JP2003327704A - Modified polymer and composition thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified polymer having good compatibility with a thermoplastic resin and / or a rubber-like polymer, and to modify the modified polymer with the thermoplastic resin and / or a rubber-like polymer. A polymer composition is provided. [MEANS FOR SOLVING PROBLEMS] Component (1), which is a modified polymer obtained by adding a modifying agent to at least one polymer selected from the following a, b, and c or a hydrogenated product thereof, reacts with a functional group of component (1). A modified polymer modified with a component (2) which is a functional oligomer having a property. a conjugated diene polymer, a polymer comprising a b conjugated diene and a vinyl aromatic hydrocarbon, and having a specific amount of a vinyl aromatic hydrocarbon polymer block, a c vinyl aromatic hydrocarbon polymer

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modified polymer having good compatibility with a thermoplastic resin and / or a rubber-like polymer, and more specifically, a specific modified polymer having a functional group of the modified polymer. The present invention relates to a modified polymer modified with a functional oligomer having reactivity with. Further, the present invention relates to a composition having excellent mechanical strength and impact resistance, and more specifically, a modified polymer obtained by modifying a specific modified polymer with a functional oligomer having reactivity with a functional group of the modified polymer. The present invention relates to a modified polymer composition composed of a polymer, a thermoplastic resin and / or a rubber-like polymer.

[0002]

2. Description of the Related Art In recent years, thermoplastic elastomers, which are rubber-like soft materials and do not require a vulcanization step and have the same moldability as thermoplastic resins, are used in automobile parts, home electric appliances parts, wire coating materials and medical parts. It is used in fields such as, sundries, and footwear. Among these, a block copolymer comprising a conjugated diene and a vinyl aromatic compound having a relatively low vinyl aromatic compound content as a thermoplastic elastomer, for example, a vinyl aromatic compound content of about 30% by weight, and a block copolymer thereof Hydrogenated products are preferably used because they show properties similar to vulcanized rubber. Attempts have also been made to improve mutual properties by combining such block copolymers and hydrogenated products thereof with various thermoplastic resins and rubber-like polymers. For the same purpose, an attempt has been made to use a conjugated diene polymer or a polymer composed of a conjugated diene and a vinyl aromatic hydrocarbon, or a hydrogenated product thereof in combination with a thermoplastic resin or a rubber-like polymer.
In this case, there is a problem in that mutual compatibility is insufficient and the desired improvement effect cannot be obtained.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a modified polymer having good compatibility with a thermoplastic resin and / or a rubber-like polymer, and the modified polymer and the thermoplastic resin /
Another object of the present invention is to provide a composition which is made of a rubber-like polymer and has excellent mechanical strength and impact resistance.

[0004]

The present inventors have conducted extensive studies to develop a polymer having good compatibility with a thermoplastic resin and / or a rubber-like polymer, and as a result, have found that a specific modified polymer It was found that the above-mentioned problems can be effectively solved by a modified polymer obtained by modifying the above with a functional oligomer having reactivity with the functional group of the modified block copolymer, and the present invention has been completed. That is, the present invention is as follows. 1. The following a, b, and c a. Conjugated diene polymer b. A polymer c which is a polymer composed of a conjugated diene and a vinyl aromatic hydrocarbon, and in which the proportion of the vinyl aromatic hydrocarbon polymer block to the total vinyl aromatic hydrocarbon content in the polymer is less than 50% by weight. ． The component (1) which is a primary modified polymer obtained by addition reaction of a functional group-containing modifier with at least one polymer selected from vinyl aromatic hydrocarbon polymers or a hydrogenated product thereof is A modified polymer modified with the component (2) which is a functional oligomer having reactivity with a functional group.

2. 1 to 99 parts by weight of the component (A) which is the modified polymer described in 1 above, and at least one component (B) 9 selected from the group consisting of a thermoplastic resin and a rubbery polymer.
A modified polymer composition comprising 9 to 1 part by weight. The present invention will be specifically described below. The component (1) used in the present invention is a primary modified polymer obtained by addition reaction of a functional group-containing modifier with at least one polymer selected from the following a, b, and c, or a hydrogenated product thereof. . a. Conjugated diene polymer b. A polymer c which is a polymer composed of a conjugated diene and a vinyl aromatic hydrocarbon, and in which the proportion of the vinyl aromatic hydrocarbon polymer block to the total vinyl aromatic hydrocarbon content in the polymer is less than 50% by weight. ． Vinyl aromatic hydrocarbon polymer The vinyl aromatic hydrocarbon content of the primary modified polymer composed of the conjugated diene and vinyl aromatic hydrocarbon used in the present invention or the hydrogenated product thereof is generally 5 to 95% by weight, more preferably Is 10 to 90% by weight, more preferably 15 to 85% by weight. In the present invention, when the vinyl aromatic hydrocarbon content is less than 5% by weight, it is considered to be substantially a conjugated diene polymer, and when the vinyl aromatic hydrocarbon content exceeds 95% by weight, it is substantially vinyl aromatic. Considered to be a group hydrocarbon polymer. The vinyl aromatic hydrocarbon in the modified polymer comprising the conjugated diene and the vinyl aromatic hydrocarbon or the hydrogenated product thereof may be distributed uniformly or in a taper shape.
Further, in the polymer, a plurality of portions in which vinyl aromatic hydrocarbons are uniformly distributed and / or a plurality of portions in which taper distribution is formed may coexist.

The primary modified polymer composed of a conjugated diene and a vinyl aromatic hydrocarbon or a hydrogenated product thereof used in the present invention is
Ratio of vinyl aromatic hydrocarbon polymer block to total vinyl aromatic hydrocarbon content in the polymer (hereinafter referred to as content of vinyl aromatic hydrocarbon polymer block to total vinyl aromatic hydrocarbon content in the polymer) The amount ratio is referred to as the vinyl aromatic hydrocarbon block ratio) is less than 50% by weight,
Preferably 40% by weight or less, more preferably 20% by weight
Is a polymer that is: When the blocking rate is less than 50% by weight, a composition having good flexibility can be obtained.

The content of the vinyl aromatic hydrocarbon polymer block is measured, for example, by oxidatively decomposing the copolymer before hydrogenation with tert-butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLT).
HOFF, et al. J. Polym. Sci. 1,
429 (1946)), using the weight of the vinyl aromatic hydrocarbon polymer block component (provided that the vinyl aromatic hydrocarbon polymer component having an average degree of polymerization of about 30 or less is excluded). Then, it can be obtained from the following equation. Content of vinyl aromatic hydrocarbon polymer block (% by weight) = (weight of vinyl aromatic hydrocarbon polymer block in polymer before hydrogenation / weight of polymer before hydrogenation) ×
100

In the present invention, the primary modified polymer before the hydrogenation reaction is obtained by addition reaction of the modifying agent described below to the living terminal of the polymer obtained by a known method using an organic lithium compound as a polymerization catalyst, For example, it has a structure represented by the following general formula. (A) _n- X, (B) _n- X (AB) _n- X, A- (BA) _n- X, B- (A
_{-B) n -X, X- (A} -B) n, X- (A-B) n
-X, X-A- (B-A) _n- X, X-B- (A-
B) _n- X, [(B-A) _n ] _m- X, [(A-B)
_n ] _m- X, [(B-A) _n- B] _m- X, [(A-B)
_n- A] _m- X (In the above formula, A is a vinyl aromatic hydrocarbon polymer or a vinyl aromatic hydrocarbon polymer segment, and B is a conjugated diene polymer or a conjugated diene and a vinyl aromatic hydrocarbon. It is a copolymer or a conjugated diene polymer segment or a copolymer segment composed of a conjugated diene and a vinyl aromatic hydrocarbon, n is an integer of 1 or more, preferably 1
Is an integer of ~ 5. m is an integer of 2 or more, preferably 2
It is an integer of 11. X represents a modifier residue to which an atomic group having a functional group described later is bonded. When X is added by a metallation reaction described below, A and / or B
Is attached to the side chain of. Further, the structures of the polymer chains bonded to X in plural may be the same or different. The polymer used in the present invention may be any mixture of the polymers represented by the above general formula.

In the present invention, the microstructure (ratio of cis, trans, vinyl) of the conjugated diene moiety in the polymer is
It can be optionally changed by using a polar compound described below, and when 1,3-butadiene is used as the conjugated diene, the 1,2-vinyl bond amount is preferably 5 to 90.
%, More preferably 10 to 80%, when isoprene is used as the conjugated diene or when 1,3-butadiene and isoprene are used in combination, 1,2-vinyl bond and 3,
The total amount of 4-vinyl bonds is preferably 3 to 80%, more preferably 5 to 70%.

However, when the hydrogenated product is used as the polymer, the microstructure is such that when 1,3-butadiene is used as the conjugated diene, the 1,2-vinyl bond content is preferably 10 to 80%, It is more preferably 15 to 75%, particularly preferably 20 to 50%. When isoprene is used as the conjugated diene or 1,3-butadiene and isoprene are used in combination, 1,2-vinyl bond and 3, 4-
It is recommended that the total amount of vinyl bonds is preferably 5-70%, more preferably 10-50%.

In the present invention, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, when 1,3-butadiene is used as the conjugated diene,
-Vinyl bond content) is hereinafter referred to as vinyl bond content. In the present invention, a conjugated diene polymer or a copolymer comprising a conjugated diene and a vinyl aromatic hydrocarbon, or a conjugated diene polymer segment or a copolymer segment comprising a conjugated diene and a vinyl aromatic hydrocarbon has a vinyl bond content of There may be at least one different portion.

For example, at least one portion having a vinyl bond content of 25% or less, preferably 10 to 23% and at least one portion having a vinyl bond content of more than 25%, preferably 28 to 80% may be present. Further, in a polymer having two or more segments B, the vinyl bond content of each segment B may be the same or different. In the present invention, the conjugated diene 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-butadiene, 1,3-pentadiene,
1,3-hexadiene and the like, but particularly common ones include 1,3-butadiene and isoprene. These may be used not only in one kind but also in two or more kinds in the production of one polymer.

As the vinyl aromatic hydrocarbon, styrene, o-methylstyrene, p-methylstyrene, p-
There are tert-butyl styrene, 1,3-dimethyl styrene, α-methyl styrene, vinyl naphthalene, vinyl anthracene, and the like, but styrene is particularly common. These may be used not only in one kind but also in two or more kinds in the production of one polymer. In the present invention, when isoprene and 1,3-butadiene are used in combination as the conjugated diene, the mass ratio of isoprene and 1,3-butadiene is preferably 95/5 to 5/95, more preferably 90/10 to 10/90. , And more preferably 85
/ 15 to 15/85. In particular, when obtaining a composition having good low-temperature characteristics, the mass ratio of isoprene and 1,3-butadiene is preferably 49/51 to 5/95, more preferably 45/55 to 10/90, and further preferably 40 /
It is recommended to be 60 to 15/85. When isoprene and 1,3-butadiene are used in combination, a modified polymer or the like or a composition thereof having a good balance of appearance properties and mechanical properties even in molding at high temperature can be obtained.

In the present invention, as the solvent used for producing the polymer, butane, pentane, hexane, isopentane, heptane, octane, isooctane and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, Alicyclic hydrocarbons such as ethylcyclohexane, or hydrocarbon solvents such as aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene can be used. These may be used alone or as a mixture of two or more.

The organolithium compound used in the production of the polymer is a compound having one or more lithium atoms bonded in the molecule, such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, Examples include sec-butyllithium, tert-butyllithium, hexamethylenedilithium, butadienyldilithium, and isoprenyldilithium. These may be used alone or as a mixture of two or more.
In addition, the organolithium compound may be dividedly added once or more during the polymerization in the production of the polymer.

In the present invention, the polymerization rate during the production of the polymer is adjusted, the microstructure of the polymerized conjugated diene moiety is changed,
A polar compound or a randomizing agent can be used for the purpose of adjusting the reactivity ratio between the conjugated diene and the vinyl aromatic hydrocarbon. Examples of the polar compound and the randomizing agent include ethers, amines, thioethers, phosphoramide, potassium salt or sodium salt of alkylbenzene sulfonic acid, potassium or sodium alkoxide, and the like.

Examples of suitable ethers are dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether,
It is diethylene glycol dibutyl ether. As amines, tertiary amine, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines can be used. Examples of the phosphine and phosphoramide include triphenylphosphine and hexamethylphosphoramide.

In the present invention, the polymerization temperature for producing the polymer is preferably -10 to 150 ° C, more preferably 30 to 120 ° C. The time required for the polymerization varies depending on the conditions, but it is preferably within 48 hours, particularly preferably 0.5 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within the range of the above-mentioned polymerization temperature and is a pressure sufficient to maintain the monomer and the solvent in the liquid phase. Further, it is preferable that impurities such as water, oxygen, carbon dioxide gas, etc. which inactivate the catalyst and the living polymer are not mixed in the polymerization system.

Component (1), which is a primary modified polymer obtained by using the organolithium compound used in the present invention as a polymerization catalyst, is
A functional group-containing modifier is added to the living end of the polymer to give a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxylic acid group, a thiocarboxylic acid group, an aldehyde group. , Thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group,
One functional group selected from quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silanol group, alkoxysilane, silicon halide group, tin halide group, alkoxytin group, phenyltin group, etc. It is a modified polymer having at least one functional group bonded thereto.

A method for obtaining a primary modified polymer or a hydrogenated product thereof in which an atomic group having such a functional group is bonded is selected from the above functional groups in the polymer by an addition reaction with the living end of the polymer. A modifying agent having a functional group that forms a primary modified polymer in which at least one atomic group having one functional group is bound, or a modification in which an atomic group having the functional group protected by a known method is bound It can be obtained by a method in which an agent is subjected to an addition reaction. As another method, there is a method in which an organic alkali metal compound such as an organic lithium compound is reacted with the polymer (metalation reaction), and the above modifier is added to the polymer to which the organic alkali metal has been added. In the latter case, the hydrogenation product of the polymer may be obtained and then the metalation reaction may be carried out to react the above-mentioned modifier. Depending on the type of modifier, the hydroxyl group, amino group, etc. may generally be an organic metal salt at the stage of reaction with the modifier, in which case it should be treated with a compound having active hydrogen such as water or alcohol. Thus, a hydroxyl group or an amino group can be obtained.

In the present invention, when the modifier is reacted with the living end of the polymer, a partially unmodified polymer may be mixed with the primary modified polymer of the component (1). It is recommended that the proportion of the unmodified polymer mixed in the primary modified polymer of the component (1) is preferably 70 wt% or less, more preferably 60 wt% or less, and further preferably 50 wt% or less. Particularly preferred as the primary modified polymer of the component (1) used in the present invention or a hydrogenated product thereof is an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group. Is a primary modified polymer having at least one bound thereto or a hydrogenated product thereof. In the present invention, a hydroxyl group,
Preferred atomic groups as the atomic group having at least one functional group selected from an epoxy group, an amino group, a silanol group and an alkoxysilane group are those represented by the following general formulas (1) to (14). Selected atomic groups are raised.

[0022]

[Chemical 2]

(In the above formula, R ^{1 to} R ⁴ are hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, a hydroxyl group, an epoxy group,
A hydrocarbon group having 1 to 24 carbon atoms having a functional group selected from an amino group, a silanol group and an alkoxysilane group. R ⁵
Is a C1-C48 hydrocarbon chain or a C1-C48 hydrocarbon chain having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group. In addition, in the hydrocarbon group of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ , elements such as oxygen, nitrogen and silicon are bonded in a bonding mode other than hydroxyl group, epoxy group, amino group, silanol group and alkoxysilane group. May be combined. R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms. ) In the present invention, a hydroxyl group, an epoxy group, an amino group, a silanol group,
At least one functional group selected from alkoxysilane groups
Examples of the modifying agent used for obtaining the primary modified polymer in which at least one of the atomic groups possessed by the compound is bonded or its hydrogenated product include the following.

For example, tetraglycidyl metaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane,
Diglycidyl aniline and diglycidyl orthotoluidine. Further, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, They are γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane and γ-glycidoxypropylethyldiethoxysilane.

Further, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ -Glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ -Glycidoxypropylmethyldiisopropeneoxysilane, bis (γ-glycidoxypropyl) dimethoxysilane, bis (γ-glycidoxypropyl) diethoxysilane.

Further, bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) dibutoxysilane, bis (γ-glycidoxypropyl) diphenoxysilane, bis (γ-glycid) Xypropyl) methylmethoxysilane, bis (γ-glycidoxypropyl) methylethoxysilane, bis (γ-glycidoxypropyl) methylpropoxysilane, bis (γ-
Glycidoxypropyl) methylbutoxysilane, bis (γ-glycidoxypropyl) methylphenoxysilane, tris (γ-glycidoxypropyl) methoxysilane, γ-methacryloxypropyltrimethoxysilane,
γ-methacryloxypropyltriethoxysilane, γ-
Methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, bis (γ-methacryloxypropyl) dimethoxysilane and tris (γ-methacryloxypropyl) methoxysilane.

Further, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyl-triethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-
Tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β- (3,4
-Epoxycyclohexyl) ethyl-triphenoxysilane, β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyl-ethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldiethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyl-methyldiethoxysilane.

Further, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane, β-
(3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4
-Epoxycyclohexyl) ethyl-dimethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β
-(3,4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylbutoxysilane, β- (3,3
4-epoxycyclohexyl) ethyl-dimethylphenoxysilane, β- (3,4-epoxycyclohexyl)
Ethyl-diethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane. Furthermore, 1,3-dimethyl-2
-Imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N'-dimethylpropyleneurea, N-
Methylpyrrolidone and the like can be mentioned.

By reacting the above-mentioned modifying agent, the residue of the modifying agent to which an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded. A bonded primary modified polymer is obtained. When a functional group-containing modifier is added to the living ends of a polymer having segment A and segment B, the living end of the polymer is segment A
However, any of the segments B may be used, but in order to obtain a composition having good mechanical strength and the like, it is preferable that the segment B is bonded to the end of the segment A.

The amount of the above modifier used is more than 0.5 equivalents and not more than 10 equivalents, preferably more than 0.7 equivalents and not more than 5 equivalents, and more preferably 1 equivalent to the living end of the polymer. It is recommended to use more than 1 equivalent and 4 equivalents or less. In the present invention, the amount of the living terminal of the polymer may be calculated from the amount of the organolithium compound used for the polymerization and the number of lithium atoms bonded to the organolithium compound, or the obtained weight. It may be calculated from the number average molecular weight of the coalescence.

In the present invention, the hydrogenated product of the primary modified polymer is obtained by hydrogenating the primary modified polymer obtained above. The hydrogenation catalyst is not particularly limited,
(1) A conventionally known supported heterogeneous hydrogenation catalyst in which a metal such as Ni, Pt, Pd, Ru, etc. is supported on carbon, silica, alumina, diatomaceous earth, etc. (2) Ni, Co,
An organic acid salt such as Fe or Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum are used.
So-called Ziegler type hydrogenation catalyst, (3) Ti, Ru, R
A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as h or Zr is used.

As a specific hydrogenation catalyst, Japanese Patent Publication No.
8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-39700,
The hydrogenation catalysts described in JP-B-1-53851 and JP-B-2-9041 can be used. Preferred hydrogenation catalysts include a mixture with a titanocene compound and / or a reducing organometallic compound. As the titanocene compound, compounds described in JP-A-8-109219 can be used, and specific examples thereof include (substituted) biscyclopentadienyl titanium dichloride, monopentamethylcyclopentadienyl titanium trichloride and the like. Examples thereof include compounds having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton or a fluorenyl skeleton. Examples of the reducing organic metal compound include organic alkali metal compounds such as organic lithium, organic magnesium compounds, organic aluminum compounds, organic boron compounds and organic zinc compounds.

The hydrogenation reaction is preferably carried out in the temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used in the hydrogenation reaction is preferably 0.1 to
15 MPa, more preferably 0.2 to 10 MPa, further preferably 0.3 to 5 MPa is recommended. The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction is a batch process,
Either a continuous process or a combination thereof can be used.

In the hydrogenated product of the primary modified polymer used in the present invention, the total hydrogenation rate of unsaturated double bonds based on the conjugated diene compound can be arbitrarily selected according to the purpose and is not particularly limited. Greater than 70% of unsaturated double bonds based on conjugated diene compounds in the polymer, preferably 7
5% or more, more preferably 85% or more, particularly preferably 90% or more may be hydrogenated, or only a part thereof may be hydrogenated. In the case of hydrogenating only a part, the hydrogenation rate is preferably 10 to 70%, or 15 to 65%, particularly preferably 20 to 60%.

Further, in the present invention, in the hydrogenated polymer, the hydrogenation rate of the vinyl bond based on the conjugated diene before hydrogenation is preferably 85% or more, more preferably 9%.
It is recommended to be 0% or more, more preferably 95% or more in order to obtain a composition having excellent thermal stability. here,
The hydrogenation rate of vinyl bonds means the proportion of hydrogenated vinyl bonds in the vinyl bonds based on the conjugated diene before hydrogenation incorporated in the polymer.

The hydrogenation ratio of the aromatic double bond based on the vinyl aromatic hydrocarbon in the polymer is not particularly limited, but it is preferably 50% or less, more preferably 30% or less, still more preferably 20%. % Or less is recommended. The hydrogenation addition rate can be known by a nuclear magnetic resonance apparatus (NMR). The weight average molecular weight of the primary modified polymer or its hydrogenated product used in the present invention is 30,000 or more from the viewpoint of the mechanical strength of the primary modified polymer, its hydrogenated product or its composition, processability and thermoplastic resin. And from the viewpoint of compatibility with the rubber-like polymer, it is preferably 1.5 million or less, more preferably 40,000 to 10
It is 0,000, more preferably 5 to 800,000. The molecular weight distribution is 1.05 to 6, preferably 1.1 to 6, more preferably 1.55 to 5.0, and particularly preferably 1.6 to 4. It is recommended that the molecular weight distribution be within such a range in terms of molding processability of the primary modified polymer or its hydrogenated product or composition.

In the present invention, the amount of vinyl bond based on the conjugated diene compound in the polymer is determined by the nuclear magnetic resonance apparatus (NM
R) can be used to find out. The hydrogenation rate can also be known using the same device. The weight average molecular weight of the polymer or its hydrogenated product is measured by gel permeation chromatography (GPC), and the molecular weight of the peak of the chromatogram is determined by measuring a commercially available standard polystyrene. The peak molecular weight is used for the calculation). The molecular weight distribution of the polymer can be similarly determined from the measurement by GPC.

The solution of the primary modified polymer or its hydrogenated product obtained as described above may be separated from the solution by removing the catalyst residue, if necessary. it can. As a method for separating the solvent, for example, a method in which a polar solvent which is a poor solvent for the polymer such as acetone or alcohol is added to a solution after polymerization or hydrogenation to precipitate and recover the polymer, a primary modified polymer or A method in which the solution of the hydrogenated product is poured into hot water with stirring and the solvent is removed by steam stripping to recover, or a method in which the polymer solution is directly heated to distill off the solvent can be mentioned. The primary modified polymer or its hydrogenated product used in the present invention includes various phenol-based stabilizers, phosphorus-based stabilizers,
Stabilizers such as sulfur stabilizers and amine stabilizers can be added.

In the present invention, the particularly preferred primary modified polymer or hydrogenated product thereof is such that the difference between the maximum value and the minimum value of the vinyl bond content in the polymer chain before hydrogenation is less than 10% by weight,
Preferably, the primary modified polymer or its hydrogenated product is 8% by weight or less. In the present invention, particularly preferred primary modified polymer or hydrogenated product thereof is GPC / FTI.
Examples of the primary modified polymer or its hydrogenated product satisfy the relationship of the following formula in the relationship between the molecular weight obtained by R measurement and the number of terminal methyl carbon atoms. Va-Vb ≧ 0.03 Vc, preferably Va-Vb
≧ 0.05 Vc (where Va is the number of terminal methyl carbon atoms contained in 1000 carbon atoms in the polymer at a molecular weight twice the peak top molecular weight, and Vb is ½ of the peak top molecular weight). (The same number in the molecular weight and Vc are the same number in the peak top molecular weight.)

GPC-FTIR is an FTI as a detector of GPC (gel permeation chromatograph).
It uses R (Fourier transform infrared spectrophotometer),
The microstructure of each fraction fractionated by molecular weight can be measured. The number of terminal methyl carbon atoms is, the absorbance I _(-CH 2 -) which is attributable to a methylene group <absorption wave numbers: 2925 cm ^-1> to the absorbance I attributed to methyl groups
_(-CH 3) <absorption wave: 2960cm ^-1> ratio of, I
Can be obtained from _{- (-CH 3) / I (} -CH 2). This method is, for example, NICOLET FT-IR.
CUSTOMER NEWSLETTER Vol.
2, No. 2, 1994, etc. In the present invention, the particularly preferred primary modified polymer or hydrogenated product thereof has a vinyl aromatic hydrocarbon content of 50% by weight or less, preferably 40% by weight or less, more preferably 3% by weight or less.
5% by weight or less of a primary modified polymer or a hydrogenated product thereof. Particularly in a polymer composed of a conjugated diene and a vinyl aromatic hydrocarbon, the content of the vinyl aromatic compound is 5 to
It is recommended to be 40% by weight, preferably 10-35% by weight.

In the present invention, the particularly preferred primary modified polymer or hydrogenated product thereof has a vinyl aromatic hydrocarbon content of more than 50% by weight and 90% by weight or less, preferably more than 60% by weight and 88% by weight. % Or less, and the content of the vinyl aromatic hydrocarbon polymer block in the polymer is 40% by weight or less, preferably 10 to 40% by weight of the primary modified polymer or its hydrogenated product. Particularly preferable as such a primary modified polymer or a hydrogenated product thereof is a hydrogenated product in which a crystallization peak is substantially absent in a temperature range of -50 to 100 ° C. in a differential scanning calorimetry (DSC method). .. Here, “the crystallization peak is substantially absent in the temperature range of −50 to 100 ° C.” means that the peak due to crystallization does not appear in this temperature range.
Alternatively, even when a peak due to crystallization is observed, the crystallization peak calorific value due to the crystallization is less than 3 J / g, preferably less than 2 J / g, more preferably 1 J / g.
It is less than 1, and particularly preferably has no crystallization peak calorific value.

The modified polymer of the present invention is a component (1) which is a functional oligomer having reactivity with the functional group bonded to the component (1) in the primary modified polymer of the component (1) or a hydrogenated product thereof. It can be obtained by reacting 2). The functional group bonded to the functional oligomer of the component (2) is particularly limited as long as it is a functional group reactive with the functional group bonded to the primary modified polymer of the component (1) or a hydrogenated product thereof. There is no. Preferred functional oligomers include hydroxyl groups, amino groups, carboxyl groups, acid anhydride groups, isocyanate groups,
It is a functional oligomer having at least one functional group selected from an epoxy group, a silanol group and an alkoxysilane group. The molecular weight of these functional oligomers is generally 3
00 or more and less than 30,000, preferably 500 or more and 1
Less than 5000, more preferably 1000 or more, 2000
It is less than 0. These may be produced by any known method, for example, those produced by anionic polymerization method, cationic polymerization method, radical polymerization method, polycondensation method, polyaddition reaction or the like can be used.

Specific examples of the functional oligomer of the component (2) include a polybutadiene oligomer having at least one of the above functional groups or a hydrogenated product thereof, a polyisoprene oligomer having at least one of the above functional groups or a hydrogenated product thereof, Polyethylene oligomer having at least one functional group, polypropylene oligomer having at least one functional group, polyethylene oxide oligomer, polypropylene oxide oligomer, ethylene oxide-propylene oxide copolymer oligomer, saponified ethylene-vinyl acetate copolymer oligomer, Examples thereof include silicone oil and a copolymerized oligomer of a functional vinyl monomer having at least one of the above functional groups and another vinyl monomer which can be copolymerized with the functional vinyl monomer.

Examples of the functional vinyl monomer having at least one functional group include glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, allyl glycidyl ether, and monoglycidyl maleate. Ester, itaconic acid monoglycidyl ester,
3,4-epoxybutene can be mentioned. Also, 3,4-
Epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, styrene-P- Examples thereof include glycidyl ether, hydroxystyrene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, allyl alcohol, maleic anhydride and itaconic anhydride.

Other vinyl monomers which can be copolymerized with the above-mentioned functional vinyl monomer include ethylene and C3-C3.
12 α-olefins such as propylene, 1-butene, isobutylene, 4-methyl-1-pentene, 1-octene, styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3 -Dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, vinyl acetate, vinyl chloride and acrylonitrile.

Further, methacrylonitrile, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl. Acrylate, butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate and the like can be mentioned, and a mixture of two or more of these vinyl monomers can also be used. Further, in the present invention, the polyamide oligomer, polyester oligomer, polyurethane oligomer and the like having the above-mentioned molecular weight range can also be used.

In the present invention, when the primary modified polymer of the component (1) or its hydrogenated product and the functional oligomer of the component (2) are reacted, the functional group 1 bonded to the component (1) is used.
It is recommended that the component (2) is 0.3 to 10 mol, preferably 0.4 to 5 mol, and more preferably 0.5 to 4 mol per equivalent. The method of reacting the primary modified polymer of the component (1) or its hydrogenated product with the functional oligomer of the component (2) is not particularly limited, and a known method can be used.

For example, a melt-kneading method in which a general kneader such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a co-kneader, or a multi-screw extruder is used for the reaction, each component is dissolved in a solvent or the like. Alternatively, a method may be used in which the solvent is removed by heating after the mixture is dispersed and mixed and reacted. In the case of the melt kneading method, the kneading temperature is generally 50 to 2
At 50 ° C, preferably in the range 100-230 ° C,
The kneading time is generally 3 hours or less, preferably several seconds to
It's an hour.

Further, in the method of dissolving or dispersing and mixing each component in a solvent and reacting, the solvent is not particularly limited as long as it dissolves or disperses each component, and aliphatic hydrocarbon, alicyclic carbon In addition to hydrocarbon solvents such as hydrogen and aromatic hydrocarbons, halogen-containing solvents, ester solvents, ether solvents and the like can be used. In such a method, the temperature for reacting each component is generally -10 to 150 ° C, preferably 30 to 120 ° C. Although the time required for the reaction varies depending on the conditions, it is generally within 3 hours, preferably from several seconds to 1 hour.

In the present invention, a primary modified polymer of component (1) or a hydrogenated product thereof is modified with a functional oligomer of component (2) (hereinafter referred to as component (A)),
It can be used as a composition containing at least one component (B) selected from the group consisting of a thermoplastic resin and a rubbery polymer. The amount of component (B) used is 1/99 to 99/1, preferably 3 in terms of the ratio of component (A) / component (B) or the ratio of component (A-1) / component (B).
/ 97 to 97/3, more preferably 5/95 to 95/5
Is.

In the present invention, the thermoplastic resin used as the component (B) is not particularly limited, but the following thermoplastic resins can be used. As the thermoplastic resin, a block copolymer resin of a conjugated diene compound and a vinyl aromatic compound different from the modified polymer defined in the present invention, a vinyl aromatic compound polymer resin such as polystyrene, a vinyl aromatic compound and others Vinyl monomers such as ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid esters such as acrylic acid and acrylmethyl, methacrylic acid esters such as methacrylic acid and methylmethacrylate, acrylonitrile, methacrylonitrile, etc. Is a copolymer resin.

Further, rubber modified styrene resin (HIP
S), acrylonitrile-butadiene-styrene copolymer resin (ABS), methacrylic acid ester-butadiene-
Copolymer of styrene copolymer resin (MBS), polyvinyl chloride, polyvinylidene chloride, vinyl chloride and / or vinylidene chloride containing 50% by weight or more of vinyl chloride and / or vinylidene chloride and other monomer copolymerizable therewith Combined polyvinyl chloride resin, polyvinyl acetate resin having a vinyl acetate content of 50 wt% or more and another monomer copolymerizable therewith, and a hydrolyzate thereof. is there.

Copolymerization with acrylic acid and its ester or amide polymers, methacrylic acid and its ester or amide polymers, and other copolymerizable monomers containing 50 wt% or more of these acrylic acid type monomers. It is a polyacrylate resin which is a combination, a polymer of acrylonitrile and / or methacrylonitrile, and a nitrile resin which is a copolymer with other copolymerizable monomers containing 50 wt% or more of these acrylonitrile monomers.

Further, linear polymers in which structural units of the polymer are bonded by repeating amide group bonds, for example, ring-opening polymers and copolymers such as ε-aminocaprolactam and ω-aminolaurolactam, ε-amino Polycondensation of undecanoic acid, hexamethylenediamine and adipic acid,
Condensation polymer with dibasic acid such as sebacic acid, specifically nylon-46, nylon-6, na-nylon-66, nylon-610, nylon-11, nylon-12, nylon-6-nylon-12 co-polymer Polyamide-based resin such as coalesced.

