JP6352030B2 - Polycarbonate resin composition and molded article - Google Patents

Description

  The present invention relates to a polycarbonate resin composition and a molded product, and more specifically, a polycarbonate resin composition having excellent light transmittance even in a thick molded product, having high heat resistance and high flame resistance, and molding the same. It relates to a molded product.

  Polycarbonate resin is a resin excellent in heat resistance, mechanical properties, and electrical characteristics, and is widely used in, for example, automobiles, electrical and electronic equipment, home appliances, housing materials, and other parts manufacturing materials in industrial fields. . In particular, the flame retardant polycarbonate resin composition is suitably used as a part of OA / information equipment such as a computer, notebook type or tablet type personal computer, various portable terminals, printers, copying machines and the like.

In recent years, there has been a strong demand for flame resistance of resin materials to be used, mainly in applications such as electrical and electronic equipment or peripheral equipment.
As means for imparting flame retardancy to a polycarbonate resin, conventionally, a halogen-based flame retardant or a phosphorus-based flame retardant has been added to the polycarbonate resin.
However, a polycarbonate resin composition containing a halogen-based flame retardant containing chlorine or bromine may lead to a decrease in thermal stability or corrosion of a molding machine screw or molding die during molding processing. there were. In addition, the polycarbonate resin composition containing a phosphorus-based flame retardant inhibits the high transparency that is characteristic of the polycarbonate resin and causes a decrease in impact resistance and heat resistance, so that its use is limited. was there. In addition, these halogen-based flame retardants and phosphorus-based flame retardants may cause environmental pollution at the time of product disposal and recovery, and in recent years, these flame retardants can be made flame retardant without using these flame retardants. It is desired.

  Under such circumstances, in recent years, many organic metal salt compounds represented by organic alkali metal salt compounds and organic alkaline earth metal salt compounds have been studied as useful flame retardants. When an organometallic salt compound is used as a flame retardant, the effect can be obtained in a relatively small amount, and it is difficult without impairing the mechanical properties such as impact resistance, heat resistance, and electrical properties inherent to the polycarbonate resin. This is because flammability can be imparted.

  Examples of the flame-retarding technology of polycarbonate using an organic metal salt compound include, for example, a method using an alkali metal salt of perfluoroalkylsulfonic acid having 4 to 8 carbon atoms (see Patent Document 1), and a perfluoroalkane having 1 to 3 carbon atoms. A method of imparting flame retardancy to an aromatic polycarbonate resin by using an alkali metal salt compound of perfluoroalkanesulfonic acid, such as a method of blending an alkali metal salt of sulfonic acid (see Patent Document 2); non-halogen aromatic Fragrance using an alkali metal salt compound of an aromatic sulfonic acid such as a method of containing a sulfonic acid sodium salt (see Patent Document 3) or a method of containing a non-halogenated aromatic sulfonic acid potassium salt (see Patent Document 4) A technique for imparting flame retardancy to an aromatic polycarbonate resin composition has been proposed.

  However, such flame retardancy by an organometallic salt compound has a problem that in the case of a molded product having a thick part, white turbidity is generated inside the molded product when the molded product is slowly cooled. The difference in transparency and translucency between the outside and the outside is a fatal defect in many products that require high light transmission and high-quality feeling without white turbidity, such as electrical and electronic equipment and home appliances. . In addition, the flame retardancy is V-2 level at a thickness of 1 mm in UL94 flammability evaluation, and has a problem that the V-0 level cannot be achieved.

Japanese Patent Publication No. 47-40445 Japanese Patent Publication No.54-32456 JP 2000-169696 A JP 2001-181493 A

  The present invention has been made in view of such problems, and has a polycarbonate resin composition having excellent light transmittance even in a thick molded product, high heat resistance and high flame retardancy, and molding the same. An object of the present invention is to provide a molded product.

As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have identified a fluoropolymer having an apparent density of 0.4 g / ml or more in a resin composition in which a polyphosphonate homopolymer is blended with a polycarbonate resin. It has been found that the polycarbonate resin composition contained in an amount has excellent light transmittance even in a thick molded product, has high heat resistance and high flame retardancy, and has completed the present invention.
The present invention provides the following polycarbonate resin composition and molded article.

[1] Polycarbonate resin (A) 50 to 95% by mass and a polyphosphonate homopolymer (B) 50 to 5% by mass consisting of a repeating unit represented by the following formula (1) and having a weight average molecular weight of 10,000 or more: 100 A polycarbonate resin composition comprising 0.005 to 0.5 parts by mass of a fluoropolymer (C) having an apparent density of 0.4 g / ml or more with respect to parts by mass.
(In the formula, Y represents an alkylidene having 1 to 10 carbon atoms, an alkylene having 1 to 10 carbon atoms, a cycloalkylene having 5 to 12 carbon atoms, a cycloalkylidene having 5 to 12 carbon atoms, -O-, -S-,- SO—, —SO ₂ — or —CO— is represented, and R represents an alkyl group having 1 to 10 carbon atoms.)
[2] The content of the fluoropolymer (C) is 0.18 parts by mass or less with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the polyphosphonate homopolymer (B). Polycarbonate resin composition.
[3] The polycarbonate resin composition according to the above [1] or [2], wherein the total light transmittance (D65 light source, 10 ° field of view) at 3 mm thickness is 72% or more.
[4] The polycarbonate resin composition according to any one of [1] to [3], which has a flame retardancy of V-0 at a thickness of 1.0 mm.
[5] The polycarbonate resin composition according to any one of [1] to [4], which does not contain a fibrous reinforcing material.
[6] A molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [5].
[7] The molded product according to [6], in which light from the light emitting unit accommodated in the molded product is visible from the outside.

  The polycarbonate resin composition of the present invention has a high light transmittance such that the total light transmittance is 72% or more even in a thick molded product such as 3 mm thick, and the deflection temperature under load (DTUL) is 100 ° C. or more. High heat resistance and high flame retardancy of V-0 even at 1 mm thickness, satisfying all of excellent transparency in thick molded products, high heat resistance and high flame retardance. Therefore, the polycarbonate resin composition of the present invention can be suitably applied as a part of electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, lighting equipment, etc., and in particular, light emission of LED lamps and the like housed inside molded products. It can be suitably used as a molded part in which the light from the part is visible from the outside.

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

[Overview]
The polycarbonate resin composition of the present invention comprises 50 to 95% by mass of a polycarbonate resin (A) and a repeating unit represented by the following formula (1), and a polyphosphonate homopolymer (B) having a weight average molecular weight of 10,000 or more. It is characterized by containing 0.005 to 0.5 parts by mass of fluoropolymer (C) having an apparent density of 0.4 g / ml or more with respect to a total of 100 parts by mass of 5% by mass.
(In the formula, Y represents an alkylidene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, a cycloalkylidene group having 5 to 12 carbon atoms, -O-,- S—, —SO—, —SO ₂ — or —CO— is represented, and R represents an alkyl group having 1 to 10 carbon atoms.)

[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 is a polymer having a basic structure having a carbonic acid bond, represented by a general formula: — [— O—X—O—C (═O) —] —. In the formula, X is generally a hydrocarbon group, but for imparting various properties, X introduced with a hetero atom or a hetero bond may be used.

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

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

Among monomers used as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include:
Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl;
2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

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

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

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-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;

4,4′-dihydroxydiphenyl sulfoxide,
Dihydroxydiaryl sulfoxides such as 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 And cyclic ethers such as -1,2-epoxycyclohexane, 2,3-epoxynorbornane, and 1,3-epoxypropane;

  Among the monomers used as the raw material for the 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 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 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, 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-oxinebenzoic 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, 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 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, 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 aromatic polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

-Other matters regarding polycarbonate resin The molecular weight of the polycarbonate resin is arbitrary and may be appropriately selected and determined. The viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more, preferably 16,000. Above, more preferably 17,000 or more, and usually 40,000 or less, preferably 30,000 or less, more preferably 24,000 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 making the viscosity average molecular weight not more than the upper limit of the above range, it is possible to suppress and improve the fluidity of the polycarbonate resin composition of the present invention, and it is also possible to improve the molding processability and easily perform the thin-wall 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.

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 1,000 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.

  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 a copolymer with an oligomer or polymer having a siloxane structure; a monomer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability A copolymer with an oligomer or polymer; a copolymer with an oligomer or polymer having an olefinic structure such as polystyrene to improve optical properties; a polyester resin oligomer or polymer for the purpose of improving chemical resistance You may comprise as a copolymer which has polycarbonate resin as a main body, such as a copolymer.

  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 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Furthermore, the polycarbonate oligomer 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.

[Polyphosphonate homopolymer (B)]
The polycarbonate resin composition of the present invention contains a polyphosphonate homopolymer (B) having a weight average molecular weight of 10,000 or more, and the content thereof is the sum of the polycarbonate resin (A) and the polyphosphonate homopolymer (B). As 100 mass%, it is 5-50 mass%, It is characterized by the above-mentioned. By containing the polyphosphonate homopolymer (B) in such an amount, the flame retardancy of the polycarbonate resin composition can be improved, and while maintaining the heat resistance and impact resistance of the polycarbonate resin, It is possible to suppress the occurrence of white turbidity that tends to occur in meat molded products and achieve high total light transmittance. The preferable content of the polyphosphonate homopolymer (B) is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, preferably 47% by mass or less, more preferably 45%. It is at most mass%, more preferably at most 43 mass%, particularly preferably at most 41 mass%.

The polyphosphonate homopolymer (B) used in the present invention is a polyphosphonate homopolymer composed of a repeating unit represented by the following formula (1) and having a weight average molecular weight of 10,000 or more.
(In the formula, Y represents an alkylidene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, a cycloalkylidene group having 5 to 12 carbon atoms, -O-,- S—, —SO—, —SO ₂ — or —CO— is represented, and R represents an alkyl group having 1 to 10 carbon atoms.)

(1) Y in the formula may be linear or branched as the C1-C10 alkylidene group of Y. For example, ethylidene group, isopropylidene group, butylidene, hexylidene and the like are preferable. Particularly preferred are those having 1 to 10 carbon atoms.
Preferred examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylylene group, and a hexylene group, and those having 1 to 6 carbon atoms are particularly preferable.
Preferred examples of the cycloalkylene group having 5 to 12 carbon atoms include a cyclopentylene group, cyclohexylene, 2-isopropyl-1,4-cyclohexylene group and the like, and those having 6 to 10 carbon atoms are particularly preferable.
Preferred examples of the cycloalkylidene group having 5 to 12 carbon atoms include a cyclopentylidene group and a cyclohexylidene group, and those having 6 to 10 carbon atoms are particularly preferable.

  In particular, Y is preferably a cyclohexylidene group or a 2,2-propylidene group, particularly preferably a 2,2-propylidene group. In the above formula (1), 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol) A) A polymer composed of a residue and a phosphonic acid residue is particularly preferred.

  R in the phosphonic acid residue in the formula (1) is an alkyl group having 1 to 10 carbon atoms as described above, and is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a heptyl group. A group, an octyl group, a nonyl group, and a decyl group, and these may be branched. Preferred alkyl groups are alkyl groups having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms, particularly methyl groups, ethyl groups, and propyl groups. Among them, a methyl group and an ethyl group are preferable, and a methyl group is most preferable.

  In addition, polyphosphonate homopolymer (B) may use 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The weight average molecular weight of the polyphosphonate homopolymer (B) is 10,000 or more, more preferably 15,000 or more, and still more preferably 20,000 or more. Moreover, Preferably it is 300000 or less, More preferably, it is 200000 or less. When the weight average molecular weight is less than 10,000, the heat resistance of the polycarbonate resin composition is lowered, and when it exceeds 300,000, problems such as poor compatibility and poor appearance occur. The weight average molecular weight is determined by polystyrene-based gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

  Polyphosphonate homopolymers can be produced by known methods described in, for example, JP-A-56-5823 and JP-A-56-104934. For example, diphenyl alkylphosphonate and bisphenol are known. Can be obtained by melt transesterification in the presence of a transesterification catalyst. The product is also commercially available from the US FRX Polymer under the trade name “Nofia HM1100”.

[Fluoropolymer (C)]
The polycarbonate resin composition of the present invention contains a fluoropolymer (C) having an apparent density of 0.4 g / ml or more. The content is 0.005-0.5 mass part with respect to a total of 100 mass parts of polycarbonate resin (A) and a polyphosphonate homopolymer (B). By containing the fluoropolymer (C) having an apparent density of 0.4 g / ml or more in combination with the polyphosphonate homopolymer (B), it has been conventionally thin while maintaining excellent light transmittance and high heat resistance. It was possible to achieve a flame retardance of 1 mm thick and a V-0 level high flame retardancy with a small content.

As the fluoropolymer (C), a fluoroolefin resin is preferred. 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 a fluoropolymer (C), 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.

  In addition, an organic polymer-coated fluoroolefin resin can also be suitably used as the fluoropolymer (C). By using the organic polymer-coated fluoroolefin resin, the dispersibility is improved, the surface appearance of the molded product is improved, and the surface foreign matter can be suppressed. The organic polymer-coated fluoroolefin resin can be produced by various known methods. For example, (1) a polyfluoroethylene particle aqueous dispersion and an organic polymer particle aqueous dispersion are mixed and powdered by coagulation or spray drying. (2) A method of polymerizing a monomer constituting an organic polymer in the presence of an aqueous dispersion of polyfluoroethylene particles, and then pulverizing or producing the powder by solidification or spray drying. 3) After emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing an aqueous dispersion of polyfluoroethylene particles and an aqueous dispersion of organic polymer particles, a powder is obtained by coagulation or spray drying. And the like, and the like.

  From the viewpoint of dispersibility when blended with a polycarbonate resin, a monomer having a high affinity with the polycarbonate resin is preferable as the monomer for producing the organic polymer that coats the fluoroolefin resin. Monomers, (meth) acrylic acid ester monomers, and vinyl cyanide monomers are more preferred.

  One type of fluoropolymer (C) may be used, or two or more types may be used in any combination and in any ratio.

  The apparent density of the fluoropolymer (C) is 0.4 g / ml or more, preferably more than 0.45 g / ml, more preferably more than 0.47 g / ml, still more preferably more than 0.48 g / ml, especially Preferably it is 0.485 g / ml or more, preferably 0.8 g / ml or less, more preferably 0.7 g / ml or less, still more preferably 0.65 g / ml or less, particularly preferably 0.6 g / ml or less. is there. When the apparent density of the fluoropolymer (C) is below the lower limit, flame retardancy at a thickness of 1.0 mm can be achieved only at the V-2 level.

  As described above, the content of the fluoropolymer (C) is 0.005 to 0.5 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the polyphosphonate homopolymer (B). When the amount is less than 0.005 parts by mass, the effect of improving the flame retardancy tends to be insufficient, and when the amount exceeds 0.5 parts by mass, the appearance of the molded article is easily deteriorated and the mechanical strength is easily lowered. The content of the fluoropolymer (C) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the polyphosphonate homopolymer (B). More preferably, it is 0.07 parts by mass or more, preferably 0.4 parts by mass or less, more preferably 0.3 parts by mass or less, and particularly preferably 0.2 parts by mass or less.

[Phosphorus stabilizer]
The polycarbonate resin composition of the present invention preferably contains a phosphorus stabilizer. Any known phosphorous stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, 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 part by mass or more, preferably 0.01 part by mass or more, more preferably 100 parts by mass in total of the polycarbonate resin (A) and the polyphosphonate homopolymer (B). Is 0.03 parts by mass or more, and is usually 1 part by mass or less, preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass 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 phenol-based stabilizer. As a phenol type stabilizer, a hindered phenol type stabilizer 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 phenol-based stabilizer include “Irganox 1010”, “Irganox 1076” manufactured by BASF, “Adekastab AO-50”, “Adekastab AO-60” manufactured by ADEKA, and the like. Can be mentioned.
In addition, 1 type may be contained for the phenol type stabilizer, and 2 or more types may be contained by arbitrary combinations and ratios.

  The content of the phenol-based stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the polyphosphonate homopolymer (B). Moreover, it is 1 mass part or less normally, Preferably it is 0.5 mass part 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.

[Release agent]
Moreover, it is also preferable that the polycarbonate resin composition of this invention contains a mold 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, polysiloxane silicone oils, and the like.

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

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

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

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

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

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 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 release agent mentioned above, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, particularly preferably 100 parts by mass in total of the polycarbonate resin (A) and the polyphosphonate homopolymer (B). It is 0.05 mass part or more, and is 2 mass parts or less normally, Preferably it is 1 mass part or less, More preferably, it is 0.8 mass part or less, More preferably, it is 0.5 mass part or less. When the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the range, hydrolysis resistance And mold contamination during injection molding are likely to occur.

[Other ingredients]
The polycarbonate resin composition of the present invention may contain other components in addition to those described above 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 other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer ( AS resins), polyolefin resins such as polyethylene resins and polypropylene resins, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, and the like. It is done.
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 ultraviolet absorbers, dyes and pigments (including carbon black), antistatic agents, antifogging agents, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents Etc. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
However, when a fibrous reinforcing material such as carbon fiber is contained, the transmittance is reduced in addition to the deterioration of the appearance. Therefore, in the present invention, it is preferable not to contain a fibrous reinforcing material such as carbon fiber.

[Production Method of Polycarbonate Resin Composition]
There is no restriction | limiting in the manufacturing method of the polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely.
Specific examples include polycarbonate resin (A), polyphosphonate homopolymer (B) and fluoropolymer (C), and other components blended as necessary, for example, various mixtures such as a tumbler or Henschel mixer. Examples thereof include a method of premixing using a machine and then melt-kneading with a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, or kneader.

In addition, for example, without mixing each component in advance, or only a part of the components is mixed in advance, and fed to an extruder using a feeder and melt-kneaded to produce the polycarbonate resin composition of the present invention. You can also.
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. The polycarbonate resin composition of the present invention can also be produced.
In addition, for example, when mixing a component that is difficult to disperse, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance, and kneaded with the solution or the dispersion. It can also improve sex.

The polycarbonate resin composition of the present invention preferably has a total light transmittance (D65 light source, 10 ° field of view) at a thickness of 3 mm of 72% or more. Since the polycarbonate resin composition of the present invention has such a total light transmittance, in particular, the visibility from the outside of the light from the light emitting part accommodated in the molded product can be further improved. The total light transmittance is more preferably 73% or more, still more preferably 74% or more, particularly 75% or more, and particularly preferably 76% or more.
The details of the method for measuring the total light transmittance (D65 light source, 10 ° field of view) at a thickness of 3 mm are as described in the examples.

  Further, the polycarbonate resin composition of the present invention is characterized by having flame retardancy of V-0 even in a thin wall of preferably 1.0 mm thickness in the UL94 test. Details of the UL94 test measurement method are as described in the examples.

  As a method for producing the molded article, a molding method generally employed for the polycarbonate resin composition can be arbitrarily adopted. For example, injection molding method, ultra high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulation mold, rapid heating mold were used. Molding method, 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 method, Examples thereof include a blow molding method, and a molding method using a hot runner method can also be used. Of these, injection molding methods such as injection molding, ultra-high speed injection molding, and injection compression molding are preferred.

[Molding]
Examples of molded products include parts such as electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, and lighting equipment. Among these, it is suitable for use in components such as electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, and lighting equipment. In particular, in a molded product in which a light emitting part such as an LED lamp is accommodated inside the molded product, and the light emitted from the light emitting unit is visible from the outside of the molded product by an ON / OFF signal or information. Can be used particularly preferably. Specific examples of such molded products include heat and flame resistance, various electrical and electronic equipment parts, household electrical appliance parts, various portable terminals, storage media parts, etc. that are required to have non-mottle visibility. Preferred examples include various battery charger housings for portable terminals, USB memory housings, personal computer and camera power switch ON / OFF display parts, and the like.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
Each component used in Examples and Comparative Examples is as shown in Table 1 below.

(Examples 1-4, Comparative Examples 1-6)
[Production of resin pellets]
Each component described in Table 1 was blended in the ratio (mass ratio) described in Table 3 below, mixed for 20 minutes with a tumbler, and then a twin screw extruder (TEX30HSST) manufactured by Nippon Steel Works, Ltd. equipped with 1 vent. , Kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 280 ° C., the molten resin extruded into a strand is quenched in a water tank, pelletized using a pelletizer, and polycarbonate resin composition A product pellet was obtained.

[Manufacture of ISO multipurpose test pieces]
The pellets obtained above were dried at 100 ° C. for 5 hours, and then injection molded under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using an SG75MII type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. A multi-purpose test piece (4 mm thick) was molded.

[Evaluation of heat resistance Deflection temperature under load (DTUL)]
Using the ISO multipurpose test piece, the deflection temperature under load (DTUL, unit: ° C.) was measured in accordance with ISO 75-1 & 2 under the condition of load 1.80 MPa (Method A).
In the table, “DTUL” is used.

[Total light transmittance]
After the pellets obtained by the above production method were dried at 100 ° C. for 5 hours, the cylinder temperature was 280 ° C., the mold temperature was 80 ° C., and the molding cycle was performed with an injection molding machine (“SE50DUZ” manufactured by Sumitomo Heavy Industries, Ltd.). A flat plate test piece (110 × 36 × 3 mm) obtained by injection molding under the conditions of 30 seconds, according to JIS K 7105, using an NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd., D65 light source The total light transmittance (unit:%) was measured in a 10 ° field of view.

[Flame retardancy evaluation UL94 test]
After drying the pellets obtained by the above-mentioned manufacturing method at 100 ° C. for 4 hours, injection was performed under conditions of a cylinder temperature of 270 ° C. and a mold temperature of 80 ° C. using an SE100DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. A UL test specimen having a length of 125 mm, a width of 13 mm, and a thickness of 1.0 mm was molded.
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 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.
In the table, “combustibility” is indicated.

[Appearance evaluation of thick molded product]
After the pellets obtained by the above production method were dried at 100 ° C. for 5 hours, using a SE100DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a cylinder temperature of 290 ° C., a mold temperature of 80 ° C., and an injection speed of 80 mm A test piece having a length of 50 mm, a width of 50 mm, and a thickness of 12 mm was molded under injection / second conditions.
The obtained test piece was visually observed to determine whether it was cloudy or transparent with no cloudiness.
The above evaluation results are shown in Table 3 below.

  The polycarbonate resin composition of the present invention has a high light transmittance such that the total light transmittance is 72% or more even in a thick molded product having a thickness of 3 mm, and has high heat resistance and high flame retardancy. Since it has, it can be applied suitably as components of electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, lighting equipment, etc., and in particular, light from a light emitting part such as an LED lamp housed inside the molded product is from the outside It can be suitably used as a molded part that can be visually recognized, and its industrial utility is very high.

Claims (3)

Polycarbonate resin (A) 50 to 95% by mass and a repeating unit represented by the following formula (1), and a polyphosphonate homopolymer (B) having a weight average molecular weight of 10,000 or more in a total of 100 parts by mass of 50 to 5% by mass. On the other hand, the fluoropolymer (C) having an apparent density of 0.4 g / ml or more is contained in an amount of 0.005 to 0.18 parts by mass ,
A polycarbonate resin composition having a total light transmittance (D65 light source, 10 ° field of view) at 3 mm thickness of 72% or more and a flame retardancy of V-0 at 1.0 mm thickness .
(In the formula, Y represents an alkylidene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, a cycloalkylidene group having 5 to 12 carbon atoms, -O-,- S—, —SO—, —SO ₂ — or —CO— is represented, and R represents an alkyl group having 1 to 10 carbon atoms.) The polycarbonate resin composition of Claim 1 which does not contain a fibrous reinforcement. Claim 1 or 2 molded article obtained by molding the polycarbonate resin composition according to.