JP2002275340A - Thermoplastic resin composition and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition and its molded product excellent in thermostability, strength, workability and a laser marking property by a laser, and useful for various uses. SOLUTION: A thermoplastic resin composition comprises containing (A) a rubber-reinforced thermoplastic resin, (B) an acrylic resin and (C) a thermoplastic norbornene resin, etc.

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 containing a rubber-reinforced thermoplastic resin and a thermoplastic norbornene resin. More specifically, the present invention relates to a thermoplastic resin composition capable of obtaining a printed portion having good visibility by irradiating a laser beam, that is, having excellent laser marking properties. The present invention also provides a molded article containing the above thermoplastic resin composition.

[0002]

2. Description of the Related Art Rubber-reinforced thermoplastic resins represented by ABS resins have excellent strength and workability, and are molded and used for various purposes. For the molded body, designs such as letters, symbols, patterns and pictures are printed on the surface by stamping,
It is applied by silk printing and is used for various purposes. However, these methods have problems such as poor printing due to scattering of ink, printing on uneven portions, and difficulty in fine characters. In addition, in consideration of recycling of moulds and silk printed products, it is necessary to peel off the printed portion and recycle. Recently, a laser printing method has been used in response to market requirements for recycling and environmental measures.

However, when a rubber-reinforced thermoplastic resin such as an ABS resin is used for applications requiring heat resistance and requiring laser marking, the degree of color development and sharpness of characters and symbols printed by a laser beam are problematic. May occur. Furthermore, in recent years, use in more severe environments has been demanded in many cases, and the appearance of a resin material not only capable of laser marking but also more durable such as heat resistance has been desired.

On the other hand, addition (co) polymers and ring-opening (co) polymers of norbornene derivatives are known as thermoplastic norbornene resins. These thermoplastic norbornene-based resins have good optical properties, low hygroscopicity, and excellent heat resistance, and are therefore expected to be applied in various fields. However, these thermoplastic norbornene-based resins have problems of low impact resistance and poor toughness. Therefore, blending of a rubbery polymer for the purpose of improving these problems has been proposed in, for example,
Although it is disclosed in Japanese Patent Application Laid-Open No. 7-3701, even if such a means is used, a sufficient effect may not always be obtained, and further, for example, heat resistance is reduced, and other properties are adversely affected. In some cases.

[0005]

SUMMARY OF THE INVENTION As a result of intensive studies on the above-mentioned problems, the present invention has shown that the heat resistance and the heat resistance of the rubber-reinforced thermoplastic resin and the thermoplastic norbornene-based resin can be improved by further blending an acrylic resin. It has been found that a thermoplastic resin composition having excellent strength, workability, and excellent laser marking properties can be obtained, and the present invention has been completed.

[0006]

The present invention provides a thermoplastic resin composition containing (A) a rubber-reinforced thermoplastic resin, (B) an acrylic resin, and (C) a thermoplastic norbornene resin. Things. Further, these composition ratios are (A) 1 to 95 parts by weight of a rubber-reinforced thermoplastic resin,
(B) 1 to 90 parts by weight of an acrylic resin and (C) 1 to 95 parts by weight of a thermoplastic norbornene resin, and more preferably (A) 10 to 80 parts of a rubber-reinforced thermoplastic resin.
Parts by weight, (B) 2 to 50 parts by weight of an acrylic resin, and (C) 10 to 80 parts by weight of a thermoplastic norbornene-based resin (however, (A) + (B) + (C) = 100 parts by weight). Further, the present invention provides (A) a rubber-reinforced thermoplastic resin,
The present invention provides a thermoplastic resin composition containing (B) an acrylic resin, (C) a thermoplastic norbornene resin, and (D) a styrene resin other than the component (A). These composition ratios are as follows: (A) rubber-reinforced thermoplastic resin 1
To 95 parts by weight, (B) 1 to 90 parts by weight of an acrylic resin,
(C) 1 to 95 parts by weight of a thermoplastic norbornene resin and (D) 1 to 95 styrene resins other than the component (A).
Parts by weight [However, (A) + (B) + (C) + (D) = 1
00 parts by weight]. Further, the present invention provides a molded article obtained by molding any one of the thermoplastic resin compositions described above, and a molded article marked with a laser.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Component (A) The component (A) is a rubber-reinforced thermoplastic resin. The component (A) is, for example, in the presence of a rubbery polymer,
Monomers or monomer mixtures copolymerizable therewith, for example, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylates, maleic anhydride, maleimide compounds and other vinyl monomers copolymerizable therewith. It is a copolymer obtained by copolymerizing a monomer or the like. Here, examples of the rubbery polymer for obtaining the rubber-reinforced thermoplastic resin (A) include ethylene and α such as ethylene-propylene random and block copolymers and ethylene-butene random and block copolymers. A copolymer of ethylene and an unsaturated carboxylic acid ester such as ethylene-methacrylate and ethylene-butyl acrylate; a copolymer of ethylene and a fatty acid vinyl such as ethylene-vinyl acetate; ethylene-propylene -Ethylene-propylene such as ethylidene norbornene copolymer, ethylene-propylene-hexadiene copolymer;
Non-conjugated diene terpolymer; polybutadiene, isoprene, random and block copolymers of styrene-butadiene, and hydrogenated products of these random and block copolymers; acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, etc. Diene rubber; butylene-isoprene copolymer, silicone rubber, and the like. These 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-non-conjugated 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, Bromostyrene, pt-butylstyrene, ethylstyrene, vinylnaphthalene, dimethylstyrene, and the like, and not only one of these but also two or more thereof can be used. 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. −
Chlorphenylmaleimide, N-cyclohexylmaleimide and the like can be used alone or in combination of two or more.

