JP2006257167A - Method for producing a thermoplastic elastomer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition excellent in moldability, heat resistance and oil resistance, particularly a thermoplastic elastomer composition excellent in heat resistance comprising a (meth)acrylic block copolymer. <P>SOLUTION: The method for producing the thermoplastic elastomer composition comprises kneading in an extruder a composition comprising a (meth)acrylic block copolymer (A) having an acid anhydride group and/or a carboxyl group together with an acrylic polymer (B) having a reactive functional group (C). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a method for producing a thermoplastic elastomer composition. More specifically, the present invention relates to a method for producing a thermoplastic elastomer composition containing a (meth) acrylic block copolymer.

As a (meth) acrylic block copolymer having properties as a thermoplastic elastomer, for example, Patent Document 1 discloses a (meth) acrylic block copolymer having a methacrylic block and an acrylic block produced by an iniferter method, and its Mechanical properties are disclosed.

A thermoplastic elastomer composition comprising a (meth) acrylic block copolymer has a feature that it is excellent in weather resistance, heat resistance, durability and oil resistance. Moreover, it is possible to give a very flexible elastomer compared with other thermoplastic elastomers, such as a styrene-type block body, by selecting suitably the component which comprises a block body.

However, the heat resistance of thermoplastic elastomers produced by ordinary manufacturing methods is limited to about 100 ° C for thermoplastic elastomer compositions using (meth) acrylic block copolymers, providing thermoplastic elastomers with better heat resistance. There is a need for a production method that can be used.

Japanese Patent No. 2553134

The present invention provides a method for producing a thermoplastic elastomer composition excellent in moldability, heat resistance and oil resistance, particularly a thermoplastic elastomer composition containing a (meth) acrylic block copolymer excellent in heat resistance. is there.

As a result of intensive studies on a method for producing a thermoplastic elastomer composition excellent in moldability, heat resistance and oil resistance, the present inventors have found that a (meth) acrylic block copolymer having an acid anhydride group and / or a carboxyl group ( By kneading the composition containing A), it has been found that a thermoplastic elastomer excellent in moldability, heat resistance and oil resistance can be produced, and the present invention has been completed.

That is, the present invention relates to a composition containing a (meth) acrylic block copolymer (A) having an acid anhydride group and / or a carboxyl group as an acrylic polymer (B) having a reactive functional group (C). And a method for producing a thermoplastic elastomer composition characterized by being kneaded in an extruder.

As a preferred embodiment, the present invention relates to a method for producing the thermoplastic elastomer composition, wherein the extruder is a twin screw extruder.

In a preferred embodiment of the thermoplastic elastomer composition, the reactive functional group (C) is at least one selected from the group consisting of an epoxy group, a hydroxyl group, an amino group, and a carboxyl group. It relates to a manufacturing method.

In a preferred embodiment, the (meth) acrylic block copolymer (A) is 15 to 50% by weight of methacrylic polymer block (a) and 85 to 50% by weight of acrylic polymer block (b). It is related with the manufacturing method of the said thermoplastic-elastomer composition characterized by the above-mentioned.

As a preferred embodiment, the acrylic polymer (B) having the reactive functional group (C) is set such that the total shear strain amount ε in the extruder represented by the following formula is 100 <ε <8,000. It is related with the manufacturing method of the said thermoplastic elastomer composition characterized by adding to.

In the formula, π is the circumference ratio, D is the diameter of the extruder (mm), N is the number of rotations (rpm), h is the depth of the screw groove (mm), and t is the acrylic polymer (B) in the extruder. This is the time (seconds) from adding to the die.

As a preferred embodiment,
(I) Main feed section at the entrance of the extruder,
(Ii) a primary kneading zone from the main feed part to the intermediate addition part,
(Iii) midway addition part,
(Iv) A secondary kneading zone from the midway addition part to the die,
In an extruder containing
Supplying a composition containing the (meth) acrylic block copolymer (A) having the acid anhydride group and / or carboxyl group from the main feed portion;
The present invention relates to a method for producing the thermoplastic elastomer composition, wherein the acrylic polymer (B) having the reactive functional group (C) is added from the intermediate addition portion and kneaded.

As a preferred embodiment,
(I) Main feed section at the entrance of the extruder,
(Ii) a primary kneading zone from the main feed part to the intermediate addition part,
(Iii) midway addition part,
(Iv) A secondary kneading zone from the midway addition part to the die,
(Meth) acrylic block copolymer (A) comprising methacrylic polymer block (a) and 85 to 50% by weight acrylic polymer block (b) in the above-mentioned primary kneading zone. It is related with the manufacturing method of the said thermoplastic elastomer composition characterized by setting and setting kneading | mixing temperature of the cylinder of this to [(Glass transition temperature of a methacrylic polymer block (a))-10] degree C or less.

As a preferred embodiment, the present invention relates to a method for producing the thermoplastic elastomer composition, wherein the primary kneading zone and the secondary kneading zone are kneaded at different set temperatures.

As a preferred embodiment, an acrylic polymer having a reactive functional group (C) is used as a composition containing a (meth) acrylic block copolymer (A) having an acid anhydride and / or a carboxyl group in an extruder. B) Keeping the thermoplastic elastomer composition obtained by kneading together with the crosslinking temperature of the acid anhydride group and / or carboxyl group and the reactive functional group (C) when molding into a final product. The manufacturing method of the said thermoplastic-elastomer composition characterized by these.

Molding, characterized in that the thermoplastic elastomer composition obtained by the production method is molded at a temperature equal to or higher than the crosslinking temperature of the acid anhydride group and / or carboxyl group and the reactive functional group (C). The present invention relates to a method for manufacturing a body.

By using the production method of the present invention, it becomes possible to easily produce a thermoplastic elastomer composition excellent in moldability, heat resistance and oil resistance.

Hereinafter, the present invention will be described in more detail.

The present invention provides a composition containing a (meth) acrylic block copolymer (A) having an acid anhydride group and / or a carboxyl group, together with an acrylic polymer (B) having a reactive functional group (C). It is characterized by kneading in an extruder.

The acrylic polymer (B) has a reactive functional group (C), and the reactive functional group (C) is present in the (meth) acrylic polymer block copolymer (A). The (meth) acrylic block copolymer (A) reacts with a group or a carboxyl group at the time of molding, and the molecular weight is increased or crosslinked.

Below, each component of the thermoplastic elastomer composition which concerns on this invention is demonstrated in detail.

<(Meth) acrylic block copolymer (A)>
The (meth) acrylic block copolymer (A) used in the present invention is not particularly limited as long as it contains a (meth) acrylic monomer as a monomer component, but the (meth) acrylic monomer is the main component. It is preferable that In the present invention, “having a (meth) acrylic monomer as a main component” means an acrylic monomer or a methacrylic monomer among the monomer units constituting the main chain of the polymer (the “(meth)) This means that the monomer unit derived from “acrylic monomer” is 50% by weight or more. Further, among the monomer units constituting the main chain of the (meth) acrylic block copolymer (A), the monomer unit derived from the (meth) acrylic monomer is more preferably 70% by weight or more. 90% by weight or more is particularly preferable.

Examples of the acrylic monomer constituting the (meth) acrylic block copolymer (A) include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, and n-acrylate. -Acrylic aliphatic hydrocarbons such as pentyl, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate (For example, alkyl having 1 to 18 carbon atoms) ester; acrylic acid alicyclic hydrocarbon ester such as cyclohexyl acrylate and isobornyl acrylate; acrylic acid aromatic hydrocarbon ester such as phenyl acrylate and toluyl acrylate; benzyl acrylate Acrylic acid aralkyl Esters: Esters of acrylic acid such as 2-methoxyethyl acrylate and 3-methoxybutyl acrylate and functional group-containing alcohols having etheric oxygen; trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, acrylic 2-perfluoroethylethyl acid, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethyl methyl acrylate, 2-peracrylate Fluorinated alkyl esters such as fluoromethyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl acrylate, etc. Kill.

