JP2008132474A - Hydrophilic member and substrate for hydrophilic member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface hydrophilic member which is excellent in adhesion between a hydrophilic layer and a base material and excellent in durability of the hydrophilic layer and to provide a substrate for the hydrophilic member, which can be used in the surface hydrophilic member. <P>SOLUTION: The substrate for the hydrophilic member has an undercoat layer of a partial structure represented by M-OH (wherein M is Si, Ti, Zr or Al) on the base material, in which a value of M-OH/M on the surface of the undercoat layer is 1-0.4, and the hydrophilic layer on the undercoat layer. The undercoat layer is preferably formed by hydrolyzing and polycondensing a composition containing an alkoxide of a metal selected from Si, Ti, Zr and Al, preferably, at 30-200°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a surface hydrophilic member and a hydrophilic member substrate, and more specifically, a surface hydrophilic member excellent in adhesion between a hydrophilic layer and a substrate and excellent in durability of the hydrophilic layer, and to be used for the surface hydrophilic member. The present invention relates to a hydrophilic substrate.

  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.

International Publication No. 96/29375 Pamphlet Chemical Daily, January 30, 1995

  The objective of this invention is providing the surface hydrophilic member which is excellent in the adhesiveness of a hydrophilic layer and a base material, and is excellent in the durability of a hydrophilic layer, and the board | substrate for hydrophilic members which can be used for it.

As a result of intensive studies to achieve the above-mentioned problems, it is found that the adhesion of the interface between the undercoat layer and the hydrophilic layer is improved by providing an undercoat layer having many hydroxyl groups on the surface. The headline and the present invention were completed.
That is, the present invention is as follows.

(1) On a base material, it has at least an undercoat layer and a hydrophilic layer containing a partial structure represented by the following general formula (1) in this order, and M-OH / M of the surface of the undercoat layer A hydrophilic member having a value of 1 to 0.4.
M-OH Formula (1)
(In the formula, M represents Si, Ti, Zr or Al.)
(2) The hydrophilic member according to (1), wherein the M-OH / M value on the substrate surface is smaller than the M-OH / M value on the surface of the undercoat layer.
(3) The hydrophilic property of (1) or (2), wherein the undercoat layer is obtained by hydrolyzing and polycondensing a metal alkoxide compound selected from Si, Ti, Zr, and Al. Element.
(4) The hydrophilic member according to (3), wherein the hydrolysis and polycondensation are performed at 30 to 200 ° C.
(5) The hydrophilic member according to (1) to (4) above, wherein the surface roughness (Ra) of the undercoat layer is 1.0 to 50 nm.
(6) The hydrophilic member as described in (1) to (5) above, wherein the undercoat layer is mixed with plasma etching treatment or particles.
(7) The hydrophilic layer hydrolyzes and polycondenses a) a hydrophilic polymer, b) a metal alkoxide compound selected from Si, Ti, Zr, and Al, c) the metal alkoxide compound of b), The hydrophilic member according to any one of (1) to (6) above, wherein the composition containing a catalyst that causes a bond with the hydrophilic polymer in a) is hydrolyzed and polycondensed.
(8) The hydrophilic member according to (7), wherein the hydrophilic polymer of a) is represented by at least one selected from the following general formulas (I), (II), and (III).

In the general formulas (I) to (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a hydrocarbon group. M and n represent the molar ratio of monomers. However, m1 ≧ 5, m2 ≧ 50, m1 + n1 = 100, and m2 + n2 = 100. X represents a hydrolyzable silyl group (hereinafter sometimes referred to as a reactive group), A, L ¹ , L ² , L ³ , L ⁴ and L ⁵ each independently represent a single bond or a linking group, Y represents —NHCOR ¹¹ , —CONH ₂ , —CON (R ¹¹ ) ₂ , —COR ¹¹ , —O, —CO ₂ M, —SO ₃ M, —PO ₃ M, —OPO ₃ M or —N (R ¹¹ ₃ represents Z ¹ . Here, R ¹¹ represents an alkyl group having 1 to 18 carbon atoms, an aryl group, or an aralkyl group, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, or onium, and Z ¹ represents a halogen ion. B represents the following general formula (IV).

In general formula (IV), R ¹ , R ² , L ¹ and Y represent the same as those in general formula (I).
(9) The hydrophilic member as described in (1) to (8) above, wherein the base material contains a Si—OH structure.

(10) The hydrophilic member according to (1), which is an automotive glass.
(11) The hydrophilic member according to (1), which is a glass for building materials.

(12) An undercoat layer containing a partial structure represented by the following general formula (1) is provided on the substrate, and the M-OH / M value of the undercoat layer surface is 1 to 0.4. A substrate for a hydrophilic member, characterized in that it exists.
M-OH Formula (1)
(In the formula, M represents Si, Ti, Zr or Al.)
(13) The hydrophilic member substrate according to (12), wherein a value of M-OH / M on the surface of the base material is smaller than a value of M-OH / M on the surface of the undercoat layer.
(14) The hydrophilic property of (12) or (13), wherein the undercoat layer is obtained by hydrolyzing and polycondensing a metal alkoxide compound selected from Si, Ti, Zr, and Al. Substrate for member.
(15) The hydrophilic member substrate according to (14), wherein the hydrolysis and polycondensation are performed at 30 to 200 ° C.
(16) The hydrophilic member substrate according to (12) to (15) above, wherein the surface roughness (Ra) of the undercoat layer is 1.0 to 50 nm.
(17) The substrate for hydrophilic member as set forth above in (12) to (16), wherein the undercoat layer is mixed with plasma etching treatment or particles.
(18) The substrate for hydrophilic member as set forth above in (12) to (17), wherein the base material contains a Si—OH structure.

(19) On the substrate, a composition containing at least a metal alkoxide compound selected from Si, Ti, Zr, and Al is applied, heated at 30 to 200 ° C., and dried to coat an undercoat layer. Then, the manufacturing method of the hydrophilic member characterized by providing a hydrophilic layer on this undercoat. (20) The method for producing a hydrophilic member according to (18), wherein the composition contains a catalyst.
(21) On the substrate, a composition containing at least a metal alkoxide compound selected from Si, Ti, Zr, and Al is applied, and an undercoat layer is applied by heating and drying at 30 to 200 ° C. The manufacturing method of the board | substrate for hydrophilic members characterized by the above-mentioned.
(22) The method for producing a hydrophilic member substrate according to (19), wherein the composition contains a catalyst.

In addition, the following embodiments are preferable.
(23) The hydrophilic member according to (7), wherein the hydrophilic layer further contains d) colloidal silica.
(24) The hydrophilic member according to (1), wherein the hydrophilic film has a surface free energy of 70 mN / m to 95 mN / m.
(25) The hydrophilic member according to (7), wherein a) the hydrophilic group density of the hydrophilic polymer is 1 to 30 meq / g.
(26) The hydrophilic member according to (7), wherein the viscosity of the a) hydrophilic polymer is 0.1 to 100 cPs (5% aqueous solution).
(27) The hydrophilic member according to (1), wherein the light transmittance of the hydrophilic layer is 100% to 70%.

The present invention comprises, on a base material, an undercoat layer containing a partial structure represented by the following general formula (1) and having a surface M-OH / M value of 1 to 0.4. Adhesion at the interface between the undercoat layer and the hydrophilic layer is improved, and as a result, a surface hydrophilic member excellent in durability of the hydrophilic layer and a hydrophilic member substrate usable for the surface can be provided.
M-OH Formula (1)
(In the formula, M represents Si, Ti, Zr or Al.)

The present invention is described in detail below.
The substrate for a hydrophilic member of the present invention contains a partial structure represented by the following general formula (1) on an appropriate base material such as glass or plastic, and the surface M-OH / M value is 1 to 1. The hydrophilic member of the present invention having an undercoat layer of 0.4 further has a hydrophilic layer (also referred to as a hydrophilic film or a hydrophilic layer) on the undercoat layer.
M-OH Formula (1)
(In the formula, M represents Si, Ti, Zr or Al.)
In the present specification, in describing the hydrophilic member substrate and the hydrophilic member of the present invention, they may be collectively referred to as a hydrophilic member or a hydrophilic member substrate for convenience.

In the hydrophilic member of the present invention, M-OH / M means the ratio of metal atoms having hydroxyl groups to the total amount of metal atoms, and when M-OH / M = 0, no hydroxyl groups are present. Represents. M-OH / M is calculated by using TOF-SIMS as a measuring instrument, using V and Bi ₃ ⁺ primary ion gun (0.2pA, 10kHz), and using 20eV electron gun for charge correction. It is determined by the intensity ratio of M.
And in the hydrophilic member of this invention, the value of M-OH / M in the base-material surface is smaller than the value of M-OH / M in the said undercoat layer surface. This means that the amount of —OH groups on the surface of the undercoat layer is larger than the amount of —OH groups on the substrate surface. When the amount of -OH groups on the surface of the undercoat layer is larger than the amount of -OH groups on the surface of the base material, the undercoat layer is provided on the surface rather than directly providing the hydrophilic layer described later on the base material surface. However, the adhesion of the hydrophilic layer is improved and the durability of the hydrophilic layer is excellent.

In the hydrophilic member of the present invention, the method for setting the M-OH / M value of the surface of the undercoat layer to 1 to 0.4 is not particularly limited, but the undercoat layer is made of Si, Ti, Zr, It is preferable that a metal alkoxide compound selected from Al (hereinafter also simply referred to as metal alkoxide) is hydrolyzed and polycondensed. And it is preferable that the hydrolysis and polycondensation were made at 30-200 degreeC.
More specifically, a composition containing at least a metal alkoxide compound selected from Si, Ti, Zr, and Al is applied on a substrate, heated at 30 to 200 ° C., and dried to form the above-mentioned undercoat layer. Can be painted.
By performing heating and drying after coating of the composition containing the above metal alkoxide compound in a temperature range of 30 to 200 ° C., the undercoat layer is not completely hydrolyzed although the metal alkoxide compound is not perfect. , Having a polycondensed cross-linked structure, and having a moderate amount of M-OH structure because the metal alkoxide compound is not completely hydrolyzed and polycondensed.
The cross-linked structure formed by hydrolysis and polycondensation of the metal alkoxide as described above is hereinafter appropriately referred to as a sol-gel cross-linked structure.

In the hydrophilic member of the present invention, when the value of M-OH / M on the surface of the undercoat layer exceeds 1, the sol-gel crosslinking structure in the undercoat layer becomes insufficient, and the durability of the hydrophilic member is insufficient. It may be a thing.
Further, if the M-OH / M value on the surface of the undercoat layer is less than 0.4, the amount of -OH groups on the surface of the undercoat layer is insufficient, and the adhesion with the hydrophilic layer is also insufficient. In this case as well, the durability of the hydrophilic member is insufficient.

In addition, the metal alkoxide selected from Si, Ti, Zr, and Al is a hydrolyzable polymerizable compound having a functional group capable of being hydrolyzed and polycondensed in its structure and serving as a crosslinking agent. Metal alkoxides are polycondensed to form a strong crosslinked film having a crosslinked structure. The metal alkoxide can be represented by general formula (IV-1) and general formula (IV-2), wherein R ⁸ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁹ represents an alkyl group or an aryl group. Z represents Si, Ti or Zr, and m represents an integer of 0-2. The number of carbon atoms when R ⁸ and R ⁹ represent an alkyl group is preferably 1 to 4. The alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, and a mercapto group. This compound is a low molecular compound and preferably has a molecular weight of 2000 or less.

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

  Specific examples of the hydrolyzable compounds represented by general formula (IV-1) and general formula (IV-2) are shown below, but the present invention is not limited thereto. When Z is Si, that is, the hydrolyzable compound containing silicon includes, for example, trimethoxysilane, tetramethoxysilane, tetraethoxycin, tetrapropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, γ- Examples include chloropropyl triethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, and the like. Among these, particularly preferred are trimethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane and the like.

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

  Among metal alkoxides, Si alkoxides are preferable from the viewpoint of reactivity and availability, and specifically, compounds used for silane coupling agents can be suitably used.

When applying a composition containing the metal alkoxide compound, heating and drying at 30 to 200 ° C., and coating an undercoat layer, the hydrolysis and polycondensation are applied to the composition containing the metal alkoxide compound. It is preferable to contain the catalyst for reaction.
Although it does not specifically limit as this catalyst, A metal chelate compound, a silane coupling agent, etc. are mentioned.

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

  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 thereof such as lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate, 4-hydroxy-4-methyl-2 -Keto 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, tetraethyl orthotitanate, teto Iso propoxy zirconium and the like. 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, zirconium tris (ethylacetoacetate), tetraethyl orthotitanate, and tetraisopropoxyzirconium are preferred.

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

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

  Examples of the silane coupling agent include, but are not limited to, those having a functional group exhibiting acidity or alkalinity, and more specifically, phosphoric acid, peroxoacid, carboxylic acid, carbohydrazone acid, carboxyimide acid, Silanes having a functional group showing acidity such as sulfonic acid, sulfinic acid, sulfenic acid, selenonic acid, selenic acid, selenic acid, telluronic acid, and the above alkali metal salts, or a basic functional group such as amino group A coupling agent is mentioned.

  In addition to the metal chelate compound and silane coupling agent described above, the catalyst used for the undercoat layer is hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, Carbonic acid, carboxylic acids such as formic acid and acetic acid, substituted carboxylic acids obtained by substituting R in the structural formula represented by RCOOH with other elements or substituents, compounds exhibiting acidity such as sulfonic acids such as benzenesulfonic acid, or ammonia A basic compound such as an ammoniacal base such as water or an amine such as ethylamine or aniline may be used.

  However, in order to further improve the adhesion with the hydrophilic layer, the undercoat layer is heated and dried in order to efficiently perform hydrolysis and polycondensation of the metal alkoxide compound at a relatively low temperature of 30 to 200 ° C. A metal chelate compound and a silane coupling agent are preferable in that the catalyst can remain active in the inside. Further, the stability of the coating solution for the undercoat layer and the surface quality of the undercoat layer are improved, and the durability is high. From the viewpoint of satisfying the properties, metal chelate compounds are preferred.

The undercoat layer of the hydrophilic member of the present invention is obtained by applying a composition having at least the above metal alkoxide compound on a substrate, heating the substrate, and drying the composition. Although it can be formed by condensation, the heating temperature for forming the undercoat layer is preferably in the range of 30 to 200 ° C., and the heating temperature is more preferably 150 ° C. or less from the viewpoint of manufacturability.
The heating time is not particularly limited as long as the solvent in the sol solution can be removed and a strong film can be formed, but is preferably within 1 hour from the viewpoint of production suitability and the like.
The undercoat layer in the hydrophilic member of the present invention can be prepared by a known coating method, and is not particularly limited. For example, spray coating method, dip coating method, flow coating method, spin coating method, roll coating method. A film applicator method, a screen printing method, a bar coater method, a brush coating, a sponge coating or the like can be applied.

  Further, the undercoat layer of the hydrophilic member of the present invention is formed by mixing particles in plasma etching or an undercoat layer coating solution to provide fine irregularities, whereby -OH per apparent area of the undercoat layer surface. The amount of the base can be increased, and thereby the adhesiveness at the interface of the hydrophilic layer can be further increased.

The hydrophilic member of the present invention further has a hydrophilic layer on the undercoat layer.
The hydrophilic layer is not particularly limited, but a) a hydrophilic polymer, b) a metal alkoxide compound selected from Si, Ti, Zr, and Al, c) the metal alkoxide compound of b) is hydrolyzed and polycondensed. The composition containing a catalyst that causes a bond with the hydrophilic polymer of a) is preferably hydrolyzed and polycondensed.
The hydrophilic layer as described above has the same sol-gel cross-linking structure as the undercoat layer, a metal alkoxide compound, a compound having a hydrophilic functional group capable of forming a hydrophilic graft chain, and an appropriate catalyst. And can be appropriately formed. Among metal alkoxides, Si alkoxides are preferable from the viewpoint of reactivity and availability, and specifically, compounds used for silane coupling agents can be suitably used.

  Such a hydrophilic layer in which one end of the polymer chain is not fixed and the polymer chain has high mobility is represented by, for example, (A) the following general formula (I) having a reactive group such as a silane coupling group at the end. A polymer compound represented by the following general formulas (II) and (III) having the reactive group as a side chain of the trunk polymer, and (B) a hydrolyzable metal alkoxide compound It can be easily formed by preparing a hydrophilic coating liquid composition containing a catalyst that causes hydrolysis and polycondensation, and coating and drying it to form a surface hydrophilic layer. Below, each component contained in the hydrophilic coating liquid composition for forming the hydrophilic layer which is this preferable aspect is demonstrated.

[Hydrophilic polymer]
The hydrophilic polymer used in the present invention is a polymer having a hydrophilic group and a group that forms a bond with a metal alkoxide compound selected from Si, Ti, Zr, and Al by the action of a catalyst or the like. The hydrophilic group is preferably a carboxy group, an alkali metal salt of a carboxy group, a sulfonic acid group, an alkali metal salt of a sulfonic acid group, a hydroxyl group, an amide group, a carbamoyl group, a sulfonamide group, a sulfamoyl group or the like. Can be mentioned. These groups may be present at any position in the polymer. A polymer structure in which a plurality of polymers are bonded directly from a polymer main chain or via a linking group, or bonded to a polymer side chain or a graft side chain, is preferred. Examples of the group that forms a bond with the metal alkoxide compound by the action of a catalyst include a carboxyl group, an alkali metal salt of a carboxy group, a carboxylic anhydride group, an amino group, a hydroxy group, an epoxy group, a methylol group, a mercapto group, an isocyanate group, Examples thereof include reactive groups such as a block isocyanate group, an alkoxysilyl group, an alkoxytitanate group, an alkoxyaluminate group, an alkoxyzirconate group, an ethylenically unsaturated group, an ester group, and a tetrazole group. The polymer structure having a hydrophilic group and a group that forms a bond with a metal alkoxide compound by the action of a catalyst or the like includes an ethylenically unsaturated group (for example, an acrylate group, a methacrylate group, an itaconic acid group, a crotonic acid group, a cinnamic acid group). Styrene group, vinyl group, allyl group, vinyl ether group, vinyl ester group, etc.), polymer obtained by vinyl polymerization, polycondensation polymer such as polyester, polyamide, polyamic acid, etc., addition polymer such as polyurethane, etc. Preferred examples include natural cyclic polymer structures such as cellulose, amylose and chitosan.

Moreover, it is preferable that logP of the monomer which is the structural unit of the hydrophilic polymer used for this invention is -3-2, and it is more preferable that it is -2-0. 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.

  Specific examples include structures represented by general formulas (I), (II), and (III).

In the general formulas (I) to (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a hydrocarbon group. M and n represent the molar ratio of monomers. However, m1 ≧ 5, m2 ≧ 50, m1 + n1 = 100, and m2 + n2 = 100. X represents a hydrolyzable silyl group (hereinafter sometimes referred to as a reactive group), A, L ¹ , L ² , L ³ , L ⁴ and L ⁵ each independently represent a single bond or a linking group, Y represents —NHCOR ¹¹ , —CONH ₂ , —CON (R ¹¹ ) ₂ , —COR ¹¹ , —OH, —CO ₂ M, —SO ₃ M, —PO ₃ M, —OPO ₃ M or —N (R ¹¹ ₃ represents Z ¹ . Here, R ¹¹ represents an alkyl group having 1 to 18 carbon atoms, an aryl group, or an aralkyl group, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, or onium, and Z ¹ represents a halogen ion. B represents the following general formula (IV).

In general formula (IV), R ¹ , R ² , L ¹ and Y represent the same as those in general formula (I).

The hydrophilic polymer used in the present invention has a reactive group and a hydrophilic group. There may be a case where the reactive group is present only at one end of the main chain or a case where a plurality of reactive groups are present in the main chain.
The “reactive group” means a functional group capable of forming a chemical bond by reacting with a hydrolysis or polycondensate of a metal alkoxide. Moreover, reactive groups may form a chemical bond. The hydrophilic polymer is preferably water-soluble, and preferably becomes water-insoluble by reacting with a hydrolysis or polycondensate of a metal alkoxide.
The chemical bond includes a covalent bond, an ionic bond, a coordination bond, and a hydrogen bond in the usual meaning. The chemical bond is preferably a covalent bond.
The reactive group is generally the same as the reactive group contained in the crosslinking agent of the polymer, and is a compound that can form a crosslink by heat or light. The crosslinking agent is described in “Crosslinking agent handbook” by Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha (1981).

Examples of reactive groups are carboxyl (HOOC-), salts thereof (MOOC-, where M is a cation), carboxylic anhydride groups (eg monovalent groups derived from succinic anhydride, phthalic anhydride or maleic anhydride). ), Amino (H ₂ N—), hydroxyl (HO—), epoxy group (eg, glycidyl group), methylol (HO—CH ₂ —), mercapto (HS—), isocyanate (OCN—), block isocyanate Group, alkoxysilyl group, alkoxy titanate group, alkoxy zirconate group, ethylenically unsaturated double bond, ester bond, tetrazole group. As the reactive group, an alkoxysilyl group is most preferable. One end may have two or more reactive groups. Two or more reactive groups may be different from each other.

It is preferable that a linking group is interposed between the repeating unit of the hydrophilic polymer and the reactive group, or between the repeating unit of the hydrophilic polymer and the main chain. The linking groups A and L ¹ , L ² and L ³ are each independently a single bond, or —O—, —S—, —CO—, —NH—, —N <, an aliphatic group, an aromatic group, a complex It is preferably selected from cyclic groups and combinations thereof. The linking group is preferably —O—, —S—, —CO—, —NH—, or a combination containing —O—, —S—, —CO— or —NH—.

(Hydrophilic polymer having a reactive group at the terminal (I))
Hydrophilic polymers having a reactive group at one end are, for example, chain transfer agents (described in radical polymerization handbook (NTS, Mikiji Tsunoike, Takeshi Endo)) and Iniferter (Macromolecules 1986, 19, p287- (Otsu)). In the presence of a hydrophilic monomer (eg, acrylamide, acrylic acid, potassium salt of 3-sulfopropyl methacrylate) by radical polymerization. Examples of chain transfer agents include 3-mercaptopropionic acid, 2-aminoethanethiol hydrochloride, 3-mercaptopropanol, 2-hydroxyethyl disulfide, 3-mercaptopropyltrimethoxysilane. Alternatively, a hydrophilic monomer (eg, acrylamide) may be radically polymerized using a radical polymerization initiator having a reactive group (eg, carboxyl) without using a chain transfer agent.
The mass average molecular weight of the hydrophilic polymer having a reactive group at one end is preferably 1,000,000 or less, more preferably 1,000 to 1,000,000, and most preferably 2,000 to 100,000.

The polymer compound represented by the general formula (I) is a hydrophilic polymer having a reactive group at the terminal. In the general formula ^{(I), R 1, R} 2 each independently represents a hydrocarbon group having 8 or less hydrogen atom or a carbon. 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 and R ² are preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoints of effects and availability.

  These hydrocarbon groups may further have a substituent. When the alkyl group has a substituent, the substituted alkyl group is composed of a bond between the substituent and the alkylene group, and a monovalent nonmetallic atomic group excluding hydrogen is used as the substituent. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkylamino groups, acyloxy groups, 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-dialkyl Carbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfuryl group Famoyl group, N-alkyl-N- Lillesulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphonate group, phosphonooxy group, phosphonate An oxy group, an aryl group, and an alkenyl group are mentioned.

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

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

A and L ^{1 each} represents a single bond or an organic linking group. Here, when A and L ¹ represent an organic linking group, A and L ¹ represent a polyvalent linking group composed of a nonmetallic atom, specifically, 1 to 60 carbon atoms, 0 To 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 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.

Y represents —NHCOR ⁷ , —CONH ₂ , —CON (R ⁷ ) ₂ , —COR ⁷ , —OH, —CO ₂ M, —SO ₃ M, —PO ₃ M, —OPO ₃ M, or —N ( R ⁷ ) ₃ Z ¹ , wherein R ⁷ represents a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, an aryl group, or an aralkyl group, and M represents a hydrogen atom, an alkali metal, or an alkaline earth. It represents a similar metal or onium, and Z ¹ represents a halogen ion. Also, if having a plurality of R ⁷ as -CON (R ⁷⁾ _2, may form a ring by bonding R ⁷ together, and the formed ring is an oxygen atom, a sulfur atom, a nitrogen It may be a heterocycle containing a heteroatom such as an atom. R ⁷ may further have a substituent, and examples of the substituent that can be introduced here include those listed as the substituents that can be introduced when R ¹ and R ² are alkyl groups. Can do.

Specific examples of R ⁷ include 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, Preferable examples include 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. The Y, _{specifically, -NHCOCH 3, -CONH 2, -COOH} , -SO 3 - NMe 4 +, morpholyl group and the like.

  Specific examples (Exemplary Compound 1 to Exemplified Compound 38) of a) hydrophilic polymers that can be suitably used in the present invention are shown below, but the present invention is not limited thereto.

  The hydrophilic polymer exemplified above uses a radical polymerizable monomer represented by the following general formula (i) and a silane coupling agent having chain transfer ability in the radical polymerization represented by the following general formula (ii). Can be synthesized by radical polymerization. Since the silane coupling agent (ii) has chain transfer ability, it is possible to synthesize a polymer in which a silane coupling group is introduced at the end of the polymer main chain in radical polymerization.

In the above formula (i) and ^{(ii), A, R 1} ~R 2, L 1, Y is as defined in the above formula (I). These compounds are commercially available and can be easily synthesized.

(Hydrophilic polymer having multiple reactive groups (II))
As the hydrophilic polymer having a plurality of reactive groups represented by the above formula (II), a hydrophilic graft polymer obtained by introducing a hydrophilic polymer side chain into a trunk polymer having a functional group capable of reacting with a metal alkoxide is used. be able to.
In the above formula (II), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent the same substituent as R ¹ and R ² in the above formula (I). L ² and L ³ have the same meaning as L ^{1 in the} above formula (I). B is represented by the above formula (IV), and R ¹ , R ² , L ¹ and Y in the formula (IV) are the same as those in the formulas (I) and (II). X is synonymous with the above formula (I).
This hydrophilic graft polymer can be prepared using a method generally known as a method for synthesizing a graft polymer. Specifically, a general method for synthesizing a graft polymer is described in “Graft Polymerization and its Applications” by Fumio Ide, published in 1977, “Polymer Publishing”, and “New Polymer Experiments 2, Polymer Synthesis / Reaction "edited by Polymer Society of Japan, Kyoritsu Shuppan Co., Ltd. 1995, and these can be applied.

  As a method for synthesizing the graft polymer, basically, 1. 1. Polymerize the branch monomer from the trunk polymer. 2. Link the branch polymer to the trunk polymer. It can be divided into three methods of copolymerizing a branch polymer with a trunk polymer (macromer method). Any of these three methods can be used to produce the hydrophilic graft polymer used in the present invention, but “3. Macromer method” is particularly excellent from the viewpoint of production suitability and control of the membrane structure. ing.

  The synthesis of graft polymer using a macromonomer is described in the aforementioned “New Polymer Experiments 2, Polymer Synthesis / Reaction” edited by Polymer Society of Japan, Kyoritsu Publishing Co., Ltd. 1995. It is also described in detail in Yamashita Yu et al., “Macromonomer Chemistry and Industry”, IPC, 1989. The graft polymer used in the present invention first comprises a hydrophilic macromonomer (corresponding to a precursor of a hydrophilic polymer side chain) synthesized by the above method and a monomer having a functional group capable of reacting with a crosslinking agent. It can be synthesized by copolymerization.

(Hydrophilic macromonomer)
Among the hydrophilic macromonomers used in the present invention, particularly useful are macromonomers derived from carboxyl group-containing monomers such as acrylic acid and methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, and vinylstyrene. Derived from sulfonic acid macromonomer derived from sulfonic acid and its monomer, amide macromonomer such as acrylamide and methacrylamide, N-vinylcarboxylic amide monomer such as N-vinylacetamide and N-vinylformamide Amide macromonomers, macromonomers derived from hydroxyl-containing monomers such as hydroxyethyl methacrylate, hydroxyethyl acrylate, glycerol monomethacrylate, methoxyethyl acrylate, methoxypolyethylene Glycol acrylate, macromonomers derived from alkoxy group or ethylene oxide group-containing monomers such as polyethylene glycol acrylate. A monomer having a polyethylene glycol chain or a polypropylene glycol chain can also be usefully used as the macromonomer of the present invention. Among these macromonomers, the useful polymer has a mass average molecular weight (hereinafter simply referred to as molecular weight) in the range of 400 to 100,000, preferably 1000 to 50,000, and particularly preferably 1500 to 20,000. . If the molecular weight is 400 or more, effective hydrophilicity is obtained, and if it is 100,000 or less, the polymerizability with the copolymerization monomer forming the main chain tends to be high, both of which are preferable.

  Examples of the reactive functional group of the monomer having a functional group that can be copolymerized with the hydrophilic macromonomer and that can react with the crosslinking agent (hereinafter, appropriately referred to as a reactive functional group) include a carboxyl group or a salt thereof, an amino group, Examples include hydroxyl groups, phenolic hydroxyl groups, epoxy groups such as glycidyl, methyl groups, (block) isocyanate groups, and silane coupling agents. Common monomers include “Crosslinking agent handbook” by Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha [1981], “Ultraviolet curing system” by Kiyomi Kato, published by General Technology Center [1989], “UV / EB curing” "Handbook (raw material)" written by Kiyomi Kato, Polymer Publishing Society [1985], "Actual Technology of New Photosensitive Resins" written by Kiyoshi Akamatsu, CMC Publishing (pages 102-145) [1987], etc. Monomer. Specifically, (meth) acrylic acid or its alkali, amine salt, itaconic acid or its alkali, amine salt, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, represented by the following formula (1) A phenolic hydroxyl group-containing monomer such as glycidyl methacrylate, allyl glycidyl ether, N-methylol methacrylamide, 2-methacryloyloxyethyl isocyanate, and a blocked isocyanate monomer such as a blocked isocyanate monomer exemplified by the following formula (2); Examples include vinyl alkoxysilane and γ-methacryloxypropyltrialkoxysilane.

  As these graft polymers, those having a mass average molecular weight of 1,000,000 or less are preferably used, and those having a molecular weight of 1,000 to 1,000,000, more preferably 20,000 to 100,000. When the molecular weight is 1,000,000 or less, there is a problem in handling properties, such as the ability to form a uniform coating film without lowering the solubility in a solvent when preparing a coating solution for forming a hydrophilic coating film, without lowering the solubility in the solvent. This is preferable.

The hydrophilic polymer has a hydrophilic functional group that expresses the hydrophilicity represented by Y in the formula, and the higher the density of this functional group, the higher the surface hydrophilicity, which is preferable. The hydrophilic functional group density can be represented by the number of moles of functional groups per 1 g of the hydrophilic polymer, preferably 1 to 30 meq / g, more preferably 2 to 20 meq / g, and most preferably 3 to 15 meq / g.
The copolymerization ratio of the hydrophilic polymer (II) can be arbitrarily set so that the amount of the hydrophilic functional group Y falls within the above range. Preferably, the molar ratio (m) of the monomer containing B and the molar ratio (n) of the monomer containing X are preferably in the range of m / n = 30/70 to 99/1, and m / n = 40 / 60 to 98/2 is more preferable, and m / n = 50/50 to 97/3 is most preferable. If m is a ratio of m / n = 30/70 or more, hydrophilicity is not insufficient. On the other hand, if n is a ratio of m / n = 99/1 or more, the reactive group amount is sufficient, Sufficient curing is obtained and the film strength is sufficient.

  Specific examples of the hydrophilic polymer represented by the general formula (II) that can be suitably used in the present invention (Exemplary Compound (II) -1 to Exemplary Compound (II) -50) are shown below. It is not limited.

(Hydrophilic polymer having a plurality of reactive groups (III))
In the above formula (III), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent the same substituent as R ¹ and R ² in the above formula (I). L ⁴ and L ⁵ have the same meaning as L ^{1 in the} above formula (I). Y and X are the same as in formulas (I) and (II). In the present invention, L ⁴ is a single bond or a link having one or more structures selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. The group is preferable because it exhibits high hydrophilicity.
A side chain type silane polymer represented by the general formula (III) is most preferable because a large number of hydrolyzable silyl groups per molecule can be introduced and a very good curability can be obtained by drying at room temperature. .

  The copolymerization ratio of the polymer represented by the general formula (III) is preferably when the molar ratio (m2) of the monomer containing Y and the molar ratio (n2) of the monomer containing X is m2 + n2 = 100 M2 ≧ 50, preferably m2 is 70 to 95. By setting the molar ratio of each monomer within this range, the effect that the high stability of the coating liquid, high film strength and hydrophilicity are exhibited is exhibited.

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

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

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

  The mass average molecular weight of the polymer represented by the general formula (III) is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, and most preferably 1,000 to 200,000. .

  The above-mentioned hydrophilic polymer forms a crosslinked film in a state where it is mixed with a hydrolysis and polycondensate of metal alkoxide. The hydrophilic polymer, which is an organic component, is involved in the film strength and film flexibility. In particular, the hydrophilic polymer has a viscosity of 0.1 to 100 cPs (5% aqueous solution, measured at 25 ° C.), preferably 0.8. When it is in the range of 5 to 70 cPs, more preferably 1 to 50 cPs, good film physical properties are provided.

  The above-mentioned hydrophilic polymer forms a crosslinked film in a state where it is mixed with a hydrolysis and polycondensate of metal alkoxide. The hydrophilic polymer, which is an organic component, is involved in the film strength and film flexibility. In particular, the hydrophilic polymer has a viscosity of 0.1 to 100 cPs (5% aqueous solution, measured at 25 ° C.), preferably 0.8. When it is in the range of 5 to 70 cPs, more preferably 1 to 50 cPs, good film physical properties are provided.

The metal alkoxide used in the hydrophilic layer having a sol-gel cross-linking structure of the hydrophilic member of the present invention has a functional group that can be hydrolyzed and polycondensed in the structure, and is a hydrolysis that functions as a cross-linking agent. It is a polymerizable compound and forms a strong cross-linked film having a cross-linked structure by polycondensation of metal alkoxides, and further chemically bonds with the hydrophilic polymer.
Examples of such metal alkoxides are the same as those mentioned for the above-mentioned undercoat layer.

The catalyst for hydrolyzing and polycondensing the metal alkoxide compound used in the hydrophilic layer having a sol-gel cross-linking structure of the hydrophilic member of the present invention to cause a bond with the hydrophilic polymer is not particularly limited, The thing similar to what was mentioned by the above-mentioned undercoat is illustrated and used.
Among them, a metal chelate compound and a silane coupling agent are preferable in terms of efficiently performing hydrolysis and polycondensation of the metal alkoxide compound at a relatively low temperature, and further, stability over time of the coating liquid for the hydrophilic layer and A metal chelate compound is preferred from the viewpoint of improving the hydrophilic layer film surface quality and satisfying high durability.

The hydrophilic layer of the present invention may contain inorganic fine particles in order to improve hydrophilicity, prevent cracking of the film, and improve film strength. As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, or a mixture thereof is preferably exemplified.
The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, and more preferably 0.5 to 3 μm. Within the above range, it is possible to form a hydrophilic member that is stably dispersed in the hydrophilic layer, sufficiently retains the film strength of the hydrophilic layer, and has high durability and excellent hydrophilicity.
Among the inorganic fine particles as described above, a colloidal silica dispersion is particularly preferable and can be easily obtained as a commercial product.
The content of the inorganic fine particles is preferably 80% by mass or less, and more preferably 50% by mass or less, based on the total solid content of the hydrophilic layer.

Hereinafter, various additives that can be used in the coating solution for forming the hydrophilic layer of the hydrophilic member of the present invention as necessary are described.
1) Surfactant You may add surfactant to the coating liquid for hydrophilic layer formation of the hydrophilic member of this invention.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. For example, anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks Nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compounds include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). No. (columns 8 to 17) and those described in JP-A Nos. 62-135826.

2) Ultraviolet Absorber In the present invention, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance and durability of the hydrophilic member.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Bezotriazole compounds, benzophenone compounds described in JP-A-46-2784, JP-A-5-194443, US Pat. No. 3,214,463, etc., JP-B-48-30492, JP-A-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, Special Tables 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.

3) Antioxidant In order to improve the stability of 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. No. 5, JP-A-54-262447, JP-A-63-113536, JP-A-63-163351, JP-A-2-262654, JP-A-2-71262, JP-A-3-121449, Examples thereof include those described in 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.

4) Solvent When forming the hydrophilic layer of the hydrophilic member of the present invention, it is also effective to appropriately add an organic solvent to the hydrophilic layer forming coating solution in order to ensure the formation of a uniform coating film on the substrate. is there.
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.

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

In addition to this, as necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, tackifiers to the extent that hydrophilicity is not impaired 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.

〔Base material〕
The substrate used in the present invention is not particularly limited, but glass, plastic, metal, ceramics, wood, stone, cement, concrete, fiber, fabric, paper, leather, combinations thereof, and laminates thereof are all used. It can be suitably used. A particularly preferred substrate is a glass substrate or a plastic substrate.
As the glass substrate, any glass such as soda glass, lead glass or borosilicate glass may be used. Depending on the purpose, float plate glass, mold plate glass, ground glass, wire-filled glass, wire-filled glass, tempered glass, laminated glass, double-glazed glass, vacuum glass, security glass, highly heat-insulated Low-E double-glazed glass should be used. Can do. In addition, the hydrophilic layer can be applied as it is with the base glass, but if necessary, surface hydrophilic treatment is performed on one or both sides by an oxidation method, a roughening method or the like for the purpose of improving the adhesion of the hydrophilic layer. be able to. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. As a roughening method, it can also be mechanically roughened by sandblasting, brush polishing or the like.

  The plastic substrate used in the present invention is not particularly limited, but polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol And films or sheets of polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetherketone, acrylic, nylon, fluororesin, polyimide, polyetherimide, polyethersulfone, and the like. Of these, polyester films such as polyethylene terephthalate and polyethylene naphthalate are particularly preferred. In addition, in terms of optical properties, it is often preferable to have excellent transparency, but depending on the application, translucent or printed materials may be used. The thickness of the plastic substrate varies depending on the mating partner. For example, in a portion with many curved surfaces, a thin one is preferred, and one having about 6 to 50 μm is used. Moreover, 50-400 micrometers is used for a plane or the place where intensity | strength is requested | required.

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

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

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

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

[Form of structure]
The structure having a hydrophilic layer of the present invention may be supplied in the form of a sheet, a roll, or a ribbon, or may be supplied as a material that has been cut in advance in order to be attached to an appropriate substrate.

[Surface free energy]
The hydrophilicity of the hydrophilic layer surface is generally measured by the water droplet contact angle. However, on a very hydrophilic surface such as the present invention, the water droplet contact angle may be 10 ° or less, and 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, an aqueous solution of an inorganic electrolyte such as magnesium chloride uses the property that the surface tension increases with the concentration. After measuring the contact angle in air and at room temperature using the aqueous solution, the horizontal axis indicates the surface of the aqueous solution. Take the value obtained by converting the contact angle into cos θ on the vertical axis and plot the points of aqueous solutions of various concentrations to obtain a linear relationship. Cos θ = 1, that is, the surface tension when the contact angle = 0 °, It is a measurement method defined as the surface free energy of a solid. The surface tension of water is 72 mN / m, and the higher the surface free energy value, the higher the hydrophilicity.
A 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 is hydrophilic. Excellent performance.

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

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

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

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

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
Example 1
Float plate glass (thickness 2 mm, SiO ₂ concentration 70 wt%), which is the most common transparent plate glass, is prepared, and the surface of the plate glass is hydrophilized by UV / O ₃ treatment for 10 minutes, and then the first layer coating having the following composition is applied. The solution was spin coated and oven dried at 100 ° C. for 10 minutes to form a first layer having a dry coating amount of 1.0 g / m ² . After sufficiently cooling at room temperature, the second layer coating solution having the following composition is spin-coated on the first layer coating surface, oven dried at 100 ° C. for 10 minutes, and the second layer having a dry coating amount of 1.0 g / m ² . Formed. The surface free energy of this hydrophilic member was 87 mN / m, and the surface was very hydrophilic. The visible light transmittance of the hydrophilic layer was 90% (measured with a Hitachi spectrophotometer U3000).
The Si—OH / Si of the first layer was 0.80. (Measured with TOF-SIMS manufactured by ION-TOF)
Ra of the first layer was 1.6. (Measured using a SPA400 manufactured by SII-NT, SI-DF20 manufactured by SII-NT, and a scanning speed of 1 to 2 Hz and a contact pressure of 10 to 20% in DFM mode.)

<First layer coating solution>
-Colloidal silica dispersion 20% by weight aqueous solution (Snowtex C) 100g
・ 500g of the following sol-gel preparation (1)
・ 30 g of 5% by weight aqueous solution of the following anionic surfactant
・ Purified water 450g
<Second layer coating solution>
-Colloidal silica dispersion 20% by weight aqueous solution (Snowtex C) 100g
・ 500g of the following sol-gel preparation (2)
・ 30 g of 5% by weight aqueous solution of the following anionic surfactant
・ Purified water 450g

<Sol-gel preparation liquid (1)>
Into 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.) was mixed and stirred at room temperature for 2 hours to prepare.
<Sol-gel preparation liquid (2)>
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 5 g of a hydrophilic polymer having a silane coupling group at the following terminal are mixed. Stir 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 (polystyrene 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.

(Evaluation) The following evaluation was performed on the hydrophilic member.
Hydrophilicity: Measurement of the contact angle of water droplets in the air (measured with DropMaster500 manufactured by Kyowa Interface Science Co., Ltd.).
Durability Abrasion test: A non-woven fabric (BEMCOT, manufactured by Asahi Chemical Fiber Co., Ltd.) was rubbed 200 times with a weight of 100 g, 200 g, 500 g, and 1000 g, and the weight at which damage was generated was evaluated. The durability is better when there is no damage even if the load is large.
Scratch test: Starting from 5 g on a 0.1 mm diameter sapphire needle, the surface of the hydrophilic layer was scanned in 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.). The durability is better when there is no damage even if the load is large.

  As a result, the water contact angle was 5 ° or less and the hydrophilicity was very high. In the abrasion test, there was no damage up to 200 g, and in the scratch test, there was no damage up to 100 g, and the durability was excellent.

Example 2
A hydrophilic layer was prepared in the same manner as in Example 1 except that the drying temperature of the first layer coating solution was changed to 80 ° C. The obtained hydrophilic member was highly hydrophilic at a water droplet contact angle of 5 ° or less. The abrasion test showed no damage up to 200 g, and the scratch test showed no damage up to 150 g.
The undercoat layer had Si—OH / Si of 0.88 and Ra of 1.6 nm.

Example 3
A hydrophilic layer was prepared in the same manner as in Example 1 except that the sol-gel solution catalyst of the first layer coating solution was changed to 1.5 g of 1N nitric acid aqueous solution (nitric acid catalyst) and the drying temperature was changed to 80 ° C. The obtained hydrophilic member was not damaged up to 100 g in the abrasion test. In the scratch test, scratches were applied at a load of 80 g.
The undercoat layer had a Si—OH / Si ratio of 0.76 and Ra of 1.5 nm.

Example 4
A hydrophilic film was prepared in the same manner as in Example 1 except that Snowtex C was removed from the first layer coating solution. The obtained hydrophilic member was highly hydrophilic at a water droplet contact angle of 5 ° or less. The abrasion test was not damaged up to 100 g, and the scratch test was not damaged up to 70 g.
The undercoat layer had a Si—OH / Si ratio of 0.75 and Ra of 0.9 nm.

Example 5
A hydrophilic film was prepared in the same manner as in Example 1 except that Snowtex C of the first layer coating solution was changed to Snowtex OXS (particle size: 4 to 6 nm). The obtained hydrophilic member was highly hydrophilic at a water droplet contact angle of 5 ° or less. The abrasion test was not damaged up to 100 g, and the scratch test was not damaged up to 90 g.
The undercoat layer had Si—OH / Si of 0.78 and Ra of 1.2 nm.

Example 6
A hydrophilic film was prepared in the same manner as in Example 1 except that Snowtex C of the first layer coating solution was changed to Snowtex XL (particle size: 40 to 60 nm). The obtained hydrophilic member was highly hydrophilic at a water droplet contact angle of 5 ° or less. The abrasion test was not damaged up to 200 g, and the scratch test was not damaged up to 130 g.
The undercoat layer had a Si—OH / Si ratio of 0.84 and Ra of 3.4 nm.

Example 7
A hydrophilic film was prepared in the same manner as in Example 1 except that Snowtex C of the first layer coating solution was changed to Snowtex YL (particle size: 50 to 80 nm). The obtained hydrophilic member was highly hydrophilic at a water droplet contact angle of 5 ° or less. The abrasion test was not damaged up to 200 g, and the scratch test was not damaged up to 180 g.
The undercoat layer had a Si—OH / Si ratio of 0.90 and Ra of 10.3 nm.

Example 8
After applying and drying the first layer, a hydrophilic layer was prepared in the same manner as in Example 1 except that plasma etching was performed for 30 seconds. The obtained hydrophilic member was highly hydrophilic at a water droplet contact angle of 5 ° or less. The abrasion test was not damaged up to 200 g, and the scratch test was not damaged up to 220 g.
The undercoat layer after plasma etching had an Si—OH / Si ratio of 0.91 and Ra of 21.2 nm.

Example 9
After applying and drying the first layer, a hydrophilic layer was prepared in the same manner as in Example 1 except that the coated substrate was subjected to ultrasonic treatment for 30 seconds in a cleaning solution (Furuuchi Chemical Co., Ltd. Semico Clean 56). The obtained hydrophilic member was highly hydrophilic at a water droplet contact angle of 5 ° or less. The abrasion test was not damaged up to 200 g, and the scratch test was not damaged up to 120 g.
In addition, Si-OH / Si of the undercoat layer after washing was 0.82, and Ra was 0.7 nm.

Example 10
A hydrophilic layer was prepared in the same manner as in Example 1 except that a hydrophilic polymer having a silane coupling group in the side chain was used instead of the hydrophilic polymer having a silane coupling group at the terminal.
<Synthesis of hydrophilic polymer having a silane coupling group in the side chain>
A 500 ml three-necked flask is charged with 12.9 g of acrylamide, 11.6 g of acrylamide-3- (ethoxysilyl) propyl, and 280 g of 1-methoxy-2-propanol, and 2,2′-azobis (2-methyl) under a nitrogen stream at 80 ° C. 1.8 g of dimethyl propionate) was added. The mixture was kept at the same temperature with stirring for 6 hours, and then cooled to room temperature. The mixture was put into 2 liters of acetone, and the precipitated solid was collected by filtration. The obtained solid was washed with acetone to obtain a hydrophilic polymer (2). The mass after drying was 22.7 g. It was a polymer having a mass average molecular weight of 15,000 according to GPC (polyethylene oxide standard).

Example 11
A hydrophilic layer was prepared in the same manner as in Example 7 except that a hydrophilic polymer having a silane coupling group in the side chain was used instead of the hydrophilic polymer having a silane coupling group at the terminal.
In addition, the evaluation result of the hydrophilic member of Examples 1-11 is put together in the following table | surface.

Comparative Example 1
A hydrophilic film was prepared in the same manner as in Example 1 by applying only the second layer coating solution without applying the first layer coating solution. The obtained hydrophilic member was highly hydrophilic at a water droplet contact angle of 5 ° or less. The abrasion test was damaged even at 100 g. The scratch test was damaged at 20 g, and the durability was not sufficient. The glass substrate had Si—OH / Si of 0.26 and Ra of 0.7 nm.

Comparative Example 2
A hydrophilic film was prepared in the same manner as in Example 1 except that the substrate was plasma-etched for 30 seconds without applying the first layer coating solution. The obtained hydrophilic member was highly hydrophilic at a water droplet contact angle of 5 ° or less. The abrasion test was damaged even at 100 g. The scratch test was scratched at 40 g, and the durability was not sufficient.
In addition, Si-OH / Si of the glass substrate after plasma etching was 0.31, and Ra was 19.5 nm.

Comparative Example 3
After applying the first layer coating solution, a hydrophilic layer was formed in the same manner as in Example 1 except that heating at 1000 ° C. and plasma etching treatment were performed for 30 seconds. The obtained hydrophilic member was highly hydrophilic at a water droplet contact angle of 5 ° or less. The abrasion test was not damaged up to 100 g, and the scratch test was not damaged up to 30 g.
The Si—OH / Si of the undercoat layer after plasma etching was 0.35, and Ra was 18.2 nm.

Comparative Example 4
A hydrophilic layer was prepared in the same manner as in Example 1 except that the sol-gel solution catalyst of the first layer coating solution was changed to 1.5 g of 1N nitric acid aqueous solution (nitric acid catalyst) and the drying temperature was changed to 500 ° C. The obtained hydrophilic member was not damaged up to 100 g in the abrasion test. In the scratch test, scratches were applied at a load of 30 g.
The undercoat layer had a Si—OH / Si ratio of 0.33 and Ra of 1.6 nm.

Comparative Example 5
A hydrophilic layer was prepared in the same manner as in Example 1 except that the drying temperature of the first layer coating solution was changed to 1000 ° C. The obtained hydrophilic member was highly hydrophilic at a water droplet contact angle of 5 ° or less. The abrasion test was not damaged up to 100 g, and the scratch test was not damaged up to 30 g.
The undercoat layer had Si—OH / Si of 0.36 and Ra of 1.5 nm.

  In addition, the evaluation result of the hydrophilic member of Comparative Examples 1-5 is put together in the following table | surface.

  From the above results, an undercoat layer containing a partial structure represented by the general formula (1) between the substrate and the hydrophilic layer and having a M-OH / M value on the surface of 1 to 0.4. The hydrophilic member of the present invention had excellent durability of the hydrophilic layer.

Claims (19)

On the base material, at least an undercoat layer containing a partial structure represented by the following general formula (1) and a hydrophilic layer are provided in this order, and the M-OH / M value of the surface of the undercoat layer is 1 A hydrophilic member characterized by being -0.4.
M-OH Formula (1)
(In the formula, M represents Si, Ti, Zr or Al.)   The hydrophilic member according to claim 1, wherein a value of M-OH / M on the surface of the base material is smaller than a value of M-OH / M on the surface of the undercoat layer.   The hydrophilic member according to claim 1, wherein the undercoat layer is obtained by hydrolyzing and polycondensing a metal alkoxide compound selected from Si, Ti, Zr, and Al.   The hydrophilic member according to claim 3, wherein the hydrolysis and polycondensation are performed at 30 to 200 ° C. 5.   The hydrophilic member according to claim 1, wherein the undercoat layer has a surface roughness (Ra) of 1.0 to 50 nm.   The hydrophilic member according to claim 1, wherein the undercoat layer is mixed with plasma etching treatment or particles.   The hydrophilic layer is a) a hydrophilic polymer, b) a metal alkoxide compound selected from Si, Ti, Zr, and Al, c) the metal alkoxide compound of b) is hydrolyzed and polycondensed; The hydrophilic member according to any one of claims 1 to 6, wherein the composition containing a catalyst that causes a bond with a hydrophilic polymer is hydrolyzed and polycondensed.   The hydrophilic member according to claim 1, wherein the base material contains a Si—OH structure. It has an undercoat layer containing a partial structure represented by the following general formula (1) on the substrate, and the M-OH / M value of the surface of the undercoat layer is from 1 to 0.4. A hydrophilic substrate for a substrate.
M-OH Formula (1)
(In the formula, M represents Si, Ti, Zr or Al.)   The hydrophilic member substrate according to claim 9, wherein a value of M-OH / M on the surface of the base material is smaller than a value of M-OH / M on the surface of the undercoat layer.   The hydrophilic member substrate according to claim 9 or 10, wherein the undercoat layer is obtained by hydrolyzing and polycondensing a metal alkoxide compound selected from Si, Ti, Zr, and Al.   The hydrophilic member substrate according to claim 11, wherein the hydrolysis and polycondensation are performed at 30 to 200 ° C.   The surface roughness (Ra) of the undercoat layer is 1.0 to 50 nm, The hydrophilic member substrate according to any one of claims 9 to 12.   The hydrophilic member substrate according to any one of claims 9 to 13, wherein the undercoat layer is mixed with a plasma etching process or particles.   The substrate for a hydrophilic member according to claim 9, wherein the base material contains a Si—OH structure.   On the base material, a composition containing at least a metal alkoxide compound selected from Si, Ti, Zr, and Al is applied, and heated and dried at 30 to 200 ° C. to coat an undercoat layer, A method for producing a hydrophilic member, comprising providing a hydrophilic layer on an undercoat layer.   The method for producing a hydrophilic member according to claim 16, wherein the composition contains a catalyst.   A composition comprising at least a metal alkoxide compound selected from Si, Ti, Zr, and Al is applied onto a substrate, and the primer layer is coated by heating and drying at 30 to 200 ° C. A method for producing a hydrophilic member substrate.   The method for producing a hydrophilic member substrate according to claim 18, wherein the composition contains a catalyst.