JP6356050B2 - Polycarbonate resin composition and molded article - Google Patents

Description

  The present invention relates to a polycarbonate resin composition and a molded article, and more specifically, relates to a polycarbonate resin composition and a molded article comprising the polycarbonate resin composition that simultaneously achieve both rigidity / proof strength and moldability / fluidity at a higher level.

Conventionally, polycarbonate resin is excellent in transparency, impact resistance, heat resistance, etc., and the resulting molded product is also excellent in dimensional stability, so electrical / electronic equipment parts, OA equipment parts, machine parts, It is used in a wide range of fields such as vehicle parts.
Furthermore, a polymer alloy composed of a polycarbonate resin and a thermoplastic polyester resin is a material with improved chemical resistance and molding processability, which are disadvantages of the aromatic polycarbonate resin, while taking advantage of the above-mentioned excellent features of the polycarbonate resin. It is used in vehicle interior / exterior parts, various housing members and other wide fields.
A polymer alloy composed of a polycarbonate resin and a thermoplastic polyester resin is often mixed with an inorganic filler in order to improve its rigidity and dimensional stability. However, the resin composition containing an inorganic filler has a problem that molding processability (fluidity) decreases.

In recent years, in the above-mentioned various parts applications, the demand for thin and high rigidity is extremely strong, and even if it contains a large amount of inorganic filler, it has high rigidity and proof strength, and is excellent in fluidity and moldability. There is a strong demand.
In order to improve the moldability and fluidity of a polymer alloy composed of a polycarbonate resin and a thermoplastic polyester resin, it is possible to lower the viscosity of the resin itself, but the rigidity and proof stress are lowered. Rigidity and proof stress, moldability and fluidity are contradictory, and it is necessary to solve them in a balanced manner.

  In the resin composition containing the wollastonite in the polycarbonate resin and the thermoplastic polyester resin in Patent Document 1, the applicant of the present invention is characterized in that the wollastonite is present in the polycarbonate resin phase. However, it has been proposed to be excellent in rigidity, fluidity, impact resistance and the like. It is also described that various rubber polymers are blended for improving impact resistance, and examples using various core / shell type graft copolymers are also disclosed in the examples. However, it is not necessarily sufficient in terms of balancing both rigidity / proof strength and formability / fluidity at a higher level.

JP 2009-35616 A

  An object of the present invention is to provide a polycarbonate resin composition and a molded article thereof that simultaneously achieve both the rigidity / proof strength and the moldability / fluidity characteristics at a higher level in view of the problems of the prior art. .

As a result of intensive studies to achieve the above-mentioned problems, the present inventors blended a specific amount of a thermoplastic polyester resin and an inorganic filler into an aromatic polycarbonate resin having a specific viscosity average molecular weight, and unsaturated into this. It was found that when a specific amount of the carboxylic acid-modified styrenic rubber polymer was blended, both the rigidity / proof strength and the moldability / flowability characteristics were simultaneously achieved at a higher level, and the present invention was completed. .
The present invention is the following polycarbonate resin composition and molded article.

[1] Aromatic polycarbonate resin (A) having a viscosity average molecular weight of 18,000 to 50,000 contains more than 50% by mass to 90% by mass and thermoplastic polyester resin (B) of 10% by mass to less than 50% by mass. 5 to 25 parts by mass of the inorganic filler (C) and 3 of the unsaturated carboxylic acid-modified styrenic rubber polymer (D) with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). A polycarbonate resin composition comprising ˜15 parts by mass.
[2] The polycarbonate resin composition according to the above [1], wherein the inorganic filler (C) is an acicular inorganic filler.
[3] The polycarbonate resin composition according to the above [1] or [2], wherein the inorganic filler (C) is wollastonite.
[4] The polycarbonate resin composition according to any one of [1] to [3], wherein the thermoplastic polyester resin (B) is polybutylene terephthalate.
[5] The polycarbonate resin composition according to any one of [1] to [4], wherein the unsaturated carboxylic acid-modified styrenic rubber polymer (D) is an unsaturated carboxylic acid-modified SEBS resin.
[6] A molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [5].

