JPH03250014A - Hydrophilic polyurethane - Google Patents

Abstract

PURPOSE:To form a hydrophilic polyurethane excellent in solubility and dispersibility in an organic solvent and useful for uses of polyurethane resin by copolymerizing a specified double bond-terminated polyurethane with a hydrophilic vinyl monomer. CONSTITUTION:The title polyurethane is formed by copolymerizing a double bond-containing polyurethane prepared by reacting a polyurethane having an active hydrogen group or an isocyanate group on each end and a number- average mol.wt. of 2000-100000 with 0.05-1.4mol, per mol of the polyurethane, of a vinyl monomer having one isocyanate or hydroxyl group in the molecule with a hydrophilic vinyl monomer. The hydrophilic vinyl monomer may be either or nonionic and ionic ones. Examples of the nonionic monomers include vinyl monomers having hydroxyl, polyoxyethylene, glycidyl, amide or the like group. Examples of the ionic monomers include vinyl monomers having carboxyl, sulfonic, sodium sulfonate, phosphoric or the like group.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel hydrophilic polyurethane obtained by copolymerizing a polyurethane containing unsaturated double bonds and a hydrophilic vinyl monomer.

More specifically, the present invention relates to hydrophilic polyurethanes that have good solubility and dispersibility in organic solvents and are useful as emulsifiers and dispersants for polyurethane resins, as well as paints, adhesives, and various other modifiers.

(Prior Art) Conventionally, as a method for modifying polyurethane by copolymerizing it with a vinyl monomer, so-called polyurethane acrylate, in which an acrylic compound is bonded to the active terminal group of a polyfunctional polyurethane, is mixed with a vinyl monomer and exposed to ultraviolet light,
Common methods include copolymerization using electron beams, light, heat, radical initiators, etc., and are used in paints and adhesives.

However, these methods use polyfunctional polyurethane acrylate to obtain a cured product through a crosslinking reaction, and the modified copolymers are essentially insoluble in organic solvents and cannot be handled in liquid form.

In addition, as a method for obtaining a graft polymer by introducing an unsaturated double bond into the polyurethane main chain and copolymerizing it with a monomer, J. Macromol, Sci., C.
hem, A19 (7), 1041 1048 (198
3), J, Polym, Sci, Polym, Chem
, Ed, 20.2879 2885 (1982), Japanese Patent Publication No. 63-31506, Japanese Patent Publication No. 63-65697, Japanese Patent Publication No. 63-65698, etc., but all of them involve grafting. It has been difficult to obtain a satisfactory product because the copolymerization tends to be insufficient and the uniformity and solubility of copolymerization are low.

(Problems to be Solved by the Invention) The present invention overcomes the problems of the conventional techniques, has excellent solubility and dispersibility in organic solvents, and is useful for various uses of polyurethane resins and other uses. This was developed with the aim of providing a hydrophilic polyurethane.

(Means for Solving the Problems) As a result of intensive studies to achieve the above object, the present inventors have found that copolymerization of a specific polyurethane having an unsaturated double bond at the end and a hydrophilic vinyl monomer. The inventors have found a way to achieve the objective and have completed the present invention.

That is, the present invention is directed to a polyester having a number average molecular weight of 2.000 to 1oo, oo, which has active hydrogen groups or isocyanate groups at both ends.
1 mole of a vinyl monomer having one isocyanate group or hydroxyl group in the molecule is added to the polyurethane o.

The present invention provides a hydrophilic polyurethane obtained by copolymerizing a polyurethane containing unsaturated double bonds that has been reacted with 5 to 1.4 moles and a hydrophilic vinyl monomer.

The present invention will be explained in detail below.

In the present invention, the polyurethane itself having active hydrogen groups or isocyanate groups at both ends is a known one, and the polyurethane itself can be reacted with an organic diisocyanate, a polymer diol, and if necessary a chain extender without a solvent or in an organic solvent. This is a polyurethane that has a linear structure as its basic structure.

Here, the active hydrogen group is a hydroxyl group or an amino group possessed by a polyol or a chain extender, and by adjusting the equivalent ratio of organic diisocyanate to those equivalents, a polyurethane with a number average molecular weight of 2,000 to ioo, ooo is obtained. It is something.

