JP3055167B2 - Method for producing polyurethane resin having functional group and polyurethane resin composition comprising the resin - Google Patents

Description

The present invention relates to a method for producing a novel urethane resin having a functional group having excellent reactivity (crosslinkability) and functionality, and a resin composition comprising the urethane resin. About.

(Prior Art) Conventionally, as a method of introducing a functional group into a polyurethane resin, a method of introducing a carboxylic acid group or a hydroxyl group into a side chain of a polyester used as a polyol is known.

However, dimethylolpropionic acid and 3-methyl 1,3,5 trihydroxypentane are used for this, but these are carboxylic acid groups or hydroxyl groups attached to quaternary carbon, and have very poor reactivity.

Further, other functional groups such as glycidyl group, phosphate group, phosphate group, phosphate group, sulfonic group, sulfonate group, amino group, amine base hydroxyl group, polyoxyethylene group, perfluoroalkyl group, polysiloxane group. It was very difficult to attach.

(Problems to be Solved by the Invention) An object of the present invention is to provide a method for producing a polyurethane resin having a functional group having good reactivity or excellent functionality.

(Means for Solving the Problems) The present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention.

That is, the present invention relates to a mercaptan-based chain transfer agent having two hydroxyl groups and one mercapto group, which is obtained by radical polymerization of a monomer having a radically polymerizable unsaturated bond having a functional group as an essential component. A method of producing a polyurethane resin (C), comprising reacting a polyol component (A) containing a macromonomer having two hydroxyl groups and having a functional group (excluding a hydroxyl group) with a polyisocyanate (B), Preferably a monomer having a radical polymerizable unsaturated bond having a functional group, a glycidyl group, a phosphate group, a phosphate group, a phosphate group, a carboxylate group, a carboxylate group, a sulfonate group, a sulfonate group,
It has at least one functional group selected from an amino group, an amine base, a polyoxyethylene group, a perfluoroalkyl group, and a polysiloxane group, and contains the obtained polyurethane resin (C) and an organic solvent as essential components. Is a polyurethane resin composition.

(Constitution) Examples of the mercaptan-based chain transfer agent having two or more hydroxyl groups and one mercapto group used in the present invention include:
For example, 1-mercapto-1,1-methanediol, 1-
Mercapto-1,1-ethanediol, 3-mercapto-
1,2-propanediol, 2-mercapto-1,3-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1- Mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,
3-propanediol and the like.

Examples of the monomer having a radical polymerizable unsaturated bond used in the present invention include glycidyl group-containing monomers such as glycidyl (meth) acrylate and aryl glycidyl ether, methacryloyloxyethyl acid phosphate, and methacryloyloxypropyl acid. Phosphate and phosphoric acid group-containing monomers such as esters or salts thereof, (meth) acrylic acid, carboxylic acid group-containing monomers such as 2-methacryloyloxyethyl phthalic acid and salts thereof, styrenesulfonic acid, and the like Sulfonic acid group-containing monomers such as salts, amino group-containing monomers such as dimethylaminomethyl (ethyl) (meth) acrylate and quaternary salts thereof, amide group-containing monomers such as (meth) acrylamide, and perfluoro Octylethyl (meth) acrylate, N-methyl ( (Ropyr) Perfluoroalkyl group-containing monomer such as perfluorooctylsulfonamidoethyl (meth) acrylate, polysiloxane group-containing monomer such as polydimethylsiloxylpropyl methacrylate, and poly such as methoxypolyethylene glycol (meth) acrylate An oxyethylene group-containing monomer is used. These functional group-containing monomers may be used alone or in a copolymer. In some cases, it is possible to copolymerize with a monomer having no functional group as shown below. Examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, alkyl acrylate and / or methacrylate such as octyl methacrylate, acrylonitrile, methacrylonitrile, styrene, vinyl acetate and the like. No.

In the present invention, various polyester polyols can be used as the polyol component. Examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-
1,4-diol, cyclohexane-1,4-dimethanol,
Glycerin, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol,
One or more of various polyhydric alcohols represented by sorbitol, methyl glycoside, etc., and succinic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid Acid, terephthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, glutaric acid, maleic acid, maleic anhydride, polybasic acid such as hexahydroisophthalic acid or one or more acid anhydrides And the like. Further, γ using the polyol as an initiator
And ring-opening polymers such as -butyrolactone and ε-caprolactone. Furthermore, a polycarbonate diol such as poly (hexamethylene carbonate) diol may also be used.

Polyether polyols can also be used as the polyol component. Examples thereof include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, and the like, in which one or more of the above polyols and polyamines are used as initiators. Singly or two or more ring-opened polymers.

In the present invention, low-molecular compounds having two or more groups that react with an isocyanate group can also be used. Examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, , 3-butylene glycol, 1,4-butylene glycol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol,
3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, glycerin , Trimethylolpropane, trimethylolethane, hexanetriol,
Pentaerythritol, sorbitol, polyols such as methyl glycoside, ethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, hexamethylenediamine, hydrazine, piperazine, N, N'-diaminopiperazine, 2-methylpiperazine, 4, One or a mixture of two or more polyamines such as 4 'diaminodicyclohexylmethane, isophoronediamine, diaminobenzene, diphenylmethanediamine, and methylenebisdichloroaniline can be used.

Polyisocyanate is used in the production of the polyurethane resin of the present invention, and examples thereof include tolylene diisocyanate, diphenylmethane diisocyanate,
Naphthalene diisocyanate, aromatic diisocyanate such as phenylene diisocyanate and hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate,
Various aliphatic or alicyclic (cycloaliphatic) diisocyanates, such as dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, etc., triphenylmethane triisocyanate, polyphenyl polymethylene polyisocyanate, Examples thereof include a polyisocyanate having a carbodiimide group, a polyisocyanate having an allophanate group, and a polyisocyanate having an isocyanurate group.

In the method for producing a polyurethane resin of the present invention, the order of the reaction is not particularly limited. The reaction can be carried out in the absence of any solvent, or in an organic solvent or in water, but usually in an organic solvent.
It is carried out at 120120 ° C., preferably 30-100 ° C.

The macromonomer, the total hydroxyl groups of low-molecular compounds having two or more groups that react with the polyol and isocyanate groups, and the equivalent ratio of the isocyanate groups of the polyisocyanate is not particularly limited, but is usually 2: 1 to 1: 2
It is performed at a ratio as follows.

In the method for producing the polyurethane resin of the present invention, the reaction can be promoted by using a tertiary amine catalyst and / or an organometallic catalyst as necessary.

Examples of the organic solvent that can be used in the polyurethane resin production method of the present invention include, for example, ethyl acetate, butyl acetate,
Cellosolve, cellosolve acetate, acetone, methyl ethyl ketone, cyclohexanone, toluene, xylene, dimethylformamide, dimethylacetamide, isopropanol and the like. Of course, these organic solvents can be added during the reaction.

In the method for producing a polyurethane resin of the present invention, an alcohol such as methanol, ethanol, propanol, 1,3-butylene glycol, and the like, if necessary, at the beginning of the reaction, during the reaction, or at the end of the reaction, and An amine compound such as dimethylamine, diethylamine, dipropylamine, dibutylamine and / or the like may be added for the purpose of terminating the reaction or controlling the molecular weight.

In the polyurethane resin composition according to the present invention, if necessary, an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, various known and commonly used additives such as dyes and pigments, It goes without saying that various known and commonly used fillers such as calcium carbonate can be added.

As described in detail above, the polyurethane resin according to the present invention itself has, among other things, various functions such as crosslinkability, adhesiveness, hydrophilicity, moisture permeability, water repellency, oil repellency, lubricity and dispersibility. From the point of having, the polyurethane resin according to the present invention becomes new and useful either by itself or in the form of the polyurethane resin composition according to the present invention. , Respectively, as adhesives, paints and surface treatment agents, as films and molding materials, and as synthetic leather, etc.
It can be widely used and applied.

(Examples) Next, the present invention is further described by Examples and Comparative Examples.
Although described in detail, the present invention is in no way limited to only these illustrative examples. In the following, all parts and percentages are by weight unless otherwise specified. The procedure of each evaluation judgment test is as follows.

<Method of forming film> A film (film) of about 50 microns was prepared by casting a polyurethane resin solution or compound on release paper and drying at 80 ° C for 30 minutes.

<Guide for Measurement of Adhesive Strength to Steel Sheet> A polyurethane resin compound was applied on a steel sheet degreased with acetone at a coating amount of 6 g / m ₂ using a bar coater. Then, the sheet was heated in a drier at 195 ° C. for 1 minute, and immediately thereafter, a polyvinyl chloride sheet (PVC sheet) was laminated through a hot roll at 120 ° C. Thereafter, the peel strength of this PVC sheet after 24 hours was examined.

<Solubility in tetrahydrofuran> The film prepared by the method described above was cut into 5 cm squares, placed in a flask with 100 ml of tetrahydrofuran, heated at 50 ° C for 5 hours, and then heated. Was observed.

<Water absorbency and moisture permeability> First, the film prepared by the method described above was measured for the water absorbency by a method in accordance with JIS K-6505, and the other moisture permeable was measured for JIS Z-505. The measurement was performed by a method according to 0208.

<Water repellency and oil repellency of the film> Using the film prepared by the above method, the contact angle of water and n-dodecane was measured at 23 ° C.

<Dynamic friction coefficient of the film> Using the film prepared by the above method, the dynamic friction coefficient was measured using a surface property measuring device (Model 14 manufactured by Haydon Co., Ltd.) to a load of 20.
It was measured at a g speed of 130 mm / min.

Example 1 and Comparative Example 1 100 parts of sebacic acid / isophthalic acid / ethylene glycol / neopentyl glycol-based polyester diol having a molecular weight of 2,000 and a glycidyl methacrylate-based macromonomer having a molecular weight of 6,000 (methyl methacrylate and glycidyl methacrylate were added in the presence of thioglycerin to form 1 Oligomer having a diol group at one end copolymerized at a weight ratio of 1/10
0 parts, 49 parts of diphenylmethane diisocyanate, 0.05 parts of stannous octoate, and 110 parts of toluene were mixed and reacted at 70 ° C. for 2 hours.
Ethylene glycol (8 parts) was added and reacted at 70 ° C. for 12 hours. Further, methanol (3 parts) was added and reacted at 60 ° C. for 1 hour to obtain a polyurethane resin solution having a resin concentration of 30% and a viscosity of 7,000 centipoise. This polyurethane resin solution 10
0 g and 12 g of an epoxy resin curing agent lactamide EA-240 (manufactured by Dainippon Ink) were thoroughly mixed, and the adhesion to a steel sheet and the solubility in tetrahydrofuran were examined. A control polyurethane resin composition was prepared in the same manner as in Example 1 except that the use of the glycidyl methacrylate-based macromonomer was changed so that it was completely absent. Was served. The results of the comparative tests on Example 1 and Comparative Example 1 thus obtained are summarized in Table 1.

From the above results, the polyurethane resin using the glycidyl methacrylate-based macromonomer was superior in the adhesive force to the steel sheet as compared with the polyurethane resin not using the glycidyl methacrylate-based macromonomer, and was insoluble in tetrahydrofuran because it was crosslinked.

Example 2 and Comparative Example 2 Polyhexylene adipate diol 100 having a molecular weight of 2,000
Part, polydimethylaminoethyl methacrylate-based macromonomer having a molecular weight of 2,000 (dimethylaminoethyl methacrylate oligomer having a diol group at one end obtained by copolymerizing butyl methacrylate and dimethylaminoethyl methacrylate at a 1/1 weight ratio in the presence of thioglycerin) 50
Parts, 36 parts of diphenylmethane diisocyanate, 0.04 parts of stannous octylate and 83 parts of toluene were mixed and reacted at 70 ° C. for 2 hours. Then, 370 parts of methyl ethyl ketone and 8 parts of 1,6 hexanediol were added and reacted at 70 ° C. for 12 hours. And
Further, 3 parts of methanol was added and reacted at 60 ° C. for 1 hour to obtain a polyurethane resin solution having a resin concentration of 30% and a viscosity of 6,500 centipoise. By thoroughly mixing 100 g of this polyurethane resin solution and 5 g of a polyepoxy compound Denacol EX-211 (manufactured by Nagase Kasei), the polyurethane resin composition obtained in this example had an adhesive force to a steel sheet and a solubility in tetrahydrofuran, respectively. Was examined. A control polyurethane resin composition was prepared in the same manner as in Example 2 except that the use of the dimethylaminoethyl methacrylate-based macromonomer was changed so as to be completely absent. Used for testing. The results of the comparative tests on Example 2 and Comparative Example 2 thus obtained are summarized in Table 2
Shown in

From the above results, the polyurethane resin using the dimethylaminoethyl methacrylate methacrylate-based macromonomer was superior in the adhesive force to the steel sheet as compared with the polyurethane resin not using it, and was insoluble in tetrahydrofuran because it was crosslinked.

Example 3 and Comparative Example 3 Polyhexylene adipate diol 100 having a molecular weight of 2,000
Part, a polydimethylaminoethyl methacrylate quaternary salt macromonomer having a molecular weight of 2,000 (having a diol group at one end obtained by copolymerizing butyl methacrylate and methyl chloride salt of dimethylaminoethyl methacrylate in the presence of thioglycerin in a 2/1 weight ratio) After mixing 50 parts of dimethylaminoethyl methacrylate quaternary salt oligomer), 36 parts of diphenylmethane diisocyanate, 0.04 parts of stannous octylate and 83 parts of toluene, the mixture was reacted at 70 ° C. for 2 hours.
After adding 370 parts of methyl ethyl ketone and 8 parts of 1,6 hexanediol and reacting at 70 ° C. for 12 hours, and further adding 3 parts of methanol, at 60 ° C.
By letting it react for one hour, the resin concentration
A solution of a polyurethane resin having 30% and a viscosity of 8,500 centipoise was obtained.

Next, the degree of water absorption and moisture permeability of the film obtained from this polyurethane resin solution was measured.

On the other hand, a control polyurethane resin solution was prepared in the same manner as in Example 3 except that the use of the dimethylaminoethyl methacrylate quaternary salt-based macromonomer was changed so that it was completely absent. This was used for a comparative test. The results of the comparative tests on Example 3 and Comparative Example 3 thus obtained are summarized in Table 3.

From the above results, the polyurethane resin using the dimethylaminoethyl methacrylate quaternary salt-based macromonomer was superior to the polyurethane resin not using the film in the water absorption and moisture permeability of the film.

Example 4 and Comparative Example 4 Polybutylene adipate diol 100 having a molecular weight of 2,000
Part, 50 parts of a phosphoric acid group-containing macromonomer having a molecular weight of 2,000 (a phosphoric acid group-containing oligomer having a diol group at one end and copolymerized with butyl methacrylate and methacryloyloxyethyl acid phosphate at a weight ratio of 9/1 in the presence of thioglycerin), diphenylmethane 36 parts of diisocyanate,
0.04 parts of stannous octoate and 83 parts of toluene mixed at 70 ° C
After reacting for 2 hours in methyl ethyl ketone.
And 8 parts of 1,4-butanediol, react at 70 ° C. for 12 hours, then add 3 parts of methanol and react at 60 ° C. for 1 hour. The resin concentration is 30%, and
A solution of a polyurethane resin having a viscosity of 9,000 centipoise was obtained.

Next, the adhesive strength of the polyurethane resin solution to the steel plate was measured.

On the other hand, a control polyurethane resin solution was prepared in the same manner as in Example 4 except that the use of the phosphate group-containing macromonomer was changed so as to be completely absent. Served for The results of the comparative tests on Example 4 and Comparative Example 4 thus obtained are summarized in Table 4.

From the above results, the polyurethane resin using the phosphoric acid group-containing macromonomer was superior in the adhesive force to the steel sheet as compared to the polyurethane resin not using the polyurethane resin.

Example 5 and Comparative Example 5 Polybutylene adipate diol 100 having a molecular weight of 2,000
Part, 50 parts of a carboxylic acid group-containing macromonomer having a molecular weight of 2,000 (a carboxylic acid group-containing oligomer having a diol group at one end and copolymerized with butyl methacrylate and methacrylic acid at a weight ratio of 8/2 in the presence of thioglycerin), and 50 parts of diphenylmethane diisocyanate Parts, stannous octoate 0.04
Parts and 83 parts of toluene at 70 ° C.
After reacting for 2 hours, 370 parts of methyl ethyl ketone and 8 parts of 1,4-butanediol were added, and 70
At 12 ° C. for 12 hours, further adding 3 parts of methanol and reacting at 60 ° C. for 1 hour to obtain a resin concentration of 30%, and
A solution of a polyurethane resin having a viscosity of 9,000 centipoise was obtained.

Next, the adhesive strength of the polyurethane resin solution to the steel plate was measured.

On the other hand, a control polyurethane resin solution was prepared in the same manner as in Example 5 except that the use of the carboxylic acid group-containing macromonomer was changed so as to be completely absent. Used for testing.

The results of the comparative tests on Example 5 and Comparative Example 5 thus obtained are summarized in Table 5.

From the above results, the polyurethane resin using the carboxylic acid group-containing macromonomer was superior in the adhesive force to the steel sheet as compared with the polyurethane resin not using the same.

Example 6 and Comparative Example 6 100 parts of sebacic acid / isophthalic acid / ethylene glycol / neopentyl glycol polyester diol having a molecular weight of 2,000 and a glycidyl methacrylate macromonomer having a molecular weight of 6,000 (methyl methacrylate and glycidyl methacrylate were added in the presence of thioglycerin to form 1 Oligomer having a diol group at one end copolymerized at a weight ratio of 1/10
0 parts, 49 parts of diphenylmethane diisocyanate, 0.05 parts of stannous octoate, and 110 parts of toluene were mixed and reacted at 70 ° C. for 2 hours.
Ethylene glycol (8 parts) was added and reacted at 70 ° C. for 12 hours. Further, methanol (3 parts) was added and reacted at 60 ° C. for 1 hour. Then, add 5 g of diethanolamine and add 60 ° C
And reacting for 5 hours to open the glycidyl group with diethanolamine, so that the hydroxyl group is introduced into the molecule, the resin concentration is 30%, and the viscosity is
A polyurethane resin solution of 7,000 centipoise was obtained.

Next, 100 g of this polyurethane resin solution and 7.5 g of "Tyforce CL100" (trade name of a polyisocyanate compound manufactured by Dainippon Ink and Chemicals, Inc.)
By mixing well, the polyurethane resin composition of this example was prepared.

Subsequently, the adhesive strength to the steel sheet and the solubility in tetrahydrofuran of the polyurethane resin composition were examined.

On the other hand, except that the use of chrysidyl methacrylate-based macromonomer was changed to be completely absent,
A control polyurethane resin composition was prepared in the same manner as in Example 6, and then subjected to a comparative test.

The results of the comparative tests on Example 6 and Comparative Example 6 thus obtained are summarized in Table 6.

From the above results, the polyurethane resin treated with diethanolamine using the glycidyl methacrylate-based macromonomer had better adhesion to the steel sheet than the polyurethane resin not used, and was insoluble in tetrahydrofuran because it was crosslinked.

Example 7 and Comparative Example 7 Polybutylene adipate diol 100 having a molecular weight of 2,000
Parts, a perfluoroalkyl group-containing macromonomer having a molecular weight of 6,000 (in the presence of thioglycerin methyl methacrylate and perfluorooctylethyl acrylate 9/1
Oligomer having one end diol group copolymerized by weight ratio) 100 parts, diphenylmethane diisocyanate 49 parts,
A mixture of 0.05 parts of stannous octylate and 110 parts of toluene
After reacting at 0 ° C. for 2 hours, methyl ethyl ketone 489 was added.
And 8 parts of ethylene glycol, and reacted at 70 ° C. for 12 hours. Further, 3 parts of methanol was added and the mixture was reacted at 60 ° C. for 1 hour.
After reacting for a time, a polyurethane resin solution having a resin concentration of 30% and a viscosity of 7,000 centipoise was obtained.

Next, the water repellency and the oil repellency of the film (film) obtained from this polyurethane resin solution were measured using water, n
-At each contact angle with dodecane.

On the other hand, except that the use of the perfluoroalkyl group-containing macromonomer was changed to be completely absent,
A control polyurethane resin solution was prepared in the same manner as in Example 7 above, and then subjected to a comparative test.

The results of the comparative tests on Example 7 and Comparative Example 7 thus obtained are summarized in Table 7.

From the above results, it was found that a polyurethane resin using a perfluoroalkyl group-containing macromonomer had a larger contact angle between water and n-dodecane and was superior in water / oil repellency as compared with a polyurethane resin not using the same.

Example 8 and Comparative Example 8 Polybutylene adipate diol 100 having a molecular weight of 2,000
Parts, a polysiloxane group-containing macromonomer having a molecular weight of 6,000 (in the presence of thioglycerin methyl methacrylate and polydimethylsiloxylpropyl methacrylate 9 /
100 parts of an oligomer having a diol group at one end copolymerized at a weight ratio of 100 parts, diphenylmethane diisocyanate 49
Parts, 0.05 parts of stannous octylate and 110 parts of toluene were mixed and reacted at 70 ° C. for 2 hours. Then, 489 parts of methyl ethyl ketone and 8 parts of ethylene glycol were added, and the mixture was reacted at 70 ° C. for 12 hours. Furthermore, by adding 3 parts of methanol and then reacting at 60 ° C. for 1 hour, the resin concentration is 30%,
In addition, a solution of a polyurethane resin having a viscosity of 7,000 centipoise was obtained.

Next, the dynamic friction coefficient and the water repellency of the film obtained from this polyurethane resin solution were examined.

On the other hand, a control polyurethane resin solution was prepared in the same manner as in Example 8, except that the use of the polysiloxane group-containing macromonomer was changed so as to be completely absent. Was served.

The results of the comparative tests on Example 8 and Comparative Example 8 thus obtained are summarized in Table 8.

From the above results, it was found that the polyurethane resin using the polysiloxane group-containing macromonomer had a larger water contact angle and was superior in water repellency as compared with the polyurethane resin not using the polyurethane resin. It was also found that the coefficient of kinetic friction was small and the lubricity was excellent.

Example 9 and Comparative Example 9 Polyhexylene adipate diol 100 having a molecular weight of 2,000
Part, 50 parts of a polyoxyethylene group-containing macromonomer having a molecular weight of 2,000 (oligomer having one terminal diol group obtained by polymerizing methoxypolyethylene glycol methacrylate in the presence of thioglycerin), 36 parts of diphenylmethane diisocyanate, 0.04 part of stannous octylate of
After mixing 83 parts and reacting at 70 ° C. for 2 hours, 370 parts of methyl ethyl ketone and 8 parts of 1,6-hexanediol are added, and the mixture is reacted at 70 ° C. for 12 hours. After adding 3 parts of methanol and reacting at 60 ° C. for 1 hour, the resin concentration is 30% and the viscosity is
A polyurethane resin solution of 8,500 centipoise was obtained.

Next, the water absorption and moisture permeability of a film obtained from this polyurethane resin solution were measured.

On the other hand, a control polyurethane resin solution was prepared in the same manner as in Example 9 except that the use of the polyoxyethylene group-containing macromonomer was changed so as to be completely absent. Served for

The results of the comparative tests on Example 9 and Comparative Example 9 thus obtained are summarized in Table 9.

As is clear from the results described above, the polyurethane resin in which the polyoxyethylene group-containing macromonomer is used has a lower use of the macromonomer than the control polyurethane resin in a form lacking at all. It is easy to know that the films are remarkably excellent in both water absorption and moisture permeability.

(Effect of the Invention) According to the production method of the present invention, it is possible to easily introduce various functional groups into the polyurethane resin, and the polyurethane resin thus obtained has its reactivity and function. By utilizing the properties and the like, the polyurethane resin obtained by the production method according to the present invention, of course, in addition to the present invention,
The resin composition comprising this polyurethane resin is also
New and useful, respectively, widely used as adhesives, paints and surface treatment agents, as films and molding materials, and also as synthetic leather, etc.
It can be applied.

Claims (3)

(57) [Claims] 1. One end obtained by radical polymerization of a mercaptan-based chain transfer agent having two hydroxyl groups and one mercapto group as an essential component with a monomer having a radically polymerizable unsaturated bond having a functional group. A method for producing a polyurethane resin (C), comprising reacting a polyol component (A) containing a macromonomer having two hydroxyl groups and having a functional group (excluding a hydroxyl group) with a polyisocyanate (B). 2. A monomer having a radical polymerizable unsaturated bond having a functional group according to claim 1, wherein the monomer is a glycidyl group, a phosphate group, a phosphate group, a phosphate group, a carboxylate group, a carboxylate group, or sulfonic acid. Group, sulfonate group, amino group,
A method for producing a polyurethane resin, comprising at least one functional group selected from an amine base, a polyoxyethylene group, a perfluoroalkyl group, and a polysiloxane group. 3. A polyurethane resin composition comprising the polyurethane resin (C) obtained by the production method according to claim 1 and an organic solvent as essential components.