JP2007224189A - Bathroom member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bathroom member exhibiting water-repellent, oil-repellent and antifouling functions that hardly allows hydrophilic/lipophilic stains to adhere thereto and permits ready removal of adhering stains therefrom. <P>SOLUTION: An antifouling layer is formed on the surface of the bathroom member using a coating agent comprising a polymer (A) comprised of a monomer (a) having an ethylenically unsaturated double bond and a polyorganosiloxane chain, a monomer (b) having an ethylenically unsaturated double bond and a crosslinkable functional group other than (a), and a monomer (c) having an ethylenically unsaturated double bond and an acidic functional group other than (a) and (b), a polymer (B) comprised of the monomer (b), the monomer (c) and a monomer (d) having an ethylenically unsaturated double bond other than the monomers (a), (b) and (c), and a crosslinking agent (C) having a reactive functional group reactive with the crosslinkable functional group in the polymers (A) and (B). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antifouling bathroom member that has an antifouling layer on the surface of the member and can be suitably used in, for example, a bathroom / shower room.

Conventionally, in order to prevent the bathroom member from being soiled in a bathroom / shower room, etc., hydrophilicity is imparted to the surface of the member. As a method of imparting hydrophilicity, a method of applying a surfactant to a member surface, a method of applying a hydrophilic substance such as a hydrophilic monomer / polymer, a method of coating a photocatalyst on a member surface (Patent Document 1), a member surface Discloses a method for forming a film having a concavo-convex structure (Patent Document 2).
However, when applying hydrophilic substances such as surfactants and hydrophilic monomers / polymers, surfactants / hydrophilic substances are likely to flow off due to moisture, especially in environments where water is frequently used, such as bathrooms, to maintain efficacy. There was a problem with sex. Furthermore, hydrophilic substances such as hydrophilic monomers / polymers tend to be easily damaged when they absorb water. In addition, all have the drawback of easily adsorbing dirt in the air.
In addition, in the method of coating the photocatalyst, for example, when used in a bathroom where the excitation light included in the room lighting has a low illuminance and a large dirt load, the photocatalyst photoexcitation makes it time-consuming to make the photocatalyst hydrophilic. For this reason, the contact angle with water on the surface increases with the passage of time, and there is a problem that it is not possible to remove the dirt sufficiently only by applying water. In the method of forming a film having a concavo-convex structure, the holes forming the concavo-convex structure have various complicated and intricate shapes such as a wedge shape, and therefore when used in an environment with a high contamination load such as a bathroom. In the case of water washing, contaminants cannot be completely removed and antifouling properties cannot be obtained.

In addition to dirt, soap scum and sebum, etc. due to metal ions in tap water, the bathroom has a detergent used for washing and washing hair, a cationic substance for obtaining a smooth feeling, hydrophilic, lipophilic, etc. There are a lot of various pollutants. If the surface of the bathroom member is hydrophilic, it is easy to adsorb hydrophilic dirt, and if the surface of the bathroom member is oleophilic, it is easy to adsorb lipophilic dirt. It was necessary to make the surface of the bathroom member water and oil repellent.
WO96 / 29375 JP-A-8-11631

  An object of the present invention is to provide a bathroom member having a water repellency, oil repellency, and antifouling function that is difficult to be attached with hydrophilic / lipophilic dirt and that can be easily removed.

  The antifouling bathroom member of the present invention is a copolymer having a crosslinkable functional group and a polyorganosiloxane chain, utilizing the fact that a polymer containing a silicon atom having a low surface energy is localized on the surface of a coating film. By crosslinking a polymer having a crosslinkable functional group and not having a polyorganosiloxane chain with a crosslinking agent, a high antifouling function is imparted to the surface of a bathroom member with a small silicon content, and antifouling is further performed over a long period of time. The function is retained.

  That is, in the first invention, on the surface of the bathroom member, the monomer (a) having an ethylenically unsaturated double bond and a polyorganosiloxane chain is 0.5 to 84.9% by weight, the ethylenically unsaturated double Monomer other than (a) having bond and crosslinkable functional group (b) 15 to 50% by weight, monomer other than (a) and (b) having ethylenically unsaturated double bond and acidic functional group (C) 0.1 to 5% by weight, and monomers other than (a), (b), and (c) having an ethylenically unsaturated double bond (d) 0 to 84.4% by weight Polymer (A), monomer (b) other than (a) having ethylenically unsaturated double bond and crosslinkable functional group 15 to 50% by weight, ethylenically unsaturated double bond and acidic functional group (A) having a monomer other than (a) and (b) (c) 0.1 to 5% by weight, and having an ethylenically unsaturated double bond (a) (B) and a monomer (d) other than (c) (d) 45 to 84.9% by weight of the polymer (B), the polymer (A) and the crosslinkable functional group in the polymer (B) The present invention relates to an antifouling bathroom member having an antifouling layer formed from a coating agent comprising a crosslinking agent (C) having a reactive functional group capable of reacting.

  The second invention relates to the antifouling bathroom member according to the first invention, wherein the crosslinkable functional group of the monomer (b) is a hydroxyl group.

  Furthermore, the third invention relates to the antifouling bathroom member of the first or second invention, wherein the acidic functional group of the monomer (c) is a carboxyl group.

  In the fourth invention, the amount of the monomer (a) constituting the polymer (A) is 0 in 100% by weight of the total of the monomers constituting the polymer (A) and the polymer (B). .05 to 10% by weight, the antifouling bathroom member according to any one of the first to third inventions.

  Moreover, 5th invention is the monomer (a) which has an ethylenically unsaturated double bond and a polyorganosiloxane chain 0.5-84.9 weight%, an ethylenically unsaturated double bond and a crosslinkable functional group Monomer (b) other than (a) having 15 to 50% by weight, monomer (a) having ethylenically unsaturated double bond and acidic functional group (c) 0.1 A polymer (A) consisting of ˜5 wt% and monomers (d) other than (a), (b), and (c) having an ethylenically unsaturated double bond (d) 0 to 84.4 wt% , Monomer (b) other than (a) having an ethylenically unsaturated double bond and a crosslinkable functional group (b) 15 to 50% by weight, (a) having an ethylenically unsaturated double bond and an acidic functional group, ( (a), (b), and (b) having 0.1 to 5% by weight of a monomer other than b) and an ethylenically unsaturated double bond ) Other than the monomer (d) 45 to 84.9% by weight, and the reactive functional group capable of reacting with the crosslinkable functional group in the polymer (A) and the polymer (B). The present invention relates to a method for producing an antifouling bathroom member, characterized in that the surface of a bathroom member is coated with a coating agent comprising a crosslinking agent (C) having an anti-fouling property to form an antifouling layer by heat crosslinking.

  By utilizing the fact that a polymer containing a silicon atom having a low surface energy is localized on the surface of the coating film according to the present invention, the surface has water repellency, oil repellency and antifouling functions with a small silicon content, and is hydrophilic. -It has become possible to provide a bathroom member that is difficult to get oleophilic stains and that can easily remove adhered stains and that retains its antifouling function even in environments where water is frequently applied.

The antifouling bathroom member of the present invention can be produced by applying a coating agent containing the polymer (A), the polymer (B) and the crosslinking agent (C) to the surface of the bathroom member, followed by heat crosslinking.
First, the polymer (A) and polymer (B) contained in the coating agent will be described.
The monomer (a) having an ethylenically unsaturated double bond and a polyorganosiloxane chain constituting the polymer (A) is indispensable for providing the antifouling layer with a function of preventing the adhesion of dirt to the bathroom member. The compounds represented by the following formula (A) can be used.

In the formula (A),
_{R1: CH 2 = CHCOO- (CH} 2) m1 -,
_{CH 2 = C (CH 3)} COO- (CH 2) m1 -,
CH ₂ = CH- (CH ₂ ) _m1- ,
Or CH ₂ = C (CH ₃ )-(CH ₂ ) _m1-
(M1 is an integer from 0 to 10)
R2: hydrogen atom, methyl group, or the same functional group as R1 R3-R8: alkyl group, phenyl group, hydroxyl group, or carboxyl group n: a positive integer, preferably an integer of 10-300, respectively.

Specific examples of the monomer (a) include one-terminal vinyl group-containing polyorganosiloxane compounds such as TSL9705 manufactured by Toshiba Silicone Corp., Silaplane FM-0711, FM-0721, FM- manufactured by Chisso Corp. Examples thereof include one-terminal (meth) acryloxy group-containing polyorganosiloxane compounds such as 0725, and one or a mixture of two or more of these can be used according to the required performance.
The monomer (a) is used at a copolymerization ratio of 0.5 to 84.9% by weight in a total of 100% by weight of the monomers constituting the polymer (A), but in order to obtain sufficient surface characteristics. It is desirable that the copolymerization ratio is 5% by weight or more, and further, 60% by weight or less copolymerization is required in order to obtain sufficient coating film performance such as adhesion to a bathroom member, toughness, and solubility in a solvent. A ratio is desirable.

  The monomer (b) other than (a) having an ethylenically unsaturated double bond and a crosslinkable functional group constituting the polymer (A) and the polymer (B) is coated with a coating agent on the surface of the bathroom member. The polymer (A) and the polymer (B) are cross-linked and cured after the process, and are used to form an antifouling layer having high weather resistance that is in close contact with the bathroom member. Examples of the crosslinkable functional group include a hydroxyl group, an isocyano group, and an epoxy group. The curability of the coating agent, the adhesion of the antifouling layer to the bathroom member, the polymers (A) and (B) From the viewpoint of ease of production and the like, a hydroxyl group is most preferable.

Examples of the monomer (b) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, hydroxystyrene and the like.

Examples of the monomer (b) having an isocyano group include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl ( Examples thereof include those obtained by reacting a hydroxy (meth) acrylate such as (meth) acrylate with a polyisocyanate such as toluene diisocyanate or isophorone diisocyanate.
Examples of the monomer (b) having an epoxy group include glycidyl methacrylate, glycidyl cinnamate, glycidyl allyl ether, glycidyl vinyl ether, vinylcyclohexene monoepoxide, 1,3-butadiene monoepoxide, and the like.

The monomer (b) can be used singly or as a mixture of two or more of them according to the required performance. The monomer (b) can be used in the polymer (A) and the polymer (B ) Are not necessarily the same as those used in the above.
The monomer (b) has a copolymerization ratio of 15 to 50% by weight, preferably 20 to 40% by weight, out of a total of 100% by weight of the monomers constituting the polymer (A) in the polymer (A). In the polymer (B), it is used at a copolymerization ratio of 15 to 50% by weight, preferably 20 to 40% by weight, out of a total of 100% by weight of the monomers constituting the polymer (B). In the copolymer (A) or (B), when the copolymerization ratio is less than 15% by weight, sufficient adhesion to the substrate cannot be obtained, and sufficient curing is possible at low temperature and short time. Unable to develop surface characteristics. If it is larger than 50% by weight, stable production of the polymer may be difficult.

Monomers (c) other than (a) and (b) having an ethylenically unsaturated double bond and an acidic functional group constituting the polymer (A) and the polymer (B) are the polymer (A) and In the polymer (B), it is used to act as an internal catalyst for promoting the crosslinking reaction of the polymer (A) and the polymer (B) with the crosslinking agent (C). This makes it possible to form an antifouling layer having a high crosslink density, a toughness and high weather resistance at a low temperature and in a short time. Moreover, surface characteristics can be expressed in a short time.
Examples of the acidic functional group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. From the viewpoint of the balance between curing speed and pot life, polymer productivity, solubility in solvents, and cost, Is most preferred.

Examples of the monomer (c) having a carboxyl group include acrylic acid and methacrylic acid.
Examples of the monomer (c) having a sulfonic acid group include styrene sulfonic acid.
Examples of the monomer (c) having a phosphoric acid group include 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, and the like.

The monomer (c) can be used alone or in combination of two or more thereof depending on the required performance, and the monomer (c) and the polymer (B) ) Are not necessarily the same as those used in the above.
The monomer (c) is 0.1 to 5% by weight, preferably 0.5 to 3% by weight, out of the total 100% by weight of the monomers constituting the polymer (A) in the polymer (A). Used in the copolymerization ratio, in the polymer (B), 0.1 to 5% by weight, preferably 0.5 to 3% by weight of the total of 100% by weight of the monomers constituting the polymer (B). Used in polymerization ratio. In the copolymer (A) or (B), if the copolymerization ratio is less than 0.1% by weight, it takes time to cure, and if it is greater than 5% by weight, the usable time of the coating agent is shortened. It may be difficult to use industrially.

Monomers (d) other than (a), (b), and (c) having an ethylenically unsaturated double bond constituting the polymer (A) and the polymer (B) are hardness, toughness, It is used to impart various coating film properties such as scratch resistance, flexibility and gloss improvement to the antifouling layer.
As the monomer (d), (i) (meth) acrylic acid derivatives, (ii) aromatic vinyl monomers, (iii) olefinic hydrocarbon monomers, (iv) vinyl ester monomers, ( v) vinyl halide monomers, (vi) vinyl ether monomers and the like can be used.
(I) Examples of (meth) acrylic acid derivatives include (meth) acrylonitrile, (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Hexyl (meth) acrylate, ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, stearyl ( Examples include meth) acrylate, octadecyl (meth) acrylate, and benzyl (meth) acrylate.

(Ii) Examples of the aromatic vinyl monomer include styrene, methylstyrene, ethylstyrene, chlorostyrene and the like.
(Iii) Examples of the olefinic hydrocarbon monomer include ethylene, propylene, butadiene, isobutylene, isoprene, 1,4-pentadiene and the like.
(Iv) Examples of the vinyl ester monomer include vinyl acetate.
Examples of (v) vinyl halide monomers include vinyl chloride, vinylidene chloride, monofluoroethylene, difluoroethylene, trifluoroethylene and the like.
(Vi) Examples of vinyl ether monomers include vinyl methyl ether. Two or more of these may be used.

The monomer (d) can be used singly or as a mixture of two or more of them depending on the required performance. The monomer (d) can be used in the polymer (A) and the polymer (B ) Are not necessarily the same as those used in the above.
The monomer (d) is a copolymer of not more than 84.4% by weight, preferably not more than 74.5% by weight, out of a total of 100% by weight of the monomers constituting the polymer (A) in the polymer (A). Although it can be used in a ratio, it is preferably used in a copolymerization ratio of 10% by weight or more.
Further, the monomer (d) is 45 to 84.9% by weight, preferably 57 to 79.5% by weight, out of 100% by weight in total of the monomers constituting the polymer (B) in the polymer (B). % Copolymerization ratio.
When the copolymerization ratio in the copolymer (A) exceeds 84.4% by weight or the copolymerization ratio in the copolymer (B) exceeds 84.9% by weight, sufficient surface characteristics, Adhesiveness and curability with a member cannot be obtained.

  A polymer (A) and a polymer (B) are obtained by a well-known method, for example, solution polymerization. Solvents include alcohols such as ethanol, propanol, butanol, ethylene glycol methyl ether, diethylene glycol methyl ether, diacetone alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol Ethers such as 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. The solvent may be a mixture of two or more. The monomer concentration during synthesis is preferably 80% by weight or less.

Examples of the polymerization initiator include conventional peroxides or azo compounds such as benzoyl peroxide, di-t-butyl peroxide, t-butyl perbenzoate, t-butyl peroctoate, cumene hydroxy peroxide, azoisobutyl valenonitrile. And azobisisobutyronitrile are used, and the polymerization temperature is 50 to 140 ° C, preferably 70 to 140 ° C.
The weight average molecular weight of the polymer (A) is preferably 10,000 to 50,000, more preferably 20,000 to 40,000. When the weight average molecular weight is less than 10,000, coating properties and weather resistance may be lowered. On the other hand, if it is larger than 50,000, sufficient pot life may not be obtained.
The weight average molecular weight of the polymer (B) is preferably 20,000 to 150,000, more preferably 30,000 to 100,000. When the weight average molecular weight is less than 20,000, coatability and weather resistance may be lowered. On the other hand, if it is larger than 150,000, sufficient pot life may not be obtained.

Next, the crosslinking agent (C) contained in the coating agent will be described.
The crosslinking agent (C) reacts with the crosslinkable functional groups in the polymer (A) and the polymer (B) to crosslink and cure the coating agent to obtain a highly weather-resistant antifouling layer in close contact with the bathroom member. Used for.
Typical crosslinking agents (C) include melamine, benzoguanamine, amino resin, hydrazine-based compound, linear or cyclic polyamine, polyvalent isocyanate, dicarboxylic acid and its anhydride, dialdehyde, amino acid and its lactam, hydroxy Examples thereof include carboxylic acids and lactones thereof, polyhydric alcohols, polyhydric phenols, bisepoxy compounds, and epoxy resins.

Specific examples of the amino resin include benzoguanamine resin and melamine resin, and specific examples of the hydrazine-based compound include hydrazine and adipic acid dihydrazide.
Specific examples of the linear polyamine include ethylenediamine, propanediamine, butanediamine, pentanediamine, 1,6-hexamethylenediamine, diaminooctane, diaminodecane, diaminododecane, 2,5-dimethyl-2,5-hexamethylene. Examples include diamine, polyoxypropylene diamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

  Specific examples of the cyclic polyamine include mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) 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, methylenebis (furanmethanamine) and the like.

  Specific examples of the polyvalent isocyanate include toluylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, Di-isocyanates such as m-xylene diisocyanate, p-xylene diisocyanate, lysine diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, etc., or both terminal isocyanates which are reaction products of these with glycols or diamines Adduct body, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate Doors and the like.

Specific examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, hexanedioic acid, citric acid, maleic acid, methylnadic acid, dodecenyl succinic acid, sebacic acid, pyromellitic acid, hexahydrophthalic acid, tetrahydrophthalic acid An acid etc. are mentioned.
Specific examples of the dialdehyde include glyoxal and terephthalaldehyde. Specific examples of amino acids include glycine and alanine.
Specific examples of the hydroxycarboxylic acid include citric acid, 12-hydroxystearic acid, and 6-hydroxypentanoic acid.

Specific examples of the polyhydric alcohol include diols such as 1,4-butanediol and 2,3-butanediol, 1,1,1-trimethylolpropane ethylene glycol, diethylene glycol, glycerin, erythritol, arabinitol, xylitol, and sorbitol. , Dulcitol, mannitol, and the like, and alkoxy-modified products thereof.
Specific examples of the polyhydric phenol include catechol, resorcin, hydroquinone, guaiacol, hexyl resorcin, pyrogallol, trihydroxybenzene, phloroglucin, dimethylolphenol, and alkoxy modified products thereof.

  Specific examples of the bisepoxy compound include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6 -Hexanediol diglycidyl ether, phthalic acid diglycidyl ester and the like.

  Specifically, as an epoxy resin, the product name Epicoat 801, 802, 807, 815, 827, 828, 834, 815X, 815XA1, 828EL, 828XA, 1001, 1002, 1003, 1055, 1004, manufactured by Yuka Shell Epoxy Co., Ltd. 1004AF, 1007, 1009, 1010, 1003F, 1004F, 1005F, 1100L, 834X90, 1001B80, 1001X70, 1001X75, 1001T75, 5045B80, 5046B80, 5048B70, 5049B70, 5050T60, 5050, 5051, 152, 154, 103S1 1032H60, 604, 157S70 and the like.

Among these crosslinking agents, when a monomer having a hydroxyl group is used as the monomer (b), it is preferable to use an amino resin, a polyvalent isocyanate, an epoxy resin, and the like. Polyisocyanates are preferred in terms of adhesion to bathroom members.
In addition, when a monomer having an isocyano group is used as the monomer (b), it is preferable to use a hydrazine compound, a polyamine, a dicarboxylic acid, a polyhydric alcohol, a polyhydric phenol, a bisepoxy compound, an epoxy resin, or the like. .

When a monomer having an epoxy group is used as the monomer (b), dicarboxylic acid and its anhydride, polyhydric alcohol, polyhydric phenol, amino resin, polyvalent isocyanate, amino acid and its lactam, hydroxy The use of carboxylic acid and its lactone, polyamine and the like is preferred.
Depending on the required performance, these crosslinking agents (C) are based on the total number of crosslinkable functional groups in the polymer (A) and the polymer (B), and the reactive functional groups in the crosslinker (C). One or a mixture of two or more can be used in such a ratio that the total number is preferably 0.5 times to 5.0 times, more preferably 1.0 times to 3.0 times.

Further, in the present invention, in order to promote the crosslinking reaction between the crosslinking functional groups in the copolymers (A) and (B), and further the crosslinking reaction between the crosslinking functional group and the crosslinking agent, Depending on the functional group, various crosslinking catalysts can be used.
Typical crosslinking catalysts include acids and their ammonium or lower amine salts, amines, organometallic compounds and the like. When the monomer (b) having a hydroxyl group or an isocyano group is used, it is preferable to use acids and their ammonium salts or lower amine salts, amines, organometallic compounds and the like. Moreover, when the monomer (b) which has an epoxy group is used, use of amines, an organometallic compound, etc. is preferable.

Specific examples of acids and their ammonium salts or lower amine salts include p-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, phthalic anhydride, oxalic acid, maleic acid, benzoic acid, itaconic acid, formic acid, acetic acid , Propionic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, monoalkyl phosphorous acid, dialkyl phosphorous acid, and ammonium salts or lower amine salts thereof.
Examples of amines include diethylamine, triethylamine, diethanolamine, triethanolamine, cyclohexylethylamine, dicyclohexylamine, N, N-dimethylbenzylamine, N, N, N ′, N′-tetramethyl-1,3-butanediamine and the like. Can be mentioned.

Organic metal compounds include tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin malate dibutyltin di ( 2-ethylhexoate), diethyl zinc and the like.
Two or more kinds of these crosslinking catalysts may be used, and the total amount used is 0.01 to 10 weights with respect to 100 parts by weight of the total of the polymers (A) and (B) and the crosslinking agent (C). Parts, particularly 0.1 to 5 parts by weight.

  In the coating agent, the silane coupling agent, filler, thixotropy imparting agent, coloring pigment, extender pigment, dye, anti-aging agent, antioxidant, antistatic agent, as long as the effects according to the present invention are not hindered as necessary. Various additives such as flame retardants, thermal conductivity improvers, plasticizers, anti-sagging agents, antifouling agents, antiseptics, bactericides, antifoaming agents, and leveling agents may be added.

The coating agent is obtained by mixing and dissolving the polymer (A), the polymer (B), the crosslinking agent (C), and if necessary, a crosslinking catalyst and an additive in a solvent.
Solvents include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether, diethylene glycol methyl ether, diacetone alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether. Depending on the resin composition, ethers such as diethylene glycol dimethyl ether, hydrocarbons such as hexane, heptane and octane, aromatics such as benzene, toluene, xylene and cumene, esters such as ethyl acetate and butyl acetate, etc. Use an appropriate one. Two or more solvents may be used.

The mixing method is not particularly limited, but usually, the polymer solution used at the time of polymerization may be mixed as it is and stirred with a stirring blade, a shaker, a rotary stirrer, or the like. In order to improve coatability, a solvent may be further added or concentrated.
The mixing ratio of the polymer (A) and the polymer (B) is such that the amount of the monomer (a) constituting the polymer (A) constitutes the polymer (A) and the polymer (B). It is preferable to be 0.05 to 10% by weight in the total 100% by weight of the monomers. When the amount of the monomer (a) is less than 0.05% by weight, sufficient antifouling property cannot be obtained, and when it is more than 10% by weight, sufficient film hardness cannot be obtained, and the cost Also gets higher.

The coating agent thus obtained was used as a wall member, wall joint, flooring, floor joint, ceiling, faucet fitting, shower hose, shower head, shower discharge part, shower hook, bathtub, which are bathroom members. , Bathtub handgrip, bathtub apron, bathtub drain valve, window, window frame, window sill, window floor, lighting fixture, snowboard, grating, drainage pan, drain pit, drainage trap, drain trap, trap envelope , Doors, door frames, door bars, mats, soap rests, handrails, wash basins, bath chairs, transfer boards, storage shelves, handrails, bath lids, towel racks, shower chairs, wash basins, ventilation fans The antifouling bathroom member of the present invention can be obtained by coating on the surfaces of handrails, counters, wash bowls, touch panels, sealants and the like, followed by heat crosslinking or room temperature crosslinking.
The coating method of the coating agent is not particularly limited, and various methods such as knife coating, gravure coating, dip coating, spray coating, lip coating, and brush coating can be used.

  The applied coating agent is air-dried or heated at 40 to 300 ° C. for several seconds to several weeks to accelerate the crosslinking reaction, thereby to have a tough and highly weather-resistant antifouling layer adhered to the bathroom member. A bathroom member can be obtained.

  Hereinafter, the present invention will be described in detail by way of examples.

(Synthesis Example A1)
45 g of one-terminal methacryloxy group-containing polysiloxane compound (“Silane Plan FM-0721” manufactured by Chisso Corporation), 4-hydroxybutyl acrylate 25 g, acrylic acid 3 g, normal butyl methacrylate 27 g, and methyl ethyl ketone (MEK) 200 g were cooled and stirred. Charge to a four-necked flask equipped with an apparatus and thermometer, and heat up to 80 ° C. with stirring under a nitrogen stream, add 2.0 g of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and then add azobis. 0.5 g of isobutyronitrile was added and polymerization was performed for 2 hours to obtain a polymer (A1) solution having a weight average molecular weight of about 23,000.

(Synthesis Example A2)
85 g of one-terminal methacryloxy group-containing polysiloxane compound (“Silaplane FM-0721” manufactured by Chisso Corporation), 10 g of 4-hydroxybutyl acrylate, 1 g of acrylic acid, 4 g of normal butyl methacrylate, and 200 g of methyl ethyl ketone (MEK) were cooled and stirred. Charge to a four-necked flask equipped with an apparatus and thermometer, heat up to 80 ° C. with stirring under a nitrogen stream, add 2.0 g of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and then add azobis. 0.5 g of isobutyronitrile was added and polymerization was performed for 2 hours to obtain a polymer (A2) solution having a weight average molecular weight of about 28,000.

(Synthesis Example A3)
One-terminal methacryloxy group-containing polysiloxane compound ("Silaplane FM-0721" manufactured by Chisso Corporation) 0.1 g, 4-hydroxybutyl acrylate 20 g, acrylic acid 1 g, normal butyl methacrylate 78.9 g, methyl ethyl ketone (MEK) 200 g Charge into a four-necked flask equipped with a condenser, stirrer, and thermometer, raise the temperature to 80 ° C while stirring under a nitrogen stream, add 2.0 g of azobisisobutyronitrile, and conduct a polymerization reaction for 2 hours. Further, 0.5 g of azobisisobutyronitrile was added and polymerization was carried out for 2 hours to obtain a polymer (A3) solution having a weight average molecular weight of about 23,000.

(Synthesis Example A4)
55 g of one-terminal methacryloxy group-containing polysiloxane compound ("Silaplane FM-0721" manufactured by Chisso Corporation), 4-hydroxybutyl acrylate 5 g, acrylic acid 3 g, normal butyl methacrylate 37 g, and methyl ethyl ketone (MEK) 200 g were cooled and stirred. Charge to a four-necked flask equipped with an apparatus and thermometer, heat up to 80 ° C. with stirring under a nitrogen stream, add 2.0 g of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and then add azobis. 0.5 g of isobutyronitrile was added and polymerization was performed for 2 hours to obtain a polymer (A4) solution having a weight average molecular weight of about 26,000.

(Synthesis Example A5)
45 g of one-terminal methacryloxy group-containing polysiloxane compound (“Silaplane FM-0721” manufactured by Chisso Corporation), 25 g of 4-hydroxybutyl acrylate, 30 g of normal butyl methacrylate, and 200 g of methyl ethyl ketone (MEK) were added to a condenser, a stirrer, and a thermometer. Was added to a four-necked flask with stirring, heated to 80 ° C. while stirring under a nitrogen stream, added with 2.0 g of azobisisobutyronitrile, and subjected to a polymerization reaction for 2 hours, and further azobisisobutyronitrile. 0.5 g was added and polymerization was performed for 2 hours to obtain a polymer (A5) solution having a weight average molecular weight of about 26,000.

(Synthesis Example B1)
While charging 25 g of 2-hydroxyethyl methacrylate, 41 g of methyl methacrylate, 32 g of butyl acrylate, 2 g of acrylic acid, and 100 g of methyl ethyl ketone (MEK) into a four-necked flask equipped with a condenser, a stirrer, and a thermometer, stirring under a nitrogen stream The temperature was raised to 80 ° C. and 0.2 g of azobisisobutyronitrile was added to carry out a polymerization reaction for 2 hours. Further, 0.1 part of azobisisobutyronitrile was added to carry out the polymerization for 2 hours to obtain a weight average molecular weight of about 82. A polymer (B1) solution having a glass transition temperature (Tg) of 30 ° C. was obtained.

(Synthesis Example B2)
10 g of 2-hydroxyethyl methacrylate, 52.6 g of methyl methacrylate, 35.4 g of butyl acrylate, 2 g of acrylic acid, and 100 g of methyl ethyl ketone (MEK) were charged into a four-necked flask equipped with a condenser, a stirrer, and a thermometer, under a nitrogen stream. The mixture was heated to 80 ° C. with stirring at 0.2 ° C., 0.2 g of azobisisobutyronitrile was added to conduct a polymerization reaction for 2 hours, and 0.1 part of azobisisobutyronitrile was further added to carry out the polymerization for 2 hours. A polymer (B2) solution having an average molecular weight of about 85,000 and a glass transition temperature (Tg) of 30 ° C. was obtained.

(Synthesis Example B3)
25 g of 2-hydroxyethyl methacrylate, 43 g of methyl methacrylate, 32 g of butyl acrylate, and 100 g of methyl ethyl ketone (MEK) were charged into a four-necked flask equipped with a condenser, a stirrer, and a thermometer, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. Warm, 0.2 g of azobisisobutyronitrile is added to conduct a polymerization reaction for 2 hours, 0.1 part of azobisisobutyronitrile is further added to carry out the polymerization for 2 hours, a weight average molecular weight of about 83,000, glass A polymer (B3) solution having a transition temperature (Tg) of 30 ° C. was obtained.

(Examples 1-3, Comparative Examples 1-5)
The weight shown in Table 1 in terms of solid content of the obtained polymer (A) solution and polymer (B) solution and a predetermined amount of the crosslinking agent (C) are mixed, and methyl isobutyl ketone (MIBK) is further added. Thus, a coating agent having a solid concentration of 40% by weight was obtained.
The coating agent prepared by the above method is coated on a polyethylene terephthalate (PET) bathroom wall material with a gravure coater so as to have a dry film thickness of 20 μm, dried with hot air at 100 ° C. for 5 minutes, and subsequently at 50 ° C. for 7 minutes. Anti-fouling bathroom wall material was obtained by heat treatment for a day.

About the obtained antifouling bathroom wall material, initial water repellency, antifouling property and water repellency after use in the bathroom for one month were evaluated by the following methods. The results are shown in Table 2.
[Evaluation methods]
Initial water repellency: The water repellency was evaluated by measuring the contact angle of the antifouling bathroom wall surface obtained by heat treatment with water.
(The smaller the contact angle, the better the water repellency.)
Antifouling property: In order to evaluate the antifouling property as a bathroom wall material, install the obtained antifouling bathroom wall material in the bathroom, observe the surface condition after one month of use, and adhere dirt such as scales The situation and the ease of scale removal under running water were evaluated on a five-point scale.
5: There is no adhesion of dirt such as scales 4: The adhesion of dirt such as scales can be confirmed by visual observation, but the dirt can be easily removed with running water.
3: Although a large amount of dirt such as scale can be visually confirmed, the dirt can be easily removed with running water.
2: Adherence of dirt such as scale can be visually confirmed, but dirt can be removed by rubbing with a running water sponge.
1: Large amount of dirt such as scale can be visually confirmed, and dirt cannot be removed by rubbing with running sponge.
Of the above evaluation criteria, 3 or more can be determined to have good antifouling properties.
Water repellency after time: The water repellency was evaluated by measuring the contact angle with water on the surface of the bathroom wall material after one month of use in the bathroom in the same manner as the antifouling property.

Claims (5)

On the surface of the bathroom member, the monomer having an ethylenically unsaturated double bond and a polyorganosiloxane chain (a) 0.5 to 84.9% by weight, having an ethylenically unsaturated double bond and a crosslinkable functional group Monomer (b) other than (a) 15 to 50% by weight, monomer (a) having ethylenically unsaturated double bond and acidic functional group (c) 0.1 to 5 A polymer (A) comprising 0% to 84.4% by weight of a monomer (d) other than (a), (b), and (c) having an ethylenically unsaturated double bond, and ethylene Monomers other than (a) having an ethylenically unsaturated double bond and a crosslinkable functional group (b) 15 to 50% by weight, (a) and (b) having an ethylenically unsaturated double bond and an acidic functional group (C) 0.1 to 5% by weight of a monomer other than (a), (b), and (c) having an ethylenically unsaturated double bond A polymer (B) composed of 45 to 84.9% by weight of a monomer (d) other than the above and a reactive functional group capable of reacting with the crosslinkable functional group in the polymer (A) and the polymer (B). An antifouling bathroom member having an antifouling layer formed from a coating agent comprising a crosslinking agent (C). The antifouling bathroom member according to claim 1, wherein the crosslinkable functional group of the monomer (b) is a hydroxyl group. The antifouling bathroom member according to claim 1 or 2, wherein the acidic functional group of the monomer (c) is a carboxyl group. The amount of the monomer (a) constituting the polymer (A) is 0.05 to 10% by weight in a total of 100% by weight of the monomers constituting the polymer (A) and the polymer (B). The antifouling bathroom member according to any one of claims 1 to 3. Monomers having an ethylenically unsaturated double bond and a polyorganosiloxane chain (a) 0.5 to 84.9% by weight, and monomers other than (a) having an ethylenically unsaturated double bond and a crosslinkable functional group Monomer (b) 15-50% by weight, monomer (c) having ethylenically unsaturated double bond and acidic functional group (c) 0.1-5% by weight other than (b), and ethylenic A polymer (A) comprising 0 to 84.4% by weight of a monomer (d) other than (a), (b) and (c) having an unsaturated double bond, and an ethylenically unsaturated double bond; And monomers other than (a) having a crosslinkable functional group (b) 15 to 50% by weight, monomers other than (a) and (b) having an ethylenically unsaturated double bond and an acidic functional group ( c) a monomer other than (a), (b), and (c) having 0.1 to 5% by weight and an ethylenically unsaturated double bond (d) From a polymer (B) comprising 45 to 84.9% by weight, and a crosslinking agent (C) having a reactive functional group capable of reacting with the crosslinking functional group in the polymer (A) and the polymer (B). A method for producing an antifouling bathroom member, comprising: coating a surface of a bathroom member on the surface of the bathroom member and forming an antifouling layer by heat crosslinking.