Further, linear polymers in which the structural units of the polymer are bonded by repeating ester bonds, for example, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, P, P'-dicarboxydiphenyl, 2,6- Dibasic acids such as naphthalene dicarboxylic acid or derivatives thereof, ethylene glycol, propylene glycol, 1,
4-butanediol, 1,6-hexanediol, 1,
Polyester resins such as 4-cyclohexanediol, P-xylene glycol, condensation polymers with glycol (or diol) such as bisphenol A, and ring-opening polymers such as pivalolactone, β-propiolactone, and ε-caprolactone.

Poly (1,4-butylene adipate), poly (1,6-hexane adipate), polyester diols such as polycaprolactone, polyether diols such as polyethylene glycol, polypropylene glycol and polyoxytetramethylene glycol,
Ethylene glycol, 1,4-butanediol, 1,6
A glycol component selected from glycols such as hexanediol and an aromatic, alicyclic or aliphatic diisocyanate such as tolylene diisocyanate, 4,4,
It is a thermoplastic polyurethane polymer obtained by a polyaddition reaction with a diisocyanate component such as 4′-diphenylmethane diisocyanate or hexamethylene diisocyanate.

Further, a linear polymer in which structural units of the polymer are bonded by repeating carbonic acid ester bonds, for example, 4,4'-dihydroxydiphenylalkane, 4,
A polymer obtained by reacting a dihydroxy compound such as 4′-dihydroxydiphenyl sulfide with phosgene,
Alternatively, a polymer obtained by a transesterification reaction between the dihydroxy compound and diphenyl carbonate, specifically poly-4,4′-dioxydiphenyl-2,2 ′
-Polycarbonate-based polymers such as propane carbonate, thermoplastic polysulfones such as polyether sulfone and polyallyl sulfone, specifically poly (ether sulfone), poly (4,4'-bisphenol ether sulfone), poly (thioether sulfone) And other polysulfone-based resins.

Further, polyoxymethylene-based resins such as polymers of formaldehyde or trioxane, copolymers of formaldehyde or trioxane with other aldehydes, cyclic ethers, epoxides, isocyanates, vinyl compounds, etc., poly (2,6-dimethyl) Polyphenylene ether resin such as -1,4-phenylene) ether,
Polyphenylene sulfide resins such as polyphenylene sulfide and poly 4,4′-diphenylene sulfide,
It is a polyarylate resin which is a polycondensation polymer composed of bisphenol A and a phthalic acid component, a polyetherketone polymer or copolymer, and specifically a polyketone resin such as polyetheretherketone.

Further, a polymer having a structure in which a part or all of hydrogen atoms in the chain hydrocarbon polymer compound is replaced with fluorine,
Specifically, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer, chlorotrifluoro Fluorine-based resins such as ethylene-ethylene copolymer, polyvinylidene fluoride and polyvinyl fluoride.

Further, paraoxybenzoic acid, terephthalic acid, isophthalic acid, 4,4'-dihydroxydiphenyl or derivatives thereof are used to prepare polyoxy compounds such as polymers or copolymers produced by solution polycondensation or melt polycondensation. Benzoyl polymer, polymer having imide bond in the main chain,
For example, polyimide, polyamino bismaleimide (poly bismaleimide), bismaleimide / triazine resin, polyimide resin such as polyamideimide and polyetherimide, and polybutadiene resin such as 1,2-polybutadiene and trans polybutadiene.

The number average molecular weight of these thermoplastic resins is preferably 1,000 or more, more preferably 5,000 to 50.
It is 0,000, and more preferably 10,000 to 1,000,000. Two or more of these thermoplastic resins may be used in combination. The rubber-like polymer used as the component (B) in the present invention is
Although not particularly limited, the following rubber-like polymers can be used. As the rubber-like polymer, a butadiene rubber different from the modified polymer and the like specified in the present invention and a hydrogenated product thereof,
Styrene-butadiene rubber and its hydrogenated product, isoprene rubber, acrylonitrile-butadiene rubber and its hydrogenated product, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber,
Examples include ethylene-octene rubber, butyl rubber, and chloroprene rubber.

Acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic ester-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber,
Styrene-different butadiene block copolymers and hydrogenated products thereof different from the modified polymer defined in the present invention, styrene-isoprene block copolymers and hydrogenated products thereof,
Natural rubber etc. are mentioned. These rubbery polymers are
A modified rubber having a functional group may be used. These can be used alone or in combination.

Particularly preferred as the component (B) are polyethylene, ethylene-propylene copolymer resin, polypropylene, polystyrene, rubber-modified impact polystyrene, ABS, PMMA, styrene-butadiene-methyl methacrylate terpolymer (MBS). ), Polyester resin, polyamide resin, polycarbonate resin,
Polyurethane resin, polysulfone resin, polyphenylene ether resin, polyphenylene sulfide resin, styrene-butadiene block copolymer (SB
S), styrene-isoprene block copolymer (SI
S), and hydrogenated products thereof such as styrene-ethylene-butylene block polymer (SEBS), styrene-ethylene-propylene block polymer (SEP).
S), butadiene rubber and hydrogenated products thereof, styrene-
Examples thereof include butadiene rubber and hydrogenated products thereof, EPDM, butyl rubber and the like.

In the present invention, a rubber softening agent may be added to improve processability. Mineral oils or liquid or low molecular weight synthetic softeners are suitable as softeners for rubber. Among them, the softening agent for mineral oil-based rubber generally called process oil or extender oil, which is generally used for softening, increasing volume and improving processability of rubber, is a mixture of an aromatic ring, a naphthene ring and a paraffin chain, and a paraffin chain. Of which the carbon number of 50% or more of the total carbon is called paraffinic, the naphthene ring carbon number of 30 to 45% is naphthenic, and the aromatic carbon number of more than 30% is aromatic. Called.

The rubber softening agent used in the present invention is preferably a naphthene-based and / or paraffin-based one. As the synthetic softening agent, polybutene, low molecular weight polybutadiene, etc. can be used, but the above-mentioned mineral oil type softening agent for rubber gives better results. In the present invention, the compounding amount of the softening agent for rubber is generally 0 to 100 parts by weight, preferably 10 to 90 parts by weight based on 100 parts by weight of the modified polymer or component (A).
Parts by weight, more preferably 30 to 90 parts by weight.

In the present invention, known reinforcing fillers such as silica-based inorganic fillers, metal oxides, metal hydroxides and carbon can be used. Specifically, light calcium carbonate, heavy calcium carbonate, various surface-treated calcium carbonate, magnesium carbonate, synthetic silicates such as aluminum silicate and magnesium silicate, calcium silicate, talc, mica, clay, magnesium hydroxide. , Aluminum hydroxide, barium sulfate, magnesium sulfate, calcium sulfate, natural silicic acid, synthetic silicic acid, titanium oxide, magnesium oxide, alumina, carbon black and the like.

The reinforcing filler may be used alone or in combination of two or more. The amount of these reinforcing fillers to be added is generally the modified polymer or the component (A) 1
0.5 to 300 parts by weight, preferably 5 to 100 parts by weight
To 200 parts by weight, more preferably 20 to 100 parts by weight. In the present invention, a silane coupling agent can be used. The silane coupling agent is the component (A)
The purpose of this is to make the interaction between the component (B) and the component (B) close to each other, and the component (A) and the component (B) each have an affinity group or a binding group.

Specifically, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3
-(Triethoxysilyl) -propyl] -disulfide, bis- [2- (triethoxysilyl) -ethyl]-
Tetrasulfide, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, and 3-triethoxysilylpropylbenzothiazoletetrasulfide.

Further, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyl, methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and 3-methacryloxypropyltriethoxysilane.

Further, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3
-Aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-
Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-
(1,3-Dimethyl-butylidene) propylamine, N
-Phenyl-3-aminopropyltrimethoxysilane,
3-isocyanate propyl triethoxy silane etc. are mentioned.

A preferred silane coupling agent is one having a silanol group or an alkoxysilane and at the same time a mercapto group or / and a polysulfide bond in which two or more sulfurs are linked, and an example thereof is bis- [3-
(Triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl]
-Disulfide, bis- [2- (triethoxysilyl)
-Ethyl] -tetrasulfide, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropylbenzothiazoletetra Examples include sulfide.