Examples of the organic diisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4- or 2.
6-) Aromatic diisocyanates such as lylene diisocyanate, Examples include cyclic diisocyanates, aliphatic diisocyanates such as hexamethylene diisocyanate, and xylylene diisocyanate. These organic diisocyanates can be used alone or in combination of two or more.

Examples of the polymeric diol include polyethers having an average molecular weight of preferably 400 to 5,000, such as polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, copolymers of tetrahydrofuran and ethylene oxide, and copolymers of propylene oxide and ethylene oxide. Condensation of diols such as polyols, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 3-methylbentanediol with dicarboxylic acids such as adipic acid, succinic acid, and sebacic acid. Hydroxyl group-terminated polyester polyols obtained by reaction (typical examples include polyethylene adipate, polyethylene butylene adipate, polybutylene adipate, polypropylene adipate, polyhexylene adipate, etc.), polyester polyols such as polycaprolactone, polymethylvalerolactone, etc. Examples include polycarbonate polyols, silicone polyols, polybutadiene polyols, and polyolefin polyols. These polyols may be used alone or in combination.
Can be used in combination of more than one species. In addition, when using a chain extender, examples thereof include ethylene glycol, propylene glycol, diethylene glycol, l,4-butanediol, l,4-butanediol, and
.

Short chain diols such as 6-hexanediol, ethylenediamine, 1,2-propanediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, isophoronediamine, 4.4″ dicyclohexylmethanediamine, m-xylylenediamine, piperazine, etc. diamines, hydrazine, water, etc. These chain extenders may be used alone or in combination of two or more.

Examples of organic solvents used when synthesizing the polyurethane in an organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl-n-propyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, and ethyl formate. , ester solvents such as propyl formate, ether solvents such as tetrahydrofuran and dioxane, saturated hydrocarbon solvents such as n-hexane and cyclohexane, aromatic solvents such as benzene, toluene, and xylene, methylene dichloride, and ethylene. Chlorinated solvents such as dichloride and trichlorethylene,
Examples include dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, cellosolve acetate, and the like. In addition, alcohols such as methanol, ethanol, isopropanol, n- or 5ec-butanol, and cellosolves such as ethyl cellosolve and butyl cellosolve have hydroxyl groups and react with isocyanate groups, but chain extension reactions are performed using diamines. When performing this, the reaction between the isocyanate group and the amino group is much faster, so there is no problem even if they coexist in the solvent. These solvents may be used alone or in combination of two or more.

In the present invention, the synthesis of polyurethane is carried out by a conventional urethanization reaction method, which may be carried out without a catalyst or with a catalyst such as dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, stannous octoate, lead octylate, etc. Organic metals, tertiary amines such as triethylamine, triethylenediamine, N-methylmorpholine, etc. may also be used. In addition, the reaction temperature is usually selected in the range of 20 to 120°C, and the reaction time is usually 1 to 1
About 5 hours is sufficient. The polyurethane thus obtained is free of organic solvents or is a solution of an appropriate concentration.

In the present invention, the number average molecular weight of polyurethane is basically measured by quantitative determination of terminal groups or gel permeation chromatography (GPC). However, when the number average molecular weight is less than so or ooo, the average molecular weight of the polymer diol is determined from the OH value measurement value, and the molecular weight of the organic diisocyanate and chain extender are used to calculate the amount of polyurethane from the charging ratio during the reaction. Even if the number average molecular weight is calculated, a sufficient correspondence can be obtained.

The unsaturated double bond-containing polyurethane of the present invention is a polyurethane having a number average molecular weight of 2,000 to 100,000, both ends of which are active hydrogen groups or isocyanate groups. It is designed so that monomers are reacted in a specific ratio, and the reaction product that has an unsaturated double bond at one end of the polyurethane chain as a radically polymerizable component is the main component. The following method is used for this purpose.

(1) 0.05% of the vinyl monomer having one isocyanate group in the molecule is calculated based on the number average molecular weight of polyurethane having active hydrogen groups at both ends.
The reaction is carried out in a ratio of ~1.4 mol, preferably 0.3-1.2 mol. At this time, phenyl isocyanate, chlorine-substituted derivatives of phenyl isocyanate, methyl isocyanate, n-propylisocyanate, n-
An organic monoisocyanate such as butyl isocyanate may be used in combination to block the remaining active hydrogen groups at the terminals of the polyurethane.

(2) For 1 mole of polyurethane, calculated based on the number average molecular weight of polyurethane having isocyanate groups at both ends, 0.00.
The reaction is carried out in a ratio of 0.05 to 1.4 mol, preferably 0.3 to 1.2 mol. In this case, the remaining isocyanate groups at the end of the polyurethane may undergo a crosslinking reaction during subsequent copolymerization with a hydrophilic vinyl monomer, so they should not be reacted with an equal or excess amount of a monofunctional active hydrogen compound. It is preferable to seal it and inactivate it in advance.

The monofunctional active hydrogen compounds used in this case include methanol, ethanol, n-propanol, isopropanol, n- or 5ec-butanol, n-amyl alcohol, iso- or 5ec-amyl alcohol, n-
Monoalcohols such as hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, cyclohexanol, diethylethanolamine, methyl cellosolve, ethyl cellosolve, and butyl cellosolve are preferred.

In addition, when reacting the vinyl monomer at the end of polyurethane, it can be done in the same manner as for the polyurethane described above, but in order to prevent thermal polymerization of unsaturated double bonds during the reaction, hydroquinone or hydroquinone is added to the end of the polyurethane. Monomethyl ether, methyl hydroquinone, p
- A polymerization inhibitor such as benzoquinone may be added in advance to the extent that it does not affect the subsequent copolymerization with the hydrophilic vinyl monomer.

Examples of vinyl monomers having one isocyanate group in the molecule used in the present invention include methacryloyloxyethyl isocyanate, acryloyloxyethyl isocyanate, m- or p-impropenyl-α, α
-dimethylbenzyl isocyanate, m- or p-ethylenylbenzyl isocyanate, methacryloyl isocyanate, vinyl isocyanate, allyl isocyanate, and the like.

Examples of vinyl monomers having one hydroxyl group in the molecule include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, polypropylene glycol, polyethylene glycol, and Methacrylic acid or acrylic acid monoester compounds such as oxyethylene oxypropylene block polyol, polyoxyethylene oxytetramethylene block polyol, other glycerol methacrylate alkylate, allyl alcohol, N
-methylol acrylamide, N-methylol methacrylamide and the like.

The polyurethane containing unsaturated double bonds obtained by the above method mainly contains a reactive component having an unsaturated double bond at one end of the polyurethane chain as a radically polymerizable component,
The hydrophilic polyurethane according to the present invention is obtained as a mixture which partially contains a reaction component having unsaturated double bonds at both ends of the polyurethane chain, and the remainder contains polyurethane having no unsaturated double bonds. There is no problem in using it as it is to obtain .

What is important here is that the number average molecular weight of the polyurethane before introducing unsaturated double bonds is 2,000 to 10o, ooo
, preferably 4.000 to so, oo.

and the ratio of the vinyl monomer having one isocyanate group or hydroxyl group in the molecule to 1 mole of the polyurethane is 0.05 to 1.4 moles, preferably 0.3 to 1.2 moles. This is to introduce an unsaturated double bond by reacting with If the number average molecular weight is less than 2°000, the reaction solution will gel during the subsequent copolymerization with the vinyl monomer, probably because the molecular weight between the crosslinking points due to the reaction component having unsaturated double bonds at both ends is small. If the number average molecular weight exceeds 100,000, it becomes difficult to introduce an unsaturated double bond to the polyurethane terminal. on the other hand,
If the amount of the vinyl monomer reacted with the terminal end of the polyurethane is less than 0.05 mole per mole of the polyurethane, the polyurethane component effective for radical polymerization will be insufficient, and a sufficient effect in modifying the polyurethane will not be obtained. If the amount of the vinyl monomer exceeds 1.4 mol, the proportion of reaction components having unsaturated double bonds at both ends of the polyurethane increases, and there is a tendency for gelation during copolymerization, probably due to an increase in crosslinking points.

The hydrophilic polyurethane of the present invention is obtained by copolymerizing the above-mentioned polyurethane containing an unsaturated double bond and a hydrophilic vinyl monomer. At this time, the charging ratio of the hydrophilic vinyl monomer to the polyurethane is:
It can be selected arbitrarily and is not particularly limited.

The hydrophilic vinyl monomer may be nonionic or ionic. Examples of nonionic monomers include vinyl monomers having hydroxyl groups, polyoxyethylene groups, glycidyl groups, tetrahydrofurfuryl groups, amide groups, pyrrolidone groups, etc. Specific examples include acrylic acid, methacrylic acid, etc. 2-hydroxyethyl ester, 2-hydroxypropyl ester, glycerin ester, polyethylene glycol ester, methoxypolyethylene glycol ester, polyoxyethylene oxybrobylene block polyol ester, polyoxytetramethylene block polyol ester, glycidyl ester, tetrahydrofurfuryl alcohol Examples include ester, acid amide, N-methylolamide, N-vinylformamide, and N-vinylpyrrolidone.

In addition, examples of ionic monomers include vinyl monomers having carboxyl groups, sulfonic acid groups, sodium sulfonate bases, phosphoric acid groups, tertiary amino groups, quaternary ammonium bases, etc. is acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinyl sulfonic acid, sulfonated styrene, sodium styrene sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, mono(2-methacryloyloxyethyl) acid phosphate, mono (2-Acryloyloxyethyl) acid phosphate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, vinylpyridine, hydroxypropyltrimethylammonium methacrylate, hydroxyethyltrimethylammonium methacrylate, etc. It will be done. In addition, when a vinyl monomer having a carboxyl group or a sulfonic acid group is used, the copolymer may be treated with an alkali such as caustic soda to form an alkali metal salt, or a vinyl monomer having a tertiary amino group may be used. If so, the copolymer may be converted into a quaternary ammonium salt using benzyl chloride or the like.

These hydrophilic vinyl monomers may be used alone or in combination of two or more, but in order to adjust the degree of hydrophilicity and solubility of the resulting hydrophilic polyurethane, other hydrophobic monomers may be used. vinyl monomers such as acrylic acid and methacrylic acid, methyl, ethyl, propyl, n- and t-
Alkyl esters such as ert-butyl, isobutyl, 2-ethylhexyl, and cyclohexyl, esters consisting of hydrophobic groups such as benzyl, styrene monomers such as styrene, methylstyrene, ethylstyrene, dimethylstyrene, methoxystyrene, and chlorostyrene; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl esters such as vinyl acetate and vinyl propionate, and the like can be used in combination.

These copolymerizations can be carried out without a solvent or in the presence of the above-mentioned organic solvents by any known method using heat, light, ultraviolet rays, electron beams, radical initiators, or a combination of these. can be used as is in liquid form,
In addition, a solution polymerization method using the above-mentioned organic solvent is preferred from the viewpoint of easy handling. At this time, polymerization initiators conventionally used in radical polymerization, such as organic peroxides such as benzoyl peroxide and lauroyl peroxide, azo compounds such as azobisisobutyronitrile, etc., can be used, and the polymerization degree In order to adjust the amount, chain transfer agents such as mercaptans and carbon tetrachloride, or conventional polymerization inhibitors may be used. Polymerization is usually carried out in a reaction system in which oxygen is eliminated as much as possible by nitrogen substitution, etc.
It is carried out by heating at a temperature in the range of 0° C. for about 1 to 24 hours. The hydrophilic polyurethane obtained in this case is an organic solvent solution or dispersion, and may contain water. The solid content is not particularly limited, but is usually 5 to 70
% by weight.

In addition to being used as a solution or dispersion, the hydrophilic polyurethane of the present invention may be used without a solvent, and if necessary, additives such as plasticizers, deterioration inhibitors, colorants, crosslinking agents, fillers, etc. can also be blended.

(Function) The hydrophilic polyurethane of the present invention is a radically polymerizable polyurethane mainly composed of a kind of macromonomer having an unsaturated double bond at one end of the polyurethane chain and partially containing a polyurethane having unsaturated double bonds at both ends. It is thought that the polyurethane chain is made into a branched polymer by copolymerization of the polyurethane component and the hydrophilic vinyl monomer, and the copolymer generally has a graft structure partially crosslinked by the polyurethane chain. By setting the chain length of polyurethane and the amount of unsaturated double bonds introduced to the polyurethane terminal within the range of the present invention, gelation due to crosslinking reaction during copolymerization is suppressed,
Moreover, even if a polyurethane component that does not participate in the copolymerization coexists, it is considered that a uniform reaction product can be obtained because of the good compatibility with the copolymer.

(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, the number average molecular weight of polyurethane below is calculated value (-
(rounded to the nearest whole number).

Example-1 Polypropylene glycol 101 with average molecular f2020
0 parts by weight and 88.8 parts by weight of isophorone diisocyanate were charged into a reactor, mixed uniformly, 0.22 parts by weight of dibutyltin dioctoate was added, and 88.8 parts by weight of isophorone diisocyanate was added.
The reaction was carried out at a temperature of about 5 hours to obtain a hydroxyl-terminated polyurethane having a number average molecular weight of 10,990. Next, 17.0 parts by weight of methacryloyl othiethylisocyanate (1.1 mol per 1 mol of the above polyurethane) was added and reacted at 80°C for about 8 hours, with a number average molecular weight of 1-1) 60. Viscosity 86
A polyurethane (A) containing unsaturated double bonds at the ends of 000 cp/25° C. was obtained.

In another reactor, 94 parts by weight of the above-mentioned unsaturated double bond-containing polyurethane, 56 parts by weight of polyethylene glycol monomethacrylate with an average molecular weight of 440, and 350 parts by weight of methyl ethyl ketone (hereinafter abbreviated as MEK) were charged, and after uniformly dissolving, Azobisisobutyronitrile (hereinafter referred to as AIBN)
) was added and reacted at 70°C for about 8 hours under a nitrogen stream, resulting in a solid content of 30% and a viscosity of 60 cp/25.
A homogeneous hydrophilic polyurethane solution at ℃ was obtained.

Example-2 Polypropylene glycol 101 with an average molecular weight of 12020
0 parts by weight, diphenylmethane diisocyanate (MDI
) 83.3 parts by weight were charged into a reactor, mixed uniformly at 50°C, 0.108 parts by weight of dibutyltin dioctoate was added, and reacted for about 3 hours at 70°C under a nitrogen stream to obtain a mixture with a number average molecular weight of 6560. After obtaining the hydroxyl group-terminated polyurethane, 25.8 parts by weight of methacryloyloxyethyl isocyanate (1 mole per mole of the above polyurethane) was added and reacted at 70°C for about 10 hours to obtain a number average molecular weight of 6720 and a viscosity of 46000 cp/ A polyurethane containing unsaturated double bonds at 25° C. at the ends was obtained.

In another reactor, 82 parts by weight of the above-mentioned unsaturated double bond-containing polyurethane, 68 parts by weight of polyethylene glycol monomethacrylate with an average molecular weight of 170, and 350 parts by weight of MEK were charged, and after uniformly dissolving them, 3 parts by weight of AIBN was added, and nitrogen The reaction was carried out for about 7 hours at 70°C under an air stream to obtain a uniform hydrophilic polyurethane dispersion having a solid content of 30% and a viscosity of 45 cp/25°C.

Example-3 196.5 parts by weight of polytetramethylene ether glycol with an average molecular weight of 1965, 26.1 parts by weight of 2.4-)lylene diisocyanate, and 339 parts by weight of MEK were charged into a reactor and uniformly dissolved, and dibutyltin dilaurate was 0. .023 parts by weight was added and reacted at 50°C for 4 hours to form an isocyanate group-terminated polyurethane solution with a number average molecular weight of 4450. IM weighing part 6.5 parts by weight of 2-hydroxyethyl methacrylate (1 mol per 1 mol of the above polyurethane) and 16 parts by weight of MEK were added and further reacted at 50°C for about 3 hours to obtain a number average molecular weight of 4650 and a solid content of 40. % and a viscosity of 80 cp/25° C., a polyurethane solution (B) containing unsaturated double bonds was obtained.

In another reactor, 200 parts by weight of the above unsaturated double bond-containing polyurethane solution, 26.4 parts by weight of 2-hydroxyethyl methacrylate, and 13.6 parts by weight of n-butyl methacrylate.
Parts by weight, 0.36 parts by weight of n-dodecyl mercaptan and 160 parts by weight of MEK were charged and evenly dissolved.
Add 2.4 parts by weight of BN and react at 70°C for about 10 hours under a nitrogen stream to obtain a solid content of 30% and a viscosity of 240 cp.
/ A homogeneous hydrophilic polyurethane solution at 25°C was obtained.

Example-4 130 parts by weight of the unsaturated double bond-containing polyurethane (A) obtained in Example 1, 20 parts by weight of N,N'-dimethylaminoethyl acrylate, and MEK350 were placed in a reactor.
After adding parts by weight and uniformly dissolving, 3 parts by weight of AIBN was added and reacted at 70°C for about 8 hours under a nitrogen stream to obtain a uniform hydrophilic polyurethane solution with a solid content of 30% and a viscosity of 30 cp/25°C.

Example 5 In a reactor, 142 parts by weight of the unsaturated double bond-containing polyurethane (A) obtained in Example 1, 8 parts by weight of hydroxyethyltrimethylammonium chloride methacrylate, 0.75 parts by weight of n-dodecylmercaptan, MEK After 175 parts by weight and 175 parts by weight of isopropanol were charged and dissolved uniformly, 3 parts by weight of AEBN was added, and 7 parts by weight was added under a nitrogen stream.
React at 0℃ for about 7 hours, solid content 30%, viscosity 50c
A homogeneous hydrophilic polyurethane solution at p/25°C was obtained.

Example-6 100 parts by weight of the unsaturated double bond-containing polyurethane (A) obtained in Example-1, 15 parts by weight of methacrylic acid, 2
- 5 parts by weight of acrylamide-2-methylpropanesulfonic acid, 30 parts by weight of n-butyl methacrylate, and ME
After preparing and uniformly dissolving 150 parts by weight of K and 300 parts by weight of methanol, 1.5 parts by weight of benzoyl peroxide was added and reacted at 60°C for about 12 hours under a nitrogen stream.
A homogeneous hydrophilic polyurethane solution with a solids content of 25% and a viscosity of 160 cp/25° C. was obtained.

Example 7 In a reactor, 100 parts by weight of the unsaturated double bond-containing polyurethane (A) obtained in Example 1, 10 parts by weight of dimethylaminopropylacrylamide, 10 parts by weight of N-vinylformamide, and 0° of n-dodecylmercaptan were added. 36 parts by weight and M
After charging 360 parts by weight of EK and dissolving it uniformly, 1.2 parts by weight of benzoyl peroxide was added and reacted at 70°C for about 7 hours under a nitrogen stream, resulting in a solid content of 25% and a viscosity of 780.
A homogeneous hydrophilic polyurethane solution with c p /25 °C was obtained.

Example-8 250 parts by weight of the unsaturated double bond-containing polyurethane (B) obtained in Example-3 and 1 part of glycidyl methacrylate were placed in a reactor.
5 parts by weight, 25 parts by weight of methoxypolyethylene glycol methacrylate with an average molecular weight of 500 and MEK 177
After adding parts by weight and uniformly dissolving, 2.1 parts by weight of AlBN was added and reacted at 70°C for about 8 hours under a nitrogen stream to obtain a uniform hydrophilic polyurethane solution with a solid content of 30% and a viscosity of 90Cp/25°C. .

Example-9 100 parts by weight of the unsaturated double bond-containing polyurethane (A) obtained in Example-1 and 1 part of sodium styrene sulfonate were placed in a reactor.
0 parts by weight, 30 parts by weight of 2-hydroxyethyl methacrylate, and 794 parts by weight of methanol were charged and dissolved uniformly, then 4 parts by weight of ArBNl was added, and the
React at 0℃ for about 12 hours, solid content 15%, viscosity 27c
A homogeneous hydrophilic polyurethane dispersion with p/25°C was obtained.

Example-10 In a reactor, 100 parts by weight of the unsaturated double bond-containing polyurethane (A) obtained in Example-1, 20 parts by weight of mono (2-methacryloyloxyethyl) acid phosphate, 20 parts by weight of ethyl acrylate, n- 0.7 parts by weight of dodecyl mercaptan and 420 parts by weight of MEK were charged and dissolved uniformly, 2.1 parts by weight of ArBN was added, and the reaction was carried out at 70°C for about 7 hours under a nitrogen stream, resulting in a solid content of 25% and a viscosity of 2.
A homogeneous hydrophilic polyurethane solution of 40 cp/25° C. was obtained.

Example-1) Polymethylvalerolactone 193 with an average molecular weight of 1930
．． 2 parts by weight of 4,4'-dicyclohexylmethane diisocyanate, 28.2 parts by weight, and 333 parts by weight of MEK were charged into a reactor and dissolved uniformly. 0.1 part by weight of dibutyltin dioctoate was added, and about 10 parts by weight of dibutyltin dioctoate was added. After a period of reaction, a hydroxyl-terminated polyurethane solution with an average molecular weight of 30,000 was obtained.

Next, 1.6 parts by weight of m-isopropenyl-α,α-dimethylbenzyl isocyanate (1.1 mol per 1 mol of the above polyurethane), 82 parts by weight of MEK and 0.1 parts by weight of dibutyltin dioctoate were added, and the mixture was heated at 50°C. After reacting for about 6 hours, a polyurethane solution containing unsaturated double bonds with an average molecular weight of 30,220, a solid content of 35%, and a viscosity of 350 Q Cp/25°C was obtained.

In another reactor, 200 parts by weight of the above unsaturated double bond-containing polyurethane solution, 20 parts by weight of tetrahydrofurfuryl methacrylate, 710 parts by weight of N-vinylpyrrolid, n-
0.5 parts by weight of dodecyl mercaptan and MEK 270
After adding 5 parts by weight of AIBNI and reacting at 70°C for about 10 hours under a nitrogen stream, a uniform hydrophilic polyurethane dispersion with a solid content of 20% and a viscosity of 480 cp/25°C was obtained. I got the liquid.

Comparative Example-1 (The number average molecular weight of polyurethane is outside the range) Polypropylene glycol 8 with an average molecular weight of 440 was placed in the reactor.
After adding 80 parts by weight and 222 parts by weight of isophorone diisocyanate and mixing them uniformly, 0 parts of dibutyltin dioctoate were added.
．． Add 22 parts by weight and heat at 80°C under nitrogen stream to approx.
After a time reaction, a hydroxyl-terminated polyurethane with a number average molecular weight of 1)00 was obtained.Next, 108 parts by weight of methacryloyloxyethyl isocyanate (0.7 mol per 1 mol of the above polyurethane) was added and reacted at 70°C for about 8 hours. Number average molecular weight 1210, viscosity 24000 cp
/ 25° C. A polyurethane containing unsaturated double bonds at the ends was obtained.

Copolymerization was carried out in a separate reactor under the same recipe and conditions as in Example 1, except that the above polyurethane was used.
The reaction solution underwent gelation.

Comparative Example-2 (Amount of unsaturated double bonds introduced into polyurethane is out of range) Polyurethane before introducing unsaturated double bonds is Example-
Using the same material as in 1, 1099 parts by weight of it and 27.9 parts by weight of methacryloyloxyethyl isocyanate (1.8 mol per 1 mol of the above polyurethane) were charged into a reactor and reacted at 80°C for about 8 hours. Average molecule 1) 127
A polyurethane containing unsaturated double bonds at the ends with a viscosity of 1) 0,000 cp/25° C. was obtained.

When copolymerization was carried out in a separate reactor under the same recipe and conditions as in Example 71 except that the above polyurethane was used, the reaction solution took on a gel-like appearance.

As described above, the hydrophilic polyurethanes obtained in Examples 1 to 1) did not gel in the copolymerization of the polyurethane containing unsaturated double bonds and the hydrophilic vinyl thread. It exhibited the state of a homogeneous and relatively low viscosity solution or dispersion. These are useful for various uses of polyurethane resins in terms of ease of handling and blending.

On the other hand, as shown in Comparative Examples 1 and 2, those outside the scope of the present invention caused gelation and poor solubility during copolymerization, and were unsuitable for practical use.

(Effects of the Invention) The present invention has excellent solubility and dispersibility in organic solvents, and can be used as an emulsifier and dispersant for polyurethane resins, as well as paints, adhesives, antistatic agents, compatibilizers, and various other modifiers. Hydrophilic polyurethanes useful for a wide range of applications, such as agents, can be provided.

Claims (2)

[Claims] (1) For a polyurethane with a number average molecular weight of 2,000 to 100,000, which has active hydrogen groups or isocyanate groups at both ends, a vinyl monomer having one isocyanate group or hydroxyl group in the molecule is added to the polyurethane. A hydrophilic polyurethane obtained by copolymerizing a polyurethane containing an unsaturated double bond that has been reacted with 0.05 to 1.4 moles per mole and a hydrophilic vinyl monomer. (2) A nonionic monomer group in which the hydrophilic vinyl monomer has a hydroxyl group, a polyoxyethylene group, a glycidyl group, a tetrahydrofurfuryl group, an amide group, or a pyrrolidone group, or a carboxyl group, a sulfonic acid group, or a sodium sulfonate group. 2. The hydrophilic polyurethane according to claim 1, wherein the hydrophilic polyurethane is at least one monomer selected from the group of ionic monomers having a phosphoric acid group, a tertiary amino group, or a quaternary ammonium base.