JP2001040251A - Antifouling treatment agent, antifouling treatment method and antifouling-treated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antifouling treatment agent capable of giving films having high water resistance and foulingproofness. SOLUTION: This antifouling treatment agent comprises (A) 0.01-10 pts.wt. of the nonvolatiles of an inorganic oxide sol selected from silicon oxide sol, aluminum oxide sol, antimony oxide sol, zirconium oxide sol, titanium oxide sol and tin oxide sol, (B) 0.01-10 pts.wt. of a silicone compound or partially hydrolyzed condensate of the formula R1mSi(OR2)n (R1 is phenyl, an alkoxyl or 1-18C alkyl; R2 is a 1-6C alkyl; m is an integer of 0-2; n is an integer of 2-4; m+n=4), (C) 0.01-10 pts.wt. of a resin having functional group reactive with the OR2 group in the component B, and (D) 10-100 pts.wt. of a mixture of water and an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling agent which can be applied to the surface of a substrate exposed to a polluted environment outdoors or indoors to prevent the surface from being soiled.
The present invention relates to a stain prevention treatment method and a stain prevention treated article.

[0002]

2. Description of the Related Art Conventionally, for example, in a car, if dirt adheres during running, a method of washing the car and finishing the original state with a water-repellent wax is generally used. However, in recent years, the amount of detergent used by car washing has increased, and the sea, rivers,
It causes water quality of lakes and marshes to deteriorate. In addition, many water-repellent waxes are oily, and are not only a cause of water pollution, but also tend to easily adhere to oil stains because the coating film is made lipophilic. Therefore, recently, by making the coating film hydrophilic, water enters between the contaminant and the coating film, causing the contaminant to rise,
There is an increasing number of ideas for imparting a stain resistance function (coating technology, October 1996 extra edition, pages 87 to 102).
As a specific method for making the coating film hydrophilic, for example, International Publication WO94 / 06870 discloses a coating composition obtained by blending a specific organic silicate composition with a specific organosilicate and / or a condensate thereof. It is disclosed that a coating film having a contact angle of 70 degrees or less after the acid treatment is obtained. Further, International Publication WO97 / 23572 discloses that a high degree of hydrophilicity can be imparted by applying a photocatalytic coating to the surface of a substrate.

[0003]

However, in the method of International Publication WO94 / 06870, the coating film itself may be made hydrophilic so as to exhibit the stain resistance function. In some cases, a silicate condensate may be unevenly present, and the water resistance tends to decrease, such as partial whitening of the coating film when exposed to water.
In addition, according to the method of International Publication WO97 / 23572, the coating film can be highly hydrophilized when irradiated with light, but the effect is reduced or reduced when the light is blocked for a long time at night or in a garage. It was not always a sufficient method because it could disappear.

[0004]

Means for Solving the Problems The inventors of the present invention have enthusiastically studied a method for stably hydrophilizing a treated film irrespective of the presence or absence of light irradiation so as to impart antifouling property and not to impair the water resistance of the treated film. As a result of repeated studies, inorganic oxide fine particles,
Specific silicon compound and OR of the silicon compound
^The above problems can be solved at once by forming a thin film on the substrate surface with a treating agent comprising a resin having a functional group capable of reacting with ^two groups or a water-soluble amino resin and / or a methyl etherified amino resin. And completed the present invention. That is, the present invention relates to (A)
The nonvolatile content of the inorganic oxide sol selected from the group consisting of silicon oxide sol, aluminum oxide sol, antimony oxide sol, zirconium oxide sol, titanium oxide sol and tin oxide sol is 0.01 to 10 parts by weight, and the formula (B) R ¹ _m Si ( OR ² )
_n (in the formula, ^{R 1} is a phenyl group, an alkoxyl group or an alkyl group having 1 to 18 carbon atoms, ^{R 2} is 1 to carbon atoms
6 is an alkyl group, m is an integer of 0 to 2, n is an integer of 2 to 4, and m + n = 4. )) Or a partially hydrolyzed condensate thereof in an amount of 0.0
1-10 parts by weight, (C) (B) 0.01~10 parts by weight of a resin having a functional group capable of reacting with the OR ² group of components, and (D) the mixture from 10 to 100 parts by weight of water and an organic solvent And (F) an amino resin in an amount of 0.01 to 10 parts by weight as needed (hereinafter referred to as the first invention of the present application). is there.

Further, the present invention provides (A) a silicon oxide sol,
0.01 to 10 parts by weight of a non-volatile content of an inorganic oxide sol selected from aluminum oxide sol, antimony oxide sol, zirconium oxide sol, titanium oxide sol and tin oxide sol, formula (B) R ¹ _m Si (OR ² ) _n Wherein R ¹ is a phenyl group, an alkoxyl group or an alkyl group having 1 to 18 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, m is an integer of 0 to 2, and n Is an integer of 2 to 4, and m + n = 4.) 0.01 to 10 parts by weight of the silicon compound represented by
(E ′) 0.01 to 10 parts by weight of a water-soluble amino resin and / or a methyl etherified amino resin and (D ′)
At least one selected from water and an organic solvent
100 parts by weight, and further if necessary (C ′)
(B) an antifouling treatment agent (hereinafter referred to as the second invention) characterized by containing a water-soluble resin having a functional group capable of reacting with the OR ² group of the component in a ratio of 0.01 to 10 parts by weight. To provide. Further, the present invention provides the antifouling agent according to the above, wherein the inorganic oxide sol of the component (A) is treated with a coupling agent having at least two or more alkoxyl groups in one molecule. Is provided. The present invention also provides a stain prevention treatment method, which comprises applying the stain prevention treatment agent onto a substrate. Further, the present invention provides
An object of the present invention is to provide a stain-resistant treated article characterized by being treated by the stain-preventing treatment method.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the antifouling agent of the present invention, the inorganic oxide sol of the component (A) comprises a silicon oxide sol,
An inorganic oxide sol selected from aluminum oxide sol, antimony oxide sol, zirconium oxide sol, titanium oxide sol and tin oxide sol. Specific examples of the inorganic oxide sol include, for example, Snowtex 40, Snowtex O, Snowtex C, Snowtex N, Snowtex IPA-ST, Snowtex EG-ST, Snowtex XBA-ST, Snowtex MIBK −
ST (all trade names, manufactured by Nissan Chemical Industries, Ltd.), Cataroid S-30H, Cataloid SI-30, Cataroid SN, Cataloid SA, Oscar 1132, Oscar 1
232, Oscar 1332 (both trade names, manufactured by Catalyst Chemical Industry Co., Ltd.), Adelite AT-30, Adelite A
T-20N, Adelite AT-20A, Adelite AT
-20Q (all trade names, manufactured by Asahi Denka Kogyo KK), Silica Doll 30, Silica Doll 20A, Silica Doll 2
Silicon oxide sol such as OB (all trade names, manufactured by Nippon Chemical Industry Co., Ltd.); alumina sol 100, alumina sol 20
0, alumina sol 520 (all trade names, manufactured by Nissan Chemical Industries, Ltd.), alumina clear sol, aluminum sol 1
0, aluminum sol 20, aluminum sol SV-102, aluminum sol SH-5, aluminum sol CSA-55, aluminum sol C
Aluminum oxide sol such as SA-110AD (all trade names, manufactured by Kawaken Fine Chemical Co., Ltd.); A-155
AZS-0, A-2550, Sun Colloid ATL-130, Sun Colloid AMT-130 (all trade names, manufactured by Nissan Chemical Industries, Ltd.); NZS-30
A, zirconium oxide sol such as NZS-30B (all trade names, manufactured by Nissan Chemical Industries, Ltd.);
8, tin oxide sols such as Ceramese C-10 (both trade names, manufactured by Taki Kagaku Co., Ltd.); Tynoc A-6, Tynoc M-6 (both trade names, Taki Chemical Co., Ltd.) and the like Titanium oxide sols; inorganic oxide sols composed of tin oxide and antimony oxide such as Ceramese F-10 (trade name, manufactured by Taki Kagaku Co., Ltd.), and preferably silicon oxide sol and aluminum oxide sol. Can be These inorganic oxide sols may be used alone or in combination of two or more.

[0007] The inorganic oxide sol may be treated with a coupling agent having at least two or more alkoxyl groups in one molecule (hereinafter sometimes simply referred to as a coupling agent). The upper limit of the number of alkoxyl groups in the coupling agent is not particularly limited, but is preferably 4 or less,
Particularly, 3 or less is preferable. Further, the carbon number of the alkoxyl group in the coupling agent is not particularly limited, but is preferably 1 to 6, and particularly preferably 1 to 4. By this treatment, the hydrolysis reaction of the silicon compound via the inorganic oxide sol particles can be promoted more uniformly, and a strong hydrophilic film can be formed on the substrate surface. Examples of the coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, methyltrimethoxysilane , Methyltriethoxysilane,
Silane coupling agents such as dimethyldimethoxysilane, diphenyldimethoxysilane and phenyltrimethoxysilane; tetraisopropoxytitanium, tetrabutoxytitanium, tetrakis (2-ethylhexyloxy) titanium, tetrastearyloxytitanium, di-isopropoxybis (acetyl) Acetonato) titanium, dibutoxy
Titanium coupling agents such as bis (triethanolaminato) titanium; aluminum isopropylate, mono-secondary
-Aluminum coupling agents such as butoxyaluminum diisopropylate, aluminum 2-butyrate, aluminum ethylate and alkyl acetoacetate aluminum diisopropylate; zirconium coupling agents such as tetrabutoxyzirconium. One of these coupling agents may be used,
Two or more kinds may be used in combination.

When treating with the coupling agent, the amount of the coupling agent is preferably 1 to 100% by weight, more preferably 2 to 50% by weight, based on the nonvolatile content of the inorganic oxide sol. The dispersion medium at that time is not particularly limited,
Any of water, an organic solvent or a mixture of water and an organic solvent may be used. Furthermore, the processing temperature is not particularly limited.
Usually, it is preferably in the range of 20 to 100 ° C, particularly preferably in the range of 30 to 90 ° C. In the first invention of the present application, the inorganic oxide sol of the component (A) is used in a range of 0.01 to 10 parts by weight, preferably 0.02 to 5 parts by weight as a nonvolatile component of the inorganic oxide sol. . Here, when the component (A) is less than 0.01 part by weight, the desired stain prevention function is not sufficiently exhibited, so that it is not preferable. When the component (A) exceeds 10 parts by weight, the thickness of the treated film is not increased. Is non-uniform, and processing unevenness may be seen in appearance, which is not preferable.

The component (B) silicon used in the present invention
The compound has the formula R¹ _mSi (OR²) _n(Where R¹Is
Enyl group, alkoxyl group or alkyl having 1 to 18 carbon atoms
A kill group,²Is an alkyl group having 1 to 6 carbon atoms
M is an integer of 0 to 2 and n is an integer of 2 to 4
M + n = 4. )
Is a partially hydrolyzed condensate thereof. R¹The alkoxyl
The carbon number of the group is not particularly limited, but is preferably 1 to 6,
Is preferably 1 to 4. R¹Has 1 carbon atom
To 18 are preferred. The component (B) used in the present invention
Is effective on the substrate surface efficiently after application
Non-volatile formula R¹ _mSi (OR²)_nPartial hydrolysis of
Condensates are more preferred.

Specific examples of the silicon compound (B) include tetramethoxysilane, tetraethoxysilane,
Examples thereof include tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraisobutoxysilane and the like, and partial hydrolysis condensates of these alone or in combination. In addition, methyl trimethoxy silane, methyl triethoxy silane, methyl tripropoxy silane, methyl triisopropoxy silane, methyl tributoxy silane, methyl triisobutoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, phenyl tripropoxy silane, phenyl Triisopropoxysilane, phenyltributoxysilane, phenyltriisobutoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyl Dibutoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldipropoxy , Methylphenyldibutoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, lauryltrimethoxysilane, lauryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-glyc Sidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and the like, and partially hydrolyzed condensates of these alone or in combination are exemplified.

The partially hydrolyzed condensate of the silicon compound is
Although it can be manufactured by an ordinary method, commercially available products such as MKC silicates MS51, MS56, MS57, MS56S,
MS56SB5, ES40, EMS31, BTS (all trade names, manufactured by Mitsubishi Chemical Corporation), methyl silicate 5
1, ethyl silicate 40, ethyl silicate 40T,
Ethyl silicate 48 (all trade names, manufactured by Colcoat Co., Ltd.) can be used alone or in combination of two or more. Further, those obtained by further hydrolyzing these condensates and proceeding with condensation may be used. The partially hydrolyzed condensate of the silicon compound is preferably a 2- to 500-mer.
As the silicon compound or the partially hydrolyzed condensate thereof as the component (B), either the silicon compound or the partially hydrolyzed condensate thereof may be used alone, or both may be used in combination. As the component (B), one type may be used, or two or more types may be used in combination. In the first invention of the present application, the silicon compound (B) or the partially hydrolyzed condensate thereof is 0.01 to 10 parts by weight, preferably 0.0 to 10 parts by weight.
It is used in the range of 2 to 5 parts by weight. Here, when the component (B) is less than 0.01 part by weight, it is difficult to exhibit the stain prevention function for a long period of time.
If the component (B) exceeds 10 parts by weight, the water resistance of the treated film may decrease, which is not preferable.

In the present invention, a catalyst capable of hydrolyzing the silicon compound as the component (B) can be used if necessary. Such catalysts include, for example, organic tin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate, tin octylate, dibutyltin oxide, paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalene Organic acids such as disulfonic acid and methanesulfonic acid; amines such as triethylamine, dimethylbenzylamine, dimethylethanolamine, dimethyllaurylamine, dibutylamine, di-2-ethylhexylamine, tetramethylbutanediamine, pyridine and triethanolamine; Other examples include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. The catalyst is preferably used in the range of 0.001 to 5 parts by weight based on 100 parts by weight of the silicon compound (B). Here, when the amount is less than 0.001 part by weight, the ability to promote the hydrolysis of the silicon compound is hardly recognized, and it is not preferable. When the amount exceeds 5 parts by weight, the hydrolysis reaction of the silicon compound rapidly progresses and the treatment is performed. This is not preferable because the properties of the layer become non-uniform and clouding and spots may occur.

The first invention of the present application contains the following components (C) and (D) in addition to the components (A) and (B), and further contains a component (E) if necessary. I do. The component (C) used in the first invention of the present application is a resin having a functional group capable of reacting with the OR ² group of the component (B), and further improves the durability of the antifouling treatment film formed by the present invention. Used for here,
Examples of the functional group capable of reacting with the OR ² group of the component (B) include a hydroxyl group, a carboxyl group, and an alkoxyl group. Specific examples of the resin as the component (C) include those having a hydroxyl group, for example, an acrylic resin, a polyester resin, a polyurethane resin, a polyol resin, a vinyl resin and a cellulose resin having at least two or more hydroxyl groups in one molecule. Resins. Examples of those containing a carboxyl group include acrylic resins, polyester resins, and polyurethane resins having at least two or more carboxyl groups in one molecule. Examples of those containing an alkoxyl group include, for example, 1
An acrylic resin and a silicone resin having at least two or more alkoxyl groups in a molecule are exemplified.

Among these, particularly preferred are acrylic resins and polyester resins having two or more hydroxyl groups in one molecule. The acrylic resin is obtained by polymerizing a radical polymerizable monomer having a hydroxyl group and another radical polymerizable monomer by a known method, for example, solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization, or precipitation polymerization. can get. Here, as the radical polymerizable monomer containing a hydroxyl group, for example, 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, acrylate-3
-Hydroxypropyl, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxycrotonate Ethyl, crotonic acid
2-hydroxypropyl, 3-hydroxypropyl crotonic acid, 3-hydroxybutyl crotonic acid, 4-hydroxybutyl crotonic acid, 5-hydroxypentyl crotonic acid, 6-hydroxyhexyl crotonic acid,
Allyl alcohol, adduct of acrylic acid and glycidyl versatate, adduct of methacrylic acid and glycidyl versatate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate or ε-caprolactone adduct of 4-hydroxybutyl methacrylate, acrylic acid 2-hydroxyethyl, acrylic acid-
2-hydroxypropyl, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate or -4-methacrylic acid Examples include hydroxybutyl ethylene oxide and / or propylene oxide adducts, which are used as one kind or as a mixture of two or more kinds.

Further, other radical polymerizable monomers include:
For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid
t-butyl, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, adamantyl acrylate, dodecyl acrylate, isobornyl acrylate, methyl methacrylate,
Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate,
Isobutyl methacrylate, t-butyl methacrylate,
Pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, adamantyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, allyl acrylate, methacrylic acid Allyl,
Benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, acrylic acid-N,
N-dimethylaminoethyl, methacrylic acid-N, N-dimethylaminoethyl, maleic anhydride, itaconic anhydride, maleic ester, fumaric ester, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, styrene, α-methyl Examples thereof include styrene, p-vinyltoluene, trimethoxypropyl methacrylate, and vinyl acetate, and are used as one kind or as a mixture of two or more kinds.

As the polymerization initiator used in the radical polymerization, for example, t-butyl hydroperoxide,
Cumene hydroperoxide, t-butylperoxyneodecanate, t-butylperoxypivalate, t
Organic peroxides such as -butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, and methyl ethyl ketone peroxide, or 2,2'-azobis Azo initiators such as (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropionitrile), and 2,2′-azobis (2-methylbutyronitrile) are preferred. it can. Of course, the polymerization initiator is not limited to these, and these polymerization initiators are used as one kind or as a mixture of two or more kinds. The polyester resin having two or more hydroxyl groups in one molecule can be obtained by subjecting a polybasic acid and a polyhydric alcohol to a condensation reaction in excess of hydroxyl groups according to a conventional method.

Examples of the polybasic acid include aliphatic polycarboxylic acids having 2 to 22 carbon atoms such as oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and decamethylene dicarboxylic acid. Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid, tetrahydrophthalic acid,
Alicyclic polycarboxylic acids such as hexahydrophthalic acid, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, Examples thereof include acid anhydrides such as pyromellitic anhydride and the like, and are used as one kind or as a mixture of two or more kinds.

The polyhydric alcohols include, for example, ethylene glycol, 1,2-propylene glycol, 1,
3-propylene glycol, 1,3-butanediol,
1,4-butanediol, 2,3-butanediol, 1,
6-hexanediol, diethylene glycol, pentanediol, dimethylbutanediol, hydrogenated bisphenol A, glycerin, sorbitol, neopentyl glycol, 1,8-octanediol, 1,4-hexanedimethanol, 2-methyl-1,3- Propanediol, 2-
Butyl-2-ethylpropanediol, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, quinitol, mannitol, trishydroxyethylisocyanurate, dipentaerythritol ,
Polyethylene glycol, polypropylene glycol,
Examples include ε-caprolactone polyol, urethane diol, ester diol, and the like, and they are used as one kind or as a mixture of two or more kinds. Of course, at this time,
To 22 monocarboxylic acids, fatty acids, 1 to 22 carbon atoms
A hydric alcohol can also be used.

The resin of the component (C) may be used alone or in combination of two or more. In the first invention of the present application, the resin of the component (C) is insoluble in a water-only medium from the viewpoint of the durability of the treated film, and is dissolved or dispersed only when another organic solvent coexists in water. Are preferred. (C) Component resin is 0.01 to 1
0 parts by weight, preferably in the range of 0.02 to 5 parts by weight. Here, if the amount of the component (C) is less than 0.01 part by weight, the stain prevention function cannot be exerted for a longer period of time, which is not preferable, and the amount of the component (C) exceeds 10 parts by weight. In such a case, the processing workability may be reduced, which is not preferable.

The component (D) used in the first invention of the present application includes:
It is a mixture of water and an organic solvent. Specific examples of the organic solvent include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, second butanol, tertiary butanol, 2-ethylhexanol, ethyl cellosolve, butyl cellosolve,
Alcohols such as diethylene glycol butyl ether, propylene glycol methyl ether, and propylene glycol ethyl ether; aromatic solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride and dichloromethane; dibutyl ether;
Ethers such as tetrahydrofuran and 1,4-dioxane, ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone and isophorone, ethyl acetate, butyl acetate, amyl acetate, hexyl acetate, ethyl propionate, butyl propionate,
Esters such as cellosolve acetate, n-hexane,
Examples thereof include aliphatic hydrocarbon solvents such as n-heptane and n-octane, and amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and preferably include alcohols, ethers, and ketones. Can be Such organic solvents may be used alone or as a mixture of two or more. The mixing ratio of water and the organic solvent is preferably such that water / organic solvent (weight ratio) is in the range of 1/99 to 99/1, but the components (A), (B) and (C) The mixing ratio of water and the organic solvent may be selected within a range that does not cause aggregation or precipitation. In the first invention of the present application,
The mixture of water and the organic solvent as the component (D) is 10 to 10
0 parts by weight, preferably in the range of 20 to 99.9 parts by weight. Here, when the component (D) is less than 10 parts by weight, the thickness of the treated film is not uniform, and the processing unevenness may be seen in appearance, which is not preferable. When the component (D) exceeds 100 parts by weight, It is not preferable because the desired stain prevention function becomes insufficient.

The amino resin (E) used in the first invention of the present application includes melamine resin, glycoluril resin, urea resin and the like. Specific examples of the amino resin include, for example, Cymer 300, Cymel 301, Cymel 303, Cymel 350, Cymel 370, Cymel 771, Cymel 325, Cymel 3 as commercial products.
27, Cymel 703, Cymel 712, Cymel 70
1 (all trade names, manufactured by Mitsui Cytec Co., Ltd.), Nikarac MW-30M, Nikarac MW-30, Nikarac MW-22, Nikarac MW-12FL, Nikarac MW-24X, Nikarac MS-21, Nikarac MS
-11, Nikarac MS-001, Nikarac MX-0
02, Nikarac MX-750, Nikarac MX-73
0, Nikarac MX-720, Nikarac MX-70
6, Nikarac MX-025, Nikarac MX-03
1. Nikarac MX-041 (all are trade names, Co., Ltd.)
Sumimar M-30W, Sumimar M-40W, Sumimar M-50W, Sumimar MC-
Melamine resin such as No. 1 (all trade names, manufactured by Sumitomo Chemical Co., Ltd.); glycoluril resin such as Cymel 1172 (trade name, manufactured by Mitsui Cytec Co., Ltd.); UFR-300
(Trade name, manufactured by Mitsui Cytec Co., Ltd.), Nikarac MX
-201 (trade name, manufactured by Sanwa Chemical Co., Ltd.).

The amino resin (E) may be used alone or in combination of two or more. Application
(1) In the invention, the amino resin as the component (E) is required to improve workability when applying the antifouling agent of the present invention and to improve durability of the antifouling film. It is used in the range of 0.01 to 10 parts by weight, preferably 0.02 to 5 parts by weight. Here, the component (E) is 0.
When the amount is less than 01 parts by weight, it is difficult to exhibit the desired effect of improving workability, and thus it is not preferable.
If the component (E) exceeds 10 parts by weight, the desired stain prevention function may be undesirably reduced.

In the second invention of the present application, the components (A) and (B) are the same as the components (A) and (B). In the second invention of the present application, the inorganic oxide sol of the component (A) has a non-volatile content of 0.1% as a nonvolatile component of the inorganic oxide sol.
It is used in the range of 0.01 to 10 parts by weight, preferably 0.02 to 5 parts by weight. Here, when the component (A) is less than 0.01 part by weight, the desired stain prevention function is not sufficiently exhibited, so that it is not preferable. When the component (A) exceeds 10 parts by weight, the thickness of the treated film is not increased. Is non-uniform, and processing unevenness may be seen in appearance, which is not preferable. Application
In the second invention, the silicon compound (B) or its partially hydrolyzed condensate is used in an amount of 0.01 to 10 parts by weight, preferably 0.02 to 5 parts by weight. Here, when the component (B) is less than 0.01 part by weight, it is difficult to exhibit the stain prevention function for a long period of time, and thus it is not preferable. When the component (B) exceeds 10 parts by weight, the treatment is performed. This is not preferable because the water resistance of the film may be reduced.

The component (E '), which is an essential component of the second invention of the present application, is a water-soluble amino resin or a methyl etherified amino resin among the components (E) of the first invention of the present application. In the second invention of the present application, the water-soluble amino resin or methyl etherified amino resin as the component (E ′) improves the workability when applying the anti-smudge treatment agent of the present invention, and improves the anti-smudge treatment film. Necessary for improving durability, 0.0
It is used in the range of 1 to 10 parts by weight, preferably 0.02 to 5 parts by weight. Here, when the component (E ′) is less than 0.01 part by weight, it is difficult to exhibit a desired effect of improving workability, so that it is not preferable, and the component (E ′) exceeds 10 parts by weight. In such a case, the desired stain prevention function may be undesirably reduced. The component (D ′) which is an essential component of the second invention of the present application is water and / or an organic solvent. The organic solvent of the component (D ′) of the second invention of the present application includes:
It is the same as the organic solvent of the component (D).

The component (D ') of the second invention of the present application may be water alone, a single organic solvent or a mixture of two or more thereof, or one or more of water and an organic solvent. May be used as a mixture. The water and / or organic solvent of the component (D ′), which is an essential component in the second invention of the present application,
It is used in the range of 10 to 100 parts by weight, preferably 20 to 99 parts by weight. Here, when the component (D ') is less than 10 parts by weight, the thickness of the treated film is not uniform, and the treatment unevenness may be seen in appearance, which is not preferable.
If the amount of the component (D ') exceeds 100 parts by weight, the desired stain prevention function becomes insufficient, which is not preferable. Second application
In the present invention, the component (C ′) blended as necessary includes:
It is a water-soluble resin of the component (C).

The water-soluble resin of the component (C ′) is 0.01 to
It is used in an amount of 10 parts by weight, preferably 0.02 to 5 parts by weight. Here, when the component (C ′) is less than 0.01 part by weight, the stain prevention function cannot be exhibited for a longer period of time, which is not preferable.
If the amount of the component (C ′) exceeds 10 parts by weight, the desired stain prevention function may be undesirably reduced. The antifouling treatment agent of the present invention may contain, if necessary, a preservative, a fragrance, a pigment, an ultraviolet absorber, a light stabilizer, a leveling agent, a polishing agent, a matting agent, an antistatic agent, a surfactant, a buffer, and a dispersant. , And one or more additives such as catalysts. The antifouling treatment agent of the first invention of the present application includes the above (A) to
It can be manufactured by mixing the component (D) and, if necessary, the component (E), and further mixing an additive as necessary. The antifouling treatment agent of the second invention of the present application is further required by mixing the above components (A), (B), (E ′) and (D ′) and, if necessary, mixing the component (C ′). It can be produced by mixing additives accordingly.

The stain prevention treatment method of the present invention is carried out by applying the stain prevention treatment agent of the present invention onto a substrate.
The application of the stain preventive treatment agent can be applied to articles to be used without any particular limitation such as usual spray coating, roller coating, brush coating, dip coating, wipe coating by soaking into cloth, paper, sponge, etc., and wet tissue form You can choose together.
However, at this time, the thickness of the stain prevention treatment film is 0.01 to
It is desirable to be within the range of 1 μm. If the thickness of the treated film is less than 0.01 μm, it is not preferable because the intended stain prevention function cannot be sufficiently exhibited, and if it exceeds 1 μm, clouding and cracking may occur, which is not preferable. . The application temperature of the antifouling agent is not particularly limited, but is usually 0 to 100 ° C., preferably 0 to 50 ° C., and particularly preferably 5 to 50 ° C.
~ 35 ° C. In the antifouling treatment method of the present invention, the antifouling function can be exhibited only by applying the antifouling treatment agent on the base material.However, in some cases, after the application, post-treatment such as immersion in water or spraying with water is performed. May go. The temperature of immersion water or spray water is not particularly limited, but is usually 2 to 50 ° C.
Is good.

After the application of the stain preventing agent to the substrate or after the post-treatment, it is preferable to dry the substrate. Drying can be performed by various drying methods such as natural drying and drying by blowing, and is preferably natural drying. Air drying means that the substrate is left at room temperature until moisture on the substrate evaporates.
The drying temperature is not particularly limited, but is usually preferably 2 to 50 ° C, particularly preferably 5 to 40 ° C. The blowing speed in drying by blowing is not particularly limited, but is 0.01 to 100 m /.
sec is preferred. The substrate used in the antifouling treatment method of the present invention is not particularly limited, and various substrates can be used, for example, wood, glass, metal, cloth, plastic, foam, and elastic material. , Paper, ceramic, concrete, gypsum board, and other organic materials and inorganic materials. These substrates may be those which have been subjected to a surface treatment in advance, or those having a coating film formed on the surface in advance. A coating film is usually formed on an outer panel of an automobile, but the type of the coating film is not particularly limited, and the stain prevention treatment method of the present invention can be applied to various coating films.

The type of the treated article applied by the stain prevention treatment method of the present invention is not particularly limited. Examples thereof include structures, wood products, metal products, plastic products, rubber products, processed paper, and ceramics. Products, glass products and the like. More specifically, automobiles, automobile parts (for example, parts such as bodies, bumpers, spoilers, mirrors, wheels, interior materials, etc., of various materials), metal plates such as steel plates, motorcycles, motorcycle parts , Road materials (for example, guardrails, traffic signs, soundproof walls, etc.), tunnel materials (for example, side wall boards, etc.), ships, railway vehicles, aircraft, vending machines, furniture, musical instruments, home appliances,
Examples include building materials, containers, office supplies, sporting goods, toys and the like.

[0030]

Next, the present invention will be described more specifically with reference to examples. Note that the present invention is not limited by these examples. In addition, the performance of the stain prevention treated article obtained by the stain prevention treatment method of the present invention was determined as follows. (1) Contact Angle A 4 μl water droplet (20 ° C.) was placed on a test plate, and the contact angle of water was measured using a goniometer type contact angle measuring device manufactured by Elma Corporation. (2) Water resistance After the test plate was immersed in warm water at 40 ° C. for 10 days, the appearance was visually evaluated. (3) Pollution resistance The test plate was installed outdoors at an angle of 45 degrees to the south,
Exposure. The color of the test plate after 3 months and 6 months was measured with a color difference meter, and the lightness L value was obtained (JIS K-5400 (1)
995) 7.4.2 Measurement method), the ΔL value was calculated by subtracting the L value at the time of no exposure from the L value after the exposure, and the stain resistance was determined. The closer the ΔL value is to 0, the better the stain resistance is.

Production Example 1 Production of Silicon Oxide Sol A-1 as Component (A) Snowtex IPA-ST (trade name, Nissan Chemical Industries, Ltd.) was placed in a flask equipped with a thermometer, a reflux condenser, and a stirrer.
Sol, nonvolatile content: 30% by weight, solvent: isopropanol), 100 parts by weight and methyltrimethoxysilane (15 parts by weight), and heated and maintained at 80 ° C. for 8 hours to obtain a surface with a silane coupling agent. Treated silicon oxide sol A-1 (silicon oxide content: 26
% By weight).

Production Example 2 Production of aluminum oxide sol A-2 as component (A) Aluminum sol CSA-55 (trade name, manufactured by Kawaken Fine Chemical Co., Ltd.) was placed in a flask equipped with a thermometer, a reflux condenser, and a stirrer. 100 parts by weight of aluminum sol, nonvolatile content: 6.4% by weight, solvent: water / methanol) and 3.2 parts by weight of methyltrimethoxysilane are charged, heated and maintained at 50 ° C. for 8 hours, thereby performing silane coupling. An aluminum oxide sol A-2 (aluminum oxide content: 3% by weight) surface-treated with the agent was obtained.

Production Example 3 Production of Resin Solution C-1 as Component (C) In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 49.0 parts by weight of n-butanol, 10 parts by weight of cyclohexanone 0.0 parts by weight, and heated to 115 ° C.
The temperature was raised to and maintained. There methyl methacrylate 3
6.7 parts by weight, 31.4 parts by weight of ethyl methacrylate, 31.9 parts by weight of 2 mol ε-caprolactone adduct of 2-hydroxyethyl methacrylate, t-butylperoxy-2-ethylhexanoate A mixture of 5 parts by weight was dropped from the dropping funnel over 2 hours while maintaining the reflux state. After completion of the dropping, stirring was continued at 115 ° C. for 30 minutes, then 0.5 part by weight of t-butylperoxy-2-ethylhexanoate was added, and the mixture was further heated at 115 ° C. for 2 hours.
And continued stirring. After completion of the polymerization, a resin solution C-1 having a nonvolatile content of 64% by weight and a number average molecular weight of 5,000 was obtained.

Production Example 4 Production of Resin Solution C-2 as Component (C) Neopentyl glycol 20.0 was placed in a four-necked flask equipped with a thermometer, reflux condenser, stirrer, water separator, and rectification tube.
Parts by weight, 15.0 parts by weight of 1,6-hexanediol, 6.5 parts by weight of trimethylolpropane, and 26.0 parts by weight of ε-caprolactone were charged and heated to 100 ° C. After the raw materials are melted and can be stirred, isophthalic acid 57.0
A part by weight was charged and the temperature was raised to 180 ° C. Thereafter, the temperature was raised to 230 ° C. at a constant heating rate over 3 hours. The generated condensed water was distilled out of the reaction system. After stirring at 230 ° C. for 3 hours, 5.0 parts by weight of xylene was gradually added, the reaction was continued in a solvent cooking state, and the acid value was 7.0 mg KOH.
/ G was reached, the reaction was terminated, the mixture was cooled to 100 ° C, and 54.0 parts by weight of n-butanol was added.
A polyester resin solution C-2 having 5.0% by weight and a number average molecular weight of 4000 was obtained.

Production Example 5 Production of Resin Solution C-3 as Component (C) In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 48.7 parts by weight of isopropyl alcohol was charged and heated. Then, the temperature was raised and maintained until a reflux state was reached. There 2-hydroxypropyl methacrylate 1
8.0 parts by weight, styrene 6.0 parts by weight, methacrylamide 3.0 parts by weight, -N, N-dimethylaminoethyl methacrylate 3.0 parts by weight, 2,2′-azobis (2-methylbutyro) A mixture of 0.2 parts by weight of nitrile) and 20.0 parts by weight of isopropyl alcohol was dropped from the dropping funnel over 2 hours while maintaining the reflux state. After the completion of the dropwise addition, the stirring was continued while maintaining the reflux state for another 30 minutes.
A mixture of 0.1 part by weight of 2'-azobis (2-methylbutyronitrile) and 1.0 part by weight of isopropyl alcohol was added, and stirring was continued for 2 hours under reflux. After completion of the polymerization, the nonvolatile content was 31.0% by weight, the number average molecular weight was 11
000 resin solution C-3 was obtained.

Production Example 6 Production of Resin Solution C-4 as Component (C) In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 48.7 parts by weight of isopropyl alcohol was charged and heated. Then, the temperature was raised and maintained until a reflux state was reached. There, 2-hydroxyethyl methacrylate15.
0 parts by weight, 6.0 parts by weight of acrylic acid, 9.0 parts by weight of methyl methacrylate, 0.2 parts by weight of 2,2′-azobis (2-methylbutyronitrile), isopropyl alcohol 2
A mixture of 0.0 parts by weight was dropped from the dropping funnel over 2 hours while maintaining the reflux state. After the completion of the dropwise addition, the mixture was kept under reflux for 30 minutes and the stirring was continued, and then 2,2'-
0.1 parts by weight of azobis (2-methylbutyronitrile)
A mixture of 1.0 part by weight of isopropyl alcohol was added, and the mixture was further stirred under reflux for 2 hours. After completion of the polymerization, the nonvolatile content was 30.5% by weight, and the number average molecular weight was 9800.
To obtain a resin solution C-4.

Examples 1 to 10 (1) Production of antifouling agent A raw material having the composition shown in Table 1 was mixed to obtain an antifouling agent. (2) Preparation of Substrate A cationic electrodeposition paint Aqua No. was applied to a zinc phosphate-treated mild steel plate (length 30 cm × width 10 cm). 4200 (registered trademark, manufactured by Nippon Oil & Fats Co., Ltd.) is electrodeposited to a dry film thickness of 20 μm and baked at 175 ° C. for 25 minutes. 500 middle coating (registered trademark, NOF Corporation)
Co., Ltd.) was spray-painted to a dry film thickness of 30 μm and baked at 140 ° C. for 30 minutes. 2
000 One coat solid white top coat (registered trademark,
Nippon Oil & Fats Co., Ltd.) was applied by air spray coating to a dry film thickness of 30 μm and baked at 140 ° C. for 30 minutes to obtain a white top-coated substrate. (3) Preparation of test plate and performance test After the paper towels were impregnated with the antifouling treatment agent of (1) above, they were evenly applied on the substrate, and then room temperature (23 ° C.)
For 1 day to obtain a stain-resistant treated plate having a stain-resistant treating agent layer having a dry film thickness of 0.02 to 0.1 μm (measured by cross-sectional observation with a transmission electron microscope). The performance test results are shown in Table 1. In each case, good appearance, high hydrophilicity, and excellent stain resistance were shown.

[0038]

[Table 1]

[0039]

[Table 2]

The subscripts, symbols and trade names in the table indicate the following. 1) Snowtex O (trade name, Nissan Chemical Industries, Ltd.)
2) Alumina sol-100 (trade name, manufactured by Nissan Chemical Industries, Ltd., aluminum oxide sol, nonvolatile content 10% by weight) 3) Coupling-treated oxidation of Production Example 1 Silicon sol A
-1 (nonvolatile content 26% by weight) 4) Coupling-treated aluminum oxide sol A-2 of Production Example 2 (nonvolatile content 3% by weight) 5) Snowtex C (trade name, Nissan Chemical Industry Co., Ltd.)
Manufactured, silicon oxide sol, nonvolatile content 20% by weight)

MS51: MKC silicate MS51
(Trade name, manufactured by Mitsubishi Chemical Corporation, partially hydrolyzed condensate of tetramethoxysilane, effective component 100% by weight) MS56: MKC silicate MS56 (trade name, manufactured by Mitsubishi Chemical Corporation, partially hydrolyzed tetramethoxysilane) MS56SB5: MKC silicate MS56SB5
(Trade name, manufactured by Mitsubishi Chemical Corporation, partially hydrolyzed condensate of tetraalkoxysilane having an alkoxyl group having 1 and 4 carbon atoms, effective content: 100% by weight) Ethyl silicate 40: trade name, Colcoat Co., Ltd.
C-1: Acrylic resin solution of Production Example 3 (64% by weight of non-volatile content) C-2: Acrylic resin solution of Production Example 4 (Non-volatile content of 65%) C-3: Acrylic resin solution of Production Example 5 (31% by weight of non-volatile content) C-4: Acrylic resin solution of Production Example 6 (Non-volatile content of 30.% by weight)
5% by weight)

Cymel 303: trade name, manufactured by Mitsui Cytec Co., Ltd., methylated melamine resin, nonvolatile content 100% by weight. Cymel 327: trade name, manufactured by Mitsui Cytec Co., Ltd.
Methylated melamine resin, nonvolatile content 90% by weight Cymel 701: trade name, manufactured by Mitsui Cytec Co., Ltd.
Methylated melamine resin, non-volatile content 82% by weight Cymer 1172: trade name, Mitsui Cytec Co., Ltd.
Glycoluril resin, nonvolatile content 45% by weight UFR-300: trade name, manufactured by Mitsui Cytec Co., Ltd.
Urea resin, non-volatile content 60% by weight ・ PEG-1000: trade name, manufactured by NOF Corporation, polyethylene glycol, effective component 100% by weight ・ TG-3000: Uniol TG-3000 (trade name, manufactured by NOF Corporation) , Polypropylene triol, effective content 100% by weight)

Comparative Examples 1 and 2 In Comparative Examples 1 and 2, each component having the composition shown in Table 3 was mixed to prepare a stain preventing agent, and a stain preventing plate was prepared in the same manner as in Example 1. Was prepared and its performance was evaluated. In Comparative Example 3, the performance of the substrate without the stain prevention treatment was evaluated.

[0044]

[Table 3]

In Examples 1 to 10, there was no abnormality in the appearance of the treated film, a contact angle of 50 ° or less was obtained in each case, and the treated film remained clean even after exposure for 6 months. On the other hand, in Comparative Examples 1 and 2, the amount of the component (A) was too large, so that the stain prevention treatment was not uniform, the treatment unevenness was conspicuous, and spots occurred after the water resistance test. In Comparative Example 3, since the stain prevention treatment was not performed, the treated film after three months of exposure was significantly stained. In the present invention,
The hydrolysis reaction of the silicon compound and the crosslinking reaction of the silicon compound and the resin or the curing reaction of the water-soluble amino resin proceed on the substrate surface via the inorganic oxide sol particles, and a dense cured film is formed. By aligning hydrophilic atomic groups such as silanol groups on the outermost surface of the thin film, a high degree of hydrophilicity with a contact angle to water of 50 degrees or less was imparted, and contamination of the substrate could be prevented for a long time. It seems to be.

[0046]

By treating the antifouling agent of the present invention, it is possible to prevent the substrate from being stained over a long period of time with excellent water resistance.

Continuing from the front page F term (reference) 4J038 CE011 CF021 CG011 CG071 CG081 CG131 CG141 CG161 CH071 CH081 CH121 CH131 CH171 CH201 DA141 DA161 DB221 DB301 DB471 DD021 DD061 DD081 DD121 DD171 DF021 DG321 DL021 DL031 DL0810 NA0811 PB05 PB06 PB07 PB09 PC02 PC03 PC04 PC06 PC08 PC10

Claims (5)

[Claims] (A) a silicon oxide sol, an aluminum oxide sol, an antimony oxide sol, a zirconium oxide sol,
The nonvolatile content of the inorganic oxide sol selected from the titanium oxide sol and the tin oxide sol is 0.01 to 10 parts by weight;
¹ _m Si (OR ² ) _n (wherein R ¹ is a phenyl group, an alkoxyl group or an alkyl group having 1 to 18 carbon atoms,
R ² is an alkyl group having 1 to 6 carbon atoms, and m is 0 to 2
And n is an integer of 2 to 4, and m + n = 4. 0.01 to 10 parts by weight of silicon compound or a partial hydrolysis-condensation product thereof represented by), the resin having a functional group capable of reacting with OR ² group of (C) (B) component 0.01
10 to 10 parts by weight, and (D) 10 to 100 parts by weight of a mixture of water and an organic solvent, and optionally (E) 0.01 to 10 parts by weight of an amino resin. A stain preventive agent characterized by the following. 2. (A) silicon oxide sol, aluminum oxide sol, antimony oxide sol, zirconium oxide sol,
The nonvolatile content of the inorganic oxide sol selected from the titanium oxide sol and the tin oxide sol is 0.01 to 10 parts by weight;
¹ _m Si (OR ² ) _n (wherein R ¹ is a phenyl group, an alkoxyl group or an alkyl group having 1 to 18 carbon atoms,
R ² is an alkyl group having 1 to 6 carbon atoms, and m is 0 to 2
And n is an integer of 2 to 4, and m + n = 4. ), 0.01 to 10 parts by weight of (E ′) a water-soluble amino resin and / or methyl etherified amino resin, and (D ′) ') 10 to 100 parts by weight of at least one selected from water and organic solvent, and if necessary, OR ^{2 of} component (C') (B)
Water-soluble resin having a functional group capable of reacting with
An antifouling agent characterized by containing 10 parts by weight. 3. The method according to claim 1, wherein the inorganic oxide sol of the component (A) has been treated with a coupling agent having at least two alkoxyl groups in one molecule. Antifouling treatment. 4. A stain prevention treatment method comprising applying the stain prevention treatment agent according to claim 1 to a substrate surface. 5. A stain-prevention treated article processed by the stain-prevention treatment method according to claim 4.