TW201005025A - B-pinene polymer composition and molded object obtained by using the same - Google Patents

Abstract

Disclosed are: a polymer composition from which is obtained a molded body that has high heat resistance, low water absorbency, a low specific gravity, and excellent shock resistance; and a molded object which uses the polymer composition. The polymer composition is manufactured by combining a) a b-pinene polymer having a specific gravity of 0.85 or higher but less than 1.0 and a glass transition temperature of 80 DEG C or higher and b) an aromatic series vinyl block copolymer that comprises 10-35 mass% of an aromatic series vinyl polymer block and 65-90 mass% of a hydrogenated conjugate diene polymer block and that has a weight-average molecular weight of 100,000-250,000, these being combined such that the component a) is 60-95 parts by mass and the component b) is 5-40 parts by mass, with the total amount of component a) and component b) being 100 parts by mass.

Description

201005025 VI. INSTRUCTIONS: I: TECHNICAL FIELD OF THE INVENTION FIELD OF THE INVENTION The present invention relates to a stone-pinene polymer composition and a shaped body produced therefrom, particularly in the production of opticals requiring good transparency. Optical molded articles such as films, lens sheets, optical substrate materials, transparent materials for lamps, diffusers, and light guide plates, or transparent materials for construction, and insulation for communication and electrical and electronic equipment. A polymer composition which can be advantageously used in the case of a molded body, a medical related device, or the like. BACKGROUND OF THE INVENTION A hydrocarbon-based polymer (alicyclic hydrocarbon-based polymer) having an alicyclic skeleton in a molecule has excellent dielectric constant, transparency, heat-resistant dimensional stability, solvent resistance, flatness, and the like. Used as a material for various industrial parts. Such an alicyclic hydrocarbon-based polymer is produced by a method in which a petroleum-derived monomer is polymerized or copolymerized, or a polymer obtained therefrom is hydrogenated. For example, the patent document 揭示 discloses a method of subjecting a cyclic olefin to ring-opening shift polymerization followed by hydrogenation to produce a hydrogenated ring-opening polymer of a cyclic olefin. Further, in Patent Document 2 and Patent Document 3, a cycloolefin copolymer of an alicyclic hydrocarbon-based polymer obtained by copolymerization of a heterocyclic-like dilute smoke and a bond-like olefin in the presence of a rich lining is taught. . Further, since the alicyclic hydrocarbon-based polymer is amorphous and has high transparency, it is widely used as various optical materials of 201005025, particularly in the form of a lens, a film or a sheet. Specifically, Patent Document 4 discloses an optical film composed of a polymer having an alicyclic structure. On the other hand, in recent years, in order to form a recycling society and prevent global warming, etc., (4), from the viewpoint of carbon neutrality, effective utilization of plant-derived biomass is affected. For example, the natural richness of nature is rich in the amount of «terpene" in the skin of turpentine or citrus, and such olefins have been widely used as raw materials for pharmaceuticals or spices. That is, among the olefins, those having an alicyclic ethylene monomer structure have long been known to have polymerizability; and in the non-patent literature, cations such as cations are described. polymerization. However, the spinach polymer "obtained by the method described in the non-patent document" has a small molecular weight and has insufficient heat resistance and strength. Therefore, even if the polymer is not used, it is difficult to obtain a stable molded article or the like. As described above, the /3-masked polymer which is not in the non-patent document 1 is difficult to use as a molding material because it is difficult to use as a resin.

Further, although it is described in Non-Patent Document 2, when a /5-diluted cationic polymerization is carried out, a 2,6-di-t-butyl-methyl group is added, and a larger molecular weight can be obtained. 3-decene polymer, but the obtained glass transition temperature of η玛歌歌 is 65 ° C, which is not very practical. In such a situation, the inventors of the present invention have developed, in part, a transgenic acid-derived alicyclic-thin-diluted cation by a transaminic acid catalyst in the presence of a bismuth-containing vinyl compound. In the manner of polymerization or cationic copolymerization, an alicyclic hydrocarbon-based polymer (/3-slattered polymer) having a large molecular weight which is not known in the art can be produced (Patent Document 5, Non-Patent Document 201005025 3). However, the terpene polymer disclosed therein is a substance having good properties such as heat resistance, low water absorption, and low specific gravity, but is used as a molded body for, for example, a communication device or an electric or electronic device. Impact is hard enough. Therefore, the terpene polymer which is a starting point of transparency has been developed on the one hand, and the molded body containing the /3 -pinene polymer has been developed, while maintaining a good shape which is excellent in impact and excellent in impact resistance. Expected. [Previous Technical Literature]

[Patent Document 1] International Publication No. 00/73366 [Patent Document 2] Japanese Laid-Open Patent Publication No. 2001-506293 (Patent Document 3) Japanese Patent Publication No. 2001-506689 (Patent Document 4) International Publication No. 03 [Patent Document 4] International Publication No. 08/44640 [Non-Patent Document] [Non-Patent Document 1] William J. Roberts and Allan R. Day, "A Study of the Polymerization of a -and Cold - Pinene with Friedel-Crafts Type Catalysts", Journal of the American Chemical Society, 1950, Vol. 72, pp. 1226~1230 [Non-Patent Document 2] B. Keszler, JP Kennedy, "Synthesis of High Moleculer Weight Poly (yS- Pinene)", Advances in Polymer Science, 1992, Vol. 100, pp. 1-9 [Non-Patent Document 3] K. Satoh, H. Sugiyama and Μ Kamigaito, "Biomass-derived heat-resistant alicyclic 201005025 hydrocarbon polymers : Poly(terpenes) and their hydrogenated derivatives", Green Chemistry, 2006, Vol. 8, pp. 878~882 C. Summary of inventions in the invention In the present invention, the present invention has been completed in the context of the related circumstances, and a problem to be solved is to provide a polymer composition of a molded body which can obtain high heat, low water absorption, low specific gravity, and excellent impact resistance. Further, a molded body made of such a polymer composition is provided. In order to solve such a problem, the inventors of the present invention have found through repeated studies that a polymer containing a predetermined cold-pinene polymer and a predetermined aromatic vinyl-based copolymer is used. The formed body formed of the article has excellent impact resistance, and the present invention has been completed. That is, the gist of the present invention is a polymer composition characterized in that it has a 'a) specific gravity of 0.85 or more and less than 1.0 and a glass transition temperature of 8 〇 ° C or more / 3 - 蒎 dilute polymer and b) An aromatic vinyl block copolymer having a weight average molecular weight of 100,000 to 250,000 formed from 10 to 35 mass% of the aromatic vinyl polymer block and 65 to 90 mass% of the hydrogenated co-diuretic polymer The mixture is mixed at a ratio of 60 to 95 parts by mass of the component a) and 5 to 4 parts by mass of the component b), and the total amount of the components a) and b) is 1 mass%. Further, if a suitable aspect of the polymer composition according to the present invention is utilized, the above terpene polymer is formed by hydrogenation, 201005025 and ([hydrogenated olefinic double bond number] / [hydrogenation] The number of olefinic double bonds in the front polymer]) xl 〇〇 is 95% or more. Further, in another suitable aspect of the polymer composition of the present invention, the aromatic vinyl-based block copolymer is polymerized from 10 to 25% by mass of the aromatic vinyl polymer block, and hydrogenated co-diene is polymerized. Blocks of 75 to 90 mass / 〇 formed by the block. Further, the polymer composition relating to the present invention is preferably a total light transmittance of 80% or more. ® On the other hand, the shaped body obtained by using the polymer composition as described above is also the gist of the present invention. Advantageous Effects of Invention The polymer composition according to the present invention is a /3 -pinene polymer having a specific gravity of 0.85 or more and less than 1.0 and a glass transition temperature of 80 ° C or more, and an aromatic vinyl polymer. An aromatic vinyl-based block copolymer having a weight average molecular weight of 100,000 to 250,000, which is formed by blocking 10 to 35 mass% of the block and 65 to 90% by mass of the hydrogenated conjugated diene polymer block, and is mixed at a predetermined ratio of Further, since the molded article formed by using the polymer composition of the present invention has high impact resistance, it can be advantageously used in the production of, for example, a casing for protecting a precision machine from impact. In addition, the yS-pinene polymer is a hydrogenated stone-pinene polymer, and ([hydrolated olefinic double bond number] / [number of olefinic double bonds in the polymer before hydrogenation]) xl 〇〇 The polymer composition of the present invention having a value of 95% or more, and a molded article formed therefrom, is excellent in not only impact resistance but also light resistance and heat resistance. 201005025 Further, the present invention uses an aromatic ethyl fluorene-based polymer portion ι 〇 25% by mass and a hydrogenated co-light diene polymer block 75 to 9 (% by mass) in the form of a (tetra) aromatic vinyl-based segment polymer. (4) The secret of the composition group, and the formed body formed by the material can exhibit more excellent transparency. Further, since the present invention-polymer composition is a definitive r-masked polymer as a main component, the following effects can be obtained by using the excellent properties of the polymer (10). (1) The polymer composition of the present invention has a small specific gravity, and the molded body produced therefrom is also light in weight. (7) The residue of the (four) compound of the present invention contains a material having a very large molecular weight (yttrium compound) at the (fourth) degree, and since the melt viscosity is very low, it is easy to follow a molding method which has been known in the past. Formed on the ground. () The polymer composition of this month is characterized by being environmentally friendly because it is (8)% by mass or more and is a terminally-packed dilute polymer which can be obtained from a raw material derived from natural materials. (4) The molded article obtained by using the polymer composition having such a good characteristic has high heat resistance and a small water absorption rate, so that deformation due to heat or deformation due to excessive adsorption of water can be prevented. (5) In addition, such a molded body does not generate harmful gases even after incineration after being discarded. (6) Further, the molded article is not only excellent in light resistance but also inferior in performance after deterioration due to long-term use. BRIEF DESCRIPTION OF THE DRAWINGS 201005025 FIG. 1 is an illustration of a self-contained method. FIG. 10 is a DSC curve for calculating a glass transition temperature in an embodiment. [Example of implementing a cold type] In the polymer composition, the = masking polymer is a polyene polymer having a specific gravity of 〇85 or more and less than 1 〇 and a glass transition temperature of ^ or more. More precisely, this specification and application

