JP6087745B2 - Polycarbonate resin composition and molded product - Google Patents

Description

  The present invention relates to a polycarbonate resin composition and a molded article, and more specifically, a polycarbonate resin composition excellent in flame retardancy, impact resistance, heat resistance, hue, light-shielding property, and also excellent in heat discoloration resistance and the same. It relates to molded products.

  Polycarbonate resin is a resin excellent in heat resistance, mechanical properties, and electrical characteristics, and is widely used in, for example, automotive materials, electrical / electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. . In particular, the flame-retardant polycarbonate resin composition is suitably used as a member for electric / electronic devices such as computers, notebook computers, various portable terminals, printers, copying machines, and OA / information devices.

  Among these, polycarbonate resin compositions flame-retarded with a phosphate ester flame retardant are widely used because of excellent moldability due to the plasticizing effect of the phosphate ester compound.

  However, the polycarbonate resin composition containing the phosphoric acid ester compound has a drawback that impact resistance and heat resistance are remarkably lowered. Moreover, since the wet heat stability is poor and heat-resistant discoloration is likely to occur, it cannot be used for a member having a light source such as a lighting device, an electric display device, or a projector, to which relatively high heat is applied.

  On the other hand, the method of making it flame-retardant using an aromatic phosphazene compound is proposed (for example, refer patent documents 1-3). However, in such a polycarbonate resin composition, the flame retardance level that can be obtained in the UL94 standard is V-0 at a thickness of 1.5 to 2.5 mm, which is not a sufficiently satisfactory level.

  In Patent Document 4, a specific siloxane flame retardant, an aromatic phosphazene compound, a sulfonic acid metal salt, and polytetrafluoroethylene are blended as a flame retardant with respect to a polycarbonate resin, and titanium oxide and a siloxane surface treatment agent are further added. Formulated compositions have been proposed. However, the composition as described above has a fatal defect that the flame retardancy level is improved because the flame retardant is highly blended, but the hue and heat discoloration are inferior.

  In this way, the balance of flame retardancy, impact resistance, heat resistance, hue, light shielding properties, and heat discoloration, which is particularly suitable for members for electronic devices to which high heat is applied, such as lighting devices, electric display devices, projectors, etc. A satisfactory polycarbonate resin composition has not yet been obtained, and such a polycarbonate resin composition has been strongly desired.

JP 2011-178873 A JP 2012-1580 A JP2013-1801A JP 2004-67881 A

  The present invention was devised in view of the above-mentioned problems of the prior art, and is a polycarbonate resin composition excellent in flame retardancy, impact resistance, heat resistance, hue, light shielding properties, and heat discoloration resistance, and molding thereof. The purpose is to provide goods.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have determined that the polycarbonate resin has a specific amount of a cyclic aromatic phosphazene compound composed of two specific phosphazene compounds, a fluoropolymer, and titanium oxide. Surprisingly, the polycarbonate resin composition contains high flame retardancy despite the extremely low content of flame retardant, and furthermore, impact resistance, heat resistance, hue, light shielding And the present invention has been completed.
The present invention provides the following polycarbonate resin composition, polycarbonate resin molded article, and polycarbonate resin sheet or film.

[1] For 100 parts by mass of the polycarbonate resin (A), hexaphenoxytricyclophosphazene (B1) represented by the following formula (1) and octaphenoxytetracyclophosphazene (B2) represented by the following formula (2) In the mass ratio of 75/25 to 95/5, 1.3 to 8 parts by mass of the cyclic aromatic phosphazene compound (B), 0.01 to 2 parts by mass of the fluoropolymer (C) and 0. A polycarbonate resin composition comprising 5 to 30 parts by mass.

[2] The polycarbonate resin composition as described in [1] above, wherein the value of deflection temperature under load measured in accordance with ISO 75-1 under a condition of 1.8 MPa is 105 ° C. or higher.
[3] A polycarbonate resin molded article obtained by molding the polycarbonate resin composition according to [1] or [2].
[4] The polycarbonate resin molded product according to [3], which is a lighting fixture member.
[5] The polycarbonate resin molded article according to the above [3], which is an electro-optical display housing.
[6] The polycarbonate resin molded product according to [3], which is a projector housing.
[7] A polycarbonate resin sheet or film obtained by molding the polycarbonate resin composition according to [1] or [2].

