JP2004231940A - Thermoplastic elastomer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new thermoplastic elastomer composition having excellent balance between hardness and mechanical strength, having excellent rubber elasticity, high-temperature creep performance, and moldability, in a wide temperature range, and having excellent oil resistance and heat resistance. <P>SOLUTION: This thermoplastic elastomer composition comprises (A) an (meth)acrylic block copolymer, (B) a compound containing two or more amino radicals in its molecule, and (C) a thermoplastic resin, wherein the (meth)acrylic block copolymer (A) is composed of (A1) an (meth)acrylic copolymer block and (A2) an acrylic copolymer block, at least one of the copolymer blocks has at least one (a1) acid anhydride radical expressed by general formula (1) (R<SP>1</SP>is H or methyl; n is an integer of 0 to 3; and m is 0 or 1) in its main chain, and the (meth)acrylic block copolymer (A) and the compound (B) are dynamically crosslinked in the thermoplastic resin (C). <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a thermoplastic elastomer, which has good physical properties, rubber elasticity over a wide temperature range, high-temperature creep performance, excellent moldability, and oil resistance, heat resistance while being a thermoplastic elastomer. The present invention relates to a novel thermoplastic elastomer composition having excellent heat resistance.

  Vulcanized rubber has excellent flexibility and rubber elasticity, but at the time of molding, it is necessary to add an additive to the rubber and vulcanize, so the molding cycle time is long, and the process is complicated, There is a problem with moldability. Further, after vulcanized rubber is once molded and vulcanized, it does not melt even if reheated, so that post-processing such as joining cannot be performed, and there is a problem that it is difficult to recycle after use.

  From these points, in recent years, thermoplastic elastomers have been used in place of vulcanized rubber. For example, in automobile vehicles, various seal components such as glass run channels, weather strips, various boots, and draining moldings are used, and most of them use vulcanized rubber. In recent years, lightweight and recyclable olefin-based thermoplastic elastomers have begun to be used as part of the sealing parts from the viewpoint of improving fuel efficiency and environmental issues.

  As such a thermoplastic elastomer, there is a type in which hard segments and soft segments are alternately contained in a copolymer chain (for example, see Patent Document 1). These can be manufactured from those having high flexibility to those having rigidity by changing the ratio of each segment. Furthermore, a composition obtained by melt-kneading a monoolefin copolymer rubber and a polyolefin resin using a crosslinking agent and partially crosslinking, that is, a material having improved compression set by dynamically heat-treating (dynamically crosslinking) is also available. It is known (for example, see Patent Document 2).

  However, in the former case of a thermoplastic elastomer having a structure in which hard segments and soft segments are alternately contained in a copolymer chain, a large amount of soft segments must be contained in order to obtain a flexible thermoplastic elastomer. Is required. In addition, since the constraining component is a hard segment, it flows at high temperatures, but has disadvantages such as poor heat resistance (the heat resistance in this case means physical properties at high temperatures) and compression set. In addition, since the soft segment has low tensile strength and poor heat resistance and oil resistance, a flexible thermoplastic elastomer composition containing a large amount of such a soft segment still has low tensile strength, heat resistance, and oil resistance. However, it cannot be used for various applications over a wide range. The technology disclosed as a conventional styrene-based elastomer belongs to this category, so the moldability is very good, but due to the above problems, it is used for a wide range of applications such as industrial mechanical parts. I can't. On the other hand, as a thermoplastic elastomer having excellent oil resistance, an acrylic block copolymer having a methacrylic copolymer block and an acrylic copolymer block has recently been disclosed. Is very good, but has disadvantages such as poor heat resistance and compression set (for example, see Patent Document 3).

  In the latter polyolefin, in the case of a thermoplastic elastomer having a structure in which an olefin copolymer rubber is partially cross-linked, if the thermoplastic elastomer alone cannot provide sufficient performance, such as good compression set at high temperatures Attempts have been made to improve performance.

  However, crystalline polyolefins such as polyethylene and polypropylene have the drawbacks of relatively low melting point and poor oil resistance, and the resulting composition is used only in areas where oil resistance and heat resistance are unnecessary. Have been restricted. In recent years, as a solution to the above problems, polyester, polycarbonate, various thermoplastic resins such as polyamide and acrylic rubber, ethylene-acrylate copolymer rubber, by the combination of various polar rubbers such as nitrile rubber, Although a partially crosslinked thermoplastic elastomer has been studied (see, for example, Patent Documents 4, 5, and 6), when a thermoplastic resin having heat resistance is used, it is difficult to control crosslinking because of a high melting temperature. The disadvantage that a good composition cannot be obtained, and the conventional cross-linking agent for a polar rubber has a disadvantage such as deteriorating a thermoplastic resin during a curing process, thereby lowering the physical properties of the obtained composition. ing. In order to improve this point, a method using a cross-linking agent such as a polyfunctional oxazoline has been disclosed (for example, see Patent Document 7). However, disadvantages such as availability, easiness of handling, and limitation of the type of cross-linking agent are disclosed. Have. Therefore, there has been a demand for the development of a thermoplastic elastomer which is easy to obtain and has a hardening process, that is, easy to manufacture, and excellent in oil resistance and heat resistance.

JP-A-61-34050 JP-B-53-21021 Japanese Patent No. 2553134 JP-A-10-53697 JP-A-11-34973 JP-A-2000-26720 Japanese Patent Application Laid-Open No. H11-246749

  The present invention relates to a thermoplastic elastomer, more specifically, excellent in balance between hardness and mechanical strength, over a wide temperature range, rubber elasticity, high-temperature creep performance, excellent moldability, and while being a thermoplastic elastomer, The present invention relates to a novel thermoplastic elastomer composition having excellent oil resistance and heat resistance.

  The present inventors have proposed (A) a (meth) acrylic block copolymer composed of (A1) a (meth) acrylic polymer block and (A2) an acrylic polymer block, and (B) 2 per molecule. By dynamically heat-treating a thermoplastic elastomer composition comprising a compound containing two or more amino groups and (C) a thermoplastic resin, it has excellent balance between hardness and mechanical strength, rubber elasticity over a wide temperature range, and high-temperature creep. They have found that they are excellent in performance, low-temperature impact resistance, mechanical strength, moldability, and are excellent in oil resistance and heat resistance while being a thermoplastic elastomer, and have completed the present invention.

That is, the present invention provides a thermoplastic elastomer composition comprising (A) a (meth) acrylic block copolymer, (B) a compound containing two or more amino groups in one molecule, and (C) a thermoplastic resin. The (meth) acrylic block copolymer (A) comprises (A1) a (meth) acrylic polymer block and (A2) an acrylic polymer block, and has a main chain of at least one of the polymer blocks. In the general formula (1):

(Wherein, R ¹ is hydrogen or a methyl group, which 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). The present invention relates to a thermoplastic elastomer composition having one, wherein a (meth) acrylic block copolymer (A) and a compound (B) are dynamically crosslinked in a thermoplastic resin (C).

(Meth) acrylic block copolymer (A) is selected from the group represented by the general formula (x-y) _n, the formula y- (x-y) _n, the general formula (x-y) _n -x It is preferable that at least one of them be used.

  The (meth) acrylic block copolymer (A) is composed of 0.1 to 60% by weight of the (meth) acrylic polymer block (A1) and 99.9 to 40% by weight of the acrylic polymer block (A2). Preferably.

  The (meth) acrylic polymer block (A1) preferably has an acid anhydride group (a1).

  It is preferable that the acrylic polymer block (A2) has an acid anhydride group (a1).

  It is preferable that the (meth) acrylic block copolymer (A) is a polymer obtained by controlled polymerization by atom transfer radical polymerization.

  The thermoplastic resin (C) is preferably a polyamide resin and / or a polyester resin.

  It is preferable that the thermoplastic resin (C) is a polyamide resin.

  It is preferable to contain (D) 1 to 300 parts by weight of a softening agent based on 100 parts by weight of the (meth) acrylic block polymer (A).

  The thermoplastic elastomer composition of the present invention has an excellent balance between hardness and mechanical strength, rubber elasticity over a wide temperature range, excellent high-temperature creep performance, excellent moldability, and oil resistance and heat resistance while being a thermoplastic elastomer. Therefore, it can be suitably and widely used as various sealed containers, gaskets, oil-resistant hoses, covering sheets, and the like.

The present invention relates to a thermoplastic elastomer composition comprising a (meth) acrylic block copolymer (A), a compound (B) containing two or more amino groups in one molecule, and a thermoplastic resin (C). The (meth) acrylic block copolymer (A) is composed of a (meth) acrylic polymer block (A1) and an acrylic polymer block (A2), and in the main chain of at least one of the polymer blocks. In general formula (1):

(Wherein, R ¹ is hydrogen or a methyl group, which may be the same or different; n is an integer of 0 to 3, m is an integer of 0 or 1), and at least an acid anhydride group (a1) represented by The present invention relates to a thermoplastic elastomer composition having one, wherein a (meth) acrylic block copolymer (A) and a compound (B) are dynamically crosslinked in a thermoplastic resin (C).

  Here, dynamically cross-linking refers to a (meth) acrylic block copolymer (A), a compound (B) containing two or more amino groups in one molecule, and a thermoplastic resin (C). Melt-kneading the system to crosslink (meth) acrylic block copolymer (A) and compound (B) having two or more amino groups in one molecule in thermoplastic resin (C). Thus, a thermoplastic elastomer composition having improved physical properties can be obtained. The morphology of the thermoplastic elastomer is that the crosslinked (meth) acrylic block copolymer (A) is dispersed in the thermoplastic resin (C) matrix which is a continuous phase in terms of rubber elasticity. Preferably, the crosslinked (meth) acrylic block copolymer (A) and the thermoplastic resin (C) have a co-continuous structure in terms of flexibility and the like.

<(Meth) acrylic block copolymer (A)>
The structure of the (meth) acrylic block copolymer (A) used in 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 include the required physical properties of the (meth) acrylic block copolymer (A), processing properties and mechanical properties required for the composition with the thermoplastic resin, and the like. The linear block copolymer is preferred in terms of cost and ease of polymerization.

The (meth) acrylic block copolymer (A) is composed of a (meth) acrylic polymer block (A1) and an acrylic polymer block (A2), and has physical properties of the composition such as tensile mechanical properties and compression set. in view of the general formula: (x-y) _n, the general _{formula: y- (x-y) n} , the general formula: (x-y) _n -x acrylic (n is an integer of 1 or more) is expressed by It is preferably at least one acrylic block copolymer selected from the group consisting of block copolymers. Although not particularly limited, among these, from the viewpoint of ease of handling during processing and physical properties of the composition, an xy type diblock copolymer, an xyx type triblock copolymer, or these Are preferred.

The (meth) acrylic block copolymer (A) is dynamically crosslinked with the compound (B) containing two or more amino groups in one molecule.
General formula (1):

(Wherein, R ¹ is hydrogen or a methyl group, which may be the same or different; n is an integer of 0 to 3, m is an integer of 0 or 1), and has an acid anhydride group (a1) Is preferred.

  The acid anhydride group (a1) represented by the general formula (1) can be one or two or more per polymer block, and when the number is two or more, the monomer is The mode being polymerized can be block copolymerization. Taking the xyx type triblock copolymer as an example, (x / z) -yx type, (x / z) -y- (x / z) type, zxy- x-type, z-x-y-x-z-type, x- (y / z) -x-type, x-y-x-x-type, x-z-y-x-type, x-z-y-z Any of -x type and the like may be used. Here, z represents a monomer or polymer block containing an acid anhydride group (a1), and (x / z) means a monomer containing an acid anhydride group (a1) in a block (x). (Y / z) indicates that a monomer containing an acid anhydride group (a1) is copolymerized in the block (y).

  The number average molecular weight of the (meth) acrylic block copolymer (A) is not particularly limited, but is required for each of the (meth) acrylic polymer block (A1) and the acrylic polymer block (A2). May be determined from the molecular weight. When the molecular weight is small, sufficient mechanical properties as an elastomer cannot be exhibited, and when the molecular weight is unnecessarily large, the processing properties are reduced, and the number average molecular weight is preferably 3,000 to 500,000. It is preferably 4000 to 400,000, more preferably 5000 to 300,000.

  The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the (meth) acrylic block copolymer (A) measured by gel permeation chromatography is not particularly limited. , 1 to 1.8, more preferably 1 to 1.5. If Mw / Mn exceeds 1.8, the uniformity of the acrylic block copolymer may be reduced.

  The composition ratio of the (meth) acrylic polymer block (A1) and the acrylic polymer block (A2) constituting the (meth) acrylic block copolymer (A) is not particularly limited, and is required in the application to be used. It may be determined from the physical properties, the moldability required during processing of the composition, and the molecular weights required for the (meth) acrylic polymer block (A1) and the acrylic polymer block (A2). To illustrate a preferred composition ratio range of the (meth) acrylic polymer block (A1) and the acrylic polymer block (A2), the (meth) acrylic polymer block (A1) is 0.1 to 80% by weight. And the acrylic polymer block (A2) is preferably 99.9 to 20% by weight. More preferably, the content of the (meth) acrylic polymer block (A1) is 0.1 to 70% by weight, and the content of the acrylic polymer block (A2) is 99.9 to 30% by weight. More preferably, the content of the (meth) acrylic polymer block (A1) is 0.1 to 60% by weight, and the content of the acrylic polymer block (A2) is 99.9 to 40% by weight. If the proportion of the (meth) acrylic polymer block (A1) is less than 0.1% by weight, rubber elasticity at high temperatures may decrease. The properties, particularly the elongation at break, may be reduced, and the flexibility of the composition with the thermoplastic resin may be reduced.

