JP2005281459A - (meth)acrylic block copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a (meth)acrylic block copolymer which is rich in flexibility and is excellent in mechanical strength, molding processability, oil resistance, heat resistance and resistance to thermal decomposition, and its composition. <P>SOLUTION: The (meth)acrylic block copolymer is obtained by reacting a block copolymer (A) with a monofunctional amine compound (B), wherein the block copolymer (A) comprises a methacrylic polymer block (a) and an acrylic polymer block (b) and has an acid anhydride group (c) of formula (1) (wherein R<SP>1</SP>s are identical to or different from each other and are each a hydrogen atom or a methyl group; n is an integer of 0-3; and m is an integer of 0 or 1) and/or a carboxyl group (d) in a main chain of at least one of the polymer blocks chosen from the methacrylic polymer block (a) and the acrylic polymer block (b). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a (meth) acrylic block copolymer and a composition thereof, which have not been heretofore present, which are rich in flexibility, excellent in mechanical strength, molding processability, oil resistance, heat resistance and heat decomposition resistance.

Vulcanized rubber has excellent flexibility and rubber elasticity, but at the time of molding, it is necessary to add additives to the rubber and vulcanize, so the molding cycle time is long and the process is complicated, There is a problem in formability. Further, since the vulcanized rubber is not melted even after re-heating after being molded and vulcanized, there is a problem that post-processing such as joining cannot be performed and it is difficult to recycle after use.
In view of the above, in recent years, thermoplastic elastomers have been used in place of vulcanized rubber. For example, in automobile vehicles, various seal parts such as glass run channels, weather strips, various boots, and draining moldings are used. Most of them use vulcanized rubber, but from the viewpoint of improving fuel efficiency and environmental problems, lightweight and recyclable olefin-based thermoplastic elastomers have recently begun to be used for some of the seal parts.

In general, thermoplastic elastomers have an alloy structure consisting of a rubber component (soft segment) that exhibits entropy elasticity and a constraining component (hard segment) that flows at high temperatures but prevents plastic deformation at room temperature and gives the rubber component a reinforcing effect. Is taking. For example, in a styrene-based elastomer, styrene blocks aggregate to serve as hard segments, and butadiene-based blocks or isoprene-based blocks serve as a matrix and serve as soft segments. The olefin-based elastomer has an alloy structure in which a rubber such as ethylene-propylene-diene copolymer rubber (EPDM) is dispersed in a resin such as polypropylene (PP). In any case, thermoplastic processing such as injection molding is possible because the hard segment flows at a high temperature. However, conventional styrene-based or olefin-based thermoplastic elastomers do not have sufficient rubber elasticity and heat resistance (in this case, heat resistance means compression set characteristics at high temperatures, etc.) compared to vulcanized rubber, and oil resistance It has the disadvantage of poor performance.

On the other hand, as a thermoplastic elastomer excellent in oil resistance, a (meth) acrylic block body having a methacrylic block and an acrylic block has been disclosed in recent years (for example, see Patent Document 1). Although the moldability is very good, it has the disadvantage of being inferior in heat resistance. Thermoplastic elastomers can be processed thermoplastically, such as injection molding, because the hard segments flow at high temperatures. However, if the thermal decomposition temperature of the thermoplastic elastomer is lower than the injection molding temperature, There are cases where thermal deterioration of the plastic elastomer may occur. In particular, many methacrylic polymers are decomposed into monomers by depolymerization at 170 to 250 ° C. (see, for example, Non-Patent Document 1), and high temperature heat It also has the disadvantage that it cannot be used when stability is required.

On the other hand, it is already known that a thermoplastic elastomer is added for the purpose of resin modification, such as improving the impact resistance of a thermoplastic resin, or used as a soft material by compounding with a thermoplastic resin (for example, Patent Document 2). However, in styrene elastomers and olefin elastomers, it is possible to modify nonpolar resins due to their polarities, but because of their poor compatibility with polar resins, It is necessary to perform modification by adding a compatibilizer separately or by grafting and adding a compound such as maleic anhydride to a thermoplastic elastomer (see, for example, Patent Document 3 and Patent Document 4). In this case, although the modification can be performed, the oil resistance is lowered due to the characteristics of the styrene-based or olefin-based thermoplastic elastomer itself. In the case of the (meth) acrylic block body, the oil resistance and compatibility were better than those of the styrene or olefin thermoplastic elastomer, but the level was insufficient. Therefore, it has been desired to develop a thermoplastic elastomer that is excellent in oil resistance, heat resistance, and heat decomposition resistance, and that is excellent in modification of a thermoplastic resin and compound characteristics.

Japanese Patent No. 2553134 JP 10-29738 A JP-A-7-173390 JP 2000-265033 A Polymer Handbook Third Edition: Wiley-Interscience 1989

The object of the present invention is to provide a (meth) acrylic block copolymer and a composition thereof, which have not existed in the past and have excellent flexibility, mechanical strength, molding processability, oil resistance, heat resistance, and heat decomposability. It is to be.

As a result of intensive studies, the present inventor has found that the above-described problems can be solved by the present invention.
That is, the present invention comprises a methacrylic polymer block (a) and an acrylic polymer block (b), and at least one of the methacrylic polymer block (a) and the acrylic polymer block (b). In the main chain of the polymer block, the general formula (1):

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and may be the same or different from each other. N represents an integer of 0 to 3, and m represents an integer of 0 or 1.)
A (meth) acryl obtained by reacting a block copolymer (A) having an acid anhydride group (c) and / or a carboxyl group (d) represented by the formula (1) with a monofunctional amine compound (B). The present invention relates to a system block copolymer.

The present invention also provides:
The block copolymer (A) is composed of 10 to 60% by weight of a methacrylic polymer block (a) and 90 to 40% by weight of an acrylic polymer block (b). Block copolymers;
Acrylic polymer block (b) is copolymerized with at least one monomer selected from the group consisting of n-butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate, and these. The above (meth) acrylic block copolymer characterized by comprising 50 to 0% by weight of an acrylic ester and / or other vinyl monomer other than those described above;
The block copolymer (A) is represented by the general formula (ab) _r , general formula b- (ab) _r , general formula (ab) _r -a (wherein r is an integer of 1 or more) The (meth) acrylic block copolymer, which is at least one selected from the group consisting of block copolymers represented by:
The (meth) acrylic block copolymer, wherein the block copolymer (A) is produced by atom transfer radical polymerization;
The (meth) acrylic block copolymer, wherein the monofunctional amine compound (B) is at least one amine selected from methylamine, dimethylamine, ethylamine, diethylamine, butylamine, dibutylamine and aniline Concerning;

Furthermore, the present invention provides
A thermoplastic elastomer composition comprising the (meth) acrylic block copolymer;
It relates to a method for producing the above (meth) acrylic block copolymer, wherein the reaction of the block copolymer (A) and the monofunctional amine compound (B) is carried out under melting conditions.

The present invention will be described in detail below.
<< Block copolymer (A) >>
The block copolymer (A) in the present invention comprises a methacrylic polymer block (a) and an acrylic polymer block (b), and the methacrylic polymer block (a) and an acrylic polymer. In the main chain of at least one of the polymer blocks (b), the general formula (1):

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and may be the same or different from each other. N represents an integer of 0 to 3, and m represents an integer of 0 or 1.)
It has an acid anhydride group (c) and / or a carboxyl group (d).

The structure of the block copolymer (A) is preferably a linear block copolymer or a branched (star) block copolymer, and may be a mixture thereof. The structure of such a block copolymer can be properly used as needed, such as the physical properties, processing characteristics and mechanical properties of the required block copolymer (A), from the viewpoint of cost and ease of polymerization, A linear block copolymer is preferred.

The linear block copolymer has a general formula (ab) when the methacrylic polymer block (a) is expressed as a and the acrylic polymer block (b) is expressed as b from the viewpoint of physical properties of the composition. at least one block selected from the group consisting of block copolymers represented by: _r , b- (ab) _r , (ab) _r- a (wherein r is an integer of 1 or more). A copolymer is preferred. Among these, an ab type diblock copolymer, an abb type triblock copolymer, and a mixture thereof are more preferable from the viewpoint of easy handling during processing and physical properties of the composition. .

Also, the acid anhydride group (c) and / or carboxyl group (d) can be one or more per polymer block, and when there are two or more, the monomer is polymerized. The mode being done can be random copolymerization or block copolymerization.
For example, an aba type triblock copolymer is represented by (a / z) -ba type, (a / z) -b- (a / z) type, zab- a-type, za-b-a-z type, a- (b / z) -a-type, a-b-za-type, a-z-b-za-type, (a / z) -(B / z)-(a / z) type etc. may be sufficient.
Here, z represents a monomer or polymer block containing an acid anhydride group (c) and / or a carboxyl group (d), and (a / z) means an acid anhydride group (c ) And / or a monomer containing a carboxyl group (d) is copolymerized, and (b / z) is an acid anhydride group (c) and / or a carboxyl group (d) in the block b. It represents that the monomer containing is copolymerized.
Further, in a or b, the part containing z and the form contained may be freely set, and can be properly used according to the purpose.

The number average molecular weight of the block copolymer (A) in the present invention may be determined from the molecular weights required for the methacrylic polymer block (a) and the acrylic polymer block (b), respectively, and is not particularly limited. . The number average molecular weight of the block copolymer (A) is preferably from 30,000 to 500,000, more preferably from 40,000 to 400,000, still more preferably from 50,000 to 300,000. If the number average molecular weight is less than 30000, sufficient mechanical properties as an elastomer tend to be difficult to develop. Conversely, if the number average molecular weight exceeds 500000, the processing characteristics may deteriorate.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the block copolymer (A) in the present invention is 1 to 1.8. It is preferable that it is 1 to 1.5. When Mw / Mn exceeds 1.8, the uniformity of the block copolymer (A) may be lowered.

