JP2001026706A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in moldability and surface appearances of molded articles. SOLUTION: This thermoplastic resin composition mainly comprises (A) 50-99.9 wt.% of at least one thermoplastic resin selected from the group consisting of polycarbonate resin, thermoplastic polyester resin, polyamide resin and polyphenylene resin and (B) 50-0.1 wt.% of (meth)acrylate-based (co)polymer having >=50% percentage of syndiotactic structure and an intrinsic viscosity [η]of >=1.0 dL/g measured at 30 deg.C in methyl ethyl ketone as a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent moldability and surface appearance.

[0002]

2. Description of the Related Art Thermoplastic polyester resins such as polycarbonate resin, polybutylene terephthalate (PBT) and polyethylene terephthalate (PET), polyamide resins such as nylon 6, nylon 6,6, polyphenylene sulfide resin (PPS), and polyphenylene ether resin ( Engineering resins typified by polyphenylene resins such as PPE) have excellent physical, chemical and electrical properties, and molded products of these resins obtained by various molding methods are used in a wide range of fields. ing. However, when a molded article is obtained by various molding methods, there is a drawback that the molding workability area is narrow depending on the shape of the molded article and the molding method. For example, during injection molding,
Flow marks, sink marks and warpage are likely to occur. Further, in extrusion molding, die lines and eye burrs are generated, and the expansion ratio is hardly increased during foam extrusion molding. Further, at the time of blow molding, there is a problem that it is difficult to control the drawdown property of the parison, and the thickness of the molded article becomes large.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has as its object to provide a thermoplastic resin composition having excellent moldability and surface appearance of a molded article. .

[0004]

According to the present invention, there is provided (A) at least one thermoplastic resin selected from the group consisting of a polycarbonate resin, a thermoplastic polyester resin, a polyamide resin and a polyphenylene resin in an amount of 50 to 99.9% by weight. And (B) 50% of the syndiotactic structure
(Meth) acrylic acid ester-based (co) polymer having an intrinsic viscosity [η] (30 ° C., methyl ethyl ketone solvent) of at least 1.0 dl / g.
It is intended to provide a thermoplastic resin composition having [(A) + (B) = 100% by weight] as a main component. Here, the thermoplastic resin (A) is preferably a polycarbonate resin. Further, the intrinsic viscosity [η] of (B) (meth) acrylate-based (co) polymer (30 ° C.
Methyl ethyl ketone solvent) is 1.5 to 5.0 dl / g.
It is preferable that Further, the (B) (meth) acrylate-based (co) polymer is preferably a copolymer obtained by copolymerizing methyl methacrylate and butyl acrylate.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Thermoplastic resin The (A) thermoplastic resin of the present invention is at least one type of thermoplastic resin selected from the group consisting of polycarbonate resin, thermoplastic polyester resin, polyamide resin, and polyphenylene resin. Resin. As the polycarbonate resin used for the component (A), those obtained by the reaction of various dihydroxyaryl compounds with phosgene (phosgene method) or those obtained by the transesterification reaction of the dihydroxyaryl compound with diphenyl carbonate ( Transesterification method). Preferred polycarbonate resins are aromatic polycarbonates. As a representative aromatic polycarbonate,
2,2'-bis (4-hydroxyphenyl) propane,
That is, it is a polycarbonate obtained by reacting bisphenol A with phosgene. Aliphatic polycarbonates are not preferred because of poor heat stability.

Here, as the dihydroxyaryl compound serving as a raw material of the aromatic polycarbonate, 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, 2,2'-bis (4-hydroxyphenyl) phenylmethane, 2,2'-bis (4-
(Hydroxy-3-methylphenyl) propane, 2,2 ′
-Bis (4-hydroxy-3-t-butylphenyl) propane, 2,2'-bis (4-hydroxy-3-bromophenyl) propane, 2,2'-bis (4-hydroxy-3,5-dichlorophenyl ) Propane, 1,1′-bis (4-hydroxyphenyl) cyclopentane,
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'-dimethylphenylsulfide, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxyphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone, hydroquinone, resorcin and the like. The dihydroxyaryl compound,
One or two or more are used. Particularly preferred is 2,2'-bis (4-hydroxyphenyl) propane, or bisphenol A.

