JP2011063638A - Polycarbonate resin composition and molding comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition excellent in balance among all of total light transmittance, diffusivity, and dispersity and also excellent in flame retardancy, and a molding comprising the same. <P>SOLUTION: The polycarbonate resin composition contains: 0.01-5 pts.mass of polyalkylsilsesquioxane particles with an average particle diameter of 1-3 μm when measured by the Coulter Counter method within the diameter range of 0.4-12 μm and the highest peak and the second highest peak of the particle size distribution are both within the range of 1-3 μm; 0.005-1 pts.mass of a metal salt compound of an organic acid; and 0.025-0.45 pts.mass of a fluororesin based on 100 pts.mass of a polycarbonate resin. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin composition and a molded article comprising the same, and more specifically, a polycarbonate resin composition excellent in all balances of total light transmittance, diffusivity, and dispersity, and excellent in flame retardancy, and molded article comprising the same. Related to goods.

  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 reduced. As a light diffusing polycarbonate resin with improved such defects, a polycarbonate resin composition (for example, see Patent Document 1) containing acrylic resin particles such as polymethyl methacrylate has been proposed. Since the stability is low, there are problems such as gas during molding and the tendency to yellow when formed into a molded product.

It has also been proposed to add polyorganosiloxane (silicone) resin particles in place of the acrylic resin. For example, Patent Document 2 and Patent Document 3 propose a polycarbonate resin containing polyalkylsilsesquioxane particles. , The transmittance is reduced, the haze is improved, and a certain diffusion effect is exhibited.
However, the specs of diffusible polycarbonate resin compositions for optical applications that are required in recent years are becoming more and more strict, and the specifications and specs vary for each application, so simply adding such polyorganosiloxanes. However, not all the requirements in these various fields are satisfied.
There is a need for a polycarbonate resin composition that is excellent in all the balances of transmittance, diffusivity, and dispersity.

Japanese Patent Laid-Open No. 03-143950 Japanese Patent No. 3263895 Japanese Patent No. 4220829

  An object of the present invention is to provide a polycarbonate resin composition excellent in all the balances of total light transmittance, diffusivity, and dispersity, and excellent in flame retardancy, and a molded article comprising the same, in view of the above-mentioned problems of the prior art. It is to provide.

  As a result of intensive studies to achieve the above problems, the present inventors have various particle size distributions even if the average particle size of the polyalkylsilsesquioxane particles is the same. When a specific amount of a compound having a specific particle size distribution is blended in a polycarbonate resin and further combined with a specific amount of an organic acid metal salt compound and a fluororesin, the total balance of total light transmittance, diffusivity, and degree of dispersion is achieved. The present inventors have found that a polycarbonate resin composition excellent in heat resistance and flame retardancy can be obtained, and has completed the present invention.

  That is, according to 1st invention of this invention, with respect to 100 mass parts of polycarbonate resin (A), the average particle diameter at the time of measuring in the range of diameter 0.4-12 micrometers by the Coulter counter method is 1-3 micrometers. And 0.35 to 3 parts by mass of polyalkylsilsesquioxane particles (B) in which both the maximum peak and the second maximum peak of the particle size distribution are in the range of 1 to 3 μm, and an organic acid metal salt compound (C) A polycarbonate resin composition characterized by containing 0.005 to 1 part by mass and a fluororesin (D) 0.025 to 0.45 part by mass is provided.

  Further, according to the second invention of the present invention, in the first invention, the polyalkylsilsesquioxane particles (B) are in a number-based frequency (%) in the range of 0.4 to 12 μm in diameter by the Coulter counter method. ) Is measured, the number reference frequency (%) in the range of 0.5 to 1 μm is 0.1 to 8%, and a polycarbonate resin composition is provided.

  Moreover, according to the third invention of the present invention, in the first or second invention, the polyalkylsilsesquioxane particles (B) are in volume range of 0.4 to 12 μm in diameter by the Coulter counter method. A volume-based frequency (%) in the range of 4 to 11 μm when measuring the frequency (%) is 0.005 to 2.5%, and a polycarbonate resin composition is provided.

  According to a fourth invention of the present invention, in any one of the first to third inventions, the polyalkylsilsesquioxane particles (B) are polymethylsilsesquioxane. A resin composition is provided.

