Hydrophilic antifouling treatment agent

Abstract

To provide a hydrophilic antifouling treatment agent which has less environmental loads without using a fluorine-based solvent, is excellent in production suitability, and forms a hydrophilic antifouling layer having balanced antifouling property, scratch resistance, abrasion resistance, adhesion and hydrophilic property, while having simple layer constitution, and an antifouling laminate related to a hydrophilic antifouling laminate manufactured using the hydrophilic antifouling treatment agent.MEANS FOR SOLVING THE PROBLEM: A hydrophilic antifouling treatment agent contains specific colloidal silica (A), a silicate binder (B), and a solvent (C), and forms a hydrophilic antifouling layer on a base material layer.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a hydrophilic antifouling treatment agent for forming a hydrophilic antifouling layer having a small environmental load, excellent production suitability, and excellent balance of antifouling property, scratch resistance, abrasion resistance, adhesion, and hydrophilicity, and a hydrophilic antifouling laminate produced using the hydrophilic antifouling treatment agent.

Background Art

[0002] On the surfaces of automobile bodies, aluminum coils of room air conditioners, car evaporators of car air conditioners, indoor plumbing products (toilets, bathtub kilns, bathroom floors), outer layers of houses (outer walls, building materials), displays for personal computers, etc., showcases, partitions, lamps, etc., an antifouling layer is generally provided to prevent dirt. Generally, the antifouling layer is formed by spray treatment or the like using a treatment agent containing a fluorine-based silane coupling agent and adhered to the surface to be coated to impart water repellency. However, since the fluorine-based silane coupling agent is hardly compatible with general solvents, it is necessary to dilute it with a fluorine-based solvent and use it, so the environmental load is large and it is very expensive (Patent Documents 1 to 4).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention aims to provide an antifouling laminate related to a hydrophilic antifouling laminate which has a small environmental load without using a fluorine-based solvent, is excellent in production suitability, has a simple layer structure, and is excellent in the balance of antifouling property, scratch resistance, abrasion resistance, adhesion, and hydrophilicity, and particularly excellent in hydrophilic durability.

Means for Solving the Problems

[0005] As a result of various studies, the present inventors have found that a hydrophilic antifouling treatment agent containing at least a specific colloidal silica (A), a specific silicate binder (B), and a solvent (C) achieves the above problems.

[0006] That is, the present invention is characterized by the following points. [1] A hydrophilic antifouling treatment agent for forming a hydrophilic antifouling layer on a base material layer, The hydrophilic antifouling treatment agent contains colloidal silica (A), a silicate binder (B) having a weight average molecular weight of 1500 to 100,000, and a solvent (C), The content of colloidal silica (A) in the solid content of the hydrophilic antifouling treatment agent is 60% by mass or more and 96% by mass or less, The above hydrophilic antifouling treatment agent. [2] A hydrophilic antifouling treatment agent further containing a hydrophilic resin (D), The content of the hydrophilic resin (D) in the solid content of the hydrophilic antifouling treatment agent is 40% by mass or less. The hydrophilic antifouling treatment agent according to [1] above. [3] The hydrophilic antifouling treatment agent according to [1] or [2] above, wherein 40% by mass or more of the colloidal silica (A) is chain silica and / or pearl necklace-shaped silica. [4] The hydrophilic antifouling treatment agent according to any one of [1] to [3] above, further containing an adhesion promoter (E). [5] The hydrophilic antifouling treatment agent according to any one of [1] to [4] above, further containing a quaternary ammonium salt (F). [6] The hydrophilic antifouling treatment agent according to any one of [1] to [5] above, further containing a sliding material (G). [7] The hydrophilic antifouling treatment agent according to any one of the above [1] to [6], which is a room temperature curing type. [8] The hydrophilic antifouling treatment agent according to any one of the above [1] to [7], which is a cross coating type. [9] A method for producing a hydrophilic antifouling laminate, comprising forming a hydrophilic antifouling layer made of the hydrophilic antifouling treatment agent according to any one of claims 1 to 8 on a base material layer, and surface-treating the surface of the hydrophilic antifouling layer with a surface treatment agent containing an oxidizing agent.

[10] A hydrophilic antifouling laminate having a base material layer and a hydrophilic antifouling layer as a surface layer, wherein the hydrophilic antifouling layer is a layer made of the hydrophilic antifouling treatment agent according to any one of the above [1] to [8]. The above-mentioned hydrophilic antifouling laminate.

[11] The hydrophilic antifouling laminate according to claim 10, wherein the surface of the hydrophilic antifouling layer is a surface treatment surface surface-treated with a surface treatment agent containing an oxidizing agent.

Advantages of the Invention

[0007] According to the present invention, without using a fluorine-based solvent, it has a small environmental load, excellent production suitability, and a simple layer structure. Moreover, it has an excellent balance of antifouling property, scratch resistance, abrasion resistance, adhesion, and hydrophilicity, and particularly excellent hydrophilic persistence. A hydrophilic antifouling treatment agent for forming a hydrophilic antifouling layer and a hydrophilic antifouling laminate produced using the hydrophilic antifouling treatment agent can be obtained.

Brief Description of the Drawings

[0008]

Figure 1

Embodiments for Carrying Out the Invention

[0009] The hydrophilic antifouling treatment agent and the hydrophilic antifouling laminate of the present invention will be further described in detail below. Although the description will be given with specific examples, the present invention is not limited thereto.

[0010] 1. Hydrophilic antifouling treatment agent The hydrophilic antifouling treatment agent of the present invention is a treatment agent for forming a hydrophilic antifouling layer on a base material layer, and contains colloidal silica (A), a silicate binder (B), and a solvent (C). The hydrophilic antifouling treatment agent of the present invention may be a cross-application type that can be impregnated into a cloth and applied, or may also be a room-temperature curing type that can be dried and cured at room temperature (15 to 40 °C).

[0011] The hydrophilic antifouling treatment agent of the present invention may further contain a hydrophilic resin (D) in order to enhance hydrophilicity. The hydrophilic antifouling treatment agent of the present invention may further contain an adhesion promoter (E) in order to enhance adhesion. The hydrophilic antifouling treatment agent of the present invention may further contain a quaternary ammonium salt (F) in order to improve the wettability with the base material layer. The hydrophilic antifouling treatment agent of the present invention may further contain a sliding material (G) in order to enhance the slidability of the hydrophilic antifouling layer.

[0012] In addition, the hydrophilic antifouling treatment agent may further contain, as necessary, a wetting agent, a viscous material (thickener), a surface conditioning material, a coloring material (pigment, dye), an antistatic material, a conductivity-imparting agent, an antibacterial and antiviral material, various fillers, etc., within a range that does not adversely affect the properties of the hydrophilic antifouling treatment agent or the hydrophilic antifouling laminate.

[0013] By containing colloidal silica (A), the hydrophilic antifouling treatment agent of the present invention can enhance the surface hardness and slidability of the hydrophilic antifouling layer formed from the hydrophilic antifouling treatment agent, enhance the adhesion to the base material layer, and enhance scratch resistance and wear resistance. The content of colloidal silica (A) in the solid content (non-volatile content) of the hydrophilic antifouling treatment agent is preferably 60% by mass or more and 96% by mass or less, and more preferably 70% by mass or more and 90% by mass or less. If it is less than the above range, the surface hardness and slidability tend to be insufficient, and if it is more than the above range, it tends to become brittle.

[0014] The hydrophilic antifouling treatment agent of the present invention contains a silicate binder (B), thereby coating and connecting colloidal silica (A), increasing the surface hardness of the hydrophilic antifouling layer, and enhancing the adhesiveness between the hydrophilic antifouling layer and the substrate layer.

[0015] The hydrophilic antifouling treatment agent of the present invention can be applied to a substrate layer for use. The substrate layer may have a paint layer such as an acrylic clear coating film on its surface. The materials constituting the substrate layer include inorganic materials and / or organic materials. Examples of inorganic materials include ceramics, glass, aluminum, Ni plating, etc. As an example of a substrate using glass, a glass plate, a glass cloth, etc. can also be used. Examples of organic materials include resins, and specific examples of resins include PMMA (polymethyl methacrylate), PC (polycarbonate), PET (polyethylene terephthalate), PP (polypropylene), etc., but are not limited thereto. Among these, PMMA is preferred.

[0016] The thickness of the hydrophilic antifouling layer formed from the hydrophilic antifouling treatment agent of the present invention is preferably 50 to 2000 nm, more preferably 100 to 500 nm. If it is thinner than the above range, the hydrophilicity is likely to decrease. If it is thicker than the above range, uneven appearance is likely to occur and the manufacturing cost increases, but the hydrophilic effect does not change much.

[0017] The hydrophilic antifouling layer formed from the hydrophilic antifouling treatment agent of the present invention is excellent in hydrophilic persistence. The contact angle measured in accordance with JIS R3257 in the initial stage after the formation of the hydrophilic antifouling layer is preferably 15 degrees or less, more preferably 10 degrees or less in the initial stage after the formation of the hydrophilic antifouling layer. If the contact angle is larger than the above range, the hydrophilicity is likely to be inferior. There is no particular lower limit for the contact angle, but it is substantially difficult to obtain a contact angle of 3 degrees or less. And the contact angle after 80°C, 16-hour drying for 10 cycles after 8-hour immersion in ion-exchanged water is preferably 45 degrees or less, more preferably 40 degrees or less. If the contact angle is larger than the above range, the hydrophilicity is likely to be inferior. There is no particular lower limit for the contact angle, but preferably it is 20 degrees or more. Since the substantial hydrophilic wettability does not change much even if it is less than 20 degrees, it is difficult to further improve the antifouling effect. Furthermore, the contact angle after 80°C, 16-hour drying for 10 cycles after 8-hour immersion in ion-exchanged water, after rubbing several times back and forth with a wet finger or the like on the hydrophilic antifouling layer (rubbing cycle), is preferably 50 degrees or less, more preferably 45 degrees or less. If the contact angle is larger than the above range, the rubbing resistance is likely to be inferior. There is no particular lower limit for the contact angle, but even if it is less than 25 degrees, it is difficult to further improve the antifouling effect.

[0018] The surface hardness of the hydrophilic antifouling layer of the present invention preferably has a surface hardness measured in accordance with JIS K5600-5-4 "Scratch hardness (pencil method)" of H or more. Conventional antifouling layers having hydrophobicity (water repellency) can easily increase the surface hardness by containing a silicate having a water-repellent functional group, and the apparent surface hardness tends to increase as the sliding property is improved by containing a fluorine compound. In addition, since conventional hydrophilic antifouling layers mainly contain hydrophilic resins or silica particles, it has been difficult to increase the surface hardness. However, the hydrophilic antifouling layer of the present invention uses colloidal silica (A) as the silica particles, and further coats the colloidal silica (A) with a silicate binder (B), so that while containing a large amount of silica particles, it achieves both hydrophilicity and high surface hardness. In addition, since general antifouling layers are monomolecular films or quite thin films, there is a problem that it is difficult to maintain water repellency and antifouling properties due to scratches and environmental factor contamination. However, the hydrophilic antifouling layer of the present invention can form a film thickness in a wide range, so it is easy to maintain various properties such as hydrophilicity and antifouling properties.

[0019] <Colloidal silica (A)> Colloidal silica (A) is silica particles in a colloidal solid content state and is dispersed in a solvent. Also, the mixture of colloidal silica and the solvent is a colloidal silica sol. Colloidal silica (A) is preferably nanosilica. The average particle diameter of colloidal silica (A) is preferably 2 to 500 nm, more preferably 5 to 50 nm, and even more preferably 8 to 20 nm. By using colloidal silica with an average particle diameter smaller than the above range, secondary aggregation is likely to occur. If the average particle diameter is larger than the above range, it becomes difficult to balance surface hardness, slidability, and adhesion to the base material layer.

[0020] Colloidal silica (A) preferably contains chain-like colloidal silica and / or pearl necklace-like colloidal silica. When colloidal silica (A) is chain-like colloidal silica and / or pearl necklace-like colloidal silica, the surface hardness and slidability of the hydrophilic antifouling layer can be enhanced, and the adhesion to the base material layer can be enhanced. The content of chain-like colloidal silica and / or pearl necklace-like colloidal silica in colloidal silica (A) is preferably 40% by mass or more and 100% by mass or less, and more preferably 60% by mass or more and 95% by mass or less. If it is less than the above range, the effect of enhancing the surface hardness and slidability of the hydrophilic antifouling layer and the adhesion to the base material layer is likely to be insufficient. Even if it is more than the above range, the effect of enhancing the surface hardness and slidability of the hydrophilic antifouling layer and the adhesion to the base material layer is not improved much.

[0021] <Silicate binder (B)> The silicate binder (B) contains an alkyl silicate partial hydrolysis condensation oligomer. And the silicate binder (B) may further contain an alkoxysilane monomer or a catalyst as required. The content rate of the alkyl silicate partial hydrolysis condensation oligomer in the hydrophilic antifouling treatment agent is preferably 5 to 30% by mass, and more preferably 10 to 20% by mass.

[0022] [Alkyl silicate partial hydrolysis condensation oligomer, alkyl silicate] The alkyl silicate partial hydrolysis condensation oligomer is an oligomer formed by partial hydrolysis and dehydration condensation of an alkyl silicate (alkoxysilane) and is soluble in the solvent (C). The alkyl silicate is a silane compound having one or more alkoxys and may have one or more alkyl groups. Further, the alkyl silicate may be an alkyl silicate having a functional group, an amino group-containing alkyl silicate, or an epoxy group-containing alkyl silicate. In the present invention, the alkyl silicate partial hydrolysis condensation oligomer can be used alone or in combination of two or more.

[0023] Specific examples of the alkyl silicate include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, propyltripropoxysilane, butyltributoxysilane, etc. In the present invention, the above compounds can be used alone or in combination of two or more as the alkyl silicate.

[0024] Specific examples of the amino group-containing alkyl silicate include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropyldiethylethoxysilane, 8-aminooctyltrimethoxysilane, etc. Among these, 3-aminopropyltrimethoxysilane is preferred. In the present invention, the above compounds can be used alone or in combination of two or more as the amino group-containing alkyl silicate.

[0025] Specific examples of the epoxy group-containing alkyl silicate include, but are not limited to, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-glycidoxypropyldiethylethoxysilane, 8-glycidoxyoctyltrimethoxysilane, and the like. Among these, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane are preferred. In the present invention, as the epoxy group-containing alkyl silicate, the above compounds can be used alone or in combination of two or more.

[0026] [Catalyst] The catalyst can promote the hydrolysis reaction and dehydration condensation reaction of the alkyl silicate partial hydrolysis condensation oligomer, alkoxysilane monomer, and colloidal silica (A). Therefore, the catalyst can be used as a catalyst when synthesizing the alkyl silicate partial hydrolysis condensation oligomer in the silicate binder (B) and / or when curing the hydrophilic antifouling layer formed from the hydrophilic antifouling treatment agent.

[0027] The content of the catalyst in the silicate binder (B) is preferably 0.05 to 10% by mass, more preferably 0.1 to 5.0% by mass. If it is less than the above range, the effect of promoting the formation of the alkyl silicate partial hydrolysis condensation oligomer tends to be insufficient, and if it is more than the above range, the formation of the alkyl silicate partial hydrolysis condensation oligomer tends to be non-uniform. When the content of the catalyst in the hydrophilic antifouling treatment agent of the present invention is less than the above range, the surface hardness of the hydrophilic antifouling layer is increased

[0028] preferably 0.05 to 10% by mass, more preferably 0.1 to 5.0% by mass. The promoting effect is likely to be insufficient, and if it is more than the above range, the surface hardness of the hydrophilic antifouling layer is likely to become non-uniform.

[0029] As the catalyst, an acid catalyst or a base catalyst can be used. Specific examples of the acid catalyst include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzenesulfonic acid, 10-camphorsulfonic acid, formic acid, oxalic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, lactic acid, etc. Specific examples of the base catalyst include triethylenediamine, dimethylaminoethanol, aqueous ammonia, etc. Among these, nitric acid as the acid catalyst is preferable. In the present invention, as the catalyst, the above compounds can be used alone or in combination of two or more.

[0030] <Solvent (C)> The solvent (C) is not particularly limited as long as it can dissolve or disperse the colloidal silica (A) and the silicate binder (B), but it preferably contains an alcohol-based solvent and / or a glycol-based solvent. Also, when the hydrophilic antifouling treatment agent of the present invention is cured at a low temperature, in order to dry it at a low temperature, it is preferable to use a solvent with a low boiling point. When the hydrophilic antifouling treatment agent of the present invention is dried and cured, for example, at 40 °C or below within 1 hour, it is preferable to use a solvent having 10 or less carbon atoms and a boiling point of 50 to 90 °C. Solvents with a lower boiling point than the above range are difficult to handle, and solvents with more carbon atoms and a higher boiling point than the above range will require high temperature and long time for drying the hydrophilic antifouling layer formed from the hydrophilic antifouling treatment agent. When drying at 80 °C or higher, the appearance can be made smoother by using a high-boiling solvent having a boiling point of 120 °C to 220 °C in combination.

[0031] Specific examples of alcohol solvents include methanol (carbon number 1, boiling point 65°C), ethanol (carbon number 2, boiling point 78°C), normal propanol (carbon number 3, boiling point 97°C), isopropyl alcohol (carbon number 3, boiling point 82°C), tertiary butanol (carbon number 4, boiling point 82°C), normal butanol (carbon number 4, boiling point 118°C), isobutanol (carbon number 4, boiling point 108°C), secondary butanol (carbon number 4, boiling point 100°C), 1-pentanol (carbon number 5, boiling point 138°C), 2-methyl-1-butanol (carbon number 5, boiling point 128°C), 3-methyl-1-butanol (carbon number 5, boiling point 131°C), 2-pentanol (carbon number 5, boiling point 119°C), 1-ethyl-1-propanol (carbon number 5, boiling point 116°C), 2-methyl-2-butanol (carbon number 5, boiling point 102°C), etc., but are not limited thereto. Among these, ethanol and normal butanol are preferred.

[0032] Specific examples of glycol solvents include alkylene glycols and alkylene glycol ethers. Specific alkylene glycols include ethylene glycol (carbon number 2, boiling point 197°C), propylene glycol (carbon number 3, boiling point 189°C), butylene glycol (carbon number 4, boiling point 207°C), hexylene glycol (carbon number 6, boiling point 197°C), octylene glycol (carbon number 8, boiling point 175°C), etc., but are not limited thereto.

[0033] Specific examples of alkylene glycol ethers include ethylene glycol monomethyl ether (carbon number 3, boiling point 124 °C), ethylene glycol monoethyl ether (carbon number 4, boiling point 135 °C), ethylene glycol diethyl ether (carbon number 6, boiling point 121 °C), ethylene glycol monoisopropyl ether (carbon number 5, boiling point 141 °C), ethylene glycol monobutyl ether (carbon number 6, boiling point 171 °C), propylene glycol monomethyl ether (carbon number 4, boiling point 120 °C), propylene glycol monoethyl ether (carbon number 5, boiling point 132 °C), propylene glycol mononormal propyl ether (carbon number 6, boiling point 149 °C), propylene glycol mononormal butyl ether (carbon number 7, boiling point 171 °C), but are not limited thereto. Among these, propylene glycol monomethyl ether is preferred. In the present invention, as the solvent (C), the above solvents can be used alone or in combination of two or more.

[0034] <Hydrophilic resin (D)> The hydrophilic resin (D) can enhance the hydrophilicity of the hydrophilic antifouling layer. When the hydrophilic antifouling treatment agent contains the hydrophilic resin (D), the content of the hydrophilic resin (D) in the solid content of the hydrophilic antifouling treatment agent is preferably 5% by mass or more and 40% by mass or less. If it is less than the above range, it is difficult to show the effect of containing the hydrophilic resin (D), and if it is more than the above range, the film-forming property of the hydrophilic antifouling treatment agent may decrease. Specific examples of the hydrophilic resin (D) include polyvinyl alcohol (PVA), polyacrylic acid, polyacrylamide, polyethylene oxide (PEO), polyvinyl sulfonic acid, polystyrene sulfonic acid, polyglutamic acid, polyvinyl formamide, polyamide, etc., but are not limited thereto. Among these, polyvinyl alcohol is preferred.

[0035] <Adhesive (E)> The adhesive (E) is preferably a urethane resin, an acrylic resin, or a silicate partial hydrolysis condensation oligomer having an alkoxysilyl group or a phenyl group. The alkoxysilyl group can react with the silicate binder (B), colloidal silica (A), or the substrate layer to form a crosslink. And the urethane resin, resin having a phenyl group, and (meth)acrylic resin can enhance the affinity and adhesion with the resin substrate layer. Specific examples of the adhesion material (E) include an acrylic resin having an alkoxysilyl group, a urethane resin having an alkoxysilyl group, and a partially hydrolyzed and condensed oligomer of a phenyl group-substituted alkyl silicate having an alkoxysilyl group. In order to obtain high adhesion, for example, the weight average molecular weight of the acrylic resin having an alkoxysilyl group by gel permeation chromatography (GPC) is preferably 1500 to 100000.

[0036] <Quaternary ammonium salt (F)> The quaternary ammonium salt (F) can improve the wettability of the hydrophilic antifouling treatment agent with the substrate layer. The quaternary ammonium salt (F) is not particularly limited as long as it is a quaternary ammonium salt, and it may be a neutralized salt with any acid. It may be a polymer or a monomer, but a polymer is preferred because it is more likely to remain in the hydrophilic antifouling layer and has excellent hydrophilic persistence. The quaternary ammonium salt (F) preferably has a functional group such as a hydroxyl group or a silyl group for interacting or crosslinking with other components in the hydrophilic antifouling treatment agent or the substrate layer. By having such a functional group, it can easily remain in the hydrophilic antifouling layer and has excellent hydrophilic persistence.

[0037] Examples of the polymer of the quaternary ammonium salt include quaternary ammonium salts having an organic polymer such as an acrylic resin or a urethane resin or an inorganic polymer of a silicate condensation system as the main skeleton.

[0038] Examples of the monomer of the quaternary ammonium salt include monoalkylammonium chloride and dialkylammonium chloride.

[0039] Specific examples of the monoalkylammonium chloride include, but are not limited to, N,N,N-trimethyl-1-octadecylammonium chloride, N,N,N-trimethyl-1-octadecylammonium chloride, alkyl (C14 - C18) trimethylammonium chloride, hexadecyltrimethylammonium chloride, N,N,N-trimethyl-1-octadecylammonium chloride, behenyltrimethylammonium chloride, benzalkonium chloride, etc. Specific examples of the dialkylammonium chloride include, but are not limited to, didecyldimethylammonium chloride, jatropha oil alkyl dimethylammonium chloride, dialkyldimethylammonium chloride, etc. In the present invention, the quaternary ammonium salt (F) can be used alone or in combination of two or more.

[0040] <Sliding material (G)> For the sliding material (G), a silicone-based sliding material and / or a fluorine-based sliding material can be used. The silicone-based sliding material and the fluorine-based sliding material can reduce the surface friction coefficient of the hydrophilic antifouling layer and enhance the slidability.

[0041] [Silicone-based sliding material] The silicone-based sliding material is a polydimethylsiloxane-modified silicate oligomer. The polydimethylsiloxane-modified silicate oligomer can be synthesized, for example, by subjecting a polydimethylsiloxane having a hydroxy group and a silicate oligomer having an alkoxy group to a dehydration condensation reaction. In order to obtain high slidability, the number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) of the polydimethylsiloxane-modified silicate oligomer is preferably from 1500 to 100000.

[0042] [Fluorine-based sliding material] The fluorine-based sliding material is a fluorine-substituted silane-modified silicate oligomer. The fluorine-substituted silane-modified silicate oligomer can be synthesized, for example, by subjecting a fluorine-substituted silane compound and a silicate oligomer having an alkoxy group to a dehydration condensation reaction.

[0043] Specific examples of the fluorine-substituted silane compound include trifluoropropyltrimethoxysilane, dimethoxy(methyl)(3,3,3-trifluoropropyl)silane, trimethoxy(1H,1H,2H,2H-perfluorohexyl)silane, triethoxy(1H,1H,2H,2H-perfluorohexyl)silane, trimethoxy(1H,1H,2H,2H-perfluoro-n-octyl)silane, triethoxy(1H,1H,2H,2H-perfluoro-n-octyl)silane, triethoxy[5,5,6,6,7,7,7-heptafluoro-4,4-bis(trifluoromethyl)heptyl]silane, trimethoxy(1H,1H,2H,2H-heptadecafluorodecyl)silane, triethoxy-1H,1H,2H,2H-heptadecafluorodecylsilane, etc., but are not limited thereto. Among these, trimethoxy(1H,1H,2H,2H-perfluoro-n-octyl)silane and triethoxy(1H,1H,2H,2H-perfluoro-n-octyl)silane are preferred. The above fluorine-substituted silane compounds can be used singly or in combination of two or more.

[0044] <Method for producing hydrophilic antifouling treatment agent> The hydrophilic antifouling treatment agent of the present invention can be produced, for example, by the following method. 1) A catalyst composed of an acid or a base is dropped into a solvent and stirred and mixed to prepare a catalyst solution. 2) Colloidal silica (A), silicate binder (B), and solvent (C) are stirred and mixed. 3) While dropping the catalyst solution prepared above, it is stirred and mixed at 10 to 60 ° C for about 1 hour. 。 4) If necessary, a solvent, an adhesion material (D), and a sliding material (E) are added and stirred and mixed. 5) Add a solvent so that the concentration and viscosity are adjusted according to the desired coating method and coating conditions to obtain a hydrophilic antifouling treatment agent. 6) The obtained hydrophilic antifouling treatment agent may be filtered, for example, through a filter with a mesh size of 0.5 to 2 μm.

[0045] <Method of using the hydrophilic antifouling treatment agent> The hydrophilic antifouling treatment agent of the present invention can be applied to the base material layer by cross coating, spray coating, dip coating, spin coating, or roll coating, but is not limited thereto. The hydrophilic antifouling treatment agent of the present invention cures at room temperature, but may also be baked at a high temperature. Specifically, 1 to 75 minutes is preferable at 15 to 160 °C, 1 to 60 minutes is more preferable, and 45 to 60 minutes at 25 to 50 °C is even more preferable. However, depending on the composition of the hydrophilic antifouling treatment agent and the composition of the base material layer, it may be dried and cured at a higher temperature and for a longer time than the above. In the case of room temperature curing type, room temperature drying and curing such as 1 minute, 10 minutes, 1 hour, etc. are possible at 15 to 40 °C. However, it is preferable to contain a solvent that dries sufficiently at room temperature. Standard conditions are 80 °C for 1 to 10 minutes. However, when baked at a high temperature, the hardness of the hydrophilic antifouling layer increases, but when the base material layer is made of a resin base material, there is a risk of deformation of the base material layer.

[0046] 2. Regarding the hydrophilic antifouling laminate The hydrophilic antifouling laminate of the present invention is a laminate having at least a base material layer and a hydrophilic antifouling layer as a surface layer, and has a balance of excellent hydrophilicity, antifouling property, high adhesion between the base material layer / hydrophilic antifouling layer, appearance, and high surface hardness.

[0047] [Base material layer] The base material layer is an object to be coated with the hydrophilic antifouling treatment agent of the present invention. The base material layer may be composed of an inorganic material and / or an organic material, and the surface of the base material layer may be a paint layer such as an acrylic clear coating film. Examples of the inorganic material include ceramics, glass, aluminum, Ni plating, etc. As an example of the substrate using glass, a glass plate, a glass cloth, etc. can also be used. Examples of the organic material include, but are not limited to, resins such as PMMA, PC, PET, and PP. Among these, PMMA is preferred. The thickness of the substrate layer is not particularly limited, but is preferably 0.1 to 5.0 mm. The surface of the substrate layer may be subjected to an anti-glare treatment (AG treatment), and by the anti-glare treatment, the surface roughness Ra is preferably 0.5 to 20 nm.

[0048] [Hydrophilic antifouling layer] The hydrophilic antifouling layer is a layer formed from the hydrophilic antifouling treatment agent of the present invention, and is excellent in the balance of antifouling property, scratch resistance, abrasion resistance, adhesion, and hydrophilicity.

[0049] The surface of the hydrophilic antifouling layer may be a surface treatment surface surface-treated with a surface treatment agent containing an oxidizing agent. When the surface of the hydrophilic antifouling layer is such a surface treatment surface, the surface of the hydrophilic antifouling layer can have more excellent hydrophilicity.

[0050] The thickness of the hydrophilic antifouling layer is preferably 50 to 2000 nm, more preferably 100 to 500 nm. If it is thinner than the above range, the hydrophilicity is likely to decrease. If it is thicker than the above range, uneven appearance is likely to occur and the manufacturing cost increases, but the hydrophilic effect does not change so much. The contact angle of the hydrophilic antifouling layer measured in accordance with JIS R3257 is preferably 15 degrees or less, more preferably 12 degrees or less, at the initial stage after the formation of the hydrophilic antifouling layer. If the contact angle is larger than the above range, the hydrophilicity is likely to be inferior. There is no particular lower limit for the contact angle, but 3 degrees or more is preferred. It is substantially difficult to obtain a contact angle smaller than 3 degrees. And the contact angle after 8 h immersion in ion-exchanged water & 16 hr drying at 80 °C × 10 cycles is preferably 45 degrees or less, more preferably 40 degrees or less. If the contact angle is larger than the above range, the hydrophilicity is likely to be inferior. There is no particular lower limit for the contact angle, but 20 degrees or more is preferred. Since the substantial hydrophilic wettability does not change so much even if it is less than 20 degrees, it is difficult to further improve the antifouling effect.

[0051] The surface hardness of the hydrophilic antifouling layer preferably has a surface hardness of H or more as measured in accordance with JIS K5600-5-4 "Scratch hardness (pencil method)".

[0052] [Surface treatment agent] The surface treatment agent is a surface treatment agent for adjusting the hydrophilicity of the surface of the hydrophilic antifouling layer, and preferably contains an oxidizing agent and a solvent. Specific examples of the oxidizing agent contained in the post-treatment agent include hydrogen peroxide, hypochlorous acid, permanganic acid, ferric sulfate, sodium nitrite, etc. Among these, hydrogen peroxide is preferred. Specific examples of the solvent contained in the post-treatment agent are not particularly limited as long as they can dissolve or disperse the oxidizing agent, but preferably contain water such as deionized water. The content of the oxidizing agent in the surface treatment agent is preferably 0.1 to 5% by mass, more preferably 0.5 to 2% by mass. If it is lower than the above range, it is likely to be difficult to obtain a sufficient surface treatment effect, and even if it is higher than the above range, the surface treatment effect will not be improved much.

[0053] [Method for producing hydrophilic antifouling laminate] The hydrophilic antifouling laminate of the present invention can be produced by a production method including the following step 1.

[0054] Step 1; Step of forming a hydrophilic antifouling layer on a base material layer Base material layer temperature: 15 to 40 °C, Coating method of hydrophilic antifouling treatment agent: cross coating, spray coating, dip coating, spin coating, or roll coating, Drying and heat curing conditions of hydrophilic antifouling layer: 15 to 160 °C, 1 to 75 minutes, (standard: 80 °C, 1 to 10 minutes), Layer thickness of hydrophilic antifouling layer: 50 to 2000 nm,

[0055] By adjusting the composition of the hydrophilic antifouling treatment agent and the process conditions of step 1, the surface roughness Ra of the hydrophilic antifouling layer can be adjusted to 0.5 to 20 nm.

[0056] The hydrophilic antifouling treatment agent can be applied by any of cross coating, spray coating, dip coating, spin coating, and roll coating. However, spin coating is preferred because it has high productivity, is easy to adjust the appearance and film thickness, is environmentally friendly, and is simple.

[0057] As for the conditions of spray coating, for example, the following are preferred. Nozzle diameter: 0.1 - 10 mm, more preferably 0.1 - 2.0 mm Atomization pressure: 150 - 700 kPa Discharge rate: 0.5 - 20 ml / min Spraying distance: 10 - 200 mm Head speed: 50 - 500 mm / sec Pitch: 0.5 - 10 mm

[0058] When adjusting the surface roughness Ra of the hydrophilic antifouling layer to 0.5 - 20 nm, the nozzle diameter is particularly preferably 0.1 - 2.0 mm.

[0059] As for the conditions of spin coating, for example, the following are preferred. Rotation speed: 200 - 3000 rpm 3 - 30 seconds

[0060] When the surface of the hydrophilic antifouling layer of the hydrophilic antifouling laminate of the present invention is a surface-treated surface, it can be produced by a manufacturing method further including the following Step 2. Step 2; Surface treatment of the hydrophilic antifouling layer Base material layer or hydrophilic antifouling layer temperature: 15 - 40 °C, Coating method of the surface treatment agent: cross coating, spray coating, dip coating, spin coating, or roll coating, Drying conditions of the surface treatment agent: 5 - 160 °C, 1 - 60 minutes, (standard: 25 °C, 10 minutes),

[0061] By adjusting the composition of the surface treatment agent, the initial contact angle of the surface of the hydrophilic antifouling layer can be adjusted to 15 degrees or less or 12 degrees or less.

[0062] The surface treatment agent can be applied by any of cross coating, spray coating, dip coating, spin coating, and roll coating. However, spin coating is preferred because it has high productivity, is easy to consider the environment, and is simple.

[0063] As for the conditions of spray coating, for example, the following are preferred. Nozzle diameter: 0.1 to 10 mm, more preferably 0.1 to 2.0 mm Atomization pressure: 150 to 700 kPa Discharge rate: 0.5 to 20 ml / min Spraying distance: 10 to 200 mm Head speed: 50 to 500 mm / sec Pitch: 0.5 to 10 mm

[0064] In order to improve productivity, the nozzle diameter is particularly preferably 0.1 to 2.0 mm.

[0065] As for the conditions of spin coating, for example, the following are preferred. Rotation speed: 200 to 3000 rpm 3 to 30 seconds

Examples

[0066] Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to the following examples. The raw materials used in the examples are as follows.

[0067] <Raw materials> [Colloidal silica] · Colloidal silica sol 1: Snowtex ST-OUP manufactured by Nissan Chemical Industries, Ltd., acidic sol type chain nano silica sol. Particle size 12 nm, solid content 15 wt%, solvent is water. · Colloidal silica sol 2: Snowtex ST-PS-SO manufactured by Nissan Chemical Industries, Ltd., acidic sol type pearl necklace-like nano silica sol. Particle size 15 nm, solid content 15 wt%, solvent is water. · Colloidal silica sol 3: Snowtex IPA-ST manufactured by Nissan Chemical Industries, Ltd., a nano-silica sol. Particle size 12 nm, solid content 30 wt%, and the solvent is IPA.

[0068] [Silicate oligomer] · Silicate oligomer 1: Silicate 40 manufactured by Tama Chemical Industry Co., Ltd. A mixture of polyethyl silicate, tetraethoxysilane, and a solvent, with a non-volatile content of 100 mass%. 60 - 70 mass% of the non-volatile content is polyethyl silicate.

[0069] [Adhesive] · Adhesive 1: 8SQ-1100 manufactured by Dainippon Fine Chemical Co., Ltd. A silicone-modified acrylic polymer with a non-volatile content of 50 mass%. · Phenyl group-containing alkyl silicate 1: KBE103 manufactured by Shin-Etsu Chemical Co., Ltd., phenyltriethoxysilane. Non-volatile content 100 mass%.

[0070] [Sliding material] · Reactive polysiloxane 1: Silaplane FM-0815 manufactured by JNC. A reactive silicone having an alkoxysilyl group as a functional group. Number average molecular weight 4000. Non-volatile content 100 mass%. · Fluorine-substituted silane compound 1: Triethoxy(1H,1H,2H,2H-perfluorooctyl)silane manufactured by Unichem Co., Ltd. Non-volatile content 100 mass%.

[0071] [Quaternary ammonium salt] · Quaternary ammonium salt 1: 1WX-1020 manufactured by Dainippon Fine Chemical Co., Ltd. A quaternary ammonium salt polymer containing a hydroxyl group, with a non-volatile content of 40 mass%.

[0072] [Commercially available hydrophilic antifouling treatment agent] · Commercially available hydrophilic antifouling treatment agent 1: Honeyceran PI-400AR manufactured by Honeywell Chemical Co., Ltd.

[0073] [Surface treatment agent] · Surface treatment agent 1: 1% hydrogen peroxide solution.

[0074] <Synthesis example> [Preparation of Nitric Acid Solution 1] The following were mixed to obtain Nitric Acid Solution 1 as a catalyst. 1.0 part by mass of 10% aqueous nitric acid solution 3.0 parts by mass of water 30 parts by mass of ethanol

[0075] [Preparation of Nitric Acid Solution 2] The following were mixed to obtain Nitric Acid Solution 2 as a catalyst. 0.3 part by mass of 10% aqueous nitric acid solution 3.0 parts by mass of water 30 parts by mass of ethanol

[0076] [Preparation of Nitric Acid Solution 3] The following were mixed to obtain Nitric Acid Solution 3 as a catalyst. 2.0 parts by mass of 10% aqueous nitric acid solution 3.0 parts by mass of water 30 parts by mass of ethanol

[0077] [Preparation of Formic Acid Solution 1] The following were mixed to obtain Formic Acid Solution 1 as a catalyst. 0.3 part by mass of 10% aqueous formic acid solution 3.0 parts by mass of water 30 parts by mass of ethanol

[0078] [Preparation of Silicate Binder 1] First, the following were mixed to obtain a mixed solution. 8.0 parts by mass of silicate oligomer 1 30 parts by mass of ethanol While dropping 34 parts by mass of Nitric Acid Solution 1 obtained above, the mixture was stirred and mixed at 40 °C for 1 hour. Next, the following were further added and stirred and mixed to obtain Silicate Binder 1. 28.0 parts by mass of ethanol The weight average molecular weight of the silicate binder (B) contained in the obtained Silicate Binder 1 was 3700.

[0079] [Preparation of Silicate Binder 2] Silicate binder 2 was obtained by operating in the same manner as silicate binder 1, except that 34 parts by mass of nitric acid solution 1 was changed to 33.3 parts by mass of nitric acid solution 2. The weight average molecular weight of silicate binder (B) contained in the obtained silicate binder 2 was 1700.

[0080] [Preparation of Silicate Binder 3] Silicate binder 3 was obtained by operating in the same manner as silicate binder 1, except that 34 parts by mass of nitric acid solution 1 was changed to 35 parts by mass of nitric acid solution 3 and the mixture was stirred and mixed at 60 °C for 5 hours. The weight average molecular weight of silicate binder (B) contained in the obtained silicate binder 3 was 50000.

[0081] [Preparation of Silicate Binder 4] Silicate binder 4 was obtained by operating in the same manner as silicate binder 1, except that 34 parts by mass of nitric acid solution 1 was changed to 33.3 parts by mass of formic acid solution 1. The weight average molecular weight of silicate binder (B) contained in the obtained silicate binder 4 was 1300.

[0082] [Preparation of Adhesive 2] The following were mixed and stirred at 40 °C for 1 hour to obtain Adhesive 2. 50 parts by mass of phenyl group-containing alkyl silicate 1 10 parts by mass of water 40 parts by mass of ethanol

[0083] [Preparation of Sliding Material 1] First, the following were mixed to obtain a mixed solution. 7.7 parts by mass of silicate oligomer 1 0.3 parts by mass of reactive polysiloxane 1 30 parts by mass of ethanol While dropping 34 parts by mass of nitric acid solution 1 obtained above, the mixture was stirred and mixed at 40 °C for 1 hour. Next, the following were further added and stirred and mixed to obtain Sliding Material 1. 28.0 parts by mass of ethanol The weight-average molecular weight of the silicate polymer contained in the obtained sliding member 1 was 3900.

[0084] [Preparation of Sliding Member 2] First, the following were mixed to obtain a mixed solution. 7.7 parts by mass of silicate oligomer 1 0.3 parts by mass of fluorine-substituted silane compound 1 30 parts by mass of ethanol Then, while dropping 34 parts by mass of nitric acid solution 1 obtained above, the mixture was stirred and mixed at 40°C for 1 hour. Next, the following were further added and stirred and mixed to obtain sliding member 2. 28.0 parts by mass of ethanol The weight-average molecular weight of the silicate polymer contained in the obtained sliding member 2 was 3600.

[0085] [Example] [Example 1] The following were stirred and mixed at 40°C for 1.5 hours to obtain a hydrophilic antifouling treatment agent. 14.2 parts by mass of colloidal silica sol 1 4.7 parts by mass of silicate oligomer 1 81.1 parts by mass of ethanol Using the obtained hydrophilic antifouling treatment agent, a hydrophilic antifouling layer was formed on the substrate layer, and various evaluations were performed. The hydrophilic antifouling layer was formed by spin-coating the hydrophilic antifouling treatment agent on various substrate layers at 25°C using a spin coater (MS-A100, manufactured by Mikasa Co., Ltd.) so that the film thickness was about 200 nm, and drying and curing treatment were performed at room temperature for 15 minutes.

[0086] [Examples 2 to 14, Comparative Examples 1 to 3] According to the formulations in Table 1, stirring and mixing were carried out in the same manner as in Example 1 to obtain a hydrophilic antifouling treatment agent. Then, a hydrophilic antifouling layer was formed on the substrate layer in the same manner as in Example 1, and evaluation was carried out in the same manner.

[0087] [Example 15] A hydrophilic antifouling layer was formed on the base material layer in the same manner as in Example 2. Next, using a spin coater (MS-A100, manufactured by Mikasa Corporation), surface treatment agent 1 was spin-coated on the surface of the hydrophilic antifouling layer at 25°C, and dried at room temperature for 10 minutes to perform surface treatment, and evaluation was carried out in the same manner as in Example 1.

[0088] [Comparative Example 4] Using a commercially available hydrophilic antifouling treatment agent 1, a hydrophilic antifouling layer was formed on the base material layer in the same manner as in Example 1, and evaluation was carried out in the same manner.

[0089] [Evaluation Method] [Molecular Weight Measurement] Using a GPC device (HLC-8320GPC manufactured by Tosoh Corporation, THF solvent), the polystyrene-equivalent weight average molecular weight was measured.

[0090] [Contact Angle of Hydrophilic Antifouling Layer] Using a contact angle meter PCA-11 (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of the surface of the hydrophilic antifouling layer with respect to water was measured in accordance with JIS R3257, both at the initial stage after the formation of the hydrophilic antifouling layer on the PC substrate and after immersion in ion-exchanged water for 8 hours and drying at 80°C for 16 hours × 10 cycles.

[0091] [Contact Angle of Hydrophilic Antifouling Layer (After Rubbing Cycles)] After rubbing the hydrophilic antifouling layer formed on the PC substrate back and forth 20 times with a finger wetted with ion-exchanged water under a load of about 1 kg, immersion in ion-exchanged water for 8 hours and drying at 80°C for 16 hours × 10 cycles were carried out, and using a contact angle meter PCA-11 (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of the surface of the hydrophilic antifouling layer with respect to water was measured in accordance with JIS R3257.

[0092] [Surface Hardness of Hydrophilic Antifouling Layer] The surface hardness of the hydrophilic antifouling layer formed on the glass substrate was measured in accordance with JIS K5600 "4.4 Scratch Hardness (Pencil Method) of General Test Methods for Paints".

[0093] [Appearance of Hydrophilic Antifouling Layer] A black tape was attached to the back surface of the glass substrate layer, and sunlight was applied. The presence or absence and degree of abnormalities in the hydrophilic antifouling layer formed on the glass substrate layer were observed visually. The meanings of the symbols in the table are as follows. 〇: Uniform and transparent appearance △: Slight unevenness or other abnormalities ×: Strong unevenness or other abnormalities

[0094] [Adhesion of hydrophilic antifouling layer] A hydrophilic antifouling layer was formed on a degreased glass substrate and a PC resin substrate. After attaching cellophane tape to the hydrophilic antifouling layer and then peeling it off, the peeling condition between the hydrophilic antifouling layer and the substrate layer was evaluated by visual appearance. The meanings of the symbols in the table are as follows. 〇: No peeling of the hydrophilic antifouling layer △: Part of the hydrophilic antifouling layer peeled off ×: All of the hydrophilic antifouling layer peeled off

[0095]

Table 1

[0096]

Table 2

[0097]

Table 3

[0098] <Summary of results> The hydrophilic antifouling treatment agents of all the examples showed a balance of excellent appearance, high surface hardness, low contact angle (high hydrophilicity) after the ion-exchanged water immersion and drying cycle, rubbing cycle resistance, and high adhesion to the substrate layer, while the treatment agents of the comparative examples showed inferior results in some respects.

Industrial applicability

[0099] The hydrophilic antifouling treatment agent of the present invention can be used for automobile bodies, aluminum coils of room air conditioners, car evaporators of car air conditioners, indoor plumbing fixtures (toilets, bathtub kilns, bathroom floors), outer layers of houses (outer walls, building materials), displays for personal computers, showcases, partitions, lamps, etc.

Explanation of Signs

[0100] 1 Hydrophilic antifouling laminate 2 Base material layer 3 Hydrophilic antifouling layer 4 Surface treatment surface

Claims

1. A hydrophilic antifouling treatment agent for forming a hydrophilic antifouling layer on a base material layer, the hydrophilic antifouling treatment agent contains colloidal silica (A), a silicate binder (B) with a weight average molecular weight of 1,500 to 100,000, and a solvent (C), the content of colloidal silica (A) in the solid content of the hydrophilic antifouling treatment agent is 60% by mass or more and 96% by mass or less, the said hydrophilic antifouling treatment agent.

2. A hydrophilic antifouling treatment agent further containing a hydrophilic resin (D), the content of the hydrophilic resin (D) in the solid content of the hydrophilic antifouling treatment agent is 40% by mass or less, the hydrophilic antifouling treatment agent according to Claim 1.

3. 40% by mass or more of the colloidal silica (A) is chain silica and / or pearl necklace-shaped silica, the hydrophilic antifouling treatment agent according to Claim 1.

4. The hydrophilic antifouling treatment agent according to Claim 1, further containing an adhesion promoter (E).

5. The hydrophilic antifouling treatment agent according to Claim 1, further containing a quaternary ammonium salt (F).

6. The hydrophilic antifouling treatment agent according to Claim 1, further containing a sliding material (G).

7. The hydrophilic antifouling treatment agent according to Claim 1, which is a room temperature curing type.

8. The hydrophilic antifouling treatment agent according to Claim 1, which is a cross coating type.

9. Form a hydrophilic antifouling layer composed of the hydrophilic antifouling treatment agent according to any one of Claims 1 to 8 on the base material layer, A method for manufacturing a hydrophilic antifouling laminate, wherein the surface of the hydrophilic antifouling layer is surface-treated with a surface treatment agent containing an oxidizing agent.

10. A hydrophilic antifouling laminate having a base material layer and a hydrophilic antifouling layer as a surface layer, the hydrophilic antifouling layer is a layer composed of the hydrophilic antifouling treatment agent according to any one of Claims 1 to 8, the said hydrophilic antifouling laminate.

11. The surface of the hydrophilic antifouling layer is a surface-treated surface surface-treated with a post-treatment agent containing an oxidizing agent, the hydrophilic antifouling laminate according to Claim 10.

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