JP2011073359A - Hydrophilic member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrophilic member excelling in hydrophilic property, antifouling property, alkali resistance, acid resistance and hot water resistance. <P>SOLUTION: The hydrophilic member includes a hydrophobic under coat with a surface water drop contact angle of 45° or more and surface free energy of 65 mN/m or less on a substrate of polyethylene terephthalate or the like, and a hydrophilic layer formed of a hydrophilic composition containing a hydrophilic polymer with a silicon atom having at least one of hydroxyl group and a hydrolysis functional group, on the hydrophobic under coat. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a hydrophilic member, and more particularly, to a hydrophilic member having a hydrophobic undercoat layer on a substrate and a hydrophilic layer on the hydrophobic undercoat layer.

Various hydrophilic members having a hydrophilic film on various substrates have been proposed for the purpose of imparting antifogging properties and antifouling properties.
In Patent Document 1, an undercoat layer formed from a water-based resin composition is formed on a polyethylene terephthalate substrate, and a hydrophilic polymer containing a hydrolyzable silyl group at the main chain terminal or side chain is formed on the undercoat layer. A hydrophilic member having a hydrophilic layer is described.

JP 2008-284715 A

As a result of the study by the present inventors, the hydrophilic layer described in Patent Document 1 has excellent adhesion to a base material made of an inorganic material such as glass or metal, and is excellent in alkali resistance. It has been found that there is a problem that the hydrophilic layer is peeled off by alkali due to low adhesion to a substrate made of the above organic material. Moreover, since a hydrophilic layer generally absorbs water-soluble liquids such as alkalis and acids, it is inferior in alkali resistance and acid resistance as compared with general-purpose resins.
In addition, the hydrophilic layer described in Patent Document 1 is also required to improve hot water resistance.

  The object of the present invention is to solve the above problems and to provide a hydrophilic member excellent in hydrophilicity, antifouling property, alkali resistance, acid resistance, and hot water resistance.

The present inventors have solved the above problems by the following means.
1.
A hydrophilic member comprising a hydrophobic undercoat layer on a substrate and a hydrophilic layer on the hydrophobic undercoat layer.
2.
2. The hydrophilic member as described in 1 above, wherein the water droplet contact angle on the surface of the hydrophobic undercoat layer is 45 ° or more.
3.
3. The hydrophilic member as described in 1 or 2 above, wherein a surface free energy of the hydrophobic undercoat layer is 65 mN / m or less.
4).
4. The hydrophilic member as described in any one of 1 to 3 above, wherein the hydrophobic undercoat layer is formed from a hydrophobic composition containing a hydrophobic polymer having a crosslinkable group.
5).
5. The hydrophilic member as described in any one of 1 to 4 above, wherein the crosslinkable group contains a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group.
6).
The hydrophilic layer is formed from a hydrophilic composition containing a hydrophilic polymer having a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group. The hydrophilic member.
7).
The hydrophilic polymer is
A hydrophilic polymer (I) containing a structural unit represented by the following general formula (I-1) and a structural unit represented by the following general formula (I-2), and represented by the following general formula (II-1) A hydrophilic polymer having a partial structure represented by the following general formula (II-2) and a partial structure represented by the following general formula (II-1) at the end of the polymer chain: II)
The hydrophilic member as described in any one of 1 to 6 above, which is at least one of the above.

{In General Formulas (I-1) and (I-2), R ^{101 to} R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 to 3, and L ¹⁰¹ and L ¹⁰² each independently represent a single bond or a polyvalent organic linking group. x and y represent a composition ratio, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ¹⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , -OCON (R _a ) (R _b ), -NHCON (R _a ) (R _b ), -SO ₃ R _e , -OSO ₃ R _e , -SO ₂ R _d , -NHSO ₂ R _d , -SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _{e) (R f), -} OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. }

{Represents the general formula (II-1) and ^(II-2), each of R 201 ^{to R 205} independently represent a hydrogen atom or a hydrocarbon group. q represents an integer of 1 to 3, and L ²⁰¹ and L ²⁰² each independently represent a single bond or a polyvalent organic linking group. A ²⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _{e) (R f), -} OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. }
8).
1 to 7 above, further comprising a catalyst in at least one of the hydrophobic composition for forming the hydrophobic undercoat layer and the hydrophilic composition for forming the hydrophilic layer. The hydrophilic member in any one.
9.
The hydrophilic member as described in any one of 1 to 8 above, wherein the catalyst is a non-volatile catalyst.
10.
The hydrophilic composition contains the hydrophilic polymer (I) and the hydrophilic polymer (II), and the mass ratio of the hydrophilic polymer (I) to the hydrophilic polymer (II) (hydrophilic polymer (I) The hydrophilic member as described in any one of 7 to 9 above, wherein / hydrophilic polymer (II)) is in the range of 95/5 to 50/50.
11.
At least one of the hydrophobic composition and the hydrophilic composition further contains an alkoxide compound of at least one element selected from Si, Ti, Zr, and Al. The hydrophilic member according to any one of the above.
12
The hydrophilic member according to any one of the above 1 to 11, wherein at least one of the hydrophobic composition and the hydrophilic composition further contains a surfactant.
13.
13. The hydrophilic member as described in 12 above, wherein the surfactant is at least one selected from an anionic surfactant, an amphoteric surfactant, and a fluorosurfactant.
14
14. The hydrophilic member as described in any one of 1 to 13 above, wherein the thickness of the hydrophobic undercoat layer is larger than 10 nm and smaller than 1 μm.
15.
The hydrophilic member as described in any one of 1 to 14 above, wherein the thickness of the hydrophilic layer is larger than 10 nm and smaller than 1 μm.
16.
The hydrophobic undercoat layer is formed by applying a hydrophobic composition, heating and drying, and the hydrophilic layer is formed by applying a hydrophilic composition, heating and drying. The hydrophilic member according to any one of 1 to 15 above.
17.
The hydrophilic member as described in any one of 1 to 16 above, wherein the substrate contains a resin.

  ADVANTAGE OF THE INVENTION According to this invention, the hydrophilic member excellent in hydrophilic property, antifouling property, alkali resistance, acid resistance, and hot water resistance can be provided.

Hereinafter, the present invention will be described in detail.
The hydrophilic member of the present invention is characterized by having a hydrophobic undercoat layer on a substrate and having a hydrophilic layer on the hydrophobic undercoat layer.
In the present invention, by forming a hydrophobic film as an undercoat layer between the substrate and the hydrophilic layer, it is possible to suppress alkali and acid permeation and improve alkali resistance and acid resistance. In general, when forming a hydrophilic member having a hydrophilic layer, the undercoat layer, the intermediate layer, or the primer layer is a hydrophobic layer because of concern about wettability and lowering of adhesion. It's hard to think about that.

<Hydrophobic undercoat layer>
The hydrophilic member of the present invention has a hydrophobic undercoat layer on a substrate.
The hydrophobic undercoat layer may be one layer or two or more layers.
The surface of the hydrophobic undercoat layer is hydrophobic, but the degree of hydrophobicity of the membrane surface is generally measured by the water droplet contact angle. The hydrophobic undercoat layer in the present invention is preferably 45 ° or more, more preferably 50 ° or more and 110 ° or less, and more preferably 55 ° or more and 100 ° or less from the viewpoint of suppressing absorption of water (or an aqueous solution). More preferably, it is 60 ° or more and 90 ° or less.
As another method for evaluating the hydrophobicity of the film surface in more detail, there is a measurement of surface free energy. Various methods have been proposed. For example, the surface free energy can be measured using the Zisman plot method. Specifically, an aqueous solution of an inorganic electrolyte such as magnesium chloride uses the property that the surface tension increases with the concentration. After measuring the contact angle in air and at room temperature using the aqueous solution, the horizontal axis indicates the surface of the aqueous solution. Take the tension, the value obtained by converting the contact angle into cos θ on the vertical axis, plot the points of aqueous solutions of various concentrations to obtain a linear relationship, and the surface tension when cos θ = 1, that is, contact angle = 0 °, It is a measurement method defined as the surface free energy of a solid. The surface tension of water is 72 mN / m, and it can be said that the higher the surface free energy value, the higher the hydrophilicity.
The surface free energy of the hydrophobic undercoat layer is preferably 65 mN / m or less, more preferably 18 mN / m or more and 60 mN / m or less, because of its low affinity with water (or an aqueous solution). More preferably, it is 20 mN / m or more and 55 mN / m or less, and particularly preferably 25 mN / m or more and 50 mN / m or less.

The material for forming the hydrophobic undercoat layer is not particularly limited, but a hydrophobic composition containing a hydrophobic polymer is preferred, and the hydrophobic undercoat layer is hydrophobic so that the water droplet contact angle and the surface free energy are within the preferred ranges. A hydrophobic composition containing a polymer is preferred. In order to form the hydrophobic undercoat layer, examples of the functional group used in the hydrophobic polymer are preferably hydrocarbon-based functional groups, which may have various substituents, but more preferably no functional group.
The hydrophobic undercoat layer is preferably formed by applying a hydrophobic composition on a substrate, heating and drying.
In the hydrophilic member of the present invention, the hydrophobic undercoat layer is formed by applying the hydrophobic composition, heating and drying, and the hydrophilic layer applying the hydrophilic composition, heating and drying. It is preferable to be formed.

(Hydrophobic composition)
The hydrophobic composition for forming the hydrophobic undercoat layer will be described.
The hydrophobic composition preferably contains a hydrophobic polymer. From the viewpoint of improving the film strength of the hydrophobic undercoat layer, the hydrophobic polymer is preferably a hydrophobic polymer having a crosslinkable group.
Examples of the crosslinkable group include a group containing a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group (hydrolyzable silyl group, silanol group, etc.), a carboxyl group (HOOC-), a salt thereof (MOOC-, M is a cation), a carboxylic anhydride group (for example, a monovalent group derived from succinic anhydride, phthalic anhydride or maleic anhydride), an amino group (H ₂ N—), a hydroxyl group (HO—), an epoxy Groups (eg, glycidyl groups), methylol groups (HO—CH ₂ —), mercapto groups (HS—), isocyanate groups (OCN—), block isocyanate groups, alkoxy titanate groups, alkoxy aluminate groups, alkoxy zirconate groups Group, a group containing an ethylenically unsaturated double bond, a group containing an ester bond, a tetrazole group, and the like. A group containing a silicon atom having at least one of decomposable functional groups, and an epoxy group (eg, glycidyl group) are preferable, and a hydroxyl group and a hydrolyzable functional group can be used because acid resistance and alkali resistance can be particularly improved. What contains the silicon atom which has at least any one of group is further more preferable.

As the hydrophobic polymer containing a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group, one having at least one of a silanol group and a hydrolyzable silyl group is preferable.
It is preferable that the hydrophilic polymer has at least one of a silanol group and a hydrolyzable silyl group in at least one of a terminal portion and a side chain of the polymer.
The hydrolyzable silyl group is a group that reacts with water to produce silanol (Si—OH). For example, one or more methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n -Refers to a bond of an alkoxy group such as butoxy group, chlorine or the like.
The hydrolyzable silyl group is preferably represented by the following general formula (a).
Formula _{^{(a): -Si (R 10}} ) 3-a - (OR 11) a
In general formula (a), R ¹⁰ is a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group, R ¹¹ is a hydrogen atom or an alkyl group, and a is an integer of 1 to 3. . When a plurality of R ¹⁰ and R ¹¹ are present, they may be the same as or different from each other.

When R ¹⁰ represents an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. When an aryl group is represented, an aryl group having 6 to 25 carbon atoms is preferred, and when representing an aralkyl group, an aralkyl having 7 to 12 carbon atoms is preferred. Groups are preferred. When R < ¹¹ > represents an alkyl group, a C1-C10 alkyl group is preferable.

  The hydrolyzable silyl group can form a chemical bond by reacting with a hydrolyzed polycondensate of an alkoxide containing an element selected from Si, Ti, Zr, and Al described later. Moreover, hydrolyzable silyl groups may form a chemical bond. The chemical bond in this case includes a covalent bond, an ionic bond, a coordination bond, and a hydrogen bond in the same manner as usual. The chemical bond is preferably a covalent bond.

The weight average molecular weight of the hydrophobic polymer is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 800,000 or less, and still more preferably 3,000 or more and 500, from the viewpoint of film forming properties. 5,000 or less, particularly preferably 5,000 or more and 100,000 or less.
Specific examples of the hydrophobic polymer are shown below together with their mass average molecular weight (M.W.), but are not limited thereto. In addition, the polymer of the specific example shown below means that each structural unit described is a random copolymer or block copolymer contained in the described molar ratio.

  The solid content concentration of the hydrophobic composition is preferably 20 to 0.5 mass%, more preferably 15 to 1 mass%.

  The thickness of the hydrophobic undercoat layer is preferably larger than 5 nm and smaller than 5 μm, more preferably 0.01 μm to 3 μm. If it is too thick, the film tends to crack, and if it is too thin, performance is likely to be insufficient. The thickness can be adjusted by the solid content concentration of the composition, the coil diameter of the bar coater, etc., and can be determined by a known method.

The center average roughness Ra of the surface of the hydrophobic undercoat layer is preferably 1 nm to 10 nm. The Tg of the hydrophobic undercoat layer is preferably 40 ° C. to 150 ° C. from the viewpoint of coating strength. Further, the elastic modulus of the hydrophobic undercoat layer is preferably 1 GPa to 7 GPa.
The surface properties of the hydrophobic undercoat layer can be controlled by adjusting the surface roughness of the substrate, the viscosity of the composition, the heating temperature, the speed, and the like.

(Preparation of hydrophobic composition)
The hydrophobic composition can be prepared by dissolving a hydrophobic polymer, as appropriate, a metal alkoxide, a catalyst, a surfactant, and other additives in a solvent and then stirring. When using a curing catalyst, it may be mixed immediately before coating on the substrate. Specifically, it is preferable to coat within 1 hour immediately after mixing of the curing catalyst.
If the curing catalyst is mixed and left to stand for a long time, the composition will increase in viscosity, and defects such as uneven coating may occur.
Other components are also preferably mixed immediately before coating, but may be stored for a long time after mixing.
The reaction temperature in the preparation is from room temperature to 80 ° C., and the reaction time, that is, the time for which stirring is continued, is preferably in the range of 1 to 72 hours. Decomposition / polycondensation can proceed to obtain an organic-inorganic composite sol solution.

  The solvent used in preparing the hydrophobic composition is not particularly limited as long as each component can be uniformly dissolved and dispersed, but for example, ethanol, isopropanol, and 1-methoxy-2-propanol are preferable. .

As described above, the preparation of the organic-inorganic composite sol solution for forming a film with the hydrophilic composition of the present invention utilizes the sol-gel method. Regarding the sol-gel method, Sakuo Sakuo “Science of Sol-Gel Method”, Agne Jofusha (published) (1988), Satoshi Hirashima “Functional Thin Film Formation Technology by the Latest Sol-Gel Method” General Technology Center (Published) (1992) and the like, and the methods described therein can be applied to the preparation of the composition in the present invention.
The hydrophilic member of this invention can be obtained by apply | coating the solution containing such a composition on a base material, and drying.

The drying temperature is preferably 10 ° C to 250 ° C, more preferably 70 ° C to 220 ° C. When the drying temperature is too low, the film is not sufficiently dried and the film strength is lowered. If the temperature is too high, the film tends to crack.
The drying time is preferably 10 seconds to 200 minutes. More preferably, it is 15 seconds to 90 minutes. If the drying time is too short, the film strength may decrease due to insufficient drying. If the drying time is excessively longer than necessary, the film may crack.

<Hydrophilic layer>
The hydrophilic member of the present invention has a hydrophilic layer on the hydrophobic undercoat layer.
The hydrophilic layer may be a single layer or may have two or more layers.
The material for forming the hydrophilic layer is not particularly limited, but a hydrophilic composition containing a hydrophilic polymer is preferable.
The hydrophilic layer is preferably formed by applying a hydrophilic composition on the hydrophobic undercoat layer, heating and drying.

(Hydrophilic polymer)
The hydrophilic polymer contained in the hydrophilic composition for forming the hydrophilic layer is not particularly limited, but preferred main chain structures include acrylic resins, methacrylic resins, polyvinyl acetal resins, polyurethane resins, and polyureas. Resin, polyimide resin, polyamide resin, epoxy resin, polystyrene resin, novolac type phenol resin, polyester resin, synthetic rubber, natural rubber, etc. are mentioned, and acrylic resin and methacrylic resin are particularly preferable. A resin is more preferable. The hydrophilic polymer may be a copolymer, and the copolymer may be a random copolymer or a block copolymer.
Moreover, the hydrophilic composition in this invention may contain 1 type of hydrophilic polymers, and may contain 2 or more types.

From the viewpoint of improving the film strength of the hydrophilic layer, a hydrophilic polymer having a crosslinkable group is preferable.
Examples of the crosslinkable group include the same as those mentioned in the hydrophobic polymer, and preferable examples thereof are the same, and particularly those containing a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group. preferable.

As the hydrophilic polymer containing a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group (hereinafter also referred to as a hydrophilic polymer), one having at least one of a silanol group and a hydrolyzable silyl group is preferable.
It is preferable that the hydrophilic polymer has at least one of a silanol group and a hydrolyzable silyl group in at least one of a terminal portion and a side chain of the polymer.
The hydrolyzable silyl group is a group that reacts with water to produce silanol (Si—OH). For example, one or more methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n -Refers to a bond of an alkoxy group such as butoxy group, chlorine or the like.
The hydrolyzable silyl group is preferably represented by the following general formula (a).
Formula _{^{(a): -Si (R 10}} ) 3-a - (OR 11) a
In general formula (a), R ¹⁰ is a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group, R ¹¹ is a hydrogen atom or an alkyl group, and a is an integer of 1 to 3. . When a plurality of R ¹⁰ and R ¹¹ are present, they may be the same as or different from each other.

When R ¹⁰ represents an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹⁰ represents an aryl group, an aryl group having 6 to 25 carbon atoms is preferable. Groups are preferred. When R < ¹¹ > represents an alkyl group, a C1-C10 alkyl group is preferable.

The hydrolyzable silyl group is preferably a hydrolyzable silyl group bonded to a carbon atom.
One or more hydrolyzable silyl groups may be present at the end of the polymer main chain, or one or more hydrolyzable silyl groups may be present at the side chain. When two or more hydrolyzable silyl groups are included, the two or more hydrolyzable silyl groups may be the same as or different from each other.

  The hydrolyzable silyl group can form a chemical bond by reacting with a hydrolyzed polycondensate of an alkoxide containing an element selected from Si, Ti, Zr, and Al described later. Moreover, hydrolyzable silyl 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 in this case includes a covalent bond, an ionic bond, a coordination bond, and a hydrogen bond in the same manner as usual. The chemical bond is preferably a covalent bond.

The hydrophilic polymer preferably contains a hydrophilic group. The hydrophilic groups, _{e.g., -NHCOR, -NHCO 2 R, -NHCONR} 2, -CONH 2, -NR 2, -CONR 2, -OCONR 2, -COR, -OH, -OR, -OM, -CO _{2 M, -CO 2 R, -SO} 3 M, -OSO 3 M, -SO 2 R, -NHSO 2 R, -SO 2 NR 2, -PO 3 M, -OPO 3 M, - (CH 2 CH 2 _{O) n H, - (CH} 2 CH 2 O) such as n CH ₃ or _-NR 3 ^{Z 1} and the like. However, when two or more R exists, they may be the same as or different from each other, and each represents a hydrogen atom, an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms), an aryl group, or an aralkyl group. M represents a hydrogen atom, an alkyl group, an alkali metal, an alkaline earth metal, or onium, n represents an integer (preferably an integer of 1 to 100), and Z ¹ represents a halogen ion. Also, in the case in which a plurality of R as -CONR _2, may form a ring by bonding R together, and the formed ring is an oxygen atom, a sulfur atom, a hetero atom such as nitrogen atom Heterocycle containing may be sufficient. R may further have a substituent, and as the substituent, a substituent that can be introduced when R ¹⁰¹ and R ¹⁰² in the structure represented by the general formula (I-1) to be described later are alkyl groups. The following can be cited as well.

  Specific examples of R 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 hydrophilic _{group, -OH, -NHCOCH 3, -CONH 2} , -CON (CH 3) 2, -COOH, -SO 3 - NMe 4 +, -SO 3 - K +, - (CH 2 CH 2 O _N H, morpholyl group and the like are preferable. More _{preferably, -OH, -NHCOCH 3, -CONH 2} , -CON (CH 3) 2, -COOH, -SO 3 - K +, - (CH 2 CH 2 O) n H is, more preferably , —OH, —COOH, —CONH ₂ .

  The hydrophilic polymer includes a structure represented by the following general formula (I-1) and a hydrophilic polymer (I) having a structure represented by the following general formula (I-2), and the following general formula (II-1). Hydrophilicity having a partial structure represented by the following general formula (II-2) and a structural unit represented by the following general formula (II-2) at the end of the polymer chain The polymer (II) or at least one of the structure represented by the following general formula (III-1) and the hydrophilic polymer (III) including the structure represented by the following general formula (III-2) is preferable.

{In General Formulas (I-1) and (I-2), R ^{101 to} R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 to 3, and L ¹⁰¹ and L ¹⁰² each independently represent a single bond or a polyvalent organic linking group. x and y represent composition ratios, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ¹⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _{e) (R f), -} OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. }

{Represents the general formula (II-1) and ^(II-2), each of R 201 ^{to R 205} independently represent a hydrogen atom or a hydrocarbon group. q represents an integer of 1 to 3, and L ²⁰¹ and L ²⁰² each independently represent a single bond or a polyvalent organic linking group. A ²⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _{e) (R f), -} OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. }

{In General Formulas (III-1) and (III-2), R ^{301 to} R ³¹¹ each independently represent a hydrogen atom or a hydrocarbon group. r represents an integer of 1 to 3, and L ^{301 to} L ³⁰³ each independently represent a single bond or a polyvalent organic linking group. x and y represent composition ratios, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ³⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _{e) (R f), -} OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. }

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

{In General Formulas (I-1) and (I-2), R ^{101 to} R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 to 3, and L ¹⁰¹ and L ¹⁰² each represents a single bond or a polyvalent organic linking group. x and y represent composition ratios, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ¹⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _{e) (R f), -} OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. }

In the general formulas (I-1) and (I-2), R ^{101 to} R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. R ^{101 to} R ¹⁰⁸ are preferably a hydrogen atom, a methyl group, or an ethyl group from the viewpoints of effects and availability.

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

Aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfa Yl group, N, N- dialkylsulfamoyl group, N- aryl sulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group phosphono group _(-PO 3 _{H 2} ) And its conjugate base group (hereinafter referred to as phosphonate group), dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ), alkylaryl phosphono group (— PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (—PO ₃ H) (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphonophenyl group), phosphonooxy group (-OPO ₃ H ₂ ) And conjugated base groups thereof (hereinafter referred to as phosphonatooxy groups), dialkylphosphonooxy groups (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy groups (—OPO ₃ (aryl) ₂ ), alkylaryl phosphines A phonooxy group (—OPO (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as an alkylphosphonatooxy group), monoarylphosphono Examples thereof include an oxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonateoxy group), a morpholino group, a cyano group, a nitro group, an aryl group, an alkenyl group, and an alkynyl group.

Specific examples of the alkyl group in these substituents are the same as those of R ^{101 to} R ¹⁰⁸ , and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, Xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, acetoxyphenyl, benzoyloxyphenyl, methylthiophenyl , Phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenyl Luba carbamoylphenyl group, a phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, and a phosphonophenyl phenyl group. Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like. Examples of alkynyl group include ethynyl group, 1- A propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, etc. are mentioned. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups.

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

  On the other hand, the alkylene group in the substituted alkyl group is preferably a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Preferably, it is a straight chain having 1 to 12 carbon atoms, more preferably a straight chain having 1 to 8 carbon atoms, more preferably a branched structure having 3 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms, and More preferable examples include cyclic alkylene groups having 5 to 10 carbon atoms, and further preferably 5 to 8 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a hydroxymethyl group, a methoxymethyl group, and a methoxyethoxy group. Ethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonyl group Group, allyloxycarbonyl butyl group,

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

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

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

In General Formula (I-1), L ¹⁰¹ represents a single bond or a structure selected from the group consisting of —CONH—, —NHCONH—, —OCONH—, —SO ₂ NH—, and —SO ₃ —. It is preferably a linking group having two or more.

In the general formula (I-2), A ¹⁰¹ represents —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ). , —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _c ) ( _{R g), - PO 3 (} R e) (R f), - OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having 1 to 8 carbon atoms), and R _d is a linear, branched or cyclic group. R _e and R _f each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group (preferably having 1 to 8 carbon atoms), an alkali metal, It represents an alkaline earth metal or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. In addition, —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _e ) R _{a to} R _g may be bonded to each other to form a ring with _{respect to} (R _f ), —OPO ₃ (R _e ) (R _f ), or —PO ₃ (R _d ) (R _e ), The formed ring may be a heterocycle containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom. R _{a to} R _g may further have a substituent, and the substituent that can be introduced here is the same as the substituent that can be introduced when R ^{1 to} R ⁸ are alkyl groups. Can be listed.

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

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

  p represents an integer of 1 to 3, preferably 2 to 3, and more preferably 3.

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

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

  The mass average molecular weight of the polymer containing the structure represented by the general formula (I-1) and the structure represented by (I-2) is preferably 1,000,000 or less, and 1,000 to 1,000,000. Is more preferable, 1,000 to 500,000 is still more preferable, 1,000 to 200,000 is particularly preferable, and 2,000 to 50,000 is most preferable.

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

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

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

{Represents the general formula (II-1) and ^(II-2), each of R 201 ^{to R 205} independently represent a hydrogen atom or a hydrocarbon group. q represents an integer of 1 to 3, and L ²⁰¹ and L ²⁰² each represent a single bond or a polyvalent organic linking group. A ²⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _{e) (R f), -} OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. }

  The hydrophilic polymer (II) including the structure represented by the general formula (II-1) and the structure represented by (II-2) has a structural unit represented by the above general formula (II-2). And it is preferable to have the partial structure represented by the said general formula (II-1) at the terminal of a polymer chain.

In the structure represented by the general formula (II-1) and (II-2), R ^{201 to} R ²⁰⁵ each independently represents a hydrogen atom or a hydrocarbon group, and R ^{201 to} R ²⁰⁵ represent a hydrocarbon group. Examples of the hydrocarbon group in the case of representation include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable. Specifically, the thing similar to what was mentioned by R < ¹⁰¹ > -R < ¹⁰⁸ > of the said general formula (I-1) and (I-2) can be mentioned.
L ²⁰¹ and L ²⁰² each independently represent a single bond or a polyvalent organic linking group. Here, the single bond means that the main chain of the polymer is directly bonded to the A ²⁰¹ and Si atoms without a connecting chain. When L ²⁰¹ and L ²⁰² represent a polyvalent organic linking group, specific examples and preferred examples thereof can be the same as those described for L ¹⁰¹ in the general formula (I-1).
A ²⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _{e) (R f), -} OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . Specific examples and preferred examples of A ²⁰¹ include the same examples as those described for A ¹⁰¹ in formula (I-2).
q represents an integer of 1 to 3. Preferably it is 2-3, More preferably, it is 3.

L ²⁰¹ and L ²⁰² are more preferably —CH ₂ CH ₂ CH ₂ S—, —CH ₂ S—, —CONHCH (CH ₃ ) CH ₂ —, —CONH—, —CO—, —CO ₂ —, -CH ₂ - is.

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

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

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

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

  The mass average molecular weight of the hydrophilic polymer (II) including the structure represented by the general formula (II-1) and the structure represented by (II-2) is preferably 1,000,000 or less, and 1,000 to 1,000,000 is more preferred, 1,000 to 500,000 is still more preferred, 1,000 to 200,000 is particularly preferred, and 5,000 to 50,000 is most preferred.

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

[Hydrophilic polymer (III) including structure represented by general formula (III-1) and structure represented by (III-2)]
The hydrophilic polymer (III) includes a structure represented by the following general formula (III-1) and a structure represented by (III-2). The hydrophilic polymer (III) is preferably a hydrophilic graft polymer obtained by introducing a side chain having a hydrophilic group into a trunk polymer having a reactive group.

{In General Formulas (III-1) and (III-2), R ^{301 to} R ³¹¹ each independently represent a hydrogen atom or a hydrocarbon group. r represents an integer of 1 to 3, and L ^{301 to} L ³⁰³ each represents a single bond or a polyvalent organic linking group. x and y represent composition ratios, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ³⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _{e) (R f), -} OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. }

In the general formulas (III-1) and (III-2), R ^{301 to} R ³¹¹ each independently represent a hydrogen atom or a hydrocarbon group, and hydrocarbons in the case where R ^{301 to} R ³¹¹ represent a hydrocarbon group. Examples of the group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable. Specifically, the same thing as what was mentioned by R < ¹⁰¹ > -R < ¹⁰⁸ > of the said general formula (I-1) and (I-2) can be mentioned, A preferable range is also the same.
L ³⁰¹ , L ³⁰² and L ³⁰³ each independently represent a single bond or a polyvalent organic linking group. Here, the single bond means that the main chain of the polymer and A ³⁰¹ , the side chain, and the Si atom are directly bonded without a connecting chain. When L ³⁰¹ , L ³⁰² and L ³⁰³ represent a polyvalent organic linking group, specific examples and preferred examples are the same as those described for L ¹⁰¹ in formula (I-1). Can do.
A ³⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _{e) (R f), -} OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . Specific examples and preferred examples of A ²⁰¹ include the same examples as those described for A ¹⁰¹ in formula (I-2).
r represents an integer of 1 to 3. Preferably it is 2-3, More preferably, it is 3.

  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 Application” by Fumio Ide, published in 1977, “Polymer Publications”, “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 synthesis method of 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 is obtained by first copolymerizing a hydrophilic macromonomer (corresponding to a precursor of a hydrophilic polymer side chain) synthesized by the above method and a monomer having a reactive group. Can be synthesized.

  Particularly useful among the hydrophilic macromonomers are macromonomers derived from carboxyl group-containing monomers such as acrylic acid and methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylstyrene sulfonic acid, and salts thereof Sulfonic acid macromonomer derived from the monomer of amide, amide macromonomer such as acrylamide and methacrylamide, amide macromonomer derived from N-vinylcarboxylic amide monomer such as N-vinylacetamide and N-vinylformamide, Macromonomers derived from hydroxyl-containing monomers such as hydroxyethyl methacrylate, hydroxyethyl acrylate, glycerol monomethacrylate, methoxyethyl acrylate, methoxypolyethylene glycol acrylic Over bets, a macromonomer 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.

  In the hydrophilic polymer (III) including the structure represented by the general formula (III-1) and the structure represented by (III-2), x is preferably in the range of 1 <x <90. More preferably, x <50. y is preferably in the range of 10 <y <99, and more preferably in the range of 50 <y <99.

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

  The hydrophilic polymer (III) preferably has a mass average molecular weight of 1,000,000 or less, and has 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 film without lowering the solubility in the solvent when preparing a coating solution for forming a hydrophilic film, without lowering the viscosity of the coating solution. This is preferable.

  Specific examples of the hydrophilic polymer (III) including the structure represented by the general formula (III-1) and the structure represented by (III-2) are shown below together with its mass average molecular weight (MW). However, the present invention is not limited to these. In addition, the polymer of the specific example shown below means that each structural unit described is a random copolymer or block copolymer contained in the described molar ratio.

Of the hydrophilic polymer (I), the hydrophilic polymer (II) and the hydrophilic polymer (III), the hydrophilic polymer (I) and the hydrophilic polymer (II) are more preferable because of film-forming properties. The hydrophilic polymer (I) is more preferred because a large number of hydrolyzable silyl groups per molecule can be introduced and very good curability can be obtained by drying at room temperature.
Further, it is also preferable to include the hydrophilic polymers (I) and (II), and the mass ratio of the hydrophilic polymer (I) to the hydrophilic polymer (II) (hydrophilic polymer (I) / hydrophilic polymer (II)) is It is preferably in the range of 95/5 to 50/50.

  The hydrophilic polymer (I), the hydrophilic polymer (II), or the hydrophilic polymer (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.

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

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

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

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

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

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

  Copolymerization ratios of hydrophilic polymer (I), hydrophilic polymer (II), and hydrophilic polymer (III) are measured using a nuclear magnetic resonance apparatus (NMR) or a standard substance to create a calibration curve. It can be measured with a photometer.

  The hydrophilic polymer forms a crosslinked film in a state where it is mixed with a hydrolyzed polycondensate of metal alkoxide described later. The hydrophilic polymer is involved in the strength of the hydrophilic film and the flexibility of the film. In particular, the viscosity of the hydrophilic polymer containing a hydrolyzable silyl group is 0.1 to 100 mPa · s (5% aqueous solution, 20 degreeC measurement), Preferably 0.5-70 mPa * s, More preferably, it exists in the range of 1-50 mPa * s, and a favorable film | membrane physical property is given.

The hydrophobic composition and the hydrophilic composition in the present invention may contain other components in addition to the hydrophobic polymer and the hydrophilic polymer, respectively.
Hereinafter, the component which the hydrophobic composition and the hydrophilic composition may contain is demonstrated.

[Alkoxide compound containing any element selected from Si, Ti, Zr, and Al]
An alkoxide compound (also referred to as a metal alkoxide) containing any element selected from Si, Ti, Zr, and Al may be contained in at least one of the hydrophobic composition and the hydrophilic composition. In order to impart high film strength to the hydrophilic member, a metal alkoxide may be contained in the hydrophobic composition, and particularly when the hydrophilic composition contains the hydrophilic polymer (I), good curing is achieved. In order to obtain properties, it is preferable to contain a metal alkoxide. In addition, when the hydrophilic composition (II) or (III) is contained in the hydrophilic composition, good curability can be obtained even when the metal alkoxide is not contained, but the coating strength is extremely excellent. In order to obtain a film, a metal alkoxide may be contained.

A metal alkoxide is a hydrolyzable polymerizable compound having a functional group capable of being hydrolyzed and polycondensed in its structure and serving as a cross-linking agent, and has a cross-linked structure due to polycondensation of metal alkoxides. A strong cross-linked film can be formed and further chemically bonded to the hydrophilic polymer. The metal alkoxide can be represented by general formula (V-1) or general formula (V-2), wherein R ²⁰ represents a hydrogen atom, an alkyl group or an aryl group, and R ²¹ and R ²² represent an alkyl group or Represents an aryl group, Z represents Si, Ti or Zr, and m represents an integer of 0 to 2; The number of carbon atoms when R ²⁰ , R ²¹ and R ²² 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 20) m -Z- (OR}} 21) 4-m (V-1)
Al- (OR ²² ) ₃ (V-2)

  Although the specific example of a metal alkoxide represented by general formula (V-1) or general formula (V-2) below is given, it is not limited to this.

  When Z is Si, that is, the hydrolyzable compound containing silicon includes, for example, trimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, γ- Examples include chloropropyltriethoxysilane, 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, zirconates corresponding to the compounds exemplified as those 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 the above, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane are particularly preferable.

  It is preferable that 0-60 mass% is used for a metal alkoxide compound with respect to the total solid of a hydrophilic composition, and it is more preferable that 10-50 mass% is used. When the amount of the metal alkoxide compound is increased, the hydrophilicity is increased, but the film is cracked, resulting in poor film formability. Moreover, it is preferable that 0-30 mass% is used for a metal alkoxide compound with respect to the total solid of a hydrophobic composition, and it is more preferable that 5-20 mass% is used. When the amount of the metal alkoxide compound increases, the hydrophobicity of the hydrophobic undercoat layer decreases, and the acid resistance and alkali resistance deteriorate.

〔catalyst〕
A catalyst may be contained in at least one of the hydrophobic composition and the hydrophilic composition. In particular, when the hydrophilic composition contains a hydrophilic polymer having a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group (and further contains a metal alkoxide if necessary), it is dissolved in a solvent and stirred well. Thus, these components are hydrolyzed and polycondensed to form an organic-inorganic composite sol solution, and a hydrophilic layer having high hydrophilicity and high film strength is formed by this sol solution. In the preparation of the organic-inorganic composite sol solution, it is preferable to use a catalyst in order to promote hydrolysis and polycondensation reaction. By using a catalyst, the drying temperature for forming the hydrophilic layer can be set low, and thermal deformation on the antibacterial agent or the substrate can be suppressed.
The curing catalyst is preferably a non-volatile catalyst. Here, the non-volatile catalyst means a catalyst having a boiling point other than 125 ° C., in other words, a catalyst having a boiling point of 125 ° C. or higher, or a catalyst having no boiling point in the first place (such as thermal decomposition, phase change). Including things that do not wake up).
Preferably, the curing catalyst may be an acidic catalyst or a basic catalyst that promotes a reaction in which a crosslinking agent is hydrolyzed and polycondensed to form a bond with a hydrophilic polymer containing silicon.

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

  The type of the acidic catalyst or the basic catalyst is not particularly limited. However, when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element that hardly remains in the coating film after drying is preferable. Specifically, the acid catalyst is represented by hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid or acetic acid, and its RCOOH. Examples of the basic catalyst include ammoniacal bases such as aqueous ammonia, amines such as ethylamine and aniline, and the like. Etc.

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

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

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

  Specific examples of preferred acetylacetone derivatives include ethylcarbonylacetone, n-propylcarbonylacetone, i-propylcarbonylacetone, diacetylacetone, 1-acetyl-1-propionyl-acetylacetone, hydroxyethylcarbonylacetone, hydroxypropylcarbonylacetone, acetoacetic acid. , Acetopropionic acid, diacetacetic acid, 3,3-diacetpropionic acid, 4,4-diacetbutyric acid, carboxyethylcarbonylacetone, carboxypropylcarbonylacetone, diacetone alcohol.

  Of these, acetylacetone and diacetylacetone are particularly preferred. The complex of the above acetylacetone derivative and the above metal element is a mononuclear complex in which one to four molecules of the acetylacetone derivative are coordinated per metal element, and the coordinateable bond of the acetylacetone derivative is a coordinateable bond of the acetylacetone derivative. When the number of hands is larger than the total number of hands, ligands commonly used for ordinary complexes such as water molecules, halogen ions, nitro groups, and ammonio groups may coordinate.

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

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

  The catalyst is preferably used in an amount of 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, based on the total solid content of the hydrophobic composition and the hydrophilic composition of the present invention. preferable.

[Surfactant]
In at least one of the hydrophobic composition and the hydrophilic composition, it is preferable to use a surfactant in order to improve the film surface state. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants.

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

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

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

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

  Although the specific example of a preferable surfactant is shown below, this invention is not limited to these.

  By using a surfactant and the hydrophilic polymer (II) in combination, a higher hydrophilic surface can be formed. Although the mechanism has not been fully elucidated, this is because the hydrophilic segment in the polymer segment is a surfactant that is a low molecular weight compound that migrates to the coating surface during the drying process of the coating. It is presumed that high hydrophilicity was obtained by being attracted to the hydrophilic part.

[Inorganic fine particles]
The hydrophobic composition and the hydrophilic composition of the present invention may contain inorganic fine particles in order to improve hydrophilicity, prevent cracking of the film, and improve film strength. Inorganic fine particles are particularly preferred because of their high hydrophilicity. 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 10 nm to 10 μm, and more preferably 0.5 to 3 μm. Within the above range, it is possible to form a coating film that is stably dispersed in the coating film, sufficiently maintains the film strength of the coating film, 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 hydrophobic composition and the hydrophilic composition of the present invention.

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

[Antimicrobial agent]
In order to impart antibacterial, antifungal and antialgal properties to the hydrophobic composition and the hydrophilic composition of the present invention, an antibacterial agent can be contained. In the formation of the hydrophilic film, it is preferable to contain a hydrophilic and water-soluble antibacterial agent. By containing a hydrophilic and water-soluble antibacterial agent, a member excellent in antibacterial, antifungal and antialgal properties can be obtained without impairing surface hydrophilicity.
As the antibacterial agent, it is preferable to add a compound that does not decrease the hydrophilicity of the member. Examples of such an antibacterial agent include inorganic antibacterial agents and water-soluble organic antibacterial agents. As the antibacterial agent, those exhibiting a bactericidal effect against fungi existing around us, such as bacteria represented by Staphylococcus aureus and Escherichia coli, and fungi such as fungi and yeast are used.
The addition amount of the antibacterial agent is appropriately selected according to the purpose, but is generally 0.001 to 10% by mass with respect to the total solid content of the hydrophilic composition of the present invention, and 0.005 to 5%. % By mass is preferable, 0.01 to 3% by mass is more preferable, 0.02 to 1.5% by mass is particularly preferable, and 0.05 to 1% by mass is most preferable. If the content is 0.001% by mass or more, an effective antibacterial effect can be obtained. If the content is 10% by mass or less, the hydrophilicity is not lowered and the film strength is not adversely affected.

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

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

(Preparation of hydrophilic composition)
The hydrophilic composition of the present invention can be prepared by dissolving a hydrophilic polymer, as appropriate, a metal alkoxide, a catalyst, a surfactant, and other additives in a solvent and then stirring. It is preferable to mix the catalyst just before coating the substrate. Specifically, it is preferable to apply within 1 hour immediately after mixing of the catalyst.
If the catalyst is mixed and left to stand for a long period of time, the viscosity of the composition increases and defects such as coating unevenness may occur.
Other components are also preferably mixed immediately before coating, but may be stored for a long time after mixing.
The reaction temperature in the preparation is from room temperature to 80 ° C., and the reaction time, that is, the time for which stirring is continued, is preferably in the range of 1 to 72 hours. By this stirring, the hydrophilic polymer and metal alkoxide containing a crosslinkable group are hydrolyzed. Decomposition and polycondensation can be advanced to obtain an organic-inorganic composite sol solution.

  The solvent used in preparing the hydrophilic composition is not particularly limited as long as each component can be uniformly dissolved and dispersed. For example, an aqueous solvent such as methanol, ethanol, and water is preferable.

As described above, the preparation of the organic-inorganic composite sol solution for forming a film from the hydrophilic composition utilizes the sol-gel method. For the sol-gel method, Sakuo Sakuo “Science of Sol-Gel Method”, Agne Jofusha (published) (1988), Satoshi Hirashima “Functional Thin Film Formation Technology by the Latest Sol-Gel Method” General Technology Center (Published) (1992) and the like, and the methods described therein can be applied to the preparation of the composition in the present invention.
The hydrophilic member of the present invention can be obtained by applying a solution containing such a hydrophilic composition onto the hydrophobic undercoat layer and drying the solution.
The drying temperature is preferably 10 ° C to 250 ° C, more preferably 70 ° C to 220 ° C. When the drying temperature is too low, the film is not sufficiently dried and the film strength is lowered. If the temperature is too high, the film tends to crack.
The drying time is preferably 10 seconds to 200 minutes. More preferably, it is 15 seconds to 90 minutes. If the drying time is too short, the film strength may decrease due to insufficient drying. If the drying time is excessively longer than necessary, the film may crack.

  The solid content concentration of the hydrophilic composition is preferably 20 to 0.5 mass%, more preferably 15 to 1 mass%.

  The thickness of the hydrophilic layer is preferably larger than 10 nm and smaller than 1 μm, more preferably 20 nm to 0.8 μm. If it is too thick, the film tends to crack, and if it is too thin, performance is likely to be insufficient. The thickness can be adjusted by the solid content concentration of the composition, the coil diameter of the bar coater, etc., and can be determined by a known method.

The center average roughness Ra of the surface of the hydrophilic layer is preferably 1 nm to 10 nm. The Tg of the hydrophilic layer is preferably 40 ° C. to 150 ° C. from the viewpoint of coating film strength. The elastic modulus of the hydrophilic layer is preferably 1 GPa to 7 GPa.
The surface property of the hydrophilic layer can be controlled by adjusting the surface roughness of the substrate, the viscosity of the composition, the heating temperature, the speed, and the like.

The hydrophilic layer preferably has a hydrophilic surface. The hydrophilicity of the film surface is generally measured by the water droplet contact angle. The membrane in the present invention preferably has a surface water droplet contact angle of 40 ° or less, more preferably 30 ° or less, still more preferably 20 ° or less, and particularly preferably 15 ° or less.
As another method for evaluating the hydrophilicity of the film surface in more detail, there is a measurement of surface free energy. Various methods have been proposed. In the present invention, as an example, the surface free energy was measured using the Zisman plot method. Specifically, an aqueous solution of an inorganic electrolyte such as magnesium chloride uses the property that the surface tension increases with the concentration. After measuring the contact angle in air and at room temperature using the aqueous solution, the horizontal axis indicates the surface of the aqueous solution. Take the tension, the value obtained by converting the contact angle into cos θ on the vertical axis, plot the points of aqueous solutions of various concentrations to obtain a linear relationship, and the surface tension when cos θ = 1, that is, contact angle = 0 °, It is a measurement method defined as the surface free energy of a solid. The surface tension of water is 72 mN / m, and it can be said that the higher the surface free energy value, the higher the hydrophilicity.
A film whose surface free energy measured by such a method is in the range of 70 mN / m to 95 mN / m, preferably 72 mN / m to 93 mN / m, more preferably 75 mN / m to 90 mN / m, is hydrophilic. Excellent and good performance.

  The hydrophobic composition and the hydrophilic composition in the present invention can be applied by a known application method, and are 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.

〔Base material〕
The hydrophilic member of the present invention has a hydrophobic undercoat layer on a substrate, and has a hydrophilic layer on the hydrophobic undercoat layer. The substrate is not particularly limited, but glass, resin, metal, ceramics, wood, stone, cement, concrete, fiber, fabric, paper, leather, tile, rubber, latex, combinations thereof, laminates thereof, and the like. Can be mentioned. A preferable base material is a flexible base material having flexibility such as resin and metal. By using a flexible base material, members can be freely deformed and the degree of freedom of attachment work and place of attachment can be increased, and durability can also be increased. A substrate containing a resin is particularly preferable.

  The base material containing the resin is not particularly limited, but the base material used as an optical member is selected in consideration of optical properties such as transparency, refractive index, dispersibility, and various physical properties depending on the purpose of use. For example, it is selected in consideration of physical characteristics such as strength such as impact resistance and flexibility, heat resistance, weather resistance, durability, and the like. As a base material containing a resin, a base material made of plastic is preferable, polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, Examples thereof include films or sheets of polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetherketone, acrylic, nylon, fluorine resin, polyimide, polyetherimide, polyethersulfone, and the like. Of these, polyester films such as polyethylene terephthalate and polyethylene naphthalate are particularly preferred. These may be used alone or in combination of two or more in the form of a mixture, copolymer, laminate or the like, depending on the purpose of use. The thickness of the plastic substrate varies depending on the partner to be laminated. For example, in a portion with many curved surfaces, a thin one is preferred, and one having about 6 to 50 μm is used. Moreover, 50-400 micrometers is used for a plane or the place where intensity | strength is requested | required.

  For the purpose of improving the adhesion between the base material and the layer on the base material, 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.

  Examples of the aluminum substrate include a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, or a material in which a plastic is laminated on a thin film of aluminum or an aluminum alloy. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is preferably 10% by mass or less. In the present invention, a pure aluminum plate is preferable, but completely pure aluminum is difficult to manufacture in terms of refining technology, and therefore may contain a slightly different element. The composition of the aluminum plate is not specified, and a publicly known material can be used as appropriate.

The thickness of the base material is preferably 0.05 to 0.6 mm, and more preferably 0.08 to 0.2 mm.
The substrate preferably has a surface centerline average roughness of 0.01 to 1.2 μm.

  Prior to using the aluminum plate, it is preferable to perform a surface treatment such as roughening treatment or anodizing treatment. By the surface treatment, it becomes easy to improve the hydrophilicity of the substrate and to secure the adhesion between the undercoat layer and the substrate. Prior to roughening the aluminum plate, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like for removing rolling oil on the surface is performed as desired. The aluminum substrate can be treated by a known method.

As the base material, the base material that has been subjected to the surface treatment as described above and has an anodized film may be used as it is. However, for further improvement of the adhesiveness with the upper layer, JP 2001-253181 A and The micropore enlargement process and the sealing process of the anodized film and the surface hydrophilization process immersed in an aqueous solution containing a hydrophilic compound described in Japanese Laid-Open Patent Application No. 2001-322365 can be appropriately selected and performed. Of course, the enlargement process and the sealing process are not limited to those described above, and any conventionally known method can be performed.
For example, as the sealing treatment, in addition to the vapor sealing, single treatment with fluorinated zirconate, treatment with sodium fluoride, and vapor sealing with addition of lithium chloride are possible.

<Sealing treatment>
The sealing treatment is not particularly limited, and a conventionally known method can be used. Among them, sealing treatment with an aqueous solution containing an inorganic fluorine compound, sealing treatment with water vapor, and sealing treatment with hot water are preferable. Each will be described below.

<Sealing treatment with an aqueous solution containing an inorganic fluorine compound>
As the inorganic fluorine compound used for the sealing treatment with an aqueous solution containing an inorganic fluorine compound, a metal fluoride is preferably exemplified.
Specifically, for example, sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, sodium fluoride zirconate, potassium fluoride zirconate, sodium fluoride titanate, potassium fluoride titanate, zircon fluoride Ammonium acid, ammonium fluoride titanate, potassium fluoride titanate, zirconate fluoride, titanate fluoride, hexafluorosilicic acid, nickel fluoride, iron fluoride, phosphor fluoride, ammonium fluoride phosphate It is done. Of these, sodium fluorinated zirconate, sodium fluorinated titanate, fluorinated zirconic acid, and fluorinated titanic acid are preferable.

  The concentration of the inorganic fluorine compound in the aqueous solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of sufficiently sealing the micropores of the anodized film. Further, in terms of stain resistance, it is preferably 1% by mass or less, and more preferably 0.5% by mass or less.

It is preferable that the aqueous solution containing an inorganic fluorine compound further contains a phosphate compound. Suitable examples of the phosphate compound include phosphates of metals such as alkali metals and alkaline earth metals.
Specifically, for example, zinc phosphate, aluminum phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, monoammonium phosphate, monopotassium phosphate, monosodium phosphate, dihydrogen phosphate Potassium, dipotassium hydrogen phosphate, calcium phosphate, sodium ammonium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, ferrous phosphate, ferric phosphate, sodium dihydrogen phosphate, sodium phosphate, hydrogen phosphate Disodium, lead phosphate, diammonium phosphate, calcium dihydrogen phosphate, lithium phosphate, phosphotungstic acid, ammonium phosphotungstate, sodium phosphotungstate, ammonium phosphomolybdate, sodium phosphomolybdate, sodium phosphite , Tripolyphosphate Potassium, and sodium pyrophosphate. Among these, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate are preferable.
The combination of the inorganic fluorine compound and the phosphate compound is not particularly limited, but the aqueous solution contains at least sodium zirconate fluoride as the inorganic fluorine compound and contains at least sodium dihydrogen phosphate as the phosphate compound. Is preferred.

  The concentration of the phosphate compound in the aqueous solution is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of improving stain resistance, In this respect, it is preferably 20% by mass or less, and more preferably 5% by mass or less.

The ratio of each compound in the aqueous solution is not particularly limited, but the mass ratio of the inorganic fluorine compound and the phosphate compound is preferably 1/200 to 10/1, and preferably 1/30 to 2/1. Is more preferable.
The temperature of the aqueous solution is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
The aqueous solution preferably has a pH of 1 or more, more preferably has a pH of 2 or more, preferably has a pH of 11 or less, and more preferably has a pH of 5 or less.
The method for sealing with an aqueous solution containing an inorganic fluorine compound is not particularly limited, and examples thereof include an immersion method and a spray method. These may be used alone or in combination, or may be used in combination of two or more.
Of these, the dipping method is preferred. When the treatment is performed using the dipping method, the treatment time is preferably 1 second or longer, more preferably 3 seconds or longer, and preferably 100 seconds or shorter, and 20 seconds or shorter. More preferred.

<Sealing treatment with water vapor>
Examples of the sealing treatment with water vapor include a method in which pressurized or normal-pressure water vapor is brought into contact with the anodized film continuously or discontinuously.
The temperature of the water vapor is preferably 80 ° C. or higher, more preferably 95 ° C. or higher, and preferably 105 ° C. or lower.
The water vapor pressure is preferably in the range (1.00 × 10 ^{5 to} 1.043 × 10 ⁵ Pa) from (atmospheric pressure−50 mmAq) to (atmospheric pressure + 300 mmAq).
Further, the time for which the water vapor is contacted is preferably 1 second or longer, more preferably 3 seconds or longer, 100 seconds or shorter, more preferably 20 seconds or shorter.

<Sealing treatment with hot water>
Examples of the sealing treatment with water vapor include a method in which an aluminum plate on which an anodized film is formed is immersed in hot water.
The hot water may contain an inorganic salt (for example, phosphate) or an organic salt.
The temperature of the hot water is preferably 80 ° C. or higher, more preferably 95 ° C. or higher, and preferably 100 ° C. or lower.
Further, the time of immersion in hot water is preferably 1 second or longer, more preferably 3 seconds or longer, more preferably 100 seconds or shorter, and even more preferably 20 seconds or shorter.

<Hydrophilic treatment>
The hydrophilization treatment is described in US Pat. Nos. 2,714,066, 3,181,461, 3,280,734, and 3,902,734. There are such alkali metal silicate methods. In this method, the support is immersed in an aqueous solution such as sodium silicate or electrolytically treated. In addition, the treatment with potassium zirconate fluoride described in JP-B 36-22063, U.S. Pat. Nos. 3,276,868, 4,153,461 and 4,689, And a method of treating with polyvinylphosphonic acid as described in each specification of No.272.

  Glass substrates include silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, zirconium oxide, sodium oxide, antimony oxide, indium oxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide, ITO (Indium Tin) A glass plate provided with an inorganic compound layer formed of a metal oxide such as Oxide; a metal halide such as magnesium fluoride, calcium fluoride, lanthanum fluoride, cerium fluoride, lithium fluoride, thorium fluoride; Can be mentioned. Depending on the purpose, float plate glass, mold plate glass, ground glass, wire-filled glass, wire-filled glass, tempered glass, laminated glass, double-glazed glass, vacuum glass, security glass, highly heat-insulated Low-E double-glazed glass should be used Can do. In addition, the undercoat layer and the overcoat layer can be coated with the base glass as it is. Surface hydrophilization treatment can be performed. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. As a roughening method, it can also be mechanically roughened by sandblasting, brush polishing or the like.

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

(Middle layer)
You may have one or more intermediate | middle layers between the film | membrane formed from the hydrophilic composition of this invention, and a base material.
Although it does not specifically limit as an intermediate | middle layer, What was formed using the composition (it is also called the composition for intermediate | middle layers) containing the compound which has a hydrolyzable alkoxysilyl group is preferable.
In particular, the intermediate layer composition preferably contains at least one compound selected from tetramethoxysilane and monoalkyltrimethoxysilane.

  The intermediate layer composition can be applied by a known application method, and is not particularly limited. For example, spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, film applicator method Methods such as screen printing, bar coater, brush coating, and sponge coating can be applied.

  The thickness of the intermediate layer is preferably 5 nm to 1000 nm, more preferably 10 nm to 500 nm, because cracks occur when it is too thick, and adhesion and corrosion resistance decrease when it is too thin.

(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.

(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.

  In addition, a protective layer may be provided on the surface. 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 polymer layer used in the release layer can be used. The protective layer is peeled off after the member is attached to a suitable substrate.

  The hydrophilic member 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.

Although the use which can apply the hydrophilic composition and member of this invention is illustrated, it is not limited to these.
Vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, camera lenses, endoscope lenses, lighting lenses, semiconductor lenses, and copying machines Lenses such as lenses; prisms; window glass for buildings and monitoring towers; glass for other building materials; various vehicles such as automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, ropeway gondola, amusement park gondola, etc. Windshields; Windshields for various vehicles such as automobiles, railway cars, aircraft, ships, submersibles, snow vehicles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola, protective goggles, sports goggles, protective Mask shield, sports mask shield, helmet shield, frozen food display case glass; measuring instrument cover glass, building material, outer wall Building exteriors such as roofs, building interiors, window frames, window glass, structural members, automobiles, rail cars, aircraft, ships, bicycles, exteriors and paintings of vehicles such as motorcycles, exteriors of machinery and equipment, dust covers and Painting, traffic signs, various display devices, advertising towers, road noise barriers, railway noise barriers, bridges, guardrail exteriors and paintings, tunnel interiors and paintings, insulators, solar cell covers, solar water heater heat collection covers, greenhouses , Vehicle lighting cover, housing equipment, toilet bowl, bathtub, wash basin, lighting fixture, lighting cover, kitchenware, tableware, dishwasher, dish dryer, sink, cooking range, kitchen hood, exhaust fan, signage, transportation Signs, soundproof walls, greenhouses, insulators, vehicle covers, tent materials, reflectors, shutters, screen doors, solar battery covers, solar water heater covers, street lamps, pavements, Outdoor lighting, artificial waterfall / artificial fountain stones / tiles, bridges, greenhouses, outer wall materials, sealers between walls and glass, guardrails, verandas, vending machines, air conditioner outdoor units, air conditioner indoor units, outdoor benches, various display devices , Shutters, toll booths, toll boxes, roof lamps, vehicle lamp protection covers, dustproof covers and coating, painting of machinery and equipment, exterior and coating of advertising towers, structural members, housing equipment, toilets, bathtubs, washstands, Lighting fixtures, kitchen utensils, dishes, tableware dryers, sinks, cooking ranges, kitchen hoods, ventilation fans, window rails, window frames, tunnel inner walls, tunnel lighting, window sashes, heat exchanger fins, pavements, bathroom toilets Mirrors, greenhouse ceilings, vanities, automobile bodies, snow country roofing materials, antennas, power transmission lines, medical diagnostic devices, medical catheters, personal computers and televisions Displays, cosmetic containers, filters, automotive aluminum wheels, camera finders, CCD cover glasses, printing device components, films that can be attached to the article surface, patches, etc.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

(Synthesis of hydrophilic polymer (I-2))
A 500 ml three-necked flask is charged with 56.9 g of acrylamide, 55.1 g of acrylamide-3- (ethoxysilyl) propyl, and 260 g of 1-methoxy-2-propanol (hereinafter sometimes abbreviated as MFG). , 2'-azobis (2-methylpropionic acid) dimethyl 0.7 g was added. The mixture was kept at the same temperature with stirring for 6 hours, and then cooled to room temperature. The solution was put into 5 liters of n-hexane, and the precipitated solid was collected by filtration. The obtained solid was washed with n-hexane, and then the hydrophilic polymer (I-2) as the exemplified compound (I-2) was obtained. The mass after drying was 80.6 g. It was a polymer having a mass average molecular weight of 22,000 according to GPC (polyethylene oxide standard).

(Synthesis of hydrophilic polymer (II-1))
In a 200 ml three-necked flask, 25 g of acrylamide, 3.5 g of 3-mercaptopropyltrimethoxysilane and 51.3 g of dimethylformamide were placed, and 0.25 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added at 65 ° C. under a nitrogen stream. The reaction was started by addition. After stirring for 6 hours, the mixture was returned to room temperature and poured into 1.5 L of methanol, and a solid was precipitated. The obtained solid was washed with acetone, and then the hydrophilic compound (I-1) as the exemplified compound (I-1) was obtained. The mass after drying was 21.7 g. It was a polymer having a mass average molecular weight of 9,000 according to GPC (polyethylene oxide standard).

(Synthesis of hydrophobic polymer (1))
A 500 ml three-necked flask was charged with 50 g of styrene, 17 g of isopropyl methacrylate, and 270 g of MFG, and 2.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added under a nitrogen stream at 80 ° C. to initiate the reaction. Stir for 6 hours. After cooling to room temperature, a hydrophobic polymer (1) of the exemplified compound having a solid concentration of 20% was obtained. It was a polymer having a mass average molecular weight of 20,000 according to GPC (polystyrene standard).

(Synthesis of hydrophobic polymer (A-1))
Add 20.8 g of styrene, 49.7 g of trimethoxysilylpropyl methacrylate, and 282 g of MFG to a 500 ml three-necked flask and add 1.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) under a nitrogen stream at 80 ° C. Started. Stir for 6 hours. After cooling to room temperature, a hydrophobic polymer (A-1) of the exemplified compound having a solid content concentration of 20% was obtained. It was a polymer having a mass average molecular weight of 30,000 according to GPC (polystyrene standard).
Other hydrophilic polymers and hydrophobic polymers used in the examples can be synthesized in the same manner.

Example 1
[Hydrophobic composition]
10 g of latex (1) (manufactured by Nippon Zeon: Nipol LX430) and 240 g of purified water were mixed and stirred at room temperature for 1 hour to obtain a hydrophobic composition.
[Hydrophilic sol-gel solution]
In 90 g of purified water, 10 g of hydrophilic polymer (I-2) was mixed as a hydrophilic polymer and stirred at room temperature for 2 hours to prepare a hydrophilic sol-gel solution.
[Hydrophilic composition]
400 g of purified water and 2 g of a 5% by weight aqueous solution of surfactant (1) having the following structure were mixed with the hydrophilic sol-gel solution to prepare a hydrophilic composition.
[Coating method]
The hydrophobic composition is bar coated on a polyethylene terephthalate substrate (thickness 50 μm) whose surface has been hydrophilized by glow treatment, oven-dried at 180 ° C. for 30 seconds, thickness 50 μm, and coating dry weight 0.05 g / m. ^Two hydrophobic subbing layers were formed. Further, the hydrophilic composition was bar coated thereon and oven dried at 180 ° C. for 30 seconds to form a hydrophilic layer having a thickness of 50 μm and a coating drying amount of 0.05 g / m ² . In this way, a hydrophilic member was produced.

(Example 2)
A hydrophilic member of Example 2 was prepared in the same manner as in Example 1 except that 0.05 g of a 1N hydrochloric acid aqueous solution was added as a catalyst to the hydrophilic sol-gel solution of Example 1.

(Example 3)
Example except that latex (1) in the hydrophobic composition of Example 2 was changed to latex (2) (Nippon Zeon: Nipol LX435) and the catalyst of the hydrophilic sol-gel solution was changed to 1 g of titanium acetylacetonate. The hydrophilic member of Example 3 was produced in the same manner as in Example 2.
Titanium acetylacetonate was prepared by adding 0.5 g of acetylacetone (manufactured by Tokyo Chemical Industry) and 0.5 g of tetraethyl orthotitanate (manufactured by Tokyo Chemical Industry) to the hydrophilic sol-gel solution.

Example 4
Example except that the latex (2) in the hydrophobic composition of Example 3 was changed to latex (3) (Nippon Zeon: Nipol 1571H) and the catalyst of the hydrophilic sol-gel solution was changed to 1 g of titanium acetylacetonate. The hydrophilic member of Example 4 was produced in the same manner as in Example 3.

(Example 5)
[Hydrophobic composition]
90 g of MFG and 10 g of a 20% MFG solution of the hydrophobic polymer (1) described in the above exemplary compound were mixed and stirred at room temperature for 1 hour to obtain a hydrophobic composition.
[Coating method]
The above hydrophobic composition is bar-coated on a polyethylene terephthalate substrate (thickness 50 μm) whose surface has been made hydrophilic by glow treatment, oven-dried at 180 ° C. for 30 seconds, thickness 50 μm, and coating drying amount 0.05 g / m. ^Two hydrophobic subbing layers were formed. Further thereon, the hydrophilic composition used in Example 3 was coated with a bar and oven-dried at 180 ° C. for 30 seconds to form a hydrophilic layer having a thickness of 50 μm and a coating drying amount of 0.05 g / m ² . . In this way, a hydrophilic member was produced.

(Examples 6 and 7)
Hydrophobic polymer (1) in the hydrophobic composition of Example 5 The hydrophilic members of Examples 6 and 7 were prepared in the same manner as in Example 5 except that the 20% MFG solution was changed to the following hydrophobic polymer.
Example 6: 20% MFG solution of the hydrophobic polymer (2) described in the exemplary compound Example 7: 20% MFG solution of the hydrophobic polymer (3) described in the exemplary compound

(Example 8)
A hydrophilic member of Example 8 was prepared in the same manner as in Example 3 except that 2.0 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the hydrophilic sol-gel solution of Example 3.

(Examples 9 to 12)
The hydrophilic member of Examples 9-12 was produced like Example 3 except having changed the hydrophilic polymer (I-2) in the hydrophilic sol-gel liquid of Example 3 into the following hydrophilic polymer.
Example 9: Hydrophilic polymer (I-5) described in the exemplified compound
Example 10: Hydrophilic polymer (I-12) described in the above exemplary compound
Example 11: Hydrophilic polymer (I-82) described in the exemplified compound
Example 12: Hydrophilic polymer (II-1) described in the exemplified compound

(Example 13)
The hydrophilicity of Example 13 is the same as Example 8, except that the hydrophilic polymer (I-2) in the hydrophilic sol-gel solution of Example 8 is changed to the hydrophilic polymer (II-3) described in the exemplified compound. A member was prepared.

(Example 14)
10 g of the hydrophilic polymer (I-2) in the hydrophilic sol-gel solution of Example 3 was changed to 7.5 g of the hydrophilic polymer (I-2) and 2.5 g of the hydrophilic polymer (II-1) described in the exemplified compound. A hydrophilic member of Example 14 was produced in the same manner as Example 3 except for the change.

(Example 15)
A hydrophilic member of Example 15 was produced in the same manner as in Example 3 except that the surfactant (1) in the hydrophilic composition of Example 3 was changed to the surfactant (2) having the following structure.

(Example 16)
A hydrophilic member of Example 16 was produced in the same manner as in Example 14 except that the surfactant (1) in the hydrophilic composition of Example 14 was changed to the surfactant (3) having the following structure.

(Comparative Example 1)
In 14.2 g of ethyl alcohol and 50 g of purified water, 8.0 g of tetramethoxysilane, 0.5 g of acetylacetone, and 0.5 g of tetraethyl orthotitanate were mixed and prepared by stirring at room temperature for 2 hours. Thereto was mixed 2.2 g of a 5% by mass aqueous solution of the surfactant (1) used in Example 1 and 490 g of purified water to obtain a coating solution.
The above coating solution is bar-coated on a polyethylene terephthalate substrate (thickness 50 μm) whose surface has been hydrophilized by glow treatment, and oven-dried at 180 ° C. for 30 seconds to have a thickness of 50 μm and a coating dry amount of 0.05 g / m ² . An undercoat layer was formed. Further, a hydrophilic composition obtained by changing the hydrophilic polymer (I-2) of the hydrophilic composition used in Example 3 to the hydrophilic polymer (I-9) described in the exemplified compound was bar coated, and 180 It was oven-dried at 30 ° C. for 30 seconds to form a hydrophilic layer having a thickness of 50 μm and a coating dry amount of 0.05 g / m ² . In this way, the hydrophilic member of Comparative Example 1 was produced.

(Comparative Example 2)
A hydrophilic member of Comparative Example 2 was similarly prepared except that 8.0 g of tetramethoxysilane of Comparative Example 1 was changed to 2.4 g of tetramethoxysilane and 2.4 g of methyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.).

(Comparative Example 3)
A hydrophilic member of Comparative Example 3 was similarly prepared except that 8.0 g of tetramethoxysilane of Comparative Example 1 was changed to 4.0 g of tetramethoxysilane and 4.0 g of methyltrimethoxysilane.

(Comparative Example 4)
A hydrophilic member of Comparative Example 4 was prepared in the same manner except that the configuration of the undercoat layer of Comparative Example 1 was changed to the PVA crosslinked film described below.
PVA cross-linked film: polyvinyl alcohol (Kuraray, Kuraray Poval PVA105) + Glyoxal (manufactured by Nippon Synthetic Chemical)

(Example 17)
The procedure was carried out except that the hydrophobic polymer (1) 20% MFG solution in the hydrophobic composition of Example 5 was changed to the hydrophobic polymer (A-1) 20% MFG solution described in the above exemplified compound and no catalyst was added. A hydrophilic member of Example 17 was produced in the same manner as Example 5.

(Example 18)
Except that the hydrophobic polymer (1) 20% MFG solution in the hydrophobic composition of Example 5 was changed to the hydrophobic polymer (A-1) 20% MFG solution described in the exemplified compound, the same as in Example 5. The hydrophilic member of Example 18 was produced.

(Examples 19 to 21)
Hydrophilic members of Examples 19 to 21 were prepared in the same manner as in Example 18 except that the hydrophobic polymer (A-1) 20% MFG solution in the hydrophobic composition of Example 18 was changed to the following hydrophobic polymer. .
Example 19: 20% MFG solution of the hydrophobic polymer (A-2) described in the exemplary compound Example 20: 20% MFG solution of the hydrophobic polymer (A-10) described in the exemplary compound Example 21: 20% MFG solution of the hydrophobic polymer (A-18) described in the exemplary compound

(Example 22)
A hydrophilic member of Example 22 was produced in the same manner as in Example 18 except that 2.0 g of tetramethoxysilane was added to the hydrophilic sol-gel solution of Example 18.

(Examples 23 to 26)
The hydrophilic member of Examples 23-26 was produced similarly to Example 18 except having changed the hydrophilic polymer (I-2) in the hydrophilic sol-gel liquid of Example 18 into the following hydrophilic polymer.
Example 23: hydrophilic polymer (I-5)
Example 24: hydrophilic polymer (I-12)
Example 25: hydrophilic polymer (I-82)
Example 26: hydrophilic polymer (II-1)

(Example 27)
A hydrophilic member of Example 27 was produced in the same manner as in Example 22 except that the hydrophilic polymer (I-2) in the hydrophilic sol-gel solution of Example 22 was changed to the hydrophilic polymer (II-3).

(Example 28)
10 g of the hydrophilic polymer (I-2) in the hydrophilic sol-gel solution of Example 18 was changed to 7.5 g of the hydrophilic polymer (I-2) and 2.5 g of the hydrophilic polymer (II-1) described in the exemplified compound. A hydrophilic member of Example 28 was produced in the same manner as Example 18 except for the change.

(Example 29)
A hydrophilic member of Example 29 was produced in the same manner as in Example 18 except that the surfactant (1) in the hydrophilic composition of Example 18 was changed to the surfactant (2).

(Example 30)
A hydrophilic member of Example 30 was produced in the same manner as in Example 28 except that the surfactant (1) in the hydrophilic composition of Example 28 was changed to the surfactant (3).

(Example 31)
[Hydrophobic composition]
Hydrophobic polymer (A-1) 10 g of 20% MFG solution, 2.0 g of purified water, 88 g of MFG and 0.1 g of 1N hydrochloric acid aqueous solution as a catalyst were mixed and stirred at room temperature for 2 hours to obtain a hydrophobic composition.
[Coating method]
The above hydrophobic composition is bar-coated on a polyethylene terephthalate substrate (thickness 50 μm) whose surface has been made hydrophilic by glow treatment, oven-dried at 180 ° C. for 30 seconds, thickness 50 μm, and coating drying amount 0.05 g / m. ^Two hydrophobic subbing layers were formed. Further thereon, the hydrophilic composition of Example 1 was coated with a bar and oven dried at 180 ° C. for 30 seconds to form a hydrophilic layer having a thickness of 50 μm and a coating dry amount of 0.05 g / m ² . In this way, a hydrophilic member was produced.

(Example 32)
The catalyst of Example 31 was changed to 2.0 g of titanium acetylacetonate used in Example 3, and the hydrophilic composition was changed to the hydrophilic composition used in Example 2, as in Example 31. The hydrophilic member of Example 32 was produced.

(Example 33)
A hydrophilic member of Example 33 was produced in the same manner as in Example 32 except that the hydrophilic composition of Example 32 was changed to the hydrophilic composition used in Example 3.

(Example 34)
A hydrophilic member of Example 34 was produced in the same manner as in Example 33 except that the hydrophilic composition of Example 33 was changed to the hydrophilic composition used in Example 14.

(Example 35)
A hydrophilic member of Example 35 was produced in the same manner as in Example 33 except that 0.2 g of tetramethoxysilane was added to the hydrophobic composition of Example 33.

(Examples 36 and 37)
The hydrophilic members of Examples 36 and 37 were prepared in the same manner as in Example 35 except that the hydrophobic polymer (A-1) 20% MFG solution in the hydrophobic composition of Example 35 was changed to the following hydrophobic polymer. did.
Example 36: Hydrophobic polymer (A-2) 20% MFG solution Example 37: Hydrophobic polymer (A-10) 20% MFG solution

(Example 38)
A hydrophilic member of Example 38 was produced in the same manner as in Example 35 except that the hydrophilic composition of Example 35 was changed to the hydrophilic composition used in Example 14.

(Example 39)
The hydrophilic member of Example 39 was prepared in the same manner as in Example 35 except that 0.4 g of the 5% by weight aqueous solution of the surfactant (1) used in Example 1 was added to the hydrophobic composition of Example 35. did.

(Example 40)
The hydrophilic member of Example 40 was prepared in the same manner as in Example 33 except that 0.4 g of the 5% by weight aqueous solution of the surfactant (1) used in Example 1 was added to the hydrophobic composition of Example 33. did.

(Example 41)
A hydrophilic member of Example 41 was produced in the same manner as in Example 40 except that the hydrophobic polymer (A-1) in Example 40 was changed to the hydrophobic polymer (A-2).

(Example 42)
A hydrophilic member of Example 42 was produced in the same manner as in Example 40 except that the hydrophilic composition of Example 40 was changed to the hydrophilic composition used in Example 14.

(Examples 43 and 44)
The hydrophilic member of Examples 43 and 44 was produced similarly to Example 40 except having changed the surfactant (1) of Example 40 into the following surfactant.
Example 43: Surfactant (2) used in Example 15
Example 44: Surfactant (3) used in Example 16

  Each component of Examples 1-44 and Comparative Examples 1-3 is shown in Tables 1-3.

Latex (1): Composition Styrene / 1,3-butadiene / methacrylic acid Latex (2): Composition Styrene / 1,3-butadiene / acrylamide / acrylic acid / methacrylic acid Latex (3): Composition Acrylonitrile / 1,3-butadiene / Methacrylic acid

  In the table, “TMOS” represents tetramethoxysilane, “MTMS” represents methyltrimethoxysilane, “PVA crosslinked film” represents a polyvinyl alcohol crosslinked film, “HCl” represents hydrochloric acid, and “Ti” represents titanium acetylacetonate. .

(Evaluation of hydrophilic member)
[Surface free energy]
The surface free energy was measured by the method described above (Zisman plot method).

[Water drop contact angle]
The water droplet contact angles on the surfaces of the hydrophobic undercoat layer and the hydrophilic layer were measured with a DropMaster 500 manufactured by Kyowa Interface Science Co., Ltd.
The lower the water droplet contact angle, the higher the hydrophilicity, and the higher the water droplet contact angle, the higher the hydrophobicity.

[Acid resistance]
The obtained hydrophilic member is immersed in 10% hydrochloric acid and 10% sulfuric acid, washed with running water, and the presence or absence of the film (including the case where there is no part) is visually observed as deterioration of the film. The time until the film deterioration appeared was determined. The longer the time, the better the acid resistance.

[Alkali resistance]
The obtained hydrophilic member was immersed in Magiclin (registered trademark) (manufactured by Kao Corporation), Kabikiller (registered trademark) (manufactured by Johnson Co., Ltd.), washed with running water, (Including the case where there is no part) was visually observed, and the time from the start of immersion to the time when film deterioration appeared was determined. The longer the time, the better the alkali resistance.

[Evaluation of antifouling properties (1)]
A line was written on the surface of the obtained hydrophilic member with an oil-based ink (an oil-based marker manufactured by Mitsubishi Pencil Co., Ltd.), and it was subjected to sensory evaluation in the following three stages to determine whether or not the water continued to flow.
○: Ink can be taken within 1 minute. Δ: Ink can be taken after 1 minute. ×: Ink cannot be removed even if it is performed over 2 minutes for 10 minutes.

[Evaluation of antifouling property (2)]
An aqueous solution in which a stock solution of merit (manufactured by Kao Corporation) was diluted to 5% was dropped onto the surface of the obtained hydrophilic member and air-dried. Thereafter, the water droplet contact angle after washing with running water and drying was measured.
○: Contact angle is less than 25 ° Δ: Contact angle is 25 ° or more and less than 45 ° ×: Contact angle is 45 ° or more

[Adhesion evaluation]
The obtained hydrophilic member was immersed in purified water for 200 hours, dried, and then visually observed for film peeling.
○: No peeling △: Partial peeling ×: Whole peeling

[Evaluation of boiling water resistance]
The hydrophilic member obtained above was immersed in 95 ° C. water for 3 hours, dried, and then visually observed for film peeling.
○: No peeling △: Partial peeling ×: Whole peeling

  The above evaluation results are shown in Tables 4 to 6 below.

  As mentioned above, it turns out that the hydrophilic member of the Example of this invention is a hydrophilic member excellent in hydrophilic property, antifouling property, alkali resistance, acid resistance, and hot water resistance.

Claims (17)

  A hydrophilic member comprising a hydrophobic undercoat layer on a substrate and a hydrophilic layer on the hydrophobic undercoat layer.   The hydrophilic member according to claim 1, wherein a water droplet contact angle on the surface of the hydrophobic undercoat layer is 45 ° or more.   The hydrophilic member according to claim 1 or 2, wherein a surface free energy of the hydrophobic undercoat layer is 65 mN / m or less.   The hydrophilic member according to claim 1, wherein the hydrophobic undercoat layer is formed from a hydrophobic composition containing a hydrophobic polymer having a crosslinkable group.   The hydrophilic member according to claim 1, wherein the crosslinkable group contains a silicon atom having at least one of a hydroxyl group and a hydrolyzable functional group.   The said hydrophilic layer was formed from the hydrophilic composition containing the hydrophilic polymer which has a silicon atom which has at least any one of a hydroxyl group and a hydrolyzable functional group. The hydrophilic member described. The hydrophilic polymer is
A hydrophilic polymer (I) containing a structural unit represented by the following general formula (I-1) and a structural unit represented by the following general formula (I-2), and represented by the following general formula (II-1) A hydrophilic polymer having a partial structure represented by the following general formula (II-2) and a partial structure represented by the following general formula (II-1) at the end of the polymer chain: II)
The hydrophilic member according to claim 1, wherein the hydrophilic member is at least one of the above.

{In General Formulas (I-1) and (I-2), R ^{101 to} R ¹⁰⁸ each independently represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 to 3, and L ¹⁰¹ and L ¹⁰² each independently represent a single bond or a polyvalent organic linking group. x and y represent composition ratios, x represents a number satisfying 0 <x <100 and y represents 0 <y <100. A ¹⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _{e) (R f), -} OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. }

{Represents the general formula (II-1) and ^(II-2), each of R 201 ^{to R 205} independently represent a hydrogen atom or a hydrocarbon group. q represents an integer of 1 to 3, and L ²⁰¹ and L ²⁰² each independently represent a single bond or a polyvalent organic linking group. A ²⁰¹ is —OH, —OR _a , —COR _a , —CO ₂ R _e , —CON (R _a ) (R _b ), —N (R _a ) (R _b ), —NHCOR _d , —NHCO ₂ R _a , —OCON (R _a ) (R _b ), —NHCON (R _a ) (R _b ), —SO ₃ R _e , —OSO ₃ R _e , —SO ₂ R _d , —NHSO ₂ R _d , —SO ₂ N (R _a ) (R _b ), —N (R _a ) (R _b ) (R _c ), —N (R _a ) (R _b ) (R _c ) (R _g ), —PO ₃ (R _{e) (R f), -} OPO 3 (R e) (R f), or _-PO 3 represents an _{(R d) (R e)} . Here, R _a , R _b and R _c each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group, R _d represents a linear, branched or cyclic alkyl group, R _e and R _f independently represents a hydrogen atom or a linear, branched or cyclic alkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion, an inorganic anion, or an organic anion. }   8. A catalyst is further contained in at least one of the hydrophobic composition for forming the hydrophobic undercoat layer and the hydrophilic composition for forming the hydrophilic layer. The hydrophilic member according to any one of the above.   The hydrophilic member according to claim 1, wherein the catalyst is a non-volatile catalyst.   The hydrophilic composition contains the hydrophilic polymer (I) and the hydrophilic polymer (II), and the mass ratio of the hydrophilic polymer (I) to the hydrophilic polymer (II) (hydrophilic polymer (I) The hydrophilic member according to claim 7, wherein / hydrophilic polymer (II)) is in the range of 95/5 to 50/50.   The at least one of the hydrophobic composition and the hydrophilic composition further contains an alkoxide compound of at least one element selected from Si, Ti, Zr, and Al. The hydrophilic member according to any one of 10.   The hydrophilic member according to claim 1, wherein at least one of the hydrophobic composition and the hydrophilic composition further contains a surfactant.   The hydrophilic member according to claim 12, wherein the surfactant is at least one selected from an anionic surfactant, an amphoteric surfactant, and a fluorosurfactant.   The hydrophilic member according to claim 1, wherein a thickness of the hydrophobic undercoat layer is larger than 10 nm and smaller than 1 μm.   The hydrophilic member according to claim 1, wherein a film thickness of the hydrophilic layer is larger than 10 nm and smaller than 1 μm.   The hydrophobic undercoat layer is formed by applying a hydrophobic composition, heating and drying, and the hydrophilic layer is formed by applying a hydrophilic composition, heating and drying. The hydrophilic member according to any one of claims 1 to 15.   The hydrophilic member according to claim 1, wherein the substrate contains a resin.