JP2003055519A - Resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition comprising a hydroxystyrene-based polymer having a syndiotactic structure, and a nitrogen-containing vinylic polymer, and further to provide a method for producing the resin composition. SOLUTION: The resin composition comprises the nitrogen-containing aromatic vinylic polymer having a structural unit represented by formula (1) (wherein, Ar is a nitrogen-containing aromatic residue such as pyridinyl group) and the hydroxystyrene-based polymer which is the polymer comprising a structural unit represented by formula (2) and has >=30% tacticity expressed in terms of racemic pentad measured by a<13> C-NMR as essential compounded components. The method for producing the resin composition comprises dissolving and mixing each of the resins of the essential components in an oxygen- containing organic solvent having >=2.0 dielectric constant, and removing the solvent from the resultant solution.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a compounded resin composition comprising a hydroxystyrene polymer having a syndiotactic structure and a nitrogen-containing aromatic vinyl polymer and a method for producing the same, and particularly to a syndiotactic hydroxystyrene polymer. A blended resin composition comprising a syndiotactic hydroxystyrene block copolymer comprising a coalescing segment and a syndiotactic aromatic vinyl polymer segment and a nitrogen-containing aromatic vinyl polymer, and a method for producing the same, and The present invention relates to a blended resin composition comprising an aromatic vinyl polymer having a syndiotactic structure, a nitrogen-containing aromatic vinyl polymer and a syndiotactic hydroxystyrene block and a method for producing the same.

[0002]

2. Description of the Related Art Styrene-based polymers conventionally produced by radical polymerization or the like are molded into various shapes by various molding methods, and are used in household appliances, office equipment, household products, packaging containers, and other industries. It is widely used as a material, etc., but its three-dimensional structure has an atactic structure, which has the drawback of being poor in heat resistance and chemical resistance. As a solution to the drawbacks of the styrene-based polymer having such an atactic structure, a styrene-based polymer having a highly syndiotactic structure, and a styrene-based copolymer obtained by copolymerizing the styrene-based monomer and other components Considered (Japanese Patent Publication No. 3-7685, Japanese Patent Publication 1-
37403, JP-A-63-241009). These polymers are excellent in heat resistance, chemical resistance and electrical characteristics, and are expected to be applied in various fields.

However, the syndiotactic polystyrene-based polymers according to the techniques disclosed in these publications are homopolymers of styrene-based monomers consisting only of hydrocarbons having no polar group necessary for imparting a function, or Since it is a random copolymer in which a small amount of polar vinyl monomer is introduced, there are drawbacks that the range in which the properties can be modified is narrow and the applicable applications are limited.
In particular, the resin material was not suitable for application as a functional material such as an adhesive, a resin modifier, a compatibilizer, a pigment dispersant, and a heat-resistant sealing agent. In particular, syndiotactic polystyrene-based polymers have poor compatibility with nitrogen-containing aromatic vinyl-based polymers, which are functional polymers such as adhesives, resin modifiers and pigment dispersants. When attempting to modify the resin properties using a group vinyl polymer, the effect of modifying the nitrogen-containing aromatic vinyl polymer was low, and a large amount had to be added. For this reason, there are problems in industrial implementation, such as a decrease in mechanical strength, a deterioration in appearance, and an increase in cost.

On the other hand, Polymer, 1988, 29 volumes, 477-482
P., Polymer, J., 1994, 26, 905-911, Appl.S.
Urf. Sci., 1997, Vol. 119, pp. 60-66, discloses a resin composition of a hydroxystyrene-based polymer and a nitrogen-containing aromatic vinyl-based polymer. However, since the stereo structure of the hydroxystyrene polymer used in the above literature is an atactic structure having no stereoregularity, there is a drawback that its modification effect is not sufficient from the viewpoint of heat resistance. . A resin composition obtained by blending a block copolymer consisting of a syndiotactic hydroxystyrene polymer segment and an aromatic vinyl polymer segment having a syndiotactic structure and a nitrogen-containing aromatic vinyl polymer has heretofore been completely unknown. Therefore, it was impossible to imagine what kind of structure and characteristics this resin composition had.

Therefore, in contrast to the resin composition comprising the syndiotactic polystyrene-based polymer and the nitrogen-containing aromatic vinyl-based polymer, the syndiotactic hydroxystyrene-based polymer segment and the syndiotactic aromatic compound are used. It is completely unknown whether the addition effect of the block copolymer when the syndiotactic hydroxystyrene block copolymer composed of the vinyl polymer segment is added can be a technique for compensating for the drawbacks of the resin composition. No, I couldn't imagine it. As described above, in the conventionally disclosed technique, the heat resistance of the resin composition including the hydroxystyrene-based polymer and the nitrogen-containing aromatic vinyl-based polymer is improved, and the syndiotactic hydroxystyrene-based polymer segment and the syndiotactic A resin composition having excellent compatibility and heat resistance is produced by blending a syndiotactic hydroxystyrene block copolymer composed of an aromatic vinyl polymer segment having a structure and a nitrogen-containing aromatic vinyl polymer. However, it has not been possible to improve the compatibility of a resin composition comprising a syndiotactic polystyrene polymer having poor compatibility and a nitrogen-containing aromatic vinyl polymer.

[0006]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a hydroxystyrene polymer having a high syndiotactic structure, which is useful as a functional resin material having excellent heat resistance and adhesiveness and having a wide range of application fields. Provided are a resin composition comprising a nitrogen-containing aromatic vinyl polymer and a method for producing the same, and a syndiotactic composition comprising a syndiotactic hydroxystyrene polymer segment and an aromatic vinyl polymer segment having a syndiotactic structure. To provide a resin composition comprising a tic hydroxystyrene block copolymer and a nitrogen-containing aromatic vinyl polymer and a method for producing the same, and further to provide excellent heat resistance with functions such as adhesiveness and pigment dispersibility. And improved compatibility of syndiotactic styrene polymer and nitrogen-containing aromatic vinyl polymer, and syndyne Consisting of isotactic hydroxystyrene block copolymer resin composition and to provide a manufacturing method thereof.

[0007]

As a result of intensive studies to solve the above problems, the present inventors have found that the hydroxystyrene-based polymer having a high syndiotactic structure and the nitrogen-containing aromatic vinyl-based polymer have a high syndiotactic structure. A resin composition comprising a united body,
A resin composition comprising a syndiotactic hydroxystyrene block copolymer and a nitrogen-containing aromatic vinyl polymer, which comprises a syndiotactic hydroxystyrene polymer segment and an aromatic vinyl polymer segment having a syndiotactic structure, It was found that a resin composition comprising a syndiotactic polystyrene-based polymer, a nitrogen-containing aromatic vinyl-based polymer, and a syndiotactic hydroxystyrene-based block copolymer can solve the problems of the present invention. Has been completed.

That is, the present invention provides the following general formula (1)

[Chemical 5] (In the formula, Ar is a pyridinyl group, a substituted pyridinyl group, a pyrimidinyl group, a substituted pyrimidinyl group, a pyrazinyl group, a substituted pyrazinyl group, a triazinyl group, a substituted triazinyl group,
Quinolinyl group, substituted quinolinyl group, isoquinolinyl group,
One or more nitrogen-containing fragrances selected from the group consisting of a substituted isoquinolinyl group, an acridinyl group, a substituted acridinyl group, a phthalazinyl group, a substituted phthalazinyl group, a quinoxalinyl group, a substituted quinoxalinyl group, a phenanthrolinyl group, and a substituted phenanthrolinyl group. A group residue is shown. 1 to 99% by weight of a nitrogen-containing aromatic vinyl polymer having a structural unit represented by the following general formula (2)

[Chemical 6] Is a homopolymer or a copolymer having a degree of polymerization of 5 or more containing a structural unit represented by, and has a tacticity of ¹³ C
-Hydroxystyrene polymer having a syndiotactic structure having a racemic pentad of 30% or more by NMR 1
A resin composition containing 99 to 99% by weight as an essential component.

Further, 1 to 98% by weight of a nitrogen-containing aromatic vinyl polymer having a structural unit represented by the general formula (1), a polymerization degree of 5 or more containing the structural unit represented by the general formula (2). of a homopolymer or copolymer, and racemic pentad by the tacticity is ¹³ C-NMR 3
1 to 98% by weight of a hydroxystyrene polymer having a syndiotactic structure of 0% or more, and (C) the following general formula (3)

[Chemical 7] (In the formula, R ¹ is a hydrocarbon group having 1 to 30 carbon atoms, a substituent having 1 to 6 carbon atoms containing an oxygen atom, or a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom. A structure containing any one or more substituents, p represents an integer of 0 to 5, provided that when R is plural, each R ¹ may be the same or different) 1 to 98% by weight of an aromatic vinyl polymer having a syndiotactic structure, which is a polymer having a degree of polymerization of 5 or more and having a tacticity of 30% or more in racemic pentad by ¹³ C-NMR. It is a resin composition as a component.

Furthermore, the present invention is characterized in that the hydroxystyrene polymer having the syndiotactic structure is a hydroxystyrene homopolymer substantially consisting of the structural unit represented by the general formula (2). And a resin composition. Furthermore, the hydroxystyrene-based polymer having a syndiotactic structure comprises 1 to 99 mol% of the structural unit represented by the general formula (2) and 1 to 99 mol% of the following general formula (4).

[Chemical 8] (In the formula, R ² is a hydrocarbon group having 1 to 30 carbon atoms, a substituent having 1 to 6 carbon atoms containing an oxygen atom, or a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom. Represents a substituent containing at least one of them, and q represents an integer of 0 to 5. However, when q is plural, each R ² may be the same or different.). A resin composition comprising a syndiotactic hydroxystyrene block copolymer block-polymerized with a structural unit.

Furthermore, the present invention is a method for producing a resin composition in which a resin, which is an essential component, is dissolved in a solvent, the solutions are mixed, and then the solvent is removed. A method for producing the above resin composition, which is an oxygen-containing organic solvent having a certain ratio.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The nitrogen-containing aromatic vinyl polymer (A) used in the resin composition of the present invention has the above general formula (1).
It is a nitrogen-containing aromatic vinyl polymer represented by. Among these nitrogen-containing aromatic vinyl polymers, Ar is preferably a pyridinyl group, that is, polyvinyl pyridine, from the viewpoint of the effect of improving heat resistance and cost. Even more preferred are poly (4-vinylpyridine) and poly (2-vinylpyridine). The three-dimensional structure of the above-mentioned nitrogen-containing aromatic vinyl polymer is not particularly limited, and it is a syndiotactic structure, an isotactic or atactic structure and a mixture of these three-dimensional structures incorporated into the polymer chain. Good.

Further, the molecular weight of the nitrogen-containing aromatic vinyl polymer used in the resin composition of the present invention is 600 or more in number average molecular weight, preferably 1000 to 2,000,000, more preferably 1500 to 1,000,000, especially Preferably 2000
It is preferably in the range of up to 500,000. If the molecular weight is too small, the physical properties of the polymer will be insufficient, such as the mechanical strength being low, and if the molecular weight is too large, molding will be difficult. The molecular weight distribution is not particularly limited, but the nitrogen-containing aromatic vinyl polymer used in the resin composition of the present invention has a weight average molecular weight (M
molecular weight distribution (M) which is the ratio of w) and number average molecular weight (Mn)
The preferable range of w / Mn) is 15 or less, more preferably 10 or less, and further preferably 3.0 or less. If the molecular weight distribution is too wide, there is a problem of deterioration of physical properties, which is not preferable.

The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the nitrogen-containing aromatic vinyl polymer as referred to herein are standard polystyrenes whose molecular weight distribution is monodisperse. It is a molecular weight and a molecular weight distribution obtained by measuring a differential refractometer as a detector using calibrated gel permeation chromatography as a sample. The content of the nitrogen-containing aromatic vinyl polymer used in the resin composition of the present invention in the resin composition is 1 to 2 in the resin composition containing two components (A) and (B) as essential components. It is 99% by weight, and is 1 to 98% by weight in a resin composition containing three components (A), (B) and (C) as essential components. Preferably,
It is 5 to 95% by weight, more preferably 10 to 90% by weight. Particularly, it is preferably in the range of 30 to 70% by weight. When the content of the nitrogen-containing aromatic vinyl polymer in the resin composition is out of the above range, the effect of improving heat resistance becomes small, which is not preferable.

