JP2008088259A - Hydrophilic film-forming composition and hydrophilic member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrophilic film-forming composition giving a surface hydrophilic layer excellent in hydrophilicity, also having good durability, and excellent in transparency and preservation stability, and also a hydrophilic member equipped with a hydrophilic membrane on its substrate material surface and excellent in surface hydrophilicity and its lasting property. <P>SOLUTION: This hydrophilic film-forming composition is characterized by containing (A) a compound having a ring structure having a hydrophilic group and selected from a 5-membered structure and 6-membered structure in its molecule, and also having a silane-coupling group and (B) an alkoxide compound containing an element selected from Si, Ti, Zr and Al, and the hydrophilic member obtained by applying the hydrophilic film-forming composition is also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hydrophilic film forming composition and a surface hydrophilic member. Specifically, the present invention relates to a hydrophilic film-forming composition that provides a hydrophilic surface layer excellent in hydrophilicity, durability, transparency, and storage stability, and a surface hydrophilic member that includes the hydrophilic surface layer.

  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 and antifogging materials currently under investigation depend on hydrophilicity, water repellency and 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 a monomer having a perfluoroacrylate and an alkoxysilane group. Patent Document 4 discloses a member in which the above copolymer is formed on an optical thin film mainly composed of silicon dioxide. 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 As for the surface treatment by, there is a concern about deterioration of the function with time, and development of antifouling / antifogging members having excellent durability 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 Chemical Daily, January 30, 1995

  An object of the present invention is a hydrophilic film (hereinafter referred to as “high surface energy, antifogging property, antifouling property”) having excellent durability, transparency and storage stability. Another object of the present invention is to provide a hydrophilic film-forming composition that provides a hydrophilic layer) and a surface hydrophilic member formed by the composition.

As a result of intensive studies, the present inventors have found that the above problem can be solved by a coating obtained by crosslinking and curing a specific cyclic compound having a hydrophilic group and a silane coupling group in the molecule with a specific alkoxide compound. The headline and the present invention were completed.
That is, the hydrophilic film-forming composition of the present invention has (A) a ring structure selected from a 5-membered ring structure and a 6-membered ring structure in the molecule, and the ring structure has a hydrophilic group. In addition, a compound having a silane coupling group in the molecule [hereinafter, appropriately referred to as (A) a specific hydrophilic compound] and (B) an alkoxide compound containing an element selected from Si, Ti, Zr, and Al [ Hereinafter, (B) is referred to as a specific alkoxide as appropriate].
The hydrophilic film-forming composition of the present invention preferably further contains (C) a hydrophilic polymer and / or (D) colloidal silica from the viewpoint of improving hydrophilicity.

  As the specific hydrophilic compound (A) in the present invention, a hydrophilic saccharide, starch derivative, or cellulose derivative having a 5-membered ring structure having a hydrophilic group and / or a 6-membered ring structure having a hydrophilic group is used as a silane. Examples thereof include compounds modified with a coupling group. The mechanism for obtaining a highly hydrophilic and high-strength film by using a specific hydrophilic compound (A) typified by such a hydrophilic saccharide is not clear, but saccharides, cellulose derivatives, etc. Since one unit has many hydrophilic groups and forms a ring structure, the hydrophilic group exists toward the outside of the ring structure. When formed, it is considered that the coating surface shows high hydrophilicity. Furthermore, by introducing a silane coupling group into the saccharide molecule, high reactivity with (B) specific alkoxide coexisting as a crosslinking component is expressed, and (A) and (B) are crosslinked. In addition, (B) the component (B) is also cross-linked by hydrolysis and condensation polymerization of the specific alkoxide, and a high-density cross-linked structure is formed. Therefore, the cured film has excellent strength and durability. It is considered to be expressed.

  The hydrophilic member of the present invention is obtained by coating the above hydrophilic film forming composition on a substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the composition for hydrophilic film formation which provides the surface hydrophilic layer which is excellent in hydrophilic property, has favorable durability, and was excellent in transparency and storage stability can be provided. Furthermore, it is possible to provide a hydrophilic member having a hydrophilic film on the surface of the substrate and having excellent surface hydrophilicity and durability.

The composition for forming a hydrophilic film of the present invention (hereinafter simply referred to as “composition”) includes (A) a specific cyclic compound having a hydrophilic group and a silane coupling group in the molecule, and (B) Si, Ti. And an alkoxide compound containing an element selected from Zr and Al.
Hereinafter, the components of the present invention will be sequentially described.

<(A) Compound having a ring structure selected from a 5-membered ring structure and a 6-membered ring structure in the molecule, the ring structure having a hydrophilic group, and a silane coupling group in the molecule >
Such a 5-membered ring and 6-membered ring that form the main structure of the specific hydrophilic compound (A) can be formed of atoms arbitrarily selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom, A plurality of 5-membered rings and 6-membered rings are bonded to each other by a linking group in which carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, or carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and hydrogen atoms are combined. .
A sugar skeleton is preferably used for the 5 and 6 members constituting the main structure of the (A) specific hydrophilic compound used in the present invention.

(A) a specific hydrophilic compound used in the present invention (A) The molecule has a ring structure selected from a 5-membered ring structure and a 6-membered ring structure, and the ring structure has a hydrophilic group As compounds, glucose, fructose, mannose, galactose, growth, allose, idose, xylose, ribose, arabinose, lyxose, erythrose, threose and other monosaccharides, maltose, cellobiose, lactose, sucrose, saccharose and other disaccharides, gentianose, etc. It is possible to obtain two or more compounds having the ring structure by bonding with a linking group having a methylene group, an ether group, an ester group, an amide group, an amino group, a thioether group, an aryl group, a urethane group, a urea group, or the like. I can do it.
Further, the saccharide is an alkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, heterocyclic group, hydroxyl group, carboxyl group, amino group, ethyleneoxy group, sulfonic acid group, phosphoric acid group, urethane group, urea group. , A thiol group, an acetal group or the like, or a combination of these.
In addition, a polymer compound in which a large number of ring structures having a hydrophilic group are linked, such as a cellulose derivative and a starch derivative, can also be used as the (A) specific hydrophilic compound of the present invention.

(A) The specific hydrophilic compound needs to have a hydrophilic group in its ring structure. Examples of such a hydrophilic group include a hydroxyl group, a carboxyl group, an amino group, an ethyleneoxy group, a sulfonic acid group, Examples thereof include a phosphoric acid group, a urethane group, a urea group, a thiol group, and a sulfuric acid group.
These may be directly bonded to a 5-membered ring or a 6-membered ring, and may be bonded to a ring structure through a linking group such as a methylene group, a methyleneoxy group, or an aryl group as necessary. Of the hydrophilic groups described above, hydroxyl groups, carboxyl groups, sulfonic acid groups, phosphoric acid groups, thiol groups, sulfuric acid groups and the like can be used either in the proton form or neutralized with a base.
The amino group may be an ammonium group neutralized with an acid.

Further, (A) the specific hydrophilic compound has a silane coupling group in the molecule. The silane coupling group is represented by the following formula, m represents 0, 1 or 2, and R ⁷ and R ⁸ are the same as R ¹ and R ² described later, from the viewpoint of effects and availability, Preferably they are a hydrogen atom, a methyl group, or an ethyl group. In the following formula, L ₄ represents a linking group and is the same as L ¹ and L ² described later, preferably — (CH ₂ ) ₃ —NHCO ₂ —.

As a method for introducing a silane coupling group, an addition reaction between an isocyanate compound and an active hydrogen-containing compound, an esterification reaction between an alcohol and a carboxylic acid (chloride), an ester exchange reaction between a carboxylic acid ester and an alcohol, an alcohol and an alcohol And etherification reaction. The silane coupling group may be at least one in the molecule, but may be plural.
The silane coupling group may be any position in the molecule of the (A) specific hydrophilic compound, and is not particularly limited.

Specific examples of the specific hydrophilic compound (A) before introducing a silane coupling group that can be used in the present invention are shown below, but the present invention is not limited thereto.
Glucose, galactose, ribose, maltose, cellobiose, lactose, sucrose, hydroxymethylcellulose, hydroxypropylcellulose, carboxymethylcellulose or salts thereof, methylcellulose, carrageenan, maltoheptanose, maltohexanose, nystose, raffinose, panose, chitin, chitosan, pectin Acid, pentosan, pentose, cellulose triacetate, hydroxypropylmethylcellulose phthalate, dextrin, cellulose nitrate, cellulose acetate, cellulose carbamate, cyanoethylcellulose, ethylhydroxyethylcellulose, copolymer of glucuronic acid and N-acetylglucosamine, chondroitin 6-sulfate 6 Sugar, heparin, dextran sulfate, carotene sulfate, Lutodextrin sulfate, hemicellulose sulfate, alginic acid, alginic acid sodium salt, N-dicarboxyethylaminoethylcellulose, diethylaminoethylcellulose ethylsulfonate, N- (o-carboxyphenyl) aminodeoxycellulose, s- (o-carboxyphenyl) mercaptodeoxy Cellulose, hydrazinodeoxycellulose, amylose, methyl amylose, starch, carboxymethyl starch, phosphate starch, acetate starch, hydroxypropyl starch, acrylic acid graft starch, pullulan, curdlan, xanthan gum, duran gum, guar gum, gum arabic, carrageenan, Examples include heparan sulfate.

A preferred form of a compound having a 5-membered ring and / or a 6-membered ring structure that can be used in the present invention and having a hydrophilic group is preferably at least a hydroxyl group or a carboxylic acid in the ring structure from the viewpoint of hydrophilicity. It preferably has a group, a sulfonic acid group, a phosphoric acid group, a sulfuric acid group or a salt thereof. Most preferred is a compound having a sugar structure having a —SO ₃ ^— structure and a —OSO ₃ ^— structure. These hydrophilic groups may have at least one in the ring structure, but may have a plurality. In that case, a plurality of the same kind of hydrophilic groups may be included in the 5-membered ring and / or 6-membered ring structure. It may have a group, and may have a plurality of different hydrophilic groups. From the viewpoint of the effect, those having a plurality of hydrophilic groups in a combination of a hydroxyl group and a carboxylic acid group, a hydroxyl group and a phosphate group, a hydroxyl group and a sulfate group, and the like are preferable.

(A) The molecular weight of the specific hydrophilic compound is preferably 150 to 100,000, more preferably 180 to 50,000, and most preferably 200 to 30,000.
(A) The specific hydrophilic compound may be used alone or in combination of two or more.
(A) The specific hydrophilic compound is used in the composition for forming a hydrophilic film according to the present invention as a non-volatile component, preferably in the range of 10 to 80% by mass, more preferably 25 to 50% by mass. The Within this range, good film strength and coating properties can be obtained, and there is no concern of cracks in the film, which is preferable.

<(B) Alkoxide Compound Containing Element Selected from Si, Ti, Zr, Al>
In the present invention, the composition for forming a hydrophilic film contains (B) a specific alkoxide as a crosslinking component in addition to the (A) specific hydrophilic compound, thereby improving hydrophilicity and durability. An excellent high-strength film is formed.
(B) The alkoxide compound containing an element selected from Si, Ti, Zr, and Al is preferably a compound represented by the following general formula (2), and has a crosslinked structure for curing the hydrophilic film. In forming, it is preferable to apply and dry a composition obtained by mixing the specific hydrophilic compound and a crosslinking component represented by the following general formula (2) on the surface of the substrate. The crosslinking component represented by the following general formula (2) is a compound having a polymerizable functional group in its structure and serving as a crosslinking agent, and (A) the specific hydrophilic compound, or (B) A crosslinked structure is formed by condensation polymerization between components. Moreover, it is preferable to further contain the hydrophilic polymer (C) mentioned later in a composition from a viewpoint of the further improvement of film property and hydrophilic property.

In General Formula (2), 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 0-2. 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.

Although the specific example of the crosslinking component represented by General formula (2) below is given, this invention is not limited to this.
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, methyltrimethoxysilane, 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 specific alkoxide is used in the composition for forming a hydrophilic film according to the present invention as a non-volatile component, preferably in the range of 5 to 80% by mass, more preferably 20 to 70% by mass. Moreover, (B) specific 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) specific alkoxide, as long as the effects of the present invention are not impaired, crosslinking with a known heat, acid or radical other than the (B) specific alkoxide is performed in order to improve the properties of the hydrophilic 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 be effectively crosslinked with the (A) specific hydrophilic compound and / or the component (B). 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 hydrophilic film.

  The other crosslinking agent is preferably used in the range of 0 to 30% by mass, more preferably 0 to 15% by mass as a nonvolatile component in the composition used for forming the hydrophilic film in the present invention. Moreover, although such a crosslinking agent may be used independently or may be used together 2 or more types, it is 50 mass% or less with respect to (B) specific alkoxide which is the main crosslinking component of this invention. preferable.

<(C) hydrophilic polymer>
The hydrophilic film-forming composition of the present invention preferably further contains (C) a hydrophilic polymer from the viewpoint of improving the crosslinking density.
In the hydrophilic polymer of the present invention, the logP of the monomer as the structural unit 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.

Examples of hydrophilic polymers that can be used in the present invention include acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyls or hydrolysates thereof, styrenes, acrylic acid or salts thereof, methacrylic acids or salts thereof. , Acrylonitrile, maleic anhydrides, maleic imides, and other polymers as raw materials.
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.

In the present invention, from the viewpoint of further improving the properties of the hydrophilic membrane, at least a specific hydrophilic polymer having a structure represented by the following general formula (1) [hereinafter referred to as “(C-1) specific” It is preferable to contain a “hydrophilic polymer”. (C-1) The specific hydrophilic polymer has a silane coupling group at the terminal.
By the combined use of the (C-1) specific hydrophilic polymer having a silane coupling group at such a terminal, the interaction between the silane coupling group of the hydrophilic polymer and the crosslinking component, and further, between the silane coupling groups Due to the interaction, a cross-linked structure formed by Si (OR) ₄ is formed, the strength and durability of the hydrophilic film are improved by the strong cross-linked structure, and the terminal has a silane coupling group It is presumed that the portion having a hydrophilic group becomes free and the hydrophilicity is further improved.

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 carbon atom having 1 to 8 carbon atoms. Represents a hydrogen group. Examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 8 or less 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 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 be a straight chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, and a cyclic alkylene group 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 non-metallic 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 represents a hydrogen atom or a linear, branched or cyclic alkyl group 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) when x + y = 100, x: y represents a range of 100: 0 to 1:99, and a range of 100: 0 to 5:95 is more preferable.

  (C-1) The molecular weight of the specific 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 (1-1) to (1-23) of the specific hydrophilic polymer (C-1) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto.

<Synthesis method>
The specific hydrophilic polymer (C-1) used in combination according to the present invention in the present invention is represented by a radical polymerizable monomer represented by the following structural units (i) and (ii) and the following structural unit (iii). It can be synthesized by radical polymerization using a silane coupling agent having chain transfer ability in radical polymerization. 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 be easily synthesized.

  (C-1) As a radical polymerization method for synthesizing the specific hydrophilic polymer, any conventionally known method 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 (C-1) specific 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 must be sufficient to improve various physical properties, but if the proportion is too large, the function as a hydrophilic film is insufficient. Therefore, there is a concern that the advantage of adding the (C-1) hydrophilic polymer cannot be sufficiently obtained. Accordingly, the preferred total proportion of other monomers in the (C-1) specific hydrophilic polymer is 80% by weight or less, and more preferably 50% by weight or less.

(C) A hydrophilic polymer may be used independently or may be used together 2 or more types. Considering that the most preferable embodiment of this (C) hydrophilic polymer is (C-1) specific hydrophilic polymer, all of the (C) hydrophilic polymers used are such (C-1) specific It may be a hydrophilic polymer.
The hydrophilic polymer (C) used in combination is preferably 0 as a non-volatile component in the composition used for forming the hydrophilic 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%.

<Surfactant>
In the present invention, it is preferable to use a surfactant in order to improve the coated surface state of the hydrophilic 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 hydrophilic film of the present invention may contain inorganic fine particles in order to improve hydrophilicity and water retention.
As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, or a mixture thereof is preferably exemplified. Even if they are not photothermally convertible, they can be used for strengthening the film, enhancing interfacial adhesion by surface roughening, and the like.
The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, and more preferably 0.5 μm to 3 μm. The above range is preferable because it can be stably dispersed in the hydrophilic film and sufficiently retain hydrophilicity.
The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.
The content of the inorganic fine particles is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the hydrophilic 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 composition and the hydrophilic member.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194843, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492 and 56-21141 Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP The triazine compounds described in JP-A-8-501291, Research Disclosure No. Examples thereof include compounds described in No. 24239, compounds that emit ultraviolet light by absorbing ultraviolet rays typified by stilbene and benzoxazole compounds, so-called fluorescent brighteners, and the like.
The addition amount is appropriately selected according to the purpose, but generally it is preferably 0.5 to 15% by mass in terms of solid content.

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

<Solvent>
In the hydrophilic film forming composition of the present invention, when forming a hydrophilic layer on a substrate in forming a hydrophilic member, an organic solvent is appropriately added to ensure the formation of a uniform coating film on the substrate. 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 VOC (volatile organic solvent) in a range that does not cause a problem, and the amount thereof is preferably 0 to 50% by mass, more preferably based on the entire coating liquid when forming the hydrophilic member. Is in the range of 0-30% by weight.

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

In addition to this, if necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, tackifiers within the 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 hydrophilic film>
The hydrophilic film in the present invention is formed by dispersing or dissolving the necessary components in a solvent to prepare a coating solution, and curing the coating film on an appropriate substrate by heat. Can do.

  Moreover, in preparing the coating liquid composition for forming a hydrophilic film, (B) the specific alkoxide is used in a mass ratio of 0.1 to 4 with respect to 1 of the mass (A) of the specific hydrophilic compound. It is preferable. The upper limit of the amount of crosslinking component added is not particularly limited as long as it can be sufficiently crosslinked with the hydrophilic polymer, but when added excessively, the produced hydrophilic surface becomes sticky due to the crosslinking component not involved in crosslinking. there is a possibility.

  Among (C) hydrophilic polymers used as desired, in particular, when (C-1) a specific hydrophilic polymer having a silane coupling group at the terminal is used, (C-1) hydrophilicity having a silane coupling group at the terminal A polymer, (A) a specific hydrophilic compound, and (B) a cross-linking component such as a specific alkoxide are dissolved in a solvent and stirred well, so that these components are hydrolyzed and polycondensed to form an organic-inorganic composite A sol solution is formed, and a surface hydrophilic layer having high hydrophilicity and high film strength is formed by applying this sol solution as a hydrophilic film-forming coating liquid on a substrate. In the preparation of the organic-inorganic composite sol solution, it is preferable to use an acidic catalyst or a basic catalyst in combination in order to promote hydrolysis and polycondensation reaction. It is.

  As the catalyst, an acid or a basic compound is used as it is, or a catalyst dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst and a basic catalyst, respectively). The concentration at the time of dissolving in the solvent is not particularly limited, and may be appropriately selected according to the characteristics of the acid or basic compound to be used, the desired content of the catalyst, etc. The polymerization rate tends to increase. However, when a basic catalyst with a high concentration is used, a precipitate may be generated in the sol solution. Therefore, when a basic catalyst is used, the concentration is preferably 1 N or less in terms of concentration in an aqueous solution.

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

Examples of the other catalyst include a Lewis acid catalyst made of a metal complex. A preferred catalyst is a metal complex catalyst, which 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. It is a metal complex composed of an oxo or hydroxy oxygen-containing compound selected from the inside.
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. Among them, complexes obtained from Zr, Al and Ti are excellent and preferable.

  In the present invention, the oxo- or hydroxy-oxygen-containing compound constituting the ligand of the metal complex is, for example, acetylacetone, acetylacetone (2,4-pentanedione), β-diketones such as 2,4-heptanedione, methyl acetoacetate, Ketoesters such as ethyl acetoacetate and butylacetoacetate, hydroxycarboxylic acids and esters such as lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate, 4-hydroxy-4-methyl-2- Ketone alcohols such as pentanone, 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N-methyl -Monoethanolamine Amino alcohols such as diethanolamine and 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, A salt form such as a halogenate salt, a sulfate salt, a phosphate salt, etc., that ensures stoichiometric neutrality is 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 takes a coordination 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.

  The hydrophilic film coating solution is prepared by (A) a specific hydrophilic compound, (B) a crosslinking component such as a specific alkoxide, and preferably (C-1) a hydrophilic polymer having a silane coupling group at the end. After dissolving in a solvent such as ethanol, the catalyst can be added as desired and stirred. 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 hydrophilic film coating solution 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 (hydrophilic coating liquid composition) for forming the hydrophilic 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 hydrophilic film coating liquid composition according to the present invention.

  As described above, various additives can be used in the hydrophilic film coating solution 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 hydrophilic film coating solution composition prepared as described above to a substrate and drying it. The hydrophilic 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.
The film thickness of the hydrophilic surface can be selected depending on the purpose, but generally the coating amount after drying is in the range of 0.2 to 5.0 g / m ² , preferably 0.5 to 3.0 g / m 2. The range is ² . When the coating amount is in the above range, excellent hydrophilic effect and good film strength can be obtained.

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

<Base material>
The base material usable in the present invention is, for example, a transparent base material when antifogging effect is expected, and glass, plastic or the like can be suitably used as the material. Applications that can be applied with anti-fogging effects include vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, camera lenses, internal vision Lenses such as mirror lenses, illumination lenses, semiconductor lenses, photocopier lenses; prisms; window glass of buildings and surveillance towers; automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, ropeway gondola, amusement parks Ground gondola, vehicle window glass such as spacecraft; automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola, spacecraft-like vehicles Windshield: Protective goggles, sports goggles, protective mask shield, sports mask shield, helmet shield, frozen food display case glass ; Including cover glass instrumentation, and films to be attached to the article surface.

  When the surface hydrophilic member of the present invention is expected to have a surface cleaning effect, the base material is, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, fabric, Combinations and laminates thereof can be suitably used. Applications for which members having a surface cleaning effect are applicable include building materials, building exteriors, building interiors, window frames, window glass, structural members, exteriors and coatings of vehicles, exteriors of machinery and equipment, dustproof covers and coatings, Traffic signs, various display devices, advertising towers, noise barriers for roads, noise barriers for railways, bridges, guardrail exteriors and paintings, tunnel interiors and paintings, insulators, solar battery covers, solar water heater heat collection covers, plastic houses, vehicles Covers for lighting lamps, housing equipment, toilets, bathtubs, sinks, lighting fixtures, lighting covers, kitchenware, tableware, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods, ventilation fans, Includes film for application.

  When antistatic effect is expected for the surface hydrophilic member of the present invention, the material is, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, fabric, combinations thereof, A laminate can be suitably used. Applicable applications include cathode ray tubes, magnetic recording media, optical recording media, magneto-optical recording media, audio tapes, video tapes, analog records, household electrical appliance housings and parts, exterior and coating, OA equipment housings, Parts and exteriors and coatings, building materials, building exteriors, building interiors, window frames, window glass, structural members, exteriors and coatings for vehicles, machinery and equipment exteriors, dust covers and coatings, and for attaching to the surface of the article Includes film.

  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.

Further, one or more undercoat layers can be provided for the purpose of enhancing the adhesion between the hydrophilic 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 cross-linking agents, a water-soluble cross-linking agent is preferable from the viewpoint of easy preparation of the coating solution and prevention of a decrease in hydrophilicity of the produced hydrophilic layer.
Wherein the hydrophilic resin and / or water-dispersible latex total amount in the undercoat layer is preferably from 0.01 to 20 g / m ^2, 0.1 to 10 g / m ² is more preferable.

[Surface free energy]
The hydrophilicity of the hydrophilic layer surface is generally measured by the water droplet contact angle. However, on a very hydrophilic surface such as the present invention, the water droplet contact angle may be 10 ° or less, and even 5 ° or less, and there is a limit to the mutual comparison of the 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, using the property that an aqueous solution of an inorganic electrolyte such as magnesium chloride increases in surface tension with the concentration, after measuring the contact angle in the air 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, and the surface tension when cos θ = 1, that is, contact angle = 0 °, It is a measurement method defined as the surface free energy of a solid. The surface tension of water is 72 mN / m, and the higher the surface free energy value, the higher the hydrophilicity.
A hydrophilic layer having a surface free energy measured by such a method in the range of 70 mN / m to 95 mN / m, preferably 72 mN / m to 93 mN / m, more preferably 75 mN / m to 90 mN / m, Excellent performance and good performance.

When the hydrophilic member provided with the hydrophilic film of the present invention is used for a window glass or the like, transparency is important from the viewpoint of ensuring visibility. The hydrophilic film of the present invention is excellent in transparency, and even when the film thickness is large, the transparency is not impaired, and compatibility with durability is possible.
Transparency is evaluated by measuring the light transmittance in the visible light region (400 nm to 800 nm) with a spectrophotometer. The light transmittance is preferably 100% to 70%, more preferably 95% to 75%, and most preferably in the range of 95% to 80%. By being in this range, the hydrophilic member provided with a hydrophilic film can be applied to various applications without obstructing the field of view.

  The hydrophilic film of the present invention can be obtained by applying a coating solution composition for forming a hydrophilic layer on an appropriate substrate, heating and drying to form a surface hydrophilic layer. The heating temperature and heating time for forming the hydrophilic layer are not particularly limited as long as the solvent and the time in which the solvent in the sol solution can be removed and a strong film can be formed. It is preferably 150 ° C. or lower, and the heating time is preferably within 1 hour.

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

[Example 1]
Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, and the surface of the plate glass is hydrophilized by glow treatment, and then a hydrophilic layer coating solution having the following composition is applied to the bar at 100 ° C. for 10 minutes. And dried with an oven to form a hydrophilic layer having a dry coating amount of 1.0 g / m ² to prepare a hydrophilic member. The surface free energy of this hydrophilic member was 83 mN / m, which was a highly hydrophilic surface. The visible light transmittance of the hydrophilic layer was 95% (measured with a Hitachi spectrophotometer U3000).

<Hydrophilic layer coating solution (1)>
・ 500g of the following sol-gel preparation
・ 30 g of 5% by weight aqueous solution of the following anionic surfactant
・ Purified water 450g

Anionic surfactant (“Aerosol OT (Wako Pure Chemical Industries, Ltd.)”)

<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 4 g of a hydrophilic polymer having a silane coupling group at the following terminal, a silane cup 1 g of ring group-modified glucose (specific hydrophilic compound (A)) 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). 0.25 g 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. Moreover, the LogP value of the monomer which is a structural unit of the hydrophilic polymer was −0.61.

<Synthesis of silane coupling group-modified glucose>
A three-necked flask was charged with 10 g of glucose, 13.7 g of 3-isocyanatopropyltriethoxysilane, and 100 ml of tetrahydrofuran, and heated to 65 ° C. to initiate the reaction. After stirring for 6 hours, the temperature was returned to room temperature, and the residual solvent was concentrated and dried. It was confirmed by IR that the characteristic absorption peak (2200 cm ⁻¹ ) of the isocyanate group had disappeared. Yield 23g.

(Evaluation) The following evaluation was performed on the hydrophilic member.
Anti-fogging: A hydrophilic member is placed on a polycup with hot water of 80 ° C in the daytime under a fluorescent lamp in the room, exposed to water vapor for 1 minute, separated from the water vapor, and then placed in an environment of 25 ° C and RH 10%. Then, the degree of fogging and its change under a fluorescent lamp under the same irradiation conditions as described above were subjected to sensory evaluation in three stages according to the following criteria.
○: No cloudiness is observed Δ: Cloudy, but recovers within 10 seconds, no cloudiness is seen ×: Cloudy, no cloudiness recovers even after 10 seconds

  Antifouling property: A slurry was prepared by suspending 5 g of carbon black (FW-200, manufactured by Dexa) in 95 g of water, spray-coated on the surface of the hydrophilic member so as to be uniform throughout, and then heated at 60 ° C. Let dry for hours. The sample was washed with gauze, washed with gauze and dried, and the adhesion state of carbon black was measured by transmittance (using Hitachi spectrophotometer U3000). The transmittance was calculated according to the method of JIS standard R3106.

Water resistance: A 120 cm ² size hydrophilic member was rubbed 10 times with a sponge in water under a load of 1 kg, and the remaining film ratio was measured from the weight change before and after that.

Scratch test: Starting from 5 g on a 0.1 mm diameter sapphire needle, the surface of the hydrophilic layer was scanned with 5 g increments, and the weight at which scratching occurred was evaluated (measured with a scratch strength tester Type 18S manufactured by Shinto Kagaku Co., Ltd.). . Durability is better when there is no damage even if the load is large.
Storage stability (back surface adhesion): 50 sheets of 5cm square hydrophilic members are stacked, pressure-bonded using a vise with a torque of 300kg, and evaluated for back surface adhesion after aging for one day in a 45 ° C 75% humidity environment. did.

  The results are shown in Table 4. The antifogging and antifouling properties were good, and the water resistance was no problem with a residual film ratio of 98%. There was no decrease in hydrophilicity due to the abrasion test, and in the scratch test, there was no damage up to 50 g, and the durability was excellent. In the storage stability evaluation, the hydrophilic layer did not adhere to the back surface and was excellent in storage stability.

[Comparative Example 1]
A hydrophilic film was prepared in the same manner as in Example 1 except that the silane coupling group-modified glucose was changed to the following comparative compound 1. The results are shown in Table 4. Hydrophilicity is surface energy 65mN / m, antifogging ×, antifouling property 60%, water resistance is 95% residual film, scratches are seen at 40g in scratch test, hydrophilicity, strength, The result was inferior in durability.

[Examples 2 to 5]
A hydrophilic film was prepared in the same manner as in Example 1 except that the silane coupling group-modified glucose was changed to the specific hydrophilic compound shown in Table 1. The results are shown in Table 4.

Example 6
Float plate glass (thickness 2 mm), which is the most common transparent plate glass, is prepared, and the surface of the plate glass is hydrophilized by glow treatment, and then a hydrophilic layer coating solution having the following composition is applied to the bar at 100 ° C. for 10 minutes. And dried with an oven to form a hydrophilic layer having a dry coating amount of 1.0 g / m ² to prepare a hydrophilic member. The results are shown in Table 1.

<Hydrophilic layer coating solution (2)>
-20% by weight aqueous solution of colloidal silica dispersion ("Snow Tech C" manufactured by Nissan Chemical Co., Ltd.)
100g
・ 500g of the following sol-gel preparation
・ 30 g of 5% by weight aqueous solution of the following anionic surfactant
・ Purified water 450g

Anionic surfactant (“Aerosol OT (Wako Pure Chemical Industries, Ltd.)”)

<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 terminal [(1-1) Description Description] 4 g and 1 g of the silane coupling group-modified glucose synthesized above (specific hydrophilic compound A) were mixed and stirred at room temperature for 2 hours to prepare.

[Examples 7 to 10]
A hydrophilic membrane was prepared in the same manner as in Example 6 except that the silane coupling group-modified glucose was changed to the specific hydrophilic compound shown in Table 2. The evaluation results are shown in Table 4.

[Examples 11 to 15]
A hydrophilic membrane was prepared in the same manner as in Example 6 except that the silane coupling group-modified glucose was changed to the specific hydrophilic compound shown in Table 3, and the hydrophilic polymer having a silane coupling group at the terminal was changed to the hydrophilic polymer shown in Table 3. Created. The evaluation results are shown in Table 4.

In the hydrophilic polymer in Table 3, the Log P value of the monomer as the structural unit is shown below.
(1-2) Hydrophilic polymer: -0.3
(1-5) Hydrophilic polymer: -0.23
(1-15) Hydrophilic polymer: -1.56
(1-17) Hydrophilic polymer: -0.30
(1-21) Hydrophilic polymer: -0.13

Claims (6)

  (A) a compound having a ring structure selected from a 5-membered ring structure and a 6-membered ring structure in the molecule, the ring structure having a hydrophilic group, and a silane coupling group in the molecule; And (B) an alkoxide compound containing an element selected from Si, Ti, Zr and Al.   The composition for forming a hydrophilic film according to claim 1, further comprising (C) a hydrophilic polymer. The composition for forming a hydrophilic film according to claim 1 or 2, wherein the (C) hydrophilic polymer 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 having 1 to 8 carbon atoms, and m is 0, 1 or 2 X and y represent the composition ratio when x + y = 100, and x: y represents a range of 100: 0 to 1:99. 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 are each independently a hydrogen atom or a carbon number of 1 to 8 Represents an alkyl group, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal or onium.   Furthermore, the composition for hydrophilic film formation in any one of Claims 1-3 containing (D) colloidal silica.   A hydrophilic member, wherein the hydrophilic film-forming composition according to claim 1 is applied.   The hydrophilic member according to claim 5, wherein the hydrophilic member is formed by hydrolysis or condensation polymerization of a compound contained in the composition for forming a hydrophilic film.