WO2012036053A1

WO2012036053A1 - Antifouling article and production method therefor, and embrocation for forming antifouling layer

Info

Publication number: WO2012036053A1
Application number: PCT/JP2011/070431
Authority: WO
Inventors: 陽平佐藤; 濱口　滋生
Original assignee: セントラル硝子株式会社
Priority date: 2010-09-14
Filing date: 2011-09-08
Publication date: 2012-03-22
Also published as: CN103097475A; KR20130058747A; JP2012144695A; KR101485719B1

Abstract

This embrocation for forming an antifouling layer is an organic solvent having a surface tension of 20.0 mN/m or less, and a boiling point of 95 to 200°C, and is obtained by dissolving silane containing a perfluoropolyether group represented by general formula [1]. An antifouling article formed with an antifouling layer using the embrocation is excellent in antifouling performance and abrasion resistance, and further, even if the surface of the antifouling layer of the antifouling article is exposed to vapor such as water, dot-like or streaky cloudiness is not generated on the surface, and the appearance and the design are not impaired.

Description

Antifouling article and method for producing the same, and coating agent for forming antifouling layer

The present invention forms an antifouling layer that hardly adheres to pollutants, is easy to remove adhering pollutants, and does not have an appearance of white turbidity appearing in the form of dots or streaks when exposed to steam such as water. The present invention relates to a coating agent, an article having an antifouling layer formed using the coating agent, and a method for producing the same.

Metals, glass, plastics, ceramics and other base materials are widely used as automobile parts, household items, home appliances, and OA equipment. The surface of these substrates is often contaminated with water droplets or scales due to rain, oily substances such as floating dust or cigarette dust, and fingerprints or sebum from human hands. Further, there is a demand for an antifouling function capable of easily removing dirt once adhered.

Many methods have been proposed so far to develop such antifouling function. Patent Document 1 discloses an antifouling agent composition comprising a compound having a perfluoroalkyl ether group. Patent Document 2 discloses a water-repellent treated glass in which a treated film mainly composed of an alkoxysilane compound having a perfluoropolyether group having excellent water repellency, antifouling properties and durability is formed on a substrate. . Patent Document 3 discloses a fluorine-containing polymer excellent in antifouling properties against oily contaminants, and particularly excellent in antifouling properties against fingerprints, and an antifouling substrate in which the polymer layer is formed on the substrate surface. Patent Document 4 discloses a perfluoropoly-modified silane excellent in durability, antifouling property, particularly fingerprint wiping property, and a surface treatment agent containing this as a main component.

JP 2000-234071 A Japanese Patent Laid-Open No. 11-092177 International Publication No. 98/49218 JP 2003-238777 A

As shown in the above-mentioned patent document, when forming a coating layer (hereinafter referred to as an antifouling layer) that exhibits an antifouling function on the surface of a substrate, as a material constituting the antifouling layer, water and oil repellency In many cases, a fluorine-containing compound having a high value is used. In order to provide such a fluorine-containing compound antifouling layer on the substrate surface, the raw material for the antifouling layer is dissolved in a fluorine-based solvent, an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, a hydrocarbon-based solvent, or the like. A method of applying a dispersed liquid has been generally used. As a solvent for diluting the raw material of the antifouling layer, for example, in Patent Document 1, hexafluorobenzene, in Patent Document 2, isopropanol, in Patent Document 3, perfluorohexane, etc., in Patent Document 4, perfluoro ( 2-butyltetrahydrofuran) is used.

However, if the coating solution obtained by diluting the antifouling layer raw material with an appropriate solvent is not applied to the substrate surface, the portion where the liquid level is raised by the aggregating action of the coating solution (hereinafter referred to as “liquid pool”) And the part which is not so tends to be in a mixed state on the substrate surface. In the case of applying to a substrate in an open system, as the solvent evaporates, the coating liquid does not sufficiently spread on the surface of the substrate. As a result, coating unevenness tends to occur and the coating operation tends to be difficult. When the coating is continuously performed on a large number of substrates, the appearance and antifouling properties of the antifouling layer tend to be unstable for each substrate due to the change in the concentration of the coating agent. Moreover, if it is not applied by an appropriate application method, uneven application tends to occur. If the surface of the antifouling layer obtained after drying is wiped off, a uniform antifouling layer can be obtained by visual observation, but if the antifouling layer surface is exposed to steam such as water, the liquid pool and There is a problem that dot-like or streak-like white turbidity emerges on the surface of the antifouling layer by selectively adhering droplets to the places where there is uneven coating.

In view of the above problems, the present invention provides a coating agent for forming an antifouling layer in which dot-like or streaky white turbidity does not appear on the surface even when exposed to steam such as water, and the coating agent. An object of the present invention is to provide an antifouling article having an antifouling layer and a method for producing the same.

As a result of intensive studies, the present inventors have used a coating agent in which a perfluoropolyether group-containing silane is dissolved in a specific organic solvent, and forming a coating layer in which the perfluoropolyether group-containing silane is condensed, It has been found that the coating layer functions as an antifouling layer that exhibits an antifouling function and has an appearance that does not reveal dot-like or streaky white turbidity on the surface even when exposed to steam such as water. It came to.

That is, the present invention is an organic solvent having a surface tension of 20.0 mN / m or less and a boiling point of 95 to 200 ° C., in which a perfluoropolyether group-containing silane represented by the following general formula [1] is dissolved. An antifouling layer-forming coating agent for an antifouling article used under steam is provided.

(Wherein W represents a fluorine atom or a substituent represented by the structure of the following formula.

X is represented by the formula: — (O) _g — (CF ₂ ) _h — (CH ₂ ) _i — (where g, h and i each independently represents an integer of 0 to 50, and g and The sum of h is 1 or more, and the order of presence of each repeating unit enclosed in parentheses is arbitrary in the formula. Y represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. Z represents at least one hydrolyzable functional group selected from the group consisting of alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, chloro group, and isocyanate group. R represents an alkyl group having 1 to 10 carbon atoms. a represents an integer of 0 to 50, b represents an integer of 1 to 200, c represents an integer of 1 to 3, d represents an integer of 1 to 10, and e and f are each independently 0 Represents an integer of ˜5, m and n are each independently an integer of 0 to 50, and the sum of m and n is 1 or more. )

It is preferable that 60 to 100% by mass of a fluorinated solvent is contained in 100% by mass of the organic solvent. The fluorine-based solvent is preferably at least one selected from the group consisting of hydrofluorocarbon, perfluorocarbon, hydrofluoroether, and hydrochlorofluorocarbon, and at least one selected from the group consisting of perfluorocarbon and hydrofluoroether. More preferably.

Further, it is preferable that 0.01 to 5% by mass of the perfluoropolyether group-containing silane represented by the general formula [1] is contained in 100% by mass of the antifouling layer forming coating agent.

Furthermore, the present invention provides a method for producing an antifouling article using the above antifouling layer-forming coating agent, wherein (1) the holding member holding the coating agent is brought into contact with the substrate surface, Application A in which the coating agent is applied to the entire surface by reciprocating in a specific direction on the substrate surface, and then the holding member is brought into contact with the substrate surface again, and the holding member is applied on the substrate surface with the application A. A process having coating B for recognizing the coating agent on the entire surface by reciprocating in one direction different from the direction, and finally coating C for coating the coating agent along the edge of the substrate; (2) the coated coating agent A method for producing an antifouling article, comprising the step of drying the antifouling article, and an antifouling article produced by the production method and used under steam.

It is the schematic showing an example of the suitable coating method of the coating agent for antifouling layer formation of this invention. It is a drawing substitute appearance photograph of the surface of an antifouling layer in which dot-like white turbidity is generated by exposure to water vapor.

Hereinafter, the present invention will be described in detail.

The antifouling layer-forming coating agent of the present invention is an organic solvent having a surface tension of 20.0 mN / m or less and a boiling point of 95 to 200 ° C., which is a perfluoropolyether group represented by the following general formula [1]. Dissolved silane.

In general formula [1], W represents a fluorine atom or a substituent represented by the structure of the following formula.

X represents the formula: — (O) _g — (CF ₂ ) _h — (CH ₂ ) _i — (wherein g, h and i each independently represents an integer of 0 to 50, and The sum of g and h is 1 or more, and the order of presence of each repeating unit in parentheses is arbitrary in the formula. Y represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, and Z is selected from the group consisting of alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, chloro group, and isocyanate group And at least one hydrolyzable functional group, R represents an alkyl group having 1 to 10 carbon atoms. a represents an integer of 0 to 50, b represents an integer of 1 to 200, c represents an integer of 1 to 3, d represents an integer of 1 to 10, and e and f are each independently 0 Represents an integer of ˜5, m and n are each independently an integer of 0 to 50, and the sum of m and n is 1 or more.

In the general formula [1], — [CF ₂ ] _a —, — [C _m F _2m OC _n F _2n ] _b —, [— (O) _g — (CF ₂ ) _h — (CH ₂ ) _i —], - [CH _2] _e - and, - [CH _2] _f - can impart excellent antifouling performance and wear resistance moiety represented by. Therefore, the antifouling layer formed by condensation of the perfluoropolyether group-containing silane as represented by the general formula [1] is preferable because it can achieve both excellent antifouling performance and wear resistance.

Further, in the general formula [1], the hydrolyzable functional group Z condenses to form an antifouling layer, thereby imparting excellent adhesion between the antifouling layer and the substrate surface. it can.

In the general formula [1], if the reactivity of the hydrolyzable functional group Z is too high, not only is the handling difficult when preparing the coating agent, but the pot life of the coating agent is shortened. On the other hand, if the reactivity is too low, the hydrolysis reaction will not proceed sufficiently, and the amount of silanol groups produced will not be sufficient, so the bonds formed between the silanol groups and the active species on the substrate surface ( For example, siloxane bonds and other metalloxane bonds) and interactions (for example, van der Waals forces and electrostatic interactions) are not sufficient, and sufficient adhesion between the antifouling layer and the substrate surface Property cannot be imparted or the durability of the antifouling layer is lowered. In view of the above, the hydrolyzable functional group Z is at least one selected from the group consisting of alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, chloro group, and isocyanate group Is preferred. Among these, considering the ease of handling of hydrolyzable functional groups, the pot life of the coating agent, and the durability of the resulting antifouling layer, the hydrolyzable functional groups are preferably alkoxy groups, of which methoxy groups An ethoxy group is particularly preferred.

The perfluoropolyether group-containing silane represented by the general formula [1] is considered to be bonded to the substrate surface by Si—O— bonds by hydrolysis of the functional group represented by Z in the Si—Z site. The mole number of fluorine in the perfluoropolyether group-containing silane is about 20 to 200 with respect to 1 mol of silicon contained in the bondable site (Si group-containing site) in the perfluoropolyether group-containing silane. When it exists, since favorable water-repellent performance can be provided to a base material, it is preferable.

Among the perfluoropolyether group-containing silanes represented by the general formula [1], perfluoropolyether group-containing silanes having a structure represented by the following general formula [2] and the general formula [3] are preferable compounds. .

In the formula, Rf ¹ represents a linear perfluoroalkyl group having 1 to 100 carbon atoms, p represents an integer of 1 to 100, and q represents an integer of 0 to 2. Y, R, and d are the same as those in the general formula [1].

In the formula, Rf ² is a linear perfluoroalkylene ether containing a unit represented by the formula: — (C _t F _2t O) — (t is an integer of 1 to 6) and having no branch. A divalent group having a structure, or a perfluoroalkyl structure containing a unit represented by —C _u F _2u — (u is an integer of 1 to 8), and r and r ′ are each 1 to 5 , S and s ′ each represent an integer of 0 to 2. R, Z, and c are the same as those in the general formula [1].
Examples of commercially available products containing such compounds include OPTOOL AES series such as OPTOOL DSX and OPTOOL AES4 manufactured by Daikin Industries, KY130 and KY108 manufactured by Shin-Etsu Chemical, and Fluorosurf FG-5020 manufactured by Fluoro Technology. In addition, when preparing the coating agent of this invention using the said commercial item, the solvent contained in this commercial item shall be contained as a part of solvent in the coating agent of this invention.

The organic solvent in the coating agent of the present invention has a surface tension of 20.0 mN / m or less. When the surface tension of the organic solvent is more than 20.0 mN / m, when the coating agent is applied to the base material, the coagulation action of the coating agent causes a state in which the liquid pool portion and the portion other than the liquid pool are mixed. Cheap. The surface of the antifouling layer obtained after drying can be wiped off to remove the excess antifouling layer, and a uniform antifouling layer can be obtained by visual observation, but if the antifouling layer surface is exposed to steam such as water Since the liquid droplets selectively adhere to the place where the liquid pool is present, it is not preferable because dot-like white turbidity easily occurs on the surface of the antifouling layer. A more preferable organic solvent is a solvent having a surface tension of 19.5 mN / m or less, and more preferably a solvent having a surface tension of 19.3 mN / m or less. The surface tension of the liquid can be measured by, for example, a plate method.

The boiling point of the organic solvent is 95 to 200 ° C. When the boiling point of the organic solvent is less than 95 ° C., the drying speed after applying the chemical solution is too fast, and uneven coating tends to occur, or the chemical solution volatilizes during the application, and the substrate surface tends not to be completely spread. . In addition, when the coating is continuously applied to a large number of substrates in an open system, the concentration of the perfluoropolyether group-containing silane in the coating agent increases as the organic solvent evaporates. The soiling tends to be unstable for each substrate. When the boiling point of the organic solvent exceeds 200 ° C., high temperature or a long time is required for drying, and industrial disadvantages tend to increase. The boiling point of the organic solvent is more preferably 105 to 180 ° C.

It is preferable that the organic solvent contains 60 to 100% by mass of a fluorinated solvent. When the concentration of the fluorinated solvent in the organic solvent is less than 60% by mass, the perfluoropolyether group-containing silane represented by the general formula [1] is not sufficiently dissolved, or the surface of the antifouling layer is in the form of dots or streaks. It is not preferable because the white turbidity easily occurs. Also, when applying to a large number of substrates continuously in an open system, the appearance of the antifouling layer becomes more susceptible to changes in the concentration of the perfluoropolyether group-containing silane in the coating agent as the organic solvent evaporates. And antifouling properties tend to be difficult to stabilize for each substrate. A more preferable concentration of the fluorinated solvent in the organic solvent is 70 to 100% by mass, and further preferably 80 to 100% by mass.

The fluorinated solvent is preferably at least one selected from the group consisting of hydrofluorocarbons, perfluorocarbons, perfluoroethers, hydrofluoroethers, and hydrochlorofluorocarbons. In consideration of an appropriate surface tension and an appropriate boiling point, perfluorocarbon and hydrofluoroether are more preferable. In consideration of environmental burden, hydrofluoroether having a smaller global warming potential is particularly preferable as the fluorinated solvent.

When one organic solvent is used as the organic solvent, a fluorine-based solvent having a surface tension of 20.0 mN / m or less and a boiling point of 95 to 200 ° C. can be used. For example, perfluorocarbons such as perfluorononane, perfluorodecane, fluorine-based inert liquids (for example, “Fluorinert FC40”, “Fluorinert FC43”, “Fluorinert FC3283” manufactured by Sumitomo 3M), 1,1,1,2, Hydrofluoroethers such as 3,3-hexafluoro-4- (1,1,2,3,3,3-hexafluoropropoxy) -pentane (“Novec 7600” manufactured by Sumitomo 3M) can be used.

Further, when a plurality of organic solvents are used as the organic solvent, the organic solvent after mixing may have a surface tension of 20.0 mN / m or less and a boiling point of 95 to 200 ° C. A mixed solution can be used. In addition, the above-mentioned fluorinated solvent and a mixture thereof may be added to 1,1,2,2,3,3,4,4-octafluorobutane, 1,3-bis (trifluoromethyl) benzene, heptafluorocyclopentane ( “Zeorolla H” from Nippon Zeon), 2H, 3H-decafluoropentane (“Bertrel XF” from DuPont), hydrofluorocarbons such as 1,1,1,3,3,3-hexafluoroisopropanol, perfluorohexane, Perfluoroalkanes represented by C _n F _{2n + 2} such as fluoroheptane and perfluorooctane (“Fluorinert PF5060”, “Fluorinert PF5070” and “Fluorinert PF5080” manufactured by Sumitomo 3M, respectively) 1,3-dimethylcyclohexane, fluorine-based inert liquid Perfluorocarbons such as “Fluorinert FC series” manufactured by Sumitomo 3M), perfluoroethers such as perfluoro (2-butyltetrahydrofuran), methyl perfluorobutyl ether (“Novec7100” manufactured by Sumitomo 3M), nonafluorobutyl ethyl ether (manufactured by Sumitomo 3M) "Novec7200"), hydrofluoroethers such as methyl perfluorohexyl ether ("Novec7300" manufactured by Sumitomo 3M), 1,2-dichloro-3,3,3-trifluoropropene, 1-chloro-3,3,3- Hydrochlorofluorocarbons such as trifluoropropene, 3,3-dichloro-1,1,1,2,2-pentafluoropropane ("HCFC-225" manufactured by Asahi Glass), butane, hexane, 2-methylpentane, 2 , 2-Dimethylbutane , A mixture of hydrocarbon solvents such as 2,3-dimethylbutane and 2-methylhexane can be used.

The concentration of the perfluoropolyether group-containing silane represented by the general formula [1] is preferably 0.01 to 5% by mass. When the concentration is less than 0.01% by mass, it is not preferable because sufficient antifouling performance cannot be exhibited on the surface of the substrate or the antifouling layer becomes non-uniform. If the concentration exceeds 5% by mass, it is difficult to remove the surplus of the antifouling layer, or the surplus to be removed increases, resulting in high costs. From the viewpoint of antifouling performance, removal of surplus, and cost, a more preferable concentration range is 0.05 to 1% by mass, and a more preferable concentration range is 0.1 to 0.4% by mass.

A catalyst may be added to the antifouling layer forming coating agent for the purpose of promoting the hydrolysis reaction and condensation reaction of the perfluoropolyether group-containing silane represented by the general formula [1]. Examples of the catalyst include organic tin compounds such as dibutyltin dimethoxide and dibutyltin dilaurate, organic titanium compounds such as tetra n-butyl titanate, organic acids such as acetic acid and methanesulfonic acid, and inorganic acids such as hydrochloric acid and sulfuric acid. Can be mentioned. In particular, acetic acid, tetra n-butyl titanate, dibutyltin dilaurate and the like are preferable. The amount added is preferably 0.01 to 5% by weight, particularly 0.05 to 1% by weight, based on the weight of the perfluoropolyether group-containing silane.

Further, the antifouling layer-forming coating agent includes a surfactant, a crosslinking agent, an antioxidant, an ultraviolet absorber, an infrared absorber, a flame retardant, a hydrolysis inhibitor, an antibacterial agent as long as the object of the present invention is not impaired. A glaze or the like may be added.

The antifouling article of the present invention is produced through at least the following steps using the coating agent for forming an antifouling layer.
(1) The holding member holding the coating agent is brought into contact with the substrate surface, the holding member is reciprocated in a specific direction on the substrate surface, and applied to the entire surface, and then the holding member is again applied to the substrate surface. The holding member is moved back and forth in one direction different from the coating direction in the coating A on the surface of the base material to apply the coating agent to the entire surface, and finally applied along the edge of the base material. A coating process having coating C.
(2) A drying step of drying the applied coating agent.

In the present invention, the substrate is not particularly limited. For example, a float plate glass used for a window glass for buildings, or a plate glass having an inorganic transparency such as a soda lime glass manufactured by a roll-out method can be used. Glass substrates such as displays, touch panels, showcases, etc., glass substrates such as pachinko machine front plates, reflective substrates such as mirrors, rubbed glass, and glass with patterns. A translucent or opaque glass substrate such as can be used. In addition to the glass substrate, substrates made of ceramic materials used for tiles, tiles, sanitary ware, tableware, frames such as glass windows, cookers, scalpels, medical instruments such as scalpels, injection needles, sinks, automobiles Metal materials such as stainless steel, aluminum, steel, etc. used in the body of plastics, plastic base materials such as polycarbonate resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polyethylene resin, polyvinyl chloride resin, other plastics A substrate can be used.

Various types of molded bodies such as flat plates and bent plates can be used for the base material, and the size and thickness are not particularly limited. The antifouling layer may be formed on the surface of the base material either entirely or partially on the base material surface.

Also, in order to further improve the durability of the antifouling article, a treatment for improving the adhesive strength between the base material and the antifouling layer can be performed on the base material surface in advance. Examples of the treatment include polishing / washing / drying with various polishing liquids, surface modification treatment with acidic solution or basic solution, primer treatment, plasma irradiation, corona discharge, high-pressure mercury lamp irradiation, etc. Generation. In the formula [1], a bond formed between the hydrolyzable functional group represented by Z or a silanol group formed by hydrolysis thereof (for example, a siloxane bond) Sufficient adhesion between the antifouling layer and the substrate surface can be imparted by metalloxane bonds and the like) and interactions (for example, van der Waals force and electrostatic interaction).

In the coating step (1), the coating agent can be spread over the entire surface of the substrate by coating A. Next, the coating surface can be uniformly leveled by coating B. The reciprocating direction of the member for coating B is not particularly limited, but the angle θ formed by the reciprocating direction of the member for coating A and the reciprocating direction of the member for coating B (θ is 0 ° or more and less than 180 °). Is preferably in the direction of an angle of 20 to 160 ° because it can be applied more uniformly. More preferably, the direction is an angle of 45 to 135 °. Finally, from the coating C, the coating agent can be reliably applied to the end portion where forgetting to apply or lack of the coating agent is likely to occur.

As a holding member for holding the coating agent, there is a nonwoven fabric made of pulp, acrylic, PET, PP, nylon, rayon, etc., but a composite material of pulp and PP is particularly preferable from the viewpoint of strength and liquid absorbency. .

As a method of applying the coating agent to the substrate surface, various coating methods such as brush coating, hand coating, robot coating, and combinations thereof can be used. In addition, it can also apply | coat by making the base material surface contact this holding member in the state which fixed the holding member for hold | maintaining a coating agent, and moving this base material. Hand coating is preferable.

In the drying step (2) after the coating step (1), an antifouling layer is formed by condensing the perfluoropolyether group-containing silane represented by the general formula [1], and the perfluoropolyether group-containing Sufficient adhesion between the antifouling layer and the substrate surface is expressed by the bond or interaction formed between the silanol group generated from silane and the active species on the substrate surface. The drying step is preferably performed at 50 to 250 ° C., more preferably 100 to 200 ° C., and may be performed under normal pressure, increased pressure, reduced pressure, or inert atmosphere. Microwave heating is also effective.

If there is a surplus on the surface of the antifouling layer obtained after the drying step (2), the surplus is wiped away. An antifouling layer having a uniform surface can be obtained by wiping with a paper towel or cloth moistened with an organic solvent and / or a dry paper towel or cloth. In particular, it is preferable to wipe with disposable papers such as paper towels and tissue papers.

Further, even when the surface of the antifouling layer is exposed to steam such as water and droplets adhere, it is preferable that the appearance of white turbidity appear in the form of dots or streaks on the surface of the antifouling layer. This is because even if droplets adhere to the surface of the antifouling layer due to steam or the like, the antifouling article does not impair the appearance or design, or there is a difference in how the dirt is removed, resulting in an appearance or design. This is because there is no loss.

The fluorine count (fluorine concentration) of the antifouling article obtained by this production method varies depending on the composition of the coating agent used, coating conditions, etc., but usually it is sufficient if the fluorine count is 0.2 μg / cm ² or more. Antifouling performance is obtained, more preferably 0.4 μg / cm ² or more. Further, the obtained antifouling article can prevent dot-like or streaky white turbidity that appears on the surface of the antifouling layer as the fluorine count in the arbitrary portion has less variation. Usually, if the variation in the fluorine count (difference between the maximum value and the minimum value) is 1.6 μg / cm ² or less, the appearance of the antifouling article when exposed to water vapor or the like and droplets adhere to it The design is not impaired, more preferably 1.3 μg / cm ² or less.

The antifouling article obtained by this production method is suitable for use in an environment where antifouling properties are required, but it is particularly preferred to be used under steam. Under steam is an environment that is often exposed to steam, and includes, for example, bathrooms and washstands where a large amount of steam is generated, and kitchen areas that are exposed to steam such as water and oil. Thus, antifouling articles used under steam include, for example, bathroom faucets, mirrors, walls, partitions, windows, doors and washstand mirrors, cabinets, wash bowls, faucets, counters and around kitchens. It can be used for partitions, kitchen hoods, ventilators, cooking ranges, heat sinks around the sinks and convenience stores, etc., and is especially suitable for water-partitions such as bathroom mirrors, mirrors for washstands, kitchens and washstands.

Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples.

In this example and comparative example, an antifouling layer-forming coating agent was prepared and applied on a substrate to produce an antifouling article. The method for preparing the coating agent and the method for producing the antifouling article are as described below. Moreover, quality evaluation was performed by the method shown below about the surface tension of the organic solvent used for the coating agent and the antifouling layer of the obtained antifouling article.

[Surface tension of organic solvent]
The surface tension of the organic solvent was measured by a plate method using an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. The material of the plate was platinum, and the measurement temperature was 25 ± 2 ° C.

[Contamination resistance]
As a simulated contamination on the surface of the antifouling layer, draw a line with a sign pen (trade name: Mackey Care Black, manufactured by Zebra), observe the ink repelling condition of the sign pen, wipe off the ink with a paper towel, and visually observe the appearance. Then, the stain resistance of the antifouling layer was evaluated according to the following criteria.
○: The surface of the antifouling layer repels ink and is wiped off. Δ: The surface of the antifouling layer repels ink but cannot be wiped off. ×: The surface of the antifouling layer does not repel ink.

[Water resistance]
Industrial water is sprayed on the surface of the antifouling layer and dried at 50 ° C. for 3 hours. The surface is wiped off with a paper towel, the appearance is visually observed, and the antifouling layer is evaluated for water resistance according to the following criteria. did.
○: Dust can be wiped off from the surface of the antifouling layer. △: Dust can be almost wiped off from the surface of the antifouling layer, but there is a portion that cannot be wiped off.

[Abrasion resistance (polishing resistance)]
A cotton cloth impregnated with a ceria suspension (10% by mass) in which glass abrasives Milleak A (T) (Mitsui Mining & Mining Co., Ltd.) is dispersed in tap water. The surface of the antifouling layer is about 1.5 kg / Polished with a strength of cm ² . The number of times of polishing (reciprocation) until 70% of the polishing region became hydrophilic was evaluated. Here, the abrasion resistance (abrasion resistance) of the antifouling layer is less than 50 polishing times (represented as x in Table 1), more than 50 polishing times (represented as ○ in Table 1), Polishing frequency of 80 times or more was judged as good (indicated by “◎” in Table 1).

[Appearance when cloudy]
The surface of the antifouling layer of the antifouling article kept at room temperature was fogged by applying steam with a steamer, the appearance was visually observed, and the appearance of the antifouling layer was evaluated according to the following criteria.
○: Dot or streaky white turbidity is not confirmed when cloudy ×: Dot or streaky white turbidity is confirmed when cloudy

[Continuous productivity]
Under the same conditions, an antifouling layer was continuously formed on the surface of 100 substrates, and the continuous productivity of the antifouling article was evaluated according to the following criteria.
◎: Performance (contamination resistance, scale resistance, abrasion resistance) on all 100 sheets and no problem in appearance when cloudy, can be produced without delay ○: Performance (contamination resistance, scale resistance on all 50 sheets) And wear resistance) and can be produced without any problem in the appearance when cloudy. ×: NG products are generated in quality and appearance up to 50 sheets.

[Ease of application]
Using 10 ml of the antifouling layer-forming coating agent, the number of sheets on which the surface of a 300 mm × 300 mm size float glass substrate could be coated was evaluated as ease of coating.

[Fluorine count]
Using a fluorescent X-ray analyzer ZSX Primus II (manufactured by Rigaku Corporation), the fluorine concentration of the antifouling layer was measured at five points, and the variation (difference between the maximum value and the minimum value) was evaluated as the fluorine count.

Example 1
(I) Preparation of coating agent for antifouling layer formation OPTOOL DSX (manufactured by Daikin Industries: Perfluoropolyether group-containing silane perfluorohexane solution (solid content concentration 20% by mass), and the estimated structure is represented by the general formula [2] Novec 7600 (manufactured by Sumitomo 3M: 1,1,1,2,3,3-hexafluoro-4- (1,1) having a surface tension of 17.7 mN / m and a boiling point of 131 ° C. , 2,3,3,3-hexafluoropropoxy) pentane) 50.0 g and stirred at room temperature for 30 minutes to obtain a coating agent having a perfluoropolyether group-containing silane concentration of 0.3% by mass. .

(II) Preparation of Base Material (Glass Substrate) The surface of a 300 mm × 300 mm × 2 mm thick float glass substrate was polished with a polishing liquid, washed with water and dried. In addition, 2 mass% ceria suspension which mixed glass abrasive | polishing agent Milleak A (T) (made by Mitsui Kinzoku Kogyo) in water was used as said polishing liquid.

(III) Formation of Antifouling Layer A cotton cloth (trade name: Bencott) holding 1.0 ml of the coating agent prepared in (I) above is brought into contact with a glass substrate and specified as coating A as shown in FIG. 1 is reciprocated in one direction (lateral direction in FIG. 1) and applied to the entire surface, and then as application B, it is reciprocated in a direction (vertical direction in FIG. 1) that is about 90 ° with respect to the application direction of application A. Finally, after applying along the end as application C (described as “suitable application by hand coating (90 °)” in Table 1), the glass substrate was placed in an electric furnace. Dried for minutes. At this time, the maximum reached temperature (drying temperature) of the glass was 150 ° C. Finally, excess components remaining in the white mottle visually were wiped up with a paper towel moistened with isopropyl alcohol, and a transparent sample with a uniform surface was obtained by visual observation.

The antifouling layer of the obtained antifouling article has excellent antifouling performance and abrasion resistance, with antifouling property, ○ with water resistance, ○ with wear resistance, and ○ when cloudy. In addition, even when the antifouling layer surface of the antifouling article was exposed to steam such as water, no dot-like or streak-like white turbidity was generated on the surface. Moreover, there was no problem even if 100 sheets were produced continuously. Moreover, 10 sheets of the surface of the 300 mm x 300 mm size float glass substrate were able to be apply | coated using the coating agent for antifouling layer forming of 10 ml. Further, the variation in fluorine count was 0.2 μg / cm ² . Table 1 shows the quality evaluation results.

Examples 2-7
A transparent sample having a uniform surface by visual observation is obtained by appropriately changing the type, concentration, type of organic solvent, concentration of the fluorinated solvent in the organic solvent, and coating method of the perfluoropolyether group-containing silane of Example 1. Obtained. Table 1 shows the quality evaluation results of each sample. “KY130” in Table 1 is a metaxylene hexafluoride solution (solid content concentration 20% by mass) of a perfluoropolyether group-containing silane manufactured by Shin-Etsu Chemical Co., Ltd., and the estimated structure is the general formula [3]. .

Example 8
All the same as Example 1 except that the diluent solvent was a solvent in which the same amount of Novec7600 and hexane was mixed (described as “Novec7600 / hexane = 9/1” in Table 1), and the surface was transparent evenly by visual observation. Sample was obtained. The antifouling layer of the obtained antifouling article has a stain resistance of △, a stain resistance of △, an abrasion resistance of ◯, an appearance when cloudy, and an excellent antifouling performance and wear resistance. In addition, even when the surface of the antifouling layer of the antifouling article was exposed to water or the like, dot-like or streaky white turbidity did not occur on the surface. Moreover, there was no problem even if 100 sheets were produced continuously. Ten sheets of the surface of a 300 mm × 300 mm float glass substrate could be applied using 10 ml of the antifouling layer-forming coating agent. Further, the variation in fluorine count was 0.2 μg / cm ² . Table 1 shows the quality evaluation results.

Example 9
All samples were the same as in Example 1 except that the drying temperature was set to 100 ° C. and brush-coated (described in Table 1 as “suitable application by brush coating (90 °)”). Got. The antifouling layer of the obtained antifouling article has excellent antifouling performance and abrasion resistance, with antifouling property, ○ with water resistance, ○ with wear resistance, and ○ when cloudy. In addition, even when the antifouling layer surface of the antifouling article was exposed to steam such as water, no dot-like or streak-like white turbidity was generated on the surface. Moreover, there was no problem even if 100 sheets were produced continuously. Moreover, 10 sheets of the surface of the 300 mm x 300 mm size float glass substrate were able to be apply | coated using the coating agent for antifouling layer forming of 10 ml. Further, the variation in fluorine count was 0.2 μg / cm ² . Table 1 shows the quality evaluation results.

Example 10
Implemented except for coating B, which was applied to the entire surface by reciprocating in the direction of about 45 ° with respect to the coating direction of coating A (described in Table 1 as “suitable coating by hand (45 °)”) A transparent sample having the same surface as in Example 1 was obtained by visual observation. The antifouling layer of the obtained antifouling article has excellent antifouling performance and abrasion resistance, with antifouling property, ○ with water resistance, ○ with wear resistance, and ○ when cloudy. In addition, even when the antifouling layer surface of the antifouling article was exposed to steam such as water, no dot-like or streak-like white turbidity was generated on the surface. Moreover, there was no problem even if 100 sheets were produced continuously. Moreover, 10 sheets of the surface of the 300 mm x 300 mm size float glass substrate were able to be apply | coated using the coating agent for antifouling layer forming of 10 ml. Further, the variation in fluorine count was 0.1 μg / cm ² . Table 1 shows the quality evaluation results.

Example 11
Implementation was performed except that coating B was reciprocated in the direction of about 35 ° with respect to the coating direction of coating A and applied to the entire surface (described as “suitable coating by hand coating (35 °)” in Table 1). A transparent sample having the same surface as in Example 1 was obtained by visual observation. The antifouling layer of the obtained antifouling article has antifouling performance, wear resistance, o wear resistance, o appearance when cloudy, o antifouling performance, wear resistance At the same time, even when the antifouling layer surface of the antifouling article was exposed to steam such as water, no dot-like or streak-like white turbidity occurred on the surface. Moreover, there was no problem even if 100 sheets were produced continuously. Moreover, 10 sheets of the surface of the 300 mm x 300 mm size float glass substrate were able to be apply | coated using the coating agent for antifouling layer forming of 10 ml. Further, the variation in fluorine count was 0.2 μg / cm ² . Table 1 shows the quality evaluation results.

Comparative Example 1
All of the organic solvents were the same as in Example 1 except that isopropyl alcohol having a surface tension of 21.7 mN / m and a boiling point of 82 ° C. was used. The prepared coating agent was a cloudy liquid, but a sample having a uniform surface was obtained by visual observation. The antifouling layer of the obtained sample has a stain resistance of ×, a water resistance of ×, an abrasion resistance of ×, and the appearance when clouded is a dot-like white turbidity as shown in FIG. It was. Further, the variation in fluorine count was 1.7 μg / cm ² . Table 2 shows the quality evaluation results.

Comparative Example 2
Comparative Example 1 except that the coating method was only dip coating on the glass substrate at a pulling rate of 5 mm / sec (described as “Dip coating only” in Table 1), and then directly moved to the drying step. And the same. The prepared coating agent was a cloudy liquid, but a sample having a uniform surface was obtained by visual observation. The antifouling layer of the obtained sample had a stain resistance of x, a stain resistance of x, an abrasion resistance of x, and the appearance when clouded was a dot and streaky white turbidity and x. Moreover, the variation in fluorine count was 2.0 μg / cm ² . Table 2 shows the quality evaluation results.

Comparative Example 3
The organic solvent was the same as in Example 1 except that Zeolora H (manufactured by ZEON Corporation: heptafluorocyclopentane) having a surface tension of 20.3 mN / m and a boiling point of 83 ° C. was used, and the surface was uniform by visual observation. A clear sample was obtained. The antifouling layer of the obtained sample had a stain resistance of ◯, a water resistance of ◯, an abrasion resistance of 外観, and the appearance when clouded was dot-like white turbidity and x. Moreover, the variation in fluorine count was 2.0 μg / cm ² . Table 2 shows the quality evaluation results.

Comparative Example 4
As the coating method, all was the same as in Comparative Example 3 except that the coating was performed on the glass substrate by the Mayer bar method (described as “Meyer bar method only” in Table 1), and the drying process was directly performed. A transparent sample with a uniform surface was obtained by visual observation. The antifouling layer of the obtained sample had a stain resistance of ◯, a stain resistance of ◯, an abrasion resistance of ◯, and the appearance when clouded was dot and streak-like white turbidity occurred. Moreover, the variation in fluorine count was 2.1 μg / cm ² . Table 2 shows the quality evaluation results.

Comparative Example 5
The organic solvent was the same as Example 1 except that PF5060 (Sumitomo 3M: perfluorohexane) having a surface tension of 11.7 mN / m and a boiling point of 57 ° C. was used. A sample was obtained. The antifouling layer of the obtained sample had a contamination resistance of ○, a water resistance of ○, an abrasion resistance of ○, and an appearance when clouded. However, in the continuous production of up to 50 sheets, the solvent volatilizes and the solid content concentration of the coating agent becomes high. As a result, it becomes impossible to apply uniformly, and the appearance and antifouling property of the antifouling layer is different for each substrate. It became unstable. Therefore, productivity is x. In addition, two surfaces of a 300 mm × 300 mm size float glass substrate could be applied using 10 ml of the antifouling layer forming coating agent. Further, the variation in fluorine count was 0.2 μg / cm ² . Table 2 shows the quality evaluation results.

Comparative Example 6
The organic solvent is PF5060 (manufactured by Sumitomo 3M: perfluorohexane) having a surface tension of 11.7 mN / m and a boiling point of 57 ° C., and the flow coating method is used as the coating method (“flow coating method only” in Table 1). The sample was completely the same as Example 1 except that the process was directly transferred to the drying step, and a transparent sample having a uniform surface was obtained by visual observation. The antifouling layer of the obtained sample had a stain resistance of ◯, a stain resistance of ◯, an abrasion resistance of ◯, and an appearance when clouded. However, in the continuous production of up to 50 sheets, the solvent volatilizes and the solid content concentration of the coating agent becomes high. As a result, it becomes impossible to apply uniformly, and the appearance and antifouling property of the antifouling layer is different for each substrate. It became unstable. Therefore, productivity is x. In addition, two surfaces of a 300 mm × 300 mm size float glass substrate could be applied using 10 ml of the antifouling layer forming coating agent. Further, the variation in fluorine count was 0.8 μg / cm ² . Table 2 shows the quality evaluation results.

Comparative Example 7
The organic solvent was the same as Example 1 except that the organic solvent was 1,3-bis (trifluoromethyl) benzene having a surface tension of 20.7 mN / m and a boiling point of 115 ° C., and the surface was uniformly transparent by visual observation. Sample was obtained. The antifouling layer of the obtained sample had a stain resistance of ◯, a water resistance of ◯, an abrasion resistance of 外観, and the appearance when clouded was dot-like white turbidity and x. Further, the variation in fluorine count was 2.2 μg / cm ² . Table 2 shows the quality evaluation results.

Comparative Example 8
The organic solvent in Example 5 was a mixture of Novec 7300 and hexane. The concentration of the fluorinated solvent in the mixed solution is 50% by mass. The mixed solution has a surface tension of about 16.7 mN / m and a boiling point of about 84 ° C. As a result, a transparent sample having a uniform surface was obtained by visual observation. The antifouling layer of the obtained antifouling article had a stain resistance of Δ, a water resistance of Δ, an abrasion resistance of ◯, and a cloudy appearance when the dot was cloudy. Further, the variation in fluorine count was 1.7 μg / cm ² . Table 2 shows the quality evaluation results.

As described above, the antifouling article obtained by the present invention has excellent antifouling performance and wear resistance, and even when the antifouling layer surface of the antifouling article is exposed to steam such as water, Dot-like or streak-like white turbidity does not occur on the surface, and the appearance and design are not impaired.

Although the embodiments of the present invention have been described above, it is needless to say that the following embodiments can be appropriately changed and improved based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Absent.

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Holding member holding the coating agent 3 Direction to apply the coating agent by bringing the holding member into contact with the glass substrate

Claims

An organic solvent having a surface tension of 20.0 mN / m or less and a boiling point of 95 to 200 ° C., dissolved in a perfluoropolyether group-containing silane represented by the following general formula [1], used under steam A coating agent for forming an antifouling layer of an antifouling article.

(Wherein W represents a fluorine atom or a substituent represented by the structure of the following formula.

X is represented by the formula: — (O) g — (CF 2 ) h — (CH 2 ) i — (where g, h and i each independently represents an integer of 0 to 50, and g and The sum of h is 1 or more, and the order of presence of each repeating unit enclosed in parentheses is arbitrary in the formula. Y represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, and Z is selected from the group consisting of alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, chloro group, and isocyanate group And at least one hydrolyzable functional group, R represents an alkyl group having 1 to 10 carbon atoms. a represents an integer of 0 to 50, b represents an integer of 1 to 200, c represents an integer of 1 to 3, d represents an integer of 1 to 10, and e and f are each independently 0 Represents an integer of ˜5, m and n are each independently an integer of 0 to 50, and the sum of m and n is 1 or more. )
The coating agent for forming an antifouling layer according to claim 1, wherein 60 to 100% by mass of a fluorinated solvent is contained in 100% by mass of the organic solvent.
The said antifouling according to claim 1 or 2, wherein the fluorinated solvent is at least one selected from the group consisting of hydrofluorocarbon, perfluorocarbon, hydrofluoroether, and hydrochlorofluorocarbon. Coating agent for layer formation.
The antifouling layer-forming coating agent according to any one of claims 1 to 3, wherein the fluorinated solvent is at least one selected from the group consisting of perfluorocarbons and hydrofluoroethers. .
2. The perfluoropolyether group-containing silane represented by the general formula [1] is contained in 0.01 to 5% by mass in 100% by mass of the antifouling layer forming coating agent. The coating agent for forming an antifouling layer according to any one of claims 1 to 4.
A method for producing an antifouling article using the coating agent for forming an antifouling layer according to any one of claims 1 to 6, wherein (1) the holding member holding the coating agent is brought into contact with the substrate surface Then, the holding member is reciprocated in a specific direction on the substrate surface to apply the coating agent on the entire surface, and then the holding member is brought into contact with the substrate surface again, so that the holding member is brought into contact with the substrate. (2) a step having coating B for recognizing the coating agent over the entire surface by reciprocating in one direction different from the coating direction in the coating A on the surface, and finally coating C for coating along the edge of the substrate; ) A method for producing an antifouling article, comprising the step of drying the applied coating agent.
An antifouling article produced by the production method according to claim 6 and used under steam.
6. The antifouling article is any one of an antifouling mirror for bathrooms or a toilet, or a partition around water such as a kitchen or a washstand. Antifouling layer forming coating agent.
The method according to claim 6, wherein the antifouling article is any one of an antifouling mirror for bathrooms or a toilet and a partition around water such as a kitchen or a washstand.
The antifouling article according to claim 7, wherein the antifouling article is any one of an antifouling mirror for bathrooms or toilets, or a partition around water such as a kitchen or a washstand.