JP2003261734A - Thermoplastic elastomer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new thermoplastic elastomer composition rich in flexibility and excellent in mechanical strength, moldability and processability, oil resistance and heat resistance. <P>SOLUTION: The thermoplastic elastomer composition is obtained by compounding, as essential components, (A) a (meth)acrylate-based copolymer, (B) a transesterification catalyst and (C) a thermoplastic resin and as necessary, further adding a compound having two or more kinds of hydroxy groups in one molecule thereto. In the composition, the thermoplastic resin (C) has transesterification reactivity with a compound having hydroxy group in the presence of the transesterification catalyst (B). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer, and more particularly to a novel thermoplastic elastomer composition having excellent flexibility, mechanical strength, moldability, oil resistance and heat resistance.

[0002]

2. Description of the Related Art In recent years, thermoplastic elastomers, which are rubber-like materials and do not require a vulcanization step and have the same moldability as thermoplastic resins, have been used in the automobile field, home electric appliance parts, wire coating materials, medical products. It is used in fields such as parts, footwear, and sundries.

Such a thermoplastic elastomer has alternating hard segments and soft segments in the copolymer chain as disclosed in, for example, JP-A-61-34050. Various types of thermoplastic elastomers such as polystyrene-based, polyolefin-based, polyurethane-based, polyester-based, and polyvinyl chloride-based thermoplastic elastomers have been developed and marketed depending on the type of each segment. Also, in each thermoplastic elastomer, various grades are manufactured by varying the ratio of each segment, from those having high flexibility to those having rigidity. In the case of a thermoplastic elastomer having a structure in which hard segments and soft segments are alternately contained in such a copolymer chain, a large amount of soft segments may be contained in order to obtain a flexible thermoplastic elastomer. Will be needed. Further, since the constraining component is a hard segment, it flows at high temperatures, but it has the drawback of being inferior in heat resistance (heat resistance in this case means physical properties at high temperatures). In addition, since the soft segment has low tensile strength and poor heat resistance and oil resistance, a flexible thermoplastic elastomer composition containing a large amount of such a soft segment also has low tensile strength, heat resistance and oil resistance. It has the drawback of being poor, and cannot be used for a wide variety of purposes. The technology disclosed as a conventional styrene-based elastomer has very good molding processability because the hard segment is polystyrene, but it is inferior in heat resistance, so it is suitable for a wide range of applications such as industrial mechanical parts. It has the drawback that it cannot be used.
Further, although the olefin-based elastomer has excellent heat resistance as compared with the styrene-based elastomer, it has a drawback that it is inferior in oil resistance due to its molecular structure. On the other hand, the polyester-based and polyamide-based thermoplastic elastomers are thermoplastic elastomers, but have the characteristics of being excellent in oil resistance and heat resistance because they have crystallinity in the hard segment, but low hardness and flexibility are obtained. It has the drawback that it cannot be done. In recent years, as a thermoplastic elastomer having excellent oil resistance and flexibility, an acrylic block body having a methacrylic block and an acrylic block has been disclosed as disclosed in Japanese Patent No. 2553134. Although excellent, it has a drawback that it is inferior in heat resistance like the styrene elastomer. Therefore, a material having low hardness, flexibility, and excellent heat resistance and oil resistance has not yet been known, and its development has been strongly demanded.

[0004]

The present invention relates to a thermoplastic elastomer, and more specifically, a novel thermoplastic elastomer composition having excellent flexibility, mechanical strength, moldability, oil resistance and heat resistance. Regarding

[0005]

Means for Solving the Problems The present inventors have (A)
A compound having (meth) acrylic copolymer, (B) transesterification catalyst, and (C) thermoplastic resin as essential components, and optionally (D) having at least two or more hydroxyl groups in one molecule. A thermoplastic elastomer composition characterized in that the thermoplastic resin (C) has transesterification reactivity with a compound having a hydroxyl group in the presence of a transesterification catalyst (B). The inventors have found that they are highly flexible, and have excellent mechanical strength, moldability, oil resistance, and heat resistance, and have completed the present invention.

That is, the present invention comprises (A) a (meth) acrylic copolymer, (B) a transesterification catalyst, and (C) a thermoplastic resin as essential components, and if necessary, (D) in one molecule. In a composition comprising a compound having at least two hydroxyl groups, the thermoplastic resin (C) has transesterification reactivity with the compound having a hydroxyl group in the presence of the transesterification catalyst (B). A thermoplastic elastomer composition (claim 1) characterized in that it is dynamically heat treated.
The thermoplastic elastomer composition (Claim 2) according to claim 2, wherein the (meth) acrylic polymer (A) is an acrylic polymer rubber and / or a modified rubber obtained by grafting a vinyl monomer to the rubber as a main component. 3. A thermoplastic elastomer composition (claim 3) according to claim 1 or 2, characterized in that it comprises a rubbery polymer (A).
Is composed of (a) a methacrylic polymer block and (b) a block copolymer (E) containing an acrylic polymer block, and the thermoplastic elastomer composition (1) according to claim 1 or 2, Claim 4), (meta)
The acrylic polymer (A) has at least one hydroxyl group, and the thermoplastic elastomer composition (Claim 5) according to claim 1, wherein the methacrylic polymer block (a) is methacrylic. Methyl acid 50-
100% by weight and other methacrylic acid ester copolymerizable therewith and / or other vinyl monomers 0-5
The thermoplastic elastomer composition according to claim 4 (claim 6), wherein the block copolymer (E) has a hydroxyl group in at least one polymer block. Claim 4 or 6
8. The thermoplastic elastomer composition according to claim 7, wherein the (meth) acrylic copolymer (A) is controlled by atom transfer radical polymerization. (Claim 8) The thermoplastic resin (C) is at least one resin selected from the group consisting of polymethylmethacrylate resin, polyester resin and polycarbonate resin. The thermoplastic elastomer composition (Claim 9) according to any one of claims 1 to 9 and a phosphorus compound (F), and the thermoplastic elastomer composition according to any one of Claims 1 to 9 (Claim 10), and the softening agent (G). )
Is contained in an amount of 0 to 300 parts by weight relative to 100 parts by weight of the (meth) acrylic polymer (A) (claim 1).
Regarding 1).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention comprises (A) a (meth) acrylic copolymer, (B) a transesterification catalyst, and (C) a thermoplastic resin as essential components, and optionally (D). A thermoplastic resin (C) in the presence of a transesterification catalyst (B), which is obtained by reacting a composition obtained by mixing a compound having at least two or more hydroxyl groups in one molecule. , A thermoplastic elastomer composition having a transesterification reactivity with a compound having a hydroxyl group. Although not particularly limited, the (meth) acrylic copolymer (A) reacts with the thermoplastic resin (C) by dynamically performing heat treatment, and the (meth) acrylic polymer partially crosslinks in some cases. Is preferable in order to obtain a thermoplastic elastomer having improved physical properties. By reacting the (meth) acrylic polymer (A) with the thermoplastic resin (C), heat resistance and mechanical strength are improved, and by itself partially crosslinking, more rubber elasticity is imparted. A thermoplastic elastomer can be obtained.

<(Meth) acrylic polymer (A)> The form of the (meth) acrylic polymer (A) that can be used in the present invention is a random copolymer, an alternating copolymer, a branch portion and a trunk portion. Comb graft copolymer containing, block copolymer,
Core-shell particle type graft copolymer containing an inner layer portion (core portion) and an outer layer portion (shell portion), and methacrylic acid containing an acrylate ester in the presence of an inner layer portion (core portion) composed of an acrylate ester and a methacrylate ester. A copolymer obtained by multi-step additional polymerization of an acid ester,
A copolymer (gradient copolymer) obtained by additional polymerization of a monomer mixture consisting of acrylic acid ester and methacrylic acid ester while changing the composition of acrylic acid ester and methacrylic acid ester in multiple stages, a central part, and Examples thereof include a three-layer core-shell particle type graft copolymer containing an intermediate layer part and an outer layer part. These can be used alone or in combination of two or more. These are used in accordance with polymerization easiness, availability, physical properties of the resulting composition, etc., and random copolymers and alternating copolymers are used in terms of polymerization easiness, availability, physical properties of the obtained composition, and the like. Preferably, the block copolymerization is carried out in that it can be preferentially reacted with a certain part of the polymer, compatibility with the thermoplastic resin (C), handleability during processing, physical properties of the resulting composition and the like. Coalescence is more preferred. The (meth) acrylic polymer (A) is a polymer obtained by polymerizing a monomer containing a (meth) acrylic acid ester as a main component, and contains 50 to 100% by weight of a (meth) acrylic acid ester and It is preferably composed of 0 to 50% by weight of a copolymerizable vinyl monomer.

Examples of the methacrylic acid ester constituting the (meth) acrylic polymer (A) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and methacrylic acid. Acid-n-butyl, isobutyl methacrylate,
Methacrylic acid-t-butyl, methacrylic acid-n-pentyl, methacrylic acid-n-hexyl, cyclohexylmethacrylate, methacrylic acid-n-heptyl, methacrylic acid-n-octyl, methacrylic acid-2 -Ethylhexyl, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, benzyl methacrylate, isobornyl methacrylate, methacrylate-2
-Methoxyethyl, methacrylic acid-3-methoxybutyl, methacrylic acid-2-hydroxyethyl, methacrylic acid-2-hydroxypropyl, stearyl methacrylic acid, glycidyl methacrylic acid, methacrylic acid-
2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethyl methacrylate, methacrylic acid-2- Trifluoromethylethyl, methacrylic acid-2-perfluoroethylethyl, methacrylic acid-2-perfluoroethyl-2
-Perfluorobutylethyl, 2-perfluoroethylmethacrylate, perfluoromethylmethacrylate, diperfluoromethylmethylmethacrylate, -2-perfluoromethyl-2-perfluoroethylmethylmethacrylate, meta Examples thereof include 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl methacrylate and 2-perfluorohexadecylethyl methacrylate.