The H-thin polymer in the patent range means that the content of /5-secret is 5 Gmol% or more with respect to all monomer units in the polymer. When the 3-decene polymer is produced, the terpene as a raw material can be used in any of the conventionally known ones. For example, after purifying a plant obtained from a plant such as pine or hanged orange, it may of course be directly prepared, or a terpene derived from a plant or a compound derived from petroleum, or the like, may be used. The known method (for example, the method disclosed in the specification of U.S. Patent No. 3,286,823) is made of terpene or the like. The use of such a terpene polymer obtained from the smear of the plant is a carbon neutral material, and at this point, the polymer composition of the present invention becomes a system for forming a recycling type and preventing the earth from warming. Material that contributes. Further, the /3-decene polymer used in the present invention may be a homopolymer of the above-described fluorene-pinene, or may be formed of at least one of a monomer which is point-to-xenon and copolymerizable. There is no difference in the copolymer. Other monomers which may be dilutely copolymerized with the ruthenium-based oxime may, for example, be a cationically polymerizable monomer, a free-radical polymerizable monomer, a coordinating polymerizable monomer, and a plant-derived terpene. Further, in the present invention, the cation-free 201005025 sub-polymerizable material used in the production of the non-pinene polymer and the Φ-filament-combination-combination monomer can be used as a user of the present. Further, the plant-derived rare earth may be used as a polymerizable monomer in the polymerization of any of the cationic poly-σ/ίτ, the self-Φ-based polymerization method or the coordination polymerization method. Specifically, the cationically polymerizable monomer can be exemplified by, for example, isobutyl hydrazine, isoprene, bismuth, styrene, methyl styrene, p-methyl ethion, p-methoxy styrene, P-tert-butoxy stupyl ethylene, aralkyl vinyl ether, norbornene, and the like. Further, examples of the radical polymerizable monomer include (meth)acrylic acid methyl vinegar, (meth)acrylic acid ethyl vinegar, (methyl) acrylic acid n-butyl vinegar, and (methyl) propionic acid 2- Ethyl hexane vinegar, (meth) acrylic acid 2 _ vinegar, (mercapto) acrylic acid hydroxypropyl S 曰 (meth) acrylate propylene acrylate vinegar (four) postal coffee such as (four) buckle e), etc. Methyl)acrylic acid S; acrylonitrile, methacrylonitrile, etc. containing ethylene monomer; acetaminophen, (meth) propylamine, etc. amine group-containing ethylene monomer; vinyl acetate Ethyl esters such as ester, trimethyl vinyl acetate, ethylene benzoate, etc.; vinyl ester, vinylidene dioxide, maleic anhydride, fumaric acid, fumarate, maleic amine, and the like. Further, examples of the coordination polymerizable monomer include ethylene, propylene, p-hexene, cyclopentene, norbornene, and the like, and plant-derived terpenes can be exemplified by, for example, myrcene and belle basil. All〇〇cimene 'ocimene, 〇: terpenes, dipentene, lim〇nene, a-phellandrene α-pine oil thin (a - Terpinene), γ-terpinene, 2-carene, 3-decene, and the like. Among them, one or two or more kinds of monomers are appropriately selected in accordance with the amount of use of /5 - hydrazine, etc., and the use of the non-pinene polymer can be conveniently obtained by the cationic polymerization method. Among the polymer monomers as described above, a cationically polymerizable monomer can be particularly advantageously used. Further, 'in the case where the above copolymerizable monomer is copolymerized, the amount of copolymerization is 0.001 to 50 mol% with respect to all the monomers in the polymer, and further 〇乂υ.οι 〜2〇 Preferably, m〇1〇/〇, 0,05~l〇mol% is optimal. In addition, if there are too many total fruits in the 苴杜赘县田, it is not suitable because the water absorption rate is increased and the heat resistance is lowered. On the other hand, a small amount of a difunctional ® hereinafter referred to as a heteromonomer may be copolymerized with a co-recorded copolymerizable monomer of (4). The crosslinkable monomer is generally used as a branching agent or a crosslinking agent in the production of a polymer, but it is advantageous to obtain a so-called long-chain branched structure by borrowing a small amount thereof. Further, it has a 5-pentene polymer having a molecular weight which does not form an insoluble portion to the organic solvent. The crosslinkable monomer which can be used in the present invention, specifically, for example, m-diisopropenylbenzene, p-diisopropenylbenzene, m-divinyl, p-diphenylbenzene, 1,4 - a bifunctional vinyl compound such as cyclohexane or dimethanol diethylene hydride or ethylene glycol divinyl ether; among them, from the viewpoint of economy and reactivity, especially the use of m-diethylbenzene good. When such a crosslinkable monomer is copolymerized with non-pinene (and other monomers copolymerizable with terpene), the amount of copolymerization is relative to all monomer units in the polymer and is 〇·001~ 7 mole%, which is preferably 〇〇1~5mol%, 4mol/〇 is best. If the amount of copolymerization is too large, the obtained stone-rhenium-rich sigma will form a gel, and it is not suitable to lose the thermoplasticity. Further, the polymerization method of the yS-pinene polymer used in the present invention is not particularly limited, and can be appropriately selected from known polymerization methods. For example, any of an anionic polymerization method, a cationic polymerization method, a radical polymerization method, and a coordination polymerization method may be optionally used, but a cationic polymerization method is generally employed. Further, in the case where the /5-fluorene polymer used in the present invention is obtained by a cationic polymerization method, a polymerization catalyst is a known cationic polymerization catalyst. Specifically, for example, BF3, BF3OEt2, BBr3, BBr3OEt2, A1C13, AlBr3, A1I3, TiCl4, TiBr4, Til4, FeCl3, FeCl2 may be mentioned.