The relationship between the glass transition temperatures of the (meth) acrylic polymer block (A1) and the acrylic polymer block (A2) that constitute the (meth) acrylic block copolymer (A) is as follows: (meth) acrylic polymer It is preferable that the glass transition temperature of the block (A1) be Tg _A1 and that of the acrylic polymer block (A2) be Tg _A2 , satisfying the following relationship.
Tg _A1 > Tg _A2

The setting of the glass transition temperature (Tg) of the polymer ((meth) acrylic polymer block (A1) and acrylic polymer block (A2)) is roughly in accordance with the following Fox formula. By setting the weight ratio of the monomer.
_{1 / Tg = (W 1 /} Tg 1) + (W 2 / Tg 2) + ... + (W m / Tg m)
W ₁ + W ₂ +... + W _m = 1

Wherein, Tg represents the glass transition temperature of the _{polymer, Tg 1, Tg 2, ...} , Tg m represents the glass transition temperature of the polymer consisting of only the polymer monomers. _{Further, W 1, W 2, ...} , W m represents the weight ratio of each polymer monomer.

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

  The general formula (1):

(Wherein R ¹ is hydrogen or a methyl group, which may be the same or different; n is an integer of 0 to 3, m is an integer of 0 or 1). The method of introduction into the (meth) acrylic block copolymer (A) is not particularly limited, but is a precursor of the acid anhydride group (a1) in terms of ease of introduction and simplicity of purification after introduction. It is preferable to introduce into the acrylic block copolymer in the form of a functional group, followed by cyclization.

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

  In the general formula (1), m is an integer of 0 or 1, and when n is 0, m is also 0. When n is 1 to 3, m is preferably 1.

The acid anhydride group (a1) may be contained in only one of the (meth) acrylic polymer block (A1) and the acrylic polymer block (A2), or may be contained in both blocks. The reaction point of the (meth) acrylic block copolymer (A), the cohesive force and the glass transition temperature of the blocks constituting the (meth) acrylic block copolymer (A), and further, The (meth) acrylic block copolymer (A) may be used according to the purpose, for example, depending on the physical properties. For example, a (meth) acrylic polymer block (A1) or an acrylic polymer block (A2) is selectively formed using a compound having an amino group, a hydroxyl group, or the like with the acid anhydride group (a1) as a reaction point. When modification or reaction is desired, the acid anhydride group (a1) may be introduced into a block to be modified or reacted. When controlling the molecular weight between crosslinking points, the acid anhydride group (a1) may be introduced into the (meth) acrylic polymer block (A1) to control the compatibility with the thermoplastic resin (C). In this case, the acid anhydride group (a1) may be introduced into the acrylic polymer block (A2). Although not particularly limited, in terms of control of reaction points, heat resistance, rubber elasticity, and the like, it is provided in either (meth) acrylic polymer block (A1) or acrylic polymer block (A2). Is preferred. Further, although not particularly limited, when it is contained in the (meth) acrylic polymer block (A1), it is preferable that both R ^{1 in the} general formula (1) are methyl groups. If containing, R ¹ in the general formula (1) is preferably both hydrogen. When R ¹ is hydrogen when included in the (meth) acrylic polymer block (A1), or when R ¹ is a methyl group when included in the acrylic polymer block (A2), (meth) acrylic The polymerization operation of the system block copolymer (A) becomes complicated, and the difference in glass transition temperature between the methacrylic polymer block (A1) and the acrylic polymer block (A2) becomes small, and the (meth) acrylic The rubber elasticity of the block copolymer (A) may decrease.

The preferred range of the content of the acid anhydride group (a1) is as follows: the cohesive strength and reactivity of the acid anhydride group (a1), the structure and composition of the (meth) acrylic block copolymer (A), and (meth) It varies depending on the number of blocks constituting the acrylic block copolymer (A), the glass transition temperature, and the site and mode in which the acid anhydride group (a1) is contained. The preferred range of the content of the acid anhydride group (a1) is, for example, 0.05 to 50% by weight, preferably 0.1 to 40% by weight of the whole (meth) acrylic block copolymer (A). More preferred. When the content of the acid anhydride group (a1) is less than 0.05% by weight, the reactivity of the (meth) acrylic block copolymer (A) and the compatibility with the thermoplastic resin become insufficient. When the content exceeds 50% by weight, the rubber elasticity of the (meth) acrylic block copolymer (A) decreases, or a large amount of a reaction with a crosslinking agent (B) or a reaction with a thermoplastic resin (C) occurs. Accordingly, the fluidity of the obtained thermoplastic elastomer may decrease. In order to improve the heat resistance of the (meth) acrylic block copolymer (A), an acid anhydride group (a1) having a high Tg is introduced into the (meth) acrylic polymer block (A1) which is a hard segment. In this case, if the content of the acid anhydride group (a1) is less than 0.05% by weight, the improvement in heat resistance is insufficient, and the expression of rubber elasticity at high temperatures may be reduced. Here, the content of the acid anhydride group (a1) means the weight of the monomer having the acid anhydride group (a1) or the monomer having the acid anhydride group (a1) by a reaction or the like. %. This content can be calculated by ¹³ C-NMR analysis. Specifically, the resin is dissolved in heavy acetone or the like, and ¹³ C-NMR analysis is performed. At this time, when the skeleton of the (meth) acrylic block copolymer is (meth) acrylic ester, a signal of a carboxyl group derived from a (meth) acrylic acid ester unit is observed at 174 to 178 ppm, and the signal is at 171 to 173 ppm. A signal derived from the carbonyl site of the (meth) acrylic anhydride skeleton is observed. The acid anhydride groups can be quantified by comparing these ratios. When another copolymerizable vinyl monomer is introduced, monomer quantification by GCMS utilizing thermal decomposition or composition comparison by NMR or the like is performed.

  The content block and content of the acid anhydride group (a1) may be appropriately determined in accordance with the required reactivity, reaction point, cohesive strength, glass transition temperature, and the like.

<(Meth) acrylic polymer block (A1)>
The monomer constituting the (meth) acrylic polymer block (A1) is preferably (meth) acrylic from the viewpoints of easily obtaining a (meth) acrylic block copolymer having desired physical properties, cost, and availability. 100 to 50% by weight of a monomer having an acrylate ester and / or an acid anhydride group (a1), and 0 to 50% by weight of another vinyl monomer copolymerizable therewith, preferably (meth) It is composed of 100 to 75% by weight of a monomer having an acrylate ester and / or acid anhydride group (a1), and 0 to 25% by weight of another vinyl monomer copolymerizable therewith. When the proportion of the monomer having the (meth) acrylate and / or the acid anhydride group (a1) is less than 50% by weight, the weather resistance, the high glass transition point, which are the characteristics of the (meth) acrylate, The compatibility with the resin may be impaired.

  The molecular weight required for the (meth) acrylic polymer block (A1) may be determined from the cohesive force required for the (meth) acrylic polymer block (A1), the time required for the polymerization, and the like. .

It is said that the cohesive force depends on the degree of interaction and entanglement between molecules. As the molecular weight increases, the number of entanglement points increases and the cohesive force increases. That is, the molecular weight required for the (meth) acrylic polymer block (A1) is M _A1, and the molecular weight between the entanglement points of the polymers constituting the (meth) acrylic polymer block (A1) is Mc _{A1. When} the range of _A1 is exemplified, when cohesion is required, preferably, M _A1 > Mc _A1 . To give further examples, if further cohesion is required, it is preferable that M _A1 > 2 × Mc _A1 , and conversely, if both cohesion and creep properties are desired to be compatible, Mc _A1 < M _A1 <2 × Mc _A1 is preferred. The molecular weight between entanglement points may be referred to Wu et al.'S document (Polymer Engineering and Science (Polym. Eng. And Sci., 1990, vol. 30, p. 753)), for example, a (meth) acrylic polymer block. Assuming that (A1) is composed entirely of methyl methacrylate, the range of the number average molecular weight of the (meth) acrylic polymer block (A1) when cohesion is required is 100 or more. Further, if the number average molecular weight is large, the polymerization time tends to be long, so it may be set according to the required productivity, but is preferably 200,000 or less, more preferably 100,000 or less. When the acid anhydride group (a1) is contained in the (meth) acrylic polymer block (A1), Since the cohesive force by the group (a1) is given, the molecular weight can be set lower than this.

  Examples of the (meth) acrylate constituting the (meth) acrylic polymer block (A1) include methacrylate and acrylate, and examples of the methacrylate include methyl methacrylate and methacrylate. Ethyl acrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate Methacrylic acid aliphatic hydrocarbon (eg, alkyl) esters such as 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, and stearyl methacrylate; cyclohexyl methacrylate, methacrylic acid Isobol Alicyclic hydrocarbon esters of methacrylic acid such as benzyl methacrylate; aralkyl esters of methacrylic acid such as benzyl methacrylate; aromatic hydrocarbon esters of methacrylic acid such as phenyl methacrylate and toluyl methacrylate; Esters of methacrylic acid such as methoxyethyl and 3-methoxybutyl methacrylate with alcohols having a functional group having ethereal oxygen; trifluoromethyl methacrylate, 2-trifluoroethyl methacrylate, 2-methacrylic acid Perfluoroethylethyl, 2-perfluoroethyl-2-perfluorobutylethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethylmethyl methacrylate, methacrylic acid 2 -Perf Fluoroalkyl methacrylates such as olomethyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl methacrylate, 2-perfluorodecylethyl methacrylate, and 2-perfluorohexadecylethyl methacrylate; can give.

  Examples of the acrylate constituting the (meth) acrylic polymer block (A1) include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, and n-acrylate. Aliphatic hydrocarbons such as pentyl, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, and stearyl acrylate ( Alicyclic hydrocarbon esters such as cyclohexyl acrylate and isobornyl acrylate; aromatic aromatic hydrocarbon esters such as phenyl acrylate and toluyl acrylate; aralkyl acrylates such as benzyl acrylate Ter; esters of acrylic acid such as 2-methoxyethyl acrylate and 3-methoxybutyl acrylate with a functional group-containing alcohol having ethereal oxygen; trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, acrylic 2-perfluoroethyl ethyl acrylate, 2-perfluoroethyl acrylate-2-perfluorobutyl ethyl acrylate, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-per acrylate Fluorinated alkyl acrylates such as fluoromethyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl acrylate, and the like. It can be.

  At least one of these is used. Among these, methyl methacrylate is preferred in terms of compatibility with the thermoplastic resin to be combined, cost, and availability.

  Examples of the vinyl monomer copolymerizable with the (meth) acrylic ester constituting the (meth) acrylic block copolymer (A) include, for example, a carboxylic acid-containing unsaturated compound, an aromatic alkenyl compound, and cyanide. Examples include vinyl compounds, conjugated diene compounds, halogen-containing unsaturated compounds, silicon-containing unsaturated compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds, and maleimide compounds.

  Examples of the carboxylic acid-containing unsaturated compound include methacrylic acid and acrylic acid. Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene and the like. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Examples of the conjugated diene-based 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 silicon-containing unsaturated compound include vinyltrimethoxysilane, vinyltriethoxysilane and the like. Examples of the unsaturated dicarboxylic acid compound include maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, and the like. Examples of 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, and cyclohexylmaleimide. At least one of these is used.

  These vinyl monomers can be selected preferably depending on the compatibility when the (meth) acrylic block copolymer (A) is combined with a thermoplastic resin and / or a thermoplastic elastomer. The methyl methacrylate polymer is almost quantitatively depolymerized by thermal decomposition. In order to suppress the depolymerization, acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, and acrylic acid 2 are used. -Methoxyethyl or a mixture thereof, or styrene or the like can be copolymerized. Acrylonitrile can be copolymerized for the purpose of further improving oil resistance.

  The glass transition temperature of the (meth) acrylic polymer block (A1) is preferably 0 ° C. or higher, more preferably room temperature or higher. The glass transition temperature (Tg) of the polymer ((meth) acrylic polymer block (A1)) is set by setting the weight ratio of the monomer of each polymer portion according to the above Fox formula. Can do it. Here, the glass transition temperature is calculated according to the Fox equation using the value described in Polymer Handbook Third Edition (Wiley-Interscience 1989) as the glass transition temperature of each polymerized monomer.

<Acrylic polymer block (A2)>
The monomer constituting the acrylic polymer block (A2) is preferably an acrylate ester and / or an acid anhydride group (a1) from the viewpoint of easily obtaining a composition having desired physical properties, cost, and availability. 100 to 50% by weight of a monomer having the following formula, 0 to 50% by weight of a vinyl monomer copolymerizable therewith, preferably 100 to 50% by weight of the monomer having an acrylate ester and / or acid anhydride group (a1) 75% by weight, and 0 to 25% by weight of a vinyl monomer copolymerizable therewith. When the proportion of the acrylate is less than 50% by weight, the physical properties of the composition, particularly the impact resistance, which are characteristic when using the acrylate, may be impaired.

  The molecular weight required for the acrylic polymer block (A2) may be determined based on the elastic modulus and rubber elasticity required for the acrylic polymer block (A2), the time required for the polymerization, and the like.

The elastic modulus is closely related to the ease of movement of the molecular chain and its molecular weight, and the elastic modulus does not show the original elastic modulus unless the molecular weight exceeds a certain level. The same applies to rubber elasticity, but from the viewpoint of rubber elasticity, it is desirable that the molecular weight is large. That is, To illustrate the range molecular weight required for the acrylic polymer block (A2) as M _A2, preferably M _A2> 3000, more preferably M _A2> 5000, even more preferably M _A2> 10000, in particular Preferably M _A2 > 20,000, most preferably M _A2 > 40,000. However, if the number average molecular weight is large, the polymerization time tends to be long. Therefore, the polymerization time may be set according to the required productivity, but is preferably 500,000 or less, more preferably 300,000 or less.

  Examples of the acrylate constituting the acrylic polymer block (A2) include those described for the (meth) acrylic polymer block (A1), and at least one of them is used.

  Among these, n-butyl acrylate is preferred in terms of impact resistance, cost, and availability of the thermoplastic resin composition. When the composition requires oil resistance, n-ethyl acrylate is preferred. When low-temperature properties are required, 2-ethylhexyl acrylate is preferred. Further, when it is desired to achieve both oil resistance and low-temperature characteristics, a mixture of n-ethyl acrylate, n-butyl acrylate, and 2-methoxyethyl acrylate is preferable.

  Examples of the vinyl monomer copolymerizable with the acrylate constituting the acrylic polymer block (A2) include methacrylate, an aromatic alkenyl compound, a vinyl cyanide compound, a conjugated diene compound, and a halogen. Unsaturated compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds, maleimide compounds, and the like. Specific examples thereof include those described in the (meth) acrylic polymer block (A1). Can be. At least one of these is used.

  These vinyl monomers may be used in combination with the glass transition temperature, elastic modulus, and polarity required for the acrylic polymer block (A2), and the physical properties required for the composition, thermoplastic resin and / or thermoplastic elastomer. Preferred ones can be selected depending on the compatibility and the like. For example, acrylonitrile can be copolymerized for the purpose of improving the oil resistance of the composition.

  The glass transition temperature of the acrylic polymer block (A2) is preferably from -100 ° C to 50 ° C, more preferably from -100 ° C to 0 ° C. When the glass transition temperature is higher than 50 ° C., the rubber elasticity of the (meth) acrylic block copolymer (A) may decrease, and when the glass transition temperature is lower than −100 ° C., the obtained (meth) acrylic block copolymer ( The mechanical strength of A) may decrease.

  The setting of the glass transition temperature (Tg) of the polymer (acrylic polymer block (A2)) can be performed by setting the weight ratio of the monomer of each polymer portion according to the above Fox formula. it can. Here, the glass transition temperature is calculated according to the Fox equation using the value described in Polymer Handbook Third Edition (Wiley-Interscience 1989) as the glass transition temperature of each polymerized monomer.

<Acid anhydride group (a1)>
General formula (1):

(Wherein R ¹ is hydrogen or a methyl group, which may be the same or different, n is an integer of 0 to 3, m is an integer of 0 or 1), and an acid anhydride group (a1) represented by Since it has high reactivity with compounds having an amino group, a hydroxyl group, etc., it is used as a reaction point when modifying a polymer and as a compatibility improving site when blending with a thermoplastic resin and / or a thermoplastic elastomer. You can also. Further, the acid anhydride group (a1) can be a crosslinking point by reacting with the compound (B) containing two or more amino groups in one molecule. Further, by introducing an acid anhydride group (a1) to a desired site of the (meth) acrylic block copolymer (A), a desired site of the (meth) acrylic block copolymer (A) can be obtained. It becomes possible to crosslink. Further, since the acid anhydride group (a1) has a high glass transition temperature (Tg), when introduced into the hard segment, the effect of improving the heat resistance of the (meth) acrylic block copolymer (A) is improved. Have. The glass transition temperature of the polymer having an acid anhydride group (a1) is, for example, as high as 159 ° C. for polymethacrylic anhydride, and by introducing units constituting these, a (meth) acrylic block copolymer is obtained. The heat resistance of (A) can be improved.

The method for introducing the acid anhydride group (a1) is not particularly limited, but is introduced into the (meth) acrylic block copolymer (A) in a form to be a precursor of the acid anhydride group (a1). It is preferable to cyclize to. For example,
General formula (2):

(In the formula, R ² represents hydrogen or a methyl group; R ³ represents a hydrogen, a methyl group, or a phenyl group, and may be the same or different except that they contain at least one methyl group.) The acrylic block copolymer (A ′) containing a precursor of an acid anhydride group, which has at least one unit to be obtained, is melt-kneaded at a temperature of 180 to 300 ° C. and cyclized to form an acid anhydride group. Is preferably introduced.

  The introduction of the unit represented by the general formula (2) can be performed by copolymerizing the acrylate or methacrylate monomer as the precursor.

  The unit represented by the general formula (2) is eliminated and cyclized with an adjacent ester unit at a high temperature to produce an acid anhydride group (for example, Hatada et al., JMS-PURE APPL). Chem., A30 (9 & 10), PP. 645-667 (1993)). According to the above literature, in general, in a polymer having a bulky ester unit and β-hydrogen, the ester unit is decomposed at a high temperature, followed by cyclization to form an acid anhydride group. By using the method described in the above document, an acid anhydride group can be easily introduced into the (meth) acrylic block copolymer (A). Although not particularly limited, specific examples of such a monomer include t-butyl acrylate, isopropyl acrylate, α, α-dimethylbenzyl acrylate, α-methylbenzyl acrylate, t-butyl methacrylate, Examples thereof include isopropyl methacrylate, α, α-dimethylbenzyl methacrylate, and α-methylbenzyl methacrylate. Among them, t-butyl acrylate and t-butyl methacrylate are preferred from the viewpoints of availability, easiness of polymerization, and easiness of forming an acid anhydride group.

  The formation of the acid anhydride group (a1) is preferably performed by heating the acrylic block copolymer (A ′) containing the precursor of the acid anhydride group at a high temperature, and is not particularly limited. Heating is preferred. When the temperature is lower than 180 ° C., the generation of the acid anhydride group may be insufficient, and when the temperature is higher than 300 ° C., the acrylic block copolymer (A ′) containing the precursor of the acid anhydride group may be decomposed. is there. In addition, in general, in the process of introducing an acid anhydride group, the ester unit is decomposed at a high temperature to generate a carboxyl group, and subsequently, there is a cyclization route in which cyclization occurs and an acid anhydride group is generated, When the acid anhydride group (a1) is introduced, a part of the carboxyl group may remain.

<Production method of acrylic block copolymer (A ′) containing precursor of acid anhydride group>
The method for producing the acrylic block copolymer (A ′) containing the precursor of the acid anhydride group is not particularly limited, but it is preferable to use controlled polymerization using a polymer initiator. Examples of the controlled polymerization include living anionic polymerization, radical polymerization using a chain transfer agent, and living radical polymerization recently developed. Among them, living radical polymerization is preferred from the viewpoint of controlling the molecular weight and structure of the acrylic copolymer.

  Living radical polymerization is radical polymerization in which the activity of the polymerization terminal is maintained without loss. In a narrow sense, living polymerization refers to polymerization in which the terminal always keeps activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the activated one is in an equilibrium state. . The definition here is also the latter. In recent years, various groups have been actively studying living radical polymerization.

  Examples thereof include those using a chain transfer agent such as polysulfide, a cobalt porphyrin complex (Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943) and radicals such as nitroxide compounds. Using a scavenger (Macromolecules, 1994, Vol. 27, p. 7228), atom transfer radical polymerization using an organic halide or the like as a catalyst and a transition metal complex as a catalyst (Atom Transfer Radical Polymerization: ATRP) ) And so on. In the present invention, which method is used is not particularly limited, but atom transfer radical polymerization is preferred from the viewpoint of easy control.

  Atom transfer radical polymerization is carried out by using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a central metal of Group 8, 9, 10, or 11 of the periodic table as a catalyst (for example, Matyjaszewski 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 has a narrow molecular weight distribution (Mw / Mn = 1.1-1.5) A 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, as an organic halide or a sulfonyl halide compound used as an initiator, a monofunctional, bifunctional, or polyfunctional compound can be used. These may be properly used depending on the purpose, but when a diblock copolymer is produced, a monofunctional compound is preferable from the viewpoint of availability of an initiator, and an xy-type triblock is preferred. When a copolymer or a y-xy type triblock copolymer is produced, it is preferable to use a bifunctional compound from the viewpoint of reducing the number of reaction steps and time. In the case of production, it is preferable to use a polyfunctional compound from the viewpoint of reducing the number of reaction steps and time.

  It is also possible to use a polymer initiator as the initiator. The polymer initiator is a compound formed of a polymer having a halogen atom bonded to a molecular chain terminal, 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, it is characterized in that a block copolymer in which polymers obtained by different polymerization methods are combined can be obtained. .

As the monofunctional compound, for example,
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.

Specific examples of the alkyl group having 1 to 20 carbon atoms (including an alicyclic hydrocarbon group) as R ⁴ include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Examples include t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, isobornyl group, and the like. Specific examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a triyl group, and a naphthyl group. Specific examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenethyl group.

  Specific examples of the monofunctional compound include, for example, tosyl bromide, methyl 2-bromopropionate, ethyl 2-bromopropionate, butyl 2-bromopropionate, methyl 2-bromoisobutyrate, Examples thereof include ethyl bromide isobutyrate and 2-butyl butyl isobutyrate. Of these, ethyl 2-bromopropionate and butyl 2-bromopropionate are preferred because they have a similar structure to the structure of the acrylate monomer, so that the polymerization can be easily controlled.

As the 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 described 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 , Since the specific examples are the same as those of the aryl group having 20 and the aralkyl group having 7 to 20 carbon atoms, the description is omitted.

  Specific examples of the bifunctional compound include, for example, bis (bromomethyl) benzene, bis (1-bromoethyl) benzene, bis (1-bromoisopropyl) benzene, dimethyl 2,3-dibromosuccinate, 2,3-dibromosuccinate Diethyl acetate, dibutyl 2,3-dibromosuccinate, dimethyl 2,4-dibromoglutarate, diethyl 2,4-dibromoglutarate, dibutyl 2,4-dibromoglutarate, dimethyl 2,5-dibromoadipate, 2, Diethyl 5-dibromoadipate, dibutyl 2,5-dibromoadipate, dimethyl 2,6-dibromopimelate, diethyl 2,6-dibromopimelate, dibutyl 2,6-dibromopimelate, dimethyl 2,7-dibromosuberate 2,7-dibromosuberic acid diethyl, 2,7-dibromosuberic Such as dibutyl, and the like. Among these, bis (bromomethyl) benzene, diethyl 2,5-dibromoadipate, and diethyl 2,6-dibromopimelate are preferred from the viewpoint of availability of raw materials.

As the polyfunctional 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 trivalent phenyl group (the position of the three bonds may be any combination of the 1- to 6-positions), and X is the same as described above.

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

  When an organic halide or a sulfonyl halide compound having a functional group is used in addition to the group that initiates polymerization, a polymer in which a functional group other than the group that initiates polymerization is easily introduced into a terminal or in a molecule is obtained. Can be Examples of the functional group other than the group that initiates such polymerization include an alkenyl group, a hydroxyl group, an epoxy group, an amino group, an amide group, and a silyl group.

  The organic halide or the sulfonyl halide compound which can be used as the initiator has a carbon in which a halogen group (halogen atom) is bonded to a carbonyl group or a phenyl group, and the carbon-halogen bond is activated. Then polymerization starts. The amount of the initiator to be used may be determined from the molar ratio with the monomer in accordance with the required molecular weight of the acrylic block copolymer. That is, the molecular weight of the acrylic block copolymer can be controlled by how many initiators are used per one monomer molecule.

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

  Among these, a monovalent 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. Among them, cuprous chloride and cuprous bromide are more preferable from the viewpoint of control of polymerization. When a monovalent copper compound is used, 2,2'-bipyridyl or a derivative thereof (eg, 4,4'-dinolyl-2,2'-bipyridyl, 4,4'-di (5- 2,2'-bipyridyl compounds such as (noryl) -2,2'-bipyridyl); 1,10-phenanthroline and derivatives thereof (e.g., 4,7-dinolyl-1,10-phenanthroline, 5,6-dinolyl- 1,10-phenanthroline compounds such as 1,10-phenanthroline); and polyamines such as tetramethyldiethylenetriamine (TMEDA), pentamethyldiethylenetriamine, and hexamethyl (2-aminoethyl) amine may be added as ligands. .

Further, a tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also preferable as the catalyst. When a ruthenium compound is used as a catalyst, aluminum alkoxides may be added as an activator. Further, bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ ) ₂ ), bistriphenylphosphine complex of divalent nickel (NiCl ₂ (PPh ₃ ) ₂ ), and bistributylphosphine of divalent nickel The complex (NiBr ₂ (PBu ₃ ) ₂ ) is also preferred as a catalyst.

  The catalyst, ligand and activator to be used are not particularly limited, but may be appropriately determined from the relationship between the initiator, monomer and solvent used and the required reaction rate. For example, in the polymerization of an acrylic monomer such as an acrylate ester, it is preferable that the growth terminal of the polymer chain has a carbon-bromine bond from the viewpoint of controlling the polymerization. It is a sulfonyl bromide compound, the solvent is preferably acetonitrile, copper bromide, preferably using a metal complex catalyst having copper as a central metal contained in cuprous bromide, a ligand such as pentamethyldiethylenetriamine It is preferable to use Further, in the polymerization of methacrylic monomers such as methacrylic acid esters, it is preferable that the growth terminal of the polymer chain has a carbon-chlorine bond from the viewpoint of controlling the polymerization. It is a chloride or a sulfonyl chloride compound, and the solvent is preferably a mixed solvent with acetonitrile and, if necessary, toluene, and the like, and is a metal complex catalyst containing copper chloride, preferably copper contained in cuprous chloride as a central metal. And a ligand such as pentamethyldiethylenetriamine is preferably used.

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

  The atom transfer radical polymerization can be carried out without a solvent (bulk polymerization) or in various solvents. In addition, in bulk polymerization or polymerization performed in various solvents, the polymerization can be stopped halfway. As the solvent, for example, a hydrocarbon solvent, an ether solvent, a halogenated hydrocarbon solvent, a ketone solvent, an alcohol solvent, a nitrile solvent, an ester solvent, a carbonate solvent and the like can be used.

  Examples of the hydrocarbon solvent include benzene and toluene. Examples of the ether solvent include diethyl ether and tetrahydrofuran. Examples of the halogenated hydrocarbon-based solvent include methylene chloride and chloroform. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol and the like. Examples of the nitrile-based solvent include acetonitrile, propionitrile, benzonitrile and the like. Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the carbonate-based solvent include ethylene carbonate and propylene carbonate. At least one of these may be used.

  When a solvent is used, the amount of the solvent may be appropriately determined from the relationship between the viscosity of the entire system and the required stirring efficiency. Also, in the case of bulk polymerization and polymerization stopped in various solvents, the conversion of the monomer at the point where the reaction is stopped depends on the viscosity of the entire system and the required stirring efficiency. May be determined as appropriate.

  The polymerization can be performed in the range of 23 ° C to 200 ° C, preferably in the range of 50 ° C to 150 ° C. In order to produce an acrylic block copolymer by the above polymerization, a method of sequentially adding monomers, a method of polymerizing the next block using a polymer synthesized in advance as a polymer initiator, a polymer separately polymerized By a reaction. Any of these methods may be used, and may be properly used depending on the purpose. From the viewpoint of the simplicity of the production process, the method of successive addition of the monomer is preferable, and when it is desired to avoid that the monomer of the previous block remains and copolymerizes with the next block, it is synthesized in advance. A method of polymerizing the next block using a polymer as a polymer initiator is preferred.

  Hereinafter, in the case of successive addition of monomers, the case where the next block is polymerized using a polymer synthesized in advance as a polymer initiator will be described in detail, but the method for producing an acrylic block copolymer of the present invention will be described. There is no limitation.

  In the case of successive addition of monomers, it is desirable to charge a monomer to be subsequently polymerized when the conversion rate of the monomer previously charged for polymerization is 80 to 95%. When the polymerization is allowed to proceed until the conversion exceeds 95% (for example, to 96 to 100%), the growth reaction of the polymer chains is stochastically suppressed. In addition, since the polymer radicals easily react with each other, side reactions such as disproportionation, coupling, and chain transfer tend to occur easily. When a monomer to be subsequently polymerized is charged at a point in time when the conversion is less than 80% (for example, at a point of time of 79% or less), the monomer charged for the first polymerization is simply added to the next monomer to be polymerized. There is a case where a problem arises that the copolymer is mixed with the monomer and copolymerized.

  Also, in this case, as the order of addition of the monomers, a method of first charging and polymerizing an acrylic monomer and then charging and polymerizing a methacrylic monomer, and first, a methacrylic monomer It is considered to be a method of charging and polymerizing and then charging and polymerizing an acrylic monomer.First, a method of charging and polymerizing an acrylic monomer and then charging and polymerizing a methacrylic monomer. Is preferred from the viewpoint of controlling the polymerization. This is because it is preferable to grow the methacrylic polymer block from the terminal of the acrylic polymer block.

  As a method of polymerizing the next block using a polymer synthesized in advance as a polymer initiator, for example, at a desired point in time of the polymerization of the first block, the temperature is temporarily lowered in a living state, and the polymerization is stopped. After distilling off the monomer of the second block under reduced pressure, a method of adding the monomer of the second block can be mentioned. When it is desired to polymerize the third and subsequent blocks, the same operation as in the case of the second block may be performed. According to this method, it is possible to avoid the copolymerization of the remaining monomer of the previous block during the polymerization of the second and subsequent blocks.

  In this case, as the order of polymerization of the blocks, a method of first polymerizing the acrylic block and then polymerizing the methacrylic block, and a method of first polymerizing the methacrylic block and then polymerizing the acrylic block However, a method of first polymerizing an acrylic block and then polymerizing a methacrylic block is preferable from the viewpoint of controlling the polymerization. This is because it is preferable to grow the methacrylic polymer block from the terminal of the acrylic polymer block.

  Here, a method for determining the conversion ratio of an acrylic monomer, a methacrylic monomer, and the like will be described. To determine the conversion, a gas chromatograph (GC) method, a gravimetric method, or the like can be applied. In the GC method, the reaction solution of the polymerization system is sampled as needed before and during the reaction, GC measurement is performed, and the GC ratio is determined based on the ratio of the monomer to the internal standard substance added in advance in the polymerization system. This is a method of calculating the consumption rate. The advantage of this method is that, even when a plurality of monomers are present in the system, the conversion of each monomer can be determined independently. The gravimetric method is a method in which a polymerization reaction solution is sampled, the solid content concentration is determined from the weight before drying and the weight after drying, and the overall conversion of the monomer is determined. The advantage of this method is that the conversion can be easily determined. Among these methods, when a plurality of monomers are present in the system, for example, when an acrylic monomer is contained as a copolymer component of the methacrylic monomer, the GC method is used. preferable.

  The reaction solution obtained by polymerization contains a mixture of a polymer and a metal complex, and a carboxylic acid group, or an organic acid containing a sulfonic acid group is added to generate a metal complex and a metal salt, and the reaction solution is formed. Solids are removed by filtering the metal complex, etc., followed by basic activated alumina, basic adsorbent, solid inorganic acid, anion exchange resin, acid remaining in solution by cellulose anion exchanger adsorption treatment, etc. By removing the impurities, an acrylic block copolymer resin solution can be obtained.

  The polymer solution thus obtained is subsequently subjected to an evaporation operation to remove the polymerization solvent and unreacted monomers, thereby isolating the acrylic block copolymer. As the evaporation method, a thin film evaporation method, a flash evaporation method, a horizontal evaporation method provided with an extrusion screw, and the like can be used. Since the acrylic block copolymer has tackiness, efficient evaporation can be achieved by using the horizontal evaporation method having an extrusion screw alone or in combination with another evaporation method among the above evaporation methods.

<Production method of (meth) acrylic co-block polymer (A)>
The method for producing the (meth) acrylic copolymer (A) is preferably a method in which the acrylic block copolymer (A ′) containing the precursor of the acid anhydride group prepared above is heated at a high temperature of 180 to 300 ° C. Used. At this time, the acrylic block copolymer (A ′) containing the precursor of the acid anhydride group may be heated under pressure in the state of the polymer solution, and the solvent is evaporated while removing the solvent from the polymer solution. Alternatively, the acrylic block copolymer (A ′) containing the precursor of the acid anhydride group may be directly heated and melted, but the reactivity with the acid anhydride group and the simplicity of the production are not considered. It is preferable that the acrylic block copolymer (A ′) containing the precursor of the acid anhydride group is directly heated and melted. Further, it is more preferable to melt-knead the acrylic block copolymer (A ') containing a precursor of an acid anhydride group.

  The method for heating the acrylic block copolymer (A ') containing a precursor of an acid anhydride group in the state of a polymer solution can be performed in a pressure-resistant reaction vessel. In addition, as a method of heating the acrylic block copolymer (A ′) containing the precursor of the acid anhydride group while evaporating and removing the solvent from the polymer solution, a horizontal evaporation method equipped with an extrusion screw may be used. Can be.

  As a method of directly heating and melting the acrylic block copolymer (A ') containing the precursor of the acid anhydride group, a press machine or an injection molding machine can be used.

  As a method of melt-kneading the acrylic block copolymer (A ′) containing a precursor of an acid anhydride group, it is possible to carry out the heating and kneading in various apparatuses capable of simultaneously performing kneading. Examples include a banbury, a kneader, and a single-screw or multi-screw extruder used for processing rubber. Although not particularly limited, an extruder is suitably used in terms of reactivity with an acid anhydride group and simplicity of production. When melt-kneading the precursor-containing acrylic block copolymer (A ') of the acid anhydride group, the melt-kneading time (residence time in the extruder when using an extruder) is a temperature at which the melt-kneading is performed, It may be appropriately determined according to the screw configuration, L / D (the ratio of the effective screw length L to the screw diameter D), the number of rotations of the screw, and the like.

<Compound (B) containing two or more amino groups in one molecule>
The compound (B) containing two or more amino groups in one molecule used as a crosslinking agent in the present invention is not particularly limited as long as it is a compound having two or more primary or secondary amino groups in one molecule. However, from the viewpoint of reactivity with an acid anhydride group, a compound having a primary amino group is preferable, and a diamine having a primary amino group is preferable. Specific examples of the compound (B) containing two or more amino groups in one molecule include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. , Trimethylhexamethylenediamine, dodecamethylenediamine, polyoxypropylenepolyamine, 1,2-diaminopropane, bis (hexamethylene) triamine, tris (2-aminoethyl) amine, N, N'-dimethylethylenediamine, N, N ' -Diethyl-1,3-propanediamine, N, N'-dibutyl-1,6-hexanediamine, N, N'-diethyl-2-butene-1,4-diamine, N, N'-diethyl-1, 4-diaminocyclohexane, molecular weight Aliphatic polyamines such as 200 to 1000 polyether polyamines (such as polyoxypropylene diamine having an amino group at both terminals), cyclohexylene diamine, piperazine, isophorone diamine, 1,3-bisaminomethylcyclohexane, 1,4-bis Aminopropylpiperazine, 1,3-bisaminocyclohexane, di (aminodicyclohexyl) methane, 3,3′-dimethyldi (aminocyclohexyl) methane, 1-cyclohexylamino-3-aminopropane, 1,4-diaminocyclohexane, 4-diaminocyclopentane, di (aminocyclohexyl) methane, di (aminocyclohexyl) sulfone, 1,3-di (aminocyclohexyl) propane, 4-isopropyl-1,2-diaminocyclohexane, 2,4-di Fats such as minocyclohexane, N, N'-diethyl-1,4-diaminocyclohexane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3-aminomethyl-3,3,5-trimethylcyclohexylamine Cyclic polyamines, melamine, benzidine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, 2 And aromatic polyamine compounds such as 1,4-diaminodiphenylamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, and 2,4-diaminotoluene.

  At least one of these can be used. Among them, those having a boiling point of 100 ° C. or more are preferable, and those having a boiling point of 150 ° C. or more are more preferable in terms of availability, cost, and handling during the reaction. Further, it is preferable to use one having excellent compatibility with the (meth) acrylic block copolymer (A).

  The number of amino groups contained in the compound (B) containing two or more amino groups in one molecule may be appropriately determined according to the balance between the hardness and mechanical strength of the obtained elastomer and the properties of compression set. Regarding the compounding amount of the compound (B), the ratio of the number of moles of the amino group in the compound (B) to the number of moles of the acid anhydride group (a1) in the (meth) acrylic copolymer (A) is as follows: It is preferably in the range of 0.01 to 10, more preferably in the range of 0.05 to 10. When the compounding amount of the compound (B) containing two or more amino groups in one molecule exceeds 10, the mechanical strength of the obtained thermoplastic elastomer tends to decrease. The crosslinking reactivity of the resulting thermoplastic elastomer is reduced.

<Thermoplastic resin (C)>
The thermoplastic resin (C) that can be used in the present invention is not particularly limited, but examples thereof include polyvinyl chloride resin, polyethylene resin, polypropylene resin, cyclic olefin copolymer resin, polymethyl methacrylate resin, and polystyrene resin. , Polyphenylene ether resin, polycarbonate resin, polyester resin, polyamide resin, polyacetal resin, polyphenylene sulfide resin, polysulfone resin, polyimide resin, polyetherimide resin, polyetherketone resin, polyetheretherketone resin, polyamideimide resin , And 70 to 100% by weight of at least one vinyl monomer selected from the group consisting of aromatic alkenyl compounds, vinyl cyanide compounds and (meth) acrylates; Copolymerizable with a monomer, e.g., ethylene, propylene, other vinyl monomers 30-0 homopolymer obtained by polymerizing a weight percent or a copolymer of vinyl acetate and the like. At least one of these can be used.

  More specifically, examples of the polyvinyl chloride resin include, for example, polyvinyl chloride homopolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer having various degrees of polymerization, Polyvinyl chloride copolymers such as vinyl chloride-ethylene copolymer and vinyl chloride-propylene copolymer; alloys of polyvinyl chloride and ethylene-vinyl acetate copolymer, alloys of polyvinyl chloride and chlorinated polyethylene, Polyvinyl chloride alloys such as alloys of polyvinyl chloride and acrylic copolymers, and alloys of polyvinyl chloride and polyurethane; functionalized polyvinyl chlorides such as polyvinyl chloride / filler composites and post-chlorinated polyvinyl chloride , Polyvinylidene chloride homopolymer, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylonitrile copolymer Body, vinylidene chloride - such as polyvinylidene chloride copolymers such as acrylic acid ester copolymer.

  Examples of the polyethylene resin include polyethylene resins such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, and ultrahigh-molecular-weight polyethylene; ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, Ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-acrylic acid copolymer, ethylene and acrylic Copolymer with acid or methacrylic acid metal salt, maleic anhydride-modified polyethylene, maleic anhydride-modified ethylene-ethyl acrylate copolymer, ethylene-dimethylaminomethyl methacrylate copolymer, ethylene - vinyl alcohol copolymer, ethylene - can be exemplified a copolymer of ethylene and a polar monomer such as ethylene oxide adducts of vinyl alcohol copolymer.

  Examples of the polypropylene-based resin include homoisotactic polypropylene, an isotactic polypropylene random copolymer containing ethylene or 1-butene, an isotactic polypropylene block copolymer containing ethylene propylene, and a Ziegler-Natta catalyzed isotactic polypropylene. Examples include polypropylene such as tactic polypropylene, metallocene-catalyzed isotactic polypropylene, metallocene-catalyzed syndiotactic polypropylene, and atactic polypropylene; and functionalized polypropylene such as polypropylene / filler composite, chlorinated polypropylene, and maleic acid-modified polypropylene.

  The cyclic olefin copolymer resin is not particularly limited as long as it is a resin containing a cyclic olefin, for example, cyclopentadiene. For example, ARTON (manufactured by JSR Corporation) and ZEONEX (manufactured by Zeon Corporation) And a copolymer of a cyclic olefin and ethylene or propylene.

  Further, the polymethyl methacrylate-based resin is not particularly limited as long as it is a resin containing methyl methacrylate as a main component, and may be a polymethyl methacrylate resin in which α-methylstyrene, maleic anhydride, or the like is copolymerized. it can.

  Examples of the polystyrene resin include a polystyrene homopolymer, a syndiotactic polystyrene, and the like.

  Further, 70 to 100% by weight of at least one vinyl monomer selected from the group consisting of an aromatic alkenyl compound, a vinyl cyanide compound and a (meth) acrylate, and Examples of the polymerizable homopolymer or copolymer obtained by polymerizing 0 to 30% by weight of another vinyl monomer such as ethylene, propylene or vinyl acetate include, for example, acrylonitrile-styrene copolymer Acrylonitrile-styrene copolymer resins such as resin, acrylonitrile-butyl acrylate-styrene copolymer, acrylonitrile-ethylene-propylene-styrene copolymer, acrylonitrile-chlorinated polyethylene-styrene copolymer; methyl methacrylate-styrene And copolymer resins.

  Examples of the polyphenylene ether-based resin include polyphenylene ether-based alloys such as polyphenylene ether homopolymer; alloys of polyphenylene ether and polystyrene, alloys of polyphenylene ether and polyamide, and alloys of polyphenylene ether and polybutylene terephthalate.

  Examples of the polycarbonate resin include polycarbonate alloys such as bisphenol A type aromatic polycarbonate; polycarbonate alloys such as an alloy of polycarbonate and polybutylene terephthalate, an alloy of polycarbonate and polyarylate, and an alloy of polycarbonate and polymethyl methacrylate. Can be

  Examples of the polyester resin include aliphatic polyesters such as polyglycolic acid, polylactic acid, polycaprolactone, and polyethylene succinate; polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polycyclohexane dimethylene terephthalate. Semi-aromatic polyesters such as ethylene terephthalate / cyclohexane dimethylene terephthalate copolymer and thermotropic liquid crystal polymer type 2; all of amorphous polyarylate, thermotropic liquid crystal polymer type 1 and thermotropic liquid crystal polymer type 2 Aromatic polyesters and ester-based elastomers are exemplified.

  Examples of the polyamide resin include ring-opening polymerization type aliphatic polyamides such as PA6 (polycaproamide) and PA12 (polydodecaneamide); PA66 (polyhexamethylene adipamide), PA46 (polytetramethylene adipamide). Amide), polycondensation polyamides such as PA610, PA612 and PA11; semi-aromatic polyamides such as MXD6, PA6T, PA9T, PA6T / 66, PA6T / 6 and amorphous PA; poly (p-phenylene terephthalamide), poly (m -Phenylene terephthalamide), wholly aromatic polyamides such as poly (m-phenylene isophthalamide), and amide elastomers.

  Examples of the polyacetal resin include a polyacetal homopolymer and a copolymer of formaldehyde and trioxane. In the present invention, the thermoplastic resin (C) is not limited to these, and various thermoplastic resins can be widely used, such as styrene-based elastomer, olefin-based elastomer, PVC-based elastomer, and urethane-based elastomer. Can be used.

  Among these various thermoplastic resins, those having a softening temperature of 100 ° C. or higher and a melting temperature of 300 ° C. or lower are preferable, and among them, polymethyl methacrylate resin, polyolefin resin, polyester resin, polyamide resin, polycarbonate resin Based resins are preferred, and polyester resins and polyamide resins are more preferred in terms of compatibility with the (meth) acrylic block copolymer (A) and oil resistance and heat resistance of the obtained thermoplastic elastomer, Particularly, from the viewpoint of compatibility with the (meth) acrylic coblock polymer (A), a polyamide resin having reactivity with the acid anhydride group (a1) is preferable. For example, PA6 (polycaproamide), PA12 ( Polydodecaneamide) and PA612.

  The blending amount of the thermoplastic resin (C) is preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the (meth) acrylic block copolymer (A). If the blending amount of the thermoplastic resin (C) is more than 150 parts by weight, the rubber elasticity of the obtained thermoplastic elastomer may decrease. When the amount of the thermoplastic resin (C) is less than 5 parts by weight, the moldability and mechanical strength of the obtained thermoplastic elastomer may decrease.

<Flexibility imparting agent (D)>
To the thermoplastic elastomer composition of the present invention, various softening agents may be added in order to lower the hardness and increase the elongation of the thermoplastic elastomer composition. Further, when used in combination with a filler described later, the elongation of the cured product can be increased, and a large amount of the filler can be mixed.

  Examples of the softening agent include plasticizers usually blended with thermoplastic resins and rubbers; softeners such as process oils; oligomers; oils such as animal oils and vegetable oils; petroleum fractions such as kerosene, light oil, heavy oil, and naphtha. But are not limited thereto. Examples of the softener include process oils, and more specifically, petroleum process oils such as paraffin oil, naphthene process oil, and aromatic process oil. Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, di- (2-ethylhexyl) phthalate, diheptyl phthalate, diisodecyl phthalate, di-n-octyl phthalate, phthalate Acid derivatives such as diisononyl acid, ditridecyl phthalate, octyldecyl phthalate, butylbenzyl phthalate, dicyclohexyl phthalate, and β-hydroxyethyl-2-ethylhexyl phthalate; isophthalic acid derivatives such as dimethyl isophthalate; Tetrahydrophthalic acid derivatives such as (2-ethylhexyl) tetrahydrophthalic acid; dimethyl adipate, dibutyl adipate, di-n-hexyl adipate, di- (2-ethylhexyl) adipate, isononyl adipate, diisodecyl adipate, A Adipic acid derivatives such as dibutyl diglycol pinate; azelaic acid derivatives such as di-2-ethylhexyl azelate; sebacic acid derivatives such as dibutyl sebacate; dodecane-2-acid derivatives; dibutyl maleate and di-2-maleate Maleic acid derivatives such as ethylhexyl; fumaric acid derivatives such as dibutyl fumarate; 2-ethylhexyl o- or p-hydroxybenzoate, hexyldecyl o- or p-hydroxybenzoate, ethyldecyl o- or p-hydroxybenzoate, o Octyl octyl or p-hydroxybenzoate, decyl dodecyl o- or p-hydroxybenzoate, methyl o- or p-hydroxybenzoate, butyl o- or p-hydroxybenzoate, hexyl o- or p-hydroxybenzoate , O- or Hydroxybenzoic esters such as n-octyl p-hydroxybenzoate, decyl o- or p-hydroxybenzoate, dodecyl o- or p-hydroxybenzoate; trimellitic acid derivatives such as tris-2-ethylhexyl trimellitate; Acid derivatives; citric acid derivatives such as acetyltributyl citrate; itaconic acid derivatives; oleic acid derivatives; ricinoleic acid derivatives; stearic acid derivatives; other fatty acid derivatives; sulfonic acid derivatives; phosphoric acid derivatives; glutaric acid derivatives; adipic acid, azelaic acid Polyester plasticizers that are polymers of dibasic acids such as phthalic acid with glycols and monohydric alcohols, glycol derivatives, glycerin derivatives, paraffin derivatives such as chlorinated paraffins, and epoxy derivatives. Agents, polyether-based plasticizers, carbonate derivatives such as ethylene carbonate and propylene carbonate, benzenesulfonic acid alkylamides such as benzenesulfonic acid propylamide, benzenesulfonic acid butylamide and benzenesulfonic acid 2-ethylhexylamide; N-ethyl Alkyl amides of toluenesulfonic acid such as -o- or N-ethyl-p-toluenesulfonic acid butylamide, N-ethyl-o- or N-ethyl-p-toluenesulfonic acid 2-ethylhexylamide, and acrylic plasticizers. And vinyl polymers obtained by polymerizing the vinyl monomer to be used in various ways. In the present invention, the plasticizer is not limited to these, and various plasticizers can be used, and those widely commercially available as a plasticizer for rubber or a thermoplastic resin can also be used. Commercially available plasticizers include Thiokol TP (manufactured by Morton), Adekasizer O-130P, C-79, UL-100, P-200, RS-735 (manufactured by Asahi Denka Co., Ltd.), Sansocizer N -400 (manufactured by Nippon Rika Co., Ltd.), BM-4 (manufactured by Daihachi Chemical Industry Co., Ltd.), EHPB (manufactured by Ueno Pharmaceutical Co., Ltd.), Exepearl (manufactured by Kao Corporation), UP-1000 (manufactured by Toa) Synthetic Chemical Co., Ltd.). Vegetable oils include, for example, castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, pine oil, tall oil and the like.

  In the above, it is preferable to use one having excellent affinity with the (meth) acrylic block copolymer (A) or the thermoplastic resin (C). Although not particularly limited, adipic acid derivatives, phthalic acid derivatives, glutaric acid derivatives, trimellitic acid derivatives, pyromellitic acid derivatives, polyester plasticizers, polyester-based plasticizers, glycerin derivatives, and epoxy derivatives, which are plasticizers having low volatility and low heat loss. Vinyl polymers, hydroxybenzoic esters, benzene sulfone obtained by polymerizing vinyl monomers such as polyester-based plasticizers, polyether-based plasticizers, and acrylic plasticizers by various methods. Polymer plasticizers such as acid alkylamides and toluenesulfonic acid alkylamides are preferably used. For example, when a polyamide resin is used as the thermoplastic resin (C), phthalic acid derivatives, hydroxybenzoic esters, alkyl benzenesulfonates, etc. in terms of flexibility, hardness adjustment, oil resistance and heat resistance of the obtained thermoplastic elastomer. Amides and toluenesulfonic acid alkylamides are preferably used.

  The above softening agents may be used alone or in combination of two or more. Further, the blending amount of the above-mentioned flexibility imparting agent (D) is preferably 1 to 300 parts by weight, more preferably 1 to 200 parts by weight, based on 100 parts by weight of the (meth) acrylic block copolymer (A). , 5 to 100 parts by weight are more preferred. If the amount exceeds 300 parts by weight, the heat resistance and mechanical strength of the obtained thermoplastic elastomer may be reduced.

  The thermoplastic elastomer composition of the present invention comprises the (meth) acrylic block copolymer (A), a compound (B) containing two or more amino groups in one molecule, a thermoplastic resin (C) and a flexible resin. In addition to the property imparting agent (D), a stabilizer, a lubricant, a flame retardant, a pigment, a filler, a reinforcing agent, a tackifier, and the like can be appropriately compounded as necessary. Specifically, stabilizers such as hindered phenol, hindered amine and dibutyltin maleate; lubricants such as polyethylene wax, polypropylene wax and montanic acid wax; flame retardants such as decabromobiphenyl and decabromobiphenyl ether; titanium oxide , Zinc sulfide, zinc oxide, etc .; fillers and reinforcing agents such as carbon black, silica, glass fiber, asbestos, wollastonite, mica, talc, calcium carbonate; coumarone-indene resin, phenolic resin, terpene resin, high Tackifiers such as styrene resins, petroleum hydrocarbons (eg, dicyclopentadiene resin, aliphatic cyclic hydrocarbon resin, unsaturated hydrocarbon resin, etc.), polybutene, rosin derivatives, and the like.

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

<Method for producing thermoplastic elastomer composition>
The thermoplastic elastomer composition of the present invention comprises a composition comprising the (meth) acrylic block copolymer (A) and the thermoplastic resin (C) prepared as described above, and containing two or more amino groups in one molecule. It is produced by substantially reacting with the compound (B). Although not particularly limited, it is more preferable to melt and knead the composition containing the (meth) acrylic block copolymer (A) and the thermoplastic resin (C) at a high temperature, and knead the composition to form two or more amino groups in one molecule. And further, if necessary, other additives such as a softener (D), a stabilizer, a lubricant, a flame retardant, a pigment, a filler, a reinforcing material, a lubricant, a tackifier, etc. It is performed by adding components (dynamic crosslinking).

  As a kneading machine used for the production of the composition, various devices capable of simultaneously performing heating and kneading can be used.For example, a banbury, a kneader, a single-shaft or a multi-shaft used for ordinary rubber processing can be used. Extruders and the like can be mentioned. Further, if necessary, the composition can be molded using a press or an injection molding machine. The kneading temperature for producing the composition is preferably from 100 to 300C, more preferably from 150 to 250C.

  The thermoplastic elastomer composition obtained by dynamically dynamically cross-linking the composition obtained by combining the (meth) acrylic block copolymer (A) and the thermoplastic resin (C) obtained in the present invention is an acrylic block copolymer. Since oil resistance, heat resistance, mechanical properties, and the like are improved while maintaining the inherent properties of, they can be more suitably used as automobiles and electric / electronic parts. Specifically, the types are various oil seals such as oil seals and reciprocating oil seals, various packings such as gland packing, lip packing, squeeze packing, constant velocity joint boots, strut boots, rack and pinion boots, and brakes. Various boots such as boots for boosters and boots for steering ball joints, various hoses such as fuel hoses, gasoline hoses, air conditioning hoses, brake hoses, air hoses, air duct hoses, air cleaner hoses, dust covers for suspensions, suspension tie rods Dust covers, dust covers for stabilizers and die rods, etc., resin intake manifold gaskets, gaskets for throttle bodies, powers Gaskets for alling vane pumps, gaskets for head covers, gaskets for water heater self-contained pumps, filter gaskets, gaskets for pipe fittings (ABS & HBB), HDD top cover gaskets, HDD connector gaskets, cylinder head gaskets combined with metal, car coolers Various gaskets such as compressor gaskets, gaskets around engines, AT separate plates, general-purpose gaskets (industrial sewing machines, nailing machines, etc.), needle valves, plunger valves, water / gas valves, brake valves, drinking valves, aluminum electrolytic Various valves such as safety valves for condensers, various stoppers mainly for buffering performance such as diaphragms for vacuum boosters and water / gas diaphragms, seal washers, bore plugs and high precision stoppers Plug tube seal, the injection pipe seal, oil receiver, a brake drum seal, shielding seals, plug seals, connectors seal, and the like precision seal rubber such as keyless entry cover. In addition, there are various weather strips such as door weather strips for automobile articles, and seal products such as trunk seals and glass run channels.

  In the molding of the product, the polymer or the polymer composition is molded by any molding method such as extrusion molding, compression molding, blow molding, calender molding, vacuum molding, foam molding, injection molding, injection blow and the like. Can be processed.

  The thermoplastic elastomer composition obtained by thermally and dynamically cross-linking the composition obtained by combining the (meth) acrylic block copolymer (A) and the thermoplastic resin (C) is used in addition to automobiles and electric / electronic parts. In the fields of packaging materials, construction materials, civil engineering materials, miscellaneous goods, etc., they can be widely and suitably used as hoses, sheets, film materials, vibration damping agents, base polymers for adhesives, resin modifiers, and the like.

  Next, the present invention will be described in more detail based on examples, but the present invention is not limited to only these examples.

  BA, EA, MEA, MMA, TBMA, and TBA in Examples are butyl acrylate, ethyl acrylate, methoxyethyl acrylate, methyl methacrylate, t-butyl methacrylate, and t-butyl acrylate, respectively. Express.

<Test method>
(Molecular weight)
The molecular weight shown in this example was determined by GPC analysis using a polystyrene gel column with chloroform as a mobile phase using a GPC analyzer shown below, and the molecular weight in terms of polystyrene was determined. The GPC measurement was performed using a GPC analyzer (system: GPC system manufactured by Waters, column: Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK). Using chloroform as the mobile phase, the molecular weight in terms of polystyrene was determined.

(Acid anhydride group conversion analysis)
Confirmation of the acid anhydride group conversion reaction of the acrylic block copolymer was carried out by using an infrared spectrum (FTIR-8100, manufactured by Shimadzu Corporation) and nuclear magnetic resonance (AM400, manufactured by BRUKER). As a solvent for nuclear magnetic resonance analysis, analysis was performed using deuterated chloroform as a measurement solvent.

(hardness)
The hardness at 23 ° C. (JIS A or JIS D) was measured according to JIS K6301.

(Mechanical strength)
The measurement was performed using an autograph AG-10TB manufactured by Shimadzu Corporation according to the method described in JIS K7113. The measurement was performed at n = 3, and the average value of the strength (MPa) and elongation (%) when the test piece was broken was adopted. The test piece used had a shape of No. 2 (1/3) and a thickness of about 2 mm. The test was performed at 23 ° C. at a test speed of 500 mm / min. As a rule, the test piece used had been conditioned at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 5% for 48 hours or more before the test.

(Oil resistance)
According to ASTM D638, an ASTM oil No. 3 for 72 hours, and the weight change (% by weight) was determined. Regarding the appearance evaluation after the test, the shape of the molded body before and after the test was observed, and it was judged as ○: shape maintenance, ×: deformation.

(Heat-resistant)
This was performed by comparing the flow start temperatures. The flow starting temperature was 1 mm in inner diameter under the load of 60 kgf / cm ² under the load of 60 kgf / cm ² using a resin heated at a heating rate of 5 ° C./min using a Koka type flow tester CFT-500C manufactured by Shimadzu Corporation. When the resin was extruded from a 10 mm long nozzle, the resin extrusion piston of the flow tester was set to a temperature at which it clearly starts to drop (in the present measurement device, this is indicated as Tfb).

(Insoluble content (% by weight))
The insoluble content (% by weight) was determined by wrapping 1 g (Wu) of a sample in a 100-mesh wire gauze and immersing it in toluene at 60 ° C or acetone in 50 ° C for 24 hours. The solid content was vacuum-dried at 60 ° C., and the weight g (Wc) of the residual solid content after the drying was measured and determined from the weight of the residual solid content (Wc) relative to 1 g (Wu) of the sample. The progress of the reaction can be confirmed from the insoluble content (% by weight).

Production Example 1
(MMA-co-TBMA) -b-BA-b- (MMA-co-TBMA) (MMA / TBMA = 80/20 mol%, BA / (MMA-co-TBMA) = 70/30 wt%) acrylic Synthesis of block copolymer (hereinafter referred to as 20TBA7) After the atmosphere in the polymerization vessel of a 5 L separable flask was replaced with nitrogen, 11.3 g (78.5 mmol) of copper bromide was weighed out, and acetonitrile (nitrogen bubbling) was measured. ) 180 mL was added. After heating and stirring at 70 ° C. for 30 minutes, 5.65 g (15.7 mmol) of diethyl 2,5-dibromoadipate initiator and 900 mL (6.28 mol) of BA were added. The mixture was heated and stirred at 85 ° C., and 1.64 mL (7.85 mmol) of a ligand diethylenetriamine was added to initiate polymerization.

  At regular intervals from the start of the polymerization, about 0.2 mL of the polymerization solution was withdrawn from the polymerization solution for sampling, and the conversion of BA was determined by gas chromatogram analysis of the sampling solution. The polymerization rate was controlled by adding triamine as needed. When the conversion rate of BA is 95%, 151.9 mL (0.94 mol) of TBMA, 400.9 mL (3.77 mol) of MMA, 7.77 g (78.5 mmol) of copper chloride, 1.64 mL of diethylenetriamine (7.85 mol) Mmol) and 1093 mL of toluene (with nitrogen bubbling). Similarly, the conversion of TBMA and MMA was determined. When the conversion of TBMA was 70% and the conversion of MMA was 64%, 1500 mL of toluene was added, and the reactor was cooled with a water bath to terminate the reaction.

  The reaction solution was diluted with 2.0 L of toluene, 17.9 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 3 hours. 12.0 g of adsorbent KYOWARD 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the polymer solution, and the mixture was further stirred at room temperature for 3 hours. The adsorbent was filtered with a Kiriyama funnel to obtain a colorless and transparent polymer solution. The solution was dried to remove the solvent and the residual monomer, to obtain the target acrylic block copolymer 20TBA7.

  GPC analysis of the obtained acrylic block copolymer 20TBA7 showed that the number average molecular weight Mn was 122858 and the molecular weight distribution Mw / Mn was 1.46.

Production Example 2
(MMA-co-TBMA) -b- (BA-co-EA-co-MEA) -b- (MMA-co-TBMA) (MMA / TBMA = 80/20 mol%, (BA-co-EA-co- Synthesis of (MEA) / (MMA-co-TBMA) = 70/30 wt%) type acrylic block copolymer (hereinafter referred to as 20T3A7) After purging the polymerization vessel of a 5-L separable flask with nitrogen, bromination was carried out. 11.7 g (81.9 mmol) of copper was weighed out, and 180 mL of acetonitrile (nitrogen bubbled) was added. After heating and stirring at 70 ° C. for 30 minutes, 5.89 g (16.4 mmol) of diethyl 2,5-dibromoadipate initiator, 362 mL (2.52 mol) of BA, 344 mL (3.17 mol) of EA, and 195 mL of MEA (1. 51 mol) was added. The mixture was heated and stirred at 85 ° C., and 1.71 mL (8.2 mmol) of ligand diethylenetriamine was added to initiate polymerization. When the conversion of BA was 95%, the conversion of EA was 95%, and the conversion of MEA was 97%, 158 mL (0.98 mol) of TBMA and 418 mL (3.92 mol) of MMA were added. The reaction was terminated when the conversion of TBMA was 64% and the conversion of MMA was 59%. Otherwise, the procedure of Production Example 1 was followed to obtain the desired acrylic block copolymer 20T3A7.

  GPC analysis of the obtained acrylic block copolymer 20T3A7 showed that the number average molecular weight Mn was 111,000 and the molecular weight distribution Mw / Mn was 1.47.

Production Example 3
(MMA-co-TBMA) -b-BA-b- (MMA-co-TBMA) (MMA / TBMA = 95/5 mol%, BA / (MMA-co-TBMA) = 70/30 wt%) acrylic type Synthesis of Block Copolymer (hereinafter referred to as 5TBA7) After the atmosphere in the polymerization vessel of a 5 L separable flask was replaced with nitrogen, 6.93 g (48.3 mmol) of copper bromide was weighed out, and acetonitrile (nitrogen bubbling) was obtained. ) 180 mL was added. After heating and stirring at 70 ° C. for 30 minutes, 5.80 g (16.1 mmol) of diethyl 2,5-dibromoadipate initiator and 900 mL (6.28 mol) of BA were added. The mixture was heated and stirred at 85 ° C., and 1.68 mL (8.0 mmol) of a ligand diethylenetriamine was added to initiate polymerization. When the conversion of BA was 95%, 40.9 mL (0.252 mol) of TBMA and 512.7 mL (4.79 mol) of MMA were added to carry out polymerization, and the conversion of TBMA was 60% and the conversion of MMA was 57. The reaction was terminated at%. Otherwise, the procedure of Production Example 1 was repeated to obtain the desired acrylic block copolymer 5TBA7.

  GPC analysis of the resulting acrylic block copolymer 5TBA7 showed a number-average molecular weight Mn of 107,300 and a molecular weight distribution Mw / Mn of 1.58.

Production Example 4
(MMA-co-TBMA) -b- (BA-co-EA-co-MEA) -b- (MMA-co-TBMA) (MMA / TBMA = 95/5 mol%, (BA-co-EA-co- Synthesis of (MEA) / (MMA-co-TBMA) = 70/30% by weight) type acrylic block copolymer (hereinafter referred to as 5T3A7) After purging the polymerization vessel of a 5-L separable flask with nitrogen, bromination was carried out. 12.0 g (83.8 mmol) of copper was weighed out, and 180 mL of acetonitrile (with nitrogen bubbling) was added. After heating and stirring at 70 ° C. for 30 minutes, 6.04 g (16.8 mmol) of diethyl 2,5-dibromoadipate initiator, 362 mL (2.52 mol) of BA, 344 mL (3.17 mol) of EA, and 195 mL of MEA (1. 51 mol) was added. The mixture was heated and stirred at 85 ° C., and 1.75 mL (8.4 mmol) of ligand diethylenetriamine was added to initiate polymerization. When the conversion of BA was 95%, the conversion of EA was 95%, and the conversion of MEA was 97%, 42.5 mL (0.262 mol) of TBMA and 534 mL (5.02 mol) of MMA were added, and the polymerization was added. . The reaction was terminated when the conversion of TBMA was 63% and the conversion of MMA was 58%. Except for this, the production was carried out in the same manner as in Production Example 1 to obtain the desired acrylic block copolymer 5T3A7.

  GPC analysis of the obtained acrylic block copolymer 5T3A7 showed that the number average molecular weight Mn was 124,000 and the molecular weight distribution Mw / Mn was 1.45.

Production Example 5
MMA-b- (BA-co-TBA) -b-MMA (BA / TBA = 97.5 / 2.5 mol%, (BA-co-TBA) / MMA = 70/30% by weight) type acrylic block Synthesis of Polymer (hereinafter referred to as 2.5STBA7) After the atmosphere in the polymerization vessel of a 5 L separable flask was replaced with nitrogen, 11.3 g (78.4 mmol) of copper bromide was weighed out, and acetonitrile (nitrogen bubbling) was obtained. ) 180 mL was added. After heating and stirring at 70 ° C. for 30 minutes, 5.65 g (15.7 mmol) of diethyl diethyl 2,5-dibromoadipate, 877 mL (6.12 mol) of BA, and 22.9 mL (0.16 mol) of TBA were added. . The mixture was heated and stirred at 85 ° C., and 1.64 mL (7.8 mmol) of a ligand diethylenetriamine was added to initiate polymerization. When the conversion of BA was 95% and the conversion of TBA was 100%, 369 mL (3.45 mol) of MMA was added. The reaction was terminated when the conversion of MMA was 64%. Except for this, the product was produced in the same manner as in Production Example 1 to obtain the desired acrylic block copolymer 2.5STBA7.

  GPC analysis of the resulting acrylic block copolymer 2.5STBA7 showed a number-average molecular weight Mn of 97900 and a molecular weight distribution Mw / Mn of 1.44.

Production Example 6
(TBMA) -b- (BA-co-EA-co-MEA) -b- (TBMA) ((BA-co-EA-co-MEA) / (TBMA) = 97.1 / 2.9% by weight) Synthesis of Type Acrylic Block Copolymer (hereinafter referred to as T3A) After purging the polymerization vessel of a 5-L separable flask with nitrogen, weigh 6.35 g (44.3 mmol) of copper bromide and acetonitrile (nitrogen) 140 mL). After heating and stirring at 70 ° C. for 30 minutes, 5.31 g (14.8 mmol) of diethyl 2,5-dibromoadipate initiator, 281 mL (1.96 mol) of BA, 267 mL (2.47 mol) of EA, and 151 mL of MEA (1. 18 mol) was added. The mixture was heated and stirred at 85 ° C., and 1.54 mL (7.38 mmol) of ligand diethylenetriamine was added to initiate polymerization.

  When the conversion of BA was 87%, 29.8 mL (0.18 mol) of TBMA was added. When the conversion of BA was 95% and the conversion of TBMA was 70%, 1.0 L of toluene was added, and the reaction was terminated by cooling the reactor with a water bath. Except for this, the procedure was carried out in the same manner as in Production Example 1 to obtain the desired acrylic block copolymer T3A. GPC analysis of the obtained acrylic block copolymer T3A showed that the number average molecular weight Mn was 54,000 and the molecular weight distribution Mw / Mn was 1.24.

Production Example 7
Synthesis of TBA-b-BA-b-TBA (BA / TBA) = 94.7 / 5.3% by weight) type acrylic block copolymer (hereinafter referred to as TBA) In a polymerization vessel of a 2 L separable flask Was replaced with nitrogen, 3.34 g (23.3 mmol) of copper bromide was weighed out, and 50 mL of acetonitrile (nitrogen bubbled) was added. After heating and stirring at 70 ° C. for 30 minutes, 7.00 g (19.4 mmol) of diethyl 2,5-dibromoadipate initiator and 500 mL (3.49 mol) of BA were added. The mixture was heated and stirred at 75 ° C., and 0.16 mL (0.8 mmol) of ligand diethylenetriamine was added to initiate polymerization. When the conversion of BA was 87%, 42.3 mL (0.29 mol) of TBA was added. When the conversion of BA was 95% and the conversion of TBA was 62%, 1.0 L of toluene was added, and the reactor was cooled with a water bath to terminate the reaction.

  The reaction solution was diluted with 1.0 L of toluene, 2.2 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 3 hours. 4.8 g of adsorbent KYOWARD 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the polymer solution, and the mixture was further stirred at room temperature for 3 hours. The adsorbent was filtered with a Kiriyama funnel to obtain a colorless and transparent polymer solution. The solution was dried to remove the solvent and the residual monomer, to obtain a target acrylic block copolymer TBA.

  GPC analysis of the obtained acrylic block copolymer TBA showed that the number average molecular weight Mn was 26100 and the molecular weight distribution Mw / Mn was 1.12.

Production Example 8
MMA-b- (BA-co-TBA) -b-MMA (BA / TBA = 97.9 / 2.1 mol%, (BA-co-TBA) / MMA = 85/15% by weight) type acrylic block Synthesis of polymer (hereinafter referred to as 2STBA8.5) After the atmosphere in the polymerization vessel of a 5 L separable flask was replaced with nitrogen, 7.29 g (50.8 mmol) of copper bromide was weighed out, and acetonitrile (nitrogen bubbling was used). ) 140 mL was added. After heating and stirring at 70 ° C. for 30 minutes, 3.66 g (10.2 mmol) of diethyl 2,5-dibromoadipate, 685 mL (4.78 mol) of BA, and 15.0 mL (0.10 mol) of TBA were added. . The mixture was heated and stirred at 85 ° C., and 1.06 mL (5.1 mmol) of a ligand diethylenetriamine was added to initiate polymerization. When the conversion of BA was 96% and the conversion of TBA was 100%, 176 mL (1.65 mol) of MMA was added. The reaction was terminated when the conversion of MMA was 58%. Except for this, the production was carried out in the same manner as in Production Example 1 to obtain the intended acrylic block copolymer 2STBA8.5.

  GPC analysis of the obtained acrylic block copolymer 2STBA7 showed that the number average molecular weight Mn was 111,500 and the molecular weight distribution Mw / Mn was 1.29.

Production Example 9
MMA-b-TBA-b-BA-b-TBA-b-MMA (BA / TBA = 97.5 / 2.5 mol%, (TBA-b-BA-b-TBA) / MMA = 70/30% by weight) ) Synthesis of Type Acrylic Block Copolymer (hereinafter referred to as 2.5TBAT7) After purging the inside of the polymerization vessel of a 5 L separable flask with nitrogen, weigh out 7.50 g (52.3 mmol) of copper bromide, 120 mL of acetonitrile (with nitrogen bubbling) was added. After heating and stirring at 70 ° C. for 30 minutes, 3.77 g (10.5 mmol) of diethyl 2,5-dibromoadipate initiator and 585 mL (4.08 mol) of BA were added. The mixture was heated and stirred at 85 ° C., and 1.09 mL (5.2 mmol) of ligand diethylenetriamine was added to initiate polymerization. When the conversion of BA was 85%, 15.3 mL (0.10 mol) of TBA was added. When the conversion of BA was 98% and the conversion of TBA was 88%, 367 mL (3.43 mol) of MMA was added. The reaction was terminated when the conversion of MMA was 63%. Except for this, the procedure was carried out in the same manner as in Production Example 1 to obtain the desired acrylic block copolymer 2.5TBAT8.5. GPC analysis of the resulting acrylic block copolymer 2.5TBAT7 showed a number-average molecular weight Mn of 113500 and a molecular weight distribution Mw / Mn of 1.32.

Production Example 10
Synthesis of MMA-b-BA-b-MMA type block copolymer (BA / MMA = 70/30% by weight) (hereinafter abbreviated as MBAM) After purging the polymerization vessel of a 5-L separable flask with nitrogen, 11.3 g (78.5 mmol) of copper chloride was weighed out, and 180 mL of acetonitrile (dried with molecular sieves and bubbled with nitrogen) was added. After heating and stirring at 70 ° C. for 5 minutes, the mixture was cooled to room temperature again, and 5.7 g (15.7 mmol) of diethyl 2,5-dibromoadipate initiator and 804.6 g (900.0 mL) of n-butyl acrylate were added. added. The mixture was heated and stirred at 80 ° C., and 1.6 mL (7.9 mmol) of ligand diethylenetriamine was added to initiate polymerization. At regular intervals from the start of the polymerization, about 0.2 mL of the polymerization solution was sampled from the polymerization solution for sampling, and the conversion of butyl acrylate was determined by gas chromatogram analysis of the sampling solution. The polymerization rate was controlled by adding triamine as needed. When the conversion of n-butyl acrylate was 95%, 345.7 g (369.3 mL) of methyl methacrylate, 7.8 g (78.5 mmol) of copper chloride, 1.6 mL (7.9 mmol) of diethylenetriamine Then, 1107.9 mL of toluene (dried with molecular sieves and then subjected to nitrogen bubbling) was added. Similarly, the conversion of methyl methacrylate was determined. When the conversion of methyl methacrylate was 85% and the conversion of n-butyl acrylate was 98%, 1500 mL of toluene was added, and the reactor was cooled with a water bath to terminate the reaction. The polymerization solution was always green during the reaction. The reaction solution was diluted with 4000 mL of toluene, 22.1 g of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 3 hours. After the precipitated insoluble portion was removed by filtration using a Kiriyama funnel, 9.7 g of adsorbent Kyoward 500SH was added to the polymer solution, and the mixture was stirred at room temperature for 3 hours. The adsorbent was filtered with a Kiriyama funnel to obtain a colorless and transparent polymer solution. The solution was dried to remove the solvent and the residual monomer, to obtain the desired MBAM. GPC analysis of the obtained MBAM showed that the number average molecular weight Mn was 119,200 and the molecular weight distribution Mw / Mn was 1.51. Further, composition analysis by NMR revealed that BA / MMA = 72/28 (% by weight).

Example 1
100 rpm using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) in which 45 g of the acrylic block copolymer 20TBA7 manufactured in Production Example 1 and 0.23 g of Irganox 1010 (manufactured by Ciba Geigy) were set at 240 ° C. For 20 minutes to obtain the desired acid anhydride group-containing acrylic block copolymer (the obtained polymer is referred to as 20ANBA7). Conversion of the t-butyl ester moiety to an acid anhydride group could be confirmed by IR (infrared absorption spectrum) and ¹³ C-NMR (nuclear magnetic resonance spectrum). That is, it was confirmed by IR that an absorption spectrum derived from an acid anhydride group was observed around 1800 cm ^-1 after conversion. ^{In 13} C-NMR, it was confirmed from the disappearance of the signal of 82 ppm derived from the methine carbon of the t-butyl group and the signal of 28 ppm derived from the methyl carbon after the conversion. The obtained 20ANBA7 and polyamide; PA (UBE Nylon 3012U: manufactured by Ube Industries, Ltd.) and Irganox 1010 (manufactured by Ciba Geigy, Inc.) were set to 190 ° C. at the ratios shown in Table 1 at 190 ° C. (Made by Seiki Co., Ltd.). Further, hexamethylene diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at the ratio shown in Table 1, melt-kneaded, and the reaction was allowed to proceed (dynamic crosslinking). The obtained sample was subjected to hot press molding at a set temperature of 190 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of these molded bodies was measured. Similarly, hot press molding was performed at a set temperature of 230 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets.

Example 2
The acrylic block copolymer 20T3A7 produced in Production Example 2 was obtained in the same manner as in Example 1 to obtain the desired acid anhydride group-containing acrylic block copolymer (the obtained polymer is referred to as 20AN3A7). . The obtained 20AN3A7 and polyamide; PA (UBE nylon 3024U: manufactured by Ube Industries, Ltd.) and Irganox 1010 (manufactured by Ciba Geigy) were set at 190 ° C. in the ratio shown in Table 1 at Labo Plastomill (Toyo). (Made by Seiki Co., Ltd.). Further, hexamethylene diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at the ratio shown in Table 1, melt-kneaded, and the reaction was allowed to proceed (dynamic crosslinking). The obtained sample was subjected to hot press molding at a set temperature of 190 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of these molded bodies was measured. Similarly, hot press molding was performed at a set temperature of 190 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets.

Example 3
The acrylic block copolymer 5TBA7 produced in Production Example 3 was obtained in the same manner as in Example 1 to obtain a target acid anhydride group-containing acrylic block copolymer (the obtained polymer is referred to as 5ANBA7). . The obtained 5ANBA7 and polyamide; PA (UBE Nylon 3012U: manufactured by Ube Industries, Ltd.) and Irganox 1010 (manufactured by Ciba Geigy) were set at 210 ° C. in the ratios shown in Table 1 at 210 ° C. (Made by Seiki Co., Ltd.). Further, hexamethylene diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at the ratio shown in Table 1, melt-kneaded, and the reaction was allowed to proceed (dynamic crosslinking). The obtained sample was subjected to hot press molding at a set temperature of 210 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of these molded bodies was measured. Similarly, hot press molding was performed at a set temperature of 210 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets.

Example 4
The acrylic block copolymer 5T3A7 produced in Production Example 4 was obtained in the same manner as in Example 1 to obtain an intended acid anhydride group-containing acrylic block copolymer (the obtained polymer is referred to as 5AN3A7). . The obtained 5AN3A7 and polyamide; PA (UBE Nylon 3012U: manufactured by Ube Industries, Ltd.) and Irganox 1010 (manufactured by Ciba Geigy) were set at a ratio shown in Table 1 at 210 ° C., and set at 210 ° C. Labo Plastomill (Toyo) (Made by Seiki Co., Ltd.). Further, hexamethylene diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at the ratio shown in Table 1, melt-kneaded, and the reaction was allowed to proceed (dynamic crosslinking). The obtained sample was subjected to hot press molding at a set temperature of 210 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of these molded bodies was measured. Similarly, hot press molding was performed at a set temperature of 210 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets.

Example 5
In the same manner as in Example 1, the acrylic block copolymer 2.5STBA7 produced in Production Example 5 was used to prepare the target acid anhydride group-containing acrylic block copolymer (the obtained polymer is referred to as 2.5SANBA7. ) Got. Laboplastomill in which the obtained 2.5SANBA7 and polyamide; PA (UBE nylon 3012U: manufactured by Ube Industries, Ltd.) and Irganox 1010 (manufactured by Ciba Geigy) were set at 220 ° C. at the ratios shown in Table 1. (Made by Toyo Seiki Co., Ltd.). Further, hexamethylene diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at the ratio shown in Table 1, melt-kneaded, and the reaction was allowed to proceed (dynamic crosslinking). The obtained sample was subjected to hot press molding at a set temperature of 220 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of these molded bodies was measured. Similarly, hot press molding was performed at a set temperature of 220 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets.

Example 6
In the same manner as in Example 1, the acrylic block copolymer T3A produced in Production Example 6 was used to obtain the desired acid anhydride group-containing acrylic block copolymer (the obtained polymer is referred to as AN3A). . The obtained AN3A and polyamide; PA (UBE Nylon 3024U: manufactured by Ube Industries, Ltd.) and Irganox 1010 (manufactured by Ciba Geigy) were set to the temperature shown in Table 1 at 220 ° C., and set to 220 ° C. (Made by Seiki Co., Ltd.). Further, hexamethylene diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at the ratio shown in Table 1, melt-kneaded, and the reaction was allowed to proceed (dynamic crosslinking). The obtained sample was subjected to hot press molding at a set temperature of 220 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of each of these molded products was measured. Similarly, hot press molding was performed at a set temperature of 220 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets.

Example 7
The acrylic block copolymer 20TBA7 produced in Production Example 1 was obtained in the same manner as in Example 1 to obtain a target acid anhydride group-containing acrylic block copolymer (the obtained polymer is referred to as 20ANBA7). . The obtained 20ANBA7 and polyester; Laboplastomill (Toyo Seiki (Toyo Seiki Co., Ltd.)) in which PBT (Duranex FP300: manufactured by Wintech Polymer) and Irganox 1010 (manufactured by Ciba Geigy Co., Ltd.) were set to 240 ° C. at the ratios shown in Table 1. And melt kneading using the same. Further, 1,12-diaminododecane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added at the ratio shown in Table 1, melt-kneaded, and the reaction was allowed to proceed (dynamic crosslinking). The obtained sample was subjected to hot press molding at a set temperature of 240 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of each of these molded products was measured. Similarly, hot press molding was performed at a set temperature of 240 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets.

Example 8
The acrylic block copolymer 5T3A7 produced in Production Example 4 was obtained in the same manner as in Example 1 to obtain an intended acid anhydride group-containing acrylic block copolymer (the obtained polymer is referred to as 5AN3A7). . Laboplastomill (Toyo Seiki Co., Ltd.) in which the obtained 5AN3A7, ester-based elastomer (Perprene P46D: manufactured by Toyobo Co., Ltd.), and Irganox 1010 (manufactured by Ciba Geigy Co., Ltd.) were set to 240 ° C. at the ratios shown in Table 1. Was used for melt-kneading. Further, hexamethylene diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at the ratio shown in Table 1, melt-kneaded, and the reaction was allowed to proceed (dynamic crosslinking). The obtained sample was subjected to hot press molding at a set temperature of 240 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of each of these molded products was measured. Similarly, hot press molding was performed at a set temperature of 240 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets.

Example 9
In the same manner as in Example 1, the acrylic block copolymer 2.5STBA7 produced in Production Example 5 was used to prepare the target acid anhydride group-containing acrylic block copolymer (the obtained polymer is referred to as 2.5SANBA7. ) Got. Laboplastomill in which the obtained 2.5SANBA7 and polyamide; PA (UBE nylon 3012U: manufactured by Ube Industries, Ltd.) and Irganox 1010 (manufactured by Ciba Geigy) were set at 220 ° C. at the ratios shown in Table 1. (Made by Toyo Seiki Co., Ltd.). Further, hexamethylene diamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added and melt-kneaded at the ratios shown in Table 1, and the reaction was allowed to proceed (dynamic crosslinking). (Nippon Rika Co., Ltd.) and melt-kneaded. The obtained sample was subjected to hot press molding at a set temperature of 220 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of each of these molded products was measured. Similarly, hot press molding was performed at a set temperature of 220 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets.

Example 10
The target acid anhydride group-containing acrylic block copolymer (the resulting polymer is referred to as ANBA) was obtained from the acrylic block copolymer TBA produced in Production Example 7 in the same manner as in Example 1. . The obtained ANBA and polyamide; PA (UBE Nylon 3012U: manufactured by Ube Industries, Ltd.) and Irganox 1010 (manufactured by Ciba Geigy, Inc.) were set at 190 ° C. in the ratio shown in Table 1 at 190 ° C. (Made by Seiki Co., Ltd.). Further, hexamethylene diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at the ratio shown in Table 1, melt-kneaded, and the reaction was allowed to proceed (dynamic crosslinking). The obtained sample was subjected to hot press molding at a set temperature of 190 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of each of these molded products was measured. Similarly, hot press molding was performed at a set temperature of 190 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets.

Example 11
In the same manner as in Example 1, the acrylic block copolymer 2STBA8.5 produced in Production Example 8 was used to prepare the target acid anhydride group-containing acrylic block copolymer (the obtained polymer is referred to as 2SANBA8.5. ) Got. The obtained 2SANBA 8.5 and polyamide; PA (UBE nylon 3012U: manufactured by Ube Industries, Ltd.) and Irganox 1010 (manufactured by Ciba Geigy) were set at 190 ° C. in the ratio shown in Table 1 at 190 ° C. (Made by Toyo Seiki Co., Ltd.). Further, hexamethylene diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at the ratio shown in Table 1, melt-kneaded, and the reaction was allowed to proceed (dynamic crosslinking). The obtained sample was subjected to hot press molding at a set temperature of 190 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of each of these molded products was measured. Similarly, hot press molding was performed at a set temperature of 190 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets.

Example 12
In the same manner as in Example 1, the acrylic block copolymer 2.5TBAT7 produced in Production Example 9 was treated with the target acid anhydride group-containing acrylic block copolymer (the obtained polymer is described as 2.5ANBAAN7. ) Got. Laboplastomill obtained by setting the obtained 2.5ANBAAN7 and polyamide; PA (UBE nylon 3012U: manufactured by Ube Industries, Ltd.) and Irganox 1010 (manufactured by Ciba Geigy) at 190 ° C. in the ratio shown in Table 1. (Made by Toyo Seiki Co., Ltd.). Further, hexamethylene diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at the ratio shown in Table 1, melt-kneaded, and the reaction was allowed to proceed (dynamic crosslinking). The obtained sample was subjected to hot press molding at a set temperature of 190 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of each of these molded products was measured. Similarly, hot press molding was performed at a set temperature of 190 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets.

Example 13
In the same manner as in Example 1, the acrylic block copolymer 2.5TBAT7 produced in Production Example 5 was treated with the target acid anhydride group-containing acrylic block copolymer (the obtained polymer is referred to as 2.5SANBA7. ) Got. Laboplastomill in which the obtained 2.5 SANBA7 and polyamide; PA (UBE nylon 7024B: manufactured by Ube Industries, Ltd.) and Irganox 1010 (manufactured by Ciba Geigy) were set at 220 ° C. at the ratios shown in Table 1. (Made by Toyo Seiki Co., Ltd.). Further, hexamethylene diamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at the ratio shown in Table 1, melt-kneaded, and the reaction was allowed to proceed (dynamic crosslinking). The obtained sample was subjected to hot press molding at a set temperature of 220 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of each of these molded products was measured. Similarly, hot press molding was performed at a set temperature of 220 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets.

Comparative Example 1
Laboplastomill (manufactured by Toyo Seiki Co., Ltd.) in which MBAM and Irganox 1010 (manufactured by Ciba Geigy) manufactured in Production Example 10 were set to 190 ° C. at a screw rotation speed of 50 rpm at a rate shown in Table 1 To obtain a sample. The obtained sample was subjected to hot press molding at a set temperature of 190 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of each of these molded products was measured. Similarly, hot press molding was performed at a set temperature of 190 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets. MBAM alone has insufficient oil resistance and heat resistance.

Comparative Example 2
MBAM and polyamide manufactured in Production Example 10; PA (UBE nylon 1013B: manufactured by Ube Industries, Ltd.) and Irganox 1010 (manufactured by Ciba Geigy) at 230 ° C. at a screw rotation speed of 100 rpm at a ratio shown in Table 1. Was melt-kneaded using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.). The obtained sample was subjected to hot press molding at a set temperature of 230 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. The hardness of each of these molded products was measured. Similarly, hot press molding was performed at a set temperature of 230 ° C. to obtain a sheet-shaped molded body having a thickness of 2 mm. Oil resistance and insoluble content were measured on these sheets. It can be seen that the samples obtained by melt-kneading MBAM and PA only had insufficient oil resistance and heat resistance.

  As is clear from Table 1 (Examples 1 to 12 and Comparative Examples 1 and 2), it is understood that the thermoplastic elastomer composition of the present invention has improved oil resistance and heat resistance.

Claims (9)

A thermoplastic elastomer composition comprising (A) a (meth) acrylic block copolymer, (B) a compound containing two or more amino groups in one molecule, and (C) a thermoplastic resin, ) Acrylic block copolymer (A) is composed of (A1) (meth) acrylic polymer block and (A2) acrylic polymer block, and at least one of the polymer blocks has a general formula ( 1):

(Wherein, R ¹ is hydrogen or a methyl group, which 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). A thermoplastic elastomer composition having one, wherein the (meth) acrylic block copolymer (A) and the compound (B) are dynamically crosslinked in the thermoplastic resin (C). (Meth) acrylic block copolymer (A) has the general formula (x-y) _n, the formula y- (x-y) _n, the general formula _{(x-y) n -x (} n is 1 or more The thermoplastic elastomer composition according to claim 1, which is at least one member selected from the group represented by an integer. The (meth) acrylic block copolymer (A) is composed of 0.1 to 60% by weight of the (meth) acrylic polymer block (A1) and 99.9 to 40% by weight of the acrylic polymer block (A2). The thermoplastic elastomer composition according to claim 1 or 2, wherein 4. The thermoplastic elastomer composition according to claim 1, wherein the (meth) acrylic polymer block (A1) has an acid anhydride group (a1). 4. The thermoplastic elastomer composition according to claim 1, wherein the acrylic polymer block (A2) has an acid anhydride group (a1). The thermoplastic elastomer composition according to claim 1, 2, 3, 4, or 5, wherein the (meth) acrylic block copolymer (A) is obtained by controlled polymerization by atom transfer radical polymerization. The thermoplastic elastomer composition according to claim 1, 2, 3, 4, 5, or 6, wherein the thermoplastic resin (C) is a polyamide resin and / or a polyester resin. The thermoplastic elastomer composition according to claim 7, wherein the thermoplastic resin (C) is a polyamide resin. The (M) acrylic block polymer (A) 100 parts by weight, (D) 1 to 300 parts by weight of a softening agent is contained, 1, 2, 3, 4, 5, 6, 7 or 8. The thermoplastic elastomer composition as described in the above.