JPWO2018155577A1 - Hydrophilic structure and method for producing hydrophilic structure - Google Patents

Abstract

  The present invention is a hydrophilic structure having a layer structure in which a substrate, an intermediate layer, and a hydrophilic layer are laminated in this order, wherein the intermediate layer is a layer containing a siloxane-based polymer, A hydrophilic structure containing a zwitterionic polymer not having a silicon atom and not containing a zwitterionic polymer having a silicon atom, and a method for producing the same . ADVANTAGE OF THE INVENTION According to this invention, the hydrophilic structure which has a hydrophilic layer excellent in hydrophilic property, stain resistance, adhesiveness, and water resistance, and its manufacturing method are provided.

Description

  The present invention relates to a hydrophilic structure having a hydrophilic layer excellent in hydrophilicity, stain resistance, adhesion, and water resistance, and a method for producing the same.

Conventionally, a hydrophilic coating agent containing a polymer having a repeating unit derived from a polymerizable zwitterionic compound is known.
For example, Patent Document 1 discloses a hydrophilic coating agent containing an alkoxysilyl group-containing polymer obtained by polymerizing a monomer component containing a betaine monomer and an alkoxysilyl group-containing compound, and a hydrophilic coating agent formed using the hydrophilic coating agent. Articles having a surface with an antifogging layer formed thereon are described.

WO2014 / 084219 (US2015 / 0259570A1)

When a hydrophilic layer is formed on a substrate using the hydrophilic coating agent described in Patent Document 1, if a reactive group such as a hydroxyl group is present on the substrate surface, the alkoxysilyl group-containing polymer is chemically formed on the substrate surface. Fixed. For this reason, by using this hydrophilic coating agent, it is possible to efficiently form a hydrophilic layer having excellent adhesion to a substrate having a reactive group on the surface.
However, when producing a hydrophilic coating agent (coating solution) containing an alkoxysilyl group-containing polymer, depending on the type of monomer used, a solid is precipitated during the polymerization reaction, and a coating solution in which the components are completely dissolved or dispersed is obtained. There was a case that could not be done.

In order to stably produce a hydrophilic structure having a hydrophilic layer, the present inventors have attempted to form a hydrophilic layer using a coating solution that does not contain a zwitterionic polymer having a silicon atom. .
However, when such a coating solution is used, it has been difficult to form a hydrophilic layer having excellent adhesion to the base material layer.
Further, depending on the components of the coating solution, a hydrophilic layer having poor water resistance and stain resistance may be formed, or the coating solution may not be uniformly applied on the substrate.
The present invention has been made in view of the above circumstances, and provides a hydrophilic structure having a hydrophilic layer excellent in hydrophilicity, stain resistance, adhesion, and water resistance, and a method for producing the same. Objective.

  As a result of intensive studies to solve the above problems, the present inventors have provided a layer containing a siloxane polymer on the surface of the substrate, and a zwitterionic polymer having no silicon atom as a hydrophilic layer on the layer. By forming a layer containing no zwitterionic polymer containing silicon atoms, a hydrophilic structure having a hydrophilic layer excellent in hydrophilicity, stain resistance, adhesion, and water resistance can be stabilized. The present invention has been completed.

Thus, according to the present invention, the following hydrophilic structures [1] to [7] and a method for producing the hydrophilic structure [8] are provided.
[1] A hydrophilic structure having a layer structure in which a base, an intermediate layer and a hydrophilic layer are laminated in this order, wherein the intermediate layer is a layer containing a siloxane polymer, and the hydrophilic layer is A hydrophilic structure comprising a zwitterionic polymer having no silicon atom and a layer not containing a zwitterionic polymer having a silicon atom.
[2] The hydrophilic structure according to [1], wherein the substrate is a resin film.
[3] The hydrophilic structure according to [1] or [2], wherein the siloxane polymer is a hydrolysis polycondensate of a hydrolyzable organosilicon compound.
[4] The hydrolyzable organosilicon compound is a silicon compound represented by the following formula (1) or a hydrolytic polycondensate of a silicon compound represented by the following formula (1). Hydrophilic structure.

(In the formula, R ^a represents a hydrogen atom or a non-hydrolyzable organic group, R ^b represents a hydrolyzable group, and q represents an integer of 0 to 2.)
[5] The hydrophilic structure according to any one of [1] to [4], wherein the zwitterionic polymer having no silicon atom is a polymer having a repeating unit represented by the following formula (2).

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an ether bond with or without an ether bond. Or a C2-C11 cyanoalkyl group which does not have, a C2-C10 alkenyl group which has or does not have an ether bond, or a C6-C20 aryl group which has or does not have a substituent. R ² and R ³ may be bonded to each other to form a ring. A ¹ represents the following formulas (3) to (5)

(In the formula, A ² and A ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Or an aryl group having 6 to 20 carbon atoms with or without a substituent, n represents an integer of 1 to 10, * 1 represents a bond with a carbon atom, and * 2 represents a nitrogen atom. (Represents a bond.)
Represents a divalent group represented by any of the above. m represents an integer of 2 to 5. ]
[6] The zwitterionic polymer having no silicon atom is a repeating unit derived from a zwitterionic monomer, and a repeating unit having a carboxyl group, a sulfo group, or a group formed by reacting these groups with a base ( However, the hydrophilic structure according to any one of [1] to [5], which is a polymer having a repeating unit derived from a zwitterionic monomer.
[7] The hydrophilic structure according to any one of [1] to [6], wherein the hydrophilic layer further contains an ionic compound having a cation having 0 to 10 carbon atoms.
[8] The method for producing a hydrophilic structure according to any one of [1] to [7], comprising the following steps (1) to (3).
Step (1): A coating liquid containing a hydrolyzable organosilicon compound is applied on a substrate, and the hydrolyzable organosilicon compound in the obtained coating film is hydrolytically polycondensed to obtain a siloxane polymer. Step (2) of forming a coating film containing: In a state where the coating film containing the siloxane polymer is completely dried or in a state where a solvent remains in the coating film, A step of applying a coating solution (A) containing a zwitterionic polymer not having a silicon atom and not containing a zwitterionic polymer having a silicon atom to form a coating film of the coating solution (A) ( 3): The process of drying the undried state coating film in the structure which has the laminated structure obtained at the process (2).

  ADVANTAGE OF THE INVENTION According to this invention, the hydrophilic structure which has a hydrophilic layer excellent in hydrophilic property, stain resistance, adhesiveness, and water resistance, and its manufacturing method are provided.

  The hydrophilic structure of the present invention is a hydrophilic structure having a layer structure in which a base, an intermediate layer, and a hydrophilic layer are laminated in this order, and the intermediate layer is a layer containing a siloxane polymer. The hydrophilic layer is a layer containing a zwitterionic polymer having no silicon atom and not containing a zwitterionic polymer having a silicon atom.

[Substrate]
The substrate constituting the hydrophilic structure of the present invention is not particularly limited as long as it is solid and can carry an intermediate layer, a hydrophilic layer, and the like.

The shape of the substrate is not particularly limited, and can be any shape such as a cube, a rectangular parallelepiped, a sphere, a spindle, a sheet, a film, and a fiber.
The substrate may be subjected to surface treatment.
Examples of the surface treatment include physical surface treatment such as corona treatment, plasma treatment, and ultraviolet treatment; chemical surface treatment such as acid contact; and the like.

Examples of the material of the substrate include inorganic substances such as glass, ceramics, porcelain, glaze, tiles and ceramics; metals such as aluminum, stainless steel and brass; various synthetic resins; fibers such as cotton, silk and wool;
Among these, as the substrate, a resin film is preferable. By using a resin film as the substrate, a functional film such as an antifogging film can be obtained.

  Examples of the raw material for the resin film include polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate, polybutylene terephthalate and polynaphthalene terephthalate; polyvinyl chloride; polycarbonates; acrylic resins; styrene resins.

The resin film may contain additives such as an ultraviolet absorber, a light stabilizer, and an antioxidant.
The thickness of the resin film is usually 20 to 1000 μm, preferably 30 to 500 μm.
The resin film may be long or strip-shaped.
Here, the “long shape” means one having a length of 5 times or more with respect to the width.

[Middle layer]
The intermediate layer constituting the hydrophilic structure of the present invention is a layer containing a siloxane polymer.
By providing a layer containing a siloxane-based polymer as the intermediate layer, a hydrophilic layer having excellent adhesion can be formed without using a zwitterionic polymer having a silicon atom. This is thought to be due to the entanglement between the siloxane-based polymer and the zwitterionic polymer having no silicon atom at the interface between the intermediate layer and the hydrophilic layer.
Moreover, when the coating liquid used when forming a hydrophilic layer is a water-based thing, a coating film may not be apply | coated uniformly on the base | substrate surface.
On the other hand, if it is on this intermediate layer, a uniform coating film can be efficiently formed even when an aqueous coating solution is used.

The siloxane-based polymer contained in the intermediate layer is a polymer having a siloxane bond (Si—O—Si). The siloxane-based polymer can be usually obtained by hydrolytic polycondensation of a hydrolyzable organosilicon compound.
The siloxane-based polymer has substantially no hydrolytic polycondensation reactivity (that is, the hydrolytic polycondensation reaction of the hydrolyzable organosilicon compound that is the raw material compound is completed).
Thus, this siloxane-based polymer is distinguished from “a partially hydrolyzed polycondensate of a silicon compound represented by the formula (1)” used as a hydrolyzable organosilicon compound in terms of presence or absence of reactivity. .
In the present invention, “hydrolyzable” refers to a property of generating a silanol group by reaction with water.
The degree of polymerization of the siloxane polymer is not particularly limited. The degree of polymerization of the siloxane polymer is usually more than 100.

  The hydrolyzable organosilicon compound is an organosilicon compound having a hydrolyzable group in the molecule. The hydrolyzable organosilicon compound is also referred to as a silicon compound represented by the following formula (1) or a hydrolyzed polycondensate of the silicon compound represented by the following formula (1) (also referred to as “partially hydrolyzed polycondensate”). ).

In formula (1), R ^a represents a hydrogen atom or a non-hydrolyzable organic group, and R ^b represents a hydrolyzable group. q represents the integer of 0-2.

Examples of the non-hydrolyzable organic group for ^Ra include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, and a t-amyl group ( 1,1-dimethylpropyl group), 1,1-dimethyl-3,3-dimethylbutyl group, heptyl group, octyl group, nonyl group, decyl group and other alkyl groups having 1 to 10 carbon atoms; cyclopentyl group, cyclohexyl A cycloalkyl group having 3 to 10 carbon atoms such as a group; an alkenyl group having 2 to 10 carbon atoms such as a vinyl group and an allyl group; an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group and a propylidene group; a phenyl group and a naphthyl group , Aromatic groups having 6 to 15 carbon atoms such as anthracenyl group, and the like.

  These organic groups may have a substituent. Examples of the substituent include (meth) acryloyloxy group, epoxy group, amino group, mercapto group, hydroxyl group, halogen atom, alkoxy group, fluoroalkyl group and the like.

As the hydrolyzable group for R ^b , an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group; an acyloxy group such as an acetoxy group and a propionyloxy group; a halogen atom such as a chlorine atom and a bromine atom; Etc.

  q represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

  Examples of the silicon compound represented by the formula (1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, and tetra-s-butoxy. Si compounds with q = 0 such as silane and tetra-t-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltri Methoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-acryloyloxy Silicon compounds with q = 1 such as cypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane , Silicon compounds having q of 2, such as methylphenyldimethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane; and the like.

These silicon compounds can be used alone or in combination of two or more.
In addition to these silicon compounds, a silicon compound having a q of 3, such as trimethylmethoxysilane, triethylmethoxysilane, triethylmethoxysilane, triethylethoxysilane, trivinylmethoxysilane, and trivinylethoxysilane may be used in combination.

The hydrolyzed polycondensate of the silicon compound represented by the above formula (1) is, for example, in an organic solvent such as an alcohol solvent in the presence of a specific amount of water and a condensation catalyst, or in the presence of a specific amount of water and a condensation catalyst. In the absence of this, it can be obtained by hydrolytic polycondensation of the silicon compound represented by the formula (1).
The degree of polymerization of the partially hydrolyzed polycondensate of the silicon compound represented by the formula (1) used as the hydrolyzable organosilicon compound is not particularly limited. The degree of polymerization of this compound is usually 100 or less.
Examples of the reaction liquid obtained by carrying out this reaction include those known as alcoholic silica sols.
The reaction liquid obtained by performing this reaction may be used as it is as a coating liquid for forming an intermediate layer, or may be used as a raw material liquid for producing a coating liquid for forming an intermediate layer.

  In the present invention, methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, SS-101, HAS-1 are used as hydrolysis polycondensates of the silicon compound represented by the above formula (1). , HAS-6, HAS-10, SS-C1, Colcoat PX, Colcoat N-103X, PC-291 (above, manufactured by Colcoat Co., Ltd.) and the like can also be used.

  The intermediate layer may contain components other than the siloxane polymer. Examples of the component other than the siloxane polymer include an antistatic agent, a surfactant, and a polymer compound other than the siloxane polymer.

  The amount of the siloxane-based polymer contained in the intermediate layer is usually 50% by mass or more, preferably 60% by mass or more, based on the entire intermediate layer.

  The thickness of the intermediate layer is usually 10 to 10,000 nm, preferably 30 to 5,000 nm, more preferably 50 to 500 nm.

As described later, the boundary between the intermediate layer and the hydrophilic layer may or may not be clear. A hydrophilic structure having a clear boundary between the intermediate layer and the hydrophilic layer can be obtained by forming the hydrophilic layer after the intermediate layer is completely formed. A hydrophilic structure in which the boundary between the intermediate layer and the hydrophilic layer is not clear can be obtained by starting the formation of the hydrophilic layer in a state where the intermediate layer is not completely formed.
The method for forming the intermediate layer is not particularly limited. For example, the intermediate layer can be formed according to a method described later.

[Hydrophilic layer]
The hydrophilic layer constituting the hydrophilic structure of the present invention is a layer containing a zwitterionic polymer having no silicon atom and not containing a zwitterionic polymer having a silicon atom.
Here, the zwitterionic polymer is a polymer having a repeating unit derived from a zwitterionic monomer. The zwitterionic monomer is a compound having a betaine structure having a polymerizable carbon-carbon double bond and both positive and negative charges in the molecule.

The hydrophilic structure of the present invention is excellent in hydrophilicity by having a hydrophilic layer.
As described above, the hydrophilic layer constituting the hydrophilic structure of the present invention contains a zwitterionic polymer having no silicon atom, but does not contain a zwitterionic polymer having a silicon atom.
Examples of the zwitterionic polymer having a silicon atom include zwitterionic polymers having a group containing a silicon atom such as an alkoxysilyl group. Such a hydrophilic layer containing a zwitterionic polymer tends to be excellent in adhesion to other layers.
However, as a raw material monomer, a zwitterionic monomer having an alkoxysilyl group and a zwitterionic monomer having a carboxy group, a sulfo group or the like is used, and a solid substance is precipitated in the process of synthesizing a zwitterionic polymer having an alkoxysilyl group (monomer polymerization reaction). In some cases, however, a coating solution for forming a hydrophilic layer in which the components are completely dissolved or dispersed cannot be prepared.
On the other hand, since the hydrophilic layer constituting the hydrophilic structure of the present invention does not contain a zwitterionic polymer having a silicon atom, such a problem occurs when the hydrophilic structure of the present invention is produced. Does not occur.

The hydrophilic layer constituting the hydrophilic structure of the present invention is a zwitterionic polymer having no silicon atom (hereinafter, sometimes referred to as “zwitterionic polymer (α)”). Containing one type or two or more types of repeating units derived from a cationic ion monomer (hereinafter sometimes referred to as “zwitterionic monomer (a)”).
The zwitterionic monomer (a) is a compound having a polymerizable carbon-carbon double bond and a betaine structure having both positive and negative charges in the molecule and having no silicon atom.

The mass average molecular weight of the zwitterionic polymer (α) is usually 50,000 to 3,000,000, preferably 100,000 to 2,500,000, more preferably 200,000 to 2,000,000.
The mass average molecular weight of the zwitterionic polymer (α) can be measured according to the method described in Examples.

  Examples of the repeating unit derived from the zwitterionic monomer (a) include a polymer having a repeating unit represented by the following formula (20).

In Formula (20), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an ether bond, which may or may not have an ether bond. Represents a C2-C11 cyanoalkyl group having or not having, C2-C10 alkenyl group having or not having an ether bond, or C6-C20 aryl group having or not having a substituent. . R ² and R ³ may be bonded to each other to form a ring. “—G ⁻ ” represents —COO ⁻ or —SO ₃ ^— .

1-8 are preferable and, as for carbon number of a C1-C10 alkyl group of the C1-C10 alkyl group which has or does not have the ether bond of R < ² >, R < ³ >, 1-5 are more preferable.
Examples of the alkyl group having no ether bond include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group.
Examples of the alkyl group having an ether bond include groups represented by the following formula (6) or (7).

In Formula (6), R ⁷ represents an alkyl group having 1 to 8 carbon atoms, Z ¹ represents an alkylene group having 2 to 9 carbon atoms, and the total number of carbon atoms of R ⁷ and Z ¹ is 3 to 3. 10. * Represents a bond.
In formula (7), R ⁸ represents an alkyl group having 1 to 6 carbon atoms, Z ² represents an alkylene group having 2 to 7 carbon atoms, and Z ³ represents an alkylene group having 2 to 7 carbon atoms. , R ⁸ , Z ² , Z ³ have a total carbon number of 5-10. * Represents a bond.

Of R ^2, or without a cyanoalkyl group having 2 to 11 carbon atoms having an ether bond ^{R 3,} the carbon number of the cyanoalkyl group of 2 to 11 carbon atoms, 2 to 9 are preferred, 2 to 6 and more preferably .
Examples of the cyanoalkyl group having no ether bond include a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, a 4-cyanobutyl group, and a 6-cyanohexyl group.
Examples of the cyanoalkyl group having an ether bond include groups represented by the following formula (8) or (9).

In formula (8), R ⁹ represents a cyanoalkyl group having 2 to 9 carbon atoms, Z ⁴ represents an alkylene group having 2 to ⁹ carbon atoms, and the total number of carbon atoms of R ⁹ and Z ⁴ is 4 ~ 11. * Represents a bond.
In formula (9), R ¹⁰ represents a cyanoalkyl group having 2 to 7 carbon atoms, Z ⁵ represents an alkylene group having 2 to 7 carbon atoms, and Z ⁶ represents an alkylene group having 2 to 7 carbon atoms. And the total number of carbon atoms of R ¹⁰ , Z ⁵ , and Z ⁶ is 6-11. * Represents a bond.

Alkenyl group R ^2, or without C2-10 having an ether bond ^{R 3,} carbon atoms of the alkenyl group having 2 to 10 carbon atoms, 2 to 9 are preferred, 2 to 6 is more preferable.
Examples of the alkenyl group having no ether bond include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, and a 1-pentenyl group.
Examples of the alkenyl group having an ether bond include groups represented by the following formula (10) or (11).

In formula (10), R ¹¹ represents an alkenyl group having 2 to 8 carbon atoms, Z ⁷ represents an alkylene group having 2 to 8 carbon atoms, and the total number of carbon atoms of R ¹¹ and Z ⁷ is 4 to 10. * Represents a bond.
In formula (11), R ¹² represents an alkenyl group having 2 to 6 carbon atoms, Z ⁸ represents an alkylene group having 2 to 6 carbon atoms, and Z ⁹ represents an alkylene group having 2 to 6 carbon atoms. , R ¹² , Z ⁸ and Z ⁹ have a total carbon number of 6 to 10. * Represents a bond.

The number of carbon atoms in the aryl group having 6 to 20 carbon atoms of the aryl group having 6 to 20 carbon atoms, which may or may not have substituents R ² and R ³ , is preferably 6 to 10.
Examples of the unsubstituted aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
Examples of the substituent of the aryl group having a substituent include an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a fluorine atom and a chlorine atom And the like.

Examples of the ring formed by combining R ² and R ³ include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

In formula (2), A ¹ represents a divalent group represented by any of the following formulas (3) to (5).

In formulas (3) to (5), A ² and A ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a carbon number. An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms with or without a substituent is represented. n represents an integer of 1 to 10. * 1 represents a bond with a carbon atom, and * 2 represents a bond with a nitrogen atom.

A ^2, the number of carbon atoms of the alkylene group having 1 to 10 carbon atoms ^{A 3} is 1-8 preferably 1-6 and more preferably.
Examples of the alkylene group having 1 to 10 carbon atoms include linear alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group and pentamethylene group; propane-1,2-diyl group, butane-1,3- Examples include branched alkylene groups such as diyl groups.

Examples of the alkyl group having 1 to ⁶ carbon atoms of R ⁴ , R ⁵ and R ⁶ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n -A pentyl group, n-hexyl group, etc. are mentioned.
The number of carbon atoms of the aryl group having 6 to 20 carbon atoms of the aryl group having 6 to 20 carbon atoms, which may or may not have a substituent of R ⁴ , R ⁵ and R ⁶ , is preferably 6 to 10.
Examples of the unsubstituted aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
Examples of the substituent of the aryl group having a substituent include an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a fluorine atom and a chlorine atom And the like.
n is an integer of 1 to 10, and an integer of 1 to 5 is preferable.
In Formula (2), m is an integer of 2-5, and 3 or 4 is preferable.

  In the present invention, the zwitterionic polymer (α) having a repeating unit represented by the following formula (2) is preferable from the viewpoint of availability.

[In the formula (2), R ¹ , R ² , R ³ , A ¹ and m each have the same meaning as described above. ]
The zwitterionic monomer (a) used for the synthesis of the zwitterionic polymer (α) can be appropriately determined according to the target zwitterionic polymer.
For example, a zwitterionic polymer having a repeating unit represented by the formula (2) can be synthesized by using a zwitterionic monomer represented by the following formula (2A).

In formula (2A), R ¹ , R ² , R ³ , A ¹ , m, and “—G ⁻ ” each represent the same meaning as described above.

The method for synthesizing the zwitterionic monomer represented by the formula (2A) is not particularly limited.
In the above formula (2A), "- G ^-" is -COO ^- zwitterionic monomer represented by, for example, the corresponding amine compound [formula (2b)], the formula: hal- _{(CH 2) m} It can be obtained by a known method for producing a carboxybetaine compound such as a method of reacting a halogenated carboxylic acid represented by —COOH (hal represents a halogen atom, and m represents the same meaning as described above). (Kaihei 8-99945, JP-A-7-278071, JP-A-2006-143634, JP-A-2006-143635, etc.).

In addition, in the above formula (2A), a zwitterionic monomer [compound represented by the following formula (2a)] in which “-G ⁻ ” is —SO ₃ ^— represents a corresponding amine compound ( It can be obtained by reacting 2b) with a sultone compound (2c).

In the above ^{formula, R 1 ~R 3, A 1} , and m represent the same meaning as defined above, p is an (m-2).
The amine compound (2b) can be produced and obtained by a known method.

Examples of the sultone compound (2c) include 1,2-ethane sultone, 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, and 1,5-pentane sultone.
These are known compounds, and can be produced and obtained by known methods. Moreover, in this invention, a commercial item can also be used as these sultone compounds.

  In the reaction of the amine compound (2b) and the sultone compound (2c), the amount of the sultone compound (2c) to be used is preferably 0.8 to 1.2 equivalents, more preferably 0, relative to the amine compound (2b). .9 to 1.1 equivalents. By making the usage-amount of a sultone compound (2c) into the said range, the process of removing an unreacted substance can be abbreviate | omitted or the time concerning removal can be shortened.

The reaction of the amine compound (2b) and the sultone compound (2c) may be performed without a solvent or in the presence of an inert solvent.
As the inert solvent to be used, water: ether solvents such as tetrahydrofuran and diglyme; nitrile solvents such as acetonitrile and propionitrile; ketone solvents such as acetone and methyl ethyl ketone; aromatic hydrocarbon solvents such as toluene and xylene; Halogenated hydrocarbon solvents such as chloroform; and the like.
When using an inert solvent, the amount of use is not particularly limited, but is usually 0.1 to 100 parts by mass, preferably 1 to 100 parts by mass with respect to 1 part by mass of the amine compound (2b).

Although reaction temperature is not specifically limited, Usually, it is 0-200 degreeC, Preferably it is 10-100 degreeC, More preferably, it is the range of 20-60 degreeC. In addition, the reaction may be performed under normal pressure (atmospheric pressure), or may be performed under pressurized conditions.
Although reaction time is not specifically limited, Usually, it is 12 to 332 hours, Preferably it is 24 to 168 hours.
The reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas or argon gas from the viewpoint of preventing the yield from decreasing due to oxidation by oxygen or hydrolysis of the sultone compound (2c) by moisture in the air.
The progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR, IR and the like.

  After completion of the reaction, normal post-treatment operations in organic synthetic chemistry can be performed, and if desired, the target zwitterionic monomer can be isolated by purification by a known purification method such as recrystallization or column chromatography. .

  Among the zwitterionic monomers represented by the above formula (2A), in the present invention, from the viewpoint of availability, the zwitterionic monomer is a compound having a sulfobetaine structure represented by the following formula (2a). Use is preferred.

[In Formula (2a), R ¹ , R ² , R ³ , and m each represent the same meaning as described above. ]
Moreover, in this invention, what is marketed as a zwitterionic monomer shown by Formula (2A) can also be used as it is or refine | purified as needed.

  In addition to the repeating unit derived from the zwitterionic monomer (a), the zwitterionic polymer (α) may have a repeating unit derived from a monomer copolymerizable with this.

  In the zwitterionic polymer (α), the repeating unit derived from the monomer copolymerizable with the zwitterionic monomer (a) includes a repeating unit derived from (meth) acrylic acid, a repeating unit derived from maleic acid, and derived from crotonic acid. A repeating unit having a carboxy group such as a repeating unit derived from itaconic acid; a repeating unit having a sulfo group such as a repeating unit derived from (meth) acrylamide t-butylsulfonic acid; methyl (meth) acrylate, methacrylic And a repeating unit derived from a (meth) acrylic acid ester such as ethyl acid; a repeating unit derived from (meth) acrylamide; Here, (meth) acrylic acid means acrylic acid or methacrylic acid (the same applies hereinafter).

  Among these, as the repeating unit derived from a monomer copolymerizable with the zwitterionic monomer (a), those having a hydrophilic group are preferable. When the zwitterionic polymer (α) has these repeating units, the storage stability of the coating solution tends to be further improved, and a hydrophilic layer having more hydrophilic properties can be easily obtained.

The hydrophilic group includes a sulfo group (—SO ₃ H), a carboxy group (—CO ₂ H), a phosphonic acid group (—PO ₃ H ₂ ), a hydroxy group (—OH), and these groups react with a base. Anionic hydrophilic groups such as groups, substituted or unsubstituted amino groups, substituted or unsubstituted nitrogen-containing heterocyclic groups, cationic hydrophilic groups such as groups obtained by reacting these groups with acids, etc. Is mentioned.
Among these, as the hydrophilic group, an anionic hydrophilic group is preferable, and —SO ₃ H, —CO ₂ H, —PO ₃ H ₂ , or a group obtained by reacting these groups with a base is more preferable.

  Examples of the base used for generating “a group formed by reacting these groups with a base” include metal hydroxides of Group 1 or 2 of the periodic table and amine compounds. Therefore, the repeating unit having “a group formed by reacting these groups with a base” usually has a metal ion or ammonium ion of Group 1 or Group 2 of the periodic table, and the zwitterionic monomer as a whole It is in an electrically neutral state.

  The zwitterionic polymer (α) contained in the hydrophilic resin composition of the present invention has a repeating unit derived from the zwitterionic monomer (a) in the molecule from the viewpoint of obtaining the better effect of the present invention, A copolymer having a repeating unit derived from a monomer copolymerizable with the zwitterionic monomer (a) is preferred.

The amount of the repeating unit derived from the zwitterionic monomer (a) in the zwitterionic polymer (α) is usually 50 to 100 mol%, preferably 60 to 99, based on the entire zwitterionic polymer (α). It is mol%, More preferably, it is 70-95 mol%. When the amount of the repeating unit derived from the zwitterionic monomer (α) in the zwitterionic polymer (α) is 50 mol% or more, the hydrophilicity becomes good. Moreover, it becomes easy to introduce a crosslinking point as it is 99 mