JP2015227421A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin/styrenic resin alloy excellent in fire resistance, shock resistance and appearance, and further excellent in shock strength during high temperature molding.SOLUTION: There is provided a thermoplastic resin composition manufactured by blending total 100 pts.mass of (A) and (B) consisting of 50 to 90 mass% of a polycarbonate resin (A) consisting of 15 to 90 mass% of a polycarbonate resin having a crystal fusion heat measured by a differential scanning calorimeter (DSC) of 15 mJ/g or more (a1) and 85 to 10 mass% of a polycarbonate resin having the crystal fusion heat measured by the differential scanning calorimeter (DSC) of 5 mJ/g or less (a2) and 50 to 10 mass% of a styrenic resin (B), 3 to 30 pts.mass of a phosphorous flame retardant, 0.01 to 2 pts.mass of fluoropolymer (D) and 0 to 5 pts.mass of a silicate compound (E).

Description

  The present invention relates to a thermoplastic resin composition, and more particularly, to a polycarbonate resin / styrene resin-based thermoplastic resin composition that is excellent in flame retardancy and impact resistance during high-temperature molding and has improved appearance during molding.

  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, flame retardant polycarbonate / styrene resin alloys are suitably used as components for electrical / electronic devices such as computers, notebook computers, various portable terminals, printers, copiers, OA / information devices, etc. ing.

  Among these, polycarbonate / styrene resin alloy compositions flame-retarded with phosphorus flame retardants are extremely excellent in moldability due to the plasticizing effect of phosphorus flame retardants. It is a suitable resin material (see, for example, Patent Documents 1 to 4).

  In recent years, along with the downsizing and thinning of notebook computers and various portable devices, their casings and battery pack parts are also becoming thinner. It tends to be set higher and the residence time also increases. However, the polycarbonate / styrene resin alloy has a problem that high impact strength cannot be maintained in such high temperature molding.

  Also, in electrical / electronic equipment casings, ribs or self-tapping bosses are often provided in order to increase the strength of the molded products. When trying to mold with a styrenic resin alloy, there is a problem that a black streak-like appearance defect occurs in the rear part that has passed through the rib or boss from the gate, and the commercial value is remarkably impaired.

Furthermore, recently, the case of electronic / electrical equipment is required to have a level of 5 VB or more in a flame retardance test in accordance with UL94.
Therefore, in the electrical / electronic equipment field, a polycarbonate / styrene resin alloy that is excellent in flame retardancy of 5 VB or more, impact resistance and appearance, and also excellent in impact strength at high temperature molding is strongly desired.

Japanese Patent No. 3638806 Japanese Patent No. 4080851 Japanese Patent No. 3655979 Japanese Patent No. 4157271

  The present invention was devised in view of the above-mentioned problems of the prior art, and provides a polycarbonate / styrene resin alloy having excellent flame retardancy, impact resistance and appearance, and also excellent impact strength during high temperature molding. The purpose is to do.

As a result of intensive investigations to achieve the above-mentioned problems, the present inventor used a mixture of a crystallized polycarbonate resin having a specific heat of crystal fusion and an amorphous polycarbonate resin as a polycarbonate resin, and a styrenic resin. , A thermoplastic resin composition containing a specific amount of phosphorus-based flame retardant, fluoropolymer, and silicate compound is excellent in the balance between flame retardancy and impact resistance, and is further provided with ribs and bosses The present inventors have found that a good appearance can be obtained even when molding is performed, and that the impact strength decrease is small even when molded under high temperature conditions, and the present invention has been completed.
The present invention provides the following thermoplastic resin composition.

[1] Polycarbonate resin (a1) having a crystal melting heat of 15 mJ / g or more measured by a differential scanning calorimeter (DSC) of 15 to 90% by mass and a crystal melting heat measured by a differential scanning calorimeter (DSC) (A) and (B) consisting of 50 to 90% by mass of polycarbonate resin (A) consisting of 85 to 10% by mass of polycarbonate resin (a2) which is 5 mJ / g or less, and 50 to 10% by mass of styrene resin (B). For a total of 100 parts by mass of
A thermoplastic resin composition comprising 3 to 30 parts by mass of a phosphorus-based flame retardant (C), 0.01 to 2 parts by mass of a fluoropolymer (D) and 0 to 5 parts by mass of a silicate compound (E).
[2] The thermoplastic resin composition according to the above [1], wherein the styrene resin (B) is an ABS resin and / or an AS resin.
[3] Further, a graft copolymer obtained by graft-polymerizing at least one selected from monomers consisting of an aromatic vinyl compound, a vinyl cyanide compound component and a (meth) acrylic acid ester compound on a rubbery polymer. The thermoplastic resin according to [1] or [2] above, wherein (F) is blended in an amount of 0.5 to 10 parts by mass with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the styrene resin (B). Composition.
[4] The thermoplastic resin composition according to any one of [1] to [3], wherein the phosphorus flame retardant (C) is a condensed phosphate ester and / or a phosphazene compound.
[5] Notched Charpy impact strength of a 3 mm thick ISO multipurpose test piece molded at 260 ° C. (260 ° C. impact) against a notched Charpy impact strength (240 ° C. impact strength) of a 3 mm thick ISO multipurpose test piece molded at 240 ° C. The thermoplastic resin composition according to any one of [1] to [4], wherein a ratio of strength (260 ° C. impact strength / 240 ° C. impact strength) is 0.8 or more.
[6] The thermoplastic resin composition according to any one of [1] to [5], wherein the flame retardancy by UL94 at a thickness of 1.8 mm is 5 VA or 5 VB.

  The thermoplastic resin composition of the present invention is a polycarbonate / styrene resin alloy that is excellent in flame retardancy, impact resistance and appearance, and also excellent in impact strength during high temperature molding.

It is a top view of the flat molded object used for the external appearance evaluation in an Example.

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 thermoplastic resin composition of the present invention comprises 15 to 90% by mass of a polycarbonate resin (a1) having a crystal melting heat of 15 mJ / g or more measured by a differential scanning calorimeter (DSC) and a differential scanning calorimeter (DSC). The heat of fusion of the crystal measured in step 5 is 5 mJ / g or less, and the polycarbonate resin (a2) is composed of 85 to 10% by weight, and the styrene resin (B) is composed of 50 to 10% by weight. For a total of 100 parts by mass of (A) and (B),
It is characterized by comprising 3 to 30 parts by mass of a phosphorus-based flame retardant (C), 0.01 to 2 parts by mass of a fluoropolymer (D) and 0 to 5 parts by mass of a silicate compound (E).

