JPH04335016A - Water-soluble epoxy resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. excellent in solubility or dispersibility in water. CONSTITUTION:The title compsn. is prepd. by reacting an epoxy resin with a monoalkoxypolyethylene glycol in an amt. of 0.25-1.0mol and a polyisocyanate in an amt. of 0.5-2.0mol of isocyanate group, both based on 1mol of hydroxyl groups in the epoxy resin.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble epoxy resin composition having excellent water solubility or water dispersibility.

0002

[Prior Art] Conventionally, it has been known that water-soluble epoxy resins can be obtained by reacting an amino compound or a carboxy compound with an epoxy group in the epoxy resin to introduce an amino group or a carboxylic acid group. It was getting worse. However, these conventional water-soluble epoxy resins have a reduced content of epoxy groups, which are functional groups.
A crosslinking reaction due to epoxy groups cannot be expected. Therefore, the physical properties as an epoxy resin could not be expected. Furthermore, since these water-soluble epoxy resins are cationic and anionic, there is a problem in that there are ionic limitations when mixing other components.

0003

[Problems to be Solved by the Invention] As a result of intensive studies to find an epoxy resin that is non-ionic and can be made water-soluble by a method that does not use epoxy groups, the present inventor discovered that monoalkoxypolyethylene glycol was added to the hydroxyl groups in the epoxy resin. The present invention was completed by discovering that water solubility can be achieved by reacting polyisocyanate.

0004

[Means for Solving the Problems] That is, in the present invention, 0.25 to 1.0 mole of monoalkoxypolyethylene glycol and 0.50 to 2.0 mole of isocyanate group of polyisocyanate are added to 1 mole of hydroxyl group of epoxy resin. This is a water-soluble epoxy resin composition characterized by being obtained by reaction.

[0005] Examples of the epoxy resin of the present invention include compounds represented by the following general formula (1).

[0006]

[Chemical formula 1]

Specific examples of general formula (1) used in the present invention include polyglycidyl ether of bis(4-hydroxyphenyl)-2,2-propane.

000
8] In addition to the above-mentioned epoxy resins, polyglycidyl ethers of polyphenol compounds can be used. Examples of polyphenol compounds that can be used here include 4,4'-dihydroxybenzophenone, bis(4-
hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-
Hydroxy-tert-butyl-phenyl)-2,2-
Examples include propane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxyphenyl sulfone, phenol novolak, and cresol novolak.

Further, as special epoxy resins, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, dimer acid epoxidized products, etc. can be used.

Examples of the monoalkoxypolyethylene glycol of the present invention include compounds represented by the following general formula (2).

[0011]

[Chemical formula 2] (Here, R is a methyl group, an ethyl group, a propyl group, or a phenyl group.)

[0012] n is 5 to 120 on average. R is particularly preferably a methyl group, or n is particularly preferably 10-30.

For example, methoxypolyethylene glycol (molecular weight 650) with n=14 can be used.

Examples of the polyisocyanate used in the present invention include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, aromatic diisocyanates consisting of isomers thereof, 1,6-hexamethylene diisocyanate, 1 ,12
Examples include aliphatic diisocyanates such as -dodecane diisocyanate, alicyclic diisocyanates such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate.

[0015] Also included are isocyanate-terminated compounds obtained by reacting these compounds with active hydrogen group-containing compounds, and isocyanate-modified products obtained by reacting these compounds, such as carbodiimidization reactions.

[0016] In addition, some or all of the compounds were stabilized with a blocking agent having one active hydrogen in the molecule, such as methanol, n-butanol, benzyl alcohol, ethyl acetoacetate, ε-caprolactam, methyl ethyl ketone oxime, phenol, and cresol. Mention may also be made of polyisocyanates.

The blending ratio of the epoxy resin, monoalkoxy polyethylene glycol and polyisocyanate is 0.25 to 1.0 mole of monoalkoxy polyethylene glycol and 0.50 to 1.0 mole of polyisocyanate group per mole of hydroxyl group of the epoxy resin. It is 2.0 mol.

Less than 0.25 mole of monoalkoxypolyethylene glycol and 0.50 mole of polyisocyanate
If the amount is less than mol, the epoxy resin will not be water-solubilized, and
If the amount exceeds 1.0 mol and 2.0 mol, respectively, unreacted isocyanate groups remain in the system, causing a foaming phenomenon when water is added, which is not preferable.

The reaction method of the present invention may be a three-component simultaneous reaction method or a method in which monoalkoxypolyethylene glycol and polyisocyanate are reacted in advance and then reacted with an epoxy resin.

[0020] During the reaction, a solvent commonly used in urethanization reactions can be used. Examples of solvents include acetone, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, and the like.

[0021] During the reaction, a urethanization catalyst such as triethylenediamine or dibutyltin dilaurate may be used as required. The reaction temperature is 20-160℃
It can be carried out with

The water-soluble epoxy resin obtained by the present invention can be easily made into an aqueous solution or emulsion by adding water. In addition to water, some water-soluble solvents such as acetone and dioxane can be used.

[0023] Other resins may be added to the water-soluble epoxy resin obtained by the present invention, if necessary. Examples of other resins include polyvinyl alcohol, polyethylene glycol, polyethylene glycol, polypropylene glycol copolymers, water-soluble alkyd resins, butadiene emulsions, vinyl chloride-vinyl acetate emulsions, natural rubber latex, and water-soluble cellulose.

The water-soluble epoxy resin obtained by the present invention may also contain other substances, such as antioxidants, ultraviolet absorbers, heat resistance improvers, colorants, inorganic and organic fillers, plasticizers, A lubricant, an antistatic agent, a reinforcing agent, a dispersion stabilizer, etc. can be added.

[0025]

[Effects of the Invention] The water-soluble epoxy resin of the present invention can be used in water-based paints, adhesives, binders, various processing agents, etc. by using an amine curing agent. It can also be used as a nonaqueous system, and in this case, the antistatic effect of the cured resin can be improved.

[0026]

EXAMPLES The present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, in Examples and Comparative Examples, "parts" and "%" all refer to "parts by weight" and "parts by weight".
% by weight.

Example 1 82.9 parts of monomethoxypolyethylene glycol (molecular weight 690) (0.12 mol as hydroxyl group) was placed in a 500 ml flask equipped with a thermometer, a cooler, a stirrer, and a nitrogen gas inlet and raw material inlet. ), 20.9 parts of 2,4-tolylene diisocyanate (0.2 parts as isocyanate group)
4 mol) and 69.2 parts of acetone were charged and mixed while heating to 55°C. After 8 hours, an acetone solution (resin content 60%) of Epikote 1001 (manufactured by Shell Chemical, hydroxyl value 146) was added.
) 77.1 parts (0.12 mol of hydroxyl groups) and 0.01 part of dibutyltin dilaurate were added. After 4 hours at 55°C, it was confirmed that the isocyanate group concentration was 0.1% or less, and the reaction was terminated. When 300 parts of water was added to 150 parts of the water-soluble epoxy resin and stirred, a transparent aqueous solution was obtained.

Example 2 Into the same flask as in Example 1, 69.3 parts of monomethoxypolyethylene glycol having a molecular weight of 800 (as hydroxyl group, 0
．． 0866 mol), 15.1 parts of 2,4-tolylene diisocyanate (0.174 mol as isocyanate group)
and 56.3 parts of acetone were added and mixed while heating to 55°C. After 8 hours, Epicote 1004 (hydroxyl value 185)
acetone solution (resin content 60%) 109.3 parts (hydroxyl group 0.217 mol) and dibutyltin dilaurate 0.0
1 part was added. After 4 hours at 55°C, it was confirmed that the isocyanate group concentration was 0.1% or less, and the reaction was terminated. When 300 parts of water was added to 150 parts of the above water-soluble epoxy resin and stirred, a milky white aqueous solution was obtained. Even after this aqueous solution was heated to 68° C. to distill off acetone, it remained a stable milky white aqueous solution.

Example 3 Into the same flask as in Example 1, 78.1 parts of monomethoxypolyethylene glycol having a molecular weight of 690 (as hydroxyl group, 0
．． 113 mol), diphenylmethane diisocyanate 2
8.3 parts (0.226 mol as isocyanate group)
, 70.9 parts of acetone and 72.7 parts of an acetone solution of Epicote 1001 (resin content 60%) (0.11 parts of hydroxyl group)
3 mol) and heated and mixed at 55°C. After 2 hours at 55°C, 0.01 part of dibutyltin dilaurate was added and the reaction was continued for an additional 3 hours. Isocyanate group concentration is 0.1%
The reaction was terminated after confirming that the following conditions were met. When 300 parts of water was added to 150 parts of the above water-soluble epoxy resin and stirred, a translucent aqueous solution was obtained.

Example 4 Into the same flask as in Example 1, 73.4 parts of monomethoxypolyethylene glycol having a molecular weight of 690 (0.4 parts as hydroxyl groups) was added.
106 mol), hexamethylene diisocyanate and 17.
8 parts (0.212 mol as isocyanate groups), 60.9 parts of acetone, and 97.8 parts (0.152 mol of hydroxyl groups) of an acetone solution of Epicoat 1001 (resin content 60%) were charged and mixed under heating at 55°C. After 2 hours at 55°C, 0.07 part of dibutyltin dilaurate was added and the reaction was continued for an additional 4 hours. The reaction was terminated after confirming that the isocyanate group concentration was 0.1% or less. When 300 parts of water was added to 150 parts of the above water-soluble epoxy resin and stirred, a translucent aqueous solution was obtained.

Claims (1)

[Claims] Claim 1: Monoalkoxypolyethylene glycol 0.25 to 1.0% per mole of hydroxyl group of epoxy resin.
0 moles and 0 isocyanate groups of polyisocyanate
．． A water-soluble epoxy resin composition obtained by reacting 50 to 2.0 moles.