JPH0967508A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] [Object] An object of the present invention is to provide a thermoplastic resin composition having excellent heat resistance, fluidity, and mechanical balance such as weld strength and rigidity. [Constitution] (A) Thermotropic liquid crystal polyester 1
0 to 3% by weight, (B) thermoplastic resin 0 to 97% by weight,
A thermoplastic resin composition comprising (A) + (B) = 100 parts by weight and 0.5 to 40 parts by weight of the (C) multiphase structural polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having an excellent balance of mechanical properties such as excellent heat resistance, fluidity, weld strength and rigidity.

2. Description of the Related Art With the advanced use of plastics, plastics having various characteristics have been provided in recent years in response to market needs. Among them, thermotropic liquid crystal polymers that exhibit liquid crystallinity when melted are known to exhibit excellent fluidity and high elastic modulus due to self-strengthening due to a highly oriented rigid molecular chain. However, thermotropic liquid crystal polymers have various problems such as mechanical property anisotropy, molding shrinkage anisotropy, peeling due to fibrillation, and low weld strength due to a high degree of molecular chain orientation. On the other hand, a method of blending a liquid crystal polyester resin with an inorganic filler such as glass fiber has been proposed (for example, JP-A-63-264660 and JP-A-64-38464). There are problems that brittleness increases and weld strength and the appearance of molded products are not sufficient. Further, a method of melt-mixing polycarbonate, polyethylene terephthalate or the like with liquid crystal polyester (for example, JP-A-57-40551, JP-A-56-11537, JP-A-63-215769, JP-A-1-301749). Japanese Patent Laid-Open No. 2-26
No. 3849) was proposed, but injection molding is required because of high moldability, insufficient balance between heat resistance and moldability, and insufficient compatibility or dispersibility between components. It was not practically satisfactory, such as exfoliation of the product and less than the mechanical properties predicted from the mixing rule. On the other hand, aromatic polycarbonate is used in various fields such as OA equipment field and home appliances field due to its heat resistance and high toughness, but it has a drawback that heat resistance, fluidity, impact resistance, etc. are insufficient depending on the intended use. have.
Further, as a liquid crystal polyester resin composition having excellent fluidity and mechanical properties, liquid crystal polyester is polyester,
Although a method of blending a thermoplastic resin such as polycarbonate or polyarylene oxide with an epoxy compound (for example, JP-A-5-86266 and JP-A-5-86267) has been proposed, heat resistance, fluidity and weld strength are proposed. In terms of balance of mechanical properties such as stiffness and rigidity, it was not practically satisfactory.

The present invention has been made in view of the above-mentioned problems of the prior art, and is excellent in balance of mechanical properties such as excellent heat resistance, fluidity, weld strength and rigidity, and has a wide range of properties. It is an object to provide a flame-retardant resin composition that can be used for applications.

[0002]

Means for Solving the Problems The inventors of the present invention have earnestly made efforts to solve the above problems, and as a result, have come up with a resin composition having the following constitution. (A) Thermotropic liquid crystal polyester 100 to 3% by weight, (B) Thermoplastic resin 0 to 97% by weight With respect to (A) + (B) = 100 parts by weight, (C) olefin, epoxy group, acid A copolymer of an unsaturated compound having at least one functional group selected from anhydride groups, an aromatic vinyl compound, a vinyl cyan compound,
At least 1 selected from (meth) acrylic acid ester
A thermoplastic resin composition comprising 0.5 to 40 parts by weight of a multi-phase structure polymer obtained by graft-copolymerizing a seed. Hereinafter, the present invention will be described in detail.

As the thermotropic liquid crystal polyester which is the component (A) of the present invention, known ones can be used. For example, a thermotropic liquid crystal polyester mainly containing p-hydroxybenzoic acid and polyethylene terephthalate, a thermotropic liquid crystal polyester mainly containing p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, and p-hydroxybenzoic acid. Examples thereof include thermotropic liquid crystal polyesters containing an acid, 4,4′-dihydroxybiphenyl and terephthalic acid as main constituent units, and are not particularly limited. As the thermotropic liquid crystal polyester of the component (A) used in the present invention, those comprising the following structural units (a) and (b) and, if necessary, (c) and / or (d) are preferably used. .