  According to a fifth aspect of the present invention, there is provided a polycarbonate resin composition according to the first aspect, wherein the organic acid metal salt compound (C) is an alkali metal salt of an organic sulfonic acid. The

  According to a sixth invention of the present invention, there is provided a polycarbonate resin composition according to the fifth invention, wherein the alkali metal salt of organic sulfonic acid is an alkali metal salt of fluorine-containing aliphatic sulfonic acid. Provided.

  According to a seventh aspect of the present invention, there is provided the polycarbonate resin composition according to the sixth aspect, wherein the alkali metal salt of the fluorinated aliphatic sulfonic acid is potassium perfluorobutane sulfonate. Is done.

  According to the eighth aspect of the present invention, in the first aspect, the ultraviolet absorber (E) is further contained in an amount of 0.001 to 1 part by mass with respect to 100 parts by mass of the polycarbonate resin (A). A featured polycarbonate resin composition is provided.

  According to the ninth aspect of the present invention, there is provided a molded product having an average thickness of 0.5 to 2 mm formed by molding the polycarbonate resin composition according to any one of the first to eighth aspects.

  Further, according to a tenth aspect of the present invention, in the ninth aspect, there is provided a molded product, 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 article comprising the polycarbonate resin composition, the polycarbonate resin composition having excellent total balance of light transmittance, diffusivity and dispersibility, and excellent flame retardancy, and molded article comprising the same Can be obtained.

It is a chart which shows the particle size distribution of the polyalkylsilsesquioxane particle | grains used in the Example of this invention.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples and the like, and is within the scope of the present invention. Any change can be made.

[1. Overview]
The polycarbonate resin composition of the present invention has an average particle diameter of 1 to 3 μm with respect to 100 parts by mass of the polycarbonate resin (A), and both the maximum peak and the second maximum peak of the particle size distribution are in the range of 1 to 3 μm. The polyalkylsilsesquioxane particles (B), the organic acid metal salt compound (C), and the fluororesin (D) are contained in specific amounts.

[2. Polycarbonate resin (A)]
There is no restriction | limiting in the kind of polycarbonate resin used for the polycarbonate resin composition of this invention. In addition, one type of polycarbonate resin may be used, or two or more types may be used in any combination and in any ratio.

The polycarbonate resin in the present invention is a polymer having a basic structure having a carbonic acid bond represented by the following general formula (1).

In formula (1), X ¹ is generally a hydrocarbon, but for imparting various properties, X ¹ into which a hetero atom or a hetero bond is introduced may be used.

  The polycarbonate resin can be classified into an aromatic polycarbonate resin in which carbon directly bonded to a carbonic acid bond is aromatic carbon and an aliphatic polycarbonate resin in which aliphatic carbon is aliphatic carbon, either of which can be used. Of these, aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.

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

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

Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;

Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl;

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

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

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl) 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-bis (4-hydroxyphenyl) ethane,
2-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1-bis (4-hydroxyphenyl) butane,
2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1-bis (4-hydroxyphenyl) octane,
2-bis (4-hydroxyphenyl) octane,
1-bis (4-hydroxyphenyl) hexane,
2-bis (4-hydroxyphenyl) hexane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
10-bis (4-hydroxyphenyl) decane,
1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1-bis (4-hydroxyphenyl) cyclopentane,
1-bis (4-hydroxyphenyl) cyclohexane,
4-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
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) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

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

Dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;

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

Dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone;

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

Examples of the monomer that is a raw material for the aliphatic polycarbonate resin include ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1, 3-diol, 2-methyl-2-propylpropane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol Alkanediols such as
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 2,2′-oxydiethanol (ie, ethylene glycol), diethylene glycol, triethylene glycol, propylene glycol, spiro glycol, etc .;

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of the molecular weight regulator include aromatic phenols having a monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like. Of these, aromatic phenols are preferred. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as 0-oxine benzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

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

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

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

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

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

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

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

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

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

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

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

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

-Other matters regarding the polycarbonate resin The molecular weight of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but the viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more, preferably 16000 or more, more preferably Is 18000 or more, and is usually 40000 or less, preferably 30000 or less. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, which is more preferable when used for applications requiring high mechanical strength. On the other hand, by setting the viscosity average molecular weight to be equal to or lower than the upper limit of the above range, the polycarbonate resin composition of the present invention can be suppressed and improved in fluidity, and the molding processability can be improved and the molding process can be easily performed. Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed.

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

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

  The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the polycarbonate resin. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

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

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

Further, the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated polycarbonate resin is preferably 80% by mass or less, 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. Polyalkylsilsesquioxane particles (B)]
The polycarbonate resin composition of the present invention comprises polyalkylsilsesquioxane particles (B) having an average particle size of 1 to 3 μm and a maximum peak and a second maximum peak of the particle size distribution in the range of 1 to 3 μm. ) In an amount of 0.35 to 3 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). By blending such polyalkylsilsesquioxane particles in such amounts, the excellent light diffusibility and light transmittance of the polycarbonate resin composition of the present invention can be achieved.

Polyorganosilsesquioxane refers to a polyorganosiloxane having a trifunctional siloxane unit represented by RSiO _1.5 (R is a monovalent organic group) (hereinafter sometimes referred to as “T unit”). This refers to 50 mol% or more of the total 100 mol% of all siloxane units. The proportion of T units is more preferably 80 mol% or more, still more preferably 90 mol% or more, particularly preferably 95 mol% or more, and most preferably 100 mol%.
The polyorganosilsesquioxane particles of the present invention are monofunctional siloxane units (hereinafter referred to as “M units”) represented by R ₃ SiO _0.5 (R is a monovalent organic group) in addition to the above T units. May be included). By containing the M unit as described above, the heat resistance of the polyorganosilsesquioxane particles themselves is improved, the hue of the polycarbonate resin composition of the present invention is improved, and the dispersibility in the polycarbonate resin is improved. The advantage is that a polycarbonate resin composition having improved and uniform optical performance is easily obtained.

  Examples of the organic group R bonded to the polyorganosilsesquioxane include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a dodecyl group, an octadecyl group, etc., a C1-C20 alkyl group, a cyclohexyl group Preferred examples include cyclic alkyl groups such as phenyl groups, tolyl groups, and aryl groups such as xylyl groups, and aralkyl groups such as phenylethyl groups and phenylpropyl groups. Among these, as polyorganosilsesquioxane, polyalkylsilsesquioxane has a large refractive index difference from polycarbonate resin, tends to improve the diffusion effect, and further tends to be excellent in heat resistance. Polymethylsilsesquioxane siloxane is particularly preferable.

  In the present invention, polyalkylsilsesquioxane particles having an average particle diameter of 1 to 3 μm and a maximum peak and a second maximum peak of the particle size distribution are both in the range of 1 to 3 μm. . When the average particle size is less than 1 μm, the light diffusibility of the obtained polycarbonate resin composition is not improved, but the luminance is lowered. If it exceeds 3 μm, the light diffusing effect is also lowered and the luminance is also lowered.

  In the present invention, the particle size and particle size distribution are measured 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 size measurement of polyalkylsilsesquioxane particles eliminates the influence of extremely small fine particles and extremely large maximal particles, and ensures reliable and highly reproducible data. Defined by measuring in the range of 4-12 μm.

The polyalkylsilsesquioxane particles used in the present invention have an average particle size of 1 to 3 μm. The particle size distribution must have two or more peaks, and the maximum peak and the second maximum peak need to be in the range of 1 to 3 μm in particle size. Even when the average particle size is 1 to 3 μm, the maximum peak (hereinafter sometimes referred to as “P ₁ ”) and the second maximum peak (hereinafter also referred to as “P ₂ ”) have a particle size. If it is not in the range of 1 to 3 μm, the light diffusivity and the degree of dispersion will deteriorate.

  The polyalkylsilsesquioxane particles preferably have a number-based frequency (%) in the range of 0.5 to 1 μm in the range of 0.1 to 8%, more preferably 0.5 to 5%. Preferably there is. Furthermore, the polyalkylsilsesquioxane particles preferably have a volume-based frequency (%) in the range of 4 to 11 μm in the range of 0.005 to 2.5%, and more preferably 0.05 to 2%. It is preferable. Thus, the light diffusion effect and the transmittance can be further improved by reducing the amount of particles having a particle diameter of 0.5 to 1 μm and by setting the particle diameter of 4 to 11 μm in such a range.

Furthermore, the proportion of the second maximum peak to the maximum peak _{(P 1) (P 2)} (P 2 / P 1), is preferably 0.2 to 0.95, in particular, 0.2 It is preferable that it is -0.8. By doing so, the diffusion effect and the transmittance can be further improved. When the peak ratio is less than 0.2, it is not preferable because the degree of dispersion, which is a particularly necessary characteristic for an illumination member, tends to decrease. Moreover, it exists in the tendency for a dispersity to raise further by setting it as 0.95 or less. Thus, by containing polyorganosiloxane particles containing two or more peaks at an appropriate ratio, the dispersibility in the polycarbonate resin is specifically increased, and the diffusion performance can be improved efficiently.

  Methods for producing the preferred polyalkylsilsesquioxanes as described above are known, and for example, as described in JP-A-01-217039, organotrialkoxysilane is hydrolyzed under acidic conditions. Then, an alkaline aqueous solution is added to and mixed with the water / alcohol solution of the organosilane triol, and the organosilane triol is polycondensed in a stationary state.

  The particle size can be adjusted mainly by adjusting the pH of the aqueous alkali solution. If small particles are to be obtained, the pH is increased, and if large particles are to be obtained, the pH is decreased to reduce the particle size. The condensation reaction is usually carried out in the range of 0.5 to 10 hours, preferably 0.5 to 5 hours after alkali addition, and the condensate is aged, but the stirring during the aging is weakened. By preventing the association of particles, the particle size and particle size distribution can be adjusted. Furthermore, the obtained polyalkylsilsesquioxane particles may be further pulverized to adjust the particle size. The polyalkylsilsesquioxane particles can also be obtained by specifying the specifications of the desired particle size and distribution to the manufacturer.

  The compounding amount of the polyalkylsilsesquioxane particles (B) is 0.35 to 3 parts by mass, preferably 0.35 to 2 parts by mass, and more preferably 0 to 100 parts by mass of the polycarbonate resin (A). .4 to 1.5 parts by mass. When the use ratio of the polyalkylsilsesquioxane particles is less than 0.35 parts by mass, the effect of improving the light diffusibility of the polycarbonate resin is not sufficiently obtained. When the use ratio exceeds 3 parts by mass, the polycarbonate is used. This leads to a significant decrease in the transmittance of the resin, and also causes poor appearance.

[4. Organic acid metal salt compound (C)]
The polycarbonate resin composition of the present invention contains 0.005 to 1 part by mass of the organic acid metal salt compound with respect to 100 parts by mass of the polycarbonate resin. Thus, the flame retardance of the polycarbonate resin composition of this invention can be improved by containing an organic acid metal salt compound.

  If the content of the organic acid metal salt compound is less than 0.005 parts by mass, the flame retardancy of the resulting polycarbonate resin composition will be insufficient, and conversely if it exceeds 1 part by mass, the thermal stability of the polycarbonate resin will be reduced. In addition, the appearance defect and the mechanical strength of the molded article of the polycarbonate resin composition are reduced. The lower limit of the content is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, particularly preferably 0.75 parts by mass or more, and the upper limit is preferably 0.75 parts by mass or less. Preferably it is 0.5 mass part or less, Most preferably, it is 0.3 mass part or less.

  As a kind of metal which an organic acid metal salt compound has, it is preferable that they are an alkali metal or an alkaline-earth metal. The polycarbonate resin composition of the present invention can promote the formation of a carbonized layer at the time of combustion, can further increase the flame retardancy, and the mechanical properties such as impact resistance of the polycarbonate resin, heat resistance, electrical characteristics, etc. This is because the properties can be maintained well. Accordingly, the metal salt compound is preferably at least one metal salt compound selected from the group consisting of alkali metal salts and alkaline earth metal salts, and more preferably alkali metal salts.

  Examples of the organic acid metal salt compound include organic sulfonic acid metal salts, organic sulfonamide metal salts, organic carboxylic acid metal salts, organic boric acid metal salts, and organic phosphoric acid metal salts. Among these, from the viewpoint of thermal stability when mixed with a polycarbonate resin, an organic sulfonic acid metal salt, an organic sulfonamide metal salt, and an organic phosphoric acid metal salt are preferable, and an organic sulfonic acid metal salt is particularly preferable.

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

  Preferred examples of the organic acid metal salt compound include a fluorine-containing aliphatic sulfonic acid or a metal salt of an aromatic sulfonic acid, and a metal salt of an aromatic sulfonamide. Specific examples of preferable ones include potassium perfluorobutane sulfonate, lithium perfluorobutane sulfonate, sodium perfluorobutane sulfonate, cesium perfluorobutane sulfonate, and the like. Alkali metal salt of fluorine-containing aliphatic sulfonic acid having a bond; magnesium perfluorobutanesulfonate, calcium perfluorobutanesulfonate, barium perfluorobutanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, trifluoromethanesulfone A fluorine-containing aliphatic sulfonic acid metal salt of a fluorine-containing aliphatic sulfonic acid having at least one C—F bond in the molecule, such as barium acid;

  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 An alkali metal salt of an aromatic sulfonic acid having at least one aromatic group in the molecule; magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, (branched Aromatic sulfonic acid metal salts such as :) alkaline earth metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule, such as magnesium dodecylbenzene sulfonate, calcium (branched) calcium dodecylbenzene sulfonate etc,

  Bis (trifluoromethane) sulfonylimide lithium, bis (trifluoromethane) sulfonylimide sodium, bis (trifluoromethane) sulfonylimide potassium, bis (nonafluorobutane) sulfonylimide lithium, bis (nonafluorobutane) sulfonylimide sodium, bis (nona Chain fluorine-containing fats such as potassium fluorobutane) sulfonylimide, potassium trifluoromethane (pentafluoroethane) sulfonylimide, sodium trifluoromethane (nonafluorobutane) sulfonylimide, potassium trifluoromethane (nonafluorobutane) sulfonylimide, trifluoromethane Alkali metal salts of aromatic sulfonamides; cyclo-hexafluoropropane-1,3-bis (sulfonyl) imidolithium, Alkaline metal salts of cyclic fluorinated aliphatic sulfonic imides such as sodium chloro-hexafluoropropane-1,3-bis (sulfonyl) imide, potassium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide; Of metal salt of fluorine-containing aliphatic sulfonic acid imide,

  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 sulfonic acid imides such as alkali metal salts of aromatic sulfonic acid imides having at least one aromatic group in the molecule, such as salts.

Among the above-described examples, alkali metal salts of fluorine-containing aliphatic sulfonic acids and alkali metal salts of aromatic sulfonic acids are more preferable, alkali metal salts of fluorine-containing aliphatic sulfonic acids are particularly preferable, and perfluoroalkanesulfonic acid. The alkali metal salt is more preferable, and specifically, potassium perfluorobutanesulfonate is preferable.
In addition, 1 type may be used for a metal salt compound, and it may use 2 or more types together by arbitrary combinations and a ratio.

[5. Fluoropolymer (D)]
The polycarbonate resin composition of the present invention contains 0.025 to 0.45 parts by mass of the fluororesin with respect to 100 parts by mass of the polycarbonate resin. 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 0.025 parts by mass, the effect of improving the flame retardancy by the fluororesin is insufficient, and if it exceeds 0.45 parts by mass, the appearance of the molded product obtained by molding the polycarbonate resin composition Defects, mechanical strength, and transmittance decrease occur. The lower limit of the content is preferably 0.05 parts by mass or more, more preferably 0.075 parts by mass or more, and the upper limit of the content is preferably 0.4 parts by mass or less, particularly preferably 0.3. It is below mass parts.

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, Ltd. "," Polyflon (registered trademark) FA500 "and the like. Furthermore, as a commercial item of the aqueous dispersion of fluoroolefin resin, for example, “Teflon (registered trademark) 30J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Fluon (registered trademark) D-1” manufactured by Daikin Chemical Industries, Ltd. and the like can be mentioned. .

  Furthermore, an organic polymer-coated fluoroolefin resin can also be suitably used. By using the organic polymer-coated fluoroolefin resin, dispersibility is improved, the surface appearance of the molded body is improved, and 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 body 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.

[6. UV absorber (E)]
It is preferable to mix | blend a ultraviolet absorber with the 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. “Chemisorb 71”, “Chemisorb 72” manufactured by Chemipro Kasei 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 preferable content of the ultraviolet absorber is 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and 1 part by mass or less, preferably 0.5 parts by mass with respect to 100 parts by mass of the polycarbonate resin. 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.

[7. 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, mold release agents, dyes and pigments, fluorescent whitening agents, anti-dripping agents, antistatic agents, antifogging agents, lubricants, antiblocking agents, and flow improvers. , Plasticizers, dispersants, antibacterial agents and the like.

-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.

[Production Method of Polycarbonate Resin Composition]
There is no limitation on the method for producing the polycarbonate resin composition of the present invention, and a known method for producing a polycarbonate resin composition can be widely adopted. The polycarbonate resin and the polyalkylsilsesquioxane particles, and other components blended as necessary. Are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then melt-kneaded with a mixer such as a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. A method is mentioned.

[Molding]
The polycarbonate resin composition of the present invention is usually molded into an arbitrary shape and used as a molded product (resin composition molded product). 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 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 signboards, 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 an organic EL.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

(Examples 1-10, Comparative Examples 1-6)
[Polycarbonate resin (A)]
The following two types (A1) and (A2) were used as the polycarbonate resin.
Polycarbonate resin (A1)
Product name Iupilon E-2000 manufactured by Mitsubishi Engineering Plastics
Viscosity average molecular weight: 26,000
Aromatic polycarbonate resin produced by interfacial polymerization using bisphenol as a starting material Polycarbonate resin (A2)
Product name NOVAREX M7027BFJ manufactured by Mitsubishi Engineering Plastics
Viscosity average molecular weight: 27,000
Aromatic polycarbonate resin produced by melt transesterification using bisphenol as a starting material

[Polyalkylsilsesquioxane particles (B)]
Polyalkylsilsesquioxane particles B1 to B4 shown in Table 1 below were prepared.

  In addition, the particle size and particle size distribution of the polyalkylsilsesquioxane particles are measured by a Coulter counter method, using a particle size distribution measuring device Multisizer 4 manufactured by Beckman Coaltar Co., Ltd., dispersion medium ISOTON II, aperture diameter 20 μm , Dispersant ethanol, ultrasonic wave for 3 minutes.

  A particle size distribution chart of the polyalkylsilsesquioxane particles B1 to B4 is shown in FIG. It can be seen that the B1 to B3 polyalkylsilsesquioxane particles have a maximum particle size distribution and a second maximum peak in the range of 1 to 3 μm.

[Organic acid metal salt compound (C), fluororesin (D), ultraviolet absorber (E) and other additive components (F1 to F2)]
As the organic acid metal salt compound (C), the fluororesin (D), the ultraviolet absorber (E) and other additive components (F1 to F2), those described in Table 2 below were used.

[Production of resin composition pellets]
Each of the above components (A) to (F), except that the ultraviolet absorber (component (E)) is premixed with a polycarbonate resin (component (A)) in advance using a Henschel mixer and used as a 2% by mass masterbatch. Then, after blending in the proportions (mass%) described in Table 4 and Table 5 below and mixing with a tumbler for 20 minutes, it is supplied to a Nippon Steel Works twin screw extruder (TEX30HSST) equipped with 1 vent. Kneaded under the conditions of a screw rotation speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 290 ° C., the molten resin extruded into a strand is quenched in a water tank, pelletized using a pelletizer, and pellets of a polycarbonate resin composition are obtained. Obtained.

[Preparation of test piece]
After the pellets obtained by the above-described production method were dried at 120 ° C. for 5 hours, a cylinder temperature of 290 ° C., a mold temperature of 80 ° C., a molding cycle of 30 using a J50-EP type injection molding machine manufactured by Nippon Steel. Injection molding was performed under the conditions of seconds, and a flat test piece (90 mm × 50 mm × 1-2-3 mm thickness) and a UL test piece (length 125 mm × width 13 mm × thickness 1.2 mm) were formed.

Using these test pieces, total light transmittance, diffusion characteristics, and flame retardancy were evaluated.
Each evaluation method is as follows.

[Total light transmittance]
In accordance with JIS K-7105, the above flat plate test piece (1-2-3 mm three-stage thickness) was used as a test piece, and an NDH-2000 turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd. was used. The total light transmittance (unit “%”) of the thickness was measured. In Tables 4 and 5, it is expressed as “transmittance”.

[Diffusion characteristics]
The above-described flat test piece (1-2-3 mm thickness) is used as a test piece, and MURAKAMI
Using GP-5 GONIOPHOTOMETER made by COLOR RESEARCH LABORATORY, incident light: 0 °, tilt angle: 0 °, light receiving range: 0 ° to 90 °, luminous flux stop: 2.0, light receiving stop: 3.0 The luminance of 1 mm thickness and 2 mm thickness was measured, and the diffusivity (%) was determined by the following formula. In Table 4, it is expressed as “diffusion rate”.
Diffusivity% = {(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.
In Tables 4 and 5, it is expressed as “dispersion degree”.

[Flame retardance evaluation]
The flame resistance of each polycarbonate resin composition was evaluated by conditioning the test specimen for UL test obtained by the above method for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity. The test was conducted in accordance with UL94 test (combustion test of plastic materials for equipment parts) defined by Laboratories (UL). UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 3 below.

Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied.
The evaluation results are shown in Table 4 and Table 5.

  The difference in light diffusing performance is particularly noticeable in the case of a 1 mm-thick test piece. From Examples 1 to 10 shown in Table 4, the polyalkylsilsesquiries satisfying the particle size and particle size distribution of the present invention are shown. It can be seen that the polycarbonate resin composition containing a predetermined amount of the oxan particles (B1 to B3) is excellent in total light transmittance, diffusivity, and dispersity, and excellent in flame retardancy.

On the other hand, Comparative Example 5 in which the polyalkylsilsesquioxane particles (B4) not satisfying the particle size and particle size distribution of the present invention, and Comparative Examples 1 to 4 in which the compounding amount does not satisfy the scope of the present invention, It turns out that a total light transmittance, a diffusivity, and a dispersion degree are inferior. Moreover, in the comparative example which does not contain a fluororesin, it turns out that flame retardance is bad with V-2.
Therefore, it was confirmed from the above-mentioned Examples and Comparative Examples that the effects of being excellent in total light transmittance, diffusivity, dispersity, and excellent flame retardancy can be obtained only by the configuration of the present invention.

  According to the polycarbonate resin composition of the present invention, a polycarbonate resin molding material having an excellent balance of all light transmittance, diffusivity, and dispersity, and excellent flame retardancy can be obtained. It can be used in a wide range of fields such as signboards, transmissive screens, various displays, light diffusion sheets and light diffusion plates for liquid crystal display devices, and has very high industrial utility.

Claims (10)

  With respect to 100 parts by mass of the polycarbonate resin (A), the average particle size when measured in the range of 0.4 to 12 μm in diameter by the Coulter counter method is 1 to 3 μm, and the second largest peak in the particle size distribution 0.35 to 3 parts by mass of polyalkylsilsesquioxane particles (B) each having a maximum peak of 1 to 3 μm, 0.005 to 1 part by mass of an organic acid metal salt compound (C), and a fluororesin (D) A polycarbonate resin composition containing 0.025 to 0.45 parts by mass.   When the polyalkylsilsesquioxane particles (B) were measured for the number-based frequency (%) in the range of 0.4 to 12 μm in diameter by the Coulter counter method, the number-based frequency in the range of 0.5 to 1 μm ( %) Is 0.1 to 8%, the polycarbonate resin composition according to claim 1.   Volume reference frequency (%) in the range of 4 to 11 μm when the polyalkylsilsesquioxane particles (B) were measured for volume reference frequency (%) in the range of 0.4 to 12 μm in diameter by the Coulter counter method. Is 0.005 to 2.5%, the polycarbonate resin composition according to claim 1 or 2.   The polycarbonate resin composition according to claim 1, wherein the polyalkylsilsesquioxane particles (B) are polymethylsilsesquioxane.   The polycarbonate resin composition according to claim 1, wherein the organic acid metal salt compound (C) is an alkali metal salt of an organic sulfonic acid.   6. The polycarbonate resin composition according to claim 5, wherein the alkali metal salt of organic sulfonic acid is an alkali metal salt of fluorine-containing aliphatic sulfonic acid.   The polycarbonate resin composition according to claim 6, wherein the alkali metal salt of the fluorinated aliphatic sulfonic acid is potassium perfluorobutane sulfonate.   Furthermore, 0.001-1 mass part of ultraviolet absorbers (E) are contained with respect to 100 mass parts of polycarbonate resin (A), The polycarbonate resin composition of Claim 1 characterized by the above-mentioned.   A molded product having an average thickness of 0.5 to 2 mm formed by molding the polycarbonate resin composition according to any one of claims 1 to 8.   The molded article according to claim 9, wherein the molded article is a lighting cover, a light diffusion plate, or a sheet.

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