Further, a polycarbonate resin obtained by copolymerizing a dihydroxyaryl compound represented by the following general formula (I) is also preferably used.

[0008]

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(Where A is selected from a single bond, an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, a cycloalkylidene group having 5 to 6 carbon atoms, -S-, SO _2- ) X represents a chlorine atom or a bromine atom, n ′ is 0, 1 or 2, n is 1 or 0. R is the same or different and has a straight-chain carbon number of 1 to 20; An alkyl group, a branched alkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms,
H ₃ . m is 5 to 100, preferably 20 to 80
Is an integer. The viscosity average molecular weight of the polycarbonate resin used in the present invention is preferably 15,000 to 40,000, and more preferably 17,000 to 30,000. 1
If it is less than 5,000, the mechanical strength is poor, while
If it exceeds 000, the fluidity is reduced and the moldability is poor.

The thermoplastic polyester resin used for the component (A) is an aromatic dicarboxylic acid or an ester or an ester-forming derivative thereof, and a diol.
Those obtained by condensation by a known method,
Aromatic polyester, wholly aromatic polyester, liquid crystal polyester and the like can be used. Here, examples of the aromatic dicarboxylic acid include naphthalenedicarboxylic acid such as naphthalene-2,6-dicarboxylic acid, terephthalic acid, isophthalic acid, p-hydroxybenzoic acid, and the like. It can be used for the production of polyester resins. Examples of the diol include ethylene glycol, 1,4-butanediol,
Examples include polymethylene glycol having 2 to 6 carbon atoms such as 1,6-hexanediol, or 1,4-cyclohexanediol, bisphenol A and ester-forming derivatives thereof.

Preferred specific examples of the thermoplastic polyester resin include polyethylene terephthalate (PET),
Polybutylene terephthalate (PBT), polybisphenol A isophthalate, etc., among which PB
T is preferred. The thermoplastic polyester resin is o-
The intrinsic viscosity [η] at 25 ° C. in a chlorophenol solvent is preferably from 0.4 to 2 dl / g, more preferably from 0.6 to 1.5 dl / g.

Further, as the polyamide resin used for the component (A), a linear diamine represented by the following general formula (II) and a linear dicarboxylic acid represented by the following general formula (III) are usually used. Those produced by condensation or those produced by ring-opening polymerization of lactams can be used. _{H 2 N- (CH 2) x} -NH 2 ··· (II) ( here, x is 4 to 12 _{integer) HO 2 C- (CH 2)} y-CO 2 H ··· (III) (Where y is an integer of 2 to 12)

Preferred examples of these polyamide resins include nylon 6,6, nylon 6,9, nylon 6,
10, nylon 6,12, nylon 6, nylon 12,
Nylon 11, nylon 4, 6 and the like. In addition, nylon 6 / 6,6, nylon 6 / 6,10, nylon 6/12, nylon 6 / 6,12, nylon 6 /
Copolymerized polyamides such as 6,6 / 6,10 and nylon 6/6/6/12 can also be used. In addition, nylon 6 /
6, T (T; terephthalic acid component), aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and meta-xylylenediamine, or semi-aromatic polyamides obtained from alicyclic diamines, meta-xylylenediamine and the above-mentioned line Polyamides, polyesteramides and the like obtained from the dicarboxylic acid can also be used.

The above polyamide resin preferably has a relative viscosity [η _rel ] of 1.0 to 4.0, and more preferably 1.5 to 1.5, measured in a 90% formic acid solvent at a concentration of 1 g / 100 cc and a temperature of 25 ° C. ~ 3.5. The above polyamide resins can be used alone or as a mixture of two or more.

Further, as the polyphenylene resin used for the component (A), polyphenylene sulfide resin,
Examples include polyphenylene ether resin. The polyphenylene sulfide resin has a main structural unit represented by a general formula: -C ₆ H ₄ -S- (where S is a sulfur atom)
Is a polymer represented by Representative examples of the divalent aromatic group constituting the phenylene group include a p-phenylene group, an m-phenylene group, and respective substituents thereof. Of these, poly-p-phenylene sulfide having a non-substituted p-phenylene group (P
PS) is preferred in terms of moldability. The polyphenylene sulfide resin can be obtained by condensation polymerization of cyclobenzene and sodium sulfide, but is not limited thereto. In the present invention, the viscosity of the polyphenylene sulfide resin is usually 100 to 4,000 p.m. at a temperature of 300 ° C. and a strain rate of 1,000 sec ⁻¹ .
oise.

As the polyphenylene ether resin used in the component (A) of the present invention, a homopolymer comprising a repeating unit represented by the following formula (IV) or (V), or a compound represented by the formula (IV): Copolymers comprising a repeating unit represented by the general formula (V) are exemplified.

[0017]

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[0018]

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(However, R ^{1 to} R ⁶ are the same or different and are each an alkyl group having 1 to 4 carbon atoms, an aryl group,
Shows a halogen atom or a hydrogen atom. In addition, as the polyphenylene ether resin, a mixture of the above homopolymer and copolymer, a graft copolymer of styrene and the above homopolymer and / or a graft copolymer of styrene and the above copolymer may be used. Examples of the homopolymer of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, and poly (2-ethyl-6). -N-propyl-1,4-phenylene) ether, poly (2-methyl-6-chloro-1,4)
-Phenylene) ether and the like. Examples of the copolymer of the polyphenylene ether resin include a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure obtained by copolymerization with o-cresol or an alkyl-substituted phenol such as 2,3,6-trimethylphenol. Among the thermoplastic resins, the thermoplastic resin (A) of the present invention is preferably a polycarbonate resin.

(B) (meth) acrylate
(Co) polymer The (B) component used in the present invention is a (meth) acrylate ester (co) obtained by polymerizing a monomer mixture containing a (meth) acrylate monomer as a main component. It is a polymer. Here, as the (meth) acrylate monomer, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate Acrylates such as phenyl acrylate and benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-
Examples include methacrylates such as ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate. These may be used alone or in combination with two or more.
Mixtures of more than one species can be used. Preferably, methyl methacrylate, butyl acrylate, and 2-ethylhexyl methacrylate are used.

The amount of the (meth) acrylate monomer used in the (meth) acrylate (co) polymer (B) of the present invention is preferably at least 50% by weight, more preferably 55% by weight. The content is particularly preferably 60% by weight or more. If it is less than 50% by weight, no effect of improving the moldability is obtained.

The above (meth) acrylic acid ester monomer can be used by appropriately mixing other copolymerizable vinyl monomers to obtain a copolymer. Other copolymerizable vinyl monomers include unsaturated acids such as acrylic acid and methacrylic acid; unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; styrene, t-butyl Styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, N, N-diethyl-p-aminomethylstyrene, vinylpyridine, vinyl Xylene, monochlorostyrene,
Aromatic vinyl monomers such as dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; maleimide, N-methyl Monomers obtained by imidizing α, β-unsaturated dicarboxylic acids such as maleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; glycidyl methacrylate, allyl glycidyl ether Unsaturated carboxylic acid amides such as acrylamide and methacrylamide; acrylamine, aminomethyl methacrylate, aminoether methacrylate, aminopropyl methacrylate, aminos Amino group-containing unsaturated monomers such as tylene; 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3- Hydroxyl-containing unsaturated monomers such as hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and p-hydroxystyrene; oxazoline group-containing unsaturated monomers such as vinyl oxazoline; Poly) alkylene glycol di (meth)
Examples include polyfunctional monomers having two or more unsaturated double bonds in a molecule, such as acrylate, allyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, and divinylbenzene. These can be used alone or as a mixture of two or more. Preferred are methacrylic acid, styrene, acrylonitrile, glycidyl methacrylate, and vinyl oxazoline.

Among the (meth) acrylate-based (co) polymers obtained by polymerizing the above-mentioned monomers, polymethyl methacrylate (PMM) is preferably used as the component (B).
A), a methyl methacrylate-butyl acrylate copolymer and a methyl methacrylate-styrene-acrylonitrile copolymer, and particularly preferably a methyl methacrylate-butyl acrylate copolymer.

The proportion of the syndiotactic structure of the component (B) of the present invention is 50% or more, preferably 55 to 90%.
%, More preferably 60 to 80%. When the ratio of the syndiotactic structure is less than 50%, no effect of improving the moldability is obtained. The ratio of the syndiotactic structure can be calculated from an infrared absorption spectrum (IR) or a nuclear magnetic resonance absorption spectrum (NMR). For example, in NMR, a continuous triad (T
rid) can be calculated from the ratio of two linked racemic structures (syndiotactic), two linked mesostructures (isotactic), and random or heterostructures (atactic).

The component (B) of the present invention has an intrinsic viscosity [η] measured at 30 ° C. using methyl ethyl ketone as a solvent.
1.0 dl / g or more, preferably 1.2 to 10.0 dl
/ G, more preferably 1.5 to 5.0 dl / g. When the intrinsic viscosity is less than 1.0 dl / g, the effect of improving the moldability is not obtained. If the intrinsic viscosity is too high,
In some cases, poor dispersion occurs, which is not preferable. The ratio of the syndiotactic structure and the intrinsic viscosity [η] of the component (B) of the present invention are controlled by changing the type and amount of a polymerization initiator, a chain transfer agent, an emulsifier, a suspending agent, a solvent, and the like. Can be. The control can also be performed by changing the method of adding the monomer, the addition time, the polymerization time, the polymerization temperature, and the like.

As the component (B) polymerization method, known polymerization methods such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, or a combination thereof can be used. The component (B) of the present invention has a considerably higher molecular weight than a commonly used (meth) acrylate-based (co) polymer. Is an emulsion polymerization. For this emulsion polymerization, a polymerization initiator, an emulsifier, a chain transfer agent and the like are used.

Examples of the polymerization initiator include an oxidizing agent comprising an organic hydroperoxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, t-butylperoxylaurate, and a sugar-containing compound. Redox-based initiators in combination with reducing agents such as iron pyrophosphate formulation, sulfoxylate formulation, and mixed sugar-containing iron pyrophosphate / sulfoxylate formulation; persulfates such as potassium persulfate and ammonium persulfate; Azo compounds such as azobisisobutyronitrile (AIBN), dimethyl-2,2'-azobisisobutyrate and 2-carbamoylazoisobutyronitrile; organic peroxides such as benzoyl peroxide and lauroyl peroxide; Can be mentioned, Mashiku is a water-soluble initiator such as potassium persulfate. The amount of these polymerization initiators used is
Usually, 0.1 part by weight per 100 parts by weight of the monomer component used.
It is about 0.5 to 5 parts by weight, preferably about 0.1 to 3 parts by weight.

Examples of the emulsifier include sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium diphenyl ether disulfonate, sodium dialkali ester succinate, sodium or potassium salts of aliphatic dicarboxylic acids having 10 to 20 carbon atoms,
Examples include anionic emulsifiers such as sodium or potassium salts of rosin acid, and nonionic emulsifiers such as polyoxyethylene alkyl ester and polyoxyethylene alkyl allyl ether. These may be used alone or in combination with two or more. Mixtures of more than one species can be used. However, since a (meth) acrylic acid ester monomer is liable to be hydrolyzed, it is preferable to use an emulsifier having a neutral pH range which works effectively as a surfactant. As the emulsifier, a method using a low critical micelle concentration is preferable. Here, the critical micelle concentration is preferably 30 mmol / L or less, more preferably 15 mmol / L or less. The amount of the emulsifier to be used is usually 0.5 to 5 parts by weight based on 100 parts by weight of the monomer component.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, and tetraethyl. Thiuram sulfide, carbon tetrachloride, ethylene bromide,
Examples thereof include hydrocarbon salts such as pentaphenylethane, terpenes, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol, and α-methylstyrene dimer. These chain transfer agents can be used alone or in combination of two or more. The amount of the chain transfer agent to be used is generally 0 to 1 part by weight based on 100 parts by weight of the monomer component.

In the polymerization of the component (B) of the present invention, in addition to a polymerization initiator, an emulsifier, a chain transfer agent, etc., if necessary, various electrolytes, a pH adjuster and the like are used in combination to prepare a monomer component 100 With respect to parts by weight, usually 100 to 500 parts by weight of water and the polymerization initiator, emulsifier, chain transfer agent and the like are used in an amount within the above range, and usually, a polymerization temperature of 40 to 100 ° C,
Emulsion polymerization is preferably performed at 50 to 90 ° C. for a polymerization time of 1 to 10 hours.

The component (B) used in the present invention is purified by coagulating a latex obtained by the above emulsion polymerization by a conventional method, washing the obtained powder with water, and drying it.

Thermoplastic Resin Composition of the Present Invention The thermoplastic resin composition of the present invention contains the above components (A) and (B) as main components. The amount of the components (A) and (B) used in the composition of the present invention is as follows.
9.9% by weight, preferably 60 to 99.7% by weight, more preferably 70 to 99.5% by weight, and 50% of the component (B)
To 0.1% by weight, preferably 40 to 0.3% by weight, more preferably 30 to 0.5% by weight [however, (A) +
(B) = 100% by weight]. When the component (A) is less than 50% by weight (the component (B) exceeds 50% by weight),
(A) The mechanical properties inherent to the thermoplastic resin are impaired, which is not preferred. On the other hand, the component (A) is 99.9% by weight.
(The component (B) is less than 0.1% by weight);
The effect of improving the processability of the thermoplastic resin cannot be obtained.

Preparation of the composition of the present invention The thermoplastic resin composition of the present invention is prepared by mixing the above components (A) and (B) with generally known kneading machines, for example, various extruders.
It is obtained by kneading using a known mixer or kneader such as a Banbury mixer, kneader or roll at a melting temperature of 180 to 330 ° C. Preferably, an extruder is used. In kneading, the order of addition of each component can be arbitrarily selected, and may be added all at once or dividedly.

The composition of the present invention may contain, if necessary, a phenolic stabilizer such as hindered phenol, a phosphorus-based or sulfur-based oxidation stabilizer, a benzotriazole-based or hindered amine-based light stabilizer, etc. Lubricants such as stearyl alcohol and ethylene bisstearyl amide, ultraviolet absorbers, plasticizers, colorants, flame retardants, flame retardant aids, enhancers, compatibilizers, foaming agents, wood flour, paper, fillers, antioxidants , Weather (light) agent, metal powder, antibacterial agent, fungicide,
Known additives such as silicone oil and coupling agents can be blended.

In the composition of the present invention, another polymer can be appropriately blended in an amount of 40% by weight or less in the composition of the present invention. Other polymers include ABS resin,
MBS resin, AES resin, acrylic graft polymer,
HIPS, AS, PMMA, PS (However, AS, PM
Intrinsic viscosity [η] of MA and PS is less than 1.0 dl / g),
Silicone rubber-based graft polymer, polyethylene, polypropylene, silicone rubber, fluorine-based rubber, butyl rubber, butadiene rubber, ethylene-α / olefin-based rubber, NBR, SBR, SBS, SIS, SEPS, SE
BS, thermoplastic polyurethane, PTFE, polyamide elastomer, polyester elastomer and the like. The other polymers described above may be used alone.
Alternatively, two or more kinds can be used in combination.

Molding processing using the composition of the present invention The composition of the present invention obtained in this way has excellent workability, so that good molded articles can be obtained by various processing methods. Particularly effective processing methods for the composition of the present invention are (foaming) extrusion molding, blow molding, injection molding, calendering, vacuum molding, inflation molding, lamination molding, and compression molding.

Here, in (extrusion) extrusion molding, sheets such as pipes, hoses, sheets for building materials, sheets for vacuum forming, laminated sheets, etc., and irregularly shaped articles can be obtained.
In the blow molding, various molded products can be obtained by an extrusion blow molding method, an injection blow method, a sheet blow method, a cold parison method, or the like.

