JP3080458B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene ether (PPE) resin composition. More specifically, a PPE-based resin or a polystyrene (hereinafter sometimes referred to as PS) -based resin, a polycarbonate (hereinafter sometimes referred to as PC) -based resin, and a rubbery polymer-aromatic vinyl-vinyl cyanide and / or Alternatively, the present invention relates to a resin composition containing an α, β-unsaturated carboxylic acid or a derivative thereof copolymer.

[0002]

2. Description of the Related Art Polyphenylene ether is widely known as a resin having excellent heat resistance, mechanical properties and electrical properties. However, this polyphenylene ether has low impact resistance, processability,
It is poor in chemical resistance and has drawbacks such as thermal discoloration and gelation at high temperatures. Therefore, it is hardly used alone. Usually, polystyrene and rubber-modified polystyrene (HIPS) are used.
As a modified polyphenylene ether resin. This modified polyphenylene ether resin has excellent mechanical properties, electrical properties, workability, etc., and is therefore widely used in automobile parts, office equipment, electric appliance parts and the like.

[0003] However, although the processability is improved by blending polystyrene, rubber-modified polystyrene and the like, there is a problem that the heat resistance and impact resistance, which are the characteristics of polyphenylene ether-based resins, are significantly reduced.

Therefore, unsaturated nitrile-aromatic vinyl-diene rubbers having excellent impact resistance and solvent resistance, in which unsaturated nitriles and diene rubbers are further introduced instead of aromatic vinyl resins such as polystyrene and rubber-modified polystyrene. Attempts have been made to mix resins (ABS resins) with PPE.

[0005] However, ABS resin has poor compatibility with polyphenylene ether-based resin. Therefore, a resin composition comprising both of them is improved in processability similarly to the case of using polystyrene, but has mechanical properties such as impact resistance. The properties are significantly impaired.

Accordingly, various means have been proposed for solving the above-mentioned disadvantages of the modified polyphenylene ether resin.
For example, Japanese Patent Publication No. 57-8139 reports a composition obtained by blending a resin obtained by modifying an ABS resin with methyl methacrylate and a polyphenylene ether resin. However, this composition has poor heat stability. In addition, since methyl methacrylate is expensive, the composition itself is expensive and industrially disadvantageous. Further, the effect of improving the impact resistance is insufficient. Japanese Patent Publication No. 48-40046 reports a heat-resistant resin composition obtained by mixing a styrene-acrylonitrile copolymer having a lower acrylonitrile content than a normal product and polyphenylene ether. However, this mixture still had insufficient improvements in heat resistance and impact resistance. In addition, the compositions and mixtures disclosed in these two publications were insufficient in terms of the surface gloss of the molded articles and the coatability. Further, a composition in which a specific amount of a styrene-based resin containing a small amount of a vinylcyan compound is added to a styrene-based resin having a high content of a vinylcyanide compound, and a mixture of these and polyphenylene ether is proposed. Poor paintability and thermal stability.

Therefore, the present invention relates to a PPE resin (or a PS resin), a PC resin and a rubbery polymer-aromatic vinyl-vinyl cyanide and / or an α, β-unsaturated carboxylic acid or a derivative thereof. It is an object of the present invention to provide a thermoplastic resin composition in which a system copolymer is favorably compatibilized and which has excellent impact resistance and heat resistance.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that, together with a PPE resin (or a polystyrene resin), a polycarbonate resin having a double bond and a specific rubber. PPE having the above-mentioned excellent properties can be obtained by using a combination of a graft polymer of a polymer-aromatic vinyl-vinyl cyanide and / or an α, β-unsaturated carboxylic acid or a derivative thereof.
They have found that a resin composition can be obtained, and have reached the present invention.

That is, the present invention relates to (A) polyphenylene ether-based resin or polystyrene-based resin and polystyrene-based resin.
98 parts by weight, and (B) a (a) carbon-carbon double bond and (b) the following formula -C (= O) -Cl, -C (=
O) -Br, -C (= O) -OH, -OH, -OC
(= O) a -Cl and -O-C (= O) 98~2 parts by weight polycarbonate resin or its polycarbonate resin contains at least a compound having one group as end Tanfutome agent selected from -Br And (C) (a) a rubbery polymer, (b) an aromatic vinyl monomer component, and (c) vinyl cyanide monomer per 100 parts by weight of the total of (A) and (B). An object of the present invention is to provide a resin composition containing 1 to 50 parts by weight of a copolymer containing a component which is a copolymer and / or an α, β-unsaturated carboxylic acid or a derivative thereof as a component of the copolymer.

The PPE used in the present invention is obtained by oxidative polymerization of one or more monocyclic phenols represented by the following general formula (Formula 1) in the presence of an oxidation coupling catalyst and oxygen or an oxygen-containing gas. It is a polymer.

[0011]

Embedded image (In the formula, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, and R ₂ and R ₃ are a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms.) PPE is a simple group represented by the above general formula. It may be a homopolymer or a copolymer of a cyclic phenol.

The monocyclic phenol represented by the above general formula includes, for example, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2-methyl-6-ethylphenol, Methyl-6-propylphenol, 2-ethyl-6-propylphenol,
m-cresol, 2,3-dimethylphenol, 2,3-diethylphenol, 2,3-dipropylphenol, 2-
Methyl-3-ethylphenol, 2-methyl-3-propylphenol, 2-ethyl-3-methylphenol,
2-ethyl-3-propylphenol, 2-propyl-
3-methylphenol, 2-propyl-3-ethylphenol, 2,3,6-trimethylphenol, 2,3,6-triethylphenol, 2,3,6-tripropylphenol,
2,6-dimethyl-3-ethylphenol, 2,6-dimethyl-3-propylphenol and the like.

The oxidative coupling catalyst used in the oxidative polymerization of the phenol compound is not particularly limited, and any catalyst having a polymerization ability can be used.
For example, typical examples thereof include catalysts composed of cuprous salts and tertiary amines such as cuprous chloride-triethylamine and cuprous chloride-pyridine, and cupric chloride-pyridine-potassium hydroxide and the like. Catalyst consisting of cupric salt-amine-alkali metal hydroxide, catalyst consisting of manganese salts such as manganese chloride-ethanolamine, manganese acetate-ethylenediamine and primary amines, manganese chloride-sodium methylate, manganese chloride- Examples include a catalyst comprising a manganese salt such as sodium phenolate and an alcoholate or phenolate, and a catalyst comprising a combination of a cobalt salt and a tertiary amine.

The polyphenylene ethers obtained by polycondensation of one or more monocyclic phenols include, for example,
Poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly
(2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether , Poly (2-ethyl-6-propyl-1,4
-Phenylene) ether, 2,6-dimethylphenol /
2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymer, 2,6-diethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dipropylphenol / 2,3,
6-trimethylphenol copolymer and the like. In particular, poly (2,6-dimethyl-1,4-phenylene) ether and 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer are preferred.

Next, polystyrene resins are known per se, and have the general formula (Chemical Formula 2):

[0016]

Embedded image (Wherein R ′ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is a halogen atom or 1 to 4 carbon atoms.
Wherein m is an integer of 1 to 5), and the polymer has at least 25% by weight or more of a repeating structural unit derived from an aromatic vinyl compound represented by the following formula: There must be. Such styrenic polymers include styrene or derivatives thereof such as p-methylstyrene, α-methylstyrene, α-methyl-p-
Homopolymers and copolymers such as methylstyrene, chlorostyrene, and bromostyrene are exemplified. Also, 70-99% by weight of the above-mentioned aromatic vinyl compound and diene rubber 1
To 30% by weight of rubber-modified polystyrene (HIP
S) can be used. Examples of the diene rubber constituting HIPS include a homopolymer of a conjugated diene compound such as butadiene, isoprene, and chloroprene, a copolymer of a conjugated diene compound and an unsaturated nitrile compound or an aromatic vinyl compound, and a natural rubber. And one or more kinds can be used. Particularly, polybutadiene and butadiene-styrene copolymer are preferred.

HIPS can be obtained by emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, or a combination thereof.

The PS resin is an optional component. The mixing ratio of the PS resin to the PPE resin is preferably 90 to 0 parts by weight of the PS resin to 10 to 100 parts by weight of the PPE resin.

The polycarbonate resin used in the present invention includes copolycarbonate and the like in addition to aromatic polycarbonate.

The polycarbonate contains a carbonate component and a diphenol component. Examples of the precursor for introducing the carbonate component include phosgene and diphenyl carbonate. Suitable diphenols may have a heteroatom and may have a substituent that is inert under the conditions of polycarbonate production and inert to the influence of electromagnetic waves. Both mononuclear and polynuclear diphenols. For example, hydroquinone, resorcin, dihydroxydiphenyl, bis
-(Hydroxyphenyl) -alkane, bis- (hydroxyphenyl) -cycloalkane, bis- (hydroxyphenyl)-
Sulfide, bis- (hydroxyphenyl) -ether, bis- (hydroxyphenyl) -ketone, bis- (hydroxyphenyl) -sulfoxide, bis- (hydroxyphenyl) -sulfone and α, α′-bis- (hydroxyphenyl)-
Mention may be made of diisopropylbenzene and their ring-alkylated and ring-halogenated compounds.

Preferred diphenols are:
4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A),
2,4'-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, α, α'-bis- (4-hydroxyphenyl) -p-diisopropylbenzene, 2 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, bis- (3,5-dimethyl-4-hydroxyphenyl) methane, 2 , 2-bis- (3,5-dimethyl-4
-Hydroxyphenyl) propane, bis (3,5-dimethyl)
-4-hydroxyphenyl) sulfone, 2,4-bis- (3,5-
Dimethyl-4-hydroxyphenyl) -2-methylbutane,
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, α, α′-bis- (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis ( 3,5-dichloro-4-hydroxyphenyl) propane, 2,
2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

Examples of particularly suitable diphenols are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (3,5-
Dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane,
2-bis (3,5-dibromo-4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane. Any preferred combinations of the above diphenols can also be used. In addition to the above-mentioned monomeric diphenols, it is also possible to use oligomers or polymers having two terminal groups which can undergo a polymerization reaction under the conditions of the synthesis of the polycarbonate incidentally.
Such terminal groups are, for example, phenolic OH groups, chlorocarbonate groups and carboxylic acid chloride groups.
Pre-prepared oligomeric or polymeric blocks which already have such reactive groups or are capable of generating such groups by suitable work-up are, for example, polysiloxanes, for example hydrogenated 2 Polycondensates based on aliphatic diols and saturated aliphatic or aromatic dicarboxylic acids, such as saturated aliphatic polyesters based on dimeric fatty acids, aromatic polyether sulfones and aliphatic polyethers. For improving the flowability, trifunctional or higher-functional compounds in small amounts, preferably in an amount of 0.05 to 2.0 mol% (relative to the number of moles of diphenol used), In particular, compounds having three or more phenolic hydroxyl groups can also be used incidentally in a known manner.

Some examples of usable compounds having three or more phenolic hydroxyl groups are 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4 -Hydroxyphenyl) -ethane, 2,6-bis- (2-hydroxy-5-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl)- Ortho terephthalate, tetra- (4-hydroxyphenyl)-
Propane, hexa- (4- (2- (4-hydroxyphenyl) -prop-2-yl) -phenyl) -orthoterephthalate, tetra- (4-hydroxyphenyl) -methane and 1,4-
Bis (4 ′, 4 ″ -dihydroxy-triphenyl) -methyl) -benzene. Some other trifunctional compounds are:
2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis- (4-hydroxy-3-methylphenyl) -2-oxo-2,3-dihydro-indole.

As the copolyestercarbonate, in particular, the following formula (Formula 3):

[0025]

Embedded image And the following formula (Formula 4):

[0026]

Embedded image In the above formula, R and R 'are each independently a halogen atom, a monovalent hydrocarbon group or a hydrocarbonoxy group, and W is a divalent hydrocarbon group, -S-, -SS-, -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, b is 0 or 1, and has a structural unit represented by the formula: ) And 2 to 30 of the total amount of the structural units of
Copolyester carbonates which account for mole% are preferred. Examples of the halogen atom in the above formula include a chlorine atom and a bromine atom. Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, and a decyl group; a cycloalkyl group having 4 to 8 carbon atoms, such as a cyclopentyl group and a cyclohexyl group. An aryl group having 6 to 12 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group; an aralkyl group having 7 to 14 carbon atoms, such as a benzyl group or a cinnamyl group; or an alka group having 7 to 14 carbon atoms Examples include a reel group, for example, a tolyl group and a cumenyl group, and preferably an alkyl group. Examples of the hydrocarbon group of the hydrocarbon oxy group include the aforementioned hydrocarbon groups. Such a hydrocarbon oxy 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 preferred. When W is a divalent hydrocarbon group, an alkylene group having 1 to 30 carbon atoms, for example, a methylene group,
An ethylene group, a trimethylene group, an octamethylene group, etc., an alkylidene group having 2 to 30 carbon atoms, such as an ethylidene group, a propylidene group, or a cycloalkylene group having 6 to 16 carbon atoms, such as a cyclohexylene group,
A cyclododecylene group or a cycloalkylidene group,
For example, it is a cyclohexylidene group.

The structural unit represented by the above formula (Formula 4) comprises a diphenol component and a diacid component. For the introduction of the diphenol component, the same diphenol as described above can be used. The monomer used to introduce the diacid component is a diacid or an equivalent thereof. The divalent acid is, for example, an aliphatic diacid having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms. The divalent acid or its equivalent may be linear, branched, or cyclic. The aliphatic diacid is preferably α, ω-dicarboxylic acid. As such a divalent acid, for example, straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decandioic acid), dodecandioic acid, tetradecandioic acid, icodecandioic acid, and the like are preferable, and sebacic acid and dodecane acid are preferable. Diacids are particularly preferred. Examples of the equivalent substance include the above-mentioned divalent acids, for example, acid halides such as acid chloride, and diaromatic esters such as diphenyl ester. However, the carbon number of the ester portion of the ester is not included in the carbon number of the acid described above. The above divalent acid or its equivalent may be used alone or in combination of two or more.

The above copolyester carbonate is
It has the above two types of structural units represented by (Chemical Formula 3) and (Chemical Formula 4) in the following proportions. 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%, further preferably 7 to 7 mol% of the total amount of (Chemical Formula 3) and (Chemical Formula 4). 20 mol%.

The weight average molecular weight of the copolyester carbonate is usually from 10,000 to 100,000, preferably from 18,000 to 4
It is 0,000. Here, the weight average molecular weight is defined as GP weight using polystyrene corrected for polycarbonate.
C (gel permeation chromatography). Further, those having an intrinsic viscosity of 0.35 to 0.65 dl / g measured at 25 ° C. in methylene chloride are preferred.

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

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

In addition, the above-mentioned polycarbonate resin may be used as a terminal blocking agent for adjusting the molecular weight, for example, phenol, pt-butylphenol, isononylphenol, isooctylphenol, m- or p-cumylphenol (preferably p-cumylphenol). Cumylphenol) and chromanyl compounds.

In the present invention, (a) a carbon-carbon double bond and
(b) The following formulas -C (= O) -Cl, -C (= O) -Br,-
At least one selected from C (= O) -OH, -OH, -OC (= O) -Cl and -OC (= O) -Br
A polycarbonate containing a compound having a certain group as a copolymer component or a terminal blocking agent, that is, a polycarbonate resin having a carbon-carbon double bond in its structure is used. In particular, polycarbonates whose terminals are blocked with such compounds and which have a double bond at the terminal are preferred. Such a polycarbonate-based resin having a double bond can be obtained by allowing the above-described compound to be present when a polycarbonate-based resin is produced by polymerizing a precursor of the above-mentioned carbonate component and diphenol. Such compounds include, for example, acrylic acid,
Unsaturated monoaliphatic carboxylic acids such as methacrylic acid, crotonic acid, oleic acid and linoleic acid and maleimide benzoic acid and their acid halides; unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and their acid halogens Compounds such as isopropenyl phenol, allyl phenol, maleimide phenol and the like, and halogenocarbonates thereof. These can be used alone or as a mixture. In order to produce a polycarbonate having the above-mentioned compound copolymerized at the terminal, among the above-mentioned compounds, unsaturated monoaliphatic carboxylic acid and maleimide benzoic acid and their acid halides; isopropenylphenol, allylphenol, maleimidephenol and the like It is preferable to use these halogenocarbonates and the like.

The above-mentioned compound which serves as a copolymer component or a terminal blocking agent is usually used in an amount of 0.001 to 0.2 mol, preferably 0.002 to 0.2 mol, per 1 mol of the starting diphenol.
Add 1 mol.

As the component (B) in the present invention, only the above-mentioned polycarbonate resin having a double bond is used, or both the polycarbonate resin and a conventional (unmodified) polycarbonate resin are used. The compounding ratio of the two is from 0.5 to 0.5 polycarbonate resin having a double bond at the terminal.
100 parts by weight of conventional polycarbonate resin 0
９９99.5 parts by weight. Preferably, the amount is from 80 to 99 parts by weight of a conventional polycarbonate resin to 1 to 20 parts by weight of a polycarbonate resin having a double bond at a terminal.

The above component (B) is composed of components (A) 2 to 98
98 to 2 parts by weight based on parts by weight, preferably (A) 30
It is blended in an amount of 5 to 70 parts by weight to 95 parts by weight.
If (B) is less than 2 parts by weight, the compatibility is insufficient, and if it is more than 98 parts by weight, the excellent properties of (A) cannot be utilized.

Next, the component (C) will be described. Component (C) is a graft copolymer derived from (a), (b) and (c) above. First, (a) the rubbery polymer used in the present invention includes poly-α-olefins such as polyethylene and polypropylene, random and block copolymers of ethylene-propylene, and ethylene-propylene.
Copolymer of ethylene and α-olefin such as random copolymer of butene and block copolymer, copolymer of ethylene and unsaturated carboxylic acid ester such as ethylene-methyl methacrylate and ethylene-butyl acrylate, ethylene-vinyl acetate Copolymers of ethylene and fatty acid vinyl, such as acrylic acid ethyl, butyl, hexyl, 2-ethylhexyl, lauryl ester and other alkyl acrylate polymers, ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene- Ethylene-propylene-non-conjugated diene terpolymer such as hexadiene copolymer, random copolymer and block copolymer of polybutadiene, styrene-butadiene, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, etc. Ene rubber, butylene - isoprene copolymer, aromatic hydrocarbons and butadiene such as styrene,
There are hydrogenated products of block copolymers with aliphatic diene-based hydrocarbons such as isoprene, and these are used alone or in combination of two or more. Preferred rubbery polymers are the ethylene-propylene-non-conjugated diene terpolymers or diene rubbers, more preferably polybutadiene, styrene-butadiene copolymers, styrene-
The styrene content in the butadiene copolymer is preferably 50% by weight or less.

The aromatic vinyl compound (b) includes, for example, styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butyl. Styrene, ethylstyrene, vinyl naphthalene and the like can be mentioned, and these are used alone or in combination of two or more. Preferred aromatic vinyl compounds are styrene or those containing 50% by weight or more of styrene.

The vinyl cyanide monomer in (c) includes, for example, acrylonitrile, methacrylonitrile, etc., and these may be used alone or in combination of two or more. In the present invention, the vinyl cyanide monomer is
Preferably, it is contained in an amount of 5 to 30% by weight based on the total weight of the component (C).

As the α, β-unsaturated carboxylic acid or its derivative, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl Acrylic acid alkyl esters such as acrylate, phenyl acrylate and benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate Methacrylic acid alkyl esters such as phenyl methacrylate and benzyl methacrylate;
Unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; and the like, used alone or in combination of two or more. The above monomers are preferably 50 in the total monomer mixture.
% By weight, more preferably 30% by weight or less.

Preferred examples of the component (C) include ABS
Resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile-ethylene-propylene-styrene copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer), A
AS resin (acrylonitrile-acrylic elastic polymer-
Styrene copolymer) and MBS resin (methyl methacrylate-butadiene-styrene copolymer).

The method for producing the graft copolymer is not particularly limited, and examples thereof include a method using emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, and a combination thereof.

In the present invention, the component (C) graft copolymer has a gel phase (methyl ethyl ketone / acetone = 50/50).
Volume% of the mixed solvent insoluble portion) is preferably 50% by weight or more,
More preferably, it contains more than 60% by weight. If the gel content is less than 50% by weight, it is difficult to obtain the effect of improving impact resistance.

The above component (C) is used in an amount of 1 to 50 parts by weight, preferably 2 to 25 parts by weight, based on 100 parts by weight of the total of components (A) and (B). When the amount exceeds the above range, the heat resistance is lowered, and when the amount is less than the above range, the effect of improving the impact resistance is not seen.

The method for producing the resin composition of the present invention is not particularly limited, and ordinary methods can be used satisfactorily. However, the melt mixing method is generally preferred. Any melt mixing method can be used if it can process the molten viscous mass. The use of small amounts of solvents is possible but generally not necessary. Examples of the apparatus include, in particular, an extruder, a Banbury mixer, a roller, a kneader, etc., which are operated batchwise or continuously. The order of mixing the components is not particularly limited.

Various molded articles can be obtained from the resin composition of the present invention by injection molding, sheet extrusion, vacuum molding, profile extrusion, foam molding and the like.

In using the resin composition of the present invention,
Known antioxidants, ultraviolet absorbers, lubricants, antistatic agents, foaming agents, inorganic fillers and the like which are usually used can be blended. Furthermore, depending on the required performance, other known polymers, such as polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-propylene polymer, EPDM, styrene-butadiene block polymer, styrene-butadiene-styrene block Polymer,
Styrene-butadiene-styrene radial teleblock copolymer, polypropylene, butadiene-acrylonitrile copolymer, polyvinyl chloride, PET, PBT, polyacetal, polyamide, epoxy resin, polyvinylidene fluoride, polysulfone, ethylene-vinyl acetate copolymer, poly It may be appropriately blended with isoprene, natural rubber, chlorinated butyl rubber, chlorinated polyethylene, PPS resin, polyetherketone, or the like.

The following examples illustrate the invention.
The present invention is not limited to this.

[0049]

EXAMPLES In the examples, the following compounds were used. Component (A) PPE: poly (2,6-dimethyl-1,4-phenylene) ether having an intrinsic viscosity [η] (measured in chloroform at 25 ° C.) of 0.46 PS: polystyrene, trademark; CR3500, Dainippon HIPS manufactured by Ink Chemical Industry Co., Ltd .: High impact polystyrene, trademark: HT6
44, manufactured by Mitsubishi Monsanto Co., Ltd. Component (B) PC-1: bisphenol A polycarbonate (trade name; Lexan, manufactured by Nippon GE Plastics Co., Ltd.) having an intrinsic viscosity [η] (measured in methylene chloride at 25 ° C.) of 0.50 PC-2: Polycarbonate having a double bond at the terminal portion, prepared as follows: 2,2-bis in a mixture of 6 liters of ion-exchanged water and 7 liters of methylene chloride
2.28 kg (10 mol) of-(4-hydroxyphenyl) -propane (ie, bisphenol A), 75.6 kg (0.4 mol) of N- (p-hydroxyphenyl) maleimide and 14 ml of triethylamine were added, and the mixture was added at room temperature. Stir vigorously. Next, aqueous sodium hydroxide solution (50%)
Was added and phosgene was blown into the mixed solution at a rate of 60 g / min for 20 minutes while maintaining the pH of the solution at 10. After the addition of phosgene, the mixture was stirred for 5 minutes, and then the methylene chloride solution and the aqueous phase were separated. After washing the methylene chloride solution with water, then with 2% hydrochloric acid and then again with water,
The solvent was removed and the remaining product was dried at 100 ° C. overnight.

When the obtained product was analyzed by IR, absorption of ν _{C = O} was observed at 1704 cm ⁻¹ . Also, H
^{From 1} NMR measurement, a peak corresponding to a hydrogen atom bonded to the double bond carbon of the maleimide was found at δ 6.85 ppm. According to the molecular weight measurement by GPC, the number average molecular weight of this product was 11,300, the weight average molecular weight was 28,
It turned out to be 100. Component (C) ABS resin: UX050 (trademark, manufactured by Ube Saikon Co., Ltd.) Examples 1-3 and Comparative Examples 1-5 Each component was mixed in the ratio (weight ratio) shown in Table 1, barrel temperature 280 ° C, screw rotation 2 set to several 450rpm
It was extruded with a screw extruder (30 mm) to produce pellets. The pellet was dried at 100 ° C. for 4 hours, and then injection molded at a cylinder set temperature of 290 ° C. and a mold temperature of 80 ° C. to prepare a test piece. For this, Izod impact strength and heat distortion temperature (HDT) were measured. Table 1 shows the results.

The Izod impact strength was measured according to ASTM D256.
1/8 inch bar notched Izod impact strength was measured according to the standard and HDT was measured at 18.6 kg according to ASTM D648.
/ cm ² load.

[0052]

[Table 1]

The resin composition of the present invention comprises a PPE resin,
PC resin and rubbery polymer-Aromatic vinyl-vinyl cyanide and / or α, β-unsaturated carboxylic acid or its derivative-based copolymer is well-compatibilized, so it has impact resistance and heat resistance Is excellent. Therefore, its use is wide and industrially useful.

Claims (1)

(57) [Claims] 1. A polyphenylene ether-based resin or a polystyrene-based resin and 2-98 parts by weight of (A) a carbon-carbon double bond and (b) a compound represented by the following formula -C (= O) -Cl, -C (= O) -Br, -C (=
O) -OH, -OH, -OC (= O) -Cl and-
O-C (= O) polycarbonate resin comprising a compound having at least one group selected from -Br as end Tanfutome agent or its polycarbonate resin 98-2
(C) (a) a rubbery polymer, (b) an aromatic vinyl monomer component, and (c) cyanide, based on 100 parts by weight in total of (A) and (B). Vinyl monomer and / or α,
A resin composition comprising 1 to 50 parts by weight of a copolymer containing a component which is a β-unsaturated carboxylic acid or a derivative thereof as a component of the copolymer.