JP2018024736A - Method for producing resin composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a resin composite in which a polymer compound having a repeating unit containing a glucose residue in a main chain is uniformly dispersed in a binder resin.SOLUTION: A method for producing a resin composite is provided including a polymer compound (A) having a repeating unit containing a glucose residue having at least one group selected from the group consisting of a hydroxyl group and a carboxyl group in a main chain, and a binder resin (B). The method includes: a step of mixing the polymer compound (A-1) and the binder resin (B) to obtain a mixture; and converting at least one group selected from the group consisting of Rand Rin the polymer compound (A-1) into a hydrogen atom. The polymer compound (A-1) is a polymer compound having the repeating unit containing the glucose residue in the main chain, and the glucose residue has at least one group selected from the group consisting of the group represented by formula (1) and the group represented by formula (2).SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a resin complex containing a polymer compound having a repeating unit containing a glucose residue in the main chain.

  Conventionally, a resin composite containing cellulose as a filler is known. In recent years, cellulose microfibrils obtained by mechanically refining cellulose fibrillar materials have attracted attention as cellulose fibers. For example, Patent Document 1 discloses that a resin composite containing cellulose microfibrils has high strength. Is described.

JP 2003-201695 A

  In cellulose, since the hydroxyl group of the glucose residue in the main chain interacts between molecules, it is considered that the strength and the like of the composite containing cellulose are improved. On the other hand, since the glucose residue has a hydroxyl group, there is a problem that cellulose easily aggregates in the composite.

  Accordingly, an object of the present invention is to provide a resin in which a polymer compound having a repeating unit containing a glucose residue having at least one group selected from the group consisting of a hydroxyl group and a carboxyl group in the main chain is uniformly dispersed in a binder resin. It is in providing the method of manufacturing a composite_body | complex.

  In view of the above, as a result of various studies, the present inventors have reached the present invention. That is, the present invention provides the following [1] to [4].

（１）

（２）
（式（１）および（２）中、Ｒ^ＡおよびＲ^Ｂは、互いに独立に、下記式（３）で表される有機基、下記式（４）で表される有機基、下記式（５）で表される有機基および下記式（６）で表される有機基からなる群より選ばれる少なくとも１種の有機基を表す。）

（３）

（４）

（５）

（６）
（式（３）および（４）中、Ｒ^１、Ｒ^３およびＲ^４は、互いに独立に、水素原子または炭素原子数１〜２０の１価の有機基を表す。Ｒ^２は、炭素原子数１〜２０の１価の有機基を表す。ｒは、３〜２０の整数を表す。
式（５）および（６）中、Ｒ^５は、炭素原子数１〜２０の１価の有機基を表す。Ｒ^６〜Ｒ^１０、およびＲ^１４〜Ｒ^２９は、互いに独立に、水素原子、炭素原子数１〜２０の１価の有機基を表す。該炭素数１〜２０の１価の有機基中の水素原子はハロゲン原子で置換されていてもよい。ｓは、０〜１０の整数を表す。）
［２］ 前記バインダー樹脂（Ｂ）が、下記式（７）で表される繰り返し単位、下記式（８）で表される繰り返し単位、分子内にブロック化イソシアナト基を有する繰り返し単位、およびブロック化イソチオシアナト基を有する繰り返し単位からなる群より選ばれる少なくとも１種の繰り返し単位を含有するバインダー樹脂（Ｂ−１）である［１］に記載の樹脂複合体の製造方法。

（７）
（式（７）中、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３およびＲ^３４は、互いに独立に、水素原子、炭素数１〜２０の１価の有機基、フッ素原子、ニトロ基、シアノ基、アミノ基、または水酸基を表す。該炭素数１〜２０の１価の有機基中の水素原子はフッ素原子で置換されていてもよい。）

（８）
（式（８）中、Ｒ^３５は、水素原子、または、メチル基を表す。Ｘは、酸素原子、または、−ＮＲ^３７−を表す。Ｒ^３６およびＲ^３７は、互いに独立に、水素原子、炭素数１〜２０の１価の有機基を表す。該炭素数１〜２０の１価の有機基中の水素原子はフッ素原子で置換されていてもよい。）
［３］ 前記ブロック化イソシアナト基およびブロック化イソチオシアナト基が、式（９）で表される基または式（１０）で表される基である［１］または［２］に記載の樹脂複合体の製造方法。

（９）
（式（９）中、Ｘ^ａは、酸素原子又は硫黄原子を表し、Ｒ^３８およびＲ^３９は、互いに独立に、水素原子又は炭素数１〜２０の１価の有機基を表す。）

（１０）
（式（１０）中、Ｘ^ｂは、酸素原子又は硫黄原子を表し、Ｒ^４０、Ｒ^４１およびＲ^４２は、互いに独立に、水素原子又は炭素数１〜２０の１価の有機基を表す。） [1] A resin composite containing a polymer compound (A) having a repeating unit containing a glucose residue having at least one group selected from the group consisting of a hydroxyl group and a carboxyl group in the main chain and a binder resin (B) A method for manufacturing a body,
The following polymer compound (A-1) and binder resin (B) are mixed to obtain a mixture;
Converting at least one group selected from the group consisting of R ^A and R ^{B in the} polymer compound (A-1) to a hydrogen atom;
The manufacturing method of the resin composite containing this.
Polymer compound (A-1): a polymer compound having a repeating unit containing a glucose residue in the main chain,
A polymer compound in which the glucose residue has at least one group selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2).

(1)

(2)
(In the formulas (1) and (2), R ^A and R ^B are each independently an organic group represented by the following formula (3), an organic group represented by the following formula (4), and the following formula (5 And at least one organic group selected from the group consisting of organic groups represented by the following formula (6):

(3)

(4)

(5)

(6)
(In formulas (3) and (4), R ¹ , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ² is the number of carbon atoms. Represents a monovalent organic group of 1 to 20. r represents an integer of 3 to 20;
In formulas (5) and (6), R ⁵ represents a monovalent organic group having 1 to 20 carbon atoms. R ^{6 to} R ¹⁰ and R ^{14 to} R ²⁹ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a halogen atom. s represents an integer of 0 to 10. )
[2] The binder resin (B) is a repeating unit represented by the following formula (7), a repeating unit represented by the following formula (8), a repeating unit having a blocked isocyanate group in the molecule, and blocking. The method for producing a resin composite according to [1], which is a binder resin (B-1) containing at least one repeating unit selected from the group consisting of repeating units having an isothiocyanato group.

(7)
(In the formula (7), R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, a fluorine atom, a nitro group, or a cyano group. And a hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.

(8)
(In Formula (8), R ³⁵ represents a hydrogen atom or a methyl group. X represents an oxygen atom or —NR ³⁷ —. R ³⁶ and R ³⁷ are each independently a hydrogen atom, Represents a monovalent organic group having 1 to 20 carbon atoms, and a hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.)
[3] The resin composite according to [1] or [2], wherein the blocked isocyanato group and the blocked isothiocyanato group are a group represented by the formula (9) or a group represented by the formula (10). Production method.

(9)
(In the formula (9), ^{X a} represents an oxygen atom or a sulfur ^{atom, R 38} and ^{R 39,} independently of one another, represent a monovalent organic group having a hydrogen atom or a C 1-20.)

(10)
(In the formula (10), ^{X b} represents an oxygen atom or a sulfur ^atom, R ^{40, R 41} and ^{R 42,} independently of one another, represent a monovalent organic group having a hydrogen atom or a C 1-20. )

  According to the method for producing a resin composite of the present invention, a polymer compound having a repeating unit containing a glucose residue having at least one group selected from the group consisting of a hydroxyl group and a carboxyl group in the main chain is contained in the binder resin. A uniformly dispersed resin composite can be produced.

  Next, embodiments of the present invention will be described in more detail.

  In the present specification, the “polymer compound” means a compound containing a plurality of structural units (repeating units) which may be different from each other in the molecule. "include. In the present specification, the “low molecular compound” means a compound that does not contain a plurality of repeating units in the molecule.

Explanation of Common Terms Terms commonly used in this specification have the following meanings unless otherwise specified.

  The “monovalent organic group having 1 to 20 carbon atoms” may be linear, branched, or cyclic, and may be saturated or unsaturated.

  Examples of the monovalent organic group having 1 to 20 carbon atoms include a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and 3 to 20 carbon atoms. A cyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably a linear hydrocarbon group having 1 to 6 carbon atoms, and a branched hydrocarbon having 3 to 6 carbon atoms. Group, a cyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like.

  The straight chain hydrocarbon group having 1 to 20 carbon atoms, the branched hydrocarbon group having 3 to 20 carbon atoms, and the cyclic hydrocarbon group having 3 to 20 carbon atoms are such that the hydrogen atom contained in these groups is halogen. It may be substituted with an atom.

  In the aromatic hydrocarbon group having 6 to 20 carbon atoms, a hydrogen atom in the group may be substituted with a monovalent organic group or a halogen atom.

Specific examples of the monovalent organic group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, tert-butyl group, and cyclopropyl group. , Cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentynyl group, cyclohexynyl group, trifluoromethyl group, trifluoroethyl group, 3,3,4,4,5,5,6,6,7,7,8 , 8,8-heptadecafluorodecyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, carboxyl group, carboxymethyl group, 2-carboxyethyl group, N, N-dimethylaminoethyl group N, N-dimethylaminopropyl group, phenyl group, naphthyl group, anthryl group, tolyl group, xylyl group, dimethylphenol Group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, propylphenyl group, butylphenyl group, methylnaphthyl group, dimethylnaphthyl group, trimethylnaphthyl group, vinylnaphthyl group, ethenylnaphthyl group, methylanthryl group , Ethyl anthryl group, pentafluorophenyl group, trifluoromethylphenyl group, chlorophenyl group, bromophenyl group and the like.
As the monovalent organic group having 1 to 20 carbon atoms, an alkyl group is preferable.

