JP2002105300A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is excellent in impact resistance, heat deformation resistance, and workability, and is suitable for automobile parts, electric and electronic parts, miscellaneous goods, etc. SOLUTION: This resin composition is composed of (A) a polycarbonate resin, (B) a thermoplastic polyester resin, and (C) a copolymer which is produced by copolymerizing a (metha) acrylate monomer containing epoxy, hydroxy or alkoxy groups, another (metha) acrylate monomer and an aromatic vinyl monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which is suitably used in automobile parts, electric and electronic parts and other goods, and which provides a molded article having excellent impact resistance, heat deformation resistance, etc., and has good moldability. About things.

[0002]

2. Description of the Related Art Polycarbonate resins have the highest impact resistance among engineering plastics.
It is also known as a resin having good heat deformation resistance. Taking advantage of these features, they are widely used as components in various fields such as machines, automobiles, electricity, and electronics. However, polycarbonate-based resins have a high glass transition temperature and are expected to have high heat resistance, but in many cases, sufficient fluidity and chemical resistance cannot be obtained in the processing.

On the other hand, thermoplastic polyester resins are excellent in mechanical properties, electrical properties, chemical resistance, etc., and exhibit good molding fluidity when heated to a temperature higher than the crystal melting point of the thermoplastic polyester resin itself. Therefore, it has been widely used as a fiber, film, molding material and the like.

[0004] Attempts have been made to improve problems such as fluidity of polycarbonate resins by utilizing such properties of thermoplastic polyester resins. For example, JP-B-36-14035, JP-B-39-20
434 and JP-A-59-176345,
A polycarbonate-based polymer alloy resin composition in which a polyester-based resin such as polyethylene terephthalate and polybutylene terephthalate is added to a polycarbonate-based resin has been proposed.

[0005]

However, in recent years, there has been a demand for a polycarbonate-based polymer alloy resin composition in which the thickness of molded articles has become thinner and molded articles having complicated shapes have been increased, and the fluidity has been further improved. That is, in terms of injection molding processability, polycarbonate-based polymer alloys have a drawback that thin-walled molded products or molded products having complicated shapes have insufficient melt fluidity and are difficult to mold. Attempts have been made to add many low-viscosity polymers, lubricants or plasticizers for the purpose of improving the melt fluidity, but this is unfavorable because the mechanical properties are impaired. Accordingly, there is a need for a polycarbonate-based polymer alloy resin composition that has improved melt flowability while avoiding mechanical degradation.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, added a specific amount of a specific copolymer to an alloy composed of a polycarbonate resin and a polyester resin. The present inventors have found that the melt flowability can be improved without impairing the mechanical properties.

That is, the present invention provides a resin mixture comprising (A) 10 to 95 parts by weight of a polycarbonate resin and (B) 5 to 90 parts by weight of a thermoplastic polyester resin. On the other hand, (C) (a) 0.1 to 10% by weight of a (meth) acrylate ester containing an epoxy group, a hydroxy group or an alkoxy group,
(B) (meth) acrylates 5 to 9 other than (a)
0% by weight, (c) 5 to 70% by weight of an aromatic vinyl compound, and (d) other monomers copolymerizable with (a) to (c).
0.01 to 10 parts by weight of a copolymer obtained by copolymerizing a monomer component consisting of 50 to 50% by weight [total of (a), (b), (c) and (d) 100% by weight] The resin composition according to claim 1, wherein the thermoplastic resin composition (Claim 1) and the polycarbonate resin (A) are 2,2-bis (4-hydroxyphenylpropane-based polycarbonate resin. 2) The thermoplastic polyester resin (B) contains 80% by weight of an alkylene terephthalate unit.
3. The thermoplastic resin composition according to claim 1 or claim 2, which is a polyalkylene terephthalate having the above, further comprising (D) a graft polymer or an elastic polyolefin based on the thermoplastic resin composition according to claim 1. Resin, 0.1 to 20 parts by weight per 100 parts by weight of the resin mixture of (A) and (B)
The toluene solution of the reinforced thermoplastic resin composition (Claim 4) and the copolymer (C) to which a weight part is added has an intrinsic viscosity [η] at 30 ° C. of 0.01 to 2.0. 1,
The present invention relates to the thermoplastic resin composition according to claim 2, 3 or 4 (claim 5).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polycarbonate resin (A) used in the present invention is specifically obtained by reacting a phenol compound having a valency of 2 or more with a carbonic acid diester such as phosgene or diphenyl carbonate. Things.