Examples of vinyl cyanide compounds are acrylonitrile, methacrylonitrile, etc., of which acrylonitrile is preferred. Examples of other copolymerizable vinyl compounds include methyl acrylate,
Alkyl esters of acrylic acid such as ethyl acrylate and propyl acrylate; alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate and propyl methacrylate; and unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride These can be used not only in one kind but also in two or more kinds.

Specific examples of the rubber-reinforced thermoplastic resin (A) described above include acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-ethylene-propylene-styrene resin (AES resin), and methyl methacrylate-butadiene resin. 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 polystyrene), and the like. These may be used alone or in combination of two or more. Among them, ABS resin is particularly preferable.

(B) Acrylic resin (B) Examples of the acrylic resin include a polymer of an acrylic monomer or a copolymer of another monomer copolymerizable with the acrylic monomer. Can be Acrylic monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, etc., alkyl esters of acrylic acid having an alkyl group having 1 to 8 carbon atoms; methyl methacrylate, ethyl methacrylate, Examples thereof include alkyl esters of methacrylic acid having an alkyl group having 1 to 8 carbon atoms, such as propyl methacrylate, butyl methacrylate, hexyl methacrylate, and octyl methacrylate. The acrylic resin can be obtained by (co) polymerizing at least one of these resins. Among these monomers, methyl methacrylate and butyl acrylate are preferred.

The monomer copolymerizable with the acrylic monomer includes an aromatic vinyl compound, a maleimide compound and a vinyl cyanide compound. As specific examples of these monomers, those mentioned in the above description of the component (A) can be used. Of these, styrene, p-styrene, α-methylstyrene, N-phenylmaleimide, and N-cyclohexylmaleimide are preferred.

When the acrylic resin is a copolymer of an acrylic monomer and a copolymerizable monomer, the content of the acrylic monomer is preferably 3 to 97% by weight, more preferably. Is 5 to 95% by weight, particularly preferably 10 to 9% by weight.
0% by weight. Preferred acrylic resins include methyl methacrylate polymer and methacrylic acid-styrene copolymer.

Component (C) As the thermoplastic norbornene resin (C) used in the present invention, the following polymers can be exemplified. Addition polymer or ring-opening polymer of a monomer represented by the following general formula (1) (hereinafter, referred to as “specific monomer”). Addition copolymerization of specific monomer and copolymerizable monomer. Merged or ring-opened copolymer Hydrogenated polymer of the ring-opened (co) polymer After cyclization of the ring-opened (co) polymer by Friedel-Crafts reaction, hydrogenated (co) polymer Specific monomer Copolymers of isomers and compounds containing unsaturated double bonds

[0015]

Embedded image

[In the formula, R ^{1 to} R ⁴ each independently represent a substituted or unsubstituted C ¹ -C 1 which may have a linking group containing a hydrogen atom, a halogen atom, oxygen, nitrogen, sulfur or silicon. Represents a hydrocarbon group of 30 to 30 or a polar group,
Each may be the same or different. Alternatively, R ¹ and R ² , R ³ and R ⁴ or R ² and R ³ may be bonded to each other to form a carbocyclic or heterocyclic ring,
Further, the formed carbon ring or hetero ring may be an aromatic ring or a non-aromatic ring, or may form a monocyclic or polycyclic structure. m is 0 or a positive integer, and p is 0 or 1. However, when m is 0, p is also 0. ]

The norbornene-based resin (component (C)) obtained from the above-mentioned specific monomer is compatible or dispersible with the components (A) and (B), heat resistance, strength, sharp laser marking property and the like. In view of the above, the molecular structure preferably contains one or more polar groups.

Examples of the <specific monomer> The preferred specific monomers, the general formula (1), a hydrocarbon group of R ¹ and R ³ is hydrogen atom or a C1-10, R ² and R ⁴ is a hydrogen atom or a monovalent organic group, at least one of R ² and R ⁴ represents a polar group other than a hydrogen atom and a hydrocarbon group, m is the m integers (more preferably from 0 to 3 0
To 2, particularly preferably m is 1) and p is 0. Further, as the polar group, for example, a hydroxyl group, a carboxyl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group or an allyloxycarbonyl group having 1 to 15 carbon atoms, a cyano group, an amino group,
Examples include an amide group, an imide ring-containing group, a silyl group, and a silyl group partially or wholly substituted with a halogen atom, an alkoxy group, or an acyloxy group.

Of these, in particular, the formula-(CH ₂ ) _n CO
Specific monomer having a derivative group of alkoxycarbonyl group or allyloxycarbonyl group having 1 to 15 carbon atoms represented by OR ⁵ are those having a thermoplastic resin composition obtained high glass transition temperature and low moisture absorption Is preferable in that In the above formula relating to the derivative group of the alkoxycarbonyl group or the allyloxycarbonyl group, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group. In addition, n is generally 0 to 5, but a smaller value of n is preferable because the glass transition temperature of the obtained thermoplastic resin composition is higher. Further, the specific monomer in which n is 0 is preferable. It is preferable in that the synthesis is easy.

