JP2003301087A - Dynamically cross-linked polymer or composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dynamically cross-liked polymer or a dynamically cross- linked polymer composition excellent in softness, etc. <P>SOLUTION: The dynamically cross-linked polymer or the dynamically cross- linked polymer composition is prepared by dynamically cross-linking, in the presence of a vulcanizing agent, a modified polymer or a modified polymer composition comprising (1) 10-100 pts.wt. modified polymer prepared by the addition reaction of a functional group-containing modifying agent with living terminals of at least one polymer selected from among the below-described polymers (a) and (b) and their hydrogenated products and (2) 0-90 pts.wt. at least one component selected from among thermoplastic resins and rubbery polymers. The polymer (a) is a conjugated diene polymer. The polymer (b) is a conjugated diene-vinyl aromatic hydrocarbon copolymer of which the total vinyl aromatic hydrocarbon content is 50 wt.% or lower and the ratio of the vinyl aromatic hydrocarbon polymer block content to the total vinyl aromatic hydrocarbon content is lower than 50 wt.%. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a dynamic cross-linking polymer or a dynamic cross-linking polymer composition having good flexibility and the like, more specifically, a specific polymer or a specific polymer and a thermoplastic resin and / or The present invention relates to a dynamically crosslinked polymer or a dynamically crosslinked polymer composition obtained by dynamically crosslinking a polymer composition composed of a rubber-like polymer in the presence of a vulcanizing agent.

[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. Further, a method of partially cross-linking such a block copolymer or a hydrogenated product thereof is disclosed in JP-A-59-131613.

[0003]

Under such circumstances, there has been a demand for a material having a flexibility more similar to that of vulcanized rubber. The present invention provides a dynamic crosslinking polymer or a dynamic crosslinking polymer composition having good flexibility and the like.

[0004]

Means for Solving the Problems The present inventor has conducted diligent studies in order to develop a dynamically crosslinked polymer or a dynamically crosslinked polymer composition having good flexibility and the like. It was found that a polymer composition composed of a polymer and a thermoplastic resin and / or a rubber-like polymer can be effectively cross-linked by dynamically crosslinking the polymer composition in the presence of a vulcanizing agent. The invention was completed.

That is, the present invention is as follows. A component which is a modified polymer obtained by adding a functional group-containing modifier to the living end of at least one polymer selected from the following a and b obtained by using an organolithium compound as a polymerization catalyst or a hydrogenated product thereof ( 1) 10 to 100 parts by weight, and a. A conjugated diene polymer, and b. A polymer comprising a conjugated diene and a vinyl aromatic hydrocarbon, the total vinyl aromatic hydrocarbon content in the polymer is 50% by weight or less, and the total vinyl aromatic hydrocarbon content in the polymer. A polymer having a ratio of the vinyl aromatic hydrocarbon polymer block to less than 50% by weight. A modified polymer or modified polymer composition composed of 90 to 0 parts by weight of at least one component (2) selected from the group consisting of a thermoplastic resin and a rubbery polymer is prepared in the presence of a vulcanizing agent. A dynamically crosslinked polymer or composition that is dynamically crosslinked.

The present invention will be specifically described below.
The component (1) used in the present invention is modified by adding a functional group-containing modifier to the living end of at least one polymer selected from the following a and b obtained by using an organolithium compound as a polymerization catalyst. It is a polymer or a hydrogenated product thereof. a. A conjugated diene polymer, and b. A polymer comprising a conjugated diene and a vinyl aromatic hydrocarbon, the total vinyl aromatic hydrocarbon content in the polymer is 50% by weight or less, and the total vinyl aromatic hydrocarbon content in the polymer. The ratio of the vinyl aromatic hydrocarbon polymer block to the above is less than 50% by weight.