The compounding amount of the silane coupling agent is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, and more preferably 1 to 15% by weight, based on the reinforcing filler. The method for producing the modified polymer composition of the present invention is not particularly limited, and known methods can be used. For example, an open roll, a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, a melt kneading method using a general mixer such as a multi-screw extruder, after dissolving or dispersion mixing each component, A method of heating and removing the solvent is used. In the present invention, the melt-kneading method using an extruder is preferable from the viewpoint of productivity and good kneading property.

In the present invention, the melt-kneading temperature can be selected on the basis of the softening temperature and melting point of the thermoplastic resin and the rubber-like polymer to be used, but the melt viscosity of the thermoplastic resin and the rubber-like polymer, and the modified polymer. In general, 100 to 350 ° C. is preferable, and more preferably 150 to 350 ° C., from the viewpoint of heat deterioration.
The temperature is 350 ° C, more preferably 180 to 330 ° C. The melt-kneading time (or the average residence time in the melt-kneading step) is generally 0 in view of the kneading degree (dispersibility) and productivity, and deterioration of the modified polymer, thermoplastic resin, rubber-like polymer and the like. It is preferably from 2 to 60 minutes, more preferably from 0.5 to 30 minutes, still more preferably from 1 to 20 minutes.

In the present invention, the modified polymer or the composition comprising the component (A) and the component (B) can be vulcanized with a vulcanizing agent to give a vulcanized composition. As the vulcanizing agent, radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur,
Sulfur compounds are used, and sulfur compounds include sulfur monochloride,
Included are sulfur dichloride, disulfide compounds, and high molecular weight polysulphur compounds. The amount of the vulcanizing agent used is usually 0.01 to 2 with respect to 100 parts by weight of the modified polymer or the component (A).
It is used in an amount of 0 part by weight, preferably 0.1 to 15 parts by weight.

Specific examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl. -2,5-
Di- (tert-butylperoxy) hexyne-3,
1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-
Butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-
Butyl peroxy isopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-
Butyl cumyl peroxide and the like.

Of these, 2,5-dimethyl-2,5-di- (tert-) is preferable in terms of odor and scorch stability.
Butylperoxy) hexane, 2,5-dimethyl-
2,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane , N-butyl-4,4-bis (tert-butylperoxy) valerate, di-tert-butylperoxide and the like are preferable. Further, upon vulcanization, as a vulcanization accelerator, sulfenamide-based, guanidine-based, thiuram-based,
Aldehyde-amine type, aldehyde-ammonia type, thiazole type, thiourea type, dithiocarbamate type and the like are used in an amount according to need. Also, as a vulcanization aid,
Zinc white, stearic acid, etc. are used in an amount required.

When the above organic peroxide is used for crosslinking, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene. Peroxy crosslinking aids such as diphenylguanidine, trimethylolpropane-N, N'-m-phenylene dimaleimide, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylol Polyfunctional methacrylate monomers such as propane trimethacrylate and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be used in combination. The amount of these vulcanization accelerators used is usually 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the modified polymer or component (A). ..

The modified polymer of the present invention, or a compounded composition of a modified polymer composition and a vulcanizing agent, is vulcanized by a commonly used vulcanizing method, for example, at a temperature of 120 to 200 ° C.
It is preferably vulcanized at a temperature of 140 to 180 ° C. The resulting vulcanized product of the modified polymer and the vulcanized composition of the modified polymer composition exhibit their performance in the vulcanized product state. Further, in the present invention, the compounded composition obtained by mixing the modified polymer composition with the vulcanizing agent can also be used after being dynamically vulcanized. The dynamic vulcanization referred to in the present invention is a method of simultaneously causing dispersion and crosslinking by kneading various compounds in a molten state under a temperature condition in which a vulcanizing agent reacts. Y. Coran et al. (Rub. Chem. And Technol. V.
ol. 53.141- (1980)). The kneading machine during dynamic vulcanization is usually a Banbury mixer,
A closed kneader such as a pressure kneader, a single-screw or twin-screw extruder or the like is used. Kneading temperature is usually 130-300
C., preferably 150 to 200.degree. The kneading time is usually 1 to 30 minutes. As a vulcanizing agent for dynamic vulcanization, an organic peroxide or a phenol resin vulcanizing agent is often used.

The modified polymer or the modified polymer composition of the present invention may contain any additive, if necessary, within a range not impairing the object of the present invention. The kind of the additive is not particularly limited as long as it is generally used for blending the thermoplastic resin and the rubber-like polymer. For example, pigments such as iron oxide, stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, lubricants such as ethylene bis-stearamide, release agents, paraffin, organic polysiloxanes, softeners such as mineral oil. -Plasticizers, hindered phenol antioxidants, antioxidants such as phosphorus heat stabilizers, hindered amine light stabilizers, benzotriazole ultraviolet absorbers, flame retardants, antistatic agents, organic fibers, glass fibers, carbon Examples thereof include those described in "Rubber / Plastic Blended Chemicals" (edited by Rubber Digest Co., Ltd.) and the like such as reinforcing agents for fibers and metal whiskers, colorants, other additives, and mixtures thereof.

[0080]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. In the following examples, the properties of the polymer and its hydrogenated product were measured as follows. A. Properties of Polymers and Hydrogenated Products (1) Styrene Content Using an ultraviolet spectrophotometer (Hitachi UV200), 262
It was calculated from the absorption intensity at nm.

(2) Polystyrene block content I.I. M. Kolthoff, et al. J.
Polym. Sci. It was measured by the method described in 1,429 (1946). (3) Vinyl bond amount and hydrogenation rate Nuclear magnetic resonance apparatus (BRUXER, DPX-400)
Was measured using. (4) Molecular weight GPC (apparatus: Shimadzu LC10, column: Shimadzu Shimpac GPC805 + GPC80)
4 + GPC804 + GPC803). Tetrahydrofuran is used as the solvent, and the measurement condition is a temperature of 35 ° C.
I went there. The molecular weight is a weight average molecular weight obtained by using a calibration curve (prepared by using the peak molecular weight of standard polystyrene) obtained by measuring the standard polystyrene of the chromatogram.

(5) Ratio of Unmodified Block Copolymer A sample solution containing a modified polymer and a low molecular weight internal standard polystyrene was applied by applying the property that a modified component is adsorbed on a GPC column using silica gel as a packing material. , Above (4)
The ratio of the modified polymer to the standard polystyrene in the chromatogram measured by the method is compared with the ratio of the modified polymer to the standard polystyrene in the chromatogram measured by the silica-based column GPC [the device is Zorbax manufactured by DuPont]. The amount of adsorption to the silica column was measured from the difference of The ratio of the unmodified polymer is the ratio of those not adsorbed on the silica column.

(6) Number of terminal methyl carbon atoms (GPC
/ FTIR) GPC [apparatus manufactured by Waters] was used for measurement, and FT-IR [apparatus manufactured by Perkin Elmer] was used as a detector. The measurement conditions are as follows.・ Column; AT-807S (1 piece) [Showa Denko KK] and GMH-HT6 (2 pieces) [Tosoh Corporation] are connected in series. ・ Mobile phase: Trichlorobenzene ・ Column temperature; 140 ° C ・ Flow rate; 1.0 ml / Min-Sample concentration: 20 mg / 20 ml-Solution temperature: 140 ° C (7) Crystallization peak and crystallization peak calorific value Measured by DSC [manufactured by Mac Science Co., Ltd., DSC3200S]. The temperature was raised from room temperature to 150 ° C. at a temperature rising rate of 30 ° C./min, then the temperature was lowered to −100 ° C. at a temperature lowering rate of 10 ° C./min, and the crystallization curve was measured to confirm the presence or absence of a crystallization peak. When there is a crystallization peak, the temperature at which the peak appears is taken as the crystallization peak temperature, and the crystallization peak calorie is measured.

B. Preparation of Polymer etc. The hydrogenation catalyst used in the hydrogenation reaction was prepared by the following method. 1) Hydrogenated catalyst I 2 liters of dried and purified cyclohexane were charged into a reaction vessel purged with nitrogen, 40 mmol of bis (η5-cyclopentadienyl) titanium di- (p-tolyl) and 1 having a molecular weight of about 1,000 were used. , 2-polybutadiene (1,2-
After dissolving 150 grams of vinyl bond (about 85%), n
A cyclohexane solution containing 60 mmol of -butyllithium was added, and the mixture was reacted at room temperature for 5 minutes. Immediately, 40 mmol of n-butanol was added and stirred, and the mixture was stored at room temperature.

2) Hydrogenation catalyst II 1 liter of dried and purified cyclohexane was charged into a reaction vessel purged with nitrogen, 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride was added, and trimethylaluminum 200 was added with sufficient stirring. An n-hexane solution containing mmol was added, and the mixture was reacted at room temperature for about 3 days. The modified polymer and the like used in the present invention were prepared by the following method.

A. Polymer 1 A cyclohexane solution having a butadiene concentration of 20% by weight was fed at a feed rate of 6.19 L / hr to a stirrer having an internal volume of 10 L and a tank reactor with a jacket, and n-butyllithium was added to 100 g of butadiene in an amount of 0. The cyclohexane solution adjusted to have a concentration of 25 g was supplied at a feed rate of 2 L / hr, and a cyclohexane solution of N, N, N ′, N′-tetramethylethylenediamine was added to 0.25 to 1 mol of n-butyllithium. Each of them was fed at such a feeding rate as to give a mole, and continuously polymerized at 90 ° C. The reaction temperature is adjusted by the jacket temperature, and the temperature near the bottom of the reactor is about 8
The temperature in the vicinity of the center of the reactor was about 90 ° C, and the temperature in the vicinity of the upper part of the reactor was about 90 ° C. The average residence time in the polymerization reactor was about 45 minutes, and the conversion of butadiene was almost 100%.

The average vinyl bond content of the polymer obtained by continuous polymerization was 27%. In addition, during the polymerization reaction, it was determined from the vinyl bond content of the polymer sampled during the reaction, the butadiene supply amount at that time, and the polymer conversion rate calculated from the reaction rate (conversion rate of the polymer to the total supplied butadiene). The difference in vinyl bond content was less than 5% by weight. Next, tetraglycidyl-1,3-as a modifier is added to the living polymer obtained by continuous polymerization.
Bisaminomethylcyclohexane (hereinafter referred to as modifier M1) was reacted in 1.1 equivalents with respect to 1 equivalent of n-butyllithium used for the polymerization.

Then, 100 ppm of Ti as hydrogenation catalyst I was added to the polymer obtained as described above as Ti per 100 parts by weight of the polymer, the hydrogen pressure was 0.7 MPa, and the temperature was 65.
The hydrogenation reaction was carried out at ℃. Methanol was then added, and then octadecyl-3- (3,5-di-t- as a stabilizer.
Butyl-4-hydroxyphenyl) propionate was added in an amount of 0.3 part by mass based on 100 parts by mass of the polymer. The polymer obtained had a vinyl bond content of about 27 before hydrogenation.
%, The difference between the maximum value and the minimum value of the vinyl bond content of the polymer before hydrogenation is 5% or less, the hydrogenation addition rate is 99%, and the molecular weight is 20%.
The modified hydrogenated polymer (Polymer 1) had a molecular weight distribution of 1.6.

B. Polymer 2 Continuous polymerization was carried out using two stirrers having an internal volume of 10 L and two tank reactors with jackets. From the bottom of the first unit, add a hexane solution having a butadiene concentration of 30% by weight to 4.
At a feed rate of 6 L / hr, a hexane solution in which n-butyllithium was adjusted to a concentration of 0.097 g per 100 g of butadiene was added at a feed rate of 2 L / hr, and N, N, N ′ and N ′ were further added. -A hexane solution of tetramethylethylenediamine was added to 1 mol of n-butyllithium.
Each of them is fed at a feeding rate such that the amount becomes 06 mol,
It was continuously polymerized at ℃. The reaction temperature was adjusted by the jacket temperature. The temperature near the bottom of the reactor was about 88 ° C and the temperature near the top of the reactor was about 90 ° C.

The conversion rate of butadiene at the outlet of the first unit was almost 100%. The polymer solution discharged from the first unit was supplied from the bottom of the second unit, and at the same time, the butadiene concentration was 30%.
Wt% hexane solution at a feed rate of 6.8 L / hr,
Furthermore, a hexane solution of N, N, N ', N'-tetramethylethylenediamine was supplied at a supply rate such that 0.75 mol was obtained per 1 mol of n-butyllithium,
Continuous polymerization was carried out at 90 ° C. The temperature near the bottom of the second reactor is about 89 ° C, and the temperature near the top of the reactor is about 90 ° C.
Met. The conversion rate of butadiene at the outlet of the second unit is almost 1
It was 00%. The average vinyl bond content of the polymer obtained by the two-group continuous polymerization was 30%.

Next, 1,3-dimethyl-2-imidazolidinone (hereinafter referred to as a modifier M2) was used as a modifier in the living polymer obtained by continuous polymerization as a modifier.
-Equimolar reaction to butyllithium. afterwards,
Hydrogenated catalyst II was added to the polymer obtained as described above in an amount of 100 ppm as Ti per 100 parts by weight of the polymer, and hydrogenated at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. Thereafter, methanol was added, and then 0.3 part by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the polymer. The polymer obtained had a vinyl bond content of about 30% and a hydrogenation addition ratio of 9 before hydrogenation.
8%, molecular weight 220,000, molecular weight distribution 1.8, Va-V
It was a modified hydrogenated polymer (polymer 2) in which b was 15, and 0.03 Vc was 2.6.

C. Polymer 3 A n-hexane solution containing a monomer having a butadiene / styrene weight ratio of 82/18 at a concentration of 16% by weight was fed to a stirrer having an inner volume of 10 L and a jacketed tank reactor at a feed rate of 157 g / min. Then, the cyclohexane solution of n-butyllithium was fed at a rate of 0.15 g of n-butyllithium to 100 g of the monomer, and N, N, N ′, N′-tetramethylethylenediamine (TMEDA) was added as a polar substance. The cyclohexane solution of was fed at a feed rate such that TMEDA was 0.11 g per 100 g of the monomer, and continuous polymerization was carried out at 86 ° C.

Next, the living polymer obtained by continuous polymerization was reacted with the modifier M1 in an amount of 0.5 mol per mol of n-butyllithium used in the polymerization. When the obtained polymer was analyzed, the styrene content was 18% by weight and the vinyl bond content in the butadiene part was 30% by weight. From the analysis value of the amount of block styrene, the block of styrene was not present. Next, 100 ppm of Ti was added to the polymer obtained by continuous polymerization as Ti per 100 parts by weight of the polymer, the hydrogen pressure was 0.7 MPa, and the temperature was 6 MPa.
The hydrogenation reaction was carried out at 5 ° C. Then add methanol,
Next, as a stabilizer, octadecyl-3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate was added in an amount of 0.3 part by weight based on 100 parts by weight of the polymer. The obtained modified hydrogenated copolymer (Polymer 3) had a Mooney viscosity of 70, a molecular weight distribution of 1.9, a styrene content of 18% by weight, a vinyl bond content of the butadiene part of 30% by weight, and a hydrogenation rate of 84%. .

D. Polymer 4 Continuous polymerization was carried out using two stirrers having an internal volume of 10 L and two tank reactors with jackets. From the bottom of the first reactor, a cyclohexane solution having a butadiene concentration of 24 wt% was supplied at a feed rate of 4.51 L / hr, and a cyclohexane solution having a styrene concentration of 24 wt% was 5.97 L / hr.
N-butyllithium was added to the monomer 10 at a feed rate of
A cyclohexane solution adjusted to a concentration of 0.077 g relative to 0 g was supplied at a supply rate of 2.0 L / hr, and a cyclohexane solution of N, N, N ′, N′-tetramethylethylenediamine was added to n-butyllithium. Each was supplied at a supply rate such that 0.44 mol per 1 mol was obtained, and continuous polymerization was carried out at 90 ° C. The reaction temperature was adjusted by the jacket temperature. The temperature near the bottom of the reactor was about 88 ° C and the temperature near the top of the reactor was about 90 ° C. The average residence time in the polymerization reactor was about 45 minutes, the conversion of butadiene was almost 100%, and the conversion of styrene was 99%.

The polymer solution discharged from the first unit was fed from the bottom of the second unit, and at the same time, a cyclohexane solution having a styrene concentration of 24% by weight was fed at a feed rate of 2.38 L / hr.
It was fed to the bottom of the base and continuously polymerized at 90 ° C. The conversion rate of styrene at the outlet of the second unit was 98%. Next, the living polymer from the second group was reacted with N-methylpyrrolidone (hereinafter referred to as a modifier M3) as a modifier in equimolar reaction with n-butyllithium used for the polymerization.

Then, to the polymer obtained as described above, 100 ppm of Ti was added as hydrogen per 100 parts by weight of the polymer, and the hydrogen pressure was 0.7 MPa and the temperature was 6 MPa.
The hydrogenation reaction was carried out at 5 ° C. Then add methanol,
Next, as a stabilizer, octadecyl-3- (3,5-di-t
0.3 parts by mass of -butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the polymer. The obtained polymer has a molecular weight of 200,000 and a molecular weight distribution of 1.
9. Styrene content is 67% by weight, block styrene amount obtained from the polymer before hydrogenation is 20% by weight, vinyl bond content in the butadiene portion before hydrogenation is 14%, hydrogenation rate is 99%.
Was a modified hydrogenated polymer (Polymer 4). The block ratio of styrene was 30% based on the analysis values of the styrene content and the block styrene content. Further, in the measurement of the crystallization temperature and the crystallization peak calorie by the DSC method, the polymer 4 did not show a crystallization peak in the temperature range of -50 to 100 ° C and the crystallization peak calorie was zero.

E. Polymer 5 8 L of a cyclohexane solution having a styrene concentration of 20% by weight was charged into a stirrer having an internal volume of 10 L and a tank reactor with a jacket, and 100 g of n-butyllithium was added to styrene.
Then, 0.08 g was added and the temperature was adjusted to about 70 ° C. for polymerization. Next, the modifier M1 was added to the living polymer obtained as described above for polymerization.
-Reacted with 1.5 equivalents to 1 equivalent of butyllithium. Thereafter, methanol was added, and then 0.3 part by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the polymer. The obtained polymer was a modified polymer (polymer 5) having a molecular weight of 330,000 and a molecular weight distribution of 1.1.

C. Physical Properties of Modified Polymer and Modified Polymer Composition 1) Hardness According to JIS K6253, 1 with durometer type A
The value after 0 seconds was measured. 2) Tensile strength, elongation at break Rubber-like test pieces were measured at a pulling speed of 500 mm / min in accordance with JIS K6251. JIS for resin-like test pieces
According to K6758, the tensile speed was measured at 20 mm / min. 3) Flexural modulus (MPa) Measured in accordance with ASTM-D790. 4) Notched Izod Impact Strength (J / m) Measured in accordance with JIS-K-7110.

[0099]

Example 1 Polymer 1 and maleated polybutadiene oligomer were added to a twin screw extruder having a diameter of 30 mm at 190 to 230.
A modified polymer is obtained by melt-kneading at a temperature of ° C. PET resin is added to this modified polymer by a twin-screw extruder with a diameter of 30 mm to 190
The modified polymer composition is obtained by melt-kneading under conditions of 230 ° C. The obtained composition is molded and various physical properties are measured.

[0100]

Example 2 Polymer 4 and a maleated polybutadiene oligomer were mixed in a twin screw extruder having a diameter of 30 mm for 180 to 210.
A modified polymer is obtained by melt-kneading at a temperature of ° C. Next, the modified polymer obtained above, a hydrogenated block copolymer as a rubbery polymer (Tuftec H1062: Asahi Kasei Corp.)
), And talc (Microace P-4: manufactured by Nippon Talc Co., Ltd.) in a twin-screw extruder with a diameter of 30 mm at 190 to 23.
The modified polymer composition is obtained by melt-kneading at 0 ° C. The obtained composition is molded and various physical properties are measured.

[0101]

Example 3 A modified polymer is obtained by kneading the polymer 2 and the epoxidized polybutadiene oligomer from the outside using a closed kneading machine (internal volume 1.7 liters) equipped with a temperature control device using circulating water. Next, using the same closed kneader as above, filling rate 65%, rotor speed 66/77 rp
Under the conditions of m, 100 parts by weight of the modified polymer obtained above, 40 parts of silica, 5 parts of oil, 2 parts of an organic silane coupling agent (manufactured by Degussa: Si69), 3 parts of zinc white, stearin Add 2 parts of acid and knead. After cooling, sulfur and a vulcanization accelerator are added with an open roll set at 70 ° C., and the mixture is kneaded again. Mold the kneaded product obtained above, 160 ℃
And vulcanized in a vulcanizing press for a predetermined time to obtain a modified polymer composition. Various physical properties of the obtained polymer composition are measured.

[0102]

The modified polymer of the present invention has a good compatibility with the thermoplastic resin and / or the rubber-like polymer, and the modified polymer of the present invention is blended with the thermoplastic resin and / or the rubber-like polymer. The modified polymer composition thus obtained has excellent mechanical strength and impact resistance. The modified polymer or modified polymer composition of the present invention can be molded by a commonly used molding machine for thermoplastic resin, and can be used as a sheet, a film, an injection molded product of various shapes, a hollow molded product, or a pneumatic molding. It can be used as a variety of molded products such as molded products, vacuum molded products, and extrusion molded products. These molded products can be used as food packaging materials, medical device materials, home electric appliances and parts thereof, materials for automobile parts / industrial goods / daily miscellaneous goods / toys, footwear materials and the like. Further, the modified polymer or modified polymer composition of the present invention, in the form of a vulcanized composition, automobile interior / exterior parts, anti-vibration rubber, belts, footwear, foams,
It can be applied to various industrial parts, tire applications, etc. by utilizing its characteristics.

Continued front page    F term (reference) 4J002 AA01X AC04X BC03X BC04X                       BC05X BC06X BC07X BD04X                       BD05X BD10X BD12X BD13X                       BD14X BD15X BF02X BG01X                       BG04X BG05X BG09X BG10X                       BG11X BH02X BN15X BN16X                       BP01W BP01X BP02W BP03W                       CB00X CF03X CF04X CF05X                       CF06X CF07X CF08X CF16X                       CF19X CG01X CH07X CH09X                       CK02X CK03X CK04X CL01X                       CL02X CL03X CM04X CN01X                       CN02X CN03X GB01 GG02                       GM01 GN00 GN01 GQ00                 4J031 AA12 AA13 AA17 AA29 AA46                       AA49 AA55 AA59 AB01 AC03                       AC04 AC07 AC08 AC09 AC13                       AD01 AD03 AD05 AF03 AF05                       AF10 AF11 AF20

Claims (6)

[Claims] 1. The following a, b, and c a. Conjugated diene polymer b. A polymer c which is a polymer composed of a conjugated diene and a vinyl aromatic hydrocarbon, and in which the proportion of the vinyl aromatic hydrocarbon polymer block to the total vinyl aromatic hydrocarbon content in the polymer is less than 50% by weight. ． The component (1) which is a primary modified polymer or hydrogenated product of the functional group-containing modifier added to at least one polymer selected from vinyl aromatic hydrocarbon polymers is A modified polymer (A) modified with a component (2) which is a functional oligomer having reactivity with a functional group. 2. The component (1) contains at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group.
The modified polymer (A) according to claim 1, which is individually bonded. 3. The functional group-containing modifier is a modifier for forming an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group in the component (1). The modified polymer (A) according to claim 1 or 2, wherein 4. The functional oligomer of component (2) has at least one functional group selected from a hydroxyl group, an amino group, a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group and an alkoxysilane group. It is a functional oligomer, The modified polymer (A) in any one of Claims 1-3 characterized by the above-mentioned. 5. The component (1) is represented by the following formula (1) to formula (1)
The modified polymer (A) according to any one of claims 1 to 4, wherein at least one atomic group having at least one functional group selected from 4) is bonded. [Chemical 1] (In the above formula, R ^{1 to} R ⁴ are each a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, or a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group, and having 1 to carbon atoms. 24 hydrocarbon groups, wherein R ⁵ has 1 to 1 carbon atoms.
A hydrocarbon chain of 48 or a hydrocarbon chain of 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group. Note that R ¹
To the hydrocarbon group of R ^{4 and} the hydrocarbon chain of R ⁵ are bonded with an element such as oxygen, nitrogen or silicon in a bonding mode other than a hydroxyl group, an epoxy group, an amino group, a silanol group or an alkoxysilane group. It may be. R ⁶ is hydrogen or has 1 carbon atom
~ 8 alkyl groups. ) 6. At least one selected from the group consisting of 1 to 99 parts by weight of the component (A) which is the modified polymer according to any one of claims 1 to 5, a thermoplastic resin and a rubbery polymer. A modified polymer composition comprising 99 to 1 part by weight of component (B).