JPH061897A - High-impact resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. excellent in low-temp. impact resistance by compounding a polycarbonate resin with two specific rubbers. CONSTITUTION:100 pts.wt. compsn. comprising 1-99 pts.wt. polycarbonate resin and/or copolyester carbonate resin of formula I or II (wherein R and R' are each halogen or a monovalent hydrocarbon group; W is a divalent hydrocarbon group, S, 0. etc.; n and n' are each 0-4; X is a 6-18C divalent aliph. group; and b is O or 1) and 99-1 pts.wt. copolymer having arom. vinyl monomer units and vinyl cyanide monomer uni is is compounded with 0.5-40 pts.wt. copolymer obtd. by grafting an arom. vinyl monomer and a vinyl cyanide monomer onto a rubbery polymer and 0.5-40 pts.wt. graft copolymer obtd. by grafting a vinyl monomer onto a composite rubber contg. a polyorganosiloxane and a polyalkyl (meth)acrylate, giving the compsn.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polycarbonate resin composition having excellent impact resistance at low temperatures.

[0002]

2. Description of the Related Art Polycarbonate resins are used in various applications because of their excellent heat resistance, impact resistance, etc., but they have high molding temperature and poor fluidity. It has drawbacks such as a large thickness dependence of impact strength.

Therefore, ABS is added to the polycarbonate resin.
Attempts have been made to blend these (acrylonitrile-butadiene-styrene) resins to solve these problems (Japanese Patent Publication No. 38-15225 and Japanese Patent Publication No. 48-12170).
Gazette, Japanese Patent Publication No. 57-21530, Japanese Patent Publication No. 58-46269, etc.).

Further, when a polycarbonate resin is blended with a composite rubber-based graft copolymer obtained by grafting a vinyl-based monomer onto a composite rubber containing a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber, impact resistance is improved. It is also known that a resin composition having excellent properties can be obtained (JP-A-64-79257).

However, none of the above resin compositions has sufficient impact resistance at low temperatures.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a polycarbonate resin composition having improved impact resistance at low temperatures.

[0007]

SUMMARY OF THE INVENTION The present inventors
The present inventors have found that when a combination of different types of rubber is added to a polycarbonate-based resin, the impact resistance can be remarkably improved, especially at low temperatures, which could not be predicted when used alone, and the present invention has been completed.

That is, the present invention provides (A) a polycarbonate resin and / or the following formula (Formula 3):

[0009]

[Chemical 3] And the following formula (Formula 4):

[0010]

[Chemical 4] (In the above formula, R and R'are each independently a halogen atom, a monovalent hydrocarbon group or a hydrocarbon oxy group, and W is a divalent hydrocarbon group, -S-, -SS-S-. , -O
-, -S (= O)-,-(O =) S (= O)-, or -C (= O)-, and n and n'are each independently an integer of 0 to 4, X is a divalent aliphatic group having 6 to 18 carbon atoms, and b is 0 or 1. 1 to 99 parts by weight of a copolyestercarbonate-based resin having a structural unit represented by the formula (B). (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component,
Aromatic vinyl monomer component (C) (a) containing 99 to 1 part by weight of the copolymer as a constituent of the copolymer, and (100) parts by weight of (A) and (B) in total. 0.5 to 40 parts by weight of a copolymer containing (b) a vinyl cyanide monomer component and (c) a rubbery polymer as constituents of the copolymer, and (D) a polyorganosiloxane and a polyalkyl (meth). Composite rubber graft copolymer prepared by grafting vinyl monomer onto composite rubber containing acrylate 0.5 〜
An impact resistant resin composition containing 40 parts by weight is provided.

The present invention is characterized in that the above components (C) and (D) are combined and added to the polycarbonate resin. When both are added in combination, the impact resistance at low temperatures of the polycarbonate resin becomes unpredictably high when added alone.

In the present invention, the component (A) is a polycarbonate resin and / or a copolyestercarbonate resin. The polycarbonate resin used in the present invention is an aromatic polycarbonate resin produced by a known phosgene method or a melting method (see, for example, JP-A-63-215763 and JP-A-2-124934).

Further, the copolyestercarbonate resin used in the present invention is required to have the structural units represented by the above formulas (Formula 3) and (Formula 4). First,
The structural unit represented by (Chemical Formula 3) is composed of a diphenol component and a carbonate component. The diphenol that can be used to introduce the diphenol component is shown in the following formula (Formula 5).

[0014]

[Chemical 5] In the above formula, R, R ', W, n, n'and b have the same meanings as described above. Regarding R and R ', first, examples of the halogen atom include a chlorine atom or a bromine atom. The monovalent hydrocarbon group has 1 to 1 carbon atoms.
An alkyl group having 2 such as a methyl group, an ethyl group, a propyl group, a decyl group and the like; a cycloalkyl group having a carbon number of 4 to 8, such as a cyclopentyl group and a cyclohexyl group; an aryl group having a carbon number of 6 to 12, such as Phenyl group, naphthyl group, biphenyl group and the like; aralkyl group having 7 to 14 carbon atoms, such as benzyl group, cinnamyl group and the like; or alkaryl group having 7 to 14 carbon atoms, such as tolyl group and cumenyl group, etc. And is preferably an alkyl group. Further, the hydrocarbon group of the hydrocarbon oxy group may be the above-mentioned hydrocarbon group. Such a hydrocarbonoxy group is an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group or an alkaryloxy group, and an alkoxy group and an aryloxy group are preferable.

When W is a divalent hydrocarbon group,
Alkylene groups having 1 to 30 carbon atoms, such as methylene group, ethylene group, trimethylene group, octamethylene group, etc., Alkylidene groups having 2 to 30 carbon atoms, such as ethylidene group, propylidene group, etc., or 6 to 1 carbon atoms.
And a cycloalkylene group having 6 such as a cyclohexylene group, a cyclododecylene group and the like, or a cycloalkylidene group such as a cyclohexylidene group.

Examples of the diphenol effective in the present invention include 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A); 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane. 2,2-bis (3,5-
Dimethyl-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxy) Phenyl) decane; 1,4-bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclododecane ; 4,4-
Examples include dihydroxydiphenyl ether; 4,4-thiodiphenol; 4,4-dihydroxy-3,3-dichlorodiphenyl ether; and 4,4-dihydroxy-2,5-dihydroxydiphenyl ether.
The diphenols described in 2,999,835, 3,028,365, 3,334,154 and 4,131,575 can be used.

Further, examples of the precursor for introducing the carbonate component include phosgene and diphenyl carbonate.

Next, the constitutional unit represented by the chemical formula 4 is composed of a diphenol component and a diacid component. Regarding the introduction of the diphenol component, the same diphenol as described above can be used. The monomer used for introducing the divalent acid component is a divalent acid or its equivalent. The divalent acid is, for example, an aliphatic diacid having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms. This divalent acid or its equivalent may be linear, branched or cyclic. The aliphatic diacid is preferably α, ω-dicarboxylic acid. Examples of such a divalent acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and eicosanedioic acid, and sebacic acid and dodecane are preferred. Diacids are especially preferred. Examples of equivalent substances include acid halides such as the above-mentioned divalent acids, such as acid chlorides, and diaromatic esters such as diphenyl esters. However, the carbon number of the ester portion of the ester is not included in the carbon number of the above-mentioned acid. The above divalent acids or their equivalents may be used alone or in combination of two or more.

The copolyestercarbonate used as the component (A) is required to maintain excellent physical properties such as fluidity and mechanical strength and heat resistance equivalent to those of polycarbonate.
It is preferable to have the above-mentioned two types of structural units represented by (Chemical Formula 3) and (Chemical Formula 4) in the following ratios. That is, the amount of the structural unit represented by (Chemical Formula 4) is preferably 2 to 30 mol%, more preferably 5 to 25 mol%, and further preferably 7 to 10% of the total amount of (Chemical Formula 3) and (Chemical Formula 4). It is 20 mol%.

The weight average molecular weight of the copolyestercarbonate is usually 10,000 to 100,000, preferably 18,000 to 4
It is 0,000. The weight average molecular weight here means GPC using polystyrene corrected for polycarbonate.
(Gel permeation chromatography).

The above copolyester carbonate can be produced by a known method for producing polycarbonate, for example, an interfacial polymerization method using phosgene, a melt polymerization method and the like. For example, it can be produced by the method described in Quinn U.S. Pat. No. 4,238,596 and Quinn and Markezich U.S. Pat. No. 4,238,597. Specifically, first, an acid halide is formed prior to the reaction between the ester-forming group and diphenol, and then reacted with phosgene. Goldberg (Goldb
erg) basic solution method (US Pat. No. 3,169,121)
In, a pyridine solvent can be used and a dicarboxylic acid is used. α, ω-dicarboxylic acid (eg sebacic acid)
Melt polymerization processes using diesters of, for example, diphenylesters can also be used. The preferred manufacturing method is
U.S. Pat.No. 4,286,083, Kochanowski
Nowski) improved method. In this method, a lower diacid such as adipic acid is made into a salt form (preferably an alkali metal salt such as sodium salt) in advance and then added to a reaction vessel containing diphenol. During the reaction with phosgene, the aqueous phase is brought to an alkaline pH, preferably between about pH 8 and
9 and then the minimum remaining reaction with phosgene of about 5
%, Raise to pH 10-11.

In the case of the interfacial polymerization method such as the bischloroformate method, it is preferable to use a general catalyst system well known in the synthesis of polycarbonate or copolyestercarbonate. Main catalyst systems include tertiary amines, amines such as amidines or guanidines. Tertiary amines are commonly used, of which trialkylamines such as triethylamine are particularly preferred.

Further, the copolyestercarbonate of the component (A) has sufficient impact resistance even if its terminal is phenol, but pt-butylphenol, isononylphenol, isooctylphenol, m- or p-cumylphenol. By introducing a bulkier end group (preferably p-cumylphenol) or a chromanyl compound, for example, chroman, a copolyestercarbonate having excellent low temperature impact resistance can be obtained.

When the component (A) contains both polycarbonate and copolyestercarbonate, the compounding ratio of both is arbitrary.

The component (A) is 25% in methylene chloride.
It is preferable that the intrinsic viscosity measured at ° C is 0.32 to 0.65 dl / g.

Next, the component (B) is a copolymer containing (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component. (a) As the aromatic vinyl monomer component, for example, styrene, α-methylstyrene, o-, m- or p-
Methyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, etc. can be mentioned, and one or more of them are used. To do. Styrene and α-methylstyrene are preferred.

(B) As the vinyl cyanide monomer component,
For example, acrylonitrile, methacrylonitrile, etc. can be mentioned, and these are used 1 type (s) or 2 or more types.
The composition ratio of these is not particularly limited and is selected according to the application.

The composition ratio of (a) / (b) is not particularly limited,
In the component (B), (a) is preferably 95 to 50% by weight, (b) is 5 to 50% by weight, and more preferably
(a) is 92 to 65% by weight, and (b) is 8 to 35% by weight.

A preferred example of (B) is SAN resin (styrene-acrylonitrile copolymer).

There are no particular restrictions on the method for producing the copolymer of component (B), and bulk polymerization, solution polymerization, bulk suspension polymerization,
Conventionally known methods such as suspension polymerization and emulsion polymerization are used.
It can also be obtained by blending separately copolymerized resins.

The blending ratio of the above-mentioned components (A) and (B) is such that (B) is 99-1 with respect to 1-99 parts by weight of (A).
The amount of (B) is 90 to 1 part by weight, preferably 10 to 99 parts by weight of (A).

Next, the component (C) will be described. (C) is
A copolymer containing (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubbery polymer.
As the aromatic vinyl monomer component (a) and the vinyl cyanide monomer component (b), those shown in the above component (B) can be mentioned. (c) The rubbery polymer includes polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers. Diene rubbers such as polymers, random copolymers and block copolymers of ethylene-propylene, random copolymers and block copolymers of ethylene-butene, copolymers of ethylene and α-olefins, ethylene-methacrylate , Copolymers with ethylene-unsaturated carboxylic acid esters such as ethylene-butyl acrylate, acrylic acid ester-butadiene copolymers, acrylic elastic polymers such as butyl acrylate-butadiene copolymer, ethylene-
Copolymers of ethylene and fatty acid vinyl such as vinyl acetate, ethylene-propylene-ethylidene norbornene copolymers, ethylene-propylene-hexadiene copolymers and other ethylene-propylene non-conjugated diene terpolymers, butylene-isoprene copolymers, Chlorinated polyethylene and the like can be used, and these are used alone or in combination of two or more. Preferred rubbery polymers are ethylene-propylene rubber, ethylene-propylene non-conjugated diene terpolymer, diene rubber and acrylic elastic polymer, particularly preferably polybutadiene and styrene-butadiene copolymer. The styrene content in the butadiene copolymer is preferably 50% by weight or less.

