JP3018378B2 - Thermoplastic resin composition - Google Patents

Description

The present invention relates to a thermoplastic resin composition comprising a specific hydrogenated polymer and a thermoplastic resin and having excellent heat resistance, light resistance and moldability. About things.

[Conventional technology]

BACKGROUND ART Ring-opening polymers or ring-opening copolymers of norbornene derivatives have good optical properties, low hygroscopicity, and excellent heat resistance, and are therefore expected to be applied in various fields.

[Problems to be solved by the invention]

However, this ring-opened polymer (including a ring-opened copolymer; the same applies hereinafter) is difficult to mold due to low fluidity. Therefore, when the thermoplastic resin composition is put to practical use, for example, mechanical parts such as automobile parts, electric and electronic parts, and OA equipment, which cannot be easily manufactured, having excellent characteristics. was there.

[Means for solving the problem]

As a result of intensive studies on the above-mentioned problems, the present invention has found that a hydrogenated polymer obtained by further hydrogenating a ring-opened polymer of a monomer comprising a norbornene derivative having a polar substituent has a thermoplastic property. By containing the resin in a specific ratio, in the thermoplastic resin composition, excellent heat resistance and light resistance are developed, and the fluidity is improved. As a result, excellent physical properties and good light-forming processability are obtained. Are obtained together, and are completed by this.

That is, the thermoplastic resin composition of the present invention is characterized by containing 10 to 95% by weight of the following component (a) and 90 to 5% by weight of the following component (b).

Component (a): Ring-opening polymerization of a monomer comprising at least one tetracyclododecene derivative represented by the following general formula (I) or this monomer and a copolymerizable monomer copolymerizable therewith. A hydrogenated polymer obtained by further hydrogenating a ring-opened polymer obtained by the above.

General formula (I) Wherein A and B are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X is a hydrogen atom, a halogen atom or a monovalent organic group, and R is a hydrocarbon group having 1 to 20 carbon atoms. Show. ].

Component (b): (a) selected from styrene resins, vinyl chloride resins, acrylic resins, polyphenylene ether resins, polyarylene sulfide resins, polyester resins, polyamide resins, polyether sulfone resins, polysulfone resins, and polyimide resins. ) Thermoplastic resins other than the components.

 Hereinafter, the present invention will be described specifically.

The component (a) contained in the thermoplastic resin composition of the present invention is a monomer comprising a tetracyclododecene derivative represented by the above general formula (I) (hereinafter, referred to as “specific monomer”)
A ring-opened polymer obtained by ring-opening copolymerization of a specific monomer alone or with a copolymerizable monomer copolymerizable therewith using a metathesis polymerization catalyst is further obtained by hydrogenation. And is also referred to as “hydrogenated polymer (a)” below.

The molecular weight of the hydrogenated polymer (a) is from 20,000 to 700,000 in terms of weight average molecular weight in terms of polystyrene, particularly 3
Preferably it is between 0,000 and 500,000.

The hydrogenated polymer (a) in the present invention is, for example, a polymer obtained by hydrogenating a ring-opening (co) polymer of a compound having a tetracyclododecene ring described in JP-A-1-132626. is there. This specific monomer is such that the resulting polymer has a high glass transition temperature and a low hygroscopicity.

When the number of the polar substituents composed of the carboxylic acid ester groups per molecule of the specific monomer is 1, the obtained polymer has low hygroscopicity.

Further, the polar substituent in the general formula (I) is represented by -COOR, and the carboxylic acid ester group represented by the formula CH ₂ ) _n COOR has a value of n of 0. According to the specific monomer, the glass transition temperature of the obtained polymer is increased, its synthesis is easy, and good characteristics are obtained in the polymer.

Further, in the general formula (I), R is a hydrocarbon group having 1 to 20 carbon atoms, and it is preferable that as the number of carbon atoms increases, hygroscopicity of the obtained polymer decreases. However, from the viewpoint of the balance with the glass transition temperature of the obtained polymer, a chain alkyl group having 1 to 4 carbon atoms or a (poly) cyclic alkyl group having 5 or more carbon atoms is preferable, and a methyl group is particularly preferable. It is preferred that

Further, the carbon atom to which the carboxylic acid ester group is bonded,
At the same time, the specific monomer in which a hydrocarbon group having 1 to 10 carbon atoms is bonded as a substituent is preferable because it reduces the hygroscopic property without lowering the glass transition temperature of the obtained polymer. And the specific monomer in which this substituent is a methyl group,
It is preferable in that the synthesis is easy.

The ring-opening polymer according to the hydrogenated polymer (a) in the present invention may be one obtained by subjecting a specific monomer to ring-opening polymerization alone, but the specific monomer and a copolymerizable monomer may be used. And ring-opening copolymerization of When a copolymerizable monomer is used as described above, the ratio of the specific monomer in the ring-opened polymer is at least 5 mol%, preferably at least 20 mol%. Examples of the copolymerizable monomer to be used include a monomer capable of undergoing ring-opening polymerization with a metathesis polymerization catalyst and a partially polymerized low-polymer having a carbon-carbon double bond in the main chain of the polymer. be able to.

According to the tetracyclododecene derivative represented by the general formula (I), a polymer having a high glass transition point can be obtained. Among such tetracyclododecene derivatives, examples of preferred compounds, 8-carboxymethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methyl-8
- carboxymethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10]
-3-dodecene, 5-carboxymethyl-bicyclo [2.
2.1] -2-heptene and the like.

The specific monomer can also be copolymerized with a cyclic olefin compound.

Specific examples of such a cyclic olefin compound include cycloolefins such as cyclopentene, cyclooctene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene; bicyclo [2.2.1] -2-heptene; Tricyclo [5.2.1.0 ^2,6 ] -8-decene, tricyclo [5.2.1.0
^2,6 ] -3-decene, tricyclo [6.2.1.0 ^1,8 ] -9-
Undecene, tricyclo [6.2.1.0 ^1,8] -4- undecene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13] -4-pentadecene, pentacyclo [6.6.1.1 ^3,6 .0 ^2,7 .0 ^9,14]
-4-hexadecene, pentacyclo [6.5.1.1 ^3,6 .0 ^2,7.
0 ^9,13 ] -11-pentadecene, dicyclopentadiene,
Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} - pentadeca-4,11 may be mentioned poly cycloalkene such as dienes.

Further, as a copolymerizable monomer that can be copolymerized with the specific monomer, polybutadiene, polyisoprene, styrene-
Unsaturated hydrocarbon polymers containing a carbon-carbon double bond in the main chain of polymers such as butadiene copolymer, ethylene-propylene non-conjugated diene copolymer rubber, polynorbornene, and polypentenamer can also be mentioned.

A method of ring-opening polymerization of a specific monomer and a copolymerizable monomer copolymerizable therewith and a method of hydrogenation are disclosed in
The same method as the method described in JP-A-2626 can be mentioned.

The hydrogenation rate of the obtained hydrogenated polymer (a) is usually
It is 50% or more, preferably 70% or more, and more preferably 80% or more. When the hydrogenation ratio is less than 50%, the thermal stability of the finally obtained thermoplastic resin composition becomes low, which is not preferable.

The component (b) contained in the thermoplastic resin composition of the present invention is a thermoplastic resin other than the component (a), and is a styrene resin, a vinyl chloride resin, an acrylic resin, a polyphenylene ether resin, a polyarylene. Sulfide resin,
It is selected from polyester resin, polyamide resin, polyether sulfone resin, polysulfone resin and polyimide resin.

The thermoplastic resin used as the component (b) is a polymer having a glass transition temperature of 25 ° C. or higher, and may be an amorphous polymer, a crystalline polymer, a liquid crystal polymer, or the like.

Styrene resins useful in the present invention include polystyrene, polychlorostyrene, polyα-methylstyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene- α-methylstyrene copolymer, styrene-α-methylstyrene-methyl methacrylate copolymer, styrene-α-methylstyrene-acrylonitrile-methyl methacrylate copolymer, and the like. In addition, two or more types can be used.

Examples of the vinyl chloride resin useful in the present invention include polyvinyl chloride, vinyl chloride and a compound having at least one double bond copolymerizable with 50% by weight or less, preferably 45% by weight or less of vinyl chloride. Copolymers can be mentioned.

Specific examples of the compound having at least one copolymerizable double bond include vinylidene chloride, ethylene, propylene, vinyl acetate, (meth) acrylic acid and their esters, maleic acid and their esters, and acrylonitrile. Can be mentioned.

The polymerization degree of the vinyl chloride resin is usually 400 to 4500,
Particularly, 400 to 1500 is preferable.

The vinyl chloride resin is obtained by (co) polymerizing vinyl chloride alone or with vinyl chloride and the copolymerizable compound in the presence of a free radical catalyst, and its production method is widely known. ing.

The polyarylene sulfide resin useful in the present invention contains at least 70 mol% of the structural unit represented by the formula Ar-S. Here, Ar is an aromatic group having 6 or more carbon atoms, such as p-phenylene, m-phenylene, 2,6-naphthalene, 4,4'-biphenylene, p, p'-bibenzyl, and their nuclear substituents. Represents a group. Of these, the nuclear-unsubstituted p-phenylene nucleus, ie, the formula: Poly-p-phenylene sulfide having a structural unit represented by the following formula (1) is preferred from the viewpoint of moldability.

When a resin having a structural unit represented by the formula Ar-S of less than 70 mol% is used, undesired results such as a decrease in crystallinity of the obtained polymer, a decrease in transition temperature, and a decrease in physical properties of a molded article are produced. If less than 30 mol%, 1,2,
An aromatic group, an aliphatic group, a hetero atom-containing group, or the like having a trivalent or higher bond such as a 4-bonded phenylene nucleus may be contained.

The method for producing the polyarylene sulfide resin includes a condensation reaction between a dihalogenated aromatic compound and a dithiol aromatic compound or a monohalogenated aromatic thiol, or a dihalogenated aromatic compound and an alkali sulfide or an alkali hydrosulfide and an alkali or sulfide. A method using a desalination condensation reaction from hydrogen and an alkali compound can be exemplified, but the method is not limited thereto.

As a typical example of the polyester resin useful in the present invention,
Obtained from aromatic dicarboxylic acids such as poly (ethylene terephthalate) (PET), poly (propylene terephthalate), poly (butylene terephthalate) (PBT), poly (pentamethylene terephthalate), poly (hexamethylene terephthalate) and dihydric alcohols Is an aromatic polyester resin obtained from a polyester resin and an aromatic dicarboxylic acid and an aromatic diphenol,
A so-called polyarylate resin can be used. Specific examples of the polyarylate resin include bisphenol A
And terephthalanolic acid or isophthalic acid. Particularly preferred among these are PET and PBT.

. Useful polyamide resin in the present invention is typically a linear diamine represented by the formula _{H 2 NCH 2) x -NH 2} ( wherein, x is 3 to 12 integer), formula HOOCCH _{2) y} - COOH (wherein, y is an integer of 2 to 12), and those produced by condensation with a linear dicarboxylic acid or those produced by ring-opening polymerization of a lactam.

Preferred examples of these polyamide resins include nylon 6,6, nylon 6,10, nylon 6,12, nylon 4,6,
Nylon 3,4, Nylon 6,9, Nylon 6, Nylon 12,
There are nylon 11, nylon 4, and the like. Also nylon 6/6,
10, nylon 6 / 6,12, nylon 6 / 4,6, nylon 6/12,
Nylon 6 / 6,6, Nylon 6 / 6,6 / 6,10, Nylon 6 / 4,6 /
Copolymer polyamides such as 6,6, nylon 6 / 6,6 / 6,12, nylon 6 / 4,6 / 10, nylon 6 / 4,6 / 12 and the like can be mentioned.

Furthermore, semi-aromatic polyamide resin obtained from aromatic dicarboxylic acid such as nylon 6/6, T (T: terephthalic acid component), terephthalic acid, isophthalic acid and metaxylylenediamine or alicyclic diammine; Examples thereof include polyamide resins, polyester amide resins, polyether amide resins, and polyester ether amide resins obtained with the above-mentioned linear dicarboxylic acid.

The above components (a) and (b) are mixed to obtain the thermoplastic resin composition of the present invention.

In the present invention, the weight ratio of the component (a) to the component (b) is 10 to 95:90 to 5, preferably 15 to 90:85 to 1 by weight.
0, more preferably 20 to 80:80 to 20. If the proportion of the component (a) in the thermoplastic resin composition is too small, the excellent heat resistance and light resistance of the obtained thermoplastic resin composition will be impaired. The molding properties are low and sufficient molding workability cannot be exhibited.

The thermoplastic resin composition of the present invention may contain, as optional components, a rubbery polymer and a rubber-reinforced thermoplastic resin, each alone or both. As described above, the impact resistance of the thermoplastic resin composition can be improved by further containing the rubbery polymer and / or the rubber-reinforced thermoplastic resin.

Here, the rubbery polymer is a polymer having a glass transition temperature of 0 ° C. or lower, and includes ordinary rubbery polymers and thermoplastic elastomers.

Examples of the rubbery polymer include ethylene-α-olefin-based rubbery polymers; ethylene-α-olefin-polyene copolymer rubber; and ethylene-unsaturated carboxylic acid esters such as ethylene-methyl methacrylate and ethylene-butyl acrylate. Copolymer; Copolymer of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; Polymer of alkyl acrylate such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate Polybutadiene, polyisoprene, styrene-butadiene or styrene-isoprene random copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meth) acrylic acid alkyl ester copolymer, butadiene -(Meth) acrylic acid alkyl ester-acrylonitrile copolymer, butadiene-
Diene rubbers such as alkyl (meth) acrylate-acrylonitrile-styrene copolymer; butylene-
There are isoprene copolymers and the like, and not only one kind thereof but also two or more kinds thereof can be used.

The rubbery polymer may be obtained by crosslinking the above rubbery polymer using a known crosslinking agent such as divinylbenzene.

In the ethylene-α-olefin rubbery polymer, the ratio of ethylene and α-olefin is 95: 5 to
5:95, preferably 95: 5 to 20:80, more preferably 92: 8 to 6
0:40, particularly preferably 85:15 to 70:30.

The α-olefin used here has 3 to 20 carbon atoms.
Is an unsaturated hydrocarbon compound, specific examples of which include:
Propylene, butene-1, pentene-1, hexene-
1, heptene-1, 4-methylbutene-1, 4-methylpentene-1 and the like. Particularly preferred is propylene.

The cyclohexane-insoluble component in the ethylene-α-olefin-based rubbery polymer is a component that affects the moldability and impact resistance of the finally obtained thermoplastic resin composition. The proportion is 50% by weight or less, preferably 5% by weight or less.

Examples of the polyene compound for the ethylene-α-olefin-polyene copolymer include 1,4-pentadiene,
1,5-hexadiene, 2-methyl-1,5-hexadiene,
3,3-dimethyl-1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 6-methyl-1,5-hexadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 9-methyl-1,9-undecadiene, isoprene,
1,3-pentadiene, 1,4,9-decatriene, 4-vinyl-1-cyclohexadiene, cyclopentadiene, 2-
Methyl-2,5-norbornadiene, 5-methyl-2-norbornadiene, 5-ethylidene-2-norbornene,
5-isopropylidene-2-norbornene, 5-isopropenyl-2-norbornene, dicyclopentadiene,
Tricyclopentadiene and the like can be mentioned.

The rubbery polymer comprising the above rubbery polymer preferably has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 5 to 200.

Examples of the thermoplastic elastomer used as the rubbery polymer include styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, and hydrogenated styrene-isopropylene block copolymer. Such as aromatic vinyl-conjugated diene block copolymer, low crystalline polybutadiene resin, ethylene-propylene elastomer, styrene-grafted ethylene-propylene elastomer, thermoplastic polyester elastomer, and ethylene ionomer resin.

Examples of the aromatic vinyl-conjugated diene-based block copolymer include α-β, α-β-α, α-β-γ, and α-β _1-.
β ₂ , α / β, α-α / β, α-α / β-γ, α-α /
β-α, β ₂ -β ₁ -β ₂ , γ-β, γ-β-γ, γ-
α / β-γ, γ-α-β [wherein α: aromatic vinyl compound polymer β: conjugated diene compound polymer β ₁ : conjugated diene compound polymer having a vinyl bond content of 20% by weight or more β ₂ : A conjugated diene compound polymer having a vinyl bond content of less than 20% by weight α / β: a random copolymer of an aromatic vinyl compound / conjugated diene compound γ: a copolymer of a conjugated diene compound and an aromatic vinyl compound, And a taper polymer in which the aromatic vinyl compound gradually increases. And hydrogenated products thereof.

