JPH0616997A - Aqueous coating agent - Google Patents

Abstract

PURPOSE:To obtain an aqueous polyurethane coating agent extremely good in the persistence of surface lubricity and abrasion resistance. CONSTITUTION:Methacryloyloxypropylpolydimethylsiloxane is copolymerized with methyl methacrylate in the presence of thioglycerol to produce a dihydroxymacromonomer having the hydroxy groups at one molecula end. The macromonomer is reacted with poly (butylene adipate) diol, dimethylolpropionic acid, neopentyl glycol, and dicyclohexylmethane diisocyanate to produce an isocyanate-ended prepolymer, which is mixed with trimethylamine and water, emulsified, and then subjected to a chain elongation reaction to provide an aqueous coating agent comprising a polyurethane aqueous dispersion locally having silicone chains in the side chains. The aqueous polyurethane coating agent extremely good in the persistence of surface lubricity and abrasion resistance is obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous coating agent. More specifically, it relates to an aqueous coating agent having excellent surface slipperiness, abrasion resistance and blocking resistance.

[0002]

2. Description of the Related Art Conventionally, various water-based coating agents have been used for the purpose of modifying the surface function of polyester films. Among them, water-based resins such as polyurethane resins and colloidal silica are used for the purpose of imparting surface lubricity. It is known to blend inorganic particles or silicone emulsion for coating.

[0003]

However, in the above coating agents, the transparency of the coating film is poor, or the silicone oil bleeds over the surface of the coating film over time, and therefore, the surface lubricity and the abrasion resistance are persistent. However, there is a drawback that the adhesiveness to the substrate is also poor.

[0004]

Means for Solving the Problems The inventors of the present invention have made diligent studies in view of the above situation. As a result, when a polyurethane resin aqueous dispersion having a polyorganosiloxyl group in a side chain is used as a coating agent, it is simply mixed. Compared to a film obtained from an emulsion, it is significantly more transparent, has no bleeding of silicone, and the film has excellent surface lubricity and durability of abrasion resistance, and also has excellent adhesion to the substrate. The present invention has been completed and the present invention has been completed.

The present invention is one terminal obtained by radical polymerization of a (meth) acryloyl group-containing silicone monomer as an essential component in the presence of a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group. It is intended to provide an aqueous coating agent characterized by dispersing a polyurethane resin obtained by reacting a polyhydroxy macromonomer (A) and a polyisocyanate (B) as essential components in an aqueous medium. (Structure) Examples of the mercaptan chain transfer agent having two or more 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, 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.

As the (meth) acryloyl group-containing silicone monomer used in the present invention, any of known and commonly used silicone monomers can be used, and examples thereof include those having a structure represented by the following formula (I). .

[0007]

[Chemical 1] (However, R _{1 to} R ₇ are an alkyl group or an aryl group, R ₈ is a C _{3 to} C ₁₀ alkylene group, R ₉ is H or a methyl group,
n is an integer of 10 to 200. ) In formula (I),
All of R _{1 to} R ₇ are preferably methyl groups, and R ₈ is preferably a propylene group.

Specific examples of the (meth) acryloyl group-containing silicone monomer of the present invention include methacryloxypropyl polydimethyl siloxane, acryloxy propyl polydimethyl siloxane, methacryloxy butyl polydimethyl siloxane and acryloxy butyl polydimethyl siloxane. , Methacryloxypropyl polymethylphenyl siloxane and the like.

The (meth) acryloyl group-containing silicone monomer of the formula (I) is produced, for example, as follows. That is, the aryl methacrylate obtained by reacting methacrylic acid with an aryl alcohol is further reacted with chlorodimethylsilane to give methacryloxypropyldimethylchlorosilane, which is reacted with cyclic siloxane.

In obtaining the macromonomer (A), the (meth) acryloyl group-containing silicone monomer is
If necessary, other radically polymerizable unsaturated monomers may be copolymerized.

Examples of the above-mentioned other radically polymerizable unsaturated monomers include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate,
Examples thereof include alkyl (meth) acrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate and octyl methacrylate, acrylonitrile, methacrylonitrile, styrene and vinyl acetate, and among these, methyl methacrylate is preferable.

In addition to these, the following radically polymerizable unsaturated monomers having a functional group, for example, glycidyl group-containing monomers such as glycidyl (meth) acrylate and aryl glycidyl ether; (meth) acrylic acid , Itaconic acid, 2-methacryloyloxyethyl phthalic acid and salts thereof; methacryloyloxyethyl acid phosphate, methacryloyloxypropyl acid phosphate and phosphoric acid group-containing monomers such as esters or salts thereof; styrene sulfonic acid and their 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; perfluoro Octylethyl (meth) acrylate, N-methyl (Propyl) perfluoroalkyl group-containing monomers such as perfluorooctyl sulfonamide ethyl (meth) acrylate, polyoxyethylene group-containing monomer such as methoxy polyethylene glycol (meth) acrylate can be used.

As a method for producing the silicone chain-containing macromonomer (A) of the present invention, a conventionally known method can be applied. For example, the presence of the above-mentioned mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group. The radical-polymerizable unsaturated monomer containing the (meth) acryloyl group-containing silicone monomer as an essential component is radical-polymerized by using a polymerization catalyst, if necessary. Examples of the polymerization catalyst include acyl peroxides such as benzoyl peroxide, tertiary butyl hydroperoxides, alkyl hydroperoxides such as p-methane hydroperoxide, and dialkyl peroxides such as di-tertiary butyl peroxide. Examples thereof include peroxide compounds, azobisisobutyronitrile compounds, and the like.

Macromonomer (A) used in the present invention
Is usually 1,000 to 100,000, and preferably 2,000 to 50,000. The amount of the above-mentioned silicone chain-containing macromonomer (A) used to obtain the polyurethane resin of the present invention depends on the surface functionality of the finally obtained aqueous coating agent, that is, surface slipperiness, abrasion resistance and blocking resistance. It is necessary to use a sufficient amount to impart a silicone chain content of 0.1 to 50 parts, preferably 0.1 part to 100 parts of the polyurethane resin solid content. 2 to 20 parts. When the polyurethane aqueous dispersion copolymerized with the silicone chain-containing macromonomer (A) is blended with another aqueous dispersion, the solid content of the resin in the finally mixed aqueous coating agent is used. On the other hand, it is also possible to prepare the above proportion.

Examples of the polyisocyanate (B) used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate and 4,4'-diphenylmethane. Diisocyanate,
2,4'-diphenylmethane diisocyanate, 2,
2'-diphenylmethane diisocyanate, 3,3'-
Dimethyl-4,4'-biphenylene diisocyanate,
3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate , 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,
4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,
4'-dicyclohexylmethane diisocyanate, 3,
3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate and the like can be mentioned.

Other active hydrogen-containing compounds capable of reacting with isocyanate groups used in the production of the polyurethane aqueous dispersion of the present invention are, for convenience, an average molecular weight of 300 to 1
It is divided into high molecular weight compounds of preferably 500 to 5,000 and low molecular weight compounds of 300 or less.

Examples of the high molecular weight compound include polyester polyol, polyether polyol, polycarbonate polyol, polyacetal polyol,
Examples thereof include polyacrylate polyol, polyester amide polyol, polythioether polyol and the like.

As the polyester polyol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6,000), dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, glycol components such as hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts, and succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid Acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4
Of naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid and these dicarboxylic acids Anhydrides or ester-forming derivatives; polyesters obtained by dehydration condensation reaction with acid components such as p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these hydoxycarboxylic acids Other examples include polyesters obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone and copolymerized polyesters thereof.

As the polyether, ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, trimethylene glycol, 1,
3-butanediol, 1,4-butanediol, 1,6
-Hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, aconit sugar, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxy Ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin with one or more compounds having at least two active hydrogen atoms such as phthalic acid, 1,2,3-propanetrithiol and the like as an initiator. Examples thereof include those obtained by addition-polymerizing one or more monomers such as tetrahydrofuran and cyclohexylene by a conventional method.

As the polycarbonate polyol,
1,4-butanediol, 1,6-hexanediol,
Examples thereof include compounds obtained by reacting a glycol such as diethylene glycol with diphenyl carbonate or phosgene.

The low molecular weight compound has a molecular weight of 30.
A compound containing at least two active hydrogens in the molecule of 0 or less, for example, a glycol component used as a raw material for polyester polyol; a polyhydroxy compound such as glycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, and the like; Ethylenediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, 3,
3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, 1,2-propanediamine, hydrazine, diethylenetriamine,
Examples include amine compounds such as triethylenetetramine.

The method for producing the aqueous dispersion of polyurethane resin of the present invention may be any of the well-known methods, and the polyurethane resin having no hydrophilic group is forcibly placed in an aqueous medium by an external emulsifier. It is also possible to disperse the pigment in the above manner, but those obtained by such a method are not so preferable. Examples of the method different from the above include the following methods. A macromonomer (A), other active hydrogen-containing compound, and a hydrophilic group-containing compound, in an organic solvent solution or organic solvent dispersion of a hydrophilic group-containing polyurethane resin obtained by reacting the polyisocyanate (B), A method of obtaining an aqueous dispersion by optionally mixing an aqueous solution containing a neutralizing agent. A neutralizing agent is added to the hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting the macromonomer (A), other active hydrogen-containing compound, and the hydrophilic group-containing compound with the polyisocyanate (B). A method of obtaining an aqueous dispersion by mixing with an aqueous solution containing the same or by adding a neutralizing agent to a prepolymer in advance and then mixing and dispersing the water in water, followed by reacting with a polyamine. The hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting the macromonomer (A), other active hydrogen-containing compound, and the hydrophilic group-containing compound with the polyisocyanate (B), a neutralizing agent and A method of obtaining an aqueous dispersion by mixing with an aqueous solution containing a polyamine or by previously adding a neutralizing agent to a prepolymer and then mixing with an aqueous solution containing a polyamine.

Examples of the raw material used for introducing a hydrophilic group into the polyurethane resin or urethane prepolymer having a terminal isocyanate group of the present invention include, for example, at least one active hydrogen atom in the molecule and a carboxyl group. A compound having at least one functional group selected from the group consisting of an acid salt, a sulfonic acid salt, a carboxylic acid group, and a sulfonic acid group, which is basically ionic, or at least one or more active compounds in the molecule. Has a hydrogen atom,
Further, a nonionic compound containing a group consisting of repeating units of ethylene oxide and a group consisting of repeating units of ethylene oxide and other alkylene oxides can be mentioned. Among these hydrophilic groups, an anionic group consisting of a carboxylic acid group and a salt of a carboxylic acid and / or a nonionic group containing a repeating unit of ethylene oxide is particularly preferable.

Examples of the hydrophilic group-containing compound include 2-oxyethanesulfonic acid, phenolsulfonic acid,
Sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine-
4,6-disulfonic acid, 2,4-diaminotoluene-5
-Sulfonic acid-containing compounds such as sulfonic acid and their derivatives or polyester polyols obtained by copolymerizing these; 2,2-dimethylolpropionic acid, 2,2-
Dimethylol butyric acid, 2,2-dimethylol valeric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, 3,4-
Carboxylic acid-containing compounds such as diaminobenzoic acid and derivatives thereof or polyester polyols obtained by copolymerizing these; at least 30% by weight or more of repeating units of ethylene oxide, and at least 1 in the polymer.
Molecular weight 300 to 20,000 containing one or more active hydrogens
0, polyoxyethylene glycol or polyoxyethylene-polyoxypropylene copolymer glycol, polyoxyethylene-polyoxybutylene copolymer glycol, polyoxyethylene-polyoxyalkylene copolymer glycol or nonionics such as monoalkyl ethers thereof Examples thereof include group-containing compounds and polyester polyether polyols obtained by copolymerizing these, and these are used alone or in combination.

When producing the aqueous polyurethane resin used in the present invention, the content of the hydrophilic group bonded in the molecule is the same as the final content when the hydrophilic group is an ionic group such as a carboxyl group or a sulfonic acid group. Of at least 0.005 to 0.
2 equivalents, preferably 0.01 to 0.1 equivalents are necessary,
Particularly, a hydrophilic group such as a carboxyl group is preferable.

When a nonionic compound is used,
It is preferably at least 20 parts by weight, and more preferably at most 10 parts by weight, per 100 parts by weight of the solid content of the polyurethane resin finally obtained.

In the present invention, an external emulsifier may be used in combination with the hydrophilic group-containing compound. Examples of such emulsifiers include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrenated phenyl ether, and polyoxyethylene sorbitol tetraoleate; fatty acid salts such as sodium oleate; Ester salt, alkylbenzene sulfonate,
Anionic emulsifiers such as alkyl sulfosuccinates, naphthalene sulfonates, sodium alkane sulfonates, sodium alkyl diphenyl ether sulfonates; nonionic anionic emulsifiers such as polyoxyethylene alkyl sulfates and polyoxyethylene alkylphenyl sulfates Can be mentioned.

The polyurethane resin and the urethane prepolymer containing a terminal isocyanate group according to the present invention are produced by a conventionally known method. For example, the polyisocyanate and the active hydrogen-containing compound (the macromonomer (A) and the hydrophilic group-containing compound are also included). In the case of polyurethane resin, the equivalent ratio of isocyanate group and active hydrogen group is 0.
8: 1 to 1.2: 1, preferably 0.9: 1 to 1.1: 1
In the case of urethane prepolymer containing terminal isocyanate group, the ratio is 1.1: 1 to 3: 1, preferably 1.
20 to 120 ° C., preferably 3 at a ratio of 2: 1 to 2: 1
Reacted at 0-100 ° C.

These reactions can be carried out without a solvent, but an organic solvent can be used for the purpose of controlling the reaction of the reaction system or reducing the viscosity. The organic solvent is not particularly limited, but examples thereof include aromatic hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; acetic acid esters such as ethyl acetate and butyl acetate; dimethylformamide, N Amides such as methylpyrrolidone. When such an organic solvent is removed by distillation from the finally obtained polyurethane resin aqueous dispersion, it is preferable to use an organic solvent having a relatively low boiling point, which is easily removed by distillation. Even when it is necessary to use an organic solvent having a boiling point of 100 ° C. or higher, it is preferable to keep the amount used to the minimum necessary.

Examples of the neutralizing agent that can be used in the production of the aqueous polyurethane dispersion of the present invention include non-volatile bases such as sodium hydroxide and potassium hydroxide; trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine, and triethylamine. Examples include tertiary amines such as ethanolamine and volatile bases such as ammonia. The neutralization time may be during the urethanization reaction or after the urethanization reaction.

Examples of the polyamine that can be used in the production of the aqueous polyurethane dispersion of the present invention include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine and 2,5-. Dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,
3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine, aminoethylpropanolamine,
Examples thereof include diamines such as aminopropylpropanolamine and aminohexylpropanolamine; polyamines such as diethylenetriamine, dipropylenetriamine and triethylenetetramine; hydrazines; acid hydrazides, which may be used alone or in combination.

The aqueous polyurethane resin thus obtained may be used as it is, but it is also possible to use it by distilling off the organic solvent, if necessary. Various types of distillation apparatuses can be used for removing the organic solvent by distillation, but a distillation apparatus that does not release the distilled solvent and the organic solvent that has been distilled off to the atmosphere is preferable, and a thin-film evaporation apparatus is particularly preferable.

In addition, in the production methods 1 to 3 of the present invention,
If necessary, in addition to water, other aqueous dispersions or aqueous dispersions, for example, vinyl acetate-based, ethylene vinyl acetate-based, acrylic-based, acrylic styrene-based emulsions; styrene / butadiene-based, acrylonitrile-butadiene-based, acrylic -Butadiene-based latex; polyethylene-based or polyolefin-based ionomer; various aqueous dispersions of polyurethane, polyester, polyamide, epoxy resin, etc.
You may use together an aqueous dispersion.

The polyurethane resin aqueous dispersion thus obtained by removing the organic solvent is a substantially solvent-free aqueous dispersion having a solid content of about 10 to 60% by weight, preferably 15 to 50% by weight. However, even if it is unavoidable that an organic solvent having a boiling point of 100 ° C. or higher must be used in the production of the aqueous polyurethane resin, the amount of the organic solvent is 2
The use of such organic solvents should be stopped up to 0% by weight.

The aqueous polyurethane resin of the present invention thus obtained is used as it is, or as an emulsion of other water dispersions such as vinyl acetate, ethylene vinyl acetate, acrylic, acrylic styrene; styrene / butadiene. ,
Acrylonitrile-butadiene-based, acrylic-butadiene-based latex; polyethylene-based, polyolefin-based ionomer; polyurethane, polyester, polyamide, epoxy-based water dispersion blended at an arbitrary ratio and used as the aqueous coating agent of the present invention can do. In addition to the above-mentioned aqueous dispersion, a film forming aid such as an alkylene glycol derivative or a dialkyl ester of an aliphatic dicarboxylic acid for the purpose of improving the film forming property, and a fluorine-based leveling for the purpose of improving coating suitability. Agents, dialkyl sulfosuccinate-based emulsifiers, and various leveling agents such as acetylene glycol derivatives may be added. For the purpose of suppressing foaming of the compounded liquid, mineral oil-based,
It is also possible to add various antifoaming agents such as amide type and silicone type, or a small amount of alcohols such as ethanol and isopropyl alcohol. Further, when used as an ink or paint, various inorganic or organic pigments which are water-soluble or water-acidic can be added. Further, for the purpose of improving various durability such as light resistance, heat resistance, water resistance, and solvent resistance of the above water dispersion, a stabilizer such as an antioxidant, an ultraviolet absorber and a hydrolysis inhibitor is added to the polyurethane resin water dispersion. Can be added during or after the production step of, or a crosslinking agent such as an epoxy resin, a melamine resin, an isocyanate compound, an aziridine compound or a polycarbodiimide compound can be blended and used.

[0036]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the present invention, parts and% are based on weight unless otherwise specified.
The coefficient of friction in the text was measured using a surface property measuring machine (Model 14 manufactured by Haydon Co.) at a load of 20 g and a speed of 130 mm / min. Abrasion test, load 1kg, stroke 14
It was performed by a plane friction test (JIS M-403B) at 0 mm. Example 1 Polybutylene adipate diol 101 having a molecular weight of 1,000
7 parts, macromonomer of the present invention having an average molecular weight of 5,000 [methylmethacrylate and methacryloxypropylpolydimethylsiloxane in the presence of thioglycerin (Cilaplane FM-0721 manufactured by Chisso Corporation, molecular weight 5
000) at a ratio of 6/4 (weight ratio) and an oligomer having a diol group at one terminal] 302.5 parts, dimethylolpropionic acid 144 parts, neopentyl glycol 36.
2 parts, 4,4′-dicyclohexylmethane diisocyanate (917 parts), stannous octylate (0.6 parts), methyl ethyl ketone (1007 parts) and N-methylpyrrolidone (604 parts) were mixed and reacted at 75 ° C. for 8 hours to prepare an isocyanate-terminated prepolymer. A polymer was obtained. To this prepolymer solution was added 108.5 parts of triethylamine for neutralization, and water 7
166 parts of the solution was gradually added dropwise with stirring to emulsify, and then 425 parts of an aqueous solution containing 85 parts of isophoronediamine was added, and I
The reaction is completed by stirring until no absorption of isocyanate groups is observed at R. Further, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous polyurethane resin having a solid content concentration of 30%. This aqueous polyurethane resin was applied onto a PET film of 125 μm so that the film thickness when dried was 50 μm, and dried at 80 ° C. to obtain a urethane film. This film is transparent and has a haze of 90% and a friction coefficient of 0.1.
In No. 1, it was possible to withstand wear of 500 times or more. Comparative Example 1 An aqueous urethane resin containing no silicone chain was synthesized in the same manner except that the macromer of Example 1 was omitted.

1348 parts of polybutylene adipate diol having a molecular weight of 1,000 and dimethylolpropionic acid 144
Parts, neopentyl glycol 8.1 parts, 4,4′-dicyclohexylmethane diisocyanate 917 parts, stannous octylate 0.6 parts, methyl ethyl ketone 1007
And 604 parts of N-methylpyrrolidone were mixed and reacted at 75 ° C. for 8 hours to obtain an isocyanate-terminated prepolymer. To this prepolymer solution, 108.5 parts of triethylamine was added for neutralization, and 7166 parts of water was gradually added dropwise with stirring to emulsify, and then 425 parts of an aqueous solution containing 85 parts of isophoronediamine was added, and IR was used. The reaction is completed by stirring until no absorption of isocyanate groups is observed. Further, methyl ethyl ketone is distilled off under reduced pressure,
An aqueous polyurethane resin having a solid content concentration of 30% was obtained. To 100 parts of this aqueous polyurethane resin, a commercially available silicone emulsion of polydityl siloxane (solid content 30
%) In an amount of 125 μPET as in Example 1.
A urethane film was obtained by coating on a film so that the film thickness when dried was 50 μm and drying at 80 ° C. This film is transparent and has a haze of 65%, a coefficient of friction of 0.56,
After 100 cycles of wear, the film cracked. Example 2 Polyester having a molecular weight of 2,000 (ethylene glycol / neopentyl glycol / isophthalic acid / adipic acid) 1
149 parts, macromonomer of the present invention having a molecular weight of 2,000 [methylmethacrylate and methacryloxypropylpolydimethylsiloxane in the presence of thioglycerin (Cilaplane FM-0711 manufactured by Chisso Corporation, molecular weight 1
000) copolymerized with 7/3 (weight ratio) having one terminal diol group] 244.5 parts, dimethylolpropionic acid 98.3 parts, 3-methylpentanediol 8.3 parts, isophorone diisocyanate 333 parts , 1833 parts of methyl ethyl ketone and 0.9 parts of dibutyltin dilaurate were mixed and reacted at 75 ° C. for 18 hours for urethanization, and then 16.6 parts of 25% ammonium hydroxide was added for neutralization to obtain 5483 parts of water. The mixture was gradually added dropwise with stirring to emulsify, and then methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous polyurethane resin having a solid content concentration of 30%. This aqueous polyurethane resin was applied onto a PET film of 125 μm so that the film thickness when dried was 50 μm, and dried at 80 ° C. to obtain a urethane film. This film was transparent, had a haze of 92%, had a coefficient of friction of 0.12, and was able to withstand wear of 500 times or more. Example 3 921 parts of polycaprolactone diol having a molecular weight of 2,000,
Macromonomer of the present invention having a molecular weight of 6,000 [Methylmethacrylate and methacryloxypropylpolydimethylsiloxane (Silaprene FM-0721 manufactured by Chisso Corporation) in the presence of thioglycerin 6/4 (weight ratio)
Having a diol group at one terminal copolymerized with
96.4 parts, dimethylolpropionic acid 147.3 parts,
3,5.2 parts of 1,4-butanediol, 578 parts of isophorone diisocyanate, 0.4 parts of stannous octylate, and 1318 parts of methyl ethyl ketone were mixed and reacted at 75 ° C. for 6 hours to synthesize an isocyanate group-terminated prepolymer. After that, triethylamine 110.9 parts, 100%
The reaction is completed by adding dropwise to 6114 parts of an aqueous solution in which 24 parts of hydrated hydrazine is dissolved with stirring and stirring until no absorption of isocyanate groups is observed by IR. Subsequently, methyl ethyl ketone was distilled off under reduced pressure to obtain a solid content of 30
% Aqueous polyurethane resin was obtained. This aqueous polyurethane resin was applied onto a PET film of 125 μm so that the film thickness when dried was 50 μm, and dried at 80 ° C. to obtain a urethane film. This film was transparent and had a haze of 90%, a coefficient of friction of 0.10, and was able to withstand wear of 500 times or more.

[0038]

The aqueous coating agent obtained by the present invention has a silicone chain directly copolymerized with the polyurethane skeleton, as compared with the conventional silicone emulsion blended with the polyurethane emulsion. Without bleeding, it is possible to impart surface durability, abrasion resistance, and blocking resistance with excellent durability and durability.

Further, in the aqueous coating agent of the present invention, since the silicone chain is localized in the side chain of the polyurethane skeleton, compared with the case where silicone is added later, the amount of the solid content is smaller than that in the conventional case. Copolymerization can give sufficient surface functionality, the characteristics that polyurethane resin has originally,
For example, it is possible to provide a water-based coating agent having a well-balanced combination without impairing the adhesion, transparency, film strength, water resistance, and solvent resistance to various base materials.

The aqueous coating agent of the present invention thus obtained is polyester, nylon, vinyl chloride, ABS, OP.
P, CPP and other plastic film or sheet primer coating agent, top coating agent or water-based gravure ink base polymer, iron plate, steel plate, aluminum plate surface coating of various metal plates, thermal paper, etc. As a top coat agent for functional paper, or paints for various fabrics, natural leather, artificial leather, synthetic leather, wood, etc.
It is useful for surface coating agents, water-based gravure inks, etc.

Claims (4)

[Claims] 1. In the presence of a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group (meth).
Polyurethane resin obtained by reacting polyisocyanate (B) with one-terminal polyhydroxy macromonomer (A) obtained by radical polymerization of silicone monomer containing acryloyl group as an essential component was dispersed in an aqueous medium. An aqueous coating agent characterized in that 2. The aqueous coating agent according to claim 1, wherein the polyurethane resin has a carboxylate group and / or an ethylene oxide unit as a hydrophilic group. 3. The aqueous coating according to claim 1, wherein the macromonomer (A) is obtained by radical polymerization of a (meth) acryloyl group-containing silicone monomer and methyl methacrylate as essential components. Agent. 4. The macromonomer (A) has a molecular weight of 2,000.
A macromonomer having a molecular weight of 0 to 50,000.
~ 3 aqueous coating agent.