The total vinyl aromatic hydrocarbon content of the modified polymer comprising the conjugated diene and vinyl aromatic hydrocarbon used in the present invention or the hydrogenated product thereof is generally 5 to 50% by weight, more preferably 10 to 45%. % By weight, more preferably 15 to
40 weight. In the present invention, a vinyl aromatic hydrocarbon content of less than 5% by weight is considered to be substantially a conjugated diene polymer. In the present invention, the content of the vinyl aromatic compound in the hydrogenated product may be grasped as the content of the vinyl aromatic compound in the polymer before modification or in the polymer before hydrogenation. 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 modified polymer composed of a conjugated diene and a vinyl aromatic hydrocarbon used in the present invention or a hydrogenated product thereof is a vinyl aromatic hydrocarbon polymer block based on the total vinyl aromatic hydrocarbon content in the polymer. (Hereinafter, the ratio of the vinyl aromatic hydrocarbon polymer block content to the total vinyl aromatic hydrocarbon content in the polymer is referred to as the vinyl aromatic hydrocarbon block ratio) is less than 50% by weight, preferably The polymer is 40% by weight or less, more preferably 20% by weight or less. When the blocking rate is less than 50% by weight, a composition having better flexibility is 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 modified polymer before the hydrogenation reaction is obtained by subjecting the living terminal of the polymer obtained by a known method using an organolithium compound as a polymerization catalyst to a reaction with a modifying agent which will be described later. It has a structure represented by the following general formula. (B) _n -X (AB) _n -X, A- (BA) _n -X, B- (AB) _n -X, X- (AB) _n , X- (A -B) _n- X, X-A- (BA) _n- X, X-B- (AB) _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 segment, B is a conjugated diene polymer or a copolymer composed of a conjugated diene and a vinyl aromatic hydrocarbon,
Alternatively, it is 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 an integer of 1 to 5. m is an integer of 2 or more, preferably 2 to 11. X represents a modifier residue to which an atomic group having a functional group described later is bonded. When X is added by the metallation reaction described later, it is bonded to the side chains of A and / or B. 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 (cis, trans, vinyl ratio) 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, the 1,2-vinyl bond amount) 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 together, a composition having good processability can be obtained even at high temperature.

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. Further, the organolithium compound used for producing the polymer is a compound having one or more lithium atoms bonded in the molecule, such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyl. lithium,
Examples thereof include tert-butyl lithium, hexamethylene dilithium, butadienyl dilithium, and isoprenyl dilithium. These may be used alone or as a mixture of two or more. Also, the organolithium compound is
In the production of the polymer, it may be added one or more times during the polymerization.

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,
Examples are diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, and 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 modified polymer obtained by using the organolithium compound used in the present invention as a polymerization catalyst, or a hydrogenated product thereof, is obtained by adding a functional group-containing modifier to the living end of the polymer. , Hydroxyl group, 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, Sulfonate group, phosphate group,
Phosphate group, amino group, imino group, nitrile group,
Functional group selected from pyridyl group, 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. A modified polymer in which at least one atomic group having at least one is bonded or a hydrogenated product thereof.

A method for obtaining a modified polymer having an atomic group having such a functional group bonded thereto or a hydrogenated product thereof is selected from the above functional groups in the polymer by an addition reaction with the living end of the polymer. A modified polymer having a functional group forming at least one atomic group having at least one functional group bonded thereto or a hydrogenated product thereof, or an atomic group having the functional group protected by a known method is bonded. It can be obtained by a method in which the modifying agent used 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 in the modified polymer of the component (1). The proportion of the unmodified polymer mixed in the modified polymer of the component (1) is preferably 70 wt% or less, more preferably 60 w.
It is recommended to be t% or less, and more preferably 50 wt% or less. In the kinematic crosslinked polymer or the kinematic crosslinked polymer composition of the present invention, the modified polymer or the hydrogenated group thereof has at least one functional group selected from the above-mentioned functional groups. High affinity with a plastic resin or a rubber-like polymer, the interaction is effectively expressed by a physical affinity such as a chemical bond or a hydrogen bond with a thermoplastic resin or a rubber-like polymer, and the present invention is It is possible to obtain a composition having excellent target properties.