[Polycarbonate resin (A)]
In the thermoplastic resin composition of the present invention, the polycarbonate resin (A) includes a polycarbonate resin (a1) having a crystal melting heat of 15 mJ / g or more measured by a differential scanning calorimeter (DSC) and a differential scanning calorimeter. A polycarbonate resin (a2) having a heat of crystal melting measured by (DSC) of 5 mJ / g or less is used. The blending ratio is 15 to 90% by mass of the polycarbonate resin (a1) and 85 to 10% by mass of the polycarbonate resin (a2) on the basis of a total of 100% by mass of (a1) and (a2).

  In the present invention, the heat of crystal fusion measured with a differential scanning calorimeter (DSC) of a polycarbonate resin is specifically a sample of a polycarbonate resin using a differential scanning calorimeter DSC7020 manufactured by Seiko Instruments Inc. Is defined as the endothermic amount derived from crystal melting at 220 ° C. to 280 ° C., which is near the melting point of the polycarbonate resin, when the temperature is raised from 30 ° C. to 320 ° C. at 20 ° C./min.

  The polycarbonate resin (a1) is a crystallized polycarbonate resin having an endotherm at 220 to 280 ° C. derived from crystal melting in the process of temperature rise of 15 mJ / mg or more, and the polycarbonate resin (a2) is similarly derived from crystal melting. Is an amorphous polycarbonate resin having an endotherm at 220 to 280 ° C. of 5 mJ / m or less or having no clear endothermic peak.

The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the general formula: [—O—X—O—C (═O) —]. As the polycarbonate resins (a1) and (a2) in the present invention, In the above formula, those in which X in the above formula is a hydrocarbon group are usually used, but X may be introduced with a hetero atom or a hetero bond for imparting various properties.
The polycarbonate resin can be classified into an aromatic polycarbonate resin in which the carbon directly bonded to the carbonic acid bond is an aromatic carbon and an aliphatic polycarbonate resin in which the carbon is an aliphatic carbon, respectively, as polycarbonate resins (a1) and (a2). Any of them can be used, and among them, an aromatic polycarbonate resin is preferable from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.

Although there are no restrictions on the raw material components and the formation reaction of the polycarbonate resins (a1) and (a2), for example, a polycarbonate resin obtained by reacting a dihydroxy compound and a carbonate precursor can be mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Alternatively, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used.
The polycarbonate resins (a1) and (a2) may be linear or branched. Further, the polycarbonate resins (a1) and (a2) may be a single polymer 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 the monomers used as raw materials for the polycarbonate resins (a1) and (a2), 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;

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

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

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

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

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

  Examples of the monomer that is a raw material for the aliphatic polycarbonate resin include ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1, 3-diol, 2-methyl-2-propylpropane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol Alkanediols such as

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

  Glycols such as 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;

  Of the monomers used as the raw materials for the polycarbonate resins (a1) and (a2), examples of the carbonate precursor include carbonyl halides and carbonate esters. 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 (a1) and (a2) The manufacturing method of polycarbonate resin (a1) and (a2) 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.

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

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

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

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

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

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

  Examples of the molecular weight regulator include aromatic phenols having a monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like. Of these, aromatic phenols are preferred. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropenyl 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 thermoplastic resin composition can be improved.

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

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

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

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

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

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

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

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

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

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

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

-Preferred production method of polycarbonate resin (a1) As described above, the polycarbonate resin (a1) is a crystallized polycarbonate resin having an endotherm at 220 to 280 ° C derived from crystal melting of 15 mJ / mg or more in the course of temperature increase. However, as a method for producing such a crystallized polycarbonate resin, a known method can be adopted, and examples include a method by heat treatment, a method by solvent treatment, and a method by plasticizer treatment.

  In the heat treatment method, a polycarbonate resin having a low crystallinity is heat treated at a high temperature, for example, over 72 hours.

The crystallization method by solvent treatment is a method in which a polycarbonate resin is dissolved in a solvent and then precipitated in a poor solvent, and is a preferred method for producing the polycarbonate resin (a1).
Preferred examples of the solvent include chlorinated aliphatic or aromatic hydrocarbons such as chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene, and particularly chlorine such as dichloromethane. Hydrocarbons are preferred. As the poor solvent, those having a boiling point higher than that of the above solvent are preferable, and hexane, heptane, toluene, water and the like are preferable.
The poor solvent is preferably about 0.2 to 0.6 times the volume of the polycarbonate resin solution dissolved in the solvent, and the polycarbonate resin is precipitated in a powder form in the poor solvent, and is usually a crystalline polycarbonate resin in the form of flakes. Is obtained.
This method is preferable because it is possible to deposit the produced polycarbonate resin solution in a poor solvent in the above-mentioned interfacial polymerization method.

  The polycarbonate resin (a1) has an endotherm at 220 to 280 ° C. derived from crystal melting in the process of temperature rise of 15 mJ / mg or more, preferably 20 mJ / mg or more, more preferably 25 mJ / mg or more. The endothermic amount can be adjusted by the precipitation rate and the combination of the solvent and the poor solvent.

-Preferred production method of the polycarbonate resin (a2) As described above, the polycarbonate resin (a2) is an amorphous material having an endotherm at 220 to 280 ° C derived from crystal melting of 5 mJ / m or less or having no clear endothermic peak. Although it is a polycarbonate resin, the polycarbonate resin is usually amorphous and has an endotherm of 5 mJ / m or less, or does not have a clear endothermic peak. As a method for producing the polycarbonate resin (a2), it can be produced by a known ordinary method (such as an interfacial polymerization method or a melt transesterification method), and a commercially available amorphous polycarbonate resin can also be used. Further, in the interfacial polymerization method, etc., the polycarbonate powder crystallized by precipitation under a solvent is pelletized after melting the crystal using an extruder or the like, and the endothermic amount is 5 mJ / m or less, or It is also possible to use an amorphous polycarbonate adjusted to have no clear endothermic peak.

-Mixing ratio of polycarbonate resin (a1) and (a2) As above-mentioned, the mixing ratio of polycarbonate resin (a1) and (a2) is 15-90 mass% of polycarbonate resin (a1), and polycarbonate resin (a2) 85-10. % By mass. By setting it as such a mixture ratio, the thermoplastic resin composition of this invention will be excellent in the impact resistance at the time of high temperature shaping | molding, and excellent in a flame retardance. The preferred blending ratio is 20 to 85% by mass of the polycarbonate resin (a1) and 80 to 15% by mass of the polycarbonate resin (a2), more preferably 25 to 80% by mass of the polycarbonate resin (a1) and 75 to 75% of the polycarbonate resin (a2). 20 mass%, More preferably, they are 30-75 mass% of polycarbonate resin (a1), and 70-25 mass% of polycarbonate resin (a2).

-Other matters regarding the polycarbonate resins (a1) and (a2) The molecular weights of the polycarbonate resins (a1) and (a2) are arbitrary and may be appropriately selected and determined, but the viscosity average molecular weight converted from the solution viscosity [Mv] is usually 10,000 or more, preferably 16,000 or more, more preferably 17,000 or more, and usually 40,000 or less, preferably 30,000 or less, more preferably 24,000 or less. It is.
By making the viscosity average molecular weight equal to or higher than the lower limit of the above range, the mechanical strength of the thermoplastic 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 drop of the thermoplastic resin composition of the present invention, and to improve the molding processability and to facilitate the molding process. . The polycarbonate resins (a1) and (a2) may be used by mixing two or more kinds of polycarbonate resins having different viscosity average molecular weights. In this case, the viscosity average molecular weight is outside the above preferred range. A certain polycarbonate resin 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 resins (a1) and (a2) 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 thermoplastic resin composition of this invention 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 the thermoplastic 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 (A) may further contain a polycarbonate resin other than the polycarbonate resins (a1) and (a2), and is used in combination with an alloy (mixture) of the polycarbonate resin and another thermoplastic resin. Also good. Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; A copolymer with an oligomer or polymer having an olefin structure; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Good.

  In addition, the polycarbonate resin (A) may contain a polycarbonate oligomer in order to improve the appearance and fluidity of the molded product. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

[Styrene resin (B)]
The thermoplastic resin composition of the present invention contains a styrene resin (B). By containing the styrene resin (B), the fluidity (moldability) of the thermoplastic resin composition can be improved.
Here, the styrenic resin (B) is selected from aromatic vinyl monomers alone or other vinyl monomers and rubbery polymers copolymerizable with aromatic vinyl monomers as required. It is a resin obtained by polymerizing more than one species.

Examples of the aromatic vinyl monomer (b1) used in the styrene resin (B) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert. -Styrene derivatives such as butyl styrene, vinyl naphthalene, methoxy styrene, monobromo styrene, dibromo styrene, fluoro styrene, tribromo styrene and the like are mentioned, and styrene is particularly preferable.
These may be used alone or in combination of two or more.

  The other vinyl monomer copolymerizable with these aromatic vinyl monomers (b1) is preferably a vinyl cyanide monomer (b2), and examples thereof include acrylonitrile and methacrylonitrile.

In addition, as other monomers (b4), aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate Alkyl esters of acrylic acid such as cyclohexyl acrylate and dodecyl acrylate; aryl methacrylates such as phenyl methacrylate and benzyl methacrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl Methacrylate, cyclohexyl methacrylate Methacrylic acid alkyl esters such as acrylate and dodecyl methacrylate; epoxy group-containing methacrylic acid esters such as glycidyl methacrylate; maleimide monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide; acrylic acid, methacrylic acid, maleic acid, Examples include α, β-unsaturated carboxylic acids such as maleic anhydride, phthalic acid, and itaconic acid, and anhydrides thereof. Preferred are alkyl acrylates and alkyl methacrylates.
These other monomers (b4) may be used individually by 1 type, and 2 or more types may be mixed and used for them.

As the rubbery polymer (b3) copolymerizable with the aromatic vinyl monomer (b1), a rubber having a glass transition temperature of 10 ° C. or lower is suitable. Specific examples of such rubbery polymers include diene rubber, acrylic rubber, ethylene / propylene rubber, silicone rubber, polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber component so that they cannot be separated from each other. Composite rubber (IPN type rubber) having a structure entangled with each other is preferable, and diene rubber, acrylic rubber and the like are preferable.
In the present specification, “(meth) acrylate” refers to one or both of “acrylate” and “methacrylate”. The same applies to “(meth) acryl” and “(meth) acrylo”.

Examples of the diene rubber include polybutadiene, styrene-butadiene random copolymer and block copolymer, acrylonitrile-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, and ethylene-propylene-hexadiene copolymer. Examples thereof include a copolymer of ethylene, propylene and a non-conjugated diene, a lower alkyl ester copolymer of butadiene- (meth) acrylic acid, a lower alkyl ester copolymer of butadiene-styrene- (meth) acrylic acid, and the like.
Examples of the lower alkyl ester of (meth) acrylic acid include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.
The proportion of the lower alkyl ester of (meth) acrylic acid in the lower alkyl ester copolymer of butadiene- (meth) acrylic acid or the lower alkyl ester copolymer of butadiene-styrene- (meth) acrylic acid is that of the rubber polymer. It is preferable that it is 30 mass% or less of quantity.

  Examples of the acrylic rubber include acrylic acid alkyl ester rubber, and the carbon number of the alkyl group is preferably 1-8. Specific examples of the alkyl acrylate include ethyl acrylate, butyl acrylate, hexyl acrylate and the like. An ethylenically unsaturated monomer may optionally be used in the acrylic acid alkyl ester rubber. Specific examples of such compounds include di (meth) acrylate, divinylbenzene, trivinylbenzene, triallyl cyanurate, allyl (meth) acrylate, butadiene, isoprene and the like. Examples of the acrylic rubber include a core-shell type polymer having a crosslinked diene rubber as a core.

  As for these rubbery polymers (b3), one kind may be used alone, or two or more kinds may be mixed and used.

  The styrene resin (B) is composed of 50 to 100% by mass of the aromatic vinyl monomer component (b1), 0 to 30% by mass of the vinyl cyanide monomer component (b2), and the rubbery polymer component (b3). It is preferably composed of 0 to 30% by mass, other monomer component (b4) 0 to 30% by mass, aromatic vinyl monomer component (b1) 45 to 80% by mass, vinyl cyanide monomer component ( b2) 10-30% by mass, rubbery polymer component (b3) 10-25% by mass, other monomer component (b4) 0-40% by mass, more preferably aromatic vinyl monomer component (B1) 55 to 70% by mass, vinyl cyanide monomer component (b2) 15 to 25% by mass, rubbery polymer component (b3) 15 to 20% by mass, other monomer components (b4) 0 to More preferably, it consists of 5% by mass.

Specific examples of the styrenic resin (B) used in the present invention include, for example, a homopolymer of styrene, a copolymer of styrene and (meth) acrylonitrile, and a copolymer of styrene and an alkyl (meth) acrylate. Copolymers, copolymers of styrene and (meth) acrylonitrile and other copolymerizable monomers, graft copolymers obtained by polymerizing styrene in the presence of rubber, styrene and (meth) in the presence of rubber Preferable examples include graft copolymers obtained by graft polymerization with acrylonitrile.
More specifically, polystyrene, high impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), styrene-maleic anhydride copolymer (SMA resin), acrylonitrile-butadiene-styrene copolymer. Polymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer ( MABS resin), styrene-butadiene-styrene copolymer (SBS resin), hydrogenated styrene-butadiene-styrene copolymer (hydrogenated SBS), hydrogenated styrene-isoprene-styrene copolymer (SEPS), Acrylonitrile-acrylic rubber-styre System copolymer (AAS resin), acrylonitrile - ethylene-propylene rubber - styrene copolymer (AES resin) and styrene -IPN type rubber copolymer resin, or mixtures thereof. Further, it may have stereoregularity such as syndiotactic polystyrene. In addition, aromatic vinyl monomers can be widely used in place of the above styrene.

  Among these, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene system A rubber-styrene copolymer (AES resin) is preferred.

  Examples of the method for producing these styrene resins (B) include known methods such as an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk polymerization method. As the styrene resin (B), a bulk polymerization method is used. Is preferable because it is excellent in wet heat stability and thermal stability.

  These styrenic resins (B) may be used alone or in a combination of two or more.

  The content of the styrene resin (B) is 10 to 50% by mass, preferably 10 to 40% by mass, more preferably based on a total of 100% by mass of the polycarbonate resin (A) and the styrene resin (B). It is 10-35 mass%, Most preferably, it is 15-35 mass%. If the content of the styrenic resin body (B) exceeds 50% by mass, the strength tends to be unsatisfactory, and if it is less than 1% by mass, the fluidity improving effect becomes insufficient.

[Phosphorus flame retardant (C)]
The phosphorus-based flame retardant (C) in the present invention is a compound containing phosphorus in the molecule, which may be a low molecule, an oligomer, or a polymer, but from the viewpoint of thermal stability. For example, a condensed phosphate compound represented by the general formula (1) and a phosphazene compound represented by the general formulas (2) and (3) are particularly preferable.

-Condensed phosphate ester compound The condensed phosphate ester compound represented by the above general formula (1) may be a mixture of compounds having different numbers of k, and in the case of a mixture of condensed phosphate esters having different k K is the average of their mixture. k is usually an integer of 0 to 5, and in the case of a mixture of compounds having different k numbers, the average k number is preferably 0.5 to 2, more preferably 0.6 to 1.5, and even more preferably. Is in the range of 0.8 to 1.2, particularly preferably 0.95 to 1.15.

X ¹ represents a divalent arylene group such as resorcinol, hydroquinone, bisphenol A, 2,2′-dihydroxybiphenyl, 2,3′-dihydroxybiphenyl, 2,4′-dihydroxybiphenyl, 3,3 ′. -Dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, Divalent derivatives derived from dihydroxy compounds such as 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene It is a group. Of these, divalent groups derived from resorcinol, bisphenol A, and 3,3′-dihydroxybiphenyl are particularly preferable.

  Further, p, q, r and s in the general formula (1) each represent 0 or 1, and 1 is particularly preferable.

R ¹ , R ² , R ³ and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. Examples of such aryl groups include phenyl group, cresyl group, xylyl group, isopropylphenyl group, butylphenyl group, tert-butylphenyl group, di-tert-butylphenyl group, and p-cumylphenyl group. Group, cresyl group and xylyl group are more preferred.

As a specific example of the condensed phosphate ester compound represented by the general formula (1),
Triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate, bis- ( aromatic phosphates such as tert-butylphenyl) phenyl phosphate, tris- (tert-butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate;
Condensed phosphate esters such as resorcinol bis-diphenyl phosphate (RDP), resorcinol bis-dixylenyl phosphate (RDX), bisphenol A bis-diphenyl phosphate (BDP), biphenyl bis-diphenyl phosphate;
Etc.

  The acid value of the condensed phosphate ester compound represented by the general formula (1) is preferably 0.2 mgKOH / g or less, more preferably 0.15 mgKOH / g or less, still more preferably 0.1 mgKOH or less, Especially preferably, it is 0.05 mgKOH / g or less. The lower limit of the acid value can be substantially zero. On the other hand, the content of the half ester is more preferably 1.1 parts by mass or less, and still more preferably 0.9 parts by mass or less. When the acid value exceeds 0.2 mgKOH / g or the half ester content exceeds 1.5 mg, the thermal stability and hydrolysis resistance of the polycarbonate resin composition of the present invention are reduced.

  As the phosphoric ester compound, in addition to the above, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,3-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,4-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, containing phosphate ester moiety Naturally, polyester resins, polycarbonate resins or epoxy resins are also included.

-Phosphazene compounds As the phosphazene compounds represented by the general formulas (2) and (3), for example, phenoxyphosphazene, (poly) tolyloxyphosphazene (for example, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyl) Oxyphosphazenes, o, m-tolyloxyphosphazenes, o, p-tolyloxyphosphazenes, m, p-tolyloxyphosphazenes, o, m, p-tolyloxyphosphazenes), (poly) xylyloxyphosphazenes and the like / or or linear _{C 1-6} alkyl _{C 6-20} aryloxy phosphazene, (poly) phenoxy tolyloxy phosphazene (e.g., phenoxy o- tolyloxy phosphazene, a phenoxy m- tolyloxyethyl phosphazene, a phenoxy p- tolyloxy phosphatidyl Zen, phenoxy o, m-tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o, m, p-tolyloxyphosphazene, etc.), (poly) phenoxyxyloxyphosphazene And cyclic and / or chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxy phosphazene such as (poly) phenoxytolyloxyxyloxyphosphazene.
Of these, cyclic and / or chain phenoxyphosphazene, cyclic and / or chain C _1-3 alkyl C _6-20 aryloxyphosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20 Aryloxyphosphazenes (eg, cyclic and / or chain tolyloxyphosphazenes, cyclic and / or chain phenoxytolylphenoxyphosphazenes, etc.).

In the cyclic phosphazene compound represented by the general formula (2), R ⁵ and R ⁶ may be the same or different and each represents an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, and a benzyl group. Among them, cyclic phenoxyphosphazene in which R ⁵ and R ⁶ are phenyl groups is particularly preferable.
Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene, octachlorocyclohexane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group. .

  Moreover, in formula (2), t represents an integer of 3 to 25. Among them, a compound in which t is an integer of 3 to 8 is preferable, and a mixture of compounds having different t may be used. Among them, a mixture of compounds in which t = 3 is 50% by mass or more, t = 4 is 10 to 40% by mass, and t = 5 or more is 30% by mass or less is preferable.

In formula (3), R ⁷ and R ⁸ may be the same or different and each represents an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, a benzyl group, and the like, and a chain phenoxyphosphazene in which R ⁷ and R ⁸ are phenyl groups is particularly preferable.
Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above-described method to reverse polymerization at a temperature of 220 to 250 ° C., and the obtained linear dichloromethane having a polymerization degree of 3 to 10,000. Examples thereof include compounds obtained by substituting phosphazene with a phenoxy group.

Also, R ⁹ is represented by -N = P (OR ⁷ ) ₃ groups, -N = P (OR ⁸ ) ₃ groups, -N = P (O) OR ⁷ groups, and -N = P (O) OR ⁸ groups. At least one selected is shown, and R ¹⁰ is -P (OR ⁷ ) ₄ group, -P (OR ⁸ ) ₄ group, -P (O) (OR ⁷ ) ₂ group, -P (O) (OR ⁸ ) At least one selected from _two groups.

  Moreover, in Formula (3), u shows the integer of 3-10,000, Preferably it is 3-1,000, More preferably, it is 3-100, More preferably, it is 3-25.

Further, the phosphazene compound may be a crosslinked phosphazene compound partially crosslinked. By having such a crosslinked structure, the heat resistance tends to be improved.
Examples of such crosslinked phosphazene compounds include compounds having a crosslinking structure represented by the following general formula (4), for example, 4,4′-sulfonyldiphenylene (bisphenol S residue), 2,2- (4 , 4′-diphenylene) isopropylidene group-crosslinked structure, 4,4′-oxydiphenylene group-crosslinked structure, 4,4′-thiodiphenylene group-crosslinked structure, etc. Examples thereof include compounds having a crosslinked structure of 4,4′-diphenylene group.

［式（４）中、Ｘ^３は−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−Ｓ−、又は−Ｏ−であり、ｖは０又は１である。］

[In Formula (4), X ³ is —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—, and v is 0 or 1. ]

In addition, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound in which R ⁵ and R ⁶ are phenyl groups in the general formula (2) with a crosslinking group represented by the general formula (4). Alternatively, a crosslinked phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound in which R ⁷ and R ⁸ are phenyl groups in the general formula (3) with a crosslinking group represented by the general formula (4) is flame retardant. From the above point, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound with a crosslinking group represented by the general formula (4) is more preferable.

  The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (2) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (3) and Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  In the present invention, the phosphazene compound is a crosslinked phenoxy obtained by crosslinking the cyclic phenoxyphosphazene compound represented by the general formula (2) and the cyclic phenoxyphosphazene compound represented by the general formula (3) with a crosslinking group. In view of flame retardancy and mechanical properties, at least one selected from the group consisting of phosphazene compounds is preferable.

  The content of the phosphorus flame retardant (C) is 3 parts by mass or more, preferably 5 parts by mass or more, more preferably 8 parts, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the styrene resin (B). It is not less than 30 parts by mass, preferably not more than 25 parts by mass, more preferably not more than 20 parts by mass. When the blending amount of the phosphorus-based flame retardant (C) is less than 3 parts by mass, the flame retardancy is insufficient, and when it exceeds 30 parts by mass, a remarkable decrease in heat resistance and a decrease in mechanical properties are caused.

[Fluoropolymer (D)]
The thermoplastic resin composition of the present invention contains 0.01 to 2 parts by mass of the fluoropolymer (D) with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the styrene resin (B). One type of fluoropolymer (D) may be used, or two or more types may be used in any combination and in any ratio.

  Examples of the fluoropolymer (D) 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 a 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, Ltd. ”,“ 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 “Fullon D-210C” 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, 1 type may contain the dripping inhibitor and 2 or more types may contain it by arbitrary combinations and a ratio.

  The fluoropolymer (D) in the present invention preferably has a standard specific gravity value of 2.15 to 2.22. When the standard specific gravity is less than 2.15, the appearance of the molded product tends to deteriorate, which is not preferable. On the other hand, when the standard specific gravity exceeds 2.22, the drip resistance tends to decrease, such being undesirable. The standard specific gravity value is preferably 2.155 to 2.215, more preferably 2.16 to 2.1, particularly preferably 2.16 to 2.20, 2.165. Most preferred is ˜2.19. The standard specific gravity (also referred to as SSG) is a value measured by a water displacement method using a sample molded according to ASTM D4895.

  The average particle size of the fluoropolymer (D) in the present invention is not particularly limited, but is preferably 300 to 1,000 μm. If the average particle size is less than 300 μm, the drip resistance of the thermoplastic resin composition of the present invention may be reduced, and if it exceeds 1,000 μm, the fluoropolymer tends to aggregate, In such a case, the appearance defect such as white spot foreign matter may be caused, which is not preferable. From such a viewpoint, the average particle size of the fluoropolymer is more preferably 350 to 800 μm, further preferably 380 to 750 μm, and particularly preferably 400 to 700 μm.

  As described above, the content of the fluoropolymer (D) is 0.01 parts by mass or more, preferably 0.03 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the styrene resin (B). Part or more, more preferably 0.05 part by weight or more, particularly preferably 0.1 part by weight or more, and 2 parts by weight or less, preferably 1 part by weight or less, more preferably 0.7 parts by weight or less. It is. When the content of the fluoropolymer (D) is less than 0.01 parts by mass, the flame retardancy effect due to the anti-dripping agent is insufficient, and when the content exceeds 2 parts by mass, the thermoplastic resin composition is Appearance defects and mechanical strength of the molded product are likely to occur.

[Silicate compound (E)]
A silicate compound (E) is blended with the thermoplastic resin composition of the present invention. The silicate compound (E) has a large effect of preventing dripping of the molten resin at the time of combustion, can further improve the flame retardancy of the resin composition, and can improve rigidity and dimensional stability.
Specific examples of the silicate compound (E) include kaolin, talc, clay, mica, montmorillonite, wollastonite, natural silica, synthetic silica, various glass fillers, zeolite and diatomaceous earth, or a mixture thereof. However, talc, mica and wollastonite are preferred, and talc is most preferred from the balance of flame retardancy and dimensional stability. Among the above, talc is particularly effective in preventing molten resin drip during combustion.

Talc is not particularly limited, but is preferably 1.0 to 20.0 μm, more preferably 1.5 to 10 .mu.m in terms of a number average particle diameter measured by a sedimentation method (Asada method) using a light transmission particle size distribution analyzer. The talc is 0 μm, more preferably 2.0 to 7.0 μm. When the number average particle size is 1.0 μm or more, flame retardancy tends to be improved, and when it is 20.0 μm or less, the appearance of the molded product tends to be further improved.
The content of the Fe component and the Al component in talc is preferably 0.001 to 0.4% by mass, more preferably 0.001 to 0.2% by mass as Fe ₂ O ₃ and Al ₂ O ₃ , respectively. preferable.

The silicate compound (E) used in the present invention is for the purpose of increasing the affinity or interfacial binding force with the polycarbonate resin (A), the styrene resin (B) and the graft copolymer (F) described later. Various coupling agents can also be used.
As the coupling agent, silane-based, chromium-based and titanium-based coupling agents are usually used. Among them, those containing silane coupling agents such as epoxy silane compounds such as γ-glycidoxypropyltrimethoxysilane, vinyltrichlorosilane compounds and γ-aminopropyltriethoxysilane compounds are preferable. At this time, in order to improve mechanical strength and kneadability, treatment with various surfactants such as nonionic, cationic, and anionic types and dispersants such as fatty acids, metal soaps, and various resins may be performed. preferable.

  The preferable content of the silicate compound (E) is 0 to 5 parts by mass, and 0.5 to 4 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the styrene resin (B). More preferred.

[Graft Copolymer (E)]
The thermoplastic resin composition of the present invention preferably contains an elastomer. By containing the elastomer, the impact resistance of the thermoplastic resin composition can be improved.

The elastomer used in the present invention is preferably a graft copolymer obtained by graft copolymerizing a rubbery polymer with a monomer component copolymerizable therewith. Of course, this graft copolymer is different from the styrene resin (B) described above.
The production method of the graft copolymer may be any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft.

The rubbery polymer generally has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower.
Specific examples of the rubbery polymer include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate, poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate-2-ethylhexyl acrylate copolymer, and polyorganosiloxane rubber. Such as silicone rubber, butadiene-acrylic composite rubber, composite rubber made of polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-α- such as ethylene-octene rubber Examples thereof include olefin rubber, ethylene-acrylic rubber, and fluorine rubber. These may be used alone or in admixture of two or more.
Among these, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferable from the viewpoint of mechanical properties and surface appearance.

Examples of monomer components that can be graft copolymerized with the rubbery polymer include epoxy compounds such as aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and glycidyl (meth) acrylates. Group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (For example, maleic anhydride). These monomer components may be used alone or in combination of two or more.
Of these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and more preferably aromatic vinyl compounds, A vinyl cyanide compound and a (meth) acrylic acid ester compound are preferred, and a (meth) acrylic acid ester compound is more preferred. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, (meta ) Phenyl acrylate and the like.

The graft copolymer obtained by copolymerizing the rubbery polymer is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubbery polymer selected from polybutadiene-containing rubber, polybutylacrylate-containing rubber, polyorganosiloxane rubber, and composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber is used as a core layer, A core / shell type graft copolymer comprising a shell layer formed by copolymerizing (meth) acrylic acid ester is particularly preferred.
The core / shell type graft copolymer preferably contains 40% by mass or more of a rubbery polymer, more preferably 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid is preferable.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone IPN rubber) copolymers. Such rubbery polymers may be used alone or in combination of two or more.

  Examples of such core / shell type graft copolymers include “Paraloid EXL2602”, “Paraloid EXL2603”, “Paraloid EXL2655”, “Paraloid EXL2311”, “Paraloid EXL2313”, manufactured by Rohm and Haas Japan. “Paraloid EXL2315”, “Paraloid KM330”, “Paraloid KM336P”, “Paraloid KCZ201”, manufactured by Mitsubishi Rayon Co., Ltd., “Metabrene C-223A”, “Metabrene E-901”, “Metabrene S-2001”, “Metabrene SRK-” 200, manufactured by Kaneka Corporation, “Kane Ace M-511”, “Kane Ace M-600”, “Kane Ace M-400”, “Kane Ace M-580”, “Kane Ace MR-01”, and the like.

  The content of such a graft copolymer is preferably 0.5 parts by mass or more, more preferably 0.75 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the styrene resin (B). As mentioned above, More preferably, it is 1 mass part or more, Preferably it is 10 mass parts or less, More preferably, it is 7.5 mass parts or less, More preferably, it is 6 mass parts or less. When the graft copolymer is less than the lower limit of the above range, the impact resistance improvement effect by the elastomer may be insufficient, and when the content of the graft copolymer exceeds the upper limit of the above range, There is a possibility that the appearance defect, heat resistance, and flame retardancy of a molded product obtained by molding the polycarbonate resin composition may be reduced.

  The above-mentioned polycarbonate resin (a1), polycarbonate resin (a2), and styrene resin (B) are blended with a phosphorus-based flame retardant (C), a fluoropolymer (D), and a silicate compound (E). By blending the graft copolymer in the specific amounts described above, a polycarbonate / styrene resin alloy having excellent flame retardancy, impact resistance and appearance, and also excellent impact strength during high temperature molding is possible. Become.

[Carbon black]
The thermoplastic resin composition of the present invention preferably contains carbon black from the viewpoint of improving the high-quality feeling of the molded product. There are no restrictions on the production method of carbon black to be used, the raw material species, etc., and any conventionally known ones such as oil furnace black, channel black, acetylene black, ketjen black and the like can be used. Among these, oil furnace black is preferable from the viewpoint of colorability and cost.

  The average particle size of the carbon black to be used may be appropriately selected and determined, and among these, 5 to 60 nm is preferable, 7 to 55 nm is more preferable, and 10 to 50 nm is particularly preferable. By setting the average particle diameter within the above range, the aggregation of carbon black is suppressed and the appearance tends to be improved. The average particle diameter of carbon black can be obtained using a transmission electron microscope.

Nitrogen adsorption specific surface area of the carbon black used in the present invention is preferably usually less than 1000 m ² / g, is preferably Among them 50 to 400 m ² / g. By making the nitrogen adsorption specific surface area less than 1000 m ² / g, the fluidity of the thermoplastic resin composition of the present invention and the appearance of the molded product tend to be improved, which is preferable. The nitrogen adsorption specific surface area can be measured according to JIS K6217 (unit: m ² / g).

The DBP absorption of carbon black ^is preferably less than 300 cm 3/100 g, is preferably Among them 30~200cm ³ / 100g. The DBP absorption amount by less than 300 cm ^3/100 g, preferably tends to increase the appearance of fluidity and a molded article of the thermoplastic resin composition of the present invention.

Incidentally, DBP absorption amount can be measured according to JIS K6217 (unit ^cm 3 / 100g). The carbon black used in the present invention is not particularly limited with respect to its pH, but it is usually 2 to 10, preferably 3 to 9, and more preferably 4 to 8.

  Carbon black can be used alone or in combination of two or more. Furthermore, carbon black can be granulated using a binder, and can also be used in a masterbatch that is melt-kneaded at a high concentration in another resin. By using the melt-kneaded master batch, the handling property during extrusion and the dispersibility improvement in the resin composition can be achieved. Examples of the resin include polystyrene resin, polycarbonate resin, acrylic resin, and the like.

  The content of carbon black is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and still more preferably with respect to 100 parts by mass in total of the polycarbonate resin (A) and the styrene resin (B). It is 0.001 part by mass or more, preferably 2 parts by mass or less, more preferably 1 part by mass or less. When the carbon black is less than the lower limit of the range, the appearance and jet blackness may be inferior, and when the carbon black content exceeds the upper limit of the range, the heat of the thermoplastic resin composition of the present invention. Stability may be reduced.

[Phenolic stabilizer]
The thermoplastic resin composition of the present invention preferably contains a phenol-based 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-hydroxyphenyl) propionamide], 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 ″-( Mesitylene-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- ert- 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 stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the styrene resin (B). The amount is usually 1 part by mass or less, preferably 0.5 part 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.

[Release agent]
It is also preferable to contain a release agent (lubricant). Preferable 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 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 mold 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, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the styrene resin (B). Usually 2 parts by mass or less, preferably 1 part by mass 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 may occur.

[Phosphorus stabilizer]
The thermoplastic resin composition of the present invention preferably contains a phosphorus stabilizer. 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 100 parts by mass in total of the polycarbonate resin (A) and the styrene resin (B). It is 0.03 mass part or more, and 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.

[Other ingredients]
The thermoplastic 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 those described above 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, polybutylene terephthalate resin; polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resins; polyimide resins; Examples include imide resins; polyurethane resins; polyphenylene ether resins; polyphenylene sulfide resins;
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.

-Resin additive Examples of the resin additive include an ultraviolet absorber, a dye / pigment, an antistatic agent, an antifogging agent, an antiblocking agent, a fluidity improver, a plasticizer, a dispersant, and an antibacterial agent. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
Hereinafter, the example of an additive suitable for the thermoplastic resin composition of this invention is demonstrated concretely.

..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 thermoplastic 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- (2H-benzotriazol-2-yl) phenol], among others, 2- (2′-hydroxy-5′-tert-octylphenyl) ) Benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-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 Yakuhin 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, “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 with respect to 100 parts by mass in total of the polycarbonate resin (A) and the styrenic resin (B). Usually, it is 3 parts by mass or less, preferably 2 parts by mass or less, more preferably 1 part by mass or less. 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 in total of the polycarbonate resin (A) and the styrene resin (B). . If the content of the dye / pigment is too large, the impact resistance may not be sufficient.

[Method for producing thermoplastic resin composition]
There is no restriction | limiting in the manufacturing method which manufactures the thermoplastic resin composition of this invention, The manufacturing method of a well-known thermoplastic resin composition can be employ | adopted widely.
Specific examples include polycarbonate resin (A), styrene resin (B), phosphate ester compound (C), fluoropolymer (D), silicate compound (E), and blended as necessary. Other components are mixed in advance using various mixers such as tumblers and Henschel mixers, and then melt-kneaded with a mixer such as a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, or kneader. The method of doing is mentioned.

In addition, for example, the thermoplastic resin composition of the present invention is manufactured without 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. 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 thermoplastic 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 thermoplastic resin composition of the present invention is flame retardant according to the UL94 test at a thickness of 1.8 mm in the UL94 test (combustion test of plastic materials for equipment parts) defined by US Underwriters Laboratories (UL). However, it has a very high flame retardancy of preferably 5 VA or 5 VB.
Further, the thermoplastic resin composition of the present invention has a feature that there is little reduction in impact resistance even when it is molded at a high temperature. Specifically, a 3 mm thick ISO multipurpose test piece molded at 260 ° C. (notched Charpy impact strength (260 ° C. impact strength) of a 3 mm thick ISO multipurpose test piece molded at 240 ° C. (260 The ratio of (° C. impact strength) (260 ° C. impact strength / 240 ° C. impact strength) is preferably 0.8 or more.

[Molded body]
The thermoplastic resin composition of the present invention is usually molded into an arbitrary shape and used as a molded body (resin composition molded body). There is no restriction | limiting in the shape, pattern, color, dimension, etc. of this molded object, What is necessary is just to set arbitrarily according to the use of the molded object.

  Examples of the molded body include parts such as electric / electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, and lighting equipment. Among these, it is particularly suitable for use in housings of electric / electronic devices and OA devices, and is particularly suitable for housings such as printers, copiers, projectors, modems and routers.

The manufacturing method of a molded object is not specifically limited, The molding method generally employ | adopted about the thermoplastic resin composition can be employ | adopted arbitrarily. 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 insulating 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. A molding method using a hot runner method can also be used.
The obtained molded article of the present invention is excellent in flame retardancy, impact resistance and appearance.

  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 1-14, Comparative Examples 1-4)
[Production of resin pellets]
Of the components listed in Table 1, the components other than the component (C) were blended at the ratios (mass ratios) described in Tables 3 to 6 and mixed for 20 minutes with a tumbler. Supply to the twin screw extruder (TEX30α) from the upstream feeder, and further knead with the component (C) from the middle of the barrel at a rotational speed of 250 rpm, a discharge rate of 45 kg / hour, and a barrel temperature of 260 ° C. The molten resin extruded in a strand shape was quenched in a water tank and pelletized using a pelletizer to obtain a resin composition pellet.

[Preparation of test piece]
After drying the pellets obtained by the above-mentioned production method at 80 ° C. for 5 hours, injection is performed under the conditions of a cylinder temperature of 240 ° C. and a mold temperature of 40 ° 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 1.8 mm was molded.
Similarly, after the pellets obtained by the above-described production method are dried at 80 ° C. for 5 hours, the cylinder temperature is 240 using an injection molding machine CYCAP M-2 (clamping force 75T) manufactured by Sumitomo Heavy Industries, Ltd. Injection molding was performed under the conditions of ℃ and mold temperature of 60 ℃, and a 240 ℃ molded ISO multipurpose test piece (3 mm) was molded.
Further, injection molding was performed under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C., and a 260 ° C. molded ISO multipurpose test piece (3 mm) was molded.

[Flame retardance evaluation]
The flame retardancy of each resin composition was evaluated by conditioning the test piece (1.8 mm thickness) obtained above for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity. The test was conducted in accordance with the 94-5V standard of the UL94 test (combustion test of plastic materials for parts of equipment) defined by Underwriters Laboratories (UL).
The 94-5V test uses 1.8 mm-thick UL test specimens (two types of rod and plate), the afterflame time of the rod-shaped test piece after 5 seconds of flame contact, drip properties, The method of evaluating flame retardance from the presence or absence of through-holes in a plate-shaped test piece, and the determination criteria are as shown in Table 2 below. Those not satisfying any criteria of 5VA and 5VB were expressed as NR.

[Shock resistance]
Using the 240 ° C. molded ISO multipurpose test piece (3 mm) and the 260 ° C. molded ISO multipurpose test piece (3 mm) obtained by the above-described method, the Charpy impact strength with a notch was measured in accordance with ISO179. In Tables 3 to 5, they are expressed as “240 ° C. impact resistance (unit: kJ / m ² )” and “260 ° C. impact resistance (unit: kJ / m ² )”, respectively.
In addition, when the value of “240 ° C. impact resistance” is 1, the ratio of “260 ° C. impact resistance” (260 ° C. impact resistance / 240 ° C. impact resistance) is obtained as “impact resistance retention rate”. It was. A larger value means that there is less deterioration in physical properties even at high temperature molding, which means that when molding a large and thin molded product, the decrease in physical properties is small and it is easy to design.

[Appearance evaluation]
FIG. 1 is a top view (viewed from the design surface on the front side) showing the shape of a flat molded body formed for appearance evaluation. The flat molded body is a rectangular flat plate having a length of 200 mm, a width of 150 mm, and a thickness of 2 mm. Molding is performed by injecting resin from a gate provided at the right end of the flat molded body. On the back side of the flat molded body, three ribs having a length of 30 mm, a thickness of 1.1 mm and a height of 5 mm in the resin flow direction are arranged at three positions at the position shown in FIG. 1 (the numerical value is mm). One rib having a length of 100 mm, a thickness of 1.1 mm and a height of 5 mm is provided on the back surface side of the flat plate-shaped body in parallel with the resin flow direction.
The pellets obtained by the above production method were dried at 80 ° C. for 5 hours, and then injection molded under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C. using an EC160 type injection molding machine manufactured by Toshiba Machine. On the design surface (the left side of the three flow direction ribs in FIG. 1) after forming the flat plate shaped body, passing through the ribs orthogonal to the flow direction of the resin, and further passing through the three ribs provided in the flow direction The number of black streaky appearance defects that occurred was visually observed, and the number of streaky appearance defects of 0 to 3 was “◯” (passed), and 4 or more were “x” (failed). ).

From Table 3 and Table 5 above, the polycarbonate resins (a1) and (a2), the styrene resin (B), the phosphorus flame retardant (C), the fluoropolymer (D), and the silicate compound (E) defined in the present invention. ) In the range specified in the present invention, the UL flame retardance at 1.8 mm thickness achieves 5 VB, excellent impact resistance, and impact resistance retention rate It is high and it can be seen from the appearance evaluation that there are few black streak-like appearance defects.
On the other hand, from Table 4, since Comparative Examples 1 and 2 do not contain the polycarbonate resin (a2) or the content is low, the impact resistance and the impact resistance retention rate are poor, and the fluoropolymer (D) and the silicate compound ( It can be seen that Comparative Example 3 containing no E) has poor flame retardancy and cannot achieve 5 VB, and Comparative Example in which the content of the silicate compound (E) is too large has extremely poor impact resistance. .

  Since the thermoplastic resin composition of the present invention is a polycarbonate resin / styrene resin alloy having excellent flame retardancy, impact resistance and appearance, and also excellent impact strength at high temperature molding, It is suitable for parts such as equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, lighting equipment, etc., and has high industrial applicability.

Claims (6)

15 to 90% by mass of polycarbonate resin (a1) having a crystal melting heat of 15 mJ / g or more measured with a differential scanning calorimeter (DSC) and 5 mJ / g of crystal melting heat measured with a differential scanning calorimeter (DSC) Polycarbonate resin (A2) 50 to 90% by mass consisting of 85 to 10% by mass of polycarbonate resin (a2), and (A) and (B) consisting of 50 to 10% by mass of styrene resin (B) 100 in total For mass parts
A thermoplastic resin composition comprising 3 to 30 parts by mass of a phosphorus-based flame retardant (C), 0.01 to 2 parts by mass of a fluoropolymer (D) and 0 to 5 parts by mass of a silicate compound (E).   The thermoplastic resin composition according to claim 1, wherein the styrenic resin (B) is an ABS resin and / or an AS resin.   Further, a graft copolymer (F) obtained by graft-polymerizing at least one selected from a monomer comprising an aromatic vinyl compound, a vinyl cyanide compound component and a (meth) acrylic ester compound on a rubber polymer. The thermoplastic resin composition according to claim 1 or 2, wherein 0.5 to 10 parts by mass is blended with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the styrene resin (B).   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the phosphorus-based flame retardant (C) is a condensed phosphate ester and / or a phosphazene compound.   Notched Charpy impact strength (260 ° C. impact strength) of 3 mm thick ISO multi-purpose test piece molded at 260 ° C. relative to notched Charpy impact strength (240 ° C. impact strength) of 3 mm thick ISO multi-purpose test piece molded at 240 ° C. The thermoplastic resin composition according to claim 1, wherein the ratio (260 ° C. impact strength / 240 ° C. impact strength) is 0.8 or more.   The thermoplastic resin composition according to any one of claims 1 to 5, wherein the flame retardancy by UL94 at a thickness of 1.8 mm is 5 VA or 5 VB.

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