  The polycarbonate resin composition of the present invention can exhibit high flame retardancy despite the extremely low content of the flame retardant, and also has impact resistance, heat resistance, hue, light shielding properties, and heat discoloration. Excellent in properties.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. You can change it to

[Overview]
The polycarbonate resin composition of the present invention comprises hexaphenoxytricyclophosphazene (B1) represented by the above formula (1) and octaphenoxy represented by the above formula (2) with respect to 100 parts by mass of the polycarbonate resin (A). 1.3-8 parts by mass of cyclic aromatic phosphazene compound (B) containing tetracyclophosphazene (B2) at a mass ratio of 75 / 25-95 / 5, 0.01-2 parts by mass of fluoropolymer (C) and oxidation It contains 0.5 to 30 parts by mass of titanium (D).

[Polycarbonate resin (A)]
There is no restriction | limiting in the kind of polycarbonate resin used for the polycarbonate resin composition of this invention, A polycarbonate resin may use 1 type and may use 2 or more types together by arbitrary combinations and arbitrary ratios.

The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the following general formula.
In the formula, X ¹ is generally a hydrocarbon, but X ¹ into which a hetero atom or a hetero bond is introduced may be used for imparting various properties.

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

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

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

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

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

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

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

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

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

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

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

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

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

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are 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.

In addition, when an example of a monomer that is a raw material of the aliphatic polycarbonate resin is given,
Ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3- Alkanediols such as diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol;

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin 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 like, the melt polycondensation reaction is preferably carried out continuously.

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

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

-Other matters 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 17000 or more, and is usually 40000 or less, preferably 30000 or less, more preferably 24000 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 resin composition 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 less than the upper limit of the above range, it is possible to suppress and improve the fluidity of the resin composition, and to improve the molding processability and easily perform the molding process.
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.

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

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

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

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

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

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

[Cyclic aromatic phosphazene compound (B)]
The cyclic aromatic phosphazene compound used in the present invention comprises a phosphazene compound (B1) represented by the following formula (1) and a phosphazene compound (B2) represented by the following formula (2): B1 / B2 = 75/25 It contains by the mass ratio of 95/5.

  This phosphazene compound (B1) has a high heat resistance and an excellent flame retardant effect in terms of good compatibility with the polycarbonate resin, but has a drawback that the hue of the molded product tends to deteriorate. On the other hand, when the phosphazene compound (B2) having a melting point slightly lower than that of the phosphazene compound (B1) is contained at a mass ratio of B1 / B2 = 75/25 to 95/5, the hue of the molded product is deteriorated. It has been found that the problem of heat discoloration can be solved, and by containing this together with titanium oxide (D), surprisingly, flame retardancy is further improved, and heat resistance and impact resistance are improved. It has been found that the property and the light shielding property are improved.

  Therefore, the cyclic aromatic phosphazene (B) needs to contain the phosphazene compound (B1) and the phosphazene compound (B2) in a mass ratio of B1 / B2 of 75/25 to 95/5. Preferably, B1 / B2 = 77/23 to 95/5, and more preferably 80/20 to 93/7.

  Content of cyclic aromatic phosphazene (B) is 1.3-8 mass parts with respect to 100 mass parts of polycarbonate resin (A), Preferably it is 1.4 mass parts or more, More preferably, it is 1.5 mass. Part or more, and preferably 7 parts by weight or less.

[Fluoropolymer (C)]
The polycarbonate resin composition of the present invention contains 0.01 to 2 parts by mass of the fluoropolymer (C) with respect to 100 parts by mass of the polycarbonate resin (A). Thus, the flame retardance of a polycarbonate resin composition can be effectively improved by containing a fluoropolymer (C).
One type of fluoropolymer (C) may be used, or two or more types may be used in any combination and in any ratio.

  Examples of the fluoropolymer (C) include a fluoroolefin resin. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure. Specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. Examples of the fluoroethylene resin include a fluoroethylene resin having a fibril forming ability.

Examples of the fluoroethylene resin having fibril forming ability include “Teflon (registered trademark) 6J”, “Teflon (registered trademark) 640J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Polyflon F201L”, “Polyflon F103” manufactured by Daikin Industries ”,“ Polyflon FA500B ”,“ Polyflon FA500H ”and the like. Further, examples of commercially available aqueous dispersions of fluoroethylene resin include “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and “Fluon D-1” manufactured by Daikin Industries, Ltd.
Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such a fluoroethylene polymer include polystyrene-fluoroethylene composites, polystyrene-acrylonitrile-fluoroethylene. Examples include composites, polymethyl methacrylate-fluoroethylene composites, polybutyl methacrylate-fluoroethylene composites, etc. Specific examples include “Metablene A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex” manufactured by GE Specialty Chemical Co., Ltd. 449 "and the like.
In addition, a fluoropolymer may mix | blend 1 type and may mix | blend 2 or more types by arbitrary combinations and a ratio.

  The content of the fluoropolymer (C) is 0.01 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A), preferably 0.02 parts by mass or more, more preferably 0.03 parts by mass or more. And 2 parts by mass or less, preferably 1 part by mass or less, more preferably 0.75 parts by mass or less, and particularly preferably 0.5 parts by mass or less.

[Titanium oxide (D)]
The polycarbonate resin composition of the present invention contains 0.5 to 30 parts by mass of titanium oxide (D) with respect to 100 parts by mass of the polycarbonate resin (A). By containing titanium oxide (D) in combination with the cyclic aromatic phosphazene compound (B) and the fluoropolymer (C) in this way, surprisingly, the flame retardancy is further improved, and the heat resistance and resistance. It is possible to effectively enhance the flame retardancy that improves the impact and light shielding properties.

  The production method, crystal form and average particle size of titanium oxide are not particularly limited. There are sulfuric acid method and chlorine method in the production method of titanium oxide, but titanium oxide produced by sulfuric acid method tends to be inferior in whiteness of the composition to which this is added. Is preferred.

  The crystal form of titanium oxide includes a rutile type and an anatase type, but a rutile type crystal form is preferred from the viewpoint of light resistance. The average particle size of the titanium oxide-based additive is usually 0.1 to 0.7 μm, preferably 0.1 to 0.4 μm. When the average particle diameter is less than 0.1 μm, the light shielding property of the molded product is poor, and when it exceeds 0.7 μm, the surface of the molded product is roughened or the mechanical strength of the molded product is lowered. In the present invention, two or more types of titanium oxides having different average particle diameters may be mixed and used.

  The titanium oxide is preferably surface-treated with an organosiloxane-based surface treatment agent as described later, but before that, it is preferably pretreated with an alumina-based surface treatment agent. Alumina hydrate is preferably used as the alumina-based surface treatment agent. Furthermore, it may be pretreated with silicic acid hydrate together with alumina hydrate. The pretreatment method is not particularly limited, and any method can be used. The pretreatment with alumina hydrate and, if necessary, silicic acid hydrate is preferably carried out in the range of 1 to 15% by weight with respect to titanium oxide.

  Titanium oxide with alumina hydrate, pretreated with silicic acid hydrate if necessary, further improves the thermal stability by surface-treating the surface with an organosiloxane surface treatment agent. In addition, the uniform dispersibility in the polycarbonate resin composition and the stability of the dispersed state are improved, which is preferable. As the organosiloxane-based surface treatment agent, a polyorganohydrogensiloxane compound is preferable.

  Surface treatment methods using an organosiloxane-based surface treatment agent of titanium oxide include a wet method and a dry method. In the wet method, a mixture of an organosiloxane-based surface treatment agent and a solvent is added with alumina hydrate, and if necessary, titanium oxide pretreated with silicic acid hydrate. Further, the heat treatment is performed at 100 to 300 ° C. thereafter. In the dry method, pretreated titanium oxide and polyorganohydrogensiloxane are mixed with a Henschel mixer in the same manner as described above, and an organic solution of polyorganohydrogensiloxane is sprayed on the pretreated titanium oxide. And a method of heat-treating at 100 to 300 ° C. The amount of the siloxane-based surface treatment agent is not particularly limited, but in consideration of the reflectivity of titanium oxide, the moldability of the resin composition, etc., usually in the range of 1 to 5% by weight with respect to titanium oxide. is there.

  Content of a titanium oxide (D) is the range of 0.5-30 mass parts with respect to 100 mass parts of polycarbonate resin (A). When the content of titanium oxide is less than 0.5 parts by mass, the effect of improving flame retardancy, heat resistance, impact resistance and light shielding properties is insufficient, and when it exceeds 30 parts by mass, the impact resistance of the resin composition The property becomes insufficient. The preferable content of titanium oxide is 1 part by mass or more, particularly preferably 2 parts by mass or more, preferably 28 parts by mass or less, more preferably 25 parts by mass or less, with respect to 100 parts by mass of the polycarbonate resin. In addition, the mass of a titanium oxide type additive means the total mass also including these processing agents, when the surface treatment is carried out with an alumina hydrate, silicic acid hydrate, and an organosiloxane type surface treating agent.

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

Other resins Examples of the other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin;
Styrenic resin such as polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin); polyolefin resin such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; Polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; polymethacrylate resin; various elastomers.
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and a ratio.

-Resin additives Examples of resin additives include stabilizers, antioxidants, mold release agents, lubricants, fillers, other flame retardants, flame retardant aids, ultraviolet absorbers, dyes and pigments, antistatic agents, Antifogging agents, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like can be mentioned. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.

.. Phosphorus stabilizer The polycarbonate resin composition of the present invention preferably contains a phosphorus stabilizer as necessary. Any known phosphorous stabilizer 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 Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Particularly preferred.

Organic phosphite compounds include 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) octyl phosphite and the like.
Specific examples of such organic phosphite compounds include, for example, “ADEKA STAB 1178”, “ADEKA STAB 2112”, “ADEKA STAB HP-10” manufactured by ADEKA, “JP-351” manufactured by Johoku Chemical Industry Co., Ltd., “ JP-360 ”,“ JP-3CP ”,“ Irgaphos 168 ”manufactured by BASF, and the like.
In addition, 1 type may contain phosphorus stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the phosphorus stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, with respect to 100 parts by mass of the polycarbonate resin (A). Moreover, it is 1 mass part or less normally, Preferably it is 0.7 mass part or less, More preferably, it is 0.5 mass part or less. If the content of the phosphorus stabilizer is less than the lower limit of the range, the thermal stability effect may be insufficient, and if the content of the phosphorus stabilizer exceeds the upper limit of the range, the effect May stop and become economical.

..Phenolic stabilizer The polycarbonate resin composition of the present invention preferably contains a phenolic stabilizer. As a phenol type stabilizer, a hindered phenol type 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 ″-(me Citylene-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, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-t rt- pentylphenyl acrylate.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such a phenolic antioxidant include “Irganox 1010”, “Irganox 1076” manufactured by BASF, “Adekastab AO-50”, “Adekastab AO-60” manufactured by ADEKA, and the like. Is mentioned.
In addition, 1 type may contain the phenol type stabilizer, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the phenol-based stabilizer 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 100 parts by mass of the polycarbonate resin (A). 0.5 parts by mass or less. When the content of the phenol-based stabilizer is less than the lower limit of the range, the effect as the phenol-based stabilizer may be insufficient, and the content of the phenol-based stabilizer exceeds the upper limit of the range. If this is the case, the effect may reach its peak and not economical.

..Lubricant It is also preferable to contain a lubricant if necessary. Examples of the lubricant 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.

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

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

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

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine to form one ester may be used alone or in combination of two or more in any combination and ratio.

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

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 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. Further, these hydrocarbons may be partially oxidized.

Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

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

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

  The content of the lubricant 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 with respect to 100 parts by mass of the polycarbonate resin (A). It is as follows. When the content of the lubricant is less than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the lubricant exceeds the upper limit of the above range, degradation of hydrolysis resistance, injection There is a possibility of mold contamination during molding.

..Ultraviolet absorbers Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, Examples include organic ultraviolet absorbers such as hindered amine compounds. In these, an organic ultraviolet absorber is preferable and a benzotriazole compound is more preferable. 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], among others, 2- (2′-hydroxy-5′-tert-octylphenyl) ) Benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], particularly 2- (2 ′ -Hydroxy-5'-tert-octylphenyl) benzotriazole is preferred.
Specific examples of such a benzotriazole compound include “Seesorb 701”, “Seesorb 705”, “Seesorb 703”, “Seesorb 702”, “Seesorb 704”, and “Seesorb 709” manufactured by Sipro Kasei Co., Ltd. “Biosorb 520”, “Biosorb 582”, “Biosorb 580”, “Biosorb 583” manufactured by Yakuhin Kagaku Co., Ltd. “Chemisorb 71”, “Chemisorb 72” manufactured by Chemipro Kasei Co., Ltd. “Siasorb UV5411” manufactured by Cytec Industries, “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, “TINUVIN P”, “TINUVIN 234”, “TINUVIN 326”, “TINUVIN 327” manufactured by BASF ”,“ Tinuvin 328 ”and the like.