Particularly preferred as the modified polymer of the component (1) used in the present invention or its hydrogenated product is at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group. It is a modified polymer having at least one atomic group bonded thereto or a hydrogenated product thereof. In the present invention, a preferable atomic group as 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 general atomic group represented by the following formulas (1) to (14). The atomic groups selected from those represented by the formula are raised.

[0023]

[Chemical 2]

(In the above formula, R ^{1 to} R ⁴ are hydrogen or C 1
A hydrocarbon group having 1 to 24 carbon atoms or a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group. R ⁵ has 1 to 1 carbon atoms
A hydrocarbon chain having 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group. Elements such as oxygen, nitrogen, and silicon are bound to the hydrocarbon groups of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ in a bonding mode other than hydroxyl group, epoxy group, silanol group, and alkoxysilane group. It may be. R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms) In the present invention, 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 is bonded. Examples of the modifying agent used to obtain the modified polymer or hydrogenated product thereof 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, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldisilane It is propoxysilane.

Further, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldiethylethoxysilane, γ-glycine Sidoxypropyldimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropylmethyldiisopropeneoxysilane, bis (γ-glycidoxypropyl) dimethoxy Silane and 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.

Furthermore, 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 and β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane.

Furthermore, 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- (3,4-epoxycyclohexyl) ethyl-dimethylphenoxysilane, β-
(3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane and β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane.

Further, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone,
Examples thereof include N, N'-dimethylpropyleneurea and N-methylpyrrolidone. By reacting the above 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 is bonded. A modified polymer is obtained. When the functional group-containing modifier is added to the living ends of the polymer having the segment A and the segment B, the living end of the polymer may be either the segment A or the segment B, but a composition excellent in heat resistance and the like should be used. In order to obtain it, it is preferable that it is bound to the end of 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, relative to 1 equivalent of the living end of the polymer,
It is recommended to use 5 equivalents or less, more preferably 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 from the number average molecular weight of the obtained polymer. It may be calculated.

In the present invention, the hydrogenated product of the modified polymer is
It is obtained by hydrogenating the modified polymer obtained above. The hydrogenation catalyst is not particularly limited and is a conventionally known (1) supported heterogeneous hydrogenation in which a metal such as Ni, Pt, Pd or Ru is supported on carbon, silica, alumina, diatomaceous earth or the like. Catalyst, (2) Ni, Co, Fe, C
A so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as r or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum, (3) Ti, Ru, Rh, Zr
A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound 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 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. More than 70%, preferably 75% or more, more preferably 85% or more, particularly preferably 90% or more of the unsaturated double bonds based on the conjugated diene compound in the polymer may be hydrogenated. Only part 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 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 rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the polymer is not particularly limited, but is preferably 50.
% Or less, more preferably 30% or less, and further preferably 2
0% 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 modified polymer or hydrogenated product thereof used in the present invention is 30,000 or more from the viewpoint of mechanical strength of the dynamically crosslinked polymer or the dynamically crosslinked polymer composition, and 1.5 million or less from the viewpoint of processability. Is preferable, more preferably 40,000 to 1,000,000, and further preferably 5 to 800,000. The molecular weight distribution is 1.05
6, preferably 1.1 to 6, more preferably 1.55
5.0, particularly preferably 1.6 to 4. Setting the molecular weight distribution within this range is recommended in terms of processability.

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.

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

In the present invention, a particularly preferred modified polymer or hydrogenated product thereof has a difference between the maximum value and the minimum value of the vinyl bond content in the polymer chain before hydrogenation of less than 10% by weight, preferably 8% by weight. The following modified polymers or hydrogenated products thereof may be mentioned. Further, in the present invention, as a particularly preferred modified polymer or hydrogenated product thereof, a modified polymer or its water whose relation between the molecular weight obtained by GPC / FTIR measurement and the number of terminal methyl carbon atoms satisfies the following formula: An accessory is mentioned. Va-Vb ≧ 0.03Vc, preferably Va-V
b ≧ 0.05 Vc (where Va is the number of terminal methyl carbon atoms contained per 1000 carbon atoms in the polymer at a molecular weight twice the peak top molecular weight, Vb
Is the same number in the molecular weight of 1/2 of the peak top molecular weight, and Vc is the same number in the peak top molecular weight. )

GPC-FTIR is a FTI as a detector of GPC (gel permeation chromatograph).
Using 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 numbers: 2960 cm ^-1> ratio, I (-
_{CH 3) / I (-CH 2} - can be obtained from). This method is described in, for example, NICOLET FT-IR CU.
STOMER NEWSLETTER Vol. 2, No
2, 1994 and the like.