Specific examples of the specific monomer represented by the above general formula (1) include the following compounds. Bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 ^2,6 ] -8-decene, 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 [7.4.0.1 ^2,5 . 1
^9,12 . 0 ^8,13 ] -3-pentadecene, tricyclo [4.
4.0.1 ^2,5 ] -3-undecene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-
Methyl-5-methoxycarbonylbicyclo [2.2.
1] Hept-2-ene, 5-cyanobicyclo [2.2.
1] hept-2-ene, 8-methyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methoxycarbonyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene, 8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene, 8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] -3-dodecene, 8-
n-butoxycarbonyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7
, 10} ] -3-dodecene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^{17 , 10} ] −
3-dodecene, 8-methyl -8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3
- dodecene, 8-methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-
Dodecene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, pentacyclo [8.4.0.1 ^2,5 . 1 ^9,12. 0
^8,13] -3-hexadecene, heptacyclo [8.7.
0.1 ^3,6 . 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16 ] -4
-Eicosene, heptacyclo [8.8.0.1 ^4,7 . 1
^11,18 . 1 ^13,16 . 0 ^3,8. 0 ^12,17 ] -5- ^heneicosene , 5-ethylidenebicyclo [2.2.1] hept-2
-Ene, 8-ethylidenetetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 5-phenylbicyclo [2.2.1] hept-2-ene, 8-phenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 5-fluorobicyclo [2.2.1] hept-2-
Ene, 5-fluoromethylbicyclo [2.2.1] hept-2-ene, 5-trifluoromethylbicyclo [2.
2.1] Hept-2-ene, 5-pentafluoroethylbicyclo [2.2.1] hept-2-ene, 5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2
-Ene, 5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-
Ene, 5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5,5,6-trifluorobicyclo [2.2.1] hept-2-ene, 5,
5,6-tris (fluoromethyl) bicyclo [2.2.
1] Hept-2-ene, 5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene, 5,5
6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-difluoro-5,
6-bis (trifluoromethyl) bicyclo [2.2.
1] Hept-2-ene, 5,5,6-trifluoro-5
-Trifluoromethylbicyclo [2.2.1] hept-
2-ene, 5-fluoro-5-pentafluoroethyl-
6,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-difluoro-5-
Heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5-
Chloro-5,6,6-trifluorobicyclo [2.2.
1] Hept-2-ene, 5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5,6-trifluoro-6-tri Fluoromethoxybicyclo [2.2.1] hept-2-ene, 5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene, 8
-Fluorotetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-difluoromethyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene, 8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,
8-difluorotetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene, 8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . ^{17 , 10} ] -3-dodecene, 8,
9-bis (trifluoromethyl) tetracyclo [4.
4.0.1 ^2,5 . ^{17 , 10} ] -3-dodecene, 8-methyl-8-trifluoromethyltetracyclo [4.4.0.
^12.5 . 1 ^{7, 10]} -3-dodecene, 8,8,9- trifluoro-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] −
3-dodecene, 8,8,9- tris (trifluoromethyl) tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3
- dodecene, 8,8,9,9- tetrafluoro-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene,
8,8,9,9-Tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene, 8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^{2, 5.}
1 ^7,10 ] -3-dodecene, 8,9-difluoro-8,9
-Bis (trifluoromethyl) tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,
8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10]
-3-dodecene, 8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8-heptafluoroiso-propyl-9-trifluoromethyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-chloro-
8,9,9-trifluorotetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8,9-dichloro-
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
(2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene and the like.

Further, as the silyl group-containing monomer, 5
-Trimethoxysilyl-2-norbornene, 5-dimethoxychlorosilyl-2-norbornene, 5-methoxychloromethylsilyl-2-norbornene, 5-methoxyhydridomethylsilyl-2-norbornene, 5-dimethoxyhydridosilyl-2-norbornene , 5-methoxydimethylsilyl-2-norbornene, 5-triethoxysilyl-2-norbornene, 5-diethoxychlorosilyl-2-norbornene, 5-ethoxychloromethylsilyl-2-norbornene, 5-diethoxyhydridosilyl-
2-norbornene, 5-ethoxydimethylsilyl-2-
Norbornene, 5-ethoxydiethylsilyl-2-norbornene, 5-propoxydimethylsilyl-2-norbornene, 5-triphenoxysilyl-2-norbornene, 5-diphenoxymethylsilyl-2-norbornene, 5-trimethoxysilylmethyl- 2-norbornene, 5- (2-trimethoxysilyl) ethyl-2-norbornene, 5- (2-dimethoxychlorosilyl) ethyl-2-norbornene, 5- (1-trimethoxysilyl)
Ethyl-2-norbornene, 5- (2-trimethoxysilyl) propyl-2-norbornene, 5- (1-trimethoxysilyl) propyl-2-norbornene, 5-triethoxysilylethyl-2-norbornene, 5-dimethoxy Methylsilylmethyl-2-norbornene, 5-trimethoxypropylsilyl-2-norbornene, trimethoxysilylpropyl 5-norbornene-2-carboxylate, triethoxysilylpropyl 5-norbornene-2-carboxylate, 5-norbornene-2 -Dimethoxymethylsilylpropyl carboxylate, trimethoxysilylpropyl 2-methyl-5-norbornene-2-carboxylate,
2-methoxy-5-norbornene-2-carboxylate dimethoxymethylpropyl, 2-methyl-5-norbornene-
And triethoxysilylpropyl 2-carboxylate.