<Polymer compound (A) having a repeating unit containing a glucose residue having at least one hydroxyl group in the main chain>
First, the polymer compound (A) having a repeating unit containing a glucose residue having at least one hydroxyl group in the main chain will be specifically described.
Examples of the polymer compound (A) include dextrin compounds, dextrin derivatives, cellulose compounds, and cellulose derivatives.
Examples of dextrin compounds include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.
Examples of dextrin derivatives include hydroxyethylated products of dextrin compounds, hydroxypropylated products of dextrin compounds, and carboxymethylated products of dextrin compounds.
Examples of the cellulose compound include cellulose and refined cellulose fibers (cellulose nanofibers).
Cellulose nanofibers can be used for plants (for example, wood, bamboo, hemp, jute, kenaf, agricultural waste, cloth, pulp, recycled pulp, waste paper), animals (for example, ascidians), algae, microorganisms (for example, acetic acid bacteria (Acetobacter). )), A cellulose fiber-containing material produced by using microorganisms as a raw material is pulverized and / or beaten with a refiner, a high-pressure homogenizer, a medium stirring mill, a stone mill, a grinder, and the like to be defibrated or refined.
Examples of cellulose derivatives include hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose.
As said high molecular compound (A), a cellulose compound and a cellulose derivative are preferable.
The cellulose derivative can be produced by reacting cellulose with ethylene oxide, propylene oxide, chloroacetic acid or the like in the presence of an alkali catalyst.
When the number of all repeating units constituting the main chain of the polymer compound (A) is 100%, the number of repeating units containing a glucose residue in the main chain is preferably 95% or more, more preferably 100%.

（１）

（２）
式（１）および（２）中、Ｒ^ＡおよびＲ^Ｂは、互いに独立に、下記式（３）で表される有機基、下記式（４）で表される有機基、下記式（５）で表される有機基および下記式（６）で表される有機基からなる群より選ばれる少なくとも１種の有機基を表す。

（３）

（４）

（５）

（６）
式（３）および（４）中、Ｒ^１、Ｒ^３およびＲ^４は、互いに独立に、水素原子または炭素原子数１〜２０の１価の有機基を表す。Ｒ^２は、炭素原子数１〜２０の１価の有機基を表す。ｒは、３〜２０の整数を表す。
式（５）および（６）中、Ｒ^５は、炭素原子数１〜２０の１価の有機基を表す。Ｒ^６〜Ｒ^１０、およびＲ^１４〜Ｒ^２９は、互いに独立に、水素原子、炭素原子数１〜２０の１価の有機基を表す。該炭素数１〜２０の１価の有機基中の水素原子はハロゲン原子で置換されていてもよい。ｓは、０〜１０の整数を表す。
Ｒ^１〜Ｒ^１０およびＲ^１４〜Ｒ^２９である１価の有機基の定義、具体例等は、既に説明した１価の有機基の定義、具体例等と同様である。
式（１）および（２）中、Ｒ^ＡおよびＲ^Ｂは、互いに独立に、下記式（３）で表される有機基および下記式（４）で表される有機基からなる群より選ばれる少なくとも１種の有機基が好ましい。
式（３）および（４）において、一実施形態ではＲ^３およびＲ^４は、水素原子であり、Ｒ^１はメチル基であり、Ｒ^２はブチル基であり、ｒは４であることが好ましい。
グルコース残基としては、α−グルコース残基、β−グルコース残基が挙げられる。
高分子化合物（Ａ−１）の主鎖を構成する全繰り返し単位の数を１００％として、グルコース残基を主鎖に含む繰り返し単位の数は、好ましくは９５％以上、より好ましくは１００％である。高分子化合物（Ａ−１）は、さらに好ましくは、グルコース残基からなる主鎖を有する高分子化合物である。 <Polymer Compound (A-1)>
The polymer compound (A-1) is a polymer compound having a repeating unit containing a glucose residue in the main chain,
The glucose residue is a polymer compound having at least one group selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2).

(1)

(2)
In the formulas (1) and (2), R ^A and R ^B are independently of each other an organic group represented by the following formula (3), an organic group represented by the following formula (4), and the following formula (5). And at least one organic group selected from the group consisting of an organic group represented by the following formula (6).

(3)

(4)

(5)

(6)
In formulas (3) and (4), R ¹ , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ² represents a monovalent organic group having 1 to 20 carbon atoms. r represents an integer of 3 to 20.
In formulas (5) and (6), R ⁵ represents a monovalent organic group having 1 to 20 carbon atoms. R ^{6 to} R ¹⁰ and R ^{14 to} R ²⁹ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a halogen atom. s represents an integer of 0 to 10.
The definition and specific examples of the monovalent organic group which is R ^{1 to} R ¹⁰ and R ^{14 to} R ²⁹ are the same as the definition and specific examples of the monovalent organic group already described.
In the formulas (1) and (2), R ^A and R ^B are independently selected from the group consisting of an organic group represented by the following formula (3) and an organic group represented by the following formula (4). At least one organic group is preferred.
In formulas (3) and (4), in one embodiment, R ³ and R ⁴ are hydrogen atoms, R ¹ is a methyl group, R ² is a butyl group, and r is preferably 4. .
Examples of the glucose residue include α-glucose residue and β-glucose residue.
The number of all repeating units constituting the main chain of the polymer compound (A-1) is 100%, and the number of repeating units containing a glucose residue in the main chain is preferably 95% or more, more preferably 100%. is there. The polymer compound (A-1) is more preferably a polymer compound having a main chain composed of glucose residues.

  Examples of the monovalent organic group represented by the formula (3) include methoxymethyl group, methoxyethoxymethyl group, 1-ethoxyethyl group, 1-propoxyethyl group, 1-butoxyethyl group, 1-methoxypropyl. Group, 1-ethoxypropyl group.

  Examples of the monovalent organic group represented by the formula (4) include an oxiranyl group, an oxetanyl group, a hydrofuranyl group, a hydropyranyl group, a hydrooxepinyl group, and a hydrooxosinyl group, and these groups are substituted. It may have a group.

  Here, the hydrofuranyl group means a group excluding one hydrogen atom directly bonded to the carbon atom constituting the ring of dihydrofuran or tetrahydrofuran. Examples of the substituent that the hydrofuranyl group may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, and a hydroxyl group. Examples of the hydrofuranyl group include a dihydrofuranyl group and a tetrahydrofuranyl group.

  The hydropyranyl group means a group excluding one hydrogen atom directly bonded to a carbon atom constituting a dihydropyran or tetrahydropyran ring. Examples of the substituent that the hydropyranyl group may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, and a hydroxyl group. Examples of the hydropyranyl group include a dihydropyranyl group, a tetrahydropyranyl group, and a 4-methoxytetrahydropyranyl group.

  Hydrooxepinyl group means a ring of 2,3-dihydrooxepin, 2,3,4,5-tetrahydrooxepin, 2,3,6,7-tetrahydrooxepin or hexahydrooxepin Is a group excluding one hydrogen atom directly bonded to the carbon atom constituting, and examples of the substituent that the hydrooxepinyl group may have include an alkyl group, a cycloalkyl group, an alkoxy group, A cycloalkoxy group and a hydroxyl group are mentioned. Examples of the hydrooxepinyl group include a 2,3-dihydrooxepinyl group.

  The hydrooxosinyl group is 3,4-dihydro-2H-oxocine, 5,6-dihydro-2H-oxocine, 7,8-dihydro-2H-oxocine, 3,4,5,6-tetrahydro-2H-oxocin , 5,6,7,8-tetrahydro-2H-oxocine or hexahydro-2H-oxocine is a group in which one hydrogen atom directly bonded to the carbon atom constituting the ring is removed. Examples of the substituent that the hydrooxosinyl group may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, and a hydroxyl group. Examples of the hydrooxosinyl group include a 3,4-dihydro-2H-oxosinyl group.

  Examples of the organic group represented by the formula (5) include 1-methyl-1-cyclopropyl group, 1-ethyl-1-cyclopropyl group, 1-methyl-1-cyclobutyl group, 1-ethyl-1 -Cyclobutyl group, 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, 1-ethyl-1-cyclohexyl group can be mentioned.

  Examples of the organic group represented by the formula (6) include a 2-methyl-2-adamantyl group and a 2-ethyl-2-adamantyl group.

  Examples of the organic group represented by the formula (1) include a methoxymethyloxy group, a methoxyethoxymethyloxy group, a 1-ethoxyethyloxy group, a 2-ethoxyethyloxy group, a 1-methoxypropyloxy group, 1- Ethoxypropyloxy group, oxetanyl-2-oxy group, 2,3-dihydrofuranyl-2-oxy group, tetrahydrofuranyl-2-oxy group, 3,4-dihydro-2H-pyranyl-2-oxy group, 3, 6-dihydro-2H-pyranyl-2-oxy group, tetrahydropyranyl-2-oxy group, 2,3-dihydrooxepinyl-2-oxy group, 2,3,4,5-tetrahydrooxepinyl-2 -Oxy group, 2,3,6,7-tetrahydrooxepinyl-2-oxy group, hexahydrooxepinyl-2-oxy group, 3,4-dihydro 2H-oxosinyl-2-oxy group, 5,6-dihydro-2H-oxosinyl-2-oxy group, 7,8-dihydro-2H-oxosinyl-2-oxy group, 3,4,5,6-tetrahydro-2H -Oxosinyl-2-oxy group, 5,6,7,8-tetrahydro-2H-oxosinyl-2-oxy group, hexahydro-2H-oxosinyl-2-oxy group, 1-methyl-1-cyclopropyloxy group, 1 -Ethyl-1-cyclopropyloxy group, 1-methyl-1-cyclobutyloxy group, 1-ethyl-1-cyclobutyloxy group, 1-methyl-1-cyclopentyloxy group, 1-ethyl-1-cyclopentyloxy group Group, 1-methyl-1-cyclohexyloxy group, 1-ethyl-1-cyclohexyloxy group, 2-methyl-2-adamantyloxy Include 2-ethyl-2-adamantyl group.

  Examples of the organic group represented by the formula (2) include a methoxymethyloxycarbonyl group, a methoxyethoxymethyloxycarbonyl group, a 1-ethoxyethyloxycarbonyl group, a 1-butoxyethyloxycarbonyl group, and 1-ethoxyethyloxy. Carbonyl group, 1-methoxypropyloxycarbonyl group, 1-ethoxypropyloxycarbonyl group, oxiranyl-2-oxycarbonyl group, oxetanyl-2-oxycarbonyl group, 2,3-dihydrofuranyl-2-oxycarbonyl group, tetrahydrofuran Nyl-2-oxycarbonyl group, 3,4-dihydro-2H-pyranyl-2-oxycarbonyl group, 3,6-dihydro-2H-pyranyl-2-oxycarbonyl group, tetrahydropyranyl-2-oxycarbonyl group, 2,3-dihydro Xepinyl-2-oxycarbonyl group, 2,3,4,5-tetrahydrooxepinyl-2-oxycarbonyl group, 2,3,6,7-tetrahydrooxepinyl-2-oxycarbonyl group, hexahydrooxepi Nyl-2-oxycarbonyl group, 3,4-dihydro-2H-oxosinyl-2-oxycarbonyl group, 5,6-dihydro-2H-oxosinyl-2-oxycarbonyl group, 7,8-dihydro-2H-oxosinyl- 2-oxycarbonyl group, 3,4,5,6-tetrahydro-2H-oxosinyl-2-oxycarbonyl group, 5,6,7,8-tetrahydro-2H-oxosinyl-2-oxycarbonyl group, hexahydro-2H- Oxosinyl-2-oxycarbonyl group, 1-methyl-1-cyclopropyloxycarbonyl group, 1- Til-1-cyclopropyloxycarbonyl group, 1-methyl-1-cyclobutyloxycarbonyl group, 1-ethyl-1-cyclobutyloxycarbonyl group, 1-methyl-1-cyclopentyloxycarbonyl group, 1-ethyl-1 -Cyclopentyloxycarbonyl group, 1-methyl-1-cyclohexyloxycarbonyl group, 1-ethyl-1-cyclohexyloxycarbonyl group, 2-methyl-2-adamantyloxycarbonyl group, 2-ethyl-2-adamantyloxycarbonyl group Can be mentioned.

The polymer compound (A-1) is produced by reacting a polymer compound (A) having at least one group selected from the group consisting of a hydroxyl group and a carboxyl group with a blocking agent in the presence of a catalyst. I can do it.
Examples of the blocking agent include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 3,4-dihydro-2H-pyran, 1-methyl-1-cyclopentane, 1-methyl-1-cyclopentanol, Examples include 2-methylene adamantane and 2-methyl-2-adamantanol.
Examples of the catalyst include pyridinium p-toluenesulfonate, p-toluenesulfonic acid, hydrochloric acid, and the like.

<Binder resin (B)>
Next, the binder resin (B) will be specifically described.
The binder resin (B) used in the present invention is not particularly limited, and examples thereof include thermoplastic resins and thermosetting resins.
Examples of the thermoplastic resin include polyamide, polyester, polyethylene, polypropylene, polystyrene, polymethacrylate, polyacrylate, polyvinyl chloride, polyvinyl acetate, polyurethane, ABS resin, AS resin, polysulfone, and polycarbonate.
As the thermoplastic resin, polyamide, polyester, polystyrene, polymethacrylate, polyacrylate, polyvinyl acetate, polyurethane, ABS resin, AS resin, and polycarbonate are preferable.
Examples of the thermosetting resin include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyimide, resin having a block isocyanato group, resin having a block isothiocyanate group, and the like. It is done.
The thermosetting resin has a functional group capable of reacting with a hydroxyl group in a glucose residue which is a repeating unit, a phenol resin, an epoxy resin, a melamine resin, a resin having a block isocyanato group, and a block isothiocyanate group. A resin is preferable, and a resin having a block isocyanato group and a resin having a block isothiocyanato group are more preferable.

（７）
式（７）中、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３およびＲ^３４は、互いに独立に、水素原子、炭素数１〜２０の１価の有機基、フッ素原子、ニトロ基、シアノ基、アミノ基、または水酸基を表す。該炭素数１〜２０の１価の有機基中の水素原子はフッ素原子で置換されていてもよい。
ある一形態では、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３およびＲ^３４は水素原子である。

（８）
式（８）中、Ｒ^３５は、水素原子、または、メチル基を表す。Ｘは、酸素原子、または、−ＮＲ^３７−を表す。Ｒ^３６およびＲ^３７は、互いに独立に、水素原子、炭素数１〜２０の１価の有機基を表す。該炭素数１〜２０の１価の有機基中の水素原子はフッ素原子で置換されていてもよい。
ある一形態では、Ｒ^１２はメチル基であり、Ｘは酸素原子であり、Ｒ^１３はメチル基である。 The binder resin (B) used in the present invention comprises a repeating unit represented by the formula (7), a repeating unit represented by the formula (8), a repeating unit having a blocked isocyanato group in the molecule, and a blocked isothiocyanate. The polymer compound (B-1) containing at least one repeating unit selected from the group consisting of repeating units having a group is preferred.

(7)
In the formula (7), R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, a fluorine atom, a nitro group, a cyano group, Represents an amino group or a hydroxyl group. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
In one certain form, R < ^{30 >} , R ^{< 31 >} , R ^{< 32>} , R ^<33> and R ^<34> are hydrogen atoms.

(8)
In the formula (8), R ³⁵ represents a hydrogen atom or a methyl group. X represents an oxygen atom or —NR ³⁷ —. R ³⁶ and R ³⁷ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.
In one certain form, R < ¹² > is a methyl group, X is an oxygen atom, and R < ¹³ > is a methyl group.

  The blocked isocyanato group and blocked isothiocyanato group that the polymer compound (B-1) used in the present invention may have are represented by the group represented by the following formula (9) or the following formula (10). It is preferably a group.

（９）
（式（９）中、Ｘ^ａは、酸素原子又は硫黄原子を表し、Ｒ^３８およびＲ^３９は、互いに独立に、水素原子又は炭素数１〜２０の１価の有機基を表す。）

（１０）
式（１０）中、Ｘ^ｂは、酸素原子又は硫黄原子を表し、Ｒ^４０、Ｒ^４１およびＲ^４２は、互いに独立に、水素原子又は炭素数１〜２０の１価の有機基を表す。Ｒ^３８〜Ｒ^４２である１価の有機基の定義、具体例等は、既に説明した１価の有機基の定義、具体例等と同様である。

(9)
(In the formula (9), ^{X a} represents an oxygen atom or a sulfur ^{atom, R 38} and ^{R 39,} independently of one another, represent a monovalent organic group having a hydrogen atom or a C 1-20.)

(10)
Wherein (10), ^{X b} represents an oxygen atom or a sulfur ^atom, R ^{40, R 41} and ^{R 42,} independently of one another, represent a monovalent organic group having a hydrogen atom or a C 1-20. The definition and specific examples of the monovalent organic group as R ^{38 to} R ⁴² are the same as the definition and specific examples of the monovalent organic group already described.

In one embodiment of the present invention, R ³⁸ and R ³⁹ in the formula (9), independently of one another, is preferably a group selected from the group consisting of methyl and ethyl. In another embodiment, R ⁴⁰ and R ^{42 in} formula (10) are preferably methyl groups, and R ⁴¹ is preferably a hydrogen atom.

  Examples of the blocked isocyanate group that the polymer compound (B-1) may have include an O- (methylideneamino) carboxyamino group, an O- (1-ethylideneamino) carboxyamino group, and O- (1-methylethylideneamino). ) Carboxyamino group, O- [1-methylpropylideneamino] carboxyamino group, (N-3,5-dimethylpyrazolylcarbonyl) amino group, (N-3-ethyl-5-methylpyrazolylcarbonyl) amino group, N-3,5-diethylpyrazolylcarbonyl) amino group, (N-3-propyl-5-methylpyrazolylcarbonyl) amino group, (N-3-ethyl-5-propylpyrazolylcarbonyl) amino group and the like.

  Examples of the blocked isothiocyanato group that the polymer compound (B-1) may have include an O- (methylideneamino) thiocarboxyamino group, an O- (1-ethylideneamino) thiocarboxyamino group, and O- (1-methyl). Ethylideneamino) thiocarboxyamino group, O- [1-methylpropylideneamino] thiocarboxyamino group, (N-3,5-dimethylpyrazolylthiocarbonyl) amino group, (N-3-ethyl-5-methylpyrazolylthio) Carbonyl) amino group, (N-3,5-diethylpyrazolylthiocarbonyl) amino group, (N-3-propyl-5-methylpyrazolylthiocarbonyl) amino group, (N-3-ethyl-5-propylpyrazolylthiocarbonyl) ) Amino group and the like.

  As the at least one group (first functional group) selected from the group consisting of a blocked isocyanato group and a blocked isothiocyanato group according to the polymer compound (B-1), a blocked isocyanato group is preferable.

  When the blocked isocyanato group and / or the blocked isothiocyanato group possessed by the polymer compound (B-1) is the first functional group, the first functional group does not react with active hydrogen. However, when an electromagnetic wave or heat acts on the first functional group, a second functional group is generated, and the generated second functional group can react with active hydrogen. In other words, this first functional group is a functional group that can generate a second functional group that reacts with active hydrogen by elimination of the protective group derived from the blocking agent by the action of electromagnetic waves or heat. is there.

  Here, the active hydrogen refers to a hydrogen atom bonded to an atom other than a carbon atom such as an oxygen atom, a nitrogen atom and a sulfur atom.

  The second functional group that reacts with the active hydrogen is preferably protected (blocked) until the storage stability of the composition is performed. That is, the first functional group is preferably a functional group that generates a second functional group that reacts with active hydrogen by being removed by treatment with electromagnetic waves or heat treatment.

  The structure of the repeating unit having at least one group selected from the group consisting of a repeating unit having a blocked isocyanato group and a repeating unit having a blocked isothiocyanato group is based on the chemical structure of the monomer as the raw material. The example of the monomer used as the raw material of the repeating unit which has at least 1 type of group chosen from the group containing a blocked isocyanato group and a blocked isothiocyanato group below is shown.

  Examples of the polymerizable monomer having a blocked isocyanato group or a blocked isothiocyanato group include a monomer having a blocked isocyanato group or a blocked isothiocyanato group and an unsaturated bond in the molecule.

  A polymerizable monomer having a blocked isocyanato group or a blocked isothiocyanato group and an unsaturated bond in the molecule is obtained by reacting a compound having an isocyanato group or an isothiocyanato group and an unsaturated bond in the molecule with a blocking agent. Can be manufactured. Here, the unsaturated bond is preferably an unsaturated double bond.

  Examples of the compound having an unsaturated double bond and an isocyanato group in the molecule include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2- (2′-methacryloyloxyethyl) oxyethyl isocyanate, and the like. It is done. Examples of the compound having an unsaturated double bond and an isothiocyanato group in the molecule include 2-acryloyloxyethyl isothiocyanate, 2-methacryloyloxyethyl isothiocyanate, 2- (2′-methacryloyloxyethyl) oxyethyl isothiocyanate. Etc.

  Examples of the monomer having an unsaturated double bond and a blocked isocyanate group in the molecule include 2- [O- [1′-methylpropylideneamino] carboxyamino] ethyl-methacrylate, 2- [N- [1 ′]. , 3′-dimethylpyrazolyl] carboxyamino] ethyl-methacrylate and the like.

  The compound having a blocked isocyanato group or the compound having a blocked isothiocyanato group has, for example, a blocking agent having only one active hydrogen capable of reacting with the isocyanato group or isothiocyanato group and an isocyanato group or isothiocyanato group. It can be produced by reacting with a compound.

  The blocking agent is preferably a compound that can be removed from these groups at a temperature of 170 ° C. or lower even after reacting with an isocyanato group or isothiocyanato group. Examples of the blocking agent include alcohol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, urea compounds, oxime compounds, amine compounds, imine compounds, and bisulfite. Examples thereof include salts, pyridine compounds, and pyrazole compounds. These blocking agents may be used alone or in admixture of two or more. Examples of preferable blocking agents include oxime compounds and pyrazole compounds.

Hereinafter, the applicable blocking agent will be specifically described.
Examples of the alcohol compound which is a blocking agent include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexanol and the like.

  Examples of the phenol compound that is a blocking agent include phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoic acid ester, and the like.

  Examples of active methylene compounds that are blocking agents include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, and the like.

  Examples of mercaptan compounds that are blocking agents include butyl mercaptan and dodecyl mercaptan.

  Examples of acid amide compounds that are blocking agents include acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, and the like.

  Examples of the acid imide compound which is a blocking agent include succinimide and maleic imide.

  Examples of imidazole compounds that are blocking agents include imidazole and 2-methylimidazole.

  Examples of urea compounds that are blocking agents include urea, thiourea, ethyleneurea and the like.

  Examples of oxime compounds that are blocking agents include formaldoxime, acetoaldoxime, acetoxime, methylethylketoxime, cyclohexanone oxime, and the like.

  Examples of amine compounds that are blocking agents include diphenylamine, aniline, carbazole and the like.

  Examples of imine compounds that are blocking agents include ethyleneimine and polyethyleneimine.

  Examples of the bisulfite that is a blocking agent include sodium bisulfite.

  Examples of pyridine compounds that are blocking agents include 2-hydroxypyridine, 2-hydroxyquinoline, and the like.

  Examples of the pyrazole compound which is a blocking agent include 3,5-dimethylpyrazole, 3,5-diethylpyrazole and the like.

  In reacting a compound having an isocyanato group or isothiocyanato group and an unsaturated bond in the molecule with a blocking agent, an organic solvent, a catalyst or the like can be added and reacted as necessary.

  The weight average molecular weight of the binder resin (B) or the polymer compound (B-1) is preferably 3000 to 1000000, and more preferably 5000 to 500000.

  The binder resin (B) or the polymer compound (B-1) may be linear, branched, or cyclic.

  Examples of the polymer compound containing at least one repeating unit selected from the group consisting of a repeating unit having a blocked isocyanato group and a repeating unit having a blocked isothiocyanato group that can be used in the composition of the present invention include, for example, poly (Styrene-co-pentafluorobenzyl methacrylate-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (styrene-co-pentafluorobenzyl methacrylate-co- [ 2- [1 '-(3', 5'-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate]), poly (styrene-co-pentafluorobenzyl methacrylate-co-acrylonitrile-co- [2- [O- (1 '-Methylpropylideneamino) carboki Amino] ethyl-methacrylate]), poly (styrene-co-pentafluorobenzyl methacrylate-co-acrylonitrile-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate]) , Poly (styrene-co-pentafluorobenzyl methacrylate-co-acrylonitrile-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly ( Styrene-co-pentafluorobenzyl methacrylate-co-acrylonitrile-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (methyl Methacrylate -Pentafluorobenzyl methacrylate-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (methyl methacrylate-co-pentafluorobenzyl methacrylate-co- [2- [ 1 ′-(3 ′, 5′-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate]), poly (styrene-co-pentafluorobenzyl methacrylate-co- (2,2,2-trifluoroethyl methacrylate) -co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (styrene-co-pentafluorobenzyl methacrylate-co- (2,2,2-trifluoroethyl methacrylate)- Co- [2- [1 '-(3', 5'-dimethylpi Lazolyl) carboxyamino] ethyl-methacrylate]), poly (styrene-co-4-trifluorobenzylmethacrylate-co- [2- [O- (1'-methylpropylideneamino) carboxylamino] ethyl-methacrylate]), Poly (styrene-co-4- (1-ethoxyethyl) styrene-co-pentafluorobenzylmethacrylate-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (Styrene-co-4- (1-ethoxyethyl) styrene-co-pentafluorobenzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate]), Poly (styrene-co-4- (1-ethoxyethyl) styrene-cope Tafluorobenzyl methacrylate-co-acrylonitrile-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (styrene-co-4- (1-ethoxyethyl) styrene -Co-pentafluorobenzyl methacrylate-co-acrylonitrile-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate]), poly (styrene-co-4- (1 -Ethoxyethyl) styrene-co-pentafluorobenzylmethacrylate-co-acrylonitrile-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (Styrene-co-4- (1-ethoxyethyl Styrene-co-pentafluorobenzyl methacrylate-co-acrylonitrile-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (methyl Methacrylate-co-4- (1-ethoxyethyl) styrene-co-pentafluorobenzylmethacrylate-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (methyl Methacrylate-co-4- (1-ethoxyethyl) styrene-co-pentafluorobenzylmethacrylate-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate]), poly (Styrene-co-4- (1-ethoxyethyl) Styrene-co-pentafluorobenzyl methacrylate-co- (2,2,2-trifluoroethyl methacrylate) -co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), Poly (styrene-co-4- (1-ethoxyethyl) styrene-co-pentafluorobenzyl methacrylate-co- (2,2,2-trifluoroethyl methacrylate) -co- [2- [1 '-(3' , 5'-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate]), poly (styrene-co-4- (1-ethoxyethyl) styrene-co-4-trifluorobenzylmethacrylate-co- [2- [O- ( 1'-methylpropylideneamino) carboxylamino] ethyl-methacrylate]), poly (styrene- -{4-vinyl- (tetrahydro-2-pyranyl) benzoate} -co-pentafluorobenzyl methacrylate-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (Styrene-co- {4-vinyl- (tetrahydro-2-pyranyl) benzoate} -co-pentafluorobenzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carboxyamino] ethyl -Methacrylate]), poly (styrene-co- {4-vinyl- (tetrahydro-2-pyranyl) benzoate} -co-pentafluorobenzyl methacrylate-co-acrylonitrile-co- [2- [O- (1'-methyl Propylideneamino) carboxyamino] ethyl-methacrylate]), poly Styrene-co- {4-vinyl- (tetrahydro-2-pyranyl) benzoate} -co-pentafluorobenzyl methacrylate-co-acrylonitrile-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carboxy Amino] ethyl-methacrylate]), poly (styrene-co- {4-vinyl- (tetrahydro-2-pyranyl) benzoate} -co-pentafluorobenzyl methacrylate-co-acrylonitrile-co- [2- [O- (1 '-Methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (styrene-co- {4-vinyl- (tetrahydro-2-pyranyl) benzoate} -co-pentafluorobenzyl methacrylate- Co-acrylonitrile-co- [2- [ 1 '-(3', 5'-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (methyl methacrylate-co- {4-vinyl- (tetrahydro-2-pyranyl) benzoate}- Co-pentafluorobenzyl methacrylate-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (methyl methacrylate-co- {4-vinyl- (tetrahydro-2- Pyranyl) benzoate} -co-pentafluorobenzyl methacrylate-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate]), poly (styrene-co- {4-vinyl -(Tetrahydro-2-pyranyl) benzoate} -co Pentafluorobenzyl methacrylate-co- (2,2,2-trifluoroethyl methacrylate) -co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (styrene- Co- {4-vinyl- (tetrahydro-2-pyranyl) benzoate} -co-pentafluorobenzyl methacrylate-co- (2,2,2-trifluoroethyl methacrylate) -co- [2- [1 '-(3 ', 5'-dimethylpyrazolyl) carboxyamino] ethyl-methacrylate]), poly (styrene-co-4- (1-ethoxyethyl) styrene-co- {4-vinyl- (tetrahydro-2-pyranyl) benzoate}- Co-4-trifluorobenzyl methacrylate-co- [2- [O- (1′-methylpropylide Amino) carboxylamino] ethyl-methacrylate]) and the like.

<Method for Producing Polymer Compound (B-1)>
The polymer compound (B-1) used in the composition of the present invention is a polymerizable monomer serving as a raw material for the repeating unit represented by the formula (5), and a raw material for the repeating unit represented by the formula (6). "Other monomer" used as a raw material for "other repeating units" other than the polymerizable monomer and the polymerizable monomer having a blocked isocyanato group or a blocked isothiocyanato group is added during the production of the polymer compound (B) Is preferred.

  The polymer compound (B-1) includes, for example, a polymerizable monomer that is a raw material of the repeating unit represented by the formula (5) and a polymerizable monomer that is a raw material of the repeating unit represented by the formula (6). And at least one selected from the group consisting of a polymerizable monomer having an unsaturated double bond and a blocked isocyanato group or a blocked isothiocyanato group in the molecule, using a photopolymerization initiator or a thermal polymerization initiator. It can be produced by a polymerization method.

  In the production of the polymer compound (B-1), the charged molar ratio of the polymerizable monomer having an unsaturated double bond and a blocked isocyanato group or a blocked isothiocyanato group in the molecule is determined based on all monomers involved in the polymerization. Among them, the content is preferably 5 mol% or more and 60 mol% or less, more preferably 10 mol% or more and 50 mol% or less. By adjusting the charged molar ratio of the monomer within this range, a crosslinked structure is sufficiently formed inside the resin composite, and solvent resistance, mechanical strength, and gas barrier properties are improved.

Hereinafter, the polymerizable monomer used for the manufacturing method of a high molecular compound (B-1) is demonstrated. The “polymerizable monomer having a blocked isocyanato group or a blocked isothiocyanato group” is as described above.
Examples of the polymerizable monomer that is a raw material for the repeating unit represented by the formula (5) include styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene. 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5 -Trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p- Bromostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α -Methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,4-dimethyl-α-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl- α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, divinylbiphenyl, diisopropylbenzene, 4-aminostyrene, 4- (methoxymethoxy) styrene, 4- (methoxy Ethoxymethyloxy) styrene, -(1-ethoxyethyloxy) styrene, 2- (methoxymethoxycarbonyl) styrene, 2- (methoxyethoxymethyloxycarbonyl) styrene, 2- (1-ethoxyethyloxycarbonyl) styrene, 2- (tetrahydropyranyloxycarbonyl) ) Styrene, 3- (methoxymethoxycarbonyl) styrene, 3- (methoxyethoxymethyloxycarbonyl) styrene, 3- (1-ethoxyethyloxycarbonyl) styrene, 3- (tetrahydropyranyloxycarbonyl) styrene, 4- (methoxy Methoxycarbonyl) styrene, 4- (methoxyethoxymethyloxycarbonyl) styrene, 4- (1-ethoxyethyloxycarbonyl) styrene, 4- (tetrahydropyranyloxycarbonyl) styrene, and the like. It is.

  Examples of the polymerizable monomer that is a raw material of the repeating unit having the organic group represented by the formula (6) include methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n. -Butyl, isobutyl acrylate, -sec-butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isobornyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, acrylic 2-hydroxyethyl acid, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyphenylethyl acrylate, 2-cyanoethyl acrylate, ethylene glycol dia Chestnut , Propylene glycol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol pentaacrylate, N, N-dimethylacrylamide N, N-diethylacrylamide, N-acryloylmorpholine, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2- (perfluorobutyl) ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2- (perfluorohexyl) ethyl acrylate, 3-perfluorohexyl-2-hydroxypro Acrylate, 2- (perfluorooctyl) ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluoro-3-methylbutyl) ethyl acrylate, 3- (Perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 2- (perfluoro-5-methylhexyl) ethyl acrylate, 2- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 3- (perfluorocarbon) Fluoro-5-methylhexyl) -2-hydroxypropyl acrylate, 2- (perfluoro-7-methyloctyl) ethyl acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl acrylate, 1H, 1 H, 3H-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 7H-dodecafluoroheptyl acrylate, 1H, 1H, 9H-hexadecafluorononyl acrylate, 1H-1- (trifluoro Methyl) trifluoroethyl acrylate, 1H, 1H, 3H-hexafluorobutyl acrylate, 2- (methoxymethoxy) ethyl acrylate, 2- (methoxyethoxymethyloxy) ethyl acrylate, 2- (1-ethoxyethyloxy) ethyl acrylate, 2- (methoxymethoxy) ethyl methacrylate, 2- (methoxyethoxymethyloxy) ethyl methacrylate, 2- (1-ethoxyethyloxy) ethyl methacrylate, 2,3,4,5,6-pentaful Robenzyl acrylate, 2,3,4,5,6-pentafluorobenzyl methacrylate, 2-fluorobenzyl acrylate, 2-fluorobenzyl methacrylate, 3-fluorobenzyl acrylate, 3-fluorobenzyl methacrylate, 4-fluorobenzyl acrylate, 4 -Fluorobenzyl methacrylate, 4-trifluoromethylbenzyl acrylate, 4-trifluoromethylbenzyl methacrylate, methoxymethyl acrylate, methoxyethoxymethyl acrylate, 1-ethoxyethyl acrylate, 2-acryloyloxyoxirane, 2-acryloyloxyoxetane 2-acryloyl Oxy-2,3-dihydrofuran, 2-acryloyloxytetrahydrofuran, 2-acryloyloxy-3,4 Dihydro-2H-pyran, 2-acryloyloxy-3,6-dihydro-2H-pyran, 2-acryloyloxy-tetrahydropyran, 2-acryloyloxy-2,3-dihydrooxepin, 2-acryloyloxy-2, 3,4,5-tetrahydrooxepin, 2-acryloyloxy-2,3,6,7-tetrahydrooxepin, 2-acryloyloxy-hexahydrooxepin, 2-acryloyloxy-3,4-dihydro -2H-oxocin, 2-acryloyloxy-5,6-dihydro-2H-oxocine, 2-acryloyloxy-7,8-dihydro-2H-oxocine, 2-acryloyloxy-3,4,5,6-tetrahydro- 2H-oxocin, 2-acryloyloxy-5,6,7,8-tetrahydro-2H-o Xoxosin, 2-acryloyloxy-hexahydro-2H-oxocine, methoxymethyl-methacrylate, methoxyethoxymethyl-methacrylate, 1-ethoxyethyl-methacrylate, 2-methacryloyloxyoxirane, 2-methacryloyloxyoxetane 2-methacryloyloxy-2,3 -Dihydrofuran, 2-methacryloyloxytetrahydrofuran, 2-methacryloyloxy-3,4-dihydro-2H-pyran, 2-methacryloyloxy-3,6-dihydro-2H-pyran, 2-methacryloyloxy-tetrahydropyran, 2- Methacryloyloxy-2,3-dihydrooxepin, 2-methacryloyloxy-2,3,4,5-tetrahydrooxepin, 2-methacryloyloxy-2,3,6,7-teto Hydrooxepin, 2-methacryloyloxy-hexahydrooxepin, 2-methacryloyloxy-3,4-dihydro-2H-oxocine, 2-methacryloyloxy-5,6-dihydro-2H-oxocine, 2-methacryloyloxy-7, 8-dihydro-2H-oxocine, 2-methacryloyloxy-3,4,5,6-tetrahydro-2H-oxocin, 2-methacryloyloxy-5,6,7,8-tetrahydro-2H-oxocin, 2-methacryloyloxy -Hexahydro-2H-oxocin, methacrylate ester and derivatives thereof include, for example, methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate , Methacrylate Butyl, methacrylate-sec-butyl, hexyl methacrylate, octyl methacrylate, -2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, methacryl Acid benzyl, methacrylate-2-hydroxyethyl, methacrylate-2-hydroxypropyl, methacrylate-3-hydroxypropyl, methacrylate-2-hydroxybutyl, methacrylate-2-hydroxyphenylethyl, methacrylate 2-cyanoethyl acrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, triethyleneglycol Dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol pentamethacrylate, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N-acryloylmorpholine, 2,2 , 2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (perfluorobutyl) ethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2, -(Perfluorohexyl) ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2- (perfluorooctyl) ethyl methacrylate, 3-perfluoroio Til-2-hydroxypropyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-3-methylbutyl) ethyl methacrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate Acrylate, 2- (perfluoro-5-methylhexyl) ethyl methacrylate, 2- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxy Propyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, 1H, 1H, 3H-tetrafluoropropyl metaacrylate 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 7H-dodecafluoroheptyl methacrylate, 1H, 1H, 9H-hexadecafluorononyl methacrylate, 1H-1- (trifluoromethyl) trifluoroethyl Methacrylate, 1H, 1H, 3H-hexafluorobutyl methacrylate, acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, 3- (N, N-dimethylamino) propylacrylamide, N -(2-Hydroxyethyl) acrylamide and acryloylmorpholine are mentioned.

  The polymer compound (B-1) used in the composition of the present invention is a polymerizable monomer that is a raw material for the repeating unit represented by the formula (5) and a raw material for the repeating unit that is represented by the formula (6). In addition to at least one selected from the group consisting of a polymerizable monomer and a polymerizable monomer having a blocked isocyanato group or a blocked isothiocyanato group, in addition to “other repeating units” as a raw material of “others” "Monomer" may be added during the production of the polymer compound (B-1).

  “Other monomers” include, for example, methacrylonitrile and derivatives thereof, acrylonitrile and derivatives thereof, vinyl esters and derivatives of organic carboxylic acids, allyl esters and derivatives of organic carboxylic acids, dialkyl esters and derivatives of fumaric acid, Examples thereof include dialkyl esters of maleic acid and derivatives thereof, dialkyl esters of itaconic acid and derivatives thereof, maleimide and derivatives thereof, terminal unsaturated hydrocarbons and derivatives thereof, and organic germanium derivatives.

  Examples of acrylonitrile and its derivatives which are “other monomers” include acrylonitrile. Examples of methacrylonitrile and its derivatives which are “other monomers” include methacrylonitrile and the like.

  Examples of vinyl esters of organic carboxylic acids and derivatives thereof that are “other monomers” include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, divinyl adipate, and the like.

  Examples of allyl esters of organic carboxylic acids and derivatives thereof that are “other monomers” include allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, diallyl phthalate, and the like.

  Examples of the “other monomer” dialkyl ester of fumaric acid and its derivatives include dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-fumarate. Examples include butyl, di-2-ethylhexyl fumarate, and dibenzyl fumarate.

  Dialkyl esters of maleic acid that are “other monomers” and derivatives thereof include dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, Examples include di-2-ethylhexyl maleate and dibenzyl maleate.

  Examples of the “other monomers” itaconic acid dialkyl esters and derivatives thereof include dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-itaconate Examples include butyl, di-2-ethylhexyl itaconate, dibenzyl itaconate, and the like.

  Examples of maleimide which is “another monomer” and derivatives thereof include N-phenylmaleimide, N-cyclohexylmaleimide and the like.

  Examples of terminal unsaturated hydrocarbons and derivatives thereof that are “other monomers” include 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, vinyl chloride, allyl alcohol, and the like.

  Examples of organic germanium derivatives that are “other monomers” include allyltrimethylgermanium, allyltriethylgermanium, allyltributylgermanium, trimethylvinylgermanium, triethylvinylgermanium, and the like.

  Examples of the photopolymerization initiator used for the production of the polymer compound (B-1) include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 4-isopropyl-2-hydroxy. 2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 4,4′-bis (diethylamino) benzophenone, benzophenone, methyl (o-benzoyl) benzoate, 1-phenyl-1,2-propanedione -2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin Okuchi Ether, benzyl, benzyldimethyl ketal, benzyl diethyl ketal, carbonyl compounds such as diacetyl, anthraquinone or thioxanthone derivatives such as methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diphenyl disulfide, dithiocarbamate, etc. A sulfur compound is mentioned.

  The thermal polymerization initiator used for the production of the polymer compound (B-1) may be any thermal polymerization initiator, for example, 2,2′-azobisisobutyronitrile, 2,2 '-Azobisisovaleronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), 1,1'-azobis (cyclohexanecarbonitrile) Azo compounds such as 2,2′-azobis (2-methylpropane), 2,2′-azobis (2-methylpropionamidine) dihydrochloride, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone Ketone peroxide such as peroxide, isobutyl peroxide, benzoyl peroxide, 2, -Diacyl peroxides such as dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene Hydroperoxides, hydroperoxides such as tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, dialkyl peroxides such as tris (tert-butylperoxy) triazine, Peroxyketals such as 1,1-di-tert-butylperoxycyclohexane and 2,2-di (tert-butylperoxy) butane, tert-butylperoxypivalate, tert-butyl -Oxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyazelate, tert-butylperoxy-3,5,5 Alkyl peresters such as trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, di-tert-butylperoxytrimethyladipate, diisopropyl peroxydicarbonate, di-sec-butylperoxydicarbonate Percarbonate such as tert-butylperoxyisopropyl carbonate.

The polymer compound (B-1) of the present invention may have a functional group that forms a crosslinked structure by the action of light or heat. Examples of the functional group that forms a crosslinked structure by the action of light or heat include a group having an unsaturated double bond and a benzyl halide group.
Examples of the group having an unsaturated double bond include a styryl group, vinyloxy group, vinyl group, acryloyl group, methacryloyl group, cinnamyl group, cinnamoyl group and the like.
Examples of the halogenated benzyl group include a chloromethylphenyl group.
The polymer compound (B-1) having a functional group that forms a crosslinked structure by the action of light or heat is obtained by photopolymerizing a polymerizable monomer that is a raw material of a repeating unit having a functional group that forms a crosslinked structure by the action of light. Photopolymerization of a polymerizable monomer that is a raw material of a repeating unit containing a group that reacts with a compound having a functional group that forms a crosslinked structure by the action of light, or a method of copolymerization using an initiator or a thermal polymerization initiator After copolymerization using an initiator or a thermal polymerization initiator, it can be produced by a method of reacting a compound having a functional group that forms a crosslinked structure by the action of light.
Examples of the polymerizable monomer that is a raw material of the repeating unit having a functional group that forms a crosslinked structure by the action of light include cinnamyl methacrylate, cinnamyl acrylate, cinnamoyl methacrylate, and cinnamoyl acrylate.
Examples of the polymerizable monomer that is a raw material of the repeating unit containing a group that reacts with a compound having a functional group that forms a crosslinked structure by the action of light include aminostyrene, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, and vinyl benzoate. Examples include acids.
Examples of the compound having a functional group that forms a crosslinked structure by the action of light include glycidyl methacrylate and 2-isocyanatoethyl methacrylate.
When the polymer compound (B-1) having a functional group that forms a crosslinked structure by the action of light or heat is used, it is preferable to add a radical initiator that decomposes by heating to generate radicals.
The temperature at which the radical initiator decomposes by heating to generate radicals is usually 200 ° C. or lower, preferably 50 ° C. or higher and 150 ° C. or lower, more preferably 60 ° C. or higher and 120 ° C. or lower.
Examples of the radical initiator include photopolymerization initiators and thermal polymerization initiators used in the production of the curable resin (B) and the curable resin (B-1).

  As the binder resin (B) used in the present invention, an epoxy resin having a functional group capable of reacting with a hydroxyl group and / or a carboxyl group in the polymer compound (A), a repeating unit containing a blocked isocyanate group, and A resin containing at least one repeating unit selected from the group consisting of repeating units containing a blocked isothiocyanato group is preferred.

Production method of resin composite The production method of the resin composite of the present invention comprises the steps of mixing the polymer compound (A-1) and the binder resin (B) to obtain a mixture,
Converting at least one group selected from the group consisting of R ^A and R ^{B in the} polymer compound (A-1) to a hydrogen atom;
including.

<Step of mixing the polymer compound (A-1) and the binder resin (B) to obtain a mixture>

  A step of mixing the polymer compound (A-1) and the binder resin (B) to obtain a mixture (hereinafter sometimes referred to as a resin composite precursor) (hereinafter referred to as a resin composite precursor manufacturing step). Explain).

In the case where the binder resin (B) is a thermoplastic resin, as one embodiment of the resin composite precursor manufacturing process, the polymer compound (A-1) and the binder resin (B) are kneaded while heating, which is conventionally known. And a method of producing a resin composite precursor by the heat kneading method. The heating temperature is ^RA and R from at least one group selected from the group consisting of the group represented by formula (1) and the group represented by formula (2) in the polymer compound (A-1). It is preferable that the temperature is not higher than the temperature at which at least one group selected from the group consisting of ^B dissociates and at least one group selected from the group consisting of a hydroxyl group and a carboxyl group is generated. When the heating temperature is equal to or higher than the above temperature, the compatibility with the binder resin (B) may decrease due to the interaction between the generated hydroxyl group and / or carboxyl group, and uniform mixing may not be possible.

Further, as another embodiment of the resin complex precursor production process, a resin complex precursor solution is produced by a solvent mixing method in which both the thermoplastic resin and the polymer compound (A-1) are dissolved in a solvent. The resin composite precursor solution is applied by a conventionally known spin coating method, die coating method, screen printing method, ink jet method, casting method, or other coating method, and the solvent is dried to produce a resin composite precursor. A method is mentioned.

When the binder resin (B) is a thermosetting resin, the polymer compound (A-1) and the binder resin (B) are heated at a temperature equal to or lower than the thermosetting temperature as an embodiment of the resin composite precursor manufacturing process. And a method of producing a resin composite precursor by a conventionally known heat kneading method in which kneading is performed.
Moreover, as one embodiment of the resin complex precursor production process, a resin complex precursor solution is produced by a solvent mixing method in which both a thermosetting resin and the polymer compound (A-1) are dissolved. A method of producing a resin composite precursor by applying the resin composite precursor solution and drying the solvent in the same manner as described above.
Moreover, when using the said high molecular compound (B-1) as binder resin (B), as one embodiment of a resin composite precursor manufacturing process, by selecting a solvent suitably, the said high molecular compound (A- 1) A resin complex precursor solution is produced by producing the polymer compound (B-1) in the presence, and the resin complex precursor solution is applied in the same manner as described above, and the solvent is dried. The method of manufacturing a resin composite precursor by this is mentioned.

The resin complex precursor may contain a catalyst that promotes a reaction in which at least one group selected from the group consisting of R ^A and R ^B in the polymer compound (A-1) is a hydrogen atom. .
The catalyst is a compound that generates acid upon decomposition by irradiation with electromagnetic waves or electron beams, or by heating.

  Examples of the electromagnetic wave include infrared rays, visible rays, and ultraviolet rays, and preferably ultraviolet rays. The wavelength of the electromagnetic wave is preferably 450 nm or less, more preferably 200 nm or more and 410 nm or less.

  Examples of the catalyst include sulfonic acid ester compounds, triazine compounds, iodonium salts, and sulfonium salts.

  As the sulfonic acid ester compound, a fluorinated alkyl sulfonic acid ester compound or a toluene sulfonic acid ester compound is preferable.

  Examples of the fluorinated alkyl sulfonic acid ester compound include N-hydroxynaphthalimide triflate, N-hydroxynaphthalimide perfluorobutyl triflate, N-hydroxyphthalimide triflate, and N-hydroxyphthalimide perfluorobutyl triflate. .

  Examples of the toluenesulfonic acid ester compound include α- (p-toluenesulfonyloxymethyl) benzoin, α- (p-toluenesulfonyloxy) -o-nitrotoluene, α- (p-toluenesulfonyloxy) -p-nitrotoluene, 2-hydroxy-2- (p-toluenesulfonyloxymethyl) -1,2-diphenylethanone is mentioned.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6-methyl-1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2 , 4-bis (trichloromethyl) -6-phenyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4′-methoxyphenyl) -1,3,5-triazine, 2 , 4-bis (trichloromethyl) -6- (3 ′, 4′-dimethoxyphenyl) -1,3,5-triazine.

  Examples of the iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and tolylcumyl iodonium tetrakis (pentafluorophenyl) borate.

  Examples of the sulfonium salt include triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4,4′- Bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyl-di (4-methylphenyl) sulfonium hexafluoro Examples include phosphate.

  The catalyst may be a compound described in JP-A-9-118663 or a compound described in JP-A-2007-262401.

  The said catalyst may be only 1 type and may be contained 2 or more types.

<Step of converting at least one group selected from the group consisting of R ^A and R ^{B in the} polymer compound (A-1) to a hydrogen atom>
The mixture (resin composite precursor) produced by the heat kneading method is molded into a desired shape by a conventionally known method, and the group represented by the formula (1) in the polymer compound (A-1) and the formula ( 2) at least a temperature at which at least one selected from the group consisting of R ^A and R ^B dissociates from at least one group selected from the group consisting of the group represented by 2), or represented by the formula (1) At least one group selected from the group consisting of a group and a group represented by formula (2) above the activation temperature of the catalyst that promotes dissociation of at least one type selected from the group consisting of R ^A and R ^B After heating, the group represented by the formula (1) or the group represented by the formula (2) after the group represented by R ^A or the group represented by R ^B is dissociated with R ^A hydrogen atoms bonded to carbon atoms of the group represented by group or R ^B is expressed By moving the at least one group selected from the group consisting of R ^A and R ^B in the polymeric compound (A-1) and a hydrogen atom, the polymeric compound (A) and the binder resin (B) Can be produced.
In addition, by using the resin complex precursor solution produced by the solvent solution method and heat-treating the resin complex precursor produced by the coating method in the same manner as described above, the polymer compound (A) and the binder resin ( B) can be produced.
Examples of the method for heating the resin composite precursor include a heating method using a hot plate and a heating method using an oven.

  The resin composite obtained by the production method of the present invention can be suitably used as an engineering plastic for automobile members, electronic device members, display members and the like, and as an insulating material for electronic devices or batteries. .

  Hereinafter, the present invention will be described with reference to examples. The present invention is not limited by the following examples. The numbers in parentheses in the formulas shown in the following description of the examples represent the mole fraction of repeating units.

Synthesis example 1
10.00 g of hydroxypropyl cellulose (Nippon Soda Co., Ltd .; trade name HPC SSL SFP), 40.00 g of butyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), 80.00 g of cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-methyl-2 -20.00 g of pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.00 g of pyridinium paratoluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), and a stirrer were placed in a 300 mL eggplant flask, sealed, and stirred for 24 hours at room temperature with a magnetic stirrer. I let you. The obtained viscous uniform solution was transferred to a separating funnel, and the organic layer was washed with ion-exchanged water three times. After drying the organic layer with anhydrous magnesium sulfate, the salt is filtered, the filtrate is concentrated with a rotary evaporator, the solvent is removed with a vacuum pump, and the hydroxyl group is blocked with a 1-butoxyethyl group. (Hereinafter referred to as blocked cellulose (1)) was obtained as a viscous liquid. Yield 18.56 g.

  The weight average molecular weight of the obtained blocked cellulose (1) in terms of standard polystyrene was 46000 (using Shimadzu GPC, Tskel super HM-H (1) and Tskel super H2000 (1)) Tetrahydrofuran (THF) was used as the phase.

Synthesis example 2
Hydroxypropyl cellulose (hereinafter referred to as blocked cellulose (2)) in which the hydroxyl group was blocked with a 2-tetrahydropyranyl group in the same manner as in Synthesis Example 1 except that 3,4-dihydropyran was used instead of butyl vinyl ether. Was obtained as a viscous liquid. Yield 16.82 g.

  The weight average molecular weight in terms of standard polystyrene of the obtained blocked cellulose (2) was 48,000 (using Shimadzu GPC, Tskel super HM-H (1) and Tskel super H2000 (1)) THF was used as the phase.)

Synthesis example 3
4.00 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.07 g of 2- [O- [1′-methylpropylideneamino] carboxyamino] ethyl methacrylate (manufactured by Showa Denko KK, trade name: Karenz MOI-BM), Blocked cellulose (1) 2.53 g, 2,2′-azobis (2-methylpropionitrile) 0.03 g, and cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.) 11.46 g were added to a 50 mL pressure vessel (ACE GLASS). The product was bubbled with nitrogen gas, sealed, and sealed in a 60 ° C. oil bath in the presence of blocked cellulose (1) with methyl methacrylate and 2- [O- [1′-methylpropylideneamino]. Carboxyamino] ethyl-methacrylate is copolymerized for 16 hours to form a block with a resin having the following repeating unit and composition: A viscous resin composite precursor cyclopentanone solution (1) in which cellulose (1) was dissolved was obtained.

Synthesis example 4
Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.00 g, blocked cellulose (2) 2.50 g, 2,2′-azobis (2-methylpropionitrile) 0.03 g, and cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.) 11.33 g was put in a 50 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and methyl methacrylate was added in the presence of blocked cellulose (2) in an oil bath at 60 ° C. for 16 hours. Polymerization was performed to obtain a viscous resin composite precursor cyclopentanone solution (2) in which a resin having the following repeating unit and composition and the blocked cellulose (2) were dissolved.

Synthesis example 5
Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.00 g, blocked cellulose (1) 2.50 g, 2,2′-azobis (2-methylpropionitrile) 0.03 g, and cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.) 11.33 g was put in a 50 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and methyl methacrylate was added for 16 hours in the presence of blocked cellulose (1) in an oil bath at 60 ° C. Polymerization was performed to obtain a viscous resin composite precursor cyclopentanone solution (3) in which a resin having the following repeating unit and composition and the blocked cellulose (1) were dissolved.

Synthesis Example 6
5.00 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.50 g of hydroxypropylcellulose (manufactured by Nippon Soda Co., Ltd .; trade name HPC SSL SFP), 0.03 g of 2,2′-azobis (2-methylpropionitrile), And 11.33 g of cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.) are put into a 50 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and the presence of hydroxypropylcellulose in an oil bath at 60 ° C. Then, methyl methacrylate was polymerized for 16 hours to obtain a viscous resin composite precursor cyclopentanone solution (4) in which a resin having the following repeating unit and composition and hydroxypropyl cellulose were mixed.

Synthesis example 7
Styrene monomer (manufactured by Junsei Kagaku) 2.31 g, 2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich) 3.24 g, 2- [O- [1′-methylpropylideneamino] carboxyamino ] 4.00 g of ethyl-methacrylate (made by Showa Denko KK, trade name: Karenz MOI-BM), 0.05 g of 2,2′-azobis (2-methylpropionitrile), and propylene glycol monomethyl ether acetate (Tokyo Kasei Co., Ltd.) 6.40 g was put into a 50 mL pressure vessel (ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 60 ° C. for 16 hours to have the following repeating units and composition: A propylene glycol monomethyl ether acetate solution of the binder resin (1) was obtained.

  The weight average molecular weight in terms of standard polystyrene of the obtained binder resin (1) was 80,000 (using Shimadzu GPC, Tskel super HM-H (1) and Tskel super H2000 (1), mobile phase) As THF).

Synthesis example 8
Styrene monomer (manufactured by Junsei Kagaku) 9.53 g, 2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich) 9.71 g, 2- [O- [1′-methylpropylideneamino] carboxyamino ] Ethyl-methacrylate (made by Showa Denko KK, trade name: Karenz MOI-BM) 4.00 g, 2-hydroxyethyl methacrylate (produced by Tokyo Chemical Industry Co., Ltd.) 1.08 g, 2,2'-azobis (2-methylpropionitrile) ) 0.06 g and 36.67 g of cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.) are put into a 125 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and 12 in a 60 ° C. oil bath. By polymerizing for a time, a cyclopentanone solution of binder resin (2) having the following repeating units and composition was obtained.

  The weight average molecular weight of the obtained binder resin (2) in terms of standard polystyrene was 120,000 (using Shimadzu GPC, Tskel super HM-H (1) and Tskel super H2000 (1), mobile phase) As THF).

Synthesis Example 9
Hydroxypropylcellulose (manufactured by Nippon Soda Co., Ltd .; trade name HPC L-FP) 10.00 g, cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.) 160.00 g, and stir bar were placed in a 300 mL eggplant flask, sealed, and magnetic stirrer. And stirred at room temperature for 24 hours. 20.00 g of butyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.00 g of pyridinium paratoluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) are added to the resulting viscous homogeneous solution, and further stirred at room temperature for 24 hours with a magnetic stirrer. Reacted. After completion of the reaction, unreacted butyl vinyl ether in the resulting viscous reaction solution was removed with a rotary evaporator, and a viscous cyclopentanone solution of hydroxypropyl cellulose in which the hydroxyl group was blocked with 1-butoxyethyl group ( 5) was obtained. 10 g of the cyclopentanone solution (5) was placed in a 100 ml eggplant flask and dried overnight at 60 ° C. in a vacuum dryer to obtain a solid content concentration of 23% by weight.

Example 1
0.49 g of NACURE X49-110 (manufactured by Enomoto Kasei Co., Ltd.) was added to 19.10 g of the resin complex precursor cyclopentanone solution (1) obtained in Synthesis Example 3, and the mixture was stirred and dissolved to obtain a coating solution ( 1) was adjusted.

The obtained coating liquid (1) was applied on a glass substrate using an applicator (gap: 250 μm), and then baked on a hot plate at 150 ° C. for 30 minutes to form a coating film. The formed coating film was peeled off from the glass substrate, and the thickness was measured with a micrometer to be 21 μm.
It was 84.3% as a result of measuring the transmittance | permeability in 600 nm with a spectrophotometer.
Agglomerated particles were not observed.

Example 2
0.43 g of NACURE X49-110 (manufactured by Enomoto Kasei Co., Ltd.) was added to 18.88 g of the resin complex precursor cyclopentanone solution (2) obtained in Synthesis Example 4, and the mixture was stirred and dissolved to obtain a coating solution ( 2) was adjusted.

The obtained coating solution (2) was applied on a glass substrate using an applicator (gap: 300 μm), and then baked on a hot plate at 150 ° C. for 30 minutes to form a coating film. The formed coating film was peeled from the glass substrate, and the thickness was measured with a micrometer to be 38 μm.
As a result of measuring the transmittance at 600 nm with a spectrophotometer, it was 53.6%.
Agglomerated particles were not observed.

Example 3
To the resin complex precursor cyclopentanone solution (3) obtained in Synthesis Example 5, 0.30 g of NACURE X49-110 (manufactured by Enomoto Kasei Co., Ltd.) was added and stirred to dissolve the coating solution ( 3) was adjusted.

The obtained coating liquid (3) was applied on a glass substrate using an applicator (gap: 350 μm), and then baked on a hot plate at 150 ° C. for 30 minutes to form a coating film. The formed coating film was peeled off from the glass substrate, and the thickness was measured with a micrometer to be 49 μm.
The transmittance at 600 nm was measured with a spectrophotometer and found to be 13.3%.
Agglomerated particles were not observed.

Example 4
2.00 g of the propylene glycol monomethyl ether acetate solution of the binder resin (1) obtained in Synthesis Example 7; 1.30 g of the cyclopentanone solution (5) obtained in Synthesis Example 9; The coating solution (4) was prepared by stirring and mixing with a magnetic stirrer.

The obtained coating solution (4) was applied on a glass substrate using an applicator (gap: 500 μm), and then baked on a hot plate at 150 ° C. for 30 minutes to form a coating film. When the thickness was measured with a micrometer, it was 41 μm.
The transmittance at 600 nm was measured with a spectrophotometer and found to be 72.3%.
Agglomerated particles were not observed.

Example 5
2.00 g of the binder resin cyclopentanone solution obtained in Synthesis Example 8 and 1.73 g of the cyclopentanone solution (5) obtained in Synthesis Example 9 and a stirrer were placed in a 10 ml sample bottle, and a magnetic stirrer was used. The coating liquid (5) was adjusted by mixing with stirring.

The obtained coating solution (5) was applied on a glass substrate using an applicator (gap: 500 μm), and then baked on a hot plate at 150 ° C. for 30 minutes to form a coating film. It was 48 micrometers when the thickness of the formed coating film was measured with the micrometer.
As a result of measuring the transmittance at 600 nm with a spectrophotometer, it was 46.9%.
Agglomerated particles were not observed.

Example 6
2.00 g of propylene glycol monomethyl ether acetate solution of the binder resin (1) obtained in Synthesis Example 7, 1.30 g of the cyclopentanone solution (5) obtained in Synthesis Example 9, 2-hydroxy-2- (p -Toluenesulfonyloxymethyl) -1,2-diphenylethanone (manufactured by Midori Kagaku Co., Ltd .; trade name MBZ-101) 0.03 g and a stir bar are placed in a 10 ml sample bottle and mixed by stirring with a magnetic stirrer. The coating liquid (6) was adjusted by this.

The obtained coating solution (6) was applied on a glass substrate using an applicator (gap: 500 μm), and then baked on a hot plate at 150 ° C. for 30 minutes to form a coating film. It was 54 micrometers when the thickness of the formed coating film was measured with the micrometer.
As a result of measuring the transmittance at 600 nm with a spectrophotometer, it was 73.2%.
Agglomerated particles were not observed.

Comparative Example 1
To the resin complex precursor cyclopentanone solution (4) obtained in Synthesis Example 6, 0.30 g of NACURE X49-110 (manufactured by Enomoto Kasei Co., Ltd.) is added and stirred to dissolve the coating solution ( 7) was adjusted.

  The obtained coating liquid (7) was applied on a glass substrate using an applicator (gap: 350 μm) and then baked on a hot plate at 150 ° C. for 30 minutes. No membrane was obtained.

  As is apparent from Table 1, the membranes obtained in Examples 1 to 6 according to the present invention have high permeability and are high molecular compounds having a repeating unit containing a glucose residue having at least one hydroxyl group in the main chain. It can be said that the dispersibility of (A) is high.

Claims (3)

Production of a resin complex containing a polymer compound (A) having a repeating unit containing a glucose residue having at least one group selected from the group consisting of a hydroxyl group and a carboxyl group in the main chain and a binder resin (B) A method,
The following polymer compound (A-1) and binder resin (B) are mixed to obtain a mixture;
Converting at least one group selected from the group consisting of R ^A and R ^{B in the} polymer compound (A-1) to a hydrogen atom;
The manufacturing method of the resin composite containing this.
Polymer compound (A-1): a polymer compound having a repeating unit containing a glucose residue in the main chain,
A polymer compound in which the glucose residue has at least one group selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2).

(1)

(2)
(In the formulas (1) and (2), R ^A and R ^B are each independently an organic group represented by the following formula (3), an organic group represented by the following formula (4), and the following formula (5 And at least one organic group selected from the group consisting of organic groups represented by the following formula (6):

(3)

(4)

(5)

(6)
(In formulas (3) and (4), R ¹ , R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ² is the number of carbon atoms. Represents a monovalent organic group of 1 to 20. r represents an integer of 3 to 20;
In formulas (5) and (6), R ⁵ represents a monovalent organic group having 1 to 20 carbon atoms. R ^{6 to} R ¹⁰ and R ^{14 to} R ²⁹ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a halogen atom. s represents an integer of 0 to 10. ) The binder resin (B) comprises a repeating unit represented by the following formula (7), a repeating unit represented by the following formula (8), a repeating unit having a blocked isocyanato group in the molecule, and a blocked isothiocyanato group. The method for producing a resin composite according to claim 1, which is a polymer compound (B-1) containing at least one type of repeating unit selected from the group consisting of repeating units.

(7)
(In the formula (7), R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, a fluorine atom, a nitro group, or a cyano group. And a hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.

(8)
(In Formula (8), R ³⁵ represents a hydrogen atom or a methyl group. X represents an oxygen atom or —NR ³⁷ —. R ³⁶ and R ³⁷ are each independently a hydrogen atom, Represents a monovalent organic group having 1 to 20 carbon atoms, and a hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.) The method for producing a resin composite according to claim 1 or 2, wherein the blocked isocyanato group and the blocked isothiocyanato group are a group represented by the formula (9) or a group represented by the formula (10).

(9)
(In the formula (9), ^{X a} represents an oxygen atom or a sulfur ^{atom, R 38} and ^{R 39,} independently of one another, represent a monovalent organic group having a hydrogen atom or a C 1-20.)

(10)
(In the formula (10), ^{X b} represents an oxygen atom or a sulfur ^atom, R ^{40, R 41} and ^{R 42,} independently of one another, represent a monovalent organic group having a hydrogen atom or a C 1-20. )