JP2006249173A - Thermoplastic elastomer composition and molded article using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition which has excellent heat resistance, weather resistance, chemical resistance, adhesiveness, flexibility, abrasion resistance, and melt flowability on molding. <P>SOLUTION: This thermoplastic elastomer composition is characterized by comprising a prescribed acrylic block copolymer (A), an acrylic polymer (B) having at least ≥1.1 epoxy groups in the molecule, and an alkyl glycidyl ether (C). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thermoplastic elastomer composition excellent in moldability, heat resistance, weather resistance, chemical resistance, adhesion, flexibility, abrasion resistance, and strain recovery. The present invention also relates to a composition suitable for powder slush molding and a powder slush molded article using the composition.

  It is known that an acrylic block copolymer having methyl methacrylate as a hard segment and butyl acrylate as a soft segment has characteristics as a thermoplastic elastomer. By appropriately selecting the components constituting the block body, it is possible to give an extremely flexible elastomer as compared with other thermoplastic elastomers such as a styrene block body.

  In addition, the acrylic block copolymer has a feature that it is excellent in weather resistance, heat resistance, durability, oil resistance, and abrasion resistance. Further, in Patent Document 1, it is manufactured by an iniferter method. It is described that an acrylic block copolymer having a methacrylic block and an acrylic block exhibits excellent mechanical properties (such as tensile strength and elongation).

  There are various skin materials and interior materials as applications utilizing the characteristics of such an acrylic block copolymer. In addition, there are materials for members that directly touch human hands by making use of tactile sensation.

  The physical properties necessary for these skin materials include resistance to chemicals that can be contacted in addition to the mechanical properties (such as tensile strength and elongation), scratch resistance, heat resistance, and strain recovery. Furthermore, when the skin and the base material are directly bonded, the adhesion between the skin and the base material, and when the buffer material is provided between the skin and the base material, the adhesion between the skin and the base material is mentioned. It is done.

 As a method for molding the skin material, there is a powder slush molding method that is a powder molding method using a soft powder material. This method is widely used for molding the skin of automobile interior parts such as instrument panels, console boxes and door rims. This is because, according to the powder slush molding method, a product with a soft feel can be obtained, and leather textures and stitches can be provided on the product, the degree of design freedom is great, and the design is good. Unlike other injection molding and compression molding methods, this molding method does not apply shaping pressure during molding. For this reason, it is necessary to uniformly adhere the powder material to a complicatedly shaped mold at the time of molding, and it is required to have excellent powder fluidity. At the same time, since the powder adhering to the mold needs to melt and flow even under no pressure to form a film, the melt viscosity is also required to be low.

  However, it has been difficult for conventional acrylic block copolymers to achieve both melt fluidity and heat resistance.

Japanese Unexamined Patent Publication No. 1-26619

  The object of the present invention is to provide the melt flowability, heat resistance and strain recovery during molding while having the weather resistance, chemical resistance, adhesiveness, flexibility and wear resistance that are the characteristics of acrylic block copolymers. It is to obtain an acrylic block copolymer composition having excellent properties.

  As a result of intensive studies to solve the above problems, the inventors of the present invention, at the time of molding, increase the molecular weight or cross-link the acrylic block copolymer by a predetermined method, and blend a glycidyl alkyl ether compound. Thus, it has been found that the above problem can be effectively solved.

  That is, the present invention comprises a methacrylic polymer block (a) whose main component is a methacrylic polymer and an acrylic polymer block (b) whose main component is an acrylic polymer, and these polymer blocks 100 parts by weight of an acrylic block copolymer (A) having an acid anhydride group and / or a carboxyl group in at least one of them, and an acrylic polymer having at least 1.1 epoxy groups in one molecule ( B) 0.5 to 50 parts by weight and the general formula (1):

（式中、ｎは３〜２０の整数）
で表されることを特徴とする化合物（Ｃ）０.０１〜１０重量部からなることを特徴とする熱可塑性エラストマー組成物に関する。

(Where n is an integer from 3 to 20)
It is related with the thermoplastic elastomer composition characterized by consisting of 0.01-10 weight part of compounds (C) characterized by these.

  A preferred embodiment relates to a thermoplastic elastomer composition characterized in that an acid anhydride group and / or a carboxyl group are present in the main chain of the acrylic block copolymer (A).

  In a preferred embodiment, the acid anhydride group has the general formula (2):

（式中、Ｒ¹は水素またはメチル基で、２つのＲ¹は互いに同一でも異なっていてもよい。ｎは０〜３の整数、ｍは０または１の整数）で表されることを特徴とする熱可塑性エラストマー組成物に関する。

Wherein R ¹ is hydrogen or a methyl group, and two R ^{1 s} may be the same or different from each other. N is an integer of 0 to 3, and m is an integer of 0 or 1. And a thermoplastic elastomer composition.

  In a preferred embodiment, the acrylic block copolymer (A) comprises 10 to 60% by weight of the methacrylic polymer block (a) and 90 to 40% by weight of the acrylic polymer block (b). The thermoplastic elastomer composition characterized by these is mentioned.

  As a preferred embodiment, the methacrylic polymer block (a) is selected from the group consisting of 50 to 100% by weight of methyl methacrylate and ethyl acrylate, acrylic acid n-butyl and acrylic acid-2-methoxyethyl. A thermoplastic elastomer composition characterized in that it is a block copolymer comprising 50 to 0% by weight of at least one acrylate monomer selected.

  A preferred embodiment includes a thermoplastic elastomer composition wherein the methacrylic polymer block (a) is a block copolymer comprising methyl methacrylate and ethyl acrylate.

  As a preferred embodiment, the acrylic polymer block (b) is at least one monomer selected from the group consisting of acrylic acid-n-butyl, ethyl acrylate, and 2-methoxyethyl acrylate, and these And a thermoplastic elastomer composition comprising 50 to 100% by weight of a different kind of acrylic ester copolymerizable with 50% to 0% by weight of a vinyl monomer.

  A preferred embodiment is a thermoplastic elastomer composition characterized in that the number average molecular weight of the acrylic block copolymer (A) measured by gel permeation chromatography is 30,000 to 200,000. It is done.

  As a preferred embodiment, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography of the acrylic block copolymer (A) is 1.8 or less. And a thermoplastic elastomer composition characterized in that.

  A preferable embodiment includes a thermoplastic elastomer composition in which the acrylic block copolymer (A) is a block copolymer produced by atom transfer radical polymerization.

  A preferred embodiment includes a thermoplastic elastomer composition characterized in that the acrylic polymer (B) has a weight average molecular weight of 30,000 or less.

  A preferable embodiment includes a thermoplastic elastomer composition characterized in that the glass transition temperature of the acrylic polymer (B) is 100 ° C. or lower.

  A preferable embodiment includes a thermoplastic elastomer composition characterized in that the acrylic polymer (B) has a weight average molecular weight of 500 to 10,000.

  As a preferred embodiment, a thermoplastic elastomer composition is characterized in that the acrylic polymer (B) has a viscosity of 35,000 mPa · s or less.

  A preferred embodiment includes a thermoplastic elastomer composition wherein the compound (C) is stearyl glycidyl ether.

  A preferable embodiment includes a thermoplastic elastomer composition characterized by further adding 5-200 parts by weight of a filler to 100 parts by weight of the acrylic block copolymer (A).

  A preferred embodiment includes a thermoplastic elastomer composition characterized by further adding 0.1 to 20 parts by weight of a lubricant to 100 parts by weight of the acrylic block copolymer (A).

  A preferred embodiment includes a thermoplastic elastomer composition characterized by being used for powder slush molding.

  The present invention also relates to a powder slush molded article using the above composition.

  As a preferred embodiment, an automobile interior skin characterized by powder slush molding of the above composition can be mentioned.

  The thermoplastic elastomer composition according to the present invention is excellent not only in weather resistance, chemical resistance, adhesion, flexibility and wear resistance, but also in moldability, heat resistance and strain recovery. For this reason, the composition of this invention can be used conveniently for powder slush molding.

  The thermoplastic elastomer composition according to the present invention comprises a methacrylic polymer block (a) mainly composed of a methacrylic polymer and an acrylic polymer block (b) mainly composed of an acrylic polymer. , 100 parts by weight of an acrylic block copolymer (A) having an acid anhydride group and / or a carboxyl group in at least one of these polymer blocks, and at least 1.1 epoxy groups in one molecule The acrylic polymer (B) having 0.5 to 50 parts by weight and the glycidyl alkyl ether compound (C) 0.01 to 10 parts by weight. In the present composition, the acid anhydride group and carboxyl group of the acrylic block copolymer (A), the acrylic polymer (B) and the glycidyl alkyl ether compound (C) represented by the general formula (1) Epoxy groups usually react and crosslink by heating during molding. As a result, the heat resistance of the molded body is improved. Further, the glycidyl alkyl ether compound (C) acts as a plasticizer at the time of molding and not only improves the melt fluidity but also has an effect of preventing the pellets from adhering as a blocking inhibitor after molding. Moreover, it acts as a lubricant, and as a result, it is possible to improve the abrasion resistance of the obtained molded body.

  Hereinafter, each component of the present invention will be described in detail.