  Specific examples of the benzophenone compound include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxy Benzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4 4,4′-dimethoxybenzophenone and the like. Specific examples of such a benzophenone compound include “Seesorb 100”, “Seesorb 101”, “Seesorb 101S”, “Seesorb 102”, and “Seesorb 102” manufactured by Cypro Kasei Co., Ltd. Seesorb 103 ", joint medicine “Biosorb 100”, “Biosorb 110”, “Biosorb 130”, manufactured by Kemipro Kasei Co., Ltd. “Chemisorb 10”, “Chemisorb 11”, “Chemisorb 11S”, “Chemisorb 12”, “Chemsorb 13”, “Chemisorb 111” BASF “Ubinur 400”, BASF “Ubinur M-40”, BASF “Ubinur MS-40”, Cytec Industries “Thiasorb UV9”, “Thiasorb UV284”, “Thiasorb UV531”, “Thiasorb” UV24 "," ADEKA STAB 1413 "manufactured by ADEKA," ADEKA STAB LA-51 "and the like.

  Specific examples of the salicylate compound include phenyl salicylate and 4-tert-butylphenyl salicylate. Specific examples of such a salicylate compound include, for example, “Seesorb 201” and “Seesorb” manufactured by Sipro Kasei Co., Ltd. 202 ”,“ Kemisorb 21 ”,“ Kemisorb 22 ”manufactured by Chemipro Kasei Co., Ltd., and the like.

  Specific examples of the cyanoacrylate compound include, for example, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like. Specifically, for example, “Seasorb 501” manufactured by Sipro Kasei Co., Ltd., “Biosorb 910” manufactured by Kyodo Pharmaceutical Co., Ltd., “Ubisolator 300” manufactured by Daiichi Kasei Co., Ltd., “Ubinur N-35” manufactured by BASF, 539 "and the like.

  Examples of the triazine compound include a compound having a 1,3,5-triazine skeleton. Specific examples of such a triazine compound include, for example, “LA-46” manufactured by ADEKA, “Tinuvin” manufactured by BASF. 1577ED "," Tinuvin 400 "," Tinuvin 405 "," Tinuvin 460 "," Tinuvin 477-DW "," Tinuvin 479 "and the like.

  Specific examples of the oxanilide compound include, for example, 2-ethoxy-2′-ethyl oxalinic acid bis-arinide and the like. Specific examples of such an oxalinide compound include “Sanduboa” manufactured by Clariant Corporation. VSU "etc. are mentioned.

  As the malonic acid ester compound, 2- (alkylidene) malonic acid esters are preferable, and 2- (1-arylalkylidene) malonic acid esters are more preferable. Specific examples of such a malonic ester compound include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by BASF, and the like.

  The content of the ultraviolet absorber is usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and usually 3 parts by mass or less, preferably 1 with respect to 100 parts by mass of the polycarbonate resin (A). It is below mass parts. If the content of the ultraviolet absorber is less than the lower limit of the range, the effect of improving the weather resistance may be insufficient, and if the content of the ultraviolet absorber exceeds the upper limit of the 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.

-Dye / pigment Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.
Examples of inorganic pigments include sulfide pigments such as cadmium red and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc-iron brown , Titanium Cobalt Green, Cobalt Green, Cobalt Blue, Oxide Pigment such as Copper-Chromium Black, Copper-Iron Black, Chromic Acid Pigment such as Yellow Lead and Molybdate Orange; Ferrocyan Pigment such as Bitumen Etc.

  Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; anthraquinone, heterocyclic and methyl dyes.

Of these, titanium oxide, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.
In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the dye / pigment is usually 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 2 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A). If the content of the dye / pigment is too large, the impact resistance may not be sufficient.

[Production of polycarbonate resin composition]
There is no restriction | limiting in particular in the method of manufacturing the polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely.
Specific examples include polycarbonate resin (A), cyclic aromatic phosphazene compound (B), fluoropolymer (C) and titanium oxide (D), and other components blended as necessary, such as a tumbler, Examples thereof include a method of mixing in advance using various mixers such as a Henschel mixer and then melt-kneading with a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader.

  Moreover, for example, it is also possible to manufacture by mixing each component in advance or by mixing only a part of the components in advance and supplying the mixture to an extruder using a feeder and melt-kneading. Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, this master batch is again mixed with the remaining components and melt-kneaded. A polycarbonate resin composition can also be produced.

  The polycarbonate resin composition of the present invention has a deflection temperature under load (measured under conditions of 1.8 MPa in accordance with ISO 75-1), preferably a value of 105 ° C. or higher, and is excellent in heat resistance.

[Molding method]
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.

[Molding]
A molded product obtained by molding the polycarbonate resin composition of the present invention is excellent in flame retardancy, impact resistance, heat resistance, hue, light-shielding property, and also in heat-resistant discoloration. It is suitably used for parts and members of various devices and instruments.
Examples include covers, lampshades, bathroom lights, chandeliers, stands, brackets, lamps, ceiling lights, pendant lights, garage lights, eaves under lighting fixtures using LEDs, fluorescent lamps, incandescent bulbs, or organic EL. Members for various lighting fixtures such as lights, gatepost lights, pouch lights, garden lights, entrance lights, foot lights, stair lights, guide lights, security lights, downlights, base lights, vehicle lamp covers;
Lightning of flat panel display devices represented by LCD, personal computers, office automation equipment, televisions, interior lighting display panels, neon signs, LED light guides, advertising display signs, road signs, illuminated game consoles, etc. A housing for a display device;
Preferred examples include a housing such as a projector (including a liquid crystal projector).
Further, the film or sheet can be suitably used for applications such as light reflection and light diffusion.

  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. In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.

(Examples 1-5 , 8-11 , Reference Examples 6-7 , Comparative Examples 1-7)
Each component used in Examples and Comparative Examples is as shown in Table 1 below.

[Manufacture of resin pellets]
Each component described in Table 1 above was blended in the proportions (mass ratio) described in Tables 3 to 5, mixed for 20 minutes with a tumbler, and then an injection molding machine (TEX30HSST manufactured by Nippon Steel Works Co., Ltd.) equipped with 1 vent. ), Kneaded under the conditions of a screw rotation speed of 250 rpm, a discharge rate of 25 kg / hour, and a barrel temperature of 280 ° C., the molten resin extruded into a strand is rapidly cooled in a water tank, pelletized using a pelletizer, and polycarbonate resin A pellet of the composition was obtained.

[Preparation of test piece]
After the pellets obtained by the above production method were dried at 100 ° C. for 5 hours, the cylinder temperature was 270 ° C., the mold temperature was 80 ° C., and the molding cycle was 30 seconds using a J55 type injection molding machine manufactured by Nippon Steel. Injection molding was performed under the conditions, and a test piece for UL test having a length of 125 mm, a width of 13 mm, and a thickness of 1.0 mm was injection molded.
Moreover, after drying the pellet obtained by said manufacturing method at 100 degreeC for 5 hours, using a Sumitomo Heavy Industries, Ltd. injection molding machine (Cycap M-2, clamping force 75T), cylinder temperature 280 An ISO multipurpose test piece (3 mm thickness, 4 mm thickness) was injection molded under the conditions of ℃ and mold temperature of 80 ℃.
Moreover, after drying the pellet obtained by said manufacturing method at 100 degreeC for 5 hours, using the J55 type | mold injection molding machine by Nippon Steel Works, on the conditions of cylinder temperature 280 degreeC and mold temperature 80 degreeC. A two-stage plate having both a thickness of 3 mm and a thickness of 2 mm was injection molded.

[Evaluation of flame retardancy: UL flame retardancy (1 mm thickness)]
The flame retardant evaluation of each polycarbonate resin composition was performed by conditioning the test piece for UL test (1.0 mm thickness) obtained by the above method for 48 hours in a thermostatic chamber at a temperature of 23 ° C. and a humidity of 50%. The test was conducted in accordance with the UL94 test (combustion test of plastic materials for equipment parts) established by the US Underwriters 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 2 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.

[Evaluation of impact resistance: Notched Charpy impact strength]
For the impact resistance evaluation, the ISO multipurpose test piece (3 mm thickness) obtained by the above method was used, and in accordance with ISO179, a V notch of R = 0.25 was inserted, and a notched Charpy resistance was obtained at 23 ° C. Impact strength (unit: kJ / m ² ) was measured.

[Evaluation of heat resistance: deflection temperature under load]
For heat resistance evaluation, using the ISO multi-purpose test piece (4 mm thickness) obtained by the above-mentioned method, the deflection temperature under load (DTUL, unit: ° C) is measured under the condition of load 1.8 MPa in accordance with ISO 75-1. did.