SnCl2, SnCl4, WC16, MoC15, SbCl5, TeCl2, etc., metal halides of Group 3 to Ιό of the periodic table; hydrogen acids of HF, HCL, HBr, etc.; H2S〇4 'H3BO3 ' HCl〇4 'CH3COOH ' CH2CICOOH 'CHCl2COOH, CCl3COOH, CF3COOH, p-toluenesulfonic acid, CF3S〇3H, H3P04, p2〇5, etc., and molecular compounds such as ion-exchange resins containing these groups; phosphomolybdic Acid), heteropolyacid such as phosphotungstic acid; SiO2, Al2〇3, SiO2-Al203, MgO-SiO2, B203-Al2〇3, W03-A120 3, Zr2〇3-Si〇 2. Sulfation and oxidation, town © acid zirconium oxide, zeolite exchanged with H+ or rare earth elements, activated earth, acid earth, r _ Al2〇3, supporting algae A solid acid such as solid phosphoric acid formed by P2〇5. These cationic polymerization catalysts may be used in combination, or other compounds or the like may be added to the polymerization system. Such other compounds and the like are, for example, compounds which are added to increase the activity of the catalyst. Further, an example of a compound which increases the activity of the metal halide as an acidic compound can be exemplified by 12 201005025, for example, MeLi, EtLi, BuLi, Et2Mg, EtMgBr, Et3Al, Et2AlCl, EtAlCl2, Et3Al2Cl3, (i-Bu)3Al, Et2Al ( Metal alkane compounds such as OEt), Me4Sn, Et4Sn, Bu4Sn, Bu3SnCl; 2-nonoxy-2-phenylpropane, tert-butanol, 1,4-bis(2-decyloxy-2-propyl)benzene A compound such as 2-phenyl-2-propanol which can be used as a polymerization initiator for living cationic polymerization. Further, the polymerization method of the yS-derived dilute polymer used in the present invention can also be carried out by a solution polymerization method using a solvent. Since the solvent which can be used differs depending on the polymerization method to be used, it is difficult to define it in one sense, and examples thereof include an aromatic hydrocarbon solvent such as benzene, toluene or xylene; pentane, hexane, heptane, An aliphatic hydrocarbon solvent such as octane, cyclopentane, cyclohexane, methylcyclohexane or decahydronaphthalene (deCaHn); methyl chloride, methylene chloride, 12_2 gas, 1, 1, 2 - a halogenated hydrocarbon solvent such as triethylene glycol; an oxygen-containing solvent such as an ester or a shim. Further, in consideration of reactivity, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an activated hydrocarbon solvent or the like is preferably used. These solvents may be used singly or in combination of two or more. =~~ Such a solvent is not particularly limited in its use amount, but the phase of the olefinic body is 1.1〇0 mass minutes, usually about 100 to 10,000 mass minutes, preferably 150 to 5000 mass%, 2〇〇~ 3 〇〇〇 quality is better. When the solvent is too small, the polymerization catalyst is difficult to mix and knead. Therefore, the reaction becomes uneven and the amount of the resin is not uniform. The uniform resin is not obtained, and the control of the reaction becomes difficult. On the other hand, if the amount of solvent is large, there is a problem that productivity is lowered. Party. However, when the polymerization reaction is carried out, the reaction temperature is usually ~8 annihilation ~ C is better, which is again thief ~ 8 〇. 〇 better, _ thief ~ 8 generations of the best 13 201005025 If the reaction temperature is too low, the reaction proceeds slowly, if it is too high, the reaction control is difficult, and it is difficult to obtain reproducibility. Further, the reaction pressure for carrying out the reaction is not particularly limited, but it is preferably 0.5 to 50 Torr, and 〇 7 to 1 Torr is preferred. Usually, the polymerization is carried out at about 1 atmosphere. Further, the stone-pinene polymer produced by the polymerization reaction can be removed by, for example, precipitation, solvent removal under heating, solvent removal under reduced pressure, solvent removal by steam (steam. stripping), and the like. The general operation when the polymer is separated from the 'salt liquid is separated from the reactant. The 0-pinene polymer used in the present invention preferably has an olefinic double bond from the viewpoint of light resistance, impact resistance and heat resistance. However, the hydrogenation rate is generally 90. /. The above is preferably hydrogenated, wherein more than 95% is hydrogenated, and more preferably 99% or more is hydrogenated. In particular, in the present invention, the /3-decene polymer is hydrogenated to indicate its hydrogenation rate ([hydrogenated olefinic double bond number] / [olefinic double bond in the polymer before hydrogenation] Number]) The value of χ100 should be above 95%. Furthermore, the hydrogenation rate of the unsaturated double bond (carbon-carbon double bond) in the hydrogenated dot-terpene polymer can be analyzed by titration, infrared spectrometry, nuclear magnetic resonance spectroscopy (iH_NMp spectroscopy), etc. The method is calculated. Therefore, the hydrogenation method of the /3-decene polymer used in the present invention is not particularly limited, and a known method can be used. For example, nickel, palladium, platinum, etc. may be used by using an in-phase catalyst such as a wilkinson complex, a acetamate/triacetin, a nickel acetylacetonate/triisobutyl sulphate or the like. Catalyst metal supported on diatomaceous earth, oxidized town, oxidized, 14 201005025 - emulsified bismuth - magnesium oxide, cerium oxide oxide, synthetic zeolite, etc.

Further, the solvent which can be used in carrying out such hydrogenation can be used as long as it is an organic solvent which is soluble in the polymer and inactive to the hydrogenation catalyst. Specifically, an aromatic hydrocarbon solvent such as benzene, toluene or xylene may be used; decane: fat of hexanol, Gengyuan, Xinyuan, cyclopentene, cyclohexanol, methylcyclohexene, decyl naphthalene, etc. A hydrocarbon-based solvent; a gas-containing hydrocarbon solvent such as methane, methylene chloride, dioxane, 1,1,2-diethylene, etc. Further, when considering the reactivity, an aromatic hydrocarbon solvent and a ruthenium group are used. These sprays may be used alone or in combination of two or more kinds, and there is no difference. In addition, although the hydrogenation reaction temperature depends on the chloride catalyst used and the pressure of chlorine, it is better to use thieves ~ bullying, which is best for hunger ~ 15 〇 j good especially 4C ~ l 〇〇 c. If the reaction temperature becomes too low, it is particularly difficult to carry out smoothly, and if the reaction temperature is too high, the by-twisting-rolling enthalpy, the alumina-magnesia reaction and the molecular weight decrease are likely to occur. Further, the hydrogen pressure which can be used is preferably about g / cm of normal dust, preferably 5 to the position of ^. If the hydrogen pressure is too low, the reaction will not proceed smoothly, and if the hydrogen pressure is too high, the device will be limited. Further, the concentration of the stone-masked polymer in such a hydrogenation reaction system is usually from about 3% by mass to about 4% by mass. /. Preferably, it is preferably 30% by mass, and 5% by mass is preferably 2% by mass. (4) If the concentration of the dilute polymer is low, it is easy to reduce the yield, and * the concentration of the polymer suitable for the n-passage is as high as the Abbe'] not only the hydrogenated polymer will precipitate, but also the viscosity of the reaction mixture is increased by 201005025. It is not suitable for the case where the mixing cannot be carried out smoothly. In addition, the reaction time of the hydrogenation reaction depends on the hydrogenation catalyst and hydrogen pressure used, and the reaction temperature, but it is usually about 0.1 hour to 5 hours, preferably 0.2 hours to 20 hours, and 5 hours to less hours. good. Further, the non-pinene polymer after the argonization reaction can be removed from the solvent by, for example, re-sinking, solvent removal under heating, solvent removal under reduced pressure, solvent removal by steam (lifting), and the like. The general operation when the polymer is isolated is separated from the reactants. Further, the molecular weight of the /3 -blockene polymer used in the present invention is from 30,000 to 10,000 in terms of weight average molecular weight from the viewpoint of viscosity or explosive viscosity, formability, and heat recovery of the polymerization solution. The left and right are better, 40,000 to 500,000 is better, 60,000 to 250,000 is better, and the best is 90,000 to 200,000. Further, the weight average molecular weight of the polymer is calculated by a known analytical method such as gel permeation chromatography (GPC) or static light scattering (SLS) obtained in terms of polystyrene.

Further, the glass transition temperature (Tg) of the /5-regular polymer used in the present invention is preferably high in consideration of the use environment of the formed body formed by using the polymer composition of the present invention. Above C °, preferably 1 〇 (rc Q or more, more preferably 110 ° C or more. The upper limit of the glass transition temperature is not particularly limited, but it is preferably about 200X: This is because the glass transition temperature is too high. 'The intertwining of the polymer reduces the case where the molded article becomes brittle. Furthermore, the total light transmittance of the terpene polymer used in the present invention is preferably high, usually 80% or more is preferable, and 85% thereof is further The above is preferred, and more than 9% by weight is the best. In addition, the total light transmittance is measured by root. 16 201005025 In addition, the ten-terpene polymer used in the present invention is from the viewpoint of size stability. The water absorption rate should be low. The water absorption rate of the stone-terpene polymer when placed under 60 ° C '90% RH fog is preferably 〇2 乂, which is less than 0.1%. Preferably, it is preferably 0.05% or less. It is advantageous to select a stone that exhibits such water absorption. - terpene polymer.