<Acrylic block copolymer (A)>
The acrylic block copolymer (A) of the present invention is a linear block copolymer or a branched (star) block copolymer, and may be a mixture thereof. The structure of such a block copolymer may be appropriately selected according to the required physical properties of the acrylic block copolymer (A). However, from the viewpoint of cost and ease of polymerization, the linear block copolymer is selected. Polymers are preferred. The linear block copolymer may have any structure. From the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the methacrylic polymer block (a) is a. When the acrylic polymer block (b) is expressed as b, (ab) _n type, b- (ab) _n type and (ab) _n -a type (n is an integer of 1 or more) For example, it is preferably at least one acrylic block copolymer selected from the group consisting of 1 to 3). Among these, an ab type diblock copolymer, an abb type triblock copolymer, or a mixture thereof is preferable from the viewpoint of easy handling during processing and physical properties of the composition.

  One or more acid anhydride groups and / or carboxyl groups are introduced per block into at least one of the methacrylic polymer block (a) and the acrylic polymer block (b). When the number is two or more, the manner in which the monomers are polymerized can be random copolymerization or block copolymerization. For example, when an a-b-a type triblock copolymer is taken as an example, (a / z) -b-a type, (a / z) -b- (a / z) type, za-b -A type, za-b-a-z type, a- (b / z) -a type, a-b-za type, az-b-za type, (a / z )-(B / z)-(a / z) type, za-z-b-z-az type, and the like. Here, z represents a monomer or polymer block containing an acid anhydride group and / or a carboxyl group, and (a / z) represents an acid anhydride group and a methacrylic polymer block (a). // represents that a monomer containing a carboxyl group is copolymerized, and (b / z) is a monomer containing an acid anhydride group and / or a carboxyl group in the acrylic polymer block (b) Represents being copolymerized.

  Moreover, the site | part containing z and the form to contain in a methacrylic polymer block (a) or an acrylic polymer block (b) may be set freely, and can be used properly according to the objective.

  The molecular weight of the acrylic block copolymer (A) is not particularly limited, and may be determined from the molecular weights required for the methacrylic polymer block (a) and the acrylic polymer block (b). However, if the molecular weight is small, sufficient mechanical properties as an elastomer may not be exhibited. Conversely, if the molecular weight is larger than necessary, the processing properties may deteriorate. In the case of powder slush molding, it is necessary to flow even under no pressure. In particular, if the molecular weight is large, the melt viscosity becomes high and the moldability may be deteriorated. From such a viewpoint, the molecular weight of the acrylic block copolymer (A) is preferably 30,000 to 200,000 in terms of number average molecular weight, more preferably 35,000 to 150,000, still more preferably 40,000. ~ 100,000.

  The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography of the acrylic block copolymer (A) is not particularly limited, but is 1.8 or less. It is preferable that it is 1.5 or less. If Mw / Mn exceeds 1.8, the uniformity of the acrylic block copolymer may deteriorate.

  The composition ratio of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the acrylic block copolymer (A) is 5 to 90% by weight of the methacrylic polymer block (a). The acrylic polymer block (b) is preferably 95 to 10% by weight. From the viewpoint of maintaining the shape during molding and elasticity as an elastomer, the methacrylic polymer block (a) is more preferably 10 to 60% by weight, and the acrylic polymer block (b) is more preferably 90 to 40% by weight. Preferably, the methacrylic polymer block (a) is 15 to 50% by weight, and the acrylic polymer block (b) is 85 to 50% by weight. When the proportion of the methacrylic polymer block (a) is less than 5% by weight, the shape tends to be difficult to be maintained at the time of molding, and when the proportion of the acrylic polymer block (b) is less than 10% by weight, an elastomer is obtained. There is a tendency that the elasticity and the meltability at the time of molding are lowered.

  From the viewpoint of the hardness of the elastomer composition, when the proportion of the methacrylic polymer block (a) is small, the hardness is low, and when the proportion of the acrylic polymer block (b) is small, the hardness tends to be high. Yes, the composition is appropriately set according to the required hardness of the elastomer composition. From the viewpoint of processing, when the proportion of (a) is small, the viscosity tends to be low, and when the proportion of (b) is small, the viscosity tends to be high, and the composition is appropriately set according to the required processing characteristics. .

The relationship between the glass transition temperature of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the acrylic block copolymer (A) is that it gives elastomer properties and rubber elasticity. It is preferable that the glass transition temperature of one polymer block is higher than the glass transition temperature of the other polymer block. The glass transition temperature of the methacrylic polymer block (a) is Tg _a , and the acrylic polymer block (b It is more preferable to satisfy the relationship of the following formula from the ease of adjustment of the glass transition temperature, where Tg _b is the glass transition temperature of
Tg _a > Tg _b

The glass transition temperature (Tg) of the polymer (the methacrylic polymer block (a) and the acrylic polymer block (b)) is set according to the following Fox formula. This can be done by setting.
_{1 / Tg = (W 1 /} Tg 1) + (W 2 / Tg 2) + ... + (W m / Tg m)
W ₁ + W ₂ + ... + W _m = 1
In the formula, Tg represents the glass transition temperature of the polymer portion, and Tg ₁ , Tg ₂ ,..., Tg _m represent the glass transition temperature of each polymerization monomer. W ₁ , W ₂ ,..., W _m represent the weight ratio of each polymerization monomer.

  As the glass transition temperature of each polymerization monomer in the Fox formula, for example, a value described in Polymer Handbook Third Edition (Wiley-Interscience 1989) may be used.

  The glass transition temperature can be measured by DSC (differential scanning calorimetry) or tan δ peak of dynamic viscoelasticity, but the polarities of the methacrylic polymer block (a) and the acrylic polymer block (b). If they are too close, or if the number of monomer chains in the block is too small, the measured values may be misaligned with the calculation formula based on the Fox equation.

<Methacrylic polymer block (a)>
The methacrylic polymer block (a) is a block formed by polymerizing a monomer having a methacrylic acid ester as a main component. It is preferably composed of 0 to 50% by weight of monomer. Moreover, the monomer which has an acid anhydride group and / or a carboxyl group may be included as methacrylic ester. When the proportion of the methacrylic acid ester is less than 50% by weight, the weather resistance, which is a feature of the methacrylic acid ester, may be impaired.

  Examples of the methacrylic acid ester constituting the methacrylic polymer block (a) include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, N-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, Methacrylic acid aliphatic hydrocarbons (eg, alkyl having 1 to 18 carbon atoms) such as stearyl methacrylate; Methacrylic acid alicyclic hydrocarbon esters such as cyclohexyl methacrylate and isobornyl methacrylate; Benzyl methacrylate Etc. Acid aralkyl esters; methacrylic aromatic hydrocarbon esters such as phenyl methacrylate and toluyl methacrylate; methacrylic acid such as 2-methoxyethyl methacrylate and 3-methoxybutyl methacrylate and etheric oxygen Esters with functional group-containing alcohols; trifluoromethyl methacrylate, trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-trifluoroethyl methacrylate, 2-perfluoroethyl methacrylate Ethyl, 2-perfluoroethyl-2-perfluorobutyl ethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, 2-perfluoro methacrylate Fluoroalkyl methacrylates such as romethyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluorohexadecylethyl methacrylate, etc. can give. At least one of these is used. Among these, methyl methacrylate is preferable in terms of processability, cost, and availability.

  Examples of vinyl monomers copolymerizable with the methacrylic acid ester constituting the methacrylic polymer block (a) include, for example, acrylic acid esters, aromatic alkenyl compounds, vinyl cyanide compounds, conjugated diene compounds, Examples thereof include halogen-containing unsaturated compounds, vinyl ester compounds, maleimide compounds, and the like.

  Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, N-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, and the like, acrylate aliphatic hydrocarbon (eg, alkyl having 1 to 18 carbon atoms) ester; cyclohexyl acrylate Acrylic acid cycloaliphatic hydrocarbon esters such as isobornyl acrylate; Acrylic aromatic hydrocarbon esters such as phenyl acrylate and toluyl acrylate; Aralkyl acrylates such as benzyl acrylate; 2-methoxyethyl acrylate , An ester of acrylic acid such as 3-methoxybutyl acrylate and a functional group-containing alcohol having etheric oxygen; trifluoromethyl methyl acrylate, 2-trifluoromethyl ethyl acrylate, 2-perfluoroethyl ethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethyl acrylate Examples thereof include fluorinated alkyl acrylates such as methyl, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, and 2-perfluorohexadecylethyl acrylate.

  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.

  Examples of the conjugated diene compound include butadiene and isoprene.

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

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

  Examples of the maleimide compound include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and the like.

  These compounds can be used alone or in combination of two or more. These vinyl monomers are preferably selected from the viewpoints of adjusting the glass transition temperature required for the methacrylic polymer block (a) and compatibility with the acrylic block (b).

In particular, in the case of powder slush molding should be flowing at no pressure, the cohesive force and glass transition temperature Tg _a of the methacrylic polymer block (a) is increased, the higher the melt viscosity, the moldability It tends to get worse. For this reason, the glass transition temperature of the methacrylic polymer block (a) is preferably from 25 to 130 ° C, more preferably from 50 to 130 ° C, from the viewpoints of thermal deformability and moldability of the elastomer composition. Preferably it is 70-100 degreeC. From this point, it is desirable that the methacrylic polymer block (a) is mainly composed of methyl methacrylate, the increase in the glass transition temperature due to the introduction of an acid anhydride group or a carboxyl group, and the methacrylic polymer. For the purpose of adjusting the glass transition temperature of the block (a), polymerizing at least one monomer selected from the group consisting of ethyl acrylate, acrylic acid-n-butyl and acrylic acid-2-methoxyethyl. preferable. Of these, ethyl acrylate is particularly preferable from the viewpoint of compatibility with methyl methacrylate.

Tg _a configuration of the methacrylic polymer block (a) in accordance with said Fox equation, can be performed by setting the weight ratio of the monomers of each polymer portion.

<Acrylic polymer block (b)>
The acrylic polymer block (b) is a block obtained by polymerizing a monomer having an acrylic ester as a main component, and includes 50 to 100% by weight of the acrylic ester and a vinyl monomer copolymerizable therewith. It is preferably composed of 0 to 50% by weight. Moreover, the monomer which has an acid anhydride group and / or a carboxyl group may be included as acrylic ester. If the proportion of the acrylic ester is less than 50% by weight, the physical properties of the composition, particularly flexibility and oil resistance, which are characteristics when using the acrylic ester, may be impaired.

  Examples of the acrylate ester constituting the acrylic polymer block (b) include the same monomers as the acrylate ester exemplified as the monomer constituting the methacrylic polymer block (a). it can.

  These can be used alone or in combination of two or more thereof. Among these, acrylate-n-butyl is preferable from the viewpoint of rubber elasticity, low-temperature characteristics, and cost balance. If oil resistance and mechanical properties are required, ethyl acrylate is preferred. In addition, when it is necessary to impart low temperature characteristics and oil resistance and to improve the surface tackiness of the resin, 2-methoxyethyl acrylate is preferred. Further, when a balance between oil resistance and low-temperature characteristics is required, it is preferable to use a combination of ethyl acrylate, acrylic acid-n-butyl and acrylic acid-2-methoxyethyl.

  Examples of vinyl monomers copolymerizable with the acrylic ester constituting the acrylic polymer block (b) include methacrylic ester, aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound, halogen, and the like. -Containing unsaturated compounds, silicon-containing unsaturated compounds, unsaturated carboxylic acid compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds, maleimide compounds, etc., and specific examples thereof include methacrylic polymer blocks The thing similar to the said thing used for (a) can be mention | raise | lifted.

  These vinyl monomers can be used alone or in combination of two or more. These vinyl monomers are appropriately selected in consideration of the balance of the glass transition temperature and oil resistance required for the acrylic polymer block (b), compatibility with the methacrylic polymer block (a), and the like. Choose the preferred one. For example, acrylonitrile may be copolymerized for the purpose of improving the oil resistance of the composition.

  From the viewpoint of rubber elasticity of the elastomer composition, the glass transition temperature of the acrylic polymer block (b) is preferably 25 ° C. or less, more preferably 0 ° C. or less, and further preferably −20 ° C. or less. When the glass transition temperature of the acrylic polymer block (b) is higher than the temperature of the environment in which the elastomer composition is used, flexibility and rubber elasticity are hardly exhibited.

The Tg _b of the acrylic polymer block (b) can be set by setting the weight ratio of the monomers in each polymer portion according to the Fox formula.

<Acid anhydride group and carboxyl group>
An acid anhydride group and a carboxyl group are added to a methacrylic heavy group in order to retain mechanical properties at high temperatures while imparting chemical resistance and rubber elasticity to a molded product obtained from the thermoplastic elastomer composition according to the present invention. One or more per block is introduced into at least one of the combined block (a) and the acrylic polymer block (b). An acid anhydride group and a carboxyl group are the reactivity of an acrylic block copolymer (A) and an acrylic polymer (B), a methacrylic polymer block (a), and an acrylic polymer block (b). Either an acid anhydride group or a carboxyl group is introduced depending on the cohesive strength and glass transition temperature of the acrylic block copolymer, the required physical properties of the acrylic block copolymer (A), and ease of introduction. It may be introduced together.

  In the present invention, the acid anhydride group and the carboxyl group may act as a reaction point with the acrylic polymer (B), and as a reaction point or a crosslinking point for the block copolymer to have a high molecular weight or to be crosslinked. It is preferable to act. The acid anhydride group and the carboxyl group are introduced into the block copolymer in a form in which the acid anhydride group and the carboxyl group are protected with an appropriate protecting group, or in the form of a precursor of an acid anhydride group or a carboxyl group. Later, an acid anhydride group and a carboxyl group can be generated by a known chemical reaction.

  The content of the acid anhydride group and carboxyl group is the interaction between the acid anhydride group and the carboxyl group, the reactivity, the structure and composition of the acrylic block copolymer (A), and the acrylic block copolymer (A). It changes with the number of the blocks which comprise, and a glass transition temperature. The number needs to be appropriately set according to need, but is preferably 1.0 or more, more preferably 2.0 or more, per block copolymer molecule. This is because when the number is less than 1.0, improvement in heat resistance due to increase in the molecular weight or crosslinking of the block copolymer may be insufficient.

Incidentally, the acid anhydride group and cohesive force and glass transition temperature Tg _a of the carboxyl group of the methacrylic polymer block by introducing (a) and the acrylic polymer block (b), the Tg _b is increased, flexibility , Rubber elasticity, low temperature characteristics may deteriorate. Therefore, when an acid anhydride group or a carboxyl group is introduced into the methacrylic polymer block (a) and the acrylic polymer block (b), the flexibility of the acrylic block copolymer (A), rubber elasticity, It is preferable to introduce it within a range where the low temperature characteristics do not deteriorate. Specifically, the glass transition temperature of the methacrylic polymer block (a) after introducing an acid anhydride group or a carboxyl group is 25 to 130 ° C, more preferably 50 to 130 ° C, still more preferably 70 to 100 ° C. Thus, it is preferable to introduce the acrylic polymer block (b) in such a range that the glass transition temperature Tg _b is 25 ° C. or lower, more preferably 0 ° C. or lower, and further preferably −20 ° C. or lower.

  Below, an acid anhydride group and a carboxyl group are demonstrated.

<Acid anhydride group>
When the composition contains a compound having active protons, the acid anhydride groups in the methacrylic polymer block (a) and the acrylic polymer block (b) It reacts easily with the epoxy group in the polymer (B). The introduction position of the acid anhydride group is not particularly limited, and the acid anhydride group is introduced into the main chain of the methacrylic polymer block (a) and / or the acrylic polymer block (b). It may be introduced to the side chain. The acid anhydride group is an anhydride of a carboxyl group and is introduced into the main chain from the viewpoint of ease of introduction into the methacrylic polymer block (a) and the acrylic polymer block (b). In particular, it is represented by the general formula (2). General formula (2):

（式中、Ｒ¹は水素またはメチル基で、２つのＲ¹は互いに同一でも異なっていてもよい。ｎは０〜３の整数、ｍは０または１の整数）で表される形で含有される。

(Wherein R ¹ is hydrogen or a methyl group, two R ^{1 s} may be the same or different from each other, n is an integer of 0 to 3, and m is an integer of 0 or 1) Is done.

  N in General formula (2) is an integer of 0-3, Preferably it is 0 or 1, More preferably, it is 1. When n is 4 or more, polymerization tends to be complicated, and cyclization of the acid anhydride group tends to be difficult.

  As a method for introducing the acid anhydride group, it is preferable that the acid anhydride group is introduced into the acrylic block copolymer in the form of a precursor of the acid anhydride group and then cyclized. In particular, the general formula (3):

（式中、Ｒ²は水素またはメチル基を表わす。Ｒ³は水素、メチル基またはフェニル基を表わし、３つのＲ³のうち少なくとも２つはメチル基および／またはフェニル基から選ばれ、３つのＲ³は互いに同一でも異なっていてもよい。）で表される単位を少なくとも１つ有するアクリル系ブロック共重合体を、溶融混練して環化導入することが好ましい。

(Wherein R ² represents hydrogen or a methyl group; R ³ represents hydrogen, a methyl group or a phenyl group; at least two of the three R ³ are selected from a methyl group and / or a phenyl group; R ³ may be the same or different from each other.) It is preferable that the acrylic block copolymer having at least one unit represented by:

  Introduction of the unit represented by the general formula (3) into the methacrylic polymer block (a) and the acrylic polymer block (b) is an acrylate ester derived from the general formula (3) or methacrylic acid. This can be done by copolymerizing an ester monomer. Examples of the monomer include t-butyl (meth) acrylate, isopropyl (meth) acrylate, α, α-dimethylbenzyl (meth) acrylate, α-methylbenzyl (meth) acrylate, It is not limited to these. Among these, (meth) acrylic acid-t-butyl is preferable from the standpoints of availability, ease of polymerization, and ease of acid anhydride group formation. In the present application, (meth) acrylic acid means acrylic acid and methacrylic acid.

  The formation of the acid anhydride group is preferably performed by heating the acrylic block copolymer having a precursor of the acid anhydride group at a high temperature, and preferably by heating at 180 to 300 ° C. . When the temperature is lower than 180 ° C., the formation of acid anhydride groups may be insufficient, and when the temperature is higher than 300 ° C., the acrylic block copolymer itself having a precursor of acid anhydride groups may be decomposed.

<Carboxyl group>
The carboxyl group in the methacrylic polymer block (a) and the acrylic polymer block (b) easily reacts with the epoxy group in the acrylic polymer (B) by heating at a predetermined temperature. The introduction position of the carboxyl group is not particularly limited, and the carboxyl group may be introduced into the main chain of the methacrylic polymer block (a) and / or the acrylic polymer block (b). And it may be introduced into the side chain. However, it is preferably introduced into the main chain from the viewpoint of ease of introduction into the methacrylic polymer block (a) and the acrylic polymer block (b).

  When the monomer having a carboxyl group does not poison the catalyst under the polymerization conditions, it is preferable to introduce the carboxyl group by direct polymerization, and the monomer having the carboxyl group is polymerized. When the catalyst is sometimes deactivated, it is preferably carried out by a method of introducing a carboxyl group by functional group conversion.

  In the method of introducing a carboxyl group by functional group conversion, the carboxyl group is introduced into an acrylic block copolymer in the form of protecting the carboxyl group with an appropriate protecting group or in the form of a functional group that is a precursor of the carboxyl group. Later, a functional group can be generated by a known chemical reaction.

  Examples of a method for synthesizing the acrylic block copolymer (A) having a carboxyl group include a functional group that becomes a precursor of a carboxyl group, such as (meth) acrylic acid-t-butyl, (meth) acrylic acid trimethylsilyl, and the like. A method of synthesizing an acrylic block copolymer containing a monomer having a group and generating a carboxyl group by a known chemical reaction such as hydrolysis or acid decomposition (JP-A-10-298248, JP-A-2001-234146) Gazette) and general formula (3):

（式中、Ｒ²は水素またはメチル基を表わす。Ｒ³は水素、メチル基またはフェニル基を表わし、３つのＲ³のうち少なくとも２つはメチル基および／またはフェニル基から選ばれ、３つのＲ³は互いに同一でも異なっていてもよい。）で表わされる単位を少なくとも１つ有するアクリル系ブロック共重合体を、溶融混練して導入する方法がある。一般式（３）で示される単位は、高温下でエステルユニットが分解してカルボキシル基を生成し、そのカルボキシル基の一部が環化することにより生成する。これを利用して、一般式（２）で示される単位の種類や含有量に応じて、加熱温度や時間を適宜調整することでカルボキシル基を導入することができる。

(Wherein R ² represents hydrogen or a methyl group; R ³ represents hydrogen, a methyl group or a phenyl group; at least two of the three R ³ are selected from a methyl group and / or a phenyl group; R ³ may be the same or different from each other.) There is a method of introducing an acrylic block copolymer having at least one unit represented by melt kneading. The unit represented by the general formula (3) is produced by decomposition of the ester unit at a high temperature to produce a carboxyl group, and a part of the carboxyl group is cyclized. Utilizing this, the carboxyl group can be introduced by appropriately adjusting the heating temperature and time according to the type and content of the unit represented by the general formula (2).

  Moreover, a carboxyl group can also be introduce | transduced by hydrolyzing the said acid anhydride group.

<Method for producing acrylic block copolymer (A)>
The method for producing the acrylic block copolymer (A) is not particularly limited, but it is preferable to use controlled polymerization using an initiator. Examples of controlled polymerization include living anion polymerization, radical polymerization using a chain transfer agent, and recently developed living radical polymerization. Of these, living radical polymerization is preferred from the viewpoint of controlling the molecular weight and structure of the acrylic block copolymer.

  Living radical polymerization is radical polymerization in which the activity at the polymerization terminal is maintained without loss. In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the terminal is in equilibrium. . The definition here is also the latter. Living radical polymerization has been actively researched by 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, 116, 7943), Atom transfer radical polymerization using radical scavengers such as nitroxide compounds (Macromolecules, 1994, Vol. 27, 7228), organic halides as initiators and transition metal complexes as catalysts ( Atom Transfer Radical Polymerization (ATRP). In the present invention, there is no particular restriction as to which of these methods is used, but atom transfer radical polymerization is preferred from the viewpoint of ease of control.

  Specific examples of the atom transfer radical polymerization include the method described in JP-A-2004-107447.

<Acrylic polymer (B)>
The acrylic polymer (B) constituting the thermoplastic elastomer composition according to the present invention is a polymer containing at least 1.1 or more epoxy groups in one molecule. The acrylic polymer (B) improves molding fluidity as a plasticizer during molding of the composition, and at the same time reacts with an acid anhydride group or carboxyl group in the acrylic block copolymer (A) during molding, The acrylic block copolymer (A) can be increased in molecular weight or crosslinked. In addition, the number here represents the average number of the epoxy group which exists in an acrylic polymer (B) molecule | numerator.

  The average number of epoxy groups per acrylic polymer (B) molecule is 1.1 or more, preferably 1.5 or more, more preferably 2.0 or more. The number depends on the reactivity of the epoxy group, the site and manner in which the epoxy group is contained, and the number, location and manner of acid anhydride groups and carboxyl groups per molecule of the acrylic block copolymer (A). Change. When the epoxy group content is less than 1.1, the block copolymer tends to have a high molecular weight or insufficient crosslinking, and the heat resistance of the acrylic block copolymer (A) tends to be insufficient. is there.

  The acrylic polymer (B) is obtained by polymerizing one or two or more (meth) acrylic monomers, or one or two or more (meth) acrylic monomers and (meth). It is preferably obtained by polymerizing other monomers other than acrylic monomers.

  Examples of (meth) acrylic monomers include acryloyl group-containing monomers and methacryloyl group-containing monomers. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) Propyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ( Examples include glycidyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, phenoxyethyl acrylate, and the like. As the other monomer, a monomer copolymerizable with an acrylic monomer such as vinyl acetate or styrene can be used.

  The ratio of the acryloyl group-containing monomer unit to the total monomer unit in the acrylic polymer (B) is preferably 70% by mass or more. When the proportion is less than 70% by mass, the weather resistance of such a polymer is relatively low, and the compatibility with the acrylic block copolymer (A) tends to decrease. Moreover, discoloration tends to occur in the molded product.

  The acrylic polymer (B) is composed of at least one monomer selected from the group consisting of -n-butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate, and a heterogeneous acrylic copolymerizable therewith. What consists of 50 to 100% by weight of an acid ester and 50 to 0% by weight of a vinyl monomer is preferred in terms of compatibility with the acrylic block copolymer (A). As the vinyl monomer, styrene is preferable.

  The weight average molecular weight of the acrylic polymer (B) is not particularly limited, but is preferably a low molecular weight of 30,000 or less, more preferably 500 to 30,000, and more preferably 500 to 10,000. Those are particularly preferred. When the weight average molecular weight is less than 500, the molded product tends to be sticky. On the other hand, when the weight average molecular weight exceeds 30,000, plasticization of the molded product becomes insufficient.

  The viscosity of the acrylic polymer (B) is preferably 35,000 mPa · s or less when measured with a cone-plate type rotational viscometer (E-type viscometer) at 25 ° C. A more preferable viscosity is 10,000 mPa · s or less. A particularly preferred viscosity is 5,000 mPa · s or less. When the viscosity is higher than 35,000 mPa · s, the plasticizing effect of the composition tends to decrease. There is no particular lower limit of the preferred viscosity, but the normal viscosity of the acrylic polymer is preferably 10 mPa · s or more.

  The glass transition temperature Tg of the acrylic polymer (B) measured by differential scanning calorimetry (DSC) is preferably 100 ° C. or lower, more preferably 25 ° C. or lower, and further preferably 0 ° C. or lower. Yes, particularly preferably -30 ° C or lower. When glass transition temperature Tg exceeds 100 degreeC, there exists a tendency for the effect which improves a moldability as a plasticizer to become inadequate, and it exists in the tendency for the softness | flexibility of the molded object obtained to fall.

  The acrylic polymer (B) is produced by polymerizing by a known predetermined method. The polymerization method may be appropriately selected as necessary. For example, suspension polymerization, emulsion polymerization, bulk polymerization, living anion polymerization, polymerization using a chain transfer agent, and controlled polymerization such as living radical polymerization may be performed. However, controlled polymerization in which a polymer having good weather resistance and heat resistance and a relatively low molecular weight and a small molecular weight distribution is obtained is preferable, and the method using high-temperature continuous polymerization described below is more preferable in terms of cost.

  The acrylic polymer (B) is preferably obtained by a polymerization reaction at a temperature of 180 to 350 ° C. At this polymerization temperature, a relatively low molecular weight acrylic polymer can be obtained without using a polymerization initiator or a chain transfer agent, so that the acrylic polymer is an excellent plasticizer and has good weather resistance. It is. Specifically, the method by high-temperature continuous polymerization disclosed in JP-A-57-502171, JP-A-59-6207, JP-A-60-215007 and WO01 / 083619 is exemplified. . That is, it is a method in which a mixture of the above monomers is continuously supplied into a reactor set at a predetermined temperature and pressure at a constant supply rate, and an amount of reaction liquid corresponding to the supply amount is withdrawn.

  Specific examples of the acrylic polymer (B) include ARUFON (registered trademark) XG4000, ARUFON UG4000, ARUFON XG4010, ARUFON UG4010, ARUFON XD945, ARUFON XD950, ARUFON UG4030, ARUFON UG40ON, and ARUONON 40, URU70ON from Toagosei Co., Ltd. Can be used for These are acrylic polymers such as all acrylic and acrylate / styrene, and contain 1.1 or more epoxy groups in one molecule.

  The acrylic polymer (B) is preferably used in the range of 0.5 to 50 parts by weight and used in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the acrylic block copolymer (A). It is more preferable to use in the range of 1.5 to 20 parts by weight. If the blending amount is less than 0.5 parts by weight, the moldability and the heat resistance of the resulting molded product may not be sufficient, and if it exceeds 50 parts by weight, the mechanical properties of the resulting composition tend to be reduced. .

<Compound (C)>
The compound (C) constituting the thermoplastic elastomer composition according to the present invention is represented by the general formula (1).

（式中、ｎは３〜２０の整数）

(Where n is an integer from 3 to 20)

  Compound (C) not only improves molding fluidity as a plasticizer during molding of the composition, but also prevents molding from adhering as pellets after molding or acts as a lubricant to obtain molding. It is possible to improve the wear resistance of the body. Furthermore, when the obtained sheet is used as a skin material for automobiles or the like, it is generally necessary to adhere the sheet to polyurethane or the like used as a base material, but the epoxy group contained in the compound (C) It is possible to give good adhesiveness. Furthermore, by reacting with the acid anhydride group or carboxyl group in the acrylic block copolymer (A) during molding, bleeding out to the surface of the molded body is suppressed, and contamination of the surface of the molded body and changes in gloss are suppressed. It is possible to prevent.

  The compound (C) preferably has a boiling point of 200 ° C. or higher, more preferably a boiling point of 250 ° C. or higher. When the boiling point is lower than 200 ° C., the molded body may be volatilized during molding or the molded body may be deformed due to volatilization after molding. Moreover, when giving abrasion resistance to the obtained molded object, stearyl glycidyl ether (n = 18 in General formula (1)) is preferable, and when giving a low temperature characteristic to a moldability and the obtained molded object Is preferably 2-ethylhexyl glycidyl ether (n = 8 in the general formula (1)).

  The compound (C) is preferably used in the range of 0.01 to 10 parts by weight, and in the range of 0.05 to 7.5 parts by weight with respect to 100 parts by weight of the acrylic block copolymer (A). It is more preferable to use it, and it is particularly preferable to use it in the range of 0.1 to 5 parts by weight. If the blending amount is less than 0.01 parts by weight, the formability, the wear resistance of the resulting molded body and the imparting of low temperature characteristics may not be sufficient. Characteristics and heat resistance tend to decrease.

<Thermoplastic elastomer composition>
While the thermoplastic elastomer composition of the present invention has a low melt viscosity during molding and excellent moldability, the acid anhydride group and / or carboxyl group in the acrylic block copolymer (A) during molding and an acrylic polymer. It is preferable that the acrylic block copolymer (A) is increased in molecular weight or cross-linked by reacting with the epoxy group in (B), in terms of improving heat resistance and improving melt fluidity at the time of molding. More preferably, it is crosslinked.

  Various additives and catalysts may be added to the thermoplastic elastomer composition of the present invention as needed in order to promote the reaction during molding. For example, it is possible to use a curing agent generally used for epoxy resins such as acid anhydrides such as acid dianhydrides, amines, and imidazoles.

  The thermoplastic elastomer composition of the present invention can be suitably used by blending a filler as necessary. The filler is not particularly limited, but wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, silica (fumed silica, sedimentation) Silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, etc.), reinforcing filler such as carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, Fillers such as clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, red pepper, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc dust, zinc carbonate and shirasu balloon; asbestos, Glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber And fibrous fillers such as and the like.

  Among these fillers, inorganic fillers are more preferable from the viewpoint of improving mechanical properties, reinforcing effect, cost, etc., and titanium oxide, carbon black, calcium carbonate, silica, and talc are more preferable.

  In the case of silica, silica whose surface has been previously hydrophobically treated with an organosilicon compound such as organosilane, organosilazane, or diorganopolysiloxane may be used. Furthermore, calcium carbonate is surface-treated using surface treatment agents such as organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents. You may use what has been given.

  The addition amount in the case of using the filler is preferably in the range of 5 to 200 parts by weight, more preferably in the range of 10 to 100 parts by weight, with respect to 100 parts by weight of the acrylic block copolymer (A). More preferred. If the blending amount is less than 5 parts by weight, the reinforcing effect of the resulting molded product may not be sufficient, and if it exceeds 200 parts by weight, the molding of the resulting composition tends to be reduced. A filler can be used 1 type or in combination of 2 or more types.

  If necessary, the thermoplastic elastomer composition of the present invention may be blended with various lubricants for moldability, mold releasability from the mold, and low friction of the surface of the resulting molded article.

  Examples of the lubricant include fatty acids such as stearic acid and palmitic acid, fatty acid metal salts such as calcium stearate, zinc stearate, magnesium stearate, potassium palmitate and sodium palmitate, polyethylene wax, polypropylene wax, and montanic acid wax. Waxes, low molecular weight polyolefins such as low molecular weight polyethylene and low molecular weight polypropylene, polyorganosiloxanes such as dimethylpolysiloxane, amide-based lubricants such as octadecylamine, alkyl phosphate, fatty acid ester, ethylenebisstearylamide, tetrafluoroethylene Fluorine resin powder such as resin, molybdenum disulfide powder, silicone resin powder, silicone rubber powder, silica and the like can be used. These can be used alone or in combination of two or more. Among these, stearic acid, zinc stearate, calcium stearate, fatty acid ester, and ethylene bisstearyl amide are preferable because of excellent cost and moldability.

  When the lubricant is used, the addition amount is preferably in the range of 0.1 to 20 parts by weight, and in the range of 0.2 to 10 parts by weight with respect to 100 parts by weight of the acrylic block copolymer (A). More preferably. If the blending amount is less than 0.1 parts by weight, the effect of improving the moldability and low friction of the resulting molded product may be insufficient, and if it exceeds 20 parts by weight, the mechanical properties of the molded product obtained And chemical resistance tend to deteriorate. At least one lubricant can be used.

  Various additives other than the above may be added to the thermoplastic elastomer composition of the present invention, if necessary, for the purpose of adjusting the physical properties of the thermoplastic elastomer composition and the molded article to be obtained. As such additives, stabilizers, plasticizers, flexibility imparting agents, flame retardants, pigments, antistatic agents, antibacterial and antifungal agents and the like may be added.

  Examples of the stabilizer include an antioxidant, a light stabilizer, and an ultraviolet absorber. Examples of the anti-aging agent include phenyl-α-naphthylamine (PAN), octyldiphenylamine, N, N′-diphenyl-p-phenylenediamine (DPPD), N, N′-di-β-naphthyl-p-phenylenediamine. (DNPD), N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine (IPPN), N, N′-diallyl-p -Phenylenediamine, phenothiazine derivatives, diallyl-p-phenylenediamine mixture, alkylated phenylenediamine, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine, N-phenyl-N '-(3-methacryloyloxy- 2-hydropropyl) -p-phenylenediamine, diallylphenylenedia Amine mixtures, diallyl-p-phenylenediamine mixtures, N- (1-methylheptyl) -N′-phenyl-p-phenylenediamine, amine-based antioxidants such as diphenylamine derivatives, 2-mercaptobenzimidazole (MBI), etc. Phenol-based aging such as imidazole-based anti-aging agent, 2,6-di-t-butyl-4-methylphenol, pentaerythrityltetrakis [3- (5-di-t-butyl-4-hydroxyphenol) -propinate] Inhibitors, phosphate anti-aging agents such as nickel diethyl-dithiocarbamate, secondary anti-aging agents such as triphenyl phosphite, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5 -Methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di Such as t- pentylphenyl) ethyl] -4,6-di -t- pentylphenyl acrylate. Examples of light stabilizers and ultraviolet absorbers include 4-t-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, ethyl-2-cyano-3,3′-. Diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, 2-hydroxy-5-chlorobenzophenone, 2-hydroxy-4-methoxybenzophenone-2-hydroxy-4-octoxybenzophenone, monoglycol sari Examples include tyrates, oxalic acid amides, 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the like.

  Industrial products include Irganox (registered trademark) 1010 (manufactured by Ciba Specialty Chemicals), Sanol (registered trademark) LS770 (Sankyo Lifetech Co., Ltd.), Adekastab (registered trademark) LA-57 (Asahi Denka Kogyo Co., Ltd.) Adeka Stub LA-68 (Asahi Denka Kogyo Co., Ltd.), Chimassorb (registered trademark) 944 (Ciba Specialty Chemicals Co., Ltd.), Sanol LS765 (Sankyo Lifetech Co., Ltd.), Adeka Stub LA-62 (Asahi Denka) Industrial Co., Ltd.), TINUVIN (registered trademark) 144 (Ciba Specialty Chemicals Co., Ltd.), ADK STAB LA-63 (Asahi Denka Kogyo Co., Ltd.), TINUVIN 622 (Ciba Specialty Chemicals Co., Ltd.), ADK STAB LA -3 (Asahi Denka Kogyo Co., Ltd.), ADK STAB LA-36 (Asahi Denka Kogyo Co., Ltd.), TINUVIN571 (Ciba Specialty Chemicals Co., Ltd.), TINUVIN234 (Ciba Specialty Chemicals Co., Ltd.), ADK STAB LA-31 (Asahi Denka Kogyo Co., Ltd.), TINUVIN 1130 (Ciba Specialty Chemicals Co., Ltd.), ADK STAB AO-20 (Asahi Denka Kogyo Co., Ltd.), ADK STAB AO-50 (Asahi Denka Kogyo Co., Ltd.), ADK STAB 2112 Asahi Denka Kogyo Co., Ltd.), Adekastab PEP-36 Asahi Denka Kogyo Co., Ltd.), Sumizer GM (Sumitomo Chemical Co., Ltd.), Sumiser GS (Sumitomo Chemical Co., Ltd.), Sumiser TP-D (Sumitomo Chemical Co., Ltd.) ) Etc. These may be used alone or in combination of two or more. Among them, Sanol LS770, Irganox 1010, Sumilizer GS, and TINUVIN234 are preferable because they are an effect of preventing deterioration and cost due to heat and light of the acrylic block body.

  Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, di- (2-ethylhexyl) phthalate, diheptyl phthalate, diisodecyl phthalate, and di-n-octyl phthalate. Phthalic acid derivatives such as diisononyl phthalate, ditridecyl phthalate, octyl decyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate; isophthalic acid derivatives such as dimethyl isophthalate; and di- (2-ethylhexyl) tetrahydrophthalic acid Tetrahydrophthalic acid derivatives; adipic acid derivatives such as dimethyl adipate, dibutyl adipate, di-n-hexyl adipate, di- (2-ethylhexyl) adipate, isononyl adipate, diisodecyl adipate, dibutyl diglycol adipate ; Azelaic acid derivatives such as di-2-ethylhexyl xylate; sebacic acid derivatives such as dibutyl sebacate; dodecane-2-acid derivatives; maleic acid derivatives such as dibutyl maleate and di-2-ethylhexyl maleate; dibutyl fumarate etc. Fumaric acid derivatives; trimellitic acid derivatives such as tris-2-ethylhexyl trimellitic acid; pyromellitic acid derivatives; citric acid derivatives such as acetyltributyl citrate; itaconic acid derivatives; oleic acid derivatives; ricinoleic acid derivatives; stearic acid derivatives; Derivatives; sulfonic acid derivatives; phosphoric acid derivatives; glutaric acid derivatives; polyester plasticizers that are polymers of dibasic acids such as adipic acid, azelaic acid, and phthalic acid and glycols and monohydric alcohols, glycol derivatives, glycerin derivatives, Paraffin derivatives of fluorinated paraffin, epoxy derivatives polyester polymerization type plasticizers, polyether polymerization type plasticizers, ethylene carbonate, or the like carbonate derivatives such as propylene carbonate. In the present invention, the plasticizer is not limited to these, and various plasticizers can be used, and those commercially available as rubber plasticizers can also be used. These compounds can be expected to lower the viscosity of the acrylic block copolymer (A). Commercially available plasticizers include Thiocol TP (Morton), Adekasizer (registered trademark) O-130P, C-79, UL-100, P-200, RS-735 (Asahi Denka). Can be mentioned. Examples of other high molecular weight plasticizers include acrylic polymers, polypropylene glycol polymers, polytetrahydrofuran polymers, polyisobutylene polymers, and the like. Although not particularly limited, adipic acid derivatives, phthalic acid derivatives, glutaric acid derivatives, trimellitic acid derivatives, pyromellitic acid derivatives, polyester plasticizers, glycerin derivatives, epoxies, which are low volatility and low weight loss due to heating, are not particularly limited Derivative polyester polymerization plasticizers, polyether polymerization plasticizers, and the like are preferable.

  The flexibility-imparting agent is not particularly limited, and examples thereof include softeners such as process oils; oils such as animal oils and vegetable oils; petroleum fractions such as kerosene, light oil, heavy oil, and naphtha. Examples of the softening agent include process oil, and more specifically, paraffin oil; naphthenic process oil; petroleum process oil such as aromatic process oil, 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. A combination of the above can be used.

  The flame retardant is not particularly limited, and examples thereof include triphenyl phosphate, tricresyl phosphate, decabromobiphenyl, decabromobiphenyl ether, and antimony trioxide. These may be used alone or in combination.

  The pigment is not particularly limited, and for example, carbon black, titanium oxide, zinc sulfide, zinc oxide and the like can be used. These may be used alone or in combination.

<Method for producing thermoplastic elastomer composition>
There is no restriction | limiting in particular in the manufacturing method of a thermoplastic elastomer composition, A thermoplastic elastomer composition can be manufactured by using a batch-type kneading apparatus or a continuous kneading apparatus. As the batch kneader, for example, a mixing roll, a Banbury mixer, a pressure kneader, or a high shear mixer can be used. Moreover, as a continuous kneading apparatus, a single screw extruder, a twin screw extruder, a KCK extrusion kneader, etc. can be used. Furthermore, existing methods such as a method of mechanically mixing and shaping into pellets can be used.

  The temperature at the time of kneading for producing the thermoplastic elastomer composition is preferably a temperature at which the moldability is not lowered by the reaction between the acrylic block copolymer (A) and the acrylic polymer (B). The temperature at which the acrylic block copolymer (A) and the acrylic polymer (B) react and the moldability deteriorates depends on the type of acid anhydride group, carboxyl group and epoxy group, the amount introduced, and the acrylic block copolymer weight. It is determined by the composition of the polymer (A) and the acrylic polymer (B), the compatibility between the acrylic block copolymer (A) and the acrylic polymer (B). For this reason, it changes so that it may react at desired temperature by changing these conditions. Here, the reaction temperature is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, and even more preferably 150 ° C. or lower, in order to allow the resulting composition to be molded.

  It is preferable to knead at a temperature at which high molecular weight and cross-linking do not occur, but it is only necessary to be moldable even if high molecular weight or partial cross-linking occurs.

  In the case of powder slush molding, it is preferable to obtain the thermoplastic elastomer composition as a powder. As a method for obtaining a powder, the thermoplastic elastomer composition in the block state or pellet state processed by the above method is finely pulverized using an impact type fine pulverizer such as a turbo mill, a pin mill, a hammer mill, or a centrifugal mill. There is a way. The pulverization is usually performed at room temperature, but can be mechanically pulverized using a refrigerant or a cooling facility.

<Method of molding thermoplastic elastomer composition>
The composition obtained in the section of the method for producing a thermoplastic elastomer can be molded by various methods. For example, it can be applied to powder slush molding, injection molding, injection blow molding, blow molding, extrusion blow molding, extrusion molding, calendar molding, vacuum molding, press molding, etc., but powder slush molding is more preferably used. Here, the powder slush molding is a method in which the composition powder is poured into a molding die heated to a high temperature, melt-molded, and a molded body cooled and solidified after a certain time has passed. In powder slush molding, it is necessary to flow and melt-mold even under no pressure, while the molded body after molding is exposed to a use environment of 100 ° C. or higher. For this reason, it is difficult to balance moldability and heat resistance. However, in the composition of the present invention, the acrylic block copolymer (A), the acrylic polymer (B) and the compound (C) are in an unreacted state before molding, and (B) and (C) are By effectively acting as a plasticizer, it is excellent in meltability in the mold, while the acrylic block copolymer (A), the acrylic polymer (B), and the compound within a certain time until cooling and solidification. (C) reacts, and the acrylic block copolymer (A) is increased in molecular weight or crosslinked to improve the heat resistance after molding. From this, it can be said that it is a material suitable for powder slush molding.

  In powder slush molding, the acrylic block copolymer (A) has a high molecular weight or is cross-linked to improve the heat resistance after molding, but the acrylic block copolymer (A) has a high molecular weight. When the number average molecular weight of the acrylic block copolymer (A) after molding is preferably 100,000 or more, more preferably 150,000 or more, and 200,000 or more. More preferably. When the number average molecular weight is lower than 100,000, the effect of improving heat resistance is lowered.

  In addition, when heat resistance is imparted by crosslinking at the time of molding, the insoluble fraction (% by weight) of the molded article after molding is preferably 50% by weight or more, and more preferably 70% by weight or more. 80% by weight or more is more preferable. This is because when the insoluble content is lower than 50% by weight, the effect of improving the heat resistance is lowered. On the other hand, the insoluble fraction before molding is preferably 30% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less. This is because moldability tends to deteriorate when the content is 30% by weight or more.

  The insoluble fraction (% by weight) was determined by wrapping 1 g of the thermoplastic elastomer composition in a 350 mesh wire net and immersing it in 80 ° C. toluene or 60 ° C. acetone for 24 hours. The polymer is soluble), the toluene or acetone soluble fraction is fractionated, the residual solid content is vacuum dried at 80 ° C., and the weight of the residual solid content after drying is measured to determine the thermoplastic elastomer composition. By expressing the weight of residual solids per gram of product.

  EXAMPLES Although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these Examples. In the examples, BA, EA, TBA, MMA, and TBMA each represent -n-butyl acrylate, ethyl acrylate, tert-butyl acrylate, methyl methacrylate, and tert-butyl methacrylate. Moreover, the molecular weight described in the examples, the conversion rate of the polymerization reaction, and the evaluation of each physical property were performed according to the following methods.

<Molecular weight measurement method>
The molecular weight 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, a GPC system manufactured by Waters was used, and Shodex K-804 (polystyrene gel) manufactured by Showa Denko Co., Ltd. was used for the column.

