI after heat aging). Comparative Example 8 containing a polycarbonate resin composition of Comparative Examples 5 and 6 containing acrylic resin fine particles (B2 or B3) not satisfying the particle size and particle size distribution of the present invention, and an aryl group-containing polysilane containing more than a predetermined amount 9 indicate that the initial hue is inferior. Moreover, in the comparative example 7 using other polysilane, it turns out that there exists a problem that a resin composition pellet becomes cloudy.
Therefore, from the above examples and comparative examples, the effects of excellent total light transmittance and dispersibility, and excellent impact resistance, flame retardancy, initial hue, and heat discoloration can be obtained for the first time by the configuration of the present invention. It was confirmed to be a thing.

  According to the polycarbonate resin composition of the present invention, it is excellent in mechanical properties such as impact resistance, excellent in total light transmittance, light diffusibility, and dispersibility, and in moldability, flame retardancy, initial hue, and heat discoloration. Can be used in a wide range of fields such as various light covers, light signboards, transmissive screens, various displays, light diffusion sheets and light diffusion plates for liquid crystal display devices, and industrial applicability. Is very expensive.

Claims (16)

For 100 parts by mass of the polycarbonate resin (A),
(I) The average particle diameter measured on a number basis in the range of 0.4 to 12 μm in diameter by the Coulter counter method is 1 to 4 μm, and (ii) the proportion of particles having a particle diameter of 1 μm or more and less than 2 μm, the particle diameter is 2 μm. The proportion of particles having a particle size of less than 3 μm and the proportion of particles having a particle size of 3 μm or more are in the range of 20 to 40%, respectively, and (iii) acrylic resin-based fine particles containing substantially no particles having a particle size of 10 μm or more 0.1 to 5 parts by mass of (B),
A polycarbonate resin composition comprising 0.05 part by mass or more and less than 0.3 part by mass of an aryl group-containing polysilane compound (C).   The acrylic resin-based fine particles (B) are copolymer fine particles composed of 90 to 99% by mass of a non-crosslinkable acrylic monomer (B1) and 10 to 1% by mass of a crosslinkable monomer (B2). The polycarbonate resin composition described in 1.   The polycarbonate resin composition according to claim 1 or 2, wherein the acrylic resin-based fine particles (B) are polymethyl methacrylate-based fine particles. The polycarbonate according to any one of claims 1 to 3, wherein the aryl group-containing polysilane compound (C) has at least one structural unit among structural units represented by the following formulas (1) to (3). Resin composition.

[In the formulas (1) to (3), R ¹ , R ² and R ³ represent at least one selected from a monovalent hydrocarbon group, a hydrogen atom and a silyl group, and are the same in each repeating unit. May be different. However, R ¹ , R ² and R ³ contain at least one aryl group. x, y, z represents 0 or an integer, and satisfies x + y + z ≧ 2. a, b and c each represents 0 or 1; ]   The polycarbonate resin composition according to claim 1, wherein the aryl group is a phenyl group. The polycarbonate resin composition according to any one of claims 1 to 5, wherein the aryl group-containing polysilane compound (C) is a cyclic aryl group-containing silane represented by the following formula (4).

[In Formula (4), R ⁴ and R ⁵ represent at least one selected from a monovalent hydrocarbon group, a hydrogen atom, and a silyl group, and may be the same or different in each repeating unit. However, R ⁴ and R ⁵ contain at least one or more aryl groups. m represents 4-12. ] 7. The polycarbonate resin composition according to claim 6, wherein in the aryl group-containing polysilane of the formula (4), R ⁴ and R ⁵ are both phenyl groups, and d and e are both 0. The polycarbonate resin composition according to any one of claims 1 to 7, wherein the aryl group-containing polysilane compound (C) is decaphenylcyclopentasilane.
  The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin (A) contains 20% by mass or more of a polycarbonate resin having a structural viscosity index N of 1.2 or more.   Furthermore, 0.01-1 mass part of organic sulfonic acid metal salt (D) is contained with respect to 100 mass parts of polycarbonate resin (A), The polycarbonate resin in any one of Claims 1-9 characterized by the above-mentioned. Composition.   11. The polycarbonate resin composition according to claim 10, wherein the organic sulfonic acid metal salt (D) is an organic sulfonic acid alkali metal salt or an alkaline earth metal salt.   The polycarbonate resin composition according to claim 10 or 11, wherein the organic sulfonic acid metal salt (D) is a perfluoroalkanesulfonic acid alkali metal salt.   Furthermore, 0.001-1 mass part of fluororesin (E) is contained with respect to 100 mass parts of polycarbonate resin (A), The polycarbonate resin composition in any one of Claims 1-12 characterized by the above-mentioned.   Furthermore, 0.05-1 mass part of ultraviolet absorbers (F) are contained with respect to 100 mass parts of polycarbonate resin (A), The polycarbonate resin composition in any one of Claims 1-13 characterized by the above-mentioned.   The molded article obtained from the polycarbonate resin composition in any one of Claims 1-14.   The molded article according to claim 15, wherein the molded article is a lighting cover, a light diffusion plate, or a sheet.