JPH0468343B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a composition of a block copolymer and a thermoplastic resin having excellent impact resistance, compatibility, heat deterioration resistance, and low-temperature properties. The present invention relates to a composition of a block copolymer obtained by specifically hydrogenating a block copolymer of a conjugated diene and a thermoplastic resin, etc. [Prior art] Block copolymers made of conjugated dienes and vinyl aromatic hydrocarbons are different from natural rubber or ordinary synthetic rubbers in that they can be vulcanized using a vulcanizing agent, an accelerator, and a filler such as carbon black. It has strength and elastic properties equivalent to those of elastomers vulcanized at room temperature without vulcanization, and exhibits processability similar to thermoplastics at high temperatures, so it is currently being used extensively due to these properties. has been done. Examples include injection molded products, extrusion molded products, blow molded products such as hoses, footwear, window frames, containers, toys, household goods, etc. In these various uses, block copolymers are generally used in combination with inorganic fillers, organic fillers, thermoplastic resins, and the like. For example, the special public interest public corporation in 1977-
19388, Japanese Patent Publication No. 51-36292, and Japanese Patent Application Publication No. 53-96048, block copolymers contain thermoplastic resins such as polystyrene and polyethylene, softeners such as naphthenic oils, and organic fillers such as clay and calcium carbonate. It has been described that a composition containing the following is used for footwear. Also, Special Publication No. 1977-7126, Special Publication No. 1977
No. 43618 and Japanese Patent Publication No. 52-21012 describe a method of improving impact resistance by blending the above block copolymer with polystyrene or rubber-modified polystyrene. Similarly, Japanese Patent Publication No. 42-19935, Japanese Patent Publication No. 45-4624, Japanese Patent Publication No. 46-5067, Japanese Patent Publication No. 46-1867, and Japanese Patent Application Laid-Open No. 48-62851 respectively contain polypropylene, polyethylene, Attempts have been made to improve the properties of acrylic resins, vinyl chloride resins, and polyphenylene ether resins by blending them with the above block copolymers. [Problems to be Solved by the Invention] However, compositions containing block copolymers of vinyl aromatic hydrocarbons and conjugated dienes generally have poor moldability at high temperatures, and when molding the compositions, production If molded at a relatively high temperature for the purpose of improving properties, the impact resistance may drop sharply, or even if a block copolymer is blended with engineering resins that require molding at high temperatures, the desired performance may not be achieved. The problem arises that it is not possible to obtain Therefore, for the purpose of improving high temperature moldability,
Attempts have been made to blend a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene into a thermoplastic resin by hydrogenating the block copolymer and converting the conjugated diene polymer block into a saturated olefin polymer block. There is. For example, JP-A-52-150464 and JP-A-53-94540 disclose a block copolymer in which 80% or more, preferably 99% or more of the resin group double bond moiety based on a conjugated diene is hydrogenated. A composition blended with an engineering resin is described. However, in such compositions, the compatibility between the hydrogenated block copolymer and the thermoplastic resin is poor, and depending on the amount blended, molded products of the composition may suffer from delamination or have poor low-temperature properties. At times, there are problems such as the desired performance not being exhibited. [Means and effects for solving the problem] Under the current situation, the present inventors have developed a method for improving heat deterioration resistance and high temperature molding when using a block copolymer in combination with a thermoplastic resin, an inorganic/organic filler, etc. As a result of conducting studies to obtain a composition with excellent processability, compatibility, impact resistance, and low-temperature properties, we found that aliphatic double bonds in a block copolymer with a vinyl bond content in a specific range based on a conjugated diene compound The present invention was completed based on the discovery that the object can be achieved by using a block copolymer which is specifically hydrogenated. That is, the present invention provides (a) a polymer block mainly composed of at least one vinyl aromatic compound and a polymer block mainly composed of at least one conjugated diene compound; A block copolymer having a content [V] of 80% or less is hydrogenated, and (1) the hydrogenation rate [A] of the entire aliphatic double bond based on a conjugated diene compound is 5% or more and 75%. and (2) a specific hydrogenated block copolymer in which the hydrogenation rate [B] of the vinyl bond based on the conjugated diene compound satisfies [B]/[V] ^1/2 = 3 to 20. ,1
-99 parts by weight (b) A composition comprising 99 to 1 part by weight of a thermoplastic resin, and a composition in which the above components (a) and (b) are further combined with an inorganic filler and/or an organic filler. The present invention will be explained in detail below. The specific hydrogenated block copolymer used as component (a) of the present invention comprises a polymer block A mainly composed of at least one, preferably two or more vinyl aromatic compounds, and at least one conjugated A block copolymer consisting of a polymer block B mainly composed of a diene compound, and having a vinyl bond content [V] based on a conjugated diene compound of 80% or less, preferably 10 to 70%, more preferably 15 to 65%. is hydrogenated (hydrogenated), and the hydrogenation rate [A] of the entire aliphatic double bond based on the conjugated diene compound in the copolymer is 5% or more and less than 80%, preferably 10 to 60.
%, more preferably 10 to 45%, particularly preferably 15 to 45%, and the hydrogenation rate of the vinyl bond based on the conjugated diene compound in the copolymer [B]
satisfies [B]/[V] ^1/2 = 3 to 20, preferably [B]/[V] ^1/2 = 5 to 18, and more preferably [B]/[V] ^1/2 = 7 to 16. This is a specific hydrogenated block copolymer.
Vinyl bond content based on conjugated diene compound [V]
If it can reach 80%, it is not preferable because the low temperature properties are poor. In addition, when the hydrogenation rate [A] of the entire aliphatic double bond based on the conjugated diene compound in the block copolymer is less than 5%, the heat deterioration resistance is poor,
If it exceeds 75%, the low-temperature properties and compatibility with thermoplastic resins will be poor. Furthermore, if [B]/[V] ^1/2 is less than 3, the heat deterioration resistance is poor, and [B]/[V] ^1/2 is 20.
If it exceeds the above range, it is not preferable because the low temperature properties and compatibility with the thermoplastic resin are poor. In the present invention, the vinyl bond content based on the conjugated diene compound refers to the vinyl bond content of the conjugated diene compound incorporated into the block copolymer in the bonding modes of 1,2-bond, 3,4-bond, and 1,4-bond. Among them, 1, 2-bond and 3,
This is the total percentage of those incorporated in the 4-bond binding mode. The vinyl bond content can be determined using an infrared spectrophotometer, nuclear magnetic resonance apparatus, or the like.