In the injection molding, in addition to the usual molding method, various molding methods such as gas assist molding, in-mold molding, two-color molding, thermoejection molding, and sandwich molding are used.
A molded article can be obtained. In the calendering process, it is possible to obtain surface-decorated molded products by various thicknesses of films, sheets, and embossing. In vacuum forming, straight forming, drape forming, plug assist forming, plug assist reverse draw forming, air slip forming, snapback forming, reverse draw forming, air cushion forming, plug assist air slip forming, free forming,
There are matched mold molding, plug ring molding, slip molding, contact heating molding, and the like, and various molded products can be obtained using various sheets, films or embossed sheets and films.

In inflation molding, molded articles such as tubes, general films, stretchable films, and multilayer films can be obtained. In lamination molding, a sheet of the thermoplastic resin composition of the present invention, a method of obtaining a molded article by heating and pressing after laminating a film and the like, other types of sheets,
A molded product can be obtained by, for example, a method of obtaining a molded product by laminating a film or the like in a layered form and then heating and applying pressure. The various molded products obtained by the above-mentioned molding method can be used for various parts such as OA / home electric appliances, automobile parts, building material products, daily necessities, etc. by utilizing their excellent properties.

[0040]

EXAMPLES The present invention will now be described more specifically with reference to examples. Parts and% in Examples are parts by weight and% by weight unless otherwise specified. During the implementation, various measurement items were as described below.

The limiting viscosity copolymer was completely dissolved in methyl ethyl ketone, and five points having different concentrations were prepared.
The intrinsic viscosity [η] was determined from the result of measuring the reduced viscosity at each concentration at ° C. Ratio of syndiotactic structure Using JNM-EX270 manufactured by JEOL Ltd., ¹³ C-
It was calculated from the observation results of the NMR spectrum.

Evaluation of Adhesion The thermoplastic resin composition was kneaded under the following conditions using a Rheocord system 90 manufactured by Haake Co., and then the ease of peeling of the resin from the rotor was evaluated according to the following evaluation criteria. <Test Conditions> Temperature (° C.): The measurement was carried out while changing depending on the resin type of the component (A). Rotor speed: 30 rpm Sample amount: 60 g Kneading time: 10 minutes <Evaluation criteria> A: Almost no sticking to the rotor, resin is easily peeled off from the rotor. ；: Little adhesion to the rotor, and the resin peeled off the rotor relatively easily. ×: Adhesion to the rotor was strong, and the resin did not peel off from the rotor.

[0043] Using the molded product surface appearance evaluation thermoplastic resin composition, a flat plate having a direct gate moldings central injection molded, and evaluated the state of the flow marks of the molded article surface according to the following evaluation criteria. ；: Good without flow mark ×: poor with flow mark

When evaluating the resin composition using a twin-screw extruder, the state of the eye drop at the nozzle outlet was evaluated according to the following evaluation criteria. ；: Almost no occurrence of eye stains. ×: Eye tanning occurred. A blow molded product having an average thickness of 1.5 mm was obtained using the blow molding evaluation resin composition. A part corresponding to the upper part of the mold was cut out, and the minimum thickness (mm) was measured.

Reference Example 1 [Preparation of Component (A)] A-1: Polycarbonate resin (viscosity average molecular weight 22,000 obtained from the reaction of bisphenol A and phosgene)
Aromatic polycarbonate) was used. A-2: Polybutylene terephthalate (polybutylene terephthalate having an intrinsic viscosity of 0.85 obtained from the reaction of terephthalic acid and butanediol) was used. A-3: Polyethylene terephthalate (polyethylene terephthalate with an intrinsic viscosity of 0.85 obtained from the reaction of terephthalic acid and ethylene glycol) was used. A-4: Nylon 6 [manufactured by Toray Industries, Inc.
Amilan CM1007] was used. A-5: Polyphenylene sulfide resin (polyphenylene sulfide resin obtained from the reaction between dichlorobenzene and sodium sulfide) was used. A-6: Polyphenylene ether resin (poly-2,6-dimethyl-1,4-phenylene ether) was used.

Reference Example 2 [Preparation of Component (B)] Sodium dodecylbenzenesulfonate was used as an emulsifier.
A redox initiator combining diisopropylbenzene hydroperoxide and a reducing agent as a polymerization initiator, methyl methacrylate and n-butyl acrylate as monomers, and further, if necessary, styrene, acrylonitrile, methacrylic acid, glycidyl methacrylate, or vinyl Using oxazoline and emulsion polymerization, the (co) polymers (B-1) to (B-12) having the composition, intrinsic viscosity [η], and syndiotactic structure ratio shown in Table 1
I got The intrinsic viscosity [η] and the ratio of the syndiotactic structure were changed to desired values by changing the polymerization temperature, the amounts of the emulsifier and the polymerization initiator, and the method of adding the monomer.

[0047]

[Table 1]

Examples 1 to 21 and Comparative Examples 1 to 14 The above components were blended at the ratios shown in Tables 2 and 3 and mixed with a Henschel mixer. The mixture was melted by a twin-screw extruder, kneaded, extruded, and pelletized. The obtained pellets were sufficiently dried, and the adhesiveness, the surface appearance of the molded product, the evaluation of the die build, and the evaluation of the blow molding were performed by the above evaluation methods. The evaluation results are shown in Tables 2 and 3.

[0049]

[Table 2]

[0050]

[Table 3]

Examples 1 to 21 are the thermoplastic resin compositions of the present invention, and all of the evaluation results were excellent in adhesiveness, surface appearance of the molded product, dent, and blow moldability. On the other hand, Comparative Examples 1 to 6 have compositions in which the use amount of the component (A) of the present invention is large outside the range of the present invention, and the use amount of the component (B) is small outside the range of the present invention, and (A) The case where the type of the component is changed, which is inferior in tackiness, surface appearance of a molded article, die-set, and blow moldability. Comparative Examples 7 to 12 are compositions in which the amount of the component (A) used in the present invention is small outside the scope of the present invention, the amount of the component (B) used is large outside the range of the present invention, and the component (A) is used. Are inferior in adhesiveness, surface appearance of a molded product, eye resilience, and blow moldability. Comparative Example 13 is a case where the intrinsic viscosity [η] of the component (B) of the present invention is low outside the range of the present invention, and is inferior in tackiness, surface appearance of a molded product, dent, and blow moldability. In Comparative Example 14, the ratio of the syndiotactic structure of the component (B) of the present invention was low outside the range of the present invention, and the adhesiveness, the surface appearance of the molded product, the adhesion, and the blow moldability were poor.

[0052]

Industrial Applicability The thermoplastic resin composition of the present invention is excellent in moldability and surface appearance of a molded article, and can provide a useful molded article in a wide range of fields. Various molded products obtained by the present invention, utilizing its excellent properties,
It can be used for various parts such as OA / home appliances, automobile parts, building materials, daily necessities, etc.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Katsuo Omura 1-1-18 Kyobashi, Chuo-ku, Tokyo Techno Polymer Co., Ltd. F-term (reference) 4J002 BG042 BG052 BG062 BG072 BN181 CF041 CF061 CF071 CF081 CG011 CG021 CG031 CH071 CL011 CL031 CL051 CL081 CN011 FD010 FD020 FD040 FD050 FD070 FD080 FD090 FD130 FD170 FD180 FD200 FD320 GC00 GL00 GN00 GQ00

Claims (4)

[Claims] (1) 50 to 99.9% by weight of at least one thermoplastic resin selected from the group consisting of (A) a polycarbonate resin, a thermoplastic polyester resin, a polyamide resin, and a polyphenylene resin; and (B) syndiotactic. The ratio of the structure is 50% or more, and the intrinsic viscosity [η] (30 ° C., methyl ethyl ketone solvent) is 1.0 d
1 / g or more (meth) acrylic acid ester (co)
50-0.1% by weight of polymer [however, (A) + (B) =
100% by weight] as a main component. 2. The thermoplastic resin composition according to claim 1, wherein (A) the thermoplastic resin is a polycarbonate resin. 3. The (B) (meth) acrylate-based (co) polymer having an intrinsic viscosity [η] (30 ° C., methyl ethyl ketone solvent) of 1.5 to 5.0 dl / g. Thermoplastic resin composition. 4. The thermoplastic resin composition according to claim 1, wherein (B) the (meth) acrylate-based (co) polymer is a copolymer obtained by copolymerizing methyl methacrylate and butyl acrylate. .