JP2008222998A - Hydrophilic composition and hydrophilic member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrophilic composition to be used in forming a hydrophilic film excellent in soiling resistance and fogging resistance and having better abrasion resistance, and to provide a hydrophilic member provided with a hydrophilic film formed of the hydrophilic composition and having a surface excellent in soiling resistance, fogging resistance and abrasion resistance. <P>SOLUTION: The hydrophilic composition contains (A) a hydrophilic polymer having a specific structure and (B) an alkoxide compound of an element selected from Si, Ti, Zr and Al. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is a hydrophilic composition useful for forming hydrophilic films having excellent antifouling properties, antifogging properties, quick drying properties such as water, and better wear resistance on various substrate surfaces, and The present invention also relates to a hydrophilic member having an antifouling and antifogging surface provided with a hydrophilic film made of the hydrophilic composition.

Various techniques for preventing oily dirt from adhering to the member surface have been proposed. In particular, optical members such as antireflection films, optical filters, optical lenses, spectacle lenses, mirrors, etc., when used by humans, are contaminated with fingerprints, sebum, sweat, cosmetics, etc. Since removal of dirt is complicated, it is desired to perform effective dirt prevention treatment.
In recent years, with the spread of mobile devices, displays are often used outdoors. When used in an environment where external light is incident, the incident light is regularly reflected on the display surface. As a result, the reflected light is mixed with the display light to cause problems such as difficulty in viewing the display image. For this reason, an antireflection optical member is often disposed on the display surface.
As such an antireflection optical member, for example, a surface of a transparent substrate in which a high refractive index layer and a low refractive index layer made of a metal oxide or the like are laminated, and a surface of a transparent substrate such as an inorganic or organic fluoride compound is used. Known are those in which a low refractive index layer is formed as a single layer, or those in which a coating layer containing transparent fine particles is formed on the surface of a transparent plastic film substrate and external light is irregularly reflected by the uneven surface. These anti-reflective optical member surfaces, like the optical members described above, can easily be contaminated with fingerprints, sebum, and other dirt when used by humans. In addition to the problem, the surface of the antireflection film usually has fine irregularities, and there is a problem that it is difficult to remove dirt.

Various techniques have been proposed for forming on the surface an anti-smudge function that makes it difficult to get dirt on the surface of a solid member or that makes it easier to remove the attached dirt. In particular, as a combination of the antireflection member and the antifouling member, for example, an antireflection and abrasion resistant material (for example, an antireflection film mainly composed of silicon dioxide and a compound containing an organosilicon substituent) Patent Document 1), and an antifouling and wear-resistant CRT filter (for example, see Patent Document 2) in which a substrate surface is coated with a terminal silanol organopolysiloxane has been proposed. Further, an antireflection film containing a silane compound including a silane compound containing a polyfluoroalkyl group (see, for example, Patent Document 3), an optical thin film mainly composed of silicon dioxide, a perfluoroalkyl acrylate, and an alkoxysilane group. A combination with a copolymer with a monomer having a hydrogen atom (see, for example, Patent Document 4) has been proposed.
However, the antifouling layer formed by the conventional method has insufficient antifouling property, and in particular, it is difficult to wipe off dirt such as fingerprints, sebum, sweat, cosmetics, etc., and surface energy such as fluorine and silicon is low. The surface treatment with a material is concerned with a decrease in antifouling performance over time, and therefore, development of an antifouling member having excellent antifouling properties and durability is desired.

  In general, a resin film generally used for the surface of an optical member or the like or an inorganic material such as glass or metal has a hydrophobic surface or a weak hydrophilic surface. When the surface of a substrate using a resin film or inorganic material is made hydrophilic, the attached water droplets spread uniformly on the surface of the substrate and form a uniform water film. It is useful for preventing devitrification due to moisture and ensuring visibility in rainy weather. In addition, combustion products such as carbon black contained in exhaust gas from automobile dust, automobiles, etc., and hydrophobic pollutants such as oil and fat and sealant elution components are difficult to adhere. Therefore, it is useful for various applications.

  Conventionally proposed surface treatment methods for hydrophilization, such as etching treatment and plasma treatment, are highly hydrophilized, but their effects are temporary and maintain the hydrophilized state for a long time. I can't. Further, a surface hydrophilic coating film using a hydrophilic graft polymer as one of hydrophilic resins has also been proposed (see, for example, Non-Patent Document 1), although this coating film has a certain degree of hydrophilicity, Affinity with the substrate is not sufficient, and higher durability is required.

  In addition, as a film having excellent surface hydrophilicity, a film using titanium oxide has been conventionally known. For example, a technique of forming a photocatalyst-containing layer on a substrate surface and making the surface highly hydrophilic according to photoexcitation of the photocatalyst. It is reported that if this technology is applied to various composite materials such as glass, lenses, mirrors, exterior materials, water-circulating members, etc., excellent antifouling properties can be imparted to these composite materials ( For example, see Patent Document 5.) However, the hydrophilic film using titanium oxide does not have sufficient film strength, and since there is a problem that the use site is limited because the hydrophilization effect is not expressed unless photoexcited, and is durable, and There is a need for an antifouling member having good wear resistance.

In order to achieve the above-mentioned problems, the anti-fogging and anti-fogging properties of the hydrophilic surface with a cross-linked structure by hydrolyzing and condensation-polymerizing the hydrophilic polymer and the alkoxide are focused on the characteristics of the sol-gel organic-inorganic hybrid film. It has been found that it exhibits fouling and has good wear resistance (see Patent Document 6). A hydrophilic surface layer having such a crosslinked structure can be easily obtained by combining a specific hydrophilic polymer having a reactive group at its terminal and a crosslinking agent.
JP-A 64-86101 JP-A-4-338901 Japanese Patent Publication No. 6-29332 Japanese Patent Laid-Open No. 7-16940 International Publication No. 96/29375 Pamphlet JP 2002-361800 A Newspaper "Chemical Industry Daily" article dated January 30, 1995

  The object of the present invention is to further advance research on the sol-gel organic-inorganic hybrid film to develop the above-described prior art, and is excellent in antifouling properties, antifogging properties, quick drying properties such as water on various substrate surfaces, and more. It is an object of the present invention to provide a hydrophilic composition used for forming a hydrophilic film having good abrasion resistance. Further, another object of the present invention is to provide an antifouling property, antifogging property, quick drying property such as water, wear resistance and scratch resistance provided with a hydrophilic film formed of the hydrophilic composition on an appropriate substrate surface. An object of the present invention is to provide a hydrophilic member having an excellent surface.

As a result of further development of research on sol-gel organic-inorganic hybrid membranes, the present inventors have appropriately developed a hydrophilic surface layer having a crosslinked structure formed by hydrolysis and condensation polymerization of a hydrophilic polymer and an alkoxide. Specified by creating on the surface of the substrate, and the hydrophilic surface layer having such a crosslinked structure has a reactive group in the side chain, and the reactive group is connected to the main chain by a highly hydrophilic connecting chain This product is obtained by combining a hydrophilic polymer with a cross-linking agent, and has the same antifogging property, antifouling property, and quick-drying property such as water as the prior art, and exhibits superior wear resistance and scratch resistance. The present invention has been completed by finding out what can be done.
That is, the hydrophilic composition according to claim 1 of the present invention includes (A) a hydrophilic polymer represented by the following general formula (I), (B) an alkoxide of an element selected from Si, Ti, Zr, and Al. It is a hydrophilic composition characterized by containing a compound.

In formula (I), representative of the R ¹ to R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ) or —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), and —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.

  The hydrophilic member according to claim 3 of the present invention is selected from (A) a hydrophilic polymer represented by the following general formula (I), (B) Si, Ti, Zr, and Al on the substrate. It is characterized by having a hydrophilic film formed by coating a hydrophilic composition containing an alkoxide compound of an element, heating and drying. This hydrophilic film has a crosslinked structure formed by adjusting and coating the hydrophilic film composition.

In formula (I), representative of the R ¹ to R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b
), -N (R _a ) (R _b ) (R _c ) or -N (R _a ) (R _b ) (R _c ) (R _g ), -PO ₃ (R _e ) (R _f ), -OPO ₃ (R _e ) (R _f ), —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.

  The hydrophilic composition according to claim 1 of the present invention or the hydrophilic composition used for forming the hydrophilic member according to claim 3 preferably further contains (C) a catalyst, and the (C) catalyst (B) an alkoxide compound of an element selected from Si, Ti, Zr, and Al (hereinafter also referred to as a specific alkoxide as appropriate) and (A) a hydrophilic polymer represented by the following general formula (I) ( Hereinafter, a compound that promotes the reaction with a specific hydrophilic polymer) may be mentioned.

In formula (I), representative of the R ¹ to R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.

  The hydrophilic member according to claim 5 is a hydrophilic member characterized by having an undercoat layer containing a nonvolatile catalyst between the substrate and the hydrophilic film, and further the undercoat layer Is preferably obtained by hydrolyzing and polycondensing a composition having at least an alkoxide compound of an element selected from Si, Ti, Zr, and Al and a nonvolatile catalyst. At least one of the catalyst used in the undercoat layer and the catalyst used in the hydrophilic layer is a metal chelate compound and a silane coupling agent, and the metal chelate compound is 2A, 3B, 4A in the periodic table, and It is composed of a metal element selected from Group 5A and a β-diketone, ketoester, hydroxycarboxylic acid or ester thereof, amino alcohol, an enolic active hydrogen compound, an oxo- or hydroxy-oxygen-containing compound, and the silane More preferably, the coupling agent has a functional group that exhibits acidity or alkalinity.

  A hydrophilic composition according to claim 9 is a hydrophilic composition characterized in that it contains (A) a hydrophilic polymer represented by the following general formula (I).

In formula (I), representative of the R ¹ to R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.

  The hydrophilic member according to claim 12 is formed by applying (A) a hydrophilic composition containing a hydrophilic polymer represented by the following general formula (I) on a substrate, and heating and drying. It is a hydrophilic member characterized by having a hydrophilic film formed.

In formula (I), representative of the R ¹ to R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃
It represents (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.

  The hydrophilic composition according to claim 9 of the present invention or the hydrophilic composition used for forming the hydrophilic member according to claim 12 preferably further contains (C) a catalyst, and the (C) catalyst As (A), a compound that accelerates the reaction of a hydrophilic polymer represented by the following general formula (I) (hereinafter also referred to as a specific hydrophilic polymer as appropriate) can be mentioned.

In formula (I), representative of the R ¹ to R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.

  The hydrophilic composition according to claim 9 of the present invention or the hydrophilic composition used for forming the hydrophilic member according to claim 12 includes (B) an alkoxide of an element selected from Si, Ti, Zr, and Al. It is preferable to include a compound (hereinafter also referred to as a specific alkoxide as appropriate).

The hydrophilic member according to claim 12 is a hydrophilic member characterized by having an undercoat layer containing a nonvolatile catalyst between the substrate and the hydrophilic film, and further the undercoat layer. Is preferably obtained by hydrolyzing and polycondensing a composition having at least an alkoxide compound of an element selected from Si, Ti, Zr, and Al and a nonvolatile catalyst. At least one of the catalyst used in the undercoat layer and the catalyst used in the hydrophilic layer is a metal chelate compound and a silane coupling agent, and the metal chelate compound is 2A, 3B, 4A in the periodic table, and It is composed of a metal element selected from Group 5A and a β-diketone, ketoester, hydroxycarboxylic acid or ester thereof, amino alcohol, an enolic active hydrogen compound, an oxo- or hydroxy-oxygen-containing compound, and the silane More preferably, the coupling agent has a functional group that exhibits acidity or alkalinity.