The hydroxystyrene polymer having a syndiotactic structure (B) used in the resin composition of the present invention is a homopolymer having a degree of polymerization of 5 or more containing the structural unit represented by the general formula (2). Alternatively, it is a copolymer and is a syndiotactic hydroxystyrene polymer having a tacticity of 30% or more in racemic pentad by ¹³ C-NMR. The syndiotactic hydroxystyrene-based polymer has a high degree of syndiotactic structure, and the syndiotactic structure here means that the stereochemical structure is a syndiotactic structure, that is, a carbon-carbon bond. It has a three-dimensional structure in which phenyl groups and substituted phenyl groups, which are side chains with respect to the main chain, are alternately located in opposite directions, and its tacticity is nuclear magnetic resonance method using isotope carbon ( ¹³ C-NMR method). Quantified by

The tacticity measured by the ¹³ C-NMR method is indicated by the abundance ratio of a plurality of continuous structural units, for example, diad in the case of 2, triad in the case of 3 and pen dadd in the case of 5. be able to. The syndiotacticity of the syndiotactic hydroxystyrene polymer of the present invention is represented by the tacticity of C ₁ carbon of the phenyl group by ¹³ C-NMR, and is 75% or more, more preferably 85% in racemic dyad. As described above, most preferably 90% or more, or racemic pentad 30% or more, preferably 50% or more,
It is more preferable to show one having a syndiotacticity of 70% or more, particularly preferably 80% or more. However, the degree of syndiotacticity varies slightly depending on the type of substituent.

In the syndiotactic hydroxystyrene-based polymer used in the resin composition of the present invention, the repeating units bonded are not limited to one type of structural unit but also to two or more types of both structural units. Each has a syndiotactic structure (co-syndiotactic structure). Further, the copolymer composed of these structural units has various aspects such as block copolymerization, random copolymerization and alternating copolymerization. The syndiotactic hydroxystyrene-based polymer of the present invention is a hydroxystyrene-based homopolymer or a syndiotactic hydroxystyrene-based block copolymer substantially consisting of the structural unit represented by the general formula (2). Is preferred.

Here, the hydroxystyrene homopolymer essentially consists of the structural unit represented by the general formula (2), and its tacticity is ¹³ C-NMR.
Is a hydroxystyrene polymer having a syndiotactic structure with a racemic pentad of 30% or more. The number average molecular weight of the hydroxystyrene homopolymer is preferably 1200 to 20,000,000, more preferably 3000 to 10,000,000, and particularly preferably 8000.
It is desirable to be in the range of 2,000,000. If the molecular weight is too small, the physical properties of the polymer such as low mechanical strength will be insufficient, and if the molecular weight is too large, molding will be difficult. Regarding the molecular weight distribution,
The preferred range of the molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 15 or less, preferably 3.5 or less, more preferably 2.5 or less, most preferably 1.5 or less. Is. If the molecular weight distribution is too wide, there is a problem of deterioration of physical properties, which is not preferable.

The syndiotactic hydroxystyrene block copolymer has a polymer segment having a degree of polymerization of 5 or more, which is composed of the structural unit represented by the general formula (2), and C of the phenyl group in the polymer segment. A hydroxystyrene polymer segment (I) having a syndiotactic structure in which the tacticity of _one carbon is 30% or more in a racemic pentad by ¹³ C-NMR, and one or more kinds represented by the general formula (4). Aromatic vinyl polymer segment with syndiotactic structure having structural unit (I
I) is a syndiotactic hydroxystyrene block copolymer having a structure in which it is connected in series, and the tacticity of C ₁ carbon of the phenyl group in the polymer segment (II) is racemic pentad by ¹³ C-NMR. 30
%, And the content of the polymer segment (I) is in the range of 1 to 99 mol%, which is a syndiotactic hydroxystyrene block copolymer.

On the other hand, specific examples of the monomer forming the structural segment (II) represented by the general formula (4) are as follows.
Styrene, p-methylstyrene, m-methylstyrene, o
-Methylstyrene, 2,4-dimethylstyrene, 2,5-
Dimethylstyrene, 3,4-Dimethylstyrene, 3,5-
Alkyl styrenes such as dimethyl styrene and p-tertiary butyl styrene; p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene,
Halogenated styrene such as m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene

Vinyl biphenyls such as 4-vinyl biphenyl, 3-vinyl biphenyl and 2-vinyl biphenyl;
1- (4-vinylphenyl) naphthalene, 2- (4-vinylphenyl) naphthalene, 1- (3-vinylphenyl) naphthalene, 2- (3-vinylphenyl) naphthalene, 1-
Vinylphenyl naphthalenes such as (2-vinylphenyl) naphthalene, 2- (2-vinylphenyl) naphthalene; 1- (4-vinylphenyl) anthracene, 2- (4-
Vinylphenyl) anthracene, 9- (4-vinylphenyl) anthracene, 1- (3-vinylphenyl) anthracene, 2- (3-vinylphenyl) anthracene, 9-
Vinyl anthracenes such as (3-vinylphenyl) anthracene, 1- (2-vinylphenyl) anthracene, 2- (2-vinylphenyl) anthracene, 9- (2-vinylphenyl) anthracene;

1- (4-vinylphenyl) phenanthrene, 2- (4-vinylphenyl) phenanthrene, 3-
(4-vinylphenyl) phenanthrene, 4- (4-vinylphenyl) phenanthrene, 9- (4-vinylphenyl) phenanthrene, 1- (3-vinylphenyl) phenanthrene, 2- (3-vinylphenyl) phenanthrene,
3- (3-vinylphenyl) phenanthrene, 4- (3-vinylphenyl) phenanthrene, 9- (3-vinylphenyl) phenanthrene, 1- (2-vinylphenyl) phenanthrene, 2- (2-vinylphenyl) phenanthrene,
Vinylphenylphenanthrenes such as 3- (2-vinylphenyl) phenanthrene, 4- (2-vinylphenyl) phenanthrene, 9- (2-vinylphenyl) phenanthrene; 1- (4-vinylphenyl) pyrene, 2- (4 Vinylphenylpyrene such as -vinylphenyl) pyrene, 1- (3-vinylphenyl) pyrene, 2- (3-vinylphenyl) pyrene, 1- (2-vinylphenyl) pyrene, 2- (2-vinylphenyl) pyrene Kind;

4-vinyl-p-terphenyl, 4-vinyl-
m-terphenyl, 4-vinyl-o-terphenyl, 3-vinyl-p-terphenyl, 3-vinyl-m-terphenyl,
Vinyl terphenyls such as 3-vinyl-o-terphenyl, 2-vinyl-p-terphenyl, 2-vinyl-m-terphenyl, 2-vinyl-o-terphenyl; 4- (4-vinylphenyl) vinylphenyl terphenyls such as -p-terphenyl; 4-vinyl-4'-methylbiphenyl, 4-vinyl-3'-methylbiphenyl, 4-vinyl-2'-methylbiphenyl, 2-methyl-4-vinyl Biphenyl, 3-methyl-
Vinylalkylbiphenyls such as 4-vinylbiphenyl; 4-vinyl-4'-methoxybiphenyl, 4-vinyl-
3'-methoxybiphenyl, 4-vinyl-2'-methoxybiphenyl, 4-vinyl-2-methoxybiphenyl, 4-vinyl
-3-Methoxybiphenyl, 4-vinyl-4'-ethoxybiphenyl, 4-vinyl-3'-ethoxybiphenyl, 4-vinyl-2'-ethoxybiphenyl, 4-vinyl-2-ethoxybiphenyl, 4-vinyl-3 -Alkoxybiphenyls such as ethoxybiphenyl;

Alkoxycarbonylvinylbiphenyls such as 4-vinyl-4'-methoxycarbonylbiphenyl, 4-vinyl-4'-ethoxycarbonylbiphenyl and the like; Alkoxyalkylvinylbiphenyls such as 4-vinyl-4'-methoxymethylbiphenyl and the like; Trialkylsilyl vinyl biphenyls such as 4-vinyl-4'-trimethylsilyl biphenyl; 4-vinyl-4'-methylstannyl biphenyl and trialkylstannyl vinyl biphenyls such as 4-vinyl-4'-tributylstannyl biphenyl ; 4-
Trialkylsilylmethylvinylbiphenyls such as vinyl-4'-trimethylsilylmethylbiphenyl;4-vinyl-4'-trimethylstannylmethylbiphenyl, 4-
Arylstyrenes such as trialkylstannylmethylvinylbiphenyls such as vinyl-4′-tributylstannylmethylbiphenyl;

P-methoxystyrene, m-methoxystyrene, o-methoxystyrene, p-ethoxystyrene, m-
Alkoxystyrenes such as ethoxystyrene and o-ethoxystyrene; alkoxycarbonylstyrenes such as p-methoxycarbonylstyrene and m-methoxycarbonylstyrene; acyloxystyrenes such as acetyloxystyrene, ethanoyloxystyrene and benzoyloxystyrene; p-vinylbenzyl. Alkyl ether styrene such as propyl ether; Alkyl silyl styrene such as p-trimethyl silyl styrene; Alkyl stannyl styrene such as p-trimethylstannyl styrene, p-tributylstannyl styrene, p-triphenylstannyl styrene; Vinylbenzene sulfonic acid Examples thereof include ethyl, vinylbenzyldimethoxyphosphide, vinylstyrene such as p-vinylstyrene, and the like. Among these, styrene, alkyl styrenes and vinyl biphenyl are preferable from the viewpoints of economy, polymerization reactivity and heat resistance. Particularly preferred is styrene, an alkyl styrene having an alkyl having 1 to 6 carbon atoms.

The syndiotactic hydroxystyrene block copolymer used in the resin composition of the present invention is
It has a structure in which a polymer segment (I) composed of the structural unit represented by the general formula (2) and a polymer segment (II) composed of the structural unit represented by the general formula (4) are connected in series. There is something. Therefore, each of the polymer segments represented by the general formulas (2) and (4) may be a polymer or copolymer segment composed of one kind or a combination of two or more kinds of different monomers. Absent. That is, each of the polymer segments represented by the general formulas (2) and (4) constituting the syndiotactic styrene block copolymer of the present invention does not necessarily represent only one type, but two or more types. Since it also includes the structural unit of
The polymer segment that constitutes the syndiotactic hydroxystyrene block copolymer of the present invention includes homopolymers and two-dimensional copolymers as well as multi-component copolymers such as terpolymers and quaternary copolymers. Also includes.

The syndiotacticity of the syndiotactic hydroxystyrene block copolymer used in the present invention is represented by the tacticity of C ₁ carbon of the phenyl group by ¹³ C-NMR, and the syndiotacticity of the polymer segment (I ) And (II), the racemic diad is 75% or more, more preferably 85% or more, most preferably 90% or more, or the racemic pentad is 30% or more, preferably 50% or more, more preferably 70%. As described above, those having a syndiotacticity of 80% or more are particularly preferable. However, the degree of syndiotacticity varies slightly depending on the type of substituent.

In the syndiotactic hydroxystyrene block copolymer of the present invention, the polymer segments (I) and (II) comprising the structural units represented by the above general formulas (2) and (4) are bound to each other. Repeating unit is 1
Not only between the two types of structural units but also between two or more types of both structural units are syndiotactic structures (co-syndiotactic structures). Further, the copolymer composed of these structural units has various aspects such as block copolymerization, random copolymerization and alternating copolymerization.

In addition, it has a structure in which a polymer segment composed of the structural unit represented by the general formula (2) and a polymer segment composed of the structural unit represented by the general formula (4) are connected in series. Each polymer segment (I) and (II) of the syndiotactic hydroxystyrene block copolymer used in the resin composition according to claim 4 of the present invention is not necessarily a single polymer. There is no. As long as the syndiotacticity is within the above range, a mixture with a styrene-based polymer having an isotactic or atactic structure or a styrene-based polymer having an atactic structure may be incorporated in the polymer chain.

The content of the polymer segment (I) contained in the syndiotactic hydroxystyrene block copolymer of the present invention is preferably in the range of 1 to 99 mol%. It is preferably 15 to 85 mol%. Particularly preferably, it is 30 to 70 mol%. When the content of the polymer segment (I) is out of this range, the polymer segment (I) and the polymer segment (II)
Of Syndiotactic Hydroxystyrene Block Copolymers Consisting of Polyamides, which have the polymer segments with extremely different polarities, in one molecule Is reduced, which is not preferable.

Further, the syndiotactic hydroxystyrene block copolymer of the present invention has a number average molecular weight of preferably 1200 to 20,000,000, more preferably 3000 to 10,000,000, and particularly preferably 8000 to 2,000,000.
It is preferably in the range of, 000,000. If the molecular weight is too small, the physical properties of the polymer such as low mechanical strength will be insufficient, and if the molecular weight is too large, molding will be difficult. Regarding the molecular weight distribution, the preferable range of the molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn), is 15 or less. It is preferably 3.5 or less, more preferably 2.5 or less, and most preferably 1.5 or less. If the molecular weight distribution is too wide, there is a problem of deterioration of physical properties, which is not preferable.

Further, the syndiotactic hydroxystyrene polymer used in the resin composition of the present invention is, if necessary, the above-mentioned general formula (2) or (4) within a range not impairing the effects of the present invention. In addition to the structural unit represented by the above, it may be one obtained by copolymerizing another monomer other than the styrene-based monomer copolymerizable therewith. In this case, other monomers other than the copolymerizable styrene-based monomer include olefins such as ethylene, propylene and 1-butene, cyclopentene, cyclic olefins such as 2-norbornene, 1,3-butadiene and 2 -Methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2
-Chloro-1,3-butadiene, 1,3-pentadiene, conjugated dienes such as 1,3-hexadiene, 1,5-
Hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-
Non-conjugated dienes such as norbornene, and (meth) acrylic acid esters such as methyl methacrylate and methyl acrylate are included. The amount of these other monomers other than the styrene-based monomer used varies depending on the use of the polymer of the present invention and is not uniquely determined, but is preferably 45 moles in all monomers. % Or less, particularly preferably 0.0
It is in the range of 5 to 30 mol%.

The aromatic vinyl polymer having a syndiotactic structure used as the component (C) in the resin composition of the present invention is a polymer having at least one structural unit represented by the above general formula (3). A polymer having a degree of 5 or more and a tacticity of 30 in a racemic pentad by ¹³ C-NMR.
% Or more, which is an aromatic vinyl polymer having a syndiotactic structure. The syndiotacticity of the aromatic vinyl polymer having a syndiotactic structure according to the present invention is ¹³ C.
Represented by the tacticity of C ₁ carbon of the phenyl group by NMR, the racemic diad is 75% or more, more preferably 85% or more, most preferably 90% or more,
Alternatively, 30% or more, preferably 5 for racemic pentad.
Those having a syndiotacticity of 0% or more, more preferably 70% or more, and particularly preferably 80% or more are shown. However, the degree of syndiotacticity varies slightly depending on the type of substituent.

Further, a styrene-based monomer used in the aromatic vinyl-based polymer having a syndiotactic structure composed of the structural unit represented by the general formula (3) used in the resin composition of the present invention. As a specific example, styrene,
p-methylstyrene, m-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-tert-butylstyrene, etc. Alkyl styrenes; p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-
Halogenated styrene such as methyl-p-fluorostyrene

Vinyl biphenyls such as 4-vinyl biphenyl, 3-vinyl biphenyl and 2-vinyl biphenyl;
1- (4-vinylphenyl) naphthalene, 2- (4-vinylphenyl) naphthalene, 1- (3-vinylphenyl) naphthalene, 2- (3-vinylphenyl) naphthalene, 1-
Vinylphenyl naphthalenes such as (2-vinylphenyl) naphthalene, 2- (2-vinylphenyl) naphthalene; 1- (4-vinylphenyl) anthracene, 2- (4-
Vinylphenyl) anthracene, 9- (4-vinylphenyl) anthracene, 1- (3-vinylphenyl) anthracene, 2- (3-vinylphenyl) anthracene, 9-
Vinyl anthracenes such as (3-vinylphenyl) anthracene, 1- (2-vinylphenyl) anthracene, 2- (2-vinylphenyl) anthracene, 9- (2-vinylphenyl) anthracene;

1- (4-vinylphenyl) phenanthrene, 2- (4-vinylphenyl) phenanthrene, 3-
(4-vinylphenyl) phenanthrene, 4- (4-vinylphenyl) phenanthrene, 9- (4-vinylphenyl) phenanthrene, 1- (3-vinylphenyl) phenanthrene, 2- (3-vinylphenyl) phenanthrene,
3- (3-vinylphenyl) phenanthrene, 4- (3-vinylphenyl) phenanthrene, 9- (3-vinylphenyl) phenanthrene, 1- (2-vinylphenyl) phenanthrene, 2- (2-vinylphenyl) phenanthrene,
Vinylphenylphenanthrenes such as 3- (2-vinylphenyl) phenanthrene, 4- (2-vinylphenyl) phenanthrene, 9- (2-vinylphenyl) phenanthrene; 1- (4-vinylphenyl) pyrene, 2- (4 Vinylphenylpyrene such as -vinylphenyl) pyrene, 1- (3-vinylphenyl) pyrene, 2- (3-vinylphenyl) pyrene, 1- (2-vinylphenyl) pyrene, 2- (2-vinylphenyl) pyrene Kind;

4-vinyl-p-terphenyl, 4-vinyl-
m-terphenyl, 4-vinyl-o-terphenyl, 3-vinyl-p-terphenyl, 3-vinyl-m-terphenyl,
Vinyl terphenyls such as 3-vinyl-o-terphenyl, 2-vinyl-p-terphenyl, 2-vinyl-m-terphenyl, 2-vinyl-o-terphenyl; 4- (4-vinylphenyl) vinylphenyl terphenyls such as -p-terphenyl; 4-vinyl-4'-methylbiphenyl, 4-vinyl-3'-methylbiphenyl, 4-vinyl-2'-methylbiphenyl, 2-methyl-4-vinyl Biphenyl, 3-methyl-
Vinylalkylbiphenyls such as 4-vinylbiphenyl; 4-vinyl-4'-methoxybiphenyl, 4-vinyl-
3'-methoxybiphenyl, 4-vinyl-2'-methoxybiphenyl, 4-vinyl-2-methoxybiphenyl, 4-vinyl
-3-Methoxybiphenyl, 4-vinyl-4'-ethoxybiphenyl, 4-vinyl-3'-ethoxybiphenyl, 4-vinyl-2'-ethoxybiphenyl, 4-vinyl-2-ethoxybiphenyl, 4-vinyl-3 -Alkoxybiphenyls such as ethoxybiphenyl;

Alkoxycarbonylvinylbiphenyls such as 4-vinyl-4'-methoxycarbonylbiphenyl and 4-vinyl-4'-ethoxycarbonylbiphenyl; alkoxyalkylvinylbiphenyls such as 4-vinyl-4'-methoxymethylbiphenyl; Trialkylsilyl vinyl biphenyls such as 4-vinyl-4'-trimethylsilyl biphenyl; 4-vinyl-4'-methylstannyl biphenyl and trialkylstannyl vinyl biphenyls such as 4-vinyl-4'-tributylstannyl biphenyl ; 4-
Trialkylsilylmethylvinylbiphenyls such as vinyl-4'-trimethylsilylmethylbiphenyl;4-vinyl-4'-trimethylstannylmethylbiphenyl, 4-
Arylstyrenes such as trialkylstannylmethylvinylbiphenyls such as vinyl-4′-tributylstannylmethylbiphenyl;

P-methoxystyrene, m-methoxystyrene, o-methoxystyrene, p-ethoxystyrene, m-
Alkoxystyrene such as ethoxystyrene and o-ethoxystyrene; alkoxycarbonylstyrene such as p-methoxycarbonylstyrene and m-methoxycarbonylstyrene; acyloxystyrene such as acetyloxystyrene, ethanoyloxystyrene and benzoyloxystyrene; p-vinylbenzyl Alkyl ether styrene such as propyl ether; Alkyl silyl styrene such as p-trimethylsilyl styrene; Alkyl stannyl styrene such as p-trimethylstannyl styrene, p-tributylstannyl styrene, p-triphenylstannyl styrene; Vinylbenzene sulfonic acid Examples thereof include ethyl, vinylbenzyldimethoxyphosphide, vinylstyrene such as p-vinylstyrene, and the like, and mixtures thereof. Among these, styrene, alkyl styrenes and vinyl biphenyl are preferable from the viewpoints of economy, polymerization reactivity and heat resistance. Particularly preferred is styrene, an alkyl styrene having an alkyl having 1 to 6 carbon atoms.

The aromatic vinyl polymer having a syndiotactic structure according to the present invention may optionally have other structural units represented by the general formula (3) within a range not impairing the effects of the present invention. Further, it may be a copolymer of other monomer other than the styrene-based monomer copolymerizable therewith. In this case, other monomers other than the copolymerizable styrene-based monomer include olefins such as ethylene, propylene and 1-butene, cyclopentene, cyclic olefins such as 2-norbornene, 1,3-butadiene and 2 −
Methyl-1,3-butadiene, 2,3-dimethyl-1,
3-butadiene, 2-chloro-1,3-butadiene,
Conjugated dienes such as 1,3-pentadiene and 1,3-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, 5
-Non-conjugated dienes such as ethylidene-2-norbornene,
Examples include (meth) acrylic acid esters such as methyl methacrylate and methyl acrylate. The amount of these other monomers other than the styrene-based monomer used varies depending on the use of the polymer of the present invention and is not uniquely determined, but is preferably 45 moles in all monomers. % Or less, particularly preferably 0.05 to 30 mol%.

The aromatic vinyl polymer having a syndiotactic structure of the present invention has a structure in which the structural units represented by the general formula (3) are connected in series. Therefore, the structural unit represented by the general formula (3) may be a homopolymer or a copolymer each consisting of one kind or a combination of two or more different kinds of arbitrary monomers. That is, the structural unit represented by the general formula (3) that constitutes the syndiotactic hydroxystyrene-based polymer used in the resin composition of the present invention does not necessarily represent only one type, but two or more types. The aromatic vinyl polymer having a syndiotactic structure used in the resin composition of the present invention is a homopolymer and
In addition to dimensional copolymers, it also includes multi-component copolymers such as terpolymers and quaternary copolymers.

In the aromatic vinyl polymer having a syndiotactic structure of the present invention, the repeating unit bonded is 1
Not only between the two types of structural units but also between two or more types of both structural units are syndiotactic structures (co-syndiotactic structures). Further, the copolymer composed of these structural units has various aspects such as block copolymerization, random copolymerization and alternating copolymerization. The aromatic vinyl polymer mainly having a syndiotactic structure referred to in the present invention does not necessarily have to be a single polymer. As long as the syndiotacticity is within the above range, a mixture with a styrene polymer having an isotactic or atactic structure or an aromatic vinyl polymer having an atactic structure may be incorporated in the polymer chain.

The aromatic vinyl polymer having a syndiotactic structure according to the present invention has a number average molecular weight of 6 in terms of number average molecular weight.
00 or more, preferably 1000 to 2,000,000, more preferably 1500 to 1,000,000, and particularly preferably 2000 to 5
It is preferably in the range of 0,000. If the molecular weight is too small, physical properties as a polymer such as low mechanical strength and heat resistance will be insufficient, and conversely, if the molecular weight is too large, molding will be difficult.

The molecular weight distribution is not particularly limited, but the weight average molecular weight (Mw) and the number average molecular weight (Mw) of the syndiotactic aromatic vinyl polymer of the present invention are not particularly limited.
The preferable range of the molecular weight distribution (Mw / Mn), which is the ratio of n), is 15 or less, more preferably 10 or less, further preferably 3.0 or less, particularly preferably 2.0 or less, and most preferably 1.5 or less. If the molecular weight distribution is too wide, problems such as deterioration of heat resistance and physical properties occur, which is not preferable. The content of the aromatic vinyl polymer having a syndiotactic structure of the present invention in the resin composition is 1 to 98% by weight. It is preferably 5 to 95% by weight, and more preferably 10 to
90% by weight. Particularly preferably, 20 to 80% by weight
Is the range. If the addition amount of the aromatic vinyl polymer having a syndiotactic structure to the resin composition is out of the above range, the effect of improving heat resistance becomes small, which is not preferable.

For the purpose of modifying the resin, the resin composition of the present invention may contain, if necessary, conventional additives such as antistatic agents, antioxidants, ultraviolet absorbers, colorants and surface modifiers. , A dispersant, a plasticizer, an organic tin compound, a light stabilizer, a processing aid, a foaming agent, a glass fiber, and an inorganic filler such as talc can be added. Further, if desired, a thermoplastic resin or a thermosetting resin other than the above may be added to the resin composition of the present invention within a range not impairing the effects of the present invention.

The resin composition of the present invention is prepared by dissolving each resin, which is an essential blending component, in an oxygen-containing organic solvent having a dielectric constant of 2.0 or more, mixing the solution, and then removing the solvent. It can be manufactured. Examples of the oxygen-containing organic solvent having a dielectric constant of 2.0 or more include aliphatic alcohols having 1 to 6 carbon atoms, aliphatic ethers having 1 to 12 carbon atoms, aliphatic ketones having 1 to 6 carbon atoms, and 1 to carbon atoms. An aliphatic ester of 12, an N, N-dialkylamide having 1 to 12 carbon atoms, and dimethyl sulfoxide (DMSO) can be preferably used.
Specific examples include methanol, ethanol, propanol, butanol, pentanol, hexanol, dimethylformamide (DMF), dimethylacetamide (D
MAc), ethyl lactate, 2-methoxyethyl ether (diglyme), ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, tetrahydrofuran (THF), 1,4-
One or more solvents can be selected from the group consisting of dioxane and 3-ethoxyethylpropionate.

Among these solvents, methanol, ethanol, propanol, butanol, pentanol, hexanol, dimethylformamide (DMF) and dimethylacetamide (DMAc) are preferably used from the viewpoint of heat resistance improving effect. Particularly suitable solvents are ethanol, propanol, dimethylformamide (DMF) and dimethylacetamide (DMAc), more preferably ethanol and dimethylformamide (DMF).
The most preferred solvent is ethanol. The resin is dissolved in these solvents. When dissolved, operations such as stirring, overheating, and ultrasonic treatment may be performed. The solution concentration is not particularly limited, but is usually 0.05% by weight or more, preferably 0.1% by weight or more. If it is less than this range, the amount of solvent used becomes large, which is not preferable.

The resin solution obtained is usually mixed with stirring. The resin composition of the present invention can be obtained by separating the deposited precipitate by a known method such as centrifugation and filtration, or by removing the solvent by a known method such as distillation under reduced pressure and distillation. Also,
In order to further enhance the effect of the present invention, it is possible to extract only the component having excellent heat resistance from the obtained resin composition using the above solvent. The composition of the present invention thus obtained, for example, solvent cast molding, injection molding,
By extrusion molding or compression molding, a film, coating film or other molded article having excellent heat resistance and mechanical properties can be obtained.

[0049]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. First,
Each evaluation and measurement method used in the examples of the present invention will be described below.

1) Molecular weight and molecular weight distribution of polymer Using SSC-7100 type gel permeation chromatography manufactured by Senshu Scientific Co., Ltd., measurement was carried out by mounting a differential refractometer as a detector. 2)% Syndiotacticity It was determined by measuring pentad (racemic pentad) by 13 C-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL.

3) Block copolymer composition It was determined by 1 H-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL. 4) Glass transition temperature (Tg) DSC320 manufactured by Mac Science Co., Ltd. for Tg measurement.
0S is used and the temperature rising rate is 10 ° C./mi under argon flow.
The measurement was performed at n.

5) Morphology observation The morphology observation of the resin composition is made by Hitachi Ltd.
Accelerating voltage using H-8100 transmission electron microscope (TEM)
Observation was performed at 100 kV. 6) Composition analysis The composition analysis of the polymer complex composed of poly (p-hydroxystyrene) and poly (4-vinylpyridine) was performed by elemental analysis.

Reference Example 1 (Production of p- (t-butyldimethylsilyloxy) styrene homopolymer) A polymerization reaction was carried out in a nitrogen atmosphere using a glass three-necked flask having an inner volume of 200 ml which was dried and purged with nitrogen. It was Toluene 68.1 ml and trioctylaluminum 0.1 mmol
Was charged and aged at room temperature for 10 minutes. Then pentamethylcyclopentadienyl titanium 0.1 mmo
l and tris (pentafluorophenyl) boron 0.
The mixture was charged with 09 mmol and aged at room temperature for 10 minutes. Next, the temperature was kept constant at -25 ° C and aging was performed for 10 minutes.

To this, a toluene solution of 0.1 mmol of p-tert-butyldimethylsilyloxystyrene was charged. Further, aging was performed for 60 minutes at a temperature of -25 ° C. Finally,
A toluene solution of 2.0 mmol of p-tert-butyldimethylsilyloxystyrene was charged, and a polymerization reaction was carried out at -25 ° C for 30 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer. The obtained polymer was redissolved in toluene, filtered, and then the solution was poured into a large amount of methanol again to precipitate the polymer. Wash, filter, dry and weigh to give 0.4
44 g (yield: 90.2 wt%) was obtained. Polymerization activity is 8.88
(g of polymer) / (mmolTi) × hr). The weight average molecular weight (Mw) of the obtained polymer was 92600, the number average molecular weight (Mn) was 80800, and the molecular weight distribution (Mw / Mn) was 1.1.
It was 5. The syndiotacticity determined by 13 C-NMR measurement is 95% for racemic pentad.
% Or more.

Reference Example 2 ((p- (t-butyldimethylsilyloxy) styrene) -b- (p-methylstyrene))
Production of Block Copolymer) A polymerization reaction was carried out in a nitrogen atmosphere using a glass three-necked flask having an internal volume of 200 ml which was dried and purged with nitrogen. 69.6 ml of toluene and 0.1 mmol of trioctylaluminum were charged into a three-necked flask and aged at room temperature for 10 minutes. (Trimethyl) pentamethylcyclopentadienyltitanium 0.1 mmol, followed by tris (pentafluorophenyl) boron 0.09 mmol were charged at room temperature.
Aged for 10 minutes. Next, the temperature was kept constant at -25 ° C., and after aging for 10 minutes, a toluene solution of pt-butyldimethylsilyloxystyrene 0.1 mmol was charged, and the aging was further performed for 60 minutes.

Then, 20 ml of a toluene solution of 2.0 mmol of pt-butyldimethylsilyloxystyrene was charged, and a polymerization reaction was carried out at -25 ° C for 30 minutes. Then p-
Add a toluene solution of methyl styrene 4.0 mmol,
After carrying out polymerization for 15 minutes at the same temperature, a small amount of methanol was added to stop the reaction, and the polymerization solution was poured into a large amount of hydrochloric acid methanol solution to precipitate a polymer. The obtained polymer was washed, filtered, dried, and then dissolved in toluene,
After separation by filtration, the polymer was reprecipitated in a large amount of methanol,
The polymer obtained was washed, filtered, dried and then weighed to obtain 0.759 g of a polymer. The polymer obtained had a weight average molecular weight (Mw) of 193,000 and a number average molecular weight (Mn) of 166000.
The molecular weight distribution (Mw / Mn) was 1.17. Furthermore, the average molecular weight and molecular weight distribution of the pt-butyldimethylsilyloxystyrene polymer segment (I) contained in the present block copolymer are from the results of Reference Example 1, and the weight average molecular weight (Mw) is 92,600. The average molecular weight (Mn) is
80800, and the molecular weight distribution (Mw / Mn) is considered to be 1.15.
The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for both the pt-butyldimethylsilyloxystyrene polymer segment and the p-methylstyrene polymer segment. Furthermore, the composition of the block copolymer determined by ¹ H-NMR measurement is pt-butyldimethylsilyloxystyrene 37.1 mol%, p-methylstyrene 62.9.
It was mol%.

Reference Example 3 ((p-hydroxystyrene) -b
-Production of (p-methylstyrene) block copolymer) A reaction was performed in a nitrogen atmosphere using a glass Schlenk bottle having an internal volume of 30 ml which was dried and purged with nitrogen. (P- (t-Butyldimethylsilyloxy) styrene) -b- (p-methylstyrene)) block copolymer obtained in Reference Example 2: 0.205 g was charged into a glass three-necked flask, followed by 30 ml of tetrahydrofuran. Is charged to dissolve the polymer. Then, add 1.0 ml of 37% hydrochloric acid and heat to 300 ° C at the reflux temperature of tetrahydrofuran.
Stir for minutes. After stopping the heating, the polymer solution was poured into water to precipitate a polymer. The polymer obtained was washed well with water, filtered, dried and weighed to give a polymer of 0.158.
g was obtained. Weight average molecular weight (Mw) of the obtained polymer
Was 256,000, the number average molecular weight (Mn) was 188,000, and the molecular weight distribution (Mw / Mn) was 1.36. 1H-NMR
By the measurement, it was confirmed that the peak due to the t-butyldimethylsilyl group disappeared completely, and that the target (p-hydroxystyrene) -b- (p-methylstyrene) block copolymer was obtained. Further, the syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad. Furthermore, ¹ H-NMR
The composition of the block copolymer obtained by the measurement is 34.7 mol% of hydroxystyrene and 6 of p-methylstyrene.
It was 5.3 mol%.

Reference Example 4 (Production of p- (t-butyldimethylsilyloxy) styrene homopolymer) Polymerization reaction was carried out in a nitrogen atmosphere using a glass three-necked flask having an inner volume of 1000 ml which was dried and purged with nitrogen. It was 631 ml of toluene and 0.7 mmol of trioctylaluminum were charged and the mixture was aged at room temperature for 10 minutes. Then 0.7 mmol of pentamethylcyclopentadienyl titanium,
And tris (pentafluorophenyl) boron 0.63
After the addition of mmol, aging was performed at room temperature for 10 minutes.
Next, the temperature was kept constant at -25 ° C and aging was performed for 10 minutes.

To this, a toluene solution of 0.7 mmol of p-tert-butyldimethylsilyloxystyrene was charged. Further, aging was performed for 60 minutes at a temperature of -25 ° C. Finally,
p-tert-butyldimethylsilyloxystyrene 14.0 mmol
The toluene solution was charged and the polymerization reaction was carried out at -25 ° C for 20 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer. Redissolving the obtained polymer in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. Wash, filter, dry, weigh, polymer
1.750 g (yield: 50.8 wt%) was obtained. Polymerization activity is 7.5
It was 1 (g of polymer) / (mmol Ti) × hr). The weight average molecular weight (Mw) of the obtained polymer was 77100, the number average molecular weight (Mn) was 61300, and the molecular weight distribution (Mw / Mn) was
It was 1.26. Moreover, the syndiotacticity determined by 13 C-NMR measurement is 9% for racemic pentad.
It was more than 5%.

Reference Example 5 Production of p-Hydroxystyrene Homopolymer A dried and nitrogen-substituted glass Schlenk bottle with an internal volume of 100 ml was used to carry out the reaction under a nitrogen atmosphere. The p- (t-butyldimethylsilyloxy) styrene polymer: 1.608 g obtained in Reference Example 6 was charged into a glass three-necked flask, and then 50 ml of tetrahydrofuran was charged to dissolve the polymer. Then, 10.0 ml of 37% hydrochloric acid
The mixture was charged, heated, and stirred at a temperature at which tetrahydrofuran refluxed for 180 minutes. After stopping the heating, the polymer solution was poured into water to precipitate a polymer. The obtained polymer was thoroughly washed with water, filtered, dried and weighed to obtain 0.817 g of a polymer.

Weight average molecular weight (Mw) of the obtained polymer
Was 155,000, the number average molecular weight (Mn) was 111,000, and the molecular weight distribution (Mw / Mn) was 1.40. 1H-NMR
By the measurement, it was confirmed that the peak due to the t-butyldimethylsilyl group disappeared completely, and the target p-hydroxystyrene polymer was obtained. Furthermore, ¹³ C-N
The syndiotacticity determined by MR measurement was 95% or more for racemic pentad. The Tg of the obtained poly (p-hydroxystyrene) is 185.
It was ℃.

Reference Example 6 (Production of p-Methylstyrene Homopolymer) Polymerization reaction was carried out in a nitrogen atmosphere using a glass three-necked flask having an inner volume of 100 ml which was dried and purged with nitrogen. Toluene 69.2 ml and trioctylaluminum 0.1 mmol
Was charged and aged at room temperature for 10 minutes. Then pentamethylcyclopentadienyl titanium 0.1 mmo
l and tris (pentafluorophenyl) boron 0.
The mixture was charged with 09 mmol and aged at room temperature for 10 minutes. Next, the temperature was kept constant at -25 ° C and aging was performed for 10 minutes.

To this, a toluene solution of 0.1 mmol of p-tert-butyldimethylsilyloxystyrene was charged. Further, aging was performed for 60 minutes at a temperature of -25 ° C. Finally,
p-tert-butyldimethylsilyloxystyrene 15.0 mmol
The toluene solution was charged and the polymerization reaction was carried out at -25 ° C for 20 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of methanol to precipitate a polymer. Redissolving the obtained polymer in toluene,
After filtration, the solution was poured again into a large amount of methanol to precipitate a polymer. Wash, filter, dry, weigh, polymer
1.715 g (yield: 96.1 wt%) was obtained. Polymerization activity is 17.
2 (g of polymer) / (mmol Ti) × hr). The weight average molecular weight (Mw) of the obtained polymer was 630000, the number average molecular weight (Mn) was 470000, and the molecular weight distribution (Mw / Mn) was
It was 1.34. Moreover, the syndiotacticity determined by 13 C-NMR measurement is 9% for racemic pentad.
It was more than 5%.

Example 1 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
25 g and commercially available poly (4-vinylpyridine) (Sigma-Al
Purchased from drich, Mw: 60000, Tg: 136 ° C) 0.02
Separately 5 g of ethanol (dielectric constant: 25.3)
In ethanol at a concentration of 1.0% by weight, and these ethanol solutions are mixed with stirring. Syndiotactic poly (p
-Hydroxystyrene) and poly (4-vinylpyridine)
After the polymer complex consisting of and is deposited as a precipitate, stirring is continued for another hour. The precipitated polymer complex is recovered using a centrifuge. Repeat ethanol washing and centrifugation twice. The obtained resin composition was dried under reduced pressure at 85 ° C. for 24 hours or more. The yield of the resin composition was 0.047 g (yield: 94.8% by weight). The analysis was performed using a sample that had been vacuum dried until immediately before. When the composition of the obtained resin composition was examined by elemental analysis, it was found to be 51.3 mol% syndiotactic poly (p-hydroxystyrene) and 48.7 mol% poly (4-vinylpyridine). T of this resin composition
The g was 208 ° C.

Comparative Example 1 A commercially available resin composition comprising atactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Commercially available atactic poly (p-hydroxystyrene) (purchased from Sigma-Aldrich, Mw: 20000, Tg: 165 ° C) 0.025 g and commercially available poly (4-vinylpyridine) (purchased from Sigma-Aldrich, Mw : 60000, Tg: 136 ° C.) 0.025 g are separately dissolved in ethanol (dielectric constant: 25.3) at a concentration of 1.0 wt%, and these ethanol solutions are mixed with stirring. After the polymer complex consisting of syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) is deposited as a precipitate, stirring is continued for another hour. The precipitated polymer complex is recovered using a centrifuge. Ethanol wash,
Repeat centrifugation twice. The obtained resin composition was dried under reduced pressure at 85 ° C. for 24 hours or more. The yield of the resin composition was 0.046 g (yield: 92.6% by weight). The analysis was performed using a sample that had been vacuum dried until immediately before. The Tg of the obtained resin composition was 201 ° C.

Example 2 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
425 g and commercially available poly (4-vinylpyridine) (Sigma-
Purchased from Aldrich, Mw: 60000, Tg: 136 ° C) 0.0
075 g of ethanol (dielectric constant: 25.
It is dissolved in 3) at a concentration of 1.0% by weight, and these ethanol solutions are mixed with stirring. After the polymer complex consisting of syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) is deposited as a precipitate, stirring is continued for another hour. The precipitated polymer complex is recovered using a centrifuge. Repeat ethanol washing and centrifugation twice. The obtained resin composition was dried under reduced pressure at 85 ° C. for 24 hours or more. The yield of the resin composition was 0.017 g (yield: 33.2% by weight). The analysis was performed using a sample that had been vacuum dried until immediately before. When the composition of the obtained resin composition was examined by elemental analysis, it was found to be syndiotactic poly (p-hydroxystyrene): 57.4 mol% and poly (4-vinylpyridine): 42.6 mol%. The Tg of this resin composition was 210 ° C.

Example 3 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
375 g and commercially available poly (4-vinylpyridine) (Sigma-
Purchased from Aldrich, Mw: 60000, Tg: 136 ° C) 0.0
125 g of ethanol (dielectric constant: 25.
It is dissolved in 3) at a concentration of 1.0% by weight, and these ethanol solutions are mixed with stirring. After the polymer complex consisting of syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) is deposited as a precipitate, stirring is continued for another hour. The precipitated polymer complex is recovered using a centrifuge. Repeat ethanol washing and centrifugation twice. The obtained resin composition was dried under reduced pressure at 85 ° C. for 24 hours or more. The yield of the resin composition was 0.028 g (yield: 56.0% by weight). The analysis was performed using a sample that had been vacuum dried until immediately before. When the composition of the obtained resin composition was examined by elemental analysis, it was found to be syndiotactic poly (p-hydroxystyrene): 58.4 mol% and poly (4-vinylpyridine): 41.6 mol%. The Tg of this resin composition was 214 ° C.

Example 4 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
325 g and commercially available poly (4-vinylpyridine) (Sigma-
Purchased from Aldrich, Mw: 60000, Tg: 136 ° C) 0.0
175 g of ethanol (dielectric constant: 25.
It is dissolved in 3) at a concentration of 1.0% by weight, and these ethanol solutions are mixed with stirring. After the polymer complex consisting of syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) is deposited as a precipitate, stirring is continued for another hour. The precipitated polymer complex is recovered using a centrifuge. Repeat ethanol washing and centrifugation twice. The obtained resin composition was dried under reduced pressure at 85 ° C. for 24 hours or more. The yield of the resin composition is 0.038 g (yield: 76.6% by weight)
Met. The analysis was performed using a sample that had been vacuum dried until immediately before. When the composition of the obtained resin composition was examined by elemental analysis, it was found to be syndiotactic poly (p-hydroxystyrene): 57.8 mol% and poly (4-vinylpyridine): 42.2 mol%. The Tg of this resin composition was 210 ° C.

Example 5 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
125 g and commercially available poly (4-vinylpyridine) (Sigma-
Purchased from Aldrich, Mw: 60000, Tg: 136 ° C) 0.0
375 g of ethanol (dielectric constant: 25.
It is dissolved in 3) at a concentration of 1.0% by weight, and these ethanol solutions are mixed with stirring. After the polymer complex consisting of syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) is deposited as a precipitate, stirring is continued for another hour. The precipitated polymer complex is recovered using a centrifuge. Repeat ethanol washing and centrifugation twice. The obtained resin composition was dried under reduced pressure at 85 ° C. for 24 hours or more. The yield of the resin composition is 0.030 g (yield: 59.6% by weight)
Met. The analysis was performed using a sample that had been vacuum dried until immediately before. When the composition of the obtained resin composition was examined by elemental analysis, it was found to be syndiotactic poly (p-hydroxystyrene): 38.7 mol% and poly (4-vinylpyridine): 61.3 mol%. The Tg of this resin composition was 193 ° C.

Example 6 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
50 g and commercially available poly (4-vinylpyridine) (Sigma-Al
Purchased from drich, Mw: 60000, Tg: 136 ° C) 0.05
0 g of each is separately dissolved in DMF (dielectric constant: 38.25) at a concentration of 1.0% by weight, and these DMF solutions are mixed with stirring. The mixed DMF solution of the resin composition is dropped on a Teflon (registered trademark) plate on a hot plate having a temperature of 140 ° C., and the solvent is distilled off to obtain a resin composition film. The resin composition obtained was subjected to 85% under reduced pressure.
It was dried at ℃ for 48 hours or more. The analysis was performed using a sample that had been vacuum dried until immediately before. T of this resin composition
The g was 201 ° C. Moreover, this resin composition was added to DMF.
Was dissolved in, and applied on a glass substrate, and vacuum dried under heating. The resin composition coating film on the obtained glass substrate was cross-cut with a cutter at 1 mm intervals, 10 pieces, and 90 degrees, and a cellotape (registered trademark) adhesion / peel test was performed to confirm the peeling state of the coating film. It was visually confirmed. The adhesiveness between the coating film of the resin composition and the glass substrate was good, and peeling of the coating film was not observed.

Example 7 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
40 g and commercially available poly (4-vinylpyridine) (Sigma-Al
Purchased from drich, Mw: 60000, Tg: 136 ° C) 0.06
0 g of each is separately dissolved in DMF (dielectric constant: 38.25) at a concentration of 1.0% by weight, and these DMF solutions are mixed with stirring. The mixed DMF solution of the resin composition is dropped on a Teflon (registered trademark) plate on a hot plate having a temperature of 140 ° C., and the solvent is distilled off to obtain a resin composition film. The resin composition obtained was subjected to 85% under reduced pressure.
It was dried at ℃ for 48 hours or more. The analysis was performed using a sample that had been vacuum dried until immediately before. T of this resin composition
The g was 194 ° C. Moreover, this resin composition was added to DMF.
Was dissolved in, and applied on a glass substrate, and vacuum dried under heating. The resin composition coating film on the obtained glass substrate was cross-cut with a cutter at 1 mm intervals, 10 pieces, and 90 degrees, and a cellotape (registered trademark) adhesion / peel test was performed to confirm the peeling state of the coating film. It was visually confirmed. The adhesiveness between the coating film of the resin composition and the glass substrate was good, and peeling of the coating film was not observed.

Example 8 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
60 g and commercial poly (4-vinyl pyridine) (Sigma-Al
Purchased from drich, Mw: 60000, Tg: 136 ° C) 0.04
0 g of each is separately dissolved in DMF (dielectric constant: 38.25) at a concentration of 1.0% by weight, and these DMF solutions are mixed with stirring. The mixed DMF solution of the resin composition is dropped on a Teflon (registered trademark) plate on a hot plate having a temperature of 140 ° C., and the solvent is distilled off to obtain a resin composition film. The resin composition obtained was subjected to 85% under reduced pressure.
It was dried at ℃ for 48 hours or more. The analysis was performed using a sample that had been vacuum dried until immediately before. T of this resin composition
The g was 196 ° C. Moreover, this resin composition was added to DMF.
Was dissolved in, and applied on a glass substrate, and vacuum dried under heating. The resin composition coating film on the obtained glass substrate was cross-cut with a cutter at 1 mm intervals, 10 pieces, and 90 degrees, and a cellotape (registered trademark) adhesion / peel test was performed to confirm the peeling state of the coating film. It was visually confirmed. The adhesiveness between the coating film of the resin composition and the glass substrate was good, and peeling of the coating film was not observed.

Example 9 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (2-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
25 g and poly (2-vinylpyridine) synthesized by anionic polymerization (Mn: 16400, Tg: 71 ° C.) 0.025
g are separately dissolved in ethanol (dielectric constant: 25.3) at a concentration of 1.0% by weight, and these ethanol solutions are mixed with stirring. Syndiotactic poly (p-
After the polymer complex consisting of (hydroxystyrene) and poly (2-vinylpyridine) is deposited as a precipitate, stirring is continued for another hour. The precipitated polymer complex is recovered using a centrifuge. Repeat ethanol washing and centrifugation twice. The obtained resin composition was dried under reduced pressure at 85 ° C. for 24 hours or more. The yield of the resin composition was 0.045 g (yield: 90.1% by weight). The analysis was performed using a sample that had been vacuum dried until immediately before. When the composition of the obtained resin composition was examined by elemental analysis, it was found to be syndiotactic poly (p-hydroxystyrene): 47.4 mol% and poly (4-vinylpyridine): 52.6 mol%. Tg of this resin composition
Was 174 ° C.

Comparative Example 2 A resin composition composed of commercially available atactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. 0.025 g of commercially available atactic poly (p-hydroxystyrene) (purchased from Sigma-Aldrich, Mw: 20000, Tg: 165 ° C.) and poly (2-vinylpyridine) (Mn: 16400) synthesized by anionic polymerization. , Tg: 71 ° C.) are separately dissolved in ethanol (dielectric constant: 25.3) at a concentration of 1.0 wt%, and these ethanol solutions are mixed with stirring. After the polymer complex consisting of atactic poly (p-hydroxystyrene) and poly (2-vinylpyridine) is deposited as a precipitate, stirring is continued for another hour. The precipitated polymer complex is recovered using a centrifuge. Repeat ethanol washing and centrifugation twice. The resin composition obtained was subjected to 85% under reduced pressure.
It was dried at ℃ for 24 hours or more. Yield of resin composition is 0.0
It was 43 g (yield: 86.3% by weight). The analysis was performed using a sample that had been vacuum dried until immediately before. When the composition of the obtained resin composition was examined by elemental analysis, it was found that syndiotactic poly (p-hydroxystyrene): 4
6.8 mol%, poly (4-vinylpyridine): 53.2
It was mol%. The Tg of this resin composition was 165 ° C.

Example 10 Syndiotactic (p-hydroxystyrene) -b-
(P-methylstyrene) block copolymer and poly (4-
The resin composition containing vinyl pyridine) was produced by the following procedure. 0.067 g of the syndiotactic (p-hydroxystyrene) -b- (p-methylstyrene) block copolymer obtained in Reference Example 3 and commercially available poly (4-
Vinylpyridine) (Purchased from Sigma-Aldrich, Mw: 600
00, Tg: 136 ° C) DM of 0.033 g separately
F (dielectric constant: 38.25) is dissolved at a concentration of 1.0% by weight, and these DMF solutions are mixed with stirring. The mixed DMF solution of the resin composition is dropped on a Teflon (registered trademark) plate on a hot plate having a temperature of 140 ° C., and the solvent is distilled off to obtain a resin composition film. The obtained resin composition was dried under reduced pressure at 85 ° C. for 48 hours or more. The analysis was performed using a sample that had been vacuum dried until immediately before. The film of the obtained resin composition was dyed with RuO ₄ , and the morphology was observed with a transmission electron microscope (TEM). A TEM photograph of the resin composition is shown in FIG. For comparison, the syndiotactic (p-hydroxystyrene) -obtained in Reference Example 3 is shown in FIG.
A TEM photograph of the b- (p-methylstyrene) block copolymer is also shown. Looking at FIG. 1, syndiotactic (p-hydroxystyrene) -b- (p-methylstyrene)
In the TEM photograph of the block copolymer, an alternating lamella structure in which each segment in the block copolymer was arranged alternately was observed (FIGS. 1 (a) and 1 (b)). In this photograph, the syndiotactic poly (p-hydroxystyrene) phase was dyed in a darker color. The thickness of the lamella layer of the syndiotactic (p-hydroxystyrene) -b- (p-methylstyrene) block copolymer is 30 nm for the syndiotactic poly (p-hydroxystyrene) segment phase and poly (p- The (methylstyrene) segment phase was 70 nm. On the other hand, poly (4-vinylpyridine) is not dyed in a resin composition comprising syndiotactic (p-hydroxystyrene) -b- (p-methylstyrene) block copolymer and poly (4-vinylpyridine) On the contrary, the poly (p-methylstyrene) segment phase was dyed in a darker color due to the above (FIG.
(D)). Then, it was observed that the intervals of the lamellar structure of the poly (p-methylstyrene) segment phase were widened. This is because poly (4-vinylpyridine) is compatibilized with the syndiotactic poly (p-hydroxystyrene) segment phase in the block copolymer,
It is considered that this indicates that the volume fraction of the syndiotactic poly (p-hydroxystyrene) segment phase is increased. Therefore, DM this resin composition
It was dissolved in F, coated on a glass substrate, and vacuum dried under heating. The resin composition coating film on the obtained glass substrate was cross-cut with a cutter at 1 mm intervals, 10 pieces, and 90 degrees, and a cellotape (registered trademark) adhesion / peel test was performed to confirm the peeling state of the coating film. It was visually confirmed. The adhesiveness between the coating film of the resin composition and the glass substrate was good, and peeling of the coating film was not observed.

Example 11 Syndiotactic (p-hydroxystyrene) -b-
(P-methylstyrene) block copolymer, poly (p-
The resin composition consisting of methylstyrene) and poly (4-vinylpyridine) was produced by the following procedure. 0.010 g of the syndiotactic (p-hydroxystyrene) -b- (p-methylstyrene) block copolymer obtained in Reference Example 3 and 0.070 g of the poly (p-methylstyrene) obtained in Reference Example 6 , And commercially available poly (4-vinylpyridine) (purchased from Sigma-Aldrich, Mw: 60000, T
g: 136 ° C.) 0.020 g was added to DMF (dielectric constant: 38.2).
5) is dissolved and mixed under stirring at a concentration of 1.0% by weight. The mixed DMF solution of the resin composition is dropped on a Teflon (registered trademark) plate on a hot plate having a temperature of 140 ° C., and the solvent is distilled off to obtain a resin composition film. The obtained resin composition was dried under reduced pressure at 85 ° C. for 48 hours or more. The analysis was performed using a sample that had been vacuum dried until immediately before.

The obtained resin composition film was RuO ₄
Was used for morphological observation using a transmission electron microscope (TEM). TEM of resin composition
The photograph is shown in FIG. As shown in FIG. 2, it was observed that a phase having a syndiotactic poly (p-methylstyrene) phase as a matrix was present on the upper side of FIG. 2 (a).
In this poly (p-methylstyrene) phase, poly (4-vinylpyridine) phase of about 100 to 200 nm was dispersed as dispersed particles as a spherical dispersed phase (FIG. 2 (b)). Further, when this poly (4-vinylpyridine) phase is enlarged and observed, it is considered that it is a poly (p-methylstyrene) domain generated by the inclusion of the block copolymer in the poly (4-vinylpyridine) phase. It was observed that 40 nm-encapsulated particles were present (Fig. 2 (d)). In addition, an interface phase having a neutral color between the two phases was present at the interface between the dispersed poly (4-vinylpyridine) particles and the matrix resin. This indicates that the matrix polymer and the polymer in the dispersed particles penetrate each other to improve the compatibility.

On the other hand, it was observed that the poly (p-methylstyrene) phase was dispersed in the fine spherical domains having a size of about 40 nm on the lower side of FIG. 2 (a). 1 (a) and 1
Considering the morphology of the block copolymer added to the blend shown in (b), syndiotactic (p-hydroxystyrene) -b- (p-methylstyrene)
If the block copolymer forms a single phase, the internal morphology of that phase should have an alternating lamellar structure. However, the spherical domain structure did not indicate that the block copolymer was present alone, but poly (4-vinylpyridine) was added to the syndiotactic poly (p-hydroxystyrene) segment phase in the block copolymer. ) Is solubilized, which is considered to indicate that the volume fraction is increasing. In addition, the contrast of the interface of the poly (p-methylstyrene) dispersed particles was low, and in this case as well, it was shown that the compatibility between the matrix polymer and the dispersed particle polymer was improved. Therefore, this resin composition was dissolved in DMF, applied on a glass substrate, and vacuum dried under heating. The adhesiveness between the coating film of the obtained resin composition on the glass substrate and the glass substrate was good, and neither peeling nor cracking of the coating film was observed.

Comparative Example 3 A resin composition comprising syndiotactic poly (p-methylstyrene) and poly (4-vinylpyridine) was produced by the following procedure. Poly (p obtained in Reference Example 6
-Methylstyrene) 0.080 g, and commercially available poly (4
-Vinylpyridine) (purchased from Sigma-Aldrich, Mw: 6
(0000, Tg: 136 ° C.) 0.020 g is dissolved and mixed in DMF at a concentration of 1.0 wt% under stirring. The mixed DMF solution of the resin composition is dropped on a Teflon (registered trademark) plate on a hot plate having a temperature of 140 ° C., and the solvent is distilled off to obtain a resin composition film. The obtained resin composition was dried under reduced pressure at 85 ° C. for 48 hours or more.
The analysis was performed using a sample that had been vacuum dried until immediately before. The film of the obtained resin composition was dyed with RuO ₄ , and the morphology was observed with a transmission electron microscope (TEM).

A TEM photograph of the resin composition is shown in FIG. Looking at Figure 3, it can be seen that the phase of poly (4-vinylpyridine) looks white in Figure 1.2.4-7. And, syndiotactic poly (p-methylstyrene) and poly (4
-Vinyl pyridine) has a diameter of a few μm
The presence of dispersed poly (4-vinylpyridine) particles was observed (FIG. 3 (a)). Observation was carried out by enlarging the poly (4-vinylpyridine) particles which are the dispersed phase, and the inside of the poly (4-vinylpyridine) particles contained in the particles considered to be syndiotactic poly (p-methylstyrene) phase were No existence was confirmed. This means DMF
When casting a simple blend of syndiotactic poly (p-methylstyrene) and poly (4-vinylpyridine) from solution, the syndiotactic poly (p-methylstyrene) phase and poly (4-methylstyrene) phase and poly (4-methylstyrene) phase were cast at a very early stage. This is considered to suggest that phase separation with the (vinylpyridine) phase is occurring. The macroscopic phase separation structure is formed because syndiotactic poly (p-methylstyrene) and poly (4-vinylpyridine) have significantly different polarities and thus have low compatibility. This is considered to be the cause. Therefore, this resin composition was dissolved in DMF, applied on a glass substrate, and vacuum dried under heating. The adhesiveness between the coating film of the resin composition on the obtained glass substrate and the glass substrate was poor, and peeling and cracking of the coating film were observed.

Reference Example 7 ((Production of (p- (t-butyldimethylsilyloxy) styrene) -b- (styrene)) block copolymer) A glass three-necked flask having an inner volume of 200 ml and dried and replaced with nitrogen was placed. Polymerization reaction was carried out under nitrogen atmosphere. Toluene 69.6 ml and trioctylaluminum 0.1 mmol
Was charged into a three-necked flask and aged at room temperature for 10 minutes. To this, 0.1 mmol of (trimethyl) pentamethylcyclopentadienyltitanium and then 0.09 mmol of tris (pentafluorophenyl) boron were charged and aging was carried out at room temperature for 10 minutes. Next, the temperature was kept constant at -25 ° C., and after aging for 10 minutes, a toluene solution of p-t-butyldimethylsilyloxystyrene 0.1 mmol was charged, and the aging was performed for 60 minutes. Then, p-t-butyldimethylsilyloxystyrene 2.0 m
Charge 20 ml of a toluene solution of mol to 30 at -25 ° C.
A polymerization reaction was carried out for a minute. After that, a toluene solution of 20.0 mmol of styrene was added and polymerized at the same temperature for 30 minutes, then a small amount of methanol was added to stop the reaction, and the polymerization solution was poured into a large amount of hydrochloric acid methanol solution to polymerize It was deposited.

The obtained polymer was washed, filtered and dried, and then dissolved in toluene, filtered and reprecipitated with a large amount of methanol, and the obtained polymer was washed, filtered and dried. Then, it was weighed to obtain 0.835 g of a polymer. The weight average molecular weight (Mw) of the obtained polymer was 249000, the number average molecular weight (Mn) was 174000, and the molecular weight distribution (Mw / Mn) was 1.
It was 43. Furthermore, the average molecular weight and molecular weight distribution of the pt-butyldimethylsilyloxystyrene polymer segment (I) contained in the present block copolymer are shown in Reference Example 1
From the results, the weight average molecular weight (Mw) is 92600, the number average molecular weight (Mn) is 80800, and the molecular weight distribution (Mw / Mn) is
Considered to be 1.15. The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad for both the pt-butyldimethylsilyloxystyrene polymer segment and the styrene polymer segment. Further, the composition of the block copolymer determined by ¹ H-NMR measurement was pt-butyldimethylsilyloxystyrene 34.5 mol% and styrene 65.5 mol%.

Reference Example 8 ((p-hydroxystyrene) -b
-Production of (styrene) block copolymer) A glass Schlenk bottle having an inner volume of 30 ml which had been dried and replaced with nitrogen was used to carry out the reaction in a nitrogen atmosphere. (P- (t-butyldimethylsilyloxy) styrene) -b- (styrene)) block copolymer obtained in Reference Example 2:
0.203 g is charged into a glass three-necked flask, and then 30 ml of tetrahydrofuran is charged to dissolve the polymer. Thereafter, 1.0 ml of 37% hydrochloric acid was charged and heated, and the mixture was stirred at a temperature at which tetrahydrofuran refluxed for 300 minutes. After stopping the heating, the polymer solution was poured into water to precipitate a polymer. The obtained polymer was thoroughly washed with water, filtered, dried and weighed to obtain 0.167 g of a polymer.
In addition, by 1H-NMR measurement, the peak due to the t-butyldimethylsilyl group disappeared completely, and the target (p-
It was confirmed that a hydroxystyrene) -b- (styrene) block copolymer was obtained. Furthermore, ¹³ C-NM
The syndiotacticity calculated by R measurement is
It was more than 95% in racemic pentads. Furthermore, ¹ H-
The composition of the block copolymer determined by NMR measurement was 34.0 mol% of hydroxystyrene and 66.0 mol% of p-methylstyrene.

Reference Example 9 (Syndiotactic styrene
Production of homopolymer) Three glass bottles with an internal volume of 100 ml that were dried and purged with nitrogen
The polymerization reaction was carried out in a nitrogen atmosphere using a neck flask.
2-fluorotoluene (dielectric constant: 4.23) 24.3 m
l and demethylated solid methylaluminoxane 5.0 mm
ol (calculated as Al) was charged and kept at a constant temperature of 23 ° C. here
Add 2.5 ml of styrene to the container and age for 10 minutes
After that, cyclopentadienyl titanium titanium trichloride
(CpTiCl ₃) 0.0025 mmol of 2-fluorotolu
Add ene solution and perform polymerization reaction at 23 ℃ for 10 minutes
It was Add a small amount of methanol to stop the polymerization reaction and
Pour the combined solution into a large amount of acidic methanol to precipitate the polymer
Let

The obtained polymer was washed, filtered, dried and weighed to obtain a polymer yield of 0.114 g (yield 4.7%). Polymerization activity is 274 (g of PS) / (mmol
It was Ti) × hr). Next, this polymer was extracted with methyl ethyl ketone for 5 hours using a Soxhlet extractor, and an extraction residue (MIP) of 94% was obtained. The weight average molecular weight (Mw) of the obtained polymer was 308,000, the number average molecular weight (Mn) was 157,000, and the molecular weight distribution (Mw /
Mn) was 2.0. The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more in racemic pentad.

Example 12 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
25 g and commercially available poly (4-vinylpyridine) (Sigma-Al
Purchased from drich, Mw: 60000, Tg: 136 ° C) 0.02
Separately 5 g of ethanol (dielectric constant: 25.3)
And 1-propanol (dielectric constant: 20.1) in a mixed solvent (ethanol / 1-propanol = 70/30% by volume / volume%) at a concentration of 1.0% by weight, and these solutions were stirred. Mix. After the polymer complex consisting of syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) is deposited as a precipitate, stirring is continued for another hour. The precipitated polymer complex is recovered using a centrifuge. Repeat ethanol washing and centrifugation twice. The obtained resin composition was dried under reduced pressure at 85 ° C. for 24 hours or more. The yield of the resin composition was 0.045 g (yield: 90.0% by weight). The analysis was performed using a sample that had been vacuum dried until immediately before. When the composition of the obtained resin composition was examined by elemental analysis, it was found to be 51.0 mol% syndiotactic poly (p-hydroxystyrene) and 49.0 mol% poly (4-vinylpyridine). The Tg of this resin composition was 207 ° C.

Example 13 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
25 g and commercially available poly (4-vinylpyridine) (Sigma-Al
Purchased from drich, Mw: 60000, Tg: 136 ° C) 0.02
Separately 5 g of ethanol (dielectric constant: 25.3)
And 2-propanol (dielectric constant: 20.18) mixed solvent (ethanol / 2-propanol = 80/20
(Volume% / volume%) at a concentration of 1.0% by weight and these solutions are mixed with stirring. After the polymer complex consisting of syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) is deposited as a precipitate, stirring is continued for another hour. The precipitated polymer complex is recovered using a centrifuge.
Repeat ethanol washing and centrifugation twice. The obtained resin composition was dried under reduced pressure at 85 ° C. for 24 hours or more. The yield of the resin composition was 0.046 g (yield: 92.0% by weight). The analysis was performed using a sample that had been vacuum dried until immediately before. When the composition of the obtained resin composition was examined by elemental analysis, syndiotactic poly (p-
Hydroxystyrene) was 51.3 mol% and poly (4-vinylpyridine) was 48.7 mol%. The Tg of this resin composition was 207 ° C.

Example 14 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
50 g and commercially available poly (4-vinylpyridine) (Sigma-Al
Purchased from drich, Mw: 60,000, Tg: 136 ° C) 0.05
0 g of each is mixed solvent (DM: DMF (dielectric constant: 38.25) and THF (dielectric constant: 7.52) separately.
F / THF = 70/30% by volume / volume%) at a concentration of 1.0% by weight and these solutions are mixed under stirring. The mixed resin composition solution is dropped on a Teflon (registered trademark) plate on a hot plate at a temperature of 140 ° C., and the solvent is distilled off to obtain a resin composition film.
The obtained resin composition was dried under reduced pressure at 85 ° C. for 48 hours or more. The analysis was performed using a sample that had been vacuum dried until immediately before. The Tg of this resin composition was 200 ° C.
Further, this resin composition was dissolved in a mixed solvent of DMF and THF (DMF / THF = 70/30% by volume / volume%), coated on a glass substrate, and vacuum dried under heating. The resin composition coating film on the obtained glass substrate was cross-cut with a cutter at 1 mm intervals, 10 pieces, and 90 degrees, and a cellotape (registered trademark) adhesion / peel test was performed to confirm the peeling state of the coating film. It was visually confirmed. The adhesiveness between the coating film of the resin composition and the glass substrate was good, and peeling of the coating film was not observed.

Example 15 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
50 g and commercially available poly (4-vinylpyridine) (Sigma-Al
Purchased from drich, Mw: 60,000, Tg: 136 ° C) 0.05
0 g of each was separately added to a mixed solvent (DMF / acetone = 80/20% by volume / volume%) of DMF (dielectric constant: 38.25) and acetone (dielectric constant: 21.01) at a concentration of 1.0% by weight. And dissolve these solutions under stirring. The mixed resin composition solution is dropped on a Teflon (registered trademark) plate on a hot plate at a temperature of 140 ° C., and the solvent is distilled off to obtain a resin composition film. The obtained resin composition was dried under reduced pressure at 85 ° C. for 48 hours or more. The analysis was performed using a sample that had been vacuum dried until immediately before. Tg of this resin composition is 199 ° C.
Met. Further, this resin composition was dissolved in a mixed solvent of DMF and acetone (DMF / acetone = 80/20% by volume / volume%), applied on a glass substrate, and vacuum dried under heating. The resin composition coating film on the obtained glass substrate was cross-cut with a cutter at 1 mm intervals, 10 pieces, and 90 degrees, and a cellotape (registered trademark) adhesion / peel test was performed to confirm the peeling state of the coating film. It was visually confirmed. The adhesiveness between the coating film of the resin composition and the glass substrate was good, and peeling of the coating film was not observed.

Example 16 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
50 g and commercially available poly (4-vinylpyridine) (Sigma-Al
Purchased from drich, Mw: 60,000, Tg: 136 ° C) 0.05
0 g of DMF (dielectric constant: 38.25) and N, N-diethylformamide (dielectric constant: 29.6) are separately taken.
Is dissolved in a mixed solvent (DMF / N, N-diethylformamide = 80/20% by volume / volume%) at a concentration of 1.0% by weight, and these solutions are mixed with stirring. The mixed resin composition solution is dropped on a Teflon (registered trademark) plate on a hot plate at a temperature of 140 ° C., and the solvent is distilled off to obtain a resin composition film. The obtained resin composition was dried under reduced pressure at 85 ° C. for 48 hours or more. The analysis was performed using a sample that had been vacuum dried until immediately before. The Tg of this resin composition was 199 ° C. Also,
This resin composition was dissolved in a mixed solvent (DMF / N, N-diethylformamide = 80/20% by volume / volume%) consisting of DMF and N, N-diethylformamide, coated on a glass substrate, and heated under vacuum. It was dried. The resin composition coating film on the obtained glass substrate was cross-cut with a cutter at 1 mm intervals, 10 pieces, and 90 degrees, and a cellotape (registered trademark) adhesion / peel test was performed to confirm the peeling state of the coating film. It was visually confirmed. The adhesiveness between the coating film of the resin composition and the glass substrate was good, and peeling of the coating film was not observed.

Example 17 A resin composition comprising syndiotactic poly (p-hydroxystyrene) and poly (4-vinylpyridine) was produced by the following procedure. Syndiotactic poly (p-hydroxystyrene) 0.0 obtained in Reference Example 5
50 g and commercially available poly (4-vinylpyridine) (Sigma-Al
Purchased from drich, Mw: 60,000, Tg: 136 ° C) 0.05
1.0 g of each of 0 g was separately added to a mixed solvent (DMF / ethyl lactate = 80/20 volume% / volume%) consisting of DMF (dielectric constant: 38.25) and ethyl lactate (dielectric constant: 15.4). Are dissolved at a concentration of 10 and the solutions are mixed with stirring. The mixed resin composition solution is dropped on a Teflon (registered trademark) plate on a hot plate at a temperature of 140 ° C., and the solvent is distilled off to obtain a resin composition film. The obtained resin composition was dried under reduced pressure at 85 ° C. for 48 hours or more. The analysis was performed using a sample that had been vacuum dried until immediately before. The Tg of this resin composition is 198 ° C.
Met. Further, this resin composition was mixed with DMF and ethyl lactate (DMF / ethyl lactate = 80/20).
(Vol% / vol%), applied on a glass substrate, and vacuum dried under heating. The resin composition coating film on the obtained glass substrate was cross-cut with a cutter at 1 mm intervals, 10 pieces, and 90 degrees, and a cellotape (registered trademark) adhesion / peel test was performed to confirm the peeling state of the coating film. It was visually confirmed. The adhesiveness between the coating film of the resin composition and the glass substrate was good, and peeling of the coating film was not observed.

Example 18 Syndiotactic (p-hydroxystyrene) -b-
The resin composition comprising the (styrene) block copolymer and poly (4-vinylpyridine) was produced by the following procedure. The syndiotactic (p obtained in Reference Example X2
-Hydroxystyrene) -b- (styrene) block copolymer 0.067 g and commercially available poly (4-vinylpyridine)
(Purchased from Sigma-Aldrich, Mw: 60000, Tg: 136
℃) 0.033g separately DMF (dielectric constant: 3
8.25), THF (dielectric constant: 7.52) and 1,2-
Mixed solvent consisting of dichlorobenzene (DMF / THF /
1,2-dichlorobenzene = 60/20/20% by volume /
(Volume% / volume%) at a concentration of 1.0% by weight and these solutions are mixed with stirring. The mixed resin composition solution is dropped on a Teflon (registered trademark) plate on a hot plate at a temperature of 140 ° C., and the solvent is distilled off to obtain a resin composition film. The obtained resin composition was dried under reduced pressure at 85 ° C. for 48 hours or more. The analysis was performed using a sample that had been vacuum dried until immediately before. The film of the obtained resin composition was dyed with RuO ₄ , and the morphology was observed with a transmission electron microscope (TEM). The syndiotactic (p-
In the TEM photograph of the (hydroxystyrene) -b- (styrene) block copolymer, an alternating lamella structure in which each segment in the block copolymer was alternately arranged was observed in the same manner as in Example 10. At this time, the syndiotactic poly (p-hydroxystyrene) segment phase was 30 nm, and the poly (styrene) segment phase was 60 nm.

On the other hand, the syndiotactic (p-
In the resin composition composed of the hydroxystyrene) -b- (styrene) block copolymer and poly (4-vinylpyridine), it was observed that the intervals of the lamellar structure of the poly (styrene) segment phase were widened. This means that by compatibilizing poly (4-vinylpyridine) with the syndiotactic poly (p-hydroxystyrene) segment phase in the block copolymer, the syndiotactic poly (p-hydroxystyrene) segment phase It shows that the volume fraction is increasing. Therefore, this resin composition is dissolved in a mixed solvent (DMF / THF / 1,2-dichlorobenzene = 60/20/20 volume% / volume% / volume%) consisting of DMF, THF and 1,2-dichlorobenzene. , Was coated on a glass substrate, and vacuum dried under heating. The resin composition coating film on the obtained glass substrate was cross-cut with a cutter at 1 mm intervals, 10 pieces, and 90 degrees, and a cellotape (registered trademark) adhesion / peel test was performed to confirm the peeling state of the coating film. It was visually confirmed. The adhesiveness between the coating film of the resin composition and the glass substrate was good, and peeling of the coating film was not observed.

Example 19 Syndiotactic (p-hydroxystyrene) -b-
The resin composition comprising the (styrene) block copolymer, syndiotactic polystyrene and poly (4-vinylpyridine) was produced by the following procedure. Reference example X2
0.010 g of the syndiotactic (p-hydroxystyrene) -b- (styrene) block copolymer obtained in Example 1, 0.070 g of the syndiotactic polystyrene obtained in Reference Example X3, and commercially available poly (4-vinyl) Pyridine)
(Purchased from Sigma-Aldrich, Mw: 60000, Tg: 136
C) 0.020 g to DMF (dielectric constant: 38.25), T
1.0 in a mixed solvent consisting of HF (dielectric constant: 7.52) and 1,2-dichlorobenzene (DMF / THF / 1,2-dichlorobenzene = 60/20/20 volume% / volume% / volume%). Dissolve and mix at a concentration of wt% under stirring. The mixed resin composition solution is dropped on a Teflon (registered trademark) plate on a hot plate at a temperature of 140 ° C., and the solvent is distilled off to obtain a resin composition film.
The obtained resin composition was dried under reduced pressure at 85 ° C. for 48 hours or more. The analysis was performed using a sample that had been vacuum dried until immediately before. The film of the obtained resin composition is RuO ₄
Was used for morphological observation using a transmission electron microscope (TEM). TEM of resin composition
The photo shows that the dispersed particles are approximately 100-200 nm in the phase with the syndiotactic polystyrene phase as the matrix.
The poly (4-vinylpyridine) phase was dispersed as a spherical dispersed phase. Furthermore, this poly (4-vinyl pyridine)
When the phase is enlarged and observed, poly (4-vinylpyridine)
It was observed that inclusion particles of about 40 nm, which are considered to be syndiotactic polystyrene domains, formed by inclusion of the block copolymer in the phase were present.
In addition, an interface phase having a neutral color between the two phases was present at the interface between the dispersed poly (4-vinylpyridine) particles and the matrix resin. This indicates that the matrix polymer and the polymer in the dispersed particles penetrate each other to improve the compatibility. Therefore, this resin composition is
MF (dielectric constant: 38.25), THF (dielectric constant: 7.5)
It was dissolved in a mixed solvent of 2) and 1,2-dichlorobenzene, coated on a glass substrate, and vacuum dried under heating. The adhesiveness between the coating film of the obtained resin composition on the glass substrate and the glass substrate was good, and neither peeling nor cracking of the coating film was observed.

Comparative Example 4 A resin composition comprising syndiotactic polymethylstyrene and poly (4-vinylpyridine) was produced by the following procedure. 0.080 g of syndiotactic polystyrene obtained in Reference Example X3, and commercially available poly (4-
Vinylpyridine) (Purchased from Sigma-Aldrich, Mw: 600
00, Tg: 136 ° C) 0.020 g in DMF (dielectric constant: 3
8.25), THF (dielectric constant: 7.52) and 1,2-
Mixed solvent consisting of dichlorobenzene (DMF / THF /
1,2-dichlorobenzene = 60/20/20% by volume /
(Volume% / volume%) at a concentration of 1.0% by weight, and dissolved and mixed with stirring. A solution of the mixed resin composition is added to 140
It is dropped on a Teflon (registered trademark) plate on a hot plate at a temperature of ℃ and the solvent is distilled off to obtain a film of the resin composition. The resin composition obtained was heated at 85 ° C under reduced pressure for 48 hours.
Let it dry for more than an hour. The analysis was performed using a sample that had been vacuum dried until immediately before. The film of the obtained resin composition was dyed with RuO ₄ , and the morphology was observed with a transmission electron microscope (TEM).

A TEM photograph of the resin composition shows that the composition of this comparative example, which is a simple blend of syndiotactic polystyrene and poly (4-vinylpyridine), has a diameter of several μm. ) The presence of dispersed particles was observed. The dispersed phase poly (4-
The observation was conducted by enlarging the vinylpyridine) particles, but the presence of inclusion particles considered to be syndiotactic poly (p-methylstyrene) phase inside the poly (4-vinylpyridine) particles was not confirmed. This is considered to be due to the low compatibility. Therefore, this resin composition is added to DMF (dielectric constant: 38.25) and THF.
(Dielectric constant: 7.52) and 1,2-dichlorobenzene dissolved in a mixed solvent (DMF / THF / 1,2-dichlorobenzene = 60/20/20 volume% / volume% / volume%) It was applied onto a substrate and vacuum dried under heating. The adhesiveness between the coating film of the resin composition on the obtained glass substrate and the glass substrate was poor, and peeling and cracking of the coating film were observed.

[0097]

According to the present invention, a resin composition comprising a hydroxystyrene polymer having a syndiotactic structure and a nitrogen-containing aromatic vinyl polymer, a syndiotactic hydroxystyrene polymer segment and a syndiotactic structure are provided. A resin composition comprising a syndiotactic hydroxystyrene block copolymer comprising an aromatic vinyl polymer segment and a nitrogen-containing aromatic vinyl polymer,
Moreover, a resin composition comprising an aromatic vinyl polymer having a syndiotactic structure, a nitrogen-containing aromatic vinyl polymer and a syndiotactic hydroxystyrene block can be obtained. Due to the fact that the resin composition produced here contains a hydroxystyrene-based polymer and a block copolymer having a high syndiotactic structure,
Shows good compatibility with nitrogen-containing aromatic vinyl polymers. Therefore, the resin composition of the present invention can be used for various high-performance resins, functional materials and functional resin raw materials since it exhibits good heat resistance, adhesiveness, and improved compatibility, and its industrial use. The utility is widespread.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor, honesty Kawabe             2-22-13 Yanagibashi, Taito-ku, Tokyo Foundation Law             Human Chemistry Technology Strategy Promotion Organization (72) Inventor Masahide Murata             2-22-13 Yanagibashi, Taito-ku, Tokyo Foundation Law             Human Chemistry Technology Strategy Promotion Organization (72) Inventor Hiroyuki Ozaki             2-22-13 Yanagibashi, Taito-ku, Tokyo Foundation Law             Human Chemistry Technology Strategy Promotion Organization (72) Inventor Toshio Kase             2-22-13 Yanagibashi, Taito-ku, Tokyo Foundation Law             Human Chemistry Technology Strategy Promotion Organization (72) Inventor Yoshifumi Fukui             2-22-13 Yanagibashi, Taito-ku, Tokyo Foundation Law             Human Chemistry Technology Strategy Promotion Organization (72) Inventor Juante Van             2-22-13 Yanagibashi, Taito-ku, Tokyo Foundation Law             Human Chemistry Technology Strategy Promotion Organization (72) Inventor Hideaki Hagiwara             1-1-1 Higashi 1-1-1 Tsukuba City, Ibaraki Prefecture             Inside the Tsukuba Center, National Institute of Advanced Industrial Science and Technology (72) Inventor Kenji Tsuchihara             1-1-1 Higashi 1-1-1 Tsukuba City, Ibaraki Prefecture             Inside the Tsukuba Center, National Institute of Advanced Industrial Science and Technology (72) Inventor Yasuzo Suzuki             1-1-1 Higashi 1-1-1 Tsukuba City, Ibaraki Prefecture             Inside the Tsukuba Center, National Institute of Advanced Industrial Science and Technology (72) Inventor Michihiko Asai             1-1-1 Higashi 1-1-1 Tsukuba City, Ibaraki Prefecture             Inside the Tsukuba Center, National Institute of Advanced Industrial Science and Technology F-term (reference) 4F070 AA18 AA38 AB11 AC36 AC38                       AC39 AC43 AC47 AE28 FA04                       FA17                 4J002 BC10Y BC12X BJ00W GG00                       GJ01 GJ02

Claims (9)

[Claims] 1. (A) The following general formula (1): (In the formula, Ar is a pyridinyl group, a substituted pyridinyl group, a pyrimidinyl group, a substituted pyrimidinyl group, a pyrazinyl group, a substituted pyrazinyl group, a triazinyl group, a substituted triazinyl group,
Quinolinyl group, substituted quinolinyl group, isoquinolinyl group,
One or more nitrogen-containing fragrances selected from the group consisting of a substituted isoquinolinyl group, an acridinyl group, a substituted acridinyl group, a phthalazinyl group, a substituted phthalazinyl group, a quinoxalinyl group, a substituted quinoxalinyl group, a phenanthrolinyl group, and a substituted phenanthrolinyl group. A group residue is shown. 1 to 99% by weight of a nitrogen-containing aromatic vinyl polymer having a structural unit represented by the formula (2), and (B) the following general formula (2): Is a homopolymer or a copolymer having a degree of polymerization of 5 or more containing a structural unit represented by, and has a tacticity of ¹³ C
-Hydroxystyrene polymer having a syndiotactic structure having a racemic pentad of 30% or more by NMR 1
A resin composition containing 100 to 99% by weight as an essential component. 2. The (A) general formula (1) according to claim 1.
A nitrogen-containing aromatic vinyl polymer having a structural unit represented by 1 to 98% by weight, and a homopolymer having a polymerization degree of 5 or more, containing the structural unit represented by (B) the general formula (2) according to claim 1. Or 1 to 98% by weight of a hydroxystyrene polymer having a syndiotactic structure, which is a copolymer, and (C) the following general formula (3): (In the formula, R ¹ is a hydrocarbon group having 1 to 30 carbon atoms, a substituent having 1 to 6 carbon atoms containing an oxygen atom, or a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom. A structure containing any one or more substituents, p represents an integer of 0 to 5, provided that when R is plural, each R ¹ may be the same or different) 1 to 98% by weight of an aromatic vinyl polymer having a syndiotactic structure, which is a polymer having a degree of polymerization of 5 or more and having a tacticity of 30% or more in racemic pentad by ¹³ C-NMR. A resin composition as a compounding ingredient of. 3. The hydroxystyrene-based polymer having a syndiotactic structure is a hydroxystyrene-based homopolymer consisting essentially of the structural unit represented by the general formula (2). The resin composition according to 1 or 2. 4. The hydroxystyrene polymer having a syndiotactic structure comprises 1 to 99 mol% of the structural unit represented by the general formula (2) and 1 to 99 mol% of the following general formula (4): ] (In the formula, R ² is a hydrocarbon group having 1 to 30 carbon atoms, a substituent having 1 to 6 carbon atoms containing an oxygen atom, or a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom. Represents a substituent containing at least one of them, and q represents an integer of 0 to 5. However, when q is plural, each R ² may be the same or different.). A syndiotactic hydroxystyrene-based block copolymer block-polymerized with a structural unit.
Or the resin composition according to 2. 5. The resin composition according to any one of claims 1 to 4, wherein Ar in the general formula (1) is a pyridinyl group. 6. The resin composition according to claim 2, wherein R ¹ in the general formula (3) is an alkyl group having 1 to 6 carbon atoms. 7. The resin composition according to claim 4, wherein R ² in the general formula (4) is an alkyl group having 1 to 6 carbon atoms. 8. A method for producing a resin composition, which comprises dissolving each resin as an essential compounding ingredient in a solvent, mixing the solution, and then removing the solvent, wherein the solvent has a dielectric constant of 2.0 or more. The organic solvent is an oxygen organic solvent.
A method for producing the resin composition according to any one of items 1 to 7. 9. The solvent comprises an aliphatic alcohol having 1 to 6 carbon atoms, an aliphatic ether having 1 to 12 carbon atoms, an aliphatic ketone having 1 to 6 carbon atoms, an aliphatic ester having 1 to 12 carbon atoms, and a carbon number. The method for producing a resin composition according to claim 8, which is one or more solvents selected from the group consisting of 1 to 12 N, N-dialkylamides.