The component (C) includes, in addition to the components (a), (b) and (c) described above, (d) a monomer copolymerizable with these components so as not to impair the object of the present invention. Can be used in a range. Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth ) Acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate and other α, β-unsaturated carboxylic acid esters; maleic anhydride, itaconic anhydride and other α,
β-unsaturated dicarboxylic acid anhydrides; maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, No-chlorophenylmaleimide and other α, β-unsaturated dicarboxylic acid imide compounds; These monomers can be used alone or in combination of two or more.

The copolymer of the component (C) is preferably a graft copolymer obtained by graft-copolymerizing (c) a rubbery polymer with other components, and more preferably AB.
S resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile-ethylene-propylene-styrene copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer),
It is an AAS resin (acrylonitrile-acrylic elastic polymer-styrene copolymer).

In the component (C), the composition ratio of the components (a), (b) and (c) is not particularly limited, and the components are blended depending on the use. Further, as the method for producing the copolymer of the component (C), the same method as the above (B) can be used.

The above component (C) is added in an amount of 0.5 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the components (A) and (B) in total. If the amount of the component (C) is less than the above range, the effect of the present invention is not exhibited, and if it is more than the above range, the rigidity decreases.

Next, the component (D) used in the present invention is a polyorganosiloxane rubber component and a polyalkyl (meth).
It is a composite rubber-based graft copolymer obtained by graft-polymerizing one or more vinyl-based monomers to a composite rubber having a structure in which an acrylate rubber component is alternately intertwined with each other to form a composite integral.

For the production of such a composite rubber-based graft copolymer, the method described in, for example, JP-A-64-79257 can be used.

Such a composite rubber is suitably 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% by weight or more, and more preferably 70% by weight or more in the polyorganosiloxane rubber component.

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 0.1 to 30% by weight in the polyorganosiloxane rubber component.
Is preferred.

The graft crossing agent (I) has the following formula: CH ₂ ═C (R ² ) —COO— (CH ₂ ) _p —SiR ¹ _n O _{(3-n) / 2} (I-1) CH _{2 ^{= CH-SiR 1 n O (}} 3-n) / 2 (I-2) or ^{_{HS- (CH 2) p -SiR 1}} n O (3-n) / 2 (I-3) ( in the above formulas, R ¹ is a lower alkyl group, for example, 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, and γ-methacryloyloxypropyl. 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-mentioned alkyl (meth) acrylate into 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 progresses, a crosslinked network of polyalkyl (meth) acrylate rubbers entwined with each other is formed in the crosslinked network of polyorganosiloxane rubber, and they cannot be separated substantially.
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.

In order to satisfy the balance of flame retardancy, impact resistance, appearance, etc., the ratio of the polyorganosiloxane rubber component to the polyalkyl (meth) acrylate rubber component in the above composite rubber is 3 to The latter is preferably 97 to 10% by weight with respect to 90% by weight, and the average particle diameter 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 (D) is a composite rubber-based graft copolymer obtained by adding the above-mentioned vinyl-based monomer to the above-mentioned composite rubber latex 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 graft copolymer (D) is commercially available, for example, from Mitsubishi Rayon Co., Ltd. as METABLEN S-2001.

The component (D) is 0.5 to 40 parts by weight, preferably 1 to 100 parts by weight of the total of the components (A) and (B).
Use ~ 30 parts by weight. If it is less than the above range, the effect of the present invention is not exhibited, and if it is more than the above range, the rigidity is lowered.