Among these specific monomers, 8-methyl-
8-methoxycarbonyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene, pentacyclo [7.4.0.1
^2, 5. ^19,12 . 0 ^8,13 ] -3-pentadecene is preferred in that a polymer obtained by polymerizing the same has a high glass transition temperature and a low hygroscopicity, and in particular, 8-methyl-8-methoxycarbonyltetracyclo. [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene is preferred. The above-mentioned specific monomer does not necessarily have to be used alone,
The copolymerization reaction can also be performed using more than one species.

<Copolymerizable Monomer> In the polymerization step for obtaining the component (C), the above-mentioned specific monomer may be polymerized alone. And a monomer. Specific examples of the copolymerizable monomer used in this case, for example, ethylene, propylene,
Examples thereof include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. The carbon number of the cycloolefin is preferably from 4 to 20, more preferably from 5 to 12. Furthermore, in the presence of unsaturated hydrocarbon-based polymers containing a carbon-carbon double bond in the main chain such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, and polynorbornene. The specific monomer may be subjected to ring-opening polymerization. The hydrogenated product of the ring-opening polymer obtained in this case is useful as a raw material for a resin having high impact resistance.

<Ring-Opening Polymerization Catalyst> In the present invention, the ring-opening polymerization reaction is carried out in the presence of a metathesis catalyst. This metathesis catalyst comprises (a) at least one selected from compounds of W, Mo, and Re; (b) a group IA element (eg, Li, Na, K, etc.) of the periodic table of deming; and a group IIA element (eg, Mg, Ca, etc.), Group IIB elements (eg, Zn,
Cd, Hg, etc.), Group IIIB elements (eg, B, Al, etc.), Group IVA elements (eg, Ti, Zr, etc.) or IV
A catalyst which is a compound of a group B element (for example, Si, Sn, Pb, etc.) and which is a combination with at least one selected from those having at least one element-carbon bond or element-hydrogen bond. . In this case, in order to enhance the activity of the catalyst, an additive described below may be added.

<Addition polymerization catalyst> As the addition polymerization catalyst,
Usually, a cation complex such as Ni, Pd, or Co of Group 8 of the periodic table or a catalyst that forms a cation complex is used.

<Catalyst Used for Obtaining Saturated Copolymer>
As the catalyst used for the copolymerization reaction between the specific monomer and the unsaturated double bond-containing compound, a catalyst comprising a vanadium compound and an organic aluminum compound is used. As the vanadium compound, a general formula VO (OR) aXb or V (OR) cXd (where R is a hydrocarbon group, 0 ≦ a ≦
3, 0 ≦ b ≦ 3, 2 ≦ (a + b) ≦ 3, 0 ≦ c ≦ 4, 0
A vanadium compound represented by ≦ d ≦ 4, 3 ≦ (c + d) ≦ 4) or an electron donor adduct thereof is used. As electron donors, alcohols, phenols,
Oxygen-containing electron donors such as ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, and alkoxysilanes; nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates Is mentioned. As the organoaluminum compound catalyst component, at least one selected from those having at least one aluminum-carbon bond or aluminum-hydrogen bond is used. The ratio of the catalyst component is the ratio of aluminum to vanadium (Al / V)
2 or more, preferably 2 to 50, particularly preferably 3 to 2
It is in the range of 0.

<Molecular weight regulator> The molecular weight of the polymer can be controlled by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight regulator can be controlled by coexisting in the reaction system. Adjustment is preferred.
Here, suitable molecular weight regulators include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Styrene can be mentioned, among which 1-butene and 1-hexene are particularly preferred. These molecular weight regulators can be used alone or in combination of two or more. The amount of the molecular weight modifier used is 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per 1 mol of the specific monomer subjected to the ring-opening polymerization reaction.

<Solvent for Polymerization Reaction> Examples of the solvent (solvent for dissolving the specific monomer, the metathesis catalyst and the molecular weight modifier) used in the polymerization reaction include alkanes such as pentane, hexane, heptane, octane, nonane and decane. Cyclohexanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; benzene, toluene, xylene, ethylbenzene,
Aromatic hydrocarbons such as cumene; halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene; halogenated aromatic compounds; ethyl acetate, n-butyl acetate, is acetate
saturated carboxylic esters such as o-butyl and methyl propionate; dibutyl ether, tetrahydrofuran,
Ethers such as dimethoxyethane can be exemplified, and these can be used alone or as a mixture. Of these, aromatic hydrocarbons are preferred. As the amount of the solvent used, “solvent: specific monomer (weight ratio)”
Usually, the amount is 1: 1 to 10: 1, preferably the amount is 1: 1 to 5: 1. The molecular weight of the cyclic olefin polymer used in the present invention is preferably in the range of 0.2 to 5 in intrinsic viscosity [η].