In addition, the hydrogenation rate [A] of the entire aliphatic double bonds based on the conjugated diene compound refers to the hydrogenation rate [A] of the total aliphatic double bonds based on the conjugated diene compound incorporated in the block copolymer. This is the percentage of saturated hydrocarbon bonds that have been converted into saturated hydrocarbon bonds. Furthermore, the hydrogenation rate [B] of the vinyl bond based on the conjugated diene compound is based on the conjugated diene compound incorporated into the block copolymer in the bonding mode of 1,2-bond and 3,4-bond. Of the aliphatic double bonds,
It is the percentage of hydrogenated and converted to saturated hydrocarbon bonds. Note that [B] is 100% or less.
The hydrogenation rates [A] and [B] can be determined using an infrared spectrophotometer, a nuclear magnetic resonance apparatus, or the like. When determining the hydrogenation rate from a hydrogenated block copolymer, a method using a nuclear magnetic resonance apparatus is effective. The content of the vinyl aromatic compound in the specific hydrogenated block copolymer of the present invention is 5 to 95% by weight, preferably 10 to 90% by weight, and more preferably 15 to 85% by weight. Such a block copolymer exhibits properties as a thermoplastic elastomer when the vinyl aromatic compound content is 60% by weight or less, preferably 55% by weight or less; If it exceeds 65% by weight, preferably 65% by weight or more, it exhibits properties as a thermoplastic resin. In the present invention, when obtaining a rubbery composition or a composition with good impact resistance, the content of the vinyl aromatic compound is 5 to 60%.
It is preferred to use 10-55% by weight, more preferably 15-50% by weight of block copolymer. As a method for producing the block copolymer before hydrogenation used in the present invention, any known method may be used as long as the vinyl bond content is within the range specified in the present invention. 43−
Publication No. 17979, Special Publication No. 1979-31951, Special Publication No. 1973
-32415 Publication, Special Publication No. 48-2423, Special Publication Sho
Examples include the methods described in Japanese Patent Publication No. 48-4106, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 49567-1982, Japanese Patent Publication No. 28925-1987, and the like. These are methods in which a conjugated diene and a vinyl aromatic compound are block copolymerized using a polymerization initiator such as an organolithium compound in a hydrocarbon solvent, and the general formula is (A-B) _o , A-(-A) _o , B-(A-B) _o (In the above formula, A is a polymer segment mainly composed of a vinyl aromatic compound, and B is a polymer segment mainly composed of a conjugated diene.A segment and B segment It is not necessary to clearly distinguish the boundary between the block copolymer and the general formula [(B- A) _o 〕 _n+1 ---X, [(A-B-) _o 〕 _n+1
---X [(B-A-) _o B] _n+1 ---X, [(A-B-) _o
A] _n+1 ---
X (In the above formula, A and B are the same as above,
X is an initiator such as a polyfunctional organolithium compound, silicon tetrachloride, tin tetrachloride, polyepoxide such as epoxidized soybean oil, polyhalogenated hydrocarbon, carboxylic acid ester, polyacid anhydride, polyisocyanate, polyaldehyde, Residues of coupling agents such as polyketones and polyvinyl compounds are shown. m and n are integers of 1 or more, preferably integers of 1 to 5. ) It is obtained as a block copolymer represented by: In the above formula, the polymer segment mainly composed of vinyl aromatic compounds refers to
It refers to a copolymer block of a vinyl aromatic compound and a conjugated diene containing 50% by weight or more and/or a vinyl aromatic compound homopolymer block, and a polymer block mainly composed of a conjugated diene is defined as a copolymer block containing a vinyl aromatic compound and a conjugated diene. A copolymer block of a conjugated diene and a vinyl aromatic compound and/or a conjugated diene homopolymer block containing more than 50% by weight is shown. The vinyl aromatic compound in the copolymer block may be uniformly distributed or tapered. A plurality of uniformly distributed portions and/or tapered distributed portions may coexist in each block. The block copolymer used in the present invention may be any mixture of block copolymers represented by the above general formula. The conjugated diene used in the present invention is a diolefin having a pair of conjugated double bonds, such as 1,
3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-
Examples include butadiene, 1,3-pentadiene, 1,3-hexadiene, and particularly common ones include 1,3-butadiene and isoprene. These may be used not only alone, but also as a mixture of two or more. Vinyl aromatic compounds used in the present invention include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, etc. A particularly common example is styrene. These may be used not only alone, but also as a mixture of two or more. The vinyl bond content [V] can be adjusted by using a polar compound as a vinylating agent in a polymerization method using an organolithium compound as an initiator in a hydrocarbon solvent, and by controlling the type, amount used, polymerization temperature, etc. of the polar compound. can be done. Hydrocarbon solvents include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, isooctane, cyclopentane,
Alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane, or aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene can be used. Examples of the organic lithium catalyst include organic monolithium compounds, organic dilithium compounds, and organic polylithium compounds. Specific examples of these include ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec
-butyllithium, tert-butyllithium, hexamethylene dilithium, butadienyl dilithium, isoprenyl dilithium, and the like.
In addition, as polar compounds, tetrahydrofuran,
Examples include ethers such as diethylene glycol dimethyl ether and diethylene glycol dibutyl ether, amines such as triethylamine and tetramethylethylenediamine, thioethers, phosphines, phosphoramides, alkylbenzene sulfonates, potassium and sodium alkoxides, and the like. As the block copolymer before hydrogenation used in the present invention, a block copolymer in which a polar group-containing atomic group is bonded to at least one polymer chain terminal of the block copolymer can be used. By bonding a polar group-containing atomic group to the end of a polymer chain, compatibility with thermoplastic resins, impact resistance, etc. can be improved. Here, the polar group-containing atomic group refers to an atomic group containing at least one atom selected from nitrogen, oxygen, silicon, phosphorus, sulfur, and tin. Specifically, carboxyl group, carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group. group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group,
Nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothioneanate group, silicon halide group, alkoxy silicon group, tin halide group,
Examples include atomic groups containing at least one polar group selected from alkyltin groups, phenyltin groups, and the like. More specifically, among the terminally modified block copolymers described in Japanese Patent Application No. 61-129179, a terminally modified block copolymer having a vinyl bond content within the range of the present invention can be used. The terminal modification treatment agent for imparting a polar group-containing atomic group is 0.5 per atomic equivalent of lithium metal at the polymer terminal.
~2 mol is used, preferably 0.7-1.3 mol. The specific hydrogenated block copolymer used in the present invention has a number average molecular weight of 5,000 to 1,000,000, preferably
10000-800000, more preferably 30000-300000
The number average molecular weight of the block copolymer before hydrogenation is also preferably adjusted within this range. Next, the above block copolymer is subjected to a hydrogenation reaction. Catalysts used in hydrogenation reactions include (1)
Carbon, silica, metals such as Ni, Pt, Pd, Ru, etc.
The so-called Ziegler type uses a supported heterogeneous catalyst supported on a carrier such as alumina or diatomaceous earth, (2) an organic acid salt such as Ni, Co, Fe, or Cr, or an acetylacetone salt, and a reducing agent such as organic Al. Homogeneous catalysts such as catalysts or so-called organic chain catalysts such as organometallic compounds such as Ru and Rh are known. Specific methods are as described in Japanese Patent Publication No. 42-8704 and Special Publication No. 43
Hydrogenated products are produced by hydrogenation in the presence of a hydrogenation catalyst in an inert solvent by the method described in JP-A-6636, JP-A-59-133203, and JP-A-60-220147. and the specific hydrogenated block copolymer used in the present invention can be synthesized. At that time, the hydrogenation rate [A] of the entire aliphatic double bond based on the conjugated diene compound in the block copolymer and the hydrogenation rate [B] of the vinyl bond are hydrogenated within the range specified in the present invention. It is necessary to adjust the reaction temperature, reaction time, hydrogen supply amount, catalyst amount, etc. Also,
About the hydrogenation rate of aromatic double bonds based on the vinyl aromatic compound copolymerized into polymer block A mainly composed of vinyl aromatic compounds and, if necessary, polymer block B mainly composed of conjugated diene compounds. Although there is no particular restriction, it is preferable that the hydrogenation rate be 20% or less. The specific hydrogenated block copolymer used in the present invention is an α,β-unsaturated carboxylic acid or a derivative thereof, such as its anhydride, esterified product, amidated product, or imidized product (hereinafter, α,β-unsaturated carboxylic acid). It may be modified with acids (abbreviated as acids). Modified products of specific hydrogenated block copolymers (hereinafter referred to as modified block copolymers) are block copolymers.
Generally, 0.01 to 50 parts by weight, preferably 0.05 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight of α,β-unsaturated carboxylic acids added per 100 parts by weight can be used. Examples of α,β-unsaturated carboxylic acids include maleic acid, maleic anhydride, maleic anhydride, fumaric acid, itaconic acid, acrylic acid,
Methacrylic acid, acrylic ester, methacrylic ester (methyl methacrylate, glycidyl methacrylate, etc.), crotonic acid,
Cis-4-cyclohexene-1,2-dicarboxylic acid and its anhydride, endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid and its anhydride, maleimide, etc. Among these, maleic anhydride, maleic anhydride, and glycidyl methacrylate are preferred. The modified block copolymer may be produced in either a solution state or a molten state, and
The modified block copolymer may be used in the presence or absence of a radical generator such as an organic peroxide, but is not particularly limited. A manufacturing method that causes deterioration is not preferred. As an example of a preferable manufacturing method, for example, in an extruder, 150~
There is a method of melt-kneading the above hydrogenated block copolymer and α,β-unsaturated carboxylic acids at a temperature of 350°C, preferably 170 to 300°C, in the presence or absence of an organic peroxide. The obtained modified block copolymer may be ionomerized with monovalent, divalent, or trivalent metal ions. As organic peroxides,
For example, dicumyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di(tert-
butylperoxy)hexane and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, n-butyl 4,4-bis(tert-butylperoxy)valerate, 1,1-bis (tert-butylperoxy)3,3,5-trimethylcyclohexane and the like. In addition, in the modified block copolymer obtained in this way, unreacted α,β-unsaturated carboxylic acids generally remain as unreacted substances, but these unreacted substances are completely removed. or may be left as is. In particular, when blending a thermoplastic resin and a modified block copolymer, in order to improve their mutual dispersibility, unreacted materials are added to 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the modified block copolymer. It is preferable to coexist in parts by weight. The graft reaction may be carried out in the presence of stabilizers such as various phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers, and amine stabilizers. The thermoplastic resin of component (b) used in the present invention is composed of a vinyl aromatic hydrocarbon having a vinyl aromatic hydrocarbon content of 60 to 95% by weight, which is outside the range specified in the present invention (a), and a conjugated diene. Block copolymer resins, polymers of the above vinyl aromatic hydrocarbon monomers, the above vinyl aromatic hydrocarbon monomers and other vinyl monomers, such as ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate. ,
At least one type of carbonized vinyl aromatic selected from acrylic esters such as methyl acrylate, methacrylic esters such as methyl methacrylate, copolymers with acrylonitrile, methacrylonitrile, etc., rubber-modified styrenic resins (HIPS), etc. Hydrogen-based resins, polyethylene, copolymers of ethylene containing 50% or more of ethylene and other monomers that can be copolymerized with it, such as ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, and their hydrolysates , polyethylene resins such as ethylene-acrylic acid ionomers and chlorinated polyethylene, polypropylene, copolymers of propylene containing 50% or more of propylene and monomers copolymerizable with it, such as propylene-ethylene copolymers, propylene- Polypropylene resins such as ethyl acrylate copolymers and chlorinated polypropylene, polybutene-1, polybutene-based resins that are copolymers of butene-1 and other monomers that can be copolymerized with it, polyvinyl chloride, polychloride Content of vinylidene, vinyl chloride, and/or polyvinyl chloride resin that is a copolymer of vinyl chloride and/or vinylidene chloride containing 50% or more of vinylidene chloride and other monomers that can be copolymerized with it, and vinyl acetate. is 50
% or more of vinyl acetate and other copolymerizable monomers and their hydrolysates, acrylic acid and its esters and amides, methacrylic acid and its esters and amides, Polyacrylate resins that are copolymers with other copolymerizable monomers containing 50% or more of these acrylic acid monomers, polymers of acrylonitrile and/or methacrylonitrile, and containing 50% or more of these acrylonitrile monomers. nitrile resins that are copolymers with other copolymerizable monomers, linear polymers in which the constituent units of the polymer are bonded by repeated amide group bonds,
For example, polyamides such as ring-opened polymers of ε-aminocaprolactam and ω-aminolaurolactam, condensation polymers of ε-aminoundecanoic acid, and condensation polymers of hexamethylene diamine and dibasic acids such as adipic acid and sebacic acid. Linear polymers in which the constituent units of resins and polymers are bonded by repeating ester bonds, such as dibasic acids such as phthalic acid and isophthalic acid, or derivatives thereof, and ethylene glycol, propylene glycol, butylene glycol, etc. A polyester resin that is a condensate with a glycol component, a polyphenylene ether resin, or a grafted polyphenylene ether resin obtained by graft polymerizing a vinyl-substituted aromatic hydrocarbon to the resin;
Polyacetal resins such as polyphenylene sulfide resins, polyoxymethylene, copolymers of trioxane and alkylene oxide, linear polymers in which the constituent units of the polymer are bonded by repeating carbonate type bonds, for example, A polymer obtained by the reaction of a dihydroxy compound such as 4,4'-dihydroxydiphenylalkane or 4,4'-dihydroxydiphenyl sulfide with phosgene,
Alternatively, a polycarbonate resin such as a polymer obtained by transesterification of the dihydroxy compound and diphenyl carbonate, a polysulfone resin such as polyether sulfone or polyallylsulfone, or a polyaddition reaction between a diisocyanate component and a glycol component. Thermoplastic polyurethane resin, trans polybutadiene, obtained by
Part or all of the hydrogen in polybutadiene resins such as 1,2-polybutadiene, polyketone resins, polyarylate resins that are polycondensation polymers consisting of bisphenol A and phthalic acid components, and chain hydrocarbon polymer compounds. Fluorine resins having a structure substituted with fluorine, polyoxybenzoyl resins,
Polyimide resin, etc. The number average molecular weight of these thermoplastic resins is generally 1,000 or more, preferably 5,000 to 5,000,000, and more preferably 10,000 to 1,000,000. Specific examples of polar thermoplastic polymers suitable for the present invention include the following. Aliphatic unsaturated carboxylic acid-containing polymer The aliphatic unsaturated carboxylic acid-containing polymer used in the present invention is a copolymer of an aliphatic unsaturated carboxylic acid and another copolymerizable monomer. Examples of aliphatic unsaturated carboxylic acids include monocarboxylic acids such as acrylic acid and methacrylic acid, dicarboxylic acids such as fumaric acid, maleic acid, and itaconic acid, and dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride. . Other copolymerizable monomers include the vinyl aromatic hydrocarbons such as styrene, α-methylstyrene, paramethylstyrene, ester derivatives of the aliphatic unsaturated carboxylic acids and C ₁ to C ₁₂ alcohols, and fatty acids. Examples include amidotide derivatives and imidide derivatives of group unsaturated carboxylic acids, nitrile monomers such as acrylonitrile and methacrylonitrile, vinyl acetate, vinyl chloride, and vinylidene chloride. The weight ratio of aliphatic unsaturated carboxylic acids and other copolymerizable monomers is generally 1/99 to 50/50, preferably 3/97 to 40/60.
can be suitably used. Furthermore, natural rubber, butadiene rubber, styrene-butadiene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene monomer copolymer rubber, etc. may be allowed to coexist during polymerization of aliphatic unsaturated carboxylic acids and other copolymerizable monomers. Rubber-modified polymers can also be used. Particularly suitable polymers containing aliphatic unsaturated carboxylic acids include 14 to 94% by weight of methyl methacrylate;
A copolymer consisting of 5 to 85% by weight of acrylic acid or methacrylic acid and 1 to 70% by weight of vinyl aromatic hydrocarbon (weight average molecular weight 50,000 to 500,000, preferably
70000-200000), acrylic acid or methacrylic acid 3
~50% by weight, vinyl aromatic hydrocarbons 50-97% by weight
Copolymer consisting of (weight average molecular weight 100,000~
500,000, preferably 150,000 to 400,000), maleic anhydride 3 to 45% by weight, vinyl aromatic hydrocarbon 97 to
Copolymer consisting of 55% by weight (weight average molecular weight
100,000 to 500,000, preferably 150,000 to 400,000). Polyamide Polymer The polyamide polymer used in the present invention is a polycondensate of dicarboxylic acid and diamine, a polycondensate of α-aminocarboxylic acid, a ring-opening polymer of cyclic lactam, etc., and specifically, Nylon-46, nylon-
6. Nylon-66, Nylon-610, Nylon-
11, nylon-12, and copolymers thereof, ie, nylon-6-nylon 66 copolymer, nylon 6-nylon-12 copolymer, and the like. The number average molecular weight of these polyamides is 200-50000,
Preferably, it has a molecular weight of 1,000 to 30,000, and a melting point of 150 to 270°C. Polyester Polymer The polyester polymer used in the present invention is thermoplastic. Polyester polymers contain ester bonds in their molecules, and typical polyesters have a polycondensation structure of dicarboxylic acid and glycol or bisphenol. It is obtained by polycondensing an acid halide or acid anhydride with glycol or bisphenol. The raw material for this polyester is
Aromatic or aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, adipic acid, sebacic acid, azelaic acid, 1,9-nonanedicarboxylic acid, 1,
10-decanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, terephthalic acid, isophthalic acid,
Examples include p,p'-dicarboxydiphenyl, p-carboxyphenoxyacetic acid, and 2,6-naphthalene dicarboxylic acid, and any combination of these may be used. Among these, terephthalic acid and isophthalic acid are particularly preferred. Glycol (or diol), which is the other raw material for the above polyester, can be aliphatic or aromatic, examples of which include ethylene glycol, 1,3-propanediol,
1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,10-decanediol,
Examples include neopentyl glycol, p-xylene glycol bisphenol A, and these can be used alone or in any combination.
Among these, alkylene glycols having 2 to 10 carbon atoms are preferred, and ethylene glycol and 1,4-butanediol are particularly preferred. Among the polyesters comprising dicarboxylic acid units and glycol units, useful polyesters include polyethylene phthalate, polybutylene phthalate, and those in which some of these monomer units are replaced with other monomer units. The molecular weight of these polyesters used is 500 to 100,000, preferably 5,000 to 50,000. The method of polymerizing the polyester used in the present invention is not particularly limited, and the polymerization can be carried out by a conventional method. The vinegar component described above, such as terephthalic acid, isophthalic acid, aliphatic dicarboxylic acid, or an ester-forming derivative thereof, is added to one of the glycols described above.
There is a method of carrying out a direct esterification or transesterification reaction simultaneously or stepwise with more than one species, followed by polymerization, or a method of carrying out polycondensation with a dicarboxylic acid chloride. At that time, any various commonly used catalysts, stabilizers, modifiers, additives, etc. may be used. Other useful polyesters include polylactones obtained by ring-opening polymerization of cyclic lactones, such as pivalolactone, β-propiolactone, and ε-caprolactone. These polyester polymers have a hydroxy group or a carboxyl group at the molecular end,
Furthermore, this terminal is reacted with a monofunctional alcohol or a monofunctional carboxylic acid to inactivate the functional group. In the present invention, the polyester polymer preferably has a functional group that reacts with the functional group of the modified block copolymer at part or all of its molecular terminal. When a part of such functional group-containing polyester reacts with the modified block copolymer, the compatibility of the composition is significantly improved. The above polyester polymers can be used not only alone but also in combination of two or more. In addition to polyesters used in fibers, films, resins, etc., such as polyethylene terephthalate, the thermoplastic polyester polymers used in the present invention include low-crystalline polyesters with lower melting points, hard segments and soft segments. Also included are polyetherester block polymers having segments within the same molecule. Thermoplastic polyurethane polymer The thermoplastic polyurethane polymer used in the present invention is classified into completely thermoplastic type and incomplete thermoplastic type depending on the synthesis conditions. Determined by the molar ratio of OH groups and NCO groups of diisocyanate, approximately
Those synthesized with 0.95<NCO/OH≦1 are completely thermoplastic, and those synthesized with about 1<NCO/OH<1.1 are incompletely plastic. As the above-mentioned thermoplastic polyurethane, for example, there is one in which a block of polyol (polyester or polyether) and diisocyanate is used as a soft segment, and a block of diisocyanate and glycol is used as a hard segment. Examples of the polyester diol used as the raw material include poly(1,4-butylene adipate), poly(1,6-hexane adipate), polycaprolactone, etc., and examples of the polyether diol include polyethylene glycol, polypropylene glycol, and polypropylene glycol. These include oxytetramethylene glycol. Furthermore, as glycols, ethylene glycol, 1,4-butanediol,
Examples of diisocyanates include aromatic, alicyclic, and aliphatic diisocyanates, such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone. Diisocyanates, etc. In addition to the above-mentioned thermoplastic polyurethane elastomers, polyurethane polymers used for adhesives, foams, paints, etc. may also be combined with the specified water-added block copolymer, which is component (a) of the present invention. Those with sufficient compatibility can be used in the compositions of the present invention. As a thermoplastic polyurethane, the molecular weight is
5,000 to 500,000, preferably 10,000 to 300,000, can be used satisfactorily from the viewpoint of mechanical properties. Vinyl alcohol polymer Vinyl alcohol polymer is a polymer consisting of vinyl alcohol units or a copolymer containing vinyl alcohol units, and vinyl ester polymers are partially or completely saponified using an alkali. It is a polymer obtained by The ethylene-vinyl alcohol copolymer uses the corresponding ethylene-vinyl acetate copolymer as a starting material, and the ethylene-vinyl acetate copolymer has a vinyl acetate content of 0.5 to 80 mol%. is common. In the above polymer, 10 to 100 mol% of the vinyl acetate units are saponified to form an ethylene-vinyl alcohol copolymer.
In the present invention, various polyvinyl alcohols or olefin-vinyl alcohol copolymers can be used, but from the viewpoint of processability and mechanical properties, ethylene-vinyl alcohol
Vinyl alcohol copolymers are preferred. Polyoxymethylene Polymer Examples of polyoxymethylene polymers include homopolymers produced by polymerization of formaldehyde or trioxane, and copolymers containing the above monomers as main components. For homopolymers, the end groups of the polymer are generally converted into ester groups or ether groups to improve heat resistance and chemical resistance. Examples of the copolymer include copolymers of formaldehyde or trioxane with other aldehydes, cyclic ethers, cyclic carbonates, epoxides, isocyanates, vinyl compounds, and the like. Polycarbonate polymer Polycarbonate polymer has the general formula or (In the above formula, A ¹ _r represents a phenylene group or a phenylene group substituted with an alkyl group, a substituted alkyl group, an alkoxy group, a halogen or a nitro group, and A is an alkylene group, an alkylidene group, a cycloalkylene group, a cycloalkylidene group, It is an aromatic polycarbonate having a structural unit of sulfur, oxygen, sulfoxide group or sulfone group. A preferred example is poly-4,4'-dioxydiphenyl-2,2'-propane carbonate. Polysulfone polymers have the general formula -[A ² _r -B-A ² _r -SO ₂ -] or - [A ² _r -SO ₂ -] (In the above formula, A ² _r represents a phenylene group,
B represents oxygen, sulfur, an aromatic diol residue, or a bisphenol residue. ) is a thermoplastic polysulfone having the following structural units. Preferred examples include poly(ether sulfone), poly(4,4-bisphenol ether sulfone), and poly(thioether sulfone). Polyphenylene ether polymer Polyphenylene ether polymer has the general formula (In the above formula, R ¹ and R ² represent a C ₁ to C ₄ alkyl group, a substituted alkyl group, or a halogen.) A phenylene ether polymer having a structural unit of
Alternatively, it is a polyphenylene ether graft copolymer obtained by graft polymerizing a styrene compound to the phenylene ether polymer. Styrenic compounds used for graft modification include styrene, α-methylstyrene, methylstyrene, tert
-butylstyrene, chlorostyrene, etc., and two or more of these may coexist during graft polymerization, and if desired, other copolymerizable vinyl compounds such as acrylic ester, methacrylic ester, acrylonitrile, It is also possible to carry out co-graft polymerization using methacrylonitrile or the like. A preferred phenylene ether polymer is poly(2,6-dimethyl-
(1,4-phenylene) ether, and its preferred graft modified product is a styrene graft copolymer of the polymer. Polyarylene sulfide polymers Polyarylene sulfide polymers have the general formula -[A ³ _r -S-] (In the above formula, A ³ _r is substituted with a phenylene group, an alkyl group, or a substituted alkyl group. It is an arylene sulfide polymer or copolymer having the structural unit (representing a phenylene group). Suitable examples include polyphenylene sulfide and poly4,4'-diphenylene sulfide. Polyketone resin has the general formula - [A ³ _r -O-A ³ _r -CO-A ³ _r -O-] - [A ³ _r -A ³ _r -O-A ³ _r -CO-A ³ _r - O-] Or-[A ³ _r -D-A ³ _r -O-A ³ _r -CO-A ³ _r -O-] (In the above formula, A ³ _r is the same as above, and D
is oxygen, sulfur, -SO ₂ -, -CO-, alkylene group,
Indicates a biphenol group. ) is a polyetherketone polymer or copolymer having the following structural units. A suitable example is polyetheretherketone. Polyarylate resin is a polyester resin made of diphenol, and is produced by a method of reacting bisphenol acetate and carboxylic acid or bisphenol and dicarboxylic acid phenol ester in a high-temperature molten state, or by deoxidizing dicarboxylic acid dichloride and bisphenol. A method of reacting in an organic solvent in the presence of an amine as an agent, after dissolving dicarboxylic acid dichloride and bisphenol in two incompatible solvents,
It is produced by mixing and stirring two liquids in the presence of an alkali and causing a condensation reaction at the interface. A preferred example is a polycondensate of bisphenol A and a phthalic acid component. 〓 Fluororesin Fluororesin is a polymer having a structure in which part or all of the hydrogen in a chain hydrocarbon polymer compound is replaced with fluorine. Specific examples include polytetrafluoroethylene and tetrafluoroethylene-peroxide. Fluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer, chlorotrifluoroethylene-ethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride Examples include rides. Polyoxybenzoyl-based resin Polyoxybenzoyl-based resin is a polymer having paraoxybenzoic acid as a monomer unit. Manufactured by solution polycondensation or melt polycondensation. Suitable examples include homopolymers of paraoxybenzoic acid, paraoxybenzoic acid and terephthalic acid and/or isophthalic acid, 4,
Examples include copolymers with 4'-dihydroxydiphenyl. Polyimide resins Polyimide resins have imide bonds in their main chains, and include linear polyimides such as poly(oxydiphenylene-pyromellitimide) and addition-curing polyimides such as polyamino bismaleimide. be. The former includes polyamideimide and polyetherimide, which contain amide bonds and ether bonds in addition to imide bonds. A linear polyimide is obtained by a condensation reaction between an aromatic polycarboxylic acid anhydride or its derivative and an aromatic diamine, and an addition-curing polyimide is obtained by an addition reaction between bismaleimide and a diamine, a biscyanate ester, or the like. Suitable examples include polyimide, polyamino bismaleimide (polybismaleimide), bismaleimide triazine resin, polyamideimide, and polyetherimide. In the present invention, two or more of the preferred thermoplastic polymers listed below may be used in combination. The preferred thermoplastic polymers include the aforementioned polystyrene polymers, other polyethylene polymers, polypropylene polymers, polybutylene polymers, polyvinyl chloride polymers, polyvinyl ester polymers, and polyvinyl ester polymers. Acrylate polymers, polyacrylonitrile polymers, etc. can be used in combination. In the present invention, when the specified water-added block copolymer and the thermoplastic polymer are used in combination, the blending amount can be varied depending on the properties of the target composition. The weight ratio with the combined weight is 99/1 to 1/99, preferably 95/5 to 5/
Can be used with 95. Two or more thermoplastic polymers may be used in combination in any proportion. Specifically, when using a block copolymer as a modifier for a thermoplastic resin, the weight ratio of the block copolymer to the thermoplastic polymer is 2/98 to 50/5.
0, preferably 5/95 to 40/60. In addition, when improving the strength, hardness, etc. of the block copolymer, the weight ratio of the block copolymer and the thermoplastic polymer is 40/60 to 97/3, preferably 50/50 to 90/10. Common. An inorganic filler and/or an organic filler may be added to the block copolymer composition of the present invention. Specific examples include calcium carbonate, clay, silica, zinc white, magnesium carbonate, magnesium silicate, talc, diatomaceous earth, dolomite, mica powder, aluminum sulfate, barium sulfate, graphite, glass fiber, carbon black, Examples include high styrene resin, coumaron, indene resin, phenol formaldehyde resin, modified melamine resin, petroleum resin, lignin, wood flour, and carbon fiber. These are block copolymers
(a) 1 to 200 parts by weight, preferably 10 to 200 parts by weight per 100 parts by weight
150 parts by weight are used. Further, a softening agent can be blended into the block copolymer composition of the present invention, and specific examples thereof include lubricating oil, paraffinic process oil, naphthenic process oil, aromatic process oil, paraffin, and vaseline. , asphalt, vegetable oils (castor oil, cottonseed oil, rapeseed oil, soybean oil, etc.),
These include rosin, fatty acids, etc., and these are used in an amount of up to 200 parts by weight, generally 20 to 100 parts by weight, preferably 40 to 80 parts by weight, per 100 parts by weight of the block copolymer (a). Furthermore, the block copolymer composition of the present invention may contain a crosslinking agent such as an organic peroxide or an inorganic peroxide, a pigment such as titanium white, carbon black, or iron oxide, a twist retardant, an antioxidant, an ultraviolet absorber, or a blocking agent. inhibitor, antistatic agent, lubricant, plasticizer,
Other fillers or mixtures thereof may also be used. Specifically, compounds described in "Practical Handbook of Additives for Plastics and Rubber" (Kagaku Kogyo Co., Ltd.) can be used. When the block copolymer composition of the present invention is used as a material for shoe soles, 5 to 150 parts by weight of the thermoplastic resin, preferably 5 to 150 parts by weight, per 100 parts by weight of the specific hydrogenated block copolymer defined by the present invention. 10 to 100 parts by weight, inorganic filler and/or organic filler 10 to 200 parts by weight, preferably 20 to 150 parts by weight, softener 0 or
A composition containing 200 parts by weight or less, that is, 0 to 200 parts by weight, preferably 20 to 100 parts by weight, can be suitably used. In the present invention, the block copolymer composition can be produced by any conventionally known compounding method. For example, melt-kneading methods using general kneading machines such as open rolls, intensive mixers, internal mixers, co-kneaders, continuous kneaders with twin-screw rotors, extruders, etc., each component is dissolved or dispersed in a solvent, and then mixed with a solvent. A method of removing the particles by heating is used. The degree of kneading temperature in the melt-kneading method can be variously selected depending on the characteristics of the thermoplastic resin used, but is generally 120 to 350°C, preferably 150°C.
~300℃. [Effects of the Invention] The block copolymer composition of the present invention can be used for various purposes by taking advantage of its excellent impact resistance, compatibility, high-temperature moldability, and low-temperature properties. The composition of the present invention can be molded into sheets, films, foams, injection molded products of various shapes, blow molded products, pressure molded products, vacuum molded products, etc. by extrusion molding, injection molding, blow molding, etc. It can be used in food packaging containers, home appliances, automobile parts, industrial supplies, toys, etc.
In addition, the composition for soles can be used for various shoes, sandals, etc. Examples Examples are shown below, but they are representative of the present invention and are not intended to limit the scope of the present invention. Examples 1 to 3 and Comparative Examples 1 to 4 In a nitrogen gas atmosphere, n-butyllithium and tetramethylethylenediamine as a polar compound were added to a cyclohexane solution containing 10 parts by weight of styrene, and the mixture was polymerized at 60°C for 1 hour. , by adding a cyclohexane solution containing 80 parts by weight of butadiene.
Polymerization was carried out at 60°C for 2 hours. Thereafter, a cyclohexane solution containing 10 parts by weight of styrene was added and polymerized at 60°C for 1 hour. The amount of tetramethylethylenediamine added was adjusted so that the vinyl bond content of the butadiene moiety of the resulting block copolymer became the value shown in Table 1, and the amount of n-butyllithium added was: Melt flow of the specific hydrogenated block copolymer finally obtained (temperature 200℃, load 5Kg, JIS
K6870) was adjusted so that it was approximately 10g/10mm. Next, the block copolymer obtained above was hydrogenated using a Ti-based hydrogenation catalyst described in JP-A-59-133203, and the hydrogenation rate [A] of the entire butadiene part and the hydrogenation rate of the vinyl bond part were A specific hydrogenated block copolymer having a ratio [B] of the values listed in Table 1 was obtained.
To 100 parts by weight of the obtained specific hydrogenated block copolymer, 0.5 parts by weight each of 2,6-di-tert-butyl-4-methylphenol and tris(nonylphenyl) phosphorite were added, and then the solvent was heated. Distilled away. Note that the hydrogenation rate was measured using a nuclear magnetic resonance apparatus. In the polymerization reaction, for 100 parts by weight of monomer,
The polymerization was carried out using n-butyllithium (n-BuLi) as a polymerization catalyst and tetramethylethylenediamine (TMEDA) as a polar compound in the weight parts shown in the table below. The hydrogenation reaction was carried out at 50° C. using 5 kg/cm ² of hydrogen gas according to the method described in JP-A-59-133203. In addition, the hydrogenation catalyst used, bis(cyclopentadienyl) titanium dichloride, was 0.5 parts by weight per 100 parts by weight of the block copolymer before hydrogenation, regardless of the structure or hydrogenation rate of the block copolymer to be hydrogenated. Parts by weight were used. The hydrogenation rate was controlled by measuring the amount of hydrogen gas supplied using a flow meter and stopping the supply of hydrogen gas when the target hydrogenation rate was achieved.

[Table] Next, polyphenylene ether resin (PPE)
(Intrinsic viscosity measured using dichloromethane solution at 25°C: 0.6) 60 parts by weight, polystyrene (PS) 25
parts by weight, 15 parts by weight of specific hydrogenated block copolymer
The mixture was melt-kneaded in an extruder at 290°C to produce pellets. Thereafter, a test piece was obtained by injection molding at 310°C. The physical property measurement results of each composition are shown in Table 1.
It can be seen that the composition containing the specific hydrogenated block copolymer has excellent impact resistance, compatibility, and heat deterioration resistance. The Izot impact value retention rate at -20°C (impact value retention rate when the impact value at 23°C is taken as 100%) of the compositions of Examples 1 to 3 was about 38%. On the other hand, the Izod impact value retention at -20°C of the compositions of Comparative Examples 3 and 4 was about 18%, indicating that the compositions of the present invention had better low-temperature properties.

[Table] Comparative Example 5 A block copolymer of the same type as that used in Examples 1 to 3, except that the vinyl bond content before hydrogenation was 83%, was hydrogenated in the same manner as above, and the butadiene moiety The overall hydrogenation rate is 30%, and the hydrogenation rate at the vinyl bonding part is 30%.
A specific hydrogenated block copolymer with a concentration of 38% was obtained. Compositions similar to Examples 1 to 3 were obtained using the block copolymers obtained above. Although the compatibility and heat deterioration resistance of the composition were good, the Izod impact value retention rate at -20°C was 15%.
It had poor low temperature properties. Examples 4 to 6 and Comparative Examples 6 to 8 A composition containing the specific hydrogenated block copolymer and thermoplastic resin listed in Table 2 was prepared,
Its physical properties were measured. The results are shown in Table 2.

【table】

[Table] Examples 7 to 13 and Comparative Examples 9 to 15 A block copolymer having a BSBS structure with a styrene content of 40% by weight and a vinyl bond content of 20% was hydrogenated in the same manner as above, A composition consisting of a specific hydrogenated block copolymer and a thermoplastic resin in which the hydrogenation rate of the entire butadiene part is 25% and the hydrogenation rate of the vinyl bond part is 60% was prepared based on Table 3, and Physical properties were measured. The results are shown in Table 3. In the comparative example, an unhydrogenated block copolymer was used.

[Table] Examples 14 to 18 and Comparative Examples 16 to 20 In a nitrogen gas atmosphere, 0.8 parts by weight of n-butyllithium and 1.5 parts by weight of tetrahydrofuran as a polar compound were added to a cyclohexane solution containing 30 parts by weight of styrene. After polymerizing for 1 hour at ℃, a cyclohexane solution containing 25 parts by weight of 1,3-butadiene and 45 parts by weight of styrene was further added.
Polymerization was carried out at ℃ for 2 hours. The resulting block copolymer had a styrene content of 75% by weight and a vinyl bond content of the butadiene moiety of 25%. Next, the block copolymer obtained above was hydrogenated in the same manner as above, and the hydrogenation rate of the entire butadiene portion was 32%, and the hydrogenation rate of the vinyl bond portion was 70%. A block copolymer was obtained. Octadecyl-3-(3,5-di-tert-butyl-
0.5 parts by weight of each of 4-hydroxyphenyl) propionate and tris(2,4-di-tert-butylphenyl) phosphorite were added, and then the solvent was distilled off under heating. Next, a composition consisting of the specific hydrogenated block copolymer and a thermoplastic resin was prepared based on the formulation shown in Table 4, and its physical properties were measured. The results are shown in Table 4. In the comparative example, the above-mentioned unhydrogenated block copolymer was used as the block copolymer.

[Table] Examples 19 to 24 and Comparative Example 21 In a nitrogen gas atmosphere, 0.11 parts by weight of n-butyllithium and 0.2 parts by weight of tetrahydrofuran were added to a cyclohexane solution containing 15 parts by weight of 1,3-butadiene and 20 parts by weight of styrene. After adding and polymerizing at 70°C for 2 hours, a cyclohexane solution containing 45 parts by weight of 1,3-butadiene and 20 parts by weight of styrene was further added and polymerizing at 70°C for 2 hours. The active end of the obtained polymer was reacted with the terminal treatment agents shown in Table 5 in equimolar amounts with the n-butyllithium used in the polymerization, so that the styrene content was 40% by weight and the vinyl bond content of the butadiene moiety was 40% by weight. A terminally modified block copolymer with 17% was obtained. Next, the terminal-modified block copolymer obtained above was hydrogenated using a rhodium-based hydrogenation catalyst described in JP-A-52-41690, and the hydrogenation rate of the entire butadiene portion was about 15%, and the vinyl The hydrogenation rate at the joint is approximately 65%.
Specific hydrogenated end-modified block copolymers were obtained. For 100 parts by weight of these polymers,
2-tert-butyl-6(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate and tris(2,4-di-tert
−butylphenyl) phosphorite, respectively.
0.5 part by weight was added, and then the solvent was distilled off under heating. Next, 25 parts by weight of the above specific hydrogenated end-modified block copolymer and methyl methacrylate/styrene/
75 parts by weight of a methacrylic acid copolymer (weight ratio of constituent monomers 65/15/20, weight average molecular weight approximately 100,000) was melt-kneaded and molded to obtain a test piece. Table 5 shows the performance evaluation results for each composition. In addition, comparative example
The block copolymer used in 21 was obtained by treating the above block copolymer having lithium at the end of the polymer with methanol and adding hydrogen atoms to the end, but without hydrogenation treatment. It is.