The polycarbonate resin composition of the present invention and a molded product comprising the same can simultaneously achieve both the rigidity / proof strength and the moldability / flowability at a higher level.
The reason why the polycarbonate resin composition of the present invention exhibits such an effect is that, by blending the unsaturated carboxylic acid-modified styrenic rubber polymer (D) from among various rubber polymers, The surface functional group is chemically captured by the carboxylic acid grafted to the styrene rubber polymer (D), thereby providing an adhesive effect. Furthermore, the aromatic polycarbonate resin as the matrix resin, and the styrene resin Due to the compatibility of the polystyrene block, which is the hard segment of the rubber polymer (D), the individual inorganic filler (C) that usually tends to exist in the polyester resin (B) as a crystal nucleus becomes an unsaturated carboxylic acid. It exists in the form of inclusion in the modified styrenic rubbery polymer (D), which is uniformly dispersed in the polycarbonate resin matrix, Wear resistance is remarkably improved, it is considered that to improve toughness (tensile elongation, etc.). By realizing such form control, it is presumed that the styrene rubber polymer (D) acts as a buffer phase of the inorganic filler (C) in the aromatic polycarbonate resin as the matrix resin, and at the time of injection molding It is considered that the fluidity is improved by increasing the followability in the shear-flow direction.

  FIG. 1 is a diagram showing the results of observation performed to confirm such an effect from the morphology of the resin composition. 1B on the right side is a diagram showing the result of observing the micro morphology of the resin composition obtained in Example 1. FIG. In the figure, the black bar is the inorganic filler (C), but it is surrounded by the unsaturated carboxylic acid-modified styrenic rubber polymer (D) and is uniformly dispersed in the polycarbonate resin matrix. It was confirmed that On the other hand, FIG. 1-a is a micro view of Comparative Example 4 in which a rubbery polymer other than the unsaturated carboxylic acid-modified styrene-based rubbery polymer (D) is blended. As shown in the figure, an inorganic filler is used. It was confirmed that (C) became a crystal nucleus and existed in the polyester resin (B).

It is a figure which shows the result of having observed the micro form of the resin composition, FIG. 1-b is a micro form figure of the resin composition of Example 1, FIG. 1-a is the micro form of the resin composition of the comparative example 4. FIG.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is interpreted to be limited to such embodiments and specific examples. is not.
In the present specification, unless otherwise specified, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

[Overview]
The polycarbonate resin composition of the present invention comprises an aromatic polycarbonate resin (A) having a viscosity average molecular weight of 18,000 to 50,000 and more than 50% by mass to 90% by mass and thermoplastic polyester resin (B) 10% by mass to 50%. 5 to 25 parts by mass of an inorganic filler (C), unsaturated carboxylic acid-modified styrene rubbery heavy to 100 parts by mass in total of polycarbonate resin (A) and thermoplastic polyester resin (B) containing less than mass% It contains 3 to 15 parts by mass of coalesced (D).

[Aromatic polycarbonate resin (A)]
The aromatic polycarbonate resin (A) used in the polycarbonate resin composition of the present invention is not limited in its kind, and may be used alone, or two or more kinds in any combination and in any ratio, You may use together.
The aromatic polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by a general formula — (— O—X—O—C (═O) —) —. In the formula, X is an aromatic hydrocarbon, but for imparting various properties, X into which a hetero atom or a hetero bond is introduced may be used.
The aromatic polycarbonate resin refers to a polycarbonate resin in which carbons directly bonded to carbonic acid bonds are aromatic carbons. Aromatic polycarbonate is excellent from the viewpoints of heat resistance, mechanical properties, electrical characteristics, etc., among various polycarbonates.

  Although there is no restriction | limiting in the specific kind of aromatic polycarbonate resin, For example, the aromatic polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Alternatively, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. The aromatic polycarbonate polymer may be linear or branched. Furthermore, the aromatic polycarbonate polymer may be a homopolymer composed of one type of repeating unit, or may be 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. Normally, such an aromatic polycarbonate polymer is a thermoplastic resin.

  Examples of the aromatic dihydroxy compound among the monomers used as the raw material for the aromatic polycarbonate resin are as follows.

Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl;
2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

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

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,2-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) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,10-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,
1,4-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

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;
And dihydroxydiaryl sulfones such as 4,4′-dihydroxydiphenyl sulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone;

Of these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferable in terms of impact resistance and heat resistance. (Ie 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.

Among the monomers used as the raw material for the aromatic polycarbonate resin, carbonyl halides, carbonate esters and the like are used as examples of the carbonate precursor. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.
Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.
Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as

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

.. Interfacial polymerization method First, the case of producing an aromatic polycarbonate resin 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. An aromatic 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 the 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 them, sodium hydroxide and Potassium hydroxide 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. In particular, it is preferably set to 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; 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 monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides, and the like. Among them, aromatic phenols are preferable. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-oxinebenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a polycarbonate resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as the desired aromatic polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. 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 an aromatic 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. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly 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 aromatic 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. It is more preferable to use the above. 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 aromatic 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, an aromatic polycarbonate resin in which the terminal hydroxyl group amount is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound, the degree of pressure reduction during the transesterification reaction, and the like. In addition, the molecular weight of the aromatic polycarbonate resin 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 an aromatic polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.
The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing by a batch type, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily. However, considering the stability of the aromatic polycarbonate resin and the polycarbonate resin composition, the melt polycondensation reaction is preferably carried out continuously.

In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to aromatic polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

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

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

Therefore, the aromatic polycarbonate resin (A) has a structural viscosity index N of usually 1.2 or more, preferably 1.25 or more, more preferably 1.28 or more, and usually 1.8 or less, preferably It is preferable to contain a polycarbonate resin of 1.7 or less in a certain ratio or more.
Thus, the high structural viscosity index N means that the polycarbonate resin has a branched structure. By containing the polycarbonate resin having a high structural viscosity index N in this way, dripping at the time of burning of the polycarbonate resin molded product Can be suppressed and flame retardancy can be improved.

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

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

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

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

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

  The molecular weight of the aromatic polycarbonate resin (A) of the present invention is 18,000 to 50,000 in terms of viscosity average molecular weight [Mv]. When the viscosity average molecular weight is less than 18,000, the mechanical strength is not sufficient, and when the viscosity average molecular weight exceeds 50,000, the fluidity is poor and the moldability is deteriorated. The viscosity average molecular weight is preferably 19,000 or more, more preferably 20,000 or more, further preferably 21,000 or more, particularly 22,000 or more, preferably 45,000 or less, more preferably Is 40,000 or less, more preferably 36,000 or less, and particularly preferably 33,000 or less. The molecular weight can be adjusted to such a range by a known method such as controlling the amount of the molecular weight regulator as described later.

In the present specification, the viscosity average molecular weight [Mv] of the polycarbonate resin 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. This means a value calculated from 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).

Other matters regarding aromatic polycarbonate resin The terminal hydroxyl group concentration of the aromatic polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1,000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. . Thereby, the residence heat stability and color tone of the polycarbonate resin composition of the present invention can be further improved. The lower limit is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more, particularly in the case of an aromatic polycarbonate resin produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of the polycarbonate resin composition of this invention can be improved more.
In addition, the unit of a terminal hydroxyl group density | concentration displays the mass of the terminal hydroxyl group with respect to the mass of aromatic polycarbonate resin in ppm. The measuring method is performed by colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by a titanium tetrachloride / acetic acid method.

  The aromatic polycarbonate resin is not limited to an embodiment containing only one type of aromatic polycarbonate resin, and a mixture of two or more types of aromatic polycarbonate resins having different monomer compositions, molecular weights, terminal hydroxyl group concentrations, and the like is used. Also good. Moreover, you may use combining as an alloy (mixture) which mixed another thermoplastic resin with aromatic polycarbonate resin.

  Further, for example, for the purpose of further improving flame retardancy and impact resistance, an aromatic polycarbonate resin is a copolymer with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy. Copolymer with monomer, oligomer or polymer having phosphorus atom; copolymer with monomer, oligomer or polymer having dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; polystyrene to improve optical properties A copolymer with an oligomer or polymer having an olefinic structure such as; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; May be.

  Moreover, in order to aim at the improvement of the external appearance of a molded article, and the improvement of fluidity | liquidity, you may contain the polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the aromatic polycarbonate resin (including the polycarbonate oligomer).