The y3-pinene polymer used in the present invention is characterized by a small specific gravity. Since the specific gravity is small, a relatively light molded body can be obtained. Therefore, the specific gravity of the ten-terpene polymer used in the present invention must be 〇.85 or more and less than 1.0, and particularly preferably 〇85 to 〇.98. This is because a cold-blocking polymer having a specific gravity of less than 〇85 is difficult to obtain, and if the specific gravity is more than 丨.0, the object of weight reduction of the obtained molded body cannot be sufficiently achieved. On the other hand, in the polymer composition according to the present invention, the aromatic acetamethylene back-end copolymer is mixed as an essential component together with the above-mentioned stone-blown polymer. The aromatic vinyl block copolymer in the present specification and the patent application is intended to exhibit i) one of aromatic vinyl polymer blocks having a unit derived from an aromatic vinyl compound as a main constituent unit or Two or more kinds, and ii) one or more kinds of hydrogenated conjugated diene polymer blocks of a hydride of a conjugated diene polymer block in which a unit derived from a conjugated diene compound is a main constituent unit, A block copolymer of a bonded structure is formed. In the present invention, one or more of the aromatic vinyl-based block copolymers are mixed with one or more of the /5-masked polymers. Specifically, the aromatic vinyl polymer block can be exemplified by, for example, styrene, α-methylstyrene, o-nonylstyrene, m-methylstyrene, p-17 201005025 methyl styrene, and uncle Butylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, vinylnaphthalene, anthracene One or two or more kinds of polymer blocks formed of an aromatic vinyl compound such as styrene. In the present invention, a polymer block formed of styrene is particularly preferred. Further, the hydrogenated conjugated diene polymer block may, for example, be butadiene, isoprene, 1,3-hexadiene, 2,4-hexadiene, 2,3-didecyl-1 A hydride of a conjugated diene polymer block formed of a conjugated diene compound such as 3-butadiene or 1,3-pentadiene. Among them, a hydride of a conjugated diene polymer block formed of butadiene and isoprene is particularly preferable. Further, the hydrogenated conjugated diene polymer block in the present invention may be an olefinic double bond remaining, and specifically, ([hydrogenated olefinic double bond number] / [pre-hydrogenation The number of olefinic double bonds in the polymer]) xl0〇 is about 1%. The aromatic vinyl-based block copolymer which can be used in the polymer composition of the present invention may, for example, be a hydrogenated stupid ethylene-butadiene block copolymer or a hydrogenated stupid ethylene-butadiene-styrene block copolymer. , hydrogenated stupid ethylene-isoprene block copolymer, hydrogenated styrene-isoprene-styrene block copolymer, hydrogenated styrene-isoprene/butadiene-styrene block copolymer, etc. . Among them, from the viewpoint of effectively imparting impact resistance to the formed molded body, a hydrogenated styrene-butadiene-styrene block copolymer and hydrogenated stupid-isoprene-benzene are particularly used. Ethylene-based copolymer, hydrogenated styrene-isoprene/butadiene-stupid ethyl ester copolymer is preferred, preferably hydrogenated stupid-isopentadiene/butadiene- Stupid ethylene block copolymer. Further, the aromatic vinyl-based block copolymer usually has a glass transition temperature of 2010 (the glass transition temperature of 201005025 (Tg)', but even a copolymer having a plurality of glass transition temperatures or a copolymerization of glass transition temperature and melting point (Tm) As long as the lowest glass transition temperature is 30 c or less, it can be used as the aromatic vinyl-based block copolymer in the present invention. Such an aromatic vinyl-based block copolymer (hereinafter, only referred to in this paragraph) Among the copolymers, in the polymer composition of the present invention, 10 to 35 mass% of the aromatic vinyl polymer block and 65 to 90 mass of the hydrogenated conjugated diene polyblock block are used. The copolymer formed by ruthenium is preferably a copolymer formed by using 10 to 30% by mass of the aromatic vinyl polymer block and 70 to 9% by mass of the hydrogenated conjugated diene polymer, and more preferably used. Aromatic vinyl polymer block 1 〇 25% by mass and hydrogenated total dilute polymer block 75~9 〇 mass /. The copolymer formed, the best is the use of aromatic vinyl polymer slave 10 20 mass / hydrazine and hydrogenation co-light dimerization The copolymer formed in the latter stage (10) to 9% by mass. The aromatic vinyl-based polymer block in the copolymer is not included; if not, the U0 mass is difficult to maintain the shape of the copolymer. If _ σ is suitable, and 'if a copolymer having a proportion of 4 sinyl ethyl polymer blocks exceeds 35% by mass, a molded body obtained by using the polymer composition containing the copolymer may have The impact resistance (4) is sufficient, so it is not suitable. In addition, as described above, since two or more kinds of aromatic vinyl-based block copolymers can be used, even an aromatic vinyl-based polymer is embedded. The proportion of the segment is less than 10% by mass, or the aromatic ethylene-based block copolymer of the excess mass% can still be used in combination with other aromatic vinyl-based block copolymers, as long as the aromatic B The ratio of the dilute base polymer block phase to the total amount of the aromatic vinyl-based block copolymer can be used within the above-mentioned range of 19 201005025. The aromatic vinyl system used in the polymer composite of the present invention Block copolymer's weight average The amount of 100000~250000 to 100000~200000

Better for those who are better than '100000~150,000. When a polymer composition comprising an aromatic ethylenic block-based block copolymer having a weight average molecular weight of less than 丨(8) is used, the molded article formed of the polymer composition is insufficient in impact resistance and is not suitable. On the other hand, if an aromatic vinyl-based segment copolymer having a weight average molecular weight of more than 25 Å is used, the aromatic enthalpy is increased, and the copolymer of the /5-decene is polymerized in the polymer composition. The kneading becomes difficult and inappropriate. In the case of the above-mentioned S, when two or more aromatic vinyl-based fluorene-based copolymers are used, two or more kinds of aromatic vinyl-based block copolymers having a weight average molecular weight within the above range can be appropriately selected. . Further, the weight average molecular weight of the aromatic vinyl block copolymer is determined by gel permeation chromatography (GPC) in terms of conversion polystyrene.

The transparency of the 珉 shape of the cold-formed material is better than that of j, and the refractive index of the segmental copolymer must be considered in consideration of the polymer composition. Specifically, 'through the appropriate selection and mixing of the non-cycloolefin polymer, the refractive index difference is small, the final shape of the molded object will be better." The refractive index of the block copolymer depends on the ratio of copolymerization, ethylene group polymer block, by adjusting the ratio. For example, the ratio of the refractive index of the dilute homopolymer to the (4) base-segment copolymer containing the 3^ ethylene-based polycondensation segment is preferably 20 to 3 〇 mass% ‘25 to 30 mass% better* 20 201005025

26 to 28% by mass D Here, the refractive index of the phenanthrene polymer and the aromatic vinyl block copolymer can be measured at 2 rc in accordance with 玎8_^_7. When two or more types of aromatic ethylenic block copolymers are used, the refractive index of each aromatic vinyl-based block copolymer can be determined in the case where measurement of the refractive index is difficult or impossible (according to the above JIS) The refractive index is theoretically calculated based on the amount of the mixture and the like. In the polymer composition of the present invention, one or more of the above aromatic vinyl-based block copolymers are mixed with a stone-pinene polymer. The amount of the aromatic vinyl-based block copolymer in the present invention (used

Two or more materials (four) the total amount of the copolymer in the case of the block copolymer of the B-type), and the total amount of the copolymerization of the /3-spinene polymer and the aromatic vinyl group block: just the weight, The polymer of the product is ~% by mass, and the block copolymer of the aromatic vinyl group is 5 to 4 Gf. Preferably, the compound is 70 to 90 parts by mass, and the aromatic B. The ratio of the polymer 1 靖 ~ jing amount is mixed. This is because the mixing of the aromatic vinyl-based block copolymer is less than 5 parts of the polymer group, and the molded body obtained therefrom cannot exert sufficient impact resistance, @, mixed with 4 〇 mass of the polymer In the polymer composition according to the present invention, various kinds of the mixture may be used singly or in combination of two or more kinds as needed. Specific examples are as long as they are generally used by the resin industry. For example, antioxidants, ultraviolet absorption swords, melt reading, near-infrared 21 201005025 colorants, lubricants, plasticizers (softeners), antistatic A mixture of a solvent, a fluorescent whitening agent, a filler, etc., and an antioxidant, for example, a phenolic antioxidant, a phosphorus antioxidant, a sulfur-based antioxidant, etc., among which phenolic antioxidant is preferable. The anti-oxidation agent is particularly suitable. The phenolic antioxidant which can be used, specifically, those which have been known in the past, for example, 2-tert-butyl-6-(3-tert-butyl group) can be used. -2-hydroxy-5~ Benzyl)-4-toluene acrylate (_t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate), 2,4-di--tert-amyl -6-(l-(3,5-di-tert-amyl-2-hydroxyphenyl)ethyl) phenyl acrylate, which is described in JP-A-63-179953, and JP-A-1-168643 Acrylate-based compound; 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-octadecyl alcohol S (Octadecyl 3-(3,5-di-tert-butyl-4) -hydroxyphenyl)propionate), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 1,1,3-tris(2-mercapto-4-hydroxy-5-tert Butyl phenyl) butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-trans)phenyl, tetra(methylene-3) -(3',5'-di-tert-butyl-41-hydroxyphenyl)propionate) methane [ie © pentaerythrimethyl-tetrakis (3-(3,5-di-t-butyl-4-hydroxyphenyl)) Propionate)], triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (Triethyleneglycol-bis(3-(3-t-butyl-4-hydroxy-) 5-methylphenyl)propionate)), etc., substituted alkyl group; 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-di Benzyl-H5-triazine (6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-bis (octylthio)-l,3,5-triazine), 4-dioctylsulfide Base-1,3,5-tripa,2-octylthio-4,6-bis-(3,5- 22 201005025-tert-butyl 4-oxoamine)-i,3,5-5. 2-〇ctylthio-4,6-bis_(3,5-di-t-butyl-4-oxyanilino)-1,3,5-triazine) or the like containing a triazine group. Further, the phosphorus-based antioxidant is not particularly limited as long as it is generally used in the general resin industry, and examples thereof include triphenyl phosphite, diphenylisodecyl sulfite, and benzene phosphite. Diisodecyl ester, tris(nonylphenyl) phosphite, tris(didecylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, 10-(3) ,5-di-tert-butyl-4-hydroxybenzyl)-9,10-di-β-hydroxahydro-10-phosphaphenanthrene-10-oxide (10-(3,5-out+ buty l-4) -hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphen anthrene-1 Ο-oxide), such as a monophosphite compound; 4,4,-butylene-bis(3-methyl-6- 4,4-butylidene-bis-(3-methyl-6-t-butylphenyl-di-tridecyl • Phosphite), bucket/'-isopropanil Di-phosphoric acid such as 4,4'-isopropylidene-bis(phenyl-di-alkyl(C 12~ C15)phosphite) An ester compound or the like. Among them, a monophosphite compound is preferred, tris(nonylphenyl) phosphite, tris(diphenylphenyl) phosphite, and tris(2,4-di-tert-butyl phosphite). Phenyl phenyl esters and the like are particularly suitable. Further, the sulfur-based antioxidant may, for example, be dilauryl 3,3-thiodipropionate or 3,3'-dithiotetrapropanoic acid ditetradecyl ester. Dioctadecylate of 3,3-thiodipropionate, dodecyl octadecyl 3,3-thiodipropionate, pentaerythritol tetrakis(t-doct-sulphate-thiopropionate)卩61^61^1;11出〇1-161^103-(;3-131»*>1-1;1^0卩1*0卩1〇11316)),3,9-double 23 201005025 (2-Isodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5] _|--burning (3,9-bis (2-dodecylthioethyl) -2,4, 8,10-tetra〇xaSpiro [5,5] undecane) and the like, these antioxidants may be used alone or in combination of two or more. The amount of such anti-caries agent is appropriately determined within the range not impairing the object of the present invention, but is relative to the total amount of the cold-pinene polymer and the aromatic vinyl block copolymer: 1〇〇 The mass fraction is usually about 1 to 5 mass minutes, preferably in the range of 0 to 01 to 1 mass. Further, as the ultraviolet absorber, for example, 2-(2-hydroxy-5-tolylhydrazyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-tolyl)_5- can be used. Chloro-2H-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)_5_gas_211-benzotriazine, 2-(3,5-di-tert-butyl 2-hydroxyphenyl)-2H-benzotriazole, 5-hydroxy-2-(3,5-di-tert-butyl-2-phenyl)-2H-benzotrisene, 2-(3 , 5-di-tert-amyl-2-phenyl)-2H-benzotriazole, etc. Benzotriazole-based UV-absorber; 2-hydroxybenzoic acid 4-tert-butylphenyl ester (4 small Butylphenyl-2-hydroxybenzoate), phenyl 2-hydroxybenzoate, 2,5-di-tert-butyl-4-perbenzoic acid-2,4-di-tert-butylphenyl ester, 3,5-di-tert-butyl ® Benzene-4-carbamic acid hexahydrate vinegar, 2-(2H-benzotris-s-yl-2-yl)-4-methyl-6-(3,4,5,6-tetrahydroortylene 2-(2-[[2H]-Benzotriazole-2-yl)-4-methyl-6-(3,4,5,6-tetrahydro-phthalim idylmethyl phenol), 2-(2 -2-(2-hydroxyphenyl)-2H-benzotriazole (2-(2-hydroxyphenyl)-2H-benzo-triazole), 2-(2-yl-4-yl-octyl) Phenyl)-2H-benzotriazine, etc. External absorbent; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 24 201005025 2-carbyl-4-decyloxybenzhydryl-5-continuation acid 3 hydrate, 2-carbyl-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxydibenzophenone, 2 , 2', 4, 4·-tetrahydroxybenzophenone, 2,2·-dihydroxy-4,4'-dimethoxy benzophenone and the like benzophenone-based ultraviolet absorber; 2_ atmosphere Acrylate-based ultraviolet absorbers such as keto-3,3-diphenyl acrylate, 2-amino-3,3-diphenyl acrylate-2'-ethylhexyl ester; [2, 2' - Metal sulphur® such as [2,2'-thi〇bis (4-t-octylphenolate)-2-ethylhexylamine nickel) The compound is a UV absorber or the like. Further, the photostabilizer may, for example, be (2,2,6,6-tetramethyl-4-piperidyl)benzoate or bis(2,2,6,6). -tetramethyl-4-latyl) sebacate, bis(1,2,2,6,6-pentamethyl-4piperidinyl)-2-(3,5-di-tert-butyl Benzyl-4-hydroxybenzyl)-2-n-butylmalonate (1^(1,2,2,6,6-卩61^11161;11丫1-4-卩丨卩614<1^ 1)- 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl malonate) ' 4-(3,5-di-tert-butyl-4-hydroxyphenyl) Propioneoxy)-b (2-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoxy)ethyl)-2,2,6,6-tetramethyl Hindered amine light stabilizers such as piperidine. Further, the near-infrared absorbing agent may, for example, be a cyanine-based near-infrared absorbing agent; a pyrylium-based near-infrared absorbing agent; a squarylium-based near-infrared absorbing agent; a crotonium; Near-infrared absorbing agent; azulenium-based near-infrared absorbing agent; phthalocyanine-based near-infrared absorbing agent; dithiol metal complex-based near-infrared absorbing agent; naphthoquinone-based near-infrared absorbing agent; Anthraquinone is a near-infrared absorbing agent; indophenol 25 201005025 (indophenol) is a near-infrared absorbing agent; an azide-based near-infrared absorbing agent. Further, commercially available near-infrared ray absorbing agents are, for example, SIR-103, SIR-114, SIR-128, SIR-130, SIR-132, SIR-152, SIR-159, SIR-162 (above is Erjingdong) Kawasuke IR-750, Kayasorb IRG-002, Kayasorb IRG-003, Kayasorb IR-820B, Kayasorb IRG-022, Kayasorb IRG-023, Kayasorb CY-2, Kayasorb CY-4, Kayasorb CY- 9 (The above is manufactured by Nippon Kayaku Co., Ltd.) and the like. Further, the dye is uniformly dispersed in the polymer composition, that is, it is not particularly limited, but because it has good compatibility with the polymer composition of the present invention, the oil-soluble dye (various CI solvent dyes) ) is widely used. Specific examples of the oil-soluble dye include various C.I. solvent dyes described in Color Index vol. 3 of The Society of Dyers and Colourists. Further, the organic pigment may, for example, be a diarylide pigment such as Pigment Red 38; an azo lake system such as Pigment Red 48: 2, Pigment Red 53 or Pigment Red 57: 1. Pigment; Pigment Red 144, Pigment Red 166, Pigment Red 220, Pigment Red 221, Pigment Red 248, etc. condensed azo pigment; Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208, etc. Benzimidazolone pigment; quinacridone pigment such as Pigment Red 122; Pigment Red 149, Pigment Red 178, Pigment Red 179, etc. Perylene pigment, Pigment Red 177 201005025, etc. It is a pigment. Further, the inorganic pigment may, for example, be titanium oxide, carbon black, dan, chrome red, molybdenum red, lead yellow, iron oxide or the like. However, when a molded article is produced by using the polymer composition of the present invention, when it is necessary to color the molded body, both the dye and the pigment can be used in the object of the present invention. In addition, since the ultraviolet ray absorbing agent also has a yellow to red color, the near-infrared ray absorbing agent also has a black color. Therefore, it is necessary to strictly distinguish the dye from the dye, and the combination is also used. No problem. Further, the lubricant may be a vinegar of an aliphatic alcohol or a polyhydric alcohol such as a panialested organic compound or an inorganic fine particle. Examples of the organic compound include, for example, 'monostearic acid glycoside, monolauric acid glycerin vinegar, and distearyl ester. Acid glyceride, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, etc. ❹ In addition, inorganic fine particles can be generally used for other lubricants, that is, inorganic microparticles can be, for example, a cycle. Oxides, sulfides, hydroxides, nitrides, sulphides, carbonates, sulfates, acetates, phosphates, phosphites, organics of the lan, 2, 4, and 6-14 elements of the table a hydrate of a citrate, a citrate, a titanate, a borate or the like, a fine compound such as a composite compound or a natural compound centered thereon, etc. Further, for the plasticizer, for example, triphenyl phenyl phosphate, Stele acid = ' ^ \--- toluene) ester, triphenyl phosphate, triethyl phenyl phosphate, diphenyl cresyl phosphate, and male acid monophenyl dimethyl station | this S (monophenyl dieresyl Pho Sphate), diphenyl monoxylenyl phosphate, acid monophenyl di(diphenyl) 27 201005025 ester, tributyl phosphate, triethyl phosphate, etc. Plasticizer; dinonyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, dioctyl phthalate (di-2) -ethylhexyl phthalate), diisononyl phthalate, octyl sulfonate phthalate, butyl benzoic acid butyl vinegar, phthalic acid, etc. Vinegar, early oleic acid glycerin S special acid, monophatic acid ester, plasticizer, glycol ester plasticizer, oxoester plasticizer, etc. A plasticizer is preferred, and triphenyl phenyl phosphate and tris(diphenylene) phosphate are particularly suitable. Further, specific examples of the plasticizer include, for example, squalane (C30H62,

Mw=422.8), liquid paraffin (white oil, ISO VG10, ISO VG15, ISO VG32, ISO VG68, ISO VG100, ISO VG8 and ISO VG21 as specified in JIS-K-2231), polyisobutylene, hydrogenated polybutane Alkene, hydrogenated polyisoprene, and the like. Among them, squalane, liquid paraffin, and polyisobutylene are preferred. Further, examples of the antistatic agent include long-chain alkanols such as stearyl alcohol and behenyl alcohol, and polyhydric alcohols such as glyceryl monostearate and pentaerythritol monostearate. The fatty acid S is intended to be particularly suitable as stearyl alcohol or behenyl alcohol. These may be used singly or in combination of two or more kinds, and the ratio may be appropriately selected within the range not impairing the object of the present invention. The amount thereof is preferably from 0.001 to 5 parts by mass, based on the total amount of the non-pinene polymer and the aromatic vinyl block copolymer: 100 parts by mass, preferably in the range of 001 to 1 part by mass. 28 201005025 The polymer composition according to the present invention is obtained by mixing and mixing the above-mentioned lu-masking polymer, aromatic vinyl segment copolymer, and ginseng-mixing agent in a predetermined ratio; The total light transmittance of the polymer composition (measured according to JIS_K 7361-1' for a test piece having a thickness of 〇·5_) is 70% or more, preferably more than or equal to the above. At the same time, the preparation of the polymer composition is preferably made of a polymer composition according to JIS-K-736^, and the izod impact strength is preferably 4.0 kJ/m2 or more, 5 〇kj/ The work above 2 is better ' l〇.〇kJ/m2 or better. There is no particular limitation on the mixing method of m & the latter, 3~ decene, etc., and it is possible to use a biaxial kneader, a man-machine, or the like to melt-mix or dissolve or disperse it. : The agent's method (for example, heptane, cyclohexane, methyl bromide, xylene, etc.). The polymer composition obtained by using such a treatment can be formed into a film. The molding method can be carried out according to a method known in the art, and examples thereof include injection molding, extrusion molding, extrusion blow molding, and injection blow molding. Forming multilayer blow molding, connection blow molding, double wall molding, stretch blow molding, vacuum forming, rotary forming, etc., particularly preferably injection molding and extrusion molding. The molded article obtained by the above treatment is suitably used for an optical film, a lens film, and an optical substrate because it has excellent heat resistance, low water absorbability, light weight, and excellent impact resistance and transparency. An optical molded body such as a material, a substrate material, a diffusing plate, or a light guide plate, or a transparent material for building materials, and can be applied to an insulating molded body for medical use, electric power, and electronic equipment 29 201005025, and medical related equipment. Wait. EXAMPLES The following examples are intended to illustrate the invention, but are not to be construed as limiting the invention. In the present invention, the present invention is not limited to the specific embodiments described above, and various changes, modifications, and improvements may be added without departing from the gist of the present invention based on the knowledge of those skilled in the art. Etc. This should be understood. First, the hydrogen halide (H1) and the seven aromatic ethylenic block copolymers (S1 to S7) were synthesized in the following order. Further, the physical properties of each of the obtained non-pinene polymer hydride and seven kinds of aromatic vinyl block copolymers were measured by the following methods. - Molecular weight - The number average molecular weight and the weight average molecular weight are determined by polystyrene conversion by gel permeation chromatography (GPC). Gpc device Using HLC-8020 (product number) manufactured by TOSOH Co., the column is connected by two TSK gel.GMH-M and one G2000H ® manufactured by TOSOH Co., Ltd. in series. _Nitration rate - From the H-NMP spectrum, the reduction rate (%) of the olefinic double bond proton (4 to 6 Ppm) of the raw material resin is used to calculate the hydrogenation rate {([the number of dilute smoky double bonds] / [the number of olefinic double bonds in the polymer before hydrogenation]) χΐ〇〇 (10) - glass transition temperature (Tg) - using a sample that is sufficiently dried to remove the solvent, using differential scanning heat 30 201005025 assay (DSC), Sakizaki. First, it starts at 25 °C under the nitrogen flow of nitrogen/min. (: / / the heating rate is heated to 2 〇 (rc until 'Get DSC curve. Then 'use the song residue obtained, as shown in Figure 1, through its central tangent _ before the transfer of the baseline c The intersection point, the parallel line E parallel to the temperature axis, and the parallel line F parallel to the temperature axis through the central tangent line B and the parent point of the transferred baseline D. In the present specification, the two parallel lines are halved. The temperature A of the parallel line G of the lines E and F and the parent point of the DSC curve is taken as the glass transition temperature (Tg). Further, the measuring apparatus uses DSC30 (product number) manufactured by Mettler-Toledo International Inc. - Refractive index - using ATAGO CR-M2 (product number) manufactured by CO·, LTD., JIS-K-7142' is measured under conditions of 25. (%: specific gravity _ according to JIS-K-7112: A method of 1999. Synthesis of /3-pinene polymer hydride (H1)> In a fully dried glass stoppered flask, after the inside thereof was sufficiently substituted with nitrogen, dehydrated N-hexane was added to the flask. : 184 parts by mass, dehydrated di-gas methane: 210 parts by mass, dehydrated diethyl ether: 0.5 mass minutes, cooled _78 ° C. The mixture was stirred at -78 ° C while further adding a hexane solution of di-aluminum aluminum (concentration: l. 〇mol / L): 7.2 parts by mass. Next, the flask was kept at -78 At a temperature of °C, a solution of p-dicumyl chloride (concentration: 〇·1 mol/L) was added: 3.0 mass minutes, it was changed to a red color. After the terpene: 60 parts by mass, when it is added to the flask for 1 hour, it gradually turns into a thick red light, 31 201005025 The viscosity of the solution rises. After the addition of 泠-decene is completed, methanol is added: 3 〇 mass minutes' The aqueous solution formed by adding citric acid: 5 parts by mass to the flask was added to the flask, and after stirring for 5 minutes, the aqueous layer was extracted, and distilled water was added until the water layer was neutral, and then washed. The aluminum compound was removed, and the obtained organic layer was reprecipitated in a mixed solvent of methanol/acetone (5 〇/5 〇v〇l%) in 5000 parts by mass, and then sufficiently dried to obtain a styrene polymer (A1). : 60 parts by mass. Weight average molecular weight of the obtained ten-terpene polymer (A1) 116000, the number average molecular weight is 51 〇〇〇, and the glass transition temperature is 95 ° C. _ In a pressure vessel equipped with a stirring device substituted with nitrogen, cyclohexane: 70 mass minutes and as described above The non-terpene polymer (A1) obtained by the treatment: 30 mass minutes 'by stirring, the terpene polymer (A1) is completely dissolved in cyclohexanol. Then, in the cyclohexane solution, it is added as hydrogenation. 5% palladium-loaded alumina (manufactured by NE Chemcat) of a catalyst: 30 parts by mass, stirred and sufficiently dispersed, and the inside of the pressure vessel was replaced with sufficient hydrogen. Thereafter, the mixture was stirred in a vessel at 100 rpm, and reacted for 6 hours under the conditions of rc, hydrogen pressure: 40 kgf/cm 2 , and then returned to normal pressure. Further, cyclohexane: 200 was added to the solution after the reaction. After the mass fraction is diluted, it is filtered through a Teflon (registered trademark) transition apparatus of 〇·5 μηι, and then the catalyst is separated and removed. The obtained liquid is mixed in a methanol/acetone (50/50 vol%) solvent: 5000 mass. After reprecipitation in a portion, it was sufficiently dried to obtain a hydride of wan-terpene polymer (H1): 29 parts by mass. Further, hydrogenation of /3-pinene polymer hydride (H1) obtained by iH_NMR calculation The rate was 99.9%, the weight average molecular weight was 112,000, the number average molecular weight was 5〇8〇〇, the glass transition temperature was 32 201005025 130° C., the refractive index was 1.501, and the specific gravity was 0.930. Then, using a twin screw extruder (material) Cartridge temperature: 180 ° C), granules of /3-decene polymer hydride (H1) were produced. <Synthesis of aromatic vinyl-based block copolymer (S1)> Withstand voltage with stirring device In the vessel, add cyclohexane: 50kg, fully dehydrated styrene: 1000g, and sec-but Base lithium lithium cyclohexane solution (concentration: 10% by mass): 210 g, reacted at 60 ° C for 60 minutes to carry out polymerization. Next, a mixture of isoprene and butadiene was added [isoprene: butadiene =50 : 50 (weight ratio)]: 8000, reaction for 60 minutes, further adding styrene: l〇〇〇g' reaction for 60 minutes, polymerization is carried out, and finally methanol is added to stop the reaction, synthesizing styrene-isoprene / a butadiene-styrene type block copolymer (B1). The block copolymer (B1) is hydrogenated with 5 Å/0 palladium and hydrogenated under a hydrogen atmosphere to obtain an aromatic vinyl group. a block copolymer (hydrogenated styrene-isoprene/butadiene-styrene block copolymer, S1). The obtained block copolymer (S1) has a weight average molecular weight of 11 Å, hydrogenated. The rate was 97.5%. The styrene content of the 'block copolymer (S1) (corresponding to the ratio of the aromatic vinyl polymer block in S1) was 20% by mass. Then, a twin screw extruder was used. Cartridge temperature: 200 ° c) and underwater cutter 'Manufacture of particles of aromatic vinyl block copolymer (S1). <Aromatic Synthesis of Group Ethylene-Based Block Copolymer (S2)> In a pressure vessel equipped with a stirring crack, cyclohexane: 50 kg, fully dehydrated stupid ethylene: 1600 g, and sec-butyllithium Cyclohexane solution (concentration: 10% by mass): 210 g, polymerization was carried out at 6 (TC reaction for 60 minutes. Then 'addition of a mixture of isoprene and butadiene [isoprene: butadiene = 5 〇: 50 (by weight)]: 6800 g, after 60 minutes of reaction, further adding benzene 33 201005025