[0004]

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Here, the structural units (a) and (b) are a structural unit of polyester produced from p-hydroxybenzoic acid and a structural unit produced from 2-hydroxy-6-naphthoic acid, respectively. By using the structural units (a) and (b), it is possible to obtain the thermoplastic resin composition of the present invention which has an excellent balance of mechanical properties such as excellent heat resistance, fluidity, weld strength and rigidity. . X in the structural units (c) and (d) can be arbitrarily selected from the chemical formula 5 and / or the chemical formula 6 and one or more types can be selected. By selecting X in the structural unit from among X _{1 in} Chemical Formula 5, a resin composition having relatively good heat resistance and rigidity can be obtained. Further, by selecting X from among X _{2 in} Chemical Formula 6, a resin composition having a relatively good balance of moldability and mechanical properties can be obtained.

[0006]

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[Chemical 6]

In the structural formula (c), preferred are structural units formed from ethylene glycol, hydroquinone, p-hydroxybiphenyl, 2,6-dihydroxynaphthalene and bisphenol A, and more preferred are ethylene glycol and hydroquinone. , P
-Hydroxybiphenyl, particularly preferred are ethylene glycol and hydroquinone. Structural formula (d) is preferably a structural unit formed from terephthalic acid, isophthalic acid or 2,6-dicarboxynaphthalene, more preferably terephthalic acid or isophthalic acid, and particularly preferably It is terephthalic acid. As for the structural formula (C) and the structural formula (D), at least one kind or two or more kinds of the structural units listed above can be used in combination. Specifically, in the case of using two or more kinds in combination, in the structural formula (c), 1) a structural unit generated from ethylene glycol / a structural unit generated from hydroquinone, 2) a structural unit generated from ethylene glycol / p-hydroxy Structural units generated from biphenyl, 3) structural units generated from hydroquinone / structural units generated from p-hydroxybiphenyl, and the like can be mentioned. Further, in the structural formula (d), 1)
Examples thereof include a structural unit formed from terephthalic acid / a structural unit formed from isophthalic acid, 2) a structural unit formed from terephthalic acid / 2, a structural unit formed from 2,6-dicarboxynaphthalene, and the like. Here, the amount of terephthalic acid in the two components is preferably 40% by weight or more, more preferably 60% by weight or more, and particularly preferably 80% by weight or more. When the amount of terephthalic acid is 40% by weight or more in the two components, the resin composition has relatively good fluidity and heat resistance. Structural units (a), (b) in the component (A),
The use division of (C) and (D) is not particularly limited. However, the structural units (C) and (D) are basically almost equimolar amounts. Further, the chemical unit (7), which is a structural unit consisting of the structural units (C) and (D), can be used as the structural unit in the component (A). Specifically, 1) a structural unit formed from ethylene glycol and terephthalic acid, 2) a structural unit formed from hydroquinone and terephthalic acid, and 3) p-
Examples thereof include structural units formed from hydroxybiphenyl and terephthalic acid, 4) structural units formed from 2,6-dihydroxynaphthalene and terephthalic acid, and 5) structural units formed from bisphenol A and terephthalic acid.

[0008]

[Chemical 7]

The component (A) of the present invention is produced from other aromatic dicarboxylic acids, aromatic diols and aromatic hydroxycarboxylic acids, if necessary, in a small amount so as not to impair the object of the present invention. Structural units can be introduced. The component (A) of the present invention has a temperature at which it starts to exhibit a liquid crystal state at the time of melting (hereinafter referred to as liquid crystal starting temperature), preferably 150 to 350 ° C., more preferably 180 to 320.
C., particularly preferably 200 to 300.degree. Setting the liquid crystal starting temperature within this range makes the resulting resin composition well balanced in preferable rigidity, moldability and mechanical properties. Further, by setting the liquid crystal starting temperature to 150 to 250 ° C., it is particularly preferable in terms of surface appearance of the molded product. Further, by setting the liquid crystal starting temperature to 250 to 350 ° C., it is possible to maintain the wear resistance, chemical resistance, rigidity, creep resistance, rib strength and the like of the obtained composition at a high temperature within a preferable range. The heat distortion temperature (ASTM) of the component (A) of the present invention
According to D648, 1/8 "thickness x 1/2" width x 5 "length,
A load of 18.6 kg / cm ² ) is preferably 130 to 3
The temperature is 00 ° C, more preferably 150 to 280 ° C, and particularly preferably 170 to 250 ° C. By setting the heat distortion temperature within this range, the resin composition obtained has a relatively good balance between favorable heat resistance and mechanical properties. Also,
By setting the heat distortion temperature to 130 to 210 ° C., fluidity,
The resin composition has relatively good molding processability, boss cracking, and hinge characteristics. Moreover, the heat distortion temperature is set to 210 to 300.
By setting the temperature to ℃, the obtained resin composition can have relatively good creep resistance and rigidity at high temperature, and the molding cycle in injection molding can be relatively shortened. 25 of the component (A) of the present invention
The loss tangent (tan δ) at ℃ is preferably 0.0
3 to 1.5, more preferably 0.05 to 1.5
And particularly preferably 0.07 to 1.5. Setting the loss tangent within this range makes the vibration damping performance of the resulting composition preferable. Apparent melt viscosity of component (B) of the present invention (liquid crystal starting temperature + 30 ° C., shear rate 100 /
Second) is preferably 100 to 30,000 poise, more preferably 100 to 20,000 poise, and particularly preferably 100 to 10,000 poise. Setting the apparent melt viscosity within this range makes the flowability of the resulting composition preferable. The thermal conductivity of the component (B) of the present invention in the molten state (liquid crystal state) is preferably 0.1 to 2.0.
W / mK, more preferably 0.2 to 1.5 W / mK,
Particularly preferably, it is 0.3 to 1.0 W / mK. By setting the heat conductivity in the molten state (liquid crystal state) within this range,
The injection molding cycle of the resulting composition can be relatively shortened.

The component (B) thermoplastic resin used in the present invention is an aromatic polycarbonate, (rubber) modified thermoplastic resin composition, polysulfone, polyether sulfone,
Polyphenylene sulfide, polyphenylene ether,
Polybutylene terephthalate, polyethylene terephthalate, polyamide 6, polyamide 6,6, polyamide 4,6 and the like can be mentioned, preferably aromatic polycarbonate, (rubber) modified thermoplastic resin composition, polyamide 6, polyamide 4,6. Yes, more preferably aromatic polycarbonate, (rubber) modified thermoplastic resin composition, polyamide 4,6, particularly preferably aromatic polycarbonate, (rubber) modified thermoplastic resin composition, most preferably aromatic. It is polycarbonate.
These can be used alone or in combination of two or more. By using two or more kinds in combination, the characteristics of each thermoplastic resin can be exhibited. As a preferable combination when two kinds are used in combination, aromatic polycarbonate / polyamide 4,6, aromatic polycarbonate / (rubber) modified thermoplastic resin composition, and polyamide 4,6 / (rubber) modified thermoplastic resin are particularly preferable. Is an aromatic polycarbonate / (rubber) modified thermoplastic resin composition. When two kinds are used in combination, the preferable component ratio is 10 by weight.
~ 90 / 90-10, more preferably 20-80 / 8
0 to 20.

Examples of the polycarbonate used in the present invention include those obtained by the reaction of various dihydroxyaryl compounds with phosgene, and those obtained by the transesterification reaction of the dihydroxyaryl compound with diphenyl carbonate. A typical example is 2,2'-bis (4-hydroxyphenyl).
It is a polycarbonate obtained by the reaction of propane and phosgene. Examples of the dihydroxyaryl compound used as a raw material for polycarbonate include bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) propane, 2, 2'-bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2'-bis (4-hydroxy-3-methyl) Phenyl) propane, 2,2'-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2'-bis (4-hydroxy-3-promophenyl) propane,
2,2'-bis (4-hydroxy-3,5-dichlorophenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclopentane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, 4, 4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,
3'-dimethyldiphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-
3,3'-dimethylphenyl sulfide, 4.4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide, 4,4 '
-Dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfoxide, 4,4'-dihydroxyphenyl sulfone, 4,
There are 4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, hydroquinone, resorcin, and the like, and these are used alone or in combination of two or more. Particularly preferred is 2,2'-bis (4-hydroxyphenyl) propane (bisphenol A). The viscosity average molecular weight of the polycarbonate is preferably 15,000 to 40,0.
00, more preferably 17,000 to 35,000.

The (rubber) -modified thermoplastic resin composition used in the present invention comprises an aromatic vinyl compound, a vinyl cyan compound, a (meth) acrylic acid ester and an acid anhydride in the presence of the rubber-like polymer (a). Graft copolymer obtained by polymerizing at least one monomer selected from the group of monomers (b) consisting of a base monomer and a maleimide compound, or a group of monomers (b) It is at least one (rubber) -modified thermoplastic resin composition selected from polymers of at least one selected monomer. Examples of the rubber-like polymer (a) used in the (rubber) modified thermoplastic resin composition include polybutadiene, polyisoprene, butyl rubber, styrene-
Butadiene copolymer (styrene content is preferably 5 to 60% by weight), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, ethylene-α-olefin copolymer, ethylene-α-olefin-polyene copolymer, Silicon rubber, acrylic rubber, butadiene- (meth) acrylic acid ester copolymer, polyisoprene, styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated butadiene Examples thereof include a polymer and an ethylene ionomer. Styrene-
The butadiene block copolymer and the styrene-isoprene block copolymer include AB type, ABA type, taper type,
Those having a radial teleblock type structure are included. Further, the hydrogenated butadiene-based polymer is a hydride of the block copolymer of the styrene block and the styrene-butadiene random copolymer in addition to the hydride of the block copolymer, and the content of 1,2-vinyl bond in polybutadiene. Of 20% by weight or less and a hydride of a polymer comprising a polybutadiene block having a 1,2-vinyl bond content of more than 20% by weight. Examples of the aromatic vinyl constituting the component (b) include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene,
N, N-diethyl-P-aminoethylstyrene, N, N
-Diethyl-P-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, etc. are particularly preferable, and styrene and α-methylstyrene are particularly preferable. . These aromatic vinyls may be used alone or in combination of 2
Used as a mixture of two or more species. As vinyl cyanide,
There are acrylonitrile, methacrylonitrile, etc. 1
They may be used alone or as a mixture of two or more. Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amino acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate and benzyl acrylate. Acrylic acid ester of; methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amino methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate,
There are methacrylic acid esters such as cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate and benzyl methacrylate, and these are used alone or in combination of two or more. Examples of the acid anhydride-based monomer include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. Examples of the maleimide compound include maleimide compounds of α, β-unsaturated dicarboxylic acids such as maleimide, N-methylmaleimide, N-butylmaleimide, N- (P-methylphenyl) maleimide, N-phenylmaleimide and N-cyclohexylmaleimide. The compounds are used alone or in combination of two or more.

The above-mentioned aromatic vinyl, vinyl cyanide,
The (meth) acrylic acid ester, the acid anhydride monomer and the maleimide compound are used alone or in combination of two or more. Further, 30% by weight or less of another vinyl monomer copolymerizable with the above monomer may be copolymerized. As these monomers, unsaturated epoxy compounds such as glycidyl methacrylate and allyl glycidyl ether, unsaturated carboxylic acid amides such as acrylamide and methacrylamide; acrylamine, aminomethyl methacrylate, aminoethyl methacrylate, aminopropyl methacrylate,
Amino group-containing unsaturated compounds such as aminostyrene; hydroxystyrene, 3-hydroxy-1-propene, 4-
Hydroxy-1-butene, cis-4-hydroxy-2-
Butene, trans-4-hydroxy-2-butene, 3-
Hydroxyl-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and other unsaturated compounds containing hydroxyl groups; unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and vinyl sixazol. And oxazoline group-containing unsaturated compounds, and these are used alone or in combination of two or more.

The (rubber) -modified thermoplastic resin composition may be obtained by graft-polymerizing a vinyl monomer in the presence of the rubber-like polymer, or in the absence of the rubber-like polymer and vinyl monomer. What polymerized the monomer, or these may be mixed. The preferable amount of the rubber-like polymer in the (rubber) modified thermoplastic resin composition is 5 to 5 from the viewpoint of impact resistance.
It is 80% by weight, more preferably 10 to 70% by weight. Further, the average dispersion diameter of the rubber-like polymer in the rubber-modified thermoplastic resin composition is preferably 0.0 in terms of impact resistance.
1 to 50 μm, more preferably 0.05 to 30
μm. The (rubber) modified thermoplastic resin can be produced by known polymerization methods such as emulsion polymerization, solution polymerization, suspension polymerization and bulk polymerization. The graft ratio in the graft copolymer is preferably 5 to 200% by weight, more preferably 10 to 150% by weight. Also, the intrinsic viscosity (η) of the methyl ethyl ketone soluble component (in methyl ethyl ketone, 3
The measurement at 0 ° C.) is preferably 0.1 to 1.2 dl / g, and more preferably 0.2 to 0.8 dl / g. (A)
When two or more kinds of the monomer (b) components are polymerized in the presence of the components, preferable combinations are listed below. 1) Aromatic vinyl compound / vinyl cyanide compound 2) Aromatic vinyl compound / (meth) acrylic acid ester 3) Aromatic vinyl compound / vinyl cyanide compound / (meth) acrylic acid ester 4) Aromatic vinyl compound / maleimide Monomer 5) Aromatic vinyl compound / vinyl cyanide compound / maleimide monomer 6) Aromatic vinyl compound / (meth) acrylic acid ester / maleimide monomer 7) Aromatic vinyl compound / vinyl cyanide Compound / acid anhydride monomer 8) Aromatic vinyl compound / (meth) acrylic acid ester / acid anhydride monomer 9) Aromatic vinyl compound / vinyl cyanide compound / (meth) acrylic acid ester / acid Anhydride monomer 10) Aromatic vinyl compound / maleimide monomer / acid anhydride monomer 11) (meth) acrylic acid ester monomer Polymers that may be optionally added to the shift copolymer,
It is obtained by polymerizing at least one selected from the group of monomers (b). Preferred polymers are listed below. 1) Aromatic vinyl compound-vinyl cyanide compound copolymer 2) (Meth) acrylic acid ester polymer 3) Aromatic vinyl compound polymer 4) Aromatic vinyl compound-maleimide monomer copolymer 5) Aroma Group vinyl compound-maleimide monomer-vinyl cyanide compound copolymer 6) Aromatic vinyl compound-maleimide monomer-acid anhydride monomer copolymer 7) Aromatic vinyl compound- (meth) acryl Acid ester- (vinyl cyanide compound) copolymer

Polyamides 4 and 6 are polytetramethylene adipamides obtained from tetramethylene diamine and adipic acid, and include copolymerized polyamides having polytetramethylene adipamide units as a main constituent. The copolymerization component is not particularly limited, and a known amide-forming component can be used. As a typical example of the copolymerization component, 6-
Aminocaproic acid, 11-aminoundecanoic acid, 12-
Amino acids such as aminoundecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-lauryllactam, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4
-/ 2,4,4-trimethylhexamethylenediamine,
5-methylnonamethylenediamine, metaxylenediamine, paraxylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) siloxyhexane, 1-amino-3-aminomethyl-3,
Diamines such as 5,5-trimethylcyclohexane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (aminoprosyl) piperazine, and aminoethylpiperazine Adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalate Examples thereof include acids and dicarboxylic acids such as hexahydroisophthalic acid and diglycolic acid. The method for producing the polyamides 4 and 6 used in the present invention is arbitrary. For example, JP-A-56-149430 and JP-A-56-14943.
No. 1, JP-A-58-83029, JP-A-61-43631, etc., that is, first, a prepolymer having a small number of cyclic end groups is produced under specific conditions, and then this is prepared. A method for preparing high-viscosity polyamides 4 and 6 by solid phase polymerization in a steam atmosphere, or 2-
There is a method of obtaining it by heating in a polar organic solvent such as pyrrolidone or N-methylpyrrolidone. The degree of polymerization of polyamides 4 and 6 is not particularly limited,
In 96% sulfuric acid, the relative viscosity at 1 g / dl is 2.0 to
Polyamides 4,6 in the range of 6.0 are preferably used. However, the relative viscosity is a value obtained by V / V ₀ , where V is the viscosity of a solution in which a resin is dissolved and V ₀ is the viscosity of a solvent. In the present invention, 96% sulfuric acid is used as the solvent. And the solution concentration is 1 g / d
l (dl: deciliter, 1 dl = 100 ml),
It measured at 25 degreeC using the viscosity tube.

The multiphase structural polymer of the component (C) of the present invention is
An aromatic vinyl compound and vinyl cyan are added to a main chain copolymer obtained by copolymerizing an olefin and a compound mainly containing an unsaturated compound having at least one functional group selected from an epoxy group and an acid anhydride group. It is a graft copolymer having a multiphase structure obtained by graft-polymerizing at least one monomer selected from a compound and (meth) acrylic acid ester. Introducing at least one functional group selected from an epoxy group and an acid anhydride group into the main chain copolymer makes the thermoplastic resin composition of the present invention excellent in heat resistance, fluidity, weld strength and rigidity. The mechanical properties such as are excellent in balance. Specific examples of the olefin in the multiphase structure include ethylene, propylene, butene-1,3-methylbutene-
1,3-methylpentene-1,4-methylpentene-1
And the like, and ethylene and propylene are preferable, and ethylene is particularly preferable. Further, as the unsaturated compound having an epoxy group, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butylcarboxylic acid esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3, 4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, Examples thereof include vinylcyclohexene monoxide and p-glycidyl styrene, and glycidyl methacrylate is preferable.

Examples of the unsaturated compound having an acid anhydride group in the multi-phase structure polymer include maleic anhydride, itaconic anhydride and citraconic anhydride, and maleic anhydride is preferred. The unsaturated compound having at least one functional group selected from an epoxy group and an acid anhydride group can be used alone or in combination of two or more. Further, in the main chain copolymer formed by copolymerizing these with olefin,
Other unsaturated compounds such as ethyl acrylate can be used if desired. The amount of the other unsaturated compound in the main chain copolymer is preferably 30% by weight or less in order to serve the original purpose of using the multiphase structure polymer. The content of the unsaturated compound having at least one functional group selected from the epoxy group and the acid anhydride group in the multi-phase structure polymer is 0.
It is 1 to 30% by weight, preferably 0.5 to 25% by weight, and more preferably 1 to 20% by weight. If it is less than 0.1% by weight in the multi-phase structure polymer, the effect due to the addition of the multi-phase structure polymer is not sufficiently exhibited, which is not preferable, and if it exceeds 30% by weight, molding heat stability and molding processability are deteriorated. It is not preferable. The content of the main chain copolymer in the multi-phase structure polymer is preferably 10 to 90% by weight, more preferably 40% by weight.
~ 80% by weight. As the aromatic vinyl compound, vinyl cyanide compound, and (meth) acrylic acid ester in the multi-phase structure polymer, those described above can be applied as they are. Among these, one kind may be used alone, or two or more kinds may be used in combination. If necessary, other compounds may be used in the range of 30% by weight or less. In the component (C) of the present invention, one polymer is dispersed in the other polymer,
The dispersion has a particle size of 0.001 to 30 μm, preferably 0.001 to 10 μm, and is a multiphase structure polymer having a graft ratio of at least 1% by weight. By making the polymer of the component (C) of the present invention have the above-mentioned multi-phase structure, heat having an excellent balance of mechanical properties such as excellent heat resistance, fluidity, weld strength and rigidity, which is the object of the present invention, A plastic resin composition can be obtained. The multi-phase structure polymer is produced by a known method such as emulsion polymerization, solution polymerization, suspension polymerization. At this time, a polymerization initiator used for polymerization,
As the molecular weight modifier, emulsifier, dispersant, solvent and the like, those usually used in these polymerization methods can be used. The component (A) in the thermoplastic resin composition of the present invention,
The amounts of components (B) and (C) used are (A) /
(B) = 100 to 3% by weight / 0 to 97% by weight, preferably (A) / (B) = 100 to 10% by weight / 0 to 90% by weight, and more preferably (A) / (B) = 90. -20% by weight / 10-80% by weight, particularly preferably (A) / (B)
= 80 to 20% by weight / 20 to 80% by weight,
(A) + (B) = 100 parts by weight of the component (C) is 0.
It is 5 to 40 parts by weight, preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. The amount of component (A) used is 3
If it is less than wt%, heat resistance, fluidity, rigidity and the like are lowered, which is not preferable. Further, the addition of the component (B) is preferable because it improves the balance of weld strength and mechanical properties, impact resistance, boss strength, hinge properties, paintability, and the like. Further, if the amount of the component (B) used exceeds 97% by weight, heat resistance, fluidity, rigidity and the like are deteriorated, which is not preferable. If the amount of the component (C) used is less than 0.5 parts by weight with respect to (A) + (B) = 100 parts by weight, the weld strength decreases, and if it exceeds 40 parts by weight, heat resistance, fluidity, rigidity, etc. Is not preferable. The amounts of the components (A) and (B) used are preferably (A) / (B) = 5 to 50% by weight / 95 to 50% by weight, more preferably (A) / (B) = 10 to 30. By adjusting the weight ratio to 90/70% by weight, the weld strength,
Paintability, impact resistance, boss strength, and the like are further improved, which is preferable. The amount of the component (A) and the component (B) used is preferably (A) / (B) = 95 to 50% by weight.
/ 5 to 50% by weight, more preferably (A) / (B) =
90 to 70% by weight / 10 to 30% by weight is preferable because the thermoplastic resin composition has relatively good chemical resistance, heat resistance, fluidity, vibration damping property, hinge property, scratch resistance and the like.

