JP2008225466A - Anti-fogging and anti-reflection optical product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical product having superior water resistance and film strength in water absorption, while having both of anti-fog and anti-reflective effects. <P>SOLUTION: The anti-fogging and anti-reflection optical product includes a first water-absorbing layer, a high refractive index layer having a polycondensate of metal alkoxide hydrolyzate, and a second water-absorbing layer, sequentially from a substrate side on the substrate of the optical product. The first and the second water-absorbing layers are layers obtained by curing a composition comprising (a) a hydrophilic polymer containing a silane coupling group, and (c) a metal complex catalyst. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an optical article such as a lens, a filter, and a mirror, and particularly relates to an optical article excellent in antifogging property and antireflection property.

  Products and members having a resin film surface are used in a wide range of fields, and are used after being processed and imparted with functions according to the purpose. However, those surfaces generally exhibit hydrophobicity and lipophilicity due to the inherent properties of the resin. Therefore, if oil or the like adheres to these surfaces as a soiling substance, they cannot be easily removed, and accumulation may significantly reduce the functions and characteristics of products / members having the surface. It was. In addition, in products / members exposed to high humidity conditions or rain, there is a problem that the light transmission is hindered by irregular reflection of light in products / members having a transparent function due to adhesion of water droplets. . Even in products / members having an inorganic surface such as glass or metal, it cannot be said that the antifouling property against adhesion of dirt substances such as oil is sufficient, and the antifogging property due to adhesion of water droplets is not sufficient. Especially in glass for automobiles and glass for building materials, there are cases where hydrophobic pollutants such as urban dust, combustion products such as carbon black contained in exhaust gas of automobiles, oils and fats, sealant elution components adhere, In many cases, it is difficult to secure a field of view through adhesion (reflection in the case of a mirror) due to adhesion, and it has been strongly demanded to impart antifouling and antifogging functions.

From the viewpoint of antifouling properties, assuming that the soiling substance is an organic substance such as oil, it is necessary to reduce the interaction with the material surface, that is, to make it hydrophilic or to make it oil repellent in order to prevent soiling. In addition, for anti-fogging properties, it is necessary to provide extended wettability (that is, hydrophilicity) that spreads the attached water droplets uniformly on the surface, or to impart water repellency that facilitates removal of the attached water droplets. Therefore, many of the antifouling materials and antifogging materials currently under investigation depend on hydrophilicity and water / oil repellency.
Conventionally proposed surface treatment methods for hydrophilization, such as etching treatment and plasma treatment, are highly hydrophilized, but their effects are temporary and maintain the hydrophilized state for a long time. I can't. A surface hydrophilic coating film using a hydrophilic graft polymer as one of hydrophilic resins has also been proposed (Non-patent Document 1). According to this report, although this coating film has a certain degree of hydrophilicity, it cannot be said that the compatibility with the substrate is sufficient, and higher durability is required.

  As another member having a surface hydrophilic function, the use of titanium oxide as a photocatalyst has been conventionally known. This is based on the oxidative decomposition function and the hydrophilization function of organic matter by light irradiation. For example, in Patent Document 1, when a photocatalyst-containing layer is formed on the surface of a substrate, the surface becomes highly hydrophilic in response to photoexcitation of the photocatalyst. If this technology is applied to various composite materials such as glass, lenses, mirrors, exterior materials, and water circulation members, these composite materials have excellent antifogging and antifouling functions. It has been reported that it can be granted. Components coated with titanium oxide on the glass surface are used as self-cleaning materials in window glass for building materials and windshields for automobiles. It was inevitable that its properties deteriorated due to accumulation of dirt over a long period of time. Moreover, it cannot be said that the film strength is sufficient, and it is necessary to improve durability. Self-cleaning films with a titanium oxide layer on a plastic substrate are also used in automotive side mirrors, etc., but there is a need for hydrophilic materials that do not have sufficient film strength and have better wear resistance. It was done.

  On the other hand, silicone compounds and fluorine compounds are mainly used as antifouling and antifogging materials based on water and oil repellency. For example, Patent Document 2 discloses an antifouling material having a substrate surface coated with terminal silanol organopolysiloxane, Patent Document 3 discloses a material having a silane compound having a polyfluoroalkyl group, and an optical thin film and A combination of a fluoroacrylate and a copolymer of a monomer having an alkoxysilane group is disclosed in Patent Document 4. However, antifouling materials using these silicone compounds and fluorine compounds have insufficient antifouling properties, are difficult to remove dirt such as fingerprints, sebum, sweat, cosmetics, etc., and compounds with low surface energy such as fluorine and silicone In the surface treatment by, there is a concern about the deterioration of the function over time, and the development of antifouling and antifogging members having excellent durability has been desired.

Patent Document 5 discloses a first water-absorbing film having a water-absorbing polymer such as PVA or polyacrylic acid on a substrate of an optical article, and a polycondensate of a hydrolyzate of a metal alkoxide located outside the first water-absorbing film. An anti-fogging anti-reflection optical article is disclosed in which a high refractive index thin film having a second water-absorbing film having a water-absorbing polymer such as PVA or polyacrylic acid, which is positioned on the outer layer, is laminated. Although excellent in effect and antireflection effect, water resistance and film strength at the time of water absorption are insufficient, and improvement has been desired.
International Publication No. 96/29375 Pamphlet JP-A-4-338901 Japanese Patent Publication No. 6-29332 Japanese Patent Laid-Open No. 7-16940 JP 11-109105 A Chemical Daily, January 30, 1995

  An object of the present invention is to provide an optical article that is excellent in water resistance and film strength at the time of water absorption while having an antifogging effect and an antireflection effect.

In view of the above-mentioned problems of the prior art, as a result of conducting research while focusing on the characteristics of the water-absorbing polymer contained in the water-absorbing layer, the present inventors have developed a water-absorbing polymer containing a hydrophilic polymer containing a silane coupling group. A layer or a water-absorbing layer containing a crosslinked structure formed by hydrolysis and condensation polymerization of a hydrophilic polymer containing a silane coupling group and a metal alkoxide (hereinafter also referred to as “water-absorbing film”) It has been found that the problems of the prior art (water resistance and film strength upon water absorption) can be solved while providing a fogging effect and an antireflection effect. Moreover, when a metal complex catalyst was used, it discovered that while the said hydrolysis and polycondensation occurred, the storage stability of the coating liquid for water absorbing layer formation improved, and it came to this invention.
That is, the present invention is as follows.

上記一般式（１）で表される構造を有する親水性ポリマーは、構造単位（ｉ）、（ii）で表されるポリマーユニットの少なくとも一方の末端に、構造単位（iii）で表されるシランカップリング基を有する。
一般式（１）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶はそれぞれ独立に水素原子又は炭化水素基を表し、ｍは０、１または２を表し、ｘ及びｙは組成比を表し、ｘは０＜ｘ＜１００、ｙは０＜ｙ＜１００であり、ｘ＋ｙ＝１００となる数を表す。Ｌ¹、Ｌ²、Ｌ³はそれぞれ独立に単結合又は有機連結基を表し、Ｙ¹、Ｙ²はそれぞれ独立に−Ｎ（Ｒ⁷）（Ｒ⁸）、−ＯＨ、−ＮＨＣＯＲ⁷、−ＣＯＮＨ₂、−ＣＯＮ（Ｒ⁷）（Ｒ⁸）、−ＣＯＲ⁷、−ＣＯ₂Ｍ又は−ＳＯ₃Ｍを表し、ここで、Ｒ⁷、Ｒ⁸はそれぞれ独立に水素原子又はアルキル基を表し、Ｍは水素原子、アルカリ金属、アルカリ土類金属又はオニウムを表す。
６． 前記ポリマー側鎖にシランカップリング基を有する親水性ポリマーが、少なくとも下記一般式（２）で表される構造を有する化合物である前記４に記載の防曇反射防止光学物品。

一般式（２）で表される化合物は、一般式（Ｉ−ａ）及び（Ｉ−ｂ）で示される構造単位を有する。
一般式（Ｉ−ａ）及び（Ｉ−ｂ）中、Ｒ^１〜Ｒ^８はそれぞれ独立に水素原子又は炭素数８以下の炭化水素基を表す。Ｌ^１は単結合又は多価の有機連結基を表す。Ｌ^２は単結合又は−ＣＯＮＨ−、−ＮＨＣＯＮＨ−、−ＯＣＯＮＨ−、−ＳＯ_２ＮＨ−、−ＳＯ_３−からなる群より選択される構造を１つ以上有する多価の有機連結基を表す。ｍは１〜３の整数を表す。ｘ、ｙは一般式（Ｉ−ａ）で表される構造単位と一般式（Ｉ−ｂ）で表される構造単位の組成比を表し、０＜ｘ＜１００、０＜ｙ＜１００であり、ｘ＋ｙ＝１００となる数を表す。Ｘ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）、または−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または直鎖、分岐または環状のアルキル基を表し、Ｒ_ｄは、直鎖、分岐また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または直鎖、分岐または環状のアルキル基、アルカリ金属、アルカリ土類金属、またはオニウムを表し、Ｒ_ｇは、直鎖、分岐または環状のアルキル基、ハロゲン原子、無機アニオン、または有機アニオンを表す。
７．さらに、第一吸水性層および／または第二吸水性層に、ｄ）コロイダルシリカを含有することを特徴とする前記１〜６のいずれかに記載の防曇反射防止光学物品。 1. Antifogging antireflection optical system comprising a first water-absorbing layer, a high refractive index layer having a polycondensate of a hydrolyzate of metal alkoxide, and a second water-absorbing layer in order from the substrate side on the substrate of the optical article. An article, wherein the first and second water-absorbing layers are layers formed by curing a composition containing (a) a hydrophilic polymer containing a silane coupling group and (c) a metal complex catalyst. Anti-fogging anti-reflection optical article characterized.
2. The antifogging antireflection optical article according to claim 1, wherein the first and second water absorbing layers further contain (b) a metal alkoxide compound selected from Si, Ti, Zr, and Al.
3. The metal complex catalyst (c) is 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 alcohol, enolic active hydrogen compound 3. The antifogging antireflection optical article as described in 1 or 2 above, which is composed of an oxo or hydroxy oxygen compound selected from the group consisting of
4). 4. The antifogging antireflection optical article according to any one of 1 to 3, wherein the hydrophilic polymer containing a silane coupling group contains a silane coupling group at a polymer terminal or a side chain.
5. 5. The antifogging antireflection optical article as described in 4 above, wherein the hydrophilic polymer having a silane coupling group at the polymer terminal is a compound having a structure represented by at least the following general formula (1).

The hydrophilic polymer having the structure represented by the general formula (1) is a silane represented by the structural unit (iii) at least one terminal of the polymer unit represented by the structural units (i) and (ii). Has a coupling group.
In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, m represents 0, 1 or 2, x and y Represents a composition ratio, x represents 0 <x <100, y represents 0 <y <100, and represents a number satisfying x + y = 100. L ¹ , L ² and L ³ each independently represents a single bond or an organic linking group, and Y ¹ and Y ² each independently represent —N (R ⁷ ) (R ⁸ ), —OH, —NHCOR ⁷ and —CONH. ₂ , —CON (R ⁷ ) (R ⁸ ), —COR ⁷ , —CO ₂ M or —SO ₃ M, wherein R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group; Represents a hydrogen atom, an alkali metal, an alkaline earth metal or onium.
6). 5. The antifogging antireflection optical article according to 4, wherein the hydrophilic polymer having a silane coupling group in the polymer side chain is a compound having a structure represented by at least the following general formula (2).

The compound represented by the general formula (2) has structural units represented by the general formulas (Ia) and (Ib).
In general formulas (Ia) and (Ib), R ^{1 to} R ⁸ each independently represents a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y represent the composition ratio of the structural unit represented by the general formula (Ia) and the structural unit represented by the general formula (Ib), and 0 <x <100 and 0 <y <100. , X + y = 100. X is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, 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 linear, branched or cyclic alkyl group, a halogen atom, An inorganic anion or an organic anion is represented.
7). Furthermore, d) colloidal silica is contained in a 1st water absorption layer and / or a 2nd water absorption layer, The antifogging antireflection optical article in any one of said 1-6 characterized by the above-mentioned.

  ADVANTAGE OF THE INVENTION According to this invention, the optical article excellent in water resistance and the film | membrane intensity | strength at the time of water absorption can be provided, providing the anti-fogging effect and the antireflection effect.

(1) The antifogging antireflection optical article of the present invention is a high refractive index layer having a first water-absorbing layer and a polycondensate of a hydrolyzate of metal alkoxide in order from the substrate side on the substrate of the optical article, An anti-fogging antireflection optical article provided with a second water absorbing layer, wherein the first and second water absorbing layers are (a) a hydrophilic polymer containing a silane coupling group, (c) a metal complex catalyst, It is the layer formed by hardening the composition containing this.
(2) The anti-fogging antireflection optical article of the present invention has a high refraction having a first water-absorbing layer and a polycondensate of a hydrolyzate of metal alkoxide in order from the substrate side on the substrate of the optical article. An anti-fogging antireflection optical article provided with a rate layer and a second water-absorbing layer, wherein the first and second water-absorbing layers are (a) a hydrophilic polymer containing a silane coupling group, (b) Si It is a layer formed by curing a composition containing a metal alkoxide compound selected from Ti, Zr, and Al, and (c) a metal complex catalyst.
According to the mode (1), the water absorption can be further improved while maintaining a high film strength as compared with the prior art.
According to the form of (2), a hydrophilic polymer having a silane coupling group (preferably a hydrophilic polymer having a silane coupling group at the terminal or side chain) and Si, Ti, Zr, Al are selected. The water-absorbing layer having a cross-linked structure formed by hydrolysis and condensation polymerization of the alkoxide of the element is a high-strength film because the organic-inorganic composite film having a high-density cross-linked structure is formed. Specifically, a hydrophilic polymer is dissolved in an appropriate solvent and stirred in the presence of a metal complex catalyst, whereby hydrolysis and polycondensation proceed in the system, and a sol-like water-absorbing film composition is obtained. The resulting cross-link is formed by coating the base material or lower layer with the substrate and drying it to have a hydrophilic functional group on the surface of the base material or lower layer and reacting the metal alkoxide with a functional group capable of reacting with it An organic-inorganic composite film having a structure is formed. With this high-density and strong organic-inorganic composite film having this crosslinked structure, it is considered that the resulting water-absorbent layer has excellent wear resistance and can maintain high surface hydrophilicity for a long period of time. In the water-absorbing layer in the present invention, since the hydrophilic polymer forming the layer contains a silane coupling group, the hydrophilic polymer is taken into the sol-gel film by covalent bonding, and the hydrophilic polymer escapes from the surface of the layer even in water immersion. Excellent water resistance and less film breakage during water absorption.
Furthermore, moisture in the atmosphere absorbed by the second water-absorbing film passes through the high refractive index thin film mainly composed of a polycondensate of a hydrolyzate of metal alkoxide and is absorbed by the first water-absorbing film. It will be done. On the contrary, when the moisture absorbed in the first water-absorbing film is released to the outside of the film, it passes through the high refractive index thin film and is once absorbed in the second water-absorbing film, and then the atmosphere. To be released. By such a process, the phenomenon that moisture and substances in the moisture remain at the interface between the high refractive index thin film and the first and second water-absorbing films does not occur.

[First and second water-absorbing layers]
In the present invention, the first and second water-absorbing layers are layers formed by curing a composition containing (a) a hydrophilic polymer containing a silane coupling group and (c) a metal complex catalyst. (B) A metal alkoxide compound selected from Si, Ti, Zr, and Al is used.

(A) Hydrophilic polymer containing a silane coupling group (a) The hydrophilic polymer containing a silane coupling group in the present invention (hereinafter also referred to as “(a) silane-modified hydrophilic polymer”) is a structural unit thereof. The log P of a certain monomer is preferably −3 to 2, and more preferably −2 to 0. In this range, good hydrophilicity can be obtained.
Here, log P is the logarithm of the value of the octanol / water partition coefficient (P) of a compound calculated using the software PCModels developed by Medicinal Chemistry Project, Pomona College, Claremont, California and available from Daylight Chemical Information System Inc. It is.
Although it does not specifically limit as a silane coupling group, It is preferable to represent with a following formula.
(R ¹ ) _m (OR ² ) _3-m -Si-
In said formula, R < ¹ >, R < ² >, m is synonymous with R < ¹ >, R < ² >, m in general formula (I) mentioned later, respectively, A preferable range is also the same.
In the present invention, from the viewpoint of further improving the properties of the water-absorbing film, it is preferable that a silane coupling group is introduced into the terminal or side chain of the hydrophilic polymer.
The molecular weight of the hydrophilic polymer is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and most preferably 1,000 to 30,000.

<(A-1) Hydrophilic polymer having a silane coupling group at the polymer terminal (hereinafter referred to as “(a-1) terminal silane-modified hydrophilic polymer”)>
In the present invention, it is preferable that (a-1) the terminal silane-modified hydrophilic polymer contains at least a hydrophilic polymer having a structure represented by the following general formula (1).

The hydrophilic polymer compound having the structure represented by the general formula (1) is represented by the structural unit (iii) at at least one of both ends of the polymer unit represented by the structural units (i) and (ii). As long as it has a silane coupling group, the other terminal may have this functional group, and may have a hydrogen atom or a functional group having a polymerization initiating ability.
In the general formula (1), m represents 0, 1 or 2, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group (preferably carbon 1 to 8) are expressed. Examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group (preferably having a carbon number of 8 or less) is preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
R ^{1 to} R ⁶ 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 constituted by a bond between a substituent and an alkylene group, and here, 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, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy 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-N-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- Alkoxycarbonyl amino group, N- aryl -N- aryloxycarbonylamino group, a formyl group, an acyl group, a 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-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group phosphono group ( —PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonate group), dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ), alkylaryl Phosphono group (—PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphonophenyl group), phosphonooxy group (-O O ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonophenyl group), dialkyl phosphonooxy group (-OPO ₃ (alkyl) _2), diaryl phosphonooxy group (-OPO ₃ (aryl) ₂₎ , An alkylarylphosphonooxy group (—OPO (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and a conjugated base group thereof (hereinafter referred to as an alkylphosphonatooxy group), A monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatooxy group), morpholino group, cyano group, nitro group, aryl group, alkenyl group, alkynyl group Can be mentioned.

Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl 2 group, xylyl group, mesityl group, cumenyl group. Group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methyl Aminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl , It can be exemplified cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, a phosphonophenyl phenyl group. Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like. Examples of alkynyl group include ethynyl group, 1- A propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, etc. are mentioned. Examples of G ¹ in the acyl group (G ¹ CO ⁻ ) include hydrogen and the above alkyl groups and aryl groups.

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

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

L ¹ and L ² represent a single bond or an organic linking group. Here, the organic linking group refers to a polyvalent linking group composed of a nonmetallic atom, and specifically includes 0 to 60 carbon atoms, 0 to 10 nitrogen atoms, and 0 to 50 carbon atoms. It consists of up to 0 oxygen atoms, 0 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. More specific examples of the linking group include the following structural units or those formed by combining them.

L ³ represents a single bond or an organic linking group. Here, the organic linking group refers to a polyvalent linking group composed of a nonmetallic atom, and specific examples thereof include those similar to the above L ¹ and L ² . Among them, a particularly preferable structure is — (CH ₂ ) _n —S— (n is an integer of 1 to 8).

Y ¹ and Y ² represent —NHCOR ⁷ , —CONH ₂ , —CON (R ⁷ ) (R ⁸ ), —COR ⁷ , —OH, —CO ₂ M or —SO ₃ M, R ⁷ and R ⁸ each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having 1 to 8 carbon atoms). In addition, with respect to —CON (R ⁷ ) (R ⁸ ), R ⁷ and R ⁸ may be bonded to each other to form a ring, and the formed ring is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may be a heterocycle containing an atom. R ⁷ and R ⁸ may further have a substituent, and the substituents that can be introduced here are the same as the substituents that can be introduced when R ^{1 to} R ⁶ are alkyl groups. Can be listed.

Specific examples of R ⁷ and R ⁸ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, s-butyl, and t-butyl. Preferred examples include a group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, and cyclopentyl group.
Examples of M include a hydrogen atom; an alkali metal such as lithium, sodium and potassium; an alkaline earth metal such as calcium and barium; or an onium such as ammonium, iodonium and sulfonium.
Further, specifically as _{^{Y 1, Y 2, -NHCOCH 3}} , -CONH 2, -COOH, -SO 3 - NMe 4 +, a morpholino group, etc. are preferable.

  x and y represent a composition ratio (molar ratio), where x is 0 <x ≦ 100, y is 0 ≦ y <100, and x + y = 100. More preferably, x is 50 <x ≦ 100, y is 0 ≦ y <50, x is 70 <x ≦ 100, and y is further preferably 0 ≦ y <30.

  (A-1) The molecular weight of the terminal silane-modified hydrophilic polymer is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and most preferably 1,000 to 30,000.

  Specific examples 1 to 12 of the (a-1) terminal silane-modified hydrophilic polymer that can be suitably used in the present invention are shown below, but the present invention is not limited thereto.

<Synthesis method>
As the hydrophilic polymer having a silane coupling group at the polymer terminal in the present invention, for example, (a-1) a terminal silane-modified hydrophilic polymer is a radical polymerizable monomer represented by the following structural units (i) and (ii): And can be synthesized by radical polymerization using a silane coupling agent having chain transfer ability in radical polymerization represented by the following structural unit (iii). Since the silane coupling agent 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.
Although this reaction mode is not particularly limited, bulk reaction, solution reaction, suspension reaction and the like may be performed in the presence of a radical polymerization initiator or irradiation with a high-pressure mercury lamp.

Further, in the polymerization reaction, the amount of the structural unit represented by (iii) is controlled, and in order to effectively suppress the homopolymerization of the structural unit with the structural unit (i) or (ii), A polymerization method using an addition method, a sequential addition method, or the like is preferably performed.
The reaction ratio of the structural units (i) and (ii) with respect to the structural unit (iii) is not particularly limited, but the structural units (i) and (ii) are 0 with respect to 1 mol of the structural unit (iii). From the viewpoint of suppressing side reactions and improving the yield of the hydrolyzable silane compound, the range of 1 to 45 mol is more preferable, and the range of 5 to 40 mol is preferable. Most preferred.

In the structural units (i), (ii) and (iii), R ^{1 to} R ⁶ , L ^{1 to} L ³ , Y ¹ , Y ² and m are as defined in the general formula (1). These compounds are commercially available and can also be easily synthesized.

  (A-1) As a radical polymerization method for synthesizing a terminal silane-modified hydrophilic polymer, any of conventionally known methods can be used. Specifically, general radical polymerization methods include, for example, New Polymer Experimental Science 3, Polymer Synthesis and Reaction 1 (Edited by the Society of Polymer Science, Kyoritsu Shuppan), New Experimental Chemistry Course 19, Polymer Chemistry (I) (The Chemical Society of Japan, Maruzen), Materials Engineering, Synthetic Polymer Chemistry (Tokyo Denki University Press), etc., can be applied.

  The (a-1) terminal silane-modified hydrophilic polymer may be a copolymer of each structural unit described above and another monomer as described later. Examples of other monomers used include acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic imide, etc. A well-known monomer is also mentioned. By copolymerizing such monomers, various physical properties such as film forming property, film strength, hydrophilicity, hydrophobicity, solubility, reactivity, and stability can be improved.

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

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

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

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

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

  The proportion of these other monomers used in the synthesis of the copolymer needs to be sufficient to improve various physical properties, but if the proportion is too large, the function as a water-absorbing film is insufficient. Therefore, there is a concern that the advantage of adding the (a-1) terminal silane-modified hydrophilic polymer cannot be sufficiently obtained. Therefore, the preferred total proportion of other monomers in the (a-1) terminal silane-modified hydrophilic polymer is 80% by weight or less, more preferably 50% by weight or less.

  (A-1) The terminal silane-modified hydrophilic polymer may be used alone or in combination of two or more.

Moreover, it is also preferable to add the following hydrophilic polymer in combination with the (a-1) terminal silane-modified hydrophilic polymer in the composition.
Acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, vinyls or hydrolysates thereof, styrenes, acrylic acid or salts thereof, methacrylic acid or salts thereof, acrylonitrile, maleic anhydrides, maleic imides And polymers made from monomers such as
Among these monomers, monomers having an amino group, an ammonium group, a hydroxyl group, a sulfonamide group, a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, an ether group, particularly an ethyleneoxy group are preferable.
In addition to the above, hydrophilic polymers having a urethane bond, an amide bond, or a urea bond in the main chain can also be used.

  Specific examples of acrylic esters include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, hydroxybenzyl acrylate, dihydroxyphenethyl acrylate, furfuryl acrylate , Tetrahydrofurfuryl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenylcarbonyloxy) ethyl acrylate, diethylene glycol ethyl ether acrylate, 2-ethoxyethyl acrylate and the like.

  Specific examples of methacrylic acid esters include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl. Examples include methacrylate, sulfamoylphenyl methacrylate, 2- (hydroxyphenylcarbonyloxy) ethyl methacrylate, diethylene glycol ethyl ether methacrylate, 2-ethoxyethyl methacrylate, and methoxytetraethylene glycol monomethacrylate.

  Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N, N-dimethylacrylamide, N- Examples include methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide and the like.

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

Specific examples of vinyls include vinyl acetate and vinyl pyrrolidone.
Specific examples of styrenes include trimethoxystyrene, carboxystyrene, styrene sulfone or a salt thereof.

  (A-1) The terminal silane-modified hydrophilic polymer is preferably 0 as a non-volatile component in the composition used for forming the water-absorbing film in the present invention from the viewpoint of balancing the film property and hydrophilicity. It is used in a range of ˜50 mass%, more preferably 0 to 20 mass%.

<(A-2) Hydrophilic polymer having silane coupling group in polymer side chain (hereinafter referred to as “(a-2) side chain silane-modified hydrophilic polymer”)>
In the present invention, the (a-2) side chain silane-modified hydrophilic polymer preferably has a hydrophilic polymer represented by the following general formula (2). The polymer represented by the general formula (2) has structural units represented by the general formulas (Ia) and (Ib).

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

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

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

Aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfur group Sulfamoyl group, N, N- dialkylsulfamoyl group, N- aryl sulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group phosphono group _(-PO 3 _{H 2} ) And conjugated base groups thereof (hereinafter referred to as phosphonate groups), dialkyl phosphono groups (—PO ₃ (alkyl) ₂ ), diaryl phosphono groups (—PO ₃ (aryl) ₂ ), alkylaryl phosphono groups (— PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (—PO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphonophenyl group), phosphonooxy group (-OPO H ₂₎ and its conjugated base group (hereinafter referred to as phosphonophenyl group), dialkyl phosphonooxy group _(-OPO 3 _(alkyl) 2), diaryl phosphonooxy group _(-OPO 3 _(aryl) 2), alkyl An arylphosphonooxy group (—OPO (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as an alkylphosphonatooxy group), monoaryl Examples include a phosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatooxy 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 chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyl group. Oxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N- Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxy Rubonirubuchiru group,

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

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

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

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

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

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

x and y represent the composition ratio of the structural unit represented by the general formula (Ia) represented by the general formula (2) and the structural unit represented by the general formula (Ib). x and y are 0 <x <100, 0 <y <100, and represent numbers that satisfy x + y = 100. x is preferably in the range of 50 <x <100, and more preferably in the range of 70 <x <100. y is preferably in the range of 0 <y <50, more preferably in the range of 0 <y <30.
Here, the structural units constituting the polymer chain (Ia) and (Ib) may all be the same or may include a plurality of different structural units, In that case, the composition ratio of the structural unit corresponding to the general formula (Ia) and the structural unit corresponding to the general formula (Ib) is preferably in the above range.

  (A-2) The molecular weight of the side chain silane-modified hydrophilic polymer is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, and most preferably 1,000 to 200,000. .

  Specific examples of (a-2) side chain silane-modified hydrophilic polymers [Exemplary compounds (1) to (20)] are shown below together with their mass average molecular weights (M.W.). It is not limited to. In addition, the polymer of the specific example shown below means that it is a random copolymer in which each structural unit described is contained by the described molar ratio.

Each of the compounds for synthesizing the (a-2) side chain silane-modified hydrophilic polymer of the present invention is commercially available or can be easily synthesized.
(A-2) Any conventionally known method can be used as the radical polymerization method for synthesizing the side chain silane-modified hydrophilic polymer. Specifically, general radical polymerization methods are, for example, new polymer experimental science 3, polymer synthesis and reaction 1 (edited by the Society of Polymer Science, Kyoritsu Shuppan), new experimental chemistry course 19, polymer chemistry (I) (Edited by Chemical Society of Japan, Maruzen), Materials Engineering Course, Synthetic Polymer Chemistry (Tokyo Denki University Press), etc., and these can be applied.

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

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

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

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

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

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

  The proportion of these other monomers used for the synthesis of the copolymer needs to be a sufficient amount for improving various physical properties, but it has a sufficient function as a water-absorbing film, and is on the (a-2) side. In order to sufficiently obtain the advantage of adding the chain silane-modified hydrophilic polymer, the ratio is preferably not too large. Therefore, the preferred total proportion of other monomers in the (a-2) side chain silane-modified hydrophilic polymer is preferably 80% by mass or less, and more preferably 50% by mass or less.

  The (a-2) side chain silane-modified hydrophilic polymer according to the present invention is preferably 5 to 95% by mass with respect to the nonvolatile component of the water-absorbent film composition of the present invention, from the viewpoint of curability and hydrophilicity. More preferably, it is contained in the range of 15 to 90 mass%, most preferably 20 to 85 mass%. These may be used alone or in combination of two or more. Here, the non-volatile component refers to a component excluding a volatile solvent.

(B) Metal alkoxide compound containing an element selected from Si, Ti, Zr and Al (b) Metal alkoxide compound containing an element selected from Si, Ti, Zr and Al ( (Hereinafter referred to as “(b) metal alkoxide”) is preferably a compound represented by the following general formula (3). In forming a crosslinked structure in order to cure the water-absorbing film, (a Applying and drying a composition obtained by mixing a) a silane-modified hydrophilic polymer, (b) a crosslinking component represented by the following general formula (3), and (c) a metal complex catalyst described later on the substrate surface. preferable. The crosslinking component represented by the following general formula (3) is a compound having a polymerizable functional group in its structure and serving as a crosslinking agent, and (a) the silane-modified hydrophilic polymer, or (B) A cross-linked structure can be formed by condensation polymerization between metal alkoxide components.

In General Formula (3), R ^a represents a hydrogen atom, an alkyl group or an aryl group, R ^b represents an alkyl group or an aryl group, X represents Si, Al, Ti or Zr, and m represents 0 to 2. Represents an integer.
When R ^a and R ^b represent an alkyl group, the alkyl group preferably has 1 to 4 carbon atoms.
When R ^a and R ^b represent an aryl group, the aryl group preferably has 6 to 14 carbon atoms.
The alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, and a mercapto group.
This compound is a low molecular compound and preferably has a molecular weight of 1000 or less.

Specific examples of the crosslinking component represented by the general formula (3) are given below, but the present invention is not limited thereto.
In the case where X is Si, that is, those containing silicon in the hydrolyzable compound include, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxy Silane, ethyltriethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltri Methoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diph Alkenyl dimethoxysilane, mention may be made of diphenyl diethoxy silane.
Among these, tetramethoxysilane, tetraethoxysilane, methyltolumethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxy are particularly preferable. Examples include silane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.

In addition, when X is Al, that is, examples of the hydrolyzable compound containing aluminum include, for example, trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, tetraethoxy aluminate and the like. it can.
When X is Ti, i.e., those containing titanium include, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl triethoxy titanate. Examples thereof include methoxy titanate, methyl triethoxy titanate, ethyl triethoxy titanate, diethyl diethoxy titanate, phenyl trimethoxy titanate, and phenyl triethoxy titanate.
In the case where X is Zr, that is, those containing zirconium include, for example, zirconates corresponding to the compounds exemplified as those containing titanium.

  (B) The metal alkoxide is preferably used in the range of 5 to 80% by mass, more preferably 20 to 70% by mass as a non-volatile component in the composition for forming a water-absorbing film according to the present invention. Moreover, (b) metal alkoxide may be used independently or may be used together 2 or more types.

<Other cross-linking agents>
In the present invention, in addition to the (b) metal alkoxide, as long as the effects of the present invention are not impaired, (b) cross-linking with known heat, acid or radical other than the metal alkoxide to improve the properties of the water-absorbing film. A cross-linking agent that forms can be used in combination.
Examples of “other crosslinking agents” that can be used in the present invention include those described in “Crosslinking agent handbook”, Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha (1981). The number of functional groups of the crosslinking agent that can be used in the present invention is not particularly limited as long as it is 2 or more and can effectively crosslink (a) the silane-modified hydrophilic polymer and / or (b) the metal alkoxide component. However, aldehyde ketone can be used as a crosslinking agent according to the present invention as long as it has at least one functional group.
Specific thermal crosslinking agents include α, ω-alkanes such as 1,2-ethanedicarboxylic acid and adipic acid or alkenedicarboxylic acids, 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetra. Polycarboxylic acids such as carboxylic acid, trimellitic acid, polyacrylic acid, polyamine compounds such as 1,2-ethanediamine, diethylenediamine, diethylenetriamine, polyethyleneimine, ethylene or propylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether , Nonaethylene tylene glycol diglycidyl ether, polyethylene or polypropylene glycol glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylo Polyepoxy compounds such as lepropane triglycidyl ether, sorbitol polyglycidyl ether,

  Oligoalkylene or polyalkylene glycol such as ethylene glycol, propylene glycol, diethylene glycol, and tetraethylene glycol, polyhydroxy compounds such as trimethylolpropane, glycerin, pentaerythritol, sorbitol, and polyvinyl alcohol, glyoxal, terephthalaldehyde, acetaldehyde, benzaldehyde, etc. Polyaldehyde compounds, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane isocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, cyclohexyl diisocyanate, cyclohexanephenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate , Polyisocyanate compounds such as polypropylene glycol / tolylene diisocyanate addition reaction products, block polyisocyanate compounds, silane coupling agents such as tetraalkoxysilane, and metal cross-linking agents such as acetylacetonate of aluminum, copper and iron (III) And polymethylol compounds such as trimethylol melamine and pentaerythritol, and polythiol compounds such as dithioerythritol, 1,2,6-hexanetriol trithioglycolate, and pentaerythritol tetrakis (2-mercaptoacetate). Among these thermal crosslinking agents, a water-soluble crosslinking agent is preferable from the viewpoint of easy preparation of the coating solution and prevention of a decrease in hydrophilicity of the produced water-absorbing film.

  The other crosslinking agent is preferably used in the composition used for forming the water-absorbing film in the present invention in the range of 0 to 30% by mass, more preferably 0 to 15% by mass as a nonvolatile component. Such crosslinking agents may be used alone or in combination of two or more, but may be 50% by mass or less based on (b) metal alkoxide which is the main crosslinking component of the present invention. preferable.

(C) Metal complex catalyst The metal complex catalyst used in the formation of the water-absorbing film of the present invention is the above-mentioned form (1) (the first and second water-absorbing layers are hydrophilic (a) containing a silane coupling group). In the form of a layer formed by curing a composition containing a functional polymer (c) a metal complex catalyst), hydrolysis and polycondensation of silane coupling groups in the hydrophilic polymer are promoted, It plays a role in causing a bond, and the form of (2) (the first and second water-absorbing layers are formed from (a) a hydrophilic polymer containing a silane coupling group, (b) Si, Ti, Zr, and Al. Hydrolysis and polycondensation of a metal alkoxide compound selected from Si, Ti, Zr, and Al in the form of a layer formed by curing a composition containing a selected metal alkoxide compound and (c) a metal complex catalyst) Promote and parent Bonding with the aqueous polymer can occur. Particularly preferred metal complex catalysts include metal elements selected from groups 2A, 3B, 4A and 5A of the periodic table and β-diketones, ketoesters, hydroxycarboxylic acids or esters thereof, amino alcohols, and enolic active hydrogen compounds. It is a metal complex composed of a selected oxo or hydroxy oxygen-containing compound.
Among constituent metal elements, 2A group elements such as Mg, Ca, St and Ba, 3B group elements such as Al and Ga, 4A group elements such as Ti and Zr, and 5A group elements such as V, Nb and Ta are preferable. , Each forming a complex with excellent catalytic effect. Of these, complexes obtained from Zr, Al and Ti are excellent and preferred.

  In the present invention, the oxo- or hydroxy-oxygen-containing compound constituting the ligand of the metal complex is a β diketone such as acetylacetone (2,4-pentanedione) or 2,4-heptanedione, methyl acetoacetate, acetoacetic acid Ketoesters such as ethyl and butylacetoacetate, 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-heptanone, ketoalcohols such as 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N-methyl- Monoethanolamine, diethanolamine Amino alcohols such as ethanol, 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) The compound which has a substituent is mentioned.

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

  Although the description of the counter salt of the metal complex described above is omitted in this specification, the type of the counter salt is arbitrary as long as it is a water-soluble salt that maintains the neutrality of the charge as the complex compound, such as nitrate, Salt forms such as halogenates, sulfates, phosphates, etc., that ensure stoichiometric neutrality are used. The behavior of the metal complex in the silica sol-gel reaction is described in detail in J. Sol-Gel. Sci. And Tec. 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 catalysts 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. R compounds substituted with other elements or substituents, acidic compounds such as 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.
Said metal complex catalyst can be easily obtained as a commercial item, and can also be obtained by a well-known synthesis method, for example, reaction of each metal chloride and alcohol.
The metal complex catalyst is used in the hydrophilic composition of the present invention as a non-volatile component, preferably in the range of 0 to 50 mass%, more preferably 5 to 25 mass%. Moreover, (c) a metal complex catalyst may be used independently or may be used together 2 or more types.

  The composition of the first water absorbing layer and the second water absorbing layer may be the same or different.

<Surfactant>
In the present invention, it is preferable to use a surfactant in order to improve the coated surface state of the water-absorbing film-forming composition. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants. Surfactant may be used independently and may be used in combination of 2 or more type.

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

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

The cationic surfactant used in the present invention is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
The amphoteric surfactant used in the present invention is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric acid esters, and imidazolines.

  Of the above surfactants, the term “polyoxyethylene” can be read as “polyoxyalkylene” such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. These surfactants can also be used.

  More preferable surfactants include fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of such fluorosurfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates; amphoteric types such as perfluoroalkyl betaines; Cation type such as trimethylammonium salt; perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl Nonionic types such as an oligomer containing a group, a hydrophilic group and a lipophilic group, and a urethane containing a perfluoroalkyl group and a lipophilic group. Moreover, the fluorine-type surfactant described in each gazette of Unexamined-Japanese-Patent No. 62-170950, 62-226143, and 60-168144 is also mentioned suitably.

Surfactant can be used individually or in combination of 2 or more types.
The content of the surfactant is preferably 0.001 to 10% by mass and more preferably 0.01 to 5% by mass with respect to the total solid content of the composition.

<Inorganic fine particles>
The composition for forming a water-absorbing film of the present invention may contain inorganic fine particles in order to improve the strength of the cured film of the water-absorbing 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. Within the above range, it is preferable that it can be stably dispersed in the water-absorbing film and the film strength and hydrophilicity can be sufficiently maintained.
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 water-absorbing film forming 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 water absorbing 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 water-absorbent film, an antioxidant can be added to the coating liquid for forming the water-absorbent film. 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>
The water-absorbing film forming composition of the present invention is appropriately added with an organic solvent when forming a water-absorbing film on the base material or the lower layer in order to ensure the formation of a uniform coating film on the base material or the lower layer. It is also effective to do.
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 in a range that does not cause a problem due to the relationship of VOC (volatile organic solvent), and the amount is preferably 0 to 50% by mass, more preferably based on the entire coating solution at the time of water-absorbing film formation Is in the range of 0-30% by weight.

<Polymer compound>
In order to adjust the film physical properties of the water-absorbing film, various polymer compounds can be added to the composition for forming the water-absorbing film of the present invention as long as the hydrophilicity is not impaired. 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.

(Formation of water-absorbing film)
The water-absorbing film in the present invention is formed by dispersing or dissolving each of the necessary components described above in a solvent to prepare a coating solution, and curing the coating film on an appropriate substrate by heat. Can do.

  For example, (a) a silane-modified hydrophilic polymer, preferably (b) a cross-linking component such as a metal alkoxide is dissolved in a solvent and stirred well, so that these components are hydrolyzed and polycondensed to form an organic-inorganic composite. A body sol solution is formed, and this sol solution becomes a coating solution for forming a water-absorbing film according to the present invention, whereby a water-absorbing layer having high hydrophilicity and high film strength is formed. In the preparation of the organic-inorganic composite sol solution, in order to promote hydrolysis and polycondensation reaction, the above-mentioned (c) metal complex catalyst is used in combination, but the catalyst is essential when trying to obtain practically preferable reaction efficiency. It is. It is also preferable to use an acidic catalyst or a basic catalyst in combination.

  Preparation of the water-absorbing film coating solution is carried out by adding (a) a silane-modified hydrophilic polymer, and preferably (b) a crosslinking component such as a metal alkoxide, in a solvent such as ethanol, and then adding the above catalyst containing a metal complex catalyst. It can be carried out by stirring. The reaction temperature is from room temperature to 80 ° C., and the reaction time, that is, the time for continuing the stirring is preferably in the range of 1 to 72 hours. A composite sol solution can be obtained.

  The solvent used in preparing the water-absorbing film coating liquid composition is not particularly limited as long as it can uniformly dissolve and disperse these, and examples thereof include aqueous solvents such as methanol, ethanol, and water. preferable.

  As described above, the preparation of the organic-inorganic composite sol liquid (water absorbent film coating liquid composition) for forming the water absorbent film 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 water-absorbing film coating liquid composition according to the present invention.

  As described above, various additives can be used in the water-absorbing film coating liquid composition according to the present invention depending on the purpose as long as the effects of the present invention are not impaired. For example, as detailed above, a surfactant can be added to improve the uniformity of the coating solution.

  A hydrophilic surface can be formed by applying the water-absorbing film coating solution composition prepared as described above to the substrate surface and drying. The water-absorbing film of the present invention can be formed by preparing a plurality of coating solutions in which the same or different components are dispersed or dissolved in the same or different solvents, and repeating a plurality of coatings and dryings.

  Various methods can be used as the coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

Moreover, it is preferable that the film thickness of a 1st water absorbing film exists in the range of 1-20 micrometers. Preferably it is 2-15 micrometers, Most preferably, it is 5-15 micrometers, Most preferably, it is 5-10 micrometers. If the thickness of the water absorbing film is less than 1 μm, a sufficient antifogging effect cannot be obtained. On the other hand, when the thickness exceeds 20 μm, there arises a problem that a poor adhesion or a uniform film quality cannot be obtained.
The refractive index of the first water absorbing film is preferably 1.0 to 1.6. Within this range, a good antireflection effect can be obtained.

Furthermore, it is preferable that the film thickness of the second water absorbing film is in the range of 1 to 20 μm. Preferably it is 2-15 micrometers, Most preferably, it is 5-15 micrometers, Most preferably, it is 5-10 micrometers. If the thickness of the water absorbing film is less than 1 μm, a sufficient antifogging effect cannot be obtained. On the other hand, when the thickness exceeds 20 μm, there arises a problem that a poor adhesion or a uniform film quality cannot be obtained.
The refractive index of the second water absorbing film is preferably 1.0 to 1.6. Within this range, a good antireflection effect can be obtained.

[High refractive index thin film]
The high refractive index layer (hereinafter sometimes referred to as “high refractive index thin film”) used in the present invention can also play a role of bonding the first water absorbing film and the second water absorbing film at the same time. Further, since it is more flexible than a general inorganic thin film, it can follow the expansion of the water absorbing film due to moisture absorption, and the high refractive index thin film is not cracked by the expansion of the water absorbing film.

  The film thickness of the high refractive index thin film is preferably in the range of 0.01 to 0.05 μm. When the thickness of the high refractive index thin film is greater than 0.01 μm, a sufficient antireflection effect is obtained, and when the thickness is 0.05 μm or less, a uniform high refractive index thin film can be easily obtained.

The high refractive index thin film formed as the outer layer of the first water-absorbing film has a polycondensate of a hydrolyzate of metal alkoxide. As a suitable compound of the metal alkoxide, compounds represented by the following formulas (I) and (II) are used.
M (OR) _a (I) and M (OR) _n (X) _an (II)

  Here, M is an atom selected from the group consisting of Si, Al, Ti, Zr, Ca, Fe, V, Sn, Li, Be, B, and P, R is an alkyl group, and X is An alkyl group, an alkyl group having a functional group, or halogen, a is a valence of M, and n is an integer from 1 to a.

  As said X, the alkyl group which has a carbonyl group, a carboxyl group, an amino group, a vinyl group, or an epoxy group is suitable.

Particularly good metal alkoxides include aluminum alkoxides such as Al (OC ₂ H ₅ ) ₃ and Al (OCH (CH ₃ ) ₂ ) ₃ , Ti (OC ₂ H ₅ ) ₃ and Ti (OCH (CH ₃ ) _2. ) Titanium alkoxides such as ₃ , Zr (OC ₂ H ₅ ) ₃ and zirconium alkoxides such as Zr (OCH (CH ₃ ) ₂ ) ₃ , Ca (OC ₂ H ₅ ) ₂ , Fe (OC ₂ H ₅ ) ₃ , V ((O-iso-C ₃ H ₇ ) ₄ , Sn (Ot-C ₄ H ₉ ) ₄ , Li (OC ₂ H ₅ ), Be (OC ₂ H ₅ ) ₂ , B (OC ₂ H ₅ ) ₃ , P (OC ₂ H ₅ ) ₃ , P (OCH ₃ ) _{3 and the} like are used.

  The high refractive index thin film is formed by applying a solution containing one or more of a metal alkoxide, a hydrolyzate of metal alkoxide, and a low molecular weight condensate of the hydrolyzate onto the first water-absorbing film. Can be formed.

Further, the refractive index (n ₁ ) of the high refractive index thin film from the metal alkoxide or the composite of the metal alkoxide and the inorganic material is preferably higher than the refractive indexes of the first and second water-absorbing films, particularly 1.7 or more. It is preferable that

The optical film thickness (n ₁ d ₁ ) of the high-refractive index thin film is preferably 300 nm or less in that moisture easily moves to the water-absorbing film through the high-refractive index thin film.

Further, from the viewpoint of producing a good antireflection effect, the optical film thickness n ₁ d ₁ of the high refractive index film is expressed by the following formula (3) or formula (4).
_{0.8 × kλ 1/2 ≦ n} 1 d 1 ≦ 1.2 × kλ 1/2 (3)
_{0.8 × kλ 1/4 ≦ n} 1 d 1 ≦ 1.2 × kλ 1/4 (4)
(K is a positive odd number, n ₁ is the refractive index of the high refractive index layer, d ₁ is the film thickness of the high refractive index layer, and λ ₁ is a design wavelength selected in the range of 400 to 900 nm). Is preferred.

The thickness optical thickness of the second water-absorbing film (n ₂ d _2), from the viewpoint of causing a good anti-reflection effect, the following formula _{0.8 × kλ 2/4 ≦ n} 2 d 2 ≦ 1. _{2 × kλ 2/4 (5} )
(K is a positive odd number, n ₂ is the refractive index of the second water-absorbing film, d ₂ is the film thickness of the second water-absorbing film, and λ ₂ is a design wavelength selected in the range of 400 to 900 nm) It is preferable to set to.

The first and second water-absorbing films and the high-refractive index thin film are made of Ti, Ce, Zr, Sn, Sb, Ta, and Si, respectively, for controlling the refractive index (n) as necessary. metal oxides and inorganic fine particles of metal fluoride MgF ₂ or the like selected may be added.

〔Base material〕
The base material of the antifogging and antireflection optical article of the present invention is a transparent base material that requires an antifogging effect and an antireflection effect, and glass, plastic, etc. can be suitably used as the material.
Applications for which the anti-fogging and anti-reflection optical article of the present invention can be applied include vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, camera lenses , Lenses such as endoscope lenses, illumination lenses, semiconductor lenses, copier lenses; prisms; window glass of buildings and surveillance towers; Gondolas, amusement park gondola, spacecraft-like vehicle windows; automobiles, rail vehicles, aircraft, ships, submersibles, snow vehicles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola, spacecraft Windshields for various vehicles; protective goggles, sports goggles, protective mask shield, sports mask shield, helmet shield, frozen food display case Including a cover glass instrumentation, and films to be attached to the article surface; glass.

  The substrate is preferably an inorganic substrate such as glass or ceramic, or any substrate having a surface made of a polymer resin. The resin substrate is a resin itself, a substrate whose surface is coated with a resin, The surface layer includes any composite material composed of a resin layer. Typical examples of the resin itself include film base materials such as scattering prevention films, design films, and corrosion-resistant films; resin base materials such as signboards and soundproof walls on highways. Examples of the substrate coated with resin on the surface include painted plates for automobile casings, painted building materials, laminated plates with a resin film adhered to the surface, substrates treated with a primer, substrates coated with a hard coat, etc. It is given as a representative example. Typical examples of the composite material whose surface layer is a resin layer include a resin sealing material having a back surface provided with an adhesive layer, a reflection mirror, and the like.

(Undercoat layer)
Furthermore, one or more undercoat layers can be provided for the purpose of enhancing the adhesion between the water-absorbing film and the substrate. As the material for the undercoat layer, a hydrophilic resin or water-dispersible latex can be used.
Examples of hydrophilic resins include polyvinyl alcohol (PVA), cellulosic resins (methyl cellulose (MC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), etc.), chitins, chitosans, starch, and ether bonds. Examples include resins [polyethylene oxide (PEO), polyethylene glycol (PEG), polyvinyl ether (PVE), etc.], resins having a carbamoyl group [polyacrylamide (PAAM), polyvinyl pyrrolidone (PVP), etc.], and the like. Moreover, the polyacrylic acid salt which has a carboxyl group, maleic acid resin, alginate, gelatins, etc. can also be mentioned.
Among these, at least one selected from polyvinyl alcohol resins, cellulose resins, resins having an ether bond, resins having a carbamoyl group, resins having a carboxyl group, and gelatins is preferable, and in particular, polyvinyl alcohol (PVA) Of these, gelatin resins are preferred.

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

[Surface free energy]
Since the water absorbing layer in the present invention is formed including a hydrophilic polymer, it is excellent in hydrophilicity.
The hydrophilicity of the surface of the water-absorbent layer is generally measured by a 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, and there is a limit to the mutual comparison of hydrophilicity. . On the other hand, as a method for evaluating the hydrophilicity of the solid surface in more detail, there is a measurement of surface free energy. Various methods have been proposed. In the present invention, as an example, the surface free energy was measured using the Zisman plot method. Specifically, an aqueous solution of an inorganic electrolyte such as magnesium chloride uses the property that the surface tension increases with the concentration. After measuring the contact angle in air and at room temperature using the aqueous solution, the horizontal axis indicates the surface of the aqueous solution. Take the value obtained by converting the contact angle into cos θ on the vertical axis and plot the points of aqueous solutions of various concentrations to obtain a linear relationship. Cos θ = 1, that is, the surface tension when the contact angle = 0 °, It is a measurement method defined as the surface free energy of a solid. The surface tension of water is 72 mN / m, and the higher the surface free energy value, the higher the hydrophilicity.
A water-absorbing layer having a surface free energy measured by such a method is preferably in the range of 70 mN / m to 95 mN / m, more preferably 72 mN / m to 93 mN / m, and even more preferably 75 mN / m to 90 mN / m. Excellent hydrophilicity and good performance.

  The water-absorbing film of the present invention can be obtained by applying the water-absorbing film-forming coating liquid composition on an appropriate substrate or lower layer, heating and drying to form a hydrophilic layer. The heating temperature and heating time for forming the water-absorbing layer are not particularly limited as long as the solvent and the time in which 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.

[Example 1]
Preparation of the first water-absorbing film Float plate glass (thickness 2 mm) which is the most common transparent plate glass is prepared, the surface of the plate glass is hydrophilized by glow treatment, and then the water-absorbing layer coating solution having the following composition is applied to the bar Then, it was oven-dried at 100 ° C. for 10 minutes to form a first water-absorbing film. The water-absorbing film obtained was transparent and the film thickness was about 5 μm. The refractive index of the water absorbing film was 1.45.

<First water absorbing layer coating solution>
・ 500g of the following sol-gel preparation
-20% by weight aqueous solution of colloidal silica dispersion (Snowtech C)
100g
-5% by weight aqueous solution of the following anionic surfactants
30g
・ Purified water 450g

Anionic surfactant

<Sol-gel preparation solution>
200 g of ethyl alcohol, 10 g of acetylacetone, 10 g of tetraethyl orthotitanate and 100 g of purified water, 8 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and a hydrophilic polymer having a silane coupling group at the following terminals (Exemplary Compound 1) (Terminal type)) 4 g was mixed and stirred at room temperature for 2 hours to prepare.

<Synthesis of hydrophilic polymer having a silane coupling group at the terminal>
A three-necked flask was charged with 25 g of acrylamide, 3.5 g of 3-mercaptopropyltrimethoxysilane, and 51.3 g of dimethylformamide and heated to 65 ° C. under a nitrogen stream to produce 2,2′-azobis (2,4-dimethylvaleronitrile). Was added to start the reaction. After stirring for 6 hours, the mixture was returned to room temperature and poured into 1.5 L of ethyl acetate, and a solid precipitated. Thereafter, filtration was performed, and the product was sufficiently washed with ethyl acetate and dried (yield 21 g). It was confirmed by GPC (polyethylene oxide standard) that the polymer had a mass average molecular weight of 4000. The viscosity of the 5% aqueous solution was 2.5 cPs, and the functional group density of the hydrophilic group was 13.4 meq / g.

Preparation of a high refractive index film A high refractive index film coating solution having the following composition was applied to a glass substrate having a water absorbing film formed thereon by bar coating and oven-dried at 100 ° C. for 10 minutes to form a high refractive index film. . The obtained high refractive index film had an optical film thickness of 30 nm and a refractive index of 1.75.

Titanium tetraisopropoxide 200g
800 g of isobutyl acetate

Preparation of the second water-absorbing film A water-absorbing layer coating solution having the same composition as the first water-absorbing film except that the hydrophilic polymer having a silane coupling group at the terminal is changed to the exemplified compound 3 (terminal type). A bar was applied onto the film and oven-dried at 100 ° C. for 10 minutes to form a second water-absorbing film. The optical film thickness (product of the refractive index n of the water absorbing film and the film thickness d) of the obtained water absorbing film was adjusted to 135 nm. The refractive index of the second water absorbing film was 1.45.

The following performance test was performed on the optical article prepared as described above. The results are shown in Table 4.
(1) Antireflection property: Transmittance measurement of light at 550 nm (○ when transmittance is 96% or more, × when less than 96%)
(2) Anti-fogging property: In the daytime, at room temperature of 25 ° C., on a plastic cup filled with hot water of 60 ° C., when an optical article is placed and water vapor is applied, the fogging condition and its change are classified into four levels according to the following criteria. And sensory evaluation.
A: No cloudiness is observed even after 5 hours.
A: No cloudiness is observed within 5 hours.
Δ: Haze is observed at 5 min. X: Cloudy (3) Water resistance: The sponge was reciprocated 10 times in water, and the residual film ratio was measured from the weight change before and after that.
(4) Film breakage upon water absorption: The presence or absence of film breakage after standing for 500 hours in an environment of 60 ° C. and 90% was evaluated. The presence or absence of film breakage was determined by antifogging properties.
A: No cloudiness is observed.
○: Partly cloudy, but recovers within 5 seconds and no cloudiness is seen.
Δ: Cloudy and takes 1 minute or more to recover.
×: Cloudy

[Comparative Example 1]
An optical article was prepared in the same manner as in Example 1 except that the hydrophilic polymer of the first and second water absorbing films was changed to polyacrylic acid.

[Examples 2 to 5]
An optical article was prepared in the same manner as in Example 1 except that the hydrophilic polymers of the first and second water-absorbing films were changed to the compounds shown in Table 1.

In addition, the LogP value (here, the LogP value of the monomer as a structural unit) of the hydrophilic polymer used in this example is shown below.
Exemplary Compound 1 (terminal type) LogP = -0.61
Illustrative compound 2 (terminal type) LogP = -0.30
Exemplary compound 3 (terminal type) LogP = -0.17
Exemplary Compound 5 (terminal type) LogP = -0.23
Exemplified compound 9 (terminal type) LogP = -1.55

Example 6
Preparation of the first water-absorbing film Float plate glass (thickness 2 mm) which is the most common transparent plate glass is prepared, the surface of the plate glass is hydrophilized by glow treatment, and then the water-absorbing layer coating solution having the following composition is applied to the bar Then, it was oven-dried at 100 ° C. for 10 minutes to form a first water-absorbing film. The water-absorbing film obtained was transparent and the film thickness was about 5 μm. The refractive index of the water absorbing film was 1.47.

<First water-absorbing film coating solution>
・ 500g of the following sol-gel preparation
・ 30 g of 5% by weight aqueous solution of the following anionic surfactant
・ Purified water 450g

<Sol-gel preparation solution>
In 200 g of ethyl alcohol, 10 g of acetylacetone, 10 g of tetraethyl orthotitanate and 100 g of purified water, 8 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and a hydrophilic polymer having a silane coupling group in the side chain (Exemplary Compound 1 ( Side difference type)) 4 g were mixed and stirred at room temperature for 2 hours to prepare.

Preparation of a high refractive index film A high refractive index film coating solution having the following composition was applied to a glass substrate having a water absorbing film formed thereon by bar coating and oven-dried at 100 ° C. for 10 minutes to form a high refractive index film. . The obtained high refractive index film had an optical film thickness of 30 nm and a refractive index of 1.60.

200g of aluminum isopropoxide
800 g of isobutyl acetate

Preparation of second water-absorbing film A water-absorbing layer coating solution having the same composition as the first water-absorbing film was used except that the hydrophilic polymer having a silane coupling group in the side chain was changed to the exemplified compound 11 (side chain type). A bar was coated on the refractive index film and oven-dried at 100 ° C. for 10 minutes to form a second water-absorbing film. The optical film thickness (product of the refractive index n of the water absorbing film and the film thickness d) of the obtained water absorbing film was adjusted to 135 nm. The refractive index of the second water absorbing film was 1.40.

[Comparative Example 2]
An optical article was prepared in the same manner as in Example 6 except that the hydrophilic polymer of the first and second water-absorbing films was changed to polyvinyl alcohol.

[Examples 7 to 10]
An optical article was prepared in the same manner as in Example 6 except that the hydrophilic polymers of the first and second water absorbing films were changed to the compounds shown in Table 2.

In addition, the LogP value (here, the LogP value of the monomer as a structural unit) of the hydrophilic polymer used in this example is shown below.
Illustrative compound 1 (side chain type) LogP = -0.64
Illustrative compound 11 (side chain type) LogP = -0.66
Exemplary Compound 4 (Side Chain Type) LogP = -1.4
Illustrative Compound 5 (Side Chain Type) LogP = -0.32
Exemplary compound 10 (side chain type) LogP = -0.64
Exemplified compound 19 (side chain type) LogP = -1.4

[Examples 11 to 15]
An optical article was prepared in the same manner as in Example 1 except that tetraethyl orthotitanate and acetylacetone in the sol-gel preparation were changed to the compounds shown in Table 3.

Example 16
The anti-fogging antireflection optical article prepared in Example 1 was incorporated as a telescope eyepiece, moved to a room of -5 ° C to 30 ° C and 80% humidity, and the performance of the telescope at that time was checked. As a result, there was no inconvenience in observation due to cloudiness of the eyepiece, which is observed with a normal telescope.

Example 17
Preparation of the first water-absorbing film Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, the surface of the plate glass is hydrophilized by glow treatment, and then a water-absorbing layer coating solution having the following composition is applied to the bar. And oven-dried at 150 ° C. for 30 minutes to form a first water-absorbing film. The obtained water-absorbing film was transparent and the film thickness was 8 μm. The refractive index of the water absorbing film was 1.45.

<First water absorbing layer coating solution>
・ 500 g of the following polymer preparation (1)
・ 10 g of 5% by weight aqueous solution of the following anionic surfactant

<Polymer preparation liquid (1)>
50 g of a hydrophilic polymer (Exemplary Compound (1)) having a silane coupling group at its terminal is mixed in 9 g of ethyl alcohol, 0.4 g of acetylacetone, 0.5 g of tetraethyl orthotitanate, and 450 g of purified water, and the mixture is stirred for 2 hours at room temperature. The polymer preparation liquid (1) was prepared by stirring.

Preparation of High Refractive Index Film A high refractive index film coating solution having the following composition was bar-coated on a glass substrate on which water absorption was formed, and oven-dried at 100 ° C. for 10 minutes to form a high refractive index film. The obtained high refractive index film had an optical film thickness of 30 nm and a refractive index of 1.75.

200g of aluminum isopropoxide
800 g of isobutyl acetate

Preparation of the second water-absorbing film The water-absorbing layer coating solution having the same composition as that of the first water-absorbing film was used on the high refractive index film except that the hydrophilic polymer having a silane coupling group at the terminal was changed to the exemplified compound (3). And a second water-absorbing film was formed by oven drying at 150 ° C. for 30 minutes. The optical film thickness of the obtained water-absorbing film (the product of the refractive index n and the film thickness d of the water-absorbing film) was adjusted to 135 nm. The second water-absorbing film had a refractive index of 1.45 and a film thickness of 6 μm.

  Evaluation was performed in the same manner as in Example 1. The results are shown in Table 8.

[Examples 18 to 20]
An optical article was prepared in the same manner as in Example 17 except that the film thickness of the first water-absorbing film was changed to the film thickness shown in Table 5. The results are shown in Table 8.

[Examples 21 to 23]
An optical article was prepared in the same manner as in Example 17 except that the hydrophilic polymers of the first and second water-absorbing films were changed to the compounds and film thicknesses shown in Table 6.

[Examples 24-26]
An optical article was prepared in the same manner as in Example 22 except that tetraethyl orthotitanate and acetylacetone in the polymer preparation liquid (1) were changed to the compounds shown in Table 7.

Claims (7)

  Antifogging antireflection optical system comprising a first water-absorbing layer, a high refractive index layer having a polycondensate of a hydrolyzate of metal alkoxide, and a second water-absorbing layer in order from the substrate side on the substrate of the optical article. An article, wherein the first and second water-absorbing layers are layers obtained by curing a composition containing (a) a hydrophilic polymer containing a silane coupling group and (c) a metal complex catalyst. Anti-fogging anti-reflection optical article characterized.   The antifogging antireflection optical article according to claim 1, wherein the first and second water absorbing layers further contain (b) a metal alkoxide compound selected from Si, Ti, Zr, and Al.   The metal complex catalyst (c) is a metal element selected from groups 2A, 3B, 4A and 5A of the periodic table and a β-diketone, ketoester, hydroxycarboxylic acid or ester thereof, amino alcohol, enolic active hydrogen compound. The antifogging antireflection optical article according to claim 1 or 2, wherein the optical article is composed of an oxo or hydroxy oxygen compound selected from the group consisting of:   The antifogging antireflection optical article according to any one of claims 1 to 3, wherein the hydrophilic polymer containing a silane coupling group contains a silane coupling group at a polymer terminal or a side chain. 5. The antifogging antireflection optical article according to claim 4, wherein the hydrophilic polymer having a silane coupling group at the polymer terminal is a compound having at least a structure represented by the following general formula (1).

The hydrophilic polymer having the structure represented by the general formula (1) is a silane represented by the structural unit (iii) at least one terminal of the polymer unit represented by the structural units (i) and (ii). Has a coupling group.
In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, m represents 0, 1 or 2, x and y Represents a composition ratio, x represents 0 <x <100, y represents 0 <y <100, and represents a number satisfying x + y = 100. L ¹ , L ² and L ³ each independently represents a single bond or an organic linking group, and Y ¹ and Y ² each independently represent —N (R ⁷ ) (R ⁸ ), —OH, —NHCOR ⁷ and —CONH. ₂ , —CON (R ⁷ ) (R ⁸ ), —COR ⁷ , —CO ₂ M or —SO ₃ M, wherein R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group; Represents a hydrogen atom, an alkali metal, an alkaline earth metal or onium. The antifogging antireflection optical article according to claim 4, wherein the hydrophilic polymer having a silane coupling group in the polymer side chain is a compound having a structure represented by at least the following general formula (2).

The compound represented by the general formula (2) has structural units represented by the general formulas (Ia) and (Ib).
In general formulas (Ia) and (Ib), R ^{1 to} R ⁸ each independently represents a hydrogen atom or a hydrocarbon group. L ¹ represents a single bond or a polyvalent organic linking group. L ² represents a single bond or a polyvalent organic linking group having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. m represents an integer of 1 to 3. x and y represent the composition ratio of the structural unit represented by the general formula (Ia) and the structural unit represented by the general formula (Ib), and 0 <x <100 and 0 <y <100. , X + y = 100. X is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e) ) (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ). Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, 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 linear, branched or cyclic alkyl group, a halogen atom, An inorganic anion or an organic anion is represented.   Furthermore, d) colloidal silica is contained in a 1st water absorption layer and / or a 2nd water absorption layer, The antifogging antireflection optical article in any one of Claims 1-6 characterized by the above-mentioned.