JPH08269314A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition excellent in weather resistance, shock resistance and heat resistance and having excellent moldability by compounding a polycarbonate resin, etc. (meth)acrylic resin and a specific composite rubber graft copolymer. CONSTITUTION: This resin composition comprises (A) 1-99 pts.wt. of a polycarbonate resin and/or a copolyester carbonate resin and (B) 99-1 pts.wt. of a (meth) acrylic resin, and further (C) a composite rubber graft copolymer in an amount of 0.5-50 pts.wt. based on 100 pts.wt. of the total of the components A and B. This composite rubber graft copolymer is obtained by grafting 30-95wt.% of a composite rubber containing a polyorganosiloxane and a polyalkyl (meth) acrylate with 5-70wt.% of a vinyl monomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate (hereinafter sometimes referred to as PC) resin composition.

[0002]

2. Description of the Related Art Recently, in a wide range of applications such as automobile exterior parts, housings for electronic / electrical devices, building materials, etc., they are satisfied with weather resistance, impact resistance, heat resistance and moldability. There is a demand for a molding material that does. It can be said that if a PC resin having excellent heat resistance and impact resistance is blended with a (meth) acrylic resin having excellent weather resistance and moldability, these characteristics will be well balanced and a preferable combination will be obtained. However,
Sufficient impact strength could not be obtained by simply blending the PC resin and the (meth) acrylic resin.

It is also known that a pearlescent molded product can be obtained by adding a polymethylmethacrylate (referred to as PMMA) resin to a PC resin (Japanese Patent Publication No. 43/43).
-13384 publication).

An attempt to add an ABS resin, an MBS resin, an acrylic rubber or the like for the purpose of improving the impact resistance of a blend of a PC resin and a PMMA resin is known (Japanese Patent Publication No. 55-7864, Japanese Patent Publication No. 55-7864). Publication No. 57-41507). However, when ABS resin, MBS resin, etc. are added, the impact strength is improved, but the weather resistance is poor and there is a problem in using it for various exterior applications. In addition, when acrylic rubber is added, the impact strength at low temperature is drastically reduced, and therefore its use is limited.

Therefore, the present invention provides a composition of PC resin / (meth) acrylic resin which satisfies all of weather resistance, impact resistance (especially impact resistance at low temperature), heat resistance and moldability. The purpose is to provide.

[0006]

The present invention comprises (A) 1 to 99 parts by weight of a polycarbonate resin and / or copolyester carbonate resin and (B) a 99 to 1 part by weight of methacrylic resin and / or acrylic resin. Including,
Further, for 100 parts by weight in total of (A) and (B),
(C) A resin composition containing 0.5 to 50 parts by weight of a composite rubber graft copolymer obtained by grafting a vinyl monomer onto a composite rubber containing a polyorganosiloxane and a polyalkyl (meth) acrylate. is there.

In the present invention, the component (A) is a polycarbonate resin and / or a copolyestercarbonate resin. The polycarbonate used in the present invention is an aromatic homo- or co-polycarbonate obtained by reacting an aromatic dihydroxy compound with a carbonate precursor. Further, the polycarbonate may be branched.

Polycarbonate resins generally have the formula:

[0009]

Characterized as having a repeating structural unit represented by (-O-A-O-C (= O)-) (wherein A is a divalent residue of an aromatic dihydroxy compound). Be attached. The aromatic dihydroxy compound used is a mononuclear or polynuclear aromatic compound containing two hydroxy groups as functional groups, each of which is directly bonded to a carbon atom of an aromatic nucleus. The aromatic dihydroxy compound is not particularly limited, and various known compounds can be used. As an example, the following formula:

[0010]