<Method for measuring conversion rate of polymerization reaction>
The conversion rate of the polymerization reaction shown in this example was measured using the following analyzer and conditions.
Equipment used: Gas chromatography GC-14B manufactured by Shimadzu Corporation
Separation column: manufactured by J & W SCIENTIFIC INC, capillary column Supercoux-10, 0.35 mmφ × 30 m
Separation conditions: Initial temperature 60 ° C, hold for 3.5 minutes
Temperature increase rate 40 ° C / min
Final temperature 140 ° C, hold for 1.5 minutes
Injection temperature 250 ° C
Detector temperature 250 ° C
Sample preparation: The sample was diluted about 10 times with ethyl acetate, and butyl acetate or acetonitrile was used as an internal standard substance.

<Glass transition temperature>
The glass transition temperature of the methacrylic polymer block constituting the acrylic block copolymer shows the maximum value of the ratio of loss elastic modulus / storage elastic modulus (Tanδ) from 50 ° C. to 130 ° C. in the dynamic viscoelasticity measurement. Measured as temperature.
The measurement is based on JIS K-6394 (Testing method for dynamic properties of vulcanized rubber and thermoplastic rubber). A test piece having a length of 6 mm, a width of 5 mm, and a thickness of 2 mm is cut out and a dynamic viscoelasticity measuring device DVA-200 ( Using IT Measurement Control Co., Ltd.), the measurement frequency was 0.5 Hz.

<Ethanol resistance test>
The ethanol resistance shown in the examples and comparative examples was measured under the following conditions.

  The textured sheet prepared in the examples and comparative examples was placed on a flat surface, and a drop of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped with a pipette and left at room temperature for 24 hours. Thereafter, the surface was visually observed, and those having no trace were evaluated as ◎, and those having whitening were evaluated as ×.

<Oil resistance test>
The oil resistance shown in the examples and comparative examples was measured under the following conditions.

  The textured sheet prepared in the examples and comparative examples was placed on a flat surface, and one drop of liquid paraffin (manufactured by Nacalai Tesque) was dropped with a pipette and left at room temperature for 24 hours. Thereafter, the liquid paraffin was wiped off with Kimwipe (registered trademark) (manufactured by Crecia Co., Ltd.), the surface was visually observed, and ◎ was evaluated when there was no trace, and × was evaluated when whitening was observed.

<Heat resistance test>
The heat resistance shown in the examples and comparative examples was measured under the following conditions.

  The embossed sheet prepared in Examples and Comparative Examples was allowed to stand at 120 ° C. for 24 hours. Then, visually observe the surface, ◎ if the change of the wrinkle pattern is not recognized, ◎, the change of the wrinkle pattern is not clear, but the surface gloss is slightly increased compared to the initial, ○, wrinkle pattern change What was recognized was made into x.

<Urethane adhesion test>
According to the example, the composition was press-molded to prepare a skin material. A cartridge type polyurethane (manufactured by Air Tight Co., Ltd.) whose main component is 4,4′-diphenylmethane diisocyanate was applied onto a metal plate, and a skin material was immediately placed on the foam and adhered. After 12 hours or more have passed (when the foam is completely cured), peel the skin material from the foamed urethane by hand and observe the state of destruction. The case where the breakage occurred at the interface between the sheet and the urethane was indicated as x.

<Powder slash property test>
The melt fluidity (powder slash property) at the time of molding shown in the examples and comparative examples was evaluated by the method shown below.

  The block state sample produced according to the Example or the comparative example was pulverized using a pulverizer (VC210KW2.2 manufactured by Horai Iron Works Co., Ltd.) to obtain a coarse granular sample. Next, 6 parts by weight of silica powder (manufactured by Tatsumori Co., Ltd., microcrystalline soft silica A-10) is dry blended to 100 parts by weight of the obtained coarse granular sample, or pellets obtained in Examples or Comparative Examples, The pulverization process was carried out by setting the disk rotation speed of a pulverizer (UCM150 manufactured by Mitsui Mining Co., Ltd. (disk diameter 300 mm, motor output 3.7 kW)) to 10000 rpm, and a powdery sample was obtained. The obtained powder was further sieved using a stainless steel mesh (22 mesh, 710 μm) to obtain a uniform powder.

  The obtained powder was placed on a leather metal plate heated to 260 ° C., and after 10 seconds, the mold was inverted to remove excess powder, and the heat-melted powder was held for another 30 seconds. Next, the mold was water-cooled to 60 ° C., and then the sheet was peeled off to obtain a molded sheet.

  Evaluation index: The obtained molded sheet is visually observed with good wrinkle transfer and no pinholes / bubbles: ◎, wrinkle transferability is good with no pinholes / bubbles, but the back of the sheet is not smooth : ○, Poor formation of wrinkles and pinholes / bubbles: evaluated as x.

<Abrasion evaluation test>
A 3 cm × 10 cm sample was cut out from the sheet obtained by slush molding, and an abrasion test was performed with an abrasion tester.
Equipment used: Haydon-type wear tester 14DR (manufactured by Shinto Kagaku Co., Ltd.)
Movement speed: 6000 mm / min Movement length: 5 cm
Number of movements: 5 reciprocating load weight: 1 kg
Wear jig: An ASTM-type jig was fixed to the shaft so that the jig was always parallel to the sample. A semi-cylinder obtained by cutting a cylinder made of aluminum and having a diameter of 2.5 cm and a length of 1 cm in half was bonded to the lower side of the ASTM jig. On top of that, a cloth with a gold width of 3 was attached in a quadruple roll and fixed with an ASTM jig stopper.

After completion of the test, the sample was visually observed and evaluated according to the following criteria.
Those whose scratches are not clearly seen from the front; ◎
Obvious scratches such as whitening and erosion; ×

(Production Example 1)
Synthesis of Acrylic Block Copolymer (A) Precursor The following operation was performed to obtain an acrylic block copolymer (A) precursor. After replacing the inside of the 500 L pressure-resistant reactor with nitrogen, 688 g (4.80 mol) of copper bromide, 78,400 g (612 mol) of BA and 2,870 g (22.4 mol) of TBA were charged, and stirring was started. Thereafter, a solution prepared by dissolving 1,320 g (3.69 mol) of diethyl 2,5-dibromoadipate in 7140 g of acetonitrile (nitrogen bubbling) was charged, and the inner solution was heated to 75 ° C. for 30 minutes. Stir. When the internal temperature reached 75 ° C., 83.2 g (0.480 mol) of the ligand pentamethyldiethylenetriamine was added to initiate polymerization of the acrylic polymer block.

  About 100 mL of the polymerization solution was extracted from the polymerization solution for sampling at regular intervals from the start of polymerization, and the conversion rates of BA and TBA were determined by gas chromatogram analysis of the sampling solution. During polymerization, the polymerization rate was controlled by adding pentamethyldiethylenetriamine as needed. Pentamethyldiethylenetriamine was added twice in total (166 g in total) during the acrylic polymer block polymerization.

  When the conversion rate of BA is 99.1% and the conversion rate of TBA is 99.3%, MMA 48,300 g (482 mol), EA 7,840 g (78.3 mol), copper chloride 475 g (4.80 mol) Then, 83.2 g (0.480 mol) of pentamethyldiethylenetriamine and 104,000 g of toluene (nitrogen bubbled) were added to initiate polymerization of the methacrylic polymer block.

Sampling was performed when MMA and EA were added, and conversion rates of MMA and EA were determined based on this. After adding MMA and EA, the internal temperature was set to 85 ° C. During polymerization, the polymerization rate was controlled by adding pentamethyldiethylenetriamine as needed. Pentamethyldiethylenetriamine was added a total of 6 times (total 499 g) during methacrylic polymer block polymerization. When the conversion rate of MMA was 95.9%, 250,000 g of toluene was added, and the reactor was cooled to complete the reaction. When the GPC analysis of the obtained block copolymer was performed, the number average molecular weight Mn was 53,100 and molecular weight distribution Mw / Mn was 1.46. Toluene was added to the resulting reaction solution to make the polymer concentration 25% by weight. To this solution, 2,190 g of p-toluenesulfonic acid was added, the inside of the reactor was purged with nitrogen, and the mixture was stirred at 30 ° C. for 3 hours. The reaction solution was sampled to confirm that the solution was colorless and transparent, and 6,570 g of Radiolite # 3000 manufactured by Showa Chemical Industry was added. Thereafter, the reactor was pressurized to 0.1 to 0.4 MPaG with nitrogen, and the solid content was separated using a pressure filter (filter area 0.45 m ² ) equipped with polyester felt as a filter medium.

(Production Example 2)
Synthesis of acrylic block copolymer (A) To the obtained filtrate, 790 g of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was added, and TBMA as an internal standard substance was added to 100 wt% of the filtrate. 0.1 wt% was added. This solution was heated and stirred at 150 ° C. for 4 hours. After 4 hours, the solution was sampled, it was confirmed that TBMA had disappeared by GC measurement, the reaction was terminated, and the solution was cooled.

To the resulting solution, Kyoward 500SH, 13,150 g, was added, the inside of the reactor was purged with nitrogen, and the mixture was stirred at 30 ° C. for 1 hour. The solution was sampled, and it was confirmed that the solution was neutral. Thereafter, the reactor was pressurized to 0.1 to 0.4 MPaG with nitrogen, and the solid content was separated using a pressure filter (filter area 0.45 m ² ) equipped with polyester felt as a filter medium to obtain a polymer solution. It was. 790 g of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and 1,315 g of hydrotalcite DHT-4A-2 (manufactured by Kyowa Chemical Industry Co., Ltd.) as an acid trapping agent are added to the obtained polymer solution. did.

Subsequently, the solvent component was evaporated from the polymer solution. As an evaporator, SCP100 (heat transfer area 1 m ² ) manufactured by Kurimoto Steel Corporation was used. The evaporation of the polymer solution was carried out by setting the heating medium oil at the evaporator inlet to 180 ° C., the evaporator vacuum to 90 Torr, the screw rotation speed to 60 rpm, and the polymer solution supply rate to 32 kg / h. The polymer is made into a strand with a φ4 mm die through a discharger, cooled in a water tank filled with 3% suspension of Alflow H50ES (main component: ethylenebisstearic acid amide, manufactured by Nippon Oil & Fats Co., Ltd.), and then by a pelletizer. A cylindrical pellet was obtained. In this way, pellets of the acrylic block copolymer (A) were produced.

  The conversion efficiency of the t-butyl ester moiety into an acid anhydride group and a carboxyl group was measured by quantifying the amount of isobutylene generated from the t-butyl group by a 280 ° C. thermal decomposition reaction. As a result of the measurement, the conversion efficiency of the obtained resin was 95% or more. The resulting acrylic block copolymer (A) had a Tg of 101 ° C. for the methacrylic polymer block (a).

Example 1
Acrylic block copolymer obtained in Production Example 2; 100 parts by weight (38 g), all acrylic, containing 1.1 or more epoxy groups per molecule (approximate value 4 (from catalog)) ARUFON XG4010 (manufactured by Toagosei Co., Ltd.), 1 part by weight of epiol SK (manufactured by Nippon Oil & Fats Co., Ltd.) as stearyl glycidyl ether, Adekasizer RS700 (Asahi Denka Kogyo Co., Ltd.) as a plasticizer 5 parts by weight, calcium carbonate (Shiraishi Calcium Co., Ltd., Brilliant 1500) 43 parts by weight, beef tallow extremely hardened oil (Nippon Yushi Co., Ltd.) 0.14 parts by weight, carbon black (Asahi Carbon) Manufactured by Asahi # 15, Laboplast Mill 50C150 (blade shape: roller type R60 (set to 100 ° C.) at a ratio of 1.4 parts by weight. ) Toyo Seiki Seisakusho) for 15 minutes at 100rpm using a melt-kneaded to obtain a block-shaped sample.

  The obtained sample was heat-pressed at a set temperature of 200 ° C. for 5 minutes using a leather metal plate (compression molding machine NSF-50, manufactured by Kondo Metal Industry Co., Ltd.), and the thickness of the skin texture transferred. A molded body for evaluation of 1 mm was obtained. These molded bodies were subjected to an abrasion resistance test. The results are shown in Table 1. Moreover, the powder slush property test was implemented with the powder which grind | pulverized the block-shaped sample obtained above, and, thereby, the melt fluidity at the time of shaping | molding was confirmed. Furthermore, ethanol resistance, oil resistance, urethane adhesion, and heat resistance tests were measured using the sheets obtained in the powder slush property test. The results are shown in Table 1.

(Example 2)
Evaluation was performed in the same manner as in Example 1 except that the amount of the epiol SK in Example 1 was changed to 5 parts by weight, using the pellet-like sample and the molded body obtained by performing the same operation as in Example 1. Went. The results are shown in Table 1.

(Comparative Example 1)
Evaluation was performed in the same manner as in Example 1 using a pellet-like sample and a molded body obtained by performing the same operation as in Example 1 except that Epiol SK was not added in Example 1. The results are shown in Table 1.

  From Table 1, it can be seen that the composition to which no epiol SK is added is inferior in wear resistance.

  As is clear from Table 1 (Examples 1 and 2 and Comparative Example 1), the thermoplastic elastomer composition of the present invention was not only excellent in melt fluidity (powder slash moldability) during molding, but also obtained. It can be seen that the molded product is excellent in heat resistance, oil resistance, ethanol resistance, urethane adhesion, and abrasion resistance.

The molded body obtained by molding the thermoplastic elastomer composition of the present invention is excellent in heat resistance, weather resistance, chemical resistance, adhesion, flexibility, wear resistance, etc. Plastic elastomer compositions are used as materials such as skin materials, touch panels and other materials that require good tactile sensation, materials whose appearance is important, wear-resistant materials, oil-resistant materials, vibration-damping materials, adhesive materials, etc. can do. In addition, the shape of the sheet, flat plate, film, small molded body, large molded body and other arbitrary shapes, and as parts such as panels, handles, grips, switches, etc. Can also be used as a sealing member. Although it does not restrict | limit especially as a use, The object for motor vehicles, household electrical appliances, or office electrical appliances are illustrated. For example, automotive skin materials, automotive tactile materials, automotive exterior materials, automotive panels, automotive handles, automotive grips, automotive switches, and household or office electrical panels Examples thereof include switches for household or office electrical appliances. Among these, it is suitably used for an automobile interior skin.

Claims (21)

A methacrylic polymer block (a) mainly composed of a methacrylic polymer and an acrylic polymer block (b) mainly composed of an acrylic polymer, and at least one of these polymer blocks 100 parts by weight of an acrylic block copolymer (A) having an acid anhydride group and / or a carboxyl group and 0.5 acrylic polymer (B) having at least 1.1 epoxy groups in one molecule To 50 parts by weight and the general formula (1):

(Where n is an integer from 3 to 20)
A thermoplastic elastomer composition comprising 0.01 to 10 parts by weight of the compound (C) represented by the formula:   The thermoplastic elastomer composition according to claim 1, wherein an acid anhydride group and / or a carboxyl group are present in the main chain of the acrylic block copolymer (A). The acid anhydride group has the general formula (2):

Wherein R ¹ is hydrogen or a methyl group, and two R ^{1 s} may be the same or different from each other. N is an integer of 0 to 3, and m is an integer of 0 or 1. The thermoplastic elastomer composition according to claim 1 or 2.   The acrylic block copolymer (A) comprises 10 to 60% by weight of a methacrylic polymer block (a) and 90 to 40% by weight of an acrylic polymer block (b). The thermoplastic elastomer composition according to any one of 1 to 3.   The methacrylic polymer block (a) is at least one acryl selected from the group consisting of 50-100% by weight of methyl methacrylate and ethyl acrylate, acrylic acid-n-butyl and acrylic acid-2-methoxyethyl. The thermoplastic elastomer composition according to any one of claims 1 to 4, wherein the thermoplastic elastomer composition is a block copolymer comprising 50 to 0% by weight of an acid ester monomer.   The thermoplastic elastomer composition according to any one of claims 1 to 5, wherein the methacrylic polymer block (a) is a block copolymer comprising methyl methacrylate and ethyl acrylate.   The thermoplastic elastomer composition according to any one of claims 1 to 6, wherein the methacrylic polymer block (a) has a glass transition temperature of 50 to 130 ° C.   The acrylic polymer block (b) is at least one monomer selected from the group consisting of -n-butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate, and different types copolymerizable therewith. The thermoplastic elastomer composition according to any one of claims 1 to 7, comprising 50 to 100% by weight of an acrylic acid ester and 50 to 0% by weight of a vinyl monomer.   The thermoplastic resin according to any one of claims 1 to 8, wherein the acrylic block copolymer (A) has a number average molecular weight measured by gel permeation chromatography of 30,000 to 200,000. Elastomer composition.   The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography of the acrylic block copolymer (A) is 1.8 or less. The thermoplastic elastomer composition according to any one of claims 1 to 9.   The thermoplastic elastomer composition according to any one of claims 1 to 10, wherein the acrylic block copolymer (A) is a block copolymer produced by atom transfer radical polymerization.   The thermoplastic elastomer composition according to any one of claims 1 to 11, wherein the acrylic polymer (B) has a weight average molecular weight of 30,000 or less.   The thermoplastic elastomer composition according to any one of claims 1 to 12, wherein the glass transition temperature of the acrylic polymer (B) is 100 ° C or lower.   The thermoplastic elastomer composition according to any one of claims 1 to 13, wherein the acrylic polymer (B) has a weight average molecular weight of 500 to 10,000.   The thermoplastic elastomer composition according to any one of claims 1 to 14, wherein the viscosity of the acrylic polymer (B) is 35,000 mPa · s or less.   The thermoplastic elastomer composition according to any one of claims 1 to 15, wherein the compound (C) is stearyl glycidyl ether.   The thermoplastic elastomer composition according to any one of claims 1 to 16, wherein 5 to 200 parts by weight of a filler is further added to 100 parts by weight of the acrylic block copolymer (A).   The thermoplastic elastomer composition according to any one of claims 1 to 17, wherein 0.1 to 20 parts by weight of a lubricant is further added to 100 parts by weight of the acrylic block copolymer (A).   A thermoplastic elastomer composition for powder slush molding, comprising the composition according to any one of claims 1 to 18.   A molded article comprising the composition according to any one of claims 1 to 19 formed by powder slush molding. An automotive interior skin comprising the composition according to any one of claims 1 to 19 formed by powder slush molding.