For the purpose of improving the mechanical properties of the flame-retardant resin composition of the present invention, glass fiber, carbon fiber, metal fiber,
Metal flakes, glass beads, wollastonite, rock filler, calcium carbonate, talc, mica, glass flakes, milled fiber, kaolin, barium sulfate,
Fillers such as graphite, molybdenum disulfide, magnesium oxide, zinc oxide whiskers and potassium titanate whiskers can be used alone or in combination. Of these fillers, the shapes of glass fiber and carbon fiber are:
A fiber having a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more is preferable. These fillers are used in the composition 1 of the present invention.
It is usually used in the range of 5 to 150 parts by weight with respect to 00 parts by weight. Further, the composition of the present invention is blended with additives such as known flame retardants, coupling agents, light stabilizers, antioxidants, plasticizers, colorants, lubricants, antistatic agents, silicone oils and foaming agents. be able to. For flame retardants,
For example, preferably, a halogenated epoxy compound such as a halogenated epoxy oligomer or a halogenated epoxy polymer, a polycarbonate oligomer of tetrabromobisphenol A or a polycarbonate oligomer of tetrabromobisphenol A and bisphenol A, or a poly (dibromophenylene ether). ) Or bis (tribromophenoxy) ethane or a halogenated phenyl ether compound or polymer, or a polymer of a halogenated styrene compound such as poly (dibromostyrene) or poly (tribromostyrene) or a halide of polystyrene. A halogenated phenyl ether compound or polymer and a halogenated styrene compound polymer or a polystyrene halide are more preferable, and a halogenated phenyl ether compound or polymer is particularly preferable. These are used alone or in combination of two or more. The amount of flame retardant used is preferably 1 to 50 parts by weight, and particularly preferably 5 to 30 parts by weight, based on 100 parts by weight of component (A) + component (B). In addition to the above flame retardants, other flame retardants, such as preferably organic phosphorus compounds and antimony compounds that are flame retardant aids, such as preferably antimony trioxide and polytetrafluoroethylene, are contained at 1 to 20 parts by weight or less Can be used together in. The use of the above flame retardant is preferably 2 when the ratio of the component (B) of the present invention is relatively large.
When it is 0% by weight or more, particularly preferably 50% by weight or more, the effect of addition is further enhanced. In addition, the composition of the present invention,
By incorporating an antibacterial agent such as silver or a silver compound or a commercially available antifungal agent, excellent antibacterial and antifungal properties can be imparted. The content of such antibacterial agent and antifungal agent is 0.01 to 30% by weight, preferably 0.05 to 20% by weight. Further, the composition of the present invention can be appropriately blended with other polymers depending on the required performance.

The flame-retardant resin composition of the present invention can be obtained by kneading the components using various extruders, Banbury mixers, kneaders, rolls and the like. A preferred manufacturing method is a method using a twin-screw extruder. Moreover, when kneading each component, you may knead all components collectively, and you may knead them by a multistage addition system. The flame-retardant resin composition of the present invention thus obtained is molded into various molded articles by injection molding, sheet extrusion, vacuum molding, profile extrusion molding, blow molding, foam molding, injection press molding, gas injection molding, etc. can do. The various molded products obtained by the above-mentioned molding method utilize OA.
It can be used for various parts, housings, chassis, etc. in the fields of home appliances, electric and electronic fields, sundries, sanitary fields, automobile fields, etc.

[0020]

EXAMPLES The present invention will be further described below with reference to examples.
You. In the examples, parts and% are weights unless otherwise specified.
It is a quantity standard. The various evaluations in the examples are as follows.
Is the value measured.Heat-resistant Measure the heat distortion temperature (° C) according to ASTM D648
Was.Liquidity Slab flow with a cylinder temperature of 290 ° C and a thickness of 0.5 mm
-Using a mold, injection pressure 1000kg / cm²Flow length
Was evaluated and evaluated as follows. ◎: Very good flow ○: Good flow ×: Not good flowWeld strength Weld line is formed in the center of ASTM No. 1 dumbbell
The tensile strength (T
M), and then make a mold with no weld line.
Tensile strength (To) was measured using shaped test pieces.
Weld strength is calculated by the following formula from the tensile test (TM, To).
According to the above, the retention rate of the weld strength was obtained. Retention rate (%) = (TM / To) × 100rigidity Bending modulus is measured according to ASTM D790
Was. Unit is kg / cm² Flame retardance Observe the combustion state after contacting the test piece with flame and judge with ○ ×
Was. X: Continued to burn. ○: It disappeared naturally.Thermotropic liquid crystal polyester (A) -1 to (A)
-9 In a nitrogen atmosphere, p-hydroxybenzoic acid and 2-
Hydroxy-6-naphthoic acid, diol, dicarboxylic
By heating and melting with acid, ingredients, etc., polycondensation
Liquid Crystal Polyester with Theoretical Structural Formula
Got the le. In addition, the component ratio of a composition represents a molar ratio.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

[Chemical 12]

[0026]

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[0027]

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[0028]

[Chemical 15]

[0029]

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Thermoplastic resin (B) -1 to (B) -11 The following (B) -1 to (B) -as the component (B) of the present invention.
9 was used. 1. Aromatic polycarbonate: (B) -1, (B) -2 The following two types having different viscosity average molecular weights obtained by polymerization of bisphenol A and phosgene were used. (B) -1: molecular weight 21,000 (B) -2: molecular weight 25,000 2. (Rubber) modified thermoplastic resin composition: (B) -3 to
(B) -6 (Rubber) The rubber-like polymer shown in Table 1 was used as the component (a) used in the modified thermoplastic resin. Rubbery polymer (a)-
Resins obtained by graft-polymerizing various monomers in the presence of 1 to (a) -3 were obtained. The compositions of these resins are shown in Table 2. (B) -3 and (B) -4 are emulsion polymerization, and (B)-
5 and (B) -6 were obtained by solution polymerization.

[0031]

[Table 1]

[0032]

[Table 2]

3. Polyamide 4,6: (B) -7-
(B) -9 (B) -7: DSM, Netherlands, relative viscosity 2.2 (B) -8: DSM, Netherlands, relative viscosity 3.0 (B) -9: DSM, Netherlands Relative viscosity 4.5 Multiphase structure polymer (C) -1 to (C) -5 The composition shown in Table 1 was used as the (C) multiphase structure polymer of the present invention. When these were observed with a scanning electron microscope, it was found that spherical resins having a particle size of 0.3 to 0.4 μm were uniformly dispersed. The following were used as the flame retardant (D) -1 to (D) -3 flame retardant. (D) -1; poly (dibromophenylene ether) having a weight average molecular weight of 6,000 and bromine content of 62% (D) -2; poly (dibromostyrene) having a weight average molecular weight of 10,000 (D) -3: Filler (E) -1, (E) -2 with poly (tribromostyrene) having a weight average molecular weight of 10,000. The following (E) -1, (E) -2 were used as the filler. . (E) -1: Carbon fiber; Asahi Fiber Glass Co., Ltd.
A9000 (E) -2: glass fiber; EC manufactured by Nippon Electric Glass Co., Ltd.
S-03-F34

Examples 1 to 25, Comparative Examples 1 to 5 Using the compounding recipes shown in Tables 3 and 4, melt-kneading was carried out using a vented twin-screw extruder, and pelletized. Using this pellet, a test piece was prepared by an injection molding machine and evaluated by the above evaluation method. The evaluation results are also shown in Tables 3 and 4.

[0036]

[Table 3]

[0037]

[Table 4]

Examples 1 to 25 are the thermoplastic resin compositions of the present invention, which are excellent in heat resistance, fluidity, weld strength, and rigidity, and their balance is particularly excellent. Particularly in Examples 12 to 14 and 18, good flame retardancy was confirmed. On the other hand, in Comparative Example 1, the component (C) is out of the range of the present invention, and the weld strength is poor. Comparative Example 2
The component (C) is outside the scope of the present invention, and heat resistance, fluidity,
Inferior rigidity. In Comparative Example 3, the components (A) and (B) are outside the scope of the present invention, and the heat resistance, fluidity and rigidity are poor. In Comparative Example 4, the component (C) is outside the scope of the present invention,
Poor weld strength. In Comparative Example 5, the component (C) is out of the range of the present invention, and the heat resistance, fluidity and rigidity are poor.

[0039]

The thermoplastic resin composition of the present invention has an excellent balance of mechanical properties such as excellent heat resistance, fluidity, weld strength and rigidity. Therefore, it can be used in various structural materials, housings, parts, etc. in electric / electronic parts and acoustic members, OA equipment field, home appliance field, and vehicle field that require these performances.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Hisao Nagai 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. A thermoplastic polymer (A) 100 to 3% by weight, a thermoplastic resin (B) 0 to 97% by weight, and (A) + (B) = 100 parts by weight,
An aromatic vinyl compound, a vinyl cyanide compound, and a (meth) acrylic acid ester are added to a copolymer composed of (C) an olefin and an unsaturated compound having at least one functional group selected from an epoxy group and an acid anhydride group. Multiphase structure polymer obtained by graft-copolymerizing at least one selected from
A thermoplastic resin composition containing 40 parts by weight.