JPS60186532A - Production of film-forming soluble condensation product - Google Patents

Abstract

PURPOSE:To obtain a condensation product soluble only in a particular solvent to form a stable solution having high heat-resistance and giving a uniform film when coated and dried, by the condensation reaction of a compound containing phenolic hydroxyl group with a methylolated amino compound in the presence of an acid catalyst. CONSTITUTION:The objective compound can be produced by condensing (A) the compound of formula Ar1-X-Ar2 (Ar1 and Ar2 are aromatic residue and at least one of the residue contains 1 or 2 nucleus-substituted hydroxyl groups; X is -NH- or -N=N-) having phenolic hydroxyl group with (B) a methylolated amino compound in the presence of (C) an acid catalyst. The compound having phenolic hydroxyl group is selected from the hydroxydiphenylamine compound of formula I (R is H or OH), hydroxyazobenzene compound of formula II (R is same as defined in formula I ), and naphthol azobenzene compound of formula III (R1 and R2 are same as defined in formula I ), and the amino compound is a modified product selected from melamine, benzoguanamine, and urea.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing a soluble condensate having film-forming ability. can be formed,
The present invention relates to a method for producing a soluble condensate useful as a novel functional material.

Currently, various types of polymers have been developed and are used for various purposes as appropriate functional materials depending on their properties. However, for example, under the following conditions, i.e. (
1) Slightly soluble or insoluble in organic solvents such as alcohols, ketones, ethers, esters, aromatic hydrocarbons, and petroleum hydrocarbons, but soluble only in limited types of polar organic solvents; (2) Water poorly soluble or insoluble in water, but at least soluble in acidic or alkaline aqueous solutions, (3
) When dissolved in an organic solvent and applied and dried, it forms a uniform continuous film; (4) it does not melt or soften at temperatures below 100°C, nor does it react or decompose; (5)
) There is still no known polymer that satisfies all of the following conditions: a solution dissolved in an organic solvent is stable at room temperature, and long-term storage is possible.

Therefore, if a polymer that satisfies all of these conditions at the same time is developed, a new use as a new functional material will be found, and its range of applications will be significantly expanded.

In view of these circumstances, the inventors of the present invention have conducted extensive research in order to provide a polymer that satisfies all of the above conditions. discovered that the product obtained by condensation in the presence of
Based on this knowledge, we have completed the present invention.

That is, the present invention provides (A) general formula % formula % (1) (wherein Ar1 and Ar2 are substituted or unsubstituted aromatic ring residues, at least one of which is a nuclear substituted hydroxyl group 1
or 2, and X is -NH- or -I←1ku-) and (B
) and a methylolated amine compound in the presence of an acid catalyst.

The general formula (1) used as component (A) in the present invention
Examples of compounds having a phenolic hydroxyl group represented by the formula include hydroxydiphenylamines represented by the general formula (in which R is a hydrogen atom or a hydroxyl group), and compounds having a phenolic hydroxyl group represented by the general formula (in which R is a hydrogen atom or a hydroxyl group); ) or the general formula (in which R1 and R
Naphthol azobenzenes represented by the formula (2) in which each hydrogen atom is a hydroxyl group are preferred.

As specific examples of the compounds, hydroxydiphenylamines represented by the general formula (11) include p-hydroxydiphenylamine, m-hydroxydiphenylamine, 0-hydroxydiphenylamine, 2,4-dihydroquine diphenylamine, and 3,5-dihydroquine. Regarding hydroxybenzenes such as diphenylamine represented by the general formula (111), p-hydroxyazobenzene, m-hydroxyazobenzene, O-hydroxyazo-kunzene, 2,4-dihydroxyazobenzene,
Among the naphtholazobenzenes represented by the general formula OV, 4-naphtholazobenzene, 2-naphtholazobenzene and the like are mentioned. Each of these compounds may be used alone or in combination of two or more, and if necessary, other phenols such as phenol, m-cresol, 3.5-xylenol, p
-Alkylphenol, p-cumelphenol, bisphenol A rsorcinol, etc. can also be used in combination.

The methylolated amine compound used as component (B) in the present invention is obtained by modifying an amine compound with formalin or formalin and alcohol by a conventional method, and is a monomer, oligomer, or a mixture thereof. Preferred examples of such compounds include alkoxymethyl compounds of methylolated melamines, methylolated benzoguanamines, and methylolated ureas when they are also modified with alcohol; These methylolated amine compounds can be obtained by condensing melamine, benzoguanamine, and urea with formalin or formalin-alcohol, respectively. These condensation reaction solutions may be used after being strained, or may be purified and used if necessary.

In the present invention, (d) the compound having a phenolic hydroxyl group as the component (A) and the methylolated amine compound as the component (B) are condensed in the presence of an acid catalyst.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, phosphoric acid, and sulfuric acid, and organic acids such as formic acid and oxalic acid. Preferred among these catalysts are phosphoric acid, sulfuric acid, or a mixture thereof, since the degree of condensation, which is related to the solubility of the resulting condensate, can be easily controlled.

In the present invention, the properties of the condensate obtained are, for example, ω
) component and (B) component charging ratio, type and amount of catalyst,
It depends on reaction conditions such as reaction temperature and reaction time. Therefore, it is important to appropriately select these reaction conditions so that the resulting condensate satisfies all of the above-mentioned conditions.

The reaction temperature is generally in the range of 15 to 80°C, and the reaction time is usually about 1 to 100 hours, although it depends on the reaction temperature.

In the present invention, it is impossible to separate and purify the target condensate from the condensation reaction solution! /11, for example, a method in which the reaction solution is poured into water, the condensate is precipitated, filtered, washed with water, and dried; the separated condensate is once dissolved in an acid or alkaline aqueous solution, and then neutralized. The precipitate produced is filtered out,
Methods such as washing with water and drying are used.

As the organic solvent for dissolving the condensate obtained in this way, applying it, and drying it to form a film, so-called aprotic polar solvents such as dimethylformamide,
Dimethylacetamide, dinotyl sulfoxide, tetramethylurea, hexaltylphosphor(tri)amide,
Examples include N-methylpyrrolidone, acetonitrile, ethylene carbonate, and morpholine, which may be used alone or as a mixed solvent containing two or more thereof.

The soluble condensate obtained in the present invention is poorly soluble or insoluble in general organic solvents, but is soluble in special solvents such as aprotic polar solvents, and its solutions tend to be stable and soluble in water. It is a novel condensate that is poorly soluble or insoluble, but is at least soluble in acidic or alkaline aqueous solutions and can form a heat-resistant uniform film, and has been developed and used for various purposes as a new functional material. It is expected that

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 200 y of p-hydroxydiphenylamine was dissolved in an acid consisting of 98% sulfuric acid 3007 and 85% phosphoric acid 3007, and 100 y of formalin-alcohol denatured benzoguanamine was added little by little to react. The reaction temperature was maintained at 50° C., and after 24 hours of reaction, a portion of the reaction solution was taken out and purified. The remaining product was purified in the same manner after continuing the reaction for 72 hours.

Regarding the condensate obtained by drying, the one reacted for 24 hours was slightly soluble in chthone and alcohols, but 72
Those reacted for a long time were insoluble in these. When both were dissolved in dimethylacetamide and applied onto a glass substrate and dried, a uniform film was obtained in both cases. All of these films were soluble in a 1% aqueous sodium hydroxide solution.

Example 2 p-hydroxydiphenylamine, 200? f8
5 times phosphoric acid 600? Formalin-alcohol denatured urea 1002 was added little by little to the solution and reacted. After maintaining the reaction temperature at 60°C and reacting for 72 hours, the mixture was poured into water, the resulting precipitate was filtered out, washed repeatedly, and then dried with air at 60°C.

The obtained condensate was insoluble in alcohol and ketones, but soluble in dimethylacetamide, and when this solution was applied onto a glass plate and dried, a uniform film was formed.

This film was soluble in a 1% aqueous sodium hydroxide solution.

Example 3 p-hydroxyazobenzene IQO? 85% phosphoric acid 3
A solution of trimethylolmelamine ioor dissolved in water 501 was added little by little to this, and 30 minutes after the total addition, 98% sulfuric acid 1002 was added dropwise little by little. After dropping, maintain the temperature at 60°C.
Allowed time to react. Next, the reaction product was poured into pure water, and the resulting precipitate was filtered out, washed, and dried at 60°C.

The obtained condensate is insoluble in alcohol and acetone,
It showed good solubility in dimethylacetamide and 1% aqueous sodium hydroxide solution.

Example 4 4-naphthol azobenzene 50 f' 98% sulfur
To this, formalin-alcohol denatured urea 509 was added little by little, and after the entire amount was added, the mixture was heated at 45°C.
The mixture was allowed to react for 24 hours. Next, the reaction solution was poured into pure water, the generated precipitate was filtered out, and the washing was repeated.
Dry again by blowing air at 60℃.

The resulting condensate contains alcohol, acetone, and toluene KF.
Although it was poorly soluble at first, it showed good solubility in dinotylformamide. It also showed good solubility in a 1% aqueous sodium hydroxide solution.

Example 5 p--Hydroxydiphenylamine 1007 and 4-naphtholazobenzene 1002 were dissolved in 85% phosphoric acid 8002, and formalin-alcohol-denatured melamine 1 was dissolved in this.
201 was added little by little. After adding the entire amount, reduce the temperature to 55℃
The temperature was maintained at 72 hours and the reaction was carried out for 72 hours. Next, the reaction solution was poured into water, and the generated precipitate was filtered, washed, and dried.

The obtained condensate was insoluble in alcohol and ketones, but showed good solubility in dimethylacetamide and 1% aqueous sodium hydroxide solution.

Example 6 50f of m-hydroxydiphenylamine and 150 liters of 4-hydroxyazobenzene were mixed with 85% phosphoric acid 3007 and 9
8% sulfuric acid 300? was added little by little into the mixed solution.

After adding the entire amount, the temperature was maintained at 60°C and the reaction was carried out for 48 hours. Next, the reaction product was poured into water, and the generated precipitate was filtered, washed, and dried.

The obtained condensate was insoluble in alcohol and ketones, but showed good solubility in dimethylacetamide and a 1% aqueous sodium hydroxide solution, and was soluble in dimethylacetamide. After coating and drying, a uniform film was obtained.

Patent applicant Tokyo Ohka Kogyo Co., Ltd. Agent Akira Agata

Claims (1)

[Claims] NA) General formula % Formula % (Ar1 and Ar2 in the formula are substituted or unsubstituted aromatic ring residues, at least one of which is a nuclear substituted hydroxyl group 1
or 2 groups, and X is -NH- or -N=N-) and (B
1. A method for producing a soluble condensate having film-forming ability, which comprises condensing a l-notyrolated amine compound in the presence of an acid catalyst. 2. Claim 1, wherein the compound having a phenolic hydroxyl group is at least one selected from hydroxydiphenylamines represented by the general formula (R in the formula is a hydrogen atom or a hydroxyl group) Manufacturing method described. 3. Claim 1, wherein the compound having a phenolic hydroxyl group is at least one selected from among the hydroxyazobenzenes represented by the general formula (R in the formula is a hydrogen atom or a hydroxyl group) manufacturing method. - A patent claim in which the compound having 4 phenolic hydroxyl groups is at least one selected from naphtholazobenzenes represented by the general formula 1 (2 (in which R1 and R2 are each a hydrogen atom or a hydroxyl group) Claims 1, 2 and 3, wherein the methylolated amine compound is at least one modified product selected from melamine, benzoguanamine and ureas. The manufacturing method described in item 1 or 4.