There are various dihydric phenols, and in particular, 2,2-bis (4-hydroxyphenyl)
Propane (commonly known as bisphenol A) is preferred in terms of mechanical strength. Examples of the dihydric phenol other than bisphenol A include bis (4-hydroxyphenyl)
Methane; bis (4-hydroxyphenyl) phenylmethane; bis (4-hydroxyphenyl) naphthylmethane;
Bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane; bis (3,5-dimethyl-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1-naphthyl-1, 1-bis (4
-Hydroxyphenyl) ethane; 1-phenyl-1,1
-Bis (4-hydroxyphenyl) ethane; 1,2-bis (4-hydroxyphenyl) ethane; 2-methyl-
1,1-bis (4-hydroxyphenyl) propane;
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (3-methyl-4-hydroxyphenyl) ) Propane; 1,1-bis (4-hydroxyphenyl) butane; 2,2-bis (4
1,4-bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) pentane; 4-methyl-2,2-bis (4-hydroxyphenyl) pentane; 2,2-bis (4-hydroxyphenyl) hexane; 4,4-bis (4-hydroxyphenyl) heptane; 2,2-bis (4-hydroxyphenyl) nonane; 1,10-bis (4-hydroxyphenyl) decane ; 1,1-bis (4
-Hydroxyphenyl) -3,3,5-trimethylcyclohexane; dihydroxydiarylalkanes; 1,1-bis (4-hydroxyphenyl) cyclohexane; dihydroxydiaryl such as 1,1-bis (4-hydroxyphenyl) cyclodecane Dihydroxydiarylsulfones such as cycloalkanes, bis (4-hydroxyphenyl) sulfone; bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) ether; bis (3,5-
Dihydroxydiaryl ethers such as dimethyl-4-hydroxyphenyl) ether; 4,4′-dihydroxybenzophenone; dihydroxydiaryl ketones such as 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybenzophenone; Bis (4-hydroxyphenyl) sulfide; bis (3-methyl-4-hydroxyphenyl) sulfide; bis (3,5-dimethyl-4)
Dihydroxydiaryl sulfides such as -hydroxyphenyl) sulfide, dihydroxydiaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide, dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl, and 9,9-bis (4-hydroxy And dihydroxyarylfluorenes such as phenyl) fluorene. In addition to dihydric phenols, dihydroxybenzenes such as hydroquinone, resorcinol, and methylhydroquinone; and dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene are also included. These dihydric phenols and the like may be used alone, respectively.
Two or more kinds may be used in combination.

[0010] Examples of the carbonic acid diester compound include diaryl carbonates such as diphenyl carbonate and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

In the present invention, the polycarbonate resin as the component (A) may contain a branched polycarbonate, if necessary. Examples of the branching agent used to obtain the branched polycarbonate include phloroglucin, melitic acid, trimellitic acid, trimellitic acid chloride, trimellitic anhydride, gallic acid, and gallic acid n-
Propyl, protocatechuic acid, pyromellitic acid, pyromellitic dianhydride, α-resorcinic acid, β-resorcinic acid, resorcinaldehyde, isatin bis (o-cresol), benzophenonetetracarboxylic acid, 2,4,4 ′
-Trihydroxybenzophenone, 2,2 ', 4,4'
-Tetrahydroxybenzophenone, 2,4,4'-trihydroxyphenyl ether, 2,2 ', 4,4'-
Tetrahydroxyphenyl ether, 2,4,4′-trihydroxydiphenyl-2-propane, 2,2′-bis (2,4-dihydroxyphenyl) propane,
2 ', 4,4'-tetrahydroxydiphenylmethane,
2,4,4'-trihydroxydiphenylmethane, 1-
[Α-methyl-α- (4′-dihydroxyphenyl) ethyl] -3- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α-
(4′-dihydroxyphenyl) ethyl] -4-
[Α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 2,6-bis (2-hydroxy-5'-methylbenzyl) -4-methylphenol, 4,6-dimethyl-
2,4,6-tris (4'-hydroxyphenyl) -2
-Heptene, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -heptane, 1,3,5
-Tris (4'-hydroxyphenyl) benzene; 1,
1,1-tris (4-hydroxyphenyl) ethane,
2,2-bis [4,4-bis (4′-hydroxyphenyl) cyclohexyl] propane, 2,6-bis (2′-
(Hydroxy-5'-isopropylbenzyl) -4-isopropylphenol, bis [2-hydroxy-3-
(2′-hydroxy-5′-methylbenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3-
(2'-hydroxy-5'-isopropylbenzyl)-
5-methylphenyl] methane, tetrakis (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) phenylmethane, 2 ′, 4 ′, 7-trihydroxyflavan, 2,4,4-trimethyl-2 ′, 4 ', 7-
Trihydroxyflavan, 1,3-bis (2 ', 4'-
Dihydroxyphenylisopropyl) benzene, tris (4'-hydroxyphenyl) -amyl-s-triazine and the like.

In some cases, the polycarbonate resin as the component (A) includes a polycarbonate part,
A polycarbonate-polyorganosiloxane copolymer comprising a polyorganosiloxane part may be used. At this time, the degree of polymerization of the polyorganosiloxane portion is preferably 5 or more.

In addition, as the polycarbonate resin (A), for example, a linear aliphatic dicarboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid or the like may be used as a copolymer monomer. May be used.

As the terminal terminator at the time of polymerization of the polycarbonate resin, various known terminators can be used. Specifically, examples of the monohydric phenol include phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol, and nonylphenol.

Further, in order to enhance the flame retardancy, a copolymer with a phosphorus compound or a polymer whose terminal is blocked with a phosphorus compound can be used. Further, in order to enhance the weather resistance, a copolymer with a dihydric phenol having a benzotriazole group can be used.

The viscosity average molecular weight of the polycarbonate resin (A) used in the present invention is preferably from 10,000 to
60000, more preferably 15,000 to 45
000, most preferably from 18,000 to 35,000. When the viscosity average molecular weight is less than 10,000, the strength and heat resistance of the obtained resin composition are often insufficient.
If the viscosity average molecular weight exceeds 60,000, the moldability is often insufficient.

Such polycarbonate resins are used alone or in combination of two or more.
When two or more kinds are used in combination, the combination is not limited. For example, those having different monomer units, different copolymerization molar ratios, and / or different molecular weights are arbitrarily combined.

The thermoplastic polyester resin (B) used in the present invention is obtained by polycondensation of a divalent or higher carboxylic acid component, a divalent or higher alcohol and / or phenol component by a known method. It is a thermoplastic polyester. Specific examples of the thermoplastic polyester resin include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, poly (ethylene /
(Cyclohexane dimethylene) terephthalate and the like.

As the divalent or higher aromatic carboxylic acid component, divalent or higher aromatic carboxylic acids having 8 to 22 carbon atoms and ester-forming derivatives thereof are used. Specific examples of these include phthalic acid such as terephthalic acid and isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid,
Carboxylic acids such as -4'-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, diphenylsulfonedicarboxylic acid, trimesic acid, trimellitic acid, and pyromellitic acid, and esters thereof Derivatives that have the ability to form. These may be used alone or in combination of two or more. Preferred are terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. This is because they are excellent in ease of handling, ease of reaction, physical properties of the obtained resin, and the like.

The dihydric or higher alcohol and / or phenol components include aliphatic compounds having 2 to 15 carbon atoms, alicyclic compounds having 6 to 20 carbon atoms, and aromatic compounds having 6 to 40 carbon atoms, and And compounds having two or more hydroxyl groups therein, as well as ester-forming derivatives thereof. Specific examples of such alcohol and / or phenol components include ethylene glycol, propylene glycol, butanediol, hexanediol,
Decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, 2,2 '
-Bis (4-hydroxyphenyl) propane, 2,2 '
Compounds such as -bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, and the like, and derivatives thereof having an ester-forming ability are exemplified. Preferred alcohol and / or phenol components are ethylene glycol, butanediol,
Cyclohexanedimethanol. Ease of handling,
This is because the easiness of the reaction, the physical properties of the obtained resin, and the like are excellent.