Examples of the methacrylic monomer constituting the (meth) acrylic block copolymer (A) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and n methacrylate. -Methacrylic aliphatic hydrocarbons such as pentyl, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, stearyl methacrylate (For example, alkyl having 1 to 18 carbon atoms) ester; methacrylic acid alicyclic hydrocarbon ester such as cyclohexyl methacrylate and isobornyl methacrylate; aralkyl methacrylate such as benzyl methacrylate; phenyl methacrylate; Methacrylic acid aromatic hydrocarbon esters such as tolyl tacrylate; Esters of methacrylic acid such as 2-methoxyethyl methacrylate and 3-methoxybutyl methacrylate and functional group-containing alcohols having etheric oxygen; Trifluoromethyl methacrylate; Trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-trifluoroethyl methacrylate, 2-perfluoroethyl ethyl methacrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl methacrylate, methacrylic acid 2-perfluoroethyl, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, 2-perfluoromethyl-2-perfluoroethyl methyl methacrylate, 2-perfluorohexyl ethyl methacrylate 2-perfluorodecyl methacrylate, and methacrylic acid fluorinated alkyl esters such as methacrylic acid 2-perfluoroalkyl-hexadecyl ethyl.

These can be used alone or in combination of two or more. Among the acrylic monomers or methacrylic monomers, acrylic acid aliphatic hydrocarbon esters or methacrylic acid aliphatic hydrocarbon esters are preferable from the viewpoint of processability, cost, and availability, and acrylic acid alkyl esters or alkyl methacrylates. Esters are more preferred, with methyl acrylate or methyl methacrylate being particularly preferred.

The monomer other than the (meth) acrylic monomer that can be used together with the (meth) acrylic monomer constituting the (meth) acrylic block copolymer (A) is not particularly limited as long as it is a monomer capable of cationic polymerization. Examples thereof include aromatic alkenyl compounds, vinyl cyanide compounds, conjugated diene compounds, halogen-containing unsaturated compounds, vinyl ester compounds, maleimide compounds, and the like.

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 with (meth) acrylic monomers. Monomers other than these (meth) acrylic monomers are appropriately selected in consideration of the glass transition temperature of the methacrylic polymer block (a) described later, compatibility with the acrylic polymer (B), and the like.

The molecular weight of the (meth) acrylic block copolymer (A) is preferably adjusted so that the number average molecular weight measured by gel permeation chromatography is 30,000 to 200,000. If the molecular weight is smaller than 30,000, sufficient mechanical properties as an elastomer may not be exhibited. Conversely, if the molecular weight is larger than 200,000, processing properties may be deteriorated. More preferably, it is 40,000-180,000, More preferably, it is 50,000-150,000.

Moreover, 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 (meth) acrylic block copolymer (A) is 1.8 or less. It is preferable that it is 1.5 or less. When Mw / Mn exceeds 1.8, the uniformity of the (meth) acrylic block copolymer (A) may deteriorate.

The structure of the (meth) acrylic block copolymer (A) is not particularly limited, but a linear block copolymer, a branched (star) block copolymer, or a mixture thereof is more preferable. The structure of such a block copolymer is appropriately selected according to the required physical properties of the (meth) acrylic block copolymer (A), but is linear in terms of cost and ease of polymerization. A block copolymer is particularly preferred.

Among the linear block copolymers, the (meth) acrylic block copolymer (A) is composed of a methacrylic polymer block (a) that is a hard segment and an acrylic polymer block (b) that is a soft segment. Is preferably a copolymer. The methacrylic polymer block (a) provides shape retention during molding, and the acrylic polymer block (b) provides elasticity as an elastomer and meltability during molding. For this purpose, in the (meth) acrylic block copolymer (A), the proportion of the methacrylic polymer block (a) is 15 to 50% by weight, and the proportion of the acrylic polymer block (b) is 85. It is preferable to set it to -50 weight%. If the proportion of the methacrylic polymer block (a) is smaller than 15% by weight and the proportion of the acrylic polymer block (b) is larger than 85% by weight, the shape may not be maintained during molding, and the methacrylic polymer block When the proportion of (a) is larger than 50% by weight and the proportion of the acrylic polymer block (b) is smaller than 50% by weight, the elasticity as an elastomer and the meltability during molding may be lowered.

From the viewpoint of the hardness of the composition, when the proportion of the methacrylic polymer block (a) is small, the hardness tends to be low, and when the proportion of the methacrylic polymer block (b) is small, the hardness tends to be high. There is. For this reason, the composition ratio of the acrylic polymer block (a) and the methacrylic polymer block (b) needs to be appropriately set in consideration of the required hardness of the elastomer composition. Further, from the viewpoint of workability, when the proportion of the acrylic polymer block (a) is small, the viscosity is low, and when the proportion of the methacrylic polymer block (b) is small, the viscosity tends to be high. For this reason, the composition ratio of the acrylic polymer block (a) and the methacrylic polymer block (b) needs to be appropriately set in consideration of required processing characteristics.

The linear block copolymer may have any structure, but from the viewpoint of the physical properties of the linear block copolymer or 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 made of at least one (meth) 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.

The relationship between the glass transition temperature of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the (meth) acrylic block copolymer (A) is the glass of the methacrylic polymer block (a). When the transition temperature is Tg _a and the glass transition temperature of the acrylic polymer block (b) is Tg _b , it is preferable to satisfy the following relationship in terms of mechanical strength, rubber elasticity, and the like.
Tg _a > Tg _b

The glass transition temperature (Tg) of the methacrylic polymer block (a) and the acrylic polymer block (b) can be measured by DSC (differential scanning calorimetry) or tan δ peak of dynamic viscoelasticity.

<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. The methacrylic acid ester is 50 to 100% by weight and a vinyl monomer copolymerizable therewith. It is preferably composed of 0 to 50% by weight, and may contain an acid anhydride group and / or a carboxyl group. When the proportion of the methacrylic acid ester is less than 50% by weight, the weather resistance or the like that is characteristic of the methacrylic acid ester may be impaired.

Examples of the methacrylic acid ester constituting the methacrylic polymer block (a) include the methacrylic acid esters described above.

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

The glass transition temperature of the methacrylic polymer block (a) is adjusted to 50 to 130 ° C. This is because if the glass transition temperature Tg _a of the methacrylic polymer block (a) is more than 130 ° C., is because the moldability becomes high melt viscosity is deteriorated, when the glass transition temperature Tg _a is lower than 50 ° C. This is because it has fluidity at room temperature and is difficult to handle.

<Acrylic polymer block (b)>
The monomer constituting the acrylic polymer block (b) is 100 to 50% by weight of an acrylate ester from the viewpoint of easily obtaining a spherical powder having the desired physical properties, cost and availability. It preferably consists of 0 to 50% by weight of a polymerizable vinyl monomer, and consists of 100 to 75% by weight of an acrylate ester and 0 to 25% by weight of a vinyl monomer copolymerizable therewith. Is more preferable. When the proportion of the acrylic ester is less than 50% by weight, the physical properties, particularly the impact resistance, of the spherical powder, which is a characteristic when these acrylic esters are used, may be impaired. Moreover, you may contain an acid anhydride group and / or a carboxyl group.

Examples of the acrylate ester constituting the acrylic polymer block (b) include those described above as examples of the monomer that is a raw material of the (meth) acrylic block copolymer (A). These can be used alone or in combination of two or more.

Among these, acrylate aliphatic hydrocarbon esters are preferable, alkyl acrylate esters are more preferable, and n-butyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate are still more preferable. N-butyl acrylate is particularly preferable in terms of impact resistance, cost, and availability of the spherical powder. Moreover, when the spherical powder needs oil resistance, ethyl acrylate is preferable. When low temperature characteristics are required, 2-ethylhexyl acrylate is preferable. Furthermore, when it is desired to achieve both oil resistance and low temperature characteristics, a mixture of ethyl acrylate, n-butyl acrylate, and 2-methoxyethyl acrylate is preferable.

