JP2002338625A - Block copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart curability to an acrylic block copolymer to thereby provide a block copolymer which gives a cured item excellent in the balance among physical properties. SOLUTION: This block copolymer is of an A-B-A type and comprises two methacrylic polymer blocks (A) each consisting mainly of methyl methacrylate units, the number of methyl methacrylate units in this polymer block being 10-3,000, and (B) an acrylic polymer block consisting mainly of acrylic ester units, the number of acrylic ester units in this polymer block being 10-5,000. In at least one of block A, at least one vinyl monomer unit having at least one hydrolyzable silyl group is incorporated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a block copolymer which has a curing property and can be used as a rubber, a thermoplastic resin or an impact modifier for a thermoplastic resin. More specifically, the present invention relates to a block copolymer containing a methacrylic polymer and an acrylic polymer, which has a specific structure and is excellent in physical properties including curing performance.

[0002]

2. Description of the Related Art Generally, a thermoplastic elastomer is a rubber component (soft segment) exhibiting entropy elasticity.
And a constrained component (hard segment) that flows at high temperatures but prevents plastic deformation at room temperature and provides a reinforcing effect to the rubber component
It has an alloy structure consisting of For example, in a styrene-based elastomer, a styrene block aggregates and functions as a hard segment, and a butadiene or isoprene-based block functions as a matrix and functions as a soft segment. Further, the olefin elastomer has an alloy structure in which rubber such as EPDM is dispersed in a resin such as PP.

[0003] In any case, since the hard segment flows at a high temperature, thermoplastic processing such as injection molding can be performed. However, the maximum usable temperature of the elastomer is limited by the flow start temperature of the hard segment. The maximum usable temperature is generally lower than that of the crosslinked rubber. Therefore, when sufficient performance cannot be obtained with a single thermoplastic elastomer having no chemical cross-linking, attempts have been made to improve the performance by cross-linking with an appropriate cross-linking system.

For example, in order to reduce the permanent elongation of a polyurethane elastomer molded article, a method is known in which a polyisocyanate-based crosslinking agent is added at the time of melting to cause allophanate crosslinking and burette crosslinking after molding (particularly). JP-B-58-46573). Also, by post-crosslinking a thermoplastic elastomer composed of an olefin copolymer, a silicon-based crosslinking agent, a crosslinking catalyst, and a hydrolyzable silane compound with moisture, an elastomer having rubber elasticity equivalent to a crosslinked rubber in a wide temperature range can be obtained. It is known that it can be obtained (Japanese Patent Application Laid-Open No. 11-236482).

On the other hand, it is known that an acrylic block copolymer having methyl methacrylate or the like in a hard segment and butyl acrylate or the like in a soft segment can be used as a thermoplastic elastomer. For example, Japanese Patent No. 2553134 discloses mechanical properties of an acrylic block copolymer having a methacryl block and an acrylic block produced by an iniferter method. The acrylic block has a feature of being excellent in weather resistance, heat resistance, durability and oil resistance.

[0006] Further, by appropriately selecting the components constituting the block body, an elastomer that is extremely flexible as compared with other thermoplastic elastomers such as a styrene-based block body can be obtained, and thus it is expected as a substitute material for a crosslinked rubber. However, in the acrylic block copolymer, the physical properties are controlled by introducing crosslinking points,
Means for improving performance have not been known yet, and its development has been strongly demanded.

[0007]

In a block copolymer containing a methacrylic polymer block and an acrylic polymer block, a monomer having a hydrolyzable silyl group is copolymerized with the methacrylic polymer block. The inventors of the present invention have found that polymerization can impart curing performance to the acrylic block copolymer and physical properties can be controlled, thereby completing the invention.

[0008]

That is, the present invention provides a methacrylic polymer block (A) comprising methyl methacrylate as a main component, wherein the methyl methacrylate monomer has a chain number of 10 to 3000. ) And an ABA type block copolymer comprising an acrylic polymer block (B) containing an acrylate ester as a main component and having a chain number of the acrylate monomer of 10 to 5000. And at least one of the blocks A has a general formula

[0009]

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(Wherein, R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
10 alkyl groups, R ² is a hydrogen atom or a carbon atom of 1 to 1
A monovalent hydrocarbon group selected from an alkyl group having 0, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and a represents an integer of 0 to 2). At least one hydrolyzable silyl group in the molecule.
The present invention relates to a block copolymer obtained by copolymerizing at least one vinyl monomer per block.

It is preferable that the block copolymer is a triblock copolymer.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The present invention includes a block copolymer having a novel primary structure which has not existed before.
More specifically, the content includes the following block copolymer.

(A) ABA type block containing a methacrylic polymer block containing methyl methacrylate as a main component and (B) an acrylic polymer block containing a acrylate ester as a main component A copolymer,
A block copolymer, characterized in that at least one of the blocks A is copolymerized with a vinyl monomer having at least one hydrolyzable silyl group bonded to a carbon atom in the molecule.

This block copolymer can be suitably used as an elastomer material having curing performance. Further, it can be suitably used for improving its physical property balance, for example, impact resistance, by mixing with a thermoplastic resin. Further, it can be suitably used alone or as a mixture with a thermoplastic resin as a compound material having an intermediate elastic modulus between the resin and the elastomer. Further, it can be suitably used alone or as a mixture with a thermoplastic resin as a film material. Further, it can be suitably used as a paint, an adhesive, and a pressure-sensitive adhesive. Further, when mixed with a material having a silyl group or a siloxane bond, for example, a filler or a silicone material, a composition having excellent physical properties can be obtained.

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

<Block Copolymer> In the case where it is difficult to precisely synthesize only the triblock copolymer or when there is a problem of cost, the block copolymer of the present invention may be used in other block copolymers. Although a polymer may be contained, a triblock copolymer is used as a main component from the viewpoint of physical properties.
Examples of the block copolymer other than the triblock copolymer include a diblock copolymer, a multiblock copolymer, and a branched (star) block copolymer. Examples of combinations include a mixture of a triblock copolymer and a diblock copolymer, a mixture of a triblock copolymer and a multiblock copolymer, or a copolymer of a triblock copolymer and a branched (star) block. It is preferably a mixture of polymers. In these cases, A is a methacrylic polymer block, B is an acrylic polymer block, the diblock copolymer is AB type, and the triblock copolymer is ABBA. Type or BAB type, and the multi-block copolymer is A- (BA) nB type, AB- (AB) n-A where n is an integer of 1 or more
And B- (AB) nAB type. Among these, the triblock copolymer is preferably of the ABA type, and the multiblock copolymer is preferably of the A- (BA) type.
It is preferably an nB type or an AB- (AB) nA type. The branched (star) block copolymer is a block copolymer having the linear block copolymer as a basic unit. The structure of such a block copolymer is properly used depending on the application.

The block copolymer of the present invention (hereinafter referred to as (a)
) Is not particularly limited, and may be determined from the molecular weights required for the blocks A and B, respectively. Illustrating the range of the number average molecular weight of (a),
For the purpose of improving the properties of thermoplastic elastomers and thermoplastic resins, for example, impact resistance, film materials, and the like, it is preferably 30,000 to 500,000, more preferably 40,000 to 400,000, and further preferably 50,000 to 300,000. It is. Further, when the purpose is to obtain a compound material having an intermediate elastic modulus between a resin and an elastomer, it is 10,000 to 50,000.
0 is preferable, and more preferably 30,000 to 40,000
0, more preferably 50,000 to 300,000
It is. In these cases, if the number average molecular weight is less than 10,000, the physical properties tend to deteriorate, and if the number average molecular weight exceeds 500,000, the processability tends to deteriorate. Is done. When used as a paint, an adhesive, a pressure-sensitive adhesive or the like, it is preferably from 3,000 to 500,000, more preferably from 4,000 to 400,000, and still more preferably from 5,000 to 300,000. Among them, liquid resin processing method, for example, when applying in liquid state,
When applying liquid rubber injection molding (LIM), 30
00 to 50,000 is preferable, and 4000 is more preferable.
~ 40000, more preferably 5000 ~ 30
000. In this case, if the number average molecular weight is smaller than 3000, the viscosity tends to be low, and if the number average molecular weight exceeds 500,000, the viscosity tends to be high. .

The weight average molecular weight (M) of the block copolymer measured by gel permeation chromatography
w) and the number average molecular weight (Mn) ratio (Mw / Mn) is not particularly limited, but is preferably 1.8 or less,
More preferably, it is 1.5 or less. When Mw / Mn exceeds 1.8, the uniformity of the block copolymer tends to decrease.

The composition ratio of the methacrylic polymer block (A) and the acrylic polymer block (B) constituting the block copolymer is not particularly limited, and the physical properties of the intended use and the workability required therefor And the molecular weights required for the blocks (A) and (B). Block (A) and Block (B)
When the range of the composition ratio is exemplified, when used as a thermoplastic elastomer having curing performance, the block (A)
3 to 90% by weight, block (B) 97 to 10% by weight
Is more preferable, (A) is 6 to 80% by weight, (B) is 94 to 20% by weight, and further preferably, (A) is 9 to 50% by weight, and (B) is 91 to 50% by weight. % By weight. When used as a thermoplastic elastomer having curing performance, the range of applicable composition is larger than that of a general thermoplastic elastomer because the block A has the curing performance. When the proportion of (A) is less than 3% by weight, the elastic modulus and the breaking strength tend to decrease, and when the proportion of (B) is less than 10% by weight, physical properties such as elongation at break and fluidity are poor. Tends to decrease. When mainly used in combination with a thermoplastic resin, the block (A) is 5 to 90% by weight and the block (B)
Is preferably 95 to 10% by weight, more preferably,
(A) is 10 to 80% by weight, (B) is 90 to 20% by weight.
More preferably, (A) is 20 to 50% by weight and (B) is 80 to 50% by weight. When the proportion of (A) is less than 5% by weight, the compatibility with the thermoplastic resin is reduced, which tends to cause poor appearance of the molded article and a decrease in weld physical properties, and the proportion of (B) is 10% by weight. %, The impact resistance of the thermoplastic resin composition tends to decrease. When used alone as a film material, the block (A) is preferably 10 to 90% by weight, the block (B) is preferably 90 to 10% by weight, and more preferably (A) is 20 to 85% by weight. (B) is 80 to 15% by weight, more preferably (A) is 40 to 80% by weight, and (B) is 60 to 20% by weight. When the proportion of (A) is less than 10% by weight, the elastic modulus and the breaking strength tend to decrease, and when the proportion of (B) is less than 10% by weight, physical properties such as elongation at break and fluidity are poor. Tends to decrease. When used as a paint, adhesive, adhesive or the like, the block (A) is preferably 5 to 95% by weight, the block (B) is preferably 95 to 5% by weight, and more preferably (A) is 10% by weight. To 90% by weight, (B) to 90 to 10% by weight, more preferably (A) to 20 to 80% by weight, and (B) to 80 to 20% by weight. When the proportion of (A) is less than 5% by weight, the viscosity tends to decrease,
If the proportion of (B) is less than 5% by weight, the viscosity tends to be high. Therefore, it is set in accordance with the required processing characteristics together with the molecular weight of the block copolymer.