The thermoplastic polyester resin (B) includes:
In addition to the acid component and the alcohol and / or phenol component, known copolymerizable components may be copolymerized as long as the desired properties are not impaired. Examples of such copolymerizable components include carboxylic acids such as divalent or higher valent aliphatic carboxylic acids having 4 to 12 carbon atoms, divalent or higher valent alicyclic carboxylic acids having 8 to 15 carbon atoms, and esters thereof. Forming derivatives. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, maleic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and other dicarboxylic acids, or esters thereof. Derivatives having the same.

Also, oxy acids such as p-hydroxybenzoic acid and their ester-forming derivatives, cyclic esters such as ε-caprolactone, and the like can be used as the copolymerization component. In addition, polyethylene glycol,
Polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, bisphenol A copolymerized polyethylene oxide addition polymer, propylene oxide addition polymer,
An aromatic polyester resin in which a polyalkylene glycol unit such as the tetrahydrofuran addition polymer and polytetramethylene glycol is partially copolymerized in a polymer chain can also be used. The copolymerization amount of the above components is generally 20% by weight or less, preferably 15% by weight or less,
More preferably, the content is 10% by weight or less.

The thermoplastic polyester resin (B) contains an alkylene terephthalate unit, preferably 80% by weight.
The polyalkylene terephthalate is more preferably 85% by weight or more, most preferably 90% by weight or more. This is because the obtained composition has an excellent balance of physical properties (eg, moldability).

The phenol / tetrachloroethane weight ratio of the thermoplastic polyester resin (B) is generally 1/1, and the intrinsic viscosity measured at 25 ° C. in a mixed solvent is as follows:
Preferably it is 0.30 to 2.00 dl / g or more, preferably 0.40 to 1.80 dl / g, and more preferably 0.50 to 1.60 dl / g. Intrinsic viscosity is 0.
If it is less than 30, the mechanical strength of the molded article is often insufficient, and if it exceeds 2.00 dl / g, the molding fluidity tends to decrease.

The thermoplastic polyester resin (B) can be used alone or in combination of two or more.
When two or more kinds are used in combination, the combination is not limited. For example, those having different copolymer components and different molar ratios and / or those having different molecular weights are arbitrarily combined.

In the present invention, the mixing ratio of the polycarbonate resin (A) and the thermoplastic polyester resin (B) is from 95/5 to 10/90 by weight, preferably from 90/10 to 10/90. 30/80, more preferably 8
It is in the range of 5/15 to 50/50. When the weight ratio of the thermoplastic polyester resin (B) in the mixture of the polycarbonate resin (A) and the thermoplastic polyester resin (B) is less than 5, the molding fluidity of the obtained molded article is poor. If the ratio is more than 90, the impact resistance, which is a characteristic of the polycarbonate resin, is deteriorated.

The copolymer (C) in the present invention comprises (a) 0.1 to 10% by weight of a (meth) acrylate ester containing an epoxy group, a hydroxy group or an alkoxy group, (b) other than (a) 5 to 90% by weight of (meth) acrylic acid ester of (c) aromatic vinyl compound 5 to 7
0% by weight and (d) 0 to 50% by weight of other monomers copolymerizable with the above (a) to (c) [(a), (b), (c)
And (d) a total of 100% by weight].

(Meth) acrylic esters containing an epoxy group, a hydroxy group or an alkoxy group include:
Epoxy group-containing acrylates such as glycidyl acrylate; epoxy group-containing methacrylates such as glycidyl methacrylate; hydroxy acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate Hydroxy methacrylate such as acrylate; alkoxy acrylate such as methoxyethyl acrylate and ethoxyethyl acrylate; and alkoxy methacrylate such as methoxyethyl methacrylate and ethoxyethyl methacrylate. These are preferably copolymerized at 0.1 to 10% by weight from the viewpoint of improving melt fluidity. Also,
It is preferable to copolymerize glycidyl methacrylate from the viewpoint of improving melt fluidity. The other (meth) acrylic acid ester is an ester compound of acrylic acid or methacrylic acid, and specifically includes methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate and the like. (Meth) acrylic acid esters of alcohols having 1 to 8 carbon atoms are exemplified.

The aromatic vinyl compound is a compound having one vinylic double bond and one or more benzene nuclei in the same molecule, and specifically, styrene, 4-methoxystyrene, 4-ethoxystyrene, -Propoxystyrene, 4-butoxystyrene, 2-methylstyrene, 3-
Methylstyrene, 4-methylstyrene, 4-ethylstyrene, 2,5-dimethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,4
-Dichlorostyrene, 4-bromostyrene, 2,5-dichlorostyrene, α-methylstyrene and the like.
These are preferably copolymerized in an amount of 5 to 70% by weight in view of dispersion of the copolymer. Other copolymerizable components include acrylonitrile, methacrylonitrile, vinylidene cyanate, vinyl cyanide compounds such as 1,2-dicyanoethylene, maleimide compounds, and (meth) acrylic acid. If the copolymer has a high molecular weight, it is inferior in dispersibility. Therefore, the intrinsic viscosity [η] of the toluene solution at 30 ° C. is preferably 0.01 to 2.0. This copolymer is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total of the polycarbonate resin (A) and the thermoplastic polyester resin (B).
It is preferable to use parts by weight. When the amount is small, no improvement in the melt fluidity is observed, and when the amount is large, the mechanical strength is reduced.

The copolymer (C) of the present invention can be obtained by emulsion polymerization, suspension polymerization, solution polymerization, etc., but emulsion polymerization is preferred. The emulsion polymerization is produced by a known emulsification method and polymerization sequence. The molecular weight can be adjusted by adjusting the amount of the catalyst and using a chain transfer agent.

In the present invention, the impact strength of the obtained molded article
In order to enhance toughness, chemical resistance, and the like, it is preferable to add one or more elastic resins selected from (D) a graft polymer and / or an elastic polyolefin-based resin. As the elastic resin, those having at least one glass transition point at 0 ° C. or lower, more preferably −20 ° C. or lower are preferable in order to improve the impact strength of the obtained resin.

In the elastic resin (D), the graft copolymer is a graft copolymer obtained by graft copolymerizing a vinyl monomer with a rubber-like elastic material.

As the rubbery elastic body, polybutadiene,
Examples include diene rubbers such as styrene-butadiene rubber, acrylonitrile-butadiene rubber, alkyl (meth) acrylate-butadiene rubber, acrylic rubber, ethylene-propylene rubber, and siloxane rubber.

The vinyl monomer is an aromatic vinyl compound, a vinyl cyanide compound, an alkyl (meth) acrylate, or a vinyl compound which can be graft-polymerized to a rubber-like elastic material.

As the aromatic vinyl compound, styrene,
o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, vinyltoluene, and the like.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.

Examples of the alkyl (meth) acrylate include butyl acrylate, butyl methacrylate, ethyl acrylate, ethyl methacrylate, methyl acrylate and methyl methacrylate.

Examples of other vinyl compounds include unsaturated acids such as acrylic acid and methacrylic acid, glycidyl (meth) acrylate such as glycidyl acrylate and glycidyl methacrylate, vinyl acetate, maleic anhydride, and N-phenylmaleimide. And the like.

The copolymerization ratio when copolymerizing the rubber-like elastic material and the vinyl compound is not particularly limited, but a preferable ratio for further increasing the impact strength is 10/10 by weight.
90-90 / 10, further 30 / 70-80 / 20
It is. If the weight ratio of the rubber-like elastic body is less than 10, the effect of improving the impact resistance is reduced. When it exceeds 90 (A)
The compatibility with the resin (B) tends to decrease.

Among the elastic resins (D), the elastic polyolefin-based resin includes, in addition to polyolefin in a narrow sense, a polydiene, a mixture of two or more thereof, a copolymer of an olefin monomer and two or more diene monomers,
It is used as a broad concept including a copolymer of an olefin monomer and at least one other vinyl monomer copolymerizable with the olefin. For example, ethylene,
Propylene, 1-butene, 1-pentene, isobutene,
1-octene, butadiene, isoprene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene , Α, ω-non-conjugated dienes, and the like, and a homopolymer or a copolymer selected from one or a combination of two or more thereof, and further, a homopolymer or a copolymer of two or more thereof. A mixture composed of a mixture is included. Among these, polyethylene, polypropylene and the like are preferably used because the chemical resistance of the obtained composition is improved.

Further, these olefin components and (meth)
Acrylic acid, alkyl (meth) acrylate,
(Meth) glycidyl acrylate, vinyl acetate,
It may be a copolymer of a vinyl monomer copolymerizable with an olefin such as maleic anhydride, N-phenylmaleimide, carbon monoxide, or the like. Specific examples of these copolymers include ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate-carbon monoxide terpolymer, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer , Ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-
Carbon monoxide copolymer, ethylene-acrylic acid copolymer,
Examples thereof include an ethylene-maleic anhydride copolymer and an ethylene-maleic anhydride-N-phenylmaleimide copolymer.

The method for polymerizing these polyolefin resins is not particularly limited, and can be polymerized by various methods. As long as it is polyethylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and the like can be obtained by a polymerization method, and any of them can be preferably used.

As (D), by adding the graft polymer and the olefin resin in combination, the various effects described above can be further enhanced.

The amount of the elastic resin (D) to be added depends on the polycarbonate resin (A) and the thermoplastic polyester resin (B).
To 100 parts by weight of the resin component consisting of
It is 1 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, most preferably 0.2 to 12 parts by weight. If the amount exceeds 20 parts by weight, the rigidity, heat resistance and the like are undesirably reduced.

The thermoplastic resin composition of the present invention may further contain any other thermoplastic or thermosetting resin within the range not impairing the present invention, such as a liquid crystal polyester resin, a polyester ester elastomer resin, and a polyester ether elastomer. A resin, a polyolefin resin, a polyamide resin, a polystyrene resin, a polyphenylene sulfide resin, a polyphenylene ether resin, a polyacetal resin, a polysulfone resin, or the like may be added alone or in combination of two or more.

In order to make the thermoplastic resin composition of the present invention higher in performance, an antioxidant such as a phenolic antioxidant and a thioether antioxidant, a phosphorus stabilizer,
It is preferable to use heat stabilizers such as singly or in combination of two or more. Further, if necessary, usually well-known stabilizers, lubricants, mold release agents, plasticizers, flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, pigments, dyes, antistatic agents, conductive properties Additives, dispersants, compatibilizers, antimicrobial agents, and other additives can be used alone or in combination of two or more.

The method for producing the composition of the present invention is not particularly limited. For example, it can be produced by a method of drying and kneading the above components, other additives, resins, and the like, and then using a melt kneading machine such as a single screw or twin screw extruder. When the compounding agent is a liquid, it can be manufactured by adding the compounding agent to a twin-screw extruder using a liquid supply pump or the like.

The molding method of the thermoplastic resin composition produced by the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, such as injection molding, blow molding, extrusion molding, vacuum molding, and the like. Molding, press molding, calender molding, foam molding and the like can be applied.

The thermoplastic resin composition of the present invention is suitably used for various uses. Preferred applications include home appliances,
Injection molded articles such as interior and exterior parts of OA equipment, automobile parts, blow molded articles, extruded molded articles, foam molded articles, and the like.

[0050]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. The evaluation of the resin composition was performed by the following method. Evaluation method Izod impact strength: After drying the obtained pellets at 120 ° C for 4 hours, using a 35t injection molding machine, a molded body was obtained at a cylinder temperature of 280 ° C and a mold temperature of 70 ° C, and JIS
Izod impact strength was measured according to K-7110. The test piece was a molded article with a イ ン チ inch notch.

Fluidity: The obtained pellets were dried at 120 ° C. for 4 hours, and then dried according to JIS K6730.
Melt index (MI) at 0 ° C and 2160g load
Was measured to evaluate the fluidity.

Example 1 200 parts of distilled water was placed in a reaction vessel equipped with a stirrer and a condenser.
1.0 part of dioctyl sulfosuccinate soda,
0.01 parts of sodium ethylenediaminetetraacetate, F
eSO ₄ · 7H ₂ O 0.005 parts, 0.5 parts of sodium formaldehyde hydrosulfite metering, mixing. Next, after the inside of the vessel was replaced with nitrogen, the reactor was stirred for 60 hours.
℃, methyl methacrylate (MMA) 29
Part, butyl acrylate (BA) 20 parts, styrene (S
T) 50 parts, glycidyl methacrylate (GMA)
A mixture of 1.0 part and 1.0 part of cumene hydroperoxide is continuously added. After the continuous addition, the mixture was further stirred for 1 hour to complete the polymerization. After cooling, the obtained emulsion was salted out using calcium chloride, filtered and dried to synthesize a copolymer. The intrinsic viscosity of the obtained copolymer using toluene was measured, and is shown in Table 1 together with the composition. 1.0 part by weight of this copolymer is 75 parts by weight of a bisphenol A type polycarbonate resin having a viscosity average molecular weight of about 22,000, 25 parts by weight of a polyethylene terephthalate resin having an intrinsic viscosity of about 0.75 dl / g, and a phosphite-based stabilizer. 0.3 parts by weight of ADK STAB HP-10 (trade name, manufactured by Asahi Denka) and elastic resin Kaneace M-511 (trade name, manufactured by Kanegabuchi Chemical Industry)
After dry blending 10 parts by weight in advance, a vented twin-screw extruder [TEX with cylinder temperature set to 280 ° C]
44: Nippon Steel Works Co., Ltd.] and melt extruded to obtain a resin composition. Table 2 shows the evaluation results of the resin composition.

Example 2 A copolymer was synthesized in the same manner as in Example 1, except that 1.0 part of glycidyl methacrylate was used instead of 1.0 part of glycidyl methacrylate, and a copolymer was synthesized. Was measured, and the results are shown in Table 1. Also,
Table 2 shows the results of evaluating the physical properties of the resin composition obtained in the same manner as in Example 1. Example 3 In the same manner as in Example 1, a copolymer was synthesized using 1.0 part of ethoxyethyl methacrylate (EMA) instead of 1.0 part of glycidyl methacrylate, and the intrinsic viscosity was measured. The results are shown in Table 1. Table 2 shows the results of evaluating the physical properties of the resin composition obtained in the same manner as in Example 1.

Example 4 The same operation as in Example 1 was conducted except that 28 parts by weight of methyl methacrylate and 2.0 parts of glycidyl methacrylate were used.
The copolymer was synthesized in different parts and the intrinsic viscosity was measured. The physical properties of the resin composition obtained in the same manner as in Example 1 were evaluated. The results are shown in Table 2. Example 5 The same operation as in Example 1 was carried out except that methyl methacrylate was 25 parts by weight and glycidyl methacrylate was 5.0.
The copolymer was synthesized in different parts and the intrinsic viscosity was measured. The physical properties of the resin composition obtained in the same manner as in Example 1 were evaluated. The results are shown in Table 2.

Example 6 By the same operation as in Example 1, but 59 parts of methyl methacrylate, 20 parts of butyl acrylate and 20 parts of styrene
And the copolymer was synthesized. The physical properties of the resin composition obtained in the same manner as in Example 1 were evaluated. The results are shown in Table 2.

Example 7 By the same operation as in Example 1, except that 19 parts of methyl methacrylate, 15 parts of butyl acrylate and 65 parts of styrene were used.
And the copolymer was synthesized. Example 1 and Example 1
Were evaluated for physical properties. The results are shown in Table 2.

Example 8 A copolymer was synthesized in the same manner as in Example 1 except that the amount of cumene hydroperoxide was changed to 0.5 part.
The intrinsic viscosity was measured. The physical properties of Example 1 and the resin composition obtained in the same manner as in Example 1 were evaluated. The results are shown in Table 2.

Example 9 1.0 part by weight of the copolymer obtained in the same manner as in Example 1 was mixed with 75 parts by weight of a bisphenol A type polycarbonate resin having a viscosity average molecular weight of about 22,000 and an intrinsic viscosity of about 0.75.
dl / g polyethylene terephthalate resin 25 parts by weight, ADK STAB HP-1 as a phosphite-based stabilizer
0 (trade name, manufactured by Asahi Denka) was blended, and the physical properties of the resin composition obtained in the same manner as in Example 1 were evaluated.
The results are shown in Table 2.

Comparative Example 1 75 parts by weight of a bisphenol A type polycarbonate resin of about 22,000, 25 parts by weight of a polyethylene terephthalate resin having an intrinsic viscosity of about 0.75 dl / g, and ADK STAB HP-10 (manufactured by Asahi Denka) as a phosphite-based stabilizer Only 0.3 parts by weight of trade name) and 10 parts by weight of elastic resin Kaneace M-511 (trade name, manufactured by Kaneka Chemical Co., Ltd.) were used. Physical properties were similarly evaluated and are shown in Table 2.

Comparative Example 2 A copolymer was prepared in the same manner as in Example 1 except that methyl methacrylate was used in an amount of 30 parts by weight and glycidyl methacrylate was not used, and the intrinsic viscosity was measured. The physical properties of the resin composition obtained in the same manner as in Example 1 were evaluated. The results are shown in Table 2.

Comparative Example 3 A resin composition was obtained in the same manner as in Example 1 except that the amount of the copolymer obtained by the same operation as in Example 1 was changed to 15 parts by weight, and the physical properties were evaluated. The results are shown in Table 2.

Comparative Example 4 A copolymer was synthesized in the same manner as in Example 1 except that the amount of methyl methacrylate was changed to 59 parts, butyl acrylate was changed to 35 parts, and styrene was changed to 5 parts, and the intrinsic viscosity was measured. A resin composition was obtained in the same manner as in Example 1, and the physical properties were evaluated. The results are shown in Table 2.

Comparative Example 5 75 parts by weight of a 22,000 bisphenol A type polycarbonate resin, 25 parts by weight of a polyethylene terephthalate resin having an intrinsic viscosity of about 0.75 dl / g, and ADK STAB HP-10 (a product of Asahi Denka Co., Ltd.) as a phosphite-based stabilizer Name) Only 0.3 parts by weight was used. Physical properties were similarly evaluated and are shown in Table 2.

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[Table 1]

[0065]

[Table 2]

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It can be seen that the thermoplastic resin composition of the present invention can provide a molded article having excellent mechanical strength and excellent molding fluidity.

Continued on front page F term (reference) 4J002 BB00Z BB03Z BB05Z BB12Z BB14Z BB15Z BC02Y BC08Y BC11Y BG01Y BG04Y BG07Y BG10Y BL00Z BN14Z BQ00Y CF05X CF06X CF07X CF08X CG00W CG01W CG02

Claims (5)

[Claims] 1. A polycarbonate resin (A)
5 parts by weight and (B) a thermoplastic polyester resin 5 to 9
0 parts by weight of the resin mixture (A) and (B) together is 1
(C) (a) 0.1 to 10% by weight of a (meth) acrylate ester containing an epoxy group, a hydroxy group or an alkoxy group, (b) (meth) acrylic acid other than (a) 5 to 90% by weight of ester, (c) 5 to 70% by weight of aromatic vinyl compound and (d) (a) to (c)
0 to 50% by weight of other monomers copolymerizable with (a),
(B), (c) and (d) in total: 100% by weight].
A thermoplastic resin composition containing 1 to 10 parts by weight. 2. The method according to claim 1, wherein the polycarbonate resin (A) is 2,2.
The resin composition according to claim 1, which is a 2-bis (4-hydroxyphenylpropane-based polycarbonate resin). 3. The thermoplastic polyester resin (B) comprises:
3. A polyalkylene terephthalate having 80% by weight or more of alkylene terephthalate units.
The thermoplastic resin composition according to the above. 4. The thermoplastic resin composition according to claim 1,
A reinforced thermoplastic resin composition further comprising (D) a graft polymer or an elastic polyolefin resin, and 0.1 to 20 parts by weight based on 100 parts by weight of the resin mixture of (A) and (B). 5. A toluene solution of the copolymer (C) at 30 ° C.
5. The thermoplastic resin composition according to claim 1, wherein the intrinsic viscosity [η] is 0.01 to 2.0.