<Hydrogenation catalyst> The (co) polymer obtained as described above can be used as it is as the component (C). However, when an olefinically unsaturated bond is present in the molecule, it may be used. Is hydrogenated (co)
It is preferable to use a polymer as the component (C). The hydrogenation reaction is carried out in a usual manner, that is, a hydrogenation catalyst is added to a (co) polymer solution, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm is added to the solution at 0 to 200 atm.
C., preferably at 20-180.degree. As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used. As the hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are known. Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst substance such as palladium, platinum, nickel, rhodium and ruthenium is supported on a carrier such as carbon, silica, alumina and titania. Examples of the homogeneous catalyst include nickel / naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octanoate / n-butyllithium, titanocene dichloride /
Diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like can be mentioned. it can. The form of the catalyst may be powder or granular. These hydrogenation catalysts are preferably used in a ratio of “(co) polymer: hydrogenation catalyst (weight ratio)” of 1: 1 × 10 ⁻⁶ to 1: 2. As described above, the hydrogenated (co) polymer obtained by hydrogenation has excellent thermal stability, and its properties are not deteriorated by heating during molding or use as a product. Absent. Here, the hydrogenation rate is usually 50% or more, preferably 70%
Or more, more preferably 90% or more, particularly preferably 9% or more.
5% or more, especially 98% or more.

The intrinsic viscosity [η] of the component (C) used in the present invention measured in chloroform at 30 ° C. is 0.2 to 0.2.
It is preferably 5 dl / g. More preferably,
When the content exceeds 5 dl / g, the solution viscosity becomes too high, the processability decreases, and 0.2 dl / g is used.
If it is less than g, a problem may occur in the strength of the molded product.
As the molecular weight of the component (C), the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is 5,000 to 1,
00000, weight average molecular weight (Mw) of 10,000
The number average molecular weight (Mn) is preferably from 8,000 to 700,000, and the weight average molecular weight (Mw) is preferably from 20,000 to 1,000,000. .

(D) Styrene-based polymer (D) The styrene-based polymer is a (co) polymer of an aromatic vinyl compound or a monomer copolymerizable therewith. Examples of the aromatic vinyl compound include those described in the description of the component (A), such as styrene and α-methylstyrene. Examples of the copolymerizable monomer include those described in the description of the component (B) such as a maleimide compound, a vinyl cyanide compound, and maleic anhydride (however, an acrylic or methacrylic compound). Excluding compounds).

Of these, styrene and α-methylstyrene are preferred as the aromatic vinyl compound. Also,
Acrylonitrile is preferred as the copolymerizable monomer.

(D) The content of the aromatic vinyl compound in the styrene polymer is preferably 20 to 100% by weight, more preferably 30 to 95% by weight, and particularly preferably 35 to 95% by weight.
~ 90% by weight.

[Thermoplastic Resin Composition] Next, for each of the thermoplastic resin compositions of the present invention, the proportions and characteristics of the components will be described.

<Composition I> This composition I is the composition according to the first aspect. This composition I is a thermoplastic resin composition containing (A) a rubber-reinforced thermoplastic resin, (B) an acrylic resin, and (C) a thermoplastic norbornene resin. The composition ratio of (A) the rubber-reinforced thermoplastic resin, (B) the acrylic resin, and (C) the thermoplastic norbornene resin in the composition I is (A) 1 to 95 parts by weight,
(B) 1 to 90 parts by weight and (C) 1 to 95 parts by weight, more preferably (A) 10 to 80 parts by weight,
(B) 2 to 50 parts by weight and (C) 10 to 80 parts by weight,
Particularly preferably, (A) 30 to 50 parts by weight, and (B) 10 to 10 parts by weight.
30 parts by weight, (C) 30 to 50 parts by weight [however, (A)
+ (B) + (C) = 100 parts by weight]. When the content is within this range, the obtained thermoplastic resin composition has good heat resistance and impact resistance and excellent laser marking properties.

<Composition II> This composition II is the composition according to the fourth aspect. This composition II comprises a thermoplastic resin containing (A) a rubber-reinforced thermoplastic resin, (B) an acrylic resin, (C) a thermoplastic norbornene resin, and (D) a styrene resin other than the component (A). It is a plastic resin composition. (A) rubber reinforced thermoplastic resin in composition II, (B)
The composition ratio of the acrylic resin, (C) the thermoplastic norbornene resin and (D) the styrene resin other than the component (A) is (A) 1 to 95 parts by weight, (B) 1 to 90 parts by weight,
(C) 1 to 95 parts by weight and (D) 1 to 95 parts by weight, more preferably (A) 30 to 50 parts by weight.
Parts by weight, (B) 10 to 40 parts by weight, (C) 30 to 60 parts by weight, (D) 5 to 15 parts by weight, particularly preferably (A) 3
0 to 40 parts by weight, (B) 5 to 25 parts by weight, (C) 30 to
60 parts by weight and (D) 10 to 20 parts by weight.
(A) + (B) + (C) + (D) = 100 parts by weight]. When the content is within this range, the obtained thermoplastic resin composition has good heat resistance and impact resistance and excellent laser marking properties.

The compositions I and II were prepared by mixing the components (A) to (C) or the components (A) to (D) with various extruders, Banbury mixers, kneader rolls and the like.
It can be obtained by kneading at 0 to 350 ° C.
More simply, each component can be directly melt-kneaded in a molding machine and molded. During this melt-kneading, in order to improve the compatibility or dispersibility of each component in the composition, a specific functional group, for example, an epoxy group, a carboxyl group, a hydroxysyl group, an amino group, an acid anhydride, an oxazoline group, etc. The compound may have an unsaturated compound and, if necessary, an organic peroxide. The proportion of the unsaturated compound having the specific functional group is preferably in the range of 0.01 to 30% by weight of the whole composition.

In each of the thermoplastic resin compositions of the present invention described above, other polymers can be appropriately compounded in addition to the essential components of the composition according to the required performance. . Such polymers are, for example, polyethylene, polypropylene, polycarbonate, polyamide, thermoplastic polyamide elastomer, thermoplastic polyamide-polyester elastomer, thermoplastic polyester elastomer, polybutylene terephthalate, polyethylene terephthalate, polysulfone, polyphenylene ether, polyether sulfone polyimide , Polyphenyl sulfide, polyether ether ketone, vinylidene fluoride polymer and the like. Further, the thermoplastic resin composition of the present invention may contain a thermoplastic elastomer, a rubbery polymer, organic fine particles, inorganic fine particles, and the like.

Further, the thermoplastic resin composition of the present invention includes:
Various additives can be added as needed

Here, examples of the additives include the following. Antioxidants, for example 2,6-di-t
-Butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-tert-butyl-5,5'-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4-
(Hydroxy-5-t-butylphenyl) butane, 1,
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate, 2,2′-dioxy-
3,3′-di-t-butyl-5,5′-diethylphenylmethane, 3,9-bis [1,1-dimethyl-2- (β
-(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl], 2,4,8,1
0-tetraoxospiro [5.5] undecane, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-
t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4)
-Methylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite and the like; UV absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone , Pt-butylphenyl salicylate,
2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-4'-m-octoxyphenyl) benzotriazole and the like. These antioxidants and ultraviolet absorbers are used for the purpose of stabilizing the composition.

Other additives include, for example, lubricants for improving processability, for example, paraffin wax, stearic acid, hardened oil, stearylamide, methylenebisstearylamide, n-butylstearate, ketone wax, octyl alcohol Triglyceride, hydroxystearic acid; flame retardants such as antimony oxide, aluminum hydroxide, zinc borate, tricresyl phosphate, tris (dichloropropyl) phosphate, chlorinated paraffin, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A; Inhibitors such as stearylamidopropyldimethyl-β-hydroxyethyl, ammonium nitrate and the like can be mentioned. Further, known plasticizers, antistatic agents and the like can also be used.

The amount of these additives is usually 0.1 to 3 parts by weight, preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the thermoplastic resin composition.

Further, the thermoplastic resin composition of the present invention may contain, when used, glass fiber, carbon fiber, glass beads, asbestos, wollastonite, calcium carbonate, talc, barium sulfate, mica, potassium titanate, fluorine Fillers such as resin and molybdenum disulfide can be used alone or in combination of two or more. Among these, as glass fiber and carbon fiber, 6 to 60 μm
And a fiber length of 30 μm or more. These fillers are preferably contained in a proportion of 1 to 150 parts by weight based on 100 parts by weight of the thermoplastic resin composition.

The thermoplastic resin composition of the present invention further improves the laser marking property by blending (E) a coloring agent. (E) Colorants include organic pigments, inorganic pigments, dyes, and the like. Examples of the organic pigment include azo pigments; acetoacetarylide, pyrazolone, 2,3-oxonaphthoylarylamide, barbituric acid, 2,4,6-triamino-1,3 pyrimidine, and 3 -Cyano-4-methylpyridone-based monoazo compounds, metal salts of azo compounds, diazo-based pigments; acetoacetarylide-based, pyrazolone-based,
A 3-oxonaphthoylarylamide-based diazo compound, a metal salt of the diazo compound, and other organic pigments; copper phthalocyanine, chlorinated lead phthalocyanine, ultramarine, and the like can be used. Examples of inorganic pigments include red iron oxide, titanium yellow, titanium black, ketjen black, black iron oxide, graphite, carbon black,
Examples include titanium oxide, copper chromate, zinc sulfide, barium sulfate, and calcium carbonate. Examples of the dye include an anthraquinone-based dye and a black dye containing carbon black. (E) The compounding amount of the coloring agent is 0.001 to 5 parts by weight, preferably 0.01 to 4 parts by weight, and more preferably "0.5 to 3 parts by weight, based on 100 parts by weight of the resin composition of the present invention. Parts by weight.

The thermoplastic resin composition of the present invention can be formed into various molded articles by an injection molding method, a sheet extrusion method, a vacuum molding method, an irregular molding method, a foam molding method, a press molding method, a stampable molding method, or the like. it can. The various molded products obtained here can be used as exterior and interior members of automobiles and various electric and electronic parts, housings, optical materials, and the like by utilizing their excellent properties.

The thermoplastic resin composition of the present invention has excellent laser marking properties, and when the composition is formed into a molded product, it can be easily and beautifully drawn on a surface thereof with a laser. The condition of the laser mark is Nd: Y
Using AG laser, frequency 2-7Khz, current value 12
１８18 Amp and the scanning speed is 400-800 mm / sec.

The thermoplastic resin composition of the present invention can be effectively used for printing on electric parts, electronic parts, automobile parts, cases of various recording media, and the like.

[0048]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the following, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified. Each physical property was measured by the following method.

Izod impact strength (IMP); ASTM
According to D256, test piece thickness 1/4 inch,
The measurement was performed under the test condition of 23 ° C. with a notch. Unit = Kg
f-cm / cm Heat deformation temperature (HDT): Test piece wall thickness 1/2 inch, weight 18.6Kg in accordance with ASTM D648
/ Cm ² . Unit = ° C. Rockwell hardness (RH): Measured under R scale test conditions by stacking two 1 / 8-inch test piece thicknesses in accordance with ASTM D735. Melt flow rate (MFR): Measured under the test conditions of a temperature of 240 ° C. and a load of 5 kg in accordance with JIS K7210. Unit: g / 10 min Laser marking property; Nd: YAG (wavelength: 1064)
nm) Laser marker [Roffin Marubeni Laser Co., Ltd.
(Model: RSM30D), and the surface of a molded plate (40 mm x 80 mm x 3.2 mm) of the composition was printed by scanning with a laser beam. The laser marking property was measured by using a luminance meter (LS100, manufactured by Minolta Co., Ltd.) to measure the luminance of the printed portion and the non-printed portion, and evaluated from the ratio of the luminance (non-printed portion: printed portion) according to the following criteria. ○: More than 1: 5. Δ: 1: 3 to 1: 5. X: Less than 1: 3.

(A) Component ABS resin; copolymer of 22% acrylonitrile / 12% butadiene rubber / 66% styrene (melt flow rate = 15 g / 10 min) MABS resin; 58% methyl methacrylate / 5% acrylonitrile / butadiene rubber 18% / styrene 1
9% copolymer (melt flow rate = 26 g / 10 m
in) AES resin; copolymer of 23% acrylonitrile / 12% ethylene / propylene rubber / 65% styrene (melt flow rate = 15 g / 10 min) ASiS resin; acrylonitrile / silicone rubber /
Styrene copolymer (melt flow rate = 4 g / 10 m
in) AAS resin; acrylonitrile / acrylic rubber / styrene copolymer (melt flow rate = 5 g / 10 mi)
n)

Component (B) PMMA resin; methyl methacrylate polymer (melt flow rate = 2 g / 10 min) MS resin; methyl methacrylate 80% / styrene 2
0% copolymer (melt flow rate = 2 g / 10 mi)
n) (E) component Titanium black; manufactured by Mitsubishi Materials Corporation Other stabilizers; trade name Irganox 1010, manufactured by Ciba Specialty Chemicals Co., Ltd.

[0052] Component (C) <Synthesis Example 1> 8-methyl-8-carboxymethyl tetracyclo [4.4.0.1 ^2.5. 1 ^{7.1 0]} -3-dodecene (specific monomer) 250 parts of 1-hexene (molecular weight modifier) 18 parts were charged 750 parts of toluene to a reaction vessel purged with nitrogen, 60 while stirring the solution Heated to ° C. Next, 0.62 parts of a toluene solution of triethylaluminum (1.5 mol / l) as a polymerization catalyst and tungsten hexachloride modified with t-butanol and methanol (t-butanol: methanol: tungsten) were added to the solution in the reaction vessel. (0.35 mol: 0.3 mol: 1 mol) in toluene solution (concentration: 0.05 mol / l) was added, and the system was heated and stirred at 80 ° C. for 3 hours for ring opening. The polymerization reaction was performed to obtain a ring-opened polymer solution. The polymerization conversion in this polymerization reaction was 97%, and the intrinsic viscosity [η] of the obtained ring-opened polymer measured in chloroform at 30 ° C. was 0.65 dl / g.

4,000 parts of the ring-opened polymer solution thus obtained was charged into an autoclave, and RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃₀ .
48 parts were added, and the mixture was heated and stirred for 3 hours under a condition of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. to perform a hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated polymer solution), the pressure of hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and collect a coagulated product, which was dried to obtain a hydrogenated polymer (specific cyclic polyolefin-based resin).

The thus obtained hydrogenated polymer (hereinafter, referred to as “resin (a)”) has ¹ H-NM.
The hydrogenation rate measured using R was 99.9%. The glass transition temperature (Tg) of the resin (a) measured by the DSC method was 170 ° C. Further, the resin (a) is subjected to a GPC method (solvent:
When the number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polystyrene were measured with tetrahydrofuran), the number average molecular weight (Mn) was 39,000, the weight average molecular weight (Mw) was 116,000, and the molecular weight distribution ( (Mw / Mn) was 2.97. The saturation water absorption at 23 ° C. of the resin (a) was 0.4%. The intrinsic viscosity [η] of the resin (a) measured in chloroform at 30 ° C. was 0.67 dl / g.

<Synthesis Example 2> As monomers, 93.75 mmol of 5-n-hexyl-2-norbornene, 500 mmol of 2-norbornene, and 5-triethoxysilyl-2-
Norbornene 31.25 mmol, cyclohexane 500 g as solvent, molecular weight regulator (1-hexene) 3.1
Mmol was charged to a 1 liter reactor under nitrogen. The reaction system was brought to 10 ° C., and nickel octoate [Ni
(Octanoate) ₂ ], 0.25 mmol of trityltetrakis (pentafluorophenyl) borate [Ph ₃
0.5 mmol of CB (C ₆ F ₅ ) ₃ ] and 1.0 mmol of triethylaluminum were charged and polymerization was carried out. 2
Polymerization was carried out at 0 ° C. for 2 hours, and the polymerization was stopped with methanol. The conversion to the copolymer was 85%. 6 g of lactic acid was added to the copolymer solution to react with the catalyst component. The copolymer solution was placed in 4 liters of isopropanol to coagulate the copolymer, and unreacted monomers and catalyst residues were removed. The coagulated copolymer was dried to obtain a copolymer.

270 MHz ¹ H-NMR of the copolymer (4 ppm ethoxylyl group methylene absorption, solvent: D
Analysis, the content of the structure derived from 5-triethoxysilyl-2-norbornene was 4.8 mol%. The content of the structure derived from 5-n-hexyl-2-norbornene was found to be 1 based on a calibration curve based on a characteristic absorption of 721 cm ^{-1 in} infrared absorption spectrum analysis.
It was 4.0 mol%. The polystyrene equivalent number average molecular weight of the copolymer A was 220,000, and the weight average molecular weight was 350,000.

Examples 1 to 9 and Comparative Examples 1 and 2 The above components were blended according to the formulations shown in Tables 1 and 2 to obtain a thermoplastic resin composition. The physical properties of the obtained thermoplastic resin composition are shown in Tables 1 and 2.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

Industrial Applicability The thermoplastic resin composition of the present invention and a molded product thereof are excellent in heat resistance, strength, workability, and laser marking property with a laser, and are useful for various applications.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 51/04 C08L 65/00 65/00 B41J 3/00 Q (72) Inventor Akira Shimizu Yokkaichi, Mie Prefecture 4-6 Tomari Koyanagicho Nippon Color Ring Co., Ltd.

Claims (12)

[Claims] 1. A thermoplastic resin composition comprising (A) a rubber-reinforced thermoplastic resin, (B) an acrylic resin, and (C) a thermoplastic norbornene resin. 2. (A) 1 to 95 parts by weight of a rubber-reinforced thermoplastic resin, (B) 1 to 90 parts by weight of an acrylic resin, and (C) 1 to 95 parts by weight of a thermoplastic norbornene resin (provided that (A) + (B) + (C) = 100 parts by weight). 3. A rubber-reinforced thermoplastic resin (A)
Parts by weight, (B) 2 to 50 parts by weight of an acrylic resin and (C) 10 to 80 parts by weight of a thermoplastic norbornene-based resin (however, (A) + (B) + (C) = 100 parts by weight). The thermoplastic resin composition according to claim 1 or 2, which comprises: 4. A thermoplastic containing (A) a rubber-reinforced thermoplastic resin, (B) an acrylic resin, (C) a thermoplastic norbornene resin, and (D) a styrene resin other than the component (A). Resin composition. 5. (A) 1 to 95 parts by weight of a rubber-reinforced thermoplastic resin, (B) 1 to 90 parts by weight of an acrylic resin, (C) 1 to 95 parts by weight of a thermoplastic norbornene resin, and (D)
The thermoplastic resin according to claim 4, further comprising 1 to 95 parts by weight of the styrenic resin other than the component (A) (provided that (A) + (B) + (C) + (D) = 100 parts by weight). Resin composition. 6. The thermoplastic resin composition according to claim 1, wherein (A) the rubber-reinforced thermoplastic resin is a rubber-reinforced styrene resin. 7. The thermoplastic norbornene resin (C) obtained by polymerizing a monomer component containing at least one kind of monomer represented by the following general formula (1).
7. The thermoplastic resin composition according to any one of claims 6 to 6. Embedded image [Wherein, R ^{1 to} R ⁴ each independently represent a substituted or unsubstituted C ¹ -C 1 which may have a connecting group containing a hydrogen atom, a halogen atom, oxygen, nitrogen, sulfur or silicon.
Represents 30 hydrocarbon groups or polar groups, which may be the same or different. Alternatively, R ¹ and R ² ,
R ³ and R ⁴ or R ² and R ³ are bonded to each other,
A carbocyclic or heterocyclic ring may be formed, and the formed carbocyclic or heterocyclic ring may be an aromatic or non-aromatic ring, or may form a monocyclic or polycyclic structure. m is 0 or a positive integer, and p is 0 or 1. However, when m is 0, p is also 0. ] 8. The thermoplastic resin composition according to claim 1, wherein the thermoplastic norbornene-based resin (C) has a functional group. 9. A thermoplastic resin composition, which further comprises (E) a colorant in the composition according to any one of claims 1 to 8. 10. A thermoplastic resin composition for laser marking, comprising the thermoplastic resin composition according to claim 1. 11. A molded article obtained by molding the thermoplastic resin composition according to any one of claims 1 to 10. 12. The method according to claim 1, wherein the laser is marked.
2. The molded article according to 1.