The relationship between the glass transition temperature of the block (A) and the glass transition temperature of the block (B) constituting the block copolymer is represented by the following formula, where TgA is the glass transition temperature of the block (A) and TgB is that of the block (B). It is preferable to satisfy the following relationship. TgA> TgB

The above-mentioned glass transition temperature (Tg) of the polymer can be set by setting the weight ratio of the monomer of each polymer portion according to the following Fox equation. 1 / Tg = (W1 / Tg1) + (W2 / Tg2) +... + (W
m / Tgm)

.. + Wm = 1 [wherein Tg represents the glass transition temperature of the polymer portion, and Tg1, Tg2,
.., Tgm represents the glass transition temperature of each polymerizable monomer.
Further, W1, W2,..., Wm represent the weight ratio of each polymerizable monomer. ]

The glass transition temperature of each polymerizable monomer in the Fox formula is, for example, as described in Polymer Handbook Third Edit.
ion (Wiley-Interscience, 1989). The glass transition temperature can be measured by DSC (differential scanning calorimetry) or a dynamic viscoelastic tan δ peak. Is too small, the measured value may deviate from the calculation formula based on the Fox formula.

<Vinyl Monomer Having Hydrolyzable Silyl Group> The ABA block copolymer of the present invention contains two blocks (A) in one molecule. In at least one of the blocks, a vinyl monomer having at least one hydrolyzable silyl group bonded to a carbon atom in the molecule (hereinafter referred to as (C)) is copolymerized. Features.

The preferred range of the number of hydrolyzable silyl groups varies depending on the reactivity of the hydrolyzable silyl groups, the molecular weight and composition of each block of the block copolymer, and the like. When the preferred range of the number of (C) is exemplified, when emphasis is placed on overall curing performance and heat resistance after curing, the content is preferably 1.0 or more per molecule of the block copolymer, and more preferably. Is 2.0 or more. When importance is attached to the balance of physical properties of the composition with a thermoplastic resin or the like, it is preferably 0.1 or more, more preferably 0.2 or more, more preferably 0.5 or more per molecule of the block copolymer. That is all. The upper limit of the content number is not particularly defined, but can be set according to the obtained characteristics.
In the following description, when the content of (C) is numerically less than 1.0 per block copolymer molecule, a block copolymer having (C) at least 1.0 per block copolymer molecule is used. It is interpreted as a mixture of the union and the block copolymer having no (C).

Depending on the purpose, (C) is introduced into the block copolymer in the form of being protected with a suitable protecting group or in the form of a functional group which is a precursor of (C), and then is subjected to a known chemical reaction. Reactive functional groups can also be generated.

Two or more kinds of (C) can be used in combination. When two or more (C) are used in combination, (C) having different reactivity and reaction conditions can be properly used depending on the purpose. Depending on the purpose, only one kind or all kinds of (C) are introduced into the acrylic block in a form protected by an appropriate protecting group or in the form of a functional group which is a precursor, and then a known chemical compound is introduced. A reactive functional group can be generated by the reaction.

Examples of the hydrolyzable silyl group include groups represented by the general formula (1).

[0029]

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(Wherein, R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms)
10 alkyl groups, R ² is a hydrogen atom or a carbon atom of 1 to 1
A monovalent hydrocarbon group selected from an alkyl group having 0, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms, and a represents an integer of 0 to 2) Examples of a hydrolyzable silyl group Examples include a trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a tripropoxysilyl group, a triisopropoxysilyl group, a tributoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a dipropoxymethyl group. Dialkoxyalkylsilyl groups such as silyl group, dibutoxymethylsilyl group, dimethoxyethylsilyl group, diethoxyethylsilyl group, dipropoxyethylsilyl group, dibutoxyethylsilyl group, methoxydimethylsilyl group, ethoxydimethylsilyl group, propoxy Dimethylsilyl group, butoxydimethylsilyl group, meth Examples thereof include alkoxydialkylsilyl groups such as xydiethylsilyl group, ethoxydiethylsilyl group, propoxydiethylsilyl group, and butoxydiethylsilyl group. These are the desired hydrolyzability, reaction rate, availability,
It may be selected from cost and the like, and there is no particular limitation. Illustrating a design according to the desired reactivity below, when a high reaction rate is required, the alkoxy group bonded to the silicon atom is preferably a methoxy group or an ethoxy group, and is a methoxy group. Is more preferable. When a low reaction rate is required, the alkoxy group bonded to the silicon atom preferably has more than 2 carbon atoms, and more preferably has more than 3 carbon atoms. There is no particular limitation on the number of alkoxy groups bonded to the silyl group. When it is required that the density is not too high, a dialkoxyalkylsilyl group may be selected. When it is desired to extend the chain instead of crosslinking, an alkoxydialkylsilyl group may be selected.

As a method of introducing (C), a method of introducing (C) into a polymer block by a polymerization reaction is used. In this case, (C) is not particularly limited as long as it is a vinyl monomer having at least one hydrolyzable silyl group bonded to a carbon atom represented by the general formula (3) in the molecule. The monomers represented by (2) and (3) can be mentioned.

[0032]

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[0033]

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(Wherein R ¹ , R ² , and a are the same as above; R ³ is a hydrogen atom or a methyl group; R ⁴ is a hydrogen atom or a methyl group; n is an integer of 1 to 5). Examples thereof include esters of methacrylic acid with an alcohol having a hydrolyzable silyl group, and unsaturated compounds containing silicon.

Examples of the ester of methacrylic acid with an alcohol having a hydrolyzable silyl group include, for example, γ-
(Methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) triethoxysilane, γ- (methacryloyloxypropyl) tripropoxysilane, γ- (methacryloyloxypropyl) triisopropoxysilane, γ- (methacryloyloxypropyl) Tributoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, γ-
(Methacryloyloxypropyl) dimethoxymethylsilane, γ- (methacryloyloxypropyl) diethoxymethylsilane, γ- (methacryloyloxypropyl) dipropoxymethylsilane, γ- (methacryloyloxypropyl) diisopropoxymethylsilane, γ-
(Methacryloyloxypropyl) dibutoxymethylsilane and the like. The type of the hydrocarbon group connecting the methacryloyloxy group and the silyl group is not particularly limited, but a propyl group is exemplified here from the viewpoint of availability.

Examples of the silicon-containing unsaturated compound include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyldimethoxymethylsilane and vinyldiethoxymethyl. Silane, vinyldipropoxymethylsilane, vinyldiisopropoxymethylsilane, vinyldibutoxymethylsilane, vinyldimethoxyethylsilane, vinyldiethoxyethylsilane, vinyldipropoxyethylsilane, vinyldiisopropoxyethylsilane, vinyldibutoxyethyl Silane, vinylmethoxydimethylsilane, vinylethoxydimethylsilane, vinylpropoxydimethylsilane, vinylisopropoxydimethylsilane, vinylbutoxydimethylsilane It can be mentioned.

<Methacrylic polymer block (A)> The monomer constituting the block A is preferably a methyl methacrylate from the viewpoint of easily obtaining a block copolymer having desired physical properties, cost and availability. As a main component. Here, the term "main component" means that the component is contained in an amount of 50% by weight or more, preferably 75% by weight or more. That is, the block (A) is composed of 50-1 methyl methacrylate.
It is composed of 00% by weight, preferably 75 to 100% by weight, and 0 to 50% by weight, preferably 0 to 25% by weight of a vinyl monomer copolymerizable therewith. If the proportion of the methyl methacrylate is too small, the characteristics of methyl methacrylate, weather resistance, high glass transition point, and compatibility with those resins and rubbers when used in combination with resins and rubbers Tend to be impaired.

The number average molecular weight of the block (A) is 30 to 3,000 per block when represented by the degree of polymerization of the monomers constituting the block (A). The range of the number average molecular weight can be calculated by substituting the molecular weight and the number of chains of each monomer according to the following formula. The molecular weight of each monomer in this formula can be found, for example, in Polymer Handbook Third Edition
(Wiley-Interscience, 1989). Mn = (M0 * n0) + (M1 * n1) +... + (Mm *
nm)

(N0 + n1 +... + Nm) is 30 to
It takes a value of 3000. [Wherein, Mn represents the number average molecular weight of the block, and M0 represents the M
1,..., Mm represent the molecular weights of the other monomers.
Further, n0 is n1,..., Nm of methyl methacrylate.
Represents the number of chains of each of the other monomers. The molecular weight required for the block A may be determined based on the cohesion required for the block A and the time required for the polymerization. The cohesive force is said to depend on the interaction between molecules (in other words, polarity) and the degree of entanglement. As the molecular weight increases, the number of entanglement points increases and the cohesive force increases. That is, the molecular weight required for block A is determined by MA
When the molecular weight between the entanglement points of the polymer constituting the block A is McA and the range of MA is exemplified, when a cohesive force is required, preferably, MA> McA. This design is preferred when using the block copolymer as a thermoplastic elastomer and when modifying the impact resistance of a thermoplastic resin. If more cohesion is required, preferably MA> 2 * McA. This design is preferred when using the block copolymer as a rigid material. Conversely, when it is desired to achieve both a certain level of cohesive force and creep property, it is preferable that McA <MA <2 * McA. This design is preferred when the block copolymer is used as a modifier to relieve the internal stress of the thermoplastic resin. The molecular weight between entanglement points is described by Wu et al. In Polymer Engineering and Science (Polym. Eng. An
d Sci.), 1990, 30, 753). For example, assuming that block A is composed entirely of methyl methacrylate, the range of the number average molecular weight of block A when cohesion is required is as follows:
It is preferably 9200 or more. However, if the number average molecular weight is large, the polymerization time tends to be long, so it may be set according to the required productivity, but is preferably 200000 or less, more preferably 10,000
0 or less.

