JPH05262847A - Method for producing polyurethane resin - Google Patents

Abstract

(57) [Summary] [Structure] In the presence of a mercaptan chain transfer agent having two hydroxyl groups and one mercapto group, a perfluoroalkyl group-containing (meth) acrylate and, if necessary, other methyl methacrylate and the like are added. Essentially, a one-terminal dihydroxy macromonomer (A) having a molecular weight of 1,000 to 50,000, a long-chain polyhydroxy compound (B), and an organic diisocyanate (C) obtained by radical polymerization of a radically polymerizable unsaturated monomer. The present invention relates to a method for producing a polyurethane resin, which comprises reacting as a component. The polyurethane resin obtained by the method of the present invention has excellent antifouling property. Synthetic leather, film, paint,
It is useful for magnetic binders, surface treatment agents, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polyurethane resin having excellent antifouling properties.

[0002]

2. Description of the Related Art Conventionally, polyurethane resins have been used for molding materials, films,
It is used in many applications such as synthetic leather, coating materials and surface treatment agents.

However, the polyurethane resin has a serious drawback in that it easily gets dirty. No literature has been found that attempts to introduce a perfluoroalkyl group into a urethane resin in order to compensate for this drawback.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a practical method for efficiently introducing a perfluoroalkyl group into a polyurethane resin and to provide a polyurethane resin having excellent antifouling property. .

[0005]

As a result of intensive studies, the present inventors have found that the use of a perfluoroalkyl group-containing one-end dihydroxy macromonomer solves the above problems, and It came to completion.

That is, according to the present invention, in the presence of a mercaptan chain transfer agent having two hydroxyl groups and one mercapto group, a perfluoroalkyl group-containing (meth) acrylate and, if necessary, other radically polymerizable unsaturated monomer are used. Of a polyurethane resin characterized by reacting one-terminal dihydroxy macromonomer (A), a long-chain polyhydroxy compound (B) and an organic diisocyanate (C) as essential components, which are obtained by radical polymerization of a monomer A manufacturing method is provided.

As the perfluoroalkyl group-containing (meth) acrylate of the present invention, for example, the following ones are used. Perfluorooctylethyl acrylate,
Perfluorooctyl ethyl methacrylate, perfluorohexyl ethyl acrylate, perfluorohexyl ethyl methacrylate, N-methyl perfluorooctyl sulfonamide ethyl acrylate, N-methyl perfluorooctyl sulfonamide ethyl methacrylate, N-methyl perfluorohexyl sulfonamide ethyl acrylate , N-methylperfluorohexyl sulfonamide ethyl methacrylate, N-propyl perfluorohexyl sulfonamide ethyl acrylate, N-propyl perfluorooctyl sulfonamide ethyl acrylate, perfluoroheptyl carbon amide ethyl acrylate, etc. The body etc. are mentioned.

Radical polymerizable unsaturated monomers other than the perfluoroalkyl group-containing (meth) acrylate used in the present invention include methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate,
Examples thereof include alkyl acrylates and / or methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate and octyl methacrylate, acrylonitrile, methacrylonitrile, styrene and vinyl acetate.

In addition to the above, radically polymerizable unsaturated monomers having functional groups such as the following, for example, glycidyl group-containing monomers such as glycidyl (meth) acrylate and aryl glycidyl ether, and methacryloyloxyethyl acid phosphate. Phosphate group-containing monomers such as fate, methacryloyloxypropyl acid phosphate and its esters or salts, carboxylic acid group-containing monomers such as (meth) acrylic acid, 2-methacryloyloxyethylphthalic acid and salts thereof, styrene Sulfonic acid and sulfonic acid group-containing monomers such as salts thereof, dimethylaminomethyl (ethyl) (meth) acrylate and its 4
Amino group-containing monomers such as graded salts, amide group-containing monomers such as (meth) acrylamide, polysiloxane group-containing monomers such as polydimethylsiloxyl propyl methacrylate, methoxy polyethylene glycol (meth) acrylate, etc. A polyoxyethylene group-containing monomer or the like is used.

Examples of the mercaptan chain transfer agent having two hydroxyl groups and one mercapto group used in the present invention include 1-mercapto-1,1-methanediol and 1-mercapto-1,1-ethanediol. , 3-mercapto-1,2-propanediol (hereinafter referred to as thioglycerin), 2-mercapto-1,2-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 can be mentioned.

The molecular weight of the macromonomer used in the present invention is usually 1,000 to 100,000 and usually 1,000 to 5
10,000 is preferable. The long-chain polyhydroxy compound (B) of the present invention refers to a polyhydroxy compound having a molecular weight of 500 to 5,000, preferably 1,000 to 3,000.
For example, a polyether diol or a polyether diol may be used alone or a mixture thereof.

By introducing the long-chain polyhydroxy compound (B), the antifouling property of the resulting polyurethane resin can be adjusted, and the mechanical strength and the like can be improved.

Examples of polyester diols 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-pentane Diol, 1,8
-Octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol,
One or more diols such as cyclohexane-1,4-dimethanol and succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid Examples thereof include an acid and a condensate with one or more dicarboxylic acids such as hexahydroisophthalic acid. Further, γ-butyrolactone having the diol as an initiator,
Ring-opening polymers such as ε-caprolactone are also included.

Examples of the polyether diol include ethylene oxide, propylene oxide, butylene oxide and styrene oxide, which are diols described in the section of polyester diol as an initiator, or a ring-opening polymer of two or more kinds. . Further, a ring-opening polymer of tetrahydrofuran is also included.

Furthermore, known polyhydric alcohols such as diethylene glycol, triethylene glycol, 1,
5-pentanediol, 1,6-hexanediol, dimethyl-1,5-pentanediol, dimethyl-1,6
-Hexanediol, 1,8-octanediol, cyclohexane-1,4-diol, cyclohexane-1,
Also included are poly (alkylene carbonate) diols obtained by condensation of 4-dimethanol and the like with diaryl carbonate, dialkyl carbonate, or alkylene carbonate.

Examples of the organic diisocyanate (C) of the present invention include phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate,
Aliphatic or alicyclic diisocyanates such as aromatic diisocyanates such as naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate and tetramethylxylylene isocyanate.

In the present invention, the low molecular weight compound (D) having a functional group reactive with isocyanate may be reacted.
Examples of the low molecular weight compound (D) 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-
Diols such as 1,4-dimethanol, ethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, hexamethylenediamine, hydrazine, piperazine, N, N'-diaminopiperazine, 2-methylpiperazine, 4, One or a mixture of two or more diamines such as 4'-diaminodicyclohexylmethane and isophoronediamine may be mentioned.

The amount of the organic diisocyanate (C) used in the present invention is usually 0.9 to 1.1 equivalents, where 1 equivalent is the total active hydrogen of (A), (B) and (D). . The above (A), (B), (C) and (D) can be reacted by a conventionally known method. For example, the reaction can be carried out in a solvent-free or organic solvent or in water at a reaction temperature of 30 to 250 ° C. In the case of a solution reaction, an organic solvent such as ethyl acetate, butyl acetate, methyl ethyl ketone, toluene, tetrahydrofuran, isopropanol, cyclohexanone, dimethylformamide, cellosolve, cellosolve acetate is used at the beginning of the reaction, during the reaction,
It can be added at the end of the reaction and at any of these stages.

In the production of the polyurethane resin of the present invention, a monoalcohol, a trifunctional or higher functional alcohol, an organic monoamine, a trifunctional or higher functional amine, an organic monoisocyanate, or a trifunctional or higher functional polyisocyanate is used, if necessary. Good.

In producing the polyurethane resin of the present invention, a catalyst and a stabilizer can be used if necessary. These catalysts and stabilizers can be added at any stage.

Examples of the catalyst include nitrogen-containing compounds such as triethylamine, triethylenediamine and morpholine,
Examples thereof include metal salts such as potassium acetate, zinc stearate and tin octylate, and organic metal compounds such as dibutyltin dilaurate.

As the stabilizer, a stabilizer against ultraviolet rays such as substituted benzotriazoles and a stabilizer against thermal oxidation such as phenol derivatives can be added. The number average molecular weight of the polyurethane resin obtained in the present invention is usually 5,000 to 500,000.

If necessary, other resins, antioxidants, ultraviolet absorbers, hydrolysis inhibitors, pigments, dyes, flame retardants, fillers, cross-linking agents, etc. may be added to the polyurethane resin of the present invention. A polyurethane resin composition can be manufactured.

Examples of other resins include polyurethane resins other than those of the present invention, poly (meth) acrylic resins, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl propionate copolymers, polyvinyl butyral resins,
Examples include fibrous resin, polyester resin, epoxy resin, phenoxy resin, polyamide resin and the like.

Examples of the crosslinking agent include organic polyisocyanate. The resin of the present invention can be used for marking films, synthetic leather, molding materials, magnetic recording binders, coating agents, surface treatment agents and the like.

[0026]

EXAMPLES The present invention will now be described by way of examples, but this is only one mode and the present invention is not limited to the examples.

All "parts" in the text are based on weight. The test method is as follows. <Method of forming coating> A polyurethane resin solution or a compound was cast on a release paper and dried at 80 ° C for 30 minutes to form a coating of about 50 microns.

<Water and oil repellency of film> Using the film prepared by the above method, water and n- at 23 ° C are used.
The contact angle of dodecane was measured. It indicates that the larger the contact angle, the less likely it is that water-based or oil-based stains will attach.

<Anti-fouling test> The Delta E value is shown by a color difference meter on the adhesion of dirt when immersed in an artificial dirt compound made of carbon black, clay, cement, iron oxide, mineral oil, etc. for 1 hour at 70 ° C. It was The smaller the number, the less the stain.

Example 1 70 parts of adipic acid / 1,4 butylene glycol polyester diol having a molecular weight of 2000 and adipic acid / ethylene glycol polyester diol 3 having a molecular weight of 600
0 part, 40 parts of a perfluoroalkyl group-containing macromonomer having an average molecular weight of 6000 (oligomer having one terminal diol group copolymerized with methyl methacrylate and perfluorooctylethyl acrylate at a ratio of 5/5 by weight in the presence of thioglycerin), After mixing 34 parts of diphenylmethane diisocyanate and 126 parts of toluene and reacting at 70 ° C. for 2 hours, dimethylformamide 335
And 9 parts of 1,4 butylene glycol were added, and the mixture was reacted at 80 ° C. for 12 hours.
Reaction at ℃ for 1 hour, resin concentration 30%, viscosity 4
A polyurethane resin solution of 0000 centipoise was obtained.

The performance of the film obtained from this resin solution was as shown in Table 1. Comparative Example 1 A polyurethane resin solution having a resin concentration of 30% and a viscosity of 40,000 centipoise was obtained in the same manner as in Example 1 except that the perfluoroalkyl group-containing macromonomer of Example 1 was not used. The performance of the film obtained from this resin solution was as shown in Table 1.

From the results shown in Table 1, the polyurethane resin using the perfluoroalkyl group-containing macromonomer has a larger contact angle between water and n-dodecane than the polyurethane resin not using, and is excellent in water and oil repellency. It turns out that dirt is hard to attach. It was found that the polyurethane resin using the perfluoroalkyl group-containing macromonomer has excellent antifouling property because the adhesion of dirt in the antifouling test is very small as compared with the polyurethane resin not using it.

Example 2 Polyhexylene adipate diol 1 having a molecular weight of 2000
00 parts, a macromonomer of the present invention having a molecular weight of 8000 (an oligomer having a diol group at one end obtained by copolymerizing methyl methacrylate and N-methylperfluorooctylsulfonamidoethylmethacrylate in the presence of thioglycerin at a ratio of 7/3 (weight ratio)). ) 50 parts, diphenylmethane diisocyanate 32 parts, stannous octoate 0.04
After mixing 83 parts of toluene and reacting at 70 ° C. for 2 hours, 360 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 were added at 60 ° C. for 1 hour. By reacting for a time, a polyurethane resin solution having a resin concentration of 30% and a viscosity of 16500 centipoise was obtained. The performance of the film obtained from this resin solution was as shown in Table 1.

Comparative Example 2 A polyurethane resin solution having a resin concentration of 30% and a viscosity of 16500 centipoise was obtained in the same manner as in Example 2 except that the perfluoroalkyl group-containing macromonomer of Example 2 was not used. The performance of the film obtained from this resin solution was as shown in Table 1.

From the results shown in Table 1, the polyurethane resin using the perfluoroalkyl group-containing macromonomer has a large contact angle between water and n-dodecane and is excellent in water and oil repellency as compared with the polyurethane resin not used. It turns out that dirt is hard to attach. It was found that the polyurethane resin using the perfluoroalkyl group-containing macromonomer is superior in antifouling property to the polyurethane resin not using it because the adhesion of stains in the antifouling test is very small.

Example 3 Polyhexylene adipate diol 1 having a molecular weight of 2000
00 parts, having a molecular weight of 2000, the macromonomer of the present invention (methyl methacrylate and N-methylperfluorohexylsulfonamide ethyl acrylate in the presence of thioglycerin) is copolymerized at 7/3 (weight ratio) to have a diol group at one end. Oligomer) 50 parts, diphenylmethane diisocyanate 30 parts, stannous octoate 0.04
After mixing 83 parts of toluene and reacting at 70 ° C. for 2 hours, 356 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 were added at 60 ° C. After reacting for 1 hour, a polyurethane resin solution having a resin concentration of 30% and a viscosity of 25,000 centipoise was obtained. The performance of the film obtained from this resin solution was as shown in Table 1.

Comparative Example 3 A polyurethane resin solution having a resin concentration of 30% and a viscosity of 25,000 centipoise was obtained in the same manner as in Example 3 except that the perfluoroalkyl group-containing macromonomer of Example 3 was not used. The performance of the film obtained from this resin solution was as shown in Table 3.

From the results shown in Table 1, the polyurethane resin using the perfluoroalkyl group-containing macromonomer has a larger contact angle between water and n-dodecane than the polyurethane resin not using, is excellent in water repellency and oil repellency, and stains. It turned out that it was hard to adhere. It was found that the polyurethane resin using the perfluoroalkyl group-containing macromonomer is superior in antifouling property to the polyurethane resin not using it because the adhesion of stains in the antifouling test is very small.

Example 4 100 parts of a polycarbonate diol having a molecular weight of 2000,
Macromonomer of the present invention having a molecular weight of 5000 [an oligomer having a diol group at one terminal] obtained by copolymerizing methylmethacrylate and N-methylperfluorooctylsulfonamidoethylmethacrylate in the presence of thioglycerin at 7/3 (weight ratio) 50 70 parts, 1,4-butylene glycol 7 parts, isophorone diisocyanate 62 parts, stannous octylate 0.04 parts toluene 83 parts and mixed to obtain 70
After reacting at 0 ° C for 2 hours and cooling to 40 ° C, 560 parts of dimethylformamide and 83 parts of isopropyl alcohol are added, and 23 parts of isophoronediamine are gradually added while stirring well. Then, the mixture was stirred at 70 ° C. for an hour to obtain a polyurethane polyurea resin solution having a resin concentration of 25% and a viscosity of 25,000 centipoise. The performance of the film obtained from this resin solution was as shown in Table 1.

Comparative Example 4 A polyurethane polyurea resin solution having a resin concentration of 25% and a viscosity of 25,000 centipoise was obtained in the same manner as in Example 4 except that the perfluoroalkyl group-containing macromonomer of Example 4 was not used. The performance of the film obtained from this resin solution was as shown in Table 1.

[0041]

[Table 1] From the results shown in Table 1, the polyurethane resin using the perfluoroalkyl group-containing macromonomer has a larger contact angle between water and n-dodecane, is superior in water repellency and oil repellency as compared with the polyurethane resin not using the macromonomer, and is excellent in stain resistance. It turned out that it was hard to adhere. Further, it was found that the polyurethane resin using the perfluoroalkyl group-containing macromonomer is excellent in antifouling property because the adhesion of dirt in the antifouling test is very small as compared with the polyurethane resin not using it.

[0042]

The polyurethane resin obtained by the method of the present invention has excellent antifouling property. It can be applied to synthetic leather, films, paints, magnetic binders, surface treatment agents and the like that require antifouling properties.

Claims (3)

[Claims] 1. In the presence of a mercaptan chain transfer agent having two hydroxyl groups and one mercapto group, a perfluoroalkyl group-containing (meth) acrylate and, if necessary, a radical-polymerizable unsaturated monomer other than that. A method for producing a polyurethane resin, which comprises reacting one-terminal dihydroxy macromonomer (A), a long-chain polyhydroxy compound (B), and an organic diisocyanate (C), which are obtained by radically polymerizing, as an essential component. 2. A mercaptan chain transfer agent having two hydroxyl groups and one mercapto group is 3-mercapto-.
The method for producing a polyurethane resin according to claim 1, which is 1,2-propanediol. 3. One-end dihydroxy macromonomer (A)
Has a molecular weight of 1,000 to 50,000. 3. The method for producing a polyurethane resin according to claim 1, wherein