In addition to the above-mentioned components, the resin composition of the present invention may contain other conventional additives such as pigments at the time of mixing and molding the resin according to the purpose, as long as the physical properties are not impaired. Dyes, reinforcing agents (glass fiber, carbon fiber, etc.),
Fillers (carbon black, silica, titanium oxide, etc.), heat-resistant agents, antioxidants, weathering agents, lubricants, mold release agents, crystal nucleating agents, plasticizers, fluidity improvers, antistatic agents, flame retardants, etc. It 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, kneaders, etc., 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 by the following examples. The following components were used in the examples. Component (A) Polycarbonate-based resin: Polycarbonate of bisphenol A (trademark; Lexan 121, manufactured by Nippon GE Plastics Co., Ltd.), sometimes abbreviated as PC below. Copolyestercarbonate: Copolyester produced as follows Carbonate; Dodecanedioic acid (DDD
A) 7.2 g (31 mmol) and NaOH tablets 2.
Dissolve 7 g (68 mmol) in 180 ml of water and add DDD.
The disodium salt of A was prepared. Next, a 2000 ml Molton flask having a sample outlet on the bottom and five ports on the top was equipped with a stirring blade, a pH measuring end, an injection tube, and a Claisen adapter equipped with a dry ice condenser. Add bisphenol A7 to the polymerization flask.
1 g (311 mmol), triethylamine 0.9 m
1, p-cumylphenol 2.0 g (9 mmol), methylene chloride 220 ml and DDDA disodium salt prepared above were charged. Subsequently, phosgene was injected into the flask at a rate of 2 g / min. At this time,
The solution was maintained at pH 8 for 10 minutes while adding 50% aqueous NaOH solution through the injection tube. Thereafter, while continuing the injection of phosgene, a 50% NaOH aqueous solution was added through the injection tube to adjust the pH of the solution to 10.5 and maintain this pH for 10 minutes. The total amount of phosgene used was 40 g (40
Was 0 mmol). After the reaction is completed, adjust the pH of the solution to 11
Adjusted to ~ 11.5 and separated the organic solvent phase from the aqueous phase. The organic solvent phase was washed 3 times with 300 ml of 2% hydrochloric acid and then 5 times with 300 ml of deionized water, dried over anhydrous magnesium sulfate, and filtered. This is methanol 15
It was charged into 00 ml to precipitate a polymer. The obtained polymerized product was separated by filtration, and added with 500 ml of methanol to obtain 1
After washing 4 times with 500 ml of deionized water,
It was dried at 110 ° C. for 15 hours. Thus, a copolyestercarbonate having structural units of the following formulas (Formula 6) and (Formula 7) in a molar ratio of 90:10 was obtained. Its intrinsic viscosity (measured in methylene chloride at 25 ° C.) was 0.45 dl / g. Hereinafter, this is abbreviated as CPEC.

[0059]

[Chemical 6]

[0060]

[Chemical 7] Component (B) SAN resin, trademark SR 30B (manufactured by Ubesaikon Corporation) Component (C) ABS resin, trademark UX 050 (manufactured by Ubesaikon Corporation) Component (D) Metabrene S-2001: Trademark, methyl methacrylate-butyl acrylate-dimethyl Siloxane copolymers, manufactured by Mitsubishi Rayon Co., Ltd., Examples 1 to 4 and Comparative Examples 1 to 4 were mixed at a ratio (weight ratio) shown in Table 1 at 250 ° C.
It was extruded with a twin-screw extruder (30 mm) set at 150 rpm to prepare pellets. Then, this pellet is set to a set temperature of 25
Injection molding was performed at 0 ° C and a mold temperature of 60 ° C. The Izod impact strength of the obtained molded product was measured. The results are shown in Table 1.

The Izod impact strength (Kg.cm/cm)
Was measured according to ASTM D 256 at a thickness of 1/8 inch, notched, at 23 ° C and -40 ° C. The ductile fracture rate (%) was determined for the measurement (n = 5) at each temperature.

[0062]

[Table 1]

[0063]

The resin composition of the present invention is excellent in impact resistance at low temperature, so that it can be used in a wide variety of applications and has high industrial utility.

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Claims (1)

[Claims] 1. A polycarbonate resin (A) and /
Alternatively, the following formula (Formula 1): And the following formula (Formula 2): (In the above formula, R and R'are each independently a halogen atom, a monovalent hydrocarbon group or a hydrocarbon oxy group, and W is a divalent hydrocarbon group, -S-, -SS-S-. , -O
-, -S (= O)-,-(O =) S (= O)-, or -C (= O)-, and n and n'are each independently an integer of 0 to 4, X is a divalent aliphatic group having 6 to 18 carbon atoms, and b is 0 or 1. 1 to 99 parts by weight of a copolyestercarbonate-based resin having a structural unit represented by the formula (B). (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component,
Aromatic vinyl monomer component (C) (a) containing 99 to 1 part by weight of the copolymer as a constituent of the copolymer, and (100) parts by weight of (A) and (B) in total. 0.5 to 40 parts by weight of a copolymer containing (b) a vinyl cyanide monomer component and (c) a rubbery polymer as constituents of the copolymer, and (D) a polyorganosiloxane and a polyalkyl (meth). Composite rubber-based graft copolymer prepared by grafting vinyl-based monomer onto composite rubber containing acrylate 0.5
An impact resistant resin composition containing 40 parts by weight.