The vinyl monomer copolymerizable with methyl methacrylate constituting the component (A) includes, for example,
Methacrylates (excluding methyl methacrylate), acrylates, aromatic alkenyl compounds,
Examples thereof include vinyl cyanide compounds, conjugated diene compounds, halogen-containing unsaturated compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds, and maleimide compounds. These are used alone or in combination of two or more thereof. When these vinyl monomers are combined with a thermoplastic resin, preferred ones can be selected depending on the compatibility. Further, it is possible to select a preferable one for imparting a certain performance to the block copolymer. For example, for the purpose of improving the heat resistance of a block copolymer, a monomer having a higher glass transition point than a methacrylate polymer, such as isobornyl methacrylate or cyclohexyl methacrylate, is copolymerized. Is also good. Further, the polymer of methyl methacrylate is almost quantitatively depolymerized by thermal decomposition. In order to suppress the depolymerization, acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-methoxy acrylate are used. Ethyl, a mixture thereof, or styrene may be copolymerized. Acrylonitrile may be copolymerized for the purpose of further improving oil resistance. Further, in order to improve cohesion, monomers having different molecular weights or polarities between entangled points may be copolymerized.

Examples of the methacrylate (excluding methyl methacrylate) include, for example, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, T-butyl acrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate Methacrylic acid aliphatic hydrocarbon (e.g., alkyl) ester such as dodecyl methacrylate, stearyl methacrylate, methacrylic acid alicyclic hydrocarbon ester such as cyclohexyl methacrylate, isobornyl methacrylate, benzyl methacrylate What Aralkyl methacrylate, phenyl methacrylate, aromatic hydrocarbon esters of methacrylate such as toluyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-hydroxyethyl methacrylate ,
Esters of methacrylic acid such as 2-hydroxypropyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, and ethylene oxide adduct of methacrylic acid with a functional group-containing alcohol having O, N, etc., Trifluoromethylmethyl acrylate,
2-trifluoromethylethyl methacrylate, 2-perfluoroethylethyl methacrylate, 2-perfluoroethyl-2-perfluorobutylethyl methacrylate, 2-perfluoroethyl methacrylate, perfluoromethacrylate Methyl, diperfluoromethylmethyl methacrylate, 2-perfluoromethyl-2-perfluoroethylmethyl methacrylate, 2-perfluorohexylethyl methacrylate, methacrylic acid 2
-Fluoroalkyl methacrylates such as -perfluorodecylethyl and 2-perfluorohexadecylethyl methacrylate.

As the acrylate, for example,
Methyl acrylate, ethyl acrylate, acrylic acid-n
-Propyl, isopropyl acrylate, n-acrylate
Butyl, isobutyl acrylate, tert-acrylate
Acrylics such as butyl, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate Acid-aliphatic hydrocarbon (eg, alkyl) ester, cycloaliphatic acrylate such as cyclohexyl acrylate, isobornyl acrylate, aromatic acrylate hydrocarbon such as phenyl acrylate, toluyl acrylate, benzyl acrylate, etc. Aralkyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-acrylic acid
Esters of acrylic acid such as hydroxypropyl, glycidyl acrylate, 2-aminoethyl acrylate, and ethylene oxide adduct of acrylic acid with a functional group-containing alcohol having O, N, etc., trifluoromethylmethyl acrylate, acrylic acid 2 -Trifluoromethylethyl, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl acrylate-2-perfluorobutylethyl, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethyl acrylate Methyl, 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylethyl acrylate, etc. Etc. can be mentioned 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.

As the conjugated diene compound, for example,
Butadiene, isoprene and the like.

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

Examples of the unsaturated dicarboxylic acid compound include unsaturated dicarboxylic acid compounds such as maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, and the like. Can be given.

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

As the maleimide compound, for example,
Maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, and the like can be given.

As these vinyl monomers, those which are preferable for imparting a certain performance to the block copolymer can be selected. For example, for the purpose of improving the heat resistance of the block copolymer, a methacrylate having a higher glass transition point than a homopolymer of methyl methacrylate,
For example, isobornyl methacrylate or cyclohexyl methacrylate may be copolymerized. Also,
Methyl methacrylate polymer is decomposed almost quantitatively by thermal decomposition, but to suppress it, acrylates such as ethyl acrylate, butyl acrylate, 2-methoxyethyl acrylate, or a mixture thereof are used. Alternatively, styrene or the like may be copolymerized. Acrylonitrile may be copolymerized for the purpose of further improving oil resistance. Further, in order to improve cohesion, monomers having different molecular weights or polarities between entangled points may be copolymerized. When the block copolymer is combined with a thermoplastic resin, a rubber, a filler, or the like, a preferable one can be selected depending on the compatibility with the resin.

The glass transition temperature of the block (A) is preferably at least 25 ° C., more preferably at least 40 ° C., even more preferably at least 50 ° C. When the glass transition temperature is less than 25 ° C., the elastic modulus and the breaking strength may be insufficient when used as a thermoplastic elastomer, and when used in combination with a thermoplastic resin, the thermoplastic resin composition may have an insufficient resistance. Impact strength may not be sufficient.

The glass transition temperature (Tg) of the polymer can be set by setting the weight ratio of the monomer in each polymer portion according to the Fox formula. The glass transition temperature in the claims is defined as Polymer Handbook Third Edition as the glass transition temperature of each polymerized monomer.
(Wiley-Interscience, 1989).
It is assumed that the calculation is performed according to the x formula.

<Acrylic Polymer Block (B)> The monomer constituting the block (B) is obtained by converting an acrylate ester from the viewpoints of easily obtaining a composition having desired physical properties, cost and availability. Main component. That is, the block (B) contains 50 to 100% by weight of an acrylate ester,
It is preferably 75 to 100% by weight and 0 to 50% by weight, preferably 0 to 25% by weight of a vinyl monomer copolymerizable therewith.
% By weight. When the proportion of the acrylate is too small, the characteristics of the case where the acrylate is used, such as rubber elasticity, low-temperature properties, oil resistance, fluidity at the time of melting, and impact resistance when used in combination with a resin. Tend to be impaired.

The number average molecular weight of the block (B) is from 30 to 6000 per block when represented by the degree of polymerization of the monomer constituting the block (B). The range of the number average molecular weight can be calculated by substituting the molecular weight and the number of chains of each monomer according to the following formula. The molecular weight of each monomer in this formula can be found, for example, in Polymer Handbook Third Edition
(Wiley-Interscience, 1989). Mn = (M1 * n1) + (M2 * n2) +... + (Mm *
nm)

However, (n1 + n2 + n3 +... + Nm) takes a value of 30 to 6000. [Wherein, Mn represents the number average molecular weight of the block, M1 represents the acrylate ester,
M2 to Mm represent the molecular weight of the copolymerized acrylic ester and / or vinyl monomer. Also, n
1 to nm represent the number of chains of each monomer. The molecular weight required for the block B may be determined from the elastomer elasticity required for the block B and the time required for the polymerization. Elastomeric elasticity is closely related to the ease of movement of molecular chains (in other words, glass transition temperature) and its molecular weight, and elastomeric elasticity does not appear unless the molecular weight is above a certain level. That is, when the molecular weight required for the block B is MB and the range is exemplified, preferably MB> 3500, and more preferably MB> 5
000, more preferably MB> 10000, even more preferably MB> 20,000, and most preferably MB> 40000. This design is preferred when using the block copolymer as a thermoplastic elastomer. When used for modifying the impact resistance of a thermoplastic resin, the MB may be determined from the dispersion diameter of the resin in addition to the modification. However, if the number average molecular weight is large, the polymerization time tends to be long in living polymerization, so it may be set according to the required productivity, but is preferably 500000 or less, more preferably 30,000,000 or less.
0000 or less.

Examples of the acrylate constituting (B) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and t-butyl acrylate. Acrylic acid such as n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate Aliphatic hydrocarbon (e.g., alkyl) esters, cyclohexyl acrylate, alicyclic hydrocarbon esters such as isobornyl acrylate, phenyl acrylate, aromatic hydrocarbon esters such as toluyl acrylate,
Aralkyl acrylates such as benzyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, 2-aminoethyl acrylate, acrylic Esters of acrylic acid such as an ethylene oxide adduct of an acid with a functional group-containing alcohol having O, N, etc., trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoro acrylate Ethyl methyl acrylate 2-
Fluorinated alkyl acrylates such as perfluorohexylethyl, 2-perfluorodecylethyl acrylate and 2-perfluorohexadecylethyl acrylate can be mentioned. These are used alone or in combination of two or more thereof.

Among these, n-butyl acrylate and / or n-octyl acrylate are preferred in view of elastomer elasticity, cost, impact resistance of the composition when combined with a thermoplastic resin, and availability. Are preferred. When oil resistance is required, n-ethyl acrylate is preferred. Further, when it is desired to make the elastomer elasticity and the oil resistance compatible to some extent, the acrylic acid n-
It is preferable that it comprises at least one monomer selected from the group consisting of butyl and n-octyl acrylate and at least one monomer selected from the group consisting of n-methyl acrylate and n-ethyl acrylate. When low-temperature properties are required, 2-ethylhexyl acrylate is preferred. Furthermore, when it is desired to achieve both oil resistance and low-temperature characteristics, at least one monomer selected from the group consisting of n-butyl acrylate and n-octyl acrylate, and n-methyl acrylate and n-ethyl acrylate At least one monomer selected from the group consisting of
It is preferably composed of at least one monomer selected from the group consisting of methoxyethyl and 3-methoxybutyl acrylate, and among them, n-ethyl acrylate, n-butyl acrylate, and 2-methoxyethyl acrylate Combinations are more preferred.

Examples of the vinyl monomer copolymerizable with the acrylate ester constituting the block (B) include, for example, a methacrylate ester, an aromatic alkenyl compound, a vinyl cyanide compound, a conjugated diene compound, and a halogen-containing compound. Unsaturated compounds, unsaturated dicarboxylic acid compounds,
Examples thereof include vinyl ester compounds and maleimide compounds.

Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-methacrylate. -Butyl, methacrylic acid n-
Pentyl, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate,
Methacrylic acid aliphatic hydrocarbon (eg, alkyl) esters such as decyl methacrylate, dodecyl methacrylate, and stearyl methacrylate; cycloaliphatic methacrylic acid esters such as cyclohexyl methacrylate and isobornyl methacrylate; Aralkyl methacrylate such as benzyl methacrylate, aromatic hydrocarbon ester methacrylate such as phenyl methacrylate and toluyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, methacrylic Having methacrylic acid such as 2-hydroxyethyl acid, 2-hydroxypropyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, and ethylene oxide adduct of methacrylic acid, and O, N, etc. Esters of functional group-containing alcohol, methacrylic acid trifluoromethyl methyl, methacrylic acid 2-trifluoromethyl-ethyl, methacrylic acid 2-perfluoroethyl ethyl, methacrylic acid 2-
Perfluoroethyl-2-perfluorobutylethyl,
2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diperfluoromethylmethyl methacrylate, 2-perfluoromethyl-2-perfluoroethylmethyl methacrylate, 2-methacrylic acid
Fluorinated alkyl methacrylates such as methacrylates such as perfluorohexylethyl, 2-perfluorodecylethyl methacrylate, and 2-perfluorohexadecylethyl methacrylate;

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

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.

As the conjugated diene compound, for example,
Butadiene, isoprene and the like.

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

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

Examples of the vinyl ester compound include vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate.

As the maleimide compound, for example,
Maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, and the like can be given.

These may be used alone or in combination of two or more. These vinyl monomers are
It is possible to select and use preferred ones depending on physical properties required for the block (B), for example, glass transition temperature, elastic modulus, polarity, and oil resistance. For example, for the purpose of further improving the low-temperature properties of the block copolymer, a monomer that gives a polymer having a lower glass transition point than that of the acrylate copolymer may be copolymerized. Also,
Acrylonitrile may be copolymerized for the purpose of further improving oil resistance. When the block copolymer is combined with a thermoplastic resin, a rubber, a filler, or the like, a preferable one can be selected depending on the compatibility with the resin.

The glass transition temperature of the component (B) is preferably 25 ° C. or lower, more preferably 0 ° C. or lower.
More preferably, it is -20 ° C or lower. When the glass transition temperature is higher than 25 ° C., when used as a thermoplastic elastomer, physical properties such as low-temperature properties and rebound resilience, and when combined with a thermoplastic resin, the impact resistance of the thermoplastic resin composition becomes insufficient. There are cases.

The glass transition temperature (Tg) of the polymer can be set by setting the weight ratio of the monomer in each polymer portion according to the Fox formula. The glass transition temperature in the claims is defined as Polymer Handbook Third Edition as the glass transition temperature of each polymerized monomer.
(Wiley-Interscience, 1989).
It is assumed that the calculation is performed according to the x formula.

<Method for Producing Block Copolymer (a)> The method for producing the block copolymer of the present invention is not particularly limited, but it is preferable to use controlled polymerization using a polymer initiator. Examples of the controlled polymerization include living anion polymerization, radical polymerization using a chain transfer agent, and recently developed living radical polymerization. Living radical polymerization is preferred in terms of controlling the molecular weight and structure of the block copolymer.

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

Examples thereof include those using a chain transfer agent such as polysulfide, and cobalt porphyrin complexes (Journal of American Chemical Society (J. Am. Che.
m. Soc.), 1994, 116, 7943) and those using a radical scavenger such as a nitroxide compound (Macromolecules, 1994, 27, 7).
228), Atom transfer radical polymerization (Atom Transfe
r Radical Polymerization (ATRP). In the present invention, which method is used is not particularly limited, but atom transfer radical polymerization is preferred from the viewpoint of easy control.

The atom transfer radical polymerization is carried out by polymerization using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a central metal of Group 8, 9, 10, or 11 of the periodic table as a catalyst. You. For example,
Matyjaszewski 8 et al., Journal of American Chemical Society (J. Am. Chem.
Soc.), 1995, 117, 5614, Macromolecules (Macrom
olecules), 1995,28,7901, Science, 199
6,272,866 or Sawamoto et al., Macromolecules, 1995,28,1721.

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

In the atom transfer radical polymerization method, as an organic halide or a sulfonyl halide compound used as an initiator, a monofunctional, difunctional or polyfunctional compound can be used. These may be properly used depending on the purpose, but when a diblock copolymer is produced, a monofunctional compound is preferable from the viewpoint of availability of an initiator, and an ABA triblock is preferred. When producing a copolymer or a BAB type triblock copolymer, it is preferable to use a bifunctional compound from the viewpoint of reducing the number of reaction steps and time, and producing a branched block copolymer. In this case, it is preferable to use a polyfunctional compound from the viewpoint of reducing the number of reaction steps and time. It is also possible to use a polymer initiator as the initiator. The polymer initiator is a compound formed of a polymer having a halogen atom bonded to a molecular chain terminal among organic halides or sulfonyl halide compounds. Such a polymeric initiator,
Since it can be produced by a controlled polymerization method other than the living radical polymerization method, it is characterized in that a block copolymer in which polymers obtained by different polymerization methods are combined can be obtained.

As the monofunctional compound, for example, C ₆ H ₅ —CH ₂ X, C ₆ H ₅ —C (H) (X) —CH ₃ , C ₆ H ₅ —C (X) (CH ₃ ) ₂ , R ¹ -C (H) (X) -COOR ² , R ¹ -C (CH ₃ ) (X) -COOR ² , R ¹ -C (H) (X) -CO-R ² , R ^1- _{C (CH 3) (X)} -CO-R 2, R 1 -C 6 H 4 -SO 2 X, ( wherein, C ₆ H ₅ is a phenyl group, C ₆ H ₄ is a phenylene group (ortho-substituted, meta Substitution or para substitution)
Represents R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms.
-20 aralkyl groups. X represents chlorine, bromine, or iodine. R ² represents a monovalent organic group having 1 to 20 carbon atoms. And the like.

Specific examples of the alkyl group having 1 to 20 carbon atoms (including an alicyclic hydrocarbon group) as R ¹ 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 , An isobornyl group, an aryl group having 6 to 20 carbon atoms, for example, phenyl group, triyl group, naphthyl group, and an aralkyl group having 7 to 20 carbon atoms, for example, benzyl group, phenethyl group, etc. can give.

Specific examples of the monofunctional compound include, for example, tosyl bromide, methyl 2-bromopropionate, ethyl 2-bromopropionate, butyl 2-bromopropionate,
-Methyl bromide isobutyrate, 2-ethyl bromide isobutyrate, 2-
And butyl isobutyrate. Among them, ethyl 2-bromopropionate and butyl 2-bromopropionate are preferred because they are similar to the structure of the acrylate monomer, so that the polymerization can be easily controlled.

Examples of the bifunctional compound include X-CH ₂ -C ₆ H ₄ -CH ₂ -X, X-CH (CH ₃ ) -C ₆ H ₄ -CH (CH ₃ ) -X, X- _{C (CH 3) 2 -C 6} H 4 -C (CH 3) 2 -X, X-CH (COOR 3) - (CH 2) n -CH (COO
^{R 3) -X, X-C} (CH 3) (COOR 3) - (CH 2) n -C (CH
₃ ) (COOR ³ ) -X, X-CH (COR ³ )-(CH ₂ ) _n -CH (COR ³ )-
_{X, X-C (CH 3} ) (COR 3) - (CH 2) n -C (C
^{_{H 3) (COR 3) -X}} , X-CH 2 -CO-CH 2 -X, X-CH (CH 3) -CO-CH (CH 3) -X, X-C (CH 3) 2 -CO _{-C (CH 3) 2 -X,} X-CH (C 6 H 5) -CO-CH (C 6 H 5) -X, X-CH 2 -COO- (CH 2) n -OCO-CH 2 - _{X, X-CH (CH 3} ) -COO- (CH 2) n -OCO-C
_{H (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, ( wherein, R ³ is an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms
Represents an -20 aryl group or an aralkyl group having 7-20 carbon atoms. n represents an integer of 0 to 20. C ₆ H ₅ , C ₆
H ₄ and X are the same as those described above).

R ³ is an alkyl group having 1 to 20 carbon atoms,
Specific examples of the aryl group having 6 to 20 carbon atoms and the aralkyl group having 7 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms as R ¹ , an aryl group having 6 to 20 carbon atoms, and an aryl group having 7 to 20 carbon atoms. The description is omitted because it is the same as the specific example of the aralkyl group.

Specific examples of the bifunctional compound include bis (bromomethyl) benzene, bis (1-bromoethyl) benzene, bis (1-bromoisopropyl) benzene, dimethyl 2,3-dibromosuccinate, and a diethyl-substituted product thereof. And dibutyl-substituted product, dimethyl 2,4-dibromoglutarate, its diethyl-substituted product and dibutyl-substituted product, dimethyl 2,5-dibromoadipate, its diethyl-substituted product and dibutyl-substituted product, dimethyl 2,6-dibromopimelate, Examples thereof include diethyl-substituted and dibutyl-substituted products, dimethyl 2,7-dibromosuberate, and diethyl-substituted and dibutyl-substituted products thereof.
Of these, bis (bromomethyl) benzene, 2,
Diethyl 5-dibromoadipate and diethyl 2,6-dibromopimelate are preferred from the viewpoint of availability of raw materials.

Examples of the polyfunctional compound include C ₆ H ₃ — (CH ₂ —X) ₃ , C ₆ H ₃ — (CH (CH ₃ ) —X) ₃ and C ₆ H ₃ — (C (CH _{3) 2 -X) 3, C} 6 H 3 - (OCO-CH 2 -X) 3, C 6 H 3 - (OCO-CH (CH 3) -X) 3, C 6 H 3 - (OCO-C (CH ₃ ) ₂ -X) ₃ , C ₆ H _3- (SO ₂ -X) ₃ , wherein C ₆ H ₃ is a trivalent phenyl group (the positions of the three bonds are 1 to 6 May be any combination),
X is the same as described above).

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

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

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

The transition metal complex used as the catalyst for the atom transfer radical polymerization is not particularly limited, but preferred are monovalent and zero-valent copper, divalent ruthenium, divalent iron and divalent nickel. Complexes. Among these, copper complexes are preferred from the viewpoint of cost and reaction control. As the monovalent copper compound, for example,
Examples include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. Among them, cuprous chloride and cuprous bromide are preferred from the viewpoint of controlling the polymerization. When a monovalent copper compound is used, 2,2'-bipyridyl or a derivative thereof (for example, 4,4'-dinolyl-2,2'-bipyridyl, 4,4'-di (5- 2,2'-bipyridyl-based compounds such as noryl) -2,2'-bipyridyl,
0-phenanthroline, a derivative thereof (eg, 4,7-
1,1 such as dinolyl-1,10-phenanthroline, 5,6-dinolyl-1,10-phenanthroline, etc.
A polyamine such as a 0-phenanthroline-based compound, tetramethyldiethylenetriamine (TMEDA), pentamethyldiethylenetriamine, or hexamethyl (2-aminoethyl) amine may be added as a ligand.
Further, a tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also preferable as the catalyst. When using a ruthenium compound as a catalyst,
Aluminum alkoxides may be added as an activator. Further, a bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ ) ₂ ) and a bis (triphenylphosphine) complex of divalent nickel (NiCl ₂ (PP
h ₃ ) ₂ ) and bistributylphosphine complex of divalent nickel (NiBr ₂ (PBu ₃ ) ₂ ) are also preferred as the catalyst.

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

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

The atom transfer radical polymerization can be carried out without solvent (bulk polymerization) or in various solvents. In addition, in bulk polymerization and polymerization performed in various solvents, the polymerization can be stopped halfway.

Examples of the solvent include a hydrocarbon solvent, an ether solvent, a halogenated hydrocarbon solvent, a ketone solvent, an alcohol solvent, a nitrile solvent, an ester solvent, and a carbonate solvent. it can. Examples of the hydrocarbon solvent include benzene and toluene. Examples of the ether solvent include diethyl ether and tetrahydrofuran. Examples of the halogenated hydrocarbon solvent include methylene chloride and chloroform. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol and the like. Examples of the nitrile solvent include acetonitrile, propionitrile, benzonitrile and the like. Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the carbonate-based solvent include ethylene carbonate and propylene carbonate. These may be used alone or in combination of two or more.

When a solvent is used, the amount used depends on the viscosity of the entire system and the required stirring efficiency (ie, the reaction rate).
May be appropriately determined from the relationship. In addition, in the case of bulk polymerization, in which polymerization is stopped in the course of polymerization in various solvents, the conversion of the monomer at the point of stopping the reaction is determined by the viscosity of the entire system and the required stirring efficiency (ie, ,
(Reaction rate).

The above-mentioned polymerization can be carried out at room temperature to 200 ° C., preferably at 50 to 150 ° C.

In order to produce a block copolymer by the above polymerization, a method of sequentially adding monomers, a method of polymerizing the next block using a polymer synthesized in advance as a polymer initiator, and a method of separately polymerizing Examples of the method include a method in which the unions are bonded by a reaction. These methods may be used arbitrarily and may be properly used depending on the purpose.However, from the viewpoint of the simplicity of the production process, a method by successive addition of monomers is preferable, and the monomers of the previous block remain. When it is desired to avoid copolymerization to the next block, a method of polymerizing the next block using a polymer synthesized in advance as a polymer initiator is preferable. Hereinafter, in the case of successive addition of monomers, a case where the next block is polymerized using a polymer synthesized in advance as a polymer initiator will be described in detail, but the method for producing the block copolymer of the present invention is limited. Not at all.

In the case of successive addition of monomers, it is desirable to charge the monomer to be polymerized next when the conversion of the monomer previously charged for polymerization is 80 to 95%. Until the conversion exceeds 95% (for example, 96 to 10)
When the polymerization is advanced (up to 0%), the growth reaction of the polymer chains is stochastically suppressed. In addition, since the polymer radicals easily react with each other, disproportionation, coupling,
Side reactions such as chain transfer tend to occur easily.
When a monomer to be subsequently polymerized is charged at a time when the conversion is less than 80% (for example, at a time when the conversion is 79% or less),
There is a case where a problem arises in that a monomer charged for polymerization first is mixed with a monomer to be polymerized next and copolymerized. In this case, as the order of addition of the monomers, a method of first charging and polymerizing an acrylic monomer and then charging and polymerizing a methacrylic monomer (x
1) and a method (y1) in which a methacrylic monomer is charged and polymerized first, and then an acrylic monomer is charged and polymerized, is considered. First, an acrylic monomer is charged and polymerized. After that, the method (x1) in which a methacrylic monomer is charged and polymerized is preferred from the viewpoint of controlling the polymerization. This is because it is preferable to grow the methacrylic polymer block from the terminal of the acrylic polymer block.

As a method of polymerizing the next block using a polymer synthesized in advance as a polymer initiator, for example, at a desired point in time of polymerization of the first block, the temperature is temporarily lowered in a 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 then the monomer of the second block is added. When it is desired to polymerize the third and subsequent blocks, the same operation as in the case of the second block may be performed. According to this method, it is possible to avoid copolymerization of the remaining monomer of the previous block during the polymerization of the second and subsequent blocks. Also,
In this case, as the order of polymerization of the blocks, a method of first polymerizing an acrylic block and then polymerizing a methacrylic block (x2), and a method of first polymerizing a methacrylic block and then polymerizing an acrylic block. Although the method (y2) can be considered, a method (x2) of first polymerizing the acrylic block and then polymerizing the methacrylic block is preferable from the viewpoint of controlling the polymerization.
This is because it is preferable to grow the methacrylic polymer block from the terminal of the acrylic polymer block.

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

<Blending agent (b)> Various blending agents (b) can be added to the block copolymer of the present invention in order to improve the physical properties according to the desired physical properties. For example, a reinforcing effect and a reduction in cost can be achieved by adding a filler. Hardness and modulus can be improved by blending a thermoplastic resin. By blending a plasticizer or unvulcanized rubber, hardness and modulus can be reduced. Further, in order to adjust the physical property balance, a plurality of compounding agents can be compounded.

The block copolymer (a) and the compounding agent (b)
Is not particularly limited. Preferably, 99.9 to 10% by weight of the block copolymer (a) and 0.1 to 90% by weight of the compounding agent (b), more preferably 99.9 to 50% by weight of (a) and (b) Is 0.1 to 50% by weight, more preferably (A) is 99.9 to 70% by weight and (b) is 0.1 to 30% by weight. As the blending amount of the block copolymer (a) increases, the improvement effects such as oil resistance, compression set and stability tend to increase, and as the blending amount of the blending agent (b) decreases, the blending agent (b) decreases. ) Tends to be difficult to produce, and their composition can be determined according to the purpose.

The compounding agent (b) is not particularly limited, but includes, for example, thermoplastic resin, rubber, thermoplastic elastomer, composite rubber particles, stabilizer, plasticizer, lubricant, flame retardant, pigment, filler and the like. can do.

Examples of the thermoplastic resin include polyvinyl chloride resin, polyethylene resin, polypropylene resin, cyclic olefin copolymer resin, polymethyl methacrylate resin; aromatic alkenyl compound, vinyl cyanide compound and (meth) acrylate. At least one vinyl monomer selected from the group consisting of
0 to 30% by weight of other vinyl monomers (eg, ethylene, propylene, vinyl acetate) and / or diene monomers (eg, butadiene, isoprene) copolymerizable with these vinyl monomers. Homopolymer or copolymer obtained by polymerizing the following: polystyrene resin, polyphenylene ether resin, mixture of polystyrene resin and polyphenylene ether resin, polycarbonate resin, polyester resin, mixture of polycarbonate resin and polyester resin, polyamide resin, polyacetal resin And polyphenylene sulfide resin, polysulfone resin, polyimide resin, polyetherimide resin, polyetherketone resin, polyetheretherketone resin, polyamideimide resin and polyarylate resin. These can be used alone or in combination of two or more. In the present invention, the thermoplastic resin is not limited to these, and various thermoplastic resins can be widely used. Among the thermoplastic resins,
Excellent compatibility with the block copolymer used in the present invention,
It is at least one of polyvinyl chloride resin, polymethyl methacrylate resin, acrylonitrile-styrene copolymer resin, methyl methacrylate-styrene copolymer resin, polycarbonate resin, polyester resin, and polyamide resin because it is easy to obtain high impact resistance. Is preferred. The blending amount of the block copolymer and the thermoplastic resin used in the present invention is not particularly limited, but the block copolymer is 0.5 to 70% by weight and the thermoplastic resin is 99.5 to 30% by weight. Preferably, the block copolymer is 0.5 to 50% by weight and the thermoplastic resin is 99.5 to
More preferably, the content of the block copolymer is 0.5% by weight.
Most preferably, the content of the thermoplastic resin is 99.5 to 70% by weight. When the blending amount of the block copolymer is 0.5
% Or less, the effect of improving impact resistance tends to be low, and if it is 70% by weight or more, characteristics of the thermoplastic resin tend to be hardly exhibited.

The rubber is at least one kind of rubber selected from the group consisting of acrylic polymer rubber, olefin polymer rubber, diene polymer rubber, natural rubber, silicone rubber, and fluoro rubber. These rubbers can be used alone or in combination of two or more. As the acrylic polymer rubber, a rubber obtained by polymerizing a monomer containing an acrylate ester as a main component, or a conventionally known acrylic rubber can be used without any particular limitation. As the acrylic rubber, a monomer composed of ethyl acrylate and / or butyl acrylate,
Examples thereof include acrylic rubber obtained by copolymerizing a small amount of one or more of other monomers such as 2-chloroethyl vinyl ether, methyl vinyl ketone, acrylic acid, acrylonitrile, and butadiene. Examples of the olefin polymer rubber include butyl rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, isobutylene polymer rubber, and ethylene-vinyl acetate copolymer rubber. Examples of the diene polymer rubber include isoprene rubber, butadiene rubber, 1,2-polybutadiene, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, and acrylonitrile-butadiene rubber.
As the silicone rubber, MQ whose side chains are all methyl groups,
VMQ in which a part of a methyl group is replaced by a vinyl group, PMQ in which a part of a methyl group is replaced by a phenyl group, PVMQ in which a part of a methyl group is replaced by a vinyl group and a phenyl group, and an alkyl fluoride group FVMQ with the introduction of
Examples thereof include polyorganosiloxane-based rubbers, liquid silicone rubbers having an effective performance, and modified silicone rubbers in which a polyorganosiloxane chain and an organic segment are bonded. Among them, when oil resistance is required for the composition, it is preferable to select acrylic rubber, chloroprene rubber or nitrile rubber. By using an acrylic rubber as the rubber, a composition having more excellent oil resistance can be obtained. When importance is placed on the reactivity of the silyl group, it is preferable to select silicone rubber. In this case, the silicone rubber preferably has a site that reacts with the silyl group of the block. In these cases, the rubber can be a non-crosslinked rubber or a crosslinked rubber. The crosslinked rubber can be a rubber that has been dynamically crosslinked during melt mixing with the thermoplastic composition or a rubber that has been previously crosslinked before mixing with the thermoplastic composition.

Examples of the thermoplastic elastomer include, for example, an acryl-methacryl block copolymer disclosed in JP-A-2000-154329,
Isobutylene-methacrylic block copolymer disclosed in JP-A-154330, JP-A-2000-15432
No. 8 discloses a silicone-methacrylic block copolymer, a styrene-butadiene-styrene block copolymer (SBS), a styrene-isoprene-styrene block copolymer (SIS), and a styrene-ethylenebutylene-styrene block copolymer. Styrene-based block copolymers such as polymer (SEBS), styrene-ethylene propylene-styrene block copolymer (SIPS) and styrene-isobutylene-styrene block copolymer;
Olefin-based thermoplastic elastomers (TPO, TP
V), vinyl chloride thermoplastic elastomer (TPV
C), amide-based thermoplastic elastomers, ester-based thermoplastic elastomers, urethane-based thermoplastic elastomers, and the like. Among them, when oil resistance is required for the composition, it is preferable to select an acryl-methacryl block copolymer. When importance is placed on the reactivity of the silyl group, it is preferable to select a silicone-methacrylic block copolymer.

As the composite rubber particles, for example, a methyl methacrylate-butadiene-styrene copolymer (MB
S resin), acrylic graft copolymer, acrylic-silicone composite rubber-based graft copolymer, isobutylene-based graft copolymer, isobutylene-acrylic composite rubber-based graft copolymer, isobutylene-silicone composite rubber-based graft copolymer And so on. MBS
As the resin, Kane Ace B series and Kane Ace M series (all manufactured by Kaneka Chemical Industry Co., Ltd.), and as the acrylic graft copolymer, Kane Ace FM series (manufactured by Kaneka Chemical Industry Co., Ltd.), acrylic-silicone composite Examples of the rubber-based graft copolymer include Metablen S-
2001 (manufactured by Mitsubishi Rayon Co., Ltd.) and the like are available as industrial products. Further, polyisobutylene-acryl composite rubber-based graft copolymer is disclosed in JP-A-9-3021.
It can be produced by the method described in JP-A-69.

As the pigment, for example, titanium oxide, zinc sulfide, zinc oxide and the like can be mentioned.

Examples of the filler include silica, talc, mica, glass fiber, glass beads, hollow glass beads, glass flakes, neutral clays, carbon fibers, aromatic polyamide fibers, aromatic polyester fibers, vinylon fibers, and carbonized fibers. , Silicon carbide fiber, alumina fiber, potassium titanate fiber, metal fiber, carbon black, calcium carbonate, magnesium hydroxide, barium sulfate, asbestos,
And wollastonite. These may be used alone or in combination of two or more.

Examples of the stabilizer include antioxidants such as 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,
3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2-thiobis (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,
Phenol compounds such as 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and thioether compounds, or tetrakis (2,4-di-t
-Butylphenyl) -4,4'-biphenylenephosphonite, tris (2,4-di-t-butylphenyl)
Phosphorite and other phosphorus-based compounds, and the like, and as a light stabilizer, dimethyl-1- (2- (2-succinate)
(Hydroxyethyl) -4-hydroxy-2,2,6,6
-Tetramethylpiperidine polycondensate, poly [[6-
(1,1,3,3-tetramethylbutyl) imino-1,
3,5-triazine-2,4-diyl] [(2,2,2
6,6-tetramethyl-4-piperidyl) imino] hexamethylene [2,2,6,6-tetramethylpiperidyl) imino]], 2- (3,5-di-t-butyl-4-)
Hindered amine compounds such as bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-n-butylmalonate, etc., and these may be used alone or in combination of two or more. Can be

Examples of the plasticizer include paraffinic process oil, naphthenic process oil, aromatic process oil, light oil, spindle oil, machine oil, linseed oil, sesame oil, castor oil, camellia oil, liquid polybutene,
Examples include liquid polyisoprene, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, tricresyl phosphate, and the like.

Examples of the lubricant include polyethylene wax, polypropylene wax, montanic acid wax and the like.

Examples of the flame retardant include tetrabromobisphenol A, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate,
Halogenated flame retardants such as 2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, decabromodiphenyl oxide, brominated polyphosphate, chlorinated polyphosphate, chlorinated paraffin, ammonium phosphate , Tricresyl phosphate, triethyl phosphate, trischloroethyl phosphate, tris (β-chloroethyl) phosphate, trisdichloropropyl phosphate, cresyl phenyl phosphate, xylenyl diphenyl phosphate, acid phosphate, Phosphorus flame retardants such as nitrogen-containing phosphorus compounds, inorganic phosphorus flame retardants such as red phosphorus, tin oxide, antimony trioxide, zirconium hydroxide, barium metaborate, aluminum hydroxide, magnesium hydroxide, brominated polystyrene, brominated poly α And polymer flame retardants such as methylstyrene, brominated polycarbonate, brominated polyepoxy resin, chlorinated polyethylene, chlorinated polyα-methylstyrene, chlorinated polycarbonate, and chlorinated polyepoxy resin.

<Production of Composition> As a method of blending the block of the present invention with a raw material and producing a composition, a known apparatus such as a Banbury mixer, a roll mill, or a twin-screw extruder is used for mechanical mixing. An existing method such as a method of forming into a pellet shape can be used. The shaped pellets can be molded in a wide temperature range, and a usual injection molding machine, blow molding machine, extrusion molding machine, compression molding machine or the like can be used for molding. In addition, the composition can be used as a rubber material such as a packaging material, a medical material, a food material, an automobile material, a vibration damping material, a sealing material, and the like, similarly to an ordinary thermoplastic elastomer.

<Detailed Exemplification of the Present Invention> Hereinafter, in the present invention, designs according to desired physical properties will be exemplified, but the scope of the present invention is not limited thereto.

Examples of the block copolymer which can be used in the present invention will be given. Here, EA, BA, MEA, MM
A, TSMA, DSMA, IBM, 2EHA, CHM
A is ethyl acrylate, butyl acrylate, 2-methoxyethyl acrylate, methyl methacrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxysilane, isobornyl methacrylate, 2-ethylhexyl Acrylate means cyclohexyl methacrylate. Abb means a block copolymer of a block mainly composed of A and a block mainly composed of B. Further, (A / B) means that A and B are randomly copolymerized.

For example, (MMA / TSMA) -b-BA
-B- (MMA / TSMA), (MMA / TSMA)-
b-EA-b- (MMA / TSMA), (MMA / TS
MA) -b- (BA / EA / MEA) -b- (MMA /
TSMA), (MMA / TSMA) -b-2EHA-b
-(MMA / TSMA), (MMA / DSMA) -b-
BA-b- (MMA / DSMA), (MMA / DSM
A) -b-EA-b- (MMA / DSMA), (MMA
/ DSMA) -b- (BA / EA / MEA) -b- (M
MA / DSMA), (MMA / DSMA) -b-2EH
Ab- (MMA / DSMA), (CHMA / TSM
A) -b-BA-b- (CHMA / TSMA), (CH
MA / TSMA) -b-EA-b- (CHMA / TSM
A), (CHMA / TSMA) -b- (BA / EA / M
EA) -b- (CHMA / TSMA), (CHMA / T
SMA) -b-2EHA-b- (CHMA / TSM
A), (CHMA / DSMA) -b-BA-b- (CH
MA / DSMA), (CHMA / DSMA) -b-EA
-B- (CHMA / DSMA), (CHMA / DSM
A) -b- (BA / EA / MEA) -b- (CHMA /
DSMA), (CHMA / DSMA) -b-2EHA-
b- (CHMA / DSMA), (IBMA / TSMA)
-B-BA-b- (IBMA / TSMA), (IBMA
/ TSMA) -b-EA-b- (IBMA / TSM
A), (IBMA / TSMA) -b- (BA / EA / M
EA) -b- (IBMA / TSMA), (IBMA / T
SMA) -b-2EHA-b- (IBMA / TSM
A), (IBMA / DSMA) -b-BA-b- (IB
MA / DSMA), (IBMA / DSMA) -b-EA
-B- (IBMA / DSMA), (IBMA / DSM)
A) -b- (BA / EA / MEA) -b- (IBMA /
DSMA), (IBMA / DSMA) -b-2EHA-
b- (IBMA / DSMA) and the like.

Further, the present invention will be described in detail with reference to the following examples. 1. (MMA / TSMA) -b-BA-b- (MMA /
TSMA) A triblock copolymer comprising a central block mainly composed of BA, MMA, and both end blocks mainly composed of TSMA.

This block copolymer has a low elastic modulus because the glass transition point of BA is as low as about −50 ° C., and a methacrylic monomer having a hydrolyzable silyl group in the methacrylic polymer block. Characterized in that the body is copolymerized. Therefore, by hydrolyzing the silyl group under appropriate conditions, the block copolymer can be cured, and excellent heat resistance and oil resistance can be imparted. When a filler that reacts with the silyl group, such as silica, is blended, the interfacial adhesion between the block copolymer and the filler is improved, and a composition having excellent physical properties can be obtained. For this reason, it is suitably used as a thermoplastic elastomer capable of imparting heat resistance by curing and a film / sheet material capable of imparting heat resistance by curing. Further, it can also be used as a compatibilizer between a resin and a filler, a reactive adhesive, a reactive adhesive, a vibration damper capable of imparting heat resistance by curing.

Although the ratio of TSMA to the block copolymer is not particularly limited, when considered as a curable thermoplastic elastomer or a curable film / sheet material, one silyl group per molecule of the block copolymer may be used. Or more is preferable, and when considered as a compatibilizer for improving the interaction between the thermoplastic resin and the filler,
The number of silyl groups is preferably 0.1 or more per molecule of the block copolymer. When used as a thermoplastic elastomer having curability, the molecular weight is preferably 30,000 to 300,000, more preferably 50,000 to 200,000, and most preferably, from the viewpoints of elastomer elasticity, tensile strength, workability, and curability. Is 80,000 to 160,000, the preferred range of the weight ratio of MMA / TSMA and BA is 10/90 to 60/40, more preferably 15/85 to 40/60, and most preferably 20/8.
The number of silyl groups per block molecule is preferably 1 or more, more preferably 1.5 or more, and most preferably 2 or more. When used as a film / sheet material, from the viewpoint of strength and moldability, the preferred range of the molecular weight is 50,000 to 500,000, more preferably 80,000 to 300,000, and most preferably 100,000 to 200,000.
The preferred range of the weight ratio of MMA / TSMA to BA is 10
/ 90-90 / 10, more preferably 20 / 80-7
0/30, most preferably 25/75 to 50/50, and the number of silyl groups per block molecule is preferably one or more, more preferably 1.5 or more, and still more preferably two or more.

[0117] 2. (MMA / TSMA) -b-EA-b
-(MMA / TSMA) A triblock copolymer comprising a central block mainly composed of EA and both end blocks mainly composed of MMA and TSMA.

EA is characterized by being excellent in oil resistance and being copolymerized with a methacrylic monomer having a hydrolyzable silyl group in a methacrylic polymer block. Therefore, by hydrolyzing the silyl group under appropriate conditions, the block copolymer can be cured, and excellent heat resistance and oil resistance can be imparted. When a filler that reacts with the silyl group, such as silica, is blended, the interfacial adhesion between the block copolymer and the filler is improved, and a composition having excellent physical properties can be obtained. For this reason, it is suitably used as an oil-resistant thermoplastic elastomer capable of imparting heat resistance by curing and an oil-resistant film / sheet material capable of imparting heat resistance by curing. Further, it can also be used as a compatibilizer between a resin and a filler, a reactive adhesive, a reactive adhesive, a vibration damper capable of imparting heat resistance by curing.

Although the ratio of TSMA to the block copolymer is not particularly limited, when considered as a curable thermoplastic elastomer or a curable film / sheet material, one block of silyl group per molecule of the block copolymer is used. Or more is preferable, and when considered as a compatibilizer for improving the interaction between the thermoplastic resin and the filler,
The number of silyl groups is preferably 0.1 or more per molecule of the block copolymer. When used as a thermoplastic elastomer having curability, the preferred range of the molecular weight is 30,000 to 300,000, more preferably 50,000 to 200,000, and most preferably, from the viewpoint of elastomer elasticity, tensile strength, workability, and curability. Is 80,000 to 160,000, the preferred range of the weight ratio of MMA / TSMA and EA is 10/90 to 60/40, more preferably 15/85 to 40/60, and most preferably 20/8.
The number of silyl groups per block molecule is preferably 1 or more, more preferably 1.5 or more, and most preferably 2 or more. When used as a film / sheet material, from the viewpoint of strength and moldability, the preferred range of the molecular weight is 50,000 to 500,000, more preferably 80,000 to 300,000, and most preferably 100,000 to 200,000.
The preferred range of the weight ratio between MMA / TSMA and EA is 10
/ 90-90 / 10, more preferably 20 / 80-7
0/30, most preferably 25/75 to 50/50, and the number of silyl groups per block molecule is preferably one or more, more preferably 1.5 or more, and still more preferably two or more.

[0120] 3. (MMA / TSMA) -b- (BA /
EA / MEA) -b- (MMA / TSMA) EA, BA, central block mainly composed of MEA, MM
A, a triblock copolymer composed of both end blocks mainly composed of TSMA.

This block copolymer has a structure in which a specific acrylic monomer is copolymerized in an acrylic polymer block in order to achieve both oil resistance and low-temperature characteristics. A methacrylic monomer having a reactive silyl group is copolymerized. Therefore, by hydrolyzing the silyl group under appropriate conditions, the block copolymer can be cured, and excellent heat resistance and oil resistance can be imparted. When a filler that reacts with the silyl group, such as silica, is blended, the interfacial adhesion between the block copolymer and the filler is improved, and a composition having excellent physical properties can be obtained. For this reason, it is suitably used as an oil-resistant thermoplastic elastomer capable of imparting heat resistance by curing and an oil-resistant film / sheet material capable of imparting heat resistance by curing. Further, it can also be used as a compatibilizer between a resin and a filler, a reactive adhesive, a reactive adhesive, a vibration damper capable of imparting heat resistance by curing. From the viewpoint of a balance between oil resistance, low-temperature characteristics, and cost, EA, B
A preferable range of the ratio of A and MEA is that ethyl acrylate is X parts by weight, butyl acrylate is Y parts by weight, 2-methoxyethyl acrylate is Z parts by weight, and the total thereof is
When exemplified as 00 parts by weight, 0.1X ≦ Z ≦ 5X and 5 ≦ Y ≦ 90, more preferably 0.2X ≦ Z ≦ 2.5X
And 10 ≦ Y ≦ 80, more preferably 0.3X ≦ Z ≦
1.7X and 15 ≦ Y ≦ 70. Although the ratio of TSMA to the block copolymer is not particularly limited, when considered as a curable thermoplastic elastomer or a curable film / sheet material, one or more silyl groups per molecule of the block copolymer are reduced. Preferably, when considered as a compatibilizer for improving the interaction between the thermoplastic resin and the filler, the number of silyl groups is preferably 0.1 or more per molecule of the block copolymer. When used as a thermoplastic elastomer having curability, the molecular weight is preferably in the range of 30,000 to 300,000, and more preferably 5 in terms of elastomer elasticity, tensile strength, processability, and curability.
10,000 to 200,000, most preferably 80,000 to 160,000, MMA / T
The preferred range of the weight ratio of SMA to EA / BA / MEA is 10/90 to 60/40, more preferably 15/85.
４０40/60, most preferably 20/80 to 35/65
And the number of silyl groups per block molecule is 1
Or more, preferably 1.5 or more, more preferably 2
Or more is most preferred. When used as a film / sheet material, the preferred range of the molecular weight is 50,000 to 500,000, more preferably 80,000 to 30, from the viewpoint of strength and moldability.
10,000, most preferably 100,000 to 200,000, MMA / TSMA
The preferred range of the weight ratio of EA / BA / MEA is 10 /
90-90 / 10, more preferably 20 / 80-70
/ 30, most preferably 25/75 to 50/50, and the number of silyl groups per block molecule is preferably one or more, more preferably 1.5 or more, and even more preferably two or more.

[0122]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

"Parts" means "parts by weight". E
A, BA, MEA, MMA, TSMA and GMA
Ethyl acrylate, butyl acrylate, 2
-Methoxyethyl acrylate, methyl methacrylate, γ- (methacryloyloxypropyl) trimethoxysilane, and glycidyl methacrylate.

The molecular weight of the polymer was measured by the following GPC analyzer, and the molecular weight in terms of polystyrene was determined using chloroform as a mobile phase. The system used was a GPC system manufactured by Waters, and the column used was Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK.

The hardness shown in this embodiment is JIS K625.
According to No. 3, the hardness at 23 ° C. (JIS A) was measured.

The compression set shown in the present embodiment was measured in accordance with JIS.
According to K6301, the cylindrical molded body was kept at 70 ° C. for 22 hours under a condition of a compressibility of 25%, left at room temperature for 30 minutes, the thickness of the molded body was measured, and the degree of residual strain was calculated. In other words, the distortion is completely recovered at a compression set of 0%,
At 100% compression set, this is equivalent to no recovery of strain at all.

The gel fraction of the cured product shown in this example was determined by the following method. That is, 1 g (Wu) of the cured product was placed in 50 ml of toluene and stirred at room temperature for 72 hours. The weight (Wc) (g) of the insoluble matter after drying was measured, and the weight (Ww) of the insoluble matter relative to the weight (Wu) of the cured product was measured.
c) The gel fraction (%) of the cured product was determined from (g).

Example 1: MMA having a crosslinkable silyl group
Synthesis of -b-EA-b-MMA type block copolymer (hereinafter abbreviated as MEAM having a crosslinkable silyl group) The following operation was performed to obtain a MEAM block copolymer having a crosslinkable silyl group. . After the inside of the polymerization vessel of the 500 mL separable flask was replaced with nitrogen, 1.32 g (9.2 mmol) of copper bromide was weighed out, and 20 mL of acetonitrile (dried with molecular sieves and bubbled with nitrogen) was added. After heating and stirring at 70 ° C for 5 minutes, the mixture was cooled again to room temperature, and 0.66 g (1.9 mmol) of diethyl 2,5-dibromoadipate initiator and 100.0 ml (923 mmol) of EA were added. 80
The mixture was heated and stirred at a temperature of 0.19 ° C.
ml (0.9 mmol) was added to initiate polymerization.

At regular intervals from the start of the polymerization, about 0.2 mL of the polymerization solution was withdrawn from the polymerization solution for sampling, and the EA conversion was determined by gas chromatogram analysis of the sampling solution. The polymerization rate was controlled by adding triamine as needed. When the conversion of EA was 86%, 82.9 ml (775 mmol) of MMA, TSMA
2.5 ml (10.3 mmol), 1.82 g of copper chloride
(18.5 mmol), diethylenetriamine 0.19
ml (0.9 mmol) and 82.9 m of toluene (dried with molecular sieves and bubbled with nitrogen)
1 was added. Similarly, the conversion of MMA was determined.
When the conversion of MMA is 51%, the conversion of TSMA is 57% and the conversion of EA is 90%, 150 m
The reaction was terminated by cooling the reactor with a water bath.

The copper complex was removed by filtering the reaction solution through activated alumina. The obtained filtrate was added to a large amount of methanol to precipitate a polymer.
And dried under vacuum for 24 hours to obtain the desired block copolymer (B-1).

GPC analysis of the obtained block copolymer revealed that the number average molecular weight Mn was 111,000 and the molecular weight distribution Mw / Mn was 1.35. In addition, composition analysis by NMR showed that EA / MMA / TSM
A = 68/31/1 (% by weight).

100 parts of the obtained block copolymer (B-1) having a crosslinkable silyl group of the present invention and 0.5 part of a crosslinkable catalyst dibutyltin dilaurate were mixed at a set temperature of 150 ° C.
The mixture was kneaded with a plast mill at a rotation speed of 50 times / minute for 5 minutes to obtain a block sample. The obtained block-shaped sample is hot-pressed at a set temperature of 230 ° C. to obtain a 2 mm-thick molded body for evaluating physical properties and a 30 mm-diameter, 12 mm-thick cylindrical molded body for evaluating compression set. Was.

The hardness of the obtained molded body was 87, the compression set was 52%, and the gel fraction was 90%.

Example 2: MMA having a crosslinkable silyl group
Synthesis of -b- (BA / EA / MEA) -b-MMA type block copolymer (hereinafter abbreviated as M3AM having a crosslinkable silyl group) 0.69 g of diethyl 2,5-dibromoadipate (1.
9 mmol), BA 40.2 ml (280 mmol),
EA 38.2 ml (352 mmol) and MEA2
The polymerization was carried out at a charge ratio of 1.6 ml (168 mmol), and when the conversion of BA was 89%, the conversion of EA was 89% and the conversion of MEA was 90%, 81.6 ml of MMA was obtained.
(763 mmol) and 2.4 ml of TSMA (10.
1 mmol) were added sequentially. BA conversion rate is 92%,
EA conversion rate is 91%, MEA conversion rate is 93%, MM
The reaction was terminated when the conversion of A was 43% and the conversion of TSMA was 46%. Except for this, the production was carried out in the same manner as in Production Example 1 to obtain the desired block copolymer (B-2).

GPC analysis of the obtained block copolymer revealed that the number average molecular weight Mn was 98500 and the molecular weight distribution Mw / Mn was 1.27. Further, composition analysis by NMR showed that EA / BA / MEA / M
MA / TSMA = 25/31/14/29/1 (% by weight).

Instead of the block copolymer (B-1), the block copolymer having a crosslinkable silyl group (B-
A molded body was produced in the same manner as in Example 1, except that 2) was used. The hardness of the obtained molded body was 44, the compression set was 53%, and the gel fraction was 75%.

Example 3 The block copolymer (B-1) obtained in Example 2 was further heated to a set temperature of 230 without adding a catalyst.
A molded body was produced in the same manner as in Example 2, except that the mixture was kneaded with a plast mill at 100 ° C. and a rotation number of 100 times / minute for 5 minutes. The obtained molded product has a hardness of 48 and a compression set of 61.
% And the gel fraction were 75%.

Example 4 The block copolymer (B-2) obtained in Example 2 was kneaded with a plast mill for 5 minutes at a set temperature of 190 ° C. and a rotation number of 100 times / min to obtain a block sample. The obtained block-shaped sample was subjected to hot press molding at a set temperature of 190 ° C., and a molded body for physical property evaluation having a thickness of 2 mm and a diameter of 30 m.
Thus, a cylindrical molded article having a thickness of 12 mm and a thickness of 12 mm for evaluating compression set was obtained. The obtained molded body has a hardness of 36 and a gel fraction of 4
%Met. This sample was subjected to a temperature of 85 ° C. and a humidity of 98
%, The molded body obtained by curing for 120 hours under conditions of 39% had a hardness of 39, a compression set of 39%, and a gel fraction of 81%.

Comparative Example 1 MMA-b-EA-b-MMA
Synthesis of Type Block Copolymer (hereinafter abbreviated as MEAM) 0.66 g of diethyl 2,5-dibromoadipate (1.
9 mmol), EA 100.0 ml (923 mmol)
, And when the conversion of EA was 87%, 82.9 ml (775 mmol) of MMA were successively added. EA conversion is 90% and MMA conversion is 4
The reaction was terminated at 6%. Except for that, it was produced in the same manner as in Production Example 1, and the desired block copolymer (B-3)
I got

GPC analysis of the obtained block copolymer revealed that the number average molecular weight Mn was 115,000 and the molecular weight distribution Mw / Mn was 1.29. In addition, composition analysis by NMR showed that EA / MMA = 67 /
33 (% by weight).

The block copolymer (B-3) having no crosslinkable functional group was kneaded with a plastmill for 5 minutes at a set temperature of 230 ° C. and a rotation speed of 100 times / minute to obtain a block sample. The obtained block-shaped sample was set at a set temperature of 2
Hot press molding was performed at 30 ° C. to obtain a molded product having a thickness of 2 mm for evaluating physical properties and a cylindrical molded product having a diameter of 30 mm and a thickness of 12 mm for evaluating compression set.

The hardness of the obtained molded product was 44, the compression set was 78%, and the gel fraction was 0%.

Comparative Example 2: MMA-b- (BA / EA / M
EA) -b-MMA type block copolymer (hereinafter referred to as M3A
M) Diethyl 2,5-dibromoadipate 0.69 g (1.
9 mmol), BA 40.2 ml (280 mmol),
EA 38.2 ml (352 mmol), MEA 21.6
The polymerization was carried out at a charge ratio of
A conversion of 87%, EA conversion of 86% and ME
When the conversion of A was 89%, 85.7 ml of MMA (8
01 mmol) were added sequentially. BA conversion rate is 91
%, The conversion of EA was 89%, the conversion of MEA was 92%, and the conversion of MMA was 43%. Except that, the mixture was produced in the same manner as in Production Example 1 to obtain the desired block copolymer (B-4).

GPC analysis of the obtained block copolymer revealed that the number average molecular weight Mn was 90,600 and the molecular weight distribution Mw / Mn was 1.23. Further, composition analysis by NMR showed that EA / BA / MEA / M
MA = 25/31/14/30 (% by weight).

The obtained block copolymer (B-4) was used in place of the block copolymer (B-3).
A molded body was produced in the same manner as in Comparative Example 1, except that the mixture was kneaded with a plast mill at 90 ° C. and a rotation speed of 100 times / minute for 5 minutes, and hot press-molded at a set temperature of 190 ° C. The hardness of the obtained molded body was 26, the compression set was 88%, and the gel fraction was 0%.

As can be seen from Examples 1 to 4, the block copolymer having a hydrolyzable silyl group can be crosslinked, and the gel fraction is remarkably improved. It has been shown. From Comparative Examples 1 and 2, since the block copolymer having no hydrolyzable silyl group was completely dissolved in the organic solvent, the solvent resistance was remarkably inferior to Examples 1 to 4. It has been shown.

[0147]

According to the block copolymer of the present invention, it is suitable as a material having more excellent physical properties (curing performance, solvent resistance, etc.) while maintaining the inherent properties of the acrylic block copolymer. Can be used.

Therefore, the block copolymer of the present invention can be used for hoses, sheets, films, irregular shapes useful in the fields of, for example, packaging materials, construction materials, civil engineering materials, materials for automobiles, materials for home appliances, and other materials for miscellaneous goods. It can be suitably used for the production of extruded products, various injection molded products, etc.
Its industrial value is very large.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tomoki Nishiro 1-4 F-term (reference) 4F0-term HA11 HA39 HB11 HB39 HC11 HC39 HC49 HE02 4J100 BA77H CA31 HA61

Claims (2)

[Claims] 1. A method according to claim 1, wherein the main component is methyl methacrylate, and the methyl methacrylate monomer has a chain number of 10 to 300
A consisting of a methacrylic polymer block (A) of 0 and an acrylic polymer block (B) containing an acrylate ester as a main component and having a chain number of the acrylate monomer of 10 to 5000. A block copolymer of the type -BA, wherein at least one of the blocks A has the general formula (Wherein, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 10 carbon atoms.
A is a monovalent hydrocarbon group selected from aralkyl groups
A block copolymer in which at least one vinyl monomer having at least one hydrolyzable silyl group bonded to a carbon atom in the molecule represented by the following formula (1) is copolymerized per block. 2. The block copolymer according to claim 1, wherein the block copolymer is a triblock copolymer.