JP2003292719A - Elastomer composition containing block copolymer, and molded form therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an elastomer composition having high tensile strength and low rigidity and having high oil resistance and low compression set, and to provide a molded form obtained by molding the composition. <P>SOLUTION: The elastomer composition comprises (a) a block copolymer comprising methacrylic ester-based polymer blocks and acrylic ester-based polymer blocks both of which are, obtained by characteristic copolymerization in the presence of a compound with a specific structure having thiocarbonylthio group(s) and (b) a rubber component. The molded form is obtained by molding the composition. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an elastomer composition containing a block copolymer. More specifically, the present invention relates to an elastomer composition containing an acrylic block copolymer, which has an excellent balance between hardness and strength, and has excellent oil resistance and compression set. The present invention also relates to a molded product obtained by molding the elastomer composition.

[0002]

2. Description of the Related Art Generally, a thermoplastic elastomer is a rubber component (soft segment) that exhibits entropy elasticity.
And at high temperature it flows but at room temperature it prevents plastic deformation,
It has an alloy structure consisting of a restraining component (hard segment) that gives a reinforcing effect to the rubber component. For example, in a styrene-based elastomer, polystyrene blocks aggregate to serve as hard segments, and polybutadiene blocks or polyisoprene blocks serve as soft segments. Further, for example, in the case of an olefin elastomer, an ethylene-propylene-diene copolymer (EPD
It has an alloy structure in which rubber such as M) is dispersed in a resin such as polypropylene (PP). In both cases, the hard segment flows at a high temperature, so that thermoplastic processing such as injection molding is possible.

In the case where a thermoplastic elastomer alone cannot provide sufficient performance, a method of improving the performance by introducing an appropriate rubber component is known. For example,
International Patent Publication No. WO98 / 14518 discloses a block copolymer (thermoplastic elastomer) composed of a polymer block containing a vinyl aromatic compound as a monomer main component and a polymer block containing isobutylene as a monomer main component. And rubber components such as butyl rubber, brominated butyl rubber, EPDM,
A method for producing a thermoplastic resin composition excellent in moldability and compression set by a method of performing a crosslinking reaction while melt-kneading after blending with an appropriate curing agent, that is, a technique is disclosed. . However, when these butyl rubbers and EPDM are blended, there are problems in heat resistance, weather resistance, durability and oil resistance.

As one of thermoplastic elastomers excellent in weather resistance and oil resistance, a methacrylic acid ester polymer block such as polymethylmethacrylate is used as a hard segment, and an acrylate ester polymer block such as polybutyl acrylate is used as a soft segment. An acrylic block copolymer is known. However, it is difficult to industrially produce such an acrylic block copolymer, and there are almost no known methods for producing an acrylic block copolymer in which the structures of hard segments and soft segments are controlled.

As a method for producing an acrylic block copolymer having such a structure controlled, for example, JP-A-10-509475, JP-A-10-81706, JP-A-2946497, JP-A-28666.
35, Japanese Patent No. 2975967, and other atom transfer radical polymerization (AtomTr).
transfer Radial Polymeriza
(ion: ATRP) method is known. However, in the atom transfer radical polymerization method, since the metal catalyst is used, the refining process becomes complicated, and there are problems such as an increase in cost and a decrease in productivity.

A method for producing an acrylic block copolymer having a controlled structure without using a metal catalyst is as follows.
For example, Macromolecules, 1998,
Volume 31, Pages 5559, Macromolecule
s, 1999, 32, 2071, Macro
molecules, 1999, 32, 6977, and Macromolecules, 2000.
, Reversible Addition-Detachment Chain Transfer (Reversible Addit) described in Vol. 33, p. 243, etc.
ion-Fragmentation Chain T
A transfer (RAFT) polymerization method is known. According to these methods, it is possible to produce an acrylic block copolymer having a controlled structure, but in the acrylic block copolymer synthesized by such a method,
A method for improving performance by introducing a rubber component has not been known so far, and its development has been strongly demanded.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an elastomer composition having low hardness and high tensile strength, excellent oil resistance and compression set, and a molded article obtained by molding the elastomer composition. Is to provide.

[0008]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve the above problems, and have invented the following compositions and molded articles thereof. (I) (a) A block copolymer containing a methacrylic acid ester-based polymer block (A) and an acrylic acid ester-based polymer block (B), which is represented by the general formula (1):

[0009]

[Chemical 6] (In the formula, R ¹ is a p-valent organic group having 1 or more carbon atoms, and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, or a metal atom. Z ¹ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms and contains a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, or a phosphorus atom. Or a high molecular weight compound.
If there is more than ^one , they may be identical to each other,
It may be different. p is an integer of 1 or more. ) And a compound represented by the general formula (2)

[0010]

[Chemical 7] (In the formula, R ² is a monovalent organic group having 1 or more carbon atoms and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom or a metal atom, and is a high molecular weight compound. Z ² is an oxygen atom (when q = 2),
A sulfur atom (when q = 2), a nitrogen atom (when q = 3), or a q-valent organic group having 1 or more carbon atoms, which is a nitrogen atom, oxygen atom, sulfur atom, halogen atom, silicon atom, phosphorus It may contain atoms and may be a high molecular weight substance. R ² may be the same as or different from each other. q is an integer of 2 or more. And a block copolymer which is a polymer obtained by radical polymerization in the presence of a compound having at least one thiocarbonylthio group selected from the compounds represented by the formula (b), an acrylic polymer rubber and an olefin system An elastomer composition (claim 1) containing as an essential component a polymer rubber, a diene polymer rubber, and at least one rubber selected from natural rubber. (II) components (a) and (b) are replaced by (a) :( b) = 9
The elastomer composition according to claim 1, which is contained in a weight ratio of 0:10 to 10:90 (claim 2). (III) A compound having a thiocarbonylthio group is represented by the general formula (3)

[0011]

[Chemical 8] (In the formula, R ³ is a divalent organic group, and is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom,
It may contain a metal atom and may be a high molecular weight substance. Z ³ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, and may contain a hydrogen atom, a halogen atom, a silicon atom or a phosphorus atom, or may be a high molecular weight substance. Z ³ may be the same as or different from each other. ), General formula (4)

[0012]

[Chemical 9] (In the formula, R ⁴ is a monovalent organic group having 1 or more carbon atoms and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom or a metal atom, and is a high molecular weight compound. R ⁴ may be the same or different, Z ⁴ is a sulfur atom, an oxygen atom, a tertiary nitrogen atom, or a divalent organic group having 1 or more carbon atoms, and Atom, oxygen atom, sulfur atom, halogen atom, silicon atom, phosphorus atom, and may be a high molecular weight compound), and general formula (5).

[0013]

[Chemical 10] (In the formula, R ⁵ is a monovalent organic group having 1 or more carbon atoms, and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, or a metal atom, and is a high molecular weight compound. R ⁵ may be the same or different from each other), and at least one compound selected from the compounds represented by
Alternatively, the elastomer composition according to any one of (2) to (3). (IV) The rubber component (b) is obtained by graft-polymerizing an unsaturated monomer onto at least one rubber selected from acrylic polymer rubber, olefin polymer rubber, diene polymer rubber, and natural rubber. The elastomer composition according to any one of claims 1 to 3, which is a modified rubber (claim 4). (V) The block copolymer (a) is 5 to 90% by weight of the methacrylic acid ester-based polymer block (A), and 95 to
The elastomer composition according to any one of claims 1 to 4, which comprises 10% by weight of an acrylic acid ester-based polymer block (B). (VI) The block copolymer (a) has a molecular weight distribution measured by gel permeation chromatography of 2 or less, and the elastomer according to any one of claims 1 to 5. A composition (claim 6). (VII) When the block copolymer (a) and the rubber component (b) are mixed, they are melt-mixed so that the rubber component (b) is dynamically crosslinked, any one of claims 1 to 6. The elastomer composition according to claim 1 (claim 7). (VIII) The rubber component (b) is a crosslinked rubber particle having a graft chain, and the elastomer composition according to any one of claims 1 to 7 (claim 8). (IX) A molded article (claim 9) obtained by molding the elastomer composition according to any one of claims 1 to 8.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The block copolymer (a) used in the present invention is a methacrylic acid ester-based polymer block (A) and an acrylic acid ester-based polymer block (B).
It contains and. Examples of the structure of the block copolymer (a) include an AB type diblock copolymer, an ABA type triblock copolymer, a BAB type triblock copolymer, and-(A- B) Linear block copolymers such as _n -type multi-block copolymers; branched block copolymers; star block copolymers and the like, but not limited thereto. These may be used alone or in combination of two or more. Among these, diblock copolymers and triblock copolymers are preferable because the mechanical properties of the composition are good. The molecular weight of the block copolymer (a) is not particularly limited, but the number average molecular weight measured by gel permeation chromatography is preferably in the range of 5,000 to 500,000,
It is more preferably in the range of 30,000 to 400,000. If the number average molecular weight is less than 5,000, the viscosity at the time of melting tends to be low, which tends to be difficult to handle. The molecular weight distribution of the block copolymer (a) is not particularly limited, but is preferably 2 or less, more preferably 1.8 or less, and particularly preferably 1.5 or less. When the molecular weight distribution is 2 or more, the rubber component (b)
There is a case where the compatibility with and becomes low, or the transparency is deteriorated when mixed with the rubber component (b).

The composition ratio of the methacrylic acid ester-based polymer block (A) and the acrylic acid ester-based polymer block (B) in the block copolymer (a) is not particularly limited, but (A) is 5 to 5. 90% by weight, (B) 95-
10% by weight is preferred, 10 to 80% by weight of (A),
90 to 20% by weight of (B) is more preferable, and (A) is 2
0 to 60% by weight and (B) 80 to 40% by weight are particularly preferable. If the composition ratio of (A) is less than 5% by weight, the shape may not be retained during molding, and the composition ratio of (B) is 1
If it is less than 0% by weight, elasticity as an elastomer may be insufficient. By adjusting the composition ratio of (A) and (B), the hardness and processing characteristics of the elastomer composition can be adjusted. As for hardness,
When the composition ratio of (A) is small, the hardness becomes low, and when the composition ratio of (A) is large, the hardness becomes high. Regarding processing characteristics,
Generally, when the composition ratio of (A) is small, the viscosity at the time of melting becomes low, and when the composition ratio of (A) is large, the viscosity at the time of melting becomes high.

The methacrylic acid ester polymer block (A) in the block copolymer (a) is a polymer block obtained by polymerizing a monomer having a methacrylic acid ester as a main component, and usually methacrylic acid. It is obtained by copolymerizing 50 to 100% by weight of an ester monomer and 50 to 0% by weight of an unsaturated monomer copolymerizable with a methacrylic acid ester monomer. Examples of the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate,
Tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate. , Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, isopropyl methacrylate, pentyl methacrylate, hexyl methacrylate, Heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, Phenyl tacrylate, toluyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-aminoethyl methacrylate, 2-methacryloyloxypropyl trimethoxysilane, 2-methacryloyloxypropyl dimethoxymethylsilane. , Trifluoromethyl methacrylate, pentafluoroethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and the like, but are not limited thereto. These may be used alone or in combination of two or more. Of these, availability, moldability, processability,
Methyl methacrylate is preferable because it has good heat resistance. When the glass transition temperature is set high, isobornyl methacrylate, cyclohexyl methacrylate and the like are preferable. Furthermore, when compounded with a highly polar rubber, in terms of compatibility, hydroxyl groups, epoxy groups, such as 2-hydroxyethyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, etc.
Monomers having polar groups such as amino groups and carboxyl groups are preferred.