Embedded image (In the above formula, R ^a and R ^b are each independently a halogen atom or a monovalent hydrocarbon group, and X is — (R ^{c
-) C (-R d) -} , - C (= R e) -, - O -, - S
-, - SO- or -SO ₂ - and is, R ^c and R ^d
Each independently represent a hydrogen atom or a monovalent hydrocarbon group, R ^e represents a divalent hydrocarbon group, p and q each independently represent an integer of 0 to 4, and d represents 0 or 1 And a compound represented by Specifically, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A), 2,2-bis ( 4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2 -Bis (4-hydroxy-3,5-
Dimethylphenyl) propane, 1,1-bis (4-hydroxy)
Bis (hydroxyaryl) such as -t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane Alkanes; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane and other bis (hydroxyaryl) cycloalkanes; 4,4'-dihydroxydiphenyl ether, 4, 4'-dihydroxy-3,3'-dimethylphenyl ether and other dihydroxydiaryl ethers;
Dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide; 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 Dihydroxy diaryl sulfoxides such as'-dimethylphenyl sulfoxide; 4,4'-dihydroxy diphenyl sulfone, dihydroxy diaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethylphenyl sulfone; 4,4 '
-Biphenol and the like can be mentioned, but not limited to these. Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used. As aromatic dihydroxy compounds other than the above, the following formula:

[0011]

Embedded image (Wherein R ^f is each independently a hydrocarbon group having 1 to 10 carbon atoms or a halide thereof or a halogen atom, and m is an integer of 0 to 4). be able to. Examples of such compounds include resorcin, 3-methylresorcin, and 3-methylresorcin.
Ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3-cumylresorcin, 2,3,4,6-tetrafluororesorcin, 2,3,4,6 -Substituted resorcins such as tetrabromoresorcin; catechol; hydroquinone, and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-t-butylhydroquinone, 3-phenylhydroquinone, 3-cumyl Hydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetra Substituted hydroquinone such as bromohydroquinone; and the following formula:

[0012]

[Chemical 4] 2,2,2 ', 2'-tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobi- [1H-indene] -7,7'-diol, etc. You can also

These aromatic dihydroxy compounds may be used alone or in combination of two or more kinds.

A known production method can be used for producing the polycarbonate. For example, a method of synthesizing a polycarbonate by subjecting an aromatic dihydroxy compound and a carbonate precursor (eg, carbonic acid diester) to a transesterification reaction in a molten state; And a method of reacting an aromatic dihydroxy compound with a carbonate precursor (for example, phosgene) (especially an interfacial method). Regarding the manufacturing method thereof, for example, JP-A-2-75723 and JP-A-2-12
4934, U.S. Pat.No. 4,001,184, No. 4,23
No. 8,569, No. 4,238,597, No. 4,474,
It is described in the specification, etc. In the method of
As the carbonic acid diester, catalyst and the like to be used, those described in the above-mentioned JP-A-2-75723 and JP-A-2-124934 can be preferably used. Examples of such carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like. Examples of the preferred catalyst include,
The compound proposed in Japanese Patent No. 5368 can be used. Examples include (a) organic acid salts, inorganic acid salts, oxides, hydroxides, hydrides or alcoholates of metals such as alkali metals and alkaline earth metals. Specific examples of these compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate,
Potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate , Lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, bisphenol A disodium salt, dipotassium salt, dilithium salt, phenol sodium salt, potassium salt, lithium salt and the like; Calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, carbonic acid Strontium, calcium acetate, barium acetate, magnesium acetate, strontium acetate, can be mentioned strontium stearate, and the like. These compounds may be used alone or in combination of two or more. These alkali metal compounds and / or alkaline earth metal compounds are 10 ^-8 to 10 ^-3 mol, more preferably 10 ^-7 to 10 ^-6 mol, per 1 mol of the aromatic dihydroxy compound,
Particularly preferably, it is used in an amount of 10 ⁻⁷ to 8 × 10 ⁻⁷ mol.

As the catalyst, the basic compound (b) may be used together with the alkali metal compound and / or the alkaline earth metal compound. Examples of the basic compound include nitrogen-containing compounds, specifically, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, and other alkyl, aryl, or ammonium having a alkaryl group. Hydroxides; tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, etc .; secondary or primary amines having an alkyl group such as methyl group, ethyl group, etc., aryl group such as phenyl group, toluyl group, etc. Kinds; Ammonia; Tetramethylammonium borohydride, Tetrabutylammonium borohydride, Tetrabutylammonium tetraphenylborate, Tetramethylammonium tetraphe It can be exemplified basic salts such as Ruboreto but not limited to. Of these, ammonium hydroxides are particularly preferable. These basic compounds may be used alone or in combination of two or more.