The composition ratio of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the block copolymer (A) is required for physical properties required in the application to be used and when the composition is processed. What is necessary is just to determine from the moldability and the molecular weight required for each of the methacrylic polymer block (a) and the acrylic polymer block (b).
Although it does not specifically limit as a composition ratio, It is preferable that a methacrylic polymer block (a) is 10 to 60 weight%, and an acrylic polymer block (b) is 90 to 40 weight%. More preferably, the methacrylic polymer block (a) is 15 to 50% by weight, the acrylic polymer block (b) is 85 to 50% by weight, and more preferably the methacrylic polymer block (a). 20 to 40% by weight, and the acrylic polymer block (b) is 80 to 60% by weight. If the proportion of the methacrylic polymer block (a) is less than 10% by weight, the rubber elasticity at high temperature tends to decrease, and if the proportion of (a) exceeds 60% by weight, the mechanical properties as an elastomer In particular, the elongation at break tends to decrease, the flexibility of the resulting thermoplastic elastomer composition tends to decrease, and the hardness tends to increase.
In addition, when the acid anhydride group (c) and / or the carboxyl group (d) are introduced into the methacrylic polymer block (a) and the acrylic polymer block (b), (a), (b ) Is the weight including (c) and / or (d).

The relationship between the glass transition temperatures of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the block copolymer (A) in the present invention is the glass of the methacrylic polymer block (a). When the transition temperature is Tg _a and the glass transition temperature of the acrylic polymer block (b) is Tg _b , it is preferable to satisfy the relationship of the following formula.
Tg _a > Tg _b

The glass transition temperature (Tg) of the polymer can be set by roughly setting the weight ratio of the monomer of each polymer portion according to the following Fox formula.
_{1 / Tg = (W 1 /} Tg 1) + (W 2 / Tg 2) + ... + (W m / Tg m)
W ₁ + W ₂ + ... + W _m = 1
In the formula, Tg represents the glass transition temperature of the polymer portion, and Tg ₁ , Tg ₂ ,..., Tg _m represent the glass transition temperature of each polymerization monomer. W ₁ , W ₂ ,..., W _m represent the weight ratio of each polymerization monomer.
As the glass transition temperature of each polymerization monomer in the Fox formula, for example, the value described in Polymer Handbook Third Edition (Wiley-Interscience, 1989) may be used.
The glass transition temperature can be measured by DSC (differential scanning calorimetry) or tan δ peak of dynamic viscoelasticity.

<Methacrylic polymer block (a)>
The methacrylic polymer block (a) is a block mainly composed of a methacrylic polymer. The “main component” means a component occupying 50% by weight or more of the methacrylic polymer block (a).

The monomer constituting the methacrylic polymer block (a) is a methacrylic acid ester monomer from the viewpoint of easily obtaining a block copolymer (A) having desired physical properties, cost and availability. And other vinyl monomers copolymerizable therewith.

Here, the ratio of the methacrylic acid ester monomer is preferably 50% by weight or more, and more preferably 75% by weight or more in the whole methacrylic polymer block (a). If it is less than 50% by weight, the weather resistance, high glass transition point, compatibility with the resin, etc., which are characteristics of the methacrylic acid ester, tend to be impaired. The proportion of the other copolymerizable vinyl monomer is preferably 0 to 50% by weight, more preferably 0 to 25% by weight in the whole (a).

Examples of the methacrylic acid ester monomer constituting the methacrylic polymer block (a) include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and n methacrylate. -Butyl, isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, Methacrylic acid aliphatic hydrocarbon (eg alkyl) esters such as nonyl methacrylate, decyl methacrylate, dodecyl methacrylate and stearyl methacrylate; methacrylic acid alicyclics such as cyclohexyl methacrylate and isobornyl methacrylate Formula hydrocarbon ester; Methacrylic acid aralkyl esters such as benzyl acrylate, α-methylbenzyl methacrylate, and α, α-dimethylbenzyl methacrylate; methacrylic aromatic hydrocarbon esters such as phenyl methacrylate and tolyl methacrylate; Esters of methacrylic acid such as 2-methoxyethyl acrylate and 3-methoxybutyl methacrylate and functional group-containing alcohols having etheric oxygen; trifluoromethyl methacrylate, 2-trifluoroethyl methacrylate, meta 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, Meta-acrylic Methacrylic acid fluoride such as 2-perfluoromethyl-2-perfluoroethylmethyl acid, 2-perfluorohexylethyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluorohexadecylethyl methacrylate, etc. Alkyl ester and the like.
At least one of these can be used.
Among these, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and n-methacrylate in terms of cost and availability and mechanical properties of the resulting thermoplastic elastomer composition. Butyl is preferred, and methyl methacrylate is particularly preferred.

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

Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-pentyl acrylate, and acrylic acid. Acrylic aliphatic hydrocarbon (eg alkyl) esters such as n-hexyl, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate Acrylic acid alicyclic hydrocarbon esters such as cyclohexyl acrylate and isobornyl acrylate; aromatic aromatic hydrocarbon esters such as phenyl acrylate and tolyl acrylate; benzyl acrylate, α-methylbenzyl acrylate, and α , Aralkyl esters of acrylic acid such as α-dimethylbenzyl; esters of acrylic acid such as 2-methoxyethyl acrylate and 3-methoxybutyl acrylate and functional group-containing alcohols having etheric oxygen; trifluoromethylmethyl acrylate, acrylic 2-trifluoromethylethyl acid, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperacrylate Acrylates such as fluoromethylmethyl, 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl acrylate, etc. It may be mentioned acid fluorinated alkyl esters.

Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, and the like.
Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
Examples of the conjugated diene compound include butadiene and isoprene.
Examples of the halogen-containing unsaturated compound include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, and vinylidene fluoride.

Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, and the like.
Examples of maleimide compounds include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and the like.

At least one of these vinyl monomers can be used.
In addition, methyl methacrylate polymer is almost quantitatively depolymerized by thermal decomposition, but in order to suppress it, acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid 2-methoxyethyl or a mixture thereof, styrene or the like can be copolymerized. Further, acrylonitrile can be copolymerized for the purpose of improving oil resistance.

The molecular weight required for the methacrylic polymer block (a) may be determined from the cohesive force required for the methacrylic polymer block (a) and the time required for the polymerization.

The cohesive force is said to depend on the interaction between molecules and the degree of entanglement, and as the molecular weight increases, the entanglement point increases and the cohesive force increases. That is, the molecular weight required for the methacrylic polymer block (a) and M _a, when the methacrylic polymer block (a) a polymer of the entanglement molecular weight constituting the and Mc _a, cohesion If necessary, preferably M _a> Mc a, when the additional cohesion is required, preferably M _a> 2Mc a, conversely, when it is desired to achieve both a degree of cohesion and creep resistance , Mc _a <M _a <2Mc _a is preferred. The molecular weight between the entanglement points may be referred to Wu et al. (Polymer. Eng. And Sci., 1990, Vol. 30, p. 753).

For example, if the methacrylic polymer block (a) is entirely composed of methyl methacrylate, in the case where cohesion is required, the number average molecular weight of the methacrylic polymer block (a) is: It is preferably 9200 or more. Moreover, since there exists a tendency for polymerization time to become long when a number average molecular weight is large, what is necessary is just to set according to required productivity, Preferably it is 200000 or less, More preferably, it is 100000 or less. However, when the acid anhydride group (c) and / or the carboxyl group (d) is contained in the methacrylic polymer block (a), aggregation by the acid anhydride group (c) and / or the carboxyl group (d) Since force is applied, the number average molecular weight can be set lower than this.

Furthermore, the glass transition temperature (Tg _a ) of the methacrylic polymer block (a) is preferably 100 ° C. or higher, more preferably 110 ° C. or higher. When the glass transition temperature is less than 100 ° C., rubber elasticity at high temperatures tends to decrease.
The setting of Tg _a of the methacrylic polymer block (a) in accordance with said Fox equation, can be performed by setting the weight ratio of the monomers of each polymer portion.

<Acrylic polymer block (b)>
The acrylic polymer block (b) is a block mainly composed of an acrylic polymer. The “main component” means a component occupying 50% by weight or more of the acrylic polymer block (b).

The monomer composing the acrylic polymer block (b) is an acrylate monomer, and can be copolymerized with it from the viewpoint of easily obtaining a composition having desired physical properties, cost and availability. It is preferably made of a new vinyl monomer.

Here, the ratio of the acrylate monomer is preferably 50% by weight or more, and more preferably 70% by weight or more in the whole acrylic polymer block (b). If it is less than 50% by weight, the physical properties of the composition, particularly impact resistance and flexibility, which are characteristics when using an acrylic ester, tend to be impaired. Moreover, 0-50 weight% is preferable and, as for the ratio of the other vinyl-type monomer which can be copolymerized, More preferably, it is 0-25 weight%.

The acrylic ester monomer constituting the acrylic polymer block (b) is a vinyl monomer copolymerizable with the methacrylic ester monomer constituting the methacrylic polymer block (a). The same specific example as an acrylic ester monomer can be given. In addition, at least one of these can be used.

