TWI225505B - Modified block copolymer composition - Google Patents

Abstract

The present invention obtains a modified block copolymer composition having excellent mechanical strength, compression set, impact resistance and processability. This block copolymer composition is characterized in that at least one atomic group having at least one functional group selected from hydroxy group, epoxy group, amino group, silanol group and an alkoxysilane is bound to a polymer block A and/or a polymer block B in the block copolymer composition comprising (1) 100 pts. Mass of a block copolymer or its hydrogenated substance composed of at least the one polymer block A consisting essentially of a vinyl aromatic hydrocarbon and at least the one polymer block B consisting essentially of a conjugated diene and having 5-95 wt.% vinyl aromatic hydrocarbon content and (2) 0.5-50 pts. Mass of a silica inorganic filler or/and a metal oxide.

Description

1225505 A7 B7 V. Description of the invention The present invention relates to a modified block copolymer or a hydride containing a functional group selected from the group consisting of an aromatic hydrocarbon of ethylene and a conjugated diene, and a silica-based inorganic filler. A group of fillers made of additives, metal oxides and metal hydroxides, and thermoplastic modified block copolymer compositions. In the advanced technology, the research of high-performance and high-performance polymer materials is carried out by combining polymer alloy technology of different kinds of organic polymers. For example, it is a soft material with rubber properties, a thermoplastic elastomer composition that is unnecessary for the vulcanization step, or a thermoplastic resin composition with good molding processability and recyclability is used for automotive parts, home appliance parts, and wire coating , Medical parts, footwear, miscellaneous goods and other fields. As thermoplastic elastomers and thermoplastic resins, various types of polyolefins, polyurethanes, polyesters, and polystyrenes have been developed and marketed. Among them, styrene-butadiene block copolymer, or styrene. Please read the precautions on the back and then fill in this page. Binding of the Ministry of Economic Affairs Intellectual Property Bureau Employee Consumer Cooperative printed pentadiene and its content is low. Obtained, can be obtained in food and so on. However, depending on the type of ethylene aromatic hydrocarbon-conjugated diene block copolymerized hydride (hereinafter also referred to as "hydrogenated block copolymer"), such as isoblock copolymer, etc., styrene is 'flexible' at room temperature. The bottom shows good rubber elasticity, so the composition has good moldability. In addition, thermoplastic resins that are transparent when there is a large amount of styrene and have good impact resistance are used in packaging containers, home appliances, industrial parts, household goods, and toys. The functions achieved only by organic polymer materials have their characteristics. Different combinations of organic polymer materials and inorganic materials are used in the industry. The year 2000 is published in 59-1 3 1 6 1 3 and is disclosed in hydrogen.

Size of this paper _ Home Standard (CNS) A4 (27 ^ 7 ^ iT -4- 1225505 A7 B7 V. Description of the invention (2) (Please read the precautions on the back before filling this page) { The organic-peroxide and cross-linking assistant are used to partially cross-link the elastomer-like composition blended with the hydrocarbon-based oil, olefin-based polymer, and inorganic filler to 'improve the permanent compression deviation of the elastomer-like composition. Japanese Unexamined Patent Application Publication No. 10-585 0 98 discloses a highly conductive resin composition made of a polydiphenyl ether resin, a hydrogenated block copolymer, and a conductive inorganic filler. Japanese Unexamined Patent Publication No. 2 0 1-7 2 8 5 discloses a thermoplastic resin composition having good moisture absorption and vibration suppression properties by blending polycarbonate resin, styrene-butadiene block copolymer, and ceramic hollow body. . However, the composition of the thermoplastic block copolymer and the inorganic filler is one of a hydrophobic organic substance and the other is a hydrophilic inorganic substance. Therefore, the mutual affinity is low and the kneading property is poor, and the expected improvement cannot be effectively obtained. Effect: Intellectual Property of the Ministry of Economic Affairs Printed by employee consumer cooperatives Therefore, as a method to improve the affinity between thermoplastic block copolymers and heterogeneous materials was proposed to attach functional thermoplastic-based block copolymers, such as: Special Publication 6 2 — 5 4 1 3 8 The composition disclosed in Japanese Laid-Open Patent Publication and Japanese Patent Publication No. 6 2-5 4 1 4 0 is that the maleic anhydride is added to the mutual block copolymer of an ethylene aromatic hydrocarbon group and a conjugated diene compound to improve the affinity with anhydrous filling materials. In addition, JP 4-3 9 49 5, JP 4-2 8 0 34, and JP 4-3 8 7 7 7 are disclosed as having functional groups based on vinyl aromatic hydrocarbon groups. A composition that improves the mutual affinity of thermoplastic resins, adhesives, resins, and asphalt after the ends of conjugated diene compound mutual block copolymers. This paper size applies the Chinese National Standard (CNS) A4 specification (21〇 ×; 297mm) -5-! 2255〇5 Μ ___ _____B7 V. Description of the Invention (?) In this case, the composition of ethylene aromatic hydrocarbon-conjugated diene block copolymer or its hydride and inorganic filler is used. Things are even more expected to mention A high-performance, high-performance material that can more effectively exert mutual functions and characteristics. [Invention of Invention] As a result of various investigations to solve the problem, the inventor found that a specific structure containing a specific amount of (1) a specific functional group The modified block copolymer or its hydride and (2) a composition selected from the group consisting of siloxane-based inorganic fillers, metal oxides, and metal hydroxides have good heat resistance and mechanical properties. The present invention has completed the present invention in terms of physical strength, transparency, abrasion resistance, and processability. That is, the present invention is as described below. [1] Polymer block containing (1) ethylene aromatic hydrocarbon group as a main component A modified block copolymer or its hydride formed by the polymer block b composed of A and a conjugated diene, and (2) selected from the group consisting of a silica-based anhydrous filler, a metal oxide, and a metal oxide For the group of modified block copolymer composition of the tritium filler, the end of the molecular chain (1) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is selected from the group consisting of hydroxyl, epoxy, amine and silicon Alcohol and alkoxysilyl groups If the base bond has at least one functional group, the content of the vinyl aromatic hydrocarbon group in the component (1) is 5-95% by weight, and the amount of the component (2) is 100 parts by weight of the component (1). In the case of ~ 50 parts by weight, the average dispersed particle diameter of the component (2) is 0 · 0 1 to 2 // m in the modified block copolymer composition. [2] More (3) olefin-based polymer ingredients (3) 100 to 500 parts by weight (1) 10 to 500 parts by weight [This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) 1225505 A7 B7 V. Description of the invention f) 1) The modified block copolymer composition contained in 1). [3] The modified block copolymer composition contained in [1] or [2] in which the ethylene aromatic hydrocarbon group block ratio is 50% or more of the total ethylene aromatic hydrocarbon group in component (1) ° [4] 〕 The component (1) is a hydride of the modified embedded polymer. The hydride has a hydrogenation rate of more than 10%. The amide is derived from a total of two; Those who suspect that the proportion of the constituent unit is within the range of 10 to 8 5%, and that 1,20 = (: the proportion of unit unit is 15% or less of the revised [1] or [2] [5] The bond at the end of the molecular chain of the component (1) is selected from the group consisting of [1] or [2] in the functional group grouped by the following formulas (1) to (4). Modified block copolymer composition.

-NR9—R10——〇H (1) Please read the winter items

-N [R10——OH]-(2) NR9—R10—CH—CHR11…-(3) 〇 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

• N [R 10 • CH—CHR11] —— (4) 〇- This paper size is applicable to China National Standards (CNS) A4 specifications (210X297 mm) 4 ^ ο 5 5 2 2 A7 B7 V. Description of the invention CR9 —R10—NR11R12

OH (5) -C—NR9—R10—NR11R12 〇 (6) -C—RII 〇 10 -NR11R12 (7) Please read it first -CR9——NR11—R10—NR13R14…-(8)

OH CR9——R10—NR11R12 OH —NR9—R10—Si (OR11) 3 -N [R10—Si (OR11) 3] (9) (10) (11) i

f

• CR9—R10—OR11 I OH (12)

-CR9—R10—Si (OR11) OH • (13) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 〇R10—Si (〇R11) 3… (14) (Equations (1) to (14), R9 and R12 to R14 are those having a functional group selected from the group consisting of hydrogen, a hydrocarbon group having 1 to 24 carbon atoms, or a hydroxyl group, epoxy group, silanol group, and alkoxysilyl group having 1 to 24 carbon atoms. , R1C) is a hydrocarbon-based chain selected from a carbon number of 1 to 30, or a hydroxyl or epoxy base paper. Applicable to China National Standard (CNS) A4 specifications (210X297 mm) -8-1225505 A7 B7 V. Description of the invention ( 6) Hydrocarbon chain having 1 to 30 carbon atoms in the functional group formed by the silane group and the alkoxysilyl group. In addition, the hydrocarbon groups of R9 and R12 to R14 and the hydrocarbon chain have a bonding state other than a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilyl group, and elements such as oxygen, nitrogen, and silicon may also be bonded. In addition, R 1 1 is hydrogen or an alkyl group having 1 to 8 carbon atoms. ) [6] The end of the molecular chain of the component (1) is selected from the functional groups grouped by the following formulas (1) to 9). If you read [1] or [2], please read the δ Attention block copolymer composition

NR9—R10—OH item

f Install N [R10——OH] 2 (2) -NR9——R10—CH—CHR11 (3) Order —N [R10—CH—CHR11h ⑷

• CR9—R10—NR11R12 I OH (5) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 11n12 —C—NR9——R10——NRMRII 〇-C—R10—NR11R12 ---- (6) (7) This Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -9- 1225505 A7 B7 V. Description of invention 13r > 14

• CR9—NR11—R10—NR13R I OH (8)

-CR9—R10—NR11R12 I OH (9) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (Formulas (1) to (9), feet 9, and 1 ^ 12 to 1 ^ 14 are selected from hydrogen and carbon numbers A hydrocarbon group of 1 to 2 or a functional group consisting of a hydroxyl group, an epoxy group, and a silanol group having a carbon number of 1 to 2 4 'R1C) is a hydrocarbon chain selected from a carbon number of 1 to 30, or Hydroxyl, epoxy, silanol, and alkoxysilyl groups have 1 to 30 carbon chains in the functional group. In addition, the hydrocarbon groups of R 9, and R12 to R14, and R1. The hydrocarbon chain has a bonding form other than a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilyl group, and may also be bonded to oxygen, nitrogen, silicon, and the like. Elemental. R11 is hydrogen or an alkyl group having 1 to 8 carbon atoms. ) [7] Ingredient (2) is selected from the group consisting of silica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide, forged wool, glass fiber, magnesium hydroxide, and aluminum hydroxide The modified block copolymer composition contained in [1] or [2], which is a group of fillers of magnesium hydrate, aluminum silicate, basic magnesium carbonate, and hydrotalcite. [8] The silane coupling agent is the modified block copolymer composition contained in the [1] or [2] in an amount of 0.1 to 200% by weight based on the amount of the component (2). [The best form of the invention] As mentioned above, the present invention relates to the advantages of composite organic polymers (such as: light weight, flexibility, moldability, etc.) and the advantages of inorganic substances (such as heat resistance and strength, etc.). Material of characteristics. The invention particularly provides a

Please read the note of memorandum first

-10- 1225505 Α7 B7 V. Description of the invention p) A kind containing a block copolymer or a hydride thereof selected from the group consisting of an ethylene aromatic hydrocarbon group and a conjugated diene, and a silicon-based inorganic filler material, and gold. Among the filler compositions composed of oxides and metal hydroxides, those materials with more mutual effects, characteristics, higher performance, and higher performance are found. The modified block copolymer used in the present invention refers to a molecular chain end formed by a polymer block A mainly composed of an ethylene aromatic hydrocarbon group and a polymer block B mainly composed of a conjugated diene. The middle bond is at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amine group, a silanol group, and an alkoxysilyl group. For example, the active end of the block copolymer formed by polymer block A with ethylene aromatic hydrocarbon group as the main component and polymer block B with conjugated diene as the main component is obtained by additional reaction of the denaturant described later. As an example of a modified block copolymer or a hydride thereof, the modified block copolymer obtained by this method has a structure generally shown below. (Α-Β) η ×, (Β-Α) η-χ, A-(Β-A) η-X, Β- (Α-Β) η-χ, printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Χ- (Α-Β) η-χ, χ-Α- (Β-Α) η-χ 'Χ-Β- (Α-Β) η-χ, [(Β-Α) η] "X, [( Α · Β) η] mX, [(BA) rB], This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297mm) -11-1225505 A7 B7 V. Description of invention p)