When a combination of the above (a) alkali metal compound and / or alkaline earth metal compound and (b) nitrogen-containing basic compound is used as a catalyst, a high molecular weight polycarbonate can be obtained with high polymerization activity. it can.

Alternatively, a combination of (a) an alkali metal compound and / or an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (c) boric acid and / or a boric acid ester is used as a catalyst. You can When a catalyst comprising such a combination is used, (a) an alkali metal compound and / or an alkaline earth metal compound is used in an amount as described above, and (b) a nitrogen-containing basic compound,
10 ^-6 to 10 ^-1 relative to 1 mol of the aromatic dihydroxy compound
It is preferably used in an amount of mol, in particular 10 ⁻⁵ to 10 ⁻² mol.
(c) The boric acid or boric acid ester has the general formula:

[0018]

Embedded image B (OR) _n (OH) _3-n (wherein R is a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and n is 1 to 3). Is an integer of) is preferred. For example,
Examples thereof include boric acid, trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate, and trinaphthyl borate. Of these, triphenyl borate is particularly preferred. (c) When boric acid and / or boric acid ester is used as a catalyst together with the above (a) and (b), the amount thereof is 10 ^-6 to 10 ^-1 mol with respect to 1 mol of the aromatic dihydroxy compound, It is particularly preferably from 10 ⁻⁵ to 10 ⁻² mol.

Examples of the carbonate precursor used in the above method include carbonyl halide, diaryl carbonate and bishaloformate, and any of them may be used. Carbonyl halides include, for example, carbonyl bromide, carbonyl chloride (so-called phosgene) and mixtures thereof. Examples of the aryl carbonate include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate and the like. Examples of bishaloformates include 2,2-bis (4-hydroxyphenyl) propane and 2,2-
Bis (4-hydroxy-3,5-dichlorophenyl) propane, hydroquinone and other aromatic dihydroxy compounds such as bischloroformate or bisbromoformate; glycols such as ethylene glycol such as bischloroformate or bisbromoformate Can be mentioned.
While all of the above carbonate precursors are useful,
Carbonyl chloride (ie phosgene) is preferred.

It is also possible to use high molecular weight, thermoplastic, randomly branched polycarbonates by reacting polyfunctional aromatic compounds with the aromatic dihydroxy compounds and carbonate precursors mentioned above. Can be manufactured by. Examples of useful polyfunctional aromatic compounds are described in U.S. Pat. Nos. 3,028,365, 3,334,154, 4,001,184 and 4,131,575. Examples of such polyfunctional aromatic compounds include 1,1,1-tris
(4-hydroxyphenyl) ethane, 2,2 ', 2''-tris (4
-Hydroxyphenyl) triisopropylbenzene, α
-Methyl-α, α ', α'-tris (4-hydroxyphenyl) -1,4-diethylbenzene, α, α', α ''-tris (4-hydroxyphenyl) -1,3,5-triisopropyl Benzene, phloroglucin, 4,6-dimethyl-2,4,6-tri
(4-hydroxyphenyl) heptane-2,1,3,5-tri (4-
(Hydroxyphenyl) benzene, 2,2-bis- [4,4- (4,4'-
Examples thereof include dihydroxyphenyl) -cyclohexyl] -propane, trimellitic acid, trimellitic acid trichloride, 1,3,5-benzenetricarboxylic acid and pyromellitic acid.

The copolyestercarbonate resins are known per se, for example, US Pat. Nos. 3,028,365, 3,334,154, 3,275,601, 3,915,926 and 3,030,331. , No. 3,169,121, No. 3,027,814 and No. 4,188,314.

