JP2001089661A - Curable composition and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electronic material that does not deteriorate the electric properties of an electronic device. SOLUTION: This curable composition is treated by a filter material on which a zeta potential is applied and comprises sodium, lithium, potassium and calcium in an amount of at most 50 ppb of the total content of the metal elements contained in the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition in which metals such as sodium and iron contained in the composition have been removed by a specific filter medium, and a method for producing the same.

[0002]

2. Description of the Related Art Curable compositions have many uses in the field of electronics, but in these devices in the field of electronics, their structures have been increasingly miniaturized in recent years, and materials used for improving the electrical properties of materials have been used. It is required that the content of metallic impurities be extremely low.
Therefore, even when the curable composition is used as a material in the field of electronics, it is important that the metal impurities be suppressed to an extremely small amount.

[0003] As a conventionally known method of removing and reducing metal impurities in a curable composition, there is a method of adsorbing metal ions to an ion exchange resin. However, the ion-exchange resin is difficult to handle because it is often granular, and after adsorbing metal ions, reverse regeneration treatment with an alkaline (or acidic) solution, washing with water and regeneration treatment with an acidic (or alkaline) solution, There is a problem that many processing steps are required.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a curable composition in which the amount of metal in the curable composition is reduced with high efficiency, and a method for producing the same.

[0005]

Means for Solving the Problems The present inventors have conducted research to solve the problems of the conventional technology as described above, and as a result,
The above object can be achieved by treating the curable composition and / or its raw material with a specific filter medium, thereby completing the present invention.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The curable composition of the present invention is treated with a zeta-potential filter medium and has a total content of sodium, lithium, potassium, calcium and copper of 50 ppb or less, preferably 40 ppb or less. is there. [Functional Filter Media] Examples of the filter media on which the zeta potential acts (hereinafter referred to as “functional filter media”) used in the method of the present invention include:
Those which have a zeta potential acting on the filtrate to be filtered are selected. Examples of such a functional filter medium include a conventional filter medium such as cotton, pulp, cellulose, polyester, diatomaceous earth, perlite, activated carbon, zeolite, and the like, to which a cationic charge control agent is added. Preferred among these are filter media consisting of cotton, cellulose, polyester, activated carbon, and zeolites. The cationic charge control agent imparts a cationic charge to the filter medium, and generates a zeta potential between a charged substance of the filtrate, that is, a metal component, which passes through the filter medium in a filtration process. Examples of the cationic charge control agent include a reaction product of dicyandiamide, monoethanolamine and formaldehyde described in U.S. Pat. No. 2,802,820, an aminotriazine resin described in U.S. Pat. No. 2,839,506, and U.S. Pat. A melamine-formaldehyde cationic resin described in JP-B-36-20045, a resin obtained by reacting N, N'-diethanolpiperazine, melamine, formalin and glycerin phthalate;
And polyamide polyamine epichlorohydrin cation resin described in JP-A-3-17486.
Among them, a polyamide polyamine epichlorohydrin cation resin is preferable because it gives a stable cation charge.

Japanese Patent Publication No. Sho 63-17486 discloses a method for producing a filter comprising a filter material obtained by using a polyamide polyamine epichlorohydrin cation resin as a cationic charge control agent and using cellulose, diatomaceous earth and perlite as a functional filter material. Is described. The thickness of the functional filter medium used in the present invention is preferably 10 cm or less, and more preferably 0.01 to 10 cm.

[0008] One preferred form of the functional filter medium used in the present invention is to use it together with an ion exchanger and a chelate former. Here, the ion exchanger and the chelate former are polymers, for example, a styrene polymer, an acrylic polymer, a methacrylic polymer,
A functional group having an ion exchange function or a chelate forming function introduced into a vinyl alcohol polymer, polyester, cellulose or the like. The form of these ion exchangers or chelate formers is not particularly limited, and may be granular, fibrous, or porous film (hereinafter, simply referred to as “film”).
Although any shape may be used, it is usually used in a granular form.

More specifically, as the ion exchanger,
Granular, fibrous, or membrane-like materials composed of a strongly acidic cation exchanger, a weakly acidic cation exchanger, a strongly basic anion exchanger, or a weakly basic anion exchanger are used. Here, examples of the strongly acidic cation exchanger include those obtained by sulfonating a styrene polymer cross-linked with divinylbenzene and those obtained by carboxylating a methacrylic polymer. Examples of the weakly acidic cation exchanger include divinylbenzene. And a copolymer of acrylic acid and methacrylic acid. Examples of the strong basic anion exchanger include, for example, those obtained by aminomethylating a styrene polymer crosslinked with divinylbenzene and then quaternizing the styrene polymer.
Examples of the weakly basic anion exchanger include an aminomethylated styrene polymer cross-linked with divinylbenzene, and an acrylamide polymer having an aminomethyl group cross-linked with divinylbenzene.

Examples of the chelate former include a resin in which a group having an iminodiacetic acid structure is introduced into a styrene polymer cross-linked with divinylbenzene, or a group having a polyamine structure is introduced into a styrene polymer cross-linked with divinylbenzene. Granular, fibrous, or film-like materials such as resin. These various ion exchangers or chelate formers are not limited to one type, and two or more types may be contained in the same functional filter medium. The above-mentioned ion exchanger and the chelate former together form a functional filter medium.At this time, the functional filter medium may be uniformly mixed, or the layer of the ion exchanger and the chelate former may be functionally mixed. The filter medium layer may be arranged or joined adjacently, or the two layers arranged or joined in this manner may be partially mixed at the boundary.

The pore size of the above-mentioned functional filter medium or formed by the functional filter medium is generally 0.05 to 10.0 μm, preferably 0.1 to 1.0 μm. In functional filter media,
Since the charged particles present in the liquid are adsorbed by the functional filter medium due to the potential difference generated when the liquid passes through, the metal impurities smaller than the pore diameter of the functional filter medium are also captured by the functional filter medium. Since a certain portion of the trace metal exists in the form of fine particles such as a microgel, it is captured by a filter that generates a zeta potential. On the other hand, ion exchangers and chelate formers mainly capture free ions in the liquid. As a result, various metals having different forms can be widely removed by the method of the present invention. Therefore, the metal content contained in the curable composition and its raw material can be reduced more efficiently by using the ion exchanger and / or the chelate former together.

As the functional filter media used in the method of the present invention, commercially available functional media can be widely used. As a zeta-plus SH series (trade name) and a filter medium which does not contain an ion exchange resin or a chelate resin and generates a zeta potential, zeta-plus GN series and LA series of the company are preferably used.

[Curable composition] The composition of the present invention comprises (A)
(A-1) a compound represented by the following general formula (1): R ¹ _a Si (OR ² ) _4-a (1) (R ¹ is a hydrogen atom, a fluorine atom, or a monovalent organic group) Wherein R ² represents a monovalent organic group, a represents an integer of 0 to 2) and (A-2) a compound R ³ _b (R ⁴ O) represented by the following general formula (2) ^{_{3-b Si- (R 7)}} d -Si (oR 5) 3-c R 6 c ····· (2) (R 3, R 4, R 5 and R ⁶ may be the same or different Each represents a monovalent organic group, b and c may be the same or different, each represents a number of 0 to 2, and R ⁷ represents an oxygen atom or a group represented by — (CH ₂ ) _n —. And n
Represents 1 to 6, and d represents 0 or 1. ), And / or a hydrolyzate and / or condensate of at least one compound selected from the group consisting of: and (B) an organic solvent.

Component (A) Component (A-1) In the general formula (1), examples of the monovalent organic group represented by R ¹ and R ² include an alkyl group, an aryl group, an allyl group, and a glycidyl group. Can be. Further, in the general formula (1), R ¹ is preferably a monovalent organic group, particularly an alkyl group or a phenyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and the like, preferably having 1 to 5 carbon atoms, and these alkyl groups may be chain-like or branched, Further, a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), as the aryl group,
Examples include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

Specific examples of the compound represented by the general formula (1) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane, tri- sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane,
Fluorotri-n-butoxysilane, fluorotri-s
ec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane,
Tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, etc .; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltrimethylsilane -N-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane,
Methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-s
ec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri- sec-butoxysilane, vinyl tri-tert
-Butoxysilane, vinyltriphenoxysilane, n-
Propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane,
n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-
sec-butoxysilane, n-propyltri-tert
-Butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri- n-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri- n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-te
rt-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyl-i-triethoxysilane, sec-butyl-tri-
n-propoxysilane, sec-butyl-tri-iso
-Propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane, t-butyltrimethoxy Silane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-
n-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltrisilane -Iso-
Propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, etc .; dimethyldimethoxysilane , Dimethyldiethoxysilane, dimethyl-di-n-propoxysilane, dimethyl-di-iso-propoxysilane, dimethyl-di-n-butoxysilane, dimethyl-di-sec
-Butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n-propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n -Butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-
tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso- Propoxysilane, di-n-propyl-di-n-butoxysilane, di-n-propyl-di-sec-butoxysilane, di-n-propyl-di-tert-butoxysilane, di-n-propyl-di- Phenoxysilane, di-i
so-propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-
Propoxysilane, di-iso-propyl-di-iso
-Propoxysilane, di-iso-propyl-di-n-
Butoxysilane, di-iso-propyl-di-sec-
Butoxysilane, di-iso-propyl-di-tert
-Butoxysilane, di-iso-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n
-Butyldiethoxysilane, di-n-butyl-di-n-
Propoxysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane, di-n-butyl-di- tert-butoxysilane, di-n
-Butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane,
Di-sec-butyl-di-iso-propoxysilane,
Di-sec-butyl-di-n-butoxysilane, di-s
ec-butyl-di-sec-butoxysilane, di-se
c-butyl-di-tert-butoxysilane, di-se
c-butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxy Silane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxysilane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxy Silane, diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-s
ec-butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, and the like. Preferably, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-
Propoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, triethylmono Methoxysilane, triethylmonoethoxysilane, triphenylmonomethoxysilane, triphenylmonoethoxysila It is. These may be used alone or in combination of two or more.

(A-2) Component In the above general formula (2), examples of the monovalent organic group include the same organic groups as those in the above general formula (1).
Examples of the divalent organic group represented by R ⁷ in the general formula (2) include a methylene group and an alkylene group having 2 to 6 carbon atoms. In the general formula (2), as the compound in which R ⁷ is an oxygen atom, hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1,3,3-pentamethoxy-3-methyldimethyl Siloxane, 1,1,1,3,3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentamethoxy-3-phenyldisiloxane, 1,1,1,
3,3-pentaethoxy-3-phenyldisiloxane,
1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3
-Dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,1,3,
3-tetraethoxy-1,3-diphenyldisiloxane, 1,1,3-trimethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triethoxy-1,3,3
3-trimethyldisiloxane, 1,1,3-trimethoxy-1,3,3-triphenyldisiloxane, 1,1,
3-triethoxy-1,3,3-triphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,
3-tetramethyldisiloxane, 1,3-dimethoxy-
1,1,3,3-tetraphenyldisiloxane, 1,3
-Diethoxy-1,1,3,3-tetraphenyldisiloxane and the like. Of these, hexamethoxydisiloxane, hexaethoxydisiloxane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-
1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3
Dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3
Preferred examples include 3-tetraphenyldisiloxane and 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane. Compounds in which d is 0 in the general formula (2) include hexamethoxydisilane, hexaethoxydisilane, hexaphenixidisilane, 1,1,1,2,2-pentamethoxy-2
-Methyldisilane, 1,1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2-phenyldisilane, 1,1,1,2,2
-Pentaethoxy-2-phenyldisilane, 1,1,
2,2-tetramethoxy-1,2-dimethyldisilane,
1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-
1,2-diphenyldisilane, 1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,
1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2
-Tetramethyldisilane, 1,2-diethoxy-1,
1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2
-Diethoxy-1,1,2,2-tetraphenyldisilane or the like, wherein R ⁷ in the general formula (2) is-(CH ₂ ) _n-
Examples of the compound having the group represented by are bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (hexaphenoxysilyl) methane, bis (dimethoxymethylsilyl) methane, and bis (diethoxymethylsilyl) methane , Bis (dimethoxyphenylsilyl)
Methane, bis (diethoxyphenylsilyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, bis (ethoxydiphenylsilyl) methane, bis (hexamethoxysilyl) ethane , Bis (hexaethoxysilyl) ethane, bis (hexaphenoxysilyl) ethane, bis (dimethoxymethylsilyl) ethane, bis (diethoxymethylsilyl) ethane, bis (dimethoxyphenylsilyl) ethane, bis (diethoxyphenylsilyl) ethane , Bis (methoxydimethylsilyl) ethane, bis (ethoxydimethylsilyl) ethane,
Bis (methoxydiphenylsilyl) ethane, bis (ethoxydiphenylsilyl) ethane, 1,3-bis (hexamethoxysilyl) propane, 1,3-bis (hexaethoxysilyl) propane, 1,3-bis (hexaphenoxysilyl) Propane, 1,3-bis (dimethoxymethylsilyl) propane, 1,3-bis (diethoxymethylsilyl) propane, 1,3-bis (dimethoxyphenylsilyl) propane, 1,3-bis (diethoxyphenylsilyl) Propane, 1,3-bis (methoxydimethylsilyl) propane, 1,3-bis (ethoxydimethylsilyl) propane, 1,3-bis (methoxydiphenylsilyl) propane, 1,3-bis (ethoxydiphenylsilyl) propane, etc. Can be mentioned. Among them, hexamethoxydisilane, hexaethoxydisilane, hexaphenixidisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2
2-tetraethoxy-1,2-dimethyldisilane, 1,
1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2
-Tetramethyldisilane, 1,2-diethoxy-1,
1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2
-Diethoxy-1,1,2,2-tetraphenyldisilane, bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis ( Preferred examples include dimethoxyphenylsilyl) methane, bis (diethoxyphenylsilyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, and bis (ethoxydiphenylsilyl) methane. It can be mentioned as. In the present invention,
As the component (A), the components (A-1) and (A-
2) Component or any one of them can be used, and two or more of each of the component (A-1) and the component (A-2) can be used.

In the present invention, the term “hydrolysis” refers to R ² O—, R ⁴ O—, and R ² O—
^It is not necessary that all the ⁵ O-groups be hydrolyzed, for example, only one is hydrolyzed, two or more are hydrolyzed, or a mixture thereof. In the present invention, condensation refers to condensation of a silanol group of the hydrolyzate of the component (A) to form a Si—O—Si bond. In the present invention, however, it is not necessary that all of the silanol groups are condensed. The concept encompasses the formation of a mixture of a small amount of silanol groups and a mixture of those having different degrees of condensation.
In addition, the weight average molecular weight in terms of polystyrene of the hydrolysis-condensation product of the component (A) is usually from 10 to 10,000,000.

(B) Organic Solvent As the organic solvent used in the present invention, for example, n-pentane, i-pentane, n-hexane, i-hexane, n-pentane
Heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane,
Aliphatic hydrocarbon solvents such as methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-
Aromatic hydrocarbon solvents such as butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, trimethylbenzene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec -Butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol,
-Methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, s
ec-octanol, n-nonyl alcohol, 2,6-
Dimethylheptanol-4, n-decanol, sec-
Undecyl alcohol, trimethyl nonyl alcohol,
Mono-alcohol solvents such as sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl carbinol, diacetone alcohol, cresol Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4,2 Polyhydric alcohol solvents such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; acetone, methyl ethyl ketone, methyl n- propyl ketone, methyl -n-
Butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4- Ketone solvents such as pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchone; ethyl ether;
i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolan, 4-methyldioxolan, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Ethylene glycol diethyl ether, ethylene glycol mono-n-
Butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether , Diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n
-Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran Ether solvents such as diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate;
N-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, acetoacetate Ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene acetate Glycol monopropyl ether,
Propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl acetate acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, Ester solvents such as di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide;
N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide,
Nitrogen-containing solvents such as N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3
-Sulfur-containing solvents such as propane sultone. These can be used alone or in combination of two or more. In the present invention, the boiling point is 250 ° C.
It is particularly preferable to use less than an organic solvent, specifically, methanol, ethanol, alcohols such as isopropanol, ethylene glycol, polyhydric alcohols such as glycerin, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, Glycol ether solvents such as diethylene glycol diethyl ether, propylene glycol monopropyl ether and dipropylene glycol monoethyl ether; glycol acetate ether solvents such as ethylene glycol monomethyl acetate, diethylene glycol monobutyl ether acetate, ethylene glycol diacetate and propylene glycol methyl ether acetate; N , N-dimethylacetamide, N, N- Methylformamide, N- methyl -
Amide solvents such as 2-pyrrolidone, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and methyl amyl ketone; carboxylic acid ester solvents such as ethyl lactate, methoxymethyl propionate and ethoxyethyl propionate; May be used alone or in combination of two or more.

In the present invention, the amount of the organic solvent used is
It is in the range of 0.3 to 25 times (weight) the total amount of the component (A) (in terms of complete hydrolysis condensate) and the component (B).

In the present invention, a catalyst can be used in addition to the above components (A) and (B). As a catalyst,
Organic acids, inorganic acids, organic salts, inorganic salts, metal chelates and the like can be mentioned. Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid,
Maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, melitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-Aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, etc. be able to. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like. Examples of the organic salt include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, and diazabicyclononane. , Diazabicycloundecene, tetramethylammonium hydroxide and the like. Examples of the inorganic salt include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Further, a metal chelate compound can be used in the composition of the present invention. Examples of the metal chelate compound include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetylacetonate) titanium, and tri-n-butoxy.・ Mono (acetylacetonato) titanium, tri-sec-butoxy ・ Mono (acetylacetonato) titanium, tri-
t-butoxy mono (acetylacetonate) titanium,
Diethoxybis (acetylacetonato) titanium, di-n-propoxybis (acetylacetonato) titanium, di-i-propoxybis (acetylacetonato) titanium, di-n-butoxybis (acetylacetonate) Titanium, di-sec-butoxybis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, mono-n-propoxytris (acetyl) Acetonate) titanium, mono-i
-Propoxy-tris (acetylacetonato) titanium, mono-n-butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-t-butoxytris (acetylacetonate) ) Titanium, tetrakis (acetylacetonate) titanium, triethoxymono (ethylacetoacetate) titanium, tri-n-propoxymono (ethylacetoacetate) titanium, tri-i-propoxymono (ethylacetoacetate) titanium, tri -N-butoxy mono (ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium Emissions, di -n- propoxy bis (ethylacetoacetate) titanium, di -i- propoxy bis (ethylacetoacetate) titanium, di -n-
Butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate)
Titanium, di-t-butoxybis (ethylacetoacetate) titanium, monoethoxytris (ethylacetoacetate) titanium, mono-n-propoxytris (ethylacetoacetate) titanium, mono-i-propoxytris (ethyl) Acetoacetate) titanium, mono-n
-Butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetyl) Acetonate)
Titanium chelate compounds such as tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium;
Triethoxy mono (acetylacetonate) zirconium, tri-n-propoxy mono (acetylacetonate) zirconium, tri-i-propoxy mono (acetylacetonate) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonate) zirconium, tri-t-butoxy mono (acetylacetonate) zirconium, diethoxybis (acetylacetonate) zirconium, di-n-propoxybis (acetylacetonate) Nate) zirconium, di-i-propoxybis (acetylacetonate) zirconium, di-n-butoxybis (acetylacetonate)
Zirconium, di-sec-butoxybis (acetylacetonate) zirconium, di-t-butoxybis (acetylacetonate) zirconium, monoethoxytris (acetylacetonate) zirconium, mono-n-propoxytris (acetyl) Acetonato) zirconium, mono-i-propoxy tris (acetylacetonato) zirconium, mono-n-butoxytris (acetylacetonato) zirconium, mono-s
ec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri-n-propoxy. Mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy.
Mono (ethylacetoacetate) zirconium, tri-
t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate)
Zirconium, di-n-propoxybis (ethylacetoacetate) zirconium, di-i-propoxybis (ethylacetoacetate) zirconium, di-n-
Butoxy bis (ethyl acetoacetate) zirconium, di-sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono -N
-Propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-
sec-butoxy tris (ethyl acetoacetate)
Zirconium, mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) bis (ethylacetoacetate) Zirconium, tris (acetylacetonate) mono (ethylacetoacetate) zirconium,
And the like; aluminum chelate compounds such as aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate); and the like. The amount of the catalyst to be used is generally 0.0001 to 1 mol, preferably 0.001 to 0.1 mol, per 1 mol of the total amount of the compound represented by the general formula (1) and the compound represented by the general formula (2). 1 mole.

In the present invention, the curable composition may contain (C) a compound having a boiling point or a decomposition temperature of 250 to 450 ° C. Specific examples of the compound include a compound having a polyalkylene oxide structure, ) Acrylate polymers, polyesters, polycarbonates, polyanhydrides, and the like. In the present invention, the boiling point and the decomposition temperature refer to the temperature at 1 atm. Compound having a polyalkylene oxide structure Here, examples of the polyalkylene oxide structure include a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure. Specifically, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene block copolymer Ether-type compounds such as oxyethylene polyoxypropylene alkyl ether, ether-type compounds such as polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate, polyethylene Glycol fatty acid esters, ethylene glycol fatty acid esters, fatty acid monoglycerides, It can be mentioned Li glycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, ether-ester type compounds such as sucrose fatty acid esters and the like. Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structures. -(A) n- (B) m--(A) n- (B) m- (A) l- (where A is a group represented by -CH2CH2O-, and B is-
A group represented by CH2CH (CH3) O-, wherein n is 1 to
90, m is a number from 10 to 99, and l is a number from 0 to 90)

(Meth) acrylic polymer In the present invention, the acrylate and methacrylate constituting the (meth) acrylic polymer include alkyl acrylate, alkyl methacrylate, alkoxyalkyl acrylate,
Examples thereof include methacrylic acid alkyl esters and methacrylic acid alkoxyalkyl esters. Examples of the alkyl acrylate include those having 1 to 6 carbon atoms such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, pentyl acrylate, and hexyl acrylate. Alkyl esters, alkyl methacrylates, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, butyl methacrylate, pentyl methacrylate,
Alkyl esters having 1 to 6 carbon atoms such as hexyl methacrylate, alkoxyalkyl acrylates include methoxymethyl acrylate, ethoxyethyl acrylate, and alkoxyalkyl methacrylates include methoxymethyl methacrylate and ethoxyethyl methacrylate. Can be mentioned. Among these,
It is preferable to use an alkyl methacrylate, and particularly preferable to use ethyl methacrylate, isobutyl methacrylate, or the like.

In the present invention, the (meth) acrylic polymer is preferably formed by copolymerizing the above monomer with a monomer having an alkoxysilyl group. Examples of the monomer having an alkoxysyl group include 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, 3- [tri (methoxyethoxy) silyl] propyl methacrylate, and 3- (methmethoxysilyl) propyl methacrylate.
(Methyldimethoxysilyl) propyl, methacrylic acid 3
-(Methyldiethoxysilyl) propyl and the like. The monomer having an alkoxysilyl group is usually from 0.5 to all monomers constituting the acrylic polymer.
It is contained in a proportion of 10 mol%, preferably 1 to 7 mol%. In the present invention, the acrylic polymer may be copolymerized with not more than 40 mol% of a radical polymerizable monomer other than the above-mentioned acrylate, methacrylate and monomer having an alkoxysilyl group. Examples of the radical polymerizable monomer include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, N, N-dimethylacrylamide,
Examples include unsaturated amides such as N, N-dimethylmethacrylamide, unsaturated nitriles such as acrylonitrile, unsaturated ketones such as methyl vinyl ketone, and aromatic compounds such as styrene and α-methylstyrene. In the present invention, the (meth) acrylic polymer has a polystyrene reduced number average molecular weight of 1,000 to 100,000,
Preferably it is 1000-20,000. Polycondensates of polyester hydroxycarboxylic acids, ring-opening polymers of lactones, polycondensates of aliphatic polyols and aliphatic polycarboxylic acids and the like can be mentioned. Polycarbonate Polycondensates of carbonic acid and alkylene glycol, such as polyethylene carbonate, polypropylene carbonate, polytrimethylene carbonate, polytetramethylene carbonate, polypentamethylene carbonate, and polyhexamethylene carbonate, can be given. Examples include polycondensates of dicarboxylic acids such as polyanhydride polymalonyl oxide, polyadipoyl oxide, polypimeloyl oxide, polysuberoyl oxide, polyazelayl oxide, and polysebacoil oxide. Also,
In addition, poly (N-vinylacetamide), poly (N-vinylpyrrolidone, poly (2-methyl-2-oxazoline), poly (N, N-dimethylacrylamide)
And styrene-based polymers such as polystyrene, polymethylstyrene and poly-α-methylstyrene.

Compounds which are compatible or dispersed in component (A) and have a boiling point or decomposition temperature of from 250 to 450 ° C.
Usually 1 to 80 with respect to the component (complete hydrolytic condensate conversion)
% By weight, preferably 5 to 65% by weight. In the present invention, the completely hydrolyzed condensate is defined as-in component (A).
The group represented by OR ^2, —OR ⁴ and —OR ⁵ is hydrolyzed to 100% to form an OH group, which is completely condensed.

The curable composition of the present invention further comprises (D)
Compounds having a boiling point or decomposition temperature exceeding 450 ° C. can also be contained. Where the boiling point or decomposition temperature is 450 ° C
Examples of the compound exceeding the above include polyimide having a polyamic acid and / or carboxylic acid anhydride group (these are collectively referred to as “polyimide or the like”), polyarylene, and the like. The polyamide or the like preferably has a carboxylic acid anhydride group, a hydrolyzable organosilyl group, or the like. In the present invention, the polyamic acid may not be partially imidized, and the imidation ratio of the polyimide is 50% or more, preferably 90% or more.

The above-mentioned polyimide and the like are subjected to polycondensation of a tetracarboxylic dianhydride and a diamine compound in an organic solvent under the condition that an excess amount of tetracarboxylic dianhydride is present to obtain a polyamic acid solution. And (b) a method of subjecting the polyamic acid obtained by the method (a) to a dehydration ring-closing reaction in an organic solvent by a thermal method or a chemical method to obtain a polyimide solution having a carboxylic acid anhydride group. And the like. Among these methods, the method (b) is particularly preferable.

Specific examples of the tetracarboxylic dianhydride used in the above method (a) include 2,3,2 ', 3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, 9,9-bis (2,3-dicarboxyphenyl) fluorene dianhydride, 9, 9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride , 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride,
9,9-bis [4- (2,3-dicarboxyphenoxy) phenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 2, 2-bis [4- (2,
3-Dicarboxyphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] -1, 1,1,3,3,3-hexafluoropropane dianhydride and the like can be mentioned.

Specific examples of the diamine compound used in the above method (a) include 9,9-bis (2-aminophenyl) fluorene, 9,9-bis (3-aminophenyl) fluorene, , 9-bis (4-aminophenyl) fluorene, 9,9-
Bis [4- (2-aminophenoxy) phenyl] fluorene, 9,
9-bis [4- (3-aminophenoxy) phenyl] fluorene,
9,9-bis [4- (4-aminophenoxy) phenyl] fluorene, 2,2-bis (2-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2- Bis (3-aminophenyl)-
1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [ 4- (2-aminophenoxy) phenyl] -1,1,
1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl]
-1,1,1,3,3,3-hexafluoropropane, 2,2′-diaminodiphenyl ether, 2,3′-diaminodiphenyl ether, 2,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3 , 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 2,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,4 '-Diaminobiphenyl, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2'
-Diamino-4,4'-bis (trifluoromethyl) biphenyl, 2- (3-aminophenyl) -3'-aminophenyl, 2,2'-
Bis (3-aminophenyl) biphenyl, 9,9-bis [3-phenyl-4- (4-amino-2-trifluoromethylphenoxy) phenyl] fluorene and the like can be mentioned. Further, together with the diamine compound, three amino groups are contained in one molecule.
The amine compounds having the above can be used in combination. Examples of the compound having three or more amino groups include, for example, 1,
3,5-triaminobenzene, 3,3 ', 5-triaminobiphenyl, 3,3', 5-triaminodiphenyl ether, 1,1-bis (4-aminophenyl) -1-
(4-aminophenyl) ethane, 1,1-bis (4-aminophenyl) -1- (4-aminophenyl) -2,
2,2-trifluoroethane, 2-amino-9,9-bis (4-aminophenyl) fluorene, 2-amino-
Triamines such as 9,9-bis [4- (4-aminophenoxy) phenyl] fluorene and 9,9-bis (3,4
-Diaminophenyl) fluorene, 9,9-bis (3,
5-diaminophenyl) fluorene, 2,7-diamino-9,9-bis (2-aminophenyl) fluorene,
2,7-diamino-9,9-bis (3-aminophenyl) fluorene, 2,7-diamino-9,9-bis (4
-Aminophenyl) fluorene, 3,6-diamino-
9,9-bis (2-aminophenyl) fluorene, 3,
6-diamino-9,9-bis (3-aminophenyl) fluorene, 3,6-diamino-9,9-bis (4-aminophenyl) fluorene, 4,5-diamino-9,9-
Bis (2-aminophenyl) fluorene, 4,5-diamino-9,9-bis (3-aminophenyl) fluorene, 4,5-diamino-9,9-bis (4-aminophenyl) fluorene, 1,2 , 4,5-tetraaminobenzene, 3,3 ', 4,4'-tetraaminobiphenyl,
Bis (3,4-diaminophenyl) methane, bis (3
5-diaminophenyl) methane, 2,2-bis (3,4
-Diaminophenyl) propane, 2,2-bis (3,4
-Diaminophenyl) -1,1,1,3,3,3-hexafluoropropane, bis (3,5-diaminophenyl) ether, 2,7-diamino-9,9-bis [3-
(2-aminophenoxy) phenyl] fluorene, 2,
7-diamino-9,9-bis [3- (3-aminophenoxy) phenyl] fluorene, 2,7-diamino-9,
9-bis [3- (4-aminophenoxy) phenyl] fluorene, 3,6-diamino-9,9-bis [3- (2
-Aminophenoxy) phenyl] fluorene, 3,6-
Diamino-9,9-bis [3- (3-aminophenoxy) phenyl] fluorene, 3,6-diamino-9,9
-Bis [3- (4-aminophenoxy) phenyl] fluorene, 4,5-diamino-9,9-bis [3- (2-
Aminophenoxy) phenyl] fluorene, 4,5-diamino-9,9-bis [3- (3-aminophenoxy)
Phenyl] fluorene, 4,5-diamino-9,9-bis [3- (4-aminophenoxy) phenyl] fluorene, 2,7-diamino-9,9-bis [4- (2-aminophenoxy) phenyl] Fluorene, 2,7-diamino-9,9-bis [4- (3-aminophenoxy) phenyl] fluorene, 2,7-diamino-9,9-bis [4- (4-aminophenoxy) phenyl] fluorene, 3,6-diamino-9,9-bis [4- (2-aminophenoxy) phenyl] fluorene, 3,6-diamino-9,9-bis [4- (3-aminophenoxy) phenyl] fluorene, 3, 6-diamino-9,9-bis [4- (4-aminophenoxy) phenyl] fluorene, 4,5-diamino-9,9-bis [4- (2-aminophenoxy) phenyl] Fluorene, 4,5-diamino-9,9-bis [4- (3-aminophenoxy) phenyl] fluorene, 4,5-diamino-9,9-bis [4- (4-aminophenoxy) phenyl] fluorene, 9,9-bis [4- (3,5-diaminophenoxy) phenyl] fluorene, 1,3-bis (3,5-diaminophenoxy) benzene, 1,4-bis (3,5-
Diaminophenoxy) benzene, 2,2-bis [4-
(3,5-diaminophenoxy) phenyl] propane,
Examples thereof include tetraamines such as 2,2-bis [4- (3,5-diaminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane.

The organic solvent used in the above methods (a) and (b) is not particularly limited as long as it is inert to the reaction raw materials and the component (B) obtained and can dissolve them. It is not limited, and examples thereof include amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; aprotic polar solvents such as dimethylsulfoxide; and phenol solvents such as phenol and cresol. These organic solvents can be used alone or in combination of two or more. These organic solvents can be used alone or in combination of two or more. When synthesizing the polyamic acid by the method (a), the total concentration of the tetracarboxylic dianhydride and the diamine compound is usually 1 to 50% by weight, preferably 2 to 30% by weight based on the total solution weight. %, Usually at 150 ° C. or lower, preferably at 0 to 120 ° C. In the method (b), the temperature of the thermal imidization reaction when synthesizing the polyimide is usually 50 to 400.
° C, preferably 100 to 350 ° C, and the temperature of the chemical imidization reaction is usually 0 to 200 ° C.

In the present invention, the carboxylic acid anhydride group in the specific polyimide or the like is usually present at both ends of the molecular chain of polyamic acid or polyimide, but may be present at only one of the molecular chain ends. In the present invention,
The content of the carboxylic acid anhydride group in the component (B) is usually
It is 0.01 to 30% by weight, preferably 0.05 to 25% by weight, particularly preferably 0.1 to 20% by weight.

In the present invention, the specific polyimide is
In some cases, it may further have a hydrolyzable silyl group. As a method for synthesizing the specific polyimide or the like having the hydrolyzable silyl group, for example, (c) the polycondensation of a tetracarboxylic dianhydride and a diamine compound in the method (a) may be carried out with a carboxylic acid anhydride group. A silane compound having a hydrolyzable group and / or a silane compound having a functional group capable of reacting with a carboxyl group and a hydrolyzable group (hereinafter, these silane compounds are collectively referred to as “functional silane compound”). (D) Following the polycondensation of the tetracarboxylic dianhydride with the diamine compound in the method (a), a functional silane compound is added, and the functional silane compound reacts with the polyamic acid. (E) thermally treating the polyamic acid having a hydrolyzable silyl group obtained by the method (c) or (d) in an organic solvent. Or a method of performing a dehydration ring-closure reaction by a chemical method, (f) a method of adding a functional silane compound and reacting the functional silane compound with polyimide following the method of (b), In the method (a), as a part of the diamine compound,
A method using a silane compound having two amino groups and a hydrolyzable group, (h) heat-treating the polyamic acid having a hydrolyzable silyl group obtained by the method (g) in an organic solvent. And a method of causing a dehydration ring closure reaction by a chemical method or the like. The use ratio of the silane compound having two amino groups and the hydrolyzable group in the method (g) is based on the total diamine compound.
Usually, it is 50 mol% or less, preferably 30 mol% or less. Of the above methods (c) to (h), the methods (d), (v) and (v) are preferable, and particularly the methods (d) and (v)
Is preferred.

The functional silane compound used in the above method (c), (d) or (f) includes, for example, 3,3
Carboxylic anhydride group-containing silanes such as acid anhydride of 4-dicarboxyphenyltrimethoxysilane and acid anhydride of 3,4-dicarboxybenzyltrimethoxysilane; mercaptoethyltrimethoxysilane, 2-mercaptoethyltrimethoxy Mercaptosilanes such as silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-amino Propyldiethoxymethylsilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, (2-aminoethylamino) methyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) Ropirdimethoxymethylsilane, 3- [2- (2-aminoethylamino) ethylamino] propyltrimethoxysilane, N- (3-trimethoxysilylpropyl) urea, N- (3-triethoxysilylpropyl) urea, 2- (2-aminoethylthio) ethyltrimethoxysilane, 2- (2-aminoethylthio) ethyltriethoxysilane, 2- (2-aminoethylthio) ethyldimethoxymethylsilane, 2-aminophenyltriethoxysilane, Aminosilanes such as 3-aminophenyltrimethoxysilane, 3-aminophenyltriethoxysilane, 4-aminophenyltrimethoxysilane, and 4-aminophenyltriethoxysilane; bis (3-trimethoxysilylpropyl) amine, bis (3 -Triethoxysilylpropyl) amine, 3-
Cyclohexylaminopropyltrimethoxysilane, 3-
Cyclohexylaminopropyldimethoxymethylsilane, 3-phenylaminopropyltrimethoxysilane, 3-
Phenylaminopropyldimethoxymethylsilane, 3-benzylaminopropyltrimethoxysilane, 3-benzylaminopropyldimethoxymethylsilane, 3- (p-vinylbenzylamino) propyltrimethoxysilane, 3- (p-vinylbenzylamino) propyldimethoxy Iminosilanes such as methylsilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyldimethoxymethylsilane, 3-piperazinopropyltrimethoxysilane, 3-piperazinopropyldimethoxymethylsilane; 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 2- (3,4-epoxycyclohexyl)
Epoxysilanes such as ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-
Examples include isocyanate silanes such as isocyanate propyl dimethoxymethyl silane and 3-isocyanate propyl diethoxymethyl silane. These functional silane compounds can be used alone or in combination of two or more.

The logarithmic viscosity [η] (N-methylpyrrolidone, 30 ° C., 0.5 g / dl) of the specific polyimide or the like in the present invention is usually 0.05 to 5 dl / g, preferably 0.1 to 3 dl / g. In the present invention, the specific polyimide and the like can be used alone or in combination of two or more. The compounding ratio of the specific polyimide in the present invention is usually 5 to 1000 parts by weight, preferably 10 to 800 parts by weight, more preferably 15 to 100 parts by weight of the component (A) (in terms of completely hydrolyzed condensate). ~ 6
00 parts by weight.

Other Additives Components such as colloidal silica, colloidal alumina, and a surfactant may be further added to the film-forming composition obtained in the present invention. The colloidal silica is, for example, a dispersion in which high-purity silicic anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle size of 5 to 30 mμ, preferably 10 to 20 mμ, and a solid content of 10 to 10 μm. It is about 40% by weight. As such colloidal silica,
Examples thereof include methanol silica sol and isopropanol silica sol manufactured by Nissan Chemical Industries, Ltd .; Examples of the colloidal alumina include alumina sol 5 manufactured by Nissan Chemical Industries, Ltd.
20, 100 and 200; alumina clear sol, alumina sol 10, manufactured by Kawaken Fine Chemical Co., Ltd.
132 and the like. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like.
Furthermore, a silicone-based surfactant, a polyalkylene oxide-based surfactant, a poly (meth) acrylate-based surfactant, and the like can be given.

The total solid content of the curable composition of the present invention is as follows:
Preferably, it is 2 to 30% by weight, which is appropriately adjusted according to the purpose of use. When the total solid content of the composition is 2 to 30% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent. The content of alcohol having a boiling point of 100 ° C. or less in the curable composition used in the present invention is 2%.
It is preferably 0% by weight or less, particularly preferably 5% by weight or less. The alcohol having a boiling point of 100 ° C. or less may be generated during hydrolysis and / or condensation of the compound (1) and the compound (2), and the content thereof is adjusted to 20% by weight or less, preferably 5% by weight or less. It is preferable to remove by distillation or the like. Furthermore, in the present invention, the general formula R ¹⁸ COC
H2COR ¹⁹ (where, R ¹⁸ and R ¹⁹ is the same meaning as R ¹⁸ and R ¹⁹ in the general formula representing the metal chelate compound of each component (C), both of R ¹⁸ and R ^19, in each of the same Β-diketones and / or β-ketoesters represented by the following formula:

In the present invention, metals can be removed by passing the curable composition and / or its raw material through a functional filter medium. Among the monomers, water, organic solvents, catalysts, etc., which are the raw materials of the curable composition, liquid ones are used as they are or diluted with a solvent, and solid ones are dissolved in a solution and dissolved in a functional filter medium. To process. The solids concentration in the treatment liquid when passing the polymer is usually
A range from 0 to 70% by weight is preferred. The liquid passing speed when passing through the functional wax material has almost no effect on the metal separation efficiency, and is preferably in the range of 0.0001 to 100 kg / (m 2 · min). If the temperature at which the functional filter medium is passed is too high, the functional filter medium may be eluted, deteriorated, or the solvent may be decomposed, which may adversely affect the processing liquid. Since the solid content concentration of the solution increases, it becomes very difficult to pass the solution.
Therefore, the temperature range is suitably 0 to 80 ° C, preferably 10 to 50 ° C.

The substrate on which the curable composition of the present invention can be applied includes a silicon wafer, a SiO 2 wafer, a SiN wafer and the like, and application means such as spin coating, dipping, roll coating, and spraying are used. .

[0038]

EXAMPLES In order to explain the present invention in more detail, examples and comparative examples are shown below, but the present invention is not particularly limited by these examples and comparative examples. The percentages and percentages described below are based on weight.

Example 1 (1) 203 parts of methyltrimethoxysilane (MTMSi) as alkylalkoxysilane (condensate conversion: 10 parts)
0 parts) and diisopropoxytitanium bisethylacetyl acetate (DIPTiEA) as a metal chelate compound.
A, 78 parts (purity: 78%), 0.7 parts (1.3 mmol) and 250 parts of propylene glycol monopropyl ether (PFG) as an organic solvent were mixed, and then heated to 60 ° C. A mixture of 40 parts of ion-exchanged water (corresponding to 0.5 mol per 1 mol of methoxy group in methyltrimethoxysilane) and 50 parts of PFG was added at 60 ° C. for 1 hour while stirring the reaction solution with a stirrer. . Further, the reaction was carried out at 60 ° C. for 10 hours. Then
After adding 27 parts of acetylacetone (AcAc), 145 parts of a solvent containing methanol was removed at 40 ° C. under reduced pressure to obtain a curable composition. (2) A functional filter medium containing a cation exchange resin consisting of a sulfonated polystyrene cross-linked with divinylbenzene as an ion exchanger in 500 ml of the composition obtained in the above (1), Cuno Corporation 0.45 kg / (m2) at 20 ° C. on a Zetaplus SH filter (containing materials: cellulose, diatomaceous earth and perlite. Cationic charge regulator: polyamide polyamine epichlorohydrin resin; 47 mm in diameter and 3 mm in thickness) (Min). When the metal concentration of the curable composition before and after the treatment was measured by an atomic absorption spectrometer, 248 ppb before treatment with a functional filter medium, 35.5 ppb of iron, 4.2 pp of lithium
b, potassium 3.2ppb, calcium 25ppb, copper 5.3ppb
And aluminum is 4.7 ppb, and the metal concentration after treatment is 15 ppb for sodium, 5.5 ppb for iron, and 2.2 pp for potassium.
b, calcium was 3.2 ppb and copper was 2.2 ppb.

Example 2 (1) Zeta potential was applied to a methyltrimethoxysilane, and a zeta-plus GN filter manufactured by Kyuno Co., Ltd., which did not contain an ion exchanger or a chelate molded product (material: containing cellulose, diatomaceous earth and perlite) A cationic charge control agent: a polyamide polyamine epichlorohydrin resin, a circle having a diameter of 47 mm and a thickness of 3 mm) packed in a stainless steel column (diameter 50 mm, length 20 cm) at 20 ° C.
The liquid was passed at a flow rate of 45 kg / (m2 · min). (2) Example 1 except that (MTMSi) treated in (1) above was used in an amount of 203 parts (condensate equivalent: 100 parts).
A curable composition was produced in the same manner as in (1). The metal concentration of the obtained curable composition was 3 ppb for sodium and 2.
1 ppb, iron 5.5 ppb, potassium 2.0 ppb, calcium 1.
9 ppb and 1.5 ppb for copper.

Example 3 (1) Tetramethoxysilane, methyltrimethoxysilane, propylene glycol monomethyl ether and polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer [Newpole 62 (HO- PEO5-PPO30-PEO
5-OH)], a functional filter medium containing a cation exchange resin separately from water, Zetaplus S manufactured by Cuno Corporation
0.45 kg / (m2 · min) at 20 ° C in H filter (material: including cellulose, diatomaceous earth and perlite. Cationic charge control agent: polyamide polyamine epichlorohydrin resin. Circular shape of 47 mm in diameter and 3 mm in thickness) The solution was passed at a flow rate of (2) An aqueous solution prepared by dissolving 1.0 g of oxalic acid in 157.7 g of water was added to a functional filter medium as described in (1) above at 20 ° C.
The liquid was passed at a flow rate of 0.45 kg / (m2 · min). (3) 152.0 g of tetramethoxysilane treated in the above (1) (in terms of complete hydrolysis condensate: 60.0 g)
g), 284.1 g of the same methyltrimethoxysilane (equivalent to 140.0 g in terms of a completely hydrolyzed condensate) and 798.8 g of the same propylene glycol monomethyl ether, and 158 g of the oxalic acid aqueous solution treated in (2) above at room temperature. For 1 hour. After the addition of the mixture was completed, the mixture was further reacted at 60 ° C. for 2 hours, and then concentrated under reduced pressure until the total solution amount reached 1,000 g, to obtain a polysiloxane sol having a solid content of 20%. (4) 100 g of the polysiloxane sol obtained in (3) above
(Solid content: 20 g), the polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer treated by the above (1) [Newpole 62 (HO-PEO5-PPO30-PEO5-O, manufactured by Sanyo Chemical Co., Ltd.)
8.6 g was added to obtain a curable composition. The resulting curable composition had a metal concentration of 4 ppb sodium,
Iron was 3.3 ppb, iron was 5.1 ppb, potassium was 1.8 ppb, calcium was 1.8 ppb and copper was 1.2 ppb.

Example 4 (1) A nitrogen gas was flowed into a vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube, and N, N-dimethylformamide
After charging 7.28 g, 9,9-bis [4- (4-
Aminophenoxy) -phenyl] fluorene 7.99 g
(15 mmol) and 0.293 g (0.52 mmol) of 2,7-diamino-9,9-bis [4- (4-aminophenoxy) phenyl] fluorene were added and sufficiently dissolved. Thereafter, 5.36 g (18 mmol) of 2,2,3,3-biphenyltetracarboxylic dianhydride was added, and the mixture was reacted with stirring at room temperature for 5 hours to obtain a polyamic acid solution. Next, 77.28 g of N, N-dimethylformamide, 8.8 mL of pyridine and 6.9 mL of acetic anhydride were added to the solution of the polyamic acid, and the solution was added at room temperature.
And stirred at 100 ° C. for 4 hours. Thereafter, the reaction solution was added to 800 mL of diethyl ether, and the precipitated solid was filtered and dried to obtain 13.50 g of a polyimide. (2) A mixture of 1.57 g of the polyimide obtained in (1) above, 19.09 g of methyl 3-methoxypropionate, and 16.57 g of γ-butyrolactone was reacted at 60 ° C. for 1 hour, and then methyltrimethoxysilane 6 was added. .36 g was added. Next, while maintaining the reaction solution at 60 ° C., 0.016 g of maleic acid, 1.26 g of ion-exchanged water and γ-
The mixed solution of 2.52 g of butyrolactone was divided into 6 portions to give 1
After the addition over time, the mixture was further reacted at 60 ° C. for 1 hour to obtain a curable composition. (3) A functional filter medium containing the cation exchange resin of the curable composition obtained in the above (2), Zetaplus S manufactured by Cuno Corporation
0.35kg / (m2 · min) at 20 ° C in H filter (material: including cellulose, diatomaceous earth and perlite. Cationic charge control agent: polyamide polyamine epichlorohydrin resin. Circular shape of 47mm in diameter and 3mm in thickness) The solution was passed at a flow rate of The metal concentration of the obtained curable composition was 8 ppb for sodium, 4 ppb for iron, 6.5 ppb for iron, 2.8 ppb for potassium, 2.6 ppb for calcium, and 3.3 ppb for copper.

[0043]

The curable composition of the present invention has a very low content of alkali metals and heavy metals, and thus can be suitably used for electronic materials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI theme coat ゛ (reference) // C08G77 / 34 C08L 101/00 F term (reference) 4D017 AA03 BA12 CA13 CA14 CA17 CA20 DA01 DB02 4J002 BG052 BG054 BG072 CD034 CF182 CF192 CG002 CH022 CH024 CJ002 CM043 CP031 CP051 DE056 DE066 DE096 FD314 GQ00 4J035 AA03 BA03 BA06 BA16 CA01N CA022 CA152 EA01 EB04 EB10 LA03 LB20

Claims (8)

[Claims] 1. A curable composition which has been treated with a filter medium on which zeta potential acts and has a total content of sodium, lithium, potassium, calcium and copper of 50 ppb or less. 2. The curable composition according to claim 1, wherein the filter medium on which zeta potential acts is used together with an ion exchanger and / or a chelate former. 3. The curable composition is (A) (A-1) a compound represented by the following general formula (1): R ¹ _a Si (OR ² ) _4-a (1) (R) ¹ represents a hydrogen atom, a fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, a represents an integer of 0 to 2) and (A-2) the following general formula (2) a compound represented by _{^{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (OR 5) 3-c R 6 c ····· (2) (R 3, R 4, R ⁵ and R ⁶ may be the same or different and each represents a monovalent organic group, b and c may be the same or different, each represents a number of 0 to 2, and R ⁷ represents an oxygen atom Or a group represented by-(CH ₂ ) _n- ;
Represents 1 to 6, and d represents 0 or 1. 2. The curable composition according to claim 1, comprising a hydrolyzate and / or a condensate of at least one compound selected from the group consisting of (B) and (B) an organic solvent. 4. The curable composition according to claim 3, wherein the curable composition further comprises (C) a compound having a boiling point or a decomposition temperature of 250 to 450 ° C. 5. The curable composition according to claim 3, wherein the curable composition further comprises (D) a compound having a boiling point or a decomposition temperature exceeding 450 ° C. 6. The curable composition according to claim 3, wherein the curable composition further comprises (E) a surfactant. 7. (A) (A-1) a compound represented by the following general formula (1): R ¹ _a Si (OR ² ) _4-a (1) (R ¹ is a hydrogen atom, A fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, a represents an integer of 0 to 2) and (A-2) a compound represented by the following general formula (2) _{^{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (oR 5) 3-c R 6 c ····· (2) (R 3, R 4, R 5 and R ⁶ May be the same or different and each represents a monovalent organic group, b and c may be the same or different and each represents a number of 0 to 2, and R ⁷ represents an oxygen atom or — (CH ₂ ) _n - represents a group represented by, n
Represents 1 to 6, and d represents 0 or 1. A) treating a curable composition containing at least one of a hydrolyzate and a condensate of at least one compound selected from the group consisting of) and (B) an organic solvent with a filter medium on which zeta potential acts. A method for producing the curable composition according to claim 2. (A-1) A compound represented by the following general formula (1): R ¹ _a Si (OR ² ) _4-a (1) (R ¹ is a hydrogen atom, a fluorine atom or A monovalent organic group, R ² represents a monovalent organic group, a represents an integer of 0 to 2) and (A-2) a compound R ³ _b represented by the following general formula (2) _{^{(R 4 O) 3-b}} Si- (R 7) d -Si (oR 5) 3-c R 6 c ····· (2) (R 3, R 4, R 5 and R ⁶ are the same And each may represent a monovalent organic group, b and c may be the same or different, represent a number of 0 to 2, and R ⁷ represents an oxygen atom or — (CH ₂ ) _n − Represents a group represented by the formula:
Represents 1 to 6, and d represents 0 or 1. At least one compound selected from the group consisting of: (B) an organic solvent,
(C) a compound having a boiling point or decomposition temperature of 250 to 450 ° C., (D) a compound having a boiling point or decomposition temperature of more than 450 ° C., and (E) at least one of surfactants are treated with a filter medium on which zeta potential acts. The method for producing a curable composition according to claim 6, wherein: