JP2000143373A - Stain-proofing glazed product, stick film for glazed product and coating composition for glazed product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain stain-proofing glazed product capable of preventing the adhesion of aqueous stains such as urolith or fur and having sufficient durability under employment conditions even when used in an alkali environment, by forming a silicone resin film polymerized through siloxane cross-links and cross-links except the siloxane on the surface of a substrate on whose surface a glazing layer is formed. SOLUTION: This stain-proofing glazed product is obtained by coating a glazed product with a glazed product-coating composition and, if necessary, heating the coated glazed product to form the cured coating film. The glazed product-coating composition comprises a precursor capable of forming a silicone resin film polymerized through siloxane cross-links and other cross-links except the siloxane by, if necessary, hydrolyzing and subsequently polymerizing. Another method comprises sticking a stick film to the surface of the glazing agent layer of a glazed product. The stick film for the glazed product has a silicone resin film polymerized through siloxane cross-links and other cross-links except the siloxane and an adhesive layer on the back and front surfaces of the film substrate, respectively. The cross-links except the siloxane is, for example, based on the polycondensation of an acryloyl group- containing monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glazed product in which aqueous dirt such as urine stone and scale is hardly adhered to the surface, and an aqueous dirt such as urine stone and scale is hardly adhered only by sticking to the surface of the glazed product. The present invention relates to an adhesive film for a glazed product, and a coating composition for a glazed product in which water-based stains such as urine stones and scales are hardly adhered only by forming a cured film by applying to the glazed product and heating as necessary.

[0002]

2. Description of the Related Art Antifouling processing of the surface of a glazed product is performed by:
Helps to keep glazed products clean and high in hygiene and aesthetics. As a method for this purpose, a method of forming a chemically adsorbed monomolecular film containing fluorine on the surface of a glazed product via a siloxane-based monomolecular film, as shown in, for example, JP-A-4-240171, has been proposed. . It is also disclosed that by adopting such a structure, the surface of the glazed product becomes water-repellent, and water-based stains such as toilet bowl waste and tea astringency are less likely to occur.

[0003]

However, many glaze products are used in an alkaline environment. For example, toilets are constantly exposed to an ammonia-base environment due to the reaction between urea based on human urination and the enzyme urease possessed by general bacteria attached to the toilet. On the other hand, since the siloxane bond has the property of being attacked by an alkali, the antifouling treatment disclosed in JP-A-4-240171 still has a problem in durability under use conditions.

[0004]

According to the present invention, in order to solve the above-mentioned problems, a base material having a glaze layer formed on the surface thereof is provided with
Alternatively, an antifouling glazed product characterized in that a silicone resin film polymerized by siloxane cross-linking and cross-linking other than siloxane is formed on the surface of a film substrate used by being adhered to the surface of the glaze layer. I will provide a. In addition, the present invention provides a coating composition for a glazed product, comprising a precursor capable of forming a silicone resin film polymerized by siloxane crosslinking and crosslinking other than siloxane by hydrolyzing and polymerizing as necessary. I do. Since the silicone resin film formed on the base material has not only siloxane crosslinks but also crosslinks other than siloxane, even when used in an alkaline environment, it has sufficient durability under use conditions, Water-based stains such as water stains are less likely to adhere. Furthermore, although a film made of only siloxane is originally a hard film, by adding a component softer than siloxane, flexibility is given to the silicone resin film, and the film becomes flexible. Aqueous stains such as urine stones and scales are Ca compounds, S
Since it is made of a hard and brittle inorganic material such as an i-compound, if the material underneath is flexible, cracks are likely to occur in the dirt coating due to factors such as temperature change and running water, and the dirt coating is easily peeled off. Can be expected.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows an embodiment relating to the structure of the resin of the present invention. In FIG. 1, the Si-based monomer unit has a siloxane bond 1 and / or a bond 2 other than siloxane.
(In the figure, condensation crosslinking of a methacryl group is exemplified.) As the bond other than siloxane, a vinyl group, an epoxy group, an amide group and the like can be suitably used in addition to the condensation and crosslinking of the methacryl group.

In the present invention, the silicone resin film formed on the substrate is preferably water-repellent. This is because it becomes difficult for water-based stains such as water scale to adhere. Here, the degree of water repellency is such that the contact angle with water measured by a contact angle measuring device is preferably 90 degrees or more, preferably 110 degrees or more, and more preferably 140 degrees or more. When a silicone resin film containing a fluoro group is used for the silicone resin film, excellent water repellency is easily generated, which is preferable.

The coating composition for a glazed product in the present invention is a silicone in which one or more organic groups are bonded to a silicon atom in the silicone, that is, an average composition formula RpSiXqO (4-pq) / 2 ( In the formula, R is a monovalent organic group having 1 to 18 carbon atoms, X is an alkoxy group having 1 to 4 carbon atoms, and p and q are 0 <p <2, 0 <q <4,
0 <p + q <4) is a coating composition capable of forming a film obtained by curing silicone represented by the formula: It can form crosslinks.

The above-mentioned composition is, for example, a bifunctional silane derivative monomer having an organic group capable of condensation and crosslinking (2 per molecule).
And a trifunctional silane derivative monomer (having three hydrolyzable groups per molecule) having two hydrolyzable groups and two oxygen atoms bonded to each silicon atom to form a bifunctional siloxane bond. A monomer that forms a trifunctional siloxane bond in which three oxygen atoms are bonded to each silicon atom), and optionally has a bifunctional silane derivative monomer and / or a trifunctional silane derivative monomer having an optional organic group. Or a composition containing a tetrafunctional silane derivative monomer (a monomer having four hydrolyzable groups per molecule and forming a four-functional siloxane bond in which four oxygen atoms are bonded to each silicon atom), It is obtained by (partially) hydrolysis and condensation polymerization.

Here, 2 having an organic group capable of condensation and crosslinking is used.
Examples of the functional silane derivative monomer unit include γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ
-(Meth) acryloxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyldiisopropoxysilane, γ-aminopropylmethyldimethoxysilane And γ-aminopropylmethyldiethoxysilane can be suitably used.

The trifunctional silane derivative monomer units having an organic group capable of condensation and crosslinking include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, γ-glycidoxypropyltrimethoxy. Silane, γ
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltributoxysilane, β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriisopropoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltributoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, γ- (meth) Acryloxypropyltributoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltributoxysilane, etc. Can be suitably used.

Other optional bifunctional silane derivative monomer units include, for example, dimethyldimethoxysilane,
Dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, heptadecafluorooctylmethyldimethoxysilane, heptadecafluorooctylmethyldiethoxysilane, and the like can be suitably used.

Other trifunctional silane derivative monomer units having an arbitrary organic group include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane. Silane, ethyltriisopropoxysilane, ethyltrit
Butoxysilane, n-propyltrimethoxysilane,
n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltributoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltributoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-decyltributoxysilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-
Octadecyltriisopropoxysilane, n-octadecyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltributoxysilane,
Trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, trifluoropropyltributoxysilane, heptadecafluorooctyltrimethoxysilane, heptadecafluorooctyltriethoxysilane, heptadecafluorooctyltri Isopropoxysilane, heptadecafluorooctyltributoxysilane, and the like can be suitably used.

As the tetrafunctional silane derivative, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane and the like can be suitably used.

Further, a curing agent may be added to enhance the room temperature curability. Examples of the curing agent include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, sodium formate, potassium acetate, potassium formate, potassium propionate, tetramethylammonium chloride, tetramethylammonium hydroxide and the like. Basic compounds; n-hexylamine, tributylamine, diazabicycloundecene, ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenebentamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ- Aminopropylmethyldimethoxysilane, γ- (2-aminomethyl) -aminopropyltrimethoxysilane, γ- (2-aminomethyl) -aminopropylmethyldimethoxysilane, etc. Titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate; aluminum compounds such as aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetylacetonate, aluminum perchlorate, and aluminum chloride; tin acetylacetonate, dibutyltin Tin compounds such as octylate; metal-containing compounds such as cobalt octylate, cobalt acetylacetonate, iron acetylacetonate; and acidic compounds such as phosphoric acid, nitric acid, phthalic acid, p-toluenesulfonic acid, and trichloroacetic acid are preferable. Available to

Further, metal oxide fine particles may be added to improve the hardness and abrasion resistance of the cured film, or to improve the gloss by increasing the refractive index. As the metal oxide, silica, alumina, cerium oxide, tin oxide, zirconium oxide, hafnium oxide, antimony oxide, iron oxide, titanium oxide, rare earth oxide, and the like can be used.

The above-mentioned coating composition is preferably dispersed in a non-aqueous solvent in order to improve the storage stability of the coating composition. As a non-aqueous solvent,
Alcohol, ketone, ester, toluene, xylene,
Hexane and the like can be suitably used.

In the present invention, the silicone resin film or the coating composition may contain a fluorine resin or a fluorine compound for improving water repellency. Here, as the fluororesin, for example, polyvinyl fluoride, polyvinylidene fluoride, polychlorinated ethylene trifluoride, polytetrafluoroethylene, polytetrafluoroethylene-hexafluoropropylene copolymer, ethylene-polytetrafluoroethylene copolymer, ethylene-polychloride Ethylene trifluoride copolymer, ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer, perfluorocyclopolymer, vinyl ether-fluoroolefin copolymer, vinyl ester-fluoroolefin copolymer, and the like can be suitably used. Examples of the fluorine compound include lithium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, scandium fluoride, yttrium fluoride, zirconium fluoride, hafnium fluoride, manganese fluoride, and fluorinated fluoride. Iron fossil, cobalt fluoride, nickel fluoride, copper fluoride, aluminum fluoride, gallium fluoride, indium fluoride, bismuth fluoride, lanthanum fluoride, cerium fluoride, praseodymium fluoride, neodymium fluoride, samarium fluoride , Europium fluoride, terbium fluoride, dysprosium fluoride, holmium fluoride, erbium fluoride, thulium fluoride, ytterbium fluoride, lutetium fluoride and the like can be suitably used.

The silicone resin film or the coating composition for glazed products of the present invention may further contain an antibacterial agent. Here, antibacterial agents include antibacterial metals such as silver, copper, and zinc, and fine particles of the compounds or carriers carried on carriers such as silica gel and zeolite, quaternary ammonium salts, nitrile derivatives, imidazole derivatives, benzothiazole derivatives, Thiazole derivatives, thiadiazole derivatives,
Triazine derivatives, sulfone derivatives, phenol derivatives, phenol ether derivatives, pyrrole derivatives and the like can be suitably used.

The above antibacterial agent may be exposed and fixed so that a part thereof comes into contact with the outside air. By doing so, the antibacterial property in the early stage of use is improved.

(Example) Comparative example 1 (sanitary ware Sana: how to stain without a coat) As a sample, sanitary sana made by Totoki Kiki (model number: U3
07CST), color: pastel ivory (# SC1) was used. Using this sample, a urolith adhesion test, an alkali solution immersion test, and a contact angle measurement of water and a tar solution were performed. Urinary stone adhesion test, after immersing the above-mentioned sana in urine for 1 week at room temperature, and then withdrawn, lightly washed with running water,
The amount of urinary stones adhering to the sides of Sana was visually evaluated. As a result, a large amount of urolith was attached to the side of Sana. Also,
It did not fall even under running water. In the alkali-resistant solution immersion test, after the above-mentioned sana was immersed in a 5% NaOH aqueous solution for one week at room temperature and allowed to stand, the surface state of the sana side surface was evaluated by gloss measurement. The gloss was measured according to the specular gloss measurement method (JIS-Z8741) according to the 60-degree specular gloss G.
s (60 °) was measured. As a result, the glossiness after dipping (residual glossiness) with respect to the initial value was 90%. The contact angle between the sample surface, water and the tar solution was measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., CA-X150), and 30 seconds after dropping a water or tar solution droplet from the micro syringe onto the sample surface. It was measured. As a result, the contact angle of water was 30 °, and the contact angle of the tar solution was 20 °.

Comparative Example 2 (Stainage and alkali resistance test when a coat having no cross-linking other than siloxane cross-linking was applied) To 100 parts by weight of methyltriethoxysilane, 5 parts by weight of water and 1 part by weight of nitric acid were added. The solution obtained by stirring and reacting for 2 hours was spray-coated on the surface of urinal sana (U307CST, # SC1) having the same shape as that of Comparative Example 1. After drying at room temperature for 30 minutes, 20
The composition was heated and cured at 0 ° C. for 30 minutes to form a silicone coating film on the surface of Sana. When the obtained sample was evaluated in the same manner as in Comparative Example 1, the amount of attached urine stone was small, and it was possible to wash it off with running water. In the sample after the alkali resistance test, the coating film was peeled off and the glaze surface of the substrate was exposed. The gloss retention was 92%. Furthermore, the contact angle of water is 90
接触, the contact angle of the tar solution was 20 °.

Example 1 (Stain for an acrylic silicone coat and alkali resistance test) Urinal sana (U307C) having the same shape as Comparative Examples 1 and 2
ST, # SC1) JSR Glaska B603 was spray-coated on the surface. After drying at room temperature for 30 minutes, it was heated and cured at 200 ° C. for 30 minutes to form an inorganic / organic hybrid film composed of silicone and acrylic on the surface of Sana. When the obtained sample was evaluated in the same manner as in Comparative Examples 1 and 2, the attached amount of urine stone was further smaller than in Comparative Example 2, and it could be almost completely washed away with running water. Further, even after the alkali resistance test, there was no peeling or falling off of the film, and the gloss retention was 98%. Further, the contact angle of water was 95 ° and the contact angle of the tar solution was 30 °.

FIG. 2 shows the evaluation results. As shown in FIG. 2, a large amount of urine stone adheres to the glaze surface of the existing sanitary ware, and cannot be washed off under running water. on the other hand,
Although coating of a silicone film could suppress the adhesion of urinary stones, a film consisting only of siloxane crosslinks cannot be used in an alkaline environment. Here, by using a siloxane / acrylic inorganic / organic hybrid film, the film has sufficient durability even when used in an alkaline environment, and can prevent adhesion of urine stone.

[0024]

According to the present invention, even when used in an alkaline environment, while having sufficient durability under use conditions,
It is possible to provide an antifouling glazed product, an adhesive film for a glazed product, and a coating composition for a glazed product, in which water-based stains such as urine stones and scales are unlikely to adhere.

[Brief description of the drawings]

FIG. 1 is a view showing one embodiment relating to the structure of a resin of the present invention.

FIG. 2 is a table showing evaluation results of Comparative Examples 1 and 2 and Examples.

[Explanation of symbols]

 1 ... siloxane bond 2 ... bond other than siloxane

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H011 AA02 AA05 BA01 BB09 BB18 BC19 DA07 DA11 DD07 DG16 DH02 DH07 DH08 DH20 4J004 AB01 CC02 CC05 CD06 DA04 FA04 4J038 DL031 DL071 DL121 GA02 GA12 KA02 LA02 NA05 NA07 P02 P05

Claims (14)

[Claims] 1. An antifouling glazed product characterized in that a silicone resin film polymerized by siloxane crosslinking and crosslinking other than siloxane is formed on the surface of a substrate having a glaze layer formed on the surface. 2. The antifouling glazed product according to claim 1, wherein the crosslink other than the siloxane is a crosslink based on condensation polymerization of an acrylic group. 3. The antifouling glazed product according to claim 1, wherein the silicone resin film further contains an antibacterial agent. 4. The antifouling glazed product according to claim 3, wherein a part of the antibacterial agent is exposed and fixed. 5. The antifouling glazed product according to claim 1, wherein the silicone resin film is a silicone resin film containing a fluoro group. 6. A film comprising a silicone resin film polymerized by siloxane crosslinking and crosslinking other than siloxane on the surface of the substrate, and an adhesive layer formed on the back surface of the substrate. Adhesive film for glazed products, characterized in that it adheres to the surface of the glaze layer to prevent water-based stains on the glazed product surface. 7. The adhesive film for a glazed product according to claim 6, wherein the crosslinking other than the siloxane is crosslinking based on condensation polymerization of an acrylic group. 8. The adhesive film for a glazed product according to claim 6, wherein the silicone resin film and / or the base material contains an antibacterial agent. 9. The adhesive film according to claim 8, wherein a part of the antibacterial agent is exposed and fixed. 10. The adhesive film according to claim 6, wherein the silicone resin film is a silicone resin film containing a fluoro group. 11. A glaze product comprising a precursor capable of forming a silicone resin film polymerized by siloxane cross-linking and cross-linking other than siloxane by being hydrolyzed and polymerized as required, and a polymer film on the surface of the glaze product glaze layer. A coating composition for a glazed product, characterized in that the formation of a coating prevents water-based stains on the surface of the glazed product. 12. The coating composition for a glazed product according to claim 7, wherein the crosslinking other than the siloxane is crosslinking based on condensation polymerization of an acrylic group. 13. The coating composition according to claim 11, wherein the coating composition contains an antibacterial agent.
3. The coating composition for a glazed product according to item 1. 14. The adhesive film according to claim 11, wherein the silicone resin film is a silicone resin film containing a fluoro group.