Generally, the copolyestercarbonate-based resin can be produced by a process such as interfacial polymerization (that is, boundary separation), transesterification, solution polymerization, melt polymerization, etc., but interfacial polymerization is preferred. For example, in a preferred process, the reactants are dissolved or dispersed in a suitable water-immiscible solvent (such as methylene chloride) and the pH is adjusted to the presence of a suitable catalyst (such as triethylamine) and aqueous caustic (such as aqueous NaOH). The reactants are contacted with a carbonate precursor (eg phosgene) while adjusting the conditions. The reactants used are the aromatic dihydroxy compounds and carbonate precursors as mentioned under polycarbonate, and the difunctional carboxylic acids conventionally used in the production of linear polyesters. As the difunctional carboxylic acid that can be used, any of an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and an aliphatic-aromatic dicarboxylic acid can be used. Such difunctional carboxylic acids are well known and are disclosed, for example, in US Pat. No. 3,169,121. A representative example of such a bifunctional carboxylic acid is the following formula:

[0023]

Embedded image R ¹ — (R ² ) _x —COOH [In the above formula, R ¹ represents a carboxyl group or a hydroxyl group, R ² represents an alkylene group; an alkylidene group; an alicyclic group; an ethylenically unsaturated group. Containing an alkylene, alkylidene or alicyclic group; an aromatic group (for example, a phenylene group, a biphenylene group, etc.); two or more aromatic groups linked via a non-aromatic bond (for example, an alkylene group,
Two phenyl groups linked by an alkylidene group and the like); a divalent aralkyl group (for example, a tolylene group, a xylylene group, etc.), x is ¹ when R ¹ is a hydroxyl group, and R ¹ Is 0 or 1 when is a carboxyl group]. Preferred dicarboxylic acids include sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid and the like.

As the component (A), for example, JP-A-4-
It is also possible to use a copolyestercarbonate having a specific structure as disclosed in Japanese Patent No. 249569.

Next, it is used as the component (B) (meta).
The acrylic resin is not particularly limited, and known methacrylic resins and acrylic resins can be used. For example, commercially available materials for injection molding and extrusion molding can be usually used.

The (meth) acrylic resin is a polymer or copolymer obtained by polymerizing at least one of an acrylic monomer and a methacrylic monomer. Examples of acrylic or methacrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and hexyl. Examples thereof include (meth) acrylate, octyl (meth) acrylate, and phenyl (meth) acrylate.
Especially preferred is methyl methacrylate. Also,
The (meth) acrylic resin is a styrene-based monomer (eg, styrene, α-methylstyrene, p-methylstyrene, etc.), a cyanide vinyl monomer (eg, acrylonitrile) as a third component in addition to the above-mentioned (meth) acrylate monomer. Etc.) can be contained as a copolymerization component.

The molecular weight of the (meth) acrylic resin is not particularly limited, but it is preferably 1,000 to 2,000,000, more preferably 10,000 to 300,000.

The (meth) acrylic resin can be obtained by a known production method, and as the production method, radical polymerization, bulk polymerization, solution polymerization, suspension polymerization and the like are known.

The above components (A) and (B) are
(A) 1 to 99 parts by weight, (B) 99 to 1 parts by weight, preferably (A) 3 to 97 parts by weight, and (B) 97 to 3 parts by weight. If the amount of (A) is too small, the heat resistance and impact resistance will decrease, and if the amount of (B) is too small, the weather resistance and moldability will decrease.

Next, the component (C) is a composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are alternately intertwined with each other to form a composite, and one or more kinds thereof are used. Is a composite rubber-based graft copolymer obtained by graft-polymerizing the vinyl-based monomer.

Such a composite rubber graft copolymer can be produced by the method described in JP-A-64-79257.

Such a composite rubber is suitable for being produced by an emulsion polymerization method. First, a latex of polyorganosiloxane rubber is prepared, and then a monomer for synthesizing an alkyl (meth) acrylate rubber is impregnated into rubber particles of the polyorganosiloxane rubber latex. It is preferred to polymerize the monomer.

The polyorganosiloxane rubber component can be prepared by emulsion polymerization using, for example, the following organosiloxane and crosslinking agent (I), in which case a graft crossing agent (I) can also be used in combination. .

Examples of the organosiloxane include chain organosiloxanes such as dimethylsiloxane. Further, various cyclic organosiloxanes having a 3-membered ring or more, preferably a 3 to 6-membered ring can also be used. Examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane.

These organosiloxanes may be used alone or in admixture of two or more. The amount of these used is preferably 50 in the polyorganosiloxane rubber component.
It is at least wt%, more preferably at least 70 wt%.

The cross-linking agent (I) may be trifunctional or tetrafunctional.
Functional silane-based crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetrabutoxysilane and the like can be used.
Particularly, a tetrafunctional crosslinking agent is preferable, and tetraethoxysilane is particularly preferable. The crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent used is preferably 0.1 to 30% by weight in the polyorganosiloxane rubber component.

The graft crossing agent (I) has the following formula:

[0038]

Embedded image CH ₂ ═C (R ² ) —COO— (CH ₂ ) _p —SiR ¹ _n O _{(3-n) / 2} (I-1)

[0039]

Embedded image CH ₂ ═CH—SiR ¹ _n O _{(3-n) / 2} (I-2) or

[0040]

Embedded image HS- (CH ₂ ) _p —SiR ¹ _n O _{(3-n) / 2} (I-3) (In the above formula, R ¹ is a lower alkyl group such as a methyl group,
Represents an ethyl group, a propyl group or the like or a phenyl group, R ²
Represents a hydrogen atom or a methyl group, and n is 0, 1 or 2
And p represents an integer of 1 to 6) is used. Since the (meth) acryloyloxysiloxane capable of forming the unit of the above formula (I-1) has high grafting efficiency, it is possible to form an effective graft chain, which is advantageous in that it exhibits high impact resistance. Is. In addition, methacryloyloxysiloxane is particularly preferable as a unit capable of forming the unit of the formula (I-1). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl silane. Examples thereof include ethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane. These may be used alone or in combination of two or more. The amount of the graft crossing agent used is preferably 0 to 10% by weight in the polyorganosiloxane rubber component.

For the production of the latex of the polyorganosiloxane rubber component, the method described in, for example, US Pat. Nos. 2891920 and 3294725 can be used. In the practice of the present invention, for example, an organosiloxane, a cross-linking agent (I), and optionally a mixed solution of a graft crossing agent (I), an alkylbenzene sulfonic acid,
It is preferably produced by a method of shear mixing with water in the presence of a sulfonic acid-based emulsifier such as an alkyl sulfonic acid using, for example, a homogenizer. Alkylbenzene sulfonic acid is suitable because it acts as an emulsifier of the organosiloxane and at the same time serves as a polymerization initiator. At this time, it is preferable to use a metal salt of alkylbenzene sulfonic acid, a metal salt of alkyl sulfonic acid, or the like, because it is effective in maintaining the polymer stably during the graft polymerization.

Next, the polyalkyl (meth) acrylate rubber component constituting the above composite rubber may be synthesized by using the following alkyl (meth) acrylate, crosslinking agent (II) and graft crossing agent (II). it can.

As the alkyl (meth) acrylate,
Examples thereof include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and hexyl methacrylate, 2-ethylhexyl methacrylate, alkyl methacrylates such as n-lauryl methacrylate, and particularly n-butyl. The use of acrylates is preferred.

Examples of the cross-linking agent (II) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate.

Examples of the graft crossing agent (II) include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a cross-linking agent. These crosslinking agents and graft crossing agents may be used alone or in combination of two or more. The total amount of the cross-linking agent and the graft crossing agent used is preferably polyalkyl (meth)
It is 0.1 to 20% by weight in the acrylate rubber component.

The polymerization of the polyalkyl (meth) acrylate rubber component is carried out by adding the above alkyl (meth) acrylate to the latex of the polyorganosiloxane rubber component neutralized by the addition of an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide or sodium carbonate. ) An acrylate, a crosslinking agent and a graft crossing agent are added and impregnated into the polyorganosiloxane rubber particles, and then a normal radical polymerization initiator is allowed to act. As the polymerization proceeds, a crosslinked network of polyalkyl (meth) acrylate rubber entwined with each other is formed in the crosslinked network of polyorganosiloxane rubber, and it is practically impossible to separate.
A latex of a composite rubber of a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component is obtained. In the practice of the present invention, as the composite rubber, the main skeleton of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane, and the main skeleton of the polyalkyl (meth) acrylate rubber component is a repeating unit of n-butyl acrylate. A composite rubber having is preferably used.

The composite rubber thus prepared by emulsion polymerization can be graft-copolymerized with a vinyl monomer. The gel content measured by extracting this composite rubber with toluene at 90 ° C. for 12 hours is preferably 80% by weight or more.

The ratio of the polyorganosiloxane rubber component to the polyalkyl (meth) acrylate rubber component in the above composite rubber is preferably 3 to 90% by weight for the former and 97 to 10% by weight for the latter. The average particle size of the composite rubber is preferably 0.08 to 0.6 μm.

Vinyl-based monomers to be graft-polymerized on the above composite rubber include styrene, α-methylstyrene,
Aromatic alkenyl compounds such as vinyltoluene; methacrylic acid esters such as methyl methacrylate and 2-ethylhexyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. Examples thereof include vinyl monomers, which may be used alone or in combination of two or more. A particularly preferred vinyl monomer is methyl methacrylate.

The vinyl-based monomer is the above-mentioned composite rubber 30-
It is preferably contained in a proportion of 5 to 70% by weight with respect to 95% by weight.

The composite rubber-based graft copolymer (C) is a composite rubber-based graft copolymer obtained by adding the above vinyl-based monomer to the above latex of the above composite rubber and polymerizing it in one or more steps by radical polymerization technique. The combined latex can be separated and recovered by introducing it into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, salting out and coagulating.

Such a composite rubber-based graft copolymer (C) is commercially available, for example, from Mitsubishi Rayon Co., Ltd. as METABLEN S-2001.

The above component (C) composite rubber-based graft copolymer is 0.5 part by weight or more, preferably 1 part by weight or more and 50 parts by weight or less based on 100 parts by weight of the total of (A) and (B). , Preferably 40 parts by weight or less. When the amount of the component (C) is less than the above range, the effect of the present invention is not exhibited, and when it is more than the above range, rigidity and moldability are deteriorated.

The composition of the present invention optionally further comprises a component (D) UV absorber, a total of 10 parts of (A) and (B).
It is possible to add 0.01 to 10 parts by weight to 0 part by weight. UV absorbers are known per se, and commercially available products can be used. Examples of the ultraviolet absorber include benzotriazole compounds, hydroxybenzophenone compounds, salicylic acid ester compounds, and the like. Examples of such a compound include 2- (2'-hydroxy-5'-
t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dit-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- [2'-hydroxy-3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 2 -Hydroxybenzophenone, 2-ethoxy-2'-
Ethyl oxac acid bisanilide and the like can be mentioned. As the ultraviolet absorber, these may be used alone or in combination of two or more, but are not limited thereto.

The resin composition of the present invention may optionally further contain a hindered amine stabilizer (HALS), a hindered phenol stabilizer, a phosphite stabilizer and the like. Specific examples of such stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate. , Tetrakis (2,4-di-t
-Butylphenyl) 4,4'-biphenylene-di-phosphonite, tris (2,4-di-t-butylphenyl) phosphite, etc., and these may be used alone or in combination of two or more. You can The above stabilizer is
It can be blended in an amount of 1 part by weight or less, preferably 0.0005 to 100 parts by weight of (A) and (B).
0.5 weight is compounded.

In addition to the above-mentioned components, the resin composition of the present invention may further contain, for example, pigments, dyes, reinforcing materials (metal fibers, metal flakes, carbon fibers, etc.), fillers (talc, Carbon black, silica, titanium oxide, etc.), weathering agents, lubricants, release agents, crystal nucleating agents, plasticizers, fluidity improvers, antistatic agents, flame retardants and the like can be added.