Ethylene: 1600 g, reacted for 60 minutes, and polymerization was carried out. Finally, methanol was added to stop the polymerization, and a block copolymer (B2) of a styrene-isoprene/butadiene-styrene type was synthesized. The block copolymer (B2) was hydrogenated with 5% palladium on carbon and hydrogenated under a hydrogen mist to obtain an aromatic vinyl-based block copolymer (hydrogenated styrene-isoprene/butadiene) Alkene-styrene block copolymer, S2). The obtained block copolymer (S2) had a weight average molecular weight of 170,000 and a hydrogenation rate of 97.5%. Further, the styrene content (corresponding to the ratio of the aromatic vinyl polymer block in 82) of the block copolymer (S2) was 32 mass. /〇. Then, pellets of the aromatic vinyl-based block copolymer (S2) were produced by a twin-screw extruder (cylinder temperature: 200 ° C) and an underwater cutter. <Synthesis of Aromatic Vinyl Block Copolymer (S3)> In a pressure vessel equipped with a scrambler, cyclohexane: 50 kg, fully dehydrated styrene: 650 g, and sec-butyl Lithium cyclohexane solution (concentration: 10% by mass): 210 g 'The reaction was carried out at 60 ° C for 60 minutes to carry out polymerization. Connect

'Adding isoprene: 8700g' reaction for 60 minutes' further adding stupid ethylene: 650g' reaction for 60 minutes, carrying out polymerization, and finally adding methanol to stop the polymerization, synthesis of styrene-isoprene-phenylene Type block copolymer (B3). The block copolymer is hydrogenated with 5% palladium on carbon and hydrogenated under hydrogen zero to obtain an aromatic vinyl block copolymer (hydrogenated stupid-isoprene-styrene embedded) Segment copolymer, S3). The obtained block copolymer (S3) had a weight average molecular weight of 90,000' and a hydrogenation ratio of 97.5%. Further, the styrene content (corresponding to the ratio of the aromatic vinyl group & block in S3) of the block copolymer (S3) was 13 mass. /〇. Then, the particles of the aromatic vinyl-based block 34 201005025 polymer (S3) were produced by a twin-screw extruder (barrel temperature: 200 ° C) and an underwater cutter. &lt;Synthesis of Aromatic Vinyl Block Copolymer (S4)&gt; In a pressure vessel equipped with a stirring device, cyclohexane: 50 kg, fully dehydrated styrene: 1400 g, and sec-butyllithium were added. a cyclohexane solution (concentration: 10% by mass) 21 (^, reacted at 60 ° C for 40 minutes to carry out polymerization. Next, a mixture of isoprene and butyl dichloride was added [Isopentadiene: Dicedix = 50 : 50 (weight ratio)]: 7200 g, reaction for 40 minutes, further adding styrene: 1400 g, reacting for 40 minutes, carrying out polymerization, and finally adding methanol to stop the polymerization, ® synthesizing styrene-isoprene / butadiene - a styrene-type block copolymer (B4). The block copolymer (B4) is hydrogenated with a 5% palladium-supported carbon and hydrogenated under a hydrogen mist to obtain an aromatic vinyl-based block copolymer. (hydrogenated styrene-isoprene/butylene-styrene-styrene copolymer, S4). The obtained block copolymer (S4) has a weight average molecular weight of 600 Å and a hydrogenation rate of 97.5/ In addition, the styrene content of the block copolymer (S4) (corresponding to the ratio of the aromatic vinyl polymer block in μ) is 28% by mass. Then, a pellet of an aromatic vinyl® base block copolymer (S1) was produced by a twin-screw extruder (cylinder temperature: 200 Torr. and an underwater cutter). &lt;Aromatic vinyl block copolymerization Synthesis of the substance (S5) &gt; In a financial container equipped with a sand-drop device, cyclohexane: 5 〇 kg, fully dehydrated styrene: 1500 g, and a solution of sec-butyllithium in cyclohexane (concentration) : 10 mass %) 210 g, at 60. (: reaction was carried out for 60 minutes, then polymerization was carried out. Then, isoprene: 7000 g of reaction was added for 60 minutes, and then stupid ethylene: i5 〇〇g was added, and the reaction was carried out for 60 minutes to carry out polymerization. Finally, methanol was added to stop the polymerization, and a styrene-isoprene-styrene type block copolymer (B5) was synthesized. The block 35 201005025 copolymer (B5) was loaded with carbon with 5% palladium in hydrogen mist. Hydrogenation under a gas atmosphere to obtain an aromatic vinyl-based segment copolymer (hydrogenated styrene-isoindole di-styrene block copolymer, S5). The obtained block copolymer (S5) The weight average molecular weight is 90,000, and the hydrogenation rate is 97.5%. In addition, the styrene content of the segmented copolymer (S5) (equivalent to the fragrance in S5) The ratio of the vinyl polymer block is 30 mass%. Then, the aromatic vinyl block copolymer is produced by a twin-screw extruder (cylinder temperature: 2 Torr. 〇 and underwater cutter). (S1) granules. <Synthesis of aromatic vinyl-based block copolymer (S6)&gt; In a pressure vessel equipped with a stirring device, cyclohexane: 50 kg, _ fully dehydrated styrene: 2000 g And a cyclohexane solution of sec-butyllithium (concentration: 1% by mass) 21 (^, which was reacted at 60 ° C for 60 minutes to carry out polymerization. Next, a mixture of isoprene and butadiene [isoprene: butadiene = 5 〇: 5 〇 (weight ratio)]: 6000 g, reaction for 60 minutes, further adding styrene: 2000 g, reaction for 60 minutes The polymerization was carried out, and finally methanol was added to stop the polymerization, and a styrene-isoprene/butadiene-styrene type block copolymer (B6) was synthesized. The block copolymer (B6) was hydrogenated with 5% palladium on carbon and hydrogenated under a hydrogen mist to obtain an aromatic vinyl-based block copolymer (hydrogenated alum ethylene-isoprene/ Butadiene-styrene block copolymer, S6). The obtained block copolymer (S6) had a weight average molecular weight of 90,000 and a hydrogenation ratio of 97.5%. Further, the styrene content (corresponding to the ratio of the aromatic vinyl polymer block in S6) of the block copolymer (S6) was 40% by mass. Then, a pellet of an aromatic vinyl-based block copolymer (S6) was produced by a twin-screw extruder (cylinder temperature: 200 Torr. and an underwater cutter). &lt;Aromatic vinyl-based block copolymer Synthesis of (S7) 36 Futsubs. : 1 〇 mass %) 210 §, at 60. (: 120 minutes of reaction, polymerization was carried out. Then, a mixture of isoprene and butadiene was added [Isopentadiene: Dingdi = 5 〇: 5 〇 ( Weight ratio)]: 6000 g, reaction for 120 minutes, further adding styrene: 200 〇g 'reaction for 120 minutes, carrying out polymerization, and finally adding sterol to stop the polymerization' synthesis of styrene-isoprene/butadiene-styrene Type block copolymer (B7). The block copolymer (B7) is hydrogenated under a hydrogen mist by using 5 wt. palladium-supported carbon to obtain aromatic vinyl block copolymerization. Weight average of the I-segment copolymer (S7) obtained from hydrogenated styrene-isoprene/butadiene-styrene block copolymer, S7)e The amount of styrene (corresponding to the ratio of the aromatic vinyl polymer block in the block) of the block copolymer (S7) was 30% by mass. Then, the amount of the block copolymer (S7) was 30% by mass. An extruder (cylinder temperature: 20 (TC) and an underwater cutter to produce particles of an aromatic vinyl-based block copolymer (S7). The non-terpene polymer hydride obtained by the above treatment was used. (H1) and the aromatic vinyl-based block copolymers (S1 to S7) were subjected to the following experiment. Further, the physical properties of the respective molded articles obtained in the examples and the comparative examples below were The physical properties other than the specific gravity were measured by the following methods and evaluated according to the following method: - Izod impact strength - JIS-K-7110, using a molded article having a thickness of 3 mm (with a The measurement was carried out under the conditions of 25 ° C and humidity: 40%. Here, the Toyo Seiki Co., Ltd., digital impact tester 37 201005025 DG-UB (product number) was used as a measuring device. -Flexural modulus of elasticity - the standard JIS-K_7171, A test piece having a thickness of 3 mm was used as a test piece, and the measurement was carried out under the conditions of a humidity of 40% at 25 ° C. Here, Autograph AG-5000 (product number), manufactured by Izumi Corporation, Shimadzu Corporation, was used. (deflection temperature under load) ~ According to JIS-K-719, 1, 2, under the condition of 1.8 MPa, using ^〇τ VSPT, TESTER S-3M (product number; manufactured by Toyo Seiki Seisakusho Co., Ltd.) . _Full light transmittance - ◎ The total light transmittance of the molded article having a thickness of 0.5 mm was measured by HR_1〇〇, JIS-K-7361-1, manufactured by Murakami Color Research Laboratory Co., Ltd. ' - Water absorption rate - Length obtained by pressure forming: 140 mm x width: 6 〇 m Kiss thickness: 0.8 mm of the plate-shaped formed body placed under 6 (rc, 9 〇 % RH fog atmosphere, in contrast to The mass increase ratio of the initial mass is taken as the water absorption rate (%). Day, 〇 water absorption rate (%) = (increased mass / initial mass) X 100 &lt;Example 1&gt; Point-蒎 dilute polymer hydride (H Bu Refractive index: 丨5〇1) 85 parts by mass, hydrogenated styrene-isopentadiene/butadiene. Stupid MS block copolymer =, styrene content mass%, weight average molecular weight __5 mass points, By using a melt kneader (product name manufactured by Toyo Seiki Seisakusho Co., Ltd., LABOPLASTMILL), the polymer composition was obtained by mixing the polymer composition at a temperature of 100 rpm and 23 Torr at a rate of 38 minutes. The predetermined shape was formed, and various physical properties of the obtained molded body were measured. The results are shown in Table 1 below. <Example 2> In addition to hydrogenated styrene-isoprene/butadiene-styrene block copolymerization (S2, styrene content: 32% by mass, weight average molecular weight 170,000) instead of deuterated styrene-different The polymer composition was obtained in the same manner as in Example 1 except that the pentane dilute/butylene-styrene-based copolymer (S1) was used. The polymer composition was pressed to form a predetermined shape, and the obtained product was obtained. The physical properties of the molded article are shown in the following Table 1. <Comparative Example 1> Only the /3 -thracene dilute polymer hydrogenated product (H1) was pressed into a predetermined shape, and various physical properties of the obtained molded body were measured. The results are shown in the following Table 1. <Comparative Example 2> In addition to the hydrogenated stupid ethylene-isoprene-styrene block copolymer (S3, styrene content: 13 mass%, weight average molecular weight) In the same manner as in Example 1, except that the hydrogenated styrene-isoprene/butadiene-styrene block copolymer (S1) was replaced, a polymer composition was obtained. The composition was pressed to form a predetermined shape, and various physical properties of the obtained molded body were measured. The results are shown in Table 1 below. <Comparative Example 3> In addition to hydrogenated styrene 'isoprene/butadiene-styrene Segment copolymer (S4, styrene content: 28% by mass, weight average molecular weight 60000) The hydrogenated styrene-isoprene/butadiene-styrene-ethylene block copolymer (S1) 39 201005025 was treated in the same manner as in Example 1 to obtain a polymer composition. The polymer composition was pressurized. The predetermined shape was formed, and various physical properties of the obtained molded body were measured. The results are shown in Table 1 below. <Comparative Example 4> In addition to hydrogenated stupid ethylene-isoprene-stupid ethylene block copolymer (S5, styrene content) : 30 mass % 'weight average molecular weight 90000', except the argon styrene-isoprene / butadiene-styrene block copolymer (Si) except the same as Example 1, the polymer composition was obtained. . The polymer composition was pressed to form a predetermined shape, and various properties of the obtained molded body were measured. The results are shown in Table 1 below. &lt;Comparative Example 5&gt; In addition to hydrogenated acetophenone-isoprene/butylene-styrene block copolymer (S1), 15 parts by mass was hydrogenated styrene-isoprene-styrene block A polymer composition was obtained in the same manner as in Example 1 except that the copolymer (S5 'styrene content: 30% by mass, weight average molecular weight: 90,000) was substituted at 45 parts by mass. The polymer composition was pressed to form a predetermined shape, and various physical properties of the obtained molded body were measured. The results are shown in the following table. 〇&lt;Comparative Example 6&gt; In addition to hydrogenated acetamidine-isopentadiene/butyrene-styrene-segmented copolymer (S1), weathered this ethylene-isotery·one thin/dilute woman'&quot; The obtained polymer composition was treated in the same manner as in Example 1 except that the styrene block block-polymer (S6, styrene content: 40% by mass, weight average molecular weight: 1 〇〇) was substituted. The polymer composition was pressed to form a predetermined shape, and various physical properties of the obtained molded body were measured. The results are shown in Table 1 below. 40 201005025 &lt;Comparative Example 7&gt; In addition to hydrogen, the styrene-isoprene/butylene-benzene dilute segment copolymer (S1) is hydrogenated styrene-isoprene/butadiene styrene. Block this polymer (S7, benzene age: 3GfK, "average molecular other than substitution" is treated in the same manner as in Example 1; since it is difficult to uniformly mix when the polymer composition is prepared, it is interrupted [Table 1] From Table 1, it can be confirmed that, as in the present invention, a polymer composition formed by mixing a predetermined amount of an aromatic vinyl-based block copolymer in a boron-nitride polymer nitride (Solution 1~) 2) 1% of the compound will have excellent impact resistance of 5kJ/m2 or more, and the content of styrene in the aromatic vinyl-based segmental copolymer (corresponding to the aromatic in the block copolymer) The ratio of the group of vinyl group polymers is 1 G to 25 f% of the polymer composition (Example 1), and since the molded body obtained by the same has excellent transparency, it can be confirmed that it can be advantageous. The optical part requiring impact resistance is used. In addition, the mixing of 'aromatic vinyl block copolymers In the case of Comparative Example 5 in which the amount is 45% by mass, although the impact resistance is shown to be close to the value of Example 2, the bending elastic modulus and the load deformation temperature become undesirable, and it is understood that the polymer composition of the present invention is used. The formed molded body does not have a large bending elastic modulus and a load deformation temperature, and exhibits excellent impact resistance. 201005025 Comparative Example 7 280000 1.506 - 1 1 1 1 1 Comparative Example 6 in 〇100000 1.508 1800 »T) 00 0.93 &lt;0.1 Comparative Example 5 90000 1.506 〇800 ITi 0.92 &lt;0.1 Comparative Example 4 90000 1.506 1-Η (Ν 1800 ss 0.93 &lt;0.1 Comparative Example 3 00 (N 60000 1.504 in rn 1700 00 0.93 &lt;0.1 Comparative Example 2 m 90000 1.488 Ο fO 1700 tQ 0.93 &lt; 0.1 Comparative Example 1 1 1 1 1 1 rn 2500 〇 1-1 (N CTn 0.93 &lt; 0.1 Example 2 CN m 170000 ! 1.507 CTn 1700 0.93 &lt;;0.1 Example 1 110000 1.495 inch 1800 in oo 0.93 &lt;0.1 Styrene content [% by mass] Weight average molecular weight refractive index mixing amount [mass point] Cantilever beam impact strength [kJ/m2] Bending elastic system [MPa] i lean .Im.l ~ 1 ~ ^ - Total Light Transmittance [%] gravity Water absorption [° / square]

42 201005025 , * [Simple description of the drawing 3 Fig. 1 is an explanatory diagram showing a method of calculating the glass transition temperature in the embodiment from the DSC curve. [Main component symbol description] A...glass transition temperature B...central tangent C...pre-transition baseline D...post-transition baseline® E...through the intersection of B and C and parallel to the parallel axis of the temperature axis...through the intersection of B and D and parallel Parallel line G of the temperature axis... parallel line E, F 2 bisector Lu 43

Claims (1)

201005025 VII. Patent application scope: 1' kind of polymer composition, which is characterized by: a) a specific gravity of 0 85 or less and a glass transition temperature of 8 (rc or more of cold-terpene polymer and 'b) The aromatic vinyl polymer block is 1 〇 to 35 mass. /. And an aromatic vinyl-based block copolymer having a weight average molecular weight of 100,000 to 250,000 and a hydrogenated conjugated diene polymer block of from 65 to 90% by mass, and the a) component of 60 to 95 parts by mass and the b The components are mixed in a ratio of 5 to 40 parts by mass, and the total amount of the components a) and b) is 1 mass%. The polymer composition according to claim 1, wherein the above-mentioned oxime-terpene polymer is a perhydrogenated product, and ([hydrogenated olefinic double bond number] / [hydrogenated polymer] The value of the olefinic double bond number]) xl00 is 95% or more. 3. The polymer composition according to claim 1, wherein the aromatic vinyl-based block copolymer is polymerized from 10 to 25% by mass of the aromatic vinyl polymer block, and the hydrogenated conjugated diene is polymerized. The mass of the block is 75 to 90 | Q is % formed. 4. The polymer composition according to claim 1, wherein the total light transmittance is 80% or more. 5. A molded article obtained by using the polymer composition as described in claim 1 of the patent application. 44