These may be used alone or in combination of two or more. Since the crosslinking reaction proceeds by volatilizing or removing the low molecular weight alcohol component generated by transesterification, it is preferable that the boiling point of the low molecular weight alcohol component derived from the monomer used for the polymerization is 200 ° C. or less, It is more preferably 150 ° C. or lower. Among these, methyl methacrylate is preferable in terms of cost and availability, and -t-butyl methacrylate and 2-hydroxyethyl methacrylate are preferable in terms of reactivity of transesterification reaction.

Examples of the acrylic acid ester constituting the (meth) acrylic polymer (A) include methyl acrylate, ethyl acrylate, -n-propyl acrylate, isopropyl acrylate, -n-butyl acrylate, Isobutyl acrylate, -t-butyl acrylate,
Acrylic acid-n-pentyl, Acrylic acid-n-hexyl, Acrylic acid cyclohexyl, Acrylic acid-n-heptyl, Acrylic acid-n-octyl, Acrylic acid-2-ethylhexyl, Acrylic acid nonyl, Acrylic acid decyl,
Dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, acrylate -3
-Methoxybutyl, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, -2-acrylic acid
Aminoethyl, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-peracrylic acid Fluorobutylethyl, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluoroacrylate Hexylethyl, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl acrylate and the like can be mentioned.

These may be used alone or in combination of two or more. Since the crosslinking reaction proceeds by volatilizing or removing the low molecular weight alcohol component generated by transesterification, it is preferable that the boiling point of the low molecular weight alcohol component derived from the monomer used for the polymerization is 200 ° C. or less, It is more preferably 150 ° C. or lower. Among these, acrylic-n-butyl butyl is preferable in terms of availability and compression set and rubber elasticity of the obtained composition, and ethyl acrylate and acrylic acid 2 are preferable in terms of oil resistance of the obtained composition. -Methoxyethyl is preferable, and in terms of the reactivity of the transesterification reaction, -t-butyl acrylate, 2-hydroxyethyl acrylate,
Is preferred.

Examples of vinyl monomers copolymerizable with the (meth) acrylic acid ester constituting the (meth) acrylic polymer (A) include carboxylic acid compounds, aromatic alkenyl compounds and vinyl cyanide compounds. , Conjugated diene compounds, halogen-containing unsaturated compounds, silicon-containing saturated compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds, maleimide compounds, and the like. Examples of the carboxylic acid compound include methacrylic acid and acrylic acid.

Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene and the like.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.

As the conjugated diene compound, for example,
Examples thereof include butadiene and isoprene.

Examples of the halogen-containing unsaturated compound include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, vinylidene fluoride and the like.

Examples of the silicon-containing unsaturated compound include vinyltrimethoxysilane and vinyltriethoxysilane.

Examples of the unsaturated carboxylic acid compound include maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, and the like.

Examples of vinyl ester compounds include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate and the like.

Examples of the maleimide compound include:
Maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide and the like can be mentioned. These can be used alone or in combination of two or more.
These vinyl monomers should preferably be selected from the viewpoints of adjusting the glass transition temperature required for the (meth) acrylic polymer (A) and compatibility with the thermoplastic resin (C). You can

The number average molecular weight of the (meth) acrylic polymer (A) is not particularly limited, but is preferably 500 to 500,000, more preferably 5000 to 400,000. If the number average molecular weight is small, the viscosity is low, and if the number average molecular weight is large, the viscosity tends to be high, and therefore the viscosity is set according to the required processing characteristics. The molecular weight is measured in terms of polystyrene by the GPC method using chloroform as a mobile phase and a polystyrene gel column. When the (meth) acrylic polymer (A) is composed of a random copolymer or an alternating copolymer, it is preferably composed of an acrylic polymer rubber, and in terms of compatibility with the thermoplastic resin (C), It is also preferable to use a rubber-like polymer whose main component is a modified rubber obtained by grafting a vinyl monomer on the rubber. Further, the glass transition temperature in this case is preferably 50 ° C. or lower, more preferably 25 ° C. or lower, further preferably 0 ° C. in view of compression set of the composition, rubber elasticity and the like.
It is the following. When the glass transition temperature of (A) is higher than 50 ° C, compression set and rubber elasticity tend to be poor.

Examples of vinyl monomers include acrylic acid esters, methacrylic acid esters, carboxylic acid compounds, aromatic alkenyl compounds, vinyl cyanide compounds, conjugated diene compounds, halogen-containing unsaturated compounds,
Silicon-containing unsaturated compound, unsaturated dicarboxylic acid compound,
Examples thereof include vinyl ester compounds and maleimide compounds. Examples of the acrylic acid ester include the acrylic acid ester that constitutes the above-mentioned (meth) acrylic copolymer, and they can be used alone or in combination of two or more kinds. Among these,
Acrylic-n-butyl butyl is preferable in terms of availability and compression set and rubber elasticity of the obtained composition, and ethyl acrylate and 2-methoxyethyl acrylate are preferable in terms of oil resistance of the obtained composition. , T-butyl acrylate and 2-hydroxyethyl acrylate are preferable from the viewpoint of the reactivity of the transesterification reaction.

Examples of the methacrylic acid ester include the methacrylic acid ester constituting the above-mentioned (meth) acrylic copolymer, and they can be used alone or in combination of two or more kinds. Among these, methyl methacrylate is preferable in terms of cost and availability, and in terms of reactivity of transesterification reaction,
Preference is given to -t-butyl methacrylate and 2-hydroxyethyl methacrylate. Examples of the carboxylic acid compound include methacrylic acid and acrylic acid.

Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene and the like.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.

As the conjugated diene compound, for example,
Examples thereof include butadiene and isoprene.

Examples of the halogenated unsaturated compound include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, vinylidene fluoride and the like.

Examples of the silicon-containing unsaturated compound include vinyltrimethoxysilane and vinyltriethoxysilane.

Examples of unsaturated dicarboxylic acid compounds include maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, and the like.

Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate and the like.

Examples of maleimide compounds include:
Maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl maleimide and the like can be mentioned.

These can be used alone or in combination of two or more. Vinyl monomers are used to adjust the glass transition temperature, cohesive strength and processability of rubber-like polymers,
From the viewpoint of compatibility with the thermoplastic resin (C) and compatibility with a compounding agent such as a filler optionally mixed with the elastomer composition, a preferable one can be selected.

The amount of the vinyl-based monomer to be grafted on the rubber is not particularly limited, and the amount which gives the desired physical properties can be selected. The amount of the vinyl-based monomer is 0 to 100% by weight of the acrylic polymer rubber.
50% by weight is preferred.

As the acrylic polymer rubber, a rubber obtained by polymerizing a monomer containing an acrylic ester as a main component can be used without particular limitation.

Examples of acrylic acid esters include:
The acrylic acid ester that constitutes the (meth) acrylic copolymer described above can be used, and these can be used alone or in combination of two or more.

Since the crosslinking reaction proceeds by volatilizing or removing the low molecular weight alcohol component generated by transesterification, the boiling point of the low molecular weight alcohol component derived from the monomer used for the polymerization is 200 ° C. or lower. Is preferable, and it is more preferable that the temperature is 150 ° C. or lower. Among these, acrylic-n-butyl butyl is preferable in terms of availability and compression set and rubber elasticity of the obtained composition, and ethyl acrylate and 2-methoxyethyl acrylate are preferable in terms of oil resistance obtained. From the viewpoint of reactivity of transesterification reaction, -t-butyl acrylate and 2-hydroxyethyl acrylate are preferable.

It is also possible to use an acrylic polymer rubber in which a polyfunctional monomer such as divinylbenzene or allyl methacrylate is introduced.

As the acrylic polymer rubber, any conventionally known acrylic rubber can be used. As the acrylic rubber, 2-chloroethyl vinyl ether, methyl vinyl ketone, acrylic acid, a monomer made of ethyl acrylate and / or acryl-n-butyl acrylate,
Examples thereof include acrylic rubber obtained by copolymerizing a small amount of one or more kinds of other monomers such as acrylonitrile and butadiene. When the (meth) acrylic polymer (A) is a block copolymer (E), a polymer block (a) containing a methacrylic monomer as a main component and a polymer block containing an acrylic monomer as a main component. It is a block copolymer containing at least one united block (b).

The structure of the block copolymer (E) is a linear block copolymer or a branched (star) block copolymer, and may be a mixture thereof. The structure of such a block copolymer is properly selected according to the required characteristics such as processing characteristics and mechanical characteristics of the thermoplastic resin composition.

The block copolymer (E) is an ab type diblock copolymer, an abb type triblock copolymer, a bab type triblock copolymer, (Ab)
It is at least one block copolymer selected from n-type multi-block copolymers. Among these, in view of ease of processing and handling, balance between hardness and mechanical strength, compression set, compatibility with thermoplastic resin (C), and the like, a
A -b type diblock copolymer, an aba type triblock copolymer, or a mixture thereof is preferable.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the block copolymer (E) measured by gel permeation chromatography is not particularly limited, but is 1.8 or less. Is preferred,
It is more preferably 1.5 or less. When Mw / Mn exceeds 1.8, the homogeneity of the block copolymer tends to decrease.

The composition ratio of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the block copolymer (E) is such that the block (a) is 5 to 95% by weight and the block (b) is ) Is 95 to 5% by weight, and in terms of compression set and rubber elasticity of the resulting elastomer composition,
Preferably, (a) is 10 to 80% by weight, and (b) is 90%.
Is about 20% by weight, and more preferably 20% by weight of (a).
˜70 wt%, (b) is 80-30 wt%.
When the proportion of (a) is less than 5% by weight, the handling property during molding and the compatibility with the thermoplastic resin (C) tend to be lowered,
When the proportion of (b) is less than 10% by weight, the compression set and rubber elasticity of the elastomer composition tend to decrease.

The methacrylic polymer block (a) constituting the block copolymer (E) is a block obtained by polymerizing a monomer containing methacrylic acid ester as a main component, and the methacrylic acid ester 50 -100% by weight and 0 to 50% by weight of a vinyl monomer copolymerizable therewith are preferable.

Examples of the methacrylic acid ester constituting (a) include methyl methacrylic acid, ethyl methacrylic acid, n-propyl methacrylic acid, isopropyl methacrylic acid, n-butyl methacrylic acid, and methacrylic acid. Isobutyl acrylate, tert-butyl methacrylate, methacrylic acid-n-pentyl, methacrylic acid-n-
Hexyl, cyclohexyl methacrylate, -n-heptyl methacrylate, -n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate,
Phenyl methacrylate, toluyl methacrylate, benzyl methacrylate, isobornyl methacrylate,
Methacrylic acid-2-methoxyethyl, methacrylic acid-
3-methoxybutyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ- (methacryloyloxypropyl) trimethoxy Silane, γ- (methacryloyloxypropyl) dimethoxymethyl silane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethyl methacrylate, -2-trifluoromethylethyl methacrylate, -2-perfluoroethyl methacrylate Ethyl, methacrylic acid-2-perfluoroethyl-
2-perfluorobutylethyl, methacrylic acid-2-perfluoroethyl, methacrylic acid perfluoromethyl, methacrylic acid diperfluoromethylmethyl, methacrylic acid-2-perfluoromethyl-2-perfluoroethylmethyl, Examples thereof include 2-perfluorohexylethyl methacrylate, 2-perfluorodecylethyl methacrylate, and 2-perfluorohexadecylethyl methacrylate. These alone or these 2
Used in combination of two or more species. Since the crosslinking reaction proceeds by volatilizing or removing the low molecular weight alcohol component generated by transesterification, it is preferable that the boiling point of the low molecular weight alcohol component derived from the monomer used for the polymerization is 200 ° C. or less, It is more preferably 150 ° C. or lower. Among these, methyl methacrylate is preferable in terms of cost and availability, and -t-butyl methacrylate and 2-hydroxyethyl methacrylate are preferable in terms of reactivity of transesterification reaction.

Examples of the vinyl monomer copolymerizable with the methacrylic acid ester which constitutes (a) include methyl acrylate, ethyl acrylate, -n-propyl acrylate, isopropyl acrylate, acrylate- n-butyl, isobutyl acrylate, t-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, acrylate- 2-ethylhexyl,
Nonyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, acrylic acid
-2-methoxyethyl, acrylic acid-3-methoxybutyl,
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxy Methylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutyl acrylate Ethyl, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl acrylate, Ak Methacrylic acid; Le acid 2 perfluorodecyl ethyl, acrylate esters such as acrylic acid-2-perfluoroalkyl-hexadecyl ethyl
Carboxylic acid compounds such as acrylic acid; aromatic alkenyl compounds such as styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene; acrylonitrile,
Vinyl cyanide compounds such as methacrylonitrile; conjugated diene compounds such as butadiene and isoprene; halogen-containing unsaturated compounds such as vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene and vinylidene fluoride; vinyltrimethoxysilane, Silicon-containing unsaturated compounds such as vinyltriethoxysilane; unsaturated dicarboxylic acid compounds such as maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid; acetic acid Vinyl ester compounds such as vinyl, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, Hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, the various vinyl monomers such as maleimide compounds such as cyclohexyl maleimide and the like. These may be used alone or in combinations of two or more. These vinyl monomers are preferable from the viewpoint of adjusting the glass transition temperature required for the block (a), compatibility with the block (b), compatibility with the thermoplastic resin (C) to be combined, and the like. You can choose.

The glass transition temperature of (a) is 25 ° C. or higher, preferably 40 ° C. or higher, and more preferably 50 ° C. or higher. When the glass transition temperature is lower than 25 ° C., the handling property during molding tends to deteriorate, and the balance between hardness and strength of the obtained elastomer composition tends to deteriorate.

The acrylic polymer block (b) constituting the block copolymer (E) is a block obtained by polymerizing a monomer containing an acrylic ester as a main component,
It is preferably composed of 50 to 100% by weight of an acrylic acid ester and 0 to 50% by weight of a vinyl monomer copolymerizable therewith.

Examples of the acrylic acid ester constituting (b) include methyl acrylate, ethyl acrylate, acrylate-n-propyl acrylate, isopropyl acrylate, acrylate-n-butyl acrylate, isobutyl acrylate, acrylate- t-butyl, acrylic acid-n-pentyl, acrylic acid-n-hexyl, acrylic acid cyclohexyl, acrylic acid-n-heptyl, acrylic acid-n-octyl, acrylic acid-2-ethylhexyl, nonyl acrylate, decyl acrylate , Dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, -2-methoxyethyl acrylate, -3-methoxybutyl acrylate, -2-hydroxyethyl acrylate, -2-acrylic acid acrylate Hydroxypropyl, stearyl acrylate, glycidyl acrylate , 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, acrylic acid-2 -Trifluoromethylethyl, acrylic acid-2-perfluoroethylethyl, acrylic acid-2-perfluoroethyl-2-perfluorobutylethyl, acrylic acid 2-perfluoroethyl, acrylic acid perfluoromethyl, acrylic acid diper Fluoromethylmethyl, acrylate-2-perfluoromethyl-2-perfluoroethylmethyl, acrylate-2-perfluorohexylethyl, acrylate-2-perfluorodecylethyl, acrylate-2-perfluorohexadecylethyl And so on. These may be used alone or in combinations of two or more. Since the crosslinking reaction proceeds by volatilizing or removing the low molecular weight alcohol component generated by transesterification, it is preferable that the boiling point of the low molecular weight alcohol component derived from the monomer used for the polymerization is 200 ° C. or less, It is more preferably 150 ° C. or lower. Among these, acrylic-n-butyl butyl is preferable from the viewpoints of availability and compression set and rubber elasticity of the resulting composition, and ethyl acrylate and acrylic acid 2-acrylate are preferable from the viewpoint of oil resistance of the resulting composition. Methoxyethyl is preferred, and acrylic acid-t-
Butyl and 2-hydroxyethyl acrylate are preferred. Examples of the vinyl-based monomer copolymerizable with the acrylic ester forming the block (b) include methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, and methacrylic acid. Acid-n-butyl, isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate,
Methacrylic acid-n-hexyl, cyclohexylmethacrylate, methacrylic acid-n-heptyl, methacrylic acid
-n-octyl, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, benzyl methacrylate, isobornyl methacrylate, methacrylic acid Acid-2-methoxyethyl,
Methacrylic acid-3-methoxybutyl, methacrylic acid-
2-hydroxyethyl, 2-hydroxypropyl methacrylate, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ-
(Methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethyl methacrylate, methacrylic acid-2-trifluoromethylethyl, methacrylic acid Acid-2-perfluoroethylethyl, methacrylic acid 2
-Perfluoroethyl-2-perfluorobutylethyl,
Methacrylic acid-2-perfluoroethyl, methacrylic acid perfluoromethyl, methacrylic acid diperfluoromethylmethyl, methacrylic acid-2-perfluoromethyl
Methacrylic acid esters such as 2-perfluoroethylmethyl, methacrylic acid-2-perfluorohexylethyl, methacrylic acid-2-perfluorodecylethyl, methacrylic acid-2-perfluorohexadecylethyl; methacrylic acid , Carboxylic acid compounds such as acrylic acid; aromatic alkenyl compounds such as styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; conjugation of butadiene and isoprene Diene compounds; halogen-containing unsaturated compounds such as vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, vinylidene fluoride; silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride Unsaturated dicarboxylic acid compounds such as maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid; vinyl acetate,
Vinyl ester compounds such as vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide,
Examples thereof include various vinyl-based monomers such as maleimide-based compounds such as octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide. These may be used alone or in combinations of two or more. These vinyl-based monomers are used for adjusting the glass transition temperature required for the block (b), compatibility with the block (a), and combination with the thermoplastic resin (C). A preferable one can be selected from the viewpoint of compatibility and the like. (B)
Has a glass transition temperature of preferably 50 ° C. or lower, more preferably 25 ° C. or lower, and further preferably 0 ° C.
It is the following. If the glass transition temperature is higher than 50 ° C., the compression set, rubber elasticity, etc. of the resulting thermoplastic elastomer will tend to decrease.

The block copolymer (E) can be used in various block forms by combining the block (a) and the block (b), and can be used alone or in combination of two or more kinds. It can be appropriately selected depending on the reactivity of the transesterification reaction, the characteristics of the obtained thermoplastic elastomer, and the like.

The method for producing the block copolymer (E) is not particularly limited, but controlled polymerization is preferably used. Examples of the controlled polymerization include living anionic polymerization, radical polymerization using a chain transfer agent, and recently developed living radical polymerization. Living radical polymerization is preferable from the viewpoint of controlling the molecular weight and structure of the block copolymer.

Living radical polymerization is a radical polymerization in which the activity at the polymerization end is maintained without loss. In a narrow sense, living polymerization indicates polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the activated one is in an equilibrium state. . The definition in the present invention is also the latter. Living radical polymerization has been actively studied in various groups in recent years. Examples thereof include those using a chain transfer agent such as polysulfide, cobalt porphyrin complex (J. Am. Chem. Soc. 1994, 1).
16, 7943) or a radical scavenger such as a nitroxide compound (Macromolecules,
1994, 27, 7228), an atom transfer radical polymerization using an organic halide as an initiator and a transition metal complex as a catalyst (Atom Transfer Radical Po
lymerization: ATRP) and the like. In the present invention, which of these methods is used is not particularly limited, but atom transfer radical polymerization is preferable from the viewpoint of easy control.

Atom transfer radical polymerization is carried out by using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having an element of Group 8, 9, 10 or 11 of the periodic table as a central metal as a catalyst. To be done. (For example,
Matyjaszewski et al. Am. Chem.
Soc. 1995, 117, 5614, Macromo
leules 1995, 28, 7901, Scie
nce 1996, 272, 866, or Sawa
moto et al., Macromolecules 1995,
28, 1721). According to these methods, the polymerization generally has a very high polymerization rate, and although the polymerization is a radical polymerization in which a termination reaction such as a coupling between radicals is likely to occur, the polymerization proceeds in a living manner and has a narrow molecular weight distribution Mw / Mn.
= 1.1-1.5, a polymer having a molecular weight of about 1.1 to 1.5 can be obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

In the atom transfer radical polymerization method, as the organic halide or sulfonyl halide compound used as an initiator, a monofunctional, difunctional or polyfunctional compound can be used. These may be used properly according to the purpose, but in the case of producing a diblock copolymer, a monofunctional compound is preferable, and an ab-a type triblock copolymer or a b-a-b type triblock copolymer is preferable. When manufacturing a triblock copolymer, it is preferable to use a bifunctional compound, and when manufacturing a branched block copolymer, it is preferable to use a polyfunctional compound.

Examples of the monofunctional compound include compounds of the formula: C ₆ H ₅ -CH ₂ X, C ₆ H ₅ -C (H) (X) -CH ₃ , C ₆ H ₅ -C (X) (CH ₃ ) ₂ , R ¹ -C (H) (X) -COOR ² , R ¹ -C (CH ₃ ) (X) -COOR ² , R ¹ -C (H) (X) -CO-R ² , R _{^{1 -C (CH 3) (X}} ) -CO-R 2, R 1 -C 6 H 4 -SO 2 X, ( wherein, C ₆ H ₄ is a phenylene group (ortho-substituted, meta-substituted, any para-substituted R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and X is chlorine, bromine, or iodine. R ² represents a monovalent organic group having 1 to 20 carbon atoms) and the like.

Examples of the bifunctional compound include compounds represented by the formula: X-CH ₂ -C ₆ H ₄ -CH ₂ -X, X-CH (CH ₃ ) -C ₆ H ₄ -CH (CH ₃ ) -X, _{X-C (CH 3) 2} -C 6 H 4 -C (CH 3) 2 -X, X-CH (COOR 3) - (CH 2) n -CH (COOR 3) -
_{X, X-C (CH 3} ) (COOR 3) - (CH 2) n -C (CH 3)
^{(COOR 3) -X, X-} CH (COR 3) - (CH 2) n -CH (COR 3) -X, X-C (CH 3) (COR 3) - (CH 2) n -C (CH ₃ )
^{(COR 3) -X, X-} CH 2 -CO-CH 2 -X, X-CH (CH 3) -CO-CH (CH 3) -X, X-C (CH 3) 2 -CO-C ( _{CH 3) 2 -X, X-} CH (C 6 H 5) -CO-CH (C 6 H 5) -X, X-CH 2 -COO- (CH 2) n -OCO-CH 2 -X, X _{-CH (CH 3) -COO- (CH} 2) n -OCO-CH (C
_{H 3) -X, X-C} (CH 3) 2 -COO- (CH 2) n -OCO-C (C
_{H 3) 2 -X, X-} CH 2 -CO-CO-CH 2 -X, X-CH (CH 3) -CO-CO-CH (CH 3) -X, X-C (CH 3) 2 - _{CO-CO-C (CH 3} ) 2 -X, X-CH 2 -COO-C 6 H 4 -OCO-CH 2 -X, X-CH (CH 3) -COO-C 6 H 4 -OCO-CH (C
_{H 3) -X, X-C} (CH 3) 2 -COO-C 6 H 4 -OCO-C (CH 3) 2 -
X, X-SO ₂ -C ₆ H ₄ -SO ₂ -X, (In the formula, R ³ is an alkyl group having 1 to 20 carbon atoms, and 6 to 6 carbon atoms.
20 aryl group or a 7-20 carbon aralkyl group. C ₆ H ₄ is a phenylene group (ortho-substituted, meta-substituted,
Para may be substituted). C ₆ H ₅ represents a phenyl group. n represents an integer of 0-20. X represents chlorine, bromine, or iodine. ) And the like.

Examples of the polyfunctional compound include compounds represented by the formulas: C ₆ H _3- (CH ₂ -X) ₃ , C ₆ H _3- (CH (CH ₃ ) -X) ₃ , C ₆ H _3- (C (CH ₃ ) ₂ -X) ₃ , C ₆ H _3- (OCO-CH ₂ -X) ₃ , C ₆ H _3- (OCO-CH (CH ₃ ) -X) ₃ , C ₆ H _3- (OCO _{-C (CH 3) 2 -X)} 3, C 6 H 3 - (SO 2 -X) 3, ( wherein, C ₆ H ₃ is the position of the trisubstituted phenyl group (the substituent is 1
Position-6th place). X is chlorine, bromine,
Or represents iodine. ) And the like. When an organic halide having a functional group other than the one that initiates the polymerization or a sulfonyl halide compound is used, a polymer having a functional group introduced at the terminal can be easily obtained. Examples of such a functional group include an alkenyl group, a hydroxyl group, an epoxy group, an amino group, an amide group and a silyl group.

In the organic halide or sulfonyl halide compound which can be used as these initiators, the carbon to which the halogen is bonded is bonded to the carbonyl group or the phenyl group, and the carbon-halogen bond is activated. Polymerization begins. The amount of the initiator used may be determined from the ratio with the monomer in accordance with the required molecular weight of the block copolymer. That is, the molecular weight of the block copolymer can be controlled depending on the number of molecules of the monomer used per one molecule of the initiator.

The transition metal complex used as the catalyst for the atom transfer radical polymerization is not particularly limited, but as preferable ones, monovalent and zerovalent copper, divalent ruthenium, divalent iron and divalent nickel. The complex of is mentioned. Among these, a copper complex is more preferable in terms of cost and reaction control.

As the monovalent copper compound, for example, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide,
Examples include cuprous oxide and cuprous perchlorate. When using a copper compound, in order to increase the catalytic activity 2,2'-
Bipyridyl and its derivative, 1,10-phenanthroline and its derivative, polyamine such as tetramethylethylenetriamine (TMEDA), pentamethyldiethylenetriamine, and hexamethyl (2-aminoethyl) amine may be added as a ligand. Also, 2
A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also preferable as the catalyst.
When using a ruthenium compound as a catalyst, you may add aluminum alkoxide as an activator.
Further, divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ) and divalent nickel bistriphenylphosphine complex (NiCl ₂ (PP
h ₃ ) ₂ ) and a bivalent nickel bistributylphosphine complex (NiBr ₂ (PBu ₃ ) ₂ ) are also preferable as the catalyst. The amounts of the catalyst, the ligand and the activator used are not particularly limited, but may be appropriately determined depending on the relationship between the amount of the initiator, the monomer and the solvent used and the required reaction rate.

The atom transfer radical polymerization can be carried out without solvent (bulk polymerization) or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Solvents; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol; nitrile solvents such as acetonitrile, propionitrile, benzonitrile; ester solvents such as ethyl acetate, butyl acetate; ethylene Examples thereof include carbonate solvents such as carbonate and propylene carbonate. These may be used alone or in combination of two or more. As described above, when the polymerization is carried out without a solvent, bulk polymerization is performed. On the other hand, when a solvent is used, the amount to be used may be appropriately determined from the relationship between the viscosity of the entire system and the required stirring efficiency (that is, reaction rate).

The polymerization can be carried out at room temperature to 200 ° C., preferably 50 to 150 ° C. In order to produce a block copolymer by the above-mentioned polymerization, a method of sequentially adding monomers, a method of polymerizing the next block by using a pre-synthesized polymer as a polymer initiator, and a reaction of separately polymerized polymers There is a method of combining by. These methods may be selectively used according to the purpose, but from the viewpoint of simplicity of the production process, the method of sequentially adding the monomers is preferable.

<Transesterification Catalyst (B)> The thermoplastic elastomer composition of the present invention can be produced by utilizing the transesterification reaction of the (meth) acrylic polymer (A), and polycondensation as a catalyst. A catalyst or transesterification catalyst can be used. As the polycondensation catalyst and / or transesterification catalyst, those usually used when producing polyesters such as polyethylene terephthalate, polybutylene terephthalate, and unsaturated polyester can be used. As these catalysts, hydroxides of alkali metals and alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; lithium aluminum hydride, sodium borohydride, tetraborohydride Alkali metal salts of hydrides of boron and aluminum such as methylammonium, alkaline earth metal salts, quaternary ammonium salts; hydrogen compounds of alkali metals and alkaline earth metals such as lithium hydride, sodium hydride and calcium hydride Alkali and alkaline earth metal alkoxides such as lithium methoxide, sodium ethoxide, calcium methoxide; lithium phenoxide, sodium phenoxide, magnesium phenoxide, LiO—Ar—
Alyl oxides of alkali metals and alkaline earth metals such as OLi and NaO-Ar-ONa (Ar is an aryl group); Organic acid salts of alkali metals and alkaline earth metals such as lithium acetate, calcium acetate and sodium benzoate; Oxidation Zinc compounds such as zinc, zinc acetate and zinc phenoxide; boron oxide, boric acid, sodium borate,
Trimethyl borate, tributyl borate, triphenyl borate, (R1R2R3R4) NB (R1R2R3R4) or (R1R2R3R4) PB (R1R2R3R4) ammonium borate or phosphonium borate (R1, R2, R3, R4 are the above-mentioned Compounds), such as boron compounds; silicon compounds such as silicon oxide, sodium silicate, tetraalkyl silicon, tetraaryl silicon, diphenyl-ethyl-ethoxy silicon; germanium oxide, germanium tetrachloride, germanium ethoxide, germanium. Compounds of germanium such as phenoxide; tin compounds bonded to an alkoxy group or aryloxy group such as tin oxide, dialkyltin oxide, dialkyltin carboxylate, tin acetate, ethyltin tributoxide, organotin Compounds such as tin compounds; lead oxides, lead acetates, lead carbonates, basic carbonates, lead compounds such as lead and organic lead alkoxides or aryl oxides; quaternary ammonium salts, quaternary phosphonium salts, Onium compounds such as quaternary arsonium salts; antimony compounds such as antimony oxide and antimony acetate; manganese compounds such as manganese acetate, manganese carbonate and manganese borate; titanium oxide, titanium alkoxides or aryl oxides, etc. Titanium compounds; examples include catalysts such as zirconium acetate, zirconium oxide, zirconium alkoxides or aryloxides, zirconium compounds such as zirconium acetylacetone. When a catalyst is used, these catalysts can be used alone or in combination of two or more kinds. Among these, from the viewpoint of reactivity, titanium compounds, tin compounds, antimony compounds, zirconium compounds, and zinc compounds are preferable, and in terms of reactivity control, etc.
Titanium compounds are more preferred. The amount of these catalysts used may be appropriately determined, but for example, an amount of 0.00001 to 0.01 part with respect to the (meth) acrylic polymer (A) is preferably used, and 0.00005 to 0.001. The amount of parts is more preferably used.

<Thermoplastic Resin (C)> As the thermoplastic resin (C) which can be used in the present invention, the (meth) acrylic copolymer (A) reacts with the thermoplastic resin (C) and Since it is preferable that the (meth) acrylic polymer is partially crosslinked by the above in order to obtain a thermoplastic elastomer having improved physical properties, a compound having a hydroxyl group in the presence of a transesterification catalyst (B) is used. It is preferable to have transesterification reactivity. (The compound having the hydroxyl group is not particularly limited, and will be described later in 1
A compound (D) having at least two or more hydroxyl groups in the molecule can be mentioned). The thermoplastic resin (C) is not particularly limited, and examples thereof include polymethylmethacrylate resin, polycarbonate resin, polyester resin, and the like. These may be used alone or in combination of two or more. More specifically, the polymethylmethacrylate resin is not particularly limited as long as it is a resin containing methyl methacrylate as a main component, and polymethylmethacrylate resin in which α-methylstyrene, maleic anhydride, etc. are copolymerized. Can be As the polycarbonate resin, polycarbonate such as bisphenol A type aromatic polycarbonate; alloy of polycarbonate and acrylonitrile-butadiene-styrene copolymer,
Alloy of polycarbonate and polybutylene terephthalate, Alloy of polycarbonate and polyarylate,
Examples thereof include polycarbonate alloys such as alloys of polycarbonate and polymethylmethacrylate. Examples of polyester resins include aliphatic polyesters such as polyglycolic acid, polylactic acid, polycaprolactone, and polyethylene succinate; polyethylene terephthalate, polytrimethylene terephthalate,
Semi-aromatic polyesters such as polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, ethylene terephthalate / cyclohexane dimethylene terephthalate copolymer, thermotropic liquid crystal polymer type 2; amorphous polyarylate,
Examples thereof include wholly aromatic polyesters such as thermotropic liquid crystal polymer type 1 and thermotropic liquid crystal polymer type 2, alloys of polybutylene terephthalate and polyphenylene ether, and the like. Others, acrylonitrile-
At least one vinyl-based monomer selected from the group consisting of butyl acrylate-styrene copolymers, aromatic alkenyl compounds such as methyl methacrylic acid styrene copolymer resins, vinyl cyanide compounds and (meth) acrylic acid esters. 70 to 100% by weight of the copolymer, copolymerizable with these vinyl monomers, for example, ethylene, propylene,
Other vinyl monomers such as vinyl acetate and / or diene monomers such as butadiene and isoprene 0-3
Homopolymer or copolymer obtained by polymerization with 0% by weight; polyvinyl chloride copolymer such as vinyl chloride-vinyl acetate-maleic anhydride copolymer; polyvinyl chloride and methyl methacrylic acid butadiene-styrene Polyvinyl chloride alloys such as alloys with copolymers, alloys with polyvinyl chloride and acrylic copolymers; polyvinylidene chloride copolymers such as vinylidene chloride-acrylic acid ester copolymers, ethylene-methyl acrylate copolymers Polymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-acrylic acid copolymer, Of ethylene and acrylic acid or methacrylic acid Ethylene and polar homopolymers such as copolymers with group salts, maleic anhydride modified polyethylene, maleic anhydride modified ethylene-ethyl acrylate copolymer, ethylene-dimethylaminomethyl methacrylate copolymer, ethylene-vinyl alcohol copolymer, etc. Monomers having transesterification reactivity such as copolymers with polymers, polymer alloys of polypropylene and rubber, functionalized polypropylenes such as maleic acid modified polypropylene, and impact-resistant polystyrenes such as polystyrene-acrylic rubber polymer alloys. And an alloy with a thermoplastic resin having transesterification reactivity. In the present invention, the thermoplastic resin (C) is not limited to these,
Various thermoplastic resins can be widely used, (meta)
A thermoplastic elastomer having transesterification reactivity such as an acrylic elastomer or an ester elastomer may be used. Of these various thermoplastic resins, those having a softening temperature of 100 ° C. or higher and a melting temperature of 300 ° C. or lower are preferable. Among them, polymethylmethacrylate-based resin, polycarbonate-based resin, and polyester-based resin are preferable from the viewpoint of workability. Furthermore, a polyester resin is more preferable in terms of oil resistance and heat resistance of the obtained thermoplastic elastomer. Among them, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate,
Polyethylene naphthalate, polycyclohexane dimethylene terephthalate, and ethylene terephthalate / cyclohexane dimethylene terephthalate copolymer are preferred.

The blending amount of these thermoplastic resins (C) is preferably 5 to 1000 parts by weight, more preferably 10 to 500 parts by weight, based on 100 parts by weight of the (meth) acrylic polymer (A). Compounding amount of thermoplastic resin (C) is 10
If it is more than 100 parts by weight, the rubber elasticity and mechanical properties of the obtained thermoplastic elastomer tend to be deteriorated. When the amount of the thermoplastic resin (C) is less than 5 parts by weight, the heat resistance of the obtained thermoplastic elastomer tends to decrease.

<Compound (D) having at least two or more hydroxyl groups in one molecule> The compound (D) having a hydrosyl group usable in the present invention is not particularly limited, but ethylene glycol, 1, 2 may be used. -Propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2,4-pentadiol, 1,5- Pentanediol, 1,4-butenediol, 1,6-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,6-hexanediol, Diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol , Tetraethylene glycol, hexylene glycol 3,4, 1,3-butylene glycol, octanediol, 3,6-dimethyl-4
-Octene-3,6-diol, 2,5-dimethyl-3
-Hexyne-2,5-diol, 2,5-dimethyl-
2,5-hexanediol, isoprene glycol, 3
-Chloro-1,2-propanediol, 1,4-cyclohexanediol, cyclopentanol, 1,3-dihydroxyacetone, 1,4-dihydroxy-1,4-butanedisulfonic acid disodium salt, thioglycol, neopentyl glycol , Hexylene glycol, polyethylene glycol, polytetramethylene ether glycol, polypropylene glycol, 3-methyl-1,5-
Pentanediol, glycerin monoacetate, glycerin monobutyrate, glycerin-α-monomethyl ether, aliphatic divalent hydroxyl group-containing compound such as glycerin-α-monobutyl ether, catechol,
Aromatic divalent hydroxyls such as 1,4-dihydroxyanthraquinone, hydroquinone, 1,4-dihydroxynaphthalene, bisphenol A, bisphenol S, 2,3,5 trimethylhydroquinone, p-hydroxyphenethyl alcohol, protocatechuic acid and resorcin Group-containing compound, divalent hydroxyl group-containing polymer compound such as polyethylene oxide, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, aliphatic trivalent hydroxyl group-containing compound such as glycerin, Aromatic trivalent hydroxyl group-containing compounds such as 2,3,4-trihydroxybenzophenone, phloroglucinol, and lauryl gallate, and tetravalent aliphatic hydroxyl group-containing compounds such as pentaerythritol and diglycerin Things, sorbitol, polyglycerol, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, poly-para vinylphenol, polyvalent hydroxyl group-containing compound such as polyvinyl butyral and the like. These can be used alone or in combination of two or more. Among these, aliphatic compounds having a boiling point of 100 ° C. or higher are preferable, and aliphatic compounds having a boiling point of 150 ° C. or higher are more preferable from the viewpoint of handling during the reaction and availability. From the viewpoint of the reactivity of the transesterification reaction, secondary alcohols are preferable, and primary alcohols are more preferable. Further, it is preferable to use a polymer having excellent compatibility with the (meth) acrylic polymer (A). The valence of the hydroxyl group of the compound used may be appropriately selected from the viewpoint of the balance between hardness and mechanical strength of the resulting thermoplastic elastomer.

The above-mentioned compound (D) can be added as necessary and can be appropriately determined according to the compound (D) used, the balance between hardness and mechanical properties of the thermoplastic elastomer to be obtained, and compression set characteristics. However, for example, with respect to 100 parts by weight of the (meth) acrylic polymer (A),
1 to 200 parts by weight is preferable, and 1.0 to 150 parts by weight is more preferable. If the compounding amount of the compound (D) is more than 200 parts by weight, the balance between hardness and mechanical strength of the thermoplastic elastomer obtained tends to deteriorate. When the compounding amount of the compound (D) is less than 0.1 part by weight, it is preferable that the (meth) acrylic polymer (A) contains a (meth) acrylic polymer having at least one hydroxyl group. In this case, the hydroxyl group is derived from a monomer, and it is preferable that one or more hydroxyl groups are contained in one molecular chain. The upper limit of the content number is not particularly defined, but can be set according to the characteristics of the obtained cured product. When the number is less than 1 per 1 molecular chain, the compression set and rubber elasticity of the resulting thermoplastic elastomer composition tend to decrease. Also,
When the compounding amount of the compound (D) is less than 0.1 part by weight, the (meth) acrylic polymer (A) having a hydroxyl group can be set according to the obtained characteristics, but (meth) 30 to 1 in acrylic polymer (A)
00 (wt%) is preferably contained, and 50 to 100
It is more preferable that the content is wt%. When the content of the polymer (A) having a hydroxyl group is less than 30 (wt%), the rubber elasticity of the resulting thermoplastic elastomer tends to decrease. Further, when the (meth) acrylic polymer (A) is composed of a block copolymer (E) containing a methacrylic polymer block (a) and an acrylic polymer block (b), (a) or ( Having a hydroxyl group in either one of b) is preferable from the viewpoint of controlling the transesterification reaction.

<Phosphorus Compound (F)> In the production of the thermoplastic elastomer composition of the present invention, when the phosphorus compound (F) is used in combination with the transesterification catalyst, the heat resistance of the obtained thermoplastic elastomer composition is further improved. It is preferable in order to improve, further inactivate the catalyst used in the transesterification reaction, and to improve the compression set of the obtained thermoplastic elastomer. The amount of the phosphorus compound (F) used may be appropriately determined, but in the resulting thermoplastic elastomer composition, the molar ratio of phosphorus atom to metal atom of the polycondensation catalyst and / or the transesterification catalyst is M / P = 0. 000
It is preferable to add them in a ratio of 001 to 20. More preferably, M / P = 0.000005-1
0, more preferably M / P = 0.000005 to 5 (wherein M represents a metal atom of the polycondensation catalyst and / or the transesterification catalyst). Such a phosphorus compound is not particularly limited, and examples thereof include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, phosphoric acid ester and phosphorous acid ester, and these alone or Two or more kinds can be used in combination. Specifically, for example, phosphoric acid and phosphoric acid ester; trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridodecyl phosphate, trioctadecyl phosphate, dioctadecyl pentaerythrityl diphosphate, tris (2
-Triethyl phosphate such as -chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tricycloalkyl phosphate such as tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethyl Triaryl phosphates such as phenyldiphenyl phosphate, phosphites;
Trimethylphosphite, triethylphosphite, tributylphosphite, trioctylphosphite, tris (2-ethylhexyl) phosphite, trinonylphosphite, tridodecylphosphite, trioctadecylphosphite, didodecylpentaerythrityldiphosphite, Trialkyl phosphites such as tris (2-chloroethyl) phosphite, tris (2,3-dichloropropyl) phosphite, tricycloalkylphosphites such as tricyclohexylphosphite, triphenylphosphite, tricresylphosphite, Tris (ethylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (hydroxyphenyl) phosphite, tris (4-t-butylphenyl)
Triaryl phosphites such as phosphite, tris (2,4-di-t-butylphenyl) phosphite, phenyldidecylphosphite, diphenyldecylphosphite, diphenylisooctylphosphite, phenyldiisooctylphosphite, 2 -Arylalkyl phosphites such as ethylhexyl diphenyl phosphite and diphenyl nonyl phenyl phosphite, dioctadecyl pentaerythrityl diphosphite, bis (2,4
-Di-t-butylphenyl) pentaerythrityl diphosphite, bis (4,6-di-t-butyl-4-methylphenyl) pentaerythrityl diphosphite, bis (2,6-di-t-butyl) -4-Methylphenyl) pentaerythrityl diphosphite and the like can be mentioned. These can be used alone or in combination of two or more. Among these phosphorus compounds, phosphite ester is preferable from the viewpoint of heat resistance of the thermoplastic elastomer obtained.

The phosphorus compound (F) may be added at an arbitrary stage for the purpose of inactivating the catalyst used in the transesterification reaction, and it may be added at any stage. It is preferable to add it at any time thereafter. <Flexibility-imparting agent (G)> The flexibility-imparting agent (G) imparts flexibility to the thermoplastic elastomer composition to be produced and lowers its elastic modulus. Is a low molecular weight compound added to It can be added depending on the properties of the resulting thermoplastic elastomer composition. Although not particularly limited, for example, a plasticizer usually blended with a thermoplastic resin; a softening agent such as process oil; an oligomer; an animal oil,
Oil components such as vegetable oils; petroleum fractions such as kerosene, light oil, heavy oil, naphtha and the like. These may be used alone or 2
You may mix and use 1 or more types.

Examples of the softening agent include process oils, and more specifically, paraffin oil; naphthenic process oils; petroleum process oils such as aromatic process oils. As the plasticizer, for example,
Dimethyl phthalate, diethyl phthalate, di-n phthalate
-Butyl, di- (2-ethylhexyl) phthalate, diheptyl phthalate, diisodecyl phthalate, di-phthalate
Phthalic acid derivatives such as n-octyl, diisononyl phthalate, ditridecyl phthalate, octyldecyl phthalate, butylbenzyl phthalate and dicyclohexyl phthalate;
Isophthalic acid derivatives such as dimethyl isophthalate;
Tetrahydrophthalic acid derivatives such as di- (2-ethylhexyl) tetrahydrophthalic acid; dimethyl adipate, dibutyl adipate, di-n-hexyl adipate, di- (2-ethylhexyl) adipate, isononyl adipate, adipic acid Adipic acid derivatives such as diisodecyl and dibutyl diglycol adipate; Azelaic acid derivatives such as di-2-ethylhexyl azelate; Sebacic acid derivatives such as dibutyl sebacate; Dodecane-2
-Acid derivative; dibutyl maleate, di-2-maleate
Maleic acid derivatives such as ethylhexyl; Fumaric acid derivatives such as dibutyl fumarate; Trimellitic acid derivatives such as tris-2-ethylhexyl trimellitate; Pyromellitic acid derivatives; Citric acid derivatives such as acetyltributyl citrate;
Itaconic acid derivative; Oleic acid derivative; Ricinoleic acid derivative; Stearic acid derivative; Other fatty acid derivative; Sulfonic acid derivative; Phosphoric acid derivative; Glutaric acid derivative; Dibasic acids such as adipic acid, azelaic acid, phthalic acid, and glycol and monovalent Polyester plasticizers that are polymers with alcohols, glycol derivatives, glycerin derivatives, paraffin derivatives such as chlorinated paraffins, epoxy derivative polyester polymerization plasticizers, polyether polymerization plasticizers, ethylene carbonate, propylene carbonate, etc. Examples thereof include carbonate derivatives. In the present invention, the plasticizer is not limited to these,
Various plasticizers can be used, and those widely marketed as plasticizers for rubber can also be used. Examples of commercially available plasticizers include Thiokol TP (Morton), Adeka Sizer O-130P, C-79, UL-.
100, P-200, RS-735 (Asahi Denka Co., Ltd.) and the like. Examples of vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil,
Peanut oil, pine oil, tall oil and the like can be mentioned. In the above, it is preferable to use a polymer having excellent affinity with the (meth) acrylic polymer (A) or the thermoplastic resin (C). The adipic acid derivative, the phthalic acid derivative, the glutaric acid derivative, the trimellitic acid derivative, the pyromellitic acid derivative, the polyester-based plasticizer, the glycerin derivative, and the epoxy derivative, which are low-volatility plasticizers with little heat loss, are not particularly limited. Polyester polymerization plasticizer,
Polyether polymerization type plasticizers are preferably used.

In addition to the above-mentioned plasticizer and softener, a compound having one hydroxyl group in one molecule also serves as the flexibility-imparting agent (G) to impart flexibility to the resulting thermoplastic elastomer composition, or ) Acrylic polymer (A)
Can be added for the purpose of improving the compatibility between the resin and the thermoplastic resin (C). When a compound having one hydroxyl group in one molecule is used, it has a transesterification reactivity with the (meth) acrylic polymer (A) in the presence of the transesterification catalyst (B), and therefore has flexibility. And the like, and at the same time, bleeding out from the thermoplastic elastomer composition obtained can be suppressed, and therefore, it can be preferably used. Examples of the compound having one hydroxyl group in one molecule include n-amyl alcohol, isoamyl alcohol, isodecyl alcohol, isotridecyl alcohol, n-hexanol, methylamyl alcohol, n-
Heptanol, n-octanol, 2-octanol,
2-ethylhexanol, 3,5,5-trimethylhexanol, nonanol, n-decanol, undecanol, n-dodecanol, trimethylnonyl alcohol,
Tetradecanol, heptadecanol, cyclohexanol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 2,4,7,9-tetramethyl-5-decyne- 4,7 diol, 3,5-dimethyl-1-hexyn-3-ol, N, N-diethylethanolamine, N, N-dimethylethanolamine,
N- (2-aminoethyl) ethanolamine, N-methyldiethanolamine, N, N-dibutylethanolamine, 3-amino-1-propanol, 2-ethylhexyl alcohol, ethyl glycol, ethyl triglycol, butyl glycol, butyl diglycol , 3-chloro-1-propanol, diaceton alcohol,
Isononyl alcohol, methyl amyl alcohol, 2-
Aliphatic compounds such as methylcyclohexanol and 3-methyl-3-methoxy-1-butanol, benzyl alcohol, p-ethylphenol, p-octylphenol, xylenol, guaiacol, guetol, cresol, p-dodecylphenol, 2,4 , 6-tris (dimethylaminomethyl) phenol, tribenzylphenol, isoeugenol, dimethylbenzylcarbinol and other aromatic compounds, heterocyclic compounds, chlorophenol, 2,3-dibromo-1-propanol, 2
-Organohalogen compounds such as perfluoroalkyl ethanol and polyethylene glycol derivatives such as polyethylene glycol alkyl ether and polyethylene glycol alkyl phenyl ether. These may be used alone or in combination of two or more. Among these, aliphatic compounds having a boiling point of 100 ° C. or higher are preferable, and aliphatic compounds having a boiling point of 150 ° C. or higher are more preferable from the viewpoint of handling during the reaction and availability. Further, in terms of the reactivity of the transesterification reaction, a secondary alcohol is preferable, a primary alcohol is more preferable, and it is preferable to use one having excellent compatibility with the (meth) acrylic polymer (A).

The amount of the softening agent (G) blended is 0 with respect to 100 parts by weight of the (meth) acrylic polymer (A).
˜300 parts by weight is preferable, and 0 to 200 parts by weight is more preferable.

The thermoplastic elastomer composition of the present invention comprises
If necessary, the (meth) acrylic polymer (A), the transesterification catalyst (B), the thermoplastic resin (C), the compound (D) having at least two or more hydroxyl groups in one molecule, In addition to the phosphorus compound (F) and the softening agent (G), stabilizers, lubricants, flame retardants, pigments,
A filler, a reinforcing agent, a tackifier, and the like can be appropriately added. Specifically, stabilizers such as hindered phenols, hindered amines, and dibutyltin maleate; lubricants such as polyethylene wax, polypropylene wax, montanic acid wax; flame retardants such as decabromobiphenyl, decabromobiphenyl ether; titanium oxide. , Pigments such as zinc sulfide and zinc oxide; fillers and reinforcing agents such as carbon black, silica, glass fiber, asbestos, wollastonite, mica, talc, calcium carbonate; coumarone indene resin, phenol resin, terpene resin, high Examples thereof include tackifiers such as styrene resins, petroleum hydrocarbons (for example, dicyclopentadiene resins, aliphatic cyclic hydrocarbon resins, unsaturated hydrocarbon resins), polybutene, rosin derivatives and the like.

Further, in order to further improve the compatibility between the (meth) acrylic polymer (A) and the thermoplastic resin (C), various graft polymers or block polymers may be added as compatibilizers. . Clayton series (made by Shell Japan), Tuftec series (made by Asahi Kasei Kogyo), Dynaron (made by Japan Synthetic Rubber), Epofriend (made by Daicel Chemical Industries), Septon (made by Kuraray), Nofalloy (made by NOF Corporation) as compatibilizers, Lexpearl (manufactured by Nippon Polyolefin), Bond First (manufactured by Sumitomo Chemical Co., Ltd.), Bondyne (manufactured by Sumitomo Chemical Co., Ltd.), Admer (Mitsui Chemicals), Yumex (manufactured by Sanyo Kasei Co., Ltd.), VMX (manufactured by Mitsubishi Chemical), Modiper (Nippon Oil & Fats) Commercially available products such as (made by Toda Gosei Co., Ltd.), Staphyroid (made by Takeda Pharmaceutical Co., Ltd.), Kane Ace (made by Kanegafuchi Chemical Industry), and Reseta (made by Toagosei). These can be appropriately selected depending on the (meth) acrylic polymer (A) and the thermoplastic resin (C) used.

<Method for Producing Thermoplastic Elastomer Composition> The thermoplastic elastomer composition of the present invention comprises (A) a (meth) acrylic polymer and (C) a thermoplastic resin and / or (D) in one molecule. It is produced by reacting a composition containing at least one compound selected from the group consisting of a compound having at least two or more hydroxyl groups with a (B) transesterification catalyst. It is not particularly limited, but more preferably (A) and (C)
(B) is added while melting and kneading a composition containing and / or (D) at a high temperature, and further, a phosphorus compound (F), a softening agent (G), a stabilizer, a lubricant, if necessary. It is carried out by adding (dynamically heat treating) other components such as a flame retardant, a pigment, a filler, a reinforcing material, a lubricant and a tackifier.

As the kneading machine used for producing the above-mentioned composition, various devices capable of simultaneously performing heating and kneading can be used. For example, Banbury, kneader, single-screw, or single-screw machine used for usual rubber processing can be used. Examples thereof include a multi-screw extruder. Furthermore, if necessary, the composition can be molded using a pressing machine, an injection molding machine, or the like. The kneading temperature for producing the composition is preferably 100 to 300 ° C.,
-250 degreeC is more preferable.

Next, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The abbreviation B in the following description
A, EA, MEA, MMA, and HEA are acrylic-n-butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, methyl methacrylate, 2-acrylic acid, respectively.
Represents human loxyethyl. The molecular weight of the polymer shown in this example was measured by the GPC analyzer shown below, and the molecular weight in terms of polystyrene was determined using chloroform as the mobile phase.
As a system, G manufactured by Waters
Showa Denko KK Sh was used for the column using a PC system.
odex K-804 (polystyrene gel) was used.
The weight fraction of methacrylic acid ester and acrylic acid ester of the polymer was determined by ¹ H-NMR. The hardness of the material shown in this example is in accordance with JIS K6301 and is 2
The hardness at 3 ° C was measured.

Breaking strength (MPa) of the materials shown in this example
And the elongation at break (%) are applied mutatis mutandis to the method described in JIS K7113, and Autograph AG-10 manufactured by Shimadzu Corporation
It was measured using TB type. The measurement was performed at n = 3, and the average value of the values of strength (MPa) and elongation (%) when the test piece broke was adopted. A test piece having a No. 2 (1/3) shape and a thickness of about 2 mm was used. The test is 23 ℃
At a test speed of 500 mm / min. As a general rule, the test piece should have a temperature of 23 ± 2 ℃ and a relative humidity of 50 ± 5% before the test.
Was used for 48 hours or more. The oil resistance shown in this example is based on ASTM D638, and the ASTM oil N in which the molded article of the composition is kept at 150 ° C.
o. It was dipped in 3 for 72 hours and the weight change rate (wt%) was obtained.

The heat resistance shown in this example was determined by comparing the flow initiation temperatures. The flow starting temperature was 60 Kgf under a load of resin heated at a temperature rising rate of 5 ° C./min using a Shimadzu high-performance flow tester CFT-500C type.
The temperature at which the resin extruding piston of the flow tester begins to drop obviously when extruding from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a pressure of / cm ² (T
(displayed as fb). Production Example 1: MMA- (BA-co-EA-co-ME
A) -MMA type block copolymer (hereinafter abbreviated as M3AM) was synthesized in the following manner to obtain M3AM. 500 mL
Using a separable flask, 1.37 g of copper bromide (9.5
Mmol), acetonitrile (nitrogen bubbling) 20 mL, initiator diethyl 2,5-dibromoadipate 0.69 g (1.9 mmol), 40.2 ml (2
80 mmol), EA 38.2 ml (352 mmol)
Then, 21.6 ml (168 mmol) of MEA was added by the same procedure as in Example 1, and then 0.20 ml (1.0 mmol) of the ligand diethylenetriamine was added to initiate polymerization.

The BA conversion rate is 95% and the EA conversion rate is 9%.
At 5% and MEA conversion of 96%, MMA4
2.8 ml (400 mmol), 1.82 g of copper chloride (1
8.5 mmol), 0.20 ml of diethylenetriamine
(1.0 mmol) and toluene (nitrogen bubbling) 128.5 ml were added, and the conversion of BA was 97.
%, EA conversion rate is 97%, MEA conversion rate is 98%,
When the conversion rate of MMA is 82%, 150 ml of toluene
Was added, and the reaction was terminated by cooling the reactor with a water bath.

The reaction solution was diluted with 400 mL of toluene,
2.21 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 3 hours. The precipitated insoluble portion was filtered off with a Kiriyama funnel, and the polymer solution was adsorbent KYOWARD 50.
0.97 g of 0SH was added and the mixture was further stirred at room temperature for 3 hours.
The adsorbent was filtered with a Kiriyama funnel to obtain a colorless transparent polymer solution. This solution was dried to remove the solvent and the residual monomer to obtain the target M3AM. GPC analysis of the obtained block copolymer revealed that the number average molecular weight Mn was 113,000 and the molecular weight distribution Mw / Mn was 1.49. A composition analysis showed that EA / BA / MEA /
It was MMA = 24/33/15/28 (weight%).

Production Example 2: MMA- (BA-co-HE
A) -MMA type block copolymer (hereinafter abbreviated as MHBAM) was synthesized in the following manner to obtain MHBAM. 500 m
After the inside of the polymerization vessel of the separable flask of 1 was replaced with nitrogen, 1.14 g (8.0 mmol) of copper bromide, 18.0 mL of acetonitrile (with nitrogen bubbling), and initiator 2,5-dibromoadipate diethyl 0 .57 g (1.
59 mmol), BA 86.7 ml (605 mmol)
Then, 3.3 ml (31.8 mmol) of HEA was added by the same procedure as in Example 1, and then 0.17 ml (0.80 mmol) of the ligand diethylenetriamine was added to initiate polymerization.

When the conversion of BA was 95%, MMA3
7.4 ml (350 mmol), copper chloride 0.79 g
(8.0 mmol), diethylenetriamine 0.17 m
1 (0.80 mmol) and 111 ml of toluene (nitrogen bubbling) were added, and the conversion of MMA was 79.
%, When the conversion rate of BA is 97%, 160 m of toluene
1 was added and the reaction was terminated by cooling the reactor with a water bath.

The reaction solution was diluted with 400 mL of toluene,
2.21 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 3 hours. The precipitated insoluble portion was filtered off with a Kiriyama funnel, and the polymer solution was adsorbent KYOWARD 50.
0.97 g of 0SH was added and the mixture was further stirred at room temperature for 3 hours.
The adsorbent was filtered with a Kiriyama funnel to obtain a colorless transparent polymer solution. This solution was dried to remove the solvent and the residual monomer to obtain the desired MHBAM. GPC analysis of the obtained block copolymer revealed that the number average molecular weight Mn
Was 10800 and the molecular weight distribution Mw / Mn was 1.70. ^The compositional ratio measured by ¹ H-NMR is BA / HEA /
It was MMA = 72/5/23 (weight%).

Example 1 M3AM and polybutylene terephthalate prepared in Preparation Example 1; PBT (Duranex 2002: manufactured by Wintec Polymer Co., Ltd.) and Irganox 1010 (manufactured by Ciba Geigy Co.) were heated to 230 ° C. at the ratios shown in Table 1. It was melt-kneaded using the set Labo Plastomill (manufactured by Toyo Seiki). Further, triethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) was added at a ratio shown in Table 1 and melt-kneaded. further,
Titanium (IV) tetrabutoxide and a monomer (manufactured by Wako Pure Chemical Industries, Ltd.) were added while melt-kneading at 230 ° C. at a screw rotation speed of 100 rpm, and the reaction was advanced by dynamically heat treating. After that, PEP-36 (manufactured by Asahi Denka Co., Ltd.) was added to obtain a sample. The obtained sample was hot press molded at a set temperature of 230 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of these molded bodies was measured. Further, similarly, hot press molding was performed at a set temperature of 230 ° C. to obtain a sheet-shaped molded product having a thickness of 2 mm. Break strength, break elongation,
The heat resistance and oil resistance were measured.

Example 2 MHBAM and polybutylene terephthalate prepared in Preparation Example 2; PBT (Duranex 2002: manufactured by Wintech Polymer Co.) and Irganox 1010 (manufactured by Ciba Geigy) at the ratios shown in Table 1 at 230 ° C. It was melt-kneaded using the set Labo Plastomill (manufactured by Toyo Seiki). Furthermore, the screw rotation speed is 100 rpm and 230
Titanium (IV) tetrabutoxide and a monomer (manufactured by Wako Pure Chemical Industries, Ltd.) were added while melt-kneading at ℃, and the reaction was allowed to proceed by dynamically heat-treating. Then PEP-
36 (manufactured by Asahi Denka Kogyo) was added to obtain a sample. The obtained sample was hot press molded at a set temperature of 230 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of these molded bodies was measured. Also,
Similarly, hot press molding at a set temperature of 230 ℃, thickness 2mm
A sheet-shaped molded body of was obtained. Break strength, break elongation, heat resistance, and oil resistance were measured using these sheets.

Comparative Example 1 The M3AM produced in Production Example 1 was rotated at a screw rotation speed of 50 r.
A sample was obtained by melt-kneading with a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) set at 190 ° C. in pm. The sample obtained was hot press molded at a set temperature of 190 ° C.
A cylindrical molded body having a thickness of 0 mm and a thickness of 12 mm was obtained. The hardness of these molded bodies was measured. Further, similarly, hot press molding was performed at a set temperature of 190 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Break strength, break elongation, heat resistance, and oil resistance were measured using these sheets. It can be seen that the level of heat resistance is insufficient with M3AM alone.

Comparative Example 2 Perprene P30B (manufactured by Toyobo Co., Ltd.), which is an ester-based elastomer, was heated at 190 ° C. at a screw rotation speed of 50 rpm.
A sample was obtained by melt-kneading with a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) set to. The obtained sample was hot-press molded at a set temperature of 190 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of these molded bodies was measured. Similarly, the set temperature is 190 ℃
Was hot press molded to obtain a sheet-shaped molded body having a thickness of 2 mm. Break strength, break elongation, heat resistance, and oil resistance were measured using these sheets. It can be seen that the polyester elastomer having a low hardness grade has insufficient oil resistance.

Comparative Example 3 Santoprene 211 which is an olefin elastomer
A sample was obtained by melt-kneading -55 (manufactured by AES Japan Co., Ltd.) with a Labo Plastomill (manufactured by Toyo Seiki) set at 170 ° C. with a screw rotation speed of 100 rpm. The obtained sample was hot press molded at a set temperature of 170 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of these molded bodies was measured.
Further, similarly, hot press molding was performed at a set temperature of 170 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Break strength, break elongation, heat resistance, and oil resistance were measured using these sheets. It is understood that the olefin elastomer has good heat resistance but insufficient oil resistance level.

[0090]

[Table 1] As is clear from Table 1 above, Examples 1 and 2 and Comparative Examples 1 to 3, it is understood that the thermoplastic elastomer composition of the present invention has improved oil resistance and heat resistance.

[0091]

INDUSTRIAL APPLICABILITY The thermoplastic elastomer composition of the present invention is rich in flexibility and excellent in mechanical strength, moldability, oil resistance and heat resistance, and therefore various sealed containers, gaskets, oil resistant hoses and cover sheets, etc. Can be suitably used widely.

Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI theme code (reference) C08L 101/06 C08L 101/06 (72) Inventor Tomoki Hiseki 1-4F Term, Chaenbacho, Akashi-shi, Hyogo (reference) ) 4F070 AA32 AA74 AB09 AC55 AE02 AE11 GA06 GB09 4J002 AE053 BG04W BG05W BG06X CF00X CG00X EC006 EJ006 EW007 FD023 FD028

Claims (11)

[Claims] 1. An (A) (meth) acrylic copolymer,
In a composition comprising (B) a transesterification catalyst and (C) a thermoplastic resin as essential components, (D) a compound having at least two or more hydroxyl groups in one molecule, if necessary, A thermoplastic elastomer composition, wherein the plastic resin (C) has transesterification reactivity with a compound having a hydroxyl group in the presence of the transesterification catalyst (B). 2. The thermoplastic elastomer composition according to claim 1, which is dynamically heat-treated. 3. The (meth) acrylic polymer (A) is composed of an acrylic polymer rubber and / or a rubber-like polymer containing a modified rubber obtained by grafting a vinyl monomer on the rubber as a main component. The thermoplastic elastomer composition according to claim 1 or 2. 4. The (meth) acrylic polymer (A) is
The thermoplastic elastomer composition according to claim 1 or 2, which is composed of a block copolymer (E) containing (a) a methacrylic polymer block and (b) an acrylic polymer block. 5. The thermoplastic elastomer composition according to claim 1, wherein the (meth) acrylic polymer (A) has at least one hydroxyl group. 6. The methacrylic polymer block (a) comprises 50 to 100% by weight of methyl methacrylate and another methacrylic acid ester copolymerizable therewith and / or another vinylic monomer 0 to 50. The thermoplastic elastomer composition according to claim 4, characterized in that the thermoplastic elastomer composition comprises 5% by weight. 7. The thermoplastic elastomer composition according to claim 4, wherein the block copolymer (E) has a hydroxyl group in at least one polymer block. 8. The thermoplastic elastomer composition according to claim 1, wherein the (meth) acrylic copolymer (A) is controlled by atom transfer radical polymerization. 9. The thermoplastic resin (C) is at least one resin selected from the group consisting of polymethylmethacrylate-based resins, polyester-based resins and polycarbonate-based resins, according to claim 1. Thermoplastic elastomer composition. 10. The thermoplastic elastomer composition according to claim 1, further comprising a phosphorus compound (F). 11. A softening agent (G) is further added (meta).
0 to 30 relative to 100 parts by weight of the acrylic polymer (A)
The thermoplastic elastomer composition according to claim 1, wherein the thermoplastic elastomer composition contains 0 part by weight.