[Table] Examples 25 to 27 and Comparative Examples 22 to 24 Lithium is bonded to one end of the polymer, styrene content is 15% by weight, vinyl bond in isoprene part (total of vinyl group and isopropenyl group in side chain) amount)
A block copolymer with an SIS structure with a content of 15%,
The butyl lithium used in the polymerization of the block copolymer was reacted with an equimolar amount of tetraglycidyl metaxylene diamine to obtain a terminally modified block copolymer. Next, the terminal-modified block copolymer obtained above was hydrogenated using the same rhodium-based hydrogenation catalyst as above, so that the hydrogenation rate of the entire isoprene part was 12% and the hydrogenation rate of the vinyl bond part was 50%. A specific hydrogenated end-modified block copolymer was obtained. The block copolymer and thermoplastic polyurethane were melt-kneaded to prepare a composition. These compositions were pressure-bonded to a polyvinyl chloride sheet at 180°C, and the peel strength was measured. The results are shown in Table 6. Incidentally, the block copolymer used in the comparative example was obtained by treating the above-mentioned activated block copolymer with methanol, and was not subjected to hydrogenation treatment.

[Table] Examples 28 to 30 and Comparative Examples 25 to 30 A block copolymer with a BSBS structure having a styrene content of 40% by weight and a vinyl bond content of the butadiene moiety of 35% was treated with the same Ti-based hydrogenation catalyst as above. Hydrogenated,
A specific hydrogenated block copolymer was obtained in which the hydrogenation rate of the entire butadiene portion was 25% and the hydrogenation rate of the vinyl bond portion was 58%. 2- to 100 parts by weight of the block copolymer.
2 parts by weight of tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate was added, and then the solvent was distilled off under heating. Next, the above specific hydrogenated block copolymer 100
After mixing parts by weight and 4 parts by weight of maleic anhydride, the mixture was fed to a vent extruder and a modification reaction was carried out at 260°C. Unreacted maleic anhydride was removed through a vent. The amount of maleic anhydride added to the modified specific hydrogenated block copolymer thus obtained was 0.9% by weight. For comparison, the above unhydrogenated block copolymer was modified with maleic anhydride in the same manner as above to obtain a modified unhydrogenated block copolymer with an added amount of maleic anhydride of 1% by weight. Furthermore, as a comparison, a fully hydrogenated block copolymer in which the hydrogenation rate of the entire butadiene portion was substantially 100% was obtained by the same hydrogenation method as above. After mixing 100 parts by weight of the block copolymer, 2.5 parts by weight of maleic anhydride, and 0.2 parts by weight of Perhexa 25B (peroxide), the mixture was supplied to a vent extruder and subjected to a modification reaction at 250°C. The amount of maleic anhydride added to the modified fully hydrogenated block copolymer thus obtained was 1.2% by weight. Compositions consisting of the thermoplastic resins listed in Table 7 and the above-mentioned modified block copolymers were prepared, and their physical properties were measured. The results are shown in Table 7, and the composition of the present invention had good impact resistance at low temperatures and was also excellent in heat deterioration resistance.

[Table] Example 31 and Comparative Example 31 100 parts by weight of the block copolymer shown in Table 8, 50 parts by weight of naphthenic process oil, 50 parts by weight of polystyrene (Styron 679 manufactured by Asahi Kasei), 55 parts by weight of heavy calcium carbonate, A composition was prepared by kneading 5 parts by weight of titanium oxide and 0.5 parts by weight of zinc stearate using a pressure kneader, and then injection molded using a 5-ounce injection molding machine. Table 8 shows the performance of the molded product obtained.

[Table] Examples 32 to 35 According to the formulation shown in Table 9, a composition consisting of a specific hydrogenated block copolymer, a thermoplastic resin, and glass fiber (short fibers with a diameter of 9 μm and a length of 6 mm) was prepared. Created. The performance of the obtained composition is shown in Table 9. The modified specific hydrogenated block copolymer used in Example 32 was the same specific hydrogenated block copolymer used in Examples 28 to 30 to which 0.5% by weight of glycidyl methacrylate was grafted. I used something. Furthermore, the modified specific hydrogenated block copolymers used in Examples 35 and 36 were the same as those in Examples 28 to 30, except that the amount of maleic anhydride added was 0.3% by weight.
The same modified specific hydrogenated block copolymer as used in was used.

[Table] Example 37 In a nitrogen gas atmosphere, 0.06 parts by weight of n-butyllithium and 2 parts by weight of tetrahydrofuran were added to a cyclohexane solution containing 35 parts by weight of styrene, and after polymerization at 70°C for 1 hour, 1,3 - A cyclohexane solution containing 7.5 parts by weight of butadiene and 7.5 parts by weight of styrene was added and polymerized at 70°C for 1 hour.
Then, a cyclohexane solution containing 7.5 parts by weight of 1,3-butadiene and 7.5 parts by weight of styrene was added.
After polymerization at 70°C for 1 hour, a cyclohexane solution containing 35 parts by weight of styrene was further added and polymerization was performed at 70°C for 1 hour. The resulting block copolymer had a styrene content of 85% by weight and a vinyl bond content of the butadiene moiety of 33%. Next, the block copolymer obtained above was hydrogenated in the same manner as above, and the hydrogenation rate of the entire butadiene part was 45%, and the hydrogenation rate of the vinyl bond part was 86%. A block copolymer was obtained. 2 parts of phenothiazine per 100 parts by weight of the block copolymer.
Added as part by weight stabilizer. The above specific hydrogenated block copolymers include polyarylate resin, fluororesin, polyetheretherketone, polyoxybenzoyl, polyetherimide, polyamideimide, bismaleimide resin, polysulfone, polyethersulfone, polyphenylene sulfone, etc. By adding about 15% by weight of each to the liquid, the flow characteristics are changed and the injection moldability is modified.

Claims (1)

[Scope of Claims] 1 (a) A vinyl based on a conjugated diene compound, which has a polymer block mainly composed of at least one vinyl aromatic compound and a polymer block mainly composed of at least one conjugated diene compound. A block copolymer having a bond content [V] of 80% or less is hydrogenated, and (1) the hydrogenation rate [A] of the entire aliphatic double bond based on a conjugated diene compound is 5% or more75 %, and (2) the hydrogenation rate [B] of the vinyl bond based on the conjugated diene compound satisfies [B]/[V] ^1/2 = 3 to 20. Union, 1
~99 parts by weight (b) A composition comprising 99 to 1 part by weight of a thermoplastic resin. 2 (a) It has a polymer block mainly composed of at least one vinyl aromatic compound and a polymer block mainly composed of at least one conjugated diene compound, and has a vinyl bond content [V] based on the conjugated diene compound. (1) The hydrogenation rate [A] of the entire aliphatic double bond based on the conjugated diene compound is 5% or more and less than 75%, Moreover, (2) a specific hydrogenated block copolymer in which the hydrogenation rate [B] of the vinyl bond based on the conjugated diene compound satisfies [B]/[V] ^1/2 = 3 to 20;
(b) 5 to 150 parts by weight of a thermoplastic resin, (c) 10 to 200 parts by weight of an inorganic filler and/or organic filler, and (d) 0 to 200 parts by weight of a softener.