In the present invention, the modified polymer or its hydrogenated product may be used in combination with a thermoplastic resin. The thermoplastic resin used as the component (2) is not particularly limited, but is a styrene resin, an olefin resin, polycarbonate, polyethylene terephthalate, polyester such as polybutylene terephthalate, polyphenylene ether (PPE), polyphenylene sulfide (P).
Examples thereof include aromatic resins such as PS), polyamides such as 6.6 nylon and 6 nylon, methacrylic resins, acrylic resins, ethylene vinyl acetate copolymers (EVA), and the like.

As the styrene resin, polystyrene, rubber-reinforced polystyrene (high impact polyester),
Styrene / methacrylic acid ester such as block copolymer resin of conjugated diene compound and vinyl aromatic compound and hydrogenated product thereof, acrylonitrile / styrene copolymer (AS resin), styrene / methyl methacrylate copolymer (MS resin) Copolymer, acrylonitrile / butadiene / styrene terpolymer (ABS resin), rubber-reinforced MS resin, maleic anhydride / styrene terpolymer, maleic anhydride / acrylonitrile / styrene terpolymer, acrylonitrile / Examples thereof include α-methylstyrene terpolymer, methacrylonitrile / styrene copolymer, methyl methacrylate / acrylonitrile / styrene terpolymer.

Examples of the olefin resin include homopolymers such as polyethylene (PE) and polypropylene (PP),
And blocks such as butene, hexene and octene, random copolymers, polymethylpentene, polybutene-1,
Examples thereof include propylene / butene-1 copolymer, chlorinated polyolefin, ethylene / methacrylic acid and its ester copolymer, styrene / acrylic acid and its ester copolymer, ethylene / propylene copolymer (EPR) and the like. . Examples of the methacrylic resin include polymethyl methacrylate (PMMA), methyl methacrylate / methacrylic acid copolymer, and the like. You may use these thermoplastic resins in mixture of 2 or more types.

Further, in the present invention, a modified polymer or a hydrogenated product thereof may be used in combination with a rubbery polymer. The rubber-like polymer used as the component (2) is
Although not particularly limited, butadiene rubber and its hydrogenated product, styrene-butadiene rubber and its hydrogenated product, isoprene rubber, acrylonitrile-butadiene rubber and its hydrogenated product, chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber , Ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, ethylene-octene rubber and other olefin elastomers, butyl rubber, acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber,
Epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber, styrene-butadiene block copolymer and its hydrogenated product, styrene-isoprene block copolymer and its Examples thereof include styrene elastomers such as hydrogenated products and natural rubber.

These rubber-like polymers may be modified rubbers having a functional group. These can be used alone or in combination. Particularly preferred as component (2) are polyethylene, polypropylene,
Polystyrene, ABS, PMMA, styrene-butadiene-methyl methacrylate terpolymer (MBS),
Styrene-butadiene block copolymer (SBS), styrene-isoprene block copolymer (SIS), and hydrogenated products thereof, such as styrene-ethylene-butylene block polymer (SEBS), styrene-ethylene-propylene block polymer (SEPS). ), Styrene-butadiene rubber (SBR), EPDM, butyl rubber and the like.

The amount of the thermoplastic resin and / or the rubber-like polymer used as the component (2) is 90/10 to 100/0, preferably 20/80, in the weight ratio of component (1) / component (2).
To 90/10, more preferably 30/70 to 80/20
Is. The thermoplastic resin and / or rubber-like polymer of the component (2) may be dynamically vulcanized together with the modified polymer or its hydrogenated product in the presence of a vulcanizing agent. The hydrogenated product may be dynamically crosslinked, and then the component (2) may be blended and used. 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 where a vulcanizing agent reacts,
A. Y. Coran et al. (Rub. Chem. An.
d Technol. vol. 53.141- (198
0)). A kneading machine for dynamic vulcanization is usually a Banbury mixer, a closed kneading machine such as a pressure kneader, a single-screw or twin-screw extruder, or the like. The kneading temperature is usually 130 to 300 ° C, preferably 150 to 250.
℃. The kneading time is usually 1 to 30 minutes.

As a vulcanizing agent in dynamic vulcanization, an organic peroxide or a phenol resin cross-linking agent is usually often used. As the organic peroxide, specifically, dicumyl peroxide,
Di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-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, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide , Ter
Examples thereof include t-butyl peroxybenzoate, tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butyl cumyl peroxide.

Among 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-ter-butylperoxide and the like are preferable.

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 the vulcanizing agent used in the present invention is usually composed of a modified polymer or a hydrogenated product thereof, or a modified polymer or a hydrogenated product thereof and a thermoplastic resin and / or a rubber-like polymer. 0.0 per 100 parts by weight of the modified polymer composition
It is used in a proportion of 1 to 15 parts by weight, preferably 0.04 to 10 parts by weight. The composition of the present invention contains, if necessary, a softener, a heat stabilizer, an antistatic agent, a weather stabilizer, an antiaging agent, a filler, a colorant, a lubricant, etc. within a range that does not impair the object of the present invention. Additives can be added. As a softening agent that can be blended as needed to adjust the hardness and fluidity of the product, specifically, a paraffin-based, naphthene-based, aroma-based process oil, a mineral oil-based softening agent such as liquid paraffin, etc. Various types such as castor oil, linseed oil, etc. are used. These softening agents may be added at the time of kneading or may be contained in the copolymer in advance at the time of producing the modified polymer or its hydrogenated product (so-called oil-extended rubber). The addition amount of the softening agent is usually 0 to 200 parts by weight, preferably 10 to 150 parts by weight, and more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the modified polymer or its hydrogenated product.

As the filler, specifically, light calcium carbonate, heavy calcium carbonate, various surface-treated calcium carbonates, magnesium carbonate, synthetic silicates such as aluminum silicate, magnesium silicate, and calcium silicate. Salt, talc, mica, clay, magnesium hydroxide, aluminum hydroxide, barium sulfate, magnesium sulfate, calcium sulfate, natural silicic acid, synthetic silicic acid, calcium silicate, titanium oxide, magnesium oxide, alumina, carbon and the like, The addition amount of these fillers is usually 0 to 200 parts by weight, preferably 10 to 150 parts by weight, and more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the modified polymer or its hydrogenated product.

When a filler is added, it is preferable to use a silane coupling agent together. 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, 3-triethoxysilylpropylbenzothiazoletetrasulfide, Vinyltrimethoxysilane,
Examples thereof include vinyltriethoxysilane, 2- (3,4epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane.

Further, p-styryltrimethoxysilane,
3-methacryloxypropyl, methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane,
3-methacryloxypropylmethyldiethoxysilane,
3-methacryloxypropyltriethoxysilane, 3-
Acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and the like can be mentioned.

The content of the silane coupling agent is 0.1 to 30% by weight, preferably 0.5 to 2 with respect to the filler.
It is 0% by weight, more preferably 1 to 15% by weight. In the present invention, a modified polymer or a hydrogenated product thereof or a modified polymer composition, a dynamically cross-linked polymer or a dynamically cross-linked polymer composition obtained by dynamically vulcanizing in the presence of a vulcanizing agent has a gel content of (However, insoluble components such as insoluble substances such as inorganic fillers are not included in this), 5 to 80% by weight, preferably 10 to 70% by weight,
More preferably, it is recommended to vulcanize so as to be 20 to 60% by weight. Here, the gel content means that 1 g of a dynamically crosslinked polymer or a dynamically crosslinked polymer composition (sample) is refluxed for 10 hours with a Soxhlet extractor using boiling xylene, and the residue is filtered through a wire mesh of 80 mesh. Is a ratio (% by weight) of the dry weight (g) of the insoluble matter remaining on the mesh to 1 g of the sample.

[0053]

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 modified polymers and hydrogenated products thereof (hereinafter referred to as polymers) 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 Using a polymer before hydrogenation, 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: LC10 manufactured by Shimadzu Corporation, column: Shimpac GPC805 + GPC80 manufactured by Shimadzu Corporation)
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 having 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; 20mg / 20ml ・ Solution temperature; 140 ° C

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) Hydrogenated 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 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.

Thereafter, 100 ppm of Ti as hydrogenation catalyst I was added to the polymer obtained as described above per 100 parts by weight of the polymer, and 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 weight based on 100 parts by weight 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 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% by weight.
At a feed rate of 6.8 L / hr, and a hexane solution of N, N, N ′, N′-tetramethylethylenediamine was added to 1 mol of n-butyllithium at 0.
Each is fed at a feeding rate of 75 mol,
It was continuously polymerized at ℃. The temperature near the bottom of the second reactor was about 89 ° C and the temperature near the top of the reactor was about 90 ° C. The conversion rate of butadiene at the outlet of the second unit is almost 100.
%Met. 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.
-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 parts by weight of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by weight 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) having b of 15, 0.03 and Vc of 2.6.

C. Polymer 3 A n-hexane solution containing a monomer having a weight ratio of butadiene / styrene of 82/18 at a concentration of 16% by weight was supplied to a stirrer having an internal volume of 10 L and a tank reactor with a jacket at a feed rate of 157 g / min. Then, a cyclohexane solution containing 10% by weight of n-butyllithium as a polymerization initiator at a supply rate of 6.5 g / min, and N, N, N ′, N′-tetramethylethylenediamine as a polar substance was further added. An n-hexane solution containing 10% by weight was supplied at a supply rate of 4.5 g / min, and continuous polymerization was performed 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, the hydrogenation catalyst I was added to the polymer obtained by continuous polymerization in an amount of 10 as Ti per 100 parts by weight of the polymer.
0 ppm was added, and hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. Thereafter, methanol was added, and then octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to the polymer 1
0.3 parts by weight was added to 00 parts by weight. The resulting modified hydrogenated copolymer (Polymer 3) had a Mooney viscosity of 70,
Molecular weight distribution 1.9, styrene content 18% by weight, vinyl bond content of butadiene part 30% by weight, hydrogenation rate 84%
Met.

C. Each component other than the component polymer used for preparing the kinematic cross-linked polymer composition is shown below.・ Polypropylene resin: Sun Allomer PC600S
(Manufactured by Monterey SDC Sunrise) ・ Paraffin oil: Diana Process Oil P
W-380 (manufactured by Idemitsu Kosan Co., Ltd.)-Calcium carbonate: calcium carbonate surface-treated with higher fatty acid ester-Organic peroxide: Perhexa 2,5B (manufactured by NOF Corporation) -Vulcanization accelerator: divinylbenzene-antioxidant : Irganox 1010 (manufactured by Ciba Specialty Chemicals)

D. Physical properties of kinematic crosslinked polymer and kinematic crosslinked polymer composition 1) Hardness 1 according to JIS K6253, durometer type A
The value after 0 seconds was measured. 2) Tensile strength, elongation at break According to JIS K6251, measurement was performed with a No. 3 dumbbell and a crosshead speed of 500 mm / min. 3) Oil resistance No. 1 specified in JIS K6301. 3 test oils (lubricating oil) are used, 70 ° C for 2 hours, 50 mm x 50 mm x 2 mm
The test piece having the thickness was dipped and the weight change (%) before and after the dipping was determined.

[0068]

Examples 1 to 3 Polymers 1 to 3 were used as raw rubbers, each component was mixed with a Henschel mixer according to the formulation shown in Table 1, and the mixture was mixed with a twin screw extruder having a diameter of 30 mm at 190 to 230 ° C. The compound before melt-kneading and dynamic crosslinking is obtained under the conditions of (1st step). A vulcanizing agent was added to this compound, and the mixture was mixed with a twin-screw extruder having a diameter of 30 mm to 190-2.
Melt kneading is performed at 30 ° C. to obtain a dynamically vulcanized dynamically crosslinked polymer composition (second stage). The obtained composition is injection-molded and various physical properties are measured. The obtained composition is a composition having excellent properties such as flexibility.

[0069]

[Table 1]

[0070]

EFFECTS OF THE INVENTION The kinematic crosslinked polymer or kinematic crosslinked polymer composition of the present invention is excellent in properties such as flexibility and can be molded by a commonly used molding machine for thermoplastic resin, and can be used as a sheet or film. It can be used as various molded products such as injection molded products, hollow molded products, pressure molded products, vacuum molded products, and extrusion molded products of various shapes. 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.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) // (C08L 57/00 C08L 53:02 53:02) F term (reference) 4F070 AA06 AA08 AA12 AB02 AB05 AB07 GA05 GA07 GB02 GB07 4J002 AA01X AC02W AC06X AC07X AC08X AC09W AC09X AC11W BB01X BB05X BB06X BB07X BB08X BB15X BB18X BB24X BC02X BC06X BC07X BD12X BG04X BG05X BG06X BH02X BN14X BN15X BN16X BP01W BP01X CF06X CF07X CG00X CH04X CH07X CL01X CL03X CN01X CP03X EH077 EK036 EK046 EK056 ER027 ES017 EU027 EU187 FB090 FD010 FD146 FD157 GB00 GC00 GG02 GN00 GQ00

Claims (4)

[Claims] 1. A modified polymer obtained by adding a functional group-containing modifier to the living end of at least one polymer selected from the following a and b, or a hydrogenated product thereof (1) 10 to 100. Parts by weight, and a. A conjugated diene polymer, and b. A polymer comprising a conjugated diene and a vinyl aromatic hydrocarbon, the total vinyl aromatic hydrocarbon content in the polymer is 50% by weight or less, and the total vinyl aromatic hydrocarbon content in the polymer. A polymer having a ratio of the vinyl aromatic hydrocarbon polymer block to less than 50% by weight. A modified polymer or modified polymer composition composed of 90 to 0 parts by weight of at least one component (2) selected from the group consisting of a thermoplastic resin and a rubbery polymer is prepared in the presence of a vulcanizing agent. A dynamically crosslinked polymer or a dynamically crosslinked polymer composition obtained by dynamically crosslinking. 2. The polymer constituting the component (1) has a hydroxyl group,
The dynamic cross-linking according to claim 1, which is a modified polymer in which at least one atomic group having at least one functional group selected from an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded, or a hydrogenated product thereof. Polymer or dynamically crosslinked polymer composition. 3. The functional group-containing modifier has 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 polymer by an addition reaction with the living end of the polymer. The dynamic cross-linked polymer or the dynamic cross-linked polymer according to any one of claims 1 and 2, which is a modified polymer having a functional group that forms a modified polymer in which at least one atomic group is bonded or a hydrogenated product thereof. Composition. 4. The component (1) is represented by the following formula (1) to formula (1)
The kinematic crosslinked polymer or kinematic crosslinked polymer according to any one of claims 1 to 3, which is a modified polymer in which at least one atomic group having at least one functional group selected from 4) is bonded or a hydrogenated product thereof. Polymer composition. [Chemical 1] (In the above formula, R ^{1 to} R ⁴ are hydrogen, a hydrocarbon group having 1 to 24 carbon atoms, a hydroxyl group, an epoxy group, a silanol group,
A hydrocarbon group having 1 to 24 carbon atoms having a functional group selected from alkoxysilane groups. R ⁵ is a hydrocarbon chain having 1 to 48 carbon atoms, or 1 carbon atom having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group.
~ 48 hydrocarbon chains. In the hydrocarbon groups of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ , oxygen, in a bonding mode other than a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group,
Elements such as nitrogen and silicon may be bonded. R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms)