JP2011219679A - Stainproof coating agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily provide a stainproof coating agent composition for easily providing high stainproof to wall paper or the like.SOLUTION: The stainproof coating agent composition contains aqueous dispersion of the following component (1), and the following component (2). The component (1) is vinyl-urethane copolymer that has a vinyl-based polymer chain part and urethane-based polymer chain part and where the vinyl-based polymer chain part is bonded to the urethane-based polymer chain part via a connection part having bonding to silicon atoms and oxygen atoms. The component (2) is one or more types of compound selected from wax-based emulsion, silicone-based emulsion, and fluorine-based emulsion.

Description

  The present invention relates to an antifouling coating agent composition that imparts antifouling properties to wallpaper and the like.

  Conventionally, polyvinyl chloride wallpaper has often been used on the walls and ceilings of houses. The wallpaper made of polyvinyl chloride has been superior in processing characteristics, water resistance, antifouling property, workability, etc., and has been superior because it is rich in design and inexpensive. However, there are problems of sick house syndrome caused by volatilization of the phthalate plasticizer contained in the polyvinyl chloride wallpaper into the living space, and the generation of chloride compounds during combustion.

  As a method for solving the above problem, Patent Document 1 discloses that a wall covering material mainly composed of cotton fibers is not subjected to vinyl chloride resin, and a surface is provided with a concavo-convex pattern through a heated embossing roll, and the surface is repelled. A wall covering material that has been treated with water to improve antifouling property, water resistance, and wet friction resistance is disclosed. It is described that the water repellent treatment is performed by applying a silicone resin, a fluorine resin, an acrylic resin, an olefin resin, a wax or the like, but since a plurality of coating agents are applied a plurality of times, There was a problem in terms of complexity and cost.

  Patent Document 2 describes an antifouling coating agent composition for wallpaper containing an acrylic polymer, wax, and silica. However, this antifouling coating agent composition for wallpaper is not fully satisfactory in terms of antifouling properties. That is, the present condition is that the method which can provide easily enough antifouling property to wallpaper etc. is not yet found.

JP 2003-155699 A JP 2006-096796 A

  Accordingly, an object of the present invention is to provide an antifouling coating agent composition that can easily impart excellent antifouling properties to wallpaper and the like.

  As a result of intensive studies to solve the above problems, the present inventor has obtained an aqueous dispersion of a vinyl-urethane copolymer and at least one compound selected from a wax-based emulsion, a silicone-based emulsion, and a fluorine-based emulsion. It has been found that the film formed by the contained composition can exhibit an excellent antifouling effect. The present invention has been completed based on these findings.

That is, the present invention provides an antifouling coating agent composition comprising an aqueous dispersion of the following component (1) and the following component (2).
Component (1): a linkage having a vinyl polymer chain part and a urethane polymer chain part, and the vinyl polymer chain part and the urethane polymer chain part having a bond between a silicon atom and an oxygen atom Vinyl-urethane copolymer bonded via a moiety Component (2): One or more compounds selected from wax-based emulsions, silicone-based emulsions, and fluorine-based emulsions

  As said antifouling coating agent composition, it is preferable that silicon dioxide content is 20 mass parts or less with respect to 100 mass parts of component (1).

The vinyl-urethane copolymer is preferably a vinyl-urethane copolymer synthesized through the following steps (X) to (Y).
Step (X): Step of preparing an aqueous dispersion or aqueous solution of a urethane polymer (A) having a hydrolyzable silicon atom-containing group Step (Y): Urethane polymer (A) having a hydrolyzable silicon atom-containing group In an aqueous dispersion or aqueous solution of the above, the ethylenically unsaturated monomer (B) is polymerized, and one or more time points before the polymerization reaction, during the polymerization reaction, and after the polymerization reaction The step of preparing a vinyl-urethane copolymer using the compound (C) having an alkoxysilyl group and having a reactive functional group with respect to the ethylenically unsaturated bond-containing group

  As the urethane-based polymer (A) having a hydrolyzable silicon atom-containing group, a hydrophilic group-containing alkoxysilylated urethane-based polymer (A1) is preferable, and in particular, a hydrophilic group-free polyol compound (A1-a), Hydrophilic group-containing alkoxysilyl group-terminated urethane obtained by reacting hydrophilic group-containing polyol compound (A1-b), polyisocyanate compound (A1-c), and isocyanate-reactive group-containing alkoxysilane compound (A1-d) A terminal polymer is preferable, and a terminal alkoxysilylated hydrophilic group-containing urethane polymer obtained by at least partially alkoxysilylating the isocyanate group at the terminal of the hydrophilic group-containing urethane polymer is particularly preferable.

  The ethylenically unsaturated monomer (B) preferably contains an acrylic monomer.

  Moreover, it is preferable that the connection part which has the coupling | bonding of the silicon atom and oxygen atom in a vinyl type-urethane type copolymer is a silicone type polymer chain part.

  Component (2) preferably contains at least a wax-based emulsion.

  The present invention also provides an antifouling coating agent composition for wallpaper comprising the antifouling coating agent composition.

  The antifouling coating agent composition according to the present invention has a vinyl polymer chain part and a urethane polymer chain part, and the vinyl polymer chain part and the urethane polymer chain part are composed of silicon atoms and oxygen. Curing with excellent hot water resistance, water resistance, heat resistance and weather resistance, even if it is water-based because it contains a vinyl-urethane copolymer bonded through a linking part having a bond with an atom Things can be formed. In addition, excellent curing properties are exhibited upon curing. Furthermore, although the vinyl polymer chain portion and the silicone polymer chain portion have low mutual solubility, a cured product (film or the like) having excellent transparency can be formed. This has the form which the vinyl polymer chain part and the silicone polymer chain part have couple | bonded, and also has couple | bonded through the connection part which has a coupling | bonding of a silicon atom and an oxygen atom. It seems to be because.

  Moreover, the antifouling coating agent composition according to the present invention is one or more selected from a wax-based emulsion, a silicone-based emulsion, and a fluorine-based emulsion together with a vinyl-urethane copolymer having a specific structure as described above. Therefore, the hot water resistance and water resistance of the cured product obtained by curing the vinyl-urethane copolymer can be further enhanced. Therefore, a film that exhibits excellent antifouling properties can be formed by thinly applying and drying the antifouling coating agent composition according to the present invention on the surface of the adherend.

  Furthermore, the antifouling coating composition according to the present invention is applied to an adherend or the like very thinly when the silicon dioxide content is 20 parts by mass or less with respect to 100 parts by mass of the vinyl-urethane copolymer. In particular, a dense coating layer (film) that can exhibit excellent antifouling properties can be formed. Therefore, the time required for curing is short when forming the coating layer (film), and the working time can be greatly shortened. Moreover, the outstanding antifouling effect can be provided to a to-be-adhered body, maintaining the feel. Since the antifouling coating agent composition according to the present invention has the above effects, it can be suitably used as an antifouling coating agent composition for wallpaper.

[Anti-fouling coating composition]
The antifouling coating agent composition according to the present invention comprises an aqueous dispersion of the following component (1) and the following component (2).
Component (1): a linkage having a vinyl polymer chain part and a urethane polymer chain part, and the vinyl polymer chain part and the urethane polymer chain part having a bond between a silicon atom and an oxygen atom Vinyl-urethane copolymer bonded via a moiety Component (2): One or more compounds selected from wax-based emulsions, silicone-based emulsions, and fluorine-based emulsions

[Ingredient (1)]
The vinyl-urethane copolymer in the present invention has a vinyl polymer chain part and a urethane polymer chain part, and the vinyl polymer chain part and the urethane polymer chain part are composed of silicon atoms. They are bonded via a connecting portion (sometimes referred to as “Si—O bond-containing connecting portion”) having a bond with an oxygen atom (siloxane bond; Si—O bond).

The vinyl-urethane copolymer in the present invention can be synthesized, for example, through the following steps (X) to (Y).
Step (X): Step of preparing an aqueous dispersion or aqueous solution of a urethane polymer (A) having a hydrolyzable silicon atom-containing group Step (Y): Urethane polymer (A) having a hydrolyzable silicon atom-containing group In an aqueous dispersion or aqueous solution of the above, the ethylenically unsaturated monomer (B) is polymerized, and one or more time points before the polymerization reaction, during the polymerization reaction, and after the polymerization reaction And using a compound (C) having an alkoxysilyl group which is a reactive functional group for a hydrolyzable silicon atom-containing group and a reactive functional group for an ethylenically unsaturated bond-containing group, Step of preparing a copolymer

  The Si-O bond-containing connecting part in the vinyl-urethane copolymer may be a low molecular weight (or low molecular type) Si-O bond-containing connecting part as long as it has a Si-O bond. It may be a high molecular weight (or high molecular type) Si—O bond-containing connecting portion. Further, the Si—O bond-containing connecting portion (particularly, the high molecular weight Si—O bond-containing connecting portion) may have a network structure. In addition, when the Si-O bond-containing linking part is a high molecular weight Si-O bond-containing linking part (silicone polymer chain part), a plurality of urethane polymers are included in one silicone polymer chain part. The chain portion and / or a plurality of vinyl polymer chain portions may be bonded. Furthermore, conversely, a plurality of silicone polymer chain portions may be bonded to one urethane polymer chain portion or one vinyl polymer chain portion.

  The Si—O bond-containing connecting portion in the vinyl-urethane copolymer in the present invention is, among other things, high molecular weight in that it can impart flexibility to the film and improve adhesion to the adherend. The Si—O bond-containing connecting part (silicone polymer chain part) is preferred.

  The vinyl-urethane copolymer having a high molecular weight Si—O bond-containing linkage (silicone polymer chain) is, for example, an aqueous dispersion of a urethane polymer (A) having a hydrolyzable silicon atom-containing group. In the liquid or aqueous solution, after carrying out the reaction using the alkoxysilyl group in the compound (C) having an alkoxysilyl group and having a reactive functional group with respect to the ethylenically unsaturated bond-containing group, further ethylenically unsaturated In addition to polymerizing the monomer (B), a reaction using a reactive functional group for the ethylenically unsaturated bond-containing group in the compound (C) is performed, and in parallel with these reactions, an alkoxysilyl group is contained. And it can synthesize | combine by performing the hydrolysis or condensation reaction of the compound (C) which has a reactive functional group with respect to an ethylenically unsaturated bond containing group.

[Urethane polymer (A)]
The urethane polymer (A) in the present invention is a urethane polymer having a hydrolyzable silicon atom-containing group. The hydrolyzable silicon atom-containing group is preferably a hydrolyzable silyl group.

As the hydrolyzable silyl group, an alkoxysilyl group is particularly preferable, and the alkoxysilyl group preferably has 1 to 3 (preferably 2 or 3) alkoxy groups on one silicon atom. . Examples of the alkoxy group include C _1-4 alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutyloxy group, s-butyloxy group, and t-butyloxy group (particularly, methoxy Group, ethoxy group, propoxy group, particularly methoxy group and ethoxy group are preferable). When two or more alkoxy groups are contained in one silicon atom, one type of alkoxy group may be included, or two or more types may be combined.

  The urethane polymer (A) preferably has dispersibility or solubility in water. Therefore, the urethane polymer (A) preferably has a group capable of imparting dispersibility or solubility in water, and in particular, a hydrophilic group (anionic group, cationic group, nonionic property). Group) and the like.

  Therefore, as the urethane polymer (A) in the present invention, a hydrophilic group-containing alkoxysilylated urethane polymer (A1) can be suitably used.

  Examples of the hydrophilic group-containing alkoxysilylated urethane polymer (A1) include a hydrophilic group-free polyol compound (A1-a), a hydrophilic group-containing polyol compound (A1-b), and a polyisocyanate compound (A1-c). ) And an isocyanate-reactive group-containing alkoxysilane compound (A1-d).

(Hydrophilic group-free polyol compound (A1-a))
As the polyol compound (A1-a) containing no hydrophilic group, the molecule does not have a hydrophilic group (anionic group, hydrophilic group such as a cationic group or a nonionic group) in the molecule, and the molecule has The compound is not particularly limited as long as it is a compound having at least two hydroxyl groups.

  Examples of the hydrophilic group-free polyol compound (A1-a) include polyhydric alcohols, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polyacrylic polyols, and castor oil. As the hydrophilic group-free polyol compound (A1-a) in the present invention, among them, polyether polyol, polyester polyol, and polycarbonate polyol can be preferably used.

  Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol, as well as a plurality of alkylene oxides as monomer components such as an ethylene oxide-propylene oxide copolymer (alkylene oxide- Examples include other alkylene oxide) copolymers.

  Examples of the polyester polyol include a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polycarboxylic acid, and a cyclic ester. A reactant or the like can be used. Examples of the polyhydric alcohol in the condensation polymerization product of polyhydric alcohol and polycarboxylic acid include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3- Tetramethylene diol, 2-methyl-1,3-trimethylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2, 4-diethyl-1,5-pentamethylenediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol, etc.), bisphenols (bisphenol A, etc.), sugar alcohols (xyli It can be exemplified Lumpur and sorbitol), or the like. On the other hand, examples of polycarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; 1,4-cyclohexane Examples thereof include alicyclic dicarboxylic acids such as dicarboxylic acids; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid and trimellitic acid. In the ring-opening polymer of cyclic ester, examples of cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone. In the reaction product by three kinds of components, those exemplified above can be used as the polyhydric alcohol, polycarboxylic acid, and cyclic ester.

  Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymer of a cyclic carbonate (alkylene carbonate, etc.), and the like. As the polyhydric alcohol in the reaction product of polyhydric alcohol and phosgene, the polyhydric alcohols exemplified above can be used. Examples of the alkylene carbonate in the ring-opening polymer of cyclic carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. In addition, the polycarbonate polyol should just be a compound which has a carbonate bond in a molecule | numerator, and the terminal is a hydroxyl group, and may have an ester bond with a carbonate bond.

  The molecular weight of the hydrophilic group-free polyol compound (A1-a) is not particularly limited, and may be either a low molecular weight compound or a high molecular weight compound.

(Hydrophilic group-containing polyol compound (A1-b))
The hydrophilic group-containing polyol compound (A1-b) has at least one hydrophilic group (anionic group, cationic group, or nonionic group) in the molecule, and at least two in the molecule. If it is a compound which has a hydroxyl group, it will not restrict | limit in particular.

  Examples of the hydrophilic group in the hydrophilic group-containing polyol compound (A1-b) include an anionic group (for example, carboxyl group, sulfo group, etc.), a cationic group (for example, tertiary amino group (disubstituted amino group), etc.) ) And nonionic groups (for example, groups containing a polyoxyalkylene chain such as a polyoxyethylene chain, a polyoxypropylene chain, and an oxyethylene-oxypropylene copolymer chain). Among the hydrophilic groups in the present invention, anionic groups such as a carboxyl group and a sulfo group are preferable, and a carboxyl group is particularly preferable.

  From the above, the hydrophilic group-containing polyol compound (A1-b) in the present invention is preferably an anionic group-containing polyol compound in which the hydrophilic group is an anionic group, and in particular, a carboxyl group in which the hydrophilic group is a carboxyl group. A containing polyol compound is preferred.

As the carboxyl group-containing polyol compound, a low molecular weight polyol having a carboxyl group is preferable, and in particular, the following formula (3)
(HO) _a L (COOH) _b (3)
(In the formula, L represents a hydrocarbon moiety having 1 to 12 carbon atoms. A is an integer of 2 or more, and b is an integer of 1 or more.)
The polyhydroxycarboxylic acid represented by these can be used suitably.

  In the formula (3), the hydrocarbon moiety of L is preferably a linear or branched aliphatic hydrocarbon moiety. Moreover, a and b may be the same or different. Two or more hydroxyl groups may be bonded to the same carbon atom or may be bonded to different carbon atoms. Furthermore, when b is 2 or more, two or more carboxyl groups may be bonded to the same carbon atom or may be bonded to different carbon atoms.

  As the polyhydroxycarboxylic acid represented by the formula (3), dimethylolalkanoic acid (particularly 2,2-dimethylolalkanoic acid) is preferable. Examples of the dimethylol alkanoic acid include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, 2,2-dimethylolhexanoic acid, 2,2-dimethylol. Examples include methylol heptanoic acid, 2,2-dimethylol octanoic acid, 2,2-dimethylol nonanoic acid, 2,2-dimethylol decanoic acid and the like.

(Polyisocyanate compound (A1-c))
The polyisocyanate compound (A1-c) is not particularly limited as long as it is a compound having at least two isocyanate groups in the molecule, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, Examples thereof include aromatic aliphatic polyisocyanates. These can be used alone or in combination of two or more.

  Examples of the aliphatic polyisocyanate include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexa Methylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl -1,5-pentamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methyl caproate Lysine diiso Ane - and aliphatic diisocyanates such as bets like.

  Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4. '-Methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, isophorone diisocyanate And alicyclic diisocyanates such as norbornane diisocyanate.

  Examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and naphthylene. 1,4-diisocyanate, naphthylene-1,5-diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane di Isocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3, 3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl 4,4' diisocyanate - and aromatic diisocyanates such as bets like.

  Examples of the araliphatic polyisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3-bis. Aroaliphatic diisocyanates such as (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene Etc.

  Further, as the polyisocyanate compound (A1-c), the above-exemplified aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, dimer or trimer by araliphatic polyisocyanate, Reaction product or polymer (eg diphenylmethane diisocyanate dimer or trimer, reaction product of trimethylolpropane and tolylene diisocyanate, reaction product of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenyl Isocyanate, polyether polyisocyanate, polyester polyisocyanate, etc.) can also be used. In the present invention, a diisocyanate compound (for example, phenyl diisothiocyanate) can be used in combination with the polyisocyanate compound (A1-c).

  As the polyisocyanate compound (A1-c) in the present invention, among others, 1,6-hexamethylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanate methyl) cyclohexane 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, norbornane diisocyanate, and 1,3-bis (α, α-dimethylisocyanatomethyl) benzene can be suitably used. In addition, it is preferable to use an aliphatic polyisocyanate, an alicyclic polyisocyanate, or an araliphatic polyisocyanate as the polyisocyanate compound (A1-c) because a resin with less discoloration can be obtained.

(Isocyanate-reactive group-containing alkoxysilane compound (A1-d))
Isocyanate-reactive group-containing alkoxysilane compound (A1-d) is not particularly limited as long as it is a silane compound having at least one isocyanate-reactive group in the molecule and having at least one alkoxy group in the molecule. Not.

  The isocyanate-reactive group is not particularly limited as long as it is reactive to an isocyanate group. For example, a primary amino group (unsubstituted amino group), a secondary amino group (mono-substituted) Amino group), mercapto group, hydroxyl group and the like. In the present invention, a primary or secondary amino group and a mercapto group are particularly preferable. Accordingly, the isocyanate-reactive group-containing alkoxysilane compound (A1-d) in the present invention includes a primary or secondary amino group-containing alkoxysilane compound (A1-d1), a mercapto group-containing alkoxysilane compound (A1-d2). ) Is preferred.

  The primary or secondary amino group-containing alkoxysilane compound (A1-d1) has at least one primary or secondary amino group in the molecule, and at least one in the molecule. If it is a silane compound which has an alkoxy group, it will not restrict | limit in particular. The primary or secondary amino group-containing alkoxysilane (A1-d1) may contain a tertiary amino group.

  Furthermore, the primary or secondary amino group may be directly bonded to the silicon atom, but is preferably bonded via a divalent group. Examples of such a divalent group include a divalent hydrocarbon group composed only of a hydrocarbon group such as an alkylene group, an arylene group, an alkylene-arylene group, and an alkylene-arylene-alkylene group; A hydrocarbon group such as an alkylene group, an alkylene-carbonyl-oxy-alkylene group, an alkylene-oxy-carbonyl-alkylene group, an alkylene-poly (oxyalkylene) group, and other groups (oxy group, carbonyl-oxy group, etc.) Various divalent groups constituted by various combinations can be exemplified.

（式中、Ｒ¹、Ｒ²は、同一又は異なって、置換基を有していてもよいアルキル基を示し、Ｒ³、Ｒ⁴は、同一又は異なって、置換基を有していてもよいアルキレン基を示し、Ｒ⁵は置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいシクロアルキル基を示す。また、ｍは１〜３の整数である。ｍが１である場合、２個のＲ²は同一であってもよく、異なっていてもよい。ｍが２以上の整数である場合、２個以上のＲ¹Ｏ−基は同一であってもよく、異なっていてもよい）
で表される化合物を使用することが好ましい。 As the primary or secondary amino group-containing alkoxysilane compound (A1-d1) in the present invention, the following formulas (1a), (1b), (1c)

(In the formula, R ¹ and R ² are the same or different and each represents an optionally substituted alkyl group, and R ³ and R ⁴ may be the same or different and have a substituent. R ⁵ represents an aryl group that may have a substituent, an alkyl group that may have a substituent, or a cycloalkyl group that may have a substituent. m is an integer of 1 to 3. When m is 1, two R ² may be the same or different, and when m is an integer of 2 or more, 2 or more. R ¹ O— groups may be the same or different)
It is preferable to use the compound represented by these.

Examples of the alkyl group in R ¹ , R ² and R ⁵ in the above formulas (1a), (1b) and (1c) include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t -Alkyl groups having about 1 to 4 carbon atoms such as a butyl group can be mentioned. The alkylene group for R ^3, R ^4, for example, a methylene group, an ethylene group, and an alkylene group of about 1 to 3 carbon atoms such as trimethylene group. Examples of the aryl group for R ⁵ include a phenyl group, and examples of the cycloalkyl group include a cyclohexyl group.

Examples of the substituent that R ^{1 to} R ⁵ may have include, for example, an aryl group such as a phenyl group; an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; and a cycloalkyl such as a cyclohexyl group. Groups and the like. The hydrocarbon group may be further substituted with other substituents (eg, alkoxy group, aryloxy group, cycloalkyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, cycloalkyloxycarbonyl group, acyl group, amino group, etc.) You may have.

  Examples of the amino group-containing alkoxysilane having only a primary amino group as the isocyanate-reactive group represented by the formula (1a) include aminomethyltrimethoxysilane, aminomethyltriethoxysilane, and β-aminoethyl. Trimethoxysilane, β-aminoethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltri Aminoalkyltrialkoxysilanes such as butoxysilane; β-aminoethylmethyldimethoxysilane, β-aminoethylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropy It may be mentioned methyl dipropoxy silane of (aminoalkyl) alkyl dialkoxy silane or aminoalkyl dialkyl (mono) alkoxysilanes corresponding to these or the like.

  Examples of the amino group-containing alkoxysilane having a primary amino group and a secondary amino group as the isocyanate-reactive group represented by the formula (1b) include N-β (aminoethyl) -γ-amino. N- (aminoalkyl) aminoalkyltrialkoxysilane such as propyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane; N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, Examples thereof include N- (aminoalkyl) aminoalkylalkyldialkoxysilanes such as N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane.

  Examples of the amino group-containing alkoxysilane having only a secondary amino group as the isocyanate-reactive group represented by the formula (1c) include N-phenyl-β-aminoethyltrimethoxysilane, N-phenyl- N-phenyl-β-aminoethyltrialkoxysilane such as β-aminoethyltriethoxysilane; N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ -N-phenyl-γ-aminopropyltrialkoxysilane such as aminopropyltripropoxysilane, N-phenyl-γ-aminopropyltributoxysilane, and the corresponding N-phenylaminoalkyl (mono or di) alkyl (di Or mono) alkoxysilane; N-methyl-3-aminopropylto Methoxysilane, N-ethyl-3-aminopropyltrimethoxysilane, Nn-propyl-3-aminopropyltrimethoxysilane, Nn-butyl-aminomethyltrimethoxysilane, Nn-butyl-2-amino Ethyltrimethoxysilane, Nn-butyl-3-aminopropyltrimethoxysilane, Nn-butyl-3-aminopropyltriethoxysilane, Nn-butyl-3-aminopropyltripropoxysilane, etc.), Mention may be made of N-alkylaminoalkyltrialkoxysilanes such as N-alkylaminoalkyl (mono or di) alkyl (di or mono) alkoxysilanes.

  The mercapto group-containing alkoxysilane compound (A1-d2) is not particularly limited as long as it is a silane compound having at least one mercapto group in the molecule and having at least one alkoxy group in the molecule.

  Further, the mercapto group may be directly bonded to the silicon atom, but is preferably bonded via a divalent group. As such a divalent group, a primary or secondary amino group-containing alkoxysilane (A1-d1) may be bonded via a primary or secondary amino group and a silicon atom. Examples similar to those of the valent group can be given.

（式中、Ｒ¹、Ｒ²、Ｒ³、ｍは前記に同じ）
で表される化合物を使用することが好ましい。 As the mercapto group-containing alkoxysilane compound (A1-d2) in the present invention, in particular, the following formula (2a)

(Wherein R ¹ , R ² , R ³ and m are the same as above)
It is preferable to use the compound represented by these.

  Examples of the alkoxysilane having a mercapto group as the isocyanate-reactive group represented by the formula (2a) include mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, β-mercaptoethyltrimethoxysilane, and β-mercapto. Mercaptoalkyltri, such as ethyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltripropoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltributoxysilane Alkoxysilane; β-mercaptoethylmethyldimethoxysilane, β-mercaptoethylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylme Can be mentioned distearate silane, .gamma.-mercaptopropyl methyl dipropoxy silane of (mercaptoalkyl) alkyl dialkoxy silane or mercaptoalkyl dialkyl (mono) alkoxysilanes corresponding to these.

  The isocyanate-reactive group-containing alkoxysilane compound (A1-d) in the present invention is a primary or secondary amino group-containing alkoxysilane compound (A1) from the viewpoint of easy reaction, wide commercial availability, and the like. -d1) is preferred.

  Examples of the primary or secondary amino group-containing alkoxysilane compound (A1-d1) include trade names “KBM602”, “KBM6063”, “X-12-896”, “KBM576”, “X-12”. -565 "," X-12-580 "," X-12-5263 "," X-12-666 "," KBM6123 "," X-12-575 "," X-12 " -577 "," X-12-563B "," X-12-730 "," X-12-562 "," X-12-5202 "," X-12-5204 ", Commercial products such as “KBE9703” (manufactured by Shin-Etsu Chemical Co., Ltd.) may be used.

  Furthermore, the isocyanate-reactive group-containing alkoxysilane compound (A1-d) in the present invention includes a primary or secondary amino group-containing alkoxysilane compound (A1-d1) and an unsaturated carboxylic acid ester (A3). An ester-modified amino group-containing alkoxysilane (A1-d3) containing at least a secondary amino group as an isocyanate-reactive group, which is obtained by reacting the above, may be used.

  The unsaturated carboxylic acid ester (A3) is not particularly limited as long as it is a compound in which at least one (preferably all) carboxylic acid group (carboxyl group) is in the form of an ester. It may be a saturated monovalent carboxylic acid ester or an unsaturated polyvalent carboxylic acid ester.

（式中、Ｒ⁶、Ｒ⁸は、同一又は異なって、水素原子又はアルキル基を示す。Ｒ⁷はアルキル基、アリール基、シクロアルキル基から選択された基を示す。Ｒ⁹は水素原子、アルキル基、アリール基、アルコキシカルボニル基、アリールオキシカルボニル基、シクロアルキルオキシカルボニル基から選択された基を示す）
で表される化合物が好ましい。 As unsaturated carboxylic acid ester (A3) in this invention, following formula (3)

(In the formula, R ⁶ and R ⁸ are the same or different and each represents a hydrogen atom or an alkyl group. R ⁷ represents a group selected from an alkyl group, an aryl group, and a cycloalkyl group. R ⁹ represents a hydrogen atom, A group selected from an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a cycloalkyloxycarbonyl group)
The compound represented by these is preferable.

In formula (3), examples of the alkyl group for R ⁶ include alkyl groups having about 1 to 2 carbon atoms such as methyl and ethyl groups.

Examples of the alkyl group for R ⁷ include alkyl groups having about 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, isobutyl, t-butyl, hexyl, octyl, and 2-ethylhexyl groups. Examples of the aryl group for R ⁷ include a phenyl group, and examples of the cycloalkyl group for R ⁷ include a cyclohexyl group.

Examples of the alkyl group for R ⁸ include alkyl groups having about 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, isobutyl, t-butyl, and hexyl groups.

Examples of the alkyl group for R ⁹ include alkyl groups having about 1 to 2 carbon atoms such as methyl and ethyl groups. Examples of the aryl group include phenyl groups, and alkoxy groups. Examples of the alkyl group portion, aryl group portion, and cycloalkyl group portion of the carbonyl group, aryloxycarbonyl group, and cycloalkyloxycarbonyl group include the same examples as the alkyl group, aryl group, and cycloalkyl group exemplified in the above R ^7. be able to.

  Examples of the compound represented by the formula (3) include (meth) acrylic acid ester, crotonic acid ester, isocrotonic acid ester, 2-butenoic acid ester, 3-methyl-2-butenoic acid ester, and 2-pentenoic acid. In addition to esters, 2-octenoic acid esters, etc., unsaturated monovalent carboxylic acid esters such as cinnamic acid esters; maleic acid esters (mono or diesters), fumaric acid esters (mono or diesters), itaconic acid esters (mono or diesters) And esters of unsaturated divalent carboxylic acids. In the present invention, (meth) acrylic acid ester and maleic acid diester are particularly preferable.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, and (meth) acrylic. Examples include (meth) acrylic acid alkyl esters such as 2-ethylhexyl acid, dodecyl (meth) acrylate, and octadecyl (meth) acrylate. Examples of maleic acid diesters include maleic compounds such as dimethyl maleate, diethyl maleate, dibutyl maleate, dihexyl maleate, dioctyl maleate, di (2-ethylhexyl) maleate, didodecyl maleate and dioctadecyl maleate. And acid dialkyl esters.

  As the ester-modified amino group-containing alkoxysilane (A1-d3) in the present invention, the nitrogen atom of the amino group in the primary amino group-containing alkoxysilane is an unsaturated bond (carbon-carbon) of the unsaturated carboxylic acid ester (A3). Compound obtained by performing a Michael addition reaction on a double bond), the carbon atom at the β-position in the carbon-carbon double bond of the unsaturated carboxylic acid ester (A3) contains a primary amino group A compound bonded to a nitrogen atom of an amino group in alkoxysilane is preferable.

（式中、Ｒ¹〜Ｒ³、Ｒ⁶〜Ｒ⁹及びｍは前記に同じ）
で表される化合物が好ましい。 The ester-modified amino group-containing alkoxysilane (A1-d3) in which the primary amino group-containing alkoxysilane is a compound represented by the above formula (1a) includes the following formula (3a)

(Wherein R ^{1 to} R ³ , R ^{6 to} R ⁹ and m are the same as above)
The compound represented by these is preferable.

（式（3b）及び（3c）中、Ｒ¹〜Ｒ⁴、Ｒ⁶〜Ｒ⁹及びｍは前記に同じ）
で表される化合物が好ましい。 The ester-modified amino group-containing alkoxysilane (A1-d3) in which the primary amino group-containing alkoxysilane is a compound represented by the above formula (1b) includes the following formula (3b) or the following formula (3c):

(In formulas (3b) and (3c), R ^{1 to} R ⁴ , R ^{6 to} R ⁹ and m are the same as above)
The compound represented by these is preferable.

  As described above, the hydrophilic group-containing alkoxysilylated urethane polymer (A1) in the present invention includes a hydrophilic group-free polyol compound (A1-a), a hydrophilic group-containing polyol compound (A1-b), and a polyisocyanate. Compound (A1-c) is a reaction product of an isocyanate-reactive group-containing alkoxysilane (A1-d), and a hydrophilic group (especially an anion) derived from a hydrophilic group-containing polyol compound (A1-b) in the molecule ) And a urethane prepolymer having an alkoxysilyl group derived from an isocyanate-reactive group-containing alkoxysilane (A1-d) in the molecule (especially at the end of the main chain). Hydrophilic group-containing urethane obtained by the reaction of a hydrophilic group-free polyol compound (A1-a), a hydrophilic group-containing polyol compound (A1-b), and a polyisocyanate compound (A1-c) Terminal alkoxysilylation obtained by at least partially alkoxysilylating the terminal isocyanate group of the hydrophilic group-containing urethane prepolymer by reaction of the prepolymer with the isocyanate-reactive group-containing alkoxysilane (A1-d). It is preferably a hydrophilic group-containing urethane prepolymer.

  The reaction of the non-hydrophilic group-containing polyol compound (A1-a), the hydrophilic group-containing polyol compound (A1-b), and the polyisocyanate compound (A1-c) is carried out by reacting the polyol compound with the polyisocyanate compound. This can be carried out according to known or commonly used methods for preparing prepolymers. In this reaction, a polymerization catalyst can be used to promote the reaction.

  The reaction between the hydrophilic group-containing urethane prepolymer and the isocyanate-reactive group-containing alkoxysilane (A1-d) can be carried out by mixing both and heating as necessary. Due to the reaction between such a hydrophilic group-containing urethane prepolymer and an isocyanate-reactive group-containing alkoxysilane (A1-d), the isocyanate group at the end of the hydrophilic group-containing urethane prepolymer is at least partially alkoxysilylated. Thus, a terminal alkoxysilylated hydrophilic group-containing urethane prepolymer can be prepared. In this reaction, a polymerization catalyst can be used to promote the reaction.

  As the polymerization catalyst, for example, an organic tin compound, a metal complex, a basic compound such as an amine compound, an organic phosphoric acid compound, or the like can be used. Examples of the organic tin compound include dibutyltin dilaurate, dibutyltin malate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetylacetate, and dibutyltin diversate. Examples of metal complexes include titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate; carboxylic acid metal salts such as lead octylate, lead naphthenate, nickel naphthenate, and cobalt naphthenate; aluminum acetylacetate Examples thereof include metal acetylacetonate complexes such as narate complexes and vanadium acetylacetonate complexes. Furthermore, examples of basic compounds such as amine compounds include aminosilanes such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane; quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride. Linear or cyclic containing a plurality of nitrogen atoms, such as Sankyo Air Products' trade name “DABCO” series and “DABCO BL” series, 1,8-diazabicyclo [5.4.0] undec-7-ene; There may be mentioned tertiary amines or quaternary ammonium salts. Furthermore, examples of the organic phosphoric acid compound include monomethyl phosphoric acid, di-n-butyl phosphoric acid, and triphenyl phosphate.

  Hydrophilic group-containing alkoxysilylated urethane polymer (A1), hydrophilic group-free polyol compound (A1-a), hydrophilic group-containing polyol compound (A1-b), polyisocyanate compound (A1-c), isocyanate reaction The proportion of each component of the functional group-containing alkoxysilane (A1-d) is not particularly limited. For example, the polyisocyanate compound (A1-c), the hydrophilic group-free polyol compound (A1-a), and the hydrophilic group The ratio with respect to the functional group-containing polyol compound (A1-b) is that the polyisocyanate compound (A1-c) is an isocyanate group / hydrophilic group-free polyol compound (A1-a) and a hydrophilic group-containing polyol compound (A1- The hydroxyl group (NCO / OH) (equivalent ratio) in b) is larger than 1.0 and not larger than 2.0 (preferably 1.02 to 1.50, more preferably 1.05). Can be selected from a range such that 1.40). If the NCO / OH ratio is too large (for example, exceeding 2.0 (equivalent ratio)), the dispersibility tends to decrease. On the other hand, if the NCO / OH ratio is too small (for example, 1 or less (equivalent ratio)), silyl group introduction cannot be sufficiently performed, and the antifouling property tends to be lowered.

  The polyisocyanate compound (A1-c) has an isocyanate group content in the hydrophilic group-containing alkoxysilylated urethane polymer (A1) of 0.3 to 7.0% by mass (preferably 0.4 to 4.0% by mass, and more preferably 0.5 to 3.0% by mass). When the content of the isocyanate group is too large (for example, exceeding 7.0% by mass), the dispersibility tends to decrease. On the other hand, if the isocyanate group content is too small (for example, less than 0.3% by mass), the reaction time becomes very long, and further, silyl group cannot be introduced sufficiently and the antifouling property is lowered. Tend to.

  Furthermore, when the hydrophilic group is an anionic group, the hydrophilic group-containing polyol compound (A1-b) has a hydrophilic group-containing alkoxysilylated urethane polymer (A1) [that is, an anionic group-containing alkoxysilylated group. Ratio of anionic group content in the urethane-based polymer] of 0.4 meq / g or more (for example, 0.4 to 0.7 meq / g, preferably 0.4 to 0.6 meq / g). It is preferable that it is contained. When there is too much content of this anionic group, there exists a tendency for antifouling property to fall. On the other hand, if the content of the anionic group is too small (for example, less than 0.4 meq / g), the dispersion stability tends to decrease.

  The isocyanate-reactive group-containing alkoxysilane (A1-d) has a silicon atom content in the hydrophilic group-containing alkoxysilylated urethane-based polymer (A1) of, for example, 0.02 to 10% by mass (preferably 0.03 to 3% by mass, more preferably 0.05 to 2% by mass). When there is too much content of this silicon atom (for example, when it exceeds 10 mass%), there exists a tendency for stability of the obtained composition to fall. On the other hand, when the amount is too small (for example, less than 0.02% by mass), the binary or ternary copolymer is not efficiently formed, and the antifouling property tends to be lowered.

  In addition, when unsaturated carboxylic acid ester (A3) is used, the amount used is an amount in which ester-modified amino group-containing alkoxysilane (A1-d3) leaves at least one secondary amino group. Is preferred. For example, it can be selected from a range of about 0.8 to 2.0 mol with respect to 1 mol of the primary amino group in the primary amino group-containing alkoxysilane.

  For the preparation of the urethane polymer (A), a solvent may be used or may not be used. The solvent is not particularly limited, and organic solvents such as ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and pyrrolidones such as N-methylpyrrolidone can be used. Thus, when an organic solvent is used as the solvent, after preparing the urethane polymer (A), the organic solvent is removed from the reaction mixture by a known removal method (for example, a distillation method such as a vacuum distillation method). can do.

[Ethylenically unsaturated monomer (B)]
The ethylenically unsaturated monomer (B) in the present invention is not particularly limited as long as it is a monomer containing at least one ethylenically unsaturated bond-containing group in the molecule. The ethylenically unsaturated monomer (B) may be used alone or in combination of two or more.

  Examples of the ethylenically unsaturated bond-containing group include vinyl groups, 1-alkylvinyl groups such as 1-methylvinyl group (isopropenyl group), 1-ethylvinyl group, etc. (especially, vinyl group and isopropenyl group are And a vinyl group is particularly preferable.

  Examples of the ethylenically unsaturated monomer (B) in the present invention include an acrylic monomer, a carboxyl group-containing monomer, an acid anhydride group-containing monomer, a hydroxyl group-containing monomer, and an epoxy group-containing monomer. Monomer, amino group-containing monomer, cyano group-containing monomer, styrene monomer, olefin monomer, vinyl ester, vinyl ether, (meth) acrylic acid alkoxyalkyl monomer, ( N-substituted) acrylamide monomers, N-vinyl lactams, heterocyclic-containing vinyl monomers, (meth) acrylic acid alkylene glycol monomers, sulfonic acid group-containing vinyl monomers, phosphate groups It can be used by appropriately selecting from various ethylenically unsaturated monomers (polymerizable unsaturated monomers) such as vinyl-containing monomers, halogen atom-containing vinyl monomers, and polyfunctional monomers. it can. The ethylenically unsaturated monomer (B) in the present invention includes at least an acrylic monomer in that a film excellent in water resistance, heat resistance, and weather resistance can be formed. It is preferable.

  Examples of the acrylic monomer include acrylic acid esters and methacrylic acid esters [(meth) acrylic acid esters]. Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid aryl ester, and the like.

Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth ) Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylic acid Undecyl, dodecyl (meth) acrylate, tridecyl (meth) acrylate, Such as tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate ( And (meth) acrylic acid C _1-20 alkyl ester [preferably (meth) acrylic acid C _1-6 alkyl ester, more preferably (meth) acrylic acid C _1-4 alkyl ester].

  Examples of the (meth) acrylic acid cycloalkyl ester include cyclohexyl (meth) acrylate. Examples of the (meth) acrylic acid aryl ester include (meth) acrylic acid phenyl ester.

  As the ethylenically unsaturated monomer (B) in the present invention, together with the above acrylic monomer, an ethylenically unsaturated monomer that can be copolymerized with the acrylic monomer (copolymerizable unsaturated monomer) Body). As such a copolymerizable unsaturated monomer, a known or commonly used copolymerizable unsaturated monomer can be used. Examples of the copolymerizable unsaturated monomer include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and carboxyl groups such as carboxyalkyl (meth) acrylate (carboxyethyl acrylate, etc.) Monomer; Monomer, anhydride, etc. Acid anhydride group-containing monomer; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylic Hydroxyl group-containing monomers such as hydroxyhexyl acid and hydroxyoctyl (meth) acrylate; Epoxy group-containing monomers such as glycidyl (meth) acrylate; Aminoethyl (meth) acrylate, N (meth) acrylic acid, Amino groups such as N-dimethylaminoethyl and t-butylaminoethyl (meth) acrylate Monomers; Cyano group-containing monomers such as acrylonitrile and methacrylonitrile; Styrene monomers such as styrene and α-methylstyrene; Olefin monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; Vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether; (meth) acrylic acid such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Alkoxyalkyl monomers; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide and the like ( N-substituted) acrylamide monomers; N-vinylcarboxylic amides; N-vinyllactams such as N-vinylcaprolactam; N-vinylpyridine, N-vinylpyrimidine, N-vinylpyrazine, N-vinylpyrrole, Heterocycle-containing vinyl monomers such as N-vinylimidazole, N-vinylpyrrolidone, N- (1-methylvinyl) pyrrolidone, N-vinylpiperidone, N-vinylpiperazine, N-vinyloxazole, N-vinylmorpholine; (Meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid methoxypolypropylene glycol and other (meth) acrylic acid alkylene glycol monomers; styrene sulfonic acid, Allylsulfonic acid Sulfonic acid group-containing vinyl monomers; 2-phosphoric acid group-containing vinyl monomers such as hydroxyethyl acryloyl phosphate; and a halogen atom-containing vinyl monomer such as vinyl chloride. These can be used alone or in combination of two or more.

  Examples of the copolymerizable unsaturated monomer include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, divinylbenzene, Various polyfunctional monomers such as butyl di (meth) acrylate and hexyl di (meth) acrylate can be appropriately selected and used. These can be used alone or in combination of two or more.

[Compound (C)]
The compound (C) has at least one reactive functional group for the ethylenically unsaturated bond-containing group (sometimes referred to as “unsaturated bond reactive group”) in the molecule, and hydrolyzable silicon. A compound having at least one alkoxysilyl group in the molecule as a reactive functional group for the atom-containing group is preferred. A compound (C) can be used individually or in combination of 2 or more types.

  The unsaturated bond reactive group in the compound (C) is not particularly limited as long as it is a functional group reactive to a group containing an ethylenically unsaturated bond. For example, an ethylenically unsaturated bond Examples thereof include a containing group and a mercapto group.

  The ethylenically unsaturated bond-containing group as the unsaturated bond-reactive group is not particularly limited as long as it is a group containing an ethylenically unsaturated bond. For example, a vinyl group or a 1-methylvinyl group ( Isopropenyl group), 1-alkylvinyl groups such as 1-ethylvinyl group, and the like, and vinyl groups and isopropenyl groups (particularly vinyl groups) are preferable.

As the alkoxy group in the alkoxysilyl group, for example, C _1-4 alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutyloxy group, s-butyloxy group, t-butyloxy group and the like are preferable. In particular, a methoxy group, an ethoxy group, and a propoxy group (in particular, a methoxy group and an ethoxy group) are preferable.

  Such an alkoxy group is usually preferably bonded to 1 to 3 (preferably 2 or 3) to one silicon atom, and in the case of having 2 or more alkoxy groups, You may have and it may have in combination of 2 or more types.

  Specific examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a tripropoxysilyl group, a triisopropoxysilyl group, a tributoxysilyl group, a triisobutoxysilyl group, a tris-butoxysilyl group, Trialkoxysilyl groups such as tri-t-butoxysilyl group; methyldimethoxysilyl group, methyldiethoxysilyl group, methyldipropoxysilyl group, methyldibutoxysilyl group, ethyldimethoxysilyl group, ethyldiethoxysilyl group, ethyldipropoxy group Alkyl dialkoxysilyl groups such as silyl group, ethyldibutoxysilyl group, propyldimethoxysilyl group, propyldiethoxysilyl group, propyldipropoxysilyl group, propyldibutoxysilyl group, and dialkyl (mono) alkoxysilanes corresponding to these It can be exemplified Le group. Further, dialkoxysilyl groups and alkoxysilyl groups corresponding to those in which the alkyl group of these alkyl dialkoxysilyl groups or dialkyl (mono) alkoxysilyl groups are hydrogen atoms can be mentioned. Furthermore, the trialkoxysilyl group, alkyl dialkoxysilyl group or dialkyl (mono) alkoxysilyl group is hydrolyzed, and a hydroxyl group-containing silyl group corresponding to one in which at least one alkoxyl group is a hydroxyl group, etc. Can be mentioned.

  Examples of the compound (C) in the present invention include compounds in which the unsaturated bond-reactive group and the alkoxysilyl group are bonded with or without a divalent organic group. Examples of the divalent organic group include a divalent hydrocarbon group composed only of a hydrocarbon group such as an alkylene group, an arylene group, an alkylene-arylene group, and an alkylene-arylene-alkylene group; Groups and other divalent groups [eg, oxy, carbonyl, carbonyl-oxy, oxy-carbonyl, oxy-carbonyl-oxy, thiooxy, thiocarbonyl, thiocarbonyl-oxy, carbonyl-thiooxy Group, oxy-thiocarbonyl-oxy group, thiooxy-carbonyl-thiooxy group, amide bond-containing group (such as -NHCO- group and -CONH- group), imide bond-containing group (-CONHCO- group), urethane bond-containing group ( -NHCOO-group, -OCONH- group, etc.), urea bond-containing group (-NHCONH-group; urea bond-containing) Various divalent organic groups (eg, alkylene-oxy-alkylene group, alkylene-carbonyl-oxy-alkylene group, alkylene-oxy-carbonyl-alkylene group, oxy- Alkylene group, carbonyl-oxy-alkylene group, oxy-carbonyl-alkylene group, oxy-arylene group, carbonyl-oxy-arylene group, oxy-carbonyl-arylene group, alkylene-oxy-carbonyl-arylene-carbonyl-oxy-alkylene group Etc.).

  As a specific example of the compound (C) when the unsaturated bond reactive group in the present invention is an ethylenically unsaturated bond-containing group (particularly a vinyl group), a vinyl group is directly bonded to a silicon atom in an alkoxysilyl group. For example, vinyl trialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane; vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, Vinylmethyldipropoxysilane, vinylmethyldiisopropoxysilane, vinylmethyldibutoxysilane, vinylethyldimethoxysilane, vinylethyldiethoxysilane, vinylethyldipropoxysilane, vinylethyldiisopropoxysilane, vinylethyldi (Vinyl) alkyldialkoxysilanes such as toxisilane, vinylpropyldimethoxysilane, vinylpropyldiethoxysilane, vinylpropyldipropoxysilane, vinylpropyldiisopropoxysilane, vinylpropyldibutoxysilane, and the corresponding (vinyl) dialkyl (Mono) alkoxysilane and the like can be mentioned.

  In addition, when the vinyl group is bonded to the silicon atom in the alkoxysilyl group via an alkylene group, vinylmethyltrimethoxysilane, vinylmethyltriethoxysilane, β-vinylethyltrimethoxysilane, β-vinylethyltriethoxy Silane, β-vinylethyltripropoxysilane, β-vinylethyltriisopropoxysilane, β-vinylethyltributoxysilane, γ-vinylpropyltrimethoxysilane, γ-vinylpropyltriethoxysilane, γ-vinylpropyltripropoxysilane , Γ-vinylpropyltriisopropoxysilane, vinylalkyltrialkoxysilane such as γ-vinylpropyltributoxysilane; β-vinylethylmethyldimethoxysilane, β-vinylethylmethyldiethoxysilane, γ-vinylpro Rumethyldimethoxysilane, γ-vinylpropylmethyldiethoxysilane, γ-vinylpropylmethyldipropoxysilane, γ-vinylpropylmethyldiisopropoxysilane, γ-vinylpropylmethyldibutoxysilane, γ-vinylpropylethyldimethoxysilane, (vinylalkyl) alkyl dialkoxysilanes such as γ-vinylpropylethyldiethoxysilane, γ-vinylpropylethyldipropoxysilane, γ-vinylpropylethyldiisopropoxysilane, γ-vinylpropylethyldibutoxysilane, and the like The corresponding (vinylalkyl) dialkyl (mono) alkoxysilane and the like can be mentioned.

  Furthermore, when the vinyl group is bonded to the silicon atom in the alkoxysilyl group via a carbonyloxyalkylene group, (meth) acryloyloxymethyl-trimethoxysilane, (meth) acryloyloxymethyl-triethoxysilane, 2 -(Meth) acryloyloxyethyl-trimethoxysilane, 2- (meth) acryloyloxyethyl-triethoxysilane, 2- (meth) acryloyloxyethyl-tripropoxysilane, 2- (meth) acryloyloxyethyl-triisopropoxy Sisilane, 2- (meth) acryloyloxyethyl-tributoxysilane, 3- (meth) acryloyloxypropyl-trimethoxysilane, 3- (meth) acryloyloxypropyl-triethoxysilane, 3- (meth) acryloyl (Meth) acryloyloxyalkyl-trialkoxysilane such as oxypropyl-tripropoxysilane, 3- (meth) acryloyloxypropyl-triisopropoxysilane, 3- (meth) acryloyloxypropyl-tributoxysilane; (meth) acryloyl Oxymethyl-methyldimethoxysilane, (meth) acryloyloxymethyl-methyldiethoxysilane, 2- (meth) acryloyloxyethyl-methyldimethoxysilane, 2- (meth) acryloyloxyethyl-methyldiethoxysilane, 2- (meta ) Acryloyloxyethyl-methyldipropoxysilane, 2- (meth) acryloyloxyethyl-methyldiisopropoxysilane, 2- (meth) acryloyloxyethyl-methyldibutoxysilane, 3- ( T) Acryloyloxypropyl-methyldimethoxysilane, 3- (meth) acryloyloxypropyl-methyldiethoxysilane, 3- (meth) acryloyloxypropyl-methyldipropoxysilane, 3- (meth) acryloyloxypropyl-methyldiiso Propoxysilane, 3- (meth) acryloyloxypropyl-methyldibutoxysilane, 3- (meth) acryloyloxypropyl-ethyldimethoxysilane, 3- (meth) acryloyloxypropyl-ethyldiethoxysilane, 3- (meth) acryloyl Oxypropyl-ethyldipropoxysilane, 3- (meth) acryloyloxypropyl-ethyldiisopropoxysilane, 3- (meth) acryloyloxypropyl-ethyldibutoxysilane, 3- (meth) acrylic Royloxypropyl-propyldimethoxysilane, 3- (meth) acryloyloxypropyl-propyldiethoxysilane, 3- (meth) acryloyloxypropyl-propyldipropoxysilane, 3- (meth) acryloyloxypropyl-propyldiisopropoxysilane , (Meth) acryloyloxyalkyl-alkyldialkoxysilanes such as 3- (meth) acryloyloxypropyl-propyldibutoxysilane, and (meth) acryloyloxyalkyl-dialkyl (mono) alkoxysilanes corresponding to these Can do.

  Specific examples of the compound (C) when the unsaturated bond reactive group is a mercapto group include mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, β-mercaptoethyltrimethoxysilane, β-mercaptoethyltri Ethoxysilane, β-mercaptoethyltripropoxysilane, β-mercaptoethyltriisopropoxysilane, β-mercaptoethyltributoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltripropoxy Mercaptoalkyltrialkoxysilanes such as silane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltributoxysilane; β-mercaptoethylmethyldimethoxysilane, β-merca Toethylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropylmethyldipropoxysilane, γ-mercaptopropylmethyldiisopropoxysilane, γ-mercaptopropylmethyldibutoxy (Mercapto, such as silane, γ-mercaptopropylethyldimethoxysilane, γ-mercaptopropylethyldiethoxysilane, γ-mercaptopropylethyldipropoxysilane, γ-mercaptopropylethyldiisopropoxysilane, γ-mercaptopropylethyldibutoxysilane, etc. Alkyl) alkyldialkoxysilanes and (mercaptoalkyl) dialkyl (mono) alkoxysilanes corresponding to these.

  In the vinyl-urethane-based copolymer, the proportion of each component of the urethane-based polymer (A), the ethylenically unsaturated monomer (B), and the compound (C) is not particularly limited. For example, the ratio of the urethane polymer (A) to the compound (C) is the hydrolyzable silicon atom-containing group in the urethane polymer (A) / alkoxy in the compound (C). It can be selected from a range in which the silyl group (equivalent ratio) is greater than 0.01 and 20 or less (preferably 0.05 to 10). When the hydrolyzable silicon atom-containing group / alkoxysilyl group is 0.01 or less, the stability of the system tends to decrease due to condensation between the alkoxysilyl groups derived from the compound (C). On the other hand, when the hydrolyzable silicon atom-containing group / alkoxysilyl group exceeds 20, a copolymer is not efficiently formed, and the expected antifouling effect tends to be difficult to obtain.

  The ratio of the ethylenically unsaturated monomer (B) to the compound (C) is as follows: ethylenically unsaturated bond in the ethylenically unsaturated monomer (B) / unsaturated bond reaction in the compound (C) The functional group (C = C unsaturated group / C = C unsaturated reactive group) (equivalent ratio) is 0.2 to 2500 (preferably 0.6 to 500, more preferably 1 to 100). You can choose from a range. When the C = C unsaturated group / C = C unsaturated reactive group is less than 0.2, the stability of the system tends to decrease due to condensation of hydrolyzable silicon atoms derived from the compound (C). On the other hand, when the C═C unsaturated group / C═C unsaturated reactive group exceeds 2500, a copolymer is not efficiently formed and the expected antifouling effect tends to be hardly obtained.

[Component (2)]
Component (2) is one or more compounds selected from wax-based emulsions, silicone-based emulsions, and fluorine-based emulsions, and these can be used alone or in combination of two or more.

  The wax emulsion in the present invention may be at least an aqueous dispersion of a compound having releasability and / or water repellency. Examples of such wax-based emulsions include trade names “AQUACER 498”, “AQUACER 537”, “AQUACER 539”, “CERAFLOUR 990”, “CERAFLOUR 991,” “CERAFLOUR 996”, “CERAFLOUR 997”, “CERAFLOUR 998”. "(Above, Big Chemie Japan Co., Ltd.) etc. may be used. These can be used alone or in combination of two or more.

  The silicone emulsion in the present invention may be at least an aqueous dispersion of a compound having releasability and / or water repellency. Examples of such silicone emulsion include trade names “KM-780”, “KM-782”, “KM-785”, “KM-797” (above, manufactured by Shin-Etsu Chemical Co., Ltd.), “BY 22 Commercial products such as “-736EX” and “BY 22-749SR” (manufactured by Toray Dow Corning Co., Ltd.) may be used. These can be used alone or in combination of two or more.

  The fluorinated emulsion in the present invention may be at least an aqueous dispersion of a compound having releasability and / or water repellency. Examples of such fluorinated emulsions include the product names “Asahi Guard AG-7105”, “Asahi Guard AG-950”, “Asahi Guard AG-7600”, “Asahi Guard AG-1100” (above, Asahi Glass Co., Ltd.) ), “Unidyne TG-5521”, “Unidyne TG-5601”, “Unidyne TG-8711”, “Unidyne TG-470B”, “Unidyne TG-500S”, “Unidyne TG-580”, “Unidyne TG-581” Commercially available products such as “Daikin Industries, Ltd.” may be used. These can be used alone or in combination of two or more.

  The component (2) in the present invention preferably contains at least a wax-based emulsion, and in particular, a combination of a wax-based emulsion and a silicone-based emulsion can exhibit a more excellent antifouling effect. Furthermore, it is preferable in that it can exhibit blocking resistance.

  When a combination of a wax-based emulsion and a silicone-based emulsion is used as the component (2), the mixing ratio [the former: the latter (mass% ratio)] is, for example, 10/90 to 90/10, preferably 20/80. About 80/20. By adjusting the mixing ratio to the above range, an extremely high antifouling effect can be imparted.

  The antifouling coating agent composition according to the present invention is characterized by containing the component (1) and the component (2). Moreover, the antifouling coating agent composition according to the present invention preferably has a silicon dioxide content of 20 parts by mass or less (preferably 15 parts by mass or less) with respect to 100 parts by mass of the component (1). As a result, the antifouling property can be further improved, and an excellent antifouling effect can be exhibited even with a very thin film for a film obtained by applying and drying on the adherend surface and the like. This is because the amount of application to the adherend surface can be reduced and the cost can be reduced. Further, the time required for curing is short when forming the film, and the working time can be greatly shortened. The lower limit of the silicon dioxide content is zero. If the silicon dioxide content exceeds the above range, the antifouling effect tends to decrease because the film formed by the component (1) is likely to crack or because of the adsorption action by silicon dioxide.

  The antifouling coating agent composition according to the present invention can be prepared, for example, by mixing the component (1) and the component (2) in a solvent or dispersion medium, and the order of mixing is not particularly limited.

  Component (1) in the antifouling coating agent composition: The content of the vinyl-urethane copolymer can be appropriately adjusted depending on the use of the antifouling coating agent composition. For example, the antifouling coating agent composition It is about 10 to 60% by mass, preferably about 20 to 50% by mass of the total amount of the object. When content of a vinyl type-urethane type copolymer is less than the said range, there exists a tendency for the adhesiveness with respect to a to-be-adhered body to fall, and there exists a tendency for an antifouling effect to fall. On the other hand, if the content of the vinyl-urethane copolymer exceeds the above range, the antifouling effect tends to decrease, the viscosity becomes too high, and the coating tends to be difficult.

  The total content of component (2) in the antifouling coating agent composition can be appropriately adjusted depending on the use of the antifouling coating agent composition. For example, 0.5 to 50 of the total amount of the antifouling coating agent composition About 1% by mass, preferably about 1-50% by mass. When the amount of the component (2) used is less than the above range, the antifouling effect tends to be reduced. On the other hand, when the amount of the component (2) used exceeds the above range, the adhesion to the adherend tends to be reduced. There is.

  The solvent or dispersion medium for mixing component (1) and component (2) is not particularly limited as long as it is compatible with component (1) and component (2). For example, water or an organic solvent However, it is preferable to use water that does not cause the sick house syndrome or the like. As water, ion-exchange water (deionized water), pure water, or the like can be used.

  As content of a solvent or a dispersion medium, it can adjust suitably by the use of an antifouling coating agent composition, for example, about 90-40 mass% of the antifouling coating agent composition whole quantity, Preferably it is 80-50 mass%. Degree. If the content of the solvent or dispersion medium is below the above range, the viscosity tends to be too high and coating tends to be difficult. On the other hand, if the content of the solvent or dispersion medium exceeds the above range, it takes time to dry. After that, work efficiency tends to decrease.

  Furthermore, you may add another component to the antifouling coating agent composition which concerns on this invention in the range which does not impair the effect of this invention other than the said component. Examples of other components include fillers, plasticizers, anti-aging agents, ultraviolet absorbers, antioxidants, heat stabilizers, colorants (pigments and dyes), fungicides, wetting accelerators, viscosity improvers. , Fragrances, various tackifiers (emulsion tackifiers, etc.), coupling agents (titanate coupling agents, aluminum coupling agents, etc.), photocuring catalysts, emulsifiers, surfactants, emulsions, latexes, crosslinking agents, etc. An additive etc. can be mentioned.

  Examples of the filler include calcium carbonate, calcium carbonate subjected to various treatments, clay, talc, various balloons, kaolin, and aluminum silicate. Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate and dibutyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate. Examples of the tackifier include emulsion tackifiers such as stabilized rosin ester, polymerized rosin ester, terpene phenol, and petroleum resin. Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, a carbodiimide crosslinking agent, an aziridine crosslinking agent, a polyethyleneimine crosslinking agent, a melamine crosslinking agent, and colloidal silica.

  The antifouling coating agent composition of the present invention can be applied to the surface of an adherend by a method such as spraying, brushing, roller, or gravure printing. After coating on the surface of the adherend, a film exhibiting an excellent antifouling effect (particularly, an excellent antifouling effect against aqueous stains) can be formed by evaporating the solvent or the dispersion medium.

The coating amount of the antifouling coating composition according to the present invention, can be adjusted appropriately depending on the application, for example, about 1 to 100 g / m ² (preferably, about 5 to 100 g / m ²⁾ of Even with the coating amount, excellent antifouling properties can be imparted to the adherend.

  The film formed by the above method can exhibit an extremely high antifouling effect. Furthermore, since it has a softness | flexibility, it can exhibit the outstanding adhesiveness with respect to a wide base material. Examples of the substrate include various plastic materials [for example, α-olefin such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) and the like as a monomer component. Olefin-based resins; Polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT); Polyvinyl chloride (PVC); Vinyl acetate-based resins; Polyphenylene sulfide (PPS); Amide resins such as polyamide (nylon) and wholly aromatic polyamide (aramid); polyimide resins; polyetheretherketone (PEEK) etc.], rubber materials (for example, natural rubber, synthetic rubber, silicon rubber, etc.), metal materials (For example, aluminum, copper, , Stainless steel, etc.), paper materials (eg, paper, paper-like substances, etc.), wood materials (eg, wood, wood boards such as MDF, plywood, etc.), fiber materials (eg, non-woven fabric, woven fabric, etc.), leather materials, Examples include various materials such as inorganic materials (for example, stone, concrete, etc.), glass materials, porcelain materials, and the like.

  The antifouling coating agent composition according to the present invention is particularly useful for wallpaper, for textile materials such as curtains and tablecloths, for tiles, etc. (particularly for wallpaper).

[Anti-fouling coating composition for wallpaper]
The antifouling coating agent composition for wallpaper according to the present invention comprises the antifouling coating agent composition. Moreover, you may contain many components (For example, a swelling agent, a viscosity modifier, antiseptic | preservative, an antifoamer, etc.) within the range which does not impair performance.

  The material of the wallpaper to which the antifouling coating agent composition for wallpaper is applied is not particularly limited, and various materials mentioned as the base material can be used. Moreover, these raw materials can be used individually or in combination of 2 or more types.

  The antifouling coating agent composition for wallpaper according to the present invention can impart excellent antifouling properties (especially, antifouling properties against aqueous stains) to wallpaper by applying to the wallpaper surface and drying. . When drying, it may be heated or not. Moreover, it may be applied to wallpaper that has been previously embossed, etc., and after applying the antifouling coating agent composition for wallpaper according to the present invention to the wallpaper surface, heat treatment (for example, heating at a temperature of about 120 to 250 ° C.) Embossing by foaming the wallpaper substrate.

  The wallpaper whose surface is coated with the antifouling coating agent composition for wallpaper according to the present invention can exhibit an excellent antifouling effect, and can be easily and cleanly soiled by wiping with water even if dirt is attached. Can be dropped. Further, the antifouling effect of the wallpaper is not lowered by wiping with water, and a high antifouling effect can be maintained for a long time.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples. Hereinafter, unless otherwise specified, “part” means “part by mass”.

Preparation Example 1
N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane is mixed at a ratio of 2 mol of 2-ethylhexyl acrylate to 1 mol, and reacted at 50 ° C. for 7 days to give an ester-modified amino group-containing alkoxysilane. Obtained.

Preparation Example 2
To a four-necked separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser, a trade name “PTMG2000” [polytetramethylene ether glycol, number average molecular weight: 2000, hydroxyl value: 56.1 mg-KOH / g Mitsubishi Chemical Industries, Ltd.] 150 parts, isophorone diisocyanate [isocyanate content (NCO content): 37.8%] 83.2 parts, 2,2-dimethylolbutanoic acid 25 parts, 1,4-butane 6 parts of diol and 160 parts of methyl methacrylate were mixed, reacted at a temperature of 75 to 80 ° C. under a nitrogen stream for 3 hours, and a reaction mixture containing a carboxyl group-containing isocyanate group-terminated polymer having a residual isocyanate group of 1.2% was obtained. Obtained.
74.3 parts of the ester-modified amino group-containing alkoxysilane obtained in Preparation Example 1 was mixed and mixed with the total reaction mixture of the carboxyl group-containing isocyanate group-terminated polymer, and then a nitrogen stream at a temperature of 75 to 80 ° C. The reaction was continued for 1 hour to obtain a reaction mixture containing a carboxyl group-containing alkoxysilylated urethane polymer.
Next, after neutralizing the carboxyl group of the reaction mixture containing the carboxyl group-containing alkoxysilylated urethane polymer with 17 parts of triethylamine, the mixture was cooled to 40 ° C., and 1200 parts of deionized water was blended under high-speed stirring. A dispersion of a modified urethane polymer (active ingredient: 30% by weight) was obtained.

Preparation Example 3
80 parts of butyl acrylate (BA), 140 parts of butyl methacrylate (BMA), 140 parts of methyl methacrylate (MMA) and 10 parts of γ-methacryloxypropyltrimethoxysilane were weighed and used as an emulsifier under the trade name “ADEKA rear soap” SR-10 "(manufactured by ADEKA Corporation) was used for emulsification in 250 parts of water to obtain a monomer emulsion.
In a four-necked separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, 200 parts of the hydrolyzable silylated urethane polymer dispersion obtained in Preparation Example 2, γ-methacryloxypropyl 15 parts of trimethoxysilane and 300 parts of water were charged, the temperature was raised to 40 ° C. while stirring in a nitrogen atmosphere, and the reaction was continued for 1 hour while maintaining the same temperature to obtain a silicone-urethane copolymer.
Next, after raising the liquid temperature of the separable flask to 80 ° C., the above-mentioned monomer emulsion and 2,2′-azobis (2,4-dimethylvaleronitrile) (trade name “ABN-” as a polymerization initiator are used. V ”(manufactured by Nippon Finechem Co., Ltd.) 2 parts continuously from separate inlets over 2 hours, and an aqueous dispersion of vinyl-silicone-urethane copolymer (final active ingredient: 39. 7% by weight) was obtained.

Preparation Example 4
80 parts of butyl acrylate (BA), 140 parts of butyl methacrylate (BMA), 140 parts of methyl methacrylate (MMA) and 10 parts of γ-methacryloxypropyltrimethoxysilane were weighed and used as an emulsifier under the trade name “ADEKA rear soap” SR-10 "(manufactured by ADEKA Corporation) was used for emulsification in 250 parts of water to obtain a monomer emulsion.
In a four-necked separable flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, 200 parts of the hydrolyzable silylated urethane polymer dispersion obtained in Preparation Example 2, γ-methacryloxypropyl 15 parts of trimethoxysilane and 300 parts of water were charged, the temperature was raised to 40 ° C. while stirring in a nitrogen atmosphere, and the reaction was continued for 1 hour while maintaining the same temperature to obtain a silicone-urethane copolymer.
Next, after raising the liquid temperature of the separable flask to 80 ° C., the above-mentioned monomer emulsion and 2,2′-azobis (2,4-dimethylvaleronitrile) (trade name “ABN-” as a polymerization initiator are used. 2 parts of “V” (manufactured by Nippon Finechem Co., Ltd.) are continuously dropped from separate inlets over 2 hours, followed by reaction of 150 parts of colloidal silica (trade name “Adelite AT50”, manufactured by ADEKA Corporation). An aqueous dispersion of “organic-inorganic hybrid material” in which an acrylic-silicone-urethane copolymer and silica are hybridized (final active ingredient: 43.4% by weight, acrylic-silicone-urethane copolymer) Silica content to the polymer: 14.1% by weight).

Example 1
100 parts of an acrylic-silicone-urethane copolymer aqueous dispersion obtained in Preparation Example 3 (39.7 parts as component (1)), silicone emulsion (trade name “KM780”, Shin-Etsu Chemical ( 3 parts) and 10 parts of a wax-based emulsion (trade name “AQUACER 498”, Big Chemie Japan Co., Ltd.) are mixed to obtain an antifouling coating composition (1) (component (1) content: 35. 1% by weight) was obtained.

Example 2
In place of the acrylic-silicone-urethane copolymer aqueous dispersion obtained in Preparation Example 3, 100 parts of the “organic-inorganic hybrid material” aqueous dispersion obtained in Preparation Example 4 (component (1)) The antifouling coating agent composition (2) (component (1) content: 38.4% by weight) was obtained in the same manner as in Example 1 except that 43.4 parts as) was used.

Comparative Example 1
Instead of the acrylic-silicone-urethane copolymer aqueous dispersion obtained in Preparation Example 3, 100 parts of the trade name “Bond CC200” (acrylic resin-based wallpaper water-repellent coating agent, manufactured by Konishi Co., Ltd.) An antifouling coating agent composition (3) was obtained in the same manner as in Example 1 except that (50 parts of acrylic resin) was used.

Comparative Example 2
Example 1 except that a silicone emulsion (trade name “KM780”, manufactured by Shin-Etsu Chemical Co., Ltd.) and a wax emulsion (trade name “AQUACER 498”, BYK Chemie Japan Co., Ltd.) were not used. Thus, an antifouling coating agent composition (4) was obtained.

Comparative Example 3
Except that the silicone emulsion (trade name “KM780”, manufactured by Shin-Etsu Chemical Co., Ltd.) and the wax emulsion (trade name “AQUACER 498”, Big Chemie Japan Co., Ltd.) were not used, the same procedure as in Example 2 was performed. Thus, an antifouling coating agent composition (5) was obtained.

The antifouling properties of the antifouling coating agent compositions (1) to (5) obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were evaluated by the following methods.
<Test method>
Bar coater with paper (trade name “Calligraphy Hanshin No.5”, manufactured by Kuretake Co., Ltd.) and antifouling coating agent compositions (1) to (5) so that the weight of paper after drying becomes 3 g / m ² respectively. And then dried at 170 ° C. for 30 seconds to obtain a test specimen.
<Anti-fouling test>
A solution obtained by immersing Lipton black tea 1 pack (tea leaf: 2 g) in 100 g of hot water for 10 minutes on the obtained test specimen was hung on one side, and allowed to stand at 23 ° C. and 50% RH for 1 hour, Thereafter, moisture on the surface of the test specimen was completely wiped off with a wet paper wipe (trade name “Kimwipe (registered trademark)”, manufactured by Nippon Paper Crecia Co., Ltd.), and a color difference meter (trade name “CR-310”, The color difference before and after the antifouling test was measured using Minolta Co., Ltd.

The above results are summarized in the following table.

Claims (10)

An antifouling coating agent composition comprising an aqueous dispersion of the following component (1) and the following component (2).
Component (1): a linkage having a vinyl polymer chain part and a urethane polymer chain part, and the vinyl polymer chain part and the urethane polymer chain part having a bond between a silicon atom and an oxygen atom Vinyl-urethane copolymer bonded via a moiety Component (2): One or more compounds selected from wax-based emulsions, silicone-based emulsions, and fluorine-based emulsions   The antifouling coating agent composition according to claim 1, wherein the silicon dioxide content is 20 parts by mass or less with respect to 100 parts by mass of the component (1). The antifouling coating agent composition according to claim 1 or 2, wherein the vinyl-urethane copolymer is a vinyl-urethane copolymer synthesized through the following steps (X) to (Y).
Step (X): Step of preparing an aqueous dispersion or aqueous solution of a urethane polymer (A) having a hydrolyzable silicon atom-containing group Step (Y): Urethane polymer (A) having a hydrolyzable silicon atom-containing group In an aqueous dispersion or aqueous solution of the above, the ethylenically unsaturated monomer (B) is polymerized, and one or more time points before the polymerization reaction, during the polymerization reaction, and after the polymerization reaction The step of preparing a vinyl-urethane copolymer using the compound (C) having an alkoxysilyl group and having a reactive functional group with respect to the ethylenically unsaturated bond-containing group   The antifouling coating agent composition according to claim 3, wherein the urethane polymer (A) having a hydrolyzable silicon atom-containing group is a hydrophilic group-containing alkoxysilylated urethane polymer (A1).   The hydrophilic group-containing alkoxysilylated urethane-based polymer (A1) comprises a hydrophilic group-free polyol compound (A1-a), a hydrophilic group-containing polyol compound (A1-b), a polyisocyanate compound (A1-c), and The antifouling coating agent composition according to claim 4, which is a hydrophilic group-containing alkoxysilyl group-terminated urethane polymer obtained by reacting an isocyanate-reactive group-containing alkoxysilane compound (A1-d).   Hydroxyl group-containing alkoxysilylated urethane polymer (A1) is a terminal alkoxysilylated hydrophilic group-containing urethane polymer obtained by at least partially alkoxysilylating the isocyanate group at the end of the hydrophilic group-containing urethane polymer. The antifouling coating agent composition according to claim 4 or 5.   The antifouling coating agent composition according to any one of claims 3 to 6, wherein the ethylenically unsaturated monomer (B) contains an acrylic monomer.   The antifouling coating agent composition according to any one of claims 1 to 7, wherein the connecting part having a bond between a silicon atom and an oxygen atom in the vinyl-urethane copolymer is a silicone polymer chain part.   The antifouling coating composition according to any one of claims 1 to 8, which contains at least a wax-based emulsion as component (2).   The antifouling coating agent composition for wallpaper containing the antifouling coating agent composition in any one of Claims 1-9.