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

[Thermoplastic polyester resin (B)]
As the thermoplastic polyester resin (B) used in the polycarbonate resin composition of the present invention, a condensation mainly comprising a dicarboxylic acid component comprising a dicarboxylic acid or a reactive derivative thereof and a diol component comprising a diol or an ester derivative thereof. Although it is a polymer or copolymer obtained by the reaction, preferably, a thermoplastic polyester resin obtained by polycondensation reaction of an aromatic dicarboxylic acid as a main acid component and an alcohol mainly containing an aliphatic diol is used. Use.

  Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenylether dicarboxylic acid 4,4′-biphenylmethanedicarboxylic acid, 4,4′-biphenylsulfonedicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-ter-phenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, and the like, and substituted products thereof (for example, 5- Alkyl group-substituted products such as methyl isophthalic acid) and reactive derivatives (eg dimethyl terephthalate) Le, alkyl ester derivatives such as diethyl terephthalate) and the like can also be used.

  Of these, terephthalic acid, 2,6-naphthalenedicarboxylic acid and their alkyl ester derivatives are more preferred, and terephthalic acid and its alkyl ester derivatives are particularly preferred. These aromatic dicarboxylic acids may be used alone or in combination of two or more, and together with the aromatic dicarboxylic acid, an aliphatic dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, One or more alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid may be used in combination.

  Diols include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, triethylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6- Aliphatic diols such as hexanediol, decamethylene glycol, 2,2-dimethyl-1,3-propanediol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanediol, trans- or cis- Alicyclic diols such as 2,2,4,4-tetramethyl-1,3-cyclobutanediol; p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether) Etc.) It can be mentioned aromatic diol, and the like, can also be used these substituents.

  Of these, aliphatic diols are preferable, ethylene glycol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are more preferable, and ethylene glycol is particularly preferable from the viewpoints of heat resistance and dimensional stability.

  Diols may be used alone or in combination of two or more. Further, as the diol component, a long chain diol having a molecular weight of 400 to 6,000, that is, one or more of polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like are used in combination with the diols. It may be copolymerized.

  The thermoplastic polyester resin (B) can be copolymerized with a hydroxycarboxylic acid such as parahydroxybenzoic acid, other carboxylic acids, and alcohols other than the diol. In the present invention, such a copolymer resin is used. Can also be used. However, it is preferable that such a copolymerization component is a small amount, and 80% by mass or more, further 90% by mass or more of the thermoplastic polyester resin (B) is a component from an aromatic dicarboxylic acid and an aliphatic diol. Is preferred. The aromatic dicarboxylic acid and the aliphatic diol each preferably occupy 80 mol% or more, more preferably 90 mol% or more, with one compound.

  Preferable specific examples of such thermoplastic polyester resin (B) include polybutylene terephthalate, polybutylene naphthalate, polycyclohexanedimethanol terephthalate, polyethylene terephthalate, and polyethylene naphthalate. These may contain a copolymerization component. In the present invention, among these, it is preferable to use polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), and it is also preferable to use both in combination. When used in combination, the ratio is preferably PET: PBT = 1: 1 to 1: 8 (mass ratio).

  As the polymerization catalyst for producing polyethylene terephthalate, germanium compounds, antimony compounds, tin compounds, titanium compounds and the like are known. In the present invention, it is preferable to use a polymer obtained by polymerizing a germanium compound as a catalyst. When the polymerized with another catalyst is used, the thermal stability and recyclability of the composition with the finally obtained aromatic polycarbonate resin tends to be lowered. Germanium compounds used as catalysts include germanium oxides such as germanium dioxide, germanium alkoxides such as germanium tetraethoxide, germanium tetraisopropoxide, germanium hydroxide and its alkali metal salts, germanium glycolate, germanium chloride, germanium acetate, etc. Is mentioned. These may be used alone or in combination of two or more. Of these, germanium dioxide is preferably used from the viewpoint of solvent resistance and thermal stability of the resulting polyethylene terephthalate.

  The germanium catalyst is preferably used so as to be 15 ppm to 40 ppm as germanium atoms in the polyethylene terephthalate to be produced. If it is less than 15 ppm, the polymerization reaction proceeds slowly, and if it exceeds 40 ppm, a side reaction may occur due to the germanium compound remaining in the resin.

  As polybutylene terephthalate, it is preferable to use a polymer obtained by polymerizing a titanium compound as a main catalyst and a group 1 metal compound or a group 2 metal compound as a cocatalyst. Examples of the titanium compound include inorganic titanium compounds such as titanium oxide and titanium tetrachloride; titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate and tetrabutyl titanate; titanium phenolates such as tetraphenyl titanate and the like. . Of these, titanium alcoholates are preferably used. Most preferred are tetraalkyl titanates, especially tetrabutyl titanate.

  The titanium compound is preferably used in the resulting polybutylene terephthalate so as to be 20 to 50 ppm, particularly 30 to 40 ppm in terms of titanium atoms. When the amount of the titanium compound used is too large, the color tone and hydrolysis resistance of the polybutylene terephthalate to be produced may decrease, or solution haze and foreign matter increase may occur due to the deactivation of the titanium catalyst. Conversely, if the amount is too small, the polymerizability of polybutylene terephthalate tends to decrease.

  As a molecular weight of the thermoplastic polyester resin (B), an intrinsic viscosity (Iv) measured at 30 ° C. in a mixed solvent of phenol and tetrachloroethane (mass ratio = 50/50) is 0.4 to 2.0. Is preferred. If a material having an intrinsic viscosity of less than 0.4 is used, the mechanical strength of the resin composition is inferior. Conversely, if the material has a viscosity exceeding 2.0, the moldability tends to decrease. The preferable intrinsic viscosity of the thermoplastic polyester resin (B) is 0.6 to 1.2.

  In addition, as the thermoplastic polyester resin (B), not only virgin products but also those recycled from used products, so-called material-recycled ones can be used. What was reproduced | regenerated from the runner etc. can also be used and it is also preferable to use such a recycled material for a thermoplastic polyester resin (B).

The content of the aromatic polycarbonate resin (A) and the thermoplastic polyester resin (B) is based on a total of 100% by mass of the aromatic polycarbonate resin (A) and the thermoplastic polyester resin (B). Is more than 50% by mass to 90% by mass or less, and the thermoplastic polyester resin (B) is 10% by mass or more and less than 50% by mass. When the content of the thermoplastic polyester resin (B) is less than 10% by mass, the effect of improving the chemical resistance, hardness and gloss of the aromatic polycarbonate resin cannot be sufficiently obtained. The heat resistance, residence heat stability, dimensional stability, etc. of the group polycarbonate resin deteriorate.
The content of the thermoplastic polyester resin (B) is preferably 45% by mass or less, more preferably 40% by mass or less. Moreover, 15 mass% or more is preferable, More preferably, it is 20 mass% or more, Furthermore, 25 mass% or more, Especially 30 mass% or more is preferable.

[Inorganic filler (C)]
The inorganic filler which is the component (C) of the present invention includes, for example, wollastonite, zonotlite, talc, mica, glass flakes, glass beads, clay, montmorillonite, smectite, kaolin, calcium carbonate, magnesium carbonate, barium carbonate. , Silica, ceramic particles, ceramic fibers, ceramic balloons, potassium titanate, boron nitride, aluminum borate, magnesium sulfate, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, and the like. These inorganic fillers may be used alone or in combination of two or more.

  The inorganic filler (C) can be freely selected from various shapes such as needles, fibers, flakes, spheres, and hollows, but the strength and impact resistance of the resin composition are improved, and dimensional stability is achieved. A needle-like one is particularly suitable for the property. As the needle-like inorganic filler, needle-like wollastonite is particularly preferable from the viewpoint of excellent weld performance.

Wollastonite is a white acicular crystalline mineral that is naturally expressed and is CaO.SiO ₂ , or may be synthesized.
The initial fiber diameter of wollastonite is preferably 2 to 30 μm, more preferably 3 to 20 μm, still more preferably 4 to 15 μm, and particularly preferably 5 to 10 μm. If the average fiber diameter is less than 2 μm, it tends to break during processing, and if it exceeds 30 μm, the reinforcing effect tends to be small. The initial average aspect ratio of wollastonite (value obtained by dividing the initial average fiber length by the initial average fiber diameter) is preferably 4 to 40, more preferably 5 to 30, and still more preferably 6 to 20.

  In addition, the average fiber length and average fiber system of the inorganic filler (C) in the present invention are average values obtained by measuring the fiber length and fiber diameter of 100 or more particles under magnification by a microscope.

The inorganic filler (C) may be treated with a known surface treating agent for the purpose of improving the adhesion with the resin. Examples of the surface treatment agent include silane coupling agents and titanate coupling agents containing amino groups and epoxy groups. Such a surface treatment agent may be previously treated on the surface of the inorganic filler, or may be added and treated when the resin and the inorganic filler are mixed.
Examples of the coupling agent include silane-based, chromium-based and titanium-based coupling agents, among others, epoxy silane such as γ-glycidoxypropyltrimethoxysilane; vinyltrichlorosilane; γ-aminopropyltriethoxysilane. Those containing a silane coupling agent such as aminosilane are preferred.

  Content of the inorganic filler (C) in the polycarbonate resin composition of this invention is 5-25 mass parts with respect to a total of 100 mass parts of polycarbonate resin (A) and a thermoplastic polyester resin (B). If the amount of the inorganic filler (C) is less than 5 parts by mass, the effect of improving the mechanical strength is small, and if it exceeds 25 parts by mass, the surface smoothness of the molded product is lowered and the fluidity and appearance are deteriorated. . The content of the inorganic filler (C) is preferably 8 parts by mass or more and 20 parts by mass or less.

[Unsaturated carboxylic acid-modified styrenic rubber polymer (D)]
The unsaturated carboxylic acid-modified styrene rubber polymer (D) as the component (D) in the present invention is a rubber polymer (elastomer) obtained by graft-modifying a styrene rubber polymer with an unsaturated carboxylic acid.

  Styrenic rubbery polymers include those obtained by copolymerizing styrene with a diene compound, acrylonitrile, and the like, and a part or all of these styrene, diene compound and acrylonitrile are α-methylstyrene, p-methyl. Styrene monomers such as styrene and pt-butyl styrene, (meth) acrylic acid ester compounds such as methyl, ethyl, propyl and n-butyl, maleimide, N-methylmaleimide, N-cyclohexylmaleimide, N- Examples thereof include those substituted with a vinyl monomer copolymerizable with styrene, such as a maleimide monomer such as phenylmaleimide.

  Specific examples of the styrene-based rubbery polymer include, for example, a styrene-butadiene copolymer, a hydrogenated styrene-butadiene copolymer, a styrene-butadiene-styrene copolymer, a hydrogenated styrene-butadiene-styrene copolymer, Styrene-ethylene / butylene-styrene copolymer, butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-isoprene copolymer, styrene-isoprene-styrene copolymer, hydrogenated styrene-isoprene-styrene copolymer Polymer, butadiene-acrylonitrile-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butyl acrylate-styrene copolymer, octyl acrylate-butadiene-styrene copolymer, alkyl acrylate-butane Ene - acrylonitrile - styrene copolymer, butadiene - styrene copolymer, and the like. Styrenic rubbery polymers can be used alone or in combination of two or more.

  The unsaturated carboxylic acid-modified styrene-based rubber polymer (D) is a styrene-based rubber polymer as described above in which a part of the monomer such as styrene is substituted with an unsaturated carboxylic acid monomer, or Examples thereof include a block copolymer of an unsaturated carboxylic acid and a styrene rubber polymer.

  Examples of the unsaturated carboxylic acid monomer include fumaric acid derivatives such as maleic anhydride, fumaric acid, fumaric acid diester, fumaric acid metal salt, fumaric acid ammonium salt, fumaric acid halide, preferably maleic anhydride. is there. These unsaturated carboxylic acid monomers can be used individually by 1 type or in mixture of 2 or more types.

  The degree of unsaturated carboxylic acid modification in the unsaturated carboxylic acid-modified styrene rubber polymer (D) (mass% of unsaturated carboxylic acid relative to 100 mass% of unmodified styrene rubber polymer) is 0.5-20. It is preferable that it is mass%, More preferably, it is 1-10 mass%, and it is preferable that it is 1-5 mass%.

  As the unsaturated carboxylic acid-modified styrene-based rubber polymer (D), an unsaturated carboxylic acid-modified product of styrene-ethylene / butylene-styrene copolymer (SEBS) is preferable, and maleic anhydride-modified styrene-ethylene / butylene is particularly preferable. -A styrene copolymer (m-SEBS) is preferable.

  The unsaturated carboxylic acid-modified styrenic rubber polymer (D) is not limited in its production method, and known methods such as an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, a solution polymerization method, etc. Or by a combination of these.

  Moreover, a commercial item can be used as such an unsaturated carboxylic acid modification styrene-type rubbery polymer (D). For example, a maleic anhydride graft-modified styrene-ethylene / butylene-styrene copolymer, trade name “Tuftec M1913” manufactured by Asahi Chemicals Corporation, maleic anhydride graft-modified styrene-ethylene / butylene-styrene manufactured by TSRC, Taiwan. A trade name “TAIPOL SEBS-7131”, which is a copolymer, can be preferably used.

The content of the unsaturated carboxylic acid-modified styrene rubber polymer (D) is 3 to 15 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). By compounding with the inorganic filler (B) in such an amount, the carboxylic acid grafting the surface functional group of the inorganic filler (C) to the styrene rubber polymer (D) is chemically captured. This results in an adhesive effect. Furthermore, the compatibility of the aromatic polycarbonate resin, which is a matrix resin, and the polystyrene block, which is the hard segment of the styrene rubber polymer (D), usually results in crystal nuclei. Individual inorganic fillers (C) that are likely to be present in the polyester resin (B) are present in the form of inclusion in the unsaturated carboxylic acid-modified styrenic rubber polymer (D), and this is present in the polycarbonate resin matrix. By uniformly dispersing, it is considered that the interfacial adhesion can be remarkably improved, and good moldability and high fluidity can be achieved. It was also confirmed from comparative examples described later that such an effect cannot be achieved with other elastomers other than the styrene-based rubbery polymer even when the unsaturated carboxylic acid is modified.
The content of the unsaturated carboxylic acid-modified styrenic rubber polymer (D) is preferably 3.5 parts by mass or more, more preferably 4 parts by mass or more, particularly 4.5 parts by mass or more, particularly 5 parts by mass or more. It is preferably 12 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less.

[Other additives]
The polycarbonate resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Such additives include stabilizers, antioxidants, mold release agents, dyes and pigments, colorants, fluorescent brighteners, flame retardants, anti-dripping agents, antistatic agents, antifogging agents, lubricants, antiblocking agents. , Fluidity improvers, plasticizers, dispersants, antibacterial agents, flame retardants and the like.

[Phosphorus stabilizer]
The polycarbonate resin composition of the present invention preferably contains a phosphorus stabilizer. Any known phosphorous stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphonite compounds, organic phosphite compounds, zinc salts of organic phosphate compounds, etc. Among them, an organic phosphite compound and a zinc salt of an organic phosphate compound are particularly preferable.

  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.

  Preferred examples of the zinc salt of the organic phosphate compound include zinc salts of stearyl acid phosphate such as bis (distearyl acid phosphate) zinc salt and monostearyl acid phosphate zinc salt. Examples of these commercially available products include “JP-518Zn” manufactured by Johoku Chemical Industry Co., Ltd.

  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 thermoplastic polyester 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 or equal to the lower limit of the range, the thermal stability effect may be insufficient, and if the content of the phosphorus stabilizer exceeds the upper limit of the range, the effect May stop and become economical.

[Phenolic stabilizer]
The polycarbonate resin composition used in 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-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesi Tylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-te t- 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 be contained for the phenol type stabilizer, and 2 or more types may be contained by arbitrary combinations and ratios.

  The content of the phenol-based stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester 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 phenolic stabilizer is not more than the lower limit of the above range, the effect as the phenolic stabilizer may be insufficient, and the content of the phenolic stabilizer exceeds the upper limit of the above range. If this is the case, the effect may reach its peak and not economical.

[Release agent]
Moreover, it is also preferable that the polycarbonate resin composition of this invention contains a mold release agent (lubricant). Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane silicone oils, and the like.

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

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

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

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

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

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized.

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

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

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

  The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). Usually 2 parts by mass or less, preferably 1 part by mass or less. When the content of the release agent is not more than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

[Dye and pigment]
Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.
Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments.

  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; quinoline, anthraquinone, heterocyclic and methyl dyes.

Among these, carbon black, titanium oxide, cyanine, quinoline, anthraquinone, phthalocyanine dyes and the like 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. In addition, dyes and pigments may be used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. Good.

  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 thermoplastic polyester resin (B). . If the content of the dye / pigment is too large, the impact resistance may not be sufficient.

[Production Method of Polycarbonate Resin Composition]
There is no restriction | limiting in the manufacturing method of the polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely, Aromatic polycarbonate resin (A), thermoplastic polyester resin (B), inorganic filler (C ) And unsaturated carboxylic acid-modified styrenic rubber polymer (D), and other components blended as necessary, for example, various mixers such as a tumbler, Henschel mixer, super mixer, ribbon blender Examples thereof include a method of using a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader, and the like, followed by melt-kneading after mixing in advance. The inorganic filler (C) is preferably side-fed as necessary.
The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

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

[Molding]
The polycarbonate resin of the present invention is excellent in both rigidity, proof stress, moldability, and fluidity, and is therefore suitable for various molded products that require thinning, toughness, and strength. Preferred molded products include automobiles and the like. Inner and outer parts, such as door handles, roof rails, fenders, various portable terminals, personal computers, PDAs, TVs, videos, cameras, printers, fax machines, and other electrical and electronic equipment and OA equipment, etc. it can.

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

[Materials used]
The materials used in Examples and Comparative Examples are as described in Table 1 and Table 2 below.

(Examples 1-9, Comparative Examples 1-11)
Each material described in Tables 1 and 2 above was mixed in a tumbler for 20 minutes with the contents (all parts by mass) described in the following table, and then a twin-screw extruder manufactured by Nippon Steel Works, Ltd. equipped with 1 vent. (TEX30HSST), kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 270 ° C., the molten resin composition extruded in a strand shape is rapidly cooled in a water tank, and pelletized using a pelletizer To obtain pellets of the polycarbonate resin composition.

[Molding specimen]
The obtained pellets are dried at 120 ° C. for 5 hours or longer, and then injection molded on an injection molding machine (“J55AD” manufactured by Nippon Steel) under conditions of a cylinder temperature of 270 ° C., a mold temperature of 80 ° C., and a molding cycle of 50 seconds. The ISO multipurpose test piece was produced.

[Measurement and evaluation method]
<Fluidity evaluation>
After drying the obtained pellets at 120 ° C. for 5 hours or more, using a Koka flow tester according to the method described in Appendix C of JIS K7210, per unit time of the composition under the conditions of 280 ° C. and a load of 160 kgf. The flow rate Q value (unit: × 10 ⁻² cm ³ / sec) was measured to evaluate the fluidity. An orifice having a diameter of 1 mm and a length of 10 mm was used. It shows that it is excellent in fluidity | liquidity, so that Q value is high.

<Rigidity evaluation>
The ISO multipurpose test piece obtained by the above-described method was processed by a method prescribed by ISO to prepare a test piece for a bending test. Using the obtained test piece, the flexural modulus (unit: MPa) was measured according to the ISO178 standard.

<Toughness evaluation>
Using the obtained ISO multipurpose test piece, the tensile elongation (unit:%) was measured according to the ISO 527-1 & 2 standard.

<Heat resistance evaluation>
Using the obtained ISO multipurpose test piece, DTUL (load deflection temperature, unit: ° C.) was measured according to ISO 75-1 & 2 under the condition of load 1.80 MPa (Method A).
The above evaluation results are shown in the following table.

  The polycarbonate resin composition of the present invention is suitable for various molded products that require thinning, toughness, and strength, and is used in a wide range of fields such as interior / exterior parts for automobiles, electrical / electronic equipment, OA equipment, and the like. The industrial applicability is very high.

Claims (3)

Polycarbonate resin containing an aromatic polycarbonate resin (A) having a viscosity average molecular weight of 18,000 to 50,000 and more than 50 mass% to 90 mass% and polybutylene terephthalate homopolymer (B) of 10 mass% to less than 50 mass% 8 to 25 parts by mass of wollastonite (C) and 4 to 4 parts of unsaturated carboxylic acid-modified styrenic rubber polymer (D) with respect to 100 parts by mass of (A) and polybutylene terephthalate homopolymer (B). A polycarbonate resin composition comprising 15 parts by mass. The polycarbonate resin composition according to claim 1, wherein the unsaturated carboxylic acid-modified styrenic rubber polymer (D) is an unsaturated carboxylic acid-modified SEBS resin. Claim 1 or 2 molded article obtained by molding the polycarbonate resin composition according to.