When acrylic acid-n-butyl is used, the molded body obtained from the composition according to the present invention exhibits good rubber elasticity and low temperature characteristics. When ethyl acrylate is used, it shows good mechanical properties such as oil resistance and tensile strength. In addition, when 2-methoxyethyl acrylate is used, good low-temperature characteristics and oil resistance are exhibited, and the surface tackiness of the resin is improved. These are used alone or in combination of two or more according to the required properties. In addition, a softness | flexibility and oil resistance may be impaired as the ratio of these acrylic acid esters is less than 50 weight%.

Examples of the vinyl monomer copolymerizable with the acrylic acid ester constituting the acrylic polymer block (b) include, for example, the above-mentioned methacrylic acid ester, aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound, Examples include halogen-containing unsaturated compounds, silicon-containing unsaturated compounds, unsaturated carboxylic acid compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds, maleimide compounds, and the like. These vinyl monomers can be used alone or in combination of two or more. These vinyl monomers are suitably used in consideration of the balance of glass transition temperature and oil resistance required for the acrylic polymer block (b), compatibility with the methacrylic polymer block (a), and the like. Choose 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 composition, the glass transition temperature of the acrylic polymer block (b) is preferably 25 ° C. or lower, more preferably 0 ° C. or lower, and −20 ° C. or lower. Further preferred. 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.

<Acid anhydride group and / or carboxyl group>
In the present invention, the acid anhydride group and / or carboxyl group usually acts as a reaction point or a crosslinking point for the block copolymer to have a high molecular weight or to be crosslinked. The acid anhydride group and / or carboxyl group is a block copolymer in a form in which the acid anhydride group and / or carboxyl group is protected with an appropriate protecting group, or in the form of a precursor of the acid anhydride group and / or carboxyl group. It can also introduce | transduce into a polymer and can produce | generate an acid anhydride group and / or a carboxyl group by a well-known predetermined | prescribed chemical reaction after that.

The content of the acid anhydride group and / or carboxyl group is the cohesive strength of the acid anhydride group and / or carboxyl group, the reactivity, the structure and composition of the (meth) acrylic block copolymer (A), (meth) The number of blocks constituting the acrylic block copolymer (A) is changed depending on the glass transition temperature, and the number needs to be appropriately set as necessary. Preferably, the (meth) acrylic block copolymer ( A) 1.0 or more per molecule, more preferably 2.0 or more. This is because if the number is less than 1.0, the (meth) acrylic block copolymer (A) tends to have insufficient heat resistance improvement due to high molecular weight and crosslinking.

The acid anhydride group and / or carboxyl group may be contained only in one of the methacrylic polymer block (a) and the acrylic polymer block (b), or in both blocks. May be. The reaction point of the (meth) acrylic block copolymer (A), the cohesive force and glass transition temperature of the block constituting the (meth) acrylic block copolymer (A), and further required (meth) The block into which the acid anhydride group and / or carboxyl group should be introduced can be determined according to the physical properties and purpose of the acrylic block copolymer (A). For example, when controlling the molecular weight between cross-linking points, an acid anhydride group and / or a carboxyl group may be introduced into the methacrylic polymer block (a), and the compatibility with the acrylic polymer (B) is controlled. In this case, an acid anhydride group and / or a carboxyl group may be introduced into the acrylic polymer block (b). Although not particularly limited, in terms of reaction point control, heat resistance, rubber elasticity, etc., an acid anhydride group only in one of the methacrylic polymer block (a) and the acrylic polymer block (b). And / or having a carboxyl group.

The content block and content of the acid anhydride group and / or carboxyl group may be appropriately determined according to the above according to the required reactivity, reaction point, cohesive force, glass transition temperature, and the like.

Hereinafter, each of the acid anhydride group and the carboxyl group will be described in more detail.

<Acid anhydride group>
When the composition contains a compound having active protons, the acid anhydride group easily reacts with a reactive functional group such as an epoxy group. The introduction position of the acid anhydride group is not particularly limited, and the acid anhydride group may be introduced into the main chain of the methacrylic polymer block (a) or the acrylic polymer block (b). It may be good or introduced into the side chain. In view of ease of introduction into the methacrylic polymer block (a) or the acrylic polymer block (b), it is preferably introduced into the main chain. The acid anhydride group is obtained by dehydration and condensation of two carboxyl groups. Specifically, the general formula (1):

(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, m is an integer of 0 or 1) Is done.

N in General formula (1) 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.

Is not particularly limited, if the (meth) acrylic polymer block (a) containing an acid anhydride group is preferably two of R ¹ in the general formula (1) are both methyl groups, acrylic heavy When it is included in the combined block (b), it is preferable that both of R ^{1 in} the general formula (1) are hydrogen. When R ¹ is hydrogen when included in the methacrylic polymer block (a), or when R ¹ is a methyl group when included in the acrylic polymer block (b), the (meth) acrylic block The copolymerization operation of the copolymer (A) becomes complicated, the difference in glass transition temperature between the methacrylic polymer block (a) and the acrylic polymer block (b) becomes small, and the (meth) acrylic block copolymer The rubber elasticity of the coalesced (A) may decrease.

In the case where the monomer having an acid anhydride group does not poison the catalyst under the polymerization conditions, the introduction of the acid anhydride group is preferably carried out by directly introducing the acid anhydride group. In the case where there is a possibility that the monomer having a deactivation of the catalyst at the time of polymerization, it is preferably carried out by a method of introducing an acid anhydride group by functional group conversion. Although not particularly limited, it is preferably introduced into the (meth) acrylic block copolymer (A) in the form of a precursor of an acid anhydride group and then cyclized, and the general formula (2):

(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 the group consisting of a methyl group and a phenyl group; R ^{3 s} may be the same or different from each other.) The desired acid is obtained by melt-kneading and cyclizing the (meth) acrylic block copolymer (A) having at least one unit represented by More preferably, an anhydride group is introduced.

The introduction of the unit represented by the general formula (2) into the methacrylic polymer block (a) or the acrylic polymer block (b) is an acrylic ester or a methacrylic ester derived from the general formula (2). This can be done by copolymerizing monomers. Examples of the monomer include t-butyl (meth) acrylate, isopropyl (meth) acrylate, α, α-dimethylbenzyl (meth) acrylate, α-methylbenzyl (meth) acrylate, and the like. It is not limited to these. Among these, (meth) acrylic acid-t-butyl is preferable from the viewpoints of availability, ease of polymerization, ease of acid anhydride group formation, and the like.

The formation of the acid anhydride group is preferably performed by heating the (meth) acrylic block copolymer (A) having a precursor of the acid anhydride group at a high temperature, and heating at 180 to 300 ° C. Is preferred. When the temperature is lower than 180 ° C, the acid anhydride group tends to be insufficiently generated. When the temperature is higher than 300 ° C, the (meth) acrylic block copolymer (A) itself having a precursor of the acid anhydride group is decomposed. There are things to do.

<Carboxyl group>
The carboxyl group easily reacts with a reactive functional group such as an epoxy group. 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) or the acrylic polymer block (b), Although it may be introduced into the side chain, it is preferably introduced into the main chain from the viewpoint of ease of introduction into the acrylic polymer block (b).

When the monomer having a carboxyl group does not poison the catalyst under the polymerization conditions, the introduction of the carboxyl group is preferably carried out by introducing it directly by polymerization. When there is a possibility of deactivating the catalyst during the polymerization, 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, a (meth) acrylic block copolymer (A) in a form in which the carboxyl group is protected with an appropriate protecting group, or in the form of a functional group to be a precursor of the carboxyl group Then, a functional group can be generated by a known chemical reaction known in the art.

Examples of the synthesis method of the (meth) acrylic block copolymer (A) having a carboxyl group include a precursor of a carboxyl group such as t-butyl (meth) acrylate, trimethylsilyl (meth) acrylate, and the like. (Meth) acrylic block copolymer (A) containing a monomer having a functional group is synthesized, and a carboxyl group is generated by a known chemical reaction such as hydrolysis or acid decomposition (Japanese Patent Laid-Open No. 10-298248). Gazette, JP-A-2001-234146), and general formula (3):

(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 the group consisting of a methyl group and a phenyl group; one of R ³ may be the same or different.) having at least one unit represented by (meth) acrylic block copolymer (a), there is a method of introducing by melt kneading. The unit represented by the general formula (2) is produced by the 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).

It is also possible to introduce a carboxyl group by hydrolyzing the acid anhydride group described above.

<Production method of (meth) acrylic block copolymer (A)>
The method for producing the (meth) 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. Especially, it is preferable to manufacture by living radical polymerization from the point of control of the molecular weight and structure of the (meth) acrylic block copolymer (A).

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), Those using radical scavengers such as nitroxide compounds (Macromolecules, 1994, 27, 7228), atom transfer radical polymerization using 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.

Atom transfer radical polymerization is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a group 7 group, 8 group, 9 group, 10 group or 11 group element as a central metal as a catalyst. (E.g., Mattyjaszewski et al., Journal of American Chemical Society, J. Am. Chem. Soc. 1995, 117, 5614, Macromolecules. ), 1995, 28, 7901, Science, 1996, 272, 866, or Sawamoto et al., Macromolecules, 1995, 28, 1721).

According to these methods, in general, polymerization proceeds in a living manner and the molecular weight distribution is narrow (Mw / M), although the polymerization rate is very high and radical reaction such as coupling between radicals is likely to occur. Mn = 1.1 to 1.5) polymer is 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, a monofunctional, difunctional, or polyfunctional compound can be used as the organic halide or sulfonyl halide compound used as an initiator. These may be properly used depending on the purpose. However, in the case of producing a diblock copolymer, a monofunctional compound is preferable from the viewpoint of easy availability of an initiator, and an aba triblock In the case of producing a copolymer and a b-a-b type triblock copolymer, it is preferable to use a bifunctional compound from the viewpoint of the number of reaction steps and shortening of the time. In the case of production, it is preferable to use a polyfunctional compound in terms of the number of reaction steps and time reduction.

Moreover, it is also possible to use a polymer initiator as the initiator. The polymer initiator is a compound composed of a polymer in which a halogen atom is bonded to the end of a molecular chain among organic halides or sulfonyl halide compounds. Since such a polymer initiator can be produced by a controlled polymerization method other than the living radical polymerization method, a block copolymer obtained by combining polymers obtained by different polymerization methods is obtained. .

Examples of monofunctional compounds include:
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 ⁴ —C (H) (X) —COOR ⁵ ,
R ⁴ —C (CH ₃ ) (X) —COOR ⁵ ,
R ⁴ —C (H) (X) —CO—R ⁵ ,
R ⁴ —C (CH ₃ ) (X) —CO—R ⁵ ,
R ⁴ —C ₆ H ₄ —SO ₂ X
And the like.

In the formula, C ₆ H ₅ represents a phenyl group, and C ₆ H ₄ represents a phenylene group (which may be ortho-substituted, meta-substituted, or para-substituted). R ⁴ represents 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. X represents chlorine, bromine or iodine. R ⁵ represents a monovalent organic group having 1 to 20 carbon atoms.

As specific examples of the monofunctional compound, ethyl 2-bromide propionate and butyl 2-bromide propionate are preferable because they are similar to the structure of the acrylate monomer and can easily control polymerization. .

As a bifunctional compound, for example,
_{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 6) -}} (CH 2) n -CH (COOR 6) -X,
^{_{X-C (CH 3) (}} COOR 6) - (CH 2) n -C (CH 3) (COOR 6) -X
^{_{X-CH (COR 6) -}} (CH 2) n -CH (COR 6) -X,
^{_{X-C (CH 3) (}} COR 6) - (CH 2) n -C (CH 3) (COR 6) -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 (CH 3) -X,
_{X-C (CH 3) 2} -COO- (CH 2) n -OCO-C (CH 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 (CH 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
And the like.

In the formula, R ⁶ represents 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. n represents an integer of 0 to 20. C ₆ H ₅ , C ₆ H ₄ and X are the same as above.

Specific examples of the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the aralkyl group having 7 to 20 carbon atoms for R ⁶ include the alkyl group having 1 to 20 carbon atoms for R ⁴ , and 6 to 6 carbon atoms. Specific examples of 20 aryl groups and aralkyl groups having 7 to 20 carbon atoms are the same.

As specific examples of the bifunctional compound, bis (bromomethyl) benzene, diethyl 2,5-dibromoadipate and diethyl 2,6-dibromopimelate are preferable from the viewpoint of availability of raw materials.

As the multifunctional compound, for example,
_{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
And the like.

In the formula, C ₆ H ₃ is a trisubstituted benzene ring (the positions of the three bonds may be any of 1 to 6 positions, and the combination thereof can be selected as appropriate), and X is the same as above. is there.

Specific examples of the polyfunctional compound include tris (bromomethyl) benzene, tris (1-bromoethyl) benzene, tris (1-bromoisopropyl) benzene and the like. Of these, tris (bromomethyl) benzene is preferable from the viewpoint of availability of raw materials.

In addition, when an organic halide or sulfonyl halide compound having a functional group is used in addition to the group for initiating polymerization, a polymer in which a functional group other than the group for initiating polymerization is easily introduced at the terminal or in the molecule is obtained. It is done. Examples of functional groups other than the group that initiates polymerization include alkenyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, silyl groups, and the like.

The transition metal complex used as a catalyst for atom transfer radical polymerization is not particularly limited, but preferred are monovalent and zerovalent copper, divalent ruthenium, divalent iron, and divalent nickel. Complex.

Among these, a copper complex is preferable from the viewpoint of cost and reaction control. Examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. Of these, cuprous chloride and cuprous bromide are preferred from the viewpoint of polymerization control. When a monovalent copper compound is used, 2,2′-bipyridyl and its derivatives (for example, 4,4′-dinolyl-2,2′-bipyridyl, 4,4′-di (5- Noryl) -2,2'-bipyridyl and the like; 1,10-phenanthroline, derivatives thereof (for example, 4,7-dinolyl-1,10-phenanthroline, 5,6-dinolyl- 1,10-phenanthroline compounds such as 1,10-phenanthroline); polyamines such as tetramethylethylenediamine (TMEDA), pentamethyldiethylenetriamine, and hexamethyl (2-aminoethyl) amine may be added as a ligand. .

The type of catalyst, ligand and activator to be used may be appropriately determined from the relationship between the initiator, monomer and solvent to be used, and the required reaction rate.

Similarly, the amount of catalyst and ligand used may be determined from the relationship between the amount of initiator, monomer and solvent used, and the required reaction rate. For example, in order to obtain a polymer having a high molecular weight, the initiator / monomer ratio must be made smaller than in the case of obtaining a polymer having a low molecular weight. The reaction rate can be increased by increasing the number of catalysts and ligands. In addition, when a polymer having a glass transition temperature higher than room temperature is produced, the reaction rate tends to decrease when an appropriate organic solvent is added to lower the viscosity of the system and increase the stirring efficiency. In such a case, the reaction rate can be increased by increasing the number of catalysts and ligands.

Atom transfer radical polymerization can be carried out in the absence of a solvent (bulk polymerization) or in various solvents. Further, in bulk polymerization and polymerization performed in various solvents, the polymerization can be stopped halfway.

Examples of the solvent that can be used include hydrocarbon solvents, ether solvents, halogenated hydrocarbon solvents, ketone solvents, alcohol solvents, nitrile solvents, ester solvents, carbonate solvents, and the like.

The polymerization can be performed in the range of 20 ° C to 200 ° C, and is preferably performed in the range of 50 to 150 ° C.

As a method of polymerizing the (meth) acrylic block copolymer (A), a method of sequentially adding monomers, a method of polymerizing the next block using a polymer synthesized in advance as a polymer initiator, and polymerization separately And a method of bonding the obtained polymer by reaction. Any of these methods may be used and is appropriately selected according to the purpose. In addition, the method by the sequential addition of a monomer is preferable from the point of the simplicity of a manufacturing process.

The reaction liquid obtained by polymerization contains a mixture of a polymer and a metal complex, and by removing these, a solution of the (meth) acrylic block copolymer (A) can be obtained.

The polymer solution thus obtained is subsequently subjected to an evaporation operation, whereby the polymerization solvent and unreacted monomers are removed. Thereby, the (meth) acrylic block copolymer (A) can be isolated.

<Acrylic polymer (B)>
The acrylic polymer (B) constituting the thermoplastic elastomer composition according to the present invention is an acrylic polymer having a reactive functional group (C). The acrylic polymer (B) improves molding fluidity as a plasticizer at the time of molding the composition, and at the same time, an acid anhydride group and a carboxyl group in the (meth) acrylic block copolymer (A) at the time of molding. The reactive functional group (C) is reacted to increase the molecular weight or crosslink the (meth) acrylic block copolymer (A).

The acrylic polymer (B) is obtained by polymerizing one type or two or more types of acrylic monomers, or a single amount other than one type or two or more types of acrylic monomers and acrylic monomers. It is preferably obtained by polymerizing the body.

Examples of the acrylic monomer include acrylic acid esters and methacrylic acid esters described in the section of (meth) acrylic block polymer (A). Among these, it is preferable to use any one of acrylic acid-n-butyl, ethyl acrylate and acrylic acid-2-methoxyethyl, or a combination of two or more thereof.

The monomer other than the acrylic monomer is not particularly limited as long as it is a monomer copolymerizable with the acrylic monomer, and for example, vinyl acetate, styrene and the like can be used.

In addition, it is preferable that the ratio of the acryloyl group containing monomer component with respect to all the monomer components in an acrylic polymer (B) is 70 weight% or more. When the proportion is less than 70% by weight, the weather resistance is lowered and the compatibility with the (meth) acrylic block copolymer (A) tends to be lowered. Moreover, discoloration tends to occur in the molded product.

The molecular weight of the acrylic polymer (B) is not particularly limited, but is preferably a low molecular weight having an average weight molecular weight of 30,000 or less, more preferably 500 to 30,000, and more preferably 500 to 20,000. More preferred are those of 500 to 10,000. If the weight average molecular weight is less than 500, the molded product tends to be sticky. On the other hand, if the weight average molecular weight exceeds 30,000, plasticization of the molded product tends to be 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., and 10,000 mPa · s. More preferably, it 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. Although there is no particular lower limit of the preferred viscosity, the normal viscosity of the acrylic polymer (B) is 10 mPa · s or more.

The glass transition temperature Tg of the acrylic polymer (B) is preferably 100 ° C. or less, more preferably 25 ° C. or less, and more preferably 0 ° C. or less when measured by differential scanning calorimetry (DSC). More preferably, it is 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) can be obtained by polymerizing by a known predetermined method. The polymerization method may be appropriately selected as necessary. For example, the polymerization may be performed by a method such as suspension polymerization, emulsion polymerization, bulk polymerization, living anion polymerization, polymerization using a chain transfer agent, and controlled polymerization such as living radical polymerization. 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 can be 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, an acrylic polymer having a relatively low molecular weight can be obtained without using a polymerization initiator or a chain transfer agent. For this reason, the acrylic polymer (B) is an excellent plasticizer and has good weather resistance. Specifically, the method by high-temperature continuous polymerization described in JP-A-57-502171, JP-A-59-6207, JP-A-60-215007 and WO 01/083619, An example 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 the reaction liquid corresponding to the supply amount is withdrawn.

0.1-100 weight part is preferable with respect to 100 weight part of (meth) acrylic block copolymers (A), and, as for the compounding quantity of an acrylic polymer (B), 1-50 weight part is more preferable. When the blending amount of the acrylic polymer (B) is smaller than 0.1 parts by weight, the crosslinking reaction with the (meth) acrylic block copolymer (A) does not proceed sufficiently, and the heat resistance of the molded product is insufficient. If the amount is larger than 100 parts by weight, the crosslinking reaction may proceed excessively and the elongation and flexibility of the molded product may be impaired.

<Reactive functional group (C)>
Examples of the reactive functional group (C) include an epoxy group, a hydroxyl group, an amino group, and a carboxyl group. Of these functional groups, reactivity with acid anhydride groups and carboxy groups contained in the (meth) acrylic block copolymer (A) and ease of introduction of functional groups into the acrylic polymer (B) Therefore, an epoxy group is preferable.

Introduction of the reactive functional group (C) into the acrylic polymer (B) is, for example, vinyl having a reactive functional group (C) copolymerizable with the monomer constituting the acrylic polymer (B). This can be carried out by copolymerizing a monomer or the like.

The number of reactive functional groups (C) contained in one molecule of the acrylic polymer (B) is the reactivity of the reactive functional group (C), the site and manner in which the reactive functional group (C) is contained, It changes according to the number of the acid anhydride group and / or the carboxyl group contained in the (meth) acrylic block copolymer (A) and / or the mode. Although not particularly limited, 1.1 or more are preferably contained per molecule, more preferably 1.5 or more, and even more preferably 2.0 or more. When the content of the reactive functional group (C) is less than 1.1, the effect of the block copolymer as a high molecular weight reactive agent or a crosslinking agent is reduced, and the (meth) acrylic block copolymer (A ) Tends to be insufficient in improving the heat resistance. In addition, the number of reactive functional groups (C) here represents the average number of reactive functional groups (C) possessed per molecule of the acrylic polymer (B).

Specific examples of the acrylic polymer (B) having a reactive functional group (C) include ARUFON (registered trademark) XG4000, ARUFON UG4000, ARUFON XG4010, ARUFON UG4010, ARUFON XD945 and ARUFON XD950 from Toagosei Co., Ltd. ARUFON UG4030, ARUFON UG4070, etc. can be used suitably. These components are all acrylic polymers such as acrylic and acrylate / styrene, and contain 1.1 or more epoxy groups in one molecule.

<Thermoplastic elastomer composition>
Although it does not specifically limit in the manufacturing method of this invention, It is preferable to suppress high molecular weight and bridge | crosslinking as much as possible at the time of kneading | mixing in an extruder. After obtaining the elastomer, when it is molded into a final product, the acid anhydride group or carboxyl group in the block copolymer (A) of the thermoplastic elastomer composition and the reactivity in the acrylic polymer (B) It is preferable that the functional group (C) is reacted to cause the (meth) acrylic block copolymer (A) to have a high molecular weight or to be crosslinked. By suppressing high molecular weight and cross-linking as much as possible during kneading, the melt fluidity at the time of molding can be enhanced and molding becomes easy. In terms of improving heat resistance, it is more preferable to crosslink the (meth) acrylic block copolymer (A) during molding.

In order to accelerate the reaction during molding, various additives and catalysts may be added to the thermoplastic elastomer composition as necessary. 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.

You may mix | blend a filler with a thermoplastic elastomer composition as needed. Although it does not specifically limit as a filler, From the improvement of mechanical characteristics, a reinforcing effect, a cost aspect, etc., an inorganic filler is more preferable, and a titanium oxide, carbon black, calcium carbonate, silica, and talc are more preferable.

When using a filler, the addition amount is preferably in the range of 5 to 200 parts by weight, and in the range of 10 to 100 parts by weight, with respect to 100 parts by weight of the (meth) acrylic block copolymer (A). Is more preferable. When the addition amount is less than 5 parts by weight, the reinforcing effect of the obtained molded product may not be sufficient, and when it exceeds 200 parts by weight, the moldability of the resulting composition tends to deteriorate. In addition, a filler can be used 1 type or in combination of 2 or more types.

If necessary, the thermoplastic elastomer composition may be blended with various lubricants in order to reduce moldability, mold releasability from the mold, and reduce the friction of the surface of the resulting molded body. .

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 using a lubricant, the addition amount is preferably in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the (meth) acrylic block copolymer (A), and 0.2 to 10 parts by weight. It is more preferable to use the range of parts. If the amount added is less than 0.1 parts by weight, the effect of improving the moldability and lowering the friction of the resulting molded product may be insufficient. Characteristics and chemical resistance tend to deteriorate. A lubricant can be used alone or in combination of two or more.