Among these acrylate monomers, ethyl acrylate, n-butyl acrylate, 2-methoxyethyl acrylate, and 2-ethylhexyl acrylate are preferable.
More specifically, n-butyl acrylate is preferable in terms of impact resistance, cost, and availability of the thermoplastic elastomer composition. Ethyl acrylate is preferred when the composition needs oil resistance. When low temperature characteristics and flexibility are required, or when lower hardness characteristics are required, 2-ethylhexyl acrylate is preferred. When it is desired to achieve both oil resistance and low temperature characteristics, a mixture of ethyl acrylate, n-butyl acrylate, and 2-methoxyethyl acrylate is preferred.

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

Specific examples of the methacrylic acid ester, aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound, halogen-containing unsaturated compound, vinyl ester compound, and maleimide compound include a methacrylic polymer block (a), respectively. The same thing as the specific example in can be mentioned. At least one of these can be used.
These vinyl monomers can be selected according to the glass transition temperature, elastic modulus, polarity required for the acrylic polymer block (b), physical properties required for the composition, and the like.

Further, the acrylic polymer block (b) is at least one monomer selected from the group consisting of butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate, and other than the above ( More preferably, it is composed of 50 to 0% by weight of an acrylic acid ester monomer and / or copolymerizable vinyl monomer (other than butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate).
Further, the acrylic polymer block (b) is particularly preferably composed of 10 to 90% by weight of 2-methoxyethyl acrylate and 90 to 10% by weight of butyl acrylate.

The molecular weight required for the acrylic polymer block (b) may be determined from the elastic modulus and rubber elasticity required for the acrylic polymer block (b), 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 original elastic modulus is not shown unless the molecular weight exceeds a certain level. The same applies to rubber elasticity, but from the viewpoint of rubber elasticity, a higher molecular weight is desirable.
In other words, the number-average molecular weight _{M b} of the acrylic polymer block (b) is preferably 3,000 or more, more preferably 5,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, most preferably 40,000 or more. However, since the polymerization time tends to be longer when the number average molecular weight is large, the polymerization time may be set according to the required productivity, but is preferably 500,000 or less, more preferably 300,000 or less.

Furthermore, the glass transition temperature (Tg _b ) of the acrylic polymer block (b) is preferably 50 ° C. or lower, more preferably 0 ° C. or lower. If Tg _b is higher than 50 ° C., the rubber elasticity of the block copolymer (A) may decrease.
The setting of the glass transition temperature of the acrylic polymer block _(b) (Tg b), as in the case of Tg _a, and those calculated according to the Fox equation.

<Acid anhydride group (c)>
The acid anhydride group (c) has the general formula (1):

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and may be the same or different from each other. N is an integer of 0 to 3, and m is an integer of 0 or 1.) Is done.

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

Since the monomer having an acid anhydride group (c) has a high glass transition temperature (Tg), it has an effect of improving the heat resistance of the block copolymer (A) when introduced into the hard segment. . The glass transition temperature of the polymer having an acid anhydride group (c) is, for example, as high as 159 ° C. for polymethacrylic anhydride, and the heat resistance of the block copolymer (A) can be obtained by introducing the units constituting them. Can be improved.
Moreover, since the acid anhydride group (c) has reactivity with a compound having an amino group, a hydroxyl group or the like, the polymer can be modified to improve compatibility.

The acid anhydride group (c) may be contained only in one of the methacrylic polymer block (a) and the acrylic polymer block (b), or is contained in both blocks. May be. For the purpose of adjusting the reaction point of the block copolymer (A), the cohesive force of the block constituting the block copolymer (A) and the glass transition temperature, and further using the acid anhydride group (c) as the reaction point For the purpose of selectively modifying the methacrylic polymer block (a) or the acrylic polymer block (b) using the monofunctional amine compound (B), the acid anhydride group (c) is modified or What is necessary is just to introduce | transduce into the block to make it react.

Moreover, what is necessary is just to introduce | transduce an acid anhydride group (c) into a methacrylic-type polymer block (a) at the point of the heat resistance of a block copolymer (A), or a heat resistant decomposition improvement. Although not particularly limited, in terms of control of reaction points, heat resistance, rubber elasticity, etc., it is preferable to have either methacrylic polymer block (a) or acrylic polymer block (b). .
Although not particularly limited, when the acid anhydride group (c) is contained in the methacrylic polymer block (a), it is preferable that R ^{1 in the} general formula (1) is a methyl group. When the group (c) is contained in the acrylic polymer block (b), it is preferable that both R ^{1 in the} general formula (1) are hydrogen atoms. When the acid anhydride group (c) is contained in the methacrylic polymer block (a), when R ¹ is a hydrogen atom, or when the acid anhydride group (c) is contained in the acrylic polymer block (b) When R ¹ is a methyl group, the polymerization operation of the block copolymer (A) becomes complicated, or the glass transition temperature of the methacrylic polymer block (a) and the acrylic polymer block (b) A difference becomes small and there exists a tendency for the rubber elasticity of a block copolymer (A) to fall.

The preferred range of the content of the acid anhydride group (c) is the cohesive strength, reactivity, structure and composition of the block copolymer (A), and the block copolymer (A). The number of blocks to be changed, the glass transition temperature, and the site and manner in which the acid anhydride group (c) is contained vary.
As content of an acid anhydride group (c), 0.1 weight% or more in the whole block copolymer (A) is preferable, and 0.5 weight% or more is more preferable. When it is less than 0.1% by weight, the reactivity of the block copolymer (A) and the monofunctional amine compound (B) tends to be insufficient. Further, when the acid anhydride group (c) having a high Tg is introduced into the methacrylic polymer block (a), which is a hard segment, for the purpose of improving the heat resistance of the block copolymer (A), 0.1 wt. If it is less than%, the heat resistance is not sufficiently improved, and the development of rubber elasticity at high temperatures tends to be reduced. In addition, content of the said acid anhydride group (c) represents weight% of the monomer which has an acid anhydride group (c).
The content block and content of the acid anhydride group (c) may be appropriately determined according to the required reactivity, reaction point, cohesive force, glass transition temperature, and the like.

The method for introducing the acid anhydride group (c) is not particularly limited. However, in terms of ease of introduction, ease of purification after introduction, etc., the block copolymer ( It is preferably introduced into A) and then cyclized. For example, the general formula (2):

(In the formula, R ² represents a hydrogen atom or a methyl group. R ³ represents a hydrogen atom, a methyl group or a phenyl group, and a plurality of R ^{3 s} are the same as or different from each other except that at least one methyl group is contained. It is preferable that the block copolymer (A) having at least one unit represented by the following formula is melt-kneaded and cyclized and introduced.

The introduction of the unit represented by the general formula (2) into the block copolymer (A) is performed by copolymerizing an acrylate monomer or a methacrylic acid ester monomer derived from the general formula (2). Can be done by.

Examples of the monomer include t-butyl (meth) acrylate, isopropyl (meth) acrylate, α, α-dimethylbenzyl (meth) acrylate, α-methylbenzyl (meth) acrylate, and the like. It is not limited to. Among these, t-butyl (meth) acrylate is preferable from the viewpoints of availability, ease of polymerization, ease of acid anhydride group formation, and the like.

The unit represented by the general formula (2) is eliminated and cyclized with an adjacent ester unit at a high temperature to form an acid anhydride group (for example, Hatada et al., JMS-PURE). APPL.CHEM., A30 (9 & 10), PP.645-667 (1993)). According to these, generally, an ester unit is bulky, and a polymer having β-hydrogen is decomposed at a high temperature, followed by cyclization to produce an acid anhydride group. By using these methods, an acid anhydride group can be easily introduced into the block copolymer (A).

The formation of the acid anhydride group (c) is preferably performed by heating the block copolymer (A) having an acid anhydride group precursor at a high temperature, and preferably at 180 to 300 ° C. When the temperature is lower than 180 ° C., there is a tendency that the acid anhydride groups are not sufficiently generated, and when the temperature is higher than 300 ° C., the block copolymer (A) itself having a precursor of the acid anhydride group tends to be decomposed.

As a method of heating the block copolymer (A) having an acid anhydride group precursor at a high temperature, the block copolymer (A) having a precursor is heated under pressure in the state of a polymer solution. It may be heated while evaporating and removing the solvent from the polymer solution, or the block copolymer (A) having the precursor may be directly heated and melted, but the reactivity to the acid anhydride group is good. In view of ease of production and the like, the block copolymer (A) having a precursor is preferably directly melted by heating, and more preferably melt-kneaded. In the melt kneading, an antioxidant or the like can be added.

<Carboxyl group (d)>
The carboxyl group (d) has a strong cohesive force, and the monomer having a carboxyl group has a high glass transition temperature (Tg), and has an effect of improving the heat resistance and cohesive force of the block copolymer (A). . A functional group such as a hydroxyl group also has a hydrogen bonding ability, but has a lower Tg compared to the monomer having the functional group described above, and the effect of improving heat resistance is small. For example, polymethacrylic acid is as high as 228 ° C., and the heat resistance of the block copolymer (A) can be improved by introducing monomers constituting these.

The carboxyl group (d) may be contained only in one of the methacrylic polymer block (a) and the acrylic polymer block (b), or may be contained in both blocks. Good. It can be used depending on the purpose such as the reaction point of the block copolymer (A), the purpose of adjusting the cohesive force of the block constituting the block copolymer (A) and the glass transition temperature.
Although it is not particularly limited, it has an acid anhydride group (c) in terms of control of the reaction point of the block copolymer (A) and ease of introduction of the carboxyl group (d) into the block copolymer (A). It is preferable to have a carboxyl group (d) in the same block as the block. Moreover, it is more preferable to contain a carboxyl group (d) in the methacrylic polymer block (a) in terms of heat resistance and cohesion. This is because by introducing a carboxyl group (d) having a high Tg or cohesive force into the hard segment, it becomes possible to develop rubber elasticity even at a high temperature. In addition, when the acrylic polymer block (b) has a carboxyl group (d), it is preferable from the viewpoint of compatibility with a thermoplastic resin that can be added to the acrylic polymer block (b).

The preferred range of the content of the carboxyl group (d) is the cohesive strength of the carboxyl group (d), the structure and composition of the block copolymer (A), the number of blocks constituting the block copolymer (A), and It varies depending on the site and manner in which the carboxyl group (d) is contained.
The content of the carboxyl group (d) is from 0.1 to 50% by weight in the entire block copolymer (A) from the viewpoint of increasing the heat resistance and cohesion of the block copolymer (A). Preferably, 0.5 to 40% by weight is more preferable. When it exceeds 50% by weight, the carboxyl group (d) tends to be cyclized with an adjacent ester unit at a high temperature, so that the operation of introducing the carboxyl group (d) tends to be complicated. In the case of less than 0.1% by weight, when the carboxyl group (d) is introduced into the hard segment, the heat resistance and the cohesive strength may be insufficiently improved. In addition, content of the said carboxyl group (d) represents weight% of the monomer which has a carboxyl group (d).

The method for introducing the carboxyl group (d) is a block copolymer (A) in a form in which the carboxyl group (d) is protected with an appropriate protecting group, or in the form of a functional group that is a precursor of the carboxyl group (d). And then a functional group can be generated by a known chemical reaction.
For example, as disclosed in JP-A-2001-234147 and JP-A-10-298248, carboxyl groups such as t-butyl methacrylate, t-butyl acrylate, trimethylsilyl methacrylate, trimethylsilyl acrylate, etc. There is a method of synthesizing a block copolymer (A) containing a monomer having a functional group to be a precursor of the above, and generating a carboxyl group (d) by a known chemical reaction such as hydrolysis or acid decomposition. As another method, the acid anhydride group (c) can be formed in the process of introducing the acid anhydride group (c) into the block copolymer (A) or by hydrolysis of the acid anhydride group (c).
The method for introducing the carboxyl group (d) is not particularly limited, but when a monomer having a carboxyl group is introduced by direct polymerization under polymerization conditions, the monomer having a carboxyl group can be used as a catalyst during polymerization. The process of introducing the acid anhydride group (c) into the block copolymer (A) because it may be deactivated, has a problem in terms of cost, or tends to be complicated to manufacture. In addition, it is preferable that the acid anhydride group (c) be generated by hydrolysis because the introduction amount of the carboxyl group (d) is easily controlled or introduced.

Examples of the method for generating the carboxyl group (d) in the process of introducing the acid anhydride group (c) into the block copolymer (A) include the methods described below.
In the block copolymer (A) having a unit represented by the general formula (2), the unit represented by the general formula (2) is eliminated and cyclized with an adjacent ester unit at a high temperature to form an acid anhydride group ( c) is generated. At this time, the ester unit is decomposed to generate a carboxyl group (d), and subsequently, cyclization occurs to partially have a route for generating an acid anhydride group. Utilizing this, the carboxyl group (d) can be introduced by appropriately adjusting the heating temperature and time according to the type and content of the unit represented by the general formula (2). In this method, since the carboxyl group (d) tends to cyclize with an adjacent ester unit at a high temperature, when introducing a high content of the carboxyl group (d), the acid anhydride group (c) is added. A method of introducing by hydrolysis is preferred. When the carboxyl group (d) is generated in the process of introduction into the acid anhydride group (c) into the block copolymer (A), the acid anhydride is introduced in the same manner as in the method for introducing the acid anhydride group (c). The block copolymer (A) having the above precursor may be heated under pressure in the state of a polymer solution, and the block copolymer (A) having the acid anhydride group precursor may be directly heated and melted. May be. It is more preferable to melt-knead the block copolymer (A) having an acid anhydride group precursor in terms of ease of production and the like.

Further, when the carboxyl group (d) is preferably formed by hydrolyzing the acid anhydride group (c) and opening the ring, the hydrolysis method is not particularly limited, and the block copolymer having an acid anhydride group is not limited. The polymer (A) may be heated with water under pressure, or the block copolymer (A) having an acid anhydride group may be melt-kneaded with water. It is preferable to melt-knead the block copolymer (A) having an acid anhydride group together with water for ease of production. In the melt kneading, an antioxidant or the like can be added.

<Method for producing block copolymer (A)>
Next, the manufacturing method of a block copolymer (A) is demonstrated.
Although it does not specifically limit as a method to manufacture a block copolymer (A), It is preferable to use control polymerization from the point which is easy to control the molecular weight and structure of a polymer.

A general radical polymerization method is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only stochastically. However, there is a problem that it is necessary to use a large amount of this monomer, and conversely, a polymer having a low specific functionalization rate can be obtained by using a small amount. Moreover, since it is free radical polymerization, there is a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

Controlled polymerization includes living anionic polymerization, radical polymerization using a chain transfer agent, and living radical polymerization. Among these, living radical polymerization is preferable from the viewpoint of easy polymerization of the block copolymer (A) and control of the molecular weight and structure.

Living radical polymerization is radical polymerization in which the activity at the polymerization terminal is maintained without loss. In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the terminal is in equilibrium. . The definition here is also the latter. Living radical polymerization has been actively researched by various groups in recent years.

Examples thereof include radicals such as those using chain transfer agents such as polysulfides, cobalt porphyrin complexes (J. Am. Chem. Soc., 1994, 116, 7943) and nitroxide compounds. Atom transfer radical polymerization (ATRP) using a trapping agent (Macromolecules, 1994, 27, 7228), an organic halide or the like and a transition metal complex as a catalyst. And the like.

The method for producing the block copolymer (A) of the present invention is not particularly limited as to which of these methods is used, but atom transfer radical polymerization is preferred from the viewpoint of ease of control.

Atom transfer radical polymerization is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a group 7 element, 8 group, 9 group, 10 group or 11 element as a central metal in the periodic table as a catalyst. (For example, Mattyjaszewski et al., Journal of American Chemical Society, J. Am. Chem. Soc., 1995, 117, 5614, Macromolecules, 1995, 28, 7901, Science, 1996, 272, 866, or Sawamoto et al., Macromolecules, 1995, 28, 1721, JP-A-9-208616. No. 1, JP-A-8-4 117 JP).

According to these methods, in general, polymerization proceeds in a living manner and the molecular weight distribution is narrow (Mw / M), although the polymerization rate is very high and radical reaction such as coupling between radicals is likely to occur. Mn = 1.1 to 1.5) polymer is obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

In the atom transfer radical polymerization method, a monofunctional, difunctional, or polyfunctional compound can be used as the organic halide or sulfonyl halide compound used as an initiator. These may be properly used according to the purpose, and in the case of producing the block copolymer (A), in the case of producing an aba type or babb type triblock copolymer, It is preferable to use a bifunctional compound from the viewpoint of shortening the number of steps and time. When producing a branched block copolymer, a polyfunctional compound should be used from the viewpoint of shortening the number of reaction steps and time. Is preferred. Moreover, when manufacturing an ab type diblock copolymer, a monofunctional compound is preferable from the point of the availability of an initiator.

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

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

In the formula, C ₆ H ₅ represents a phenyl group, and C ₆ H ₄ represents a phenylene group (which may be ortho-substituted, meta-substituted, or para-substituted). R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ⁵ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. X represents chlorine, bromine or iodine.

Specific examples of the alkyl group having 1 to 20 carbon atoms (including alicyclic hydrocarbon group) represented by R ⁴ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl. Group, 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. It is done. Specific examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl 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.

Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ⁵ include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. . 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 are the same as those described for R ⁴ above.

Specific examples of the monofunctional compound include, for example, tosyl bromide, methyl 2-bromide propionate, ethyl 2-bromide propionate, butyl 2-bromide propionate, methyl 2-isobutyrate bromide, 2- Examples thereof include ethyl bromide isobutyrate, 2-butyl isobutyrate bromide and the like. Of these, ethyl 2-bromide propionate and butyl 2-bromide propionate are preferred because they are similar to the structure of the acrylate monomer and are easy to control polymerization.

As a bifunctional compound, for example,
_{X-CH 2 -C 6 H 4} -CH 2 -X,
_{X-CH (CH 3) -C} 6 H 4 -CH (CH 3) -X,
_{X-C (CH 3) 2} -C 6 H 4 -C (CH 3) 2 -X,
^{_{X-CH (COOR 6) -}} (CH 2) n -CH (COOR 6) -X,
^{_{X-C (CH 3) (}} COOR 6) - (CH 2) n -C (CH 3) (COOR 6) -X,
^{_{X-CH (COR 6) -}} (CH 2) n -CH (COR 6) -X,
^{_{X-C (CH 3) (}} COR 6) - (CH 2) n -C (CH 3) (COR 6) -X,
_{X-CH 2 -CO-CH 2} -X,
X—CH (CH ₃ ) —CO—CH (CH ₃ ) —X,
_{X-C (CH 3) 2} -CO-C (CH 3) 2 -X,
_{X-CH (C 6 H 5} ) -CO-CH (C 6 H 5) -X,
X—CH ₂ —COO— (CH ₂ ) _n —OCO—CH ₂ —X,
_{X-CH (CH 3) -COO-} (CH 2) n -OCO-CH (CH 3) -X,
_{X-C (CH 3) 2} -COO- (CH 2) n -OCO-C (CH 3) 2 -X,
_{X-CH 2 -CO-CO-} CH 2 -X,
_{X-CH (CH 3) -CO} -CO-CH (CH 3) -X,
_{X-C (CH 3) 2} -CO-CO-C (CH 3) 2 -X,
_{X-CH 2 -COO-C 6} H 4 -OCO-CH 2 -X,
_{X-CH (CH 3) -COO} -C 6 H 4 -OCO-CH (CH 3) -X,
_{X-C (CH 3) 2} -COO-C 6 H 4 -OCO-C (CH 3) 2 -X,
_{X-SO 2 -C 6 H 4} -SO 2 -X
And the like.

In the formula, R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. n represents an integer of 0 to 20. C ₆ H ₅ , C ₆ H ₄ and X are the same as 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 , and 6 to 6 carbon atoms. The same as the specific examples of the 20 aryl group and the aralkyl group having 7 to 20 carbon atoms.

Specific examples of the bifunctional compound include, for example, bis (bromomethyl) benzene, bis (1-bromoethyl) benzene, bis (1-bromoisopropyl) benzene, dimethyl 2,3-dibromosuccinate, and 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-dibromosuberine Dibutyl, and the like. Among these, bis (bromomethyl) benzene, diethyl 2,5-dibromoadipate, and diethyl 2,6-dibromopimelate are preferable from the viewpoint of availability of raw materials.

As the multifunctional compound, for example,
_{C 6 H 3 - (CH 2} -X) 3,
_{C 6 H 3 - (CH (} CH 3) -X) 3,
_{C 6 H 3 - (C (} CH 3) 2 -X) 3,
_{C 6 H 3 - (OCO-} CH 2 -X) 3,
_{C 6 H 3 - (OCO-} CH (CH 3) -X) 3,
_{C 6 H 3 - (OCO-} C (CH 3) 2 -X) 3,
_{C 6 H 3 - (SO 2} -X) 3
And the like.
In the formula, C ₆ H ₃ represents a trivalent phenyl group (the position of the three bonds may be any one of the positions 1 to 6), and X is the same as described above.

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

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

Specific examples of the organic halide or halogenated sulfonyl compound having the functional group include those described in JP-A-2003-82192.

In the organic halide or sulfonyl halide compound that can be used as the initiator, the carbon to which the halogen atom is bonded is bonded to the carbonyl group or the phenyl group, and the carbon-halogen bond is activated to perform polymerization. Start.

What is necessary is just to determine the quantity of an initiator from the molar ratio with a monomer according to the molecular weight of a required block copolymer (A). That is, the molecular weight of the block copolymer (A) can be controlled by the number of monomers used per molecule of the initiator.

As the transition metal complex used as the catalyst for the atom transfer radical polymerization, the stability of the transition metal complex and the control of the atom transfer radical polymerization can be easily controlled. A transition metal complex having a group or group 11 element as a central metal is preferred. Among them, monovalent and zerovalent copper, divalent ruthenium, divalent iron, and divalent nickel complexes are preferable because the control of atom transfer radical polymerization is easier. And a copper complex is preferable from the viewpoint of reaction control.

Specific examples of the catalyst include those described in JP-A-2003-82192.

For example, in the polymerization of acrylic monomers such as acrylic acid esters, it is preferable from the viewpoint of polymerization control that the growth terminal of the polymer chain has a carbon-bromine bond, so that the initiator used is an organic bromide or It is a sulfonyl bromide compound, the solvent is preferably acetonitrile, copper bromide, preferably a metal complex catalyst centered on copper contained in cuprous bromide, and a ligand such as pentamethyldiethylenetriamine Is preferably used.

For polymerization of methacrylic monomers such as methacrylic acid esters, it is preferable from the viewpoint of polymerization control that the growth terminal of the polymer chain has a carbon-chlorine bond. It is a chloride or sulfonyl chloride compound, the solvent is preferably a mixed solvent with acetonitrile, and if necessary toluene, etc., and a metal complex catalyst having copper as the central metal, preferably copper contained in cuprous chloride It is preferable to use a ligand such as pentamethyldiethylenetriamine.

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

The atom transfer radical polymerization can be performed in the absence of a solvent (bulk polymerization) or in various solvents. In addition, in bulk polymerization and polymerization performed in various solvents, the polymerization can be stopped midway.

Examples of the solvent that can be used include hydrocarbon solvents, ether solvents, halogenated hydrocarbon solvents, ketone solvents, alcohol solvents, nitrile solvents, ester solvents, carbonate solvents, and the like.
Specific examples of the solvent include those described in JP-A-2003-82192, and at least one kind can be used.

When a solvent is used, the amount used may be appropriately determined from the relationship between the viscosity of the entire system and the required stirring efficiency (ie, reaction rate). In addition, even in the case of bulk polymerization, in the case of terminating polymerization in the middle of various solvents, the monomer conversion rate at the point of stopping the reaction is determined by the viscosity of the entire system and the required stirring efficiency (that is, , Reaction rate).

The polymerization can be carried out in the range of room temperature to 200 ° C, preferably in the range of 50 to 150 ° C.

The atom transfer radical polymerization of the present invention includes so-called reverse atom transfer radical polymerization. Reverse atom transfer radical polymerization is a high oxidation state when a normal atom transfer radical polymerization catalyst generates radicals, for example, peroxidation with respect to Cu (II ′) when Cu (I) is used as a catalyst. This is a method in which a general radical initiator such as a compound is allowed to act, and as a result, an equilibrium state similar to that of atom transfer radical polymerization is produced (Macromolecules 1999, 32, 2872).

In order to produce the block copolymer (A) by the polymerization, a method of sequentially adding monomers; a method of polymerizing the next block using a polymer synthesized in advance as a polymer initiator; Examples include a method of binding the coalescence by reaction.
Any of these methods may be used depending on the purpose, but from the viewpoint of simplicity of the production process, a method by sequential addition of monomers is preferable, and the monomer of the previous block remains. When it is desired to avoid copolymerization in the next block, a method of polymerizing the next block using a polymer synthesized in advance as a polymer initiator is preferable.

Hereinafter, each of the above methods will be described in detail, but the production method of the block copolymer (A) of the present invention is not limited thereto.

In the case of sequential addition of monomers, it is desirable to charge the monomer to be polymerized next when the conversion rate of the monomer charged to be polymerized is 80 to 95%. When the polymerization is allowed to proceed until the conversion rate exceeds 95%, the growth reaction of the polymer chain can be suppressed stochastically. In addition, since the polymer radicals easily react with each other, side reactions such as disproportionation, coupling, and chain transfer tend to occur. If the monomer to be polymerized next is charged when the conversion rate is less than 80%, the monomer charged for the previous polymerization is mixed with the monomer to be polymerized next and co-polymerized. Polymerization may be a problem.
As the order of addition of the monomers, a method in which an acrylic monomer is first charged and polymerized and then a methacrylic monomer is charged and polymerized is preferable from the viewpoint of polymerization control. This is because it is preferable to grow the methacrylic polymer block from the end of the acrylic polymer block.

As a method for polymerizing the next block using a polymer synthesized in advance as a polymer initiator, for example, when the degree of polymerization of the first block is desired, the temperature is once lowered in the living state to stop the polymerization. There is a method in which the monomer of the first block is distilled off under reduced pressure and the like, and then the monomer of the second block is added. When the third and subsequent blocks are to be polymerized, the same operation as that for the second block may be performed. In this method, at the time of polymerization of the second and subsequent blocks, it is possible to avoid copolymerization of the remaining monomers of the previous block.
In this case, as a block polymerization sequence, a method in which an acrylic block is first polymerized and then a methacrylic block is polymerized is preferable from the viewpoint of polymerization control. This is because it is preferable to grow the methacrylic polymer block from the end of the acrylic polymer block.

Here, how to determine the conversion rate of acrylic monomers, methacrylic monomers, etc. will be described. In order to obtain the conversion rate, a gas chromatograph (GC) method, a gravimetric method, or the like can be applied.
In the GC method, the polymerization reaction liquid is sampled as needed before and during the reaction, and GC measurement is performed. From the abundance ratio of the monomer and the internal standard substance previously added to the polymerization system, This is a method for obtaining the consumption rate. The advantage of this method is that each conversion rate can be determined independently even when a plurality of monomers are present in the system.
The weight method is a method in which a polymerization reaction solution is sampled, the solid content concentration is obtained from the weight before drying and the weight after drying, and the conversion rate of the whole monomer is obtained. 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 included as a copolymerization component of a methacrylic monomer, the GC method is used. preferable.

The reaction liquid obtained by the polymerization contains a mixture of a polymer and a metal complex, and an organic acid containing a carboxyl group or a sulfonyl group is added to form a metal complex and a metal salt. The solid content is removed by filtration, etc., and subsequently impurities such as acids remaining in the solution by adsorption treatment of basic activated alumina, basic adsorbent, solid inorganic acid, anion exchange resin, cellulose anion exchanger. The block copolymer (A) solution can be obtained by removing.

In the polymer solution thus obtained, the polymerization solvent and unreacted monomer are subsequently removed by an evaporation operation, and the block copolymer (A) is isolated. As the evaporation method, a thin film evaporation method, a flash evaporation method, a horizontal evaporation method provided with an extrusion screw, or the like can be used. Since the block copolymer (A) has adhesiveness, efficient evaporation is possible by combining the horizontal evaporation method with an extrusion screw alone or another evaporation method among the above evaporation methods.

<< monofunctional amine compound (B) >>
The monofunctional amine compound (B) in the present invention is not particularly limited as long as it has reactivity with an acid anhydride group or a carboxyl group.
Specifically, methylamine, dimethylamine, methylethylamine, ethylamine, diethylamine, n-propylamine, isopropylamine, di (n-propyl) amine, di (isopropyl) amine, n-butylamine, di (n-butyl) Amine, isobutylamine, di (isobutyl) amine, n-amylamine, isoamylamine, isodecylamine, isotridecylamine, n-hexylamine, methylamylamine, n-heptylamine, n-octylamine, 2-octylamine 2-ethylhexylamine, 3,5,5-trimethylhexylamine, nonylamine, n-decylamine, undecylamine, n-dodecylamine, trimethylnonylamine, tetradecylamine, heptadecylamine, cyclohexylamine, N Such as ethylethanolamine, N-methylethanolamine, N- (2-aminoethyl) ethanolamine, diethanolamine, N-dibutylethanolamine, 3-amino-1-propanol, butyleneamine, 3-chloro-1-propylamine, etc. Aliphatic compounds; aromatics such as aniline, o-methylaniline, m-methylaniline, p-methylaniline, α- and β-naphthylamine, diphenylamine, di (naphthylamine), benzylamine, dibenzylamine, benzylethylamine Examples of amine compounds include amino compounds having a polymer group such as amino-modified silicone resins and polyamide resins.
These may be used alone or in combination of two or more.

From the viewpoint of reducing the hardness without reducing the heat resistance of the (meth) acrylic block copolymer obtained by the reaction, methylamine, dimethylamine, ethylamine, diethylamine, butylamine, and dibutylamine are preferable. In addition to the improvement, aromatic amine compounds such as aniline are preferred for the purpose of achieving high elasticity. In view of ease of handling, diethylamine, dibutylamine and aniline are particularly preferable.

Usually, when introducing a functional group such as an amide group into a polymer, a method is used in which an amide group-containing monomer such as (meth) acrylamide, (meth) dimethylacrylamide, or (meth) diethylacrylamide is copolymerized with an acrylic material. It is done. However, in the living polymerization for synthesizing the block copolymer, problems such as catalyst deactivation due to the monomer occur, and it is difficult to copolymerize these monomers.
However, as in the present invention, the monofunctional amine compound (B) containing a group capable of reacting with an acid anhydride group or a carboxyl group to form an amide group or the like is converted into an acid anhydride group and / or a carboxyl group. By reacting with the contained block copolymer (A), a functional group such as an amide group can be regioselectively and easily introduced into the block copolymer (A).
On the other hand, when the (meth) acrylic block copolymer containing no acid anhydride group and carboxyl group is allowed to react with the monofunctional amine compound (B), it becomes a reaction between the ester group and the amine, It is difficult to express selectivity, and formation of a non-selective amide group or the like on the methacrylic polymer block (a) and the acrylic polymer block (b) proceeds. In this case, the phase separation between the methacrylic polymer block (a) and the acrylic polymer block (b) becomes insufficient, and the properties as a thermoplastic elastomer are greatly deteriorated.

In addition, when a disubstituted amine is used in the monofunctional amine compound (B), the resulting (meth) acrylic block copolymer has an amide bond, and when a monosubstituted amine is used. The (meth) acrylic block copolymer obtained has an amide bond or an imide bond. Thus, by selecting the type of the monofunctional amine compound (B), the type of bond to be obtained can be selected, and furthermore, the polarity of the reacted site can be easily adjusted. That is, it is industrially advantageous that a large number of various resins can be produced simply by changing the amine species to be added.

The amount of the monofunctional amine compound (B) used is preferably 1 to 50 weights with respect to 100 parts by weight of the block copolymer (A), from the viewpoint of ensuring a sufficient reaction rate and easy removal of unreacted substances. Parts, more preferably 5 to 20 parts by weight.

Further, when the monofunctional amine compound (B) is reacted with the acid anhydride group (c), the monofunctional amine compound (B) is added to the acid anhydride group (c) from the viewpoint of sufficient modification effect. Preferably 0.1 to 20 times equivalent, more preferably 0.5 to 10 times equivalent is added. The remaining unreacted compound can be easily removed if necessary.

<< (Meth) acrylic block copolymer >>
The (meth) acrylic block copolymer of the present invention is obtained by reacting the block copolymer (A) with the monofunctional amine compound (B).

The method for reacting (A) and (B) is not particularly limited as long as the target reaction proceeds. For example, a method of dissolving the block copolymer (A) in an appropriate solvent and reacting the monofunctional amine compound (B); a method of reacting by a melt reaction of (A) and (B) and the like can be mentioned.

In the case of the method of dissolving in a solvent, examples of the solvent include aromatic hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; acetone Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate It is done.

The melt reaction is preferable because of easy handling, and the target is obtained by adding the block copolymer (A) and the monofunctional amine compound (B) to the melt kneader and reacting by melt kneading ( A (meth) acrylic block copolymer can be easily obtained.
Although it does not specifically limit as a melt-kneading apparatus, For example, the Banbury, kneader, single-screw or multi-screw extruder used for the process of a normal rubber | gum etc. are mentioned. Moreover, an extruder is used suitably at points, such as reactivity and the simplicity of manufacture.
When melt-kneading, the melt-kneading time (in the case of using an extruder, the residence time in the extruder) is the melt-kneading temperature, screw configuration, L / D (ratio of screw effective length L and screw diameter D). ), And may be appropriately determined according to the number of screw rotations and the like.

The reaction temperature can be appropriately set from the melting / reactivity of (A) and (B), but it is difficult to melt the resin at a low temperature, and the resin is expected to be decomposed by excessive heating. It is preferable to make it react between 100-300 degreeC. More preferably, it is 150-260 degreeC.
The reaction time is not particularly limited, but is preferably 2 minutes to 5 hours.

<< Thermoplastic elastomer composition >>
The thermoplastic elastomer composition of the present invention contains the (meth) acrylic block copolymer.
More specifically, the above (meth) acrylic block copolymer is blended with other polymers such as a crosslinked rubber and a thermoplastic resin, a lubricant, a filler, a stabilizer, a flexibility imparting agent, etc. It can be used as an elastomer composition.

Examples of the other polymer include styrene-butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), ethylene-propylene copolymer rubber (EPM), and ethylene-propylene-diene copolymer rubber (EPDM). , Acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber, butyl rubber (IIR), urethane rubber, silicone rubber, polysulfide rubber, hydrogenated nitrile rubber, fluororubber, tetrafluoroethylene-propylene rubber, tetrafluoroethylene- Examples include, but are not limited to, propylene-vinylidene fluoride rubber, acrylic rubber (ACM), chlorosulfonated polyethylene rubber, epichlorohydrin rubber (CO), ethylene-acrylic rubber, norbornene rubber, and the like. These may be used alone or in combination.

Examples of the lubricant include fatty acids such as stearic acid and palmitic acid; fatty acid metal salts such as calcium stearate, zinc stearate, magnesium stearate, potassium palmitate and sodium palmitate; polyethylene wax, polypropylene wax, and montanic acid wax Waxes; low molecular weight polyolefins such as low molecular weight polyethylene and low molecular weight polypropylene; polyorganosiloxanes such as dimethylpolysiloxane; amide-based lubricants such as octadecylamine, alkyl phosphate, fatty acid ester, ethylene bisstearyl amide, tetrafluoroethylene Examples thereof include fluororesin powder such as resin, molybdenum disulfide powder, silicone resin powder, silicone rubber powder, and silica. At least one of these can be used. Of these, stearic acid, zinc stearate, and calcium stearate, which are excellent in cost and processability, are preferable.

The filler is not particularly limited, but wood powder, pulp, cotton chips, asbestos, mica, walnut shell powder, rice husk powder, graphite, white clay, silica (fumed silica, precipitated silica, crystalline silica, fused silica) , Dolomite, silicic anhydride, hydrous silicic acid, etc.), reinforcing fillers such as carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic Filling materials such as bentonite, ferric oxide, bengara, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc powder, zinc carbonate and shirasu balloon; asbestos, glass fiber, glass filament, carbon fiber, Kevlar fiber, Examples thereof include fibrous fillers such as polyethylene fibers.

Examples of the stabilizer include compounds such as triphenyl phosphite, hindered phenol, and dibutyltin maleate, but are not limited thereto. These may be used alone or in combination.

Examples of the above-mentioned flexibility-imparting agent include plasticizers usually compounded in thermoplastic resins and rubbers; softeners such as process oils; oligomers; oils such as animal oils and vegetable oils; petroleum oils such as kerosene, light oil, heavy oil, and naphtha. Examples of the compound include, but are not limited to. These may be used alone or in combination.

The (meth) acrylic block copolymer of the present invention and the thermoplastic elastomer composition containing the same are provided with oil resistance, heat resistance, mechanical properties while maintaining the properties inherent to the (meth) acrylic block copolymer. Since the characteristics and the like are improved, it can be more suitably used as an automobile or an electric / electronic component.
Specifically, various oil seals such as oil seals and reciprocating oil seals; various packings such as gland packing, lip packing and squeeze packing; constant velocity joint boots, strut boots, rack & opinion boots, brake booster boots , Various boots such as boots for steering ball joints; various dust covers such as dust covers for suspension, dust covers for suspension and tie rods, dust covers for stabilizers and die rods; resin intake manifold gaskets, gaskets for throttle bodies, gaskets for power steering vane pumps , Head cover gaskets, water heater self-contained pump gaskets, filter gaskets, piping joints (ABS & HBB) gaskets, HDD top cover -Gaskets, HDD connector gaskets, cylinder head gaskets combined with metal, car cooler compressor gaskets, engine gaskets, AT separate plates, general-purpose gaskets (industrial sewing machines, nailing machines, etc.); needle valves, plans Various valves such as jar valves, water / gas valves, brake valves, drinking valves, safety valves for aluminum electrolytic capacitors; vacuum boosters, water / gas diaphragms, seal washers, bore plugs, high-precision stoppers, etc. Various stoppers mainly for cushioning performance; plug tube seal, injection pipe seal, oil receiver, brake drum seal, shading seal, plug seal, connector seal, keyless entry cover, etc. And the like.

The product may be any molding process such as extrusion molding, compression molding, blow molding, calendar molding, vacuum molding, foam molding, injection molding, powder slush molding, injection blow, etc., for the block copolymer or thermoplastic elastomer composition. It can be obtained by molding or the like by the method.

The (meth) acrylic block copolymer of the present invention and the thermoplastic elastomer composition containing the same are excellent in heat resistance, mechanical strength, moldability, and the like. The (meth) acrylic block copolymer and thermoplastic elastomer composition of the present invention can be selected from the monofunctional amine compound (B) as appropriate and reacted with the block copolymer (A) to provide heat resistance. Desired properties such as improvement of hardness, adjustment of hardness and elastic modulus can be performed, and it can be obtained by an easy and industrially advantageous method.

The present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
In the examples, BA, EA, MEA, MMA, and TBMA each represent n-butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, methyl methacrylate, and t-butyl methacrylate. Moreover, co means random copolymerization and b means block copolymerization.

Each physical property was measured and evaluated by the following methods.
(Molecular weight)
The molecular weight of the block copolymer was measured with a GPC analyzer (system: GPC system manufactured by Waters, column: Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK), and polystyrene as a mobile phase. The converted molecular weight was determined.

(Method of measuring conversion rate of polymerization reaction)
The conversion rate of the polymerization reaction was measured using the following analyzer and conditions.
Equipment used: Gas chromatography GC-14B manufactured by Shimadzu Corporation
Separation column: manufactured by J & W SCIENTIFIC INC, capillary column Supercoux-10, 0.35 mmφ × 30 m
Separation conditions: Initial temperature 60 ° C, hold for 3.5 minutes
Temperature increase rate 40 ° C / min
Final temperature 140 ° C, hold for 1.5 minutes
Injection temperature 250 ° C
Detector temperature 250 ° C
Sample preparation: The sample was diluted about 3 times with ethyl acetate, and butyl acetate was used as an internal standard.

(Acid anhydride conversion analysis)
The acid anhydride conversion reaction of the block copolymer was confirmed using an infrared spectrum (Shimadzu Corporation, FTIR-8100) and nuclear magnetic resonance (BRUKER AM400).

(Acid conversion analysis)
The carboxylic acid decomposition reaction of the block copolymer was confirmed using an infrared spectrum (Shimadzu Corporation, FTIR-8100) and nuclear magnetic resonance (BRUKER AM400).
As the solvent for nuclear magnetic resonance analysis, the block body having a carboxylic acid ester structure was analyzed using deuterated chloroform, and the carboxylic acid-containing block body was analyzed using deuterated methanol as a measuring solvent.

(hardness)
Hardness was measured in accordance with JIS K 6253 using a cylindrical molded body (diameter 30 mm, thickness 12 mm) as a test piece, and hardness at 23 ° C. and relative humidity 50 ± 5% (immediately after using JIS-A; type A durometer). The reading immediately after the contact of the pressing surface was measured.

(Mechanical strength)
The breaking strength (MPa) and the elastic modulus were measured by applying a method described in JIS K 7113, using an autograph AG-10TB type manufactured by Shimadzu Corporation at a test speed of 500 mm / min at 23 ° C. The measurement was performed at n = 3, and an average value of strength (MPa) and elongation (%) when the test piece broke was adopted. Note that the test piece is in the shape of 2 (1/3) and about 2 mm thick. As a general rule, the test piece is tested at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 5% for 48 hours. What was adjusted as described above was used.

(Compression set)
The compression set is based on JIS K 6301. A cylindrical molded body (diameter: 30 mm, thickness: 12 mm) is held at a predetermined temperature for 22 hours under the condition of a compression ratio of 25%, and left at room temperature for 30 minutes. The thickness of the molded body was measured at ± 2 ° C., and the residual strain was calculated. That is, it corresponds to the fact that all the distortion is recovered at a compression set of 0%, and the distortion is not recovered at all at a compression set of 100%.

(Production Example 1)
(MMA-co-methacrylic anhydride-co-methacrylic acid) -b-BA-b- (MMA-co-methacrylic anhydride-co-methacrylic acid) (monomer used; MMA / TBMA = 50/50 mol%) , BA / (MMA + TBMA) = 70/30 wt%) Synthesis of a block copolymer (hereinafter referred to as B5070) B5070 was performed as follows. After the inside of the polymerization vessel of the 5 L separable flask was purged with nitrogen, 11.3 g (78.5 mmol) of copper bromide was weighed and 180 mL of acetonitrile (nitrogen bubbling) 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 ligand pentamethyldiethylenetriamine was added to initiate polymerization.

About 0.2 mL of the polymerization solution was extracted from the polymerization solution for sampling at regular intervals from the start of polymerization, and the conversion rate of BA was determined by gas chromatogram analysis of the sampling solution. The polymerization rate was controlled by adding pentamethyldiethylenetriamine as needed.
When the conversion rate of BA was 95%, TBMA 351 ml (2.16 mol), MMA 232 ml (2.16 mol), copper chloride 7.77 g (78.5 mmol), pentamethyldiethylenetriamine 1.64 ml (7.85 mmol) ) And 1148 ml of toluene (nitrogen bubbled). Similarly, conversion rates of TBMA and MMA were determined.
When the conversion rate of TBMA was 70% and the conversion rate of MMA was 62%, 1500 ml of toluene was added, and the reactor was cooled in a water bath to complete 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 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. This solution was dried to remove the solvent and residual monomer, and a block copolymer was obtained.
When the GPC analysis of the obtained block copolymer was conducted, the number average molecular weight Mn was 108240, and molecular weight distribution Mw / Mn was 1.49.

Laboplast mill 50C150 (blade shape: roller type R60) in which 45 g of the obtained block copolymer and 0.09 g of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as an antioxidant were set to 240 ° C. , Manufactured by Toyo Seiki Co., Ltd.) at 100 rpm for 20 minutes to obtain a target acid anhydride group-containing block copolymer (the obtained polymer is hereinafter referred to as B5070).

The conversion of the t-butyl ester moiety into an acid anhydride group and a carboxyl group could be confirmed by IR (infrared absorption spectrum) and ¹³ C ( ¹ H) -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 ( ¹ H) -NMR, after conversion, the 82 ppm signal derived from the quaternary carbon of the t-butyl group and the 28 ppm signal derived from the methyl carbon disappeared, and a new 172 derived from the carbonyl carbon of the acid anhydride group. It was confirmed from the appearance of a signal of ˜173 ppm (m) and a signal of 176 to 179 ppm (m) derived from the carbonyl carbon of the carboxyl group.
The monomer having an acid anhydride group and the monomer having a carboxyl group were 24% by weight and 21% by weight, respectively, in the methacrylic polymer block of the obtained block copolymer. Each content was calculated from the integrated value of the signal in ¹³ C ( ¹ H) -NMR analysis.

(Production Example 2)
(MMA-co-methacrylic anhydride-co-methacrylic acid) -b- (BA-co-EA-co-MEA) -b- (MMA-co-methacrylic anhydride-co-methacrylic acid) (used Monomer: Synthesis of MMA / TBMA = 20/80 mol%, (BA + EA + MEA) / (MMA + TBMA) = 60/40 wt%) type block copolymer (hereinafter referred to as A2060) After nitrogen substitution, 500 L reaction evacuated in vacuo A solution in which 7686 g of acetonitrile and 10728 g of BA had been mixed in advance was charged into the machine in a state where the pressure in the reactor was reduced. Next, 741 g of cuprous bromide was charged, the temperature was raised to 68 ° C., and the mixture was stirred for 30 minutes. Thereafter, a mixed solution of 372 g of diethyl 2,5-dibromoadipate, BA 6877 g, EA17288 g, MEA 10725 g, and 864 g of butyl acetate was added, and the mixture was further stirred for 30 minutes while the temperature was raised to 75 ° C. By adding 90 g of pentamethyldiethylenetriamine, copolymerization of BA / EA / MEA to be the first block was started. The polymerization rate was controlled by adding pentamethyldiethylenetriamine as needed.
When the conversion rate of BA reached 95%, 105436 g of toluene, 511 g of cuprous chloride, 33333 g of MMA, and 11835 g of TBMA were charged, 90 g of pentamethyldiethylenetriamine was added, and copolymerization of MMA / TBMA serving as the second block was started. When the conversion rate of MMA reached 58%, 60620 g of toluene was added to dilute the reaction solution, and the reactor was cooled to stop the polymerization.
When the GPC analysis of the obtained block copolymer was conducted, the number average molecular weight Mn was 103400, and molecular weight distribution Mw / Mn was 1.36.

Toluene was added to the obtained block copolymer solution to adjust the polymer concentration to 24 wt%, and 847 g of p-toluenesulfonic acid was added, the inside of the reactor was purged with nitrogen, and the mixture was stirred at room temperature for 3 hours. . The reaction solution was sampled and neutralized to confirm that the solution was colorless and transparent, and the reaction was stopped. Thereafter, the solution was dispensed, and solid-liquid separation was performed to remove the solid content. To this block copolymer solution, 940 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) as an adsorbent was added, the inside of the reactor was purged with nitrogen, and the mixture was stirred at room temperature for 2 hours. The reaction solution was sampled, and the reaction was stopped after confirming that the solution was neutral. Thereafter, the solution was discharged, and solid-liquid separation was performed to remove the adsorbent. The polymer solution was supplied to a horizontal evaporator with a vent port (manufactured by Kurimoto Iron Works Co., Ltd., horizontal evaporator SCP-100), and the solvent and unreacted monomer were evaporated to isolate the polymer. The temperature of the trunk jacket and screw of the evaporator was adjusted to 180 ° C. with a heating medium, and the inside of the evaporator was kept at a reduced pressure of about 0.01 MPa or less by a vacuum pump. In this way, pellets of the title block copolymer were produced.

0.3 parts by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as an antioxidant is blended with 100 parts by weight of the obtained polymer, and a twin screw extruder with a vent (44 mm, L /D=42.25) (manufactured by Nippon Steel Co., Ltd.) and extrusion kneading at a rotation speed of 300 rpm and a set temperature of 240 ° C. to obtain the target acid anhydride group-containing block copolymer. At this time, an underwater cut pelletizer (CLS-6-8.1 COMPACT LAB SYSTEM manufactured by GALA INDUSTRIES INC.) Is connected to the tip of the twin screw extruder, and Alfro H is used as an anti-adhesive agent in the circulating water of the underwater cut pelletizer. By adding -50ES (Nippon Yushi Co., Ltd.), spherical pellets without adhesion were obtained.

The conversion of the t-butyl ester moiety into an acid anhydride group and a carboxyl group could be confirmed by IR (infrared absorption spectrum) and ¹³ C ( ¹ H) -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 ( ¹ H) -NMR, after conversion, the 82 ppm signal derived from the quaternary carbon of the t-butyl group and the 28 ppm signal derived from the methyl carbon disappeared, and a new 172 derived from the carbonyl carbon of the acid anhydride group. It was confirmed from the appearance of a signal of ˜173 ppm (m) and a signal of 176 to 179 ppm (m) derived from the carbonyl carbon of the carboxyl group.
The monomer having an acid anhydride group and the monomer having a carboxyl group were 3% by weight and 17% by weight, respectively, in the methacrylic polymer block of the obtained block copolymer.

(Production Example 3)
(MMA-co-methacrylic anhydride-co-methacrylic acid) -b- (BA-co-EA-co-MEA) -b- (MMA-co-methacrylic anhydride-co-methacrylic acid) (used Monomer: Synthesis of MMA / TBMA = 50/50 mol%, (BA + EA + MEA) / (MMA + TBMA) = 60/40 wt%) type block copolymer (hereinafter referred to as A5060) 425 g of diethyl 2,5-dibromoadipate, 20120 g of BA Polymerization was carried out at a charging ratio of EA19757 g and MEA12258 g. When the conversion rate of BA reached 94%, 21518 g of MMA and 30559 g of TBMA were added. The reaction was terminated when the conversion rate of MMA reached 56%, and it was produced in the same manner as in Production Example 2 to produce the title block copolymer pellets.
When the GPC analysis of the obtained block copolymer before melt modification was conducted, the number average molecular weight Mn was 101200, and molecular weight distribution Mw / Mn was 1.28.

(Production Example 4)
(MMA-co-methacrylic anhydride-co-methacrylic acid) -b- (BA-co-EA-co-MEA) -b- (MMA-co-methacrylic anhydride-co-methacrylic acid) (used Monomer: Synthesis of MMA / TBMA = 50/50 mol%, (BA + EA + MEA) / (MMA + TBMA) = 61/39 wt%) type block copolymer (hereinafter referred to as A5061) Diethyl 2,5-dibromoadipate 634 g, BA 30180 g , EA29636g and MEA18386g were charged. When the conversion rate of BA reached 95%, 95970 g of toluene, 20629 g of MMA, and 29299 g of TBMA were added. The reaction was terminated when the MMA conversion rate reached 90%. Otherwise, the same production as in Production Example 2 was carried out to produce pellets of the title block copolymer.
When the GPC analysis of the obtained block copolymer was conducted, the number average molecular weight Mn was 104400, and molecular weight distribution Mw / Mn was 1.31.
Except for the above, an acid anhydride group-containing block copolymer pellet was obtained in the same manner as in Production Example 2.
The monomer having an acid anhydride group and the monomer having a carboxyl group were 22% by weight and 18% by weight, respectively, in the methacrylic polymer block of the obtained block copolymer.

(Production Example 5)
(MMA-co-methacrylic anhydride-co-methacrylic acid) -b- (BA-co-EA-co-MEA) -b- (MMA-co-methacrylic anhydride-co-methacrylic acid) (used Monomer: Synthesis of MMA / TBMA = 40/60 mol%, (BA + EA + MEA) / (MMA + TBMA) = 60/40 wt%) type block copolymer (hereinafter referred to as A6060) Diethyl 2,5-dibromoadipate 634 g, BA 30180 g , EA29636g and MEA18386g were charged. When the conversion rate of BA reached 95%, 1000096 g of toluene, 16680 g of MMA, and 35535 g of TBMA were added. The reaction was terminated when the MMA conversion rate reached 90%. Otherwise, the same production as in Production Example 2 was carried out to produce pellets of the title block copolymer.
When the GPC analysis of the obtained block copolymer was conducted, the number average molecular weight Mn was 102100, and molecular weight distribution Mw / Mn was 1.30.
Except for the above, an acid anhydride group-containing block copolymer pellet was obtained in the same manner as in Production Example 2.
The monomer having an acid anhydride group and the monomer having a carboxyl group were 31% by weight and 22% by weight, respectively, in the methacrylic polymer block of the obtained block copolymer.

(Example 1)
6 parts by weight of aniline are added to 100 parts by weight of the block copolymer (B5070) obtained in Production Example 1, and the lab plast mill (manufactured by Toyo Seiki Co., Ltd.) at a set temperature of 190 ° C. and a rotation speed of 100 rpm for 20 minutes. ) To obtain a massive composition.
The obtained composition was hot press molded at 220 ° C. to obtain a cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm. Using the obtained molded body, hardness and compression set were measured. Moreover, the composition obtained similarly was hot-press-molded and the sheet-like molded object of thickness 2mm was obtained. Mechanical strength was measured using the obtained sheet-like molded object. The results are shown in Table 1.

(Examples 2 to 8)
Samples were prepared in the same manner as in Example 1 except that the block copolymers and monofunctional amine compounds obtained in Production Examples 2 to 5 were used in the quantitative ratios shown in Table 1 and reacted at the mill temperatures shown in Table 1. Obtained. The results are shown in Table 1.

(Comparative Examples 1-5)
The block copolymers obtained in Production Examples 1 to 5 were melt-kneaded at 100 rpm for 10 minutes using a Laboplast mill (manufactured by Toyo Seiki Co., Ltd.) set at 220 ° C., and then hot press molded at 220 ° C. A cylindrical molded body having a diameter of 30 mm and a thickness of 12 mm was obtained. These molded bodies were measured for hardness and compression set. Moreover, it heat-molded similarly and obtained the sheet-like molded object of thickness 2mm, and measured the mechanical strength using this. The results are shown in Table 1.

As is clear from Table 1, the (meth) acrylic block copolymer and thermoplastic elastomer composition of the present invention maintain suitable heat resistance (compression set) by allowing various monofunctional amine compounds to act. Accordingly, the hardness and elastic modulus can be adjusted, and the property can be modified according to the purpose, which is useful.

The (meth) acrylic block copolymer of the present invention and the thermoplastic elastomer composition containing the same are excellent in heat resistance, mechanical strength, moldability, and the like. The (meth) acrylic block copolymer and thermoplastic elastomer composition of the present invention can be selected from the monofunctional amine compound (B) as appropriate and reacted with the block copolymer (A) to provide heat resistance. Desired properties such as improvement of hardness, adjustment of hardness and elastic modulus can be performed, and it can be obtained by an easy and industrially advantageous method.

Claims (8)

A methacrylic polymer block (a) and an acrylic polymer block (b), and the main chain of at least one of the methacrylic polymer block (a) and the acrylic polymer block (b) In general formula (1):

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and may be the same or different from each other. N represents an integer of 0 to 3, and m represents an integer of 0 or 1.)
A (meth) acryl obtained by reacting a block copolymer (A) having an acid anhydride group (c) and / or a carboxyl group (d) represented by the formula (1) with a monofunctional amine compound (B). Block copolymer. The block copolymer (A) is composed of 10 to 60% by weight of a methacrylic polymer block (a) and 90 to 40% by weight of an acrylic polymer block (b). (Meth) acrylic block copolymer. Acrylic polymer block (b) is copolymerized with at least one monomer selected from the group consisting of n-butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate, and these. 3. A (meth) acrylic block copolymer according to claim 1 or 2, comprising 50 to 0% by weight of an acrylic ester and / or other vinyl monomer other than those described above. The block copolymer (A) is represented by the general formula (ab) _r , general formula b- (ab) _r , general formula (ab) _r -a (wherein r is an integer of 1 or more) The (meth) acrylic block copolymer according to claim 1, which is at least one selected from the group consisting of block copolymers represented by the formula: The (meth) acrylic block copolymer according to any one of claims 1 to 4, wherein the block copolymer (A) is produced by atom transfer radical polymerization. The monofunctional amine compound (B) is at least one amine selected from methylamine, dimethylamine, ethylamine, diethylamine, butylamine, dibutylamine and aniline, according to any one of claims 1 to 5, The (meth) acrylic block copolymer described. A thermoplastic elastomer composition comprising the (meth) acrylic block copolymer according to any one of claims 1 to 6. The (meth) acrylic block copolymer according to any one of claims 1 to 6, wherein the reaction of the block copolymer (A) and the monofunctional amine compound (B) is carried out under melting conditions. Production method.