L (A-B) n-A] m-X In the above formula, A represents a polymer block mainly composed of an ethylene aromatic hydrocarbon group, and B represents a polymer block mainly composed of a conjugated diene. Also, 'n is an integer of 1 or more, and is generally an integer of 1 to 5.' η is an integer of 2 or more, and is generally an integer of 2 to 10. X is a denaturing agent residue to which a functional group described later is bonded. In the present invention, the polymer block A having an ethylene aromatic hydrocarbon group as a main body means that the ethylene aromatic hydrocarbon group is 50% by weight or more, and more preferably, the ethylene aromatic hydrocarbon group contains 70% by weight or more of the ethylene aromatic hydrocarbon group and the co-polymer. For a conjugated diene copolymer block and / or an ethylene aromatic hydrocarbon-based single polymer block, a conjugated diene-based polymer block B means that the conjugated diene is 50% by weight or more. It is more preferable that it contains 60% by weight or more of a conjugated diene and an ethylene aromatic hydrocarbon group mutual copolymer block, and / or a conjugated diene alone polymer block. Among them, the ethylene aromatic hydrocarbon-based units in the copolymer block may be uniformly distributed or tapered. Moreover, a plurality of portions of the 'ethylene aromatic hydrocarbon-based unit in the copolymer block which are uniformly distributed and / or a portion having a tapered distribution may coexist. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Also, the modified block copolymer shown in the general formula of the modified block copolymer used in the present invention may be any mixture. As a method for producing the modified pre-block copolymer (hereinafter also referred to as "block copolymer"), for example, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 49-36 9 57, Japanese Patent Publication No. 48 — 4 Examples of methods are described in JP 06, JP 5 9 — 1 6 6 5 1 8 and the like. -12- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (21 Οχ Μ? Mm) 1225505 Α7 Β7 V. Description of the invention P) (Please read the precautions on the back first and write this page) for the use of this invention Examples of the ethylene aromatic hydrocarbon group include: one or more styrene, o-methylstyrene, p-methylstyrene, p-third-butylstyrene, 1,3-dimethyl Basic styrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, and the like are generally used. As another example of conjugated diene, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1, One or two or more of 3-butadiene, 1,3-pentadiene, 1,3-hexadiene, etc., generally 1,3-butadiene, isoprene, etc. In the present invention, For the solvents used in the manufacture of block copolymers, aliphatic hydrocarbon groups such as butane, pentane, hexane, isopentane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, etc. can be used. Alicyclic hydrocarbon groups such as alkane, cyclohexane, methylcyclohexane, ethylcyclohexane, or aromatic hydrocarbon groups such as benzene, toluene, ethylbenzene, xylene, and the like. These can be used singly or in combination of two or more. The Bureau of Intellectual Property, Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperative), and those who can use organolithium compounds as polymerization initiators for the production of block copolymers. Organolithium compounds refer to those in which one or more lithium atoms are bonded in the molecule. Compounds, such as: ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, hypo-butyllithium, third butyllithium, hexamethylenedilithium, butadienyldilithium, isopropyl Examples of propylene dienyl dilithium, etc. These can be used singly or in combination of two or more. In addition, organolithium compounds can also be added separately during the production of block copolymers. In the present invention, Control the polymerization speed during the manufacture of block copolymers, control the microstructure of the polymerized conjugated diene portion, ethylene aromatic hydrocarbon groups and copolymers_13 This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 1225505 A7 B7 V. Description of the invention (11) Chemical reducing agents for the purpose of controlling the reactivity ratio of olefins, etc. As examples of polar compounds, random, thioethers, phosphines, phosphatidylamines, and alkoxymetals of alkylbenzene. Specific examples are diethyl ether, diphenyl ether, tetrahydrofuran Examples of dibutyl ether. Examples of tertiary amines, tridiamines, other cyclic tertiary amines, etc. of amines. Examples of hexamethylphosphamide, etc. When the block copolymer of the present invention is used, it is better to use ° C, which The best is 30 ~ 12, generally within 4 to 8 hours, preferably. Also, the atmosphere of the polymerization system is made. The polymerization pressure is only required to be in the pressure range of the liquid phase at the polymerization temperature, which is not the best. Be careful not to mix in catalysts and active oxygen, carbonic acid gas, etc. The component (1) hydride used in the present invention is bonded to the amino group, silanol group and alkoxysilyl group or its hydride at the end of the molecular chain. In other words, the method of obtaining the bond is as described above, and the block copolymer is activated, or the functional group is reacted by a known method into the agent. In addition, the hydroxyl group and the amine group can also be used at the stage of the modifier. Examples of chemical agents: Potassium polar compounds of sulfonic acid, random ones such as: ethers, amine salts or sodium salts, potassium or sodium. Please read the following items to order m%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Dimethyl ether glycol dimethyl ether alcohol methylamine, triethylamine, tetramethylethylene The polymerization temperature of triphenylphosphine for phosphine and phosphatidamine is 10 ~ 15 0 t. The polymerization time varies depending on the conditions, especially 0.5 ~ 10 hours for inert gas atmosphere such as nitrogen. The full dimensions of the polymer and the solvent are particularly limited. Furthermore, the polymerized internalized polymer is an inactive impurity, that is, a denatured block copolymer or a denatured block having at least one functional group selected from a hydroxyl group, an epoxy group, and the like. The square end of the denatured block copolymer of the segment copolymer can make the type of the modified modifier contained in the modified state containing the functional group different, and the reaction is an organic metal salt, and this At this time, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -14- 1225505 A7 __B7_ __ V. Description of the invention (12) After treatment with water, alcohol and other active hydrogen compounds, it can be changed For hydroxyl and amine groups. In addition, in the present invention, after the block copolymer's activated end-reaction modifier, the unmodified block copolymer can also be partially mixed. The proportion of the non-denatured block copolymer mixed with the denatured block copolymer is preferably 60% by weight or less, and more preferably 50% by weight or less. As an example of a functional group having at least one functional group selected from a hydroxyl group, an epoxy group, an amine group, a silanol group, and an alkoxysilyl group, for example, the ring is given by the general formula (1) below.

I

(14) Groups of functional groups

• NRa——R10——OH •… ⑴ f N [R10—-〇H] •• (2)

——NR9—R10—CH—CHR11 V (3) —c—R10—NR11R12 〇 (7) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

• CR9—NR11—R10—NR13R14I OH —— · (8) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -15- 1225505 A7 B7 V. Description of the invention 〇3

.CR9—R10—NR ^ R12 OH (9) • NR9—R10—Si (OR11)-(10) N [R10—Si (〇R11) 3] 2-(11) • CR9——R10—〇R11 in (12) Please read it first. (13) Intellectual Property Bureau of the Ministry of Economic Affairs (printed by Industrial and Consumer Cooperatives)

R10—Si (〇R ”) OH O-R10—Si (〇R11) 3 (In the formulae (1) to (14), R19 and R12 to R14 are hydrocarbon groups selected from hydrogen, carbon number 1 to 2 4, Or a hydrocarbon group having 1 to 24 carbon atoms having a functional group in the group consisting of a hydroxyl group, an epoxy group, a salicyl group, and an alkoxysilyl group, R10 has a hydrocarbon chain selected from a carbon number of 1 to 30, or a hydroxyl group, a ring A hydrocarbon chain having 1 to 30 carbon atoms in the functional group group consisting of an oxy group, a silanol group, and an alkoxysilyl group. In addition, a hydrocarbon group of R 9 and R 1 2 to R 1 4 and R 1 ^ The hydrocarbon chain may have a bonding form other than a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilyl group, and may be bonded to oxygen, nitrogen, sand, etc. In addition, R 1 1 is hydrogen or an alkane having 1 to 8 carbon atoms. (). As modifiers used to obtain the modified block copolymer used in the present invention, for example: tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bisaminomethyl Cyclohexane, tetraglycidyl one-to-one diphenyl paper size applicable to Chinese National Standard (CNS) A4 specifications (210X 297 mm)-^ 6 · V. A7 B7 Description of the invention (14) Diamine, tetrashrink Glyceryl diamine diphenylmethane, dishrink , Diglycidyl-toluidine, r-glycidoxytrimethyl, r ~ glycidoxypropyltrimethoxysilane, 7'-epoxy fluorenylmethoxysilane, 7-glycidoxy Propyldiethoxy ~ glycidoxypropyltripropoxysilane, 7-glycidoxybutoxysilane, 7-glycidoxypropyltriphenoxy Methylmethyldimethoxysilane, 7, -glycidoxypropylmethoxy, y-glycidoxypropyl-glycidoxypropylmethyldipropoxysilane, 7-glycidoxypropylmethylsilane, 7'-glycidoxypropylmethyldiphenoxysilane, propoxypropyldimethylmethoxyethoxydiethoxy Silane, ^ monoepoxysilane, ethoxysilane, r-glycidoxy r propyldiethylmethoxyoxysilane, bis (r monocyclic 隹 隹 printed by the Intellectual Property Bureau employee consumer cooperative) T —Epoxypropoxy propyl propyloxy) dipropoxysilyl dimethyl dimethyl phenoxysilane, silane, 7 —glycidoxypropyl) oxy Silane- "oxysilane, bis (7 -, Bis (r-glycidoxypropyl) methylethylsilane, glycidoxypropylpropyl) methylpropoxybutoxysilane, bis-r-cyclotri (7-glycidoxy Propylpropoxypropoxy) diethane, bisglycidyl) methoxysilane bis (oxopropyloxy) methylpropoxylethoxy r —cyclopropylmethyldimethoxybis—glycidyloxy ) Diphenyl sand courtyard, oxypropyl methoxy oleyl aniline oxysilane propoxy butysilane, 7 'propyl tri, r-cycloethyl disila, γ propoxy propylene dibutoxy R-glycidyldiethylsilane, oxypropoxydiisopropylsilane, r-epoxypropyl) oxysilane bis (dioxane, bis (7-epoxypropyloxy) ) Methylpropyl) methylphenoxysilyloxysilane, r-methylpropylene glycidyloxypropylmethylbenzene Paper size applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) _ · Please read the notice on the back first

P i Binding 1225505 A7 B7 V. Description of the invention (15 fluorenylpropyltrimethoxysilane, T-methacrylfluorenylpropyltriethoxy 7-methylpropylfluorenylpropyl) methoxysilyloxy Silane, Sarain '7-methacrylmethylmethyltrimethoxysilane, diethylethyltriethoxysilane, bis (7-methylpropanyltris (r-methacrylmethylpropyl) propyl Methoxysilane β-4-epoxycyclohexyl) ethyl-trimethyl / 3-(3,4-epoxycyclohexyl) ethyl-triethoxysilane, / 3-(3 '4- Epoxycyclohexyl) ethyl-tripropoxysilane, / 3-cyclohexyl) ethyl-tributoxysilane, mono ((3 '4 -epoxy 3' 4 -epoxy ring, 4 —Epoxycyclohexyl 4 -epoxycyclohexyl, 4 monoepoxycyclohexyl 3 ′ 4 —epoxycyclohexyl) yl) propyl) ethyl) ethylhexyl) cyclohexylcyclohexyloxy ring Ethyl-triphenoxy sand-based tri-trimethoxysilane, β (30,000- (3, yl-dimethoxysilane, / 3 — (3 Please read the back δ winter i matters on this page (3 , 4 a epoxy — (3,4 —epoxy / 3 — (3,4 one ring, cold — (3,4 —epoxy epoxy, printed by mono-methyldimethoxysilyl in the Intellectual Property Bureau of the Intellectual Property Bureau, Ministry of Economic Affairs, Employees ’Consumer Cooperatives) Monoethyldimethoxy) ethylmonoethyldiethoxy) ethylmonomethyl- · ethylhexyl) ethylmonomethyldicyclohexyl) ethylmonomethylcyclohexyl) ethyl monomethyl Oxycyclohexyl) ethyl-alkane, / 3-(3,4 Shi Xiyuan, Θ-(3,4 monocyclosilane), / 3-(3,4 monoepoxycyclohexyl) ethyloxysilane , / 3-(ethoxysilane, / 5 — 3, 4 alkane, y? — (Shi Xiyuan, / 3 — Keishi Xiyuan, / 3 oxysarane, propoxysilane dibutoxysilane Diphenoxydimethylmethoxy-diethylethyl-dimethylpropoxysilane, / 3 — (3-methylbutoxysilane, / 3-(-epoxycyclohexyl) ethane 4 One epoxy cyclohexyl) ethyl one dimethyl, 4 one epoxy cyclohexyl) ethyl one 2, 3, 4 one epoxy cyclohexyl) ethyl one paper size applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) -18- 1225505 A7 ________B7 V. Description of the invention (16) Dimethyl benzyl silane, Shiyi (3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane, 3-(3, 4-epoxy Cyclohexyl) ethylmonomethyldiisopropenyloxysilane, 1,3-dimethyl-1, 2-imidazoledione, 1,3-diethyl-2, imidazoledione, N, N / --di Examples include methacryluria and N-methylpyrrolidone. After the modifier is reacted, a modifier residue is obtained in polymer block A and / or polymer block B, that is, it has a group selected from a hydroxyl group, an epoxy group, an amine »'silanol group and an alkoxy group. Modified block copolymers or their hydrides bonded to functional groups of silyl groups. The bonding position of the modified block copolymer of the modifier residue is not particularly limited, and generally, it is preferable to bond to the polymer block A in the composition having good physical properties at high temperatures. In the present invention, the amount of the functional group-containing modifier used for additional reaction at the activated end of the block copolymer is preferably 0.5 equivalent or more of the activated end of the block copolymer, and more preferably 0. 7 equivalents. Above, more preferably, it is 0. 9 equivalents or more. In addition, it is preferably 10 equivalents or less of the activated terminal of the 1 equivalent block copolymer, more preferably 5 equivalents or less, and most preferably 4 equivalents or less. In addition, the amount of the activated terminal of the block copolymer in the present invention can be determined from the amount of the organic lithium compound used in the polymerization and the number of lithium atoms bonded to the organic lithium compound. In the present invention, the hydride of the modified block copolymer is obtained by hydrogenating the modified block copolymer obtained by the method. As the hydrogenation catalyst used in the hydrogenation, there is no particular limitation. 'The known metal (i) Ni, Pt, Pd, Ru, etc. can be used to support carbon, silicon oxide, and oxidation. The paper's dimensions are applicable to Chinese national standards. (CNS) A4 specification (2i0x297 mm) -19-(Please read the winter precautions on the back first \ ^^ Write this page)-Assemble and order the bulletin printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The compound is substituted and the gold test compound 15 is hydrogenated with 0 MP and 3. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225505 A7 ______B7 V. Description of the invention (17) Unsupported heterogeneous catalysts such as aluminum and diatomite, (ii) N i, C ο, F e, C r And other organic acid salts or transition metal salts such as acetone acetone and reducing agents such as organoaluminum, that is, Ziegler-based hydrogenation catalysts, (1 1 ι) T 1, 1 ^ 11, 1111, 2]: and other organic Metal compounds and the like, that is, organometallic complexes and the like are homogeneous hydrogenation catalysts. Specific examples: Japanese Patent Publication No. 4 2-8 7 04, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, Japanese Patent Publication No. 1-53851, Japanese Patent Publication No. 2 -The oxidizing catalyst contained in the No. 9 0 41 is an example of using an ideal hydrogenation catalyst such as a mixture of a titanocene compound and a reducing organometallic substance. As examples of the titanocene compounds, for example, they have at least one () cyclopentadienyl skeleton, such as dicyclopentadienyl dichloride, monopentamethylcyclopentadienyl titanium trichloride, or fluorenyl group. Examples of backbone ligand compounds. Examples of the reducing organometallic compound include organic compounds such as organic lithium, organic magnesium compounds, organic aluminum compounds, organic borides, and organic zinc compounds. The hydrogenation reaction is usually carried out at a temperature range of 0 to 200 t, preferably 30 to 0 ° C. The hydrogen pressure used in the hydrogenation reaction is preferably 1 to 15 MPa, more preferably 0.2 to 10 a, and more preferably 0.3 to 5 MPa. The hydrogenation reaction time is preferably from minutes to 10 hours, and more preferably from 10 minutes to 5 hours. The reaction can be performed in batches, continuous operations, or a combination of them. This paper is sized for the Chinese National Standard (CNS) A4 (210X297 mm). Please read it first.

-20-… υ: > Α7 Β7 V. Description of the invention (18 The hydride of the modified block copolymer originates from the common redundancy shown in the following formulas (a) to (e). The constituent monomer of ene is-(CH —C = C—CH) R1 R2 R3 R4 • (a) R2I-(CH—C = C—CH) | II R1 R3 R4 (b)-(CH—CH—CH-I, l2 l3 R1 R2 R3 _r ---- (c) i CH—CR6 R5 CR7: CHRe (d) (e) (CH—CR6) —— | | R5 CR7H—CH2R8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (R1 ~ R8 respectively represent Hydrogen, halogen, aliphatic nicotine having 1 to 20 carbon atoms, or aromatic hydrocarbon group having 1 to 20 carbon atoms may be the same or different from each other. Moreover, formula (a) represents The C is structure and formula (b) represents the trans structure.) Among them, the hydrogenation rate of the modified block copolymer hydride is from the aspect that a composition with good thermal stability can be obtained, and it is preferably 10% or more. More preferably, it is 30 to 100%, and the most preferable is 50 to 100%. In addition, the hydrogenation rate of the modified block copolymer hydride is based on the above formulas (a) to (e). With this paper size, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applied. -21 -1225505 A7 B7 V. Description of the invention (19) The hydrogenation rate = (c + e) / (a + b + c + d + e) x100 is represented. In addition, the source of the modified block copolymer hydride originates from Among the total constituent units of the conjugated diene, the ratio of the constituent units having an ethylene bond is set to a range of 10 to 85%, and the productivity of the block copolymer and the flexibility and resistance of the composition are obtained. In terms of impact properties, the range of 30 to 75% is preferred, and the most preferred is 35 to 70%. In addition, the total constituent unit derived from the conjugated diene has a vinyl bond structure forming unit. The ratio is based on the above formulas (a) ~ (e), which can be represented by the ratio of vinyl bonds = (d + e) / (a + b + c + d + e) xl00. Moreover, the Modified block copolymer hydride originating from the total constituent units of conjugated diene in which the proportion of 1, 2 C and 2 C units is 15% or less is more suitable for obtaining a good thermal stability composition, and the better one It is 0 to 7%, and the best is 0 to 3%. In addition, the ratio of 1, 2 C = C units derived from the total constituent units of the conjugated diene is based on the above formulas (a) to (e). , By 1, 2C = C unit ratio = d / (a + b + c + d + e) x100. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Beige Consumer Cooperative. As described above, the amount of the aromatic aromatic hydrocarbon group contained in the modified block copolymer or its hydrogenated product can be determined by using an ultraviolet spectrophotometer or the like. In addition, the ratio of the ethylene bond structure-derived units derived from the conjugated diene constituent units in the modified block copolymer hydride and the hydrogenation rate in the modified block copolymer hydride can be obtained using a nuclear magnetic resonance device ( NMR). In addition, this paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -22. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____B7_ V. Description of the invention%) Outside the hydride contains ethylene aromatic The amount of hydrogen may be the content of the ethylene aromatic hydrocarbon group in the copolymer before hydrogenation. The modified block copolymer or its hydride is used as the purpose. The modified block copolymer or its hydride solution is obtained by this method. After removing the catalyst residue if necessary, it can be obtained after separating the solvent. As a method for separating the solvent, for example, adding a polar solvent of a weak solvent to a polymer such as acetone or an alcohol in the polymer solution, and then precipitating the polymer, and then recovering the polymer solution, and put the polymer solution into the hot water under stirring. After that, the solvent is removed by a siphon distiller and then recovered, or the method of distilling off the solvent after directly heating the polymer solution is exemplified. The amount of amine in the medium changes, and the heat and heat of the material, the more shrinkable% is the strongest, the base of the chemical agent, the amount of impact is done, the working force is 1, the hydrogen is fixed, and the weight is 6%.永 耐 ο Substitute instead, or it is fragrant and its low 6} super} The sulfur of the substance ο time drops to 1 amount 1 Chengguan poly, ene 8% amount {containing 彳 group surface co-agent B ~ amount% The content of the base is determined to contain 8 weight of hydrocarbon-forming hydrocarbons. The weight-addition system is 5 heavy bases, which are added by the industrial plant. The amount of the additive is 5 when the hydrocarbon is aromatic.上 分 由 经 ， 1 is more equivalent to fragrant ene and even, the agent 彳. Dafang% B% should be used. The proportion should be%, and the amount of ene equivalent is the difference between the weight and the weight of the agent. It is determined by the amount of phenol. Ο will be a 5 special 6 properties} Wan Fa Ben An weighs 7 degrees, in order to special 13 this kind of Ming 5 ~ strong and different from the {{, each dose of 90 strength. Special fat content, plus a final version ~ 1 piece of thinking, bombing, tree-building, Tianan 5 as the rationality of the time, the concept of time and nature can not be shaped, plastic surface, the paper size applies Chinese National Standards (CNS) A4 Specifications (210X297 mm) -23- 1225505 A7 ______ B7_____ V. Description of invention g1) Those below Yu are better, preferably 60,000 to 800,000, and more preferably 70,000 to 600,000. In addition, the weight average molecular weight is measured by gel permeation spectroscopy (GPC) using a standard polystyrene obtained from a commercially available standard polystyrene (based on the vertex molecular weight of the standard polystyrene). Find the molecular weight. In addition, in the component (1), the block ratio of the ethylene aromatic hydrocarbon group is adjusted to 50% or more of the total ethylene aromatic hydrocarbon group in the component (1). It is preferable that 50% to 97% by weight, more preferably It is preferably 60 to 95% by weight, and can obtain a good permanent compression deformation composition. Here, the block ratio of the ethylene aromatic hydrocarbon group refers to the proportion of the ethylene aromatic hydrocarbon-based polymer block existing in the component (1). The block ratio of ethylene aromatic hydrocarbon groups was determined by using tetrachloride as a catalyst, and the block copolymer was oxidatively decomposed by a third butyl hydroperoxide (I · M. K〇LTH〇FF, et al., J. Polym. Sci. 1,429 (1 946)) utilizes the obtained ethylene aromatic hydrocarbon-based polymer block components (however, ethylene aromatic hydrocarbon-based polymers having a degree of polymerization of about 30 or less) Except for the block component), it can be obtained by the following formula. Block ratio of ethylene aromatic hydrocarbon group (%) = [(block mass of ethylene aromatic hydrocarbon-based polymer in block copolymer) / (mass of total ethylene aromatic hydrocarbon group in block copolymer)] x 100 Next, the tincture used as the ingredient (2) in the present invention will be described. Ingredient (2) is selected from the group consisting of siloxane-based inorganic fillers, metal oxides and metal hydroxides. Among them, the siloxane-based inorganic samarium filler refers to the chemical formula S 102, or please read it first.

The paper size printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) -24- 1225505 A7 B7 V. Description of the invention P) s 1 3 A 1 as The solid particles constituting the main component of the unit are referred to as inorganic fibrous substances such as silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, and glass fiber. In addition, silica-based inorganic fillers that hydrophobize the surface, a mixture of two or more silica-based inorganic fillers, a mixture of silica-based inorganic fillers and inorganic fillers other than silica-based fillers can also be used. As the silica, dry-process white carbon black, wet-process white carbon black, synthetic silicate white carbon black, and colloidal silica can also be used. In addition, the term “metal oxidizer” refers to solid particles with the chemical formula M X〇Y (M represents a metal atom, and X and y are integers of 1 to 6) as the main component of the unit. For example, alumina, oxidation Titanium, magnesium oxide, zinc oxide, etc. It is also possible to use a mixture of two or more metal oxides, and a mixture of inorganic oxides other than metal oxides and metal oxides. More metal hydroxides refer to hydration inorganic fillers, such as: aluminum hydroxide, magnesium hydroxide, chromium hydride, hydrated aluminum silicate, magnesium silicate hydrate, alkaline magnesium carbonate, hydrotalcite, Hydrates of calcium hydroxide, barium hydroxide, tin oxide, hydrates of inorganic metal compounds such as borax, etc. It is also possible to use a mixture of two or more metal hydroxides, or a mixture of inorganic hydroxides other than metal hydroxides and metal hydroxides. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. As the tincture filler used in the present invention, it is preferable to use silica and fiberglass, especially silica. In the present invention, when dispersing the filler in the composition, the additive effect of the filler can be fully exerted. The average dispersed particle diameter of the filler is preferably from 0. 01 to 2 μm, and more preferably 〇 · 03 ~ lgm, more preferably 0 · 〇5 ~ 0 · 5 // m. In addition, the average dispersing particle of tincture is -25- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1225505 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention p) The dispersion state of the gadolinium can be observed by a transmission electron microscope (TE M), and it can be determined by an image analysis device. In addition, the amount of the ingredient (2) is preferably 0.5 to 50 parts by weight of the ingredient (1) 100 parts by weight, and more preferably 3 to 40 parts by weight. When the compounding amount of the component (2) is less than 0.5 parts by weight, the effect of adding tincture will not appear. On the other hand, if it is more than 50 parts by weight, the dispersibility of the component (2) will deteriorate, and the processability and mechanical strength will be poor. Both deteriorated and were not ideal. In addition to the component (1) and the component (2), the composition of the present invention may further contain an olefin-based polymer (hereinafter referred to as the component (3)). The olefin polymer refers to a polymer mainly composed of α-olefins such as ethylene and propylene, such as polyethylene, polypropylene, ethylene-propylene copolymer, and chlorinated polyethylene. As the olefin-based polymer, in addition to olefins such as ethylene and propylene, a small amount of ethylene-based monomers can be copolymerized. Examples include ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, and ethylene (meth) acrylic acid derivative copolymer. Furthermore, olefin-based polymers may contain hydrides of conjugated diene monolithic polymers such as butadiene and isoprene. These resins may be used in combination of two or more kinds. In consideration of the processability and mechanical properties of the obtained composition, polypropylene or a mixture of polypropylene and an ethylene-propylene copolymer is preferable. From the perspective of the permanent compression deformation of the composition, the balance of tensile strength and elasticity, the amount of the component (3) is preferably 100 to 50,000 parts by weight of the component (1), more preferably 20 ~ 300 parts by weight. In the modified block copolymer composition of the present invention, the component (1) of the modified block copolymer or its hydride contains a specific functional group. Therefore, for (please read the precautions on the back ^^ write this page first) )-The size of the paper used for the binding and binding is in accordance with the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -26- 1225505 A7 B7 V. Description of the invention 0) The ingredients in the tincture (2 while being more finely dispersed, the effect Those who can obtain the clarity, abrasion resistance, and good permanent compression block copolymer composition of the present invention, and the modified coupling agent of the present invention. The silane coupling agent is used more closely, which has affinity or bonding Modified deformation, impact resistance, block copolymers that can be used for purposes such as silicon and oxygen, and high affinity during hydrogen bonding, etc., make the ingredients (1 ingredient (1) and The base material. For this organic filler material, the copolymer makes the chemical bonding interaction of the filler material more thermal, mechanical strength, and block copolymer composition. For more properties and processability, please read the back note Event Η i Ministry of Intellectual Property Bureau employee consumer cooperative printed propyl-a composition is more acceptable) and the ingredients (2 / or the ingredients (2 silane coupling agent used by the user, such as modified with silane) interaction) , Monooxysilane, 3, ethylenetrimethoxysilane, ethylenetriethylene-epoxycyclohexyl) ethyltrimethoxymethyldiethoxysilane, 3-glycidoxy, p-styryl Trimethoxysilane, 3-methylsilane, 3-methylpropenylpropylmethyldiethoxysilane, 3-methyldimethoxy 3-methylallylpropylpropylthiothiopropyloxy Silane, 2 silane: hydrothiomethyldimethoxysilane (3,4 3 -glycidoxypropoxysilylpropyl, alkane, N — 2 (aminoethyl) 3 —amino N -2 (aminoethyl) 3 -aminopropylaminoethyl) 3-aminopropyltriethoxyoxysilane, 3-aminopropyltriethoxyalkyl-N — (1 '3 — Dimethyl-alkenyl ethoxypropene propyl methoxytrimethoxysilane, silane butylene propyl triethyl propylene propyl trimethoxy silane silane, 3 groups Propyldimethoxysilyl-methylpropmethoxysilylsilane, N-2 (3-aminopropyltrimethyl, 3-triethoxysilyl) propylamine, N-phenyl This paper is applicable to China Standard (CNS) A4 specification (210X297 mm) -27- 1225505 A7 B7 V. Description of the invention P5)-3 monoaminopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane and other examples. Please read the precautions before writing this page. The particularly desirable silane coupling agent in the present invention has a silanol group or an alkoxy stone group. At the same time, its chlorothio group and / or sulfur yellow have two or more linking polymers. For sulfide bonding, examples of the silane coupling agent are: 3-hydrothiopropyl-trimethoxysilane, 3-aminopropyltriethoxysilane, and bis [3-triethyl Oxysilyl] monopropyl] -tetrasulfide, bis ~ [3- (triethoxysilyl) monopropyl] -disulfide, bis- [3-mono (triethoxysilyl) — Propyl] -trisulphide, bis- [2- (triethoxysilyl) -ethyl] -tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthio Aminomethylfluorenyl tetrasulfide, 3-trimethoxysilylpropyl, N, N-dimethylthioaminomethylsulfanyl tetrasulfide, 3-triethoxysilylpropylbenzothiazole Examples of tetrasulfide '3 -trimethoxysilylpropylbenzothiazole tetrasulfide. The compounding amount of the silane coupling agent is to fully exert the effect of reinforcing the filling agent. It is preferably 0.1 to 20% by weight of the amount of the component (2), more preferably 0.5 to 18% by weight, and more preferably 1 to 15% by weight. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. When using silane coupling agents, sulfur and organic peroxides can also be used. In the modified block copolymer composition of the present invention, a block copolymer or a block copolymer different from the modified block copolymer or its hydride used in the present invention, such as an unmodified block copolymer, may also be blended. Hydride, thermoplastic resin, rubbery polymer, etc. As an example of the thermoplastic resin, if the modified paper is specified in the present invention, the paper size is subject to the Chinese National Standard (CNS) A4 specification (21〇χ297 public love) -28- 1225505 A7 _______ B7 5. Inventor of the invention) Copolymer or hydride conjugated diene compound and ethylene aromatic compound block copolymer resin, ethylene aromatic compound resin such as polystyrene, ethylene aromatic compound and other ethylene monomers, such as ethylene , Propylene, butene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid and acrylic acid methyl acrylate and other ethyl acrylate, methacrylic acid and methyl methacrylate and other methacrylate, propylene Mutual copolymer resins such as nitrile and methacrylonitrile, rubber modified styrene resin (系 IPS), acrylonitrile-butadiene-styrene copolymer resin (ABS), methacrylate-butadiene-benzene Ethylene copolymer resin (MBS), a polyvinyl acetate-based resin having a mutual copolymer content of vinyl acetate of 50% by weight or more and other monomers copolymerizable therewith, and its hydrolysis Acrylic acid and its esters, polymers of ammonium amines, polymers of methacrylic acid and its esters, polymers of ammonium amines, polyacrylic acid esters containing 50% by weight or more of other copolymerizable monomers of these acrylic monomers Polymers of resins, acrylonitrile and / or methacrylonitrile, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and printed with nitrile resins containing 50% by weight or more of these copolymerizable monomers and other copolymerizable monomers , Nylon—46, nylon-6, nylon-6, nylon-610, nylon-11, nylon-12, nylon-6-6 nylon-12 copolymers and other aliphatic polyfluorene-based resins, polydiphenylisophthalocyanine Aromatic polyfluorene resins such as amines, polyphenylene terephthalamide, and poly-m-xylylenediamine, -29- This paper size applies to Chinese National Standard (CNS) A4 (210 × 297 mm) 1225505 A7 B7 V. Description of the invention p) Adipic acid, sebacic acid, terephthalic acid, isophthalic acid, p, p > -dicarboxydiphenyl, 2,6-naphthalenedicarboxylic acid and other bases or derivatives Ingredients, with ethylene glycol, propylene glycol, 1, 4-butanediol, 1 , 6-hexanediol, 1, 4-monocyclohexanediol, P-xylene glycol, bisphenol A, polycondensates of glycol (or glycol) components, polyester resins, etc., poly (1,4 a Polyester diols such as butene adipate), poly (1,6-hexane adipate), polycaprolactone, polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol Ether glycol, a diol component selected from glycols such as ethylene glycol, 1,4-monobutylene glycol, 1,6-hexanediol, and toluene diisocyanate, 4,4 / diphenylmethane diisocyanate, six Polymerization of thermoplastic polyurethane polymers, poly-4,4 / dioxodiphenyl-2, 2 / --- propane carbonate, etc. obtained after addition polymerization of diisocyanate components such as methylene diisocyanate, etc. Materials, poly (ether sulfonate), poly (4,4 / —bisphenol ether sulfonate), poly (thioether sulfone) and other polysulfonic resins, polymers of formaldehyde or trioxane, formaldehyde or trioxane and others Polyoxymethylene resins such as aldehydes, cyclic ethers, epoxy groups, isocyanates, copolymers of ethylene compounds, etc., poly (2,6-dimethyl-1 Polydiphenyl ether resins such as 1,4-diphenyl) ether, polydiphenyl sulfide, polydiphenylsulfide resins such as poly 4,4 / diphenyl sulfide, polyimide, polyamine diimide Amine (polybismaleic anhydride imine), bismaleimide This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling in this page) Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau 1225505 A7 B7 V. Description of the invention p) Polyimide resins such as anhydride imine, triazine resin, polyimide, polyetherimine, etc. The number-average molecular weight of these thermoplastic resins is stated as i 1000 or more, preferably 50,000 to 500,000, and more preferably 10,000 to 1 million. These thermoplastic resins may be used in combination of two or more kinds. As a rubbery polymer, styrene-butadiene rubber and its hydride which are different from butadiene rubber and its hydride, modified block copolymer or its hydride specified in the present invention, Isoprene rubber, acrylonitrile-butadiene rubber and its hydrides, chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, butyl rubber , Ethylene-butadiene rubber, Ethylene-hexene rubber, Ethylene-octyl rubber, acrylic rubber, fluorine rubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, / 3-unsaturated nitrile -Examples of acrylate-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber, styrene-butadiene block copolymer and its hydride, styrene-isoprene block copolymer, natural rubber, and the like. These rubber-like polymers may also be modified with functional groups. Among these thermoplastic resins and rubber-like polymers, polystyrene resins and polydiphenyl ether resins are particularly preferable. Moreover, any additives can be blended for various purposes without impairing the scope of the obvious effects of the present invention. The type of the additive is not particularly limited as long as it is generally used by thermoplastic resins and rubber-like polymers. For example: naphthalene series and / or paraffin series, or polybutene, low molecular weight polybutadiene. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back to write this page). · Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225505 A7 B7 V. Description of the invention p9) Softeners for rubber, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, etc. Antioxidants such as inorganic fillers, carbon black iron oxide and other pigments, stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, bistearylamine, and hindered amines Light stabilizers, benzotriazole-based ultraviolet absorbers, flame retardants, antistatic agents, organic fibers, glass fibers, carbon fibers, metal whiskers, and other reinforcing agents, colorants, other additives, or mixtures of these "rubbers and plastics" Compatible medicines "(edited by Lab a digest). The method for producing the modified block copolymer composition of the present invention is not particularly limited, and it can be carried out according to a known method. For example, it can be manufactured by using a single-shaft extruder, a double-shaft extruder, a compact flash kneader, a heating roll, a Brabender, various kneaders and other melting kneaders. At this time, the order of adding the ingredients is not limited, and the total ingredients can be kneaded at one time, or any of the ingredients can be kneaded at one time, and the remaining ingredients can be kneaded again or in portions. In addition, after the component (1) is polymerized or the solution after the hydrogenation reaction, or the component (1) is dissolved in a solvent to disperse the component (2), the components are mixed, and the manufacturer is removed by heating to remove the solvent. Yes. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the present invention, the melt mixing method by an extruder is suitable for its producers, especially to obtain a composition with good dispersibility, and to mix in a molten medium. The method is better. In the denatured block copolymer composition of the present invention, it is found that chemical bonding such as hydrogen bonding between the specific functional group of the modified block copolymer or its hydride and the hydrogenation agent is carried out. Waiting for an integrated complex. This -32- This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1225505 A7 B7 Five 'invention description PQ) The composite state was found to refer to when the ingredients (1) and ingredients (2) were mixed in the solution 'Or when component (2) is added to the solution of component (1) and mixed' After leaving the mixed solution for a certain period of time, it can be determined that after the component (2) is separated from the mixed solution, the precipitation ratio is still small, and after microdispersion The proportion of plankton is extremely large. In particular, when the average particle diameter of the component (2) is small (for example, the secondary particle diameter is 50 m or less), the component (2) deposited on the bottom of the container hardly appears. In addition, when the component (1) does not have the functional group specified in the present invention, after the mixed solution with the component (2) is allowed to stand for a certain period of time, substantially the component (2) is precipitated on the bottom of the container. The block copolymer composition of the present invention can be generally molded using a thermoplastic resin molding machine, and formed into a sheet, a film, a mold-molded product of various shapes, a hollow molded product, an air-molded product, a vacuum molded product, and an extrusion molding. And other various molded products. These molded articles can be used in food packaging materials, medical equipment, home appliances and their parts, automotive parts, industrial products, household goods, toys and other substrates, and shoe substrates. [Examples] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The present invention will be specifically described below by way of examples, but the present invention is not limited to those examples. In the following examples, the properties of the modified block copolymer or its hydride 'and the properties of the modified block copolymer composition were measured as follows. In the following examples, the modified block copolymer and the modified block copolymer composition are referred to as "block copolymer" and "block copolymer composition", respectively. -33- This paper is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) 1225505 A7 A ____ B7 _ V. Description of the invention P1) 1 · Characteristics of block copolymer or its hydride (1) Styrene content is measured using an ultraviolet spectrophotometer ( Hitachi UV 2 0 0) is calculated from the absorption intensity of 2 6 2 nm.

(2) The hydrogenation rate, the proportion of ethylene bonds, and the proportion of 1, 2 C and 2 C units in the polybutadiene portion were measured using a nuclear magnetic resonance apparatus (0? 乂-400, manufactured by Brucker). (3) The weight average molecular weight was measured at GPC [device: LC10 manufactured by Shimadzu Corporation, cylinder: Shimpac G P C 8 0 5 + GPC804 + GPC804 + GPC803 manufactured by Shimadzu Corporation]. Tetrahydrofuran was used in the solvent, and the measurement temperature was 3 5 ° C. The calibration curve (made by using the peak molecular weight of standard polystyrene) was obtained from the standard polystyrene measured by the molecular weight of the apex of the chromatogram. . (4) The proportion of the unmodified block copolymer is used to adsorb the components modified by the GPC column with silica as the filler, and it is aimed at the polymer containing the modified block copolymer and low molecular weight internal standard polymer. Compare the sample solutions of styrene. For the chromatogram determined by (3), please read the note of T &

f The paper size printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X29 * 7 mm) -34- 1225505 A7 ___ B7 " " — .-----_________________ 1 V. Description of the invention p) The proportion of the modified block copolymer of standard polystyrene in the standard polystyrene and the chromatogram determined for the sand-oxygen column G pc [column: du ρ ο η company made ZO 1 · ba X] After the ratio of the denatured block copolymer of the standard polystyrene in the figure, the adsorption amount of the silica cylinder was measured by the difference. The proportion of unmodified block copolymer is the proportion of unadsorbed silica cylinders. (5) Content of styrene alone polymer block (block rate) The styrene alone polymer block obtained after the copolymer was oxidized and decomposed by the above method was analyzed by an ultraviolet spectrophotometer. Calculate it. Block ratio (%) = [(wt% of styrene alone polymer block in block copolymer before hydrogenation) / (wt% of total styrene in block copolymer before hydrogenation)] X 100 2 · block Measurement of the physical properties of the copolymer composition (1) Transparency (Haze) Printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs and the Consumer Cooperative Society to produce a compression molded sheet with a thickness of 2 mm from the block copolymer composition. Measured with M-D 1 003 as a reference. (2) The heat resistance was measured using a DM Spectrometer (9 8 3 DMA manufactured by Dupon Isturmant) under the conditions shown below. The paper size of the block copolymer composition is in accordance with Chinese National Standard (CNS) A4 (210X297). %) · 35-1225505 temperature change, polarization temperature measurement week at high temperature A7 B7 V. Description of the invention P3) Dynamic storage elasticity (E / degree to evaluate heat resistance. Test piece thickness · 2 mm Fiber length: 16 mm Degree: 0 ° C ~ 2 0 ° C, Heating rate: 2 ° C / m! Η Wave number form: Resonant frequency. (3) Abrasion resistance The use of a vibration-type abrasion tester (A Beta-3 0 1 manufactured by Testa Sangyo Co., Ltd.) Observe the weight change of the test piece before and after abrasion of 10,000 times. (4) Workability The biaxial open roll was used at a temperature of 200 ° C. After the block copolymer composition is melt-kneaded, the processability of the roll-wrap condition is evaluated in the following three stages. Please read the first 5 notes △ -shaped sheet. Thin, good and good. With rolls, light to roll, smart money, Ministry of Economic Affairs Printed by the Production Bureau Staff Consumer Cooperative

Easily blended with high-quality solid pieces, thin and non-X. The determined travel standard is IX ο Degree 3 Hard 6 AKII s S η IJ * ~ w} Shrinks by compression S for a long time S I I J} to κ% o 7 κ (\ 法 方 示 所 rH ο 3

Shi Xiao 2 2 X -36- This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 1225505 A7 _________B7 V. Description of the invention 0))). (7) Tensile strength (MPa) and tensile elongation (q'0) are based on J IS-K-6251. The tension speed was 500 m m / m 1 η. (8) Bending strength (MPa) Measured based on A S TM-D 790. (9) I z ◦ d impact strength (j / m) with nicks is measured based on J I S — K — 7 11 1 0. (1 0) Average dispersion particle diameter of the filler (// m) The average dispersion particle diameter of the filler is measured by a transmission electron microscope (TE M). After measurement by TE Μ, the dispersion state of the filling agent was observed at 5000 to 1 ◦ 10,000 times, and an image analysis device (ΜΙΑΝΙ (: 〇1 ^ 〇1 ^ 丁 1 (^ made image analysis system ^ 111 ^) 〇 (^) determines the number average dispersed particle size. The number of average dispersed particle size (dn) printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is defined as follows. D η = Σ η 1 di / Erii (η: Its particle size is (Number of particles of ^) In addition, the particle diameter refers to the diameter of an equivalent circle with the same area as the particle area. 3. Modification of ammoniated catalyst The paper size applies the Chinese National Standard (CNS) A4 specification (21〇χ297) (Mm) 1225505 A7 B7 V. Description of the invention 芊) 3 · Preparation of hydrogenation catalyst The block copolymer is prepared as described below. The hydrogenation catalyst used in its hydrogenation reaction is prepared according to the following method.

(1) Hydrogenation catalyst I Place 1 1 'refined cyclohexane in a reaction vessel replaced with nitrogen, and then add 10 OmM bis (7? 5-cyclopentadienyl) titanium dichloride Please it After reading the information, add the solution containing 200 while stirring thoroughly, and carry out the reaction at room temperature for about 3 days. M methylammonium n-hexane f 2-polybutyrate 0 m. M is immediately stirring the intellectual property of the Ministry of Economic Affairs. Printed by the Bureau's Consumer Cooperative

(2) Hydrogenation catalyst II was placed in a reaction vessel replaced with nitrogen, dried and purified cyclohexane, and 40 mM bis (7? 5-cyclopentadienyl) titanium- (p-toluene) was added. Group) and 1500 g of a diene with a molecular weight of about 1,000 (ethylene bond ratio: about 85%), and then a cyclohexane solution containing -butyllithium was added, and then reacted at room temperature for 5 minutes. Add 4 After 0 μM n-butanol, store it at room temperature. 4. Compounding ingredients In the following examples, the following was used as the component (1) block copolymer. Tables 1 and 2 show the characteristics of the obtained block copolymers. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -38- 1225505 A7 B7 V. Description of the invention) (2) IJ sand oxygen A: sedimentation silicon oxygen (Sipernat 5 0 by Degussa) LS ·· Secondary particle size 3 · 5 " m) Sand Oxygen B: Dry-type high-dispersion silica (HDKN 2 0 manufactured by Asahi Kasei Wakai Co., Ltd.) Silica C: Wet-type silica (Ultrasil v by Degussa) N 3: secondary particle size 16 / im) (3) olefin-based polymer polypropylene (PM801 A manufactured by Monteru SDK) Please read the back and note 4) Silane coupling agent (3-triethoxysilane Propyl) -tetrasulfide

Made by Degussa, hereinafter referred to as "S 1 6 9 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (5) Other component rubber softener: Daiana process oil PW-380 polystyrene resin made by Idemitsu Kosan Co., Ltd .: A · Polystyrene 685 polydiphenyl ether resin made by And · M · styrene Co., Ltd .: poly (2,6-dimethyl-1,4-phenylene ether) (reduced viscosity 0.54). Preparation of block copolymer Paper size applies Chinese National Standard (CNS) A4 specification (2i0x297 mm) -39-1225505 A7 B7 V. Description of the invention f) 1) Polymer 1 Wash the local pressure cooker with mixer and outer cover, dry, After the replacement with nitrogen, put 10 parts by weight of a previously purified styrene cyclohexane solution (concentration: 20% by weight). Then add n-butyllithium and tetramethylethane, and add <7 0 C to fr After 1 hour of polymerization, 'a cyclohexane solution (concentration of 20% by weight) containing 8 q parts by weight of a previously purified butadiene was added, and then polymerization was performed at 70 t for 1 hour, and 10% by weight of styrene was further added. The cyclohexane solution was polymerized at 70 t for 1 hour. After that, it was used as a denaturant. Tetraglycidyl-1,3-bisaminomethylcyclohexane (hereinafter referred to as modifier M 1) isomerized against n-butyllithium used in polymerization. Modified block copolymer obtained The styrene content is 20% by weight, and the ethylene bond ratio of the polybutadiene portion is 50%. The obtained modified block copolymer is added with 1000 ppm T 1 as the hydrogenation catalyst II, The hydrogenation reaction was performed at a hydrogen pressure of 0. 7 MPa and a temperature of 65 ° C for 1 hour. After that, methanol was added, and then octyldecyl-3 — (3,5 —di — 3rd —butyl) was added as a stabilizer. 1-4 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs, R Industrial Consumer Cooperative Co., Ltd.) Propionate is 0.3 parts by weight of 100 parts by weight of the modified hydrogenated block copolymer. The modified hydrogenated block copolymer obtained The characteristics of (Polymer 1) are shown in Table 1. In addition, the proportion of the modified block copolymer mixed with Polymer 1 was 20% by weight. 2) Polymer 2 except that no modifier was used , Polymer 2 is produced in the same way as Polymer 1. The characteristics of Polymer 2 are shown in Table 1. The paper size is applicable to the Chinese National Standard (CNS ) A4 specification (210X297 public envy) -40-1225505 A7 B7 ------- V. Description of invention p 3) Polymer 3 After washing, drying and replacing the pressure cooker with mixer and jacket, Add 10 parts by weight of pre-refined styrene ethyl cyclohexylsulfonate solution (concentration: 20% by weight). Add n-butyllithium and tetramethylethanediamine 'and polymerize at 70 ° C for 1 hour. Then, 60 parts by weight of a butadiene cyclohexane solution (concentration: 20% by weight), which was previously purified, was added, and polymerization was performed at 70 ° C for 1 hour, and cyclohexane i containing 10 parts by weight of styrene was further added. After the serum, it was polymerized at 70 ° C for 1 hour. After that, a cyclohexane solution containing 20 parts by weight of butadiene was polymerized at 70 ° C for 1 hour, and then tetraglycidyl-m-xylylenediamine (hereinafter referred to as a modifier) was used as a modifier. M 2) The isomolar reaction is performed on n-butyllithium used for the polymerization. The obtained modified block copolymer had a styrene content of 20% by weight and an ethylene bonding ratio of the polybutadiene portion of 50%. To the obtained modified block copolymer, 1000 p p Tm was added as a hydrogenation catalyst I I, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 Mpa and a temperature of 65 ° C for 1 hour. After that, add methanol, and then read the precautions as a reminder. T-octyl decyl-3 5 tertiary butyl-4-Hydroxyl Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Co., Ltd. printed phenyl) propionate 0.3 parts by weight of 100 parts by weight of the modified hydrogenated block copolymer was added. The characteristics of the obtained modified hydrogenated block copolymer (Polymer 3) are shown in Table 1. The proportion of the unmodified block copolymer mixed in the polymer 3 is 20% by weight. 4) Polymer 4 -41-This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 1225505 A7 B7 V. Description of the invention P9) Manufactured in the same way as Polymer 3 except that no modifier is used Polymer 4. The characteristics of the polymer 4 are shown in Table 1. 5) Polymer 5 The pressure cooker with a stirrer and a jacket was washed, dried, and replaced with nitrogen, and the solution was put into a solution containing 20 parts by weight of a previously purified styrene ethyl cyclohexanone (20% by weight). After adding n-butyl bond and tetramethyl ethyl bar to conduct polymerization at 70 t for one hour, add 60% by weight of a previously purified butadiene cyclohexane solution (concentration: 20% by weight), Polymerization was carried out at 70 ° C for 1 hour, and after adding cyclopentadiene solution containing 20% by weight of phenylethylbenzene, polymerization was carried out at 70 ° C for 1 hour. After that, the modifier M 1 was reacted with 1/4 mol of n-butyllithium used for polymerization. The obtained modified block copolymer has a styrene content of 40% by weight and an ethylene bonding ratio of the polybutadiene portion of 17%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, after adding methanol to the modified block copolymer and inactivating it, adding it as a stabilizer 2 —Third-butyl-6 — (3 -Third 1-butyl- 2 -hydroxy- 5 -methylcarbyl)-4 -methylphenyl acrylate is 100 parts by weight of 0.3 parts by weight of the modified block copolymer. The characteristics of the modified block copolymer (Polymer 5) after removing cyclohexane from the cyclohexane solution of the modified block copolymer by the steam stripping method are shown in Table 1. The proportion of the unmodified block copolymer mixed in the polymer 5 is 30% by weight. 6) Polymer 6 -42-This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 1225505 A7 B7 V. Description of the invention 4) S 1 C h is used instead of modifier M 1 as polymerization Polymer 6 was produced in the same manner as Polymer 5 except that 1/4 Molar of lithium monobutylene was used. The properties of the polymer 6 are shown in Table 1. 7) Polymer 7 The pressure cooker with a stirrer and a jacket was washed, dried, and replaced with nitrogen, and then a cyclohexane solution (concentration: 20% by weight) containing 35 parts by weight of previously purified styrene was charged. Add n-butyllithium and tetramethylethylenediamine, and polymerize at 70 ° C for 1 hour, and then add cyclohexane containing 20 parts by weight of butadiene and 10 parts by weight of styrene that has been purified in advance. After the solution (concentration: 20% by weight) was polymerized at 70 t for 1 hour, a cyclohexane solution containing 35 parts by weight of styrene was added, and polymerization was performed at 70 ° C for 1 hour. After that, the N- (based) -3— (triethoxysilyl) -1,3-dimethylbutylene propylamine (hereinafter referred to as the modification agent) is used as a deforming agent (please read the precautions on the back first) The printing agent M 3 of the consumer cooperative of the property bureau staff is reacted by the moles of n-butyllithium used for polymerization. The obtained modified block copolymer has a styrene content of 80% by weight and an ethylene bonding ratio of the polybutadiene portion of 35%. To the obtained modified block copolymer was added 1000 P P m of Ti as a hydrogenation catalyst I I, and a hydrogenation reaction was performed at a hydrogen pressure of 0. 7 MPa and a temperature of 65 ° C for 1 hour. After further adding methanol, octyl decyl-3- (3,5-di-tri-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of a modified hydrogenated block copolymer. 0 · 3 parts by weight. The characteristics of the obtained modified hydrogenated block copolymer (Polymer 7) are shown in Table 1. In addition, the unmodified block copolymer blended with polymer 7 is sized according to the Chinese National Standard (CNS) A4 (210X297 mm) -43- 1225505 A7 B7 V. Description of the invention f1) The weight ratio is 40 weight %By. 8) Polymer 8 The pressure cooker with a stirrer and a jacket was washed and dried, and after being replaced with nitrogen, a cyclohexane compound solution (concentration: 20% by weight) containing 15 parts by weight of previously purified styrene was charged. Add n-butyllithium and tetramethylethanediamine, polymerize at 70 ° C for 1 hour, and add 70 parts by weight of a butadiene cyclohexane solution (concentration: 20% by weight). Polymerization was performed at 0 ° C for 1 hour, and a cyclohexane solution containing 15 parts by weight of styrene was further added, and polymerization was performed at 70 ° C for 1 hour. After that, τ-glycidoxypropyltrimethoxysilane (hereinafter referred to as modifier M 4) as a modifier was reacted with iso-butyllithium used for polymerization. The obtained modified block copolymer had a styrene content of 30% by weight and an ethylene bond ratio of the polybutadiene portion of 40%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the obtained modified block copolymer was added with 100 ppm Tm as a hydrogenation catalyst II, and the hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. 1 hour. Then, after adding methanol, octyldecyl 3- (3,5-di-third-butyl-4 4-hydroxyphenyl) propionate, which is a stabilizer, was added to 1,000 parts by weight of a modified hydrogen peroxide. 0. 3 parts by weight of the segment copolymer. The characteristics of the modified hydrogenated block copolymer (Polymer 8) obtained by removing cyclohexane from the cyclohexane solution of the modified hydrogenated block copolymer by a vapor tripping method are shown in Table 1. The proportion of the unmodified block copolymer in the polymer 8 is 25% by weight. -44- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 1225505 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention f2) 9) Polymer 9 The autoclave was washed, dried, and replaced with nitrogen, and then 8 parts by weight of a previously purified styrene cyclohexane solution (concentration: 20% by weight) was charged. After further adding n-butyllithium and tetramethylethylenediamine 'for polymerization at 70 ° C for 1 hour, a solution containing 85 parts by weight of pre-refined isoprene cyclohexane (concentration 20% by weight) was added. ) Polymerization was performed at 70 ° C for 1 hour, and a cyclohexane solution containing 7 parts by weight of styrene was further added, and polymerization was performed at 70 ° C for 1 hour. After that, the modifier M 1 was made to react with 1/4 mol of n-butyllithium used for polymerization. The obtained modified block copolymer has a styrene content of 15% by weight and a ratio of ethylene bonding portion of the polyisoprene portion to 30%. In this obtained modified block copolymer, methanol was added for deactivation, and 2—third-butyl-6— (3—third—butyl—2—meridin—5— Methylhenyl) -4 monomethylphenylpropionate is 0.3 parts by weight of 100 parts by weight of the modified block copolymer. Table 1 shows the characteristics of the modified block copolymer (Polymer 9) obtained by removing cyclohexane from the cyclohexane solution of the modified block copolymer by a steam tripping method. The proportion of the unmodified block copolymer mixed in the polymer 9 is 30% by weight. 1) Polymer 10: Polymer 1 is produced in the same manner as Polymer 1 except that it uses 1,3-dimethyl-1,2-dimethyldiacetyl (hereinafter referred to as M 5) as a modifier. . The properties of polymer 10 are shown in Table 1. This paper size is in accordance with Chinese National Standard (CNS) Α4 size (210X29 * 7mm) -45- Please read the winter notice f 1225505

7 B V. Description of the invention f1 2 3) Table 1 Sampling number Content of phenylethylammonium (% by weight 〇 Proportion of ethylene (%) Weight average molecular weight (10,000) Type of modifier Hydrogenation rate (%) Polymer 1 20 50 8 Ml 98 polymer 2 20 50 8 and 98 polymer 3 20 50 8 M2 98 polymer 4 20 50 8 钿 98 polymer 5 40 17 15 Ml 0 polymer 6 40 17 15 SiCL · 0 polymer 7 80 35 20 M3 98 polymer 8 30 40 10 M4 98 polymer 9 15 30 18 Ml 0 polymer 10 20 50 8 M5 98 (Please read the precautions on the back first-¾ ^ write this page) | staff of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperative-46- 1 1) Polymer 1 1 2 The pressure cooker with mixer and jacket was washed, dried, and replaced with nitrogen for 3, and then cyclohexane containing 14.7 parts by weight of pre-refined styrene was added. 1225505 A7 -__—- 5. Description of the invention f4) To this modified block copolymer is added 1 0 0 Ρ Ρ η ι ι as hydrogenation catalyst II, under the hydrogen pressure of 0.7MPa, temperature 65 t: below The hydrogenation reaction was performed for 1 hour. After further adding methanol, octyldecyl-3- (3,5-di-third-butyl-4-residual phenyl) propionate, which is a stabilizer, was added to 100 parts by weight of the block copolymer. 0 · 3 parts by weight. Table 2 shows the analytical results of the modified hydrogenated block copolymer (Polymer 1 1) and the polymer 11 obtained by removing the cyclohexane by heating to obtain a modified hydrogenated block copolymer cyclohexane solution. The proportion of the unmodified block copolymer mixed in the polymer 11 is 20% by weight. 1 2) Polymer 1 2 A polymer 1 2 was produced in the same manner as Polymer 1 except that no modifier was used. The properties of the polymer 12 are shown in Table 2.

TX Matter Poly 3

S is using the time to converge to 5 MW agent to replace the printed matter of the consumer cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs.合 2 聚 表 and the special feature of ‘externality’ are used to make 3 4 1 \ things together to make the same method as 1 to get together m two II. r—j 4 Put alkane gas and hexanitrogen ring on it, dry ethylbenzene, cleanse and cleanse first, make a pre-portion of the pot, weigh the weight of the ancient 冋 LO, set ο outer 2 1 and have a machine with mixing and mixing Stir it up} Attachment, change the ethylenic weight of the ethylenic heavy weight after 4 and add 4 to 6 with lithium and butyl, add 1 plus positive, and add 1 when adding. Total) Poly% under the weight of the advance ο OC 2 〇 degrees 7 thicker than (V, liquid amine • soluble two paper size applicable to Chinese National Standards (CNS) A4 specifications (210X297 mm) -47 · 1225505 A7 B7 five 2. Description of the invention f1 2 3 4 5) Pre-refined butadiene cyclohexane solution (concentration: 20% by weight), and polymerize at 70 ° C for 1 hour. 'Add 18.5 parts by weight of styrene ring Hexane solution was polymerized at 70 ° C for 1 hour. After that, the modifier M 1 is made of n-butyllithium used for polymerization, and is reacted at equal moles. The obtained modified block copolymer has a styrene content of 39% by weight and a polybutadiene- * zhibu ethylene residual bond ratio of 37%. 100 p p m T 1 was added as a hydrogenation catalyst I I to the obtained block copolymer, and hydrogenation was performed at a hydrogen pressure of 0. 7 MPa and a temperature of 65 ° C for 1 hour. After further adding methanol, octyldecyl 3- (3,5-di-tri-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight of the block copolymer. · 3 parts by weight. The cyclohexane solution of the modified hydrogenated block copolymer was heated to remove the cyclohexane, and then the modified hydrogenated block copolymer (Polymer 1 4) was obtained. The analysis results of polymer 14 are shown in Table 2. The proportion of the unmodified block copolymer mixed in the polymer 14 was 25% by weight. (Please read the notes on the back to write this page)

、 1T Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. This paper is printed in accordance with Chinese National Standards (CNS) A4 (210X 297 mm) -48- 1 5) Polymer 1 5 2 Pressure cooker with mixer and jacket for washing After drying and replacing with nitrogen, a solution containing 17 · 8 parts by weight of a previously purified styrene cyclohexane solution (concentration: 20% by weight) was charged. Then add n-butyllithium and tetramethylethylene di-3 amine, polymerize at 70 ° C for 1 hour, and then add 66 parts by weight of a butadiene cyclohexane solution (concentration 20% by weight), 7 Polymerization was performed at 0 t for 1 hour, and a cyclohexane solution containing 16 · 2 parts by weight of styrene was further added, and polymerization was performed at 70 ° C for 1 hour. After that, modified block copolymer U25505 A7 was obtained. F. Description of the invention f6, the content of styrene was 34% by weight, and the polybutylene was 42%. The ethylene bond ratio of the olefinic part was obtained by adding 1000 ppm butan 1 as a hydrogenation catalyst II to the modified block copolymer, and hydrogenating at a hydrogen pressure of 0.7 M Pa and a temperature of 65 ° C. Reaction for 1 hour. After that, methanol was added, and octyldecyl 3- (3,5-di-third-butyl-4 4-lightphenyl) propionate, which was a stabilizer, was added as a modified hydrogenated block copolymer of 100 parts by weight. The weight of 0.3 parts by weight. After the cyclohexane solution of the modified hydrogenated block copolymer was obtained and the cyclohexane was removed by heating, a modified hydrogenated block copolymer (polymer 15) was obtained. The analysis results of the polymer 15 are shown in Table 2. The proportion of the unmodified block copolymer mixed in the polymer 15 is 25% by weight. 16) Polymer 16 The pressure cooker with mixer and jacket was washed, dried, and replaced with nitrogen, and it was printed with 3,5 · 1 parts by weight of cyclohexane containing pre-refined styrene. Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Solution (concentration 20% by weight). After adding n-butyllithium and tetramethylethylenediamine, polymerize at 70 ° C for 1 hour, and then add 33 parts by weight of a pre-refined butadiene cyclohexane solution (concentration: 20% by weight). Polymerization was performed at 0 ° C for 1 hour, and a cyclohexane solution containing 31.9 parts by weight of styrene was further added, and polymerization was performed at 70 ° C for 1 hour. After that, the modifier M 5 is polymerized and reacted with a mole such as n-butyllithium. The obtained modified block copolymer had a styrene content of 67% by weight and an ethylene bond ratio of the polybutadiene portion of 18%. 100 ppm was added to the obtained modified block copolymer. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 &gt; &lt; 297g € -49- ^ 5505 A7 B7 V. Description of the invention) After T 1 was used as the hydrogenation catalyst II, a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 C for 1 hour. After further adding methanol, octyl-3- (3,5-di-third-butyl-4-4-phenyl) propionate, which is a female fixative, was added in an amount of 1,000 parts by weight of a modified hydrogenated block copolymer. 0 · 3 parts by weight. After the cyclohexane solution of the modified hydrogenated block copolymer was obtained and the cyclohexane was removed by heating, a modified hydrogenated block copolymer (polymer 16) was obtained. The analysis results of Polymer 16 are shown in Table 2. In addition, the proportion of the unmodified block copolymer in the polymer 1 δ was 30% by weight. 17) Polymer 17 added 100 ppm Ti as hydrogenation catalyst I, hydrogen pressure 0.7 M Pa, and hydrogenation reaction at a temperature of 65 ° C, and the hydrogenation rate was made 60%. 6 In the same way as the polymer 1 7. The properties of polymer 17 are shown in Table 2. 18) Polymer 18 The local pressure cooker with a stirrer and a jacket was washed, dried, and replaced with nitrogen, and then a cyclohexane solution (concentration: 20% by weight) containing 20 parts by weight of previously refined styrene was charged. After adding n-butyllithium, polymerize for 1 hour at 70 t, and then add 30 parts by weight of pre-refined butadiene cyclohexane solution (concentration 20% by weight), polymerize at 70 ° C for 1 hour, and add 50 parts by weight of a cyclohexane solution of styrene was polymerized at 70 ° C for 1 hour. The obtained block copolymer had a styrene content of 70% by weight and an ethylene bonding ratio of the polybutadiene portion of 11%. Also added as a stabilizer, the size of the hard paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back first to write this page) • Packing. Printed by the Consumer Cooperative -50- 1225505 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description P8) Decyl-1-(3,5 -dione-2 -butyl-1 -4-phenylphenyl) Propionate is 0.3 parts by weight of 100 parts by weight of the block copolymer. Thereafter, after the cyclohexane solution of the obtained block copolymer is heated to remove cyclohexane, an block copolymer (polymer 1 8) is obtained. The analysis results of the polymer 18 are shown in Table 2. 19) Polymer 19 After adjusting the amount of n-butyllithium, except for reducing the molecular weight, polymer 19 was produced in the same manner as Polymer 11. The properties of this polymer 19 are shown in Table 2 20) Polymer 20 except that no modifier was used, and polymer 20 was produced in the same manner as Polymer 19. The properties of the polymer 20 are shown in Table 2. -51-This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297mm) 1225505 A7 B7 V. Description of the invention (49 Ministry of Economic Affairs &amp; Property Bureau Staff Consumer Cooperative Co., Ltd. Yinzi 2 谳 1,2C 2C Unit Proportion (%) 〇ooo 〇〇o CN ο ο Hydrogenation rate (%) 〇〇〇oo ON oo ON oo O oo On oo ON so ΟΟ Ον ΟΟ 〇 \ 酹 幼 ^ ^ &On; o ON a \ a \ ON 〇 \ cn O 〇Ν ΟΝ ΟΝ Type of modifier un S &amp; SiCN lean 2 oo 2 m S Kneaded weight average molecular weight (ten thousand) oo oo oo m 〇un CN oo oo i—Η ΟΟ ΟΟ 乙; (# Combining ratio (%) oo m oo cn oo m CN oo oo τ—Η ΟΟ m ΟΟ m m Styrene content (% by weight) oo csi oo csi oo csi On cn Ο ΟΟ Csi ΟΟ csi Sample number polymer 1 1 polymer 1 2 polymer 1 3 polymer 1 4 polymer 1 5 polymer 1 6 polymer 1 7 polymer 1 8 polymer 1 9 polymer 20 (Please read the precautions on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -52- 1225505 A7 V. Description of the invention P) [Example 1] Silicone A is added to the cyclohexane solution of polymer 1 as 10 0 parts by weight of 5 parts by weight of the polymer 1 are mixed. This part of the mixed solution was sampled and left at room temperature for one day and one night, and the silicon oxide A was uniformly dispersed ', and almost no precipitated silicon oxide separated from the mixed solution appeared. In this way, it can be confirmed that polymer 1 and silicon oxide A form a tightly integrated composite state. After the cyclohexane was removed from the mixed solution of polymer 1 and siloxane A by heating, a block copolymer-based composition was obtained. The physical properties of the composition are shown in Table 3. [Comparative Example 1] Siloxane A was added to the polymer 2 solution in the same manner as in Example 1 and mixed. After this part of the solution was sampled and left for one day and one night, it was found that silicon oxide A was precipitated, which was not in a complex state as in Example 1. The solution of the mixed polymer 2 and siloxane A was heated to remove cyclohexane to obtain a block copolymer composition. The physical properties of the obtained composition are shown in Table 3. [Comparative Examples 2 and 3] A sand-oxygen A block copolymer-based composition (Comparative Example 2) blended in an amount less than the range specified in the present invention and a silica-A block copolymer blended in more than this range were copolymerized. The system composition (Comparative Example 3) was produced in the same manner as in Example 1. The physical properties of the obtained composition are shown in Table 3. [Example 2] This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) _ 53 · Please read the back T &amp; Winter Matters written on this page Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economy 1225505 A7 B7 V. Description of the invention f1) To the cyclohexane solution of polymer 3 is added silicon oxide a in an amount of 1,000 parts by weight to 5 parts by weight of polymer 3 and mixed. This part of the solution was sampled and left for one day and one night, and the sand oxygen A was evenly dispersed, and there was almost no silica oxygen A precipitated after the solution was separated. In this way, it can be confirmed that the polymer 3 and the silicon oxide A form a tightly integrated composite state. The mixed solution of the polymer 3 and siloxy A was heated to remove cyclohexane, and a block copolymer composition was obtained. The physical properties of the composition are shown in Table 3. After the abrasion resistance of the composition was measured, the amount of abrasion was i 4 mg. [Comparative Example 4] Siloxane A was added to the cyclohexane solution of polymer 4 in the same manner as in Example 2 and mixed. After this part of the solution was sampled and left for one day and one night, the silicon oxide A was precipitated, and the compound state of Example 2 did not appear. The solution of the mixed polymer 4 and siloxane A was heated to remove the cyclohexyl compound to obtain a block copolymer composition. The physical properties of the obtained composition are shown in Table 3. In addition, after testing the abrasion resistance of this composition, if the amount of abrasion is 25 mg, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Example 3] 100 parts by weight of polymer 5 and 30 parts by weight Siloxane B was mixed with a 30-mm (/) rotary biaxial extruder in the same direction to obtain a block copolymer composition. The extrusion temperature of the extruder is 2 1 0 t, and the rotation number is 200 r pm. The Ha z e of the obtained composition was 55%. -54- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 1225505 A7 B7 V. Description of the invention p) [Comparative Example 5] Using polymer 6 and obtaining the block copolymer in the same manner as in Example 3 Composition ° The Haze of the obtained composition was 80%, which was lower than the transparency of the composition of Example 3. [Example 4] Siloxane B was added to a cyclohexane solution of polymer 7 at 1,000 parts by weight, and 5 parts by weight of polymer 7 was mixed. After sampling this part of the solution, leave it at room temperature for one day and one night. On the other hand, in the case where the silica B is uniformly and microdispersed, there is almost no precipitated silica B after separation by the solution. In this way, it can be confirmed that the polymer 7 and the silicon oxide B form a tightly integrated composite state. [Example 5] Siloxane c was added to a cyclohexane solution of polymer 8 at 10 parts by weight, and 10 parts by weight of polymer 8 was mixed. After sampling this part of the solution, leave it at room temperature for one day and one night, and the silicon oxide C is uniformly and microdispersed. Please read the first 1 and 5 notes before filling out this page. It ’s true that this is OK. 〇 〇 Seeing the state ^ Fu Weihuo C C. Oxygen dense silicon is compacted into a sinking C. The oxygen is separated from the silicon solution and dissolved. 8 is added to the oxygen solution. [Circle of] 9 6 examples of combined application of solid samples and heavy samples were collected from the uniform portion of the dispersant. The oxygenated silicon of A is mixed, and it is weighed one by one at night. Placed under 2 and placed in 9 temperature chambers. After gathering, the paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 1225505. A7 B7 V. Description of the invention P) The precipitated silica A after liquid separation hardly appeared. In this way, it can be confirmed that the polymer 9 and the silicon oxide A form a tightly integrated composite state. [Example 7] Siloxane A was added to 100 parts by weight of 5 parts by weight of polymer 10 in a cyclohexane solution of polymer 10 and mixed. After this part of the solution was sampled, it was left at room temperature for one day and one night, and the silicon oxide A was uniformly and microdispersed. The silicon oxide A precipitated after the separation of the solution hardly appeared. In this way, it can be determined that the polymer 10 and silicon oxide A form a tightly integrated composite state. Please read the winter events first

P ί Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -56- 1225505 A7 B7 V. Description of the invention (54) Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed comparative example 9 1 1 〇1 1 υη 1 1 〇 \ 〇IT) X Comparative example 8 1 〇1 1 1 υη 1 1 〇CN1 Ό un m… 〇 inch ο Comparative example 7 〇I 1 1 1 I g 1 ΙΓ) un \ DX Comparative Example 6 〇1 1 1 1 1 1 1 〇〇〇〇〇cnm 〇cn 〇 Example 11 1 1 1 1 1 〇IT) 1 1 〇m ON CN1 〇CN] Example 10 1 1 1 〇un 1 1 8 m oo ro 〇wi 〇 Example 9 〇1 1 1 1 1 1 cn ON CN] oo 〇Cs3 Example 8 〇1 1 1 1 1 1 ο CNl On CN cn 〇 &lt; N polymer 11 (parts by weight) polymer 12 (parts by weight) polymer 13 (parts by weight) polymer 14 (parts by weight) polymer 15 (parts by weight) silicon dioxide A (parts by weight) silicon dioxide B (parts by weight) two Silicon oxide C (parts by weight) Polypropylene (parts by weight) Rubber softener (parts by weight) Hardness CHS A) Permanent compression deformation (%) Tensile strength (M Pa) The average dispersed particle diameter of processable filler (V m) — “—, — clothing — (Please read the precautions on the back before filling this page) The size of the paper is applicable to Chinese National Standard (CNS) Α4 specification (210 × 297 Mm) -57- 1225505 A7 B7 V. Description of the invention f5) [Examples 8 and 9] 1 0 0 parts by weight of polymer 11 and rubber softener (p W -3 8 0) according to the composition shown in Table 4 After melt-kneading in advance with a 30 mm (/) biaxial extruder at 230 t, add silicon oxide A or C in the amount shown in Table 4 as the component ( 3) Polypropylene resin in the amount shown in Table 4, and 0.88 parts by weight of octyldecyl-3- (3,5-di-third-butyl-1,4-hydroxyphenyl) as a stabilizer is further added. After the propionate was melt-kneaded in a 25 mm 4 biaxial extruder at 230 ° C, a block copolymer composition was obtained. The physical properties of the obtained composition are shown in Table 4. [Comparative Example 6] A block copolymer composition was obtained in the same manner as in Examples 8 and 9 except that no silicon was added. Table 4 shows the physical properties of the obtained composition. [Comparative Example 7] A block copolymer composition was obtained in the same manner as in Examples 8 and 9 except that 80 parts by weight of siloxane B was blended. The physical properties of the obtained composition are shown in Table 4. [Comparative Example 8] A block copolymer composition was obtained in the same manner as in Example 8 using polymer 12 and Example 8. The physical properties of the obtained composition are shown in Table 4. [Comparative Example 9] -Installation-(Please read the precautions on the back page first) Order

C Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) · 58-1225505 Printed by the Consumers’ Cooperative of the Intellectual Property Bureau of the Ministry of Economics A7 ____ B7 V. Invention Description f6 ) A block copolymer composition was obtained in the same manner as in Example 8 using polymer 1 3. The physical properties of the obtained composition are shown in Table 4. [Comparative Example 10] 100 parts by weight of polymer 14 and 100 parts by weight of rubber softener (PW-3 0 0) at 30 mm 0 biaxial extruder at 2 30 ° C After melt-kneading, add 15 parts by weight of siloxy A as a component (2) or '3 4 parts by weight of a polypropylene resin, and 0.8 8 parts by weight of octyl-1 as a stabilizer. (3,5-Di-tertiary-butyl-4-hydroxyphenyl) propionate was melt-kneaded at 25 ° C with a 25 mm (/) twin-screw extruder to obtain inserts. Segment copolymer composition. The physical properties of the obtained composition are shown in Table 4. [Example 1 1] 100 parts by weight of polymer 15 and 100 parts by weight of rubber softener (PW — 3 8 0) were carried out at 30 mm 0 biaxial extruder at 2 3 0 t: After melt-kneading, add 15 parts by weight of Shixi oxygen A as the component (2), and 34 parts by weight of the polypropylene bridge resin as the component (3), and add 0. 88 parts by weight as stability After the octyl decyl 3-(3,5-di-tri-butyl-4-hydroxyphenyl) propionate was melt-mixed in a 25 mm 4 biaxial extruder at 230 ° C Refining to obtain a block copolymer composition. The physical properties of the obtained composition are shown in Table 4. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) _ 59-I. I n batch of clothing I n ΙΊI n order (please read this page first, read the precautions and write this page) 1225505 A7 B7 V. Invention Description f Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, 8th Industrial Cooperative, 7 00 ^ Physical properties of the composition i 〇〇〇 × 〇〇 Heat resistance Z polarization temperature (° C) 175 130 100 Can not obtain the ideal molding sheet 160 125 Transparent Haze (%) r- un cn un Component of the composition (2) Compounding amount (weight part) VO 〇VO wn Type i &lt; Π &lt; 11 &lt; Secret II &lt; Secret 1] &lt; 11 &lt; AD if η Ingredient (1) Compounding amount (weight part) 100 100 100 100 100 100 Type 1 Polymer 1 Polymer 2 Polymer 1 Polymer 1 Polymer 3 Polymer 4 / Example 1 Comparative Example 1 Comparative Example 2 m jj Example 2 Comparative Example 4 (Please read the notes on the back to write this page first)-Install · k This paper size is applicable to China National Standard for Standards (CNS) A4 (210X297 mm) _ 60 _ 1225505 A7 ____B7 V. Invention Explanation P) [Examples 1 2 and 1 3] 1 0 0 parts by weight of polymer 1 1 and 1 0 parts by weight of a softener for rubber (PW — 38 〇) was melt-kneaded with a 30 mm &lt; /) biaxial extruder at 230 seconds, and then added as the ingredient (2) in Table 5 The indicated amount of silicon oxide 2 and the amount of polypropylene resin as the ingredient (3) shown in Table 5 and 3 parts by weight of polystyrene resin, 7 parts by weight of polydiphenyl ether resin, and added 0.88 parts by weight As a stabilizer, octyldecyl 3-(3,5 -di-tertiary-butyl-4-phenylphenyl) propionic acid vinegar was fed into a 2 5 mm 4 biaxial extruder at 2 7 0 C. After fj was melt-kneaded, a block ugly substance composition was obtained. The physical properties of the obtained composition are shown in Table 5. [Comparative Example 10] A block copolymer composition was obtained in the same manner as in Example 12 except that the polymer 12 was used. The physical properties of the obtained composition are shown in Table 5. It is shown in the illustrative facts that there are 8 things, 1 thing, 1 thing group, 1 combination, and 1 get together. Than the object [Examples of the method of grouping together and obtaining the same method of embedding the same way as the 2 printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's consumer co-operatives. This paper is printed in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) -61. 1225505 Printed by the Consumer Bureau of the Property Bureau A7 B7 V. Description of the invention p) Table 5 Example 12 Example 13 Comparative Example 10 Comparative Example 11 Compounding polymer 11 (parts by weight) 100 100 — One polymer 12 (parts by weight) — — -100 — Polymer 18 (parts by weight) — 1 — 100 Siloxane B (parts by weight) 15 40 15 15 Polypropylene (parts by weight) 34 30 34 34 Rubber softener (parts by weight) 100 136 100 100 Polystyrene (Parts by weight) 3 3 3 3 Polydibenzoic acid (parts by weight) 7 7 7 7 Hardness (IIS-A) 62 60 62 Gelation and permanent compressive deformation (%) 30 26 37 Decomposition average dispersion of filler Particle diameter (β m) 0.3 0.2 0.3 (Please read the notes on the back to write this page first) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 62-1225505 A7 B7 V. The description of the invention) [Example 1 4] Add 100 parts by weight of polymer 16 and 10 parts by weight as silicone (A), 2 71 parts by weight of polypropylene resin as component (3), 8 3 4 parts by weight of polymer Styrene resin, added with 0. 88 parts by weight of octyldecyl-3-(3,5-di-tertiary-butyl-4 monohydroxyphenyl) propionate as a stabilizer, then 2 5 mm 0 double The shaft extruder was melt-kneaded at 230 ° C to obtain a block copolymer composition. The physical properties of the obtained composition are shown in Table 6. [Example 15] A block copolymer composition was obtained in the same manner as in Example 14 using polymer 17. The physical properties of the obtained composition are shown in Table 6. [Comparative Example 12] A block copolymer composition was obtained in the same manner as in Example 15 except that no silicon oxide was used. The physical properties of the obtained composition are shown in Table 6. [Comparative Example 1 3] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Using a polymer 18 without using silicon oxide 'was carried out in the same manner as in Example 15 to obtain a block copolymer composition. The physical properties of the obtained composition are shown in Table 6 -63- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 1225505

A

7 B V. Description of the invention p1) Table 6 Example 1 4 Example 1 5 Comparative Example 1 2 Comparative Example 1 3 Compounding polymer 16 (parts by weight) 100 — — — Polymer 1 7 (parts by weight) — 100 100 — Polymer 1 8 (parts by weight) — — — 100 Shixi A (parts by weight) 10 10 — — Polypropylene (parts by weight) 271 271 271 271 Polystyrene (parts by weight) 834 834 834 834 Flexural strength ( MPa) 82 82 73 71 Iz〇d Impact strength (] / m) 157 158 149 149 (Please read the precautions on the back before writing this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Example 16] Add 100 parts by weight of polymer 19 and 10 parts by weight as the silicon dioxide C of the component (2), and 0. 88 parts by weight After the octyl decyl 3- (3,5-di-tertiary-butyl-4 monohydroxyphenyl) propionate was used as a stabilizer, it was carried out with a 2 mm 4 biaxial extruder at 220 ° C. After melt-kneading, a block copolymer composition was obtained. The physical properties of the obtained composition are shown in Table 7 ° This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -64- 1225505 V. Description of the invention P) [Example 1 7] With S 1 6 9 is Except for 10% by weight of sand oxygen C ', a block copolymer composition was obtained in the same manner as in Example 16. The physical properties of the obtained composition are shown in Table 7 ° [Comparative Example 14] A block copolymer composition was obtained in the same manner as in Example 16 using polymer 20. The physical properties of the obtained composition are shown in Table 7. [Comparative Example 15] A block copolymer composition was obtained in the same manner as in Example 17 using polymer 20. The physical properties of the obtained composition are shown in Table 7. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 7 Example 16 Example 17 Comparative Example 14 Comparative Example 15 Compound 19 (parts by weight) 100 100 1 — Polymer 20 (parts by weight) — — 100 100 Silicone C (Parts by weight) 10 10 10 10 Si69 (wt% sand oxygen) — 10 — 10 Tensile strength (MPa) 28 32 17 17 Tensile elongation (%) 590 590 610 610 The paper size applies to the Chinese National Standard (CNS) A4 Specifications (210X297 mm) -65- 1225505 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ____ B7 V. Description of the invention p) The results of Examples 1 to 17 and Comparative Examples 1 to 15 prove that the present invention is embedded The segment copolymer composition has good heat resistance, mechanical strength, transparency, abrasion resistance, and processability, and the block copolymer composition that is more compatible with olefin polymers also has good mechanical strength and permanent compression deformation , Impact resistance, processability. [Industrial Applicability] The present invention (1) a modified block copolymer or a hydrogenated product thereof having a specific structure with a specific functional group, and (2) containing a specific amount selected from a silica-based inorganic filler, Modified block copolymer compositions of rhenium fillers composed of metal oxides and metal hydroxides have good heat resistance, mechanical strength, transparency, abrasion resistance, and processability. In addition, when the composition is further blended with an olefin-based polymer, it is possible to further improve the mechanical strength, permanent compression deformation, impact resistance, and processability of the composition. The modified block copolymer composition of the present invention can process various shapes of molded products by pressure injection molding, extrusion molding and the like according to the above characteristics, and can be used for automobile parts, home appliance parts, wire coating, medical supplies, footwear, This paper size for miscellaneous goods, etc. applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) _-

Claims (1)

1225505 Attachment: Patent Application No. 91108852 Amendments to Chinese Patent Application Range Amendment C8 D8 on April 29, 1993 6. Application for Patent Scope 1 1 · A modified block copolymer composition, which contains: ( 1) a modified block copolymer or a hydride thereof formed of a polymer block A mainly composed of an ethylene aromatic hydrocarbon and a polymer block B mainly composed of a conjugated diene, and, (2) Selected from silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide, wrought wool, glass fiber, magnesium hydroxide, aluminum hydroxide, hydrated silicon Magnesium acid, hydrated aluminum silicate, basic magnesium carbonate and hydrotalcite, a group of fillers made of calcium hydroxide, barium hydroxide, tin oxide hydrate, borax hydrate, among which the molecule of component (1) The chain-end bond has at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amine group, a silanol group, and an alkoxysilyl group. The content of the ethylene aromatic hydrocarbon in the component (1) is 5 ~ 9 5 wt%, the amount of ingredient (2) is relative to the ingredient 1) 0.5 to 100 parts by weight of 5~50 parts by weight, component (2) the average dispersed particle diameter of 0. 01~2 // Π1 persons. 2. The modified block copolymer composition according to item 1 of the patent application scope, which further contains (3) an olefin polymer, and the amount of component (3) is 10 to 500 parts by weight based on 100 parts by weight of component (1). By weight. 3. If the modified block copolymer composition of item 1 or item 2 of the patent application scope, wherein the block ratio of the ethylene aromatic hydrocarbon group is more than 50% of the total ethylene aromatic hydrocarbon in the component (1) By. 4 · If the modified block copolymer composition of item 1 or 2 of the patent application scope, wherein the component (1) is a hydride of the modified block copolymer, the hydrogenation rate of the hydride Above 10%, the paper size from this hydride applies the Chinese national standard (〇 奶) 8 4 specifications (210 \ 297 mm) —11 (please read the precautions on the back before filling this page) Irs Ming ^^ Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives to print out whether there is any change in the substance of the service. Order 1225505 A8 B8 C8 D8 2 ^ In the patent application scope, the conjugated diene total constituent unit has a vinyl bond. The ratio of the constituent units is in the range of 10 to 85%, and the ratio of 1, 2C = C units is 15% or less. 5. The modified block copolymer composition according to item 1 or item 2 of the scope of patent application, wherein the composition is a group of officials at the molecular bond end (1 4) of the component (1) ^ # ' (1) The bond is selected from the following formula (1) '——NR9——R10—OH ---- 1 N [R10——OH] 2-… (2) (Please read the precautions on the back before filling in this Page)-Equipment · NR9—R10—CH—CHR 11 (3), 1T »N [R10—CH—CHR11] 2 \ / 〇 ---- (4) -CR9—R10—NR11R12 I OH • (5) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs—C—NR9—R10—NR11R12II 〇_C—R10—NR11R12II 〇—CR9—NR11—R10—NR13R I OH 14 CNS) A4 specification (210X297 mm) one, — (6) (7)…-(8) 1225505 A8 B8 C8 D8 six m®9_R10-NR11R12—iH (9) —nr -N [R 9_R10—Si (ORn ) 10-Si (〇R ”) 3] 2 ---- (10) (11) -CR '· IOH, R10—OR 11 (12) ——CRW IOH -R -Si (〇R11) --- -(13) (Please read the precautions on the back before filling in this page) "Installation · Ri〇 一 Si (〇R11) ---- (14) (14), R9 and R12 ~ are functional groups with 9 4 hydrocarbon groups, or hydroxyl, epoxy, silanol groups and consumer cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (formula (1) 'selected from hydrogen, carbon number 1 _ group For those having 1 to 2 carbons in carbon, R &quot; is formed by an alkoxysilyl group and has a hydrocarbon chain selected from the group consisting of 1 to 3Q in carbon, or a hydroxyl group, an epoxy group, a salicyl group, and a hydroxyl group M. Carbon groups of functional groups with 1 to 3+ carbon atoms and R12 to R14 hydrocarbon groups, R1 ◦ hydrocarbon chain in the hydrocarbon chain, and in addition to RR in addition to hydroxyl, epoxy, silanol and alkoxy groups Bonding forms other than silane groups can also bond elements such as oxygen, nitrogen, and silicon, and Rii is hydrogen or an alkyl group having 1 to 8 carbon atoms. 6) As described in item 1 or 2 of the scope of patent application The modified block copolymer composition is based on the component (1) whose molecular chain terminal bond is selected from the functional groups grouped by the following formulas (1) to (9). P. This paper is applicable to China National Standard (CNS) A4 Specification (210X297 mm) _ 3 — 1225505 A8 B8 C8 D8 Patent Application Range——NR9—R10—OH • (1) N [R, U——〇H] 2-NR9—R10— CH—CHR11 ( 2) -0) —N [R10—CH—CHR11]-(4) ——CR9—R10—NR11R12 OH-(5) (Please read the notes on the back before filling this page) -C—NR9 ~ r ^ —NR11R12 〇1 (6) -C-R10—NR11R12 O-(7) —CR9—NR11—R10—NR13RU OH-(8) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs—CR9—R · 0—NR11R12 OH 19) (In the formulae (1) to (9), R9 and R12 to R14 are formed from a hydrocarbon group selected from hydrogen, carbon number 1 to 24, or a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilyl group. The functional group has a carbon number of 1 to 2 4 hydrocarbon groups, and the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)-4-1225505 A8 B8 C8 D8 夂, the scope of patent application R1. A hydrocarbon chain having a carbon number of 1 to 30 selected from a hydrocarbon chain having a carbon number of 1 to 30, or a functional group grouped by a radical, an epoxy group, a salicyl group, and a hydroxyl group, Furthermore, in the hydrocarbon chain of R 9 and R 1 2 to R 1 4 alkyl and R 1 ◦, bonding forms other than hydroxyl, epoxy, silanol, and alkoxysilyl groups may also be bonded. Oxygen, nitrogen, silicon and other elements, and R 1 1 is hydrogen or an alkyl group having 1 to 8 carbon atoms). 7 · If the modified block copolymer composition of item 1 or item 2 of the patent application scope contains silane coupling agent in an amount of 0 to 1 to 20% by weight relative to the component (2). -Install-(Please read the notes on the back before filling out this page) Order Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm)-5