Various additives other than those described above may be added to the thermoplastic elastomer composition as necessary for the purpose of adjusting various properties of the thermoplastic elastomer composition and the final molded article to be obtained. Examples of the additive include a stabilizer, a plasticizer, a flexibility imparting agent, a flame retardant, a pigment, an antistatic agent, and an antibacterial and antifungal agent. Among these, examples of the stabilizer include an anti-aging agent, a light stabilizer, and an ultraviolet absorber.

<Method for producing thermoplastic elastomer composition>
In the method for producing the thermoplastic elastomer composition of the present invention, an extruder having a short residence time in the apparatus and excellent in kneading performance is used as the kneading apparatus. Examples of the extruder include a single-screw extruder, a twin-screw extruder, and a multi-screw extruder, but it reacts with a composition containing the (meth) acrylic block copolymer (A) without giving a thermal history as much as possible. Since it is necessary to sufficiently knead the acrylic polymer (B) having a functional functional group (C), a twin screw extruder having excellent kneading performance and little heat history is most preferable.

The extruder used in the present invention is not particularly limited, but as a raw material supply port, in addition to the main feed portion provided at the extruder inlet, one or more intermediate addition portions that can supply the raw material from the middle are provided. It is preferable to have it. By having an addition part on the way, the acrylic polymer (B) having a reactive functional group (C) can be added after the (meth) acrylic block copolymer (A) is melt-kneaded.

Moreover, when an extruder has an intermediate addition part, other additive components, such as a filler and a lubricant, may be added from a main feed part, and may be added from an intermediate addition part. When it is desirable to sufficiently knead the added components, it is desirable to add them from the main feed part. When it is desired to suppress denaturation due to heating or the like, it is desirable to add them from the intermediate addition part. Moreover, you may have the vent for carrying out pressure reduction deaeration in the downstream of an intermediate addition part as needed.

The configuration of the extruder is not particularly limited, but preferably has at least two temperature variable zones capable of controlling the temperature of the cylinder. In particular, (i) main feed section at the inlet of the extruder, (ii) primary kneading zone from the main feed section to the intermediate addition section, (iii) intermediate addition section, (iv) secondary kneading zone from the intermediate addition section to the die Are preferred. Specifically, for example, an extruder as shown in FIG. 1 can be used.

The primary kneading zone is a zone for melting a composition mainly containing the (meth) acrylic block copolymer (A). As shown in FIG. 1, the primary kneading zone usually has a kneading section called a kneading block, a kneading disk, a rotor, or the like (portion indicated by reference numeral 6 in FIG. 1). In the extruder, shear heat is generated in this kneading section, and the temperature of the kneaded material in the extruder rises most.

When the acrylic polymer (B) having a reactive functional group (C) is added simultaneously with the (meth) acrylic block copolymer (A) from the beginning, the kneading of the primary kneading zone having the largest heat generation in the extruder is carried out. As a result of the temperature of the kneaded product rising at the part, the acid anhydride group or carboxyl group in the (meth) acrylic block copolymer (A) and the reactive functional group in the acrylic polymer (B) ( There is a high possibility that moldability will deteriorate due to progress of high molecular weight or crosslinking with C). If high molecular weight or cross-linking occurs in the extruder before molding into the final molded product, the resulting thermoplastic elastomer composition will have high melt viscosity, resulting in poor transferability during injection molding or during extrusion. In some cases, the pressure increase of the material becomes large and stable molding cannot be achieved. Furthermore, if the high molecular weight or crosslinking in the extruder proceeds too much, the resin may solidify in the extruder.

Therefore, the acrylic resin should not pass through the kneading part of the primary kneading zone in the state where the (meth) acrylic block copolymer (A) and the acrylic polymer (B) having a reactive functional group (C) coexist. It is preferable to add the system polymer (B) from the intermediate addition part after the component (A) has passed through the kneading part of the primary kneading zone. Although not particularly limited, for example,
(I) Main feed section at the entrance of the extruder,
(Ii) a primary kneading zone from the main feed part to the intermediate addition part,
(Iii) midway addition part,
(Iv) A secondary kneading zone from the midway addition part to the die,
In an extruder containing
Supplying a composition containing the (meth) acrylic block copolymer (A) having the acid anhydride group and / or carboxyl group from the main feed portion;
It is preferable to carry out the production method of the present invention by adding and mixing the acrylic polymer (B) having the reactive functional group (C) from the intermediate addition part.

Furthermore, the acrylic polymer (B) is as close as possible to the exit side of the extruder within a range where the acrylic polymer (B) is sufficiently kneaded into the (meth) acrylic block copolymer (A). It is more preferable to add in place. That is, it is preferable that the midway addition portion for introducing the acrylic polymer (B) having the reactive functional group (C) is installed as close to the extruder outlet as possible within a range where kneading is possible. By adding the acrylic polymer (B) from the addition part in the middle, the one where the heat history to the acrylic polymer (B) is made small can suppress the high molecular weight and the crosslinking in the extruder. The thermal history of the extruder is greatly influenced not only by the temperature but also by the diameter of the extruder, the screw groove depth, the number of rotations, and the addition position of the acrylic polymer (B).

Therefore, in the present invention, the total shear strain amount ε, which is an index of the heat history amount in the extruder with respect to the acrylic polymer (B), is 100 <ε <8,000, more preferably 500 <ε <5,000, It is preferable to add the acrylic polymer (B) so that 1,000 <ε <3,000. If the total shear strain ε is 100 or less, kneading may be insufficient. If the total shear strain ε is 8,000 or more, high molecular weight or cross-linking proceeds in the extruder due to thermal history due to excessive kneading. Tend.

In the present invention, the total shear strain amount ε is determined by adding the diameter of the extruder to D (mm), the screw groove depth h (mm), the rotation speed N (rpm), and the acrylic polymer (B) into the extruder. Assuming that the time t (seconds) required to exit from the die is expressed by the following equation. Note that π represents a circular ratio.

The total amount of shear strain is the product of the shear rate, which is an index of kneading, and the residence time after the acrylic polymer (B) is added to the extruder, and the thermal history experienced by the acrylic polymer (B) in the extruder. It becomes an index.

In order to reduce this thermal history, an extruder with a small diameter D / screw groove depth h ratio is used, the rotational speed is lowered, and the residence time of the acrylic polymer (B) in the extruder is shortened. Just do it.

The temperature of the kneaded material inside the extruder for producing the thermoplastic elastomer composition is such that the (meth) acrylic block copolymer (A) and the acrylic polymer (B) react and the moldability does not deteriorate. It is preferred to maintain the temperature. The temperature at which the (meth) acrylic block copolymer (A) and the acrylic polymer (B) react to deteriorate the moldability is the type of acid anhydride group, carboxyl group, or reactive functional group (C). , Introduction amount, composition of (meth) acrylic block copolymer (A) and acrylic polymer (B), compatibility of (meth) acrylic block copolymer (A) and acrylic polymer (B) Set as appropriate.

Here, after obtaining the composition, the temperature of the kneaded material inside the extruder is preferably maintained at 160 ° C. or less, and more preferably maintained at 150 ° C. or less, in order to enable molding of the composition. . When the temperature of the kneaded product exceeds 160 ° C., a high molecular weight or a crosslinking reaction occurs during the kneading and the moldability tends to be lowered. However, the temperature may be such that molding is possible even under conditions where high molecular weight and cross-linking occur in part. In the production method of the present invention, since the temperature of the kneaded material inside the extruder generally tends to rise from the extruder inlet to the die outlet, the temperature of the kneaded material inside the extruder is at the die outlet. By measuring the temperature of the kneaded product, the temperature of the kneaded product inside the extruder can be measured.

The set temperature of the cylinder of the primary kneading zone is not particularly limited, but in order to prevent high molecular weight and crosslinking reaction during kneading, for example,
(I) Main feed section at the entrance of the extruder,
(Ii) a primary kneading zone from the main feed part to the intermediate addition part,
(Iii) midway addition part,
(Iv) A secondary kneading zone from the midway addition part to the die,
When the (meth) acrylic block copolymer (A) comprising the methacrylic polymer block (a) and the acrylic polymer block (b) is kneaded with an extruder containing The temperature is preferably set to [(glass transition temperature of methacrylic polymer block (a)) − 10] ° C. or lower, and set to [glass transition temperature of methacrylic polymer block (a)) − 30] ° C. or lower. More preferably. Thereby, the temperature rise of the kneaded material by the shear heat generation in an extruder can be suppressed as much as possible. In the case where the primary kneading zone is composed of a plurality of temperature variable regions, the maximum set value is preferably equal to or lower than the above temperature.

The set temperature of the zone (secondary kneading zone) from the midway addition part to the die front is also not particularly limited, but it is set to a low range that does not affect the productivity of the thermoplastic elastomer composition obtained through the twin-screw extruder. Is preferred. However, if the set temperature of the cylinder in the secondary kneading zone is too low, it is convenient for suppressing the temperature rise of the kneaded material in the extruder, but the extrusion of the thermoplastic elastomer tends to be unstable and the productivity is deteriorated. . Therefore, specifically, it is preferable to set the [glass transition temperature of the methacryl polymer block (a)) + 20] (° C.) or less, and the glass transition temperature of the methacryl polymer block (a)) + 10] ( It is more preferable to set it to the following. In the case where the secondary kneading zone is composed of a plurality of temperature variable regions, it is preferable that the maximum set value is not more than the above temperature.

The set temperatures of the primary kneading zone and the secondary kneading zone may be the same or different, but the optimum temperature for melting the (meth) acrylic block copolymer (A) and the acrylic heavy In consideration of the optimum temperature for kneading the kneaded material after adding the coalesced (B), it is preferable to set the kneaded material at different temperatures.

Although there is no limitation in particular about the full length of an extruder, it is preferable that L / D of the screw is 15 or more. Here, L / D indicates the ratio of the screw length (L) to the diameter (D) of the extruder. When L / D is less than 15, kneading of the resulting thermoplastic elastomer composition may be insufficient. More preferably, L / D is 20 or more, and further preferably 30 or more. In consideration of the size of the apparatus, L / D is usually 100 or less.

The residence time in the primary kneading zone is not particularly limited, and the size, temperature, and additives of the extruder used are set so that the (meth) acrylic block copolymer (A) is sufficiently melt-kneaded. When it is included, it is appropriately selected in consideration of the dispersion state and the like. On the other hand, if the residence time from the secondary kneading zone to the die outlet becomes long, the heat history increases, and polymerization or crosslinking reaction proceeds in the extruder, which may deteriorate the moldability. The residence time from the kneading zone to the die exit is preferably 5 seconds or more and 3 minutes or less, more preferably 10 seconds or more and 2 minutes or less, and further preferably 15 seconds or more and 1 minute 30 seconds or less.

<Method of molding thermoplastic elastomer composition>
The method for molding the thermoplastic elastomer composition obtained by the production method of the present invention is not particularly limited, and various melt molding methods similar to those used for molding ordinary thermoplastic resins may be adopted. it can. For example, various molding methods such as injection molding, extrusion molding, blow molding, and calendar molding can be applied. In any molding, the molding temperature is a temperature at which the acid anhydride group or carboxyl group in the (meth) acrylic block copolymer (A) reacts with the reactive functional group (C) in the acrylic polymer (B). By maintaining the above, high molecular weight and crosslinking occur, and the heat resistance of the molded product can be improved.

Therefore, it is preferable to perform the molding at a temperature of 180 ° C. or higher, and more preferably at a temperature of 200 ° C. or higher. By molding at a temperature of 180 ° C. or higher, polymerization or crosslinking can be efficiently performed between the (meth) acrylic block copolymer (A) and the acrylic polymer (B). Moreover, although the upper limit of the temperature at the time of shaping | molding can be suitably set with the kind, composition, etc. of a (meth) acrylic block copolymer (A) and an acrylic polymer (B), (A) component and (B ) Molding is preferably performed at 250 ° C. or lower, more preferably 230 ° C. or lower so that the component does not decompose.

The present invention will be described in more detail based on examples. However, the present invention is not limited only to these examples, and the following abbreviations are used in production examples.
BA: n-butyl acrylate MMA: methyl methacrylate TBA: t-butyl acrylate EA: ethyl acrylate

<Measurement method of molecular weight and molecular weight distribution>
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 3 times with ethyl acetate, and butyl acetate was used as an internal standard.

<Glass transition temperature (Tg)>
The glass transition temperature of the methacrylic polymer block constituting the (meth) acrylic block copolymer (A) is a ratio of loss elastic modulus / storage elastic modulus at 50 ° C. to 130 ° C. (tan δ) in dynamic viscoelasticity measurement. Was measured as the temperature showing the maximum value of. 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 apparatus DVA-200 ( Using IT Measurement Control Co., Ltd.), the measurement frequency was 0.5 Hz.

<Formability evaluation>
The surface was visually observed for the transferability of the texture of the flat plate with a texture pattern created in the examples and comparative examples, and the moldability was evaluated according to the following criteria.
The wrinkle pattern has been transferred well; ○
Inappropriate transfer of wrinkle pattern;
A molded body cannot be obtained; ×

<Heat resistance test>
The heat resistance shown in this example was measured under the following conditions.
The flat plate with a texture pattern prepared in Examples 1 to 5 was allowed to stand at 120 ° C. for 24 hours. Thereafter, the surface was visually observed and evaluated according to the following criteria.
No change in wrinkle pattern; ○
Although the change of the wrinkle pattern is not clear, the surface gloss increased compared to the initial stage;
Changes in wrinkle pattern observed; ×

<Oil resistance test>
The oil resistance shown in this example was measured under the following conditions.
The flat plate with a textured pattern produced in Examples 1 to 5 was placed on a flat surface, and one drop of liquid paraffin (manufactured by Nacalai Tesque) was dropped onto the plate, and the plate was allowed to stand at 100 ° C. for 24 hours. Thereafter, liquid paraffin was wiped off with Kimwipe (registered trademark) (manufactured by Crecia Co., Ltd.), and the surface was visually observed and evaluated according to the following criteria.
No trace; ○
Traces are visible but not whitened;
What can be bleached; ×

(Production Example 1)
<Synthesis of (meth) acrylic block copolymer (A) precursor>
The following operation was performed to obtain a (meth) 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, 78400 g (612 mol) of BA and 2870 g (22.4 mol) of TBA were charged, and stirring was started. Thereafter, a solution prepared by dissolving 1320 g (3.69 mol) of diethyl 2,5-dibromoadipate initiator in 7140 g of acetonitrile (nitrogen bubbling) was charged, and the inner solution was stirred for 30 minutes while raising the temperature to 75 ° C. . 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 was 99.1% and the conversion rate of TBA was 99.3%, MMA 48300 g (482 mol), EA 7840 g (78.3 mol), copper chloride 475 g (4.80 mol), pentamethyldiethylenetriamine 83.2 g (0.480 mol) and 104000 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 conducted, the number average molecular weight Mn was 53100, 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. 2190 g of p-toluenesulfonic acid was added to this solution, 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 6570 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 equipped with a polyester felt as a filter medium (filtration area 0.45 m ² ).

Kyoward 500SH1310g was added to about 450kg of the block copolymer solution after filtration, the inside of the reactor was purged with nitrogen, and the mixture was stirred at 30 ° C for 1 hour. The reaction solution was sampled to confirm that the solution was neutral, and the reaction was completed. 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. 675 g of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to the obtained polymer solution and dissolved.

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. 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 0.012 MPa (90 Torr), the screw rotation speed to 60 rpm, and the polymer solution feed rate to 32 kg / h. did. 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 (meth) acrylic block copolymer (A) precursor were produced.

(Production Example 2)
1 part by weight of hydrotalcite DHT-4A-2 (manufactured by Kyowa Chemical Industry Co., Ltd.) as an acid trapping agent with respect to 100 parts by weight of the (meth) acrylic block copolymer (A) precursor obtained above. And using a twin screw extruder with a vent (44 mm, L / D = 42.25) (manufactured by Nippon Steel Works), the rotational speed of 150 rpm, the cylinder temperature of the hopper installation part (main feed part) The temperature was set to 100 ° C., and the others were all extruded and kneaded at 260 ° C. to obtain the desired acid anhydride group and carboxyl group-containing (meth) acrylic block copolymer (A). During extrusion, the vent port was closed. At this time, an underwater cut pelletizer (CLS-6-8.1 COMPACT LAB SYSTEM manufactured by GALA INDUSTRIES INC.) Is connected to the tip of the twin-screw extruder, and Alflow (registered) is added to the circulating water of the underwater cut pelletizer. (Trademark) H-50ES (manufactured by NOF Corporation) was added to obtain pellets of spherical (meth) acrylic block copolymer (A ₁ ) having no adhesion.

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. Tg of the resulting (meth) methacrylic polymer block of the acrylic block copolymer A ₁ (a) was 101 ° C..

Example 1
100 parts by weight (100 kg) of (meth) acrylic block copolymer A ₁ obtained in Production Example 2, 30 parts by weight of calcium carbonate (manufactured by Bihoku Flour Industry Co., Ltd., Softon 3200), and acrylic polymer (B ) ARUFON XG4010 (manufactured by Toagosei Co., Ltd., acrylic polymer, containing 1.1 or more epoxy groups per molecule (approximate value 4 (from catalog))) 7 parts by weight biaxially A thermoplastic elastomer was obtained by kneading with an extruder. The twin screw extruder used was a twin screw extruder manufactured by Nippon Placon (caliber 46 mm, L / D = 40). The schematic diagram of the twin-screw extruder used for FIG. 2 is shown. The temperature control of the cylinder was C1 to C8, 10 zones of adapter and die, and the temperature settings were C1 to C5 at 50 ° C, C6 to C8 at 80 ° C, the adapter at 110 ° C, and the die at 120 ° C. The primary kneading zones were C4 and C5, the acrylic polymer (B) was added at C6, and the vent was installed at C8. Main feed unit 1 via the hopper (meth) acrylic block copolymer A ₁ and calcium carbonate, respectively supplied with a constant weight feeder, ARUFON XG4010 was added midway added portion 2 using a gear pump. Kneading was performed at a discharge rate of 56 kg / h and a rotational speed of 140 rpm, and the extruded strand was cooled in a cooling water tank, and then a thermoplastic elastomer composition pellet was obtained by pelletizer cutting. The temperature of the kneaded product at the die outlet was 126 ° C., and the residence time from C6 where the acrylic polymer (B) was added to the die outlet (secondary kneading zone + die) was 39 seconds.

Using the injection molding machine (FANUC AUTOSHOT150B) having a clamping force of 150 t, the resulting thermoplastic elastomer composition pellets are flat plate with 150 mm squares with a cylinder temperature of 220 ° C. and a mold temperature of 50 ° C. Were evaluated by injection molding. The results are shown in Table 1.

(Examples 2 to 5)
Using (meth) acrylic block copolymer A ₁ pellets obtained in Preparation Example 2 was carried out in the same manner as in Experimental Example 1 in conditions described in Table 1. The results are listed in Table 1.

(Comparative Example 1)
Obtained in Production Example 2 (meth) acrylic block copolymer matter (A) as the (meth) acrylic block copolymer A ₁ 00 parts by weight (2Kg) made of calcium carbonate (Bihoku Funka Kogyo Co., , Softon 3200) 30 parts by weight into a Banbury mixer, kneaded, and then ARUFON XG4010 (manufactured by Toagosei Co., Ltd., an acrylic polymer as an acrylic polymer (B), with an epoxy group in one molecule A thermoplastic elastomer was obtained by additionally kneading 7 parts by weight of 1.1 or more (containing an approximate value of 4 (from the catalog)). The Banbury mixer used was a Banbury mixer (capacity 4 L) manufactured by Kobe Steel. The temperature control of the mixer section was 100 ° C. The kneading was performed at a rotation speed of 150 rpm for 20 minutes. The temperature of the kneaded product was 184 ° C. The obtained kneaded material was discharged and an attempt was made to extrude it using a 35 mm kneader ruder, but no pellet was obtained because it did not remelt (Table 1).

As can be seen from Table 1, it can be seen that the thermoplastic elastomer composition obtained by the production method of the present invention has good moldability or has no problem in molding, and is excellent in heat resistance and oil resistance.

The thermoplastic elastomer obtained by the production method of the present invention is used for automobiles such as weather strips, side moldings, and air spoilers, household electrical appliances, wallpaper, various sheets for building materials, sports goods, and other applications where appearance is important. It can be preferably used.

It is an example of the extruder which can be used conveniently with the manufacturing method of this invention. It is a schematic diagram of the twin-screw extruder used in Examples 1-5.

Explanation of symbols

1 Main feed part 2 Midway addition part 3 Vent
4 Primary kneading zone 5 Secondary kneading zone 6 Kneading part (kneading block) in the primary kneading zone
7 Kneading part in the secondary kneading zone (kneading block)
8 Raw material input zone 9 Adapter 10 Die

Claims (9)

A composition containing a (meth) acrylic block copolymer (A) having an acid anhydride group and / or a carboxyl group is kneaded in an extruder together with an acrylic polymer (B) having a reactive functional group (C). A process for producing a thermoplastic elastomer composition. The method for producing a thermoplastic elastomer composition according to claim 1, wherein the extruder is a twin screw extruder. The thermoplastic elastomer composition according to claim 1 or 2, wherein the reactive functional group (C) is at least one selected from the group consisting of an epoxy group, a hydroxyl group, an amino group, and a carboxyl group. Manufacturing method. A block copolymer in which the (meth) acrylic block copolymer (A) comprises 15 to 50% by weight of a methacrylic polymer block (a) and 85 to 50% by weight of an acrylic polymer block (b). The method for producing a thermoplastic elastomer composition according to any one of claims 1 to 3, wherein: The acrylic polymer (B) having the reactive functional group (C) is added so that the total shear strain ε in the extruder represented by the following formula is 100 <ε <8,000. The method for producing a thermoplastic elastomer composition according to any one of claims 1 to 4.

In the formula, π is the circumference ratio, D is the diameter of the extruder (mm), N is the number of rotations (rpm), h is the depth of the screw groove (mm), and t is the acrylic polymer (B) in the extruder. This is the time (seconds) from adding to the die. (I) Main feed section at the entrance of the extruder,
(Ii) a primary kneading zone from the main feed part to the intermediate addition part,
(Iii) midway addition part,
(Iv) A secondary kneading zone from the midway addition part to the die,
In an extruder containing
Supplying a composition containing the (meth) acrylic block copolymer (A) having the acid anhydride group and / or carboxyl group from the main feed portion;
The thermoplastic elastomer according to any one of claims 1 to 5, wherein the acrylic polymer (B) having the reactive functional group (C) is added from the intermediate addition portion and kneading is performed. A method for producing the composition. (I) Main feed section at the entrance of the extruder,
(Ii) a primary kneading zone from the main feed part to the intermediate addition part,
(Iii) midway addition part,
(Iv) A secondary kneading zone from the midway addition part to the die,
When the (meth) acrylic block copolymer (A) comprising the methacrylic polymer block (a) and the acrylic polymer block (b) is kneaded with an extruder containing The temperature is set to [(Glass transition temperature of methacrylic polymer block (a)) − 10] ° C. or lower, The production of the thermoplastic elastomer composition according to any one of claims 1 to 6, Method. The method for producing a thermoplastic elastomer composition according to claim 6 or 7, wherein the primary kneading zone and the secondary kneading zone are kneaded at different set temperatures. The thermoplastic elastomer composition obtained by the production method according to any one of claims 1 to 8, wherein the acid anhydride group and / or the carboxyl group and the reactive functional group (C) have a crosslinking temperature or higher. The manufacturing method of the molded object characterized by carrying out the shaping | molding process at the temperature of.

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