[Hue Evaluation: Initial Hue]
For the hue evaluation, a spectral color difference meter SE6000 manufactured by Nippon Denshoku Industries Co., Ltd. was used, the light source was set as C light source, the field of view was set at 2 °, and YI ( Yellow Index) was measured. It means that the smaller the YI, the better the hue.

[Total light transmittance]
Using a Nippon Denshoku Industries Co., Ltd. haze meter NDH4000, the total light transmittance of a 2 mm thick part of the two-stage plate was measured according to JIS K7361-1. The smaller the total light transmittance, the better the light shielding property.

[Heat-resistant discoloration evaluation]
The two-stage plate obtained by the above method is aged in an oven at 115 ° C. for 500 hours, the YI at the center of the 3 mm thick part of the two-stage plate before and after aging is measured by the above method, and the aging is performed from the YI after aging. A value obtained by subtracting the previous YI was divided by the YI before aging, and a value obtained by multiplying the value by 100 was defined as heat discoloration (unit:%). The smaller the heat discoloration, the better the heat discoloration.
The above evaluation results are shown in Tables 3 to 5 below.

From the above Tables 3 and 4, the cyclic aromatic phosphazene compound (B) containing the phosphazene compound (B1) and the phosphazene compound (B2) within the range specified in the present invention, the fluoropolymer (C) and the titanium oxide (D) It can be seen that the polycarbonate resin composition of the present invention each containing a predetermined amount is excellent in flame retardancy, impact resistance, heat resistance, hue and light-shielding properties, and is also excellent in heat discoloration.
On the other hand, Table 5 reveals the following. In Comparative Example 1, since the content of the cyclic aromatic phosphazene compound (B) is small, the flame retardancy is poor, and in Comparative Example 4 in which the content of the cyclic aromatic phosphazene compound (B) exceeds the specified amount, the heat resistance Is getting worse.
Further, Comparative Example 2 using a phosphazene compound in which the ratio of the phosphazene compound (B1) and the phosphazene compound (B2) is out of the scope of the present invention is poor in flame retardancy and hue, and as in Comparative Example 3, When the content is increased, the flame retardancy is improved, but the hue is further deteriorated.
Further, as in Comparative Example 5, if the content of titanium oxide is too small, the flame retardancy deteriorates to V-2, and the heat discoloration also deteriorates. Conversely, the content of titanium oxide is too large. In Comparative Example 6, the impact resistance is poor. It can be seen that when a phosphate ester compound is used as the flame retardant, the impact resistance is extremely poor and the heat discoloration is also poor.
Therefore, from the above examples and comparative examples, the effects of excellent flame retardancy, impact resistance, heat resistance, hue, light-shielding properties, and excellent heat discoloration can be obtained for the first time by the configuration of the present invention. It was confirmed to be a thing.

  The polycarbonate resin composition of the present invention is a polycarbonate resin material that is excellent in flame retardancy, impact resistance, heat resistance, hue, light-shielding properties, and also excellent in heat discoloration, and therefore has high industrial applicability. There is something.

Claims (6)

Hexaphenoxytricyclophosphazene (B1) represented by the following formula (1) and octaphenoxytetracyclophosphazene (B2) represented by the following formula (2) are added to 100 parts by mass of the polycarbonate resin (A). Cyclic aromatic phosphazene compound (B) 1.3 to 3.5 parts by mass, fluoropolymer (C) 0.01 to 2 parts by mass and titanium oxide (D) 0.5 to be contained at a mass ratio of 25 to 95/5 Contains ~ 30 parts by weight ,
The value of deflection temperature under load measured at 1.8 MPa in accordance with ISO75-1 is 116 ° C. or higher, UL94 flame retardancy at 1 mm thickness is V-0, and the initial hue at 3 mm thickness is 4.2. The polycarbonate resin composition characterized by the following .
A polycarbonate resin molded article obtained by molding the polycarbonate resin composition according to claim 1. It is a lighting fixture member, The polycarbonate resin molded product of Claim 2 characterized by the above-mentioned. The polycarbonate resin molded article according to claim 2 , wherein the polycarbonate resin molded article is a light-emitting display device casing. It is a projector housing | casing, The polycarbonate resin molded product of Claim 2 characterized by the above-mentioned. A polycarbonate resin sheet or film obtained by molding the polycarbonate resin composition according to claim 1.