There is no particular limitation on the method for producing the resin composition of the present invention, and ordinary methods can be satisfactorily used. However, melt mixing is generally preferred. The use of small amounts of solvent is possible, but generally not required. Examples of the apparatus include extruders, Banbury mixers, rollers, and kneaders, which are operated batchwise or continuously. The order of mixing the components is not particularly limited.

[0058]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

The following compounds were used in the examples. Ingredient (A) PC: Aromatic polycarbonate produced from bisphenol A and phosgene, intrinsic viscosity 0.50 dl / g (trademark; Lexan, Japan GE Plastics Co., Ltd.) measured at 25 ° C in methylene chloride Ingredient (B) PMMA: Polymethylmethacrylate resin (trademark; Sumipex LG, manufactured by Sumitomo Chemical Co., Ltd.) Component (C) Metablen S-2001 (trademark): methylmethacrylate-butylacrylate-dimethylsiloxane copolymer, manufactured by Mitsubishi Rayon Co., Ltd. Comparative component ABS resin: acrylonitrile- Butadiene-styrene copolymer (trademark; UX 050, manufactured by Ube Saikon Co., Ltd.) MBS resin: methyl methacrylate-butadiene-styrene copolymer (Kaneace B56, manufactured by Kaneka Corporation) Acrylic rubber: EXL2311, optional component by Kureha Co., Ltd. UV absorber: 2- 2'-hydroxy-5'-t-octylphenyl) benzotriazole (UV 5411, Cyanamid Co.) White Pigment: TiO _2.

Example 1 and Comparative Examples 1 to 3 The proportions (parts by weight) of each component and the white pigment (T
1 part by weight of iO ₂ ) was mixed and extruded with a twin-screw extruder (30 mm) set at 260 ° C. and 150 rpm to prepare pellets. The pellets obtained are set at a temperature of 260 ℃ and a mold temperature of 60.
Injection molding was performed under the condition of ° C. The Izod impact strength of the obtained molded product was measured and a weather resistance test was conducted. The results are shown in Table 1.

Each test was conducted as follows. (1) Izod impact strength 1/8 "notched Izod impact strength was measured at -30 ° C according to ASTM D256. (2) Weather resistance test 63 ° C using a sunshine weather O-meter (SWOM). After irradiation for 1000 hours in the presence of rainfall, the degree of discoloration was examined as compared with that before irradiation.The color difference (ΔE) before and after the weather resistance test was measured by a spectrophotometer (Hitachi, CA35).

[0062]

[Table 1] * D = Ductile fracture, B = Brittle fracture

[0063]

The resin composition of the present invention is excellent in both weather resistance and impact resistance, which are lacking in conventional PC resin / (meth) acrylic resin blends. Therefore,
The resin composition of the present invention is very useful in applications where these properties are required, especially in applications such as building materials, automobile exterior parts, and housings for electronic and electric devices.

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Claims (4)

[Claims] 1. A polycarbonate resin (A) and /
Or 1 to 99 parts by weight of a copolyestercarbonate-based resin and (B) a methacrylic resin and / or 99 to 1 parts by weight of an acrylic resin, and further (A) and (B)
0.5 to 50 parts by weight of a composite rubber-based graft copolymer obtained by grafting a vinyl-based monomer onto a composite rubber containing (C) polyorganosiloxane and polyalkyl (meth) acrylate. A resin composition containing. 2. A composite rubber of (C) a composite rubber-based graft copolymer, comprising a polyorganosiloxane rubber component 3 to
The resin composition according to claim 1, wherein the polyalkyl (meth) acrylate rubber component is contained in an amount of 97 to 10% by weight based on 90% by weight. 3. The composite rubber-based graft copolymer (C) according to claim 1, wherein the vinyl monomer is contained in a proportion of 5 to 70% by weight with respect to 30 to 95% by weight of the composite rubber. Resin composition. 4. The (D) ultraviolet absorber further comprises (A)
The resin composition according to any one of claims 1 to 3, which is contained in an amount of 0.01 to 10 parts by weight with respect to a total of 100 parts by weight of (B).