The principle of the present invention is presumed as follows.
A hydrophilic layer having a crosslinked structure formed by hydrolysis and condensation polymerization of a polymer having a hydrophilic group and a silane coupling group in the side chain and an alkoxide of an element selected from Si, Ti, Zr, and Al Since the organic-inorganic composite film having a density cross-linked structure is formed, the film has a high strength. Specifically, (A) a specific hydrophilic polymer is dissolved in an appropriate solvent and stirred, whereby hydrolysis and polycondensation proceed in the system to obtain a sol-like hydrophilic composition. An organic-inorganic composite having a crosslinked structure formed by reacting a specific alkoxide and a functional group capable of reacting with it, having a hydrophilic functional group on the substrate surface by coating on the substrate and drying A film is formed. Furthermore, by including the specific alkoxide (B), in the hydrolysis and polycondensation in the system, the reactive sites that form a cross-linkage increase by the silane coupling group and the polymerizable functional group in the hydrolyzable compound, Since an organic-inorganic composite film having a denser and stronger cross-linked structure is formed, the resulting hydrophilic layer has a higher strength, excellent wear resistance, and a high surface hydrophilicity. It is considered that the period can be maintained. In addition, when water adheres to the surface having very high hydrophilicity, the surface area with the air interface increases because water spreads, the drying speed of water becomes very fast, and the coating film has excellent quick drying properties.

Furthermore, in the prior art, by introducing a silane coupling group at the end of the hydrophilic polymer, when the hydrophilic layer is formed, the hydrophilic polymer is unevenly distributed on the surface to increase the degree of freedom of the polymer chain. However, high hydrophilicity was expressed by improving the affinity with water. In the present invention, since the silane coupling group is present in the side chain of the polymer, the above effect is not expected, and there is a concern about the deterioration of hydrophilicity. However, the silane coupling group and the polymer main chain are connected with a highly hydrophilic linking chain. It is thought that the hydrophilicity similar to the prior art could be maintained by connecting.
In addition, the introduction of a silane coupling group into the side chain of the polymer improves the compatibility between the alkoxide, which is an inorganic component, and the hydrophilic polymer, and the organic-inorganic hybrid hydrophilicity in which the organic component and the inorganic component are uniformly dispersed. A sex layer is obtained. Thereby, it is considered that a hydrophilic member having very excellent wear resistance can be obtained.

  In the present invention, it is also effective to provide an undercoat layer between the substrate and the hydrophilic layer. Adhesiveness between the support and the hydrophilic layer is realized by the reaction between the support surface and the reactive groups of the hydrophilic layer. Actually, when there are not so many reactive groups on the support, the hydrophilic layer can be adhered through an undercoat layer rich in reactive groups. Further, by using a non-volatile catalyst for the undercoat layer, it can be present in the film while maintaining its activity without volatilizing even during the drying process when producing the hydrophilic member. In this case, the crosslinking reaction can be further promoted, and the coating film has a very high strength. Furthermore, since the non-volatile catalyst exists at the interface with the substrate without losing activity, the reaction between the substrate and the hydrophilic layer proceeds with time, and high adhesion can be realized.

  According to the present invention, a hydrophilic composition used for forming a hydrophilic film excellent in anti-fouling property, anti-fogging property, quick drying property such as water and abrasion resistance on various substrate surfaces, and the hydrophilic film It is possible to provide a hydrophilic member having excellent antifouling properties, antifogging properties, quick drying properties such as water, and good abrasion resistance and scratch resistance.

Hereinafter, the present invention will be described in detail.
The hydrophilic composition of the present invention comprises (A) a hydrophilic polymer represented by the following general formula (I), and (B) an alkoxide compound of an element selected from Si, Ti, Zr, and Al. And

In formula (I), representative of the R ¹ to R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.

Below, each component contained in the hydrophilic composition of this invention is demonstrated.
[(A) Hydrophilic polymer represented by formula (I)]
The specific hydrophilic polymer (A) that can be used in the present invention has structural units represented by the following general formulas (Ia) and (Ib).

In general formulas (Ia) and (Ib), R ^{1 to} R ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO
₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.

Examples of the hydrocarbon group when R ^{1 to} R ⁸ represent a hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
R ^{1 to} R ⁸ are preferably a hydrogen atom, a methyl group, or an ethyl group from the viewpoints of effects and availability.

  These hydrocarbon groups may further have a substituent. When the alkyl group has a substituent, the substituted alkyl group is composed of a bond between the substituent and the alkylene group, and a monovalent nonmetallic atomic group excluding hydrogen is used as the substituent. Preferred examples include halogen atoms (-F, -Br, -Cl, -I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, amino groups, N-alkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, ア ル キ ル -alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-reelcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-aryl Acylamino group, ureido group, N ′ Alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N -Arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureate group, N', N'-dialkyl- N-arylureido group, N′-aryl-Ν-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl- N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N -Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group,

Aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfur group Sulfamoyl group, N, N- dialkylsulfamoyl group, N- aryl sulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group phosphono group _(-PO 3 _{H 2} ) And conjugated base groups thereof (hereinafter referred to as phosphonate groups), dialkyl phosphono groups (—PO ₃ (alkyl) ₂ ), diaryl phosphono groups (—PO ₃ (aryl) ₂ ), alkylaryl phosphono groups (— PO ₃ (alkyl) (aryl)), monoalkylphosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H) (Aryl)) and conjugated base groups thereof (hereinafter referred to as aryl phosphonate groups), phosphonooxy groups (-OPO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonophenyl group), dialkyl phosphonooxy group _(-OPO 3 _(alkyl) 2), diaryl phosphonooxy group _(-OPO 3 _(aryl) 2), An alkylarylphosphonooxy group (—OPO (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and a conjugated base group thereof (hereinafter referred to as an alkylphosphonatooxy group), mono Arylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatooxy group), morpholino group, cyano group, nitro group, aryl group, alkenyl group, alkynyl group It is done.

Specific examples of the alkyl group in these substituents are the same as those of R ^{1 to} R ⁸ , and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, Xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, acetoxyphenyl, benzoyloxyphenyl, methylthiophenyl , Phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamo Butylphenyl group include a phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, a phosphonophenyl phenyl group. Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like. Examples of alkynyl group include ethynyl group, 1- A propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, etc. are mentioned. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups.

  Among these substituents, more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkyls. Amino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfamoy Group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphonate group Group, phosphonooxy group, phosphonatooxy group, aryl group, and alkenyl group.

On the other hand, examples of the alkylene group in the substituted alkyl group include a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyl group. Oxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N- Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxy Rubonirubuchiru group,

  Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoyl Methyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (Phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, Torilho Phonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

L ¹ represents a single bond or a polyvalent organic linking group. Here, the single bond means that the polymer main chain and X are directly bonded without a linking chain. Further, the organic linking group refers to a linking group composed of non-metallic atoms, specifically, 0 to 200 carbon atoms, 0 to 150 nitrogen atoms, 0 to 200 oxygen atoms. It consists of atoms, 0 to 400 hydrogen atoms, and 0 to 100 sulfur atoms. More specific examples of the linking group include the following structural units or those formed by combining them.

L ¹ may be formed from a polymer or an oligomer, and specifically, preferably includes polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl, polystyrene, and the like made of an unsaturated double bond monomer. Preferred examples include poly (oxyalkylene), polyurethane, polyurea, polyester, polyamide, polyimide, polycarbonate, polyamino acid, polysiloxane, and the like, and preferably polyacrylate, polymethacrylate, polyacrylonitrile, polyvinyl, and polystyrene. More preferred are polyacrylates and polymethacrylates.
The structural unit used for these polymers and oligomers may be one type or two or more types. In addition, when L ¹ is a polymer or oligomer, the number of constituent elements is not particularly limited, and the molecular weight is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, and 1,000 to 200,000 is most preferred.

L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. Here, the single bond means that the polymer main chain and the Si atom are directly bonded without a linking group. Further, two or more of the structures may be present in L ² , and in that case, they may be the same as or different from each other. If one or more of the above structures are included, the other structures can have the same structure as that described for L ¹ .

X is a hydrophilic group, and is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), — NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , — NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ) ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion. _{Further, -CON (R a) (R} b), - OCON (R a) (R b), - NHCON (R a) (R b), - SO 2 N (R a) (R b) -PO 3 (R _e ) (R _f ), -OPO ₃ (R _e ) (R _f ), -PO ₂ (R _d ) (R _e ), -N (R _a ) (R _b ) (R _c ) or -N Regarding (R _a ) (R _b ) (R _c ) (R _g ), R _{a to} R _g may be bonded to each other to form a ring, and the formed ring is an oxygen atom, sulfur atom, nitrogen It may be a heterocycle containing a heteroatom such as an atom. R _{a to} R _g may further have a substituent, and the substituent that can be introduced here is the same as the substituent that can be introduced when R ^{1 to} R ⁸ are alkyl groups. Can be listed.

Specific examples of R _a , R _b or R _c include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, and s-butyl. Preferred examples include a group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
Specific examples of R _d include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, s-butyl, t-butyl, and isopentyl. Preferred examples include a group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
R _e, specifically as R _f, in addition to the alkyl groups mentioned R _a to R _d, a hydrogen atom; lithium, sodium, alkali metals such as potassium, calcium, alkaline earth such as barium metal, or, , Ammonium, iodonium, sulfonium and the like.
Specific examples of R _g include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; a nitrate anion, a sulfate anion, or a tetrafluoroborate anion, in addition to the alkyl group represented by R _{a to} R _d Inorganic anions such as hexafluorophosphate anion, and organic anions such as methanesulfonate anion, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, and p-toluenesulfonate anion.
Further, as specifically such ^{_{X, -CO 2 - Na +,}} -CONH 2, -SO 3 - Na +, -SO 2 NH 2, -PO 3 H 2 and the like are preferable.

x and y represent the polymerization molar ratio of the structural unit represented by the general formula (Ia) and the structural unit represented by the general formula (Ib) in the (A) specific hydrophilic polymer. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. The polymerization molar ratio x: y is preferably in the range of 99: 1 to 10:90, more preferably in the range of 99: 1 to 50:50.
Here, the structural units constituting the polymer chain (Ia) and (Ib) may be all the same or may include a plurality of different structural units, In that case, the polymerization molar ratio of the structural unit corresponding to the general formula (Ia) and the structural unit corresponding to the general formula (Ib) is preferably in the above range.

  (A) The molecular weight of the specific hydrophilic polymer is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, and most preferably 1,000 to 200,000.

  Specific examples of the specific hydrophilic polymer (A) [Exemplary compounds (1) to (50)] are shown below together with their mass average molecular weights (MW), but the present invention is limited to these. is not. In addition, the polymer of the specific example shown below means that it is a random copolymer in which each structural unit described is contained by the described molar ratio.

Each of the compounds for synthesizing the specific hydrophilic polymer (A) of the present invention is commercially available or can be easily synthesized.
(A) As a radical polymerization method for synthesizing a specific hydrophilic polymer, any conventionally known method can be used. Specifically, general radical polymerization methods are, for example, new polymer experimental science 3, polymer synthesis and reaction 1 (edited by the Society of Polymer Science, Kyoritsu Shuppan), new experimental chemistry course 19, polymer chemistry (I) (Edited by Chemical Society of Japan, Maruzen), Materials Engineering Course, Synthetic Polymer Chemistry (Tokyo Denki University Press), etc., and these can be applied.

  The specific hydrophilic polymer may be a copolymer with another monomer as described later. Examples of other monomers used include acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic imide, etc. These known monomers are also included. By copolymerizing such monomers, various physical properties such as film forming property, film strength, hydrophilicity, hydrophobicity, solubility, reactivity, and stability can be improved.

Specific examples of acrylic esters include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, Dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chloro Benzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxy phen Chill acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenyl carbonyloxy) ethyl acrylate.

  Specific examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chloro Benzyl methacrylate, hydroxybenzyl methacrylate, hydroxy E phenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, 2- (hydroxyphenyl carbonyloxy) ethyl methacrylate.

  Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, and N-tolylacrylamide. N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N-phenylacrylamide , N-hydroxyethyl-N-methylacrylamide and the like.

  Specific examples of methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide, N-hydroxyethylmethacrylamide, N -Phenylmethacrylamide, N-tolylmethacrylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N- (tolylsulfonyl) methacrylamide, N , N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate, and the like.
Specific examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene. Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene, and the like.

The proportion of these other monomers used in the synthesis of the copolymer needs to be an amount sufficient to improve various physical properties, but the function as a hydrophilic film is sufficient. (A) Specific hydrophilicity In order to obtain the full advantage of adding the polymer, it is preferred that the proportion is not too large. Accordingly, the preferred total proportion of other monomers in the (A) specific hydrophilic polymer is preferably 80% by mass or less, and more preferably 50% by mass or less.

  The (A) specific hydrophilic polymer according to the present invention is preferably from 5 to 95% by mass, more preferably from 15 to 95% from the viewpoint of curability and hydrophilicity with respect to the nonvolatile component of the hydrophilic composition of the present invention. It is contained in the range of 90% by mass, most preferably 20 to 85% by mass. These may be used alone or in combination of two or more. Here, the non-volatile component refers to a component excluding a volatile solvent.

[(B) an alkoxide compound of an element selected from Si, Ti, Zr, and Al]
The alkoxide compound of an element selected from (B) specific alkoxide used in the present invention, Si, Ti, Zr, and Al, has a polymerizable functional group in its structure and is a hydrolyzate that functions as a crosslinking agent. It is a decomposition-polymerizable compound, and (A) a strong film having a crosslinked structure is formed by condensation polymerization with a specific hydrophilic polymer.
(B) The specific alkoxide is preferably a compound represented by the following general formula (II). In forming a crosslinked structure in order to cure the hydrophilic film, the (A) specific hydrophilic polymer, (B) The specific alkoxide represented by the general formula (II) is mixed, coated on the substrate surface, heated and dried.

In general formula (II), R ⁹ represents a hydrogen atom, an alkyl group or an aryl group, R ¹⁰ represents an alkyl group or an aryl group, Y represents Si, Al, Ti or Zr, and k is 0 to 2. Represents an integer. The number of carbon atoms when R ⁹ and R ¹⁰ represent an alkyl group is preferably 1 to 4. The alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, and a mercapto group. This compound is a low molecular compound and preferably has a molecular weight of 1000 or less.

  Specific examples of the specific alkoxide represented by (B) the general formula (II) are shown below, but the present invention is not limited thereto. In the case where Y is Si, that is, those containing silicon in the specific alkoxide include, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, Ethyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane Γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diph Alkenyl dimethoxysilane, mention may be made of diphenyl diethoxy silane. Among these, tetramethoxysilane, tetraethoxysilane, methyltolumethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxy are particularly preferable. Examples include silane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.

In the case where Y is Al, that is, those containing aluminum in the specific alkoxide include, for example, trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, tetraethoxy aluminate and the like.
When Y is Ti, that is, those containing titanium include, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl triethoxy titanate. Examples thereof include methoxy titanate, methyl triethoxy titanate, ethyl triethoxy titanate, diethyl diethoxy titanate, phenyl trimethoxy titanate, and phenyl triethoxy titanate.
In the case where Y is Zr, that is, those containing zirconium include, for example, zirconates corresponding to the compounds exemplified as those containing titanium.
Among these, an alkoxide in which Y is Si is preferable from the viewpoint of film properties.

The (B) specific alkoxide according to the present invention may be used alone or in combination of two or more.
(B) The specific alkoxide is preferably used in the range of 5 to 80% by mass, more preferably 10 to 70% by mass with respect to the nonvolatile component in the hydrophilic composition of the present invention.
The specific alkoxide can be easily obtained as a commercial product, and can also be obtained by a known synthesis method, for example, reaction of each metal chloride with an alcohol.

[(C) Catalyst]
In the hydrophilic composition of the present invention, (A) a specific hydrophilic polymer, and (B) a cross-linking component such as a specific alkoxide is dissolved in a solvent and stirred well, so that these components are hydrolyzed and polycondensed. An organic-inorganic composite sol solution is formed, and a hydrophilic film having high hydrophilicity and high film strength is formed by the sol solution. In the preparation of the organic-inorganic composite sol solution, it is preferable to use an acidic catalyst or a basic catalyst in combination in order to promote hydrolysis and polycondensation reaction. (C) It is preferable to contain a catalyst.

  As the catalyst (C) used in the present invention, a catalyst that promotes a reaction that hydrolyzes and polycondenses the (B) alkoxide compound and (A) causes a bond with the specific hydrophilic polymer is selected. A basic compound is used as it is, or an acid or a compound in which a basic compound is dissolved in a solvent such as water or alcohol (hereinafter collectively referred to as an acidic catalyst and a basic catalyst, respectively) is used. . The concentration at which the acid or basic compound is dissolved in the solvent is not particularly limited, and may be appropriately selected depending on the characteristics of the acid or basic compound used, the desired content of the catalyst, and the like. Here, when the concentration of the acid or basic compound constituting the catalyst is high, the hydrolysis and polycondensation rates tend to increase. However, when a basic catalyst with a high concentration is used, a precipitate may be generated in the sol solution. Therefore, when a basic catalyst is used, the concentration is preferably 1 N or less in terms of concentration in an aqueous solution.

  The type of the acidic catalyst or the basic catalyst is not particularly limited. However, when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element that hardly remains in the coating film after drying is preferable. Specifically, the acid catalyst is represented by hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid or acetic acid, and its RCOOH. Examples thereof include substituted carboxylic acids in which R in the structural formula is substituted with other elements or substituents, sulfonic acids such as benzene sulfonic acid, etc., and basic catalysts include ammonia bases such as aqueous ammonia and amines such as ethylamine and aniline Etc.

A Lewis acid catalyst comprising a metal complex can also be preferably used. Particularly preferred catalysts are metal complex catalysts, metal elements selected from groups 2A, 3B, 4A and 5A of the periodic table and β-diketones, ketoesters, hydroxycarboxylic acids or esters thereof, amino alcohols, enolic active hydrogen compounds It is a metal complex comprised from the oxo or hydroxy oxygen containing compound chosen from these.
Among constituent metal elements, 2A group elements such as Mg, Ca, St and Ba, 3B group elements such as Al and Ga, 4A group elements such as Ti and Zr, and 5A group elements such as V, Nb and Ta are preferable. , Each forming a complex with excellent catalytic effect. Of these, complexes obtained from Zr, Al and Ti are excellent and preferred.

  In the present invention, the oxo- or hydroxy-oxygen-containing compound constituting the ligand of the metal complex is a β-diketone such as acetylacetone (2,4-pentanedione) or 2,4-heptanedione, methyl acetoacetate, acetoacetic acid Ketoesters such as ethyl and butyl acetoacetate, lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate and other hydroxycarboxylic acids and esters thereof, 4-hydroxy-4-methyl-2-pentanone, Ketoalcohols such as 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-heptanone, 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N-methyl-mono Ethanolamine, diethanolamine , Amino alcohols such as triethanolamine, methylol melamine, methylol urea, methylol acrylamide, and enol active compounds such as malonic acid diethyl ester, methyl group, methylene group or carbonyl carbon of acetylacetone (2,4-pentanedione) And compounds having a group.

  A preferred ligand is an acetylacetone derivative. In the present invention, the acetylacetone derivative refers to a compound having a substituent on the methyl group, methylene group or carbonyl carbon of acetylacetone. As the substituents substituted on the methyl group of acetylacetone, all are linear or branched alkyl groups having 1 to 3 carbon atoms, acyl groups, hydroxyalkyl groups, carboxyalkyl groups, alkoxy groups, alkoxyalkyl groups, and acetylacetone As a substituent for the methylene group, a carboxyl group, each of which is a linear or branched carboxyalkyl group and a hydroxyalkyl group having 1 to 3 carbon atoms, and a substituent for the carbonyl carbon of acetylacetone is a carbon number. Is an alkyl group of 1 to 3, and in this case, a hydrogen atom is added to the carbonyl oxygen to form a hydroxyl group.

  Specific examples of preferred acetylacetone derivatives include ethylcarbonylacetone, n-propylcarbonylacetone, i-propylcarbonylacetone, diacetylacetone, 1-acetyl-1-propionyl-acetylacetone, hydroxyethylcarbonylacetone, hydroxypropylcarbonylacetone, acetoacetic acid. , Acetopropionic acid, diacetacetic acid, 3,3-diacetpropionic acid, 4,4-diacetbutyric acid, carboxyethylcarbonylacetone, carboxypropylcarbonylacetone, diacetone alcohol. Of these, acetylacetone and diacetylacetone are particularly preferred. The complex of the above acetylacetone derivative and the above metal element is a mononuclear complex in which one to four molecules of the acetylacetone derivative are coordinated per metal element, and the coordinateable bond of the acetylacetone derivative is a coordinateable bond of the acetylacetone derivative. When the number of hands is larger than the total number of hands, ligands commonly used for ordinary complexes such as water molecules, halogen ions, nitro groups, and ammonio groups may coordinate.

  Examples of preferred metal complexes include tris (acetylacetonato) aluminum complex, di (acetylacetonato) aluminum / aco complex, mono (acetylacetonato) aluminum / chloro complex, di (diacetylacetonato) aluminum complex, ethylacetate Acetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), cyclic aluminum oxide isopropylate, tris (acetylacetonato) barium complex, di (acetylacetonato) titanium complex, tris (acetylacetonato) titanium complex, di-i -Propoxy bis (acetylacetonato) titanium complex salt, zirconium tris (ethyl acetoacetate), zirconium tris (benzoic acid) complex salt, etc. are mentioned. These are excellent in stability in aqueous coating solutions and in gelation promotion effect in sol-gel reaction during heat drying, and among them, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), di ( Acetylacetonato) titanium complex and zirconium tris (ethylacetoacetate) are preferred.

Although the description of the counter salt of the metal complex described above is omitted in this specification, the type of the counter salt is arbitrary as long as it is a water-soluble salt that maintains the neutrality of the charge as the complex compound, such as nitrate, Salt forms such as halogenates, sulfates, phosphates, etc., that ensure stoichiometric neutrality are used.
For the behavior of the metal complex in the silica sol-gel reaction, see J.A. Sol-Gel. Sci. and Tec. There is a detailed description in 16.209 (1999). The following scheme is estimated as the reaction mechanism. That is, in the coating solution, the metal complex has a coordinated structure and is stable, and in the dehydration condensation reaction that starts in the heat drying process after coating, it is considered that crosslinking is promoted by a mechanism similar to an acid catalyst. In any case, the use of this metal complex has led to the improvement of coating solution aging stability and film surface quality, as well as high hydrophilicity and high durability.

  The above metal complex catalyst can be easily obtained as a commercial product, and can also be obtained by a known synthesis method, for example, reaction of each metal chloride with an alcohol.

  The (C) catalyst according to the present invention is used in the hydrophilic composition of the present invention in an amount of preferably 0 to 50% by mass, more preferably 5 to 25% by mass with respect to the nonvolatile component. Moreover, (C) a catalyst may be used independently or may be used together 2 or more types.

In addition to the components (A) and (B), which are the essential components, and the (C) catalyst used in combination as required, various compounds according to the purpose are added to the hydrophilic composition of the present invention. They can be used in combination as long as the effects are not impaired. Hereinafter, components that can be used in combination will be described. [Surfactant]
In the present invention, it is preferable to use a surfactant in order to improve the surface state of the hydrophilic composition. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants.

  The nonionic surfactant used for this invention is not specifically limited, A conventionally well-known thing can be used. For example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol Fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, Polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N N- bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid ester, trialkylamine oxide, polyethylene glycol, copolymers of polyethylene glycol and polypropylene glycol.

The anionic surfactant used in the present invention is not particularly limited, and conventionally known anionic surfactants can be used. For example, fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinate esters, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl phenoxy poly Oxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, fatty acid alkyl esters Sulfates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alcohol Ruphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, styrene / maleic anhydride Examples thereof include partial saponification products of polymers, partial saponification products of olefin / maleic anhydride copolymers, and naphthalene sulfonate formalin condensates.

The cationic surfactant used in the present invention is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
The amphoteric surfactant used in the present invention is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric acid esters, and imidazolines.
Of the above surfactants, the term “polyoxyethylene” can be read as “polyoxyalkylene” such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. These surfactants can also be used.

More preferable surfactants include fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of such fluorosurfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates; amphoteric types such as perfluoroalkyl betaines; Cation type such as trimethylammonium salt; perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl Nonionic types such as an oligomer containing a group, a hydrophilic group and a lipophilic group, and a urethane containing a perfluoroalkyl group and a lipophilic group. Moreover, the fluorine-type surfactant described in each gazette of Unexamined-Japanese-Patent No. 62-170950, 62-226143, and 60-168144 is also mentioned suitably.
The surfactant is preferably used in the hydrophilic composition of the present invention in the range of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass with respect to the nonvolatile component. Moreover, surfactant can be used individually or in combination of 2 or more types.

[Antimicrobial agent]
In order to impart antibacterial, antifungal and antialgal properties to the hydrophilic member of the present invention, an antibacterial agent can be contained in the hydrophilic coating solution composition. In the formation of the hydrophilic layer, it is preferable to contain a hydrophilic and water-soluble antibacterial agent. By including a hydrophilic and water-soluble antibacterial agent, a surface hydrophilic member having excellent antibacterial, antifungal and antialgal properties can be obtained without impairing the surface hydrophilicity.
As the antibacterial agent, it is preferable to add a compound that does not lower the hydrophilicity of the hydrophilic member, and examples of such an antibacterial agent include inorganic antibacterial agents and water-soluble organic antibacterial agents. As the antibacterial agent, those exhibiting a bactericidal effect against fungi existing around us, such as bacteria represented by Staphylococcus aureus and Escherichia coli, fungi such as fungi and yeast, and the like are used.

Examples of organic antibacterial agents include phenol ether derivatives, imidazole derivatives, sulfone derivatives, N-haloalkylthio compounds, anilide derivatives, pyrrole derivatives, quaternary ammonium salts, pyridines, triazines, benzoisothiazolines, and isothiazolines. It is done.
For example, 1,2-benzisothiazolin-3-one, N-fluorodichloromethylthio-phthalimide, 2,3,5,6-tetrachloroisophthalonitrile, N-trichloromethylthio-4-cyclohexene-1,2-dicarboxyl Imido, copper 8-quinolinate, bis (tributyltin) oxide, 2- (4-thiazolyl) benzimidazole (hereinafter referred to as TBZ), methyl 2-benzimidazole carbamate (hereinafter referred to as BCM), 10,10 '-Oxybisphenoxyarsine (hereinafter referred to as OBPA) 2,3,5,6-tetrachloro-4- (methylsulfone) pyridine, bis (2-pyridylthio-1-oxide) zinc (hereinafter referred to as ZPT) >, N, N-dimethyl-N ′-(fluorodichloromethylthio) -N′-phenylsulfamide <dichloro Luanide>, poly- (hexamethylene biguanide) hydrochloride, dithio-2-2′-bis (benzmethylamide), 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 2-bromo-2 -Nitro-1,3-propanediol, hexahydro-1,3-tris- (2-hydroxyethyl) -S-triazine, p-chloro-m-xylenol, 1,2-benzisothiazolin-3-one, etc. However, it is not limited to these.
These organic antibacterial agents can be appropriately selected and used in consideration of hydrophilicity, water resistance, sublimation property, safety and the like. Among organic antibacterial agents, 2-bromo-2-nitro-1,3-propanediol, TBZ, BCM, OBPA, and ZPT are preferable from the viewpoint of hydrophilicity, antibacterial effect, and cost.

  Examples of inorganic antibacterial agents include mercury, silver, copper, zinc, iron, lead, bismuth and the like in descending order of bactericidal action. For example, the thing which carry | supported metals and metal ions, such as silver, copper, zinc, nickel, on the silicate type | system | group support | carrier, phosphate type | system | group support, an oxide, glass, potassium titanate, an amino acid, etc. is mentioned. For example, zeolite antibacterial agent, calcium silicate antibacterial agent, zirconium phosphate antibacterial agent, calcium phosphate antibacterial agent, zinc oxide antibacterial agent, soluble glass antibacterial agent, silica gel antibacterial agent, activated carbon antibacterial agent, titanium oxide Antibacterial agent, titania antibacterial agent, organometallic antibacterial agent, ion exchanger ceramic antibacterial agent, layered phosphate-quaternary ammonium salt antibacterial agent, antibacterial stainless steel, etc. Absent.

Natural antibacterial agents include chitosan, a basic polysaccharide obtained by hydrolyzing chitin contained in crabs and shrimp shells.
In the present invention, Nikko's “trade name Holon Killer Bees Sera” made of amino metal in which a metal is compounded on both sides of an amino acid is preferable.
These are not transpirationable, easily interact with the polymer and crosslinker component of the hydrophilic layer, can be stably molecularly dispersed or solid dispersed, the antibacterial agent is easily exposed effectively on the hydrophilic layer surface, and Even if it is splashed with water, it does not elute, and the effect can be maintained for a long time without affecting the human body. Moreover, it can disperse | distribute stably with respect to a hydrophilic layer or a coating liquid, and deterioration of a hydrophilic layer or a coating liquid does not occur.
Among the antibacterial agents, silver-based inorganic antibacterial agents and water-soluble organic antibacterial agents are most preferable because of their great antibacterial effects. In particular, silver zeolite in which silver is supported on zeolite, which is a silicate carrier, antibacterial agent in which silver is supported on silica gel, 2-bromo-2-nitro-1,3-propanediol, TPN, TBZ, BCM, OBPA ZPT is preferred. Particularly preferred commercially available silver zeolite antibacterial agents include “Zeomic” by Shinagawa Fuel, “Sylwell” by Fuji Silysia Chemical, and “Bactenone” by JEOL. In addition, “NOVALON” manufactured by Toa Gosei, in which silver is supported on an inorganic ion exchanger ceramic, “ATOMY BALL” manufactured by Catalytic Chemical Industry, and “Suneyeback P” used as a triazine antibacterial agent are also preferable.

  The content of the antibacterial agent is generally 0.001 to 10% by mass, preferably 0.005 to 5% by mass, based on the nonvolatile components in the hydrophilic composition, and 0.01 -3 mass% is more preferable, 0.02-1.5 mass% is especially preferable, and 0.05-1 mass% is the most preferable. If the content is 0.001% by mass or more, an effective antibacterial effect can be obtained. Further, if the content is 10% by mass or less, the hydrophilicity is not lowered, the aging is not deteriorated, and the antifouling property and antifogging property are not adversely affected.

[Inorganic fine particles]
The hydrophilic composition of the present invention may contain inorganic fine particles in order to improve the cured film strength and hydrophilicity of the hydrophilic film to be formed. As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, or a mixture thereof is preferably exemplified.
The inorganic fine particles preferably have an average particle diameter of 5 nm to 10 μm, more preferably 0.5 to 3 μm. Within the above range, it is possible to form a film that is stably dispersed in the hydrophilic layer, sufficiently retains the film strength of the hydrophilic layer, and is excellent in hydrophilicity. The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.

  The inorganic fine particles according to the present invention are used in the hydrophilic composition of the present invention in an amount of preferably 20% by mass or less, more preferably 10% by mass or less, based on the nonvolatile components. The inorganic fine particles can be used alone or in combination of two or more.

[Ultraviolet absorber]
In the present invention, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance and durability of the hydrophilic member.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194843, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492 and 56-21141 Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP The triazine compounds described in JP-A-8-501291, Research Disclosure No. Examples thereof include compounds described in No. 24239, compounds that emit ultraviolet light by absorbing ultraviolet rays typified by stilbene and benzoxazole compounds, so-called fluorescent brighteners, and the like.
The addition amount is appropriately selected according to the purpose, but generally it is preferably 0.5 to 15% by mass in terms of solid content.

〔Antioxidant〕
In order to improve the stability of the hydrophilic member of the present invention, an antioxidant can be added to the coating liquid for forming the hydrophilic layer. Examples of the antioxidant include European published patents, 223739, 309401, 309402, 310551, 310552, 359416, and 3435443. JP, 54-85535, 62-262417, 63-113536, 63-163351, JP-A-2-262654, JP-A-2-71262, Examples thereof include those described in Kaihei 3-121449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1 to 8% by mass in terms of solid content.

〔solvent〕
In forming the hydrophilic layer of the hydrophilic member of the present invention, it is also effective to add an appropriate organic solvent to the hydrophilic layer forming coating solution in order to ensure the formation of a uniform coating film on the substrate.
Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride. Solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether And ether solvents.
In this case, it is effective to add VOC (volatile organic solvent) in a range that does not cause a problem, and the amount thereof is preferably 0 to 50% by mass, more preferably based on the entire coating liquid when forming the hydrophilic member. Is in the range of 0-30% by weight.

[Polymer compound]
In order to adjust the film physical properties of the hydrophilic layer, various polymer compounds can be added to the coating liquid for forming the hydrophilic layer of the hydrophilic member of the present invention as long as the hydrophilicity is not inhibited. High molecular compounds include acrylic polymer, polyvinyl alcohol resin, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl formal resin, shellac, vinyl resin, acrylic resin. Rubber resins, waxes and other natural resins can be used. Two or more of these may be used in combination. Of these, vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, a copolymer containing “carboxyl group-containing monomer”, “methacrylic acid alkyl ester”, or “acrylic acid alkyl ester” as a structural unit is also preferably used as the copolymer composition of the polymer binder.

[Other additives]
In addition to this, if necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, and tackifiers within a range that does not impair hydrophilicity in order to improve adhesion to the substrate. Etc. can be contained.
As the tackifier, specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, 5-6p (for example, (meth) acrylic acid and an alkyl group having 1 to 20 carbon atoms). An ester with an alcohol having, an ester of (meth) acrylic acid with an alicyclic alcohol having 3 to 14 carbon atoms, a copolymer comprising an ester of (meth) acrylic acid with an aromatic alcohol having 6 to 14 carbon atoms) And a low molecular weight tackifying resin having a polymerizable unsaturated bond.

The coating liquid for forming a hydrophilic layer of the hydrophilic member of the present invention can contain zirconia chloride, nitrate, alkoxides and organic complexes from the viewpoints of wear resistance, acid resistance and alkali resistance. Examples of the zirconia chloride include zirconium chloride, zirconium oxychloride (octahydrate), chlorine-containing zirconium alkoxide Zr (OC _m H _{2m + 1} ) _x Cl _y (m, x, y: integer, x + y = 4). Zirconium nitrate includes zirconium oxynitrate (dihydrate), and zirconium alkoxide includes zirconium ethoxide, zirconium propoxide, zirconium isopropoxide, zirconium butoxide, zirconium t-butoxide and the like. Examples of the organic complex include acetylacetone derivatives. Specifically, tetrakis (acetylacetonato) zirconium, bis (acetylacetonato) zirconium dibutoxide, bis (acetylacetonato) zirconium dichloride, Trakis (3,5-heptanedionate) zirconium, tetrakis (2,2,6,6-tetramethyl-3,5-heptanedionate) zirconium, bis (2,2,6,6-tetramethyl-3, 5-heptanedionate) zirconium diisopropoxide and the like.
The zirconium compound is preferably used in the hydrophilic composition of the present invention as a nonvolatile component in the range of 0 to 50% by mass, more preferably 5 to 25% by mass.

[Hydrophilic member]
The hydrophilic member of the present invention comprises (A) a hydrophilic polymer represented by the following general formula (I), (B) a hydrophilic composition containing an alkoxide compound of an element selected from Si, Ti, Zr, and Al. It is characterized by having a hydrophilic film formed by coating, heating and drying. Preferably, the catalyst (C) can also be contained in the hydrophilic film formation. Furthermore, it is more preferable to have an undercoat layer between the substrate and the hydrophilic film.

In formula (I), representative of the R ¹ to R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.

[Undercoat layer]
The undercoat layer of the hydrophilic member of the present invention preferably contains a nonvolatile catalyst. Non-volatile catalysts are those other than those with a boiling point of less than 125 ° C. In other words, those with a boiling point of 125 ° C or higher, or those with no boiling point in the first place (those that do not cause phase change such as thermal decomposition). Including).
The nonvolatile catalyst used in the present invention is not particularly limited, and examples thereof include metal chelate compounds and silane coupling agents.

The metal chelate compound (hereinafter also referred to as a metal complex) is not particularly limited, but a metal element selected from groups 2A, 3B, 4A and 5A of the periodic table and a β-diketone, ketoester, hydroxycarboxylic acid or the like There are metal complexes composed of oxo or hydroxy oxygen-containing compounds selected from esters, amino alcohols, and enolic active hydrogen compounds.
Among constituent metal elements, 2A group elements such as Mg, Ca, St and Ba, 3B group elements such as Al and Ga, 4A group elements such as Ti and Zr, and 5A group elements such as V, Nb and Ta are preferable. , Each forming a complex with excellent catalytic effect. Of these, complexes obtained from Zr, Al and Ti are excellent and preferred.
Specifically, the same thing as what was shown by the metal complex shown by (C) catalyst is mentioned.

  In the present invention, the silane coupling agent used as the non-volatile catalyst is not particularly limited, and examples thereof include those having a functional group exhibiting acidity or alkalinity, and more specifically, peroxo acids, carboxylic acids, carbohydrazones. Acid, carboxymido acid, sulfonic acid, sulfinic acid, sulfenic acid, selenonic acid, selenic acid, selenic acid, telluronic acid, and basic groups such as amino groups that show acidity such as the above alkali metal salts Examples thereof include silane coupling agents having the functional group shown.

  The undercoat layer is preferably obtained by hydrolyzing and polycondensing a composition having at least an alkoxide compound of an element selected from Si, Ti, Zr, and Al and a nonvolatile catalyst. Examples of the alkoxide compound of an element selected from Si, Ti, Zr, and Al include the same ones as shown in (B) specific alkoxide.

  The subbing layer thus obtained contains a non-volatile catalyst without losing its activity, and is also present on the surface of the subbing layer in particular because it is present on the surface of the subbing layer. When the layer is provided, the adhesion at the interface between the undercoat layer and the hydrophilic layer is extremely high.

  In addition, the undercoat layer of the hydrophilic member of the present invention is further improved in adhesion at the interface between the undercoat layer and the hydrophilic layer by providing fine irregularities by mixing plasma etching or metal particles. Can do.

[Preparation of hydrophilic composition]
The hydrophilic composition can be prepared by stirring (A) a specific hydrophilic polymer and (B) a specific alkoxide, and more preferably (C) a catalyst in a solvent such as ethanol. The reaction temperature is from room temperature to 80 ° C., and the reaction time, that is, the time for which stirring is continued is preferably in the range of 1 to 72 hours. By this stirring, hydrolysis and polycondensation of both components are advanced, and organic inorganic A composite sol solution can be obtained.

  The solvent used for preparing the hydrophilic composition containing the (A) specific hydrophilic polymer and the (B) specific alkoxide is not particularly limited as long as these can be uniformly dissolved and dispersed. For example, an aqueous solvent such as methanol, ethanol and water is preferable.

As described above, the preparation of the organic-inorganic composite sol liquid (hydrophilic composition) for forming a hydrophilic film with the hydrophilic composition of the present invention utilizes the sol-gel method. Regarding the sol-gel method, Sakuo Sakuo “Science of Sol-Gel Method”, Agne Jofusha (published) (1988), Satoshi Hirashima “Functional Thin Film Formation Technology by the Latest Sol-Gel Method” General Technology Center (Published) (1992) and the like, and the methods described therein can be applied to the preparation of the hydrophilic composition in the present invention.
The hydrophilic member of the present invention can be obtained by coating a solution containing the hydrophilic composition of the present invention on an appropriate substrate and drying. That is, the hydrophilic member of the present invention has a hydrophilic film formed by coating the hydrophilic composition of the present invention on a substrate, heating and drying.
In the formation of the hydrophilic film, as the heating and drying conditions after coating the solution containing the hydrophilic composition, from the viewpoint of efficiently forming a high-density crosslinked structure, in the temperature range of 50 to 200 ° C., It is preferable to carry out for about 2 minutes to 1 hour, and it is more preferable to dry in the temperature range of 80 to 160 ° C. for 5 to 30 minutes. Moreover, as a heating means, it is preferable to use a well-known means, for example, the dryer etc. which have a temperature control function.

  Moreover, the hydrophilic member of this invention can be mixed just before coating a catalyst on a board | substrate, when coating a hydrophilic layer and undercoat on a board | substrate. Specifically, it is preferable to apply within 1 hour immediately after catalyst mixing. When the catalyst is mixed and left to stand for a long time, the hydrophilic composition increases in viscosity, and defects such as coating unevenness may occur. Other components are also preferably mixed immediately before coating, but may be stored for a long time after mixing.

〔substrate〕
The substrate used in the present invention is not particularly limited, but glass, plastic, metal, ceramics, wood, stone, cement, concrete, fiber, fabric, paper, leather, combinations thereof, and laminates thereof are all suitable. Available to: Particularly preferred substrates are glass substrates or plastic substrates.
Glass plates include silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, zirconium oxide, sodium oxide, antimony oxide, indium oxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide, ITO (Indium Tin
A glass plate provided with an inorganic compound layer formed of a metal oxide such as Oxide; a metal halide such as magnesium fluoride, calcium fluoride, lanthanum fluoride, cerium fluoride, lithium fluoride, thorium fluoride; Can be mentioned. Depending on the purpose, float plate glass, mold plate glass, ground glass, wire-filled glass, wire-filled glass, tempered glass, laminated glass, double-glazed glass, vacuum glass, security glass, highly heat-insulated Low-E double-glazed glass should be used. Can do. In addition, the hydrophilic layer can be applied as it is with the base glass, but if necessary, surface hydrophilic treatment is performed on one or both sides by an oxidation method, a roughening method or the like for the purpose of improving the adhesion of the hydrophilic layer. be able to. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. As a roughening method, it can also be mechanically roughened by sandblasting, brush polishing or the like.

  The inorganic compound layer can have a single layer structure or a multilayer structure. Depending on the thickness of the inorganic compound layer, the light transmittance can be maintained, and the inorganic compound layer can also function as an antireflection layer. Examples of the inorganic compound layer forming method include dip coating method, spin coating method, flow coating method, spray coating method, roll coating method, gravure coating method, etc., vacuum deposition method, reactive deposition method, ion beam A known method such as a physical vapor deposition method (PVD) such as an assist method, a sputtering method, or an ion plating method, or a vapor phase method such as a chemical vapor deposition method (CVD) can be applied.

  The plastic substrate used in the present invention is not particularly limited, but the substrate used as the optical member is selected in consideration of optical characteristics such as transparency, refractive index, and dispersibility, and various types are used depending on the purpose of use. It is selected in consideration of physical properties such as physical properties such as strength such as impact resistance and flexibility, heat resistance, weather resistance and durability. Plastic substrates include polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, polystyrene, polycarbonate, polymethylpentene, polysulfone. And films or sheets of polyether ketone, acrylic, nylon, fluororesin, polyimide, polyether imide, polyether sulfone and the like. Of these, polyester films such as polyethylene terephthalate and polyethylene naphthalate are particularly preferred. These may be used alone or in combination of two or more in the form of a mixture, copolymer, laminate or the like, depending on the purpose of use. The thickness of the plastic substrate varies depending on the mating partner. For example, in a portion with many curved surfaces, a thin one is preferred, and one having about 6 to 50 μm is used. Moreover, 50-400 micrometers is used for a plane or the place where intensity | strength is requested | required.

For the purpose of improving the adhesion between the substrate and the hydrophilic layer, one or both surfaces of the substrate can be subjected to surface hydrophilization treatment by an oxidation method, a roughening method, or the like as desired. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. As a roughening method, it can also be mechanically roughened by sandblasting, brush polishing or the like.
Furthermore, one or more undercoat layers can be provided. As the material for the undercoat layer, a hydrophilic resin or water-dispersible latex can be used.

Examples of hydrophilic resins include polyvinyl alcohol (PVA), cellulosic resins (methyl cellulose (MC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), etc.), chitins, chitosans, starch, and ether bonds. Examples include resins [polyethylene oxide (PEO), polyethylene glycol (PEG), polyvinyl ether (PVE), etc.], resins having a carbamoyl group [polyacrylamide (PAAM), polyvinyl pyrrolidone (PVP), etc.], and the like. Moreover, the polyacrylic acid salt which has a carboxyl group, maleic acid resin, alginate, gelatins, etc. can also be mentioned.
Among these, at least one selected from polyvinyl alcohol resins, cellulose resins, resins having an ether bond, resins having a carbamoyl group, resins having a carboxyl group, and gelatins is preferable, and in particular, polyvinyl alcohol (PVA) Of these, gelatin resins are preferred.

Examples of the water-dispersible latex include acrylic latex, polyester latex, NBR resin, polyurethane latex, polyvinyl acetate latex, SBR resin, polyamide latex and the like. Among these, acrylic latex is preferable.
The above hydrophilic resin and water-dispersible latex may be used alone or in combination of two or more, or a hydrophilic resin and a water-dispersible latex may be used in combination.
Moreover, you may use the crosslinking agent which bridge | crosslinks the said hydrophilic resin and water-dispersible latex.
As a cross-linking agent applicable to the present invention, a cross-linking agent that forms a cross-link by known heat can be used. General thermal crosslinking agents include those described in “Crosslinking agent handbook” by Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha (1981). The number of functional groups of the crosslinking agent used in the present invention is not particularly limited as long as it is 2 or more and can be effectively crosslinked with a hydrophilic resin or water-dispersible latex. Specific examples of the thermal crosslinking agent include polycarboxylic acids such as polyacrylic acid, amine compounds such as polyethyleneimine, ethylene or propylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene ethylene glycol diglycidyl ether, polyethylene or Polyepoxy compounds such as polypropylene glycol glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyaldehyde compounds such as glyoxal and terephthalaldehyde, tri Range isocyanate, hexamethylene diisocyanate, diphenylmethane isocyanate, xylylene Polyisocyanate compounds such as isocyanate, polymethylene polyphenyl isocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene glycol / tolylene diisocyanate addition reaction product, block polyisocyanate Examples thereof include compounds, silane coupling agents such as tetraalkoxysilane, metal cross-linking agents such as acetylacetonate of aluminum, copper and iron (III), and polymethylol compounds such as trimethylolmelamine and pentaerythritol. Among these thermal cross-linking agents, a water-soluble cross-linking agent is preferable from the viewpoint of easy preparation of the coating solution and prevention of a decrease in hydrophilicity of the produced hydrophilic layer.
Wherein the hydrophilic resin and / or water-dispersible latex total amount in the undercoat layer is preferably from 0.01 to 20 g / m ^2, 0.1 to 10 g / m ² is more preferable.

  As a plastic substrate, what formed the inorganic compound layer described in description of the glass plate on the plastic plate can also be used. In this case, the inorganic compound layer can also act as an antireflection layer. Even when the inorganic compound layer is formed on the plastic plate, it can be formed by the same method as in the inorganic substrate described above.

  When an inorganic compound layer is formed on a transparent plastic substrate, a hard coat layer may be formed between both layers. By providing the hard coat layer, the hardness of the substrate surface is improved and the substrate surface is smoothed, so that the adhesion between the transparent plastic substrate and the inorganic compound layer is improved, the scratch resistance is improved, and the substrate is bent. It is possible to suppress the occurrence of cracks in the inorganic compound layer due to the above. By using such a substrate, the mechanical strength of the hydrophilic member can be improved. The material of the hard coat layer is not particularly limited as long as it has transparency, appropriate strength, and mechanical strength. For example, a curable resin or a thermosetting resin by irradiation with ionizing radiation or ultraviolet rays can be used, and an ultraviolet irradiation curable acrylic resin, an organosilicon resin, or a thermosetting polysiloxane resin is particularly preferable. The refractive index of these resins is more preferably equal to or close to the refractive index of the transparent plastic substrate.

  The coating method of such a hard coat layer is not particularly limited, and any method can be adopted as long as it is uniformly applied. In addition, the hard coat layer having a thickness of 3 μm or more provides sufficient strength, but is preferably in the range of 5 to 7 μm from the viewpoint of transparency, coating accuracy, and handling. Furthermore, by mixing and dispersing inorganic or organic particles having an average particle diameter of 0.01 to 3 μm in the hard coat layer, a light diffusing treatment generally called anti-glare can be performed. These particles are not particularly limited as long as they are transparent, but a low refractive index material is preferable, and silicon oxide and magnesium fluoride are particularly preferable in terms of stability, heat resistance and the like. The light diffusing treatment can also be achieved by providing irregularities on the surface of the hard coat layer.

[Layer structure when using hydrophilic members]
When the hydrophilic member of the present invention is used in anticipation of expression of antifouling properties and / or antifogging effects, it may be used by appropriately adding another layer depending on the purpose, form and place of use. it can. The layer structure added as needed is described below. 1) Adhesive layer When the hydrophilic member of the present invention is used by being attached to another substrate, a pressure-sensitive adhesive that is a pressure-sensitive adhesive is preferably used as an adhesive layer on the back surface of the substrate. As an adhesive, what is generally used for an adhesive sheet, such as a rubber adhesive, an acrylic adhesive, a silicone adhesive, a vinyl ether adhesive, and a styrene adhesive, can be used.
When an optically transparent material is required, an adhesive for optical use is selected. When a pattern such as coloring, semi-transparency, or matte is required, in addition to patterning on the substrate, a dye, organic or inorganic fine particles can be added to the adhesive to produce an effect.
When a tackifier is required, a resin, for example, a rosin-based resin, a terpene-based resin, a petroleum-based resin, a styrene-based resin, or an adhesion-imparting resin such as a hydrogenated product thereof can be used alone or in combination.
The adhesive strength of the pressure-sensitive adhesive used in the present invention is generally called strong adhesion, and is 200 g / 25 mm or more, preferably 300 g / 25 mm or more, more preferably 400 g / 25 mm or more. In addition, the adhesive force here is based on JIS Z 0237 and is a value measured by a 180 degree peel test.

2) Release layer When the hydrophilic member of the present invention has the adhesive layer, a release layer can be further added. The release layer preferably contains a release agent in order to give release properties. As the release agent, generally, a silicone release agent composed of polyorganosiloxane, a fluorine compound, a long-chain alkyl modified product of polyvinyl alcohol, a long-chain alkyl modified product of polyethyleneimine, and the like can be used. In addition, various release agents such as a hot melt type release agent, a monomer type release agent that cures a release monomer by radical polymerization, cationic polymerization, polycondensation reaction, etc., and other acrylic-silicone copolymer Resins, acrylic-fluorine-based copolymer resins, urethane-silicone-fluorine-based copolymer resins, and the like, and resin blends of silicone-based resins and acrylic resins, and fluorine-based resins and acrylic-based resins. A resin blend is used. Moreover, it is good also as a hard-coat release layer obtained by hardening | curing the curable composition containing either an atom of a fluorine atom and / or a silicon atom, and an active energy ray polymeric group containing compound.

3) Other layers A protective layer may be provided on the hydrophilic layer. The protective layer has a function of preventing damage to the hydrophilic surface during handling, transportation, storage, and the like, and deterioration of hydrophilicity due to adhesion of dirt substances. As the protective layer, the hydrophilic polymer layer used in the release layer can be used. The protective layer is peeled off after the hydrophilic member is attached to an appropriate substrate.

[Form of structure]
The structure having a hydrophilic layer of the present invention may be supplied in the form of a sheet, a roll, or a ribbon, or may be supplied as a pre-cut material for attaching to a suitable substrate.

When the hydrophilic member coated with the hydrophilic film of the present invention is applied (used or attached) to a window glass or the like, transparency is important from the viewpoint of ensuring visibility. The hydrophilic film of the present invention is excellent in transparency, and even when the film thickness is large, the transparency is not impaired and compatibility with durability is possible. The thickness of the hydrophilic coating of the present invention is preferably 0.01 μm to 100 μm, more preferably 0.05 μm to 50 μm, and most preferably 0.1 μm to 20 μm. When the film thickness is 0.01 μm or more, it is preferable to obtain sufficient hydrophilicity and durability, and when the film thickness is 100 μm or less, there is no problem in film forming properties such as cracks, which is preferable.
Transparency is evaluated by measuring the light transmittance in the visible light region (400 nm to 800 nm) with a spectrophotometer. The light transmittance is preferably 100% to 70%, more preferably 95% to 75%, and most preferably in the range of 95% to 80%. By being in this range, the hydrophilic member provided with a hydrophilic film can be applied to various applications without obstructing the field of view.

The hydrophilic member of the present invention can be obtained by applying the coating solution composition for forming a hydrophilic layer on a suitable substrate, heating and drying to form a surface hydrophilic layer. The heating temperature and heating time for forming the hydrophilic layer are not particularly limited as long as the solvent and the time in which the solvent in the sol solution can be removed and a strong film can be formed. It is preferably 150 ° C. or lower, and the heating time is preferably within 1 hour.
The hydrophilic member of the present invention can be prepared by a known coating method, and is not particularly limited. For example, spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, film applicator method Methods such as screen printing, bar coater, brush coating, and sponge coating can be applied.

The hydrophilic member of the present invention can be applied to, for example, a transparent glass substrate or a transparent plastic substrate, a lens, a prism, a mirror or the like when an antifogging effect is expected.
As the glass, any glass such as soda glass, lead glass and borosilicate glass may be used. Depending on the purpose, float plate glass, mold plate glass, ground glass, wire-filled glass, wire-filled glass, tempered glass, laminated glass, double-glazed glass, vacuum glass, security glass, highly heat-insulated Low-E double-glazed glass should be used. Can do.
Applications that can be applied with anti-fogging effects include vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, camera lenses, internal vision Lenses such as mirror lenses, illumination lenses, semiconductor lenses, and copier lenses; prisms; window glass for buildings and surveillance towers; other building glass; automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, Ropeway gondola, amusement park gondola, various vehicle windows; automobiles, rail cars, aircraft, ships, submersibles, snow vehicles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola, various vehicle windshields Glass; protective goggles, sports goggles, protective mask shield, sports mask shield, helmet shield, frozen food display case Las; cover glass measuring instruments, and films to be attached to the article surface. The most preferred application is glass for automobiles and building materials.

When the surface hydrophilic member of the present invention is expected to have an antifouling effect, the substrate is made of, for example, metal, ceramics, wood, stone, cement, concrete, fiber, fabric, paper in addition to glass and plastic. , Combinations thereof, and laminates thereof can be suitably used.
Applications with antifouling components include building materials, building exteriors such as exterior walls and roofs, building interiors, window frames, window glass, structural members, automobiles, railway vehicles, aircraft, ships, bicycles, motorcycles Exterior and painting of such vehicles, machinery and equipment exteriors, dust covers and coatings, traffic signs, various display devices, advertising towers, road noise barriers, railway noise barriers, bridges, guardrail exteriors and coatings, tunnel interiors And paint, insulators, solar battery covers, solar water heater heat collector covers, greenhouses, vehicle lighting cover, housing equipment, toilets, bathtubs, sinks, lighting fixtures, lighting covers, kitchenware, dishes, dishwashers A dish dryer, a sink, a cooking range, a kitchen hood, a ventilation fan, and a film to be attached to the surface of the article.
Signs, traffic signs, sound barriers, plastic houses, insulators, vehicle covers, tent materials, reflectors, shutters, screen doors, solar battery covers, solar water heater covers, street lamps, pavements, outdoor lighting, artificial Waterfalls / artificial fountain stones / tiles, bridges, greenhouses, exterior walls, sealers between walls and glass, guardrails, verandas, vending machines, air conditioner outdoor units, outdoor benches, various display devices, shutters, toll booths, price boxes Roof coverings, vehicle lamp protection covers, dust covers and coatings, painting of machinery and equipment, exterior and coating of advertising towers, structural members, housing equipment, toilets, bathtubs, washstands, lighting fixtures, kitchen utensils, tableware, Tableware dryer, sink, cooking range, kitchen hood, ventilation fan, window rail, window frame, tunnel inner wall, tunnel lighting, window sash, heat exchanger fins, pavement, bathroom toilet mirror, Neil House ceiling, including vanity, an automobile body, and the liquid to be attached for allowing the film to them the goods, the emblem and the like.
It can also be applied to snow country roofing materials, antennas, power transmission lines, etc., and in that case, characteristics excellent in snow accretion prevention can be obtained.

In addition, when the surface hydrophilic member of the present invention is expected to have quick drying properties such as water, the base material may be, for example, metal, ceramics, wood, stone, cement, concrete, fiber, fabric in addition to glass and plastic. , Paper, combinations thereof, and laminates thereof can be suitably used. Applications that can be applied to members that have a quick-drying effect such as water include building materials, building exteriors such as outer walls and roofs, building interiors, window frames, window glass, structural members, automobiles, railway vehicles, aircraft, ships, and bicycles. , Exteriors and paintings of vehicles such as motorcycles, exteriors of machinery and articles, dust covers and paintings, traffic signs, various display devices, advertising towers, noise barriers for roads, noise barriers for railways, bridges, guard rails and paintings , Tunnel interior and painting, insulator, solar battery cover, solar water heater heat collection cover, plastic house, vehicle lighting cover, housing equipment, toilet, bathtub, wash basin, lighting fixture, lighting cover, kitchenware, tableware, It includes a dishwasher, a dish dryer, a sink, a cooking range, a kitchen hood, a ventilation fan, and a film for application to the surface of the article.
Signs, traffic signs, sound barriers, plastic houses, insulators, vehicle covers, tent materials, reflectors, shutters, screen doors, solar battery covers, solar water heater covers, street lamps, pavements, outdoor lighting, artificial Waterfalls / artificial fountain stones / tiles, bridges, greenhouses, exterior walls, sealers between walls and glass, guardrails, verandas, vending machines, air conditioner outdoor units, outdoor benches, various display devices, shutters, toll booths, price boxes Roof coverings, vehicle lamp protection covers, dust covers and coatings, painting of machinery and equipment, exterior and coating of advertising towers, structural members, housing equipment, toilets, bathtubs, washstands, lighting fixtures, kitchen utensils, tableware, Tableware dryer, sink, cooking range, kitchen hood, ventilation fan, window rail, window frame, tunnel inner wall, tunnel lighting, window sash, heat exchanger fins, pavement, bathroom toilet mirror, Neil House ceiling, including vanity, an automobile body, and the liquid to be attached for allowing the film to them the goods, the emblem and the like. Further, in the case of having a drying process in the process of manufacturing products used for these applications, the drying time can be shortened and the productivity can be expected to be improved.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
(Synthesis of specific hydrophilic polymer (1))
A 300 ml three-necked flask was charged with 28.3 g of acrylamide, 27.5 g of acrylamide-3- (triethoxysilyl) propyl, and 85 g of 1-methoxy-2-propanol, and 2,2′-azobis (2- 0.7 g of dimethyl methylpropionate) was added. The mixture was kept at the same temperature with stirring for 6 hours, and then cooled to room temperature. The solution was put into 2 liters of n-hexane, and the precipitated solid was collected by filtration. After the obtained solid was washed with n-hexane, the specific hydrophilic polymer (1) as the exemplified compound (1) was obtained. The mass after drying was 53.2 g. It was a polymer having a mass average molecular weight of 22,000 according to GPC (polyethylene oxide standard).
Thereafter, the specific hydrophilic polymer used in the examples was synthesized by the same method as described above and used for evaluation.

(Example 1)
[Hydrophilic sol-gel solution]
In 100 g of purified water, 10 g of (A) specific hydrophilic polymer (1) was mixed and stirred at room temperature for 2 hours to prepare.
[Hydrophilic composition]
A hydrophilic composition was prepared by mixing 120 g of the hydrophilic sol-gel solution with 2.5 g of a 5% by mass aqueous solution of the following anionic surfactant.
[Coating method]
Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, and the surface of the plate glass is hydrophilized by UV / O ₃ treatment for 10 minutes, and then the hydrophilic composition is spin-coated and applied at 100 ° C. It was oven dried in 10 minutes to form a hydrophilic layer having a dry coating amount of 0.1 g / m ² .

(Example 2)
A hydrophilic member was prepared in the same manner as in Example 1 except that the coating method was changed to the following method.
Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, and the surface of the plate glass is hydrophilized by UV / O ₃ treatment for 10 minutes, and then the hydrophilic composition of Example 1 is coated with a bar. It was oven dried at 150 ° C. for 30 minutes to form a hydrophilic layer having a dry coating amount of 3.0 g / m ² .

(Examples 3 to 5)
(A) A hydrophilic member was prepared in the same manner as in Example 2 except that the specific hydrophilic polymer (1) was changed to the following.
Example 3: Specific hydrophilic polymer (2)
Example 4: Specific hydrophilic polymer (11)
Example 5: Specific hydrophilic polymer (24)

(Example 6)
[Hydrophilic sol-gel solution]
10 g of the specific hydrophilic polymer (1) was mixed in 2 g of ethyl alcohol, 0.05 g of 1N hydrochloric acid aqueous solution as a catalyst (C) and 100 g of purified water, and the mixture was stirred at room temperature for 2 hours to prepare.
[Hydrophilic composition]
A hydrophilic composition was prepared by mixing 120 g of the hydrophilic sol-gel solution with 2.5 g of a 5% by mass aqueous solution of the anionic surfactant described in Example 1.
[Coating method]
Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, and the surface of the plate glass is hydrophilized by UV / O ₃ treatment for 10 minutes, and then the hydrophilic composition is spin-coated and applied at 100 ° C. It was oven dried in 10 minutes to form a hydrophilic layer having a dry coating amount of 0.1 g / m ² .

(Example 7)
(C) A hydrophilic member was prepared in the same manner as in Example 6 except that the catalyst was changed to the following.
Example 7: 0.2 g of titanium acetylacetonate
0.1 g of acetylacetone and 0.1 g of tetraethyl orthotitanate were prepared by adding to the hydrophilic sol-gel solution.

(Example 8)
A hydrophilic member was prepared in the same manner as in Example 7 except that the coating method was changed to the following method.
Float plate glass (thickness 2 mm), which is the most common transparent plate glass, was prepared, and the surface of the plate glass was hydrophilized by UV / O ₃ treatment for 10 minutes, and then the hydrophilic composition of Example 7 was applied with a bar. It was oven dried at 150 ° C. for 30 minutes to form a hydrophilic layer having a dry coating amount of 3.0 g / m ² .

(Examples 9 and 10)
(C) A hydrophilic member was prepared in the same manner as in Example 8 except that the catalyst was changed to the following.
Example 9: Ethyl acetoacetate aluminum diisopropylate (manufactured by Kawaken Fine Chemical Co., Ltd., ALCH) 0.2 g
Example 10: 0.2 g of zirconium chelate compound
In a reactor equipped with a stirrer, 50 g of tetrabutoxyzirconium and 20 g of ethyl acetoacetate were added and stirred at room temperature for 1 hour to obtain a zirconium chelate compound.

(Examples 11 to 13)
(A) A hydrophilic member was prepared in the same manner as in Example 8 except that the specific hydrophilic polymer was changed to the following.
Example 11: Specific hydrophilic polymer (2)
Example 12: Specific hydrophilic polymer (11)
Example 13: Specific hydrophilic polymer (24)

(Examples 14 to 16)
A hydrophilic member was prepared in the same manner as in Example 8 except that the substrate was changed to the following.
Example 14: Commercially available mirror cleaned with UV ozone Example 15: Polyethylene terephthalate substrate (50 μm in thickness) whose surface was hydrophilized by glow treatment
Example 16: Alkaline degreased aluminum substrate (thickness 100 μm)

(Examples 17 and 18)
A hydrophilic member was prepared in the same manner as in Example 8 except that a hydrophilic layer was formed from the hydrophilic composition of Example 8 with the following dry coating amount.
Example 17: Dry coating amount 10 g / m ²
Example 18: Dry coating amount 30 g / m ²

(Examples 19 and 20)
A hydrophilic member was prepared in the same manner as in Example 8 except that 2 g of the following compound was added to the hydrophilic composition of Example 8.
Example 19: Zirconium oxychloride Example 20: Tetrakis (acetylacetonato) zirconium

(Examples 21 and 22)
A hydrophilic member was prepared in the same manner as in Example 8 except that 0.5 g of the following compound was added to the hydrophilic composition of Example 8.
Example 21: TBZ (manufactured by China Kogyo Co., Ltd.)
Example 22: Zeomic (manufactured by Sinanen Co., Ltd.)

(Example 23)
[Hydrophilic composition]
In 100 g of purified water, 10 g of (A) specific hydrophilic polymer (1) was mixed and stirred at room temperature for 2 hours to prepare a hydrophilic sol-gel solution. A hydrophilic composition was prepared by mixing 120 g of the hydrophilic sol-gel solution with 2.5 g of a 5% by mass aqueous solution of the anionic surfactant described in Example 1.
[Catalyst solution]
In 50 g of ethyl alcohol and 2 g of purified water, 2.0 g of acetylacetone and 2.5 g of tetraethyl orthotitanate were mixed and stirred at room temperature for 1 hour to prepare.
[Coating method]
A float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, and the surface of the plate glass is hydrophilized by UV / O ₃ treatment for 10 minutes, and then the hydrophilic composition 130 g and the catalyst solution 2.5 g are used. The solution mixed and stirred at room temperature for 1 hour was bar coated and oven dried at 150 ° C. for 30 minutes to form a hydrophilic layer having a dry coating amount of 3.0 g / m ² .

(Example 24)
[Hydrophilic sol-gel solution]
In 20 g of ethyl alcohol and 100 g of purified water, 12 g of (B) tetramethoxysilane and 4 g of (A) specific hydrophilic polymer (1) were mixed and prepared by stirring at room temperature for 2 hours.
[Hydrophilic composition]
140 g of the hydrophilic sol-gel solution is mixed with 20 g of a 20% by weight aqueous solution of colloidal silica dispersion (Snowtech C), 4 g of a 5% by weight aqueous solution of the anionic surfactant described in Example 1, and 60 g of purified water. It was a thing.
[Coating method]
Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, and the surface of the plate glass is hydrophilized by UV / O ₃ treatment for 10 minutes, and then the hydrophilic composition is spin-coated and applied at 100 ° C. It was oven dried in 10 minutes to form a hydrophilic layer having a dry coating amount of 0.1 g / m ² .

(Examples 25-27)
(A) A hydrophilic member was prepared in the same manner as in Example 24 except that the specific hydrophilic polymer (1) was changed to the following.
Example 25: Specific hydrophilic polymer (2)
Example 26: Specific hydrophilic polymer (11)
Example 27: Specific hydrophilic polymer (24)

(Example 28)
[Hydrophilic sol-gel solution]
In 20 g of ethyl alcohol, 0.2 g of 1N hydrochloric acid aqueous solution as a catalyst (C) and 100 g of purified water, 12 g of tetramethoxysilane and 4 g of the specific hydrophilic polymer (1) were mixed, and the mixture was stirred at room temperature for 2 hours to prepare.
[Hydrophilic composition]
140 g of the hydrophilic sol-gel solution is mixed with 20 g of a 20% by weight aqueous solution of colloidal silica dispersion (Snowtech C), 4 g of a 5% by weight aqueous solution of the anionic surfactant described in Example 1, and 60 g of purified water. It was a thing.
[Coating method]
Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, and the surface of the plate glass is hydrophilized by UV / O ₃ treatment for 10 minutes, and then the hydrophilic composition is spin-coated and applied at 100 ° C. It was oven dried in 10 minutes to form a hydrophilic layer having a dry coating amount of 0.1 g / m ² .

(Examples 29 to 31)
(C) A hydrophilic member was prepared in the same manner as in Example 28 except that the catalyst was changed to the following.
Example 29: 2 g titanium acetylacetonate
It was prepared by adding 1 g of acetylacetone and 1 g of tetraethyl orthotitanate to the hydrophilic sol-gel solution.
Example 30: Ethyl acetoacetate aluminum diisopropylate (manufactured by Kawaken Fine Chemical Co., Ltd., ALCH) 2 g
Example 31: Zirconium chelate compound 2g
In a reactor equipped with a stirrer, 50 g of tetrabutoxyzirconium and 20 g of ethyl acetoacetate were added and stirred at room temperature for 1 hour to obtain a zirconium chelate compound.

(Examples 32-34)
(B) A hydrophilic member was prepared in the same manner as in Example 29 except that the specific alkoxide was changed to the following.
Example 32: Aluminum ethoxide Example 33: Zirconium ethoxide Example 34: Titanium ethoxide

(Examples 35-37)
(A) A hydrophilic member was prepared in the same manner as in Example 29 except that the specific hydrophilic polymer was changed to the following.
Example 35: Specific hydrophilic polymer (2)
Example 36: Specific hydrophilic polymer (11)
Example 37: Specific hydrophilic polymer (24)

(Examples 38 to 40)
A hydrophilic member was prepared in the same manner as in Example 29 except that the substrate was changed to the following.
Example 38: Commercially available mirror cleaned with UV ozone Example 39: Polyethylene terephthalate substrate having a surface hydrophilized by glow treatment (thickness 50 μm)
Example 40: Alkaline degreased aluminum substrate (thickness 100 μm)

(Examples 41 and 42)
A hydrophilic member was prepared in the same manner as in Example 29 except that the coating method was changed as follows.
Example 41: A hydrophilic composition was bar coated and oven dried at 100 ° C. for 10 minutes to form a hydrophilic layer having a dry coating amount of 1.0 g / m ² .
Example 42: A hydrophilic composition was applied to a bar and formed into a film by rotating at 200 rpm for 300 seconds with a spinner before drying to form a hydrophilic layer having a dry coating amount of 15 g / m ² .

(Examples 43 and 44)
A hydrophilic member was prepared in the same manner as in Example 29 except that 1.0 g of the following compound was added to the hydrophilic composition of Example 29.
Example 43: Zirconium oxychloride Example 44: Tetrakis (acetylacetonato) zirconium

(Examples 45 and 46)
A hydrophilic member was prepared in the same manner as in Example 29 except that 0.2 g of the following compound was added to the hydrophilic composition of Example 29.
Example 45: TBZ (manufactured by China Kogyo Co., Ltd.)
Example 46: Zeomic (manufactured by Sinanen Co., Ltd.)

(Example 47)
[Hydrophilic composition]
In 100 g of purified water, 12 g of (B) tetramethoxysilane and 4 g of (A) specific hydrophilic polymer (1) were mixed and stirred at room temperature for 2 hours to prepare. 120 g of the hydrophilic sol-gel solution described above was mixed with 20 g of a colloidal silica dispersion 20% by weight aqueous solution (Snowtech C), 4 g of a 5% by weight aqueous solution of the anionic surfactant described in Example 1, and 60 g of purified water. It was set as the composition.
[Catalyst solution]
In 50 g of ethyl alcohol and 2 g of purified water, 2.0 g of acetylacetone and 2.5 g of tetraethyl orthotitanate were mixed and stirred at room temperature for 1 hour to prepare.
[Coating method]
Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, and the surface of the plate glass is hydrophilized by UV / O ₃ treatment for 10 minutes, and then 160 g of the hydrophilic composition and 20 g of the catalyst solution are mixed. The solution stirred at room temperature for 5 minutes was spin-coated and dried in an oven at 100 ° C. for 10 minutes to form a hydrophilic layer having a dry coating amount of 0.1 g / m ² .

(Comparative Example 1)
In Example 29, the comparative hydrophilic polymer (i) (mass average molecular weight 7700) having the following structure outside the scope of the present invention was used in place of the specific hydrophilic polymer (1) of the present invention. Thus, a surface hydrophilic member of Comparative Example 1 was obtained.

(Comparative Example 2)
In Example 29, the same procedure was followed except that, instead of the specific hydrophilic polymer (1) of the present invention, a comparative hydrophilic polymer (ii) (mass average molecular weight 10,000) having the following structure outside the scope of the present invention was used. Thus, a surface hydrophilic member of Comparative Example 2 was obtained.

(Comparative Example 3)
In place of the hydrophilic film according to the present invention, a photocatalytic film (manufactured by Toyo Porcelain Co., Ltd., Hydrotect) is applied to the substrate surface used in the above examples to form a hydrophilic surface. A sex member was obtained.

(Example 48)
[Sol-gel solution for undercoat]
The mixture was prepared by mixing 8 g of tetramethoxysilane in 200 g of ethyl alcohol, 10 g of acetylacetone as a non-volatile catalyst, 10 g of tetraethyl orthotitanate, and 100 g of purified water, and stirring at room temperature for 2 hours.
[Composition for undercoat layer]
100 g of colloidal silica dispersion 20% by weight aqueous solution (Snowtech C), 30 g of 5% by weight aqueous solution of the anionic surfactant described in Example 1, and 450 g of purified water are mixed with 500 g of the above sol-gel solution for undercoat layer and coated. Liquid.
[Coating method]
Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, and the surface of the plate glass is hydrophilized by UV / O ₃ treatment for 10 minutes, and then the undercoat layer composition is applied by spin coating. It was oven-dried at 10 ° C. for 10 minutes to form an undercoat layer having a dry coating amount of 0.1 g / m ² . After sufficiently cooling at room temperature, the hydrophilic layer of Example 8 was formed on the undercoat layer.

(Examples 49-53)
A hydrophilic member was obtained in the same manner as in Example 48 except that the hydrophilic layer was changed to the following.
Example 49: Hydrophilic layer of Example 9 Example 50: Hydrophilic layer of Example 10 Example 51: Hydrophilic layer of Example 11 Example 52: Hydrophilic layer of Example 12 Example 53: Example 13 hydrophilic layers

(Examples 54 to 56)
A hydrophilic member was prepared in the same manner as in Example 48 except that the substrate was changed to the following.
Example 54: Commercially available mirror cleaned with UV ozone Example 55: Polyethylene terephthalate substrate having a surface hydrophilized by glow treatment (thickness 50 μm)
Example 56: Alkaline degreased aluminum substrate (thickness 100 μm)

(Examples 57 to 63)
A hydrophilic member was obtained in the same manner as in Example 48 except that the hydrophilic layer was changed to the following.
Example 57: Hydrophilic layer of Example 17 Example 58: Hydrophilic layer of Example 18 Example 59: Hydrophilic layer of Example 19 Example 60: Hydrophilic layer of Example 20 Example 61: Example 21 hydrophilic layer Example 62: hydrophilic layer of Example 22 Example 63: hydrophilic layer of Example 23

(Examples 64-72)
A hydrophilic member was obtained in the same manner as in Example 48 except that the hydrophilic layer was changed to the following.
Example 64: Hydrophilic layer of Example 29 Example 65: Hydrophilic layer of Example 30 Example 66: Hydrophilic layer of Example 31 Example 67: Hydrophilic layer of Example 32 Example 68: Example 33 hydrophilic layer Example 69: hydrophilic layer of Example 34 Example 70: hydrophilic layer of Example 35 Example 71: hydrophilic layer of Example 36 Example 72: hydrophilic layer of Example 37

(Examples 73 to 75)
A hydrophilic member was prepared in the same manner as in Example 64 except that the substrate was changed to the following.
Example 73: Commercially available mirror cleaned with UV ozone Example 74: Polyethylene terephthalate substrate having a surface hydrophilized by glow treatment (thickness 50 μm)
Example 75: Alkali degreased aluminum substrate (thickness 100 μm)

(Examples 76 to 82)
A hydrophilic member was obtained in the same manner as in Example 48 except that the hydrophilic layer was changed to the following.
Example 76: Hydrophilic layer of Example 41 Example 77: Hydrophilic layer of Example 42 Example 78: Hydrophilic layer of Example 43 Example 79: Hydrophilic layer of Example 44 Example 80: Example 45 hydrophilic layer Example 81: hydrophilic layer of Example 46 Example 82: hydrophilic layer of Example 47

[Evaluation of hydrophilic member]
[Surface free energy]
The hydrophilicity of the hydrophilic layer surface is generally measured with a water droplet contact angle (Kyowa Interface Science Co., Ltd., DropMaster 500). However, on a very hydrophilic surface such as the present invention, the water droplet contact angle may be 10 ° or less, and further 5 ° or less, and there is a limit to the mutual comparison of hydrophilicity. . On the other hand, as a method for evaluating the hydrophilicity of the solid surface in more detail, there is a measurement of surface free energy. Various methods have been proposed. In the present invention, as an example, the surface free energy was measured using the Zisman plot method. Specifically, an aqueous solution of an inorganic electrolyte such as magnesium chloride uses the property that the surface tension increases with the concentration. After measuring the contact angle in air and at room temperature using the aqueous solution, the horizontal axis indicates the surface of the aqueous solution. Take the value obtained by converting the contact angle into cos θ on the vertical axis and plot the points of aqueous solutions of various concentrations to obtain a linear relationship. Cos θ = 1, that is, the surface tension when the contact angle = 0 °, It is a measurement method defined as the surface free energy of a solid. The surface tension of water is 72 mN / m, and the higher the surface free energy value, the higher the hydrophilicity.

〔transparency〕
When the hydrophilic member coated with the hydrophilic film of the present invention is used for window glass or the like, transparency is important from the viewpoint of ensuring visibility. The hydrophilic film of the present invention is excellent in transparency, and even when the film thickness is large, the transparency is not impaired and compatibility with durability is possible.
Transparency is evaluated by measuring the light transmittance in the visible light region (400 nm to 800 nm) with a spectrophotometer (Hitachi spectrophotometer U3000).

[Evaluation of wear resistance]
The surface of the obtained hydrophilic member is rubbed with a nonwoven fabric (BEMCOT, manufactured by Asahi Chemical Fiber Co., Ltd.) under a load of 200 g for 250 reciprocations, and the appearance change before and after that is visually observed.
○: No scratches on the surface before and after rubbing △: About one scratch ×: Many scratches exist

[Scratch strength]
Starting from 5 g on a 0.1 mm diameter sapphire needle, a weight was applied in 5 g increments to scan the surface of the hydrophilic layer, and the weight at which scratching occurred was evaluated (measured with a scratch strength tester Type 18S manufactured by Shinto Kagaku Co., Ltd.). Durability is better when there is no damage even if the load is large.

[Evaluation of anti-fogging property]
The hydrophilic member obtained above was exposed to water vapor for 1 minute under an indoor fluorescent lamp in the daytime, separated from the water vapor, and then placed in an environment of 25 ° C. and RH 10%. The degree of fogging and its change under a fluorescent lamp were sensory evaluated in three stages according to the following criteria.
○: No cloudiness is observed Δ: Cloudy, but recovers within 10 seconds, no cloudiness is seen ×: Cloudy, no cloudiness recovers even after 10 seconds

[Evaluation of antifouling properties]
A line was written on the surface of the hydrophilic member obtained above with oil-based ink (an oil-based marker manufactured by Mitsubishi Pencil Co., Ltd.), water was continuously poured, and the sensitivity was evaluated in three stages as to whether it flowed down.
○: Ink can be taken within 1 minute. Δ: Ink can be taken after 1 minute. ×: Ink cannot be removed even if it is performed over 2 minutes for 10 minutes.

[Evaluation of water drying speed]
About 1 cc of pure water was dropped onto the hydrophilic member obtained above and allowed to stand in an environment of 25 ° C. and 50% RH, and the time until the water droplets were dried was visually observed and measured every 5 minutes.
Each evaluation result is shown in Tables 1 to 4 below.

  As is apparent from Table 1, the hydrophilic film formed using the hydrophilic composition of the present invention is excellent in antifouling properties and antifogging properties. Moreover, the hydrophilic film is excellent in scratch resistance by improving the film thickness. Furthermore, by adding a catalyst, a hydrolysis / condensation reaction proceeds, and a hydrophilic member exhibiting very excellent wear resistance and scratch resistance can be provided.

  As is clear from Table 2, a hydrophilic member having excellent scratch strength could be created by adding a specific alkoxide compound to the hydrophilic composition. By adding a specific alkoxide compound, excellent wear resistance and scratch resistance are exhibited even in a thin film. This is considered to be due to a strong crosslinked structure of the inorganic component. Moreover, it had abrasion resistance and scratch strength superior to the hydrophilic film (Comparative Example 1) using the comparative hydrophilic polymer (i) which is a hydrophilic polymer of the prior art. Further, by comparing with Comparative Example 2, it is clear that the hydrophilicity can be maintained by using a highly hydrophilic functional group for the linking group that connects the polymer main chain and the silane coupling group, and that the water can be quickly dried. Was also found to be excellent. On the other hand, the hydrophilic member (Comparative Example 3) in which the photocatalytic film was pasted on the glass substrate was low in wear resistance and scratching strength, and was at a practically problematic level.

As is apparent from Tables 3 and 4, the hydrophilic member of the present invention had better scratching strength by providing an undercoat layer between the substrate and the hydrophilic layer. This is the adhesion between the glass substrate and the undercoat layer,
It is considered that the strength of the film is improved by improving the adhesion between the undercoat layer and the hydrophilic layer.

Claims (19)

(A) A hydrophilic composition comprising a hydrophilic polymer represented by the following general formula (I), and (B) an alkoxide compound of an element selected from Si, Ti, Zr, and Al.

In formula (I), representative of the R ¹ to R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.   The hydrophilic composition according to claim 1, further comprising (C) a catalyst that promotes the reaction between the (A) hydrophilic polymer and the (B) alkoxide compound. On the substrate, (A) a hydrophilic polymer represented by the following general formula (I), (B) a hydrophilic composition containing an alkoxide compound of an element selected from Si, Ti, Zr, and Al is applied, A hydrophilic member having a hydrophilic film formed by heating and drying.

In formula (I), representative of the R ¹ to R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.   Furthermore, the hydrophilic member of Claim 3 which contains the catalyst (C) which accelerates | stimulates reaction of (A) hydrophilic polymer and (B) alkoxide compound in the said hydrophilic composition.   The hydrophilic member according to claim 4, further comprising an undercoat layer containing a non-volatile catalyst between the substrate and the hydrophilic film.   The undercoat layer is obtained by hydrolyzing and polycondensing a composition having at least an alkoxide compound of an element selected from Si, Ti, Zr, and Al and a nonvolatile catalyst. Claim | item 4 or the hydrophilic member of Claim 5.   The hydrophilic member according to claim 3, wherein the substrate is any one of glass, plastic, metal, and tile. On the substrate, (A) a hydrophilic polymer represented by the following general formula (I), (B) a hydrophilic composition containing an alkoxide compound of an element selected from Si, Ti, Zr, and Al is applied, A hydrophilic member having a hydrophilic film having a cross-linked structure formed by heating and drying.

In formula (I), representative of the R ¹ to R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion. (A) A hydrophilic composition comprising a hydrophilic polymer represented by the following general formula (I).

In formula (I), representative of the R ¹ to R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.   The hydrophilic composition according to claim 9, further comprising (C) a catalyst that promotes the reaction of the hydrophilic polymer (A).   The hydrophilic composition according to claim 9 or 10, further comprising (B) an alkoxide compound of an element selected from Si, Ti, Zr, and Al. It has a hydrophilic film formed by applying (A) a hydrophilic composition containing a hydrophilic polymer represented by the following general formula (I) on a substrate, heating and drying. Hydrophilic member.

In formula (I), representative of the R ¹ to R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.   Furthermore, (A) The hydrophilic member of Claim 12 which contains the catalyst (C) which accelerates | stimulates reaction of a hydrophilic polymer in the said hydrophilic composition.   The hydrophilic member according to claim 12 or 13, further comprising (B) an alkoxide compound of an element selected from Si, Ti, Zr, and Al.   The hydrophilic member according to claim 12, further comprising an undercoat layer between the substrate and the hydrophilic film.   The hydrophilic member according to claim 15, wherein the undercoat layer contains a nonvolatile catalyst.   The undercoat layer is obtained by hydrolyzing and polycondensing a composition having at least an alkoxide compound of an element selected from Si, Ti, Zr, and Al and a nonvolatile catalyst. Item 15. The hydrophilic member according to Item 15 or 16.   The hydrophilic member according to claim 12, wherein the substrate is any one of glass, plastic, metal, and tile. On the substrate, (A) having a hydrophilic film having a crosslinked structure formed by applying a hydrophilic composition containing a hydrophilic polymer represented by the following general formula (I), heating and drying. A hydrophilic member characterized by the above.

In formula (I), representative of the R ¹ to R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y are 100 to 0, and represent numbers that satisfy x + y = 100. X represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, R _d is a linear chain having 1 to 8 carbon atoms, Represents a branched or cyclic alkyl group, and R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkali metal, an alkaline earth metal, or onium. , R _g represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, a halogen atom, an inorganic anion, or an organic anion.