JP2985210B2 - Hydrophilic polyurethane - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel hydrophilic polyurethane obtained by copolymerizing a polyurethane containing an unsaturated double bond with a hydrophilic vinyl monomer.

More specifically, good solubility and dispersibility in organic solvents, including emulsifiers and dispersants for polyurethane resins,
The present invention relates to a hydrophilic polyurethane useful as a paint, an adhesive or other various modifiers.

(Prior art) Conventionally, as a method of modifying polyurethane by copolymerization with a vinyl monomer, a so-called polyurethane acrylate in which an acrylic compound is bonded to an active terminal group of a polyfunctional polyurethane is mixed with a vinyl monomer, and ultraviolet light, A method of copolymerization using an electron beam, light, heat, a radical initiator or the like is generally used, and is used for paints and adhesives.

However, these are to obtain a cured product by a crosslinking reaction using a polyfunctional polyurethane acrylate, and the modified copolymer is essentially insoluble in an organic solvent and cannot be handled in a liquid state.

Also, an unsaturated double bond is introduced into the polyurethane main chain,
As a method for obtaining a graft polymer by copolymerization with a vinyl monomer, J. Macromol. Sci. Chem. A19 (7), 1041-10
48 (1983), J. Polym. Sci. Polym. Chem. Ed. 20, 2879-2885
(1982), JP-B-63-31506, JP-B-63-65697, and JP-B-63-65698 have been proposed, all of which have insufficient grafting, Uniformity and solubility of the copolymer tended to be low, and satisfactory ones were difficult to obtain.

(Problems to be Solved by the Invention) The present invention overcomes such problems of the conventional technology, is excellent in solubility and dispersibility in organic solvents, and is useful for various uses of polyurethane resins and other uses. The purpose of the present invention is to provide a suitable hydrophilic polyurethane.

(Means for Solving the Problems) The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a copolymer of a specific polyurethane having an unsaturated double bond at a terminal and a hydrophilic vinyl monomer is used. As a result, it has been found that the object can be achieved, and the present invention has been completed.

That is, in the present invention, a polyurethane monomer having one isocyanate group in the molecule is reacted with 0.05 to 1.4 mol per 1 mol of the polyurethane, to a polyurethane having a number average molecular weight of 2,000 to 100,000 in which both terminals are active hydrogen groups. An object of the present invention is to provide a hydrophilic polyurethane obtained by copolymerizing a polyurethane containing an unsaturated double bond and a hydrophilic vinyl monomer in an organic solvent.

 Hereinafter, the present invention will be described in detail.

In the present invention, polyurethanes having active hydrogen groups at both ends are known per se, and an organic diisocyanate, a polymer diol, and a chain extender, if necessary, without solvent,
Alternatively, it is a polyurethane having a linear structure as a basic structure obtained by reacting in an organic solvent. Here, the active hydrogen group is a hydroxyl group or an amino group of the polyol or the chain extender, and the equivalent ratio of the organic diisocyanate to the equivalent thereof is adjusted to obtain a polyurethane having a number average molecular weight of 2,000 to 100,000.

Examples of the organic diisocyanate include aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 1,5-naphthalenediisocyanate, p- or m-phenylenediisocyanate, and isophorone diisocyanate. And alicyclic diisocyanates such as 4,4'-dicyclohexylmethane diisocyanate and 1,4-cyclohexylene diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; and xylylene diisocyanate. These organic diisocyanates can be used alone or in combination of two or more.

As the polymer diol, for example, polytetramethylene ether glycol having an average molecular weight of preferably 400 to 5000, polypropylene glycol, polyethylene glycol, a copolymer of tetrahydrofuran and ethylene oxide, a polyether such as a copolymer of propylene oxide and ethylene oxide Polyol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6
Hydroxyl-terminated polyester polyols obtained by the condensation reaction of diols such as hexanediol, neopentyl glycol and 3-methylpentanediol with dicarboxylic acids such as adipic acid, succinic acid and sebacic acid (typically polyethylene adipate, Polyethylene butylene adipate, polybutylene adipate,
Polyester polyols such as polypropylene adipate and polyhexylene adipate), polycaprolactone and polymethylvalerolactone, and other polycarbonate polyols, silicone polyols, polybutadiene polyols, and polyolefin polyols. These polyols can be used alone or in combination of two or more. When using a chain extender,
Examples thereof include ethylene glycol having a bifunctional active hydrogen group, propylene glycol, diethylene glycol, 1,4-butanediol, short-chain diols such as 1,6-hexanediol, ethylenediamine, 1,2-propanediamine, Diamines such as trimethylenediamine, tetramethylenediamine, hexamethylenediamine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, m-xylylenediamine, piperazine, hydrazine, water and the like. These chain extenders may be used alone or in combination of two or more.

Examples of the organic solvent 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, cyclohexanone, ethyl acetate, butyl acetate, ethyl formate, and formic acid. Ester solvents such as propyl, 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, ethylene dichloride, trichloroethylene and the like. And dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, cellosolve acetate and the like. Also, alcohols such as methanol, ethanol, isopropanol, n- or sec-butanol and cellosolves such as ethyl cellosolve and butyl cellosolve have a hydroxyl group and react with isocyanate groups, but perform a chain extension reaction using diamines. In such a case, the reaction between the isocyanate group and the amino group is much faster, so that they may 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 usual urethane reaction method, and may be a non-catalyst or a catalyst such as dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, stannasoctoate, lead octylate and the like. Tertiary amines such as organic metals, triethylamine, triethylenediamine, and N-methylmorpholine may be used. The reaction temperature is usually selected in the range of 20 to 120 ° C., and the reaction time is usually about 1 to 15 hours. The polyurethane thus obtained does not contain an organic solvent or is a solution having an appropriate concentration.

In the present invention, the number average molecular weight of the polyurethane is basically determined by quantification of a terminal group or by glue permeation chromatography (GPC). However, when the number average molecular weight is 50,000 or less, the high molecular weight diol is the average molecular weight obtained from the measured OH value, the organic diisocyanate and the chain extender use the respective molecular weights, and the number average of the polyurethane is calculated from the charge ratio at the time of the reaction. Even if the molecular weight is calculated, a sufficient response can be taken.

Polyurethane containing unsaturated double bond of the present invention,
Both ends are active hydrogen groups, number average molecular weight 2,000-1
A vinyl monomer capable of reacting with these ends is reacted at a specific ratio with the ends of the polyurethane of 00,000, and a reaction product having an unsaturated double bond at one end of the polyurethane chain as a radical polymerizable component is mainly designed. Is what is done. The following method is used as the method.

The amount of the vinyl monomer having one isocyanate group in the molecule is 0.05 to 1.4 mol, preferably 0.3 to 1.2 mol, per 1 mol of the calculated amount based on the number average molecular weight of the polyurethane having active hydrogen groups at both ends. To react. At this time, if necessary, phenyl isocyanate, a chlorine-substituted derivative of phenyl isocyanate, an organic monoisocyanate such as methyl isocyanate, n-propyl isocyanate, and n-butyl isocyanate are used in combination to block the remaining active hydrogen groups at the polyurethane terminals. Is also good.

When the above-mentioned vinyl monomer is reacted with the end of the polyurethane, the reaction can be carried out in the same manner as in the above-mentioned polyurethane. Monomethyl ether, methylhydroquinone,
A polymerization inhibitor such as p-benzoquinone may be added in advance within a range that does not affect the subsequent copolymerization with the hydrophilic vinyl monomer.

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

The polyurethane containing an unsaturated double bond obtained by the above method is mainly composed of a reactive component having an unsaturated double bond at one end of a polyurethane chain as a radical polymerizable component, and partially having an unsaturated double bond. Is obtained as a mixture containing a reactive component having at both ends of the polyurethane chain and a polyurethane having no unsaturated double bond as the remainder, but may be used as it is to obtain the hydrophilic polyurethane in the present invention. There is no problem.

What is important here is that the number average molecular weight of the polyurethane before the introduction of the unsaturated double bond is in the range of 2,000 to 100,000, preferably 4,000 to 50,000, and the vinyl monomer having one isocyanate group in the molecule. From 0.05 to 1.4 mol, preferably from 0.3 to 1.2 mol, per mol of the polyurethane.
The reaction is performed in a molar ratio to introduce an unsaturated double bond. When the number average molecular weight is less than 2,000, the reaction solution tends to gel during copolymerization with a vinyl monomer later, probably because the molecular weight between crosslinking points due to the reaction component having an unsaturated double bond at both ends is small. Yes, and the number average molecular weight is 100,
If it exceeds 000, it becomes difficult to introduce an unsaturated double bond into the end of the polyurethane. On the other hand, if the amount of the vinyl monomer to be reacted with the polyurethane terminal is less than 0.05 mol per mol of the polyurethane, the amount of the polyurethane component effective for radical polymerization becomes insufficient, and a sufficient effect on the modification of the polyurethane cannot be obtained. On the other hand, if the amount of the vinyl monomer exceeds 1.4 moles, the proportion of the reaction component having an unsaturated double bond at both ends of the polyurethane increases, and the gelation tends to occur during copolymerization, probably because of an increase in the number of crosslinking points.

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

The hydrophilic vinyl monomer may be nonionic or ionic. Examples of the nonionic monomer include a vinyl monomer having a hydroxyl group, a polyoxyethylene group, a glycidyl group, a tetrahydrofurfuryl group, an amide group, a pyrrolidone group, and the like.Specific examples include acrylic acid and methacrylic acid. 2-hydroxyethyl ester, 2-hydroxypropyl ester, glycerin ester, polyethylene glycol ester, methoxypolyethylene glycol ester, polyoxyethyleneoxypropylene block polyol ester, polyoxytetramethylene block polyol ester, glycidyl ester, tetrahydrofurfuryl alcohol ester, Acid amide, N-methylolamide, or N-vinylformamide, N-
And vinylpyrrolidone.

Examples of the ionic monomer include a vinyl monomer having a carboxyl group, a sulfonic acid group, a sodium sulfonate group, a phosphoric acid group, a tertiary amino group, a quaternary ammonium base, and the like. 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, hydroxypropyl methacrylate Trimethyl ammonium chloride, methacrylic acid hydroxyethyl trimethylammonium chloride, and the like. 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. In such a case, the copolymer may be converted to a quaternary ammonium salt with benzyl chloride or the like.

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

These copolymerizations are performed by a solution polymerization method using the organic solvent. At this time, polymerization initiators conventionally used for radical polymerization, for example, benzoyl peroxide, organic peroxides such as lauroyl peroxide and azo compounds such as azobisisobutyronitrile can be used,
In order to control the degree of polymerization, a chain transfer agent such as mercaptans or carbon tetrachloride, or a usual polymerization inhibitor may be used. The polymerization is carried out in a reaction system in which oxygen is reduced as much as possible by nitrogen substitution or the like, usually by heating at a temperature in the range of 40 to 100 ° C. for about 1 to 24 hours. The hydrophilic polyurethane obtained in this case is an organic solvent solution or dispersion. The solid content is not particularly limited, but is usually in the range of 5 to 70% by weight.

The hydrophilic polyurethane of the present invention may be used in the form of a solution or a dispersion, in addition to a solvent, or may be used, if necessary, with additives such as a plasticizer, a deterioration inhibitor, a coloring agent, a crosslinking agent, and a filler. Can also be blended.

(Function) The hydrophilic polyurethane of the present invention is a radical polymerizable polymer mainly containing a kind of macromonomer having an unsaturated double bond at one end of a polyurethane chain and partially containing a polyurethane having an unsaturated double bond at both ends. It is thought that the copolymer contains a copolymer having a generally graft structure having a polyurethane chain as a branch polymer by copolymerization of a polyurethane component and a hydrophilic vinyl monomer, and partially having a cross-linking by the polyurethane chain. By setting the chain length of the polyurethane and the amount of the unsaturated double bond introduced to the polyurethane terminal within the range of the present invention, gelation due to a crosslinking reaction at the time of copolymerization is suppressed, and a polyurethane component not involved in the copolymerization is removed. Even if coexisting, it is considered that a uniform reaction product can be obtained because of good compatibility with the copolymer.

(Examples) Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following, the calculated value (one-rounded) is used for the number average molecular weight of polyurethane.

Example-1 A reactor was charged with 1010 parts by weight of polypropylene glycol having an average molecular weight of 2020 and 88.8 parts by weight of isophorone diisocyanate, and after mixing uniformly, 0.22 parts of dibutyltin dioctoate was added.
The mixture was reacted at 80 ° C. for about 5 hours under a nitrogen stream to obtain a hydroxyl-terminated polyurethane having a number average molecular weight of 10,990. Then, 17.0 parts by weight of methacryloyloxyethyl isocyanate (1 mole per 1 mole of the above polyurethane).
1 mol) and react at 80 ° C for about 8 hours to obtain a number average molecular weight of 1
Polyurethane (A) having an unsaturated double bond at the terminal having a viscosity of 1160 and a viscosity of 86000 cp / 25 ° C. was obtained.

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

Example 2 A reactor was charged with 1010 parts by weight of polypropylene glycol having an average molecular weight of 2020 and 83.3 parts by weight of diphenylmethane diisocyanate (MDI). After uniformly mixing at 50 ° C., 0.108 parts by weight of dibutyltin dioctoate was added, and the mixture was added under a nitrogen stream. The mixture was reacted at 70 ° C. for about 3 hours to obtain a hydroxyl-terminated polyurethane having a number average molecular weight of 6560. Then, 25.8 parts by weight of methacryloyloxyethyl isocyanate (1 mol per 1 mol of the above polyurethane) was added, and the mixture was reacted at 70 ° C. for about 10 hours to terminate an unsaturated double bond having a number average molecular weight of 6720 and a viscosity of 46,000 cp / 25 ° C. The resulting polyurethane was obtained.

A separate reactor was charged with 82 parts by weight of the above unsaturated double bond-containing polyurethane, 68 parts by weight of polyethylene glycol monomethacrylate having an average molecular weight of 170, and 350 parts by weight of MEK.After uniformly dissolving, 3 parts by weight of AIBN was added, and nitrogen was added. Reacted in air stream at 70 ° C for about 7 hours, solid content 30%, viscosity 45cp / 2
A uniform hydrophilic polyurethane dispersion at 5 ° C. was obtained.

Example 3 A reactor was charged with 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 350 parts by weight of MEK. After dissolution, add 3 parts by weight of AIBN and add
The reaction was carried out at 0 ° C. for about 8 hours to obtain a uniform hydrophilic polyurethane solution having a solid content of 30% and a viscosity of 30 cp / 25 ° C.

Example 4 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 methacrylate chloride, 0.75 parts by weight of n-dodecylmercaptan, 175 parts by weight of MEK And 175 parts by weight of isopropanol were added and uniformly dissolved. Then, 3 parts by weight of AIBN was added, and the mixture was reacted at 70 ° C. for about 7 hours under a nitrogen stream.
A uniform hydrophilic polyurethane solution having a solid content of 30% and a viscosity of 50 cp / 25 ° C. was obtained.

Example -5 100 parts by weight of the unsaturated double bond-containing polyurethane (A) obtained in Example 1, 15 parts by weight of methacrylic acid, 2-
After 5 parts by weight of acrylamide-2-methylpropanesulfonic acid, 30 parts by weight of n-butyl methacrylate, 150 parts by weight of MEK, and 300 parts by weight of methanol were charged and uniformly dissolved, 1.5 parts by weight of benzoyl peroxide was added. Reaction for about 12 hours at 25 ℃, solid content 25%, viscosity 160c
A uniform hydrophilic polyurethane solution of p / 25 ° C. was obtained.

Example-6 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, 0.36 parts by weight of n-dodecylmercaptan Parts and MEK360 parts by weight and uniformly dissolved, then benzoyl peroxide
1.2 parts by weight were added and reacted at 70 ° C. for about 7 hours under a nitrogen stream to obtain a uniform hydrophilic polyurethane solution having a solid content of 25% and a viscosity of 780 cp / 25 ° C.

Example -7 100 parts by weight of the unsaturated double bond-containing polyurethane (A) obtained in Example 1 and sodium styrene sulfonate 10 were placed in a reactor.
Parts by weight, 30 parts by weight of 2-hydroxyethyl methacrylate and 794 parts by weight of methanol were charged and uniformly dissolved.
After adding 1.4 parts by weight, the mixture was reacted at 60 ° C. for about 12 hours under a nitrogen stream to obtain a uniform hydrophilic polyurethane dispersion having a solid content of 15% and a viscosity of 27 cp / 25 ° C.

Example-8 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 uniformly dissolved, and AIBN2.
One part by weight was added and reacted at 70 ° C. for about 7 hours under a nitrogen stream to obtain a uniform hydrophilic polyurethane solution having a solid content of 25% and a viscosity of 240 cp / 25 ° C.

Example-9 193.2 parts by weight of polymethyl valerolactone having an average molecular weight of 1930, 28.2 parts by weight of 4,4'-dicyclohexylmethane diisocyanate and 333 parts by weight of MEK were charged into a reactor and uniformly dissolved, and 0.11 part by weight of dibutyltin dioctoate was added. The reaction was carried out at 70 ° C. for about 10 hours to obtain a hydroxyl group-terminated polyurethane solution having an average molecular weight of 30,000. Then m
1.6 parts by weight of isopropenyl-α, α-dimethylbenzyl isocyanate (1.1 mol per mol of the above polyurethane), 82 parts by weight of MEK and 0.11 of dibutyltin dioctoate
The reaction was carried out at 50 ° C. for about 6 hours, and the average molecular weight was 3022.
At 0, a polyurethane solution containing 35% solids and having a viscosity of 3500 cp / 25 ° C. and containing unsaturated double bonds was obtained.

In a separate reactor, 200 parts by weight of the above unsaturated double bond-containing polyurethane solution, 20 parts by weight of tetrahydrofurfuryl methacrylate, 10 parts by weight of N-vinylpyrrolidone, 0.5 parts by weight of n-dodecylmercaptan and 270 parts by weight of MEK were uniformly charged. Dissolve, add 1.5 parts by weight of AIBN, react under nitrogen stream at 70 ° C for about 10 hours, solid content 20%, viscosity 480c
A uniform hydrophilic polyurethane dispersion at p / 25 ° C. was obtained.

Comparative Example-1 (number-average molecular weight of polyurethane is out of range) Polypropylene glycol 8 having an average molecular weight of 440 was added to a reactor.
After mixing 80 parts by weight and 222 parts by weight of isophorone diisocyanate and mixing uniformly, 0.22 parts by weight of dibutyltin dioctoate is added, and the mixture is reacted at 80 ° C. for about 3 hours under a nitrogen stream to obtain a hydroxyl-terminated polyurethane having a number average molecular weight of 1100 and a hydroxyl group end. I got Next, 108 parts by weight of methacryloyloxyethyl isocyanate (0.7 mol to 1 mol of the polyurethane)
Mol) and reacted at 70 ° C. for about 8 hours to obtain a number average molecular weight of 121
A polyurethane having an unsaturated double bond at the terminal having a viscosity of 24000 cp / 25 ° C. was obtained.

The copolymerization was carried out in another reactor under the same conditions and conditions as in Example 1 except that the above-mentioned polyurethane was used. As a result, the reaction solution gelled.

Comparative Example-2 (the amount of unsaturated double bonds introduced into the polyurethane is out of range) The same polyurethane as that of Example-1 was used before the introduction of the unsaturated double bond, and 1099 parts by weight of the same was used. 27.9 parts by weight of ethyl isocyanate (1.8 mol per mol of the above polyurethane) were charged into a reactor and charged at 80 ° C.
For about 8 hours, number average molecular weight 11270, viscosity 110,000c
A polyurethane containing an unsaturated double bond at the terminal at p / 25 ° C. was obtained.

Copolymerization was carried out in another reactor under the same conditions and conditions as in Example 1 except that the above polyurethane was used. As a result, the reaction solution was in a gel state.

As described above, the hydrophilic polyurethanes obtained in Examples-1 to 1 are uniform and relatively free from gelling in copolymerization of a polyurethane containing an unsaturated double bond and a hydrophilic vinyl monomer. The low viscosity solution or dispersion was shown. These are useful for various uses of the polyurethane resin from the viewpoint of ease of handling and blending.

On the other hand, as shown in Comparative Examples 1-2, those out of the range of the present invention caused gelation and poor solubility at the time of copolymerization, and were unsuitable for practical use.

(Effects of the Invention) According to the present invention, it has excellent solubility and dispersibility in an organic solvent, and includes various emulsifiers and dispersants for polyurethane resins, paints, adhesives, antistatic agents, compatibilizers, and other various modifications. It is possible to provide a hydrophilic polyurethane useful for a wide range of uses such as an agent.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-41380 (JP, A) JP-A-63-278922 (JP, A) JP-A-3-200828 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) C08F 290/06

Claims (2)

(57) [Claims] (1) a number average molecular weight having an active hydrogen group at both terminals of 2,
A polyurethane containing an unsaturated double bond obtained by reacting a vinyl-based monomer having one isocyanate group in a molecule with respect to a polyurethane of 100 to 100,000 per mol of the polyurethane, and a polyurethane containing a hydrophilic vinyl-based monomer. A hydrophilic polyurethane obtained by copolymerizing a monomer with an organic solvent. 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 sulfonic acid. 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 sodium group, a phosphate group, a tertiary amino group, or a quaternary ammonium group.