Particularly preferable rubbery polymer for obtaining a thermoplastic resin composition having excellent transparency is a hydrogenated styrene-butadiene random copolymer, a block copolymer or a block-random copolymer, which contains styrene. Quantity 20
And a copolymer of butadiene and an acrylate ester in which the weight ratio of butadiene to the acrylate ester is 10 to 90:90 to 10; and 100 parts by weight of styrene and And / or acrylonitrile copolymerized at a ratio of 0 to 30 parts by weight and hydrogenated products thereof.

The rubbery polymer is modified with a specific functional group such as an epoxy group, a carboxyl group, a hydroxyl group, an amino group, an acid anhydride group, an oxazoline group for the purpose of improving compatibility with the hydrogenated polymer (a). May be done.

The amount of the unsaturated compound having a specific functional group used for the modification of the rubbery polymer is preferably in the range of 0.01 to 30% by weight of the entire thermoplastic resin composition.

Rubber-reinforced thermoplastic resin used as an optional component of the thermoplastic resin composition of the present invention, in the presence of a rubbery polymer, a monomer or monomer mixture copolymerizable therewith, for example, an aromatic vinyl compound , Maleimide compounds,
It is a thermoplastic copolymer obtained by copolymerizing a vinyl cyan compound and another vinyl monomer copolymerizable therewith.

Here, examples of the rubbery polymer for obtaining the rubber-reinforced thermoplastic resin include the same ones as the rubbery polymer.

These rubbery polymers may be used alone or in combination of two or more.

Among these, preferable rubbery polymers in terms of physical properties are diene rubber, ethylene-propylene rubber, and ethylene-propylene-nonconjugated diene terpolymer.

Examples of the aromatic vinyl compound copolymerized in the presence of the rubbery polymer include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, and p-methylstyrene. -Tert-butylstyrene, ethylstyrene, vinylnaphthalene, dimethylstyrene and the like, and these can be used alone or in combination of two or more. Of these, the aromatic vinyl compound preferably used is styrene.

Examples of the maleimide-based compound include maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, No-chlorophenylmaleimide, N-cyclohexylmaleimide and the like, preferably N-phenylmaleimide, No-o. -Chlorophenylmaleimide,
N-cyclohexylmaleimide and the like, and not only one kind thereof but also two or more kinds thereof can be used.

Examples of vinylcyan compounds are acrylonitrile, methacrylonitrile, etc., of which acrylonitrile is preferred.

Examples of other copolymerizable vinyl compounds include alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, and propyl acrylate; alkyl esters of methacrylic acid, such as methyl methacrylate, ethyl methacrylate, and propyl methacrylate; maleic anhydride, Examples thereof include unsaturated acid anhydrides such as itaconic acid and citraconic anhydride, and not only one kind but also two or more kinds can be used.

Specific examples of the rubber-reinforced thermoplastic resin as described above include acrylonitrile-butadiene-styrene resin (AB
S resin), acrylonitrile-ethylene-propylene-
Styrene resin (AES resin), methyl methacrylate-butadiene-styrene resin (MBS resin), acrylonitrile-butadiene-methyl methacrylate-styrene resin (ABMS resin), acrylonitrile-n-butyl acrylate-styrene resin (AAS resin), rubber-modified polystyrene (High impact styrene) and the like, and not only one kind thereof but also two or more kinds thereof can be used.

When a rubbery polymer and / or a rubber-reinforced thermoplastic resin is contained, the content thereof is preferably in the range of 2 to 98% by weight of the entire thermoplastic resin composition finally obtained, and Preferably 5-95% by weight,
Particularly preferably, it is in the range of 10 to 90% by weight.

If the content of the rubbery polymer and / or the rubber-reinforced thermoplastic resin is less than 2% by weight, the impact resistance cannot be sufficiently improved, while if it exceeds 98% by weight, the excellent thermoplastic resin composition will be obtained. Heat resistance is impaired.

The thermoplastic resin composition of the present invention comprises the component (a) obtained by a conventional method using a single-screw extruder or a twin-screw extruder, a Banbury mixer, a kneader, a mixing roll, or the like.
It can be obtained by mixing the component (b) and optional components. As an example, a method of mixing and kneading each component with a mixer and then melt-kneading at 220 to 350 ° C. with an extruder to obtain a granulated product, as a simpler method, melt-kneading both components directly in a molding machine to form a molded product And the like.

Further, the thermoplastic resin composition of the present invention includes an antioxidant such as 2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, , 2-Methylene-bis- (4-ethyl-
6-t-butylphenol), tris (di-nonylphenyl phosphite); UV absorbers such as pt-butylphenyl salicylate, 2,2'-dihydroxy-4
-Methoxy-benzophenone, 2- (2'-dihydroxy-4'-m-octoxyphenyl) benzotriazole; lubricants such as paraffin wax, stearic acid,
Hydrogenated oil, stearoamide, methylene bis-stearamide, m-butyl stearate, ketone wax, octyl alcohol, hydroxystearic acid triglyceride, silicone oil; flame retardant such as antimony oxide, aluminum hydroxide, zinc borate, chlorinated paraffin, tetra Bromobutane, hexabromobenzene, tetrabromobisphenol A; antistatic agents such as stearoamidopropyldimethyl-β-hydroxyethyl, ammonium trate; coloring agents such as titanium oxide, carbon black; fillers such as calcium oxide, clay,
Silica, glass fibers, glass spheres, carbon fibers; pigments and the like can be added as needed.

The various molded articles obtained here can be used for automobile parts, electric and electronic parts, mechanical parts such as OA equipment, etc. by utilizing their excellent properties.

〔Example〕

Hereinafter, examples of the present invention will be described, but the present invention is not limited thereto. In the following, “parts” indicates parts by weight.

 In addition, the measurement of each characteristic was performed according to the following conditions.

Heat resistance: Heat distortion temperature (according to ASTM D 648. Thickness 1/4 ", 2
64p.si) Lightfastness: (Color difference meter “QUV” (manufactured by Suga Test Instruments Co., Ltd.), 83 ° C, 1
ΔE after 00 hours) Flowability: According to melt flow index JIS K7210.
(Measurement temperature: 280 ° C., load: 10 kg) Examples 1 to 15 The components (a) and (b) obtained as described below were blended according to the formulation shown in Table 1, and the mixture was heated at 280 ° C. using a Brabender. The mixture was kneaded for 5 minutes to obtain each thermoplastic resin composition. Each of the obtained thermoplastic resin compositions was molded at a temperature of 280 ° C. using an injection molding machine to prepare test pieces for each of the thermoplastic resin compositions, and for each of them, heat resistance, light resistance and molding. The fluidity as an index of processability was measured. The results are as shown in Table 1.

Comparative Examples 1 to 3 Example 1 was repeated except that the mixing ratio of the polymer a-1 and styrene was changed in accordance with the formulation shown in Table 1 in Example 1.
A test piece was prepared in the same manner as described above, and the physical properties were measured. The results are shown in Table 1.

Comparative Examples 4 to 8 Test pieces were prepared using the component (b) (thermoplastic resin) shown in Table 1 alone, and the physical properties were measured. The results are shown in Table 1.

(A) used in the above Examples and Comparative Examples
The component and the component (b) are as follows.

(A) Component Polymer a-1 In a reaction vessel purged with nitrogen gas, the following structural formula (1)
In shown the particular monomer 8-methyl-8-carboxymethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 50
0 g, 2000 ml of 1,2-dichloroethane, 3.8 g of 1-hexene as a molecular weight regulator, 91.6 ml of a chlorobenzene solution having a concentration of 0.05 M / tungsten hexachloride as a catalyst, and a concentration of 0.1 M / , 2-dichloroethane solution
68.7 ml, triisobutylaluminum concentration 0.5 M /
Was added to 37 ml of a toluene solution, and reacted at 60 ° C. for 10 hours to obtain 450 g of a ring-opened polymer having an intrinsic viscosity (η _inh ) of 0.56 dl / g (in chloroform, 30 ° C., concentration of 0.5 g / dl). .

This ring-opened polymer was dissolved in 9000 ml of tetrahydrofuran, 45 g of a palladium-alumina catalyst having a palladium concentration of 5% by weight was added, hydrogen gas was charged to a pressure of 100 kg / cm ^2, and a hydrogenation reaction was performed at 150 ° C. for 5 hours. I let it.

After the hydrogenation reaction, the catalyst was filtered off, and the filtrate was poured into a large excess of methanol acidic with hydrochloric acid to produce a hydrogenated polymer a-1.

The hydrogenation rate of this polymer a-1 was substantially 100%.

Structural formula (1) Polymer a-2 8-mer represented by the following structural formula (2) as a specific monomer
Carboxymethyl tetracyclo [4.4.0.1 ^2,5 .7 ^7.10] -
A ring-opened polymer having an intrinsic viscosity (η _inh ) of 0.78 dl / g (in chloroform at 30 ° C. and a concentration of 0.5 g / dl) was prepared in the same manner as in the production of the polymer a-1, except that 500 g of 3-dodecene was used. A hydrogenated polymer obtained by subjecting this to a hydrogenation reaction in the same manner as for polymer a-1.

The hydrogenation rate of this polymer a-2 was substantially 100%.

Structural formula (2) (B) Component b-1: Polystyrene "TOPOLEX 600" (manufactured by Mitsui Toatsu Co., Ltd.) b-2: Styrene-methyl methacrylate copolymer "Estyrene MS-600" (manufactured by Nippon Steel Chemical Co., Ltd.) b-3: Polystyrene Vinyl chloride “Ryuron S600” (manufactured by Tokuyama Soda Co., Ltd.) (adding an organic tin stabilizer) b-4: Acrylonitrile-styrene copolymer “JSR AS230” (manufactured by Nippon Synthetic Rubber Co., Ltd.) (b) -5: Poly Butylene terephthalate (PBT) “Toray P
BT1401 "(Toray) b-6: Polyamide (nylon 6)" T-802 "(Toyobo) b-7: High impact polystyrene The thermoplastic resin compositions of Examples 1 to 15 exhibit excellent heat resistance and light resistance and show high fluidity.

On the other hand, the thermoplastic resin of Comparative Example 1 does not contain the component (b), and the thermoplastic resin composition of Comparative Example 2 has an excessively small proportion of the component (b). The properties are remarkably low.

Since the proportion of the component (b) is excessive in the thermoplastic resin composition of Comparative Example 3, heat resistance and light resistance are not exhibited.

In Comparative Examples 4 to 8, since the component (a) was not contained, heat resistance and / or light resistance were significantly poor.

〔The invention's effect〕

According to the present invention, a specific hydrogenated polymer obtained by further hydrogenating a ring-opened polymer of a monomer comprising a tetracyclododecene derivative having a specific carboxylic acid ester group as a polar substituent, Since the thermoplastic resin is contained in a specific ratio, excellent heat resistance and light resistance are surely expressed, and a thermoplastic resin composition having improved fluidity can be obtained, and therefore, excellent heat resistance can be obtained. A thermoplastic resin composition having physical properties and good moldability can be provided.

The thermoplastic resin composition of the present invention can be suitably used in a field utilizing excellent heat resistance and light resistance, and can be used as it is as a molding material. Parts, electricity,
They are useful as electronic components or mechanical components such as OA equipment.

Continuation of the front page (56) References JP-A-60-49051 (JP, A) JP-A-1-132626 (JP, A) JP-A-51-112866 (JP, A) JP-A-57-209949 (JP) JP-A-53-91961 (JP, A) JP-A-50-59445 (JP, A) JP-A-59-22956 (JP, A) JP-A-2-276816 (JP, A) 60-26024 (JP, A) JP-A-60-168708 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 65/00-65/04

Claims (1)

(57) [Claims] 1. A thermoplastic resin composition comprising 10 to 95% by weight of the following component (a) and 90 to 5% by weight of the following component (b). Component (a): Ring-opening polymerization of a monomer comprising at least one tetracyclododecene derivative represented by the following general formula (I) or this monomer and a copolymerizable monomer copolymerizable therewith. A hydrogenated polymer obtained by further hydrogenating a ring-opened polymer obtained by the above. General formula (I) Wherein A and B are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X is a hydrogen atom, a halogen atom or a monovalent organic group, and R is a hydrocarbon group having 1 to 20 carbon atoms. Show. ]. Component (b): (a) selected from styrene resins, vinyl chloride resins, acrylic resins, polyphenylene ether resins, polyarylene sulfide resins, polyester resins, polyamide resins, polyether sulfone resins, polysulfone resins, and polyimide resins. ) Thermoplastic resins other than the components.