JP2011144302A - Hydrophilic composition, hydrophilic member and anti-fog mirror for bathroom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrophilic composition and a hydrophilic member for imparting excellent anti-fog properties, tight adhesiveness, particularly, scale adhesion resistance to the surface of a support. <P>SOLUTION: The hydrophilic composition comprises (A) at least one hydrophilic polymer having a specific silane coupling group, for example, represented by the figure and (C) an alkoxide compound containing an element selected from Si, Ti, Zr and Al, wherein the content of (C) the alkoxide compound containing an element selected from Si, Ti, Zr and Al is 12.5-22.5 mass% based on the total solid content of the hydrophilic composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a hydrophilic composition, a hydrophilic member, and a bathroom antifogging mirror that impart excellent antifogging properties and adhesion to a surface of a support, in particular, adhesion to scales.

Various techniques for preventing oily dirt from adhering to the member surface have been proposed. For example, 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 particular, the glass member has a problem that it is easily scratched and loses the shine specific to glass by physically removing dirt by rubbing with a sponge or the like. For this reason, the technique which gives a process to the surface of a glass member, provides antifouling property, and makes it easy to remove dirt is known (patent documents 1-3).

As a conventional technique for imparting antifouling properties to a glass member, Patent Document 1 discloses a substrate with a highly durable photocatalytic film in which TiO ₂ crystals are dispersed in a film forming component composed of ZrO ₂ and SiO _{2 on the} surface of the substrate. Is described. Patent Document 2 describes a glass product having a coating film containing a silicon compound such as diethyl phosphatoethyltriethoxysilane as a coating material.

  Further, a resin film generally used for the surface of an optical member or the like, or an inorganic material such as glass or metal is generally one having 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. Moreover, combustion products such as carbon black contained in exhaust gas from automobile dust, automobiles, etc., and hydrophobic pollutants such as oil and sealant elution components are difficult to adhere. Therefore, it is useful for various applications.

According to the conventionally proposed surface treatment methods for hydrophilizing a member, for example, etching treatment, plasma treatment, etc., the member is highly hydrophilized, but the effect is temporary, and the hydrophilized state is changed. It cannot be maintained for a long time.
On the other hand, 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 highly hydrophilizing the surface 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 3). 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 since the hydrophilic effect is not expressed unless photoexcited, it is durable, and There is a demand for antifouling members that can be used in any part.

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 friction resistance (see Patent Document 4). 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.

However, when the tap water is attached to the hydrophilic surface layer in a film form and dried, a white deposit (hereinafter referred to as scale) is attached. For members that are supposed to be used around water, it can be said that adhesion to water scale is an essential performance. However, it is very difficult to remove scale, and generally a strong alkaline cleaning agent is used, which leads to deterioration of the substrate. In addition, scrubbing with a scrubbing brush has a problem that the surface of the film is innumerable.
Patent Documents 5 to 7 disclose hydrophilic compositions containing a hydrophilic polymer and a metal complex catalyst in order to prevent scale adhesion.

JP 2001-70801 A JP 2002-12450 A International Publication No. 96/29375 Japanese Patent Application No. 2006-256215 JP 2009-83147 A JP 2009-67972 A JP 2009-191169 A

  The object of the present invention is to impart excellent antifogging property and adhesion to the surface of the support, in particular, adhesion to scale, and it is possible to easily remove scale with a cleaning solution containing acid, and the film remains after removal of scale. It is providing the hydrophilic composition and hydrophilic member which are excellent in a rate.

As a result of studying the sol-gel organic-inorganic hybrid hydrophilic membrane, the present inventors have found that (A) at least one hydrophilic polymer having a specific structure and (B) a hydrophilic polymer having a specific structure (different from (A)) And (C) an alkoxide compound containing an element selected from Si, Ti, Zr and Al, and (C) an alkoxide compound containing an element selected from Si, Ti, Zr and Al Has been successfully imparted to the hydrophilic member with adhesion to scales with a hydrophilic composition containing 12.5 to 22.5 mass% of the total solid content of the hydrophilic composition. Further, the present inventors have found a hydrophilic composition that can easily form a hydrophilic film that can be easily removed by a cleaning solution containing an acid when the scale adheres, and that has an excellent film remaining rate after the scale is removed.
That is, the present invention is as follows.

（一般式（Ｉ−１）及び（Ｉ−２）中、Ｒ^１０１〜Ｒ^１０８はそれぞれ独立に水素原子又は炭化水素基を表す。ｐは１〜３の整数を表し、Ｌ^１０１及びＬ^１０２は、それぞれ独立に単結合又は多価の有機連結基を表す。ｘ及びｙは組成比を表し、ｘは０＜ｘ＜１００、ｙは０＜ｙ＜１００となる数を表す。Ａ^１０１は−ＯＨ、−ＯＲ_ａ、−ＣＯＲ_ａ、−ＣＯ_２Ｒ_ｅ、−ＣＯＮ（Ｒ_ａ）（Ｒ_ｂ）、−Ｎ（Ｒ_ａ）（Ｒ_ｂ）、−ＮＨＣＯＲ_ｄ、−ＮＨＣＯ_２Ｒ_ａ、−ＯＣＯＮ（Ｒ_ａ）（Ｒ_ｂ）、−ＮＨＣＯＮ（Ｒ_ａ）（Ｒ_ｂ）、−ＳＯ_３Ｒ_ｅ、−ＯＳＯ_３Ｒ_ｅ、−ＳＯ_２Ｒ_ｄ、−ＮＨＳＯ_２Ｒ_ｄ、−ＳＯ_２Ｎ（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）、又はＰＯ_３（Ｒ_ｄ）（Ｒ_ｅ）を表す。ここで、Ｒ_ａ、Ｒ_ｂ及びＲ_ｃは、それぞれ独立に水素原子又は直鎖、分岐又は環状のアルキル基を表し、Ｒ_ｄは、直鎖、分岐又は環状のアルキル基を表し、Ｒ_ｅ及びＲ_ｆは、それぞれ独立に水素原子又は直鎖、分岐又は環状のアルキル基、アルカリ金属、アルカリ土類金属、又はオニウムを表し、Ｒ_ｇはハロゲンイオン、無機アニオン、又は有機アニオンを表す。）

（一般式（ＩＩ−１）及び（ＩＩ−２）中、Ｒ^２０１〜Ｒ^２０５はそれぞれ独立に水素原子又は炭化水素基を表す。ｑは１〜３の整数を表し、Ｌ^２０１及びＬ^２０２は、それぞれ独立に単結合又は多価の有機連結基を表す。Ａ^２０１は−ＯＨ、−ＯＲ_ａ、−ＣＯＲ_ａ、−ＣＯ_２Ｒ_ｅ、−ＣＯＮ（Ｒ_ａ）（Ｒ_ｂ）、−Ｎ（Ｒ_ａ）（Ｒ_ｂ）、−ＮＨＣＯＲ_ｄ、−ＮＨＣＯ_２Ｒ_ａ、−ＯＣＯＮ（Ｒ_ａ）（Ｒ_ｂ）、−ＮＨＣＯＮ（Ｒ_ａ）（Ｒ_ｂ）、−ＳＯ_３Ｒ_ｅ、−ＯＳＯ_３Ｒ_ｅ、−ＳＯ_２Ｒ_ｄ、−ＮＨＳＯ_２Ｒ_ｄ、−ＳＯ_２Ｎ（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）、又はＰＯ_３（Ｒ_ｄ）（Ｒ_ｅ）を表す。ここで、Ｒ_ａ、Ｒ_ｂ及びＲ_ｃは、それぞれ独立に水素原子又は直鎖、分岐又は環状のアルキル基を表し、Ｒ_ｄは、直鎖、分岐又は環状のアルキル基を表し、Ｒ_ｅ及びＲ_ｆは、それぞれ独立に水素原子又は直鎖、分岐又は環状のアルキル基、アルカリ金属、アルカリ土類金属、又はオニウムを表し、Ｒ_ｇはハロゲンイオン、無機アニオン、又は有機アニオンを表す。）
２．
前記（Ｃ）Ｓｉ、Ｔｉ、Ｚｒ、Ａｌから選択される元素を含むアルコキシド化合物が、下記一般式（Ｖ−１）又は一般式（Ｖ−２）で表される化合物であることを特徴とする上記１に記載の親水性組成物。
（Ｒ^２０）_ｍ−Ｚ−（ＯＲ^２１）_４−ｍ （Ｖ−１）
Ａｌ−（ＯＲ^２２）_３ （Ｖ−２）
（Ｒ^２０は水素原子、アルキル基又はアリール基を表し、Ｒ^２１及びＲ^２２はアルキル基又はアリール基を表し、ＺはＳｉ、Ｔｉ又はＺｒを表し、ｍは０〜２の整数を表す。）
３．
前記（Ａ）下記一般式（Ｉ−１）で表される構造単位と、下記一般式（Ｉ−２）で表される構造単位とを有する親水性ポリマーの少なくとも一つと、前記（Ｂ）下記一般式（ＩＩ−２）で表される構造単位を有し、且つ、ポリマー鎖の末端に下記一般式（ＩＩ−１）で表される部分構造を有する親水性ポリマーの少なくとも一つとの質量比（Ａ）／（Ｂ）が、８０／２０〜９０／１０であることを特徴とする上記１又は２に記載の親水性組成物。
４．
更に（Ｄ）金属触媒を含有することを特徴とする上記１〜３のいずれかに記載の親水性組成物。
５．
更に（Ｅ）界面活性剤を含有することを特徴とする上記１〜４のいずれかに記載の親水性組成物。
６．
基材上に、上記１〜５のいずれかに記載の親水性組成物を塗設した親水性層を有することを特徴とする親水性部材。
７．
前記基材がガラス基材であることを特徴とする上記６に記載の親水性部材。
８．
上記６〜７のいずれかに記載の親水性部材に付着した水垢を、ｐＨ２〜４の酸洗浄液により除去する方法。
９．
上記６〜７のいずれかに記載の親水性部材を用いた浴室用防曇ミラー。 1.
(A) at least one hydrophilic polymer having a structural unit represented by the following general formula (I-1) and a structural unit represented by the following general formula (I-2); and (B) the following general formula At least one hydrophilic polymer having a structural unit represented by (II-2) and having a partial structure represented by the following general formula (II-1) at the end of the polymer chain; and (C) Si , An alkoxide compound containing an element selected from Ti, Zr, and Al, and (C) an alkoxide compound containing an element selected from Si, Ti, Zr, and Al with respect to the total solid content of the hydrophilic composition. A hydrophilic composition containing 12.5 to 22.5% by mass.

(In the general formulas (I-1) and (I-2), R ^{101 to} R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. P represents an integer of 1 to 3, and L ¹⁰¹ and L ¹⁰² represent Each independently represents a single bond or a polyvalent organic linking group, x and y represent a composition ratio, x represents a number such that 0 <x <100, y represents 0 <y <100, and A ¹⁰¹ 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 ) ( _Rb ), -N ( _Ra ) ( _Rb ) ( _Rc ), -N ( _Ra ) ( _Rb ) ( _Rc ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or PO ₃ (R _d ) (R _e ), where R _a , R _b and R _c independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, 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, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.)

(In the general formula (II-1) and ^(II-2), .q representing each is R 201 ^{to R 205} independently represent a hydrogen atom or a hydrocarbon group represents an integer of 1 to ^{3, L 201} and ^{L 202} are Each independently represents a single bond or a polyvalent organic linking group, A ²⁰¹ 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 O ₃ represents the _{(R d) (R e)} . _Here, R a, _{R b} and _{R c} each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, _{R d} represents a linear 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, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen atom. Represents an ion, an inorganic anion, or an organic anion.)
2.
The (C) alkoxide compound containing an element selected from Si, Ti, Zr, and Al is a compound represented by the following general formula (V-1) or general formula (V-2): 2. The hydrophilic composition as described in 1 above.
_{^{(R 20) m -Z- (OR}} 21) 4-m (V-1)
Al- (OR ²² ) ₃ (V-2)
(R ²⁰ represents a hydrogen atom, an alkyl group or an aryl group, R ²¹ and R ²² represent an alkyl group or an aryl group, Z represents Si, Ti or Zr, and m represents an integer of 0 to 2.)
3.
(A) at least one hydrophilic polymer having a structural unit represented by the following general formula (I-1) and a structural unit represented by the following general formula (I-2); Mass ratio with at least one hydrophilic polymer having a structural unit represented by the general formula (II-2) and having a partial structure represented by the following general formula (II-1) at the end of the polymer chain (A) / (B) is 80 / 20-90 / 10, The hydrophilic composition of said 1 or 2 characterized by the above-mentioned.
4).
Furthermore, (D) The hydrophilic composition in any one of said 1-3 characterized by containing a metal catalyst.
5.
Furthermore, (E) surfactant is contained, The hydrophilic composition in any one of said 1-4 characterized by the above-mentioned.
6).
A hydrophilic member comprising a hydrophilic layer on which a hydrophilic composition according to any one of 1 to 5 is applied on a substrate.
7).
7. The hydrophilic member as described in 6 above, wherein the substrate is a glass substrate.
8).
8. A method for removing scale adhering to the hydrophilic member according to any one of 6 to 7 with an acid cleaning solution having a pH of 2 to 4.
9.
The anti-fog mirror for bathrooms using the hydrophilic member in any one of said 6-7.

  ADVANTAGE OF THE INVENTION According to this invention, the hydrophilic composition which provides the antifogging property and adhesiveness which were excellent in the support surface, especially water-resistant scale adhesion property, and a hydrophilic member using the same are provided.

Hereinafter, the present invention will be described in more detail.
[Hydrophilic composition]
The hydrophilic composition of the present invention comprises (A) at least a hydrophilic polymer having a structural unit represented by the following general formula (I-1) and a structural unit represented by the following general formula (I-2). One (hereinafter may be referred to as “hydrophilic polymer (A)”), (B) having a structural unit represented by the following general formula (II-2), and at the end of the polymer chain, the following general From at least one hydrophilic polymer having a partial structure represented by the formula (II-1) (hereinafter sometimes referred to as “hydrophilic polymer (B)”) and (C) Si, Ti, Zr, and Al. An alkoxide compound containing an element selected, and (C) an alkoxide compound containing an element selected from Si, Ti, Zr, and Al is 12.5 to 22 with respect to the total solid content of the hydrophilic composition. .5% by mass is contained.

  High hydrophilicity by combining hydrophilic polymer (A) and hydrophilic polymer (B) containing an alkoxysilyl group that forms a hydrophilic structure such as polyacrylamide and a crosslinked structure as a composition imparting hydrophilicity In addition to being able to be maintained, the water adhering to the hydrophilic surface does not dissolve the hydrophilic layer (hereinafter also referred to as “hydrophilic film”), and is excellent in water resistance over a long period of time. When the hydrophilic polymer (B) is not used in combination, sufficient hydrophilicity cannot be obtained, and further, the amount of hydroxyl groups in the hydrophilic composition increases, so that scale tends to adhere. Furthermore, (C) It is hydrophilic by containing 12.5-22.5 mass% of alkoxide compounds containing the element selected from Si, Ti, Zr, and Al with respect to the total solid of a hydrophilic composition. An appropriate degree of crosslinking can be obtained in the composition, and it is difficult to retain water and form a hydrophilic member to which scale does not easily adhere. If the amount is less than 12.5% by mass, the hydrophilic composition has a low degree of cross-linking, so that it is easy to hold water and scales easily adhere. On the other hand, if it exceeds 22.5%, the number of hydroxyl groups contained in the hydrophilic composition will increase and scale will easily adhere. Further, it is possible to form a hydrophilic member that can easily remove scales with an acid-containing cleaning solution and that has an excellent film remaining rate after scale removal. This is due to the fact that calcium and magnesium, which are scale components, can be removed by acid.

  [Hydrophilic polymer (A) including structure represented by general formula (I-1) and structure represented by general formula (I-2)]

In general formulas (I-1) and (I-2), R ^{101 to} R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 to 3, and L ¹⁰¹ and L ¹⁰² each represents a single bond or a polyvalent organic linking group. x and y represent composition ratios, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ¹⁰¹ 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, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.

In the general formulas (I-1) and (I-2), R ^{101 to} R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. Examples of the 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 ^{101 to} R ¹⁰⁸ 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-alkyl Sulfa Yl 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)), monoalkyl phosphono group _(-PO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphono group _(-PO 3 H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphonophenyl group), phosphonooxy group (-OPO ₃ H ₂ ) And conjugated base groups thereof (hereinafter referred to as phosphonatooxy groups), dialkyl phosphonooxy groups (—OPO ₃ (alkyl) ₂ ), diaryl phosphonooxy groups (—OPO ₃ (aryl) ₂ ), alkylaryl phosphines A phonooxy group (—OPO (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as an alkylphosphonatooxy group), monoarylphosphono Examples thereof include an oxy group (—OPO ₃ H (aryl)) and a conjugate base group thereof (hereinafter referred to as arylphosphonateoxy group), a morpholino group, a cyano group, a nitro group, an aryl group, an alkenyl group, and an alkynyl group.

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, the alkylene group in the substituted alkyl group is preferably a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Preferably, it is a straight chain having 1 to 12 carbon atoms, more preferably a straight chain having 1 to 8 carbon atoms, more preferably a branched structure having 3 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms, and More preferable examples include cyclic alkylene groups having 5 to 10 carbon atoms, and further preferably 5 to 8 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a hydroxymethyl group, a methoxymethyl group, and a methoxyethoxy group. Ethyl group, allyloxymethyl 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, methoxycarbonyl group Group, allyloxycarbonyl butyl 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.

  Of these, a hydroxymethyl group is preferred from the viewpoint of hydrophilicity.

L ^{101 to} L ¹⁰² represent a single bond or an organic linking group. Here, the single bond means that the main chain of the polymer and the A ¹⁰¹ or Si atom are directly bonded without a connecting chain.
If L ¹⁰¹ ~L ¹⁰² represents an organic linking ^group, L 101 ^{~L 102} represents a polyvalent linking group comprising non-metal atom, the carbon atoms of from 0 to 60, the nitrogen from 0 to 10 It consists of atoms, 0 to 50 oxygen atoms, 0 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. Specifically, it is preferably selected from -N <, an aliphatic group, an aromatic group, a heterocyclic group, and combinations thereof, -O-, -S-, -CO-, -NH-, or A combination containing -O- or -S- or -CO- or NH- is preferably a divalent linking group.
More specific examples of the linking group include the following structural units or those formed by combining them.

In General Formula (I-1) and General Formula (I-2), L ¹⁰¹ and L ¹⁰² each independently represent a single bond or a polyvalent organic linking group. Here, the single bond means that the main chain of the polymer and the A ¹⁰¹ or Si atom are directly bonded without a connecting chain.
In the general formula (I-1), L ¹⁰¹ is a single bond or selected from the group consisting of —CH ₂ —, —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. It is preferably a linking group having one or more structures. L ¹⁰¹ preferably contains —CH ₂ — and —CONH—, and more preferably —CONH— (CH ₂ ) _n1 — (n1 represents an integer of 1 to 5, preferably 1 to 4). 2 or 3 is more preferable).
In general formula (I-2), ^L102 is preferably a single bond.

In the general formula (I-2), A ¹⁰¹ 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 _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 (preferably having 1 to 8 carbon atoms), and R _d is a linear, branched or cyclic group. R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having 1 to 8 carbon atoms), an alkali metal, It represents an alkaline earth metal or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. In addition, —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —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 _{a to} R _g may be bonded to each other to form a ring with _{respect to} (R _f ), —OPO ₃ (R _e ) (R _f ), or PO ₃ (R _d ) (R _e ), The formed ring may be a heterocycle containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen 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 ^{101 to} R ¹⁰⁸ are alkyl groups. Can be listed.
A ¹⁰¹ is preferably —CONH ₂ , —CONH (R ⁵ ), or —CON (R ⁵ ) ₂ . In the formula, R ⁵ represents a linear, branched or cyclic alkyl group.

In R _{a to} R _f and R ⁵ , the linear, branched or cyclic alkyl group specifically includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. And 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. .
In addition, in R _{a to} R _g , preferable examples of the alkali metal include lithium, sodium, and potassium, the alkaline earth metal includes barium, and the onium includes ammonium, iodonium, and sulfonium.
Examples of the halogen ion include fluorine ion, chlorine ion, bromine ion, inorganic anion includes nitrate anion, sulfate anion, tetrafluoroborate anion, hexafluorophosphate anion, etc., organic anion includes methanesulfonate anion, Preferred examples include trifluoromethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, p-toluenesulfonic acid anion, and the like.

The A ^101, _{specifically, -NHCOCH 3, -CONH 2, -CON} (CH 3) 2, -COOH, -SO 3 - NMe 4 +, -SO 3 - K +, - (CH 2 CH 2 O) _n H, morpholyl group and the like are preferable. More _{preferably, -NHCOCH 3, -CONH 2, -CON} (CH 3) 2, -SO 3 - K +, - (CH 2 CH 2 O) n H, is. In the above, n preferably represents an integer of 1 to 100.

p represents an integer of 1 to 3, preferably 2 to 3, and more preferably 3.
R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ are hydrogen atoms, and R ¹⁰⁵ is preferably a hydrocarbon group, more preferably an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. More preferably it is.

  In the hydrophilic polymer (A) including the structures represented by the general formulas (I-1) and (I-2), x and y are represented by the general formula (I-1) in the hydrophilic polymer (A). Represents the composition ratio of the structural unit represented by formula (I-2). x is 0 <x <100, and y is 0 <y <100. x is preferably in the range of 1 <x <90, and more preferably in the range of 1 <x <50. y is preferably in the range of 10 <y <99, and more preferably in the range of 50 <y <99.

  The copolymerization ratio of the hydrophilic polymer (A) including the structures represented by the general formulas (I-1) and (I-2) is such that the amount of the general formula (I-2) having a hydrophilic group is within the above range. Can be set arbitrarily. Preferably, the molar ratio (y) of the structural unit of the general formula (I-2) and the molar ratio (x) of the structural unit of the general formula (I-1) having a hydrolyzable silyl group are y / x = 30. The range of / 70 to 99/1 is preferable, y / x = 40/60 to 98/2 is more preferable, and y / x = 50/50 to 97/3 is most preferable. If y / x is 30/70 or more, the hydrophilicity is not insufficient. On the other hand, if y / x = 99/1 or less, the hydrolyzable silyl group amount is sufficient and sufficient curing is obtained. The film strength is also sufficient.

  The mass average molecular weight of the hydrophilic polymer (A) is, for example, 1,000,000 or less, preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, and 5,000 to 50. Is most preferred.

  Specific examples of the hydrophilic polymer (A) including the structures represented by the general formulas (I-1) and (I-2) are shown below together with their mass average molecular weights (MW). The invention is not limited to these examples. In addition, the polymer of the specific example shown below means that each structural unit described is a random copolymer or block copolymer contained in the described molar ratio.

Each compound for synthesizing the hydrophilic polymer (A) including the structures represented by the general formulas (I-1) and (I-2) is commercially available, and can be easily synthesized.
As the radical polymerization method for synthesizing the hydrophilic polymer (A) including the structures represented by the general formulas (I-1) and (I-2), any conventionally known method can be used. .
Specifically, general radical polymerization methods include, for example, New Polymer Experiments 3 (1996, Kyoritsu Shuppan), Polymer Synthesis and Reaction 1 (Polymer Society of Japan, 1992, Kyoritsu Shuppan), New Experiment Chemistry Lecture 19 (1978, Maruzen), Polymer Chemistry (I) (Edited by The Chemical Society of Japan, 1996, Maruzen), Synthetic Polymer Chemistry (Materials Engineering Lecture, 1995, Tokyo Denki University Press) These can be applied.

  The hydrophilic composition uses a hydrophilic polymer (A) and a hydrophilic polymer (B) in combination.

  [Hydrophilic polymer (B) including a structure represented by general formulas (II-1) and (II-2)]

In general formulas (II-1) and (II-2), R ^{201 to} R ²⁰⁵ each independently represent a hydrogen atom or a hydrocarbon group. q represents an integer of 1 to 3, and L ²⁰¹ and L ²⁰² each represent a single bond or a polyvalent organic linking group. A ²⁰¹ 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, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.

  The hydrophilic polymer (B) including the structures represented by the general formulas (II-1) and (II-2) has a structural unit represented by the above general formula (II-2) and has a polymer chain. Has a partial structure represented by the above general formula (II-1).

In the general formulas (II-1) and (II-2), R ^{201 to} R ²⁰⁵ each independently represent a hydrogen atom or a hydrocarbon group, and hydrocarbons when R ^{201 to} R ²⁰⁵ represent a hydrocarbon group. Examples of the 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, the thing similar to what was mentioned by R < ¹⁰¹ > -R < ¹⁰⁸ > of the said general formula (I-1) and (I-2) can be mentioned.
L ²⁰¹ and L ²⁰² each independently represent a single bond or a polyvalent organic linking group. Here, the single bond means that the main chain of the polymer and A ²⁰¹ or Si atom are directly bonded without a connecting chain. When L ²⁰¹ and L ²⁰² represent a polyvalent organic linking group, specific examples thereof can be the same as those described for L ¹⁰¹ in the general formula (I-1).
L ¹⁰¹ is a single bond or a linking group having one or more structures selected from the group consisting of —CH ₂ —, —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. It is preferable that L ¹⁰¹ preferably contains —CH ₂ —, more preferably — (CH ₂ ) _n1 — (n1 represents an integer of 1 to 5, preferably 1 to 4, more preferably 2 or 3. ).
L ¹⁰² is preferably a single bond.
A ²⁰¹ 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 ). Specific examples and preferred examples of A ²⁰¹ include the same examples as those described for A ¹⁰¹ in formula (I-2).
q represents an integer of 1 to 3. Preferably it is 2-3, More preferably, it is 3.
R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ are each a hydrogen atom, and R ²⁰² is preferably a hydrocarbon group, more preferably an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. More preferably, it is a group.

L ²⁰¹ and L ²⁰² are more preferably —CH ₂ CH ₂ CH ₂ S—, —CH ₂ S—, —CONHCH (CH ₃ ) CH ₂ —, —CONH—, —CO—, —CO ₂ —, - _{(CH 2) n1} - it is. L ²⁰¹ preferably contains —CH ₂ —, more preferably — (CH ₂ ) _n1 — (n1 represents an integer of 1 to 5, preferably 1 to 4, more preferably 2 or 3. ).
L ²⁰² is preferably a single bond.

  The hydrophilic polymer (B) including the structures represented by the general formulas (II-1) and (II-2) is, for example, a chain transfer agent (radical polymerization handbook (NTS, Mikiji Tsunoike, Takeshi Endo) In the presence of Iniferter (described in Macromolecules 1986, 19, p287- (Otsu)) by radical polymerization of a hydrophilic monomer (eg, potassium salt of acrylamide, acrylic acid, 3-sulfopropyl methacrylate). Can be synthesized. Examples of chain transfer agents include 3-mercaptopropionic acid, 2-aminoethanethiol hydrochloride, 3-mercaptopropanol, 2-hydroxyethyl disulfide, 3-mercaptopropyltrimethoxysilane. Alternatively, a hydrophilic monomer (eg, acrylamide) may be radically polymerized using a radical polymerization initiator having a reactive group without using a chain transfer agent.

  The hydrophilic polymer (B) including the structures represented by the general formulas (II-1) and (II-2) includes a radical polymerizable monomer represented by the following general formula (i) and the following general formula (ii) ) Can be synthesized by radical polymerization using a silane coupling agent having chain transfer ability. Since the silane coupling agent (ii) has chain transfer ability, it is possible to synthesize a polymer in which a silane coupling group is introduced at the end of the polymer main chain in radical polymerization.

In the general formula (i) and ^{(ii), R 201 ~R 205} , L 201, L 202, A 201, q is the same as defined in the general formula (II-1). These compounds are commercially available and can also be easily synthesized. The radically polymerizable monomer represented by the general formula (i) has a hydrophilic group A ²⁰¹ , and this monomer becomes one structural unit in the hydrophilic polymer.

  In the hydrophilic polymer (B) including the structures represented by the general formulas (II-1) and (II-2), the number of moles of the structural unit of the general formula (II-1) having a hydrolyzable silyl group. The number of moles of the structural unit of the general formula (II-2) is preferably in the range of 1000 to 10 times, more preferably in the range of 500 to 20 times, and most preferably in the range of 200 to 30 times. If it is 30 times or more, the hydrophilicity is not insufficient. On the other hand, if it is 200 times or less, the amount of hydrolyzable silyl groups is sufficient, sufficient curing is obtained, and the film strength is also sufficient.

    The weight average molecular weight of the hydrophilic polymer (B) including the structures represented by the general formulas (II-1) and (II-2) is, for example, 1,000,000 or less, and 1,000 to 1,000,000. 000 is preferred, 1,000 to 500,000 is more preferred, 1,000 to 200,000 is particularly preferred, and 10,000 to 50,000 is most preferred.

  Specific examples of the hydrophilic polymer (B) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto. In specific examples, * represents a bonding position to the polymer.

  In the hydrophilic composition, the hydrophilic polymer (A) and the hydrophilic polymer (B) are used in combination. Thereby, hydrophilicity can be improved and scale adhesion can be suppressed. The ratio (mass ratio) of hydrophilic polymer (A) / hydrophilic polymer (B) is preferably in the range of 5/95 to 95/5, more preferably in the range of 60/40 to 95/5. Yes, most preferably in the range of 80/20 to 90/10.

  The hydrophilic polymer (A) and the hydrophilic polymer (B) may be a copolymer with another monomer. 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 other monomers include those described in paragraphs [0066] to [0070] of Japanese Patent Application No. 2008-15350.

  The ratio of these other monomers used for the synthesis of the copolymer needs to be an amount sufficient for improving various physical properties, but the function as the hydrophilic layer is sufficient, and the hydrophilic polymer (A) Or, in order to sufficiently obtain the advantage of adding the hydrophilic polymer (B), the ratio is preferably not too large. Accordingly, the preferred total proportion of other monomers in the hydrophilic polymer (A) or the hydrophilic polymer (B) is preferably 80% by mass or less, and more preferably 50% by mass or less.

  The measurement of the copolymerization ratio of the hydrophilic polymer (A) and the hydrophilic polymer (B) can be measured with a nuclear magnetic resonance apparatus (NMR) or a calibration curve prepared with a standard substance and measured with an infrared spectrophotometer. .

The hydrophilic composition in the present invention is used by mixing one or more of the hydrophilic polymer (A) and the hydrophilic polymer (B).
From the viewpoint of curability and hydrophilicity, the total amount of the hydrophilic polymer (A) and the hydrophilic polymer (B) is preferably 20 to 87.5% by mass based on the total solid content of the hydrophilic composition, More preferably, 30 to 87.5% by mass is used.

The hydrophilic composition contains a hydrolyzable silyl group-containing hydrophilic polymer containing the hydrophilic polymer (A) in an amount of 80% by mass or more based on the total solid content, and A in the general formula (I-2). ¹⁰¹ or A ^{201 in the} general formula (II-2) is —CONH ₂ , —CONH (R ⁵ ), or CON (R ⁵ ) ₂ (wherein R ⁵ is independently a linear or branched group) Or a cyclic alkyl group).

  The hydrophilic polymer (A) forms a crosslinked film in a state where it is mixed with a hydrolysis and polycondensate of a metal alkoxide. The hydrophilic polymer (A) which is an organic component is involved in the film strength and film flexibility. In particular, the viscosity of the hydrophilic polymer (A) is 0.1 to 100 mPa · s (5% aqueous solution, 20 C. measurement), preferably 0.5 to 70 mPa · s, more preferably 1 to 50 mPa · s, giving good film properties.

[Crosslinking agent]
When the hydrophilic composition contains the hydrophilic polymer (B), it is preferable to contain a crosslinking agent in order to obtain good curability. In addition, when the hydrophilic composition (A) is contained in the hydrophilic composition, good curability can be obtained even when the crosslinking agent is not contained, but in order to obtain a coating film having extremely excellent film strength. May contain a crosslinking agent.

  In the composition of the present invention, (C) an alkoxide compound (also referred to as a metal alkoxide) containing an element selected from Si, Ti, Zr, and Al can be used as a crosslinking agent.

[(C) Alkoxide Compound Containing Element Selected from Si, Ti, Zr, Al]
The metal alkoxide used in the present invention is a hydrolyzable polymerizable compound having a functional group capable of being hydrolyzed and polycondensed in its structure and serving as a crosslinking agent, and the metal alkoxides are polycondensed with each other. Thus, a strong cross-linked film having a cross-linked structure is formed and further chemically bonded to the hydrophilic polymer. The metal alkoxide can be represented by general formula (V-1) and general formula (V-2), in which R ⁸ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁹ represents an alkyl group or an aryl group. Z represents Si, Ti or Zr, and m represents an integer of 0-2. The number of carbon atoms when R ⁸ and R ⁹ 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 2000 or less.

^{_{(R 8) m -Z- (OR}} 9) 4-m (V-1)
Al- (OR ⁹ ) ₃ (V-2)

  Although the specific example of the hydrolysable compound represented by general formula (V-1) and general formula (V-2) below is given, this invention is not limited to this. When Z is Si, that is, the hydrolyzable compound containing silicon includes, for example, trimethoxysilane, tetramethoxysilane, tetraethoxycin, tetrapropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, γ- Examples include chloropropyl triethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, and the like. Among these, particularly preferred are trimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane and the like.

When Z is Ti, i.e., including titanium, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl Examples thereof include trimethoxy titanate, methyl triethoxy titanate, ethyl triethoxy titanate, diethyl diethoxy titanate, phenyl trimethoxy titanate, and phenyl triethoxy titanate. When Z is Zr, that is, the one containing zirconium can include, for example, zirconates corresponding to the compounds exemplified as those containing titanium.
Further, when the central metal is Al, that is, examples of those containing aluminum in the hydrolyzable compound include trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, triisopropoxy aluminate, and the like. be able to.

The (C) metal alkoxide according to the present invention may be used alone or in combination of two or more.
Among the above, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane are preferable, and tetramethoxysilane is more preferable.

  In the hydrophilic member of the present invention, (C) the metal alkoxide is contained in an amount of 12.5 to 22.5% by mass with respect to the total solid content of the hydrophilic composition. Preferably it contains 12.5-20 mass%, More preferably, it contains 12.5-15 mass%. (C) If the content of the metal alkoxide is in the above range, it is excellent in imparting water resistance.

(C) A metal alkoxide can be used in the composition for undercoat layers of this invention, Preferably it is 5-80 mass% with respect to a non-volatile component, More preferably, it can be used in 10-70 mass%.
(C) The metal 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.

[(D) metal catalyst]
The metal catalyst that can be used in the formation of the hydrophilic layer of the present invention can promote hydrolysis and polycondensation of a metal alkoxide compound selected from Si, Ti, Zr, and Al, and cause a bond with a hydrophilic polymer. it can. A particularly preferable metal catalyst is a metal complex catalyst. As the metal complex catalyst, a metal element selected from groups 2A, 3B, 4A and 5A of the periodic table and β-diketone, ketoester, hydroxycarboxylic acid or ester thereof, amino It is a metal complex composed of an oxo or hydroxy oxygen-containing compound selected from alcohols and enolic active hydrogen compounds.
Among the constituent metal elements, 2A group elements such as Mg, Ca, Sr 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 , 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, ketoalcohols such as 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N-methyl- Monoethanolamine, diethanolamine , Amino alcohols such as triethanolamine, methylol melamine, methylol urea, methylol acrylamide, 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 acetylacetone, ethylcarbonylacetone, n-propylcarbonylacetone, i-propylcarbonylacetone, diacetylacetone, 1-acetyl-1-propionyl-acetylacetone, hydroxyethylcarbonylacetone, hydroxypropylcarbonylacetone, Examples include acetoacetic acid, acetopropionic acid, diacetoacetic acid, 3,3-diacetopropionic acid, 4,4-diacetobutyric acid, carboxyethylcarbonylacetone, carboxypropylcarbonylacetone, and 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 (ethyl acetoacetate), 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.

In addition to the above-mentioned metal complex catalyst, a catalyst that promotes hydrolysis and polycondensation of a metal alkoxide compound selected from Si, Ti, Zr, and Al and can cause a bond with a hydrophilic polymer is used in combination. May be. Examples of such a catalyst include hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acids such as formic acid and acetic acid, and the structural formula represented by RCOOH. Compounds that exhibit acidity such as substituted carboxylic acids in which R is substituted with other elements or substituents, sulfonic acids such as benzenesulfonic acid, or basic compounds such as ammoniacal bases such as aqueous ammonia, amines such as ethylamine and aniline Is mentioned.
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.

[Inorganic fine particles]
The hydrophilic layer of the present invention may contain inorganic fine particles in order to improve hydrophilicity, prevent cracking of the film, and improve film strength. 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 size of 5 nm to 10 μm, and more preferably 0.5 to 3 μm. Within the above range, it is possible to stably disperse in the hydrophilic layer, sufficiently maintain the film strength of the hydrophilic layer, and form a highly durable hydrophilic material.
Among the inorganic fine particles as described above, a colloidal silica dispersion is particularly preferable and can be easily obtained as a commercial product.
The content of the inorganic fine particles is preferably 80% by mass or less, and more preferably 50% by mass or less, based on the total solid content of the hydrophilic layer.

[(E) Surfactant]
In the present invention, it is preferable to use a surfactant in order to improve the coating surface of the hydrophilic composition and the undercoat layer 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 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 range of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass with respect to the nonvolatile component in the hydrophilic composition of the present invention. Moreover, surfactant can be used individually or in combination of 2 or more types.

As the surfactant used in the present invention, an anionic surfactant is preferable.
Although the specific example of a preferable surfactant is shown below, this invention is not limited to these.

[Antimicrobial agent]
In the present invention, the hydrophilic composition of the present invention can be coated on a desired support to form a hydrophilic layer to obtain a hydrophilic member.
In order to impart antibacterial, antifungal and antialgal properties to the hydrophilic member of the present invention, the composition can contain an antibacterial agent. 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 decrease 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, and fungi such as fungi and yeast 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-dicarboxy 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 Dichlorofuranide>, 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 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, calcium silicate antibacterial, zirconium phosphate antibacterial, calcium phosphate antibacterial, zinc oxide antibacterial, soluble glass antibacterial, silica gel antibacterial, activated carbon antibacterial, 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 aminometal 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, and the antibacterial agent is effectively exposed to the hydrophilic layer surface, And even if it splashes with water, it does not elute, can maintain the effect for a long time, and does not affect the human body. Moreover, it can disperse | distribute stably with respect to a hydrophilic layer and a coating liquid, and deterioration of a hydrophilic layer and 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 “Sun Eye Back P” used as a triazine-based 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, more preferably 0.01 to 3% by mass, and 0.02 to 1.5%. Mass% is particularly preferable, and 0.05 to 1 mass% is 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 the 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 strength of the cured film of the hydrophilic film and to improve hydrophilicity and water retention.
As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, or a mixture thereof is preferably exemplified. Even if they are not photothermally convertible, they can be used for strengthening the film, enhancing interfacial adhesion by surface roughening, and the like.
The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, and more preferably 0.5 μm to 3 μm. The above range is preferable because it can be stably dispersed in the hydrophilic film and can sufficiently maintain the film strength and hydrophilicity.
The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.
The content of the inorganic fine particles is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the hydrophilic composition.

[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 film.
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 composition of the present invention and the hydrophilic film, an antioxidant can be added to the hydrophilic composition. 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 composition 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 0 to 50% by mass with respect to the entire composition for forming a hydrophilic layer when forming a hydrophilic film. Is more preferable, and the range of 0 to 30% by mass is more preferable.

[Polymer compound]
In order to adjust the film physical properties of the hydrophilic film, various polymer compounds can be added to the hydrophilic composition of the present invention as long as the hydrophilicity is not inhibited. High molecular compounds include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellacs, vinyl resins, acrylic resins. 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.

In addition to this, if necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, tackifiers, etc. 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.

[Preparation of hydrophilic composition]
The preparation of the hydrophilic composition can be carried out, for example, by dissolving various components added as necessary in a solvent such as ethanol in addition to the above-described hydrophilic polymer and metal alkoxide, followed by stirring. The reaction temperature is from room temperature to 80 ° C., and the reaction time, that is, the time during which stirring is continued, is preferably in the range of 1 to 72 hours. A composite sol solution can be obtained.
The concentration of the hydrophilic polymer in the hydrophilic composition is preferably 0.001 to 2.0% by mass of the hydrophilic polymer with respect to the hydrophilic composition from the viewpoint of applicability to the support. More preferably, the content is 0.01 to 1.0% by mass. When the concentration of the hydrophilic polymer is within this range, a layer having a uniform thickness is easily formed when the hydrophilic layer is formed on the support.

  The solvent used in preparing the hydrophilic composition is not particularly limited as long as it can uniformly dissolve and disperse these, but for example, an aqueous solvent such as methanol, ethanol, water and the like is preferable.

  As described above, the preparation of the organic-inorganic composite sol liquid (hydrophilic composition) for forming the hydrophilic layer from the hydrophilic composition of the present invention utilizes the sol-gel method. For 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.

[Hydrophilic member]
The hydrophilic member of the present invention has a hydrophilic layer coated with the hydrophilic composition of the present invention on a substrate. Hereinafter, the hydrophilic member will be described.
(Base material)
The substrate (support) 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. However, both can be suitably used. A particularly preferable base material is a glass substrate or a plastic substrate.
As the glass substrate, any glass such as soda glass, lead glass or 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. In addition, the hydrophilic layer can be applied as it is with the base glass, but for the purpose of improving the adhesion of the hydrophilic layer, if necessary, the surface is hydrophilized by oxidation or roughening on one or both sides. Can be applied. 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 plastic substrate used in the present invention is not particularly limited, but polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol And films or sheets of polystyrene, polycarbonate, polymethylpentene, polysulfone, polyether ketone, acrylic, nylon, fluororesin, polyimide, polyetherimide, polyethersulfone, and the like. Of these, polyester films such as polyethylene terephthalate and polyethylene naphthalate are particularly preferred. In addition, in terms of optical properties, it is often preferable to have excellent transparency, but depending on the application, translucent or printed materials may be used. The thickness of the plastic substrate varies depending on the partner to be laminated. 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 base material and the hydrophilic layer, one or both surfaces of the base material can be subjected to surface hydrophilization treatment by oxidation, 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.

(Undercoat layer)
In the present invention, one or more undercoat layers can be provided between the substrate and the hydrophilic layer.
The undercoat layer is preferably obtained by hydrolysis and polycondensation of a composition having at least an alkoxide compound containing an element selected from Si, Ti, Zr and Al and a nonvolatile catalyst.
An undercoat layer obtained by hydrolysis and polycondensation of a composition having at least an alkoxide compound containing an element selected from Si, Ti, Zr, and Al and a nonvolatile catalyst has a crosslinked structure. Such an alkoxide In the present invention, a crosslinked structure formed by hydrolysis and condensation polymerization of a compound is appropriately referred to as a sol-gel crosslinked structure.

  Examples of the alkoxide compound containing an element selected from Si, Ti, Zr and Al include those described above. Among these, Si alkoxides are preferable from the viewpoint of reactivity and availability, and specifically, compounds used for silane coupling agents can be suitably used.

Nonvolatile catalysts used in the undercoat layer are those other than those having a boiling point of less than 20 ° C., in other words, those having a boiling point of 20 ° C. or higher, or those having no boiling point in the first place (such as thermal decomposition, Including those that do not cause changes).
Although it does not specifically limit as a non-volatile catalyst used for this invention, A metal complex (it is also called a metal chelate compound) and a silane coupling agent are mentioned. In addition, although an acid or an alkali is used suitably as a catalyst in this industry, if these also have a boiling point of 20 degreeC or more, they are applicable without a restriction | limiting in particular. For example, hydrochloric acid having a boiling point of −83 ° C. is excluded, but nitric acid having a boiling point of 121 ° C. or phosphoric acid having a decomposition temperature of 213 ° C. is applied as a nonvolatile catalyst in the present invention.
Examples of the metal complex include those described above.

  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, peroxoacid, carboxylic acid, carbohydrazone acid, carboximide A functional group showing acidity such as acid, sulfonic acid, sulfinic acid, sulfenic acid, selenonic acid, selenic acid, selenic acid, telluronic acid and the above alkali metal salts, or a basic functional group showing amino group, etc. The silane coupling agent which has is mentioned.

The undercoat layer is formed by applying a composition having at least the alkoxide compound and the non-volatile catalyst on the base material, heating and drying the base composition, thereby hydrolyzing and polycondensing the composition. Can be formed. The heating temperature and heating time for forming the undercoat layer are not particularly limited as long as the solvent in the sol solution is 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 undercoat layer 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, screen printing Methods such as coating, bar coating, brush coating, and sponge coating can be applied.

  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 and the hydrophilic layer. The adhesion at the interface is extremely high.

  Further, the undercoat layer can be 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.

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 thermal crosslinking agents include polycarboxylic acids such as polyacrylic acid, amine compounds such as polyethyleneimine, ethylene or propylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, polyethylene or polypropylene Polyepoxy compounds such as 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, tolylene diene Isocyanate, hexamethylene diisocyanate, diphenylmethane isocyanate, xylylene diisocyanate Polyisocyanate compounds such as polymethylene polyphenyl isocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene glycol / tolylene diisocyanate addition reaction products, block poly Examples thereof include isocyanate 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 of the undercoat layer is preferably from 0.01 to 20 g / ^{m 2,} 0.1 to 10 g / ^{m 2} is more preferable.

(Layer structure when using hydrophilic members)
The hydrophilic member of the present invention can be used by appropriately adding another layer depending on the purpose, form and place of use. The layer structure added as needed is described below.
1) Adhesive layer When the hydrophilic member of the present invention is used by being affixed onto 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 the 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 a decrease in hydrophilicity due to adhesion of dirt substances. As the protective layer, the release layer or the hydrophilic polymer layer used for the undercoat layer can be used. The protective layer is peeled off after the hydrophilic member is attached to an appropriate substrate.

(Surface free energy)
The hydrophilicity of the hydrophilic layer surface is generally measured by the water droplet contact angle. 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. . 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 tension, the value obtained by converting the contact angle into cos θ on the vertical axis, plot the points of aqueous solutions of various concentrations to obtain a linear relationship, and the surface tension when cos θ = 1, that is, 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 it can be said that the higher the surface free energy value, the higher the hydrophilicity.
A hydrophilic layer whose surface free energy measured by such a method is in the range of 70 mN / m to 95 mN / m, preferably 72 mN / m to 93 mN / m, more preferably 75 mN / m to 90 mN / m is hydrophilic. Excellent performance and good performance.

The hydrophilic member 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 film 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, sufficient hydrophilicity and durability can be obtained, and when the film thickness is 100 μm or less, there is no problem in film forming properties such as cracking, which is preferable.
Preferably the dry coating amount of the hydrophilic layer ^{0.01g / m 2 ~100g / m 2} , more preferably ^{0.02g / m 2 ~80g / m 2} , particularly preferably 0.05g ^/ m 2 ~50g ^/ m ^By setting it to ² , said film thickness can be obtained.
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.

In the hydrophilic member of the present invention, tap water is sprayed on the entire surface of the hydrophilic substrate, and there is almost no adhesion of scales after 7 cycles of drying for 2 hours. This is because when the content of the metal alkoxide compound in the hydrophilic composition of the present application is 12.5 to 22.5% by mass, an appropriate degree of cross-linking is imparted to the hydrophilic composition and water is not easily retained, and scale adheres. It is because it becomes difficult to do.
The present invention also relates to a method for removing scale adhering to the hydrophilic member of the present invention with an acid cleaning solution having a pH of 2 to 4. The hydrophilic member of the present invention can be descaled with an acid cleaning solution having a pH of 2 to 4. This is because calcium and magnesium, which are scale components, are removed by the acid. Even when the hydrophilic member of the present invention is subjected to scale removal with an acid cleaning solution capable of removing scale, the hydrophilic layer has a high residual ratio. This is an effect of the configuration of the present invention.

(Acid cleaning solution)
The scale adhering to the surface of the hydrophilic composition of the present invention can be easily removed with an organic acid cleaning solution.
The acidic cleaning liquid is a cleaning liquid containing an organic acid or an inorganic acid, and is preferably a cleaning liquid containing an organic acid. The pH is preferably a 2 to 4 cleaning solution, and more preferably a pH 3 to 4 cleaning solution.
As the organic acid, for example, any compound that can chelate with calcium such as apple, glycol, sulfamine, tartaric acid, gluconic acid, ascorbic acid, lactic acid, malonic acid, or citric acid can be used. Tartaric acid or citric acid is preferable from the viewpoint of the influence on the human body, the global environment, and water-related equipment materials.
When tartaric acid or citric acid is used as the acid, the concentration of tartaric acid or citric acid used in the cleaning solution is preferably an aqueous solution of about 0.5 g / L to several tens / L, and the acid cleaning solution The pH can be 2-5. In this pH range, tartaric acid or citric acid undergoes a chelate reaction with calcium components such as inorganic calcium and fatty acid calcium in scale, and decomposes them. Tartaric acid and citric acid are also used as food additives, are harmless to the human body, and are friendly to the global environment.
A surfactant is preferably added to the acid cleaning solution in order to chemically remove organic contaminants such as fats and oils. For example, alkyl ether sulfate ethers, fatty acid alkanolamides, alkylamine oxides, polyoxyethylene alkyl ethers. And surfactants that can be used as components of detergents that are commercially available as latent products for kitchens, bathrooms and the like such as fatty acid sodium.

  The hydrophilic member of the present invention can be prepared by a known coating method, and is not particularly limited. For example, a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method, a 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, for example, in the case of expecting an antifogging effect, such as a transparent glass substrate or a transparent plastic substrate, a lens, a prism, a mirror, etc. is there. A glass substrate is preferable.
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 to members having an anti-fogging effect include vehicle rearview mirrors, bathroom mirrors, bathroom antifogging mirrors, toilet mirrors, dental mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, Lenses such as camera lenses, endoscope lenses, illumination lenses, semiconductor lenses, and copier lenses; prisms; window glass for buildings and surveillance towers; other glass for building materials; automobiles, railway vehicles, aircraft, ships, Submersibles, snowmobiles, ropeway gondola, amusement park gondola, various vehicle windows; automobiles, rail cars, aircraft, ships, submersibles, snowmobiles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola Windshields for various vehicles; protective goggles, sports goggles, protective mask shield, sports mask shield, helmet shield, cold Glass food display case; cover glass measuring instruments, and films to be attached to the article surface. Among these, a particularly preferred use is a mirror, and most preferred is a bathroom anti-fog mirror.

In addition, when the antifouling effect is expected for the surface hydrophilic member of the present invention, the base material is, for example, metal, ceramics, wood, stone, cement, concrete, fiber, fabric, in addition to glass and plastic, Any of paper, 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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

[Synthesis example]
[Purification of alkoxy group-containing monomer A]
In a 200 ml three-necked flask, 20.0 g of alkoxysilyl group-containing monomer A and 80.0 g of ethyl acetate are added and dissolved with stirring for 15 minutes. After visually confirming dissolution, 13 g of Wako Gel C-200 (silica gel) was added as an adsorbent and stirred for 30 minutes. 3 g of Celite was pre-coated on Nutsche 7 cm and filtered under reduced pressure. The filtrate was concentrated with an evaporator, and the purified alkoxy group-containing monomer A was taken out.
[Purification of alkoxy group-containing monomer B]
In a 200 ml three-necked flask, 20.0 g of alkoxysilyl group-containing monomer B and 80.0 g of ethyl acetate are added and dissolved with stirring for 15 minutes. After visually confirming dissolution, 7 g of Wako Gel C-200 (silica gel) was added as an adsorbent and stirred for 30 minutes. 3 g of Celite was pre-coated on Nutsche 7 cm and filtered under reduced pressure. The filtrate was concentrated with an evaporator, and the purified alkoxy group-containing monomer B was taken out.

[Synthesis of Compound A]
In a 200 ml three-necked flask, 25 g of acrylamide, 3.5 g of 3-mercaptopropyltrimethoxysilane (alkoxy group-containing monomer A) and 51.3 g of dimethylformamide were placed, and 2,2′-azobis (2,4- 0.25 g of dimethylvaleronitrile) was added to initiate the reaction. After stirring for 6 hours, the mixture was returned to room temperature and poured into 1.5 L of methanol to deposit a solid. The obtained solid was washed with acetone to obtain Compound A.

[Synthesis of Compound B]
Into a 200 ml four-necked flask are placed 20 g of acrylamide, 18 g of N- (3- (triethoxysilyl) propyl) acrylamide (N- (3- (triethoxysilyl) propylamide) (alkoxy group-containing monomer B), and 1-methoxy-2-propanol. Under a nitrogen stream at 60 ° C., 0.15 g of 1,2′-azobis (2-methylpropionic acid) dimethyl was added and stirred for 4 hours, then heated to 70 ° C. and stirred for 4 hours. After cooling to 40 ° C., it was poured into 2 L of n-hexane, and the precipitated solid was collected by filtration and washed with methanol to obtain Compound B.
The weight after drying was 30 g.

[Example 1]
A glass substrate (10 cm × 10 cm, thickness 3 mm) was polished with a cleanser, and the surface was washed. After cleaning, the surface was polished with an alkaline cleaning liquid (Yokohama fats and oils, semi-clean A 5% aqueous solution) and washed with water.
A hydrophilic coating solution (1) having the following composition was prepared. The content of tetramethoxysilane with respect to the total solid content of the hydrophilic coating solution was 12.5% by mass.
The hydrophilic coating liquid (1) having the following composition is coated with a bar using # 3 bar and oven-dried at 180 ° C. for 300 minutes to form a first layer having a dry coating amount of 1.0 g / m ² . Member 1 was obtained.

<Hydrophilic coating solution (1) (polymer concentration 6%)>
・ The following sol-gel preparation (1) 298.74 g
-7.33 g of 5% by weight aqueous solution of the following anionic surfactant
・ Distilled water 193.93g

<Sol-gel preparation liquid (1)>
In 6.64 g of ethyl alcohol, 0.3 g of acetylacetone, 0.34 g of tetraethyl orthotitanate, and 193.98 g of distilled water, 22.94 g of compound A, 6.41 g of compound B, tetramethoxysilane (Tokyo Chemical Industry Co., Ltd.) 3.) 3.67 g was added and mixed, and the mixture was stirred at room temperature for 2 hours to prepare.

[Evaluation]
The following evaluation was performed about the said hydrophilic member. The evaluation results are shown in Table 2.

[Contact angle]
The contact angle meter DropMaster500 manufactured by Kyowa Interface Science Co., Ltd. was used to determine the water droplet contact angle on the surface of the hydrophilic film formed on the substrate using ultrapure water.

[Adhesion test]
A cellophane tape 3 cm was stuck on the test piece, peeled off after rubbing with an index finger 20 times, and it was visually confirmed whether the hydrophilic layer was peeled off.
○: No peeling △: Partial peeling ×: Full peeling

[Water resistance]
Tap water was sprayed so that the entire surface of the glass substrate was wet, and dried in a vertical state with a dryer at 40 ° C. for 2 hours. After repeating this cycle 7 times, it was allowed to stand for 24 hours and visually confirmed for water resistance (scale adhesion).
○: Almost no adhesion ×: Adhesion

[Delase removal]
An acid cleaning solution containing tartaric acid (pH = 2, 3, 4, 5) was sprayed so that the entire surface of the glass substrate after the scale adhesion test was wet. After spraying, it was rubbed several times with a sponge and washed with distilled water. After washing, it was naturally dried and visually checked for the presence of scale. The acid cleaning solutions at pH = 2, 3, 4, and 5 were mixed with 100 mL of 2M tartaric acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 10 mL, 70 mL, 160 mL, and 195 mL of 2M NaOH (manufactured by Wako Pure Chemical Industries, Ltd.), Prepared by diluting to 1 L with distilled water.
○: Removed △: Almost removed ×: Cannot be removed

[Membrane remaining rate after removal of scale]
The hydrophilic film remaining on the glass substrate from which the scale had been removed with the acid cleaning solution was measured by reflection IR (NICOLET6700 FT-IR manufactured by Thermo SCIENTIFIC). The film residual ratio was determined by calculating the decreasing rate of the peak intensity (C═O of amide) of 1600 cm−1 to 1700 cm−1 peculiar to the compounds A and B.
○: 70% or more remaining △: 50% to 70%
×: Less than 50%

[Examples 2 to 4, Comparative Examples 1 to 9]
Except having changed the usage-amount of the compound A in Example 1, the compound B, and tetramethoxysilane into the quantity of Table 1, operation similar to Example 1 was performed and the hydrophilic members 2-9 were obtained.
The acid cleaning solution of pH = 5 was sprayed on the surfaces of the hydrophilic compositions of Examples 1 to 4 and Comparative Examples 1 to 9 so that the entire surface of the glass substrate was wetted, and the scale removal property was confirmed.

Claims (9)

(A) at least one hydrophilic polymer having a structural unit represented by the following general formula (I-1) and a structural unit represented by the following general formula (I-2); and (B) the following general formula At least one hydrophilic polymer having a structural unit represented by (II-2) and having a partial structure represented by the following general formula (II-1) at the end of the polymer chain; and (C) Si , An alkoxide compound containing an element selected from Ti, Zr, and Al, and (C) an alkoxide compound containing an element selected from Si, Ti, Zr, and Al with respect to the total solid content of the hydrophilic composition. A hydrophilic composition containing 12.5 to 22.5% by mass.

(In the general formulas (I-1) and (I-2), R ^{101 to} R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. P represents an integer of 1 to 3, and L ¹⁰¹ and L ¹⁰² represent Each independently represents a single bond or a polyvalent organic linking group, x and y represent a composition ratio, x represents a number such that 0 <x <100, y represents 0 <y <100, and A ¹⁰¹ 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 ) ( _Rb ), -N ( _Ra ) ( _Rb ) ( _Rc ), -N ( _Ra ) ( _Rb ) ( _Rc ) (R _g ), —PO ₃ (R _e ) (R _f ), —OPO ₃ (R _e ) (R _f ), or PO ₃ (R _d ) (R _e ), where R _a , R _b and R _c independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, 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, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion.)

(In the general formula (II-1) and ^(II-2), .q representing each is R 201 ^{to R 205} independently represent a hydrogen atom or a hydrocarbon group represents an integer of 1 to ^{3, L 201} and ^{L 202} are Each independently represents a single bond or a polyvalent organic linking group, A ²⁰¹ 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 O ₃ represents the _{(R d) (R e)} . _Here, R a, _{R b} and _{R c} each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, _{R d} represents a linear 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, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen atom. Represents an ion, an inorganic anion, or an organic anion.) The (C) alkoxide compound containing an element selected from Si, Ti, Zr, and Al is a compound represented by the following general formula (V-1) or general formula (V-2): The hydrophilic composition according to claim 1.
_{^{(R 20) m -Z- (OR}} 21) 4-m (V-1)
Al- (OR ²² ) ₃ (V-2)
(R ²⁰ represents a hydrogen atom, an alkyl group or an aryl group, R ²¹ and R ²² represent an alkyl group or an aryl group, Z represents Si, Ti or Zr, and m represents an integer of 0 to 2.)   (A) at least one hydrophilic polymer having a structural unit represented by the following general formula (I-1) and a structural unit represented by the following general formula (I-2); Mass ratio with at least one hydrophilic polymer having a structural unit represented by the general formula (II-2) and having a partial structure represented by the following general formula (II-1) at the end of the polymer chain (A) / (B) is 80 / 20-90 / 10, The hydrophilic composition of Claim 1 or 2 characterized by the above-mentioned.   The hydrophilic composition according to claim 1, further comprising (D) a metal catalyst.   Furthermore, (E) surfactant is contained, The hydrophilic composition in any one of Claims 1-4 characterized by the above-mentioned.   A hydrophilic member comprising a hydrophilic layer on which a hydrophilic composition according to any one of claims 1 to 5 is coated on a substrate.   The hydrophilic member according to claim 6, wherein the substrate is a glass substrate.   The method of removing the water scale adhering to the hydrophilic member in any one of Claims 6-7 with the acid cleaning liquid of pH 2-4.   An antifogging mirror for bathrooms using the hydrophilic member according to any one of claims 6 to 7.