Examples of unsaturated monomers copolymerizable with these methacrylic acid ester monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate,
Toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, 2- Acryloyloxypropyldimethoxymethylsilane, 2-acryloyloxypropyltrimethoxysilane, trifluoromethyl acrylate, pentafluoroethyl acrylate,
2,2,2-trifluoroethyl acrylate, 3-dimethylaminoethyl acrylate, isobutyl acrylate,
4-hydroxybutyl acrylate, t-butyl acrylate, alkyl modified dipentaerythritol acrylate, ethylene oxide modified bisphenol A diacrylate, carbitol acrylate, ε-caprolactone modified dipentaerythritol acrylate, caprolactone modified tetrahydrofurfuryl acrylate , Caprolactone modified hydroxypivalic acid neopentyl glycol ester diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, tetraethylene glycol acrylate, tetrahydrofurfuryl acrylate, tripropylene glycol acrylate, triacrylate Methylol propane ethoxy triacrylate, tri Tyrole propane triacrylate, neopentyl glycol diacrylate, neopentyl glycol hydroxypivalic acid ester diacrylate, 1,9-nonane acrylate acrylic acid, 1,4-butane diol acrylic acid, 2-propenoic acid [2- [1 , 1-dimethyl-2-[(1-oxo-2
-Propenyl) oxy] ethyl] -5-ethyl-1,3
-Dioxan-5-yl] methyl ester, acrylic acid 1,6-hexanediol, pentaerythritol triacrylate, 2-acryloyloxypropyl hydrogen phthalate, methyl 3-methoxyacrylate,
Acrylic esters such as allyl acrylate; aromatic alkenyl compounds such as styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, divinylbenzene and vinylnaphthalene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; Conjugated diene compounds such as butadiene and isoprene; halogen-containing unsaturated compounds such as vinyl chloride, vinylidene chloride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chloroprene; silicon containing such as vinyltrimethoxysilane and vinyltriethoxysilane Unsaturated compounds; unsaturated dicarboxylic acid compounds such as maleic anhydride, maleic acid, maleic acid monoester, maleic acid diester, fumaric acid, fumaric acid monoester, fumaric acid diester; Vinyl, vinyl propionate,
Vinyl ester compounds such as vinyl pivalate, vinyl benzoate and vinyl cinnamate; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide, etc. Examples of the maleimide compound include, but are not limited to, acrylic acid and methacrylic acid. These may be used alone or in combination of two or more. These unsaturated monomers have a glass transition temperature required for the polymer block (A), oil resistance, compatibility with the polymer block (B), and a rubber component (b) blended in the elastomer composition. From the viewpoint of compatibility with the above), preferred ones may be selected, but in view of heat resistance, oil resistance, price and availability, acrylonitrile, acrylic acid, methacrylic acid, n-butyl acrylate, t-acrylic acid t -Butyl and isobutyl acrylate are preferred.

The glass transition temperature of the methacrylic acid ester-based polymer block (A) in the block copolymer (a) is preferably 20 ° C. or higher, and 40 ° C. in view of heat resistance and shape retention of the elastomer composition. The above is more preferable, and 50 ° C. or more is particularly preferable. When the glass transition temperature of (A) is less than 20 ° C., the cohesive force may decrease depending on the environment in which the glass transition temperature is used, and thermal deformation may easily occur.

The acrylic acid ester-based polymer block (B) in the block copolymer (a) is a polymer block obtained by polymerizing a monomer containing an acrylic acid ester as a main component, and is usually acrylic acid. Ester monomer 50-
It is obtained by copolymerizing 100% by weight and 50 to 0% by weight of an unsaturated monomer copolymerizable with the acrylic acid ester monomer. Examples of acrylic acid ester monomers include, but are not limited to, the compounds exemplified above. These may be used alone or in combination of two or more. In terms of impact resistance, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-acrylate
Ethylhexyl, octyl acrylate, nonyl acrylate, decyl acrylate, alkyl acrylates such as dodecyl acrylate, and glycidyl acrylate are preferred, and methyl acrylate, ethyl acrylate, and acrylic in that a suitable polymerization reaction rate can be obtained. Acid n-propyl, isopropyl acrylate, n-butyl acrylate,
More preferred are alkyl acrylates having an alkyl group having 8 or less carbon atoms, such as isobutyl acrylate, t-butyl acrylate, and 2-ethylhexyl acrylate. Ethyl acrylate and n-acrylate are more preferable in terms of availability and price. Butyl and t-butyl acrylate are particularly preferred. For applications requiring oil resistance, acrylic acid 2
-Methoxyethyl, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate are preferred.

As the unsaturated monomer copolymerizable with the acrylic acid ester monomer, the methacrylic acid ester exemplified above: styrene, α-methylstyrene, p-
Aromatic alkenyl compounds such as methylstyrene, p-methoxystyrene, divinylbenzene and vinylnaphthalene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; conjugated diene compounds such as butadiene and isoprene; vinyl chloride, vinylidene chloride, tetrafluoro Halogen-containing unsaturated compounds such as ethylene, hexafluoropropylene, vinylidene fluoride, and chloroprene; Silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, maleic acid monoester, maleic acid Unsaturated dicarboxylic acid compounds such as diesters, fumaric acid, fumaric acid monoesters, fumaric acid diesters; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamic acid vinyl Vinyl ester compound such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, maleimide compound such as cyclohexylmaleimide; acrylic acid, methacrylic acid, etc. However, the present invention is not limited to these. These may be used alone or in combination of two or more. These unsaturated monomers have a glass transition temperature required for the polymer block (B), oil resistance, compatibility with the polymer block (A), and a rubber component (b) blended in the elastomer composition. From the viewpoint of compatibility with the above), a preferable one may be selected.

The glass transition temperature of the methacrylic polymer block (B) in the block copolymer (a) is preferably 30 ° C. or lower, more preferably 0 ° C. or lower, in view of rubber elasticity of the elastomer composition, and −20. C. or less is particularly preferable. If the glass transition temperature of (B) exceeds 30 ° C, rubber elasticity may not be exhibited depending on the environment in which it is used.

When the block copolymer (a) in the present invention is synthesized, the general formula (1) is used.

[0023]

[Chemical 11] (In the formula, R ¹ is a p-valent organic group having 1 or more carbon atoms, and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, or a metal atom. Z ¹ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms and contains a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, or a phosphorus atom. Or a high molecular weight compound.
If there is more than ^one , they may be identical to each other,
It may be different. p is an integer of 1 or more. ) And a compound represented by the general formula (2)

[0024]

[Chemical 12] (In the formula, R ² is a monovalent organic group having 1 or more carbon atoms and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom or a metal atom, and is a high molecular weight compound. Z ² is an oxygen atom (when q = 2),
A sulfur atom (when q = 2), a nitrogen atom (when q = 3), or a q-valent organic group having 1 or more carbon atoms, which is a nitrogen atom, oxygen atom, sulfur atom, halogen atom, silicon atom, phosphorus It may contain atoms and may be a high molecular weight substance. R ² may be the same as or different from each other. q is an integer of 2 or more. ) A compound having at least one thiocarbonylthio group selected from the compounds represented by

In the structure of the compound having a thiocarbonylthio group used in the present invention, R ¹ is not particularly limited, but in view of availability, it is a benzyl group, 1
-Phenylethyl group, 2-phenyl-2-propyl group,
1-acetoxyethyl group, 1- (4-methoxyphenyl) ethyl group, ethoxycarbonylmethyl group, 2-ethoxycarbonyl-2-propyl group, 2-cyano-2-propyl group, t-butyl group, 1,1, 3,3-tetramethylbutyl group, 2- (4-chlorophenyl) -2-propyl group, vinylbenzyl group, t-butylsulfide group, 2
-Carboxylethyl group, carboxylmethyl group, cyanomethyl group, 1-cyanoethyl group, 2-cyano-2-butyl group, and general formula (6)

[0026]

[Chemical 13] (In the formula, n represents an integer of 1 or more and r represents an integer of 0 or more.) The organic substituent represented by the formula is preferable.

In the structure of the compound having a thiocarbonylthio group used in the present invention, R ² is not particularly limited, but in view of availability, it is a benzyl group, 1
-Phenylethyl group, 2-phenyl-2-propyl group,
1-acetoxyethyl group, 1- (4-methoxyphenyl) ethyl group, ethoxycarbonylmethyl group, 2-ethoxycarbonyl-2-propyl group, 2-cyano-2-propyl group, t-butyl group, 1,1, 3,3-tetramethylbutyl group, 2- (4-chlorophenyl) -2-propyl group, vinylbenzyl group, t-butylsulfide group, 2
-Carboxylethyl group, carboxylmethyl group, cyanomethyl group, 1-cyanoethyl group, 2-cyano-2-butyl group, and general formula (7)

[0028]

[Chemical 14] (In the formula, n represents an integer of 1 or more and r represents an integer of 0 or more.) The organic substituent represented by the formula is preferable.

In the structure of the compound having a thiocarbonylthio group used in the present invention, Z ¹ is not particularly limited, but in view of availability, it is a phenyl group, a methyl group, an ethyl group, a benzyl group, 4- Chlorophenyl group, 1-naphthyl group, 2-naphthyl group, diethoxyphosphinyl group, n-butyl group, t-butyl group, methoxy group, ethoxy group, thiomethyl group (methyl sulfide),
Phenoxy group, thiophenyl group (phenyl sulfide), N, N-dimethylamino group, N, N-diethylamino group, N-phenyl-N-methylamino group, N-phenyl-N-ethylamino group, thiobenzyl group (benzyl sulfide) ), A pentafluorophenoxy group, and a general formula (8)

[0030]

[Chemical 15] Organic substituents represented by are preferred.

In the structure of the compound having a thiocarbonylthio group used in the present invention, Z ² is not particularly limited, but in view of availability, it is represented by the general formula (9)

[0032]

[Chemical 16] (In the formula, n is an integer of 1 or more and r is an integer of 0 or more.) The organic substituent is preferable.

In producing the block copolymer (a) of the present invention, the methacrylic acid ester type polymer block (A) and the acrylic acid ester type polymer block (B) may be polymerized by the same method, It may be different.
For example, the polymer block (A) may be first polymerized in the presence of a compound having a thiocarbonylthio group, and then the polymer block (B) may be continuously polymerized. The polymer block (B) may be polymerized after the purification by purification or after some physical or chemical treatment. Further, in the case of forming a triblock copolymer or a multiblock copolymer, the polymerization may be carried out continuously, or after isolation and purification, or after some physical or chemical treatment, the polymerization may be carried out. Further, the polymer blocks (A) and (B) may be exchanged in the order of polymerization and the polymer block (B) may be polymerized first. Further, the polymer block (A) and the polymer block (B) may be separately polymerized, and the two may be chemically bonded to each other to obtain the block copolymer (a). In this case, a compound having a thiocarbonylthio group may be present during the polymerization of both polymer blocks (A) and (B),
The compound having a thiocarbonylthio group may be allowed to be present only during the polymerization of either (A) or (B).

The block copolymer of the present invention was used as ABA.
Type or BAB type triblock copolymer, the general formula (3)

[0035]

[Chemical 17] (In the formula, R ³ is a divalent organic group, and is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom,
It may contain a metal atom and may be a high molecular weight substance. Z ³ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, and may contain a hydrogen atom, a halogen atom, a silicon atom or a phosphorus atom, or may be a high molecular weight substance. Z ³ may be the same as or different from each other. ), General formula (4)

[0036]

[Chemical 18] (In the formula, R ⁴ is a monovalent organic group having 1 or more carbon atoms and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom or a metal atom, and is a high molecular weight compound. R ⁴ may be the same or different, Z ⁴ is a sulfur atom, an oxygen atom, a tertiary nitrogen atom, or a divalent organic group having 1 or more carbon atoms, and Atom, oxygen atom, sulfur atom, halogen atom, silicon atom, phosphorus atom, and may be a high molecular weight compound), and general formula (5).

[0037]

[Chemical 19] (In the formula, R ⁵ is a monovalent organic group having 1 or more carbon atoms, and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, or a metal atom. R ⁵ may be the same as or different from each other.) In the presence of a compound having at least one thiocarbonylthio group selected from the compounds represented by Polymerization is preferred. By using such a compound having a bifunctional thiocarbonylthio group, it is not necessary to couple polymer blocks with each other even when a triblock copolymer is produced, and productivity can be improved.

In the structure of the compound having a thiocarbonylthio group used in the present invention, R ³ is not particularly limited, but in view of availability, it is represented by the general formula (10)

[0039]

[Chemical 20] The structure represented by is preferred.

In the structure of the compound having a thiocarbonylthio group used in the present invention, Z ³ is not particularly limited, but in view of availability, it is a phenyl group, a methyl group, an ethyl group, a benzyl group, 4- Chlorophenyl group, 1-naphthyl group, 2-naphthyl group, diethoxyphosphinyl group, n-butyl group, t-butyl group, methoxy group, ethoxy group, thiomethyl group (methyl sulfide),
Phenoxy group, thiophenyl group (phenyl sulfide), N, N-dimethylamino group, N, N-diethylamino group, N-phenyl-N-methylamino group, N-phenyl-N-ethylamino group, thiobenzyl group (benzyl sulfide) ), A pentafluorophenoxy group, and a general formula (8)

[0041]

[Chemical 21] Organic substituents represented by are preferred.

In the structure of the compound having a thiocarbonylthio group used in the present invention, R ⁴ is not particularly limited, but in view of availability, it is a benzyl group, 1
-Phenylethyl group, 2-phenyl-2-propyl group,
1-acetoxyethyl group, 1- (4-methoxyphenyl) ethyl group, ethoxycarbonylmethyl group, 2-ethoxycarbonyl-2-propyl group, 2-cyano-2-propyl group, t-butyl group, 1,1, 3,3-tetramethylbutyl group, 2- (4-chlorophenyl) -2-propyl group, vinylbenzyl group, t-butylsulfide group, 2
-Carboxylethyl group, carboxylmethyl group, cyanomethyl group, 1-cyanoethyl group, 2-cyano-2-butyl group, and general formula (7)

[0043]

[Chemical formula 22] (In the formula, n represents an integer of 1 or more and r represents an integer of 0 or more.) The organic substituent represented by the formula is preferable.

In the structure of the compound having a thiocarbonylthio group used in the present invention, Z ⁴ is not particularly limited, but in view of availability and reactivity,
General formula (11)

[0045]

[Chemical formula 23] (In the formula, n represents an integer of 1 or more, and r represents an integer of 0 or more.) Is preferable.

In the structure of the compound having a thiocarbonylthio group used in the present invention, R ⁵ is not particularly limited, but in view of availability, it is a benzyl group, 1
-Phenylethyl group, 2-phenyl-2-propyl group,
1-acetoxyethyl group, 1- (4-methoxyphenyl) ethyl group, ethoxycarbonylmethyl group, 2-ethoxycarbonyl-2-propyl group, 2-cyano-2-propyl group, t-butyl group, 1,1, 3,3-tetramethylbutyl group, 2- (4-chlorophenyl) -2-propyl group, vinylbenzyl group, t-butylsulfide group, 2
-Carboxylethyl group, carboxylmethyl group, cyanomethyl group, 1-cyanoethyl group, 2-cyano-2-butyl group, and general formula (7)

[0047]

[Chemical formula 24] (In the formula, n represents an integer of 1 or more and r represents an integer of 0 or more.) The organic substituent represented by the formula is preferable.

Specific examples of the above-mentioned compound having a thiocarbonylthio group used in the present invention are represented by the general formula (12)

[0049]

[Chemical 25]

[0050]

[Chemical formula 26]

[0051]

[Chemical 27]

[0052]

[Chemical 28] (In the formula, Me is a methyl group, Et is an ethyl group, Ph is a phenyl group, n is an integer of 1 or more, and r is an integer of 0 or more.) It is not limited to.

In the present invention, the block copolymer (a)
In the synthesis of, in the presence of a compound having a thiocarbonylthio group, the form of radical polymerization of the polymerizable monomer is not particularly limited, and bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and fine polymerization A conventionally known method such as suspension polymerization can be applied.

In the present invention, when the polymerizable monomer is solution-polymerized, the solvent used is, for example, heptane,
Hydrocarbon solvents such as octane and mineral spirits;
Ester-based solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone; methanol, ethanol, isopropanol, n -Alcoholic solvents such as butanol, sec-butanol, isobutanol; ether solvents such as n-butyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether; toluene, xylene, Swazol 310 (manufactured by Cosmo Oil Co., Ltd.), Swazol 1000 (Cosmo Oil Co., Ltd.)
Examples thereof include aromatic petroleum solvents such as Swasol 1500 (manufactured by Cosmo Oil Co., Ltd.), but are not limited thereto. These may be used alone or in combination of two or more. When determining the solvent type and amount of solvent to be used, the solubility of the monomer to be used, the solubility of the polymer to be obtained, an appropriate polymerization initiator concentration or monomer concentration to achieve a sufficient reaction rate, thiocarbonyl It may be determined in consideration of solubility of the compound having a thio group, influence on human body and environment, availability, price, etc., and is not particularly limited.

In the present invention, when the polymerizable monomer is emulsion-polymerized or finely suspended-polymerized, the emulsifier used is not particularly limited, and fatty acid soap, rosin acid soap, sodium naphthalenesulfonate formalin condensate, alkylbenzene are used. Sodium sulfonate, sodium alkylsulfate such as sodium dodecylsulfate, ammonium alkylsulfate, triethanolamine alkylsulfate, sodium dialkylsulfosuccinate, sodium alkyldiphenyl ether disulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate Anionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene higher alcohol ether, sorbitan fatty acid Nonionic surfactants such as tellurium, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkylalkanolamide; alkyl trimethyl ammonium chloride, etc. Examples thereof include cationic surfactants. These emulsifiers may be used alone or in combination of two or more. If necessary, a dispersant for suspension polymerization described below may be added. The amount of the emulsifier used is not particularly limited, but is usually 0.1 to 20 parts by weight with respect to 100 parts by weight of the monomer.

In the present invention, when the polymerizable monomer is subjected to suspension polymerization, the dispersant used is not particularly limited,
For example, partially saponified polyvinyl acetate, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose,
Conventionally known materials such as gelatin, polyalkylene oxide, a combination of an anionic surfactant and a dispersion aid can be used. These may be used alone or in combination of two or more. If necessary, the emulsifying agent for emulsion polymerization may be used in combination. The amount of the dispersant used is not particularly limited, but is usually 0.1 to 20 parts by weight with respect to 100 parts by weight of the monomer.

In the present invention, the radical polymerization of the polymerizable monomer in the presence of the compound having a thiocarbonylthio group is not particularly limited as to the polymerization initiator to be used or the polymerization initiation method, and it is known in the art. A polymerization initiator or a polymerization initiation method can be used. For example, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis ( (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,3 -Bis (tert-butylperoxy) -m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, te
rt-butylcumyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, bis (tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, 2, Peroxide-based polymerization initiators such as 5-dimethyl-2,5-di (benzoylperoxy) hexane;
2'-azobis (isobutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), azocumene, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisdimethyl Valeronitrile,
4,4'-azobis (4-cyanovaleric acid), 2- (te
rt-Butylazo) -2-cyanopropane, 2,2′-
Azobis (2,4,4-trimethylpentane), 2,
2'-azobis (2-methylpropane), dimethyl 2,
Azo-based polymerization initiators such as 2'-azobis (2-methylpropionate); inorganic peroxides such as potassium persulfate and sodium persulfate; monomers that thermally generate radical species such as styrene; benzoin Derivatives, benzophenones, acylphosphine oxides, photoredox compounds and other compounds that generate radical species by light; sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate, etc. as reducing agents Examples thereof include, but are not limited to, redox type polymerization initiators using potassium peroxodisulfate, hydrogen peroxide, t-butyl hydroperoxide and the like as oxidizing agents.
These polymerization initiators may be used alone or in combination of two or more. Also, electron beam irradiation, X-ray irradiation,
It is also possible to utilize a polymerization initiation system by irradiation with radiation. Regarding such a polymerization initiation method, Moad
and Solomon "The Chemistr
y of FreeRadical Polymeri
zation ”, Pergamon, London, 1
The methods described on pages 995, 53-95 can be used. The amount of the polymerization initiator used in the practice of the present invention is not particularly limited, but the amount of radical species generated during the polymerization is a compound having a thiocarbonylthio structure in that a polymer having a small molecular weight distribution can be obtained. 1 equivalent or less is preferable, and 0.5 equivalent or less is more preferable. In addition, in order to control the amount of radical species generated during the polymerization, in combination with the amount of the polymerization initiator used, in the case of a polymerization initiator that thermally dissociates, the temperature is adjusted, or by light or electron beams. In the case of a polymerization initiation system that generates radicals, it is preferable to adjust the amount of energy for irradiation.

As the block copolymer (a) used in the present invention, for the purpose of improving the compatibility with the rubber component (b), a thiocarbonylthio group is treated with a treating agent to be converted into a mercapto group. It is preferable. By converting into a mercapto group, compatibility with the rubber component (b) becomes good, and compression set and strength are improved especially when dynamically crosslinked. The treatment agent for converting a thiocarbonylthio group into a mercapto group is not particularly limited,
Mention may be made of acidic compounds, basic compounds, and hydrogen-nitrogen bond containing compounds.

Of the above-mentioned treating agents, the acidic compound is not particularly limited, and examples thereof include the following compounds: hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrobromic acid,
Borofluoric acid, chlorosulfonic acid, hydroiodic acid,
Inorganic acids such as arsenic acid and hydrosilicofluoric acid; p-toluenesulfonic acid, trifluoromethylsulfonic acid, acetic acid, trifluoroacetic acid, methylphosphoric acid, ethylphosphoric acid, n-propylphosphoric acid, isopropylphosphoric acid, n-butylphosphoric acid ,
Lauryl phosphoric acid, stearyl phosphoric acid, 2-ethylhexyl phosphoric acid, isodecyl phosphoric acid, dimethyldithiophosphoric acid,
Diethyldithiophosphoric acid, diisopropyldithiophosphoric acid,
Organic acids such as phenylphosphonic acid; strong acid ion exchange resins, weak acid ion exchange resins, etc. Furthermore, a compound which reacts with a small amount of water and exhibits acidity can also be used. Examples of such a compound include acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride, phthalic anhydride, and succinic anhydride; acyl halides such as acetic acid chloride and benzoic acid chloride; titanium tetrachloride, aluminum chloride. ,
Metal halides such as silicon chloride and thionyl chloride. These may be used alone or in combination of two or more.

Of the above treating agents, the basic compound is not particularly limited, and examples thereof include the following compounds:
Alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide, barium hydroxide and cesium hydroxide; aluminum hydroxide and hydroxide Transition metal hydroxides such as zinc; sodium methylate, sodium ethylate, sodium phenylate,
Alkali metal alcoholates such as lithium ethylate and lithium butyrate; Alkaline earth metal alcoholates such as magnesium methylate and magnesium ethylate; sodium hydride, lithium hydride, calcium hydride, lithium aluminum hydride, sodium borohydride, etc. Metal hydrides; salts of strong bases and weak acids such as sodium carbonate, potassium carbonate, sodium acetate, potassium acetate; hydrosulfite, n-butyllithium,
t-butyl lithium, ethyl magnesium bromide,
Organometallic reagents such as phenylmagnesium bromide;
Tertiary amine compounds such as triethylamine and tri-n-butylamine. Further, alkali metals such as metallic lithium, metallic sodium and metallic potassium; alkaline earth metals such as metallic magnesium and metallic calcium can also be used. These may be used alone or in combination of two or more. When a basic compound is used as a treating agent, it is possible to convert a thiocarbonylthio group into a mercaptide group under non-aqueous conditions.

Of the above treating agents, the hydrogen-nitrogen bond-containing compound is not particularly limited. For example, ammonia,
Examples thereof include hydrazine, primary amine compounds, secondary amine compounds, amide compounds, amine hydrochloride compounds, hydrogen-nitrogen bond-containing polymers, and hindered amine light stabilizers (HALS).

Of the above hydrogen-nitrogen bond-containing compounds, 1
Specific examples of the primary amine compound include N- (2-aminoethyl) ethanolamine, 12-aminododecanoic acid,
3-amino-1-propanol, allylamine, isopropylamine, 3,3′-iminobis (propylamine), monoethylamine, 2-ethylhexylamine,
3- (2-ethylhexyloxy) propylamine, 3
-Ethoxypropylamine, 3- (diethylamino) propylamine, 3- (dibutylamino) propylamine, n-butylamine, t-butylamine, sec-butylamine, n-propylamine, 3- (methylamino) propylamine, 3- (Dimethylamino) propylamine, N-methyl-3,3'-iminobis (propylamine), 3-methoxypropylamine, 2-aminoethanol, ethylenediamine, diethylenetriamine,
Triethylenetetramine, tetraethylenepentamine,
Pentaethylenehexamine, N-carboxy-4,4 '
-Methylenebiscyclohexylamine, 1,4-diaminobutane, 1,2-diaminopropane, 1,3-diaminopropane, diaminomaleonitrile, cyclohexylamine, ATU (manufactured by Ajinomoto Co., Inc.), CTU guanamine (manufactured by Ajinomoto Co., Inc.) , Thiourea dioxide, 2-hydroxyethylaminopropylamine, hexamethylenediamine, n-hexylamine, monomethylamine, monomethylhydrazine, 3- (lauryloxy) propylamine, anisidine, aniline, p-aminoacetanilide, p-aminobenzoic acid. Acid, p-aminobenzoic acid ethyl ester, 2-amino-4-chlorophenol, 2-aminothiazole, 2-aminothiophenol, 2-amino-5-nitrobenzonitrile, aminophenol, p-
Aminobenzaldehyde, 4-aminobenzonitrile,
Anthranilic acid, 3-isopropoxyaniline, 4-amino-5-hydroxy-2,7-naphthalenesulfonic acid monosodium salt, 6-amino-4-hydroxy-2-
Naphthalenesulfonic acid, xylidine, m-xylylenediamine, p-cresidine, dianisidine, 4,4'-diaminostilbene-2,2'-disulfonic acid, 2-amino-5-naphthol-7-sulfonic acid, 1,4 -Diaminoanthraquinone, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, stefanilic acid, Tobiasic acid, 2,4,5-trichloroaniline, o-tolidine, toluidine, toluylenediamine,
Sodium naphthionate, nitroaniline, m-nitro-p-toluidine, o-chloro-p-toluidine-m-
Sulfonic acid, phenylhydrazine, phenylenediamine, phenetidine, phenethylamine, benzylamine, benzophenonehydrazone, mesidine, methanilic acid, 2-methyl-4-nitroaniline, leuco-1,4
-Diaminoanthraquinone, paramine, aminopyridine, 1- (2-aminoethyl) piperazine, N- (3-
Aminopropyl) morpholine, 1-amino-4-methylpiperazine, bis (aminopropyl) piperazine, benzoguanamine, melamine, o-chloroaniline, 2,5
-Dichloroaniline, 3,4-dichloroaniline, 3,
5-dichloroaniline, 2-amino-4-chlorobenzoic acid, o-chloro-p-nitroaniline, 5-chloro-2
-Nitroaniline, 2,6-dichloro-4-nitroaniline, 2- (2-chlorophenyl) ethylamine, 3,
3'-dichloro-4,4'diaminodiphenylmethane,
3,3'-dichloro-4,4'-diaminobiphenyl,
2,4-difluoroaniline, o-fluoroaniline,
Examples thereof include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, and γ-aminopropyltriethoxysilane. It is not limited to these.

Of the above hydrogen-nitrogen bond-containing compounds, 2
Specific examples of the primary amine compound include N-methylethanolamine, diallylamine, diisopropylamine,
Diethylamine, diisobutylamine, di-2-ethylhexylamine, iminodiacetic acid, 3,3′-iminodipropionitrile, bis (hydroxyethyl) amine, N
-Ethylethylenediamine, ethyleneimine, dicyclohexylamine, 1,1-dimethylhydrazine, di-n
-Butylamine, di-t-butylamine, dimethylamine, sodium N-methylacetate, N-ethylaniline,
Diphenylamine, dibenzylamine, 7-anilino-
4-hydroxy-2-naphthalenesulfonic acid, N-methylaniline, 2-methyl-4-methoxydiphenylamine, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole , 1,3-di (4-piperidyl) propane, 2,5-dimethylpiperazine,
2,6-dimethylpiperazine, 3,5-dimethylpyrazole, 5,5'-bi-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-methyl-1H-tetrazole, 1,2,3,4-tetrahydro Examples include, but are not limited to, quinoline, (hydroxyethyl) piperazine, pipecoline, 2- (1-piperazinyl) pyrimidine, piperazine, piperidine, pyrrolidine, N-methylpiperazine, 2-methylpiperazine, morpholine, and the like.

Of the above hydrogen-nitrogen containing compounds, specific examples of the amide compounds include 2-acrylamido-2-
Methyl propane sulfonic acid, adipic acid dihydrazide,
N-isopropylacrylamide, Nt-octylacrylamide, carbohydrazide, guanylthiourea,
Glycylglycine, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino)
Propyl] methacrylamide, N, N'-ethylenebis (stearoamide), oleic acid amide, stearic acid amide, N, N'-methylenebis (stearoamide),
N- (hydroxymethyl) stearamide, diacetone acrylamide, thioacetamide, thiocarbohydrazide, thiosemicarbazide, thiourea, dodecanedioic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, 1,6-hexamethylenebis ( N, N-dimethylsemicarbazide),
Formamide, methacrylamide, N, N'-methylenebis (acrylamide), N-methylolacrylamide, acetanilide, acetoacetic acid o-anisidide, acetoacetic acid anilide, acetoacetic acid m-xylidide, acetoacetic acid o-chloroanilide, acetoacetic acid 2,5. -Dimethoxy-4-chloroanilide, acetoacetic acid toluidide,
1,1,1 ′, 1′-tetramethyl-4,4 ′-(methylenedi-p-phenylene) disemicarbazide, toluenesulfonamide, p-hydroxyphenylacetamide, phthalimide, isocyanuric acid, 3-carbamoyl-2-pyrazine Carboxylic acid, succinimide, 5,5-
Dimethylhydantoin, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, hydantoin, phenylpyrazolidone, 3-methyl-5-pyrazolone, 1-methylol-5,5-dimethylhydantoin, 3- (4 -Chlorophenyl) -1,1-dimethylurea, bromvalerylurea, 2,6-difluorobenzamide, 2,2,2-trifluoroacetamide and the like can be mentioned, but not limited thereto.

Of the above hydrogen-nitrogen containing compounds, specific examples of the amine hydrochloride compounds include acetamidine hydrochloride, 2,2'-azobis- (2-amidinopropane) dihydrochloride, monomethylamine hydrochloride, Dimethylamine hydrochloride, monoethylamine hydrochloride, diethylamine hydrochloride,
Monopropylamine hydrochloride, dipropylamine hydrochloride,
Examples thereof include monobutylamine hydrochloride, dibutylamine hydrochloride, semicarbazide hydrochloride, guanidine hydrochloride, aminoguanidine hydrochloride, 2-chloroethylamine hydrochloride, disteamine hydrochloride, and t-butylhydrazine monohydrochloride, but are not limited thereto. Not done.

Of the above hydrogen-nitrogen containing compounds, hydrogen-
Specific examples of the nitrogen bond-containing polymer include polyment (manufactured by Nippon Shokubai Co., Ltd.), polyethyleneimine, aminopolyacrylamide, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 1
2, nylon MXD6, nylon 46, polyamideimide, polyallylamine, polyurethane, and the like, but are not limited thereto.

Of the above hydrogen-nitrogen containing compounds, HAL
As S, ADEKA STAB LA-77 (Asahi Denka Co., Ltd.)
), Chimassorb 944LD (manufactured by Ciba Specialty Chemicals), Tinuvin 14
4 (manufactured by Ciba Specialty Chemicals), ADEKA STAB LA-57 (manufactured by Asahi Denka Co., Ltd.), ADEKA STAB L
A-67 (manufactured by Asahi Denka Co., Ltd.), ADEKA STAB LA-68
(Manufactured by Asahi Denka Co., Ltd.), ADEKA STAB LA-87 (manufactured by Asahi Denka Co., Ltd.), and Goodrite UV-3034.
(Manufactured by Goodrich) and the like, but not limited thereto.

The above hydrogen-nitrogen bond-containing compounds may be used alone or in combination.
When the polymer having a thiocarbonylthio group is treated with the above hydrogen-nitrogen bond-containing compound, the amount used is not particularly limited. From the viewpoint of high introduction rate of mercapto group, it is preferable to use the hydrogen-nitrogen bond-containing compound in a ratio of 0.5 to 1000 mol, and 1 to 500 mol of 1 mol of thiocarbonylthio group in the polymer. It is more preferable to use it in a ratio. The excess hydrogen-nitrogen bond containing compound can be recovered and reused. Of the above hydrogen-nitrogen bond-containing compounds, hydrogen-nitrogen bond-containing compounds having a boiling point of 100 ° C. or less, and hydrogen-nitrogen bond-containing compounds having a molecular weight of 500 or more are easily removed when they are used in excess or are unnecessary. , And HALS are preferred. When a hydrogen-nitrogen bond-containing compound having a boiling point of 100 ° C. or less is used, it can be easily distilled off from the emulsion and the molecular weight is 50% or less.
When 0 or more hydrogen-nitrogen bond-containing compounds and HALS are used, it is not necessary to remove them. Especially when HALS is used, the weather resistance and light resistance of the obtained elastomer are improved.

The block copolymer of the present invention is prepared from the above hydrogen
When treating with a nitrogen bond-containing compound, the treatment method is not particularly limited, but a method of adding to the solution or emulsion after polymerization is preferable from the viewpoint of simple steps.

The block copolymer of the present invention treated by the above method can be used by coupling mercapto groups with each other, if necessary. Coupling between mercapto groups is usually performed by forming a disulfide bond in the presence of an oxidizing agent. Examples of such an oxidizing agent include, but are not limited to, the following compounds: lead dioxide, manganese dioxide, calcium peroxide, zinc peroxide, barium peroxide, sodium peroxide, potassium peroxide, peroxide. Inorganic peroxides such as strontium and sodium peroxide; metals such as zinc oxide, lead oxide, manganese oxide, calcium oxide, barium oxide, ferrous oxide, ferric oxide, cobalt oxide, copper oxide and vanadium pentoxide Oxides; inorganic oxidizers such as potassium dichromate, sodium perchlorate, potassium permanganate; benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyl perbenzoate, Organic peroxides such as sodium peracetate and urea peroxide; nitro Hexacyanoferrate (III) potassium; benzene, dinitrobenzene, organic oxidizing agents such as squeaky Contact Parakinonji
Organic acid iron (III), tris (acetylacetonate)
Organometallic compounds such as manganese; hydrogen peroxide; oxygen (air), etc. These may be used alone or in combination of two or more. Of these, lead dioxide, zinc peroxide, calcium peroxide, barium peroxide, manganese dioxide, dichromate, hydrogen peroxide, and oxygen (air) are preferable in terms of easy handling and availability. Lead dioxide, zinc peroxide, calcium peroxide, barium peroxide, manganese dioxide, dichromate, and oxygen (air) are more preferable, and lead dioxide, calcium peroxide, and oxygen (air) are even more preferable.

When an oxidizing agent is used, the addition amount of the oxidizing agent is not particularly limited, but in the point that the coupling reaction between the mercapto groups rapidly progresses, it is 0.01 per 100 parts by weight of the block copolymer. ˜40 parts by weight is preferred, and
1 to 20 parts by weight is more preferable. When oxygen (air) is used as the oxidizing agent, there is no particular limitation on the amount added.

When it is necessary to promote the coupling reaction between mercapto groups, a tertiary amine can be added as a promoter. The tertiary amine is not particularly limited, but for example, triethylamine,
Trialkylamines such as tripropylamine and tributylamine; N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane-1,3-diamine, tetramethylguanidine, N,
N′-dimethylpiperazine, dimethylaminoethanol, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2.2] octane, bis (2-dimethylaminoethyl) ether And so on. These may be used alone,
You may use in combination of multiple. When a tertiary amine is used as the accelerator, the addition amount thereof is not particularly limited, but 0.01 to 30 parts by weight relative to 100 parts by weight of the block copolymer in terms of excellent balance between the promoting effect and the addition amount. Parts is preferred, and 0.1 to 15 parts by weight is more preferred.

When the coupling reaction between mercapto groups is carried out using oxygen (air), a metal salt can be used as a promoter. Such metal salt is not particularly limited, but for example, copper, iron, cobalt,
Examples thereof include chlorides such as nickel and palladium, iodides, sulfates and nitrates. These metal salts may be used alone or in combination of two or more. The addition amount of the metal salt is not particularly limited, but 0.01 to 30 parts by weight is preferable with respect to 100 parts by weight of the block copolymer, from the viewpoint of excellent balance between the accelerating effect and the addition amount. 1 to 20 parts by weight is more preferable.
Also in this case, the above-mentioned tertiary amine can be added.

In addition, as a method for coupling the mercapto groups with each other, for example, a method using a compound having two or more functional groups capable of forming a bond by reacting with the mercapto group in one molecule can be mentioned. Examples of the functional group capable of reacting with a mercapto group to form a bond include an isocyanato group; an unsaturated group such as a vinyl group and an allyl group; a carboxyl group, and a derivative thereof; a carbonyl group; a hydroxyl group and the like. It is not limited to these.

The rubber component (b) used in the present invention is at least one rubber selected from acrylic polymer rubber, olefin polymer rubber, diene polymer rubber, and natural rubber, or these rubbers. It is a modified rubber obtained by graft-polymerizing an unsaturated monomer with rubber. These rubbers may be used alone or in combination of two or more.

The acrylic polymer rubber used in the present invention can be used without particular limitation as long as it is a rubber obtained by polymerizing a monomer containing an acrylic ester as a main component. Examples of such acrylic acid ester include, for example,
The compounds exemplified above may be mentioned, but the invention is not limited thereto. These may be used alone or in combination of two or more. Examples of the acrylic polymer rubber include ethyl acrylate, butyl acrylate, and a mixed monomer of ethyl acrylate and butyl acrylate, 2-chloroethyl vinyl ether, methyl vinyl ketone, acrylic acid, acrylonitrile, butadiene, etc. Examples thereof include acrylic rubbers obtained by copolymerizing a small amount of one or more of the above monomers, but are not limited thereto.

Examples of the olefin polymer rubber used in the present invention include, but are not limited to, butyl rubber, ethylene-propylene-diene rubber, isobutylene polymer rubber, and ethylene-vinyl acetate copolymer rubber. Not a thing.

Examples of the diene polymer rubber used in the present invention include isoprene rubber, butadiene rubber, 1,2-polybutadiene, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, and hydrogenated products thereof. However, the invention is not limited to these.

Of these, acrylic rubber, chloroprene rubber, and nitrile rubber are preferable, and acrylic rubber is more preferable, when oil resistance is required for the elastomer composition.

In the present invention, from the viewpoint that the compatibility of the rubber component (b) with the block copolymer (a) can be improved, it is preferable to graft-polymerize an unsaturated monomer on the rubber.
Examples of such unsaturated monomers include the methacrylic acid esters exemplified above; the acrylic acid esters exemplified above; styrene, α-methylstyrene, p-methylstyrene, p
-Aromatic alkenyl compounds such as methoxystyrene, divinylbenzene and vinylnaphthalene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
Conjugated diene compounds such as butadiene and isoprene; vinyl chloride, vinylidene chloride, tetrafluoroethylene,
Halogen-containing unsaturated compounds such as hexafluoropropylene, vinylidene fluoride and chloroprene; Silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, maleic acid monoester, maleic acid diester, Unsaturated dicarboxylic acid compounds such as fumaric acid, fumaric acid monoester, fumaric acid diester; vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate; maleimide, methylmaleimide, ethyl Maleimide compounds such as maleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide. Acrylic acid, and the like methacrylic acid, but is not limited thereto. These may be used alone or in combination of two or more.

The amount of the unsaturated monomer to be graft-polymerized on the rubber is not particularly limited and can be arbitrarily selected in order to obtain the required physical properties, but it is compatible with the block copolymer (a). , And in terms of rubber elasticity, 0 to 200 parts by weight is preferable to 100 parts by weight of rubber.

The rubber component used in the present invention may be an uncrosslinked rubber or a crosslinked rubber, but is preferably a crosslinked rubber in terms of heat resistance and shape retention. Regarding the cross-linking of the rubber, it may be cross-linked before the mixing with the block copolymer (a), or may be dynamically cross-linked during the melt mixing with the block copolymer (a).

The rubber cross-linked before mixing with the block copolymer (a) is a cross-linked rubber particle, or a bulk rubber that is cross-linked as a whole. Examples of the crosslinked rubber particles include, but are not limited to, crosslinked rubber particles having a graft chain, for example, crosslinked rubber particles obtained by graft-polymerizing an unsaturated monomer in the outer layer portion. .

As a method of crosslinking the rubber, for example, a method of adding a crosslinking agent, a vulcanization accelerator, etc. at the time of melt mixing with the block copolymer (a); an uncrosslinked rubber together with a crosslinking agent, a vulcanization accelerator Examples thereof include a method of kneading to obtain a crosslinked rubber; and a method of polymerizing an unsaturated monomer with a polyfunctional monomer by emulsion polymerization or suspension polymerization to obtain crosslinked rubber particles. It is not limited to.

As the cross-linking agent used for cross-linking the rubber, conventionally known ones can be used without limitation. For example, sulfur; and thiuram-based organic sulfur compounds such as tetramethylthiuram disulfide and tetramethylthiuram monosulfide. 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylper) (Oxy) valeric acid, dicumyl peroxide, di-t-butylperoxy-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane,
Organic peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; oxime compounds such as p-quinonedioxime, p, p'-dibenzoylquinonedioxime; alkylphenols Alkylphenol resins such as formaldehyde resin and brominated alkylphenol formaldehyde resin; polyamines such as hexamethylenediamine carbamate; metal oxides; triazine thiols; polyols; selenium compounds; tellurium compounds. These may be used alone or in combination of two or more. The amount of the cross-linking agent used is not particularly limited, but in terms of the balance between the cross-linking efficiency and the rubber elasticity, the cross-linking agent is added in an amount of 0.1 to 100 parts by weight of the rubber.
It is preferable to use 30 parts by weight, more preferably 0.5 to 20 parts by weight.

When using these crosslinking agents, a vulcanization accelerator can be used to accelerate the crosslinking. Examples of such vulcanization accelerators include guadinine compounds such as diphenylguadinine; thiuram compounds such as tetramethylthiuram disulfide and tetramethylthiuram monosulfide; dithiocarbamate compounds such as zinc dimethyldithiocarbamate; 2-mercaptobenzo Examples thereof include thiazole compounds such as thiazole and dibenzothiazyl sulfide; and sulfenamide compounds such as N-cyclohexyl-2-benzothiazole sulfenamide and Nt-butyl-2-benzothiazole sulfenamide. It is not limited to these. Moreover, zinc oxide, stearic acid, or the like can also be used. These vulcanization accelerators are highly effective when cross-linked with sulfur, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, nitrile rubber, ethylene-propylene-diene rubber, butyl rubber,
Particularly effective for rubber having a double bond such as chloroprene rubber. When an organic sulfur compound is used as a crosslinking agent, it is preferable to add a small amount of sulfur, the above vulcanization accelerator, or zinc oxide. When using an organic peroxide as a crosslinking agent, it is preferable to add zinc oxide for the purpose of improving heat resistance. Crosslinking with an organic peroxide, fluorine rubber, silicone rubber, ethylene-propylene-diene rubber, nitrile rubber, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-propylene-diene rubber, chloroprene rubber,
Highly effective for acrylic rubber. When using an oxime compound as a crosslinking agent, it is preferable to use an activator together. As such an activator, lead oxide compounds such as PbO ₂ and Pb ₃ O ₄ and dibenzothiazyl sulfide can be used, but the activator is not limited to these. Crosslinking with an oxime compound is highly effective for butyl rubber, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, nitrile rubber, ethylene-propylene-diene rubber, and chloroprene rubber. When an alkylphenol resin is used as a crosslinking agent, it is preferable to add a crosslinking aid such as zinc oxide or tin chloride. Also,
Stearic acid can also be added. Crosslinking with an alkylphenol resin is highly effective for butyl rubber and the like.
Crosslinking with polyamines can be applied to rubber having a halogen atom, such as active chlorine type acrylic rubber and fluororubber.

Examples of the crosslinked rubber particles in which the unsaturated monomer is grafted on the outer layer portion include, for example, butadiene or styrene-butadiene crosslinked rubber particles which are graft-copolymerized with methyl methacrylate and, if necessary, styrene. Methyl methacrylate-butadiene-styrene copolymer (MBS) resin obtained by the following; an acrylic graft copolymer resin obtained by graft-copolymerizing methyl methacrylate on cross-linked rubber particles of butyl acrylate. However, the present invention is not limited to these.

The elastomer composition of the present invention contains the block copolymer (a) and the rubber component (b) as essential components. The weight ratio of (a) and (b) is rubber elasticity and In terms of moldability, (a) :( b) = 90: 10 to 10: 9
A weight ratio of 0 is preferable, and (a) :( b) = 80: 20-
A weight ratio of 20:80 is more preferable, and (a) :( b) =
A weight ratio of 30:70 to 70:30 is particularly preferred. If the weight ratio of the block copolymer (a) exceeds 90%, the compression set of the elastomer increases, which may be disadvantageous in terms of rubber elasticity. When the weight ratio of the block copolymer (a) is less than 10%, when the rubber component (b) is an uncrosslinked rubber, the moldability may be impaired due to adhesion during molding, and (b In the case where () is a crosslinked rubber, the melt viscosity of the elastomer component becomes high, which may impair the moldability.

In the elastomer composition of the present invention,
A wide range of physical properties can be expressed by adjusting the composition ratio of the block copolymers (a) and (b), the type and composition of the block copolymer (a), and the type and composition of the rubber component (b). Is. For example, when the uncrosslinked rubber component (b) is added to the block copolymer (a), the hardness and the modulus are reduced and the elongation is improved as compared with the case where the block copolymer (a) is used alone. In addition, the outflow or migration of low-molecular components, which is observed when a plasticizer is added, is not observed. When the rubber component (b) is butyl rubber, vibration damping properties, gas barrier properties and the like can be imparted.

When the block copolymer (a) and the rubber component (b) are dynamically crosslinked during melt mixing, the balance between hardness and compression set of the elastomer can be improved. When the rubber component (b) is acrylic rubber, excellent oil resistance can be imparted.

When the pre-crosslinked rubber component (b) is added to the block copolymer (a), the hardness and modulus of the elastomer can be improved, and the tackiness can be maintained while maintaining the physical properties of the rubber component. It is possible to obtain an elastomer having a low content.

The elastomer composition of the present invention may contain various additives as necessary other than the block copolymer (a) and the rubber component (b). Such additives are not particularly limited,
Examples thereof include tackifiers, stabilizers, antioxidants, ultraviolet absorbers, HALS, antistatic agents, flame retardants, antifungal agents, antiaging agents, inorganic fillers, and conductive fillers.

Although the tackifier is not particularly limited among the above-mentioned additives, for example, Takkyrol 101 (manufactured by Taoka Chemical Co., Ltd.), Hitanol 1501 (manufactured by Hitachi Chemical Co., Ltd.), modified alkylphenol formaldehyde resin, and hitanol. 5501 (manufactured by Hitachi Chemical Co., Ltd.) and the like can be mentioned. These may be used alone or in combination of two or more.

The stabilizer among the above-mentioned additives is not particularly limited, but examples thereof include the following compounds: cadmium stearate, zinc stearate, barium stearate, calcium stearate, lead dibutyltin dilaurate, tris. Stabilizers for vinyl chloride such as (nonylphenyl) phosphite, triphenylphosphite, diphenylisodecylphosphite; di-n-
Octyl tin bis (isooctyl thioglycolate) salt, di-n-octyl tin maleate polymer, di-n-octyl tin dilaurate, di-n-octyl tin maleate salt, di-n- Butyltin bismaleic acid ester salt, di-n-butyltin maleate polymer, di-n-butyltin bisoctylthioglycol ester salt, di-n-butyltin β-mercaptopropionate polymer, di-n-butyltin dilaurate, di -N-methyltin bis (isooctyl mercaptoacetate) salt, poly (thiobis-n-butyltin sulfide), monooctyltin tris (isooctyl thioglycolic acid ester), dibutyltin maleate, di-n-butyltin malate ester / carboxylate , And J Organotin stabilizers such as n-butyltin malate ester and mercaptide; tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, dibasic lead phthalate, lead silicate, dibasic stearin. Lead stabilizers such as lead acid and lead stearate; cadmium soap, zinc soap, barium soap, lead soap, complex metal soap, metal soap stabilizers such as calcium stearate. These may be used alone or in combination of two or more.

Of the above additives, the antioxidant is not particularly limited, but examples thereof include the following compounds: 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6. -Di-t-butyl-
4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,2′- Methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4 '
-Butylidene bis (3-methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- [β-
(3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-
Tetraoxaspiro [5.5] undecane, 1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6
-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] Glycol ester, 1,3,5-
Tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H,
3H, 5H) Phenolic antioxidants such as trione, tocopherols, topanol CA (manufactured by Ripre Co., Ltd.); dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, stearyl 3 , 3'-thiodipropionate and other sulfur-based antioxidants; triphenylphosphite, diphenylisodecylphosphite, 4,4'-butylidene-bis (3-methyl-6-t-butylphenylditridecyl) phosphite Fight, cyclic neopentanetetraylbis (octadecylphosphite), tris (nonylphenyl) phosphite, tris (monononylphenyl) phosphite, tris (dinonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, 9, 1
0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phos Fafenanthrene-10-
Oxide, 10-decyloxy-9,10-dihydro-
9-oxa-10-phosphaphenanthrene, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-)
t-Butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4)
-Methylphenyl) phosphite (ADEKA STAB PEP)
-36 (manufactured by Asahi Denka Co., Ltd.), 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, and other phosphorus-based antioxidants. These may be used alone or in combination of two or more.

Among the above additives, the ultraviolet absorber is
Although not particularly limited, examples thereof include the following compounds: salicylic acid-based UV absorbers such as phenyl salicylate, pt-butylphenyl salicylate, and p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy- 4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy Benzophenone, 2-hydroxy-4-methoxy-
5-sulfobenzophenone, bis (2-methoxy-4-
Benzophenone-based UV absorbers such as hydroxy-5-benzoylphenyl) methane; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2-
(2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'
-Di-t-butylphenyl) benzotriazole, 2-
(2'-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-
Hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- [2′-
Hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl]
Benzotriazole, 2,2-methylenebis [4-
(1,1,3,3-tetramethylbutyl) -6- (2H
-Benzotriazol-2-yl) phenol], [2
-(2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole], [2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H -Benzotriazol-2-yl)
Phenol]]]] and other benzotriazole-based UV absorbers; 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, ethyl-2-cyano-3,3 ′
Cyanoacrylate-based UV absorbers such as diphenyl acrylate; nickel bis (octylphenyl) sulfide, [2,2′-thiobis (4-t-octylphenolate)]-n-butylamine nickel, nickel complex-3,5- Nickel-based UV stabilizers such as di-t-butyl-4-hydroxybenzyl-phosphoric acid monoethylate and nickel-dibutyldithiocarbamate. These may be used alone or in combination of two or more.

HALS of the above additives is not particularly limited, and in addition to the compounds described above as the hydrogen-nitrogen bond-containing compound, TINUVIN 622LD (Ciba Spe
bioty soap 03 (manufactured by Kyodo Pharmaceutical Co., Ltd.), ADEKA STAB LA-62 (manufactured by Asahi Denka Kogyo Co., Ltd.), ADEKA STAB LA-63 (manufactured by Asahi Denka Kogyo KK), ADEKA STAB LA-82 (manufactured by Asahi Denka Kogyo Co., Ltd.) Asahi Denka Kogyo Co., Ltd., etc. can be used. These may be used alone or in combination of two or more.

The antistatic agent of the above additives is not particularly limited, but examples thereof include the following compounds: poly (oxyethylene) alkylamine, poly (oxyethylene) alkylamide, poly (oxyethylene). Nonionic antistatic agents such as alkyl ethers, poly (oxyethylene) alkylphenyl ethers, glycerin fatty acid esters, sorbitan fatty acid esters;
Anionic antistatic agents such as alkyl sulfonates, alkylbenzene sulfonates, alkyl sulfates and alkyl phosphates; cationic antistatic agents such as quaternary ammonium chlorides, quaternary ammonium sulfates and quaternary ammonium nitrates; alkyl betaine compounds, alkyls Amphoteric antistatic agents such as imidazoline compounds and alkylalanine compounds; conductive resin type antistatic agents such as polyvinylbenzyl type cationic compounds and polyacrylic acid type cationic compounds. These may be used alone or in combination of two or more.

The flame retardant among the above additives is not particularly limited, but the following compounds may be mentioned, for example: tetrabromobisphenol A, 2,2-bis (4
-Hydroxy-3,5-dibromophenyl) propane,
Halogen-based compounds such as hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, decabromodiphenyl oxide, and halogen-containing polyphosphate. Flame retardant; ammonium phosphate, tricresyl phosphate, triethyl phosphate, tris (β-chloroethyl) phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, acidic phosphate ester, containing Phosphorus flame retardants such as nitrogen phosphorus compounds; red phosphorus, tin oxide,
Inorganic flame retardants such as antimony trioxide, zirconium hydroxide, barium metaborate, aluminum hydroxide, magnesium hydroxide; poly (dimethoxysiloxane), poly (diethoxysiloxane), poly (diphenoxysiloxane), poly (methoxyphenoxy) Siloxane), methyl silicate, ethyl silicate, siloxane based flame retardants such as phenyl silicate. These may be used alone or in combination of two or more.

The antifungal agent of the above additives is not particularly limited, but the following compounds may be mentioned, for example: binadine, pribentol, thiabendazole and the like. These may be used alone or in combination of two or more.

Among the above additives, the antiaging agent is not particularly limited, but the following compounds may be mentioned, for example: poly (2,2,4-trimethyl-1,2-dihydroquinoline), 6-ethoxy. -1,2-dihydro-
2,2,4-trimethylquinoline, 1- (N-phenylamino) -naphthalene, styrenated diphenylamine,
Dialkyldiphenylamine, N, N'-diphenyl-
p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-2-
Naphthyl-p-phenylenediamine, 2,6-di-t-
Butyl-4-methylphenol, mono (α-methylbenzyl) phenol, di (α-methylbenzyl) phenol, tri (α-methylbenzyl) phenol, 2,2 ′
-Methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-)
Butylphenol), 4,4'-butylidene bis (6-
t-butyl-3-methylphenol), 4,4′-thiobis (6-t-butyl-3-methylphenol), 1,
1-bis (4-hydroxyphenyl) cyclohexane,
2,5-di-t-butylhydroquinone, 2,5-di-
t-amyl hydroquinone, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, nickel dibutyldithiocarbamate, tris (nonylphenyl) phosphite, dilauryl thiodipropionate, thiodipropionic acid Distearyl, Sunnock (manufactured by Ouchi Shinko Chemical Co., Ltd.), Suntite (Seiko Chemical Co., Ltd.)
Manufactured by Kawaguchi Chemical Industry Co., Ltd.). These may be used alone or in combination of two or more.

Among the above additives, the inorganic filler is
Although not particularly limited, the following materials can be exemplified: hydrous fine powder silicic acid, calcium silicate, furnace black, channel black, thermal lamp black, gas black, oil black, acetylene black, calcium carbonate, clay, talc. , Titanium oxide,
Zinc flower, diatomaceous earth, barium sulfate, etc. These may be used alone or in combination of two or more.

The conductive filler among the above additives is not particularly limited, but examples thereof include metal powder such as gold powder, silver powder, and copper powder. These may be used alone or in combination of two or more.

The method for producing the elastomer composition of the present invention is not particularly limited, and for example, a conventionally known method for producing a rubber composition in the rubber industry can be applied. For example, the block copolymer (a), the rubber component (b), and if necessary, a crosslinking agent, a vulcanization accelerator, an additive, etc. are mixed by a tumbler, a Henschel mixer, a riboblender, etc., and then an extruder. , A Banbury mixer, a roll, or the like. The kneading temperature in this case is the block copolymer (a) and the rubber component (b).
It is preferable to adjust the temperature in the range of room temperature to 230 ° C. depending on the weight ratio thereof. In particular, the glass transition temperature of the methacrylic polymer block (A) in the block copolymer (a) is 1
This is because when the temperature is 00 ° C. or higher and the weight ratio of the block copolymer (a) in the elastomer composition is high, the components are not sufficiently mixed when the temperature is lower than room temperature. Therefore, when the composition of the elastomer composition is less than 50 parts by weight of the block copolymer (a) with respect to 100 parts by weight of the rubber component (b), the kneading temperature is preferably room temperature to 100 ° C, and the block copolymer ( a) is 50 to 100 parts by weight
In the case of a weight part, 80-150 degreeC is preferable, and when the block copolymer (a) exceeds 100 weight part, it is 150-2.
10 ° C is preferred. However, if the kneading temperature is 210 ° C. or higher, the block copolymer (a) and the rubber component (b) may be decomposed in some cases, which is usually not preferable. When dynamically vulcanizing the rubber component (b), the kneading temperature is preferably 50 to 210 ° C. from the viewpoint of the balance between the vulcanization rate and the moldability.

The elastomer composition of the present invention can be formed into a molded body by various conventionally known methods. Examples of the method for producing the molded body include, but are not limited to, extrusion molding, compression molding, blow molding, calender molding, vacuum molding, and injection molding.

The molded product obtained by molding the elastomer composition of the present invention can be used for various purposes. Examples of applications of such a molded product include, but are not limited to, sealing materials, gaskets, oil resistant hoses, and covering sheets.

In the molded product of the present invention, as the sealing material, butyl rubber is preferably used as the rubber component (b) from the viewpoint of gas barrier property, and uncrosslinked butyl rubber or dynamically crosslinked butyl rubber is more preferable. From the viewpoint of heat resistance and durability, the methacrylic polymer block (A) of the block copolymer (a) is preferably a methyl methacrylate polymer, and the acrylic polymer block (B) is an ethyl acrylate polymer, acryl. A butyl acid polymer or an ethyl acrylate-butyl acrylate-2-methoxyethyl acrylate copolymer is preferred. The weight ratio of the block copolymer (a) and the rubber component (b) is preferably (a) :( b) = 90: 10 to 50:50 when (b) is an unvulcanized rubber,
(A) :( b) = 80: 20 to 60:40 is more preferable. When the weight ratio of (b) exceeds 50% by weight, problems such as adhesion may occur during processing. Further, when dynamically crosslinking (b), (a) :( b) = 90: 10
It is preferably 20:80, and (a) :( b) = 8.
0:20 to 20:80 is more preferable. The sealing material of the present invention can be used, for example, as a sealing material for the mouth of glass bottles, PET bottles, etc., and the elastomer composition is formed into a disk shape or a column shape by press molding, and then inserted into the mouth of the bottle or container. It can be used by inserting it into the lid.

Among the molded products of the present invention, in terms of heat resistance and durability of the gasket, the methacrylic polymer block (A) of the block copolymer (a) is a methyl methacrylate polymer. Preferably, the acrylic polymer block (B) is an ethyl acrylate polymer or an ethyl acrylate-butyl acrylate-2-methoxyethyl acrylate copolymer. Rubber component (b)
From the viewpoint of oil resistance and durability, acrylic rubber, chloroprene rubber, and nitrile rubber are preferable, acrylic rubber is more preferable, and dynamic crosslinking is preferable. From the viewpoint of durability, the weight ratio of the block copolymer (a) and the rubber component (b) is preferably (a) :( b) = 90: 10 to 20:80, and (a) :( b) = 80. : 20 to 20:80 is more preferable. INDUSTRIAL APPLICABILITY The gasket of the present invention can be used as, for example, a syringe gasket, a glass sealing gasket, an automobile gasket, and the like.

Among the molded products of the present invention, the oil resistant hose is, in terms of oil resistance and heat resistance, a block copolymer (a).
The methacrylic polymer block (A) is preferably a methyl methacrylate polymer, and the acrylic polymer block (B) is an ethyl acrylate polymer, or ethyl acrylate-butyl acrylate-2-methoxyethyl acrylate. A copolymer is preferable, and it is more preferable to copolymerize an acrylonitrile monomer. As the rubber component (b), acrylic rubber, chloroprene rubber and nitrile rubber are preferable, acrylic rubber is more preferable, and dynamic crosslinking is further preferable. The weight ratio of the block copolymer (a) and the rubber component (b) is (a) :( b) = 90: 10 to 2 in terms of oil resistance and a balance between heat resistance and moldability.
0:80 is preferable, and (a) :( b) = 80: 20 to 2
0:80 is more preferable. Such an oil resistant hose
For example, it can be manufactured by extrusion molding and can be used as a hose for vehicles such as automobiles.

Among the molded products of the present invention, the covering sheet is preferably a methyl methacrylate polymer as the methacrylic polymer block (A) of the block copolymer (a) in terms of weather resistance and heat resistance. Butyl acrylate is preferable as the acrylic polymer block (B), and butyl acrylate crosslinked rubber particles are used as the rubber component (b).
Graft-crosslinked rubber particles obtained by graft-polymerizing methyl methacrylate are preferred. The weight ratio of the block copolymer (a) to the rubber component (b) is (a) :( b) = 90: 10 to 20: from the viewpoint of the balance between weatherability, heat resistance and moldability.
80 is preferable and (a) :( b) = 80: 20-50:
50 is more preferable. The coated sheet of the present invention is an extrusion molding of the above elastomer composition, compression molding, blow molding,
The molding can be carried out by any processing method such as calender molding, vacuum molding, injection molding, but extrusion molding is preferable from the viewpoint of productivity and cost. It is also possible to perform uniaxial or biaxial stretching simultaneously with extrusion or after extrusion molding.

[0111]

EXAMPLES The present invention will be described below based on examples.
The present invention is not limited to these examples. In the following description, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC) measurement. Chloroform was used as an eluent and a polystyrene gel column (SHODEX K manufactured by Showa Denko KK)
-804) was used and analyzed in terms of polystyrene. The hardness was measured according to JIS K6253 at 23 ° C. (JIS A). The tensile strength at break and the elongation at tensile break were measured at 25 ° C. according to JIS K6251. For the compression set, according to JIS K6301, a cylindrical molded body was held at 70 ° C. for 22 hours under the condition of a compression rate of 25%, left at room temperature for 30 minutes, and then the thickness of the molded body was measured.
The residual strain was calculated. The oil resistance was determined from the weight change rate according to JIS C232 by immersing the molded body in transformer oil B at 70 ° C. for 4 hours. Gel fraction is 1g of molded product
Was immersed in 50 mL of toluene at room temperature for 72 hours, the toluene-soluble component was separated, the insoluble component was dried under reduced pressure at 60 ° C., and the weight was measured.

(Production Example 1) ((methyl methacrylate /
(Glycidyl Methacrylate) -Synthesis of n-Butyl Acrylate Diblock Copolymer) A 3 L reactor equipped with a stirrer, a thermometer, a nitrogen gas introducing pipe, a dropping funnel, and a reflux cooling pipe was charged with a methacrylic acid ester monomer. 545 g of methyl methacrylate, and glycidyl methacrylate 45 as a monomer having an epoxy group
g, a compound having the formula (1
3)

[0113]

[Chemical 29] 6.0 g of a compound represented by: and toluene 1.1 as a solvent
L and 0.7 g of 2,2′-azobis (isobutyronitrile) as a polymerization initiator were charged, and the inside of the reactor was replaced with nitrogen. Stir for 12 hours at 70 ° C and then sample
By C analysis and NMR analysis, Mw = 29900, Mn =
23700, Mw / Mn = 1.26, and confirmed formation of a methyl methacrylate / glycidyl methacrylate copolymer having 15.4 epoxy groups and one thiocarbonylthio group in one molecule. .

Subsequently, 490 g of n-butyl acrylate was placed in the dropping funnel and added dropwise to the reactor over 2 hours while stirring at 70 ° C. After completion of dropping, the mixture was further stirred at 70 ° C. for 12 hours, and then the reaction solution was poured into 5 L of methanol to precipitate a polymer as a precipitate. By GPC analysis and NMR analysis,
Mw = 54500, Mn = 38200, Mw / Mn =
1.43, having 14.1 epoxy groups and 0.9 thiocarbonylthio groups in one molecule (methyl methacrylate / glycidyl methacrylate) -acrylic acid n
It was confirmed to be a -butyl diblock copolymer.

(Production Example 2) ((methyl methacrylate /
(Methacrylic acid) -n-butyl acrylate- (methyl methacrylate / methacrylic acid) synthesis of triblock copolymer) A 1 L reactor equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a reflux cooling tube was charged with methacrylic acid. 206 g of methyl methacrylate as an acid ester monomer, 183 g of methacrylic acid as a monomer to be copolymerized with a methacrylic acid ester, and a compound having a thiocarbonylthio group of the formula (13)

[0116]

[Chemical 30] 4.0 g of the compound represented by and ethanol 50 as a solvent
0 g and 1.02 g of 2,2′-azobis (isobutyronitrile) as a polymerization initiator were charged, and the inside of the reactor was replaced with nitrogen. After heating and stirring at 70 ° C for 7 hours, the reaction solution was n-
The polymer was precipitated by pouring into 6 L of hexane, filtered and dried. The conversion rate of methyl methacrylate was 62% and the conversion rate of methacrylic acid was 67%. As a result of GPC analysis (tetrahydrofuran eluate) and NMR analysis, the obtained polymer was a (methyl methacrylate / methacrylic acid) copolymer, and the weight ratio of each composition was methyl methacrylate: methacrylic acid = 51: 49. Mn = 20000, Mw / Mn =
It was 1.34, and had 0.97 thiocarbonylthio groups per molecule.

200 g of the obtained (methyl methacrylate / methacrylic acid) copolymer was dissolved in 700 mL of ethanol, and a stirrer, a thermometer, a nitrogen gas introducing pipe, and a dropping funnel were added.
And a 1L reactor equipped with a reflux condenser, and n-butyl acrylate 240 was used as the acrylic ester monomer.
g, and 0.71 g of 2,2′-azobis (isobutyronitrile) as a polymerization initiator were added, and the inside of the reactor was replaced with nitrogen. After heating and stirring at 70 ° C. for 10 hours, the reaction solution was n-
Pour into 5 L of hexane to precipitate the polymer, filter, wash,
Dried. The conversion rate of n-butyl acrylate was 60%. As a result of GPC analysis (tetrahydrofuran eluate) and NMR analysis of the obtained polymer (308 g),
(Methyl methacrylate / methacrylic acid) -acrylic acid n
-Butyl diblock copolymer, the weight ratio of each composition is methyl methacrylate: methacrylic acid: acrylic acid n-
Butyl = 32: 31: 37, Mn = 31700, Mw /
Mn = 1.47, and had 0.95 thiocarbonylthio groups per molecule.

300 g of this diblock copolymer was dissolved in a mixed solvent of 600 mL of ethanol and 400 mL of ethyl acetate and placed in a 2 L reactor equipped with a stirrer, a thermometer, a nitrogen gas introducing tube, and a reflux cooling tube, and a secondary amine was added. 40 g of diethylamine as a compound was added and stirred at 40 ° C. for 5 hours,
Then, 20 g of 1N HCl aqueous solution was added and the mixture was mixed at 70 ° C. for 3 hours.
Stir for hours. The reaction solution was cooled to room temperature and then concentrated, n-
The polymer was precipitated by pouring into 3 L of hexane. After filtration, washing and drying, 271 g of a (methyl methacrylate / methacrylic acid) -n-butyl acrylate diblock copolymer having 0.91 mercapto groups per molecule was obtained.

271 g of this diblock copolymer having a mercapto group was mixed with 400 mL of ethanol and 40 parts of ethyl acetate.
It was dissolved in a mixed solvent with 0 mL, 100 mL of 30% hydrogen peroxide solution was added as an oxidizing agent, and the mixture was stirred at 30 ° C. for 8 hours. The reaction solution was poured into 2 L of n-hexane to precipitate a polymer, which was filtered, washed and dried to obtain 255 g of a polymer. As a result of GPC analysis (tetrahydrofuran eluate) and NMR analysis, this polymer was coupled through a disulfide bond, (methyl methacrylate / methacrylic acid) -n-butyl acrylate- (methyl methacrylate / methacrylic acid). Is a triblock copolymer, M
It was confirmed that n = 56200 and Mw / Mn = 1.87. The weight ratio of each composition did not change from that before the coupling.

(Production Example 3) (Methyl methacrylate-
(Synthesis of n-Butyl Acrylate / Ethyl Acrylate / 2-Methoxyethyl Acrylate) -Methyl Methacrylate Triblock Copolymer) A stirrer, thermometer, nitrogen gas introduction tube, reflux condenser, and dropping funnel are provided. In a 500 mL reactor, 100 g (0.999 mol) of methyl methacrylate, dimethyl 2,
421 mg (1.8) of 2'-azobis (isobutyrate)
3 mmol), formula (13)

[0121]

[Chemical 31] Compound 79 having a thiocarbonylthio group represented by
6 mg (2.92 mmol) and 100 m of toluene
L was added and the atmosphere was replaced with nitrogen. 80 ° C while stirring the reaction solution
The mixture was heated for 2 hours in a methyl methacrylate polymer (Mw = 3
8400, Mn = 34200, Mw / Mn = 1.12)
Got Subsequently, 89.6 g (0.699 mol) of n-butyl acrylate and 8 parts of ethyl acrylate were added from the dropping funnel.
8.0 g (0.879 mol), and acrylic acid 2-
A mixed solution of 54.7 g (0.420 mol) of methoxyethyl was added dropwise over 1 hour, and the mixture was further stirred with heating at 80 ° C for 5 hours. The reaction solution is cooled to room temperature and methanol 1.
Pour into 5 L of methyl methacrylate- (acrylic acid n
-Butyl / ethyl acrylate / 2-methoxyethyl acrylate) diblock copolymer (Mn = 104000,
Mw / Mn = 1.44) was obtained. The composition ratio of each component is methyl methacrylate: n-butyl acrylate: ethyl acrylate: 2-methoxyethyl acrylate = 33: 24:
It was 28:15 (weight ratio).

300 g of this diblock copolymer was dissolved in 300 mL of toluene and placed in a 1 L reaction vessel, and 100 g (1.37 m) of diethylamine as a secondary amine compound.
ol) was added and the mixture was stirred at room temperature for 20 hours. Diethylamine and toluene were distilled off under reduced pressure and then reprecipitated with toluene / methanol to have a mercapto group-terminated methyl methacrylate- (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) diblock copolymer. 295 g of coalesced was obtained. Subsequently, 300 mL of toluene was added and dissolved, and 200 mg of lead dioxide (0.837 mm
ol) and stirred at 60 ° C. for 30 hours, the reaction solution was filtered, the solvent was distilled off under reduced pressure, and the residue was reprecipitated with toluene / methanol to give methylmethacrylate- (acrylic acid coupled with a disulfide bond). n-Butyl / ethyl acrylate / 2-methoxyethyl acrylate) -methyl methacrylate triblock copolymer (M
w = 325000, Mn = 208000, Mw / Mn =
1.56) was obtained. The composition ratio of each component is methyl methacrylate: n-butyl acrylate: ethyl acrylate: 2-methoxyethyl acrylate = 33: 24: 28: 15.
(Weight ratio).

(Production Example 4) (Synthesis of Methyl Methacrylate-n-Butyl Acrylate-Methyl Methacrylate Triblock Copolymer) A stirrer, a thermometer, a nitrogen gas introducing pipe, a reflux cooling pipe, and a dropping funnel are provided. In a 1 L reactor, sodium dodecyl sulfate 410 mg (1.42 mmol) and distilled water 400 g
Was charged and the atmosphere was replaced with nitrogen while heating and stirring at 80 ° C. Formula (14)

[0124]

[Chemical 32] And a compound 80 having a thiocarbonylthio group
20 mg (0.200 m) of methyl methacrylate, which is a methacrylic acid ester monomer, was added to 0 mg (2.31 mmol).
sol) and added with heating and stirring at 80 ° C. for 20 minutes, 432 mg (1.54 mmol) of 4,4′-azobis (4-cyanovaleric acid) as a polymerization initiator was added together with 25 g of distilled water. At the time of heating and stirring at 80 ° C for 30 minutes, 80 g of methyl methacrylate was added from the dropping funnel.
(0.799 mol) was added dropwise over 1 hour and 30 minutes. Further, the mixture was stirred at 80 ° C. for 2 hours to obtain a methyl methacrylate polymer (Mn = 43300, Mw / Mn = 1.17). Subsequently, 230 g (1.79 mo) of n-butyl acrylate as an acrylic acid ester monomer was added from the dropping funnel.
1) was added dropwise over 2 hours and further heated at 80 ° C. for 14 hours. The emulsion was cooled to room temperature, an aqueous solution of calcium chloride was added for salting out, followed by filtration and washing, and then methyl methacrylate-n-butyl acrylate-methyl methacrylate triblock copolymer (Mn = 155000, Mw / Mn).
= 1.28) was obtained. The composition ratio of each component is methyl methacrylate: n-butyl acrylate = 31: 69 (weight ratio)
Met.

(Production Example 5) (Synthesis of cross-linked rubber particles (without graft)) In a 1 L reactor equipped with a stirrer, a thermometer, a nitrogen gas introducing tube, a reflux cooling tube, and a dropping funnel, 500 g of pure water and tri Sodium decyl sulfonate 1.5g (5.2mmo
l), tetrasodium ethylenediaminetetraacetate 10 mg
(0.02 mmol), ferrous sulfate heptahydrate 2.5 mg
(0.009 mmol) and 0.875 g of a 5% aqueous solution of sodium formaldehyde sulfoxylate were charged and heated to 40 ° C. with stirring in a nitrogen stream. 250 g (2.50 mo) of n-butyl acrylate
l), 3.75 g of allyl methacrylate (29.7 mmo)
l), and cumene hydroperoxide 75 mg
A mixed solution of (0.48 mmol) was added dropwise over 5 hours. At this time, 1 hour after the start of dropping, 0.75 g (2.6 mmol) of sodium tridecylsulfonate was added,
3 hours after the start of dropping, 0.75 g (2.6 m)
mol) respectively. After completion of the dropping, the mixture was stirred at 40 ° C. for 1 hour and then cooled to room temperature. The average particle size of the obtained inner layer crosslinked acrylic acid ester-based polymer latex was 100 nm (obtained by light scattering at a wavelength of 546 μm), and the monomer conversion rate was 98%.
The obtained latex was salted out and coagulated with a calcium chloride aqueous solution, heat-treated and dried to obtain white powdery butyl acrylate-based crosslinked rubber particles.

(Production Example 6) (Synthesis of Crosslinked Rubber Particles (with Graft)) A rubber-like polymer latex was produced in the same manner as in Production Example 5, and the rubber-like polymer latex was kept at 60 ° C. to give formaldehyde sulfoxyl. 0.25 g of a 5% aqueous solution of sodium acidate was added, and 26.25 g (0.262 mol) of methyl methacrylate and n-acrylic acid were added from a dropping funnel.
Butyl 1.5 g (11.7 mmol) and t-butyl hydroperoxide 82.5 mg (0.915 m)
(mol) mixed solution was added dropwise over 1 hour. After completion of the dropping, the mixture was stirred at 60 ° C. for 1 hour and cooled to room temperature.
The average particle size of the obtained graft copolymer was 110 nm, and the monomer reaction rate was 99%. This latex is salted out with calcium chloride solution, coagulated, heat-treated and dried,
White powdery methyl methacrylate-butyl acrylate graft-crosslinked rubber particles were obtained.

(Examples 1 and 2) Acrylic rubber (AR42
W Nippon Zeon Co., Ltd. and methyl methacrylate- (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) -methyl methacrylate triblock copolymer produced in Production Example 3. The weight ratios shown in Table 1 were used, and melt kneading was performed using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) set at 190 ° C. further,
Ammonium benzoate was added as a cross-linking agent in the weight ratio shown in Table 5, and melt-kneaded using a Labo Plastomill set at 190 ° C. The obtained block-shaped sample was hot-press molded at a set temperature of 190 ° C. to prepare a molded body having a thickness of 2 mm for evaluating physical properties and a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm for evaluating compression set. . These 150
It was vulcanized by heating at ℃ for 2 hours. The hardness, tensile strength at break, elongation at tensile break, compression set, oil resistance, and gel fraction of these molded products were measured, and are shown in Table 1.

(Examples 3 to 6) Instead of the methacrylic acid ester-acrylic acid ester-methacrylic acid ester triblock copolymer of Example 1, the block copolymer produced in Production Example 1 or Production Example 2 was used. The molded product was used and the physical properties were evaluated in the same manner as in Example 1 at the weight ratios shown in Table 1. The results are shown in Table 1.

(Comparative Example 1) The methyl methacrylate- (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) -methyl methacrylate triblock copolymer produced in Production Example 3 was heated to 190 ° C. Melting and kneading were performed using a set Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.). The block-shaped sample obtained is set at a temperature of 190 ° C.
Was subjected to hot press molding to prepare a molded body having a thickness of 2 mm for evaluating physical properties and a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm for evaluating compression set. For these molded bodies,
The hardness, tensile strength at break, elongation at tensile break, compression set, oil resistance, and gel fraction were measured and are shown in Tables 1 and 2.

[0130]

[Table 1] (In the table, the copolymer, the acrylic rubber, and the cross-linking agent are shown in the respective parts by weight of the blend).

From Table 1, it can be seen that the molded product obtained from the composition of the present invention has an excellent balance between hardness and compression set. Further, the molded product obtained from the composition of the present invention has excellent oil resistance and a high gel fraction, and therefore also excellent solvent resistance.

(Examples 7 to 13) Butyl rubber (butyl 3)
65 manufactured by Nippon Synthetic Rubber Co., Ltd., and methyl methacrylate- (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) -methyl methacrylate triblock copolymer produced in Production Example 3 Methyl methacrylate-n-butyl acrylate-methyl methacrylate triblock copolymer prepared in Example 4, prepared in Preparation Example 1 (methyl methacrylate / glycidyl methacrylate)
-N-butyl acrylate diblock copolymer, or (methyl methacrylate / methacrylic acid) produced in Production Example 2-n-butyl acrylate- (methyl methacrylate /
Methacrylic acid) The triblock copolymers were melt-kneaded at the weight ratios shown in Table 2 using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) set at 190 ° C. At this time, 5 parts by weight of zinc oxide and 1 part by weight of stearic acid were added to 100 parts by weight of butyl rubber. Further, brominated alkylphenol formaldehyde was added as a cross-linking agent in the weight ratio shown in Table 2, and melt-kneaded using a Labo Plastomill set at 190 ° C. The obtained block-shaped sample was hot-press molded at a set temperature of 190 ° C., and a molded body having a thickness of 2 mm for evaluating physical properties and a diameter of 30 mm
C. A cylindrical molded body for evaluation of compression set having a thickness of 12 mm was prepared. These were heated at 150 ° C. for 2 hours to be vulcanized. The hardness, tensile breaking strength, tensile breaking elongation, compression set, oil resistance, and gel fraction of these molded articles were measured and are shown in Table 2.

[0133]

[Table 2] (In the table, the parts by weight of each of the copolymer, butyl rubber, and cross-linking agent are shown.).

From Table 2, it can be seen that the composition of the present invention has an excellent balance of hardness, compression set and strength. It also has a high gel fraction and excellent solvent resistance.

(Example 14) The methyl methacrylate-n-butyl acrylate-methyl methacrylate triblock copolymer produced in Production Example 4 and the crosslinked rubber particles (without graft) produced in Production Example 5 were prepared. At the ratio shown in Table 3,
Melt-blending was performed using a Labo Plastomill set at 200 ° C. The block-shaped sample obtained is set at a temperature of 200 ° C.
Was subjected to hot press molding to prepare a molded body having a thickness of 2 mm for evaluating physical properties and a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm for evaluating compression set. For these molded bodies,
The hardness, tensile breaking strength, tensile breaking elongation, and compression set were measured and are shown in Table 3.

(Example 15) The methyl methacrylate-n-butyl acrylate-methyl methacrylate triblock copolymer produced in Production Example 4 and the crosslinked rubber particles (with graft) produced in Production Example 6 were prepared. At the ratio shown in Table 3,
Melt-blending was performed using a Labo Plastomill set at 200 ° C. The block-shaped sample obtained is set at a temperature of 200 ° C.
Was subjected to hot press molding to prepare a molded body having a thickness of 2 mm for evaluating physical properties and a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm for evaluating compression set. For these molded bodies,
The hardness, tensile breaking strength, tensile breaking elongation, and compression set were measured and are shown in Table 3.

[0137]

[Table 3] (In the table, the parts by weight of each of the copolymer and the crosslinked rubber are shown).

It can be seen that the blend of the methacrylic acid ester-acrylic acid ester block copolymer and the crosslinked rubber particles, which is one of the compositions of the present invention, has excellent mechanical properties.

[0139]

The elastomer composition of the present invention has low hardness, high tensile strength and excellent compression set. Further, oil resistance, gas barrier property, etc. can be easily imparted, and the composition can be used as a molded product such as various sealing materials, gaskets, oil resistant hoses, and covering sheets.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F071 AA75 AF02 AF18 AF24 AF26                       AH17 BB03 BB04 BB05 BB06                       BB13 BC04                 4J002 BP031 CM00 CM05 EV096                       FD206                 4J026 HA11 HA29 HA32 HA33 HA34                       HA35 HA38 HB11 HB29 HB32                       HB33 HB34 HB35 HB38 HE02

Claims (9)

[Claims] 1. An elastomer composition comprising the following two components (a) and (b) as essential components: (a) a methacrylic acid ester-based polymer block (A) and an acrylic acid ester-based polymer block (B) ) And a block copolymer having the general formula (1) (In the formula, R ¹ is a p-valent organic group having 1 or more carbon atoms, and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, or a metal atom. Z ¹ is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and a phosphorus atom. Or a high molecular weight compound; Z
If there is more than ^one , they may be identical to each other,
May be different; p is an integer of 1 or more), and a compound represented by the general formula (2): (In the formula, R ² is a monovalent organic group having 1 or more carbon atoms and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom or a metal atom, and is a high molecular weight compound. Z ² is an oxygen atom (when q = 2),
A sulfur atom (when q = 2), a nitrogen atom (when q = 3), or a q-valent organic group having 1 or more carbon atoms, which is a nitrogen atom, oxygen atom, sulfur atom, halogen atom, silicon atom, phosphorus R ² may be the same or different; q is an integer of 2 or more); A block copolymer which is a polymer obtained by radically polymerizing a monomer in the presence of a compound having a thiocarbonylthio group of the kind; and (b) an acrylic polymer rubber, an olefin polymer rubber, At least one rubber selected from diene polymer rubber and natural rubber. 2. The components (a) and (b) are replaced by (a):
(B) = 90: 10-10: 90 The weight ratio contains, The elastomer composition of Claim 1 characterized by the above-mentioned. 3. A compound having a thiocarbonylthio group is represented by the general formula (3): (In the formula, R ³ is a divalent organic group, and is a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom,
Z ³ may be a hydrogen atom, a halogen atom, or a monovalent organic group having 1 or more carbon atoms, and may be a hydrogen atom, a halogen atom, a silicon atom, It may contain a phosphorus atom and may be a high molecular weight compound; Z ^{3 s} may be the same as or different from each other), a compound represented by the general formula (4): (In the formula, R ⁴ is a monovalent organic group having 1 or more carbon atoms, and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, or a metal atom, and is a high molecular weight compound. R ⁴ may be the same or different from each other; Z ⁴ is a sulfur atom, an oxygen atom, a tertiary nitrogen atom, or a divalent organic group having 1 or more carbon atoms, and Atom, oxygen atom, sulfur atom, halogen atom, silicon atom, phosphorus atom, and may be a high molecular weight compound), and a compound represented by the general formula (5): (In the formula, R ⁵ is a monovalent organic group having 1 or more carbon atoms, and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, or a metal atom, and is a high molecular weight compound. R ⁵ may be the same or different from each other), and at least one compound selected from the compounds represented by The elastomer composition according to the item. 4. The rubber component (b) is at least one rubber selected from acrylic polymer rubber, olefin polymer rubber, diene polymer rubber, and natural rubber,
The elastomer composition according to any one of claims 1 to 3, which is a modified rubber obtained by graft-polymerizing an unsaturated monomer. 5. The block copolymer (a) comprises 5 to 90% by weight of a methacrylic acid ester-based polymer block (A).
And 95 to 10% by weight of the acrylic acid ester-based polymer block (B).
The elastomer composition according to any one of 4 above. 6. The molecular weight distribution of the block copolymer (a) measured by gel permeation chromatography is 2 or less, wherein
The elastomer composition according to any one of 5 above. 7. The method according to claim 1, wherein when the block copolymer (a) and the rubber component (b) are mixed, they are melt-mixed so that the rubber component (b) is dynamically crosslinked. The elastomer composition according to any one of 1. 8. The elastomer composition according to any one of claims 1 to 7, wherein the rubber component (b) is a crosslinked rubber particle having a graft chain. 9. A molded product obtained by molding the elastomer composition according to any one of claims 1 to 8.