JP2013063561A - Hydrophilic member and method for forming the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrophilic member which exhibits excellent adhesiveness to various base materials, which allows the surface of the base material to be excellent in water resistance, antifogging properties, antifouling properties and weatherability and have hydrophilicity, and which has a composition gradient film.SOLUTION: The hydrophilic member has the base material 2 and a film 3 which is arranged on the base material and contains a hydrophilic material (1) and a resin material (2). The film is the composition gradient film in which the composition of the hydrophilic material (1) and that of the resin material (2) change continuously in the thickness direction of the film so that a ratio of the hydrophilic material (1) may become larger and that of the resin material (2) may become smaller as it goes from the closest side thereof to the base material to the farthest side thereof from the base material. The hydrophilic material (1) contains a hydrolyzable silyl group-containing hydrophilic polymer, which has at least one specific hydrolyzable silyl group at the terminal of a main chain or a side chain of one molecule thereof and at least one hydrophilic group in one molecule thereof. The resin material (2) contains an oligomer or polymer, however the resin material (2) is different from the hydrophilic material (1).

Description

  The present invention relates to a hydrophilic member. Specifically, the adhesion between various substrates and membranes constituting the hydrophilic member is good, and the surface of the substrate has water resistance, antifogging properties, antifouling properties, and weather resistance. The present invention relates to a hydrophilic member capable of imparting a hydrophilic surface having excellent properties.

  Products and members having a resin film surface are used in a wide range of fields, and are used after being processed and imparted with functions according to the purpose. However, those surfaces generally exhibit hydrophobicity and lipophilicity due to the inherent properties of the resin. Therefore, if oil or the like adheres to these surfaces as a soiling substance, they cannot be easily removed, and accumulation may significantly reduce the functions and characteristics of products / members having the surface. It was. Therefore, various hydrophilic members having a surface hydrophilic function on various base materials 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.
Patent Document 2 discloses a hydrophobic undercoat layer formed from a hydrophobic polymer composition on a polyethylene terephthalate substrate, and a hydrophilic property containing a hydrolyzable silyl group at the main chain terminal or side chain on the undercoat layer. A hydrophilic member having a hydrophilic layer formed from a polymer is described.
Patent Document 3 discloses a self-gradient function in which an organosiloxane composition consisting of a water-based resin and an aqueous solution of an organosiloxane is coated on a substrate, whereby the organosiloxane is unevenly distributed on the surface of the coating film due to a difference in surface energy. A hydrophilic member is described.

It is described that the hydrophilic member described in Patent Document 1 has excellent adhesion to a substrate made of an inorganic material such as glass or metal, and is excellent in alkali resistance. And although it is described that this member is formed using a water-based epoxy resin as an adhesive layer on a PET support, it is not described that it has a composition gradient film.
Patent Document 2 describes a hydrophilic member having a two-layer structure of an undercoat layer formed on a substrate and a hydrophilic layer formed on the undercoat layer. However, it does not describe having a composition gradient film.
Patent Document 3 describes a hydrophilic member using a material having a low surface energy. However, it is clear that the hydrophilicity of the surface of the member is lowered due to the presence of a material having a low surface energy. Therefore, it is thought that there exists a problem which cannot achieve hydrophilic property, anti-fogging property, and antifouling property.
As described above, the conventional hydrophilic member is formed by laminating a composition including a hydrophilic material and a material relatively compatible with the substrate (for example, a silica sol-gel / organic polymer hybrid material) on the substrate, It has been obtained by providing a hydrophilic material and a material having a certain degree of adhesion to the substrate as an adhesive layer on the substrate, and laminating the hydrophilic material on the adhesive layer.

JP 2008-284715 A JP 2011-73359 A JP 2001-335690 A

However, the conventional hydrophilic member has an interface between layers formed of different materials, or the hydrophilicity on the surface of the member is not sufficient. Therefore, both the adhesion and hydrophilicity required for recent hydrophilic members are required. The performance was not always satisfactory.
The present invention has been made in view of such circumstances, and has a hydrophilic surface with good adhesion to various substrates and excellent water resistance, antifogging properties, antifouling properties, and weather resistance on the substrate surface. An object of the present invention is to provide a hydrophilic member having a composition gradient structure.

  The object of the present invention has been achieved by the following means.

[1]
A hydrophilic member having a base material and a film provided on the base material and including the following hydrophilic material 1) and resin material 2), the film being closest to the base material in the thickness direction of the film A hydrophilic member that is a composition gradient film in which the composition of 1) and 2) is continuously changed so that the ratio of 1) increases from the side toward the farthest side and the ratio of 2) decreases. .
1) A hydrolyzable silyl group-containing hydrophilic polymer is contained, and the polymer has at least one hydrolyzable silyl group represented by the following general formula (a) in the molecule at the main chain terminal or side chain. And a hydrophilic material having at least one hydrophilic group in the molecule.
Formula _{^{(a): -Si (R 10}} ) 3-a - (OR 11) a
(In formula, R < ¹⁰ >, R < ¹¹ > is a hydrogen atom or a hydrocarbon group, respectively, and a shows the integer of 1-3.)
2) A resin material containing an oligomer or polymer. However, 2) is different from the hydrophilic material of 1) above.
[2]
The hydrophilic member according to [1], wherein the oligomer or polymer is a urethane oligomer or polymer.
[3]
When the ratio of the mass of the resin material 2) to the total mass of the resin material 2) and the hydrophilic material 1) in the composition gradient film is measured for each thickness of 0.1 μm from the substrate side in the film thickness direction. Further, the hydrophilic member according to [1] or [2], wherein the difference in the ratios at adjacent measurement positions is 50% or less.
[4]
The hydrolyzable silyl group-containing hydrophilic polymer includes a hydrophilic polymer (I) having a structure represented by the following general formula (I-1) and a structure represented by the general formula (I-2), II-1) and a structure represented by the hydrophilic polymer (II) or the general formula (III-1) including the structure represented by the general formula (II-2) and the general formula (III-2) The hydrophilic member according to any one of [1] to [3], which is any one of the hydrophilic polymers (III) including a structure represented by:

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 divalent 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 or branched alkyl group or cycloalkyl group, and R _d represents a linear or branched alkyl group or cycloalkyl group. R _e and R _f each independently represent a hydrogen atom, or a linear or branched alkyl group or cycloalkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion or an inorganic group. An anion or an organic anion is represented.

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

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 divalent 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 or branched alkyl group or cycloalkyl group, and R _d represents a linear or branched alkyl group or cycloalkyl group. R _e and R _f each independently represent a hydrogen atom, or a linear or branched alkyl group or cycloalkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion or an inorganic group. An anion or an organic anion is represented.
[5]
The hydrophilic member according to any one of [1] to [4], wherein a structural unit having a hydrophilic group in the hydrolyzable silyl group-containing hydrophilic polymer is contained in an amount of 30 mol% or more of the whole polymer.
[6]
The hydrophilic member according to any one of [1] to [5], wherein the hydrophilic material of the material 1) further contains colloidal silica.
[7]
The hydrophilic member according to any one of [2] to [6], wherein in the material 2), the urethane oligomer or polymer is an oligomer or polymer containing a urethane bond and a urea bond.
[8]
The hydrophilic member according to any one of [2] to [6], wherein in the material 2), the urethane oligomer or polymer is an oligomer or polymer having a repeating unit represented by the following general formula (A): .

(In the above general formula, R _{A1 to} R _A3 each independently represents an alkylene group, an arylene group, or a biarylene group, and R _{A4 to} R _A6 each independently represent a hydrogen atom, an alkyl group, an aryl group, or heteroaryl. Represents a group.)
[9]
[1] to [8], wherein at least two kinds of ink compositions of the ink composition containing the hydrophilic material of 1) and the ink composition containing the resin material of 2) are ejected onto the substrate by an ink jet method. ] The formation method of the hydrophilic member of any one of.
[10]
As the at least two kinds of ink compositions, at least an ink composition containing the hydrophilic material of 1) and an ink composition containing the resin material of 2) are used,
The inkjet method uses at least a first inkjet head and a second inkjet head,
Supplying a first ink containing an ink composition containing the hydrophilic material of 1) to a first inkjet head;
Supplying a second ink containing an ink composition containing the resin material of 2) to a second inkjet head;
A control step of determining a ratio between the amount of the first ink ejected from the first inkjet head and the amount of the second ink ejected from the second inkjet head;
Forming a layer by discharging the first ink or the second ink from at least one of the first inkjet head and the second inkjet head according to the determined ratio;
A lamination step of repeating the formation step to obtain a composition gradient film by laminating a plurality of layers on the substrate;
With
In the control step, the ratio of the first ink increases and the ratio of the second ink decreases from the layer closest to the base material to the layer farthest in the thickness direction of the plurality of layers. The method for forming a hydrophilic member according to [9], wherein the ratio is determined.
[11]
The method for forming a hydrophilic member according to [10], wherein in the forming step, the ink amount of droplets ejected from the first and second inkjet heads is 0.3 to 100 pL.
[12]
The method for forming a hydrophilic member according to [10] or [11], wherein in the forming step, a droplet diameter of droplets discharged from the first and second inkjet heads is 1 to 300 μm.
[13]
As the at least two kinds of ink compositions, at least an ink composition containing the hydrophilic material of 1) and an ink composition containing the resin material of 2) are used,
The inkjet method uses a plurality of inkjet heads,
A mixed ink in which the first ink containing the ink composition containing the hydrophilic material of 1) and the second ink containing the ink composition containing the resin material of 2) are mixed, each having a different ratio Supplying a plurality of mixed inks mixed in step to each inkjet head of the plurality of inkjet heads;
A selection step of sequentially selecting one inkjet head from the plurality of inkjet heads, the selection step sequentially selecting from the inkjet head to which the mixed ink having a high ratio of the second ink is supplied;
Forming a layer by discharging mixed ink from the selected inkjet head; and
A lamination step of repeating the formation step to obtain a composition gradient film by laminating a plurality of layers on the substrate;
The method for forming a hydrophilic member according to [9], comprising:
[14]
The method for forming a hydrophilic member according to [13], wherein, in the forming step, the ink amount of droplets ejected from the selected inkjet head is 0.5 to 150 pL.
[15]
The method for forming a hydrophilic member according to [13] or [14], wherein in the forming step, a droplet diameter of a droplet discharged from the selected inkjet head is 2 to 450 μm.
[16]
A hydrophilic member formed by an ink jet method using at least two ink compositions, the ink composition containing at least the hydrophilic material of 1) and the ink composition containing the resin material of 2). And
The inkjet method uses at least a first inkjet head and a second inkjet head,
Supplying a first ink containing an ink composition containing the hydrophilic material of 1) to a first inkjet head;
Supplying a second ink containing an ink composition containing the resin material of 2) to a second inkjet head;
A control step of determining a ratio between the amount of the first ink ejected from the first inkjet head and the amount of the second ink ejected from the second inkjet head;
Forming a layer by discharging the first ink or the second ink from at least one of the first inkjet head and the second inkjet head according to the determined ratio;
A lamination step of repeating the formation step to obtain a composition gradient film by laminating a plurality of layers on the substrate;
With
In the control step, the ratio of the first ink is increased and the ratio of the second ink is decreased from a layer close to the base in a thickness direction of the plurality of layers toward a layer far from the base. The hydrophilic member according to any one of [1] to [8], which determines a ratio.
[17]
A hydrophilic member formed by an ink jet method using at least two ink compositions, the ink composition containing at least the hydrophilic material of 1) and the ink composition containing the resin material of 2). And
The inkjet method uses a plurality of inkjet heads,
A mixed ink in which the first ink containing the ink composition containing the hydrophilic material of 1) and the second ink containing the ink composition containing the resin material of 2) are mixed, each having a different ratio Supplying a plurality of mixed inks mixed in step to each inkjet head of the plurality of inkjet heads;
A selection step of sequentially selecting one inkjet head from the plurality of inkjet heads, the selection step sequentially selecting from the inkjet head to which the mixed ink having a high ratio of the second ink is supplied;
Forming a layer by discharging mixed ink from the selected inkjet head; and
A lamination step of repeating the formation step to obtain a composition gradient film by laminating a plurality of layers on the substrate;
The hydrophilic member according to any one of [1] to [8].

  The present invention has a base material and a film provided on the base material and including a specific hydrophilic material 1) and a resin material 2) based on a completely different idea from the conventional one, and the film is a film. In the thickness direction, the composition of 1) and 2) continuously changes so that the ratio of 1) increases and the ratio of 2) decreases from the side closest to the substrate to the side farthest. By adopting a composition that is a composition gradient film, there is no clear heterogeneous interface, and hydrophilicity (the side farthest from the substrate) and substrate adhesion (side closest to the substrate) are at a high level. We succeeded in obtaining compatible hydrophilic members.

  That is, according to the present invention, it is possible to impart a hydrophilic surface that has good adhesion to various substrates and has excellent water resistance, antifogging properties, antifouling properties, and weather resistance to the substrate surface. A hydrophilic member having a composition gradient film and a method for forming the same are provided.

Schematic diagram of a hydrophilic member comprising a composition gradient film Schematic diagram of a hydrophilic member comprising a composition gradient film Overall configuration diagram of composition gradient film production equipment Schematic of the drawing part of the composition gradient film production device Diagram for explaining composition gradient film formation by drawing mixing method The figure for demonstrating other embodiment of the drawing mixing method Overall configuration diagram of a composition gradient film manufacturing apparatus according to an embodiment of an ink mixing method Diagram for explaining composition gradient film formation by ink mixing method The figure for demonstrating the landing position of each ink in a drawing mixing method

The present invention is a hydrophilic member having a base material and a film provided on the base material and including the following hydrophilic material 1) and resin material 2), wherein the film is the base in the thickness direction of the film. A composition gradient film in which the composition of 1) and 2) continuously changes so that the ratio of 1) increases from the side closest to the material to the side farthest and the ratio of 2) decreases. And relates to a hydrophilic member.
1) A hydrolyzable silyl group-containing hydrophilic polymer (hereinafter, also simply referred to as “hydrophilic polymer”), and the polymer is represented by the following general formula (a) at the main chain terminal or side chain. A hydrophilic material having at least one hydrolyzable silyl group in the molecule and at least one hydrophilic group in the molecule.
Formula _{^{(a): -Si (R 10}} ) 3-a - (OR 11) a
(In formula, R < ¹⁰ >, R < ¹¹ > is a hydrogen atom or a hydrocarbon group, respectively, and a shows the integer of 1-3.)
2) A resin material containing an oligomer or polymer. However, 2) is different from the hydrophilic material of 1) above.

[Hydrophilic material]
(Hydrolyzable silyl group-containing hydrophilic polymer)
The hydrophilic material in the present invention contains a hydrolyzable silyl group-containing hydrophilic polymer.
The hydrophilic polymer in the present invention has at least one hydrolyzable silyl group represented by the following general formula (a) in the molecule at the main chain terminal or side chain, and has at least one hydrophilic group in the molecule. Have one.
Formula _{^{(a): -Si (R 10}} ) 3-a - (OR 11) a
(In formula, R < ¹⁰ >, R < ¹¹ > is a hydrogen atom or a hydrocarbon group, respectively, and a shows the integer of 1-3.)
When a plurality of R ¹⁰ or R ¹¹ are present, they may be the same as or different from each other.

  The hydrolyzable silyl group of the hydrolyzable silyl group-containing hydrophilic polymer is preferably bonded to the main chain or side chain carbon atom of the polymer.

In general formula (a), R ¹¹ is preferably a hydrogen atom or an alkyl group, and R ¹⁰ is preferably a monovalent hydrocarbon group selected from a hydrogen atom or an alkyl group, an aryl group, and an aralkyl group.
When R ¹¹ represents an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹⁰ represents an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. A 25 aryl group is preferable, and an aralkyl group having 7 to 12 carbon atoms is preferable.

The hydrophilic polymer used in the present invention has 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) _nH, - (such as _CH 2 _CH 2 O) nCH 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 may be a hydrogen atom, an alkyl group (preferably a linear or branched alkyl group or cycloalkyl group having 1 to 18 carbon atoms), an aryl group, or an aralkyl group. Represents a 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 examples of the substituent include substituents that can be introduced when R ¹⁰¹ and R ¹⁰² in the structure represented by the general formula (I-1) 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 ) NH, 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) nH is, more preferably, -OH, -COOH, a -CONH _2.

  In addition, the hydrophilic polymer used in the present invention is preferably a polymer having a metal alkoxide compound selected from Si, Ti, Zr, and Al, which will be described later, and a group that forms a bond by the action of a catalyst or the like. . As the group that forms a bond with the metal alkoxide compound by the action of the catalyst, in addition to the hydrolyzable silyl group represented by the general formula (a), a carboxyl group, an alkali metal salt of a carboxy group, a carboxylic anhydride group, Amino group, hydroxy group, epoxy group, methylol group, mercapto group, isocyanate group, block isocyanate group, alkoxytitanate group, alkoxyaluminate group, alkoxyzirconate group, ethylenically unsaturated group, ester group, tetrazole group, etc. These reactive groups can be mentioned. Examples of the polymer structure having a hydrophilic group and a group that generates a bond by the action of a catalyst with a metal alkoxide compound include an ethylenically unsaturated group (for example, acrylate group, methacrylate group, itaconic acid group, crotonic acid group, cinnamic acid group). Styrene group, vinyl group, allyl group, vinyl ether group, vinyl ester group, etc.), polymer obtained by vinyl polymerization, polycondensation polymer such as polyester, polyamide, polyamic acid, etc., addition polymer such as polyurethane, etc. Preferred examples include natural cyclic polymer structures such as cellulose, amylose and chitosan.

  The hydrophilic polymer in the present invention preferably contains a structural unit having a hydrophilic group.

  In the hydrophilic polymer, the structural unit having a hydrophilic group is preferably contained in an amount of 30 mol% or more of the whole polymer, and more preferably 40 to 95 mol% of the whole polymer.

  Although the structural unit which has a hydrophilic group contained in the said hydrophilic polymer is not specifically limited, For example, the structural unit represented by the following general formula (I-2), (II-2) or (III-2) is shown. Can be used.

  The hydrophilic polymer in the present invention includes a hydrophilic polymer (I) having a structure represented by the following general formula (I-1) and a structure represented by the general formula (I-2), and a general formula (II-1). The structure represented by the formula (II-2) and the hydrophilic polymer (II) containing the structure represented by the formula (II-2) or the structure represented by the formula (III-1) and the formula (III-2) It is preferably any of the hydrophilic polymers (III) containing a structure.

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 divalent 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 or branched alkyl group or cycloalkyl group, and R _d represents a linear or branched alkyl group or cycloalkyl group. R _e and R _f each independently represent a hydrogen atom, or a linear or branched alkyl group or cycloalkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion or an inorganic group. An anion or an organic anion is represented.

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

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 divalent 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 or branched alkyl group or cycloalkyl group, and R _d represents a linear or branched alkyl group or cycloalkyl group. R _e and R _f each independently represent a hydrogen atom, or a linear or branched alkyl group or cycloalkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion or an inorganic group. An anion or an organic anion is represented.

[Hydrophilic polymer (I) having a structure represented by general formulas (I-1) and (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 represent a single bond or a divalent 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 or branched alkyl group or cycloalkyl group, and R _d represents a linear or branched alkyl group or cycloalkyl group. R _e and R _f each independently represent a hydrogen atom, or a linear or branched alkyl group or cycloalkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion or an inorganic group. An anion or an organic anion is represented.

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 or branched alkyl group or cycloalkyl group having 1 to 8 carbon atoms is preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like. R ^{101 to} R ¹⁰⁸ are preferably a hydrogen atom, a methyl group, or an ethyl group from the viewpoints of effects and availability.

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

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

Specific examples of the alkyl group in these substituents are the same as those of R ^{1 to} R ⁸ , and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, Xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, acetoxyphenyl, benzoyloxyphenyl, methylthiophenyl , Phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamo Butylphenyl group include a phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, a phosphonophenyl phenyl group. Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like. Examples of alkynyl group include ethynyl group, 1- A propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, etc. are mentioned. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups.

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

  On the other hand, the alkylene group in the substituted alkyl group is preferably a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Preferably, it is a straight chain having 1 to 12 carbon atoms, more preferably a straight chain having 1 to 8 carbon atoms, more preferably a branched structure having 3 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms, and More preferable examples include cycloalkylene groups having 5 to 10 carbon atoms, and more 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.
When L ^{101 to} L ¹⁰² represent an organic linking group, L ^{101 to} L ¹⁰² represent a divalent linking group composed of a non-metal atom, and have 0 to 60 carbon atoms and 0 to 10 nitrogen atoms. 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 a divalent group represented by the following chemical formula, a methylene group, an ether group, a sulfo group, a sulfonyl group, a sulfinyl group, a thioether group, an ester group, a carbonyl group, an amino group, and an amide group. , Sulfonamide group, urea group, carbamate group, carbonate group, —CONHSO ₂ — group, phenylene group, naphthylene group, anthracenylene group, phenanthrylene group, methylalkylene group, dimethylalkylene group, or a combination thereof Can be mentioned.

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

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 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 or branched alkyl group or cycloalkyl group (preferably having 1 to 8 carbon atoms), and R _d is a linear Represents a branched alkyl group or a cycloalkyl group (preferably having 1 to 8 carbon atoms), and R _e and R _f each independently represent a hydrogen atom, or a linear or branched alkyl group or cycloalkyl group (preferably C1-8) represents an alkali metal, alkaline earth metal, or an onium, 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 or branched alkyl group or cycloalkyl group, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Preferable examples include 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 and cyclopentyl group.
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 including the structures represented by the general formulas (I-1) and (I-2), x and y are the structures represented by the general formula (I-1) in the (A) specific hydrophilic polymer. The composition ratio of the unit and the structural unit represented by 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 structures represented by the general formulas (I-1) and (I-2) is such that the amount of the general formula (I-2) having a hydrophilic group is within the above range. The structural unit having a hydrophilic group in the hydrolyzable silyl group-containing hydrophilic polymer is preferably contained in an amount of 30 mol% or more of the whole polymer. That is, 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 amount 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 structures represented by the general formulas (I-1) and (I-2) is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, 1,000 to 200,000 is most preferred.

  Specific examples of the hydrophilic polymer including the structures represented by the general formulas (I-1) and (I-2) are shown below together with their mass average molecular weights (MW). It is not limited to. 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 including the structures represented by the general formulas (I-1) and (I-2) is commercially available, and can be easily synthesized.
As the radical polymerization method for synthesizing the hydrophilic polymer containing the structures represented by the general formulas (I-1) and (I-2), any conventionally known method can be used.
Specifically, general radical polymerization methods include, for example, New Polymer Experiments 3 (1996, Kyoritsu Shuppan), Polymer Synthesis and Reaction 1 (Polymer Society of Japan, 1992, Kyoritsu Shuppan), New Experiment Chemistry Lecture 19 (1978, Maruzen), Polymer Chemistry (I) (Edited by The Chemical Society of Japan, 1996, Maruzen), Synthetic Polymer Chemistry (Materials Engineering Lecture, 1995, Tokyo Denki University Press) These can be applied.

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

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

  The hydrophilic polymer (II) including the structures represented by the general formulas (II-1) and (II-2) has a structural unit represented by the above general formula (II-2), and has a polymer chain. It preferably has a partial structure represented by the above general formula (II-1) at the terminal thereof.

In the general formulas (II-1) and (II-2), R ^{201 to} R ²⁰⁵ each independently represent a hydrogen atom or a hydrocarbon group, and hydrocarbons when R ^{201 to} R ²⁰⁵ represent a hydrocarbon group. Examples of the group include an alkyl group and an aryl group, and a linear or branched alkyl group or cycloalkyl 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 divalent 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 divalent organic linking group, specific examples and preferred examples thereof may 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 formulas (II-1) and (II-2) is, for example, a chain transfer agent (described in the radical polymerization handbook (NTS, Mikiji Tsunoike, Go Endo)). And Iniferter (described in Macromolecules 1986, 19, p287- (Otsu)) can be synthesized by radical polymerization of a hydrophilic monomer (eg, potassium salt of acrylamide, acrylic acid, 3-sulfopropyl methacrylate). 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 including the structures represented by the general formulas (II-1) and (II-2) is represented by the following general formula (i) and a radically polymerizable monomer represented by the following general formula (i). In the radical polymerization, 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.

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

   The weight average molecular weight of the hydrophilic polymer (II) including the structures represented by the general formulas (II-1) and (II-2) is preferably 1,000 to 1,000,000, and 1,000 to 500,000. 000 is more preferable, and 1,000 to 200,000 is most preferable.

  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 structures represented by general formulas (III-1) and (III-2)]
The hydrophilic polymer (III) includes structures represented by the following general formulas (III-1) and (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 represents 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 divalent 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 or branched alkyl group or cycloalkyl group, and R _d represents a linear or branched alkyl group or cycloalkyl group. R _e and R _f each independently represent a hydrogen atom, or a linear or branched alkyl group or cycloalkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion or an inorganic group. An anion or an organic anion is represented.

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 or branched alkyl group or cycloalkyl 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 divalent 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 divalent organic linking group, specific examples and preferred examples are the same as those described for L ¹⁰¹ in the general 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 Yu Yamashita et al. 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 structures represented by the general formulas (III-1) and (III-2), x is preferably in the range of 1 <x <90, and in the range of 1 <x <50. More preferably. 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 falls within the above range. The structural unit having a hydrophilic group in the conductive polymer is preferably contained in an amount of 30 mol% or more of the whole polymer. That is, 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 amount 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 coating film without lowering the solubility in a solvent when preparing a coating solution for forming a hydrophilic coating film, without lowering the solubility in the solvent. This is preferable.

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

  The hydrophilic polymer (I), (II) or (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 iso) propyl acrylate, (n-, iso, 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, chlorobenzyl 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 iso) propyl methacrylate, (n-, iso, 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, chlorobenzyl methacrylate , Hydroxybenzyl methacrylate, hydroxyphen 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 ratio of these other monomers used for the synthesis of the copolymer needs to be an amount sufficient for improving various physical properties, but the function as a hydrophilic film is sufficient, and the specific hydrophilic polymer (I ), In order to obtain the advantage of adding the specific hydrophilic polymer (II) and / or the specific hydrophilic polymer (III), it is preferable that the ratio is not too large. Accordingly, the preferred total proportion of the other monomers in the specific hydrophilic polymer (I), the specific hydrophilic polymer (II) and / or the specific hydrophilic polymer (III) is preferably 80% by mass or less, more preferably It is 50 mass% or less.

  The copolymerization ratio of the hydrophilic polymer (I), (II) or (III) can be measured with an infrared spectrophotometer by preparing a calibration curve with a nuclear magnetic resonance apparatus (NMR) or a standard substance. it can.

In the hydrophilic composition in the present invention, the hydrophilic polymers (I), (II) or (III) may be used alone or in combination of two or more.
The hydrophilic polymer (I), (II) or (III) is preferably used in an amount of 20 to 99.5% by mass based on the total solid content of the hydrophilic composition from the viewpoint of curability and hydrophilicity. More preferably, ˜99.5% by mass is used.

  The above-mentioned hydrophilic polymer forms a crosslinked film in a state where it is mixed with a hydrolysis and polycondensate of metal alkoxide. The hydrophilic polymer, which is an organic component, is involved in the film strength and film flexibility. In particular, the hydrophilic polymer has a viscosity of 0.1 to 100 mPa · s (5% aqueous solution, measured at 20 ° C.), preferably When it is in the range of 0.5 to 70 mPa · s, more preferably 1 to 50 mPa · s, good film properties are provided.

The hydrophilic water droplet contact angle of the hydrophilic polymer grafted with the hydrophilic group is very high in hydrophilicity as compared with the conventional hydrophilic polymer in which the hydrophilic group is substituted with a polymer chain. That is, in the film containing the above hydrophilic polymer grafted with a hydrophilic group, water droplets on the film surface are likely to spread as compared with a film containing a conventional hydrophilic polymer.
The reason why the hydrophilic polymer grafted with the hydrophilic group makes the water droplet spread more on the membrane surface is not clear, but the hydrophilic group grafted on the polymer chain is simply a substituted hydrophilic group. This is presumably because it has higher rotation and mobility than the above, and can make the hydrophilicity of the film surface more uniform. The hydrophilic member of the present invention is considered to be excellent in effects such as anti-fogging property because it has a hydrophilic group with high rotational property and mobility. Moreover, since the hydrophilic member of this invention contains an oligomer or a polymer, it is guessed that it is excellent in effects, such as adhesiveness.
That is, the hydrophilic member of the present invention is presumed to achieve both effects such as antifogging property and adhesion by causing the hydrophilic material and the oligomer or polymer to be compositionally inclined.

  The contact angle of the water droplets in the air of the hydrophilic polymer grafted with the hydrophilic group is preferably 0 to 5 °. The value of the aerial water droplet contact angle is very small as compared with the value (about 10 to 20 °) of the conventional hydrophilic polymer. Such a hydrophilic material exhibiting such a very small value for the contact angle of airborne water droplets is particularly called “superhydrophilic material”.

(Crosslinking agent)
When the hydrophilic polymer (I) is contained in the hydrophilic material, it is preferable to contain a crosslinking agent in order to obtain good curability. In addition, when the hydrophilic material (II) or (III) is contained in the hydrophilic material, good curability can be obtained even when the crosslinking agent is not contained, but the coating strength is extremely excellent. In order to obtain a film, a crosslinking agent may be contained.

As the crosslinking agent, an alkoxide compound (also referred to as a metal alkoxide) containing an element selected from Si, Ti, Zr, and Al is particularly preferable. 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 and R ²¹ 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.
Further, when the central metal is Al, that is, examples of those containing aluminum in the hydrolyzable compound include trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, triisopropoxy aluminate, and the like. be able to.

  Among the above, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane are particularly preferable.

  When the metal alkoxide compound selected from Si, Ti, Zr, and Al is a hydrophilic polymer containing a structure represented by the general formula (I), the total solid content of the hydrophilic composition is 0 to 0. 80% by mass is preferably used, and more preferably 0 to 70% by mass is used. When using the hydrophilic polymer containing the structure represented by the general formula (II), it is preferably used in an amount of 0 to 80% by mass, and 0 to 70% by mass based on the total solid content of the hydrophilic composition. More preferably.

(catalyst)
In the present invention, a hydrolyzable silyl group-containing hydrophilic polymer and a crosslinking agent such as a metal alkoxide compound are dissolved in a solvent and stirred well, so that these components are hydrolyzed and polycondensed to form an organic-inorganic composite. A body sol solution is formed, and a hydrophilic film having high hydrophilicity and high film strength is formed by the sol solution. In preparing the organic-inorganic composite sol solution, it is preferable to use a curing catalyst in order to promote hydrolysis and polycondensation reaction.
As the curing catalyst used in the present invention, it is preferable to use an acidic catalyst, a basic catalyst, or a metal complex catalyst.

  As the curing catalyst used in the present invention, a catalyst that promotes a reaction that causes hydrolysis and polycondensation of the crosslinking agent such as the metal alkoxide compound to cause a bond with the hydrolyzable silyl group-containing hydrophilic polymer is selected. Alternatively, a basic compound is used as it is, or an acid or a basic compound dissolved in a solvent such as water or alcohol (collectively referred to as an acidic catalyst and a basic catalyst, respectively) 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.

The catalyst that can be used in the hydrophilic material of the present invention is particularly preferably a metal complex.
The metal complex catalyst that can be used in the formation of the hydrophilic film can promote hydrolysis and polycondensation of a metal alkoxide compound selected from Si, Ti, Zr, and Al, and can cause a bond with a hydrophilic polymer. Particularly preferred metal complex catalysts include metal elements selected from groups 2A, 3B, 4A and 5A of the periodic table and β-diketones, ketoesters, hydroxycarboxylic acids or esters thereof, amino alcohols, and enolic active hydrogen compounds. It is a metal complex composed of a selected oxo or hydroxy oxygen-containing compound.
Among constituent metal elements, 2A group elements such as Mg, Ca, St and Ba, 3B group elements such as Al and Ga, 4A group elements such as Ti and Zr, and 5A group elements such as V, Nb and Ta are preferable. , Each forming a complex with excellent catalytic effect. Of these, complexes obtained from Zr, Al and Ti are excellent and preferred.

  In the present invention, the oxo- or hydroxy-oxygen-containing compound constituting the ligand of the metal complex is, for example, acetylacetone, acetylacetone (2,4-pentanedione), β-diketones such as 2,4-heptanedione, methyl acetoacetate, Ketoesters such as ethyl acetoacetate and butylacetoacetate, hydroxycarboxylic acids and esters thereof such as lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate, 4-hydroxy-4-methyl-2 -Keto alcohols such as pentanone, 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N- Methyl-monoethanolamine For amino alcohols such as diethanolamine and triethanolamine, methylol melamine, methylol urea, methylol acrylamide, enol active compounds such as malonic acid diethyl ester, methyl group, methylene group or carbonyl carbon of acetylacetone (2,4-pentanedione) The compound which has a substituent is mentioned.

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

  Specific examples of preferred acetylacetone derivatives include acetylacetone, ethylcarbonylacetone, n-propylcarbonylacetone, isopropylcarbonylacetone, 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-iso -Propoxy bis (acetylacetonato) titanium complex salt, zirconium tris (ethyl acetoacetate), zirconium tris (benzoic acid) complex salt, etc. are mentioned. These are excellent in stability in aqueous coating solutions and in gelation promotion effect in sol-gel reaction during heat drying, and among them, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), di ( Acetylacetonato) titanium complex and zirconium tris (ethylacetoacetate) are preferred.

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

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

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

(Other ingredients)
The various additives that can be included in the hydrophilic material as required are described below.

1) Surfactant In the present invention, it is preferable to use a surfactant in order to improve the surface state of the composition gradient film. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants.

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

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

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

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

2) Ultraviolet Absorber In the present invention, an ultraviolet absorbent can be used from the viewpoint of improving the weather resistance and durability of the composition gradient film.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, US Pat. No. 3,214,463, etc. Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP The triazine compounds described in JP-A-8-501291, Research Disclosure No. Examples thereof include compounds described in No. 24239, compounds that emit ultraviolet light by absorbing ultraviolet rays typified by stilbene and benzoxazole compounds, so-called fluorescent brighteners, and the like.
The addition amount is appropriately selected according to the purpose, but generally it is preferably 0.5 to 15% by mass in terms of solid content.

3) Antioxidant In order to improve the stability of the composition gradient film contained in the hydrophilic member of the present invention, an antioxidant may be contained in the hydrophilic material. Examples of the antioxidant include European published patents, 223739, 309401, 309402, 310551, 310552, 359416, and 3435443. No. 5, JP-A-54-262447, JP-A-63-113536, JP-A-63-163351, JP-A-2-262654, JP-A-2-71262, JP-A-3-121449, Examples thereof include those described in JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1 to 8% by mass in terms of solid content.

4) Polymer compound In order to adjust the film physical properties of the hydrophilic film, various polymer compounds may be added to the hydrophilic material used for forming the hydrophilic member of the present invention as long as the hydrophilic property is not inhibited. it can. 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 “carboxyl group-containing monomer”, “methacrylic acid alkyl ester”, or “acrylic acid alkyl ester” as a structural unit is also preferably used as the copolymer composition of the polymer binder.

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

5) Antibacterial agent In order to impart antibacterial, antifungal and antialgal properties to the composition gradient film of the hydrophilic member of the present invention, an antibacterial agent can be contained in the hydrophilic material. 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 composition gradient film that gives a surface hydrophilic member excellent in antibacterial, antifungal and antialgal properties without impairing the surface hydrophilicity can be obtained.
As the antibacterial agent, it is preferable to add a compound that does not lower the hydrophilicity of the hydrophilic member formed by the composition gradient film. Examples of such antibacterial agents include inorganic antibacterial agents and water-soluble organic antibacterial agents. As the antibacterial agent, those exhibiting a bactericidal effect on fungi existing around us, such as bacteria represented by Staphylococcus aureus and Escherichia coli, fungi such as fungi and yeast, and the like are used.

[Resin material]
(Oligomer or polymer)
The oligomer that can be used as the resin material of the present invention is not limited, but refers to, for example, a polymer having a molecular weight of 1,000 to 5,000. The polymer means, for example, a polymer having a molecular weight of 5,000 or more, preferably a compound having a molecular weight of 5,000 to 10,000.

The oligomer or polymer that can be used as the resin material of the present invention is not particularly limited. For example, oligo or polyethylene terephthalate, oligo or polycarbonate, oligo or polypropylene, oligo or polyethylene, cyclic oligo or polyolefin, norbornene oligomer or polymer, oligo Or polystyrene, styrene-acrylate co-oligomer or copolymer, acrylonitrile-styrene co-oligomer or copolymer, oligo or polyethylene naphthalate, oligo or polyether sulfone, oligo or polysulfone, nylon (oligomer or polymer), urethane oligomer or polymer, oligo or poly Acrylate, oligo or polymethacrylate, cellulose acetate (oligomer or polymer), cellulose Triacetate, cellophane (oligomers or polymers), vinyl oligomers or polymers chloride, oligo- or polyvinyl fluoride, oligo- or polyvinylidene fluoride, and the like. However, the resin material containing the oligomer or polymer of the present invention is different from the hydrophilic material described above.
Among these, urethane oligomer or polymer, oligo or polyacrylate, oligo or polymethacrylate, or oligo or polystyrene are preferable, and urethane oligomer or polymer is particularly preferable.

  The content of the oligomer or polymer in the ink is preferably 10% by mass or more with respect to the total mass of the ink. The more preferable content of the oligomer or polymer in the ink is 30% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and particularly preferably 40% by mass. It is in the range of 60 mass% or less.

(Urethane oligomer or polymer)
The urethane oligomer or polymer in the present invention refers to a urethane oligomer or a urethane polymer (also referred to as “polyurethane”). Among these, it is more preferable to use a urethane oligomer.

  The reason why it is preferable to use a urethane oligomer or polymer is that the urethane polymer or oligomer has a good adhesion to the base material and forms a tough polymer blend film by interaction with a hydrophilic material through hydrogen bonding. Because you can.

  The urethane oligomer or polymer of the present invention is preferably an oligomer or polymer containing a urethane bond and a urea bond, or an oligomer or polymer having a urethane bond and a reactive group.

As the oligomer or polymer containing the urethane bond and urea bond, those having a highly flexible alkylene linkage, oligomers or polymers having a functional group that reacts and cures by energy, and the like can be preferably used.
Specifically, JUX-33 (manufactured by Aika Industry Co., Ltd.) or the like can be preferably used.

  The oligomer or polymer having a urethane bond and a reactive group is more preferably an oligomer or polymer having a repeating unit represented by the following general formula (A).

In the repeating unit represented by the above general formula, R _{A1 to} R _A3 each independently represents an alkylene group, an arylene group, or a biarylene group, and R _{A4 to} R _A6 each independently represent a hydrogen atom, an alkyl group, An aryl group or a heteroaryl group is represented.

As said alkylene group, a C1-C10 alkylene group is preferable.
As said arylene group, a phenylene group or a naphthylene group is preferable.
The biarylene group is preferably a biphenylene group or a binaphthylene group.
As said alkyl group, a C1-C10 alkyl group is preferable.
The aryl group is preferably a phenyl group or a naphthyl group.
As the heteroaryl group, a pyridyl group is preferable.

  As the urethane polymer or oligomer represented by the general formula (A), UN-1225 (manufactured by Negami Kogyo), CN962, CN965, CN971 (manufactured by Sartomer) and the like can be preferably used.

(Other ingredients)
Other various additives that can be included in the resin material include the above-described other components that can be included in the hydrophilic material.

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

  The plastic substrate used in the present invention is not particularly limited, but polyester, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol And films or sheets of polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetherketone, acrylic, nylon, fluororesin, polyimide, polyetherimide, polyethersulfone, and the like. Of these, polyester films such as polyethylene terephthalate and polyethylene naphthalate are particularly preferred. In addition, in terms of optical properties, it is often preferable to have excellent transparency, but depending on the application, translucent or printed materials may be used.

Although the thickness of a base material can use about 25 micrometers-about 1000 micrometers normally, Preferably it is 25 micrometers-250 micrometers, and it is more preferable that it is 30 micrometers-90 micrometers.
Any width of the substrate can be used, but from the viewpoint of handling, yield, and productivity, a width of 1000 mm or less is usually used, preferably 800 mm or less, and more preferably 600 mm or less. preferable. The transparent support can be handled in the form of a roll, and is usually within 200 m, preferably within 100 m.
The surface of the substrate is preferably smooth, and the average roughness Ra is preferably 1 μm or less, more preferably 0.8 μm or less, and even more preferably 0.7 μm or less.

[Composition gradient film]
The hydrophilic member according to the present invention is a film that is provided on a base material and includes the following hydrophilic material 1) and resin material 2), from the side closest to the base material in the thickness direction of the film. It has a composition gradient film in which the compositions of 1) and 2) continuously change so that the ratio of 1) increases toward the farthest side and the ratio of 2) decreases.

  The thickness of the composition gradient film in the present invention is not particularly limited, but is preferably 1 μm or more, more preferably 1 μm to 20 μm, still more preferably 3 μm to 10 μm. If it is this range, the hydrophilic member which shows favorable hydrophilic property can be obtained.

In FIG. 1, the cross section of the composition inclination film | membrane contained in the hydrophilic member formed by this invention is typically shown.
The hydrophilic member 1 according to the present invention has a pattern composed of a composition gradient film 3 on a substrate 2. The composition gradient film 3 is formed from the hydrophilic material 1) to the resin in the thickness direction from the side A farthest from the base material 2 toward the side B closest to the base material 2 (that is, in the direction of the arrow in FIG. 1). The composition continuously changes to material 2).
Here, the “thickness direction” means the “film thickness direction” of the composition gradient film 3.
“The composition changes continuously from the hydrophilic material 1) to the resin material 2) in the thickness direction” means that the composition gradient film is divided into regions of a certain thickness (for example, 0.1 to 5 μm) in the thickness direction, When the ratio of the mass of the resin material 2) to the total mass of the resin material 2) and the hydrophilic material 1) in each region (hereinafter also referred to as “resin content”) is measured, This means that the difference in the resin content is 50% or less. And it means that it is preferably 30% or less. When the difference in resin content between adjacent regions is 50% or less, the change in the resin content is not stepwise, and high adhesion and hydrophilicity can be obtained. The difference in resin content between two adjacent regions may be 0%.
The content of the resin on the side A farthest from the base material of the composition gradient film 3 (for example, the content of the resin in the region from A to a thickness of 0.1 to 5 μm) is 0 to 50 from the viewpoint of obtaining high hydrophilicity. %, More preferably 0 to 30%, and still more preferably 0% (0 to 0.2%). Further, the content of the resin on the side B closest to the substrate (for example, the content of the resin in the region from B to a thickness of 0.1 to 5 μm) is 50 to 100% from the viewpoint of obtaining high adhesion. It is preferably 70 to 100%, more preferably 100% (99 to 100%).

  In the composition gradient film of the present invention, the ratio of the mass of the resin material 2) to the total mass of the resin material 2) and the hydrophilic material 1) is measured for each thickness of 0.1 μm from the substrate side in the film thickness direction. It is preferable that the difference in the ratios at adjacent measurement positions is 50% or less. Further, the difference in the ratios is more preferably 30% or less.

  The resin content in each region can be obtained by, for example, an XPS depth profile.

The composition of the composition gradient film 3 is not particularly limited as long as there is a continuous change in the resin content as described above, but a structure in which a plurality of layers having different resin contents as shown in FIG. Take as an example.
A hydrophilic member 1a shown in FIG. 2 has a composition gradient film 3 on a substrate 2, and the composition gradient film 3 includes a plurality of layers 3-1, 3-2, 3-3 having different resin contents. 3-4, 3-5. The layers 3-1, 3-2, 3-3, 3-4, 3-5 are changed from the A-side layer 3-5 farthest to the base material 2 to the B-side layer 3-1 nearest to the base material 2. Towards (that is, in the direction of the arrow in FIG. 2), the resin content continuously increases within a range of 0% to 100%.
In obtaining good adhesion and hydrophilicity, the difference in the resin content of two adjacent layers among the layers 3-1, 3-2, 3-3, 3-4, 3-5 is 50% or less. Preferably, it is 30% or less. Further, the resin content of the A-side layer 3-5 farthest from the substrate 2 is preferably 0% to 20%, more preferably 0% to 15%. The resin content of the layer 3-1 on the B side closest to the substrate 2 is preferably 80% to 100%, and more preferably 85% to 100%.
In FIG. 2, the composition gradient film 3 is formed by laminating five layers 3-1, 3-2, 3-3, 3-4, and 3-5, but the number of layers to be laminated is particularly limited. Not. Preferably it is 3-10 layers, More preferably, it is 3-7 layers. The thickness of each layer is preferably 0.1 μm to 5 μm, and more preferably 0.3 μm to 3 μm. It is preferable that the thickness of each layer is substantially equal (thickness error is in a range of ± 0.5 μm).
In addition, when the interface between layers is not clear, a region separated by a thickness of 0.1 μm to 5 μm in the thickness direction of the composition gradient film 3 may be regarded as a “layer”.
The resin content in each region can be obtained by, for example, an XPS depth profile.

According to the present invention, at least two types of ink compositions, the ink composition containing the hydrophilic material of 1) and the ink composition containing the resin material of 2), are ejected onto the substrate by an ink jet method. It also relates to a method for forming a hydrophilic member.
Hereinafter, the ink used in the present invention will be described.

(Ink composition)
The ink composition used in the present invention is roughly classified into the ink composition containing the hydrophilic material of 1) and the ink composition containing the resin material of 2). The ink composition may contain a solvent, a binder component, and other additives in addition to the hydrophilic material of 1) and the resin material of 2).
The ink composition may be used alone as an ink, or two or more ink compositions may be mixed and used as an ink.

(ink)
As the ink used in the present invention, two or more independent inks containing the ink composition containing the hydrophilic material of 1) and the ink containing the ink composition containing the resin material of 2) are used. The ink containing the ink composition containing the hydrophilic material of 1) and the ink containing the ink composition containing the resin material of 2) are mixed. It may be used as a mixed ink.
In addition to the hydrophilic material of 1) and the resin material of 2), the ink may contain a solvent, a binder component, and other additives.

(solvent)
The ink composition according to the present invention is prepared by mixing the hydrophilic material of 1), the resin material of 2) and a solvent.
As a solvent, it can select and use suitably from water and an organic solvent, It is preferable that it is a liquid whose boiling point is 50 degreeC or more, and it is more preferable that it is an organic solvent whose boiling point is the range of 60 to 300 degreeC.
It is preferable to use the solvent in such a ratio that the solid content concentration in the ink composition is 1 to 70% by mass. Furthermore, 5-60 mass% is preferable. Within this range, the resulting ink has a viscosity range with good workability.

Examples of the solvent include alcohols, ketones, esters, nitriles, amides, ethers, ether esters, hydrocarbons, halogenated hydrocarbons and the like. Specifically, alcohol (for example, methanol, ethanol, propanol, butanol, benzyl alcohol, ethylene glycol, propylene glycol, ethylene glycol monoacetate, cresol, etc.), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Methylcyclohexanone), esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl formate, propyl formate, butyl formate, ethyl lactate, etc.), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons ( For example, methylene chloride, methyl chloroform, etc.), aromatic hydrocarbons (eg, toluene, xylene, etc.), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrole) Don, etc.), ethers (eg, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), ether alcohols (eg, 1-methoxy-2-propanol, ethyl cellosolve, methyl carbinol, etc.), fluoroalcohols (eg, JP, 8-143709, A paragraph number [0020], 11-60807 gazette Paragraph number [0037], etc.).
These solvents can be used alone or in admixture of two or more. Preferred solvents include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, isopropanol, and butanol.

(Additive)
In the ink composition according to the present invention, in addition to the hydrophilic material of 1) and the resin material of 2), the surface tension adjusting agent, antifouling agent, water resistance imparting agent, chemical resistance imparting agent, and the like. Additives can be included.

(Ink properties)
The viscosity of the ink according to the present invention is preferably 5 to 40 cP, more preferably 5 to 30 cP, and even more preferably 8 to 20 cP from the viewpoints of uniformity during film formation, stability during inkjet ejection, and storage stability of the ink. preferable.
The surface tension of the ink is preferably 10 to 40 mN / m, more preferably 15 to 35 mN / m, from the viewpoints of uniformity during film formation, stability during inkjet ejection, and storage stability of the ink. 30 mN / m is more preferable.

(Creation of composition gradient film by inkjet method)
Hereinafter, preparation of a composition gradient film by the inkjet method of the present invention will be described.
In the present invention, the ink containing the ink composition containing the hydrophilic material of 1) and the ink containing the ink composition containing the resin material of 2) are used as two or more independent inks. A mixed ink formed by mixing an ink containing an ink composition containing a hydrophilic material and an ink containing an ink composition containing a resin material is ejected onto the base material by an ink jet method. Dispense up.

As an ink jet method, there is no limitation on an ink jet recording method as long as an image is recorded by an ink jet printer, and a known method, for example, a charge control method for discharging an ink composition using electrostatic attraction, a piezoelectric method, or the like. Drop-on-demand method (pressure pulse method) that uses the vibration pressure of the element, acoustic ink jet method that discharges the ink composition using radiation pressure by irradiating the ink composition by converting the electrical signal into an acoustic beam, and ink composition It is used in a thermal ink jet (Bubble Jet (registered trademark)) system or the like that uses a pressure generated by heating an object to form bubbles.
The ink droplets are mainly controlled by the print head. For example, in the case of the thermal ink jet method, it is possible to control the droplet ejection amount by the structure of the print head. That is, droplets can be ejected in a desired size by changing the sizes of the ink chamber, the heating unit, and the nozzle. Even in the case of the thermal ink jet method, it is possible to realize droplet ejection of a plurality of sizes by providing a plurality of print heads having different sizes of heating units and nozzles. In the case of a drop-on-demand method using a piezo element, it is possible to change the droplet ejection amount due to the structure of the print head, as in the case of the thermal ink jet method, but also by controlling the waveform of the drive signal that drives the piezo element. A plurality of sizes of droplets can be ejected with a print head having the same structure.

  As an ink ejection method (drawing method) on a base material, an ink containing an ink composition containing a hydrophilic material and an ink containing an ink composition containing a resin material are supplied to separate inkjet heads, There is a drawing and mixing method in which the ratio of both discharge amounts is adjusted and discharged simultaneously and mixed on the substrate. As another method, the ratio of the two is different in a mixed ink in which an ink containing an ink composition containing a hydrophilic material and an ink containing an ink composition containing a resin material are mixed in advance. The ratio of the ink containing an ink composition containing a hydrophilic material and the ink containing an ink composition containing a resin material by supplying a plurality of types of prepared materials to an inkjet head and selecting the heads in order There is a mixed ink method in which mixed inks having different values are sequentially ejected and drawn.

(Preparation of ink)
The preparation of an ink containing an ink composition containing a hydrophilic material and an ink containing an ink composition containing a resin material used in the drawing and mixing method described later will be described.
The ink can be prepared by mixing each material. When mixing each material, you may stir with a stirrer. Although stirring time is not specifically limited, Usually, it is 30 minutes-60 minutes, and 30 minutes-40 minutes are preferable. Moreover, the temperature at the time of mixing is 10 to 40 degreeC normally, and 20 to 35 degreeC is preferable.
In the ink mixing method described later, the inks prepared as described above can be mixed and used.

~ Drawing mixing method ~
The method of the present invention is a hydrophilic member having a base material and a film provided on the base material and containing the hydrophilic material 1) and the resin material 2), wherein the film is in the thickness direction of the film. The composition gradient in which the compositions of 1) and 2) continuously change so that the ratio of 1) increases from the side closest to the substrate toward the side farthest from the base material and the ratio of 2) decreases. A method for forming a hydrophilic member of the present invention, which is a film,
A method for forming a hydrophilic member, wherein at least two types of ink compositions, the ink composition containing the hydrophilic material of 1) and the ink composition containing the resin material of 2), are ejected onto the substrate by an inkjet method. In
As the at least two kinds of ink compositions, at least an ink composition containing the hydrophilic material of 1) and an ink composition containing the resin material of 2) are used,
The inkjet method uses at least a first inkjet head and a second inkjet head,
Supplying a first ink containing an ink composition containing the hydrophilic material of 1) to a first inkjet head;
Supplying a second ink containing an ink composition containing the resin material of 2) to a second inkjet head;
A control step of determining a ratio between the amount of the first ink ejected from the first inkjet head and the amount of the second ink ejected from the second inkjet head;
Forming a layer by discharging the first ink or the second ink from at least one of the first inkjet head and the second inkjet head according to the determined ratio;
A lamination step of repeating the formation step to obtain a composition gradient film by laminating a plurality of layers on the substrate;
With
In the control step, the ratio of the first ink increases and the ratio of the second ink decreases from the layer closest to the base material to the layer farthest in the thickness direction of the plurality of layers. A method of determining the ratio is preferable.

According to the drawing method, the ratio between the discharge amount of the first ink discharged from the first inkjet head and the discharge amount of the second ink discharged from the second inkjet head is determined and determined. By repeating the step of ejecting ink according to the ratio to form one layer, a plurality of layers are stacked on the base material, and the ratio of the first ink ejection amount increases as the plurality of layers move upward. The composition gradient film can be manufactured by using an ink jet technique by forming a layer having a small ratio of the ejection amount of the second ink.
In addition, this invention relates also to the hydrophilic member formed by the said drawing method.

-Embodiment by drawing mixed method-
FIG. 3 is an overall configuration diagram of the composition gradient film manufacturing apparatus 100 according to the drawing mixing method, and FIG. 4 is a schematic diagram of the drawing unit 10 of the composition gradient film manufacturing apparatus 100. As shown in these drawings, the composition gradient film manufacturing apparatus 100 includes a drawing unit 10, and the drawing unit 10 uses a flatbed type ink jet drawing apparatus. Specifically, the drawing unit 10 includes a stage 30 on which a base material that is a base material is placed, a suction chamber 40 for sucking and holding the base material placed on the stage 30, and each ink toward the base material 20. Ink jet head 50A (hereinafter referred to as ink jet head 1) and ink jet head 50B (hereinafter referred to as ink jet head 2).

  The stage 30 has a width that is wider than the diameter of the substrate 20, and is configured to be freely movable in the horizontal direction by a moving mechanism (not shown). As the moving mechanism, for example, a rack and pinion mechanism, a ball screw mechanism, or the like can be used. The stage control unit 43 (not shown in FIG. 4) can move the stage 30 to a desired position by controlling the moving mechanism.

  A number of suction holes 31 are formed on the substrate holding surface of the stage 30. An adsorption chamber 40 is provided on the lower surface of the stage 30, and the adsorption chamber 40 is vacuum-sucked by a pump 41 (not shown in FIG. 4), whereby the substrate 20 on the stage 30 is adsorbed and held. Further, the stage 30 includes a heater 42 (not shown in FIG. 4), and the base material 20 that is attracted and held on the stage 30 by the heater 42 can be heated.

  The inkjet heads 1 and 2 eject ink supplied from an ink tank 60A (hereinafter referred to as ink tank 1) and an ink tank 60B (hereinafter referred to as ink tank 2) to a desired position of the transparent support 20. Here, a head having a piezoelectric actuator is used. The inkjet heads 1 and 2 are arranged and fixed as close as possible to each other by fixing means (not shown).

  The inks supplied to the inkjet heads 1 and 2 from the ink tanks 1 and 2 are referred to as ink 1 and ink 2, respectively. In the present invention, the ink containing the ink composition containing the hydrophilic material of 1) above (hereinafter also referred to as “hydrophilic ink”) is referred to as ink 1, and the ink composition containing the resin material of 2) above. Ink 2 (hereinafter also referred to as “resin ink”) is referred to as ink 2.

[Production of composition gradient film by drawing mixing method]
Creation of a composition gradient film using the composition gradient film manufacturing apparatus 100 configured as described above will be described with reference to FIG.

  First, the base material 20 is placed on the stage 30 of the drawing unit 10 placed in a nitrogen atmosphere. The base material 20 is placed so that the back surface is in contact with the stage 30. Then, adsorption and heating of the substrate 20 to the stage 30 are performed by the adsorption chamber 40. Here, it is preferable to heat the base material 20 to 70 ° C.

  Next, one layer or several layers of ink (ink 2) supplied from the inkjet head 2 are laminated on the adsorbed / heated substrate 20 to form 24-1. 5A, the ink 2 is ejected by the inkjet head 2 while moving the stage 30 by the moving mechanism (moving leftward in the figure). Here, no ink is ejected from the inkjet head 1.

The layer 24-1 of the ink 2 thus formed is preferably dried (semi-dried / semi-cured) to such an extent that the solvent component in the ink 2 is not completely evaporated. Specifically, drying is performed with less energy than that normally given when drying (total drying / total curing).
In this specification, “semi-drying” and “full-drying” include “semi-curing” and “fully-curing” when a curable composition such as a sol-gel curable composition is used as the ink according to the present invention. It also includes intentions.
In the present invention, as described above, it is preferable to have a step of semi-drying the layer ejected in the forming step. For semi-drying, for example, after the ink ejection is finished, the ambient temperature is set to 40 to 120 ° C. It is preferable to hold for a certain time, and it is preferable to hold for a certain time at an environmental temperature of 50 to 100 ° C. The holding time is preferably 10 to 120 seconds, and more preferably 20 to 90 seconds.

  Next, the mixed layer 24-2 of the ink 1 and the ink 2 is formed on the layer 24-1 of the ink 2 in a semi-dry state. As shown in FIG. 5B, the mixed layer 24-2 is formed by ejecting the ink 1 by the inkjet head 1 while moving the stage 30, and simultaneously ejecting the ink 2 by the inkjet head 2. At this time, the discharge amount of ink 1 and the discharge amount of ink 2 are adjusted to a desired ratio. Here, the discharge amount of each nozzle of the inkjet heads 1 and 2 is adjusted and discharged so that the discharge amount of ink 2 is 75% and the discharge amount of ink 1 is 25%. The “ejection amount” of ink in the present specification means the total amount of ink ejected to form each layer. On the other hand, the “droplet amount” of an ink droplet ejected from an inkjet head, which will be described later, is the amount of one ink droplet.

  The ratio of the ink discharge amount from the inkjet heads 1 and 2 may be adjusted by the dot pitch density of drawing. For example, by controlling the number of nozzles for ejecting ink so that the inkjet heads 1 and 2 are set to 25:75 while keeping the ejection amount of each nozzle of the inkjet heads 1 and 2 constant, the ratio of the ejection amount It is also possible to make adjustments.

After ink ejection, as shown in FIG. 5C, the mixed layer 24-2 is laminated by diffusing and mixing the ink 1 and the ink 2 ejected in the respective ejection amounts. Since the layer 24-1 of the ink 1 is in a semi-dry state, the ink solvent of the mixed layer 24-2 formed thereon is received by the layer 24-1 of the ink 1 and spreads extremely wet. There is no. That is, the heating temperature by the heater 42 needs to be adjusted according to the easiness of ink evaporation. Depending on the type of the solvent, drawing may be performed at a temperature lower than 70 ° C., for example, the substrate temperature is about 50 ° C.
That is, it is preferable that the forming step includes a step of diffusing and mixing the discharged first ink and the second ink. Examples of the diffusion mixing method include a method using convection by heating and a method using ultrasonic waves.

  Further, the two inkjet heads are arranged as close as possible to prevent only one of the inks from being dried and insufficient mixing in the layers of both inks. When two inks are simultaneously ejected, the droplets of ink 1 ejected from the inkjet head 1 and the droplets of ink 2 ejected from the inkjet head 2 are collided in the air during flight and mixed. You may make it land from.

  Furthermore, although details will be described later, it is preferable that each of the two inkjet heads has a width larger than the width of the target substrate (the shorter one) and forms one layer in one scan. Thereby, the ink 1 and the ink 2 are easily mixed.

  Further, in order to promote mixing of ink, the stage 30 may be controlled to ultrasonically treat the substrate 20. At this time, it is preferable to sweep the frequency of the ultrasonic wave or change the position of the base material 20 so that the ultrasonic node is less likely to occur.

  When the mixed layer 24-2 formed in this manner is brought into a semi-dry state in the same manner as the layer 24-1 of the ink 2, the mixed layer 24-2 has a ratio of 75:25 and the resin material included in the ink 2 And the hydrophilic material contained in the ink 1 are mixed and stacked.

  Next, the mixed layer 24-3 is formed on the mixed layer 24-2. Also in the formation of the mixed layer 24-3, as shown in FIG. 5D, ink is simultaneously ejected by the inkjet head 1 and the inkjet head 2 while moving the stage 30. Here, both ink 1 and ink 2 are ejected at a ratio of the ejection amount of 50%.

  Since the mixed layer 24-2 is also in a semi-dry state, the ink solvent of the mixed layer 24-3 formed thereon is received by the mixed layer 24-2. After ink ejection, as shown in FIG. 5E, the mixed layer 24-3 is laminated by diffusing and mixing the two inks.

  Further, the mixed layer 24-3 is also semi-dried in the same manner as the ink 24-layer 24-1. The mixed layer 24-3 has a ratio of 50:50, and the resin material contained in the ink 2 and the hydrophilic material contained in the ink 1 are mixed and stacked.

  In this way, each mixed layer is formed while changing the ratio of the ejection amount of ink 1 and ink 2 stepwise (so as to be inclined), and finally, a layer in which the ejection amount of ink 1 is 100% is formed.

  After the formation of all layers, the diffusion of each layer proceeds, and the layers formed in stages become continuous. As a result, as shown in FIG. 1, a composition gradient film 3 is formed in which the composition component ratio is 100% from ink 2 to 100% from ink B from the B side to the A side in the film thickness direction.

  In this way, by forming the upper layer with the lower layer in a semi-dry state, diffusion is advanced to some extent in the upper and lower layers. At this time, it is preferable that the interface between the upper and lower layers is eliminated so that the upper and lower layers are not mixed and the upper and lower layers are not distinguished from each other.

  Note that after the formation of each layer is completed, a dummy pattern may be stacked in a region where the composition gradient film does not function, and the height of the dummy pattern may be measured by an optical displacement sensor using a laser or the like. In a state where the drying is not progressing and the solvent remains, the film thickness becomes high, so that the dry state can be detected by the height of the dummy pattern.

  As described above, the composition gradient film can be formed using the ink jet head. Further, according to the drawing mixing method of this embodiment, there is an advantage that the number of ink types and the number of ink jet heads can be reduced regardless of the number of layers to be formed. The mixed layers of the ink 1 and the ink 2 may be stacked in any number of layers as long as the mixing ratio of the respective inks is inclined stepwise.

In each layer forming step, the amount of ink droplets ejected from the first inkjet head and the second inkjet head is set to 0.3 to 100 pL from the viewpoint of film thickness control and fine line formability. Preferably, 0.5-80 pL is more preferable, and 0.7-70 pL is still more preferable.
In the formation process of each layer, the droplet diameter of the ink droplets ejected from the first inkjet head and the second inkjet head is preferably 1 to 300 μm, and preferably 5 to 250 μm from the viewpoints of film thickness control and fine line formability. Is more preferable, and 10-200 micrometers is still more preferable.
Further, in the step of forming each layer, for the ink having the smaller ejection amount ratio between the first ink and the second ink, at least one of the appropriate amount of the ink droplets ejected from the inkjet head and the droplet diameter is the ratio. Is preferably smaller than that of a large ink. For example, it is preferable that ink droplets of ink with a small ratio are 0.3 to 60 pL, and ink droplets of ink with a large ratio are 1 to 100 pL. Thereby, the time for diffusive mixing can be shortened, and the uniformity of mixing can be improved.
The “droplet diameter” of the ink droplet means the length of the droplet diameter, and can be measured from a flying state photograph at the time of ink jet discharge.

In this embodiment, the composition gradient film 3 in which the ink 2 is 100% to the ink 1 is 100% from the B side to the A side is formed. However, the ink 2 or the ink 1 is 100% on the B side or the A side. It is not always necessary to form a film, and the ratio of the ink 2 or the ink 1 on the B side or the A side can be arbitrarily changed as long as the composition gradient film 3 is obtained.
The ratio of the ink 2 or the ink 1 on the B side or the A side can be appropriately adjusted depending on the properties such as adhesion and hydrophilicity of the composition gradient film to be obtained.

  In the present embodiment, the ink jet head 1 and the ink jet head 2 eject ink simultaneously to form each layer, but they may be ejected in order.

  For example, when forming the mixed layer 24-2, as shown in FIG. 6A, the ink 2 is first ejected onto the entire surface of the ink 2-layer 24-1 by the inkjet head 2. Next, as shown in FIG. 6B, the ink 1 is ejected over the entire surface by the inkjet head 1. Thereafter, as shown in FIG. 6C, the mixed layer 24-2 can be similarly formed by diffusing and mixing the respective inks.

  In this way, when each ink is ejected in order to form one layer, there is a difference between the ejection amounts of the two inks, that is, the ratio of the ejection amounts of the two inks is not 50% each. May be configured to eject the ink with the larger ejection amount first. In particular, when the ink discharged first is severely dried, the smaller the amount, the faster the drying. Therefore, it is preferable to discharge the larger amount of ink first. Thereby, mixing of two types of ink can be advanced smoothly.

  Further, in this case, the ink having a smaller ejection amount to be ejected later may be ejected by increasing the dot pitch density with small droplets (small liquid amount or small droplet diameter). Thereby, the time for diffusive mixing can be shortened.

  Further, the ink ejected later may be overlapped and landed at the position where the ink ejected earlier is landed. In particular, when the dots are separated from each other by performing intermittent operation, if the ink is landed before being dried at the same position, it becomes easy to mix the respective inks.

  For example, when forming the mixed layer 24-2, it is assumed that the ink 2 is ejected by intermittent printing by the inkjet head 2 in the first scanning. FIG. 9A shows ink 2 (24-2-B-1) landed on the ink 1 layer 24-1.

  Next, the ink 1 is ejected by the ink jet head 1 by intermittent scanning in the second scanning. At this time, as shown in FIG. 9B, the ink-jet head 1 uses the ejected ink 1 (24-2-A-1) to be landed in the first scan, the ink 2 (24-2-2). B-1) is discharged so as to land on the same position.

  Further, the ink 2 is intermittently hit by the inkjet head 2 in the third scanning. FIG. 9C shows ink 2 (24-2-B-2) landed between inks 2 (24-2-B-1).

  Thereafter, in the fourth scanning, the ink 1 is ejected by the inkjet head 1 so as to be landed on the same landing position as the ink 2 (24-2-B-2). As shown in FIG. 9D, the ejected ink 1 (24-2-A-2) is in the same position as the ink 2 (24-2-B-2) landed in the second scan. Discharge to land repeatedly.

Thereafter, in the same manner, ink is ejected over the entire surface of the layer 1 of the ink 1 and then is diffused and mixed.
By discharging in this way, it is possible to shorten the time of diffusion mixing when forming the mixed layer 24-2.

  Further, when one of the inks is quickly dried, the ink may be ejected later.

  Further, in the present embodiment, each mixed layer is formed using two pure inks, ink 1 and ink 2, but an ink obtained by mixing these may be used in combination. For example, it is conceivable to form a mixed layer by simultaneously using three types of ink, that is, two pure inks and a mixed ink having a mixing ratio of ink 1 and ink 2 of 50:50. Although the number of inkjet heads increases by the amount of mixed ink, since two pure inks are sufficiently mixed in advance with the mixed ink, the time required for diffusion mixing after ink ejection can be shortened.

~ Ink mixing method ~
The method of the present invention is a hydrophilic member having a base material and a film provided on the base material and containing the following hydrophilic material 1) and resin material 2), wherein the film is in the thickness direction of the film. The composition gradient in which the compositions of 1) and 2) continuously change so that the ratio of 1) increases from the side closest to the substrate toward the side farthest from the base material and the ratio of 2) decreases. A method for forming a hydrophilic member of the present invention, which is a film,
A method for forming a hydrophilic member, wherein at least two types of ink compositions, the ink composition containing the hydrophilic material of 1) and the ink composition containing the resin material of 2), are ejected onto the substrate by an inkjet method. In
As the at least two kinds of ink compositions, at least an ink composition containing the hydrophilic material of 1) and an ink composition containing the resin material of 2) are used,
The inkjet method uses a plurality of inkjet heads,
A mixed ink in which the first ink containing the ink composition containing the hydrophilic material of 1) and the second ink containing the ink composition containing the resin material of 2) are mixed, each having a different ratio Supplying a plurality of mixed inks mixed in step to each inkjet head of the plurality of inkjet heads;
A selection step of sequentially selecting one inkjet head from the plurality of inkjet heads, the selection step sequentially selecting from the inkjet head to which the mixed ink having a high ratio of the second ink is supplied;
Forming a layer by discharging mixed ink from the selected inkjet head; and
A lamination step of repeating the formation step to obtain a composition gradient film by laminating a plurality of layers on the substrate;
A method comprising:

According to the above method, the first ink and the second ink are mixed inks, and a plurality of mixed inks mixed at different ratios are supplied to the respective inkjet heads, and the first ink is supplied. Since each layer is formed by sequentially ejecting mixed ink from an inkjet head to which a mixed ink having a low ratio is supplied, and a plurality of layers are laminated on the substrate, a composition gradient film is formed using an inkjet technique. Can be manufactured.
In addition, this invention relates also to the hydrophilic member formed by the said drawing method.

-Embodiment by ink mixing method-

  FIG. 7 is an overall configuration diagram of a composition gradient film manufacturing apparatus 101 according to the second embodiment. As shown in the figure, the composition gradient film manufacturing apparatus 101 according to this embodiment includes a drawing unit 11, and the drawing unit 11 includes ink tanks 60-1 to 60-5 for storing five types of ink, and each ink. Inkjet heads 50-1 to 50-5 to which ink is supplied from a tank are provided. Each inkjet head 50-1 to 50-5 discharges the ink supplied from each ink tank 60-1 to 60-5 to the substrate 20.

  The ink supplied from the ink tanks 60-1 to 60-5 to the inkjet heads 50-1 to 50-5 has a mixing ratio of ink 1 and ink 2 of 0: 100, 25:75, and 50:50, respectively. 75:25 and 100: 0. That is, the pure ink of ink 2 from the ink tank 60-1, the pure ink of ink 1 from the ink tank 60-5, and the ink 1 and ink 2 from 60-2 to 60-4 at a predetermined ratio. Mixed mixed ink is supplied.

[Production of composition gradient film by ink mixing method]
Similarly to the embodiment using the drawing mixing method, the base material 20 is placed on the stage 30 and suction and heating are performed.

  Next, one layer or several layers of the ink 2 are laminated on the adsorbed / superheated substrate to form the ink 28 layer 28-1. As shown in FIG. 8A, the ink 2 is stacked while the stage 30 is moved by the moving mechanism (moved leftward in the figure), and the ink tank 60- is applied to the substrate by the inkjet head 50-1. 1 is discharged (ink having a mixing ratio of ink 1 and ink 2 of 0: 100). At this time, ink is not discharged from the other inkjet heads 50-2 to 50-5.

Therefore, the layer 28-1 of the ink 2 formed in this way is the same layer as the layer 24-1 of the ink 2 shown in FIG. Here, when drying (semi-drying / semi-curing) is performed to such an extent that the solvent in the ink 2 evaporates, the hydrophilic materials contained in the ink 1 are stacked.
Also in the ink mixing method, it is preferable to have a step of semi-drying the layer ejected in the forming step. For semi-drying, for example, after the ink ejection is completed, the ambient temperature is maintained at 40 to 120 ° C. for a certain period of time. It is preferable to hold it at an environmental temperature of 50 to 100 ° C. for a certain period of time. The holding time is preferably 10 to 120 seconds, and more preferably 20 to 90 seconds.

  Next, mixed ink (mixed ink in which the mixing ratio of ink 1 and ink 2 is 25:75) supplied from the ink tank 60-2 by the inkjet head 50-2 is applied on the layer 2-1 of ink 2. The mixed layer 28-2 is formed by discharging.

  As shown in FIG. 8B, the mixed layer 28-2 is formed by discharging the mixed ink by the inkjet head 50-2 while moving the stage 30. As in the embodiment using the drawing mixing method, since the ink 2 layer 28-1 is in a semi-dry state, the ink solvent of the mixed layer 28-2 formed thereon is received by the ink 2 layer 28-1. It has never been extremely wet and spread. Therefore, the heating temperature needs to be adjusted according to the ease of ink evaporation.

  The mixed layer 28-2 is also semi-dried, so that the mixed layer 28-2 is in a state where the hydrophilic material contained in the ink 1 and the resin material contained in the ink 2 are stacked.

  Further, mixed ink (mixing ratio of ink 1 and ink 2 is 50:50) supplied from the ink tank 60-3 by the ink jet head 50-3 (not shown in FIG. 8) on the mixed layer 28-2. The mixed ink 28) is discharged to form the mixed layer 28-3.

  Since the mixed layer 28-2 is in a semi-dry state, the ink solvent of the mixed layer 28-3 formed thereon is received by the mixed layer 28-2. Further, the mixed layer 28-3 is also semi-dried.

  As described above, the mixed inks are ejected in the order of increasing the mixing ratio of ink 2 (in the order of decreasing the mixing ratio of ink 1) to stack the mixed layers (28-2 to 28-4), and finally the inkjet head. Ink 1 supplied from the ink tank 60-5 by 50-5 (ink having a mixing ratio of ink 1 and ink 2 of 100: 0) is ejected, and a layer 28-5 (ink 1) in which ink 1 is 100% is discharged. (FIG. 8C).

  After the formation of all the layers, a composition gradient film 3 having a composition ratio of 100% for ink 2 to 100% for ink 1 as shown in FIG. 1 is formed.

In the formation process of each layer, the amount of ink droplets ejected from the inkjet head is preferably 0.5 to 150 pL, more preferably 0.7 to 130 pL, and more preferably 1 to 100 pL from the viewpoint of stable ejection. Is more preferable.
In the step of forming each layer, the droplet diameter of the ink droplets ejected from the inkjet head is preferably 2 to 450 μm, more preferably 5 to 350 μm, and still more preferably 10 to 250 μm, from the viewpoint of good film formation.

  As described above, the composition gradient film can be formed using the mixed ink. According to the ink mixing method of the present embodiment, since the ink is sufficiently mixed at the ink stage, it is possible to create a composition gradient film with high accuracy of change in hydrophilic gradient. Further, as compared with the embodiment using the drawing mixing method, the time for diffusing and mixing the two types of functional inks is not required, and there is an advantage that the process time can be shortened.

  In this embodiment, three mixed layers of ink 1 and ink 2 are formed. However, the number of layers is not limited to this, and any number of layers can be used as long as the mixing ratio of each ink can be inclined. But you can. It is necessary to prepare ink tanks and inkjet heads as many as the number of layers to be formed.

Furthermore, in this embodiment, the composition gradient film 3 having a composition component ratio of 100% for ink 2 to 100% for ink 1 is formed. However, a composition component ratio of 100% for ink 2 or 100% for ink 1 is employed. The composition component ratio can be arbitrarily changed as long as the composition gradient film 3 can be obtained.
The composition component ratio can be appropriately adjusted depending on the properties such as adhesion and hydrophilicity of the composition gradient film to be obtained.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention should not be construed as being limited thereto.

<Example 1>
(Creation of ink containing resin material (resin ink))
~ Resin ink A1 ~
Urethane oligomer UN-1225 (manufactured by Negami Kogyo Co., Ltd.) 50 g
Methylpyrrolidone (Wako Pure Chemical Industries, Ltd.) 450g

  The material was put into a 2 L container, and the liquid temperature was kept at 40 ° C. or lower with a Silverson high speed stirrer, followed by stirring for 20 minutes. Then, it filtered with a 2 micrometer filter and created resin ink A1.

(Creation of ink containing hydrophilic material (hydrophilic ink))
~ Hydrophilic ink B1 ~
-20% by weight aqueous solution of colloidal silica dispersion (Snowtex C: manufactured by Nissan Chemical Co., Ltd.)
100g
・ 500g of the following sol-gel preparation
・ 30 g of 5% by weight aqueous solution of the following anionic surfactant
・ Purified water 450g

<Sol-gel preparation solution>
200 g of ethyl alcohol, 10 g of acetylacetone, 10 g of tetraethyl orthotitanate (catalyst), 100 g of purified water, 8 g of tetramethoxysilane (crosslinking agent: manufactured by Tokyo Chemical Industry Co., Ltd.) and a silyl group-containing hydrophilic polymer (compound) having the following structure 1) 5 g was mixed and prepared by stirring at room temperature for 2 hours.

(Compound 1)

  In the above formula, the numerical values are molar ratios, and the structural unit having a hydrophilic group is included in 70 mol% of the whole polymer. The polymer has a weight average molecular weight of 15,000.

  The raw material was put into a 1 L container, and the liquid temperature was kept at 40 ° C. or lower with a Silverson high speed stirrer, followed by stirring for 20 minutes. Then, it filtered with a 2 micrometers filter, and created hydrophilic ink B1.

(Creation of a hydrophilic member having a composition gradient film)
A hydrophilic member having a composition gradient film having a thickness of 10 μm is formed on a transparent PET substrate (film thickness 150 μm, manufactured by Fuji Film) by the following ink jet drawing method A, and the composition gradient after heating and drying at 100 ° C. The adhesion of the membrane to the substrate, hydrophilicity, water resistance, antifogging property, antifouling property, and weather resistance were evaluated.

~ Inkjet drawing method A ~
Ink tank 1 and ink tank 2 as shown in FIG. 3 were filled with hydrophilic ink B1 and resin ink A1, respectively. The inks supplied to the inkjet head 1 and the inkjet head 2 are hydrophilic ink B1 and resin ink A1, respectively.
First, the appropriate amount of ink droplets ejected from the inkjet head 2 was controlled to be 10 pL and the droplet diameter was 30 μm, and the resin ink A1 was ejected from the inkjet head 2 in a nitrogen gas atmosphere. Here, the hydrophilic ink B1 is not ejected from the inkjet head 1 (that is, the ratio (mass%) of the ejection amount of the ink ejected from the inkjet head 2 and the ejection amount of the ink ejected from the inkjet head 1 is 100: 0. The ink layer 1 was formed and dried at 80 ° C. for 30 seconds and then semi-dried.
Subsequently, the ratio (% by mass) of the amount of ink discharged from the inkjet head 2 and the amount of ink discharged from the inkjet head 1 is 75:25 (ink layer 2), 50:50 (ink layer 3), 25:75 (ink layer 4) and 0: 100 (ink layer 5) were changed, and lamination and semi-drying were repeated and finally completely dried (110 ° C. for 60 seconds) to obtain a hydrophilic member having a composition gradient film. Produced.
Here, when the ink layer 2 is formed, the appropriate amount of ink droplets of the hydrophilic ink B1 discharged from the inkjet head 1 is 5 pL, the droplet diameter is 20 μm, and the appropriate amount of ink droplets of the resin ink A1 discharged from the inkjet head 2 is used. Was 10 pL and the droplet diameter was 30 μm. When the ink layer 3 was formed, the appropriate amount of ink droplets of the hydrophilic ink B1 was 10 pL, the droplet diameter was 30 μm, the appropriate amount of ink droplets of the resin ink A1 was 10 pL, and the droplet diameter was 30 μm. When the ink layer 4 was formed, the appropriate amount of the ink droplet of the hydrophilic ink B1 was 10 pL, the droplet diameter was 30 μm, the appropriate amount of the ink droplet of the resin ink A1 was 5 pL, and the droplet diameter was 20 μm. When the ink layer 5 was formed, the appropriate amount of ink droplets of the hydrophilic ink B1 was 10 pL, and the droplet diameter was 30 μm. In addition, the film thicknesses of the ink layers 1 to 5 after being completely dried were each set to 2 μm.

(Evaluation)
<Adhesion>
A cross-hatch test (EN ISO 2409) was performed on the prepared hydrophilic member. About evaluation criteria, based on ISO2409, the result was shown by score evaluation of 0-5 points.
In the above evaluation criteria, 0 point is the highest adhesion, and 5 point is the lowest adhesion.

<Hydrophilicity>
Using DropMaster500 manufactured by Kyowa Interface Science Co., Ltd., the aerial water droplet contact angle on the composition gradient film surface of the hydrophilic member was measured.

<Water resistance>
A 120 cm ² size hydrophilic member was rubbed 20 times with a sponge in a load of 2 kg in water, and the remaining film ratio was measured from the mass change before and after that.

<Anti-fogging property>
The coated sample was covered with a polycup containing 80 ° C. hot water, and the cloudiness was visually determined according to the following criteria.
○: No fogging is observed.
(Triangle | delta): Cloudiness is observed partially.
X: The whole surface is cloudy.

<Anti-fouling>
A slurry is prepared by suspending 5 g of carbon black (FW-200, manufactured by Dexa) in 95 g of water, spray-coated on the surface of the hydrophilic member so as to be uniform, and then dried at 60 ° C. for 1 hour. It was. The sample was washed with running water, washed with gauze and dried, and the adhesion state of carbon black was measured by transmittance (%) (using Hitachi spectrophotometer U3000).

<Weather resistance>
A hydrophilic member was exposed to a sunshine carbon arc lamp type accelerated weathering tester for 500 hours, and adhesion, hydrophilicity, water resistance, antifogging property, and antifouling property were evaluated according to the above-mentioned methods. Judgment was made according to the following criteria.
○: Performance equivalent to that before exposure in all items Δ: One item is inferior before exposure ×: Two or more items are inferior before exposure

  The evaluation results of the hydrophilic member created in Example 1 are shown in Table 1 below.

<Example 2>
Ink G1 (mixing ratio (mass%) A1: B1 = 75: 25), G2 (mixing ratio (mass%) A1: B1 = 50: mixed with resin ink A1 and hydrophilic ink B1 used in Example 1 50), G3 (mixing ratio (mass%) A1: B1 = 25: 75), and five types of ink including A1 and B1 are used for each of the five print heads, and a transparent PET substrate (film) A hydrophilic member having a composition gradient film having a film thickness of 10 μm in the order of A1 (lowermost layer), G1, G2, G3, and B1 (uppermost layer) in the order of A1 (thickness 150 μm, manufactured by Fuji Film) by the following inkjet drawing method B After heating and drying at 100 ° C., the adhesion of the composition gradient film to the substrate, hydrophilicity, water resistance, antifogging property, antifouling property, and weather resistance were evaluated. The results are shown in Table 1 below.

~ Inkjet drawing method B ~
Ink tanks 60-1 to 60-5 as shown in FIG. 7 were filled with inks A1, G1, G2, G3, and B1, respectively. The inks supplied to the inkjet heads 50-1 to 50-5 are inks A1, G1, G2, G3, and B1, respectively.
First, the ink A1 was ejected from the ink jet head 50-1 in a nitrogen gas atmosphere while controlling the amount of ink droplets ejected from the ink jet head to 10 pL and the droplet diameter to 30 μm.
The ink A1 layer thus formed was dried at 80 ° C. for 30 seconds and semi-dried.
Next, the ink G1 was similarly discharged from the inkjet head 50-2, and the ink G1 layer was laminated and semi-dried. This was repeated for the inks G2, G3, and B1, lamination and semi-curing were repeated, and finally the composition was completely dried (110 ° C. for 60 seconds) to form a composition gradient film.
The film thicknesses of the ink layers A1, G1, G2, G3, and B1 after complete curing were set to 2 μm.

<Examples 3 to 10>
The hydrophilic polymer and the urethane oligomer or polymer contained in the hydrophilic ink and the resin ink are replaced with those shown in Table 1 below, and the others are the same as in Example 1 and the hydrophilicity having a composition gradient film with a film thickness of 10 μm. After forming an adhesive member and drying by heating at 100 ° C., the adhesion of the composition gradient film to the base material, hydrophilicity, water resistance, antifogging property, antifouling property, and weather resistance were evaluated. The results are shown in Table 1 below.

The structure of the hydrophilic polymer used in Examples 3 and 4 is shown below.
(Compound 2)

(Compound 3)

In the above formula, the numerical value represents the molar ratio in which each structural unit is included.
The hydrophilic inks containing the hydrophilic polymers of (Compound 2) and (Compound 3) correspond to B2 and B3, respectively.

<Comparative Example 1>
Using only the hydrophilic ink B1 used in Example 1, a hydrophilic film having a film thickness of 10 μm composed of only one layer is formed on a transparent PET base material (film thickness 150 μm, manufactured by Fuji Film) by inkjet drawing. This was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

<Comparative example 2>
In Example 1, a water-based epoxy resin paint (water-based elastic surf epoxy, manufactured by SK Kaken Co., Ltd.) was bar-coated (film thickness 2 μm) on a transparent PET substrate (film thickness 150 μm, manufactured by Fuji Film). A hydrophilic film having a film thickness of 10 μm composed of only one layer was prepared by inkjet drawing using the hydrophilic ink B1 and evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

  The hydrophilic members of Examples 1 to 10 have good adhesion between the base material and the composition gradient film, hydrophilicity, water resistance, antifogging property, antifouling property, and weather resistance, and various ink jet methods A (drawing and mixing). It is shown that the composition gradient film prepared by (Method) and B (Ink Mixing Method) is practically effective. The effects of the two ink jet methods are equivalent, and a composition gradient film having a sufficient function can be formed by either method. Regarding the adhesion, the ink containing urethanes showed better performance than the ink containing other resins. This phenomenon is considered to be because the urethane compound has improved cohesive force between the gradient film and the base material and in the gradient film due to hydrogen bond interaction, and a strong film is formed.

  On the other hand, when the hydrophilic member is formed by normal ink jet drawing using the ink of only the hydrophilic compound used in the present invention as in Comparative Example 1, the adhesion with the hydrophobic resin base material is due to the hydrophilic film. Does not develop and peels off immediately. Further, in Comparative Example 2, since the hydrophilic compound and the urethane material are laminated, the different types of interfaces of hydrophilicity and hydrophobicity are present, and sufficient adhesion to the base material is not exhibited, and the wrinkle resistance which is a durability index The problem of sex becomes prominent.

DESCRIPTION OF SYMBOLS 1 Hydrophilic member 2 Base material 3 Composition gradient film 10 Drawing part 100 Composition gradient film preparation apparatus

Claims (17)

A hydrophilic member having a base material and a film provided on the base material and including the following hydrophilic material 1) and resin material 2), the film being closest to the base material in the thickness direction of the film A hydrophilic member that is a composition gradient film in which the composition of 1) and 2) is continuously changed so that the ratio of 1) increases from the side toward the farthest side and the ratio of 2) decreases. .
1) A hydrolyzable silyl group-containing hydrophilic polymer is contained, and the polymer has at least one hydrolyzable silyl group represented by the following general formula (a) in the molecule at the main chain terminal or side chain. And a hydrophilic material having at least one hydrophilic group in the molecule.
Formula _{^{(a): -Si (R 10}} ) 3-a - (OR 11) a
(In formula, R < ¹⁰ >, R < ¹¹ > is a hydrogen atom or a hydrocarbon group, respectively, and a shows the integer of 1-3.)
2) A resin material containing an oligomer or polymer. However, 2) is different from the hydrophilic material of 1) above.   The hydrophilic member according to claim 1, wherein the oligomer or polymer is a urethane oligomer or polymer.   When the ratio of the mass of the resin material 2) to the total mass of the resin material 2) and the hydrophilic material 1) in the composition gradient film is measured for each thickness of 0.1 μm from the substrate side in the film thickness direction. Further, the hydrophilic member according to claim 1 or 2, wherein the difference in the ratios at adjacent measurement positions is 50% or less. The hydrolyzable silyl group-containing hydrophilic polymer includes a hydrophilic polymer (I) having a structure represented by the following general formula (I-1) and a structure represented by the general formula (I-2), II-1) and a structure represented by the hydrophilic polymer (II) or the general formula (III-1) including the structure represented by the general formula (II-2) and the general formula (III-2) The hydrophilic member according to any one of claims 1 to 3, which is any one of the hydrophilic polymers (III) including a structure represented by:

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 divalent 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 or branched alkyl group or cycloalkyl group, and R _d represents a linear or branched alkyl group or cycloalkyl group. R _e and R _f each independently represent a hydrogen atom, or a linear or branched alkyl group or cycloalkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion or an inorganic group. An anion or an organic anion is represented.

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

In general formulas (III-1) and (III-2), R ^{301 to} R ³¹¹ each independently represents 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 divalent 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 or branched alkyl group or cycloalkyl group, and R _d represents a linear or branched alkyl group or cycloalkyl group. R _e and R _f each independently represent a hydrogen atom, or a linear or branched alkyl group or cycloalkyl group, an alkali metal, an alkaline earth metal, or onium, and R _g represents a halogen ion or an inorganic group. An anion or an organic anion is represented.   The hydrophilic member according to any one of claims 1 to 4, wherein a structural unit having a hydrophilic group in the hydrolyzable silyl group-containing hydrophilic polymer is contained in an amount of 30 mol% or more of the whole polymer.   The hydrophilic member according to claim 1, wherein the hydrophilic material of the material 1) further contains colloidal silica.   The hydrophilic member according to any one of claims 2 to 6, wherein in the material 2), the urethane oligomer or polymer is an oligomer or polymer containing a urethane bond and a urea bond. The hydrophilic member according to any one of claims 2 to 6, wherein in the material 2), the urethane oligomer or polymer is an oligomer or polymer having a repeating unit represented by the following general formula (A).
(In the above general formula, R _{A1 to} R _A3 each independently represents an alkylene group, an arylene group, or a biarylene group, and R _{A4 to} R _A6 each independently represent a hydrogen atom, an alkyl group, an aryl group, or heteroaryl. Represents a group.)   The ink composition comprising the hydrophilic material of 1) and the ink composition comprising the resin material of 2) are ejected onto the substrate by an ink jet method. The formation method of the hydrophilic member of any one of Claims 1. As the at least two kinds of ink compositions, at least an ink composition containing the hydrophilic material of 1) and an ink composition containing the resin material of 2) are used,
The inkjet method uses at least a first inkjet head and a second inkjet head,
Supplying a first ink containing an ink composition containing the hydrophilic material of 1) to a first inkjet head;
Supplying a second ink containing an ink composition containing the resin material of 2) to a second inkjet head;
A control step of determining a ratio between the amount of the first ink ejected from the first inkjet head and the amount of the second ink ejected from the second inkjet head;
Forming a layer by discharging the first ink or the second ink from at least one of the first inkjet head and the second inkjet head according to the determined ratio;
A lamination step of repeating the formation step to obtain a composition gradient film by laminating a plurality of layers on the substrate;
With
In the control step, the ratio of the first ink increases and the ratio of the second ink decreases from the layer closest to the base material to the layer farthest in the thickness direction of the plurality of layers. The method for forming a hydrophilic member according to claim 9, wherein the ratio is determined.   The method for forming a hydrophilic member according to claim 10, wherein, in the forming step, an ink amount of droplets ejected from the first and second inkjet heads is 0.3 to 100 pL.   The method for forming a hydrophilic member according to claim 10 or 11, wherein in the forming step, a droplet diameter of droplets discharged from the first and second inkjet heads is 1 to 300 µm. As the at least two kinds of ink compositions, at least an ink composition containing the hydrophilic material of 1) and an ink composition containing the resin material of 2) are used,
The inkjet method uses a plurality of inkjet heads,
A mixed ink in which the first ink containing the ink composition containing the hydrophilic material of 1) and the second ink containing the ink composition containing the resin material of 2) are mixed, each having a different ratio Supplying a plurality of mixed inks mixed in step to each inkjet head of the plurality of inkjet heads;
A selection step of sequentially selecting one inkjet head from the plurality of inkjet heads, the selection step sequentially selecting from the inkjet head to which the mixed ink having a high ratio of the second ink is supplied;
Forming a layer by discharging mixed ink from the selected inkjet head; and
A lamination step of repeating the formation step to obtain a composition gradient film by laminating a plurality of layers on the substrate;
A method for forming a hydrophilic member according to claim 9.   The method for forming a hydrophilic member according to claim 13, wherein in the forming step, an ink amount of droplets ejected from the selected inkjet head is 0.5 to 150 pL.   The method for forming a hydrophilic member according to claim 13 or 14, wherein in the forming step, a droplet diameter of a droplet discharged from the selected inkjet head is 2 to 450 µm. A hydrophilic member formed by an ink jet method using at least two ink compositions, the ink composition containing at least the hydrophilic material of 1) and the ink composition containing the resin material of 2). And
The inkjet method uses at least a first inkjet head and a second inkjet head,
Supplying a first ink containing an ink composition containing the hydrophilic material of 1) to a first inkjet head;
Supplying a second ink containing an ink composition containing the resin material of 2) to a second inkjet head;
A control step of determining a ratio between the amount of the first ink ejected from the first inkjet head and the amount of the second ink ejected from the second inkjet head;
Forming a layer by discharging the first ink or the second ink from at least one of the first inkjet head and the second inkjet head according to the determined ratio;
A lamination step of repeating the formation step to obtain a composition gradient film by laminating a plurality of layers on the substrate;
With
In the control step, the ratio of the first ink is increased and the ratio of the second ink is decreased from a layer close to the base to a layer far from the base in the thickness direction of the plurality of layers. The hydrophilic member according to claim 1, wherein the ratio is determined. A hydrophilic member formed by an ink jet method using at least two ink compositions, the ink composition containing at least the hydrophilic material of 1) and the ink composition containing the resin material of 2). And
The inkjet method uses a plurality of inkjet heads,
A mixed ink in which the first ink containing the ink composition containing the hydrophilic material of 1) and the second ink containing the ink composition containing the resin material of 2) are mixed, each having a different ratio Supplying a plurality of mixed inks mixed in step to each inkjet head of the plurality of inkjet heads;
A selection step of sequentially selecting one inkjet head from the plurality of inkjet heads, the selection step sequentially selecting from the inkjet head to which the mixed ink having a high ratio of the second ink is supplied;
Forming a layer by discharging mixed ink from the selected inkjet head; and
A lamination step of repeating the formation step to obtain a composition gradient film by laminating a plurality of layers on the substrate;
The hydrophilic member according to claim 1, comprising: