JPS59210926A - Production of water-soluble resin - Google Patents

Abstract

PURPOSE:To obtain a water-soluble resin which can be easily handled, is excellent in safety and allows one to save material, by reacting a polycarboxylic acid with a polyalcohol, reacting the product with a polyisocyanate, and adding a basic compound thereto. CONSTITUTION:A polycarboxylic acid having at least one acid anhydride group in the molecule, or its functional derivative is reacted with a polyalcohol at a molar ratio of about 2 to 1, and the product is further reacted with a polyisocyanate. A basic compound is added to the product to form a neutral salt. As the polycarboxylic acid having at least one acid anhydride group in the molecule, or its functional derivative, trimellitic anhydride, pyromellitic anhydride or benzophenonetetracarboxylic anhydride is particularly preferable from the viewpoint of heat resistance. As the polyisocyanate, an aromatic diisocyanate such as tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate is preferable from the viewpoint of heat resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a water-soluble resin useful as a surface protection coating, an adhesive, and the like.

Generally, the resin compositions used for the above-mentioned purposes are in the form of resins dissolved in various organic solvents, and they emit a strong odor and may cause irritation if they come into contact with the skin. Additionally, working in an atmosphere of highly concentrated solvent vapor for a long period of time can cause dizziness.

It is not good for your health as you may feel like vomiting. Furthermore.

When handling, it is necessary to pay sufficient attention to fire hazards.

The present invention was arrived at as a result of studies aimed at eliminating the drawbacks of such conventional resin compositions.

That is, 1 the present invention provides - a polyhydric carboxylic acid having one or more acid anhydride groups in the molecule or a functional derivative thereof and a polyhydric alcohol in a molar ratio of about 2:1, and further a polyhydric incyanate. The present invention relates to a method for producing a water-soluble resin in which a basic compound is added to form a neutralized salt after an addition reaction.

In the present invention, the functional derivative of a polycarboxylic acid having one or more acid anhydride groups in the molecule refers to an anhydride, ester, amide or chloride of the polycarboxylic acid.

Examples of polyhydric carboxylic acids having one or more acid anhydride groups in one molecule include trimellitic acid, pyromellitic acid, 3.
a, '4.4'-benzophenonetetracarboxylic acid, 1,2,3.4-butanetetracarboxylic acid, 1,2゜4-butanetricarboxylic acid, cyclopentanetetracarboxylic acid, ethylenetetracarboxylic acid, bicyclo-( 2,
2,2'l-oct-(7)-ene-2:3°5:6-
Tetracarboxylic acid, bis(3,4-dicarboyacyphenyl)ether, 2,3,6.7-naphthalenetetracarboxylic acid, 1,2,5.6-naphthalenetetracarboxylic acid, ethylene glycol bis trimellitate, 42 '-bis(3,4-biscarboxyphenyl)propane, 2
．． 2',3.3'-diphenyltetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, 3.4-
') Carboquine phenyl sulfone, thiophene-2,3
, 4,5-tetracarboxylic acid, pyrazinetetracarboxylic acid, and the like.

- As the polyhydric carboxylic acid or its functional derivative having one or more acid anhydride groups in the molecule, trimellitic anhydride, pyromellitic anhydride, or benzophenonetetracarboxylic anhydride is particularly preferred from the viewpoint of heat resistance. If necessary, polyhydric carboxylic acids 9 other than these, such as trimesic acid, isophthalic acid, terephthalic acid, adipic acid, etc., may be used in combination.

There is no particular restriction on the polyhydric alcohol used in the present invention, and it can be selected from polyhydric alcohols having a valence of two or more. Specific compounds include ethylene glycol and diethylene glycol.

Triethylene glycol, fluoropylene gelicol.

Dipropylene glycol, 1,4-butanediol.

1.4-hexanediol, 1.6-hexanediol, glycerin, trimethylolpropane, tris(2-
Hydroxyethyl) isocyanurate, etc., are used singly or as a mixture.

When reacting a polycarboxylic acid having one or more acid anhydride groups in one molecule or a functional derivative thereof with a polyhydric alcohol, a polycarboxylic acid having one or more acid anhydride groups in one molecule is used. The molar ratio of acid or its functionally derived alcohol to polyalcohol is about 2:1, but not necessarily 2:1, but 1.8-2.2:0.8-1. It is considered to be within the range of 2.

From the point of view of reaction control, it is appropriate to use a solvent.

The solvent is preferably one with excellent solubility in water, such as alcohol, polyhydric alcohol, or derivatives thereof, such as methanol, ethanol, isopropanol, phthanol, in addition to the polyhydric alcohols mentioned above.
Ethylene glycol monomethyl ether, ethylene glycol 7-ethyl ether, ethylene glycol 7-ethyl ether acetate, ethylene glycol diacetate, ethylene glycol mottyl ether, etching glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisoglobil ether, diethylene glycol 7-ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diacetate, and basic solvents such as N.

N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methyl-
Caprolactam, N-ethyl-caprolactam, pyridine, Hegyi-sameethylene phosphonamide.

Isophorone etc. can be used. These and others may be used alone or in combination.

When a polyhydric carboxylic acid having one or more acid anhydride groups in one molecule or its functional derivative is reacted with a polyhydric alcohol, the resin concentration is preferably 10 to 90%, more preferably 30%. It is said to be ~80% heavy liquid, and if necessary, it may be necessary to dilute it during the reaction! Alternatively, the reaction may be continued. There is no limit to the reaction temperature, but 50°C to 300°C is preferable.
Preferably, the temperature is particularly preferably from 100°C to the boiling point.

According to the present invention, the resin content concentration refers to a value expressed as a ratio of the weight of the reaction material to the sum of the weight of the reaction material and the solvent (1:1).

Examples of the polyvalent incyanate used in the present invention include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and ethylene diisocyanate; 1.
Aliphatic diisocyanates such as 4-tetramethylene diisocyanate 1-,1,6-hexamethylene diisocyanate, cyclobutene-1,3-diisocyanate, cyclohexane-1+3-diisocyanate, cyclohexane-1°4-diisocyanate, in7oane diisocyanate An isocyanurate ring-containing polyvalent incyanate obtained by a polymerization reaction of alicyclic diisocyanates such as -1. and the above-mentioned aromatic diisocyanates -1.

Polyphenylmethyl polyisocyanate, for example, a condensate of aniline and formaldehyde converted to 7-osgen, isocyanurate ring-containing polyvalent isocyanate obtained by polymerization reaction of tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate. Examples include. In consideration of heat resistance, aromatic diisocyanates such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate are preferred.

The amount of polyvalent incyanate to be added is preferably 0.1 to 10 times per equivalent of the polyvalent carboxylic acid having one or more acid anhydride groups in the molecule or its functional derivative, and 0. A total of .5 to 4 equivalents is more preferable.

If it is less than 0.1 equivalent, the molecular weight of the resulting resin will not be sufficient, and if it exceeds 10 equivalents, the system will tend to gel.

When adding polyvalent incyanate, rapid foaming9
Since heat is generated, it is necessary to cool the system to below room temperature, and it is preferable to gradually raise the temperature thereafter. The resin concentration during the reaction is preferably 10 to 90% by weight, more preferably 30 to 80% by weight. Depending on the case, the reaction may be further continued by diluting it during the reaction. The reaction temperature is not particularly limited, but is preferably from 50°C to 300°C, particularly preferably from 100°C to the boiling point.

A basic compound is added to the condensate obtained through such a reaction process to form a neutralized salt, thereby producing a water-soluble resin. Basic compounds that form neutralized salts include:
There are primary amines, secondary amines, tertiary amines, quaternary amines, etc. Specific compounds include ammonia, ammonium hydroxide, dipropylamine, and diptylamine.

Monoethanolamine, jetanolamine, triethanolamine, piperidine, morpholine.

Examples include triethylamine, tributylamine, triethylenediamine, N-methylmorpholine, N,N-dimethylethanolamine, and the like. Furthermore, there is no particular restriction on the reaction temperature when forming the neutralized salt.

The temperature is preferably from 0°C to 200°C, particularly preferably from room temperature to 130°C.

The water-soluble resin obtained by the production method of the present invention is as follows.

The composition that contains the solvent during synthesis can be used to remove even more solvent.
It is then used as a composition.

After forming the neutralized salt, it may be diluted with viscosity adjusting reservoir water. In addition to this water removal, various water-soluble compounds suitable as reaction solvents as exemplified above may be used in combination.

The present invention will be explained below with reference to Examples.

Example 1 500m1 equipped with a stirrer, thermometer, and cooling pipe with trap
Trimellitic anhydride 481° diethylene glycol 13.3P and N-'f-pyrrolidone (hereinafter abbreviated as NMP) 166y were placed in a flask and reacted at 150°C for 3 hours. At this time, the acid value of the solution decreased to 92. After cooling this to room temperature, 21.8 fi' of tolylene diisocyanate (hereinafter abbreviated as TDI) was added dropwise.After the foaming became mild, the temperature was gradually raised and the temperature was gradually raised to 150°C for 2 hours.
The reaction was allowed to take place at 0°C for 1 hour. At this time, the acid value of the solution decreased to 27. At this point, the reaction was terminated, and aqueous ammonia with a concentration of 28% was added dropwise at 90°C, and 22.6 fl of ethylene glycol and 12.0 fl of diethylene glycol were added, followed by stirring at 90°C for 2 hours. The viscosity of the resulting solution was 30
It was 15 poise at °C. This solution was applied to a glass plate to a thickness of about 30 microns and heated at 200° C. for 30 minutes, and then at 250° C. for 1 hour, resulting in a strong film with good durability.

In addition, the thickness 8r specified by JiS G 3141
The resulting solution was applied to a polished steel plate in a run to a thickness of 40 microns, and further heated at 200°C for 30 minutes.
After drying at 50℃ for 1 hour, the DuPont impact value was measured.
However, 15cm (1/2 inch, 50011-
), and the Erichsen value was 6.

Example 2 In a flask similar to Example 1, 57% of trimellitic anhydride was added.
6P,) lyethylene glycol 22.55'.

200 deg of glycerin was added and reacted at 160°C for 5 hours. At this time, the acid value of the solution decreased to 65.

After cooling this to room temperature, TDI52.2y- was added dropwise.

After the foaming became mild, the temperature was gradually raised and the reaction was carried out at 150° C. for 5 hours. At this time, the acid value of the solution decreased to 19. At this point, the reaction was terminated, cooled to 90°C, and 8.6y of aqueous ammonia with a concentration of 28% was added dropwise to form an ammonium salt, followed by 20.4% of triethylene glycol. %,
29.21 g of ethylene glycol was added, and the mixture was stirred at 90° C. for 2 hours. The viscosity of the resulting solution was 47 boads at 30°C. When this solution was applied to a glass plate in the same manner as in Example 1 and dried by heating, a strong and flexible film was obtained.

Further, the DuPont impact value measured in the same manner as in Example 1 was 10 points, and the Erichsen value was 6 points.

Example 3 In a flask similar to Example 1, 57% of trimellitic anhydride was added.
6. i%, ethylene glycol 9.3P, NMP100
g- was added and reacted at 150°C for 2 hours.

At this time, the acid value of the solution decreased to 156. After cooling this to room temperature, 4,4'-diphenylmethane diisocyanate-1-37,5? was added gradually. After the foaming became mild, the temperature was gradually raised to 150°C for 2 hours and then heated to 170°C.
The reaction was carried out at ℃ for 1 hour. At this time, the acid value of the solution decreased to 35. At this point, the reaction was terminated and cooled to 90°C.
8.4f of ammonia at a concentration of
Ethylene glycol 21.1' was added and stirred at 90°C for 2 hours. The viscosity of the obtained liquid was 10 poise at 130°C. This solution was applied to a glass plate in the same manner as in Example 1 and dried under heat. Long live the film.

In addition, the DuPont shock S measured in the same manner as in Example 1
The value was 15 and the Erichsen value was 7 So.

Since the lOt fat obtained according to the present invention is water-soluble, it has a lower
It is easy to handle, has excellent safety, and can contribute to resource conservation. In addition, it can be used for practical purposes in the fields of electrical insulation paints, general metals, wood paints, adhesives, powder molded products, laminated products, fibers, glass, raw materials, natural fibers, etc. I can do it.

Industrially useful.

Claims (1)

[Claims] 1. - A polycarboxylic acid having one or more acid anhydride groups in the molecule or a functional derivative thereof and a polyhydric alcohol of about 2
A method for producing a water-soluble resin, which comprises reacting at a molar ratio of 1 to 1, further reacting by adding a polyvalent isocyanate, and then adding a basic compound to form a neutralized salt. 2. - The water-soluble resin according to claim 1, wherein the polyvalent carboxylic acid having one or more acid anhydride groups in the molecule is trimellitic anhydride, pyromellitic anhydride, or benzophenonetetracarboxylic anhydride. manufacturing method. 3. Polyvalent flucols are ethylene glycol, diethylene glycol, and triethylene glycol. The method for producing a water-soluble resin according to claim 1, which is glycerin or tris(2-hydroxyethyl)isocyanurate. 4. The method for producing a water-soluble resin according to claim 1, wherein the polyvalent incyanate is 4,4'-diphenylmethane diisocyanate or tolylene diisocyanate.