KR20130058747A - Antifouling article and production method therefor, and embrocation for forming antifouling layer - Google Patents

Abstract

The coating agent for forming an antifouling layer according to the present invention is obtained by dissolving a perfluoropolyether group-containing silane represented by the following formula (1) in an organic solvent having a surface tension of 20.0 mN / m or less and a boiling point of 95 to 200 ° C. The antifouling article in which the antifouling layer was formed using this coating agent has excellent antifouling performance and abrasion resistance, and even when the antifouling layer surface of the antifouling article is exposed to steam such as water, the surface has a dot-like or stripe-like turbidity. It does not occur, and appearance and design are not impaired.
[Formula 1]

Description

Antifouling article and manufacturing method thereof, and coating agent for antifouling layer formation {Antifouling article and production method therefor, and embrocation for forming antifouling layer}

The present invention is to form an antifouling layer that is difficult to attach contaminants, and is easy to remove contaminants attached thereto, and which does not become white or white in appearance when dot or stripe forms when exposed to steam such as water. The coating agent for this, and the article which formed the antifouling layer using this coating agent, and its manufacturing method are related.

BACKGROUND ART Substrates such as metal, glass, plastic, ceramics, and the like are widely used as automobile parts, household goods, home appliances, and OA devices. Since the surface of these substrates is often contaminated by droplets or scales caused by rain or the like, oily substances such as floating dust or cigarettes, fingerprints or sebum by human hands, and the like, they are difficult to adhere. Furthermore, there is a demand for an antifouling function capable of easily removing contaminants once attached.

In order to express such antifouling function, many methods have been proposed so far. Patent Literature 1 discloses an antifouling composition composed of a compound having a perfluoroalkyl ether group. In patent document 2, the water-repellent glass in which the processing film which has the alkoxysilane compound which has the perfluoropolyether group which is excellent in water repellency, antifouling property, and durability as a main component was formed on the base material is disclosed. Patent Literature 3 discloses an antifouling substrate in which a fluorine-containing polymer having excellent antifouling properties against oily contaminants, in particular, an antifouling property against fingerprints and a polymer layer formed on the surface of the substrate. In addition, Patent Document 4 discloses a perfluoropolymodified silane having excellent durability, antifouling properties, particularly fingerprint wiping property, and a surface treating agent containing the same as a main component.

Japanese Patent Publication No. 2000-234071 Japanese Patent Application Laid-Open No. 11-092177 International Publication No. 98/49218 Japanese Patent Publication No. 2003-238577

As shown in the above patent document, when forming a coating layer (hereinafter referred to as an antifouling layer) that exhibits an antifouling function on the surface of a base material, a fluorine-containing compound having high water / oil repellency is used as a material forming the antifouling layer. Often used. In order to provide an antifouling layer of such a fluorine-containing compound on the surface of the substrate, a method of applying a liquid obtained by dissolving or dispersing the raw material of the antifouling layer with a fluorine solvent, an alcohol solvent, an ether solvent, a ketone solvent, a hydrocarbon solvent, or the like This has been commonly used. As a solvent for diluting the raw material of the antifouling layer, for example, hexafluorobenzene in Patent Document 1, isopropanol in Patent Document 2, perfluorohexane, etc. in Patent Document 3, and perfluoro (Patent Document 4). 2-butyltetrahydrofuran) is used.

However, if the coating liquid obtained by diluting the antifouling layer raw material with an appropriate solvent is not applied to the surface of the substrate, the portion where the liquid surface swells due to the coagulation action of the coating liquid (hereinafter referred to as "liquid pool") and the other portion It is easy to be in the state mixed with this base material surface. In the case of applying to a substrate in an open system, as a result of the coating liquid not sufficiently spreading over the surface of the substrate with evaporation of the solvent, a tendency to easily cause coating unevenness and a tendency to be difficult to apply There is this. When apply | coating to many base materials continuously, since the density | concentration of a coating agent changes, there exists a tendency for the external appearance and antifouling property of an antifouling layer to become unstable for every base material. Moreover, when it does not apply | coat by an appropriate coating method, there exists a tendency for application | coating nonuniformity to generate easily. If the surface of the antifouling layer obtained after drying is shaken off, an antifouling layer without non-uniformity can be obtained by visual observation.However, if the surface of the antifouling layer is exposed to steam such as water, it is selectively provided at a location where the liquid level and coating nonuniformity existed. There is a problem that dot-like or stripe-like turbidity appears on the surface of the antifouling layer when the droplets are attached.

In view of the above problems, the present invention provides a coating agent for forming an antifouling layer in which dot-like or stripe-like turbidity does not appear on the surface even if there are many opportunities to be exposed to steam such as water, and an antifouling layer comprising the coating agent. An object of this invention is to provide the antifouling article provided and its manufacturing method.

As a result of earnest research, the present inventors used a coating agent in which a perfluoropolyether group-containing silane was dissolved in a specific organic solvent to form a coating layer in which the perfluoropolyether group-containing silane was condensed. The present invention has been found to function as an antifouling layer having an appearance in which dot-like or stripe-like turbidity does not appear on the surface even when exposed to steam such as water.

That is, the present invention is an antifouling property used under steam, which is obtained by dissolving a perfluoropolyether group-containing silane represented by the following formula (1) with an organic solvent having a surface tension of 20.0 mN / m or less and a boiling point of 95 to 200 ° C. It is to provide a coating agent for forming an antifouling layer of an article.

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

X is a formula:-(O) _g- (CF ₂ ) _h- (CH ₂ ) _i- (where g, h and i each independently represent an integer of 0-50, and the sum of g and h Is 1 or more, and the existence order of each repeating unit enclosed in parentheses is arbitrary in a formula.). Y represents a hydrogen atom or a C1-C5 lower alkyl group. Z represents at least one hydrolysable 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 each independently represent 0 to The integer of 5 is shown, m and n are each independently the integer of 0-50, and the sum of m and n is 1 or more.)

It is preferable that 60-100 mass% of fluorine-type solvents are contained in 100 mass% of said organic solvents. The fluorine-based solvent is preferably at least one selected from the group consisting of hydrofluorocarbon, perfluorocarbon, hydrofluoroether, and hydrochlorofluorocarbon, and is composed of perfluorocarbon and hydrofluoroether. It is more preferable that it is at least 1 type selected from the group.

Moreover, it is preferable that 0.01-5 mass% of perfluoro polyether group containing silane represented by the said Formula (1) is contained in 100 mass% of coating agents for antifouling layer formation.

In addition, the present invention provides a method for producing an antifouling article using the coating agent for forming an antifouling layer, which comprises (1) contacting a holding member having a coating agent to the substrate surface and reciprocating the holding member in a specific one direction on the substrate surface to obtain a coating agent. Application A applied to the entire surface, and then the holding member is brought into contact with the substrate surface again and the holding member is reciprocated on the substrate surface in one direction different from the application direction in the application A so as to infiltrate the coating agent well on the front surface. And (2) a method for producing an antifouling article, and a method for producing the antifouling article, comprising the step of having a coating C for applying the coating agent along the end of the substrate, and drying the applied coating agent. Provide antifouling goods for use under the following circumstances.

1 is a schematic view showing an example of a suitable coating method of the coating agent for forming an antifouling layer according to the present invention.
Fig. 2 is an external photograph showing the drawing on the surface of the antifouling layer in which dot-like turbidity is generated by exposure to water vapor.

Hereinafter, the present invention will be described in detail.

The coating agent for forming an antifouling layer according to the present invention is obtained by dissolving a perfluoropolyether group-containing silane represented by the following formula (1) in an organic solvent having a surface tension of 20.0 mN / m or less and a boiling point of 95 to 200 ° C.

[Formula 1]

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

In addition, X is a formula:-(O) _g- (CF ₂ ) _h- (CH ₂ ) _i- (wherein g, h and i each independently represent an integer of 0 to 50, and g and h The sum of 1 is 1 or more, and the existence order 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 It represents one or more hydrolysable functional groups, and 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 each independently represent 0 to The integer of 5 is shown, m and n are each independently the integer of 0-50, and the sum of m and n is 1 or more.

In Chemical 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 be given an excellent antifouling performance, and wear resistance by the area indicated by. Therefore, an antifouling layer formed by condensation of a perfluoropolyether group-containing silane as in Formula (1) is preferable because excellent antifouling performance and wear resistance can be achieved.

In Formula (1), by condensation of the hydrolyzable functional group (Z) to form an antifouling layer, excellent adhesion between the antifouling layer and the substrate surface can be imparted.

In the general formula (1), when the reactivity of the hydrolyzable functional group (Z) is too high, handling when combining the coating agent becomes difficult, and 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 generated will be insufficient, so that a bond formed between the silanol group and the active species on the surface of the substrate (for example, siloxane Bonds, metallox bonds, etc.) and interactions (e.g. van der Waals forces or electrostatic interactions) are insufficient, and sufficient adhesion between the antifouling layer and the surface of the substrate cannot be imparted, or the antifouling layer Its durability is lowered. In view of the above, as the hydrolyzable functional group (Z), 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 desirable. Among these, in consideration of the ease of handling of the hydrolyzable functional group, the pot life of the coating agent, and the durability of the resulting antifouling layer, an alkoxy group is preferable, and among these, a methoxy group and an ethoxy group are particularly preferable.

The perfluoropolyether group-containing silane represented by the formula (1) is considered to bond Si-O- with the surface of the substrate by hydrolysis of the functional group represented by Z in the Si-Z moiety, but the perfluoropolyether group-containing When the number of moles of fluorine in the perfluoropolyether group-containing silane is about 20 to 200 with respect to 1 mole of silicon contained in the bondable moiety (Si group-containing moiety) in the silane, good water repellency can be imparted to the substrate. It is preferable because of that.

Also in the perfluoropolyether group containing silane represented by General formula (1), the perfluoro polyether group containing silane which has a structure represented by following General formula (2) and General formula (3) is a preferable compound.

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, d are the same as 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 not having a branch. It is a perfluoroalkyl structure containing the unit represented by a bivalent group which has a structure, or -C _u F _2u- (u is an integer of 1-8.), And r and r 'are integers of 1-5, respectively. , s and s' each represent an integer of 0 to 2; R, Z and c are the same as in the general formula (1).

As a commercial item containing such a compound, Optool AES series, such as Daikin Industries Optool DSX and Optool AES4, Shin-Etsu Chemical Co., Ltd. KY130, KY108, Fluorotechnologies Fluoroprop FG-5020, etc. are mentioned. In addition, when preparing the coating agent of this invention using the said commercial item, the solvent contained in the commercial item shall be included as a part of the solvent in the coating agent of this invention.

The organic solvent in the coating agent of this invention is 20.0 mN / m or less in surface tension. If the surface tension of the organic solvent is more than 20.0 mN / m, when the coating agent is applied to the substrate, the coagulation action of the coating agent tends to result in a mixed state of the liquid pool portion and the portions other than the liquid pool. Although the surface of the antifouling layer obtained after drying can be shaken off to remove the extra antifouling layer, a non-uniform antifouling layer can be obtained by visual observation, but when the surface of the antifouling layer is exposed to steam such as water, It is not preferable to selectively attach droplets to a location, because dot-like haze tends to occur on the surface of the antifouling layer. The more preferable organic solvent is a solvent whose surface tension is 19.5 mN / m or less, More preferably, it is a solvent whose surface tension is 19.3 mN / m or less. In addition, the surface tension of a liquid can be measured by the plate method, for example.

In addition, the boiling point of the organic solvent is 95-200 degreeC. When the boiling point of the organic solvent is less than 95 ° C., the drying speed after applying the chemical solution is too high, and there is a tendency that the coating nonuniformity occurs, or the chemical solution volatilizes during application, so that the surface of the substrate is not completely spread. In addition, in the case of applying to a plurality of substrates continuously in an open system, the concentration of the perfluoropolyether group-containing silane in the coating agent increases with evaporation of the organic solvent, resulting in unstable appearance and antifouling property of each substrate. There is a tendency. When the boiling point of an organic solvent exceeds 200 degreeC, high temperature or long time is required for drying, and industrial disadvantages tend to become large. The boiling point of the organic solvent is more preferably 105 to 180 ° C.

It is preferable that 60-100 mass% of fluorine-type solvents are contained in the organic solvent. If the concentration of the fluorine-based 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 dot-like or stripe-like turbidity is likely to occur on the surface of the antifouling layer. I can't. In addition, when applying to many base materials continuously in an open system, with the evaporation of an organic solvent, it is easy to be influenced by the change of the density | concentration of the perfluoro polyether group containing silane in a coating agent, and the appearance and antifouling property of an antifouling layer There exists a tendency which is difficult for every base material to be stable. The concentration of the fluorine-based solvent in the organic solvent is more preferably 70 to 100 mass%, more preferably 80 to 100 mass%.

The fluorine-based solvent is preferably at least one selected from the group consisting of hydrofluorocarbons, perfluorocarbons, perfluoroethers, hydrofluoroethers, and hydrochlorofluorocarbons. In view of the proper surface tension and the appropriate boiling point, more preferred are perfluorocarbons, hydrofluoroethers. In consideration of environmental load, hydrofluoroether having a smaller warming coefficient is particularly preferable as the fluorine-based solvent.

When using 1 type of organic solvent as an organic solvent, the fluorine-type solvent whose surface tension is 20.0 mN / m or less and whose boiling point is 95-200 degreeC can be used. For example, perfluorononane, perfluorodecane, and fluorine-based inert liquids (for example, Sumitomo 3M "fluorine nut FC40", "fluorine nut FC43", "fluorine nut FC3283"), and the like. Locarbon or 1,1,1,2,3,3-hexafluoro-4- (1,1,2,3,3,3-hexafluoropropoxy) -pentane ("Novec7600" manufactured by Sumitomo 3M) Hydrofluoroethers, such as), can be used.

In the case where a plurality of organic solvents are used as the organic solvent, the surface tension of the organic solvent after mixing is 20.0 mN / m or less, and the boiling point is 95 to 200 ° C., and the mixed liquid of the fluorine-based solvent can be used. have. In addition, 1,1,2,2,3,3,4,4-octafluorobutane, 1,3-bis (trifluoromethyl) benzene, and heptafluorocyclopentane are added to the fluorine-based solvent and the mixture thereof. Hydrofluoro, such as Nippon Xeon "Geora H"), 2H, 3H-decafluoropentane ("Butrel XF" by DuPont), 1,1,1,3,3,3-hexafluoroisopropanol C _n F _2n such as carbon, perfluorohexane, perfluoroheptane, and perfluorooctane (respectively, Sumitomo 3M manufactured "fluorine nut PF5060", "fluorine nut PF5070", "fluorine nut PF5080"), and the like. Perfluorocarbons such as perfluoroalkane hexafluorobenzene represented by ₊₂ , perfluoro-1,3-dimethylcyclohexane, and fluorine-based inert liquid ("fluorine nut FC series" manufactured by Sumitomo 3M) Perfluoro ethers, such as fluoro (2-butyl tetrahydrofuran), methyl perfluoro butyl ether ("Novec7100" by Sumitomo 3M), nonaple Hydrofluoroethers such as orobutylethyl ether (Novec7200 manufactured by Sumitomo 3M) and methylperfluorohexyl ether (Novec7300 manufactured by Sumitomo 3M), and 1,2-dichloro-3,3,3-trifluoroprop Such as pen, 1-chloro-3,3,3-trifluoropropene, 3,3-dichloro-1,1,1,2,2-pentafluoropropane ("HCFC-225" manufactured by Asahi Glass) Hydrochlorofluorocarbon and the mixed liquid which mixed hydrocarbon solvents, such as butane, hexane, 2-methylpentane, 2, 2- dimethyl butane, 2, 3- dimethyl butane, and 2-methyl hexane, can be used.

It is preferable that the density | concentration of the perfluoro polyether group containing silane represented by General formula (1) is 0.01-5 mass%. If the concentration is less than 0.01% by mass, it is not preferable because sufficient antifouling performance cannot be expressed on the surface of the substrate or the antifouling layer becomes nonuniform. If the concentration exceeds 5% by mass, it is not preferable because it is difficult to remove the excess of the antifouling layer or the amount of excess to be removed increases and becomes expensive. From a viewpoint of antifouling performance, excess removal property, and cost, more preferable concentration range is 0.05-1 mass%, and still more preferable concentration range is 0.1-0.4 mass%.

A catalyst may be added to the coating agent for antifouling layer formation for the purpose of promoting the hydrolysis reaction and condensation reaction of the perfluoropolyether group containing silane represented by 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 sulfuric acid. Particularly preferred are acetic acid, tetra n-butyl titanate, dibutyl dilaurate and the like. The amount of addition 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.

Moreover, you may add surfactant, a crosslinking agent, antioxidant, an ultraviolet absorber, an infrared absorber, a flame retardant, a hydrolysis inhibitor, an antifungal agent, etc. to the coating agent for antifouling layer formation in the range which does not impair the objective of this invention.

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) Coating A which holds the holding member holding the coating agent on the substrate surface and applies the coating member to the front surface by reciprocating the holding member in a specific one direction on the substrate surface, and then holding the holding member again on the substrate surface and holding the holding member on the substrate surface. A coating step having a coating B for reciprocating in one direction different from the coating direction in the coating A so that the coating agent is soaked on the entire surface, and finally, the coating C for coating along the end of the substrate.

(2) The drying process of drying the applied coating agent.

In the present invention, the substrate is not particularly limited. For example, the plate glass with inorganic transparency, such as the float plate glass used for the building window glass, or the soda-lime glass manufactured by the rollout method, can be used. Displays formed using these panes, window panes such as touch panels and showcases, glass substrates such as front plates of organic machines such as slot machines, reflective substrates such as mirrors, inter glass, glass engraved shapes, and the like. Translucent or opaque glass substrates can be used. In addition to the glass base material, a base material made of ceramic materials used for tiles, tiles, sanitary ware, tableware, and the like, a frame such as a glass window, a medical device such as a cooker, a scalpel, a needle, a sink, a stainless steel used for an automobile body, etc. , Metal materials such as steel, and base materials made of plastics, for example, polycarbonate resins, polyethylene terephthalate resins, polymethyl methacrylate resins, polyethylene resins, polyvinyl chloride resins, and other plastic base materials.

Various molded objects, such as a flat plate and a curved board, can be used for said base material, The size and thickness are not specifically limited. Formation of the said antifouling layer on the surface of a base material may be the whole surface of a base material surface, or a part may be sufficient as it.

In addition, in order to further improve the durability of the antifouling article, it is also possible to perform a treatment on the surface of the substrate in advance to improve the adhesive strength between the substrate and the antifouling layer. As the above-mentioned treatment, it is possible to generate an active group on the surface of the substrate by polishing, washing, drying with various polishing liquids, surface modification treatment with an acidic solution or basic solution, primer treatment, plasma irradiation, corona discharge, high pressure mercury lamp irradiation, or the like. Can be mentioned. A bond (for example, a metal siloxane bond including a siloxane bond) formed between the active species and the hydrolyzable functional group represented by Z in Formula 1 or a silanol group formed by hydrolysis thereof; By interaction (eg, van der Waals forces, electrostatic interactions, etc.), sufficient adhesion can be imparted between the antifouling layer and the substrate surface.

In the application | coating process (1), application | coating A can make a coating agent spread evenly on the whole surface of a base material. Subsequently, by coating B, the coating film surface can be leveled uniformly. Although the reciprocation direction of the said member of the coating | coated B is not specifically limited, The angle (theta) ((theta) which the reciprocating direction of the said member of the coating | coated A and the reciprocating direction of the said member of the coating | coated B make is described in the range of 0 degrees or more and less than 180 degrees. () Is preferable because it can apply | coat more uniformly if it is a direction used as an angle of 20-160 degrees. More preferably, it is a direction which becomes an angle of 45-135 degrees. Finally, by the coating C, the coating agent can be reliably applied to an end portion where the coating is forgotten or the shortage of the coating agent tends to occur.

As a holding member for holding a coating agent, there is a nonwoven fabric made from pulp, acrylic, PET, PP, nylon, rayon, or the like, and in particular, a composite material of pulp and PP is preferable from the viewpoint of strength and liquid absorption.

As a method of apply | coating a coating agent to the surface of a base material, the coating method of various films, such as brush coating, hand coating, robot coating, and those combined use, is possible. It is also possible to apply the substrate by bringing the substrate surface into contact with the holding member while the holding member for holding the coating agent is fixed and to move the substrate. Preferably hand application.

In the drying process (2) after the application | coating process (1), the antifouling layer is formed by condensing the perfluoropolyether group containing silane represented by General formula (1), and the silanol group produced | generated from this perfluoropolyether group containing silane Sufficient adhesion is expressed between the antifouling layer and the substrate surface by the bonding or interaction formed between the active species on the substrate surface and the substrate surface. It is preferable to perform a drying process at 50-250 degreeC, More preferably, it is 100-200 degreeC, and you may carry out under normal pressure, under pressure, under reduced pressure, and in an inert atmosphere. Microwave heating is also effective.

When an excess is present on the surface of the antifouling layer obtained after the drying step (2), the excess is shaken off and removed. An antifouling layer having a uniform surface is obtained by shaking off with a paper towel or cloth and / or a dry paper towel or cloth moistened with an organic solvent. In particular, it is preferable to wipe off with paper which can be used once and discarded, such as a paper towel and a tissue paper.

In addition, even if the surface of the antifouling layer is exposed to steam such as water and the droplets are attached, it is preferable that the appearance of the cloudiness appearing as dots or stripes on the surface of the antifouling layer. This is because even if the droplets adhere to the surface of the antifouling layer by steam or the like, the antifouling article does not impair the appearance or the designability, or because the method of erasing the contaminants is different and does not impair the appearance or the designability.

The fluorine count (fluorine concentration) of the antifouling article obtained by the present production method is different depending on the composition, coating conditions, and the like of the coating agent to be used. Usually, when the fluorine count is 0.2 µg / cm 2 or more, sufficient antifouling performance is obtained, and more preferable. Preferably 0.4 µg / cm 2 or more. In addition, in the obtained antifouling article, the less the variation in the fluorine count in the arbitrary part, the more the dot-like or stripe-like cloudiness seen on the surface of the antifouling layer can be prevented. Normally, if the variation in fluorine count (difference between the maximum value and the minimum value) is 1.6 µg / cm 2 or less, the appearance and design of the antifouling article are not damaged when the droplet is attached by exposure to steam such as water, more preferably. Is 1.3 µg / cm 2 or less.

The antifouling article obtained by the present production method is suitable for use in an environment where antifouling properties are required, but is preferably used under steam. The steam bottom refers to an environment that is often exposed to steam, and includes, for example, a bathroom in which a large amount of steam is generated, a sink, a kitchen periphery exposed to steam, such as water and oil. Thus, antifouling articles used under steam are, for example, faucets, mirrors, walls, partitions, windows, doors or vanity mirrors, cabinets, sinks, faucets, partitions around the counter or kitchen, kitchen hoods, ventilation fans, for example. It can be used in cooking ranges, around sinks, and in insulating cases at convenience stores. Among them, it is suitable for partitions where water is used in buildings such as bathroom mirrors, vanity mirrors, kitchens, and sinks.

Example

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

In the present Example and the comparative example, the coating agent for antifouling layer formation was prepared, it apply | coated on the base material, and the antifouling article was manufactured. The preparation method of a coating agent and the manufacturing method of an antifouling article are as mentioned later. 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 Solvents]

The surface tension of the organic solvent was measured by the plate method by the automatic surface tension meter CBVP-Z type manufactured by Kyowa Interface Science. The material of the plate was platinum, and the measurement temperature was 25 ± 2 ° C.

[Pollution resistance]

As a simulated contamination on the surface of the antifouling layer, a line is drawn with a signature pen (trade name: Makki Care Black, manufactured by Zebra Corporation), the extrusion state of the signature pen ink is observed, the ink is wiped off with a paper towel, and the appearance is visually observed. The stain resistance of the antifouling layer was evaluated based on the following criteria.

(Circle): The antifouling layer surface pushes ink in and can wipe off

(Triangle | delta): The surface of an antifouling layer pushes out ink, but cannot wipe it off

X: The antifouling layer surface does not push ink out

[Endogenous]

Spray the industrial water on the surface of the antifouling layer and dry the scale by drying at 50 ° C. for 3 hr, wipe the surface with a paper towel, visually observe the appearance, and evaluate the water resistance of the antifouling layer by the following criteria. It was.

(Circle): A scale can be wiped off from the surface of an antifouling layer

(Triangle | delta): Although the scale was able to be wiped off substantially from the surface of an antifouling layer, there are some places which cannot be wiped off partly.

X: We cannot wipe off scale from the stainproofing surface

[Abrasion Resistance (Abrasion Resistance)]

The surface of the antifouling layer was polished to a strength of about 1.5 kg / cm 2 with a cotton cloth impregnated with a ceria suspension (10 mass%) in which a glass abrasive Mirek A (T) (manufactured by Mitsui Metal Mining Co., Ltd.) was dispersed in tap water. The number of times of polishing (round trip) until 70% of the polishing area became hydrophilic was evaluated. Here, the wear resistance (abrasion resistance) of an antifouling layer rejects less than 50 times of grinding | polishing times (it shows with X in Table 1), passes 50 times or more of grinding | polishing times (indicated by ○ in Table 1), 80 times or more Was good (marked with ◎ in Table 1).

[Appearance when it is cloudy]

Steam was steamed on the surface of the antifouling layer of the antifouling article kept at room temperature, and the appearance was visually observed. The appearance of the antifouling layer was evaluated by the following criteria.

(Circle): When cloudy, the cloudiness of a dot shape and stripe shape is not recognized.

X: When cloudy, the cloudiness of a dot shape and stripe shape is confirmed.

[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.

(Double-circle): There is no problem in performance (pollution resistance, dirt resistance, abrasion resistance) and the appearance when it becomes cloudy in 100 sheets, and it can produce without stagnation.

(Circle): It has no problem in performance (pollution resistance, dirt resistance, abrasion resistance) and the appearance when it becomes cloudy in the whole up to 50 sheets, and can produce without stagnation.

X: NG product generate | occur | produces in quality and an appearance in up to 50 sheets

[Ease of application]

The number of sheets which could apply | coat the surface of the float glass substrate of 300 mmx300 mm size using the coating agent for antifouling layer formation of 10 ml was evaluated as ease of application | coating.

[Fluorine count]

In the fluorescence X-ray analyzer ZSX Primus II (manufactured by Rigaku Co., Ltd.), five fluorine concentrations of the antifouling layer were measured, and the deviation (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, Inc., is a perfluorohexane solution of a perfluoropolyether group-containing silane (solid content concentration of 20% by mass), and an estimated structure is represented by Formula 2.) 0.75 g of surface tension of 17.7 mN / m, Novec7600 with boiling point of 131 ° C (manufactured by Sumitomo 3M: 1,1,1,2,3,3-hexafluoro-4- (1,1,2,3,3,3-hexafluoropropoxy) pentane) It melt | dissolved in 50.0g and stirred at room temperature for 30 minutes, and obtained the coating agent whose density | concentration of a perfluoropolyether group containing silane is 0.3 mass%.

(II) Preparation of Substrate (Glass Substrate)

The surface of the float glass substrate of 300 mm x 300 mm x 2 mm thickness size was polished using the polishing liquid, and washed with water and dried. In addition, 2 mass% ceria suspension which mixed glass abrasive Mirek A (T) (made by Mitsui Metal Industry) with water was used as said polishing liquid.

(III) Formation of antifouling layer

The cotton cloth (brand name: 벰 coat) which has 1.0 ml of the coating agent prepared in said (I) was made to contact on a glass substrate, and as shown in FIG. 1, it reciprocates in specific one direction (horizontal direction in FIG. 1) as coating A, and front surface Is applied to the entire surface by reciprocating in the direction (vertical direction in FIG. 1) which becomes about 90 ° with respect to the application direction of application A as application B, and finally applied along the end as application C ( In Table 1, it describes as "appropriate application | coating (90 degree) by hand application | coating), and the glass substrate was put into the electric furnace and dried for 12 minutes. At this time, the highest achieved temperature (drying temperature) of the glass was 150 ° C. Finally, the excess component remaining white mottled with the naked eye was wiped off with a paper towel moistened with isopropyl alcohol to obtain a sample with a uniform and transparent surface by visual observation.

The antifouling layer of the obtained antifouling article had a stain resistance of ○, a stain resistance of ○, abrasion resistance of ◎, an appearance when it was cloudy ○, and had excellent antifouling performance and abrasion resistance, and the surface of the antifouling layer of the antifouling article was water Even if it was exposed to steam, etc., the cloudiness of the dot shape and the stripe shape did not generate | occur | produce on the surface. Moreover, even if it produced 100 sheets continuously, there was no problem. Moreover, 10 sheets of the surface of the float glass board | substrate of 300 mm x 300 mm size could be apply | coated using the 10 ml coating agent for antifouling layer formation. In addition, the variation in the fluorine count was 0.2 µg / cm 2. Table 1 shows the results of the quality evaluation.

Examples 2-7

The type, concentration, type of organic solvent, concentration of fluorinated solvent in the organic solvent, and application method of the perfluoropolyether group-containing silane of Example 1 were appropriately changed to obtain a sample having a uniform and transparent surface by visual observation. Table 1 shows the results of the quality evaluation of each sample. "KY130" of Table 1 is the metaxylene hexafluoride solution (20 mass% of solid content concentration) of the perfluoro polyether group containing silane by Shin-Etsu Chemical Co., Ltd., and an estimated structure is General formula (3).

Example 8

All samples were the same as in Example 1, except that the dilution solvent was a solvent in which Novec7600 and hexane were mixed in the same amount (described in Table 1 as "Novec7600 / hexane = 9/1"). Got. The antifouling layer of the obtained antifouling article had a stain resistance △, a dirt resistance △, an abrasion resistance ○, and an external appearance when it was cloudy ○, and had excellent antifouling performance and abrasion resistance, and the surface of the antifouling layer of the antifouling article was water. Even if it was exposed to the above, the cloudiness of the dot shape and the stripe shape did not generate | occur | produce on the surface. Moreover, even if it produced 100 sheets continuously, there was no problem. Ten sheets of the surface of the float glass substrate of 300 mm x 300 mm size could be apply | coated using 10 ml of coating agents for antifouling layer formation. In addition, the variation in the fluorine count was 0.2 µg / cm 2. Table 1 shows the results of the quality evaluation.

Example 9

The drying temperature was 100 ° C., except that brush coating (described as “appropriate coating by brush coating (90 °)” in Table 1) was performed in the same manner as in Example 1, and the surface was uniform and transparent by visual observation. A sample was obtained. The antifouling layer of the obtained antifouling article had a stain resistance of ○, a stain resistance of ○, abrasion resistance of ◎, an appearance when it was cloudy ○, and had excellent antifouling performance and abrasion resistance, and the surface of the antifouling layer of the antifouling article was water Even if it was exposed to steam, etc., the cloudiness of the dot shape and the stripe shape did not generate | occur | produce on the surface. Moreover, even if it produced 100 sheets continuously, there was no problem. Moreover, 10 sheets of the surface of the float glass board | substrate of 300 mm x 300 mm size could be apply | coated using the 10 ml coating agent for antifouling layer formation. In addition, the variation in the fluorine count was 0.2 µg / cm 2. Table 1 shows the results of the quality evaluation.

Example 10

All of Example 1 except coating reciprocating in the direction which becomes about 45 degrees with respect to the application direction of coating A as coating B, and apply | coating to the whole surface (it describes as "appropriate coating by hand coating (45 degrees) in Table 1)). In the same manner as in the above, a uniform and transparent sample was obtained by visual observation. The antifouling layer of the obtained antifouling article had a stain resistance of ○, a stain resistance of ○, abrasion resistance of ◎, an appearance when it was cloudy ○, and had excellent antifouling performance and abrasion resistance, and the surface of the antifouling layer of the antifouling article was water Even if it was exposed to steam, etc., the cloudiness of the dot shape and the stripe shape did not generate | occur | produce on the surface. Moreover, even if it produced 100 sheets continuously, there was no problem. Moreover, 10 sheets of the surface of the float glass board | substrate of 300 mm x 300 mm size could be apply | coated using the 10 ml coating agent for antifouling layer formation. In addition, the variation in the fluorine count was 0.1 µg / cm 2. Table 1 shows the results of the quality evaluation.

Example 11

All of Example 1 except coating reciprocating in the direction which becomes about 35 degrees with respect to the application direction of coating A as coating B, and apply | coating to the whole surface (it describes as "appropriate coating by hand coating (35 degrees) in Table 1)). In the same manner as in the above, a uniform and transparent sample was obtained by visual observation. The antifouling layer of the obtained antifouling article had a stain resistance of ○, a stain resistance of ○, abrasion resistance of ◎, and an external appearance when it became cloudy ○, and had antifouling performance and abrasion resistance. Even if it was exposed to vapor | steam, the cloudiness of the dot shape and stripe shape did not generate | occur | produce on the surface. Moreover, even if it produced 100 sheets continuously, there was no problem. Moreover, 10 sheets of the surface of the float glass board | substrate of 300 mm x 300 mm size could be apply | coated using the 10 ml coating agent for antifouling layer formation. In addition, the variation in the fluorine count was 0.2 µg / cm 2. Table 1 shows the results of the quality evaluation.

Comparative Example 1

The organic solvents were all the same as in Example 1 except that the surface tension was 21.7 mN / m and the boiling point was isopropyl alcohol having 82 ° C. The prepared coating agent was a cloudy liquid, but a sample with a uniform surface was obtained by visual observation. As shown in FIG. 2, the antifouling layer of the obtained sample had x stain resistance, x dirt resistance, abrasion resistance, and cloudiness. In addition, the variation in the fluorine count was 1.7 µg / cm 2. Table 2 shows the results of the quality evaluation.

Comparative Example 2

As a coating method, only the deep coating was performed to the glass substrate at the pulling speed of 5 mm / sec (it describes only "deep coating" in Table 1), and it is the same as the comparative example 1 except having transferred to the drying process as it is. It was made. The prepared coating agent was a cloudy liquid, but a sample with a uniform surface was obtained by visual observation. The antifouling layer of the obtained sample had x stain resistance, x dirt resistance, abrasion resistance, and cloudiness. In addition, the variation in the fluorine count was 2.0 µg / cm 2. Table 2 shows the results of the quality evaluation.

Comparative Example 3

All organic solvents were the same as in Example 1 except that the surface tension was 20.3 mN / m and the boiling point was Aurora Aurora H (Nippon Xeon: heptafluorocyclopentane) having a boiling point of 83 ° C. And a transparent sample was obtained. The antifouling layer of the obtained sample had a stain-resistant ○, anti-fog resistance ○, abrasion resistance ◎, and an appearance when the cloudiness was cloudy, and a dot-like turbidity occurred and was ×. In addition, the variation in the fluorine count was 2.0 µg / cm 2. Table 2 shows the results of the quality evaluation.

Comparative Example 4

As the coating method, only the coating was applied to the glass substrate by the Meyer bar method (described in "Meyer bar method" in Table 1 only), except that it was moved to the drying process as it is, and all the same as the comparative example 3, the naked eye Observations gave samples with uniform and transparent surfaces. The antifouling layer of the obtained sample had a stain resistance of ○, a dirt resistance of ○, abrasion resistance of ○, and an appearance when the cloudiness was clouded. In addition, the variation in the fluorine count was 2.1 µg / cm 2. Table 2 shows the results of the quality evaluation.

Comparative Example 5

All samples were prepared in the same manner as in Example 1 except that the organic solvent was PF5060 (made by Sumitomo 3M: perfluorohexane) having a surface tension of 11.7 mN / m and a boiling point of 57 ° C. Got. The antifouling layer of the obtained sample had a stain resistance of ○, a stain resistance of ○, abrasion resistance of ○, and a cloudy appearance of ○. However, in the production of up to 50 sheets continuously, the solvent was volatilized and the solid content concentration of the coating agent became high. As a result, it was not possible to apply uniformly, and the appearance and antifouling property of the antifouling layer became unstable for each substrate. Therefore, productivity is x. Moreover, two sheets of the surface of the float glass board | substrate of 300 mm x 300 mm size could be apply | coated using 10 ml of coating agents for antifouling layer formation. In addition, the variation in the fluorine count was 0.2 µg / cm 2. Table 2 shows the results of the quality evaluation.

Comparative Example 6

The organic solvent was PF5060 (manufactured by Sumitomo 3M: perfluorohexane) having a surface tension of 11.7 mN / m and a boiling point of 57 ° C., using a flow coating method as a coating method (“flow coating method only” in Table 1). Except having transferred to the drying process as it was, it carried out similarly to Example 1, and the sample which the surface was uniform and transparent by visual observation was obtained. The antifouling layer of the obtained sample had a stain resistance of ○, a stain resistance of ○, abrasion resistance of ○, and a cloudy appearance of ○. However, in the production of up to 50 sheets continuously, the solvent was volatilized and the solid content concentration of the coating agent became high. As a result, it was not possible to apply uniformly, and the appearance and antifouling property of the antifouling layer became unstable for each substrate. Therefore, productivity is x. Moreover, two sheets of the surface of the float glass board | substrate of 300 mm x 300 mm size could be apply | coated using 10 ml of coating agents for antifouling layer formation. In addition, the variation in the fluorine count was 0.8 µg / cm 2. Table 2 shows the results of the quality evaluation.

Comparative Example 7

All organic solvents were the same as in Example 1 except that the surface tension was 20.7 mN / m and the boiling point was 115 ° C., 1,3-bis (trifluoromethyl) benzene. A sample was obtained. The antifouling layer of the obtained sample had a stain-resistant ○, anti-fog resistance ○, abrasion resistance ◎, and an appearance when the cloudiness was cloudy, and a dot-like turbidity occurred and was ×. In addition, the variation in the fluorine count was 2.2 µg / cm 2. Table 2 shows the results of the quality evaluation.

Comparative Example 8

The organic solvent in Example 5 was used as the liquid mixture of Novec7300 and hexane. The concentration of the fluorine-based agent in the mixed solution is 50 mass%. Moreover, the surface tension of this liquid mixture is about 16.7 mN / m, and a boiling point is about 84 degreeC. As a result, samples with a uniform and transparent surface were obtained by visual observation. The antifouling layer of the obtained antifouling article had a stain resistance?, A dirt resistance?, Abrasion resistance ○, and an appearance when the cloudiness was clouded. In addition, the variation in the fluorine count was 1.7 µg / cm 2. Table 2 shows the results of the quality evaluation.

As described above, the antifouling article obtained by the present invention has excellent antifouling performance and abrasion resistance, and even if the surface of the antifouling layer of the antifouling article is exposed to steam such as water, the surface has a dot-like or stripe-like turbidity. It does not occur, and appearance and design are not impaired.

As mentioned above, although embodiment of this invention was described, of course, the following embodiment can be suitably changed and improved based on the common knowledge of a person skilled in the art in the range which does not deviate from the meaning of this invention.

1 glass substrate
2 Retaining member with coating
3 The direction in which the holding member is brought into contact with the glass substrate and the coating agent is applied

Claims (10)

Formation of an antifouling layer of an antifouling article to be used under steam, which is obtained by dissolving a perfluoropolyether group-containing silane represented by the following formula (1) with an organic solvent having a surface tension of 20.0 mN / m or less and a boiling point of 95 to 200 ° C. Coating agent for.
[Formula 1]

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

X is a formula:-(O) _g- (CF ₂ ) _h- (CH ₂ ) _i- (where g, h and i each independently represent an integer of 0-50, and the sum of g and h Is 1 or more, and the existence order of each repeating unit enclosed in parentheses is arbitrary in a 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 It represents one or more hydrolysable functional groups, and 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 each independently represent 0 to The integer of 5 is shown, m and n are each independently the integer of 0-50, and the sum of m and n is 1 or more.) The method of claim 1,
60-100 mass% of fluorine-type solvents are contained in 100 mass% of said organic solvents, The said antifouling layer forming coating agent characterized by the above-mentioned. The method according to claim 1 or 2,
The coating agent for forming an antifouling layer, wherein the fluorine-based solvent is at least one selected from the group consisting of hydrofluorocarbon, perfluorocarbon, hydrofluoroether, and hydrochlorofluorocarbon. 4. The method according to any one of claims 1 to 3,
The said fluorine-type solvent is 1 or more types chosen from the group which consists of a perfluorocarbon and a hydrofluoroether, The said antifouling layer forming coating agent. 5. The method according to any one of claims 1 to 4,
0.01-5 mass% of perfluoro polyether group containing silane represented by the said Formula (1) is contained in 100 mass% of coating agents for antifouling layer formation, The said antifouling layer formation coating agent. A method for producing an antifouling article using the antifouling layer-forming coating agent according to any one of claims 1 to 6, wherein (1) a holding member containing the coating agent is brought into contact with the substrate surface, and the holding member is placed on the substrate surface. Coating A which reciprocates in a specific one direction on the surface to apply the coating agent to the entire surface, and then the holding member is brought into contact with the substrate surface again, and the holding member is reciprocated on the substrate surface in one direction different from the coating direction in the coating A on the substrate surface. A method of producing an antifouling article, comprising the step of having a coating B for soaking the entire surface, a coating C finally applied along the end of the substrate, and (2) drying the applied coating agent. The antifouling article manufactured by the manufacturing method of Claim 6, and used under steam. 6. The method according to any one of claims 1 to 5,
The antifouling article according to claim 1, wherein the antifouling article is any one of an antifouling mirror for a bathroom or a toilet, or a partition where water is used in a building such as a kitchen or a wash basin. The method according to claim 6,
The antifouling article is any one of an antifouling mirror for a bathroom or a toilet, or a partition where water is used in a building such as a kitchen or a wash basin. The method of claim 7, wherein
The antifouling article is any one of an antifouling mirror for a bathroom or a toilet, or a partition in which water is used in a building such as a kitchen or a sink.

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