JPH11256070A - Aqueous coating and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating of which the nonemulsion type can be made water-soluble and which exhibits surface functions such as high water repellency and oil repellency though it is low-cost since the fluorine content in it is low and to provide a process for producing the same. SOLUTION: This aq. coating is prepd. by dissolving or dispersing, in an aq. medium, (A) a polymer formed from (a) 5-95 wt.% monomer having a carbon-carbon double bond and a fluoroalkyl group, (b) 5-95 wt.% monomer having a carbon-carbon double bond and a water-soluble group, and (c) 0-90 wt.% monomer other than monomers A and B and having a carbon-carbon double bond and (B) a polymer formed from (b) 5-100 wt.% monomer having a carbon-carbon double bond and a water-soluble group and (c) 0-95 wt.% monomer other than monomers (a) and (b) and having a carbon-carbon double bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water- and water-repellent oil-repellent coating and a method for producing the water- and water-repellent oil-repellent coating.

[0002]

2. Description of the Related Art Water or oil repellent coating liquids are applied to articles that cause inconvenience due to the adhesion or penetration of water or oil to prevent the attachment or penetration of water or oil droplets. . For example, a water-repellent suit in which a fabric is subjected to a water-repellent treatment is well known. Various fluorine compounds are known as substances exhibiting such water and oil repellency, and are used as water and oil repellents. However, many water and oil repellents using these fluorine compounds are oil-based and solvent-based, and in recent years, from the viewpoint of environmental protection, water-repellency has been desired. However, conventional water-based fluorine paints are emulsions because the fluorine resin is insoluble in water, and are susceptible to problems such as difficulty in making paints and poor adhesion, and the range of application is limited. Had been. Furthermore, since these fluorine compounds are expensive, there is a problem that usable products are limited.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to make non-emulsion type water-soluble, and to provide a surface function such as high water repellency and oil repellency while being inexpensive due to a small content of fluorine. And a method for producing the same.

[0004]

Means for Solving the Problems The present inventors utilize the fact that a fluorine-containing polymer is localized on the surface of a coating film to give a polymer having a water-soluble group a water-soluble group and a fluoroalkyl group. By mixing a polymer having a group, a water-soluble coating having high surface functions such as high water repellency and oil repellency was successfully produced with a small fluorine content. That is, the present invention relates to a monomer (a) having a carbon-carbon unsaturated double bond and a fluoroalkyl group in one molecule of 5 to 95% by weight,
(B) 5-95% by weight of a monomer having a carbon-carbon unsaturated double bond and a water-soluble group in one molecule, and (a) or (b)
A polymer (A) comprising 0 to 90% by weight of a monomer (c) having a carbon-carbon unsaturated double bond in one molecule other than a carbon-carbon unsaturated double bond and a water-soluble group in one molecule From 5 to 100% by weight of a monomer (b) having the formula: and from 0 to 95% by weight of a monomer (c) having a carbon-carbon unsaturated double bond in one molecule other than (a) or (b). The present invention relates to an aqueous coating obtained by dissolving or dispersing a polymer (B) in an aqueous medium.

[0005] The amount of the monomer (a) having a carbon-carbon unsaturated double bond and a fluoroalkyl group in one molecule is 0.1% based on the total weight of the polymer (A) and the polymer (B). 01
To 10% by weight. Further, the present invention relates to the above aqueous coating, wherein the water-soluble group of the monomer (b) having a carbon-carbon unsaturated double bond and a water-soluble group in one molecule is a carboxyl group. Further, the water-soluble group of the monomer (b) having a carbon-carbon unsaturated double bond and a water-soluble group in one molecule is an amino group,
The present invention relates to the above aqueous coating, which is at least one selected from the group consisting of a sulfonic acid group, a hydroxyl group, a polyethyleneoxy group, and a tetrahydrofurfuryl group. Further, characterized by containing a curing agent,
It relates to the above aqueous coating. Furthermore, the present invention relates to the above aqueous coating, wherein the curing agent is at least one selected from the group consisting of an epoxy compound, an isocyanate compound, an amino resin, and a phenol resin. Step 1: The above polymer (A) and polymer (B) are each polymerized in a solvent. Step 2: The polymer (A) and the polymer (A) and the polymer (B) are neutralized with a neutralizing agent containing an ion serving as a counter ion of a water-soluble group derived from the monomer (b). Each solution of the coalesced (B) is neutralized and dissolved or dispersed in an aqueous medium. Step 3: The solutions of the neutralized polymer (A) and the polymer (B) are mixed at a predetermined ratio, and diluted or concentrated to adjust the concentration. The present invention relates to a method for producing an aqueous coating, comprising the above steps 1 to 3 and performing a desolvation step immediately before or immediately after step 2.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As an example of a fluorine-containing monomer (a) having a carbon-carbon unsaturated double bond and a fluoroalkyl group in one molecule used in the polymer (A) constituting the present invention, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, perfluoromethylmethyl ( Meth) acrylate, perfluoroethylmethyl (meth) acrylate, perfluorobutylmethyl (meth) acrylate,
Perfluorooctylmethyl (meth) acrylate, perfluorodecylmethyl (meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctylamyl (meth) acrylate, perfluorooctylundecyl Perfluoroalkylalkyl (meth) acrylates having a perfluoroalkyl group having 1 to 20 carbon atoms, such as (meth) acrylate, and hexafluorooctyl (meth) acrylate, octafluorodecyl (meth) acrylate, and octafluorononyl Partially fluorinated alkylalkyl (meth) acrylates such as (meth) acrylate;

Perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene,
Perfluorodecylethylene and the like can be mentioned, and one or more of these can be used in combination depending on the required performance, and used at a copolymerization ratio of 5 to 95% by weight. Preferably, it is used at a copolymerization ratio of 20 to 80% by weight, more preferably 40 to 60% by weight. When the copolymerization ratio is below the lower limit, it is difficult to obtain sufficient surface functions such as water repellency and oil repellency, and when the copolymerization ratio exceeds the upper limit, the compatibility with the polymer (B) is difficult. , The solubility in water decreases.

The monomer (b) having a carbon-carbon unsaturated double bond and a water-soluble group in one molecule is used for imparting water solubility to a polymer. Further, after coating, the water-soluble group may be used as a crosslinking agent to form a hard coating film. Water-soluble functional groups include carboxyl groups,
Examples include an amino group, a sulfonic acid group, a hydroxyl group, a polyethyleneoxy group, and a tetrahydrofurfuryl group.
Examples of the monomer (b) having a carboxyl group include:
(Meth) acrylic acid, itaconic acid, 2-carboxyethyl (meth) acrylate, monoacryloxy fumaric acid ester 2- (meth) acryloyloxyethyl succinic acid and other monoacryloxysuccinic acid esters, 2- (meth)
Monoacryloxyphthalic acid esters such as acryloyloxyethylphthalic acid and 2- (meth) acryloyloxyethylhexahydrophthalic acid are exemplified. Examples of the monomer (b) having an amino group include methylaminoethyl (meth) acrylate, ethylaminoethyl (meth) acrylate, butylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate. , N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylamino (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate -Dialkylaminoalkyl (meth) acrylate and the like. Examples of the monomer (b) having a sulfonic acid group include alkyl sulfonate (meth) acrylates such as ethoxysulfonic acid (meth) acrylate and alkyl sulfonate such as sodium sulfonate (meth) acrylate. Meta)
Acrylate and the like.

Examples of the hydroxyl group-containing monomer (b) include 2-hydroxyethyl (meth) acrylate,
1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) A) acrylate and the like. Examples of the monomer (b) having a polyethyleneoxy group include polyethylene glycol mono (meth) acrylates such as methoxydiethylene glycol mono (meth) acrylate and methoxytriethylene glycol mono (meth) acrylate; (Meth) acrylate, polypropylene glycol mono (meth) acrylate such as methoxytripropylene glycol mono (meth) acrylate, alkylphenyl polyethylene glycol mono (meth) acrylate such as nonylphenoxytetraethylene glycol mono (meth) acrylate, nonylphenyltetrapropylene Examples include alkylphenyl polypropylene glycol mono (meth) acrylates such as glycol mono (meth) acrylate It is. Examples of the monomer (b) having a tetrahydrofurfuryl group include tetrahydrofurfuryl (meth) acrylate.

Depending on the required performance, one or more of these can be used in combination. Further, the one used in the polymer (A) and the one used in the polymer (B) are not necessarily required to be the same. The monomer (b) is used in the polymer (A) at a copolymerization ratio of 5 to 95% by weight, preferably 5 to 30% by weight, more preferably 7.5 to 25% by weight. In the polymer (B), 5 to 100% by weight, preferably 5 to 30% by weight,
More preferably, it is used at a copolymerization ratio of 7.5 to 25% by weight. When the value is below the lower limit, sufficient water solubility cannot be obtained, and when it acts as a crosslinking agent, sufficient coating film hardness and adhesion to a substrate cannot be obtained. On the other hand, if the upper limit is exceeded, the water resistance of the coating film decreases.

The monomer (c) having a carbon-carbon unsaturated double bond in one molecule other than (a) or (b) used in the present invention has hardness, toughness, and adhesion to a substrate. It is used for imparting various physical properties such as. In particular, in order to obtain good adhesion to the substrate and hardness of the coating film, it is necessary to crosslink the coating film after coating to form a tough coating film. When the water-soluble group of the monomer (b) having a double bond and a water-soluble functional group does not act as a cross-linking agent after coating, one molecule other than (a) or (b) contains The monomer having a crosslinkable functional group among the monomers (c) having a saturated double bond is a very important component.
Crosslinkable functionality of monomer (c) having a crosslinkable functional group among monomers (c) having a carbon-carbon unsaturated double bond in one molecule other than (a) or (b) Examples of the group include an isocyano group, an epoxy group, an N-methylol group, and an N-alkoxymethyl group. Examples of the monomer (c) having an isocyano group include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, 2-hydroxyethyl (meth) acrylate, and 4-hydroxybutyl (meth). Examples thereof include those obtained by reacting a hydroxy (meth) acrylate such as an acrylate with a polyisocyanate such as toluene diisocyanate, isophorone diisocyanate, or coronate L.

Examples of the monomer (c) having an epoxy group include glycidyl methacrylate, glycidyl cinnamate, glycidyl allyl ether, glycidyl vinyl ether, vinylcyclohexane monoepoxide, and 1,3-butadinene monoepoxide. No. Examples of the monomer (c) having an N-methylol group or an N-alkoxymethyl group include N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N-ethoxymethyl (meth) acrylamide. , N-propoxymethyl (meth) acrylamide, (meth) acrylamide having an N-monoalkoxymethyl group such as N-butoxymethyl (meth) acrylamide, N, N-dimethylol (meth) acrylamide, N, N-di (methoxy) Methyl) (meth) acrylamide, N, N-di (ethoxymethyl) (meth) acrylamide, N, N-di (propoxymethyl) (meth) acrylamide, N, N-di (butoxymethyl) (meth) acrylamide (Meth) acrylia having N, N-dialkoxymethyl group De, and the like. Examples of the monomer (c) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth).
Examples include acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polytetramethylene glycol mono (meth) acrylate.

A monomer other than (a) or (b) having a carbon-carbon unsaturated double bond in one molecule other than the monomer having a crosslinkable functional group among the monomers (c) Examples of (c) include (meth) acrylates and styrenes having a functional group other than the crosslinkable functional group. Examples of the (meth) acrylate include alkyl (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, and stearyl (meth) acrylate, and benzyl (meth) acrylate. Can be Styrenes include styrene, methyl styrene, ethyl styrene, hydroxy styrene, chlorostyrene and the like. Examples of the vinyl compound include ethylene, propylene, butene, isobutene, vinyl acetate, vinyl chloride, 1,2 dichloroethylene, isopropenyl chloride, allyl chloride, and vinylidene chloride. One of these is selected according to the required performance.
Species or a mixture of two or more species can be used. Further, the one used in the polymer (A) and the one used in the polymer (B) are not necessarily required to be the same. The monomer (c) is 0 to 90% by weight in the polymer (A),
Preferably 10 to 70% by weight, more preferably 20 to 5% by weight.
It is used at a copolymerization ratio of 0% by weight. In the polymer (B), it is 0 to 95% by weight, preferably 10 to 70% by weight.
%, More preferably 20 to 50% by weight. If the ratio is below the lower limit, sufficient coating film hardness and adhesion to the substrate cannot be obtained. On the other hand, when the ratio exceeds the upper limit, the compatibility is lowered, and a uniform and good coating film cannot be obtained.

In the present invention, various curing agents can be used as needed to crosslink the crosslinkable functional groups in the resin and form a harder coating film.
Typical curing agents include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether,
Bisepoxy compounds such as polypropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and phthalic acid diglycidyl ester; Epicoat 801, 802, 807,
815,827,828,834,815X, 815X
A1, 828EL, 828XA, 1001, 1002,
1003, 1055, 1004, 1004AF, 100
7, 1009, 1010, 1003F, 1004F, 1
005F, 1100L, 834X90, 1001B8
0,1001X70,1001X75,1001T7
5,5045B80, 5046B80, 5048B7
0,5049B70, 5050T60, 5050,50
51, 152, 154, 180S65, 180H65,
1031S, 1032H60, 604, 157S70,
Nagase Kasei Kogyo Co., Ltd., trade name Denacol EX-6
11, 612, 614, 614B, 622, 651, 6
51A, 512, 521, 411, 421, 301, 3
13, 314, 321, 201, 211, 212, 81
0, 811, 850, 851, 821, 830, 83
2, 841, 861, 911, 941, 920, 92
1,931,2000,4000,922,111,1
21, 141, 145, 146, 171, 192, 70
1,721,203,251,711,731,14
Epoxy compounds such as 7, 221, 125, 1101, 1102, and 1103;

Toluylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p -Xylene diisocyanate,
Diisocyanates such as lysine diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, or isocyanate adducts of these with glycols or diamines, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate , A polyvalent isocyanate compound such as Coronate L, a melamine-based compound having an alkylol group or an alkoxy group such as hexamethylolated melamine, hexamethoxymethylated melamine, hexabutoxymethylated melamine, cyanuric acid, ammelide, melamine, benzoguanamine, diethanolamine , Triethanolamine, diaminopyridine, benzoguanamine resin, methanol-modified melamine resin, urea resin Fat, novolak type, resol type various phenolic resins, 1,4-butanediol, 2,3
Diols such as butanediol, 1,1,1-trimethylolpropane ethylene glycol, diethylene glycol, glycerin, erythritol, arabitol, xylitol, sorbitol, dulcitol, mannitol, catechol, resorcin, hydroquinone, guaiacol, hexylresorcin, pyrogallol, trigal Hydroxybenzene, phloroglucin, polyhydric alcohols such as dimethylolphenol, or polyhydric phenolic compounds, or alkoxy-modified products thereof,

Hydrazine, hydrazine compounds such as ADH, ethylenediamine, propanediamine, butanediamine, pentanediamine, hexanediamine, diaminooctane, diaminodecane, diaminododecane, 2,
Linear diamines such as 5-dimethyl-2,5-hexamethylenediamine, polyoxypropylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, mensendiamine, isophoronediamine, bis (4-amino-3-methyl Dicyclohexyl) methane, diaminodicyclohexylmethane, 3,9
-Bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,4-bis (2-amino-2-methylpropyl) piperazine, m-
Xylenediamine, polycyclohexylpolyamine, bis (aminomethyl) bicyclo [2,2,1] heptane,
Cyclic diamines such as methylenebis (furanmethanamine) 1,6-hexamethylenediamine, polyamines such as triethylenetetramine, tetraethylenepentamine and diethylenetriamine, oxalic acid, malonic acid, succinic acid, glutaric acid, hexanedioic acid, citric acid , Maleic acid, methyl nadic acid, dodecenyl succinic acid, dicarboxylic acids such as sebacic acid, pyromellitic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and acid anhydrides thereof such as glyoxal, terephthalaldehyde and other dialdehydes, glycine, alanine and the like Amino acids and their lactams, citric acid, 12-hydroxystearic acid, 6
-Hydroxycarboxylic acids such as hydroxypentanoic acid and lactones thereof, pyrophosphoric acid, ethyl phosphite, bisphenol A-modified polyphosphoric acid, phosphorus compounds such as triphenyl phosphite, and phosphoric dichloride compounds.

Among these curing agents, when a monomer (b) having a carboxyl group is used, a phenol resin,
It is preferable to use amino resins, diamines, polyamines, isocyanate compounds, bisepoxy compounds, epoxy resins and the like. When the monomer (b) having an amino group is used, it is preferable to use an isocyanate compound, dicarboxylic acid and its anhydride, an epoxy compound and the like. When the monomer (b) having a sulfonic acid group is used, it is preferable to use an amine, an aziridine compound or the like.
When a monomer (b) having a hydroxyl group is used, amino resin, diamine, polyamine, diisocyanate,
It is preferable to use dialdehyde, bisepoxy compound, epoxy resin, phosphorus compound, phosphoric acid dichloride compound and the like. Further, a monomer (b) having a polyethyleneoxy group
When used, amino resin, diamine, polyamine,
It is preferable to use diisocyanate, dialdehyde, bisepoxy compound, epoxy resin, phosphorus compound, phosphoric acid dichloride compound and the like. When the monomer (c) having an isocyano group is used, a hydrazine compound, a diamine, a dicarboxylic acid and its anhydride, a diol, a polyhydric alcohol or a polyphenol compound, a bisepoxy compound, an epoxy resin Use of such as is preferred. When the monomer (c) having an epoxy group is used,
Dicarboxylic acids and their anhydrides, polyhydric alcohols or polyphenolic compounds, or their alkoxy modified products, amino resins, diisocyanates, polyisocyanates, amino acids and their lactams, hydroxycarboxylic acids and their lactones, diamines, polyamines, etc. The use of is preferred. When a monomer (c) having an N-methylol group or an N-alkoxymethyl group is used,
It is preferable to use a dicarboxylic acid, a melamine compound having an alkylol group or an alkoxy group, an amino resin compound, or the like. Two or more of these curing agents may be used, and the total amount thereof is 1 to 500% by weight, preferably 10 to 200% by weight, based on 100% by weight of the resin composition, depending on the use and required physical properties. More preferably, it is in the range of 10 to 100% by weight. For use as a curing agent for an aqueous coating, it is more preferable to use a curing agent having high solubility in an aqueous medium among these curing agents. However, the compound that can be used as a curing agent is not limited to a substance having high solubility in an aqueous medium, and a substance having low solubility in an aqueous medium can be used in a form of being dispersed in an aqueous medium. Further, the above-mentioned curing agent may be used after further modifying, processing, etc. for imparting solubility to an aqueous medium.

In the present invention, in order to promote a crosslinking reaction of a crosslinkable functional group in a composition or a crosslinking reaction between a crosslinkable functional group and a crosslinking agent, the composition is prepared according to each functional group. Various crosslinking catalysts can be used. Representative crosslinking catalysts include aluminum triacetylacetonate, iron triacetylacetonate, manganese tetraacetylacetonate, nickel tetraacetylacetonate, chromium hexaacetylacetonate, titanium tetraacetylacetonate, cobalt tetraacetylacetonate, and the like. Metal complex compounds, aluminum ethoxide, aluminum propoxide, aluminum butoxide, titanium ethoxide, titanium propoxide, metal alkoxides such as titanium butoxide, sodium acetate,
Tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate,
Metal salt compounds such as cobalt naphthenate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin malate dibutyltin di (2-ethylhexoate), formic acid, acetic acid, propionic acid, p-toluenesulfonic acid, trichloroacetic acid, phosphorus Acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, phosphoric acid ester of β-hydroxyethyl (meth) acrylate, monoalkyl phosphorous acid, acidic compound such as dialkyl phosphorous acid,

P-toluenesulfonic acid, phthalic anhydride,
Acids such as benzoic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, formic acid, acetic acid, itaconic acid, oxalic acid, maleic acid and their ammonium salts, lower amine salts, polyvalent metal salts, sodium hydroxide, lithium chloride, diethyl Organometallic compounds such as zinc, tetra (n-butoxy) titanium, dicyclohexylamine, triethylamine, N, N-dimethylbenzylamine,
Examples thereof include amines such as N, N ', N'-tetramethyl-1,3-butanediamine, diethanolamine, triethanolamine, and cyclohexylethylamine.

When a monomer (b) having a carboxyl group is used among these crosslinking catalysts, it is preferable to use acids and their ammonium salts, lower amine salts, polyvalent metal salts and the like. When the monomer (b) having an amino group is used, it is preferable to use an organic peroxide, an acid anhydride, a carboxylic acid, zinc-magnesium oxide, or the like. When a monomer (b) having a hydroxyl group or a monomer (b) having a polyethyleneoxy group is used, zinc nitrate or the like is preferably used. A monomer (c) having an isocyano group;
When is used, it is preferable to use amines, metal salt compounds and the like. When a monomer (c) having an epoxy group is used, it is preferable to use an organic metal compound, an amine, or the like. When a monomer (c) having an N-methylol group or an N-alkoxymethyl group is used, an acid,
And the use of ammonium salts, lower amine salts, polyvalent metal salts and the like thereof. When the monomer (c) having a hydroxyl group is used, an acidic compound, an acid and their ammonium salts, lower amine salts, polyvalent metal salts,
Use of such as is preferred. The amount of these catalysts used is 0.01 to 10% by weight, preferably 0.1 to 10% by weight, based on the total of the polymer (A) and the polymer (B), depending on the use and required physical properties.
It is in the range of 5% by weight.

Further, in the present invention, a silane coupling agent can be used as required.
Specific examples of the silane coupling agent include tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-gly Trifunctional silanes such as sildoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-morpholinopropyltrimethoxysilane, and a part of the trifunctional silane is an alkyl group or a phenyl group , A bifunctional silane substituted with a vinyl group or the like, for example, dimethyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane and the like. In addition, hydrolysates and partial condensates of these compounds can be used. The silane coupling agent is used in an amount of 1 to 40% by weight, preferably 3% by weight, based on the total of the polymer (A) and the polymer (B), depending on the use and required physical properties.
Used at a rate of ２０20% by weight.

In the present invention, aerosil can be used as needed. Aerosil is a fine powder of silica (silicon dioxide). As a typical example, for example, trade names AEROSIL50, 130, 200, 200V, 20 manufactured by Japan Aerosil Co., Ltd.
0CF, 200FAD, 300, 300CF, 380,
R972, R972V, R972CF, R974, RX
200, RY200, R202, R805, R812,
R812S, OX50, TT600, MOX80, MO
X170, COK84, trade name SYLYSIA250, 250N, 256, 25 manufactured by Fuji Silysia Chemical Ltd.
6N, 310, 320, 350, 358, 430, 43
1,440,450,470,435,445,43
6, 446, 456, 530, 540, 550, 73
0, 740, 770, etc. Aerosil is used in an amount of 10 to 200% by weight, preferably 10 to 100% by weight, more preferably 20 to 60% by weight, based on the polymers (A) and (B) of the present invention, depending on the use and required physical properties. use. If it is less than this range, the effect of improving the water repellency is small, and if it exceeds this range, the adhesion to the substrate is impaired.

In the present invention, a filler, a thixotropy-imparting agent, a coloring pigment, an extender pigment, a dye, an antioxidant, and an antioxidant may be used according to the intended use and required physical properties, as long as the effects of the present invention are not hindered. , Antistatic agents, flame retardants, thermal conductivity improvers, plasticizers, sagging agents, antifouling agents, preservatives,
Various additives such as a bactericide, an antifoaming agent, and a leveling agent may be added.

The polymer (A) and the polymer (B) are polymerized by a known method, and the aqueous coating is produced by a known method using the polymer. The polymerization method and the production method are not limited at all. Specifically, for example, when the water-soluble group of the monomer (b) having a carbon-carbon unsaturated double bond and a water-soluble group in one molecule is an ionic group, Step 1: the method according to claim 1 The polymer (A) and the polymer (B) are each polymerized in a solvent. Step 2: The polymer (A) and the polymer (A) and the polymer (B) are neutralized with a neutralizing agent containing an ion serving as a counter ion of a water-soluble group derived from the monomer (b). Each solution of the coalesced (B) is neutralized and dissolved or dispersed in an aqueous medium. Step 3: The solutions of the neutralized polymer (A) and the neutralized polymer (B) are mixed at a predetermined ratio and diluted or concentrated to adjust the concentration. Steps 1 to 3 above
If necessary, a polymer can be polymerized by a method of performing a desolvation step immediately before or immediately after Step 2 to produce an aqueous coating.

Solvents used in the solution polymerization include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether and diethylene glycol methyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, tetrahydrofuran, dioxane, and the like. Ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, hydrocarbons such as hexane, heptane and octane, aromatics such as benzene, toluene, xylene and cumene, and esters such as ethyl acetate and butyl acetate can be used. is there. The solvent may be a mixture of two or more. The charged concentration of the monomer during the synthesis is preferably from 0 to 80% by weight. As the polymerization initiator, usual peroxides or azo compounds, for example, benzoyl peroxide, azoisobutylvalenonitrile, azobisisobutyronitrile, di-t-butyl peroxide,
t-butyl perbenzoate, t-butyl peroctoate, cumene hydroxyperoxide and the like are used,
The polymerization temperature is 50-140 ° C, preferably 70-140.
° C. The preferred average molecular weight of the obtained polymer is preferably 2,000 to 1 for both the polymer (A) and the polymer (B).
00,000.

When the water-soluble group is an anionic group such as a carboxyl group or a sulfonic acid group, the neutralizing agent containing an ion serving as a counter ion of the water-soluble group derived from the monomer (b) may be a basic neutralizer. Wetting agents such as ammonia, triethylamine, N, N, -dimethylaminoethanol, 2-amino-2-methylpropanol, diethanolamine,
Ammonia such as triethanolamine, organic amines, and an aqueous solution thereof can be used. When the water-soluble group is a cationic group such as an amino group, an acidic neutralizing agent, for example, an organic acid such as formic acid or acetic acid can be used. The desolvation step performed immediately before or immediately after step 2 is performed by a known method. Specifically, for example, a method in which heating is performed at the boiling point of the solvent under normal pressure to volatilize and remove the solvent, a method in which heating is performed at the boiling point of the solvent under reduced pressure and the solvent is volatilized and removed, and the like are exemplified. The desolvation step is a step that is performed as needed, and need not always be performed.

The coating of the present invention comprises a polymer (A),
It is obtained by mixing and dissolving the polymer (B) and, if necessary, a curing agent, a curing catalyst, Aerosil, and an additive in an aqueous medium. The aqueous medium is water and a solvent containing water.Examples of the solvent include methanol, ethanol, propanol, butanol, alcohols such as ethylene glycol methyl ether and diethylene glycol methyl ether, acetone, methyl ethyl ketone, and methyl isobutyl ketone. And the like, such as ketones, esters such as tetrahydrofuran, dioxane, ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, and the like, and appropriate ones according to the composition of the resin, the solubility of the resin, and the compatibility with water. Two or more solvents may be used. There is no particular limitation on the mixing method, and usually,
The polymer solution may be mixed as it is and stirred with a stirring blade, a shaking stirrer, a rotary stirrer or the like. In order to improve coatability, an aqueous medium may be further added or concentrated. The mixing ratio of the polymer (A) and the polymer (B) is such that the fluorine-containing monomer (a) is 0.01 to 10% by weight of the total of the polymer (A) and the polymer (B); Preferably 0.
It is necessary that the content be from 0.05 to 10% by weight, more preferably from 0.1 to 5% by weight. If the amount is below the lower limit, a sufficient water repellent effect cannot be obtained. If the amount exceeds the upper limit, the solubility and compatibility are reduced, and it becomes difficult to obtain a uniform coating film, and the cost is reduced. Will also be higher.

The aqueous coating thus obtained can be used as a windshield for automobiles, rear glass, door glass, fender mirror, door mirror and glass for transportation equipment such as railways and airplanes, window glass for high-rise buildings, general window glass, enzymes Glass bottles, ampoule bottles, reagent storage bottles, etc.
Other commonly used glass products such as glass bottles and mirrors,
For plastic products, film products, metal products, concrete, ceramic products, fabrics, leather products, various processed papers, paper products used in various industrial fields such as medical related fields, food processing, industry, agriculture and general households, Water repellency,
It is applied to places where surface functions such as oil repellency, antifouling property and weather resistance are required, and is used in various applications. The application method is not particularly limited, but application can be made by dip coating, spray coating, brush coating, bar coater coating, gravure coating, or the like. Air-dry or 30-22 painted coating
By heating at 0 ° C. for several seconds to several weeks, a tough coating film can be obtained. The film thickness after coating is not limited at all, and can be freely adjusted by the non-volatile component concentration, the coating method and the like according to the application. Even with a thin film having a thickness of about 0.1 μm to several μm, a sufficient surface function can be obtained. Water repellency,
Applications requiring surface functions such as oil repellency, antifouling properties, and weather resistance include, for example, water-repellent glass, anti-fog mirrors, enzymes, non-adherent glass bottles such as reagents, antibacterial, antifungal plastics, and inkjet printers. Head, snow, anti-icing painted plate, anti-fouling aluminum sheet for kitchen, printing plate material such as offset plate without water, paint for discarded plate used in offset printing,
It can be used as a top coat agent for printed matter and other printing plate-related products, waterproof antifouling wallpaper, waterproof antifouling curtain, release paper, anti-graffiti wallpaper, anti-graffiti concrete and the like.

[0029]

EXAMPLES Next, examples of the present invention will be described more specifically. All parts in the examples are parts by weight. All the synthesis was performed under a nitrogen atmosphere. Synthesis Method of Synthesis Examples 1 to 6 (Fluorine-containing water-soluble polymer (A)
A four-necked flask equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen inlet tube was prepared, and a fluorine-containing monomer biscoat 17F was prepared.
The polymerizable monomers shown in Table 1 containing M were charged into a four-necked flask based on the mixing ratio, and the solvent was further charged as 40 parts of isopropyl alcohol and 160 parts of methyl ethyl ketone. Five parts of butyronitrile were added and a polymerization reaction was carried out for 2 hours. Then, 1 part of azobisisobutyronitrile was added and polymerization was carried out for another 2 hours to obtain a polymer solution. The polymer solution is heated under reduced pressure to remove the solvent. Then, ammonia water or formic acid in the amount shown in Table 1 and purified water were added, and the mixture was added at 50 ° C.
The mixture was heated and stirred until dissolved to obtain a polymer aqueous solution. Further, purified water was added to obtain a polymer aqueous solution of the component (A) having a nonvolatile content of 10%.

Synthesis Method of Synthesis Examples 7 to 11 (Synthesis of Non-Fluorine Water-Soluble Polymer (B)) A four-necked flask equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen inlet tube was prepared. Based on the compounding ratio shown in the above, the solvent was charged as 40 parts of isopropyl alcohol and 160 parts of methyl ethyl ketone, the temperature was raised to 80 ° C. while stirring, 5 parts of azobisisobutyronitrile was added, and the polymerization reaction was carried out for 2 hours. To the mixture was added 1 part of azobisisobutyronitrile, and the mixture was further polymerized for 2 hours to obtain a polymer solution. The amount of ammonia water or formic acid shown in Table 1 and purified water were added to this polymer solution, and the mixture was heated to 90 ° C. to remove the distilled solvent. Thereafter, purified water was added to obtain a polymer aqueous solution of the component (B) having a nonvolatile content of 25%.

COMPARATIVE SYNTHESIS EXAMPLE 12 A single polymer having the same composition as that used in Example 1 when the two fluoropolymers and the non-fluorine polymer were mixed at a ratio of 1:99. The synthesis was performed by the method described in the synthesis methods of Synthesis Examples 7 to 11 above.

[0032]

[Table 1]

Examples 1 to 6, Comparative Example 1 The polymer solutions prepared in the synthetic examples shown in Table 2 and the comparative synthetic examples were mixed based on the mixing ratios shown in Table 2, and the curing agents shown in Table 2 were obtained. , A curing catalyst, water and the like were added to form an aqueous coating. The prepared aqueous coating was applied to an aluminum plate using a bar coater, left in an oven at 100 ° C. for 1 hour, and dried to obtain a coating having a thickness of 1 μm.
Then, the contact angles of pure water and octane with the coating film were measured. In addition, the cellophane tape was peeled off, and the adhesion to the substrate was measured. Table 2 shows the test results.

Comparative Example 2 Unidyne TG-422, a fluororesin aqueous dispersion manufactured by Daikin Industries, Ltd., was applied to an aluminum plate in the same manner as in Examples 1 to 6 and Comparative Example 1, and placed in an oven at 100 ° C. Left for 1 hour. Then, the contact angles of pure water and octane with the coating film were measured. In addition, the cellophane tape was peeled off, and the adhesion to the substrate was measured. Table 2 shows the test results.

[0035]

[Table 2]

[0036]

As described above, the present invention utilizes the fact that a fluorine-containing polymer is localized on the surface of a coating film to give a polymer having a water-soluble group a water-soluble group and a fluoroalkyl group. By mixing a polymer having a group, it was possible to produce a water-soluble coating having a surface function such as high water repellency and oil repellency with a small fluorine content.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 163/00 C09D 163/00 175/04 175/04

Claims (7)

[Claims] 1. A monomer (a) having a carbon-carbon unsaturated double bond and a fluoroalkyl group in one molecule in an amount of 5 to 95% by weight, and a carbon-carbon unsaturated double bond and a water-soluble group in one molecule. A monomer (b) having 5 to 95% by weight, and a monomer (c) having a carbon-carbon unsaturated double bond in one molecule other than (a) or (b) being 0 to 90% by weight. Polymer (A)
And 5 to 100% by weight of a monomer (b) having a carbon-carbon unsaturated double bond and a water-soluble group in one molecule, and carbon-carbon unsaturated in one molecule other than (a) or (b) Polymer (B) consisting of 0 to 95% by weight of monomer (c) having a double bond
Is dissolved or dispersed in an aqueous medium. 2. The amount of the monomer (a) having a carbon-carbon unsaturated double bond and a fluoroalkyl group in one molecule is 0.1 to the total weight of the polymer (A) and the polymer (B). 01-1
The aqueous coating according to claim 1, which is 0% by weight. 3. The aqueous solution according to claim 1, wherein the water-soluble group of the monomer (b) having a carbon-carbon unsaturated double bond and a water-soluble group in one molecule is a carboxyl group. coating. 4. A monomer (b) having a carbon-carbon unsaturated double bond and a water-soluble group in one molecule, wherein the water-soluble group is an amino group, a sulfonic acid group, a hydroxyl group, a polyethyleneoxy group, and tetrahydrofurfree. 3. The aqueous coating according to claim 1, wherein the aqueous coating is at least one member selected from the group consisting of 5. The composition according to claim 1, further comprising a curing agent.
The aqueous coating according to claim 1. 6. The method according to claim 1, wherein the curing agent is at least one selected from the group consisting of an epoxy compound, an isocyanate compound, an amino resin, and a phenol resin.
An aqueous coating according to claim 5. 7. Step 1: the polymer (A) according to claim 1,
And the polymer (B) are each polymerized in a solvent. Step 2: The polymer (A) and the polymer (A) and the polymer (B) are neutralized with a neutralizing agent containing an ion serving as a counter ion of a water-soluble group derived from the monomer (b). Coalescing (B)
Is neutralized and dissolved or decomposed in an aqueous medium. Step 3: Neutralized polymer (A) and neutralized polymer (B)
Each solution is mixed at a predetermined ratio and diluted or concentrated to adjust the concentration. A method for producing an aqueous coating, comprising the above steps 1 to 3 and performing a desolvation step immediately before or immediately after step 2.