Thermoplastic resin composition

Abstract: The invention is a thermoplastic resin composition comprising (a) a polymer comprising recurring units derived from a polycyclic (meth)acrylate represented by formula [I] wherein m is 0 or a positive integer; n is 0 or 1; R is hydrogen or methyl; R¹-R¹⁸ are each independently hydrogen, halogen or hydrocarbon; R¹⁵-R¹⁸ may be linked together to form a monocyclic or polycyclic group which may have a double bond; R¹⁵ and R¹⁶, or R¹⁷ and R¹⁸, may form an alkylidene group; p is 0 or 1, and when p is 1 R a and R b are each independently hydrogen or hydrocarbon; and (b) a soft polymer; in a weight ratio of (a):(b) of 99:1 to 40:60.

Description: The present invention relates to a thermoplastic resin composition, and more in detail to a thermoplastic resin composition comprising a polymer comprising recurring units derived from a polycyclic (meth)acrylate and an elastomer. Amorphous resins such as polyester resins, ABS resins and modified PPO resins are excellent in characteristics such as rigidity, dimension accuracy and heat resistance, and accordingly have heretofore been widely used for, for example, automobile pats, electrical appliances, office automation instruments and miscellaneous goods. However, thermoplastic resins used for products as mentioned above have recently been increasingly employed under severe conditions such as at high temperature. The severe quality is required for the thermoplastic resins used under such severe conditions depending upon the conditions of use. Few of the conventionally used amorphous resins as described above satisfy such requirements, and therefore the realization of thermoplastic resins having still higher quality has been desired. FR-A-2 332 300 describes a hot-melt adhesive comprising an addition copolymer of at least one C 1 to C 18 alkyl acrylate or alkoxyalkyl acrylate and an ethylenically unsaturated amine, carboxylic acid and/or sulphonic acid, and an addition copolymer of CH 2 = C(R)CO 2 R 1 and at least one ethylenically unsaturated amine, carboxylic acid and/or sulphonic acid. FR-A-1 568 560 describes a vinyl chloride resin composition comprising a vinyl chloride polymer containing at least 80% of vinyl chloride monomers, and a rubbery thermoplastic copolymer containing methyl methacrylate monomers and bicyclic methacrylate monomers. JP-A-63 243 108 describes an optical material comprising the polymerisation product of two alternative tricyclic acrylate monomers optionally with comonomers. The present invention has been accomplished in view of the prior art techniques as described above, and an object of the invention is to provide a thermoplastic resin composition excellent in characteristics such as heat resistance, rigidity, dimension accuracy, impact resistance and light resistance. The present invention provides a thermoplastic resin composition comprising: (a) a polymer comprising recurring units derived from a polycyclic (meth)acrylate represented by formula [I] wherein m is 0 or a positive integer; n is 0 or 1; R is hydrogen or methyl; R 1 -R 18 are each independently hydrogen, halogen or hydrocarbon; R 15 -R 18 may be linked together to form a monocyclic or polycyclic group which may have a double bond; R 15 and R 16 , or R 17 and R 18 , may form an alkylidene group; p is 0 or 1, and when p is l R a and R b are each independently hydrogen or hydrocarbon; and (b) at least one elastomer having a glass transition temperature (Tg) of not higher than 0°C, an intrinsic viscosity (η) as measured in decalin at 135°C of 0.01 to 10 dl/g, and a crystallinity index as measured by X-ray diffraction of 0 to 10%, said elastomer comprising recurring units from ethylene, an α-olefin having 3 or more carbon atoms and a cycloolefin of formula (II) wherein R 1 -R 18 , R a , R b , m, n and p are as defined for the compound of formula (I), and/or (b') an elastomer which is a graft-modified copolymer of said elastomer (b). The thermoplastic resin composition of the invention is excellent in characteristics such as rigidity, dimension accuracy, impact resistance and light resistance. Accordingly molded article excellent in characteristics such as heat resistance, rigidity, impact resistance and light resistance can be prepared from the resin composition of the invention. The thermoplastic resin composition of the invention comprises a polymer comprising recurring units derived from a specific polycyclic (meth)acrylate and an elastomer. The polymer comprising recurring units derived from a specific polycyclic (meth)acrylate may be a (co)polymer of polycylic (meth)acrylate(s), or a copolymer of a polycyclic (meth)acrylate and other copolymerizable monomers. POLYCYCLIC (METH)ACRYLATE Firstly, the polycyclic (meth)acrylate is illustrated. The polycyclic (meth)acrylate can be represented by the formula [I] In the aforementioned formula [I], m is 0 or a positive integer, and n is 0 or 1. Moreover, R is hydrogen or methyl. That is, of compounds represented by the above-mentioned formula [I], those having a hydrogen atom as R are acrylate compounds, and those having a methyl group as R are methacrylate compounds. These acrylate compounds and methacrylate compounds can both be used in the present invention. Furthermore, R 1 -R 18 are each independently an atom or a group selected from the group consisting of hydrogen, halogen and hydrocarbon groups. R a and R b are each independently hydrogen or a hydrocarbon group. The hydrocarbon groups usually have 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and are linear or branched. Concrete examples of the hydrocarbon group include aliphatic hydrocarbon groups such as methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl; alicyclic hydrocarbon groups such as cyclohexyl; and aromatic hydrocarbon groups such as phenyl, benzyl, tolyl, ethylphenyl, isopropylphenyl, α-naphthyl and anthracenyl. Examples of the halogen include fluorine, chlorine, bromine and iodine. R 1 -R 18 are not required to be the same, and may, of course, be groups or atoms different from each other. Still furthermore, R 15 -R 18 , linked together, may form a monocyclic or polycyclic group. For example, R 15 and R 17 , linked together, may form as a whole, a cyclopentyl or cyclohexyl ring, or a ring structure in which a plural number of such rings are bonded together. The monocyclic or polycyclic group may have a double bond in the ring. Moreover, R 15 and R 16 , or R 17 and R 18 may form an alkylidene group such as ethylidene and propylidene. Furthermore, p represents 0 or 1 in the formula [I]. R a and R b each independently represent a hydrogen atom or a hydrocarbon group when p is 1, and when p is 0, the corresponding two carbons are bonded together to form a 5-membered ring. Concrete examples of the polycyclic (meth)acrylate represented by the aforementioned formula [I] include the compounds described below. In the above-mentioned two formulas, R x represents an aliphatic hydrocarbon group such as methyl, ethyl, propyl, isobutyl, hexyl and stearyl, an alicyclic hydrocarbon group such as cyclohexyl, or a halogen atom such as a bromine atom and a fluorine atom. In the above-mentioned two formulas, R x represents an aliphatic hydrocarbon group such as methyl, ethyl, propyl, isobutyl, hexyl and stearyl, an alicyclic hydrocarbon group such as cyclohexyl, or a halogen atom such as a bromine atom and a fluorine atom. In the above-mentioned two formulas, R x and R y each independently represent an aliphatic hydrocarbon group such as methyl, ethyl, propyl, isobutyl, hexyl and stearyl, an alicyclic hydrocarbon group such as cyclohexyl, or a halogen atom such as a bromine atom and a fluorine atom. Examples of the polycyclic (meth)acrylate in which R 15 -R 18 together form a single ring group represented by the aforoementioned formula [I] include the compounds described below. The polycyclic (meth)acrylates as mentioned above can be prepared, for example, by reacting a polycyclic alcohol, which has been prepared by reacting a cycloolefin having a structure corresponding to the polycyclic (meth)acrylate represented by the aforementioned formula [I] with formic acid, with a (meth)acrylic acid derivative including acrylic acid or methacrylic acid, or a (meth)acrylyl halide such as an acrylyl halide or a methacrylyl halide. The cycloolefin having a structure corresponding to that of the polycyclic (meth)acrylate used in this method can be represented by the following formula [II] wherein R 1 -R 18 , R a , R b , and m, n and p are as defined in the aforementioned formula [I]. POLYCYCLIC (METH)ACRYLATE (CO)POLYMER The polymer used in the thermoplastic resin composition of the invention comprising the recurring units derived from a polycyclic (meth)acrylate may be a homopolymer of the polycyclic (meth)acrylate as mentioned above. The polymer may also be a copolymer of the polycyclic (meth)acrylates, which are different from each other, as mentioned above. The polymer may also be a copolymer of the polycyclic (meth)acrylate as mentioned above and other copolymerizable monomers. In the present invention, the term "polycyclic (meth)acrylate (co)polymer" generally refers to these (co)polymers unless otherwise noted. These other monomers to be copolymerized with the polycyclic (meth)acrylate include compounds having at least one polymerizable double bond in the molecule. Concrete examples of such a compound include acrylic acids such as (meth)acrylic acid; acrylic acid derivatives such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, cyclohexyl (meth)acrylate and benzyl (meth)acrylate; aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; acrylonitrile; maleic acid derivatives such as maleic anhydride, maleimide and phenylmaleimide; and vinyl esters such as vinyl acetate and vinyl benzoate. The polycyclic (meth)acrylate (co)polymer is a (co)polymer prepared by polymerizing polycyclic (meth)acrylate(s) and if necessary other monomers as mentioned above. When the polycyclic (meth)acrylate (co)polymer is a copolymer of a polycyclic (meth)acrylate and other monomers, the polycyclic (meth)acrylate (co)polymer comprises recurring units derived from the polycyclic (meth)acrylate in an amount of usually at least 5 mol%, preferably 10 to 99 mol% and especially 30 to 95 mol%. A resin composition excellent in heat resistance and heat stability can be obtained by using a copolymer comprising recurring units derived from a polycyclic (meth)acrylate in an amount in the range mentioned above. The polycyclic (meth)acrylate (co)polymer has an intrinsic viscosity [η], as measured in toluene at 30°C, of usually 0.002 to 20 dl/g, preferably 0.05 to 10 dl/g and especially 0.2 to 5 dl/g. The (co)polymer has a glass transition temperature, as measured by a differential scanning type calorimeter, of usually 10 to 200°C, preferably 50 to 200°C and especially 105 to 200°C. Furthermore, the polycyclic (meth)acrylate (co)polymer has a molecular weight distribution (Mw/Mn) of usually not greater than 10, preferably 1.0 to 3.0, as measured by gel permeation chromatography, a crystallinity of usually not greater than 5%, preferably not greater than 1%, as measured by X-ray diffraction, and a softening temperature of usually 20 to 220°C, preferably 70 to 220°C and especially 120 to 220°C, as measured by a thermal mechanical analyzer (TMA) (manufactured by DuPont). When the polycyclic (meth)acrylate (co)polymer is a copolymer, the copolymer has a substantially linear molecular structure in which recurring units derived from the polycyclic (meth)acrylate and recurring units derived from other selected monomers are randomly arranged. The fact that the copolymer has a substantially linear molecular structure can be proved by observing dissolution thereof in an organic solvent without leaving any insoluble component. This can be proved, for example, by the fact that the polycyclic (meth)acrylate (co)polymer completely dissolves in toluene at 30°C during the measurement of the intrinsic viscosity [η] as described above. The polycyclic (meth)acrylate (co)polymer can be prepared by various polymerization methods. For example, the polycyclic (meth)acrylate and other monomers can be copolymerized by polymerization methods such as suspension polymerization, emulsion polymerization, solution polymerization and bulk polymerization. Examples of the bulk polymerization method include a method wherein the polymerization is carried out at a temperature of usually 60 to 250°C, preferably 150 to 230°C, and a method wherein the reaction temperature is elevated, for example, from 80°C, with the progress of the polymerization reaction, and the polymerization reaction is terminated, for example, at a temperature of 180 to 230°C. In these methods, radical initiators can be used. Examples of the radical initiators include organic peroxides such as di-tert-butylperoxide, dicumyl peroxide, methyl ethyl ketone peroxide, tert-butyl perphthalate, tert-butyl perbenzoate, di-tert-butyl peracetate and tert-butyl perisobutyrate, and azo compounds such as 1,1'-azobiscyclohexanecarbonitrile and 2-cyano-2-propylazoformamide. These radical initiators are used in an amount of usually not greater than 1 mol% based on the monomers. During the (co)polymerization, there may also be used chain transfer agents such as tert-butylmercaptan, n-butylmercaptan, n-octylmercaptan and n-dodecylmercaptan in order to control the molecular weight of resultant polycyclic (meth)acrylate (co)polymer. The chain transfer agents are used in an amount of usually not greater than 1 mol% based on the monomers. Furthermore, the aforementioned (co)polymer may also be prepared by photopolymerization using energy ray irradiation with or without the use of the radical initiator as mentioned above. The procedures of polymerization as described above are disclosed in detail, for example, in Japanese Patent L-O-P No. 243108/1988, and can be utilized in the present invention. ELASTOMER The thermoplastic resin composition of the invention comprises the polycyclic (meth)acrylate (co)polymer mentioned above and an elastomer. The elastomers (b') may be graft-modified polymers with α,β-unsaturated carboxylic acid or derivatives thereof. Concrete examples of the elastomer used in the invention are illustrated below. ELASTOMER (b) COMPRISING RECURRING UNITS DERIVED FROM A CYCLOOLEFIN The elastomer (b) is a copolymer formed from ethylene, a cycloolefin represented by the formula [II], and α-olefin having 3 or more carbon atoms. A graft-modified elastomer (b') comprising recurring units derived from the cycloolefin may also be used as the elastomer. wherein R 1 -R 18 , R a , R b , and m, n and p are as defined in the above-mentioned formula [I]. Examples of the cycloolefin include bicyclo[2.2.1]hept-2-ene derivatives, tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene derivatives, hexacyclo[6.6.1.1 3,6 .1 10,13 .0 2,7 .0 9,14 ]-4-heptadecene derivatives, octacyclo[8.8.0.1 2,9 .1 4,7 .1 11,18 .1 13,16 .0 3,8 .0 12,17 ]-5-docosene derivatives, pentacyclo[6.6.1.1 3,6 .0 2,7 .0 9,14 ]-4-hexadecene derivatives, heptacyclo-5-eicosene derivatives, heptacyclo-5-heneicosene derivatives, tricyclo[4.3.0.1 2,5 ]-3-decene derivatives, tricyclo[4.3.0.1 2,5 ]-3-undecene derivatives, pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 ]-4-pentadecene derivatives, pentacyclopentadecadiene derivatives, pentacyclo[4.7.0.1 2,5 .0 8,13 .1 9,12 ]-3-pentadecene derivatives, pentacyclo[7.8.0.1 3,6 .0 2,7 .1 10,17 .0 11,16 .1 12,15 ]-4-eicosene derivatives, nonacyclo[9.10.1.1.4.7.0 3,8 .0 2,10 .0 12,21 .1 13,20 .0 14,19 .1 15,18 ]-5-pentacosene derivatives, phenylbicyclo[2.2.1]-2-ene derivatives, benzylbicyclo[2.2.1]-2-ene derivatives, 1,4-methano-1,1a,4,4a-tetrahydrofluorene derivatives, 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene derivatives, cyclopentadiene-acenaphthylene adducts, pentacyclo[7.4.0.1 2,5 .0 8,13 .1 9,12 ]pentadecene-3-derivatives, heptacyclo[8.7.0.0 2,7 .1 3,6 .1 10,17 .0 11,16 .1 12,15 ]eicosene-4 derivatives and nonacyclo[10.9.1.0 2,10 .0 3,8 .1 4,7 .0 12,21 .1 13,20 .0 14,19 .1 15,18 ]pentacosene-5 derivatives. Concrete examples of the compounds mentioned above are described below. Bicyclo [2,2.1]hept-2-ene derivatives such as those mentioned below. Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene derivatives such as those described below. Hexacyclo[6.6.1.1 3,6 .1 10,13 .0 2,7 .0 9,14 ]-4-heptadecene derivates such as those mentioned below. Octacyclo[8.8.0.1 2,9 .1 4,7 .1 11,18 .1 13,16 .0 3,8 .0 12,17 ]-5-docosene derivatives such as those mentioned below. Pentacyclo[6.6.1.1 3,6 .0 2,7 .0 9,14 ]-4-hexadecene derivatives such as those mentioned below. Heptacyclo-5-eicosene derivatives or heptacyclo-5-heneicosene derivatives such as those mentioned below. Tricyclo[4,3.0,1 2,5 ]-3-decene derivatives such as those mentioned below. Tricyclo[4.4,0,1 2,5 ]-3-undecene derivatives such as those mentioned below. Pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 ]-4-pentadecene derivatives such as those mentioned below. Diene compounds such as mentioned below. Pentacyclo[4.7.0,1 2,5 .0 8,13 .1 9.12 ]-3-pentadecene derivatives such as those mentioned below. Heptacyclo[7.8.0.1 3,6 .0 2,7 .1 10,17 .0 11,16 .1 12,15 ]-4-eicosene derivatives such as those mentioned below. Nonacyclo[9.10.1.1 4,7 .0 3,8 .0 2,10 .0 12,21 .1 13,20 .0 14.19 .1 15,18 ]-5-pentacosene derivatives such as those mentioned below. Furthermore, the cycloolefins used in the invention include the compounds described below. Furthermore, examples of the cycloolefins which can be used in the present invention include the compounds described below. Useful α-olefins having 3 or more carbon atoms include propylene, butene-1, 4-methylbutene-1, hexene-1, octene-1, decene-1, dodecene-1, tetradecene-1, hexadecene-1, octadecene-1 and eicosene-1. Of these, preferred is α-olefin having 3 to 20 carbon atoms. Cycloolefins and cyclodienes such as norbornene, ethylidenenorbornene and dicyclopentadiene may also be used. The elastomer (b) comprises recurring units derived from ethylene in an amount of usually 40 to 98 mol%, preferably 50 to 90 mol%, recurring units derived from α-olefin in an amount of usually 2 to 50 mol%, and recurring units derived from a cycloolefin in an amount of usually 2 to 20 mol%, preferably 2 to 15 mol%. The elastomer (b) has a glass transition temperature (Tg) of not higher than 0°C, preferably not higher than -10°C, an intrinsic viscosity [η], as measured in decalin at 135°C, of 0.01 to 10 dl/g, preferably 0.8 to 7 dl/g, and a crystallinity index, as measured by X-ray diffraction, of usually 0 to 10%, preferably 0 to 7% and especially 0 to 5%. The elastomer (b) as described above can be manufactured according to the method proposed by the present applicant in Japanese Patent L-O-P Nos. 168708/1985, 120816/1986, 115912/1986, 115916/1986, 271308/1986, 272216/1986 and 252406/1987. In addition to the polymers (b), there may also be used as elastomers copolymers (so-called block copolymers) obtained by graft polymerizing the elatomers (b) with a polycyclic (meth)acrylate represented by the above-mentioned formula [I] or other monomers polymerizable with the polycyclic (meth)acrylate. A resin composition having excellent impact resistance can be obtained using such block copolymers. THERMOPLASTIC RESIN COMPOSITION The thermoplastic resin composition of the invention comprises the polycyclic (meth)acrylate (co)polymer and the elastomer as described above in the proportion by weight of the (co)polymer to the soft polymer of 99/1 to 40/60. The composition having the proportion in the range of 95/5 to 50/50, preferably 93/7 to 60/40, is particularly excellent in heat resistance, rigidity, dimension accuracy, impact resistance and light resistance. The thermoplastic resin composition of the invention as described above has a melt flow rate (MFR, as measured according to ASTM D 1238) of usually 0.1 to 100. The thermoplastic-resin composition of the invention can be prepared by mixing the polycyclic (meth)acrylate (co)polymer and the elastomer as described above in a predetermined proportion, and kneading the mixture using, for example, a melt kneading apparatus. Furthermore, the thermoplastic resin composition of the invention may be the one having a crosslinked structure among the components of the composition. For example, a crosslinked structure can be formed between the polycyclic (meth)acrylate (co)polymer and the elastomer as mentioned above by using, for example, an organic peroxide. Moreover, in forming the crosslinked structure by using such organic peroxide, the crosslinking reaction may also be conducted by incorporating such a compound having at least two polymerizable functional groups in the molecule as divinylbenzene, vinyl acrylate and vinyl methacrylate. OTHER ADDITIVES The thermoplastic resin composition of the invention may be incorporated with heat stabilizers, weathering stabilizers, antistatic agents, slip agents, anti-blocking agents, anti-haze agents, lubricants, dyes, pigments, natural oil, synthetic oil, wax, organic or inorganic fillers, etc. so long as the incorporation does not impair the object of the invention. Stabilizers to be used as optional components include, for example, phenolic antioxidants such as tetrakis[methylene-3-13,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, alkyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 2,2'-oxamidobis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate, aliphatic acid metal salts such as zinc stearate, calcium stearate and calcium 1,2-hydroxystearate, and aliphatic acid esters of polyhydric alcohols such as glycerin monostearate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate and pentaerythritol tristearate. These stabilizers may be used singly or in combination. For example, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, zinc stearate and glycerin monostearate may be used in combination. Useful organic or inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloons, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fibers, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fibers, silicon carbide fibers, polyethylene fibers, polypropylene fibers, polyester fibers and polyamide fibers. These other components can be mixed with the thermoplastic resin composition of the invention by any known method. For example, each of these other components can be simultaneously mixed with the thermoplastic resin composition. Furthermore, the thermoplastic resin composition of the invention may be incorporated with other resins so long as the incorporation does not impair the object of the invention. Examples of these other resins include polyolefins, halogen-containing vinyl polymers, poly(meth)acrylate, polyacrylamide, polyacrylonitrile, acrylonitrile/butadiene/styrene copolymer, acrylonitrile styrene copolymer, acrylonitrile/styrene/acrylic acid ester copolymers, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl butyral, polyallyl phthalate, polyallylmelamine, ethylene/vinyl acetate copolymer, polyethylene oxide, polyacetal, polyphenylene oxide, polycarbonate, polysulfone, polyurethane, urea resins, polyamides, polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, phenol/formaldehyde resin, urea/formaldehyde resin, melamine/formaldehyde resin, unsaturated polyester resins and natural polymers. USE OF THERMOPLASTIC RESIN COMPOSITION Molded articles in various forms can be prepared by using the thermoplastic resin composition of the invention, and utilizing conventional molding methods such as injection molding. For example, molded articles in a film or sheet form can be manufactured by extrusion molding, and refrigerator interior boxes and trays can be manufactured by vacuum molding. Moreover, there can be manufactured containers for, for example, chemicals and drinks, air ducts, sun visors, consoles, automobile interiors, various toys and floats, by blow molding. Concrete examples of molded articles which can be manufactured from the thermoplastic resin composition of the invention include (1) automobile parts: instrument panels, console boxes, meter clusters, column covers, grille door mirrors, bumpers, fenders, bonnets and radiators; (2) machine housings: tools (e.g., electric tools), business machines (e.g., word processors, personal computers, copying machines, printers, FDD and CRT), precision instruments (e.g., cameras) and electrical appliances (e.g., electric ovens, electric rice cookers, pots and cleaners); and (3) others: toys, miscellaneous goods, furniture and sports goods. EFFECT OF THE INVENTION The thermoplastic resin composition of the present invention is excellent in characteristics such as rigidity, dimension accuracy, impact strength and light resistance. Accordingly, molded articles excellent in characteristics such as heat resistance, rigidity, impact strength and light resistance can be prepared from the resin composition of the invention. Examples The present invention is illustrated below with reference to examples, but it should be construed that the invention is in no way limited to these examples. Methods for measuring and evaluating various physical properties in the invention are described below. (1) Melt flow rate (MFR T ) The melt flow rate is measured according to ASTM D 1238 at a predetermined temperature of T°C under a load of 2.16 kg. (2) Preparation of test pieces Test pieces are molded under the following conditions using an injection molding machine (trade name of IS-55 EPN, manufactured by Toshiba Kikai K.K.) and a mold for the test pieces: a cylinder temperature of 270°C and a mold temperature of 90°C, primary/secondary injection pressures of 1000/800 kg/cm 2 , and an injection speed (primary) of 30 mm/sec. (3) Flexural test The flexural test is carried out according to ASTM D 790 under the following conditions: the shape of the test piece: a size of 127 x 12·7 x 3·2 mm (5x1/2x1/8 t inches) and a span of 51 mm, a test speed of 20 mm/min, and test temperatures of 23°C, 80°C and 100°C. (4) Heat Deflection Temperature (HDT) The heat deflection temperature is measured according to ASTM D 628 under the following conditions: a test piece size of 127 x 6·35 x 12·7 mm (5x1/4x1/2 t inches), and a load of 1820 kPa (264 psi). (5) Softening temperature (TMA) The softening temperature is measured by observing the heat deformation behavior of a sheet 1 mm thick using Thermo Mechanical Analyzer (trade name, manufactured by DuPont). That is, a quartz needle is placed on the sheet, and the sheet is heated at a rate of 5°C/min while a load of 49 g is applied to the needle. The TMA is a temperature at which the needle penetrates the sheet to the depth of 0.635 mm. (6) Glass transition temperature (Tg) and melting point (Tm) The glass transition temperature and the melting point are measured by using DSC 20 (trade name, manufactured by SEIKO Denshi Kogyo K.K.) and heating the test piece at a rate of 10°C/min. (7) Rockwell hardness The Rockwell hardness is measured at 23°C according to ASTM D 785. (8) Izod impact test The Izod impact test is carried out according to ASTM D 256 under the following conditions; a test piece (notched) size of 127 x 3·2 x 12·7 mm (5/2x1/8x1/2t inches), and a test temperature of 23°C. (9) Tensile test The tensile test is carried out according to ASTM D 638 under the following conditions: a test piece shape: type IV, a test speed of 50 mm/min, and a test temperature of 23°C. Example 1 [Preparation of a polycyclic (meth)acrylate polymer (PTDMAC)] In a nitrogen atmosphere were mixed 99 parts by weight of tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodecyl-3-methacrylate (TDMAC), 0.05 part by weight of n-octylmercaptan (OM) and 0.05 part by weight of 2,2'-azobisisobutyronitrile (AIBN), and polymerization was carried out at 80°C for 24 hours. [Preparation of an elastomer] To 100 parts by weight of an ethylene/propylene/ethylidenenorbornene random copolymer (having an ethylene content of 75 mol%, an ethylidenenorbornene content of 3 mol% and an intrinsic viscosity [η] of 2.4 dl/g as measured in decalin at 135°C) were added 30 parts by weight of TDMAC, 1 part by weight of n-octylmercaptan (OM) and 1 part by weight of 2,2'-azobisisobutyronitrile (AIBN) to obtain a latex. The latex was heated to 80°C in a nitrogen atmosphere. The reaction was carried out for additional 24 hours to obtain a TDMAC-grafted ethylene/propylene/ethylidenenorbornene random copolymer. [Preparation of a resin composition] Eighty five parts by weight of the thus obtained PTDMAC pellets and 15 parts by weight of the elastomer prepared above were sufficiently premixed. The mixture was melt blended by a twin screw extruder (trade name of PCM 45, manufactured by Ikegai Tekkosho K.K.) at a cylinder temperature of 230°C to be pelletized. Test pieces were prepared from the resin composition, and physical properties thereof were measured. Example (wt.parts) Flexural modulus (kg/cm 2 ) Flexural strength (kg/cm 2 ) Tensile strength (kg/cm 2 ) Tensile elongation (%) Heat Deflect. Temp. (°C) Rockwell hardness (R-scale) Izod impact strength (kg·cm/cm) 1 85/15 21800 750 470 15 114 110 20

Claims: A thermoplastic resin composition comprising: (a) a polymer comprising recurring units derived from a polycyclic (meth)acrylate represented by formula [I] wherein m is 0 or a positive integer; n is 0 or 1; R is hydrogen or methyl; R 1 -R 18 are each independently hydrogen, halogen or hydrocarbon; R 15 -R 18 may be linked together to form a monocyclic or polycyclic group which may have a double bond; R 15 and R 16 , or R 17 and R 18 , may form an alkylidene group; p is 0 or 1, and when p is 1 R a and R b are each independently hydrogen or hydrocarbon; and (b) at least one elastomer having a glass transition temperature (Tg) of not higher than 0°C, an intrinsic viscosity (η) as measured in decalin at 135°C of 0.01 to 10 dl/g, and a crystallinity index as measured by x-ray diffraction of 0 to 10%, said elastomer comprising recurring units from ethylene, an α-olefin having 3 or more carbon atoms and a cycloolefin of formula (II): wherein R 1 -R 18 , R a , R b , m, n and p are as defined for the compound of formula (I), and/or (b') an elastomer which is a graft-modified copolymer of said elastomer (b) A composition according to claim 1 wherein said polymer (a) is a copolymer comprising said units in an amount of at least 5 mol %. A composition according to claim 1 or 2 wherein said polymer (a) has an intrinsic viscosity (η) of 0.002 to 20 dl/g, as measured in toluene at 30°C. A composition according to any one of the preceding claims wherein said polymer (a) has a glass transition temperature of 10 to 200°C, as measured by a differential scanning type calorimeter. A composition according to any one of the preceding claims wherein said polymer (a) has a molecular weight distribution (Mw/Mn) of not greater than 10, as measured by gel permeation chromatography. A composition according to any one of the preceding claims wherein said polymer (a) has a crystallinity of not greater than 5%, as measured by X-ray diffraction. A composition according to any one of the preceding claims wherein said polymer (a) has a softening temperature of 20 to 220°C, as measured by a thermal mechanical analyzer. A composition according to any one of the preceding claims wherein said polymer (a) is a copolymer having a substantially linear molecular structure in which units of formula [I] and units derived from at least one other monomer are randomly arranged. A molded article comprising a resin composition claimed in any one of the preceding claims.

Inventors: YAMAMOTO YOHZOH, YAMAMOTO, YOHZOH, YAMAMOTO, YOHZOH, MITSUI PETROCHEMICAL IND. LTD.
Applicants: MITSUI CHEMICALS INC, MITSUI CHEMICALS, INC.
Application year: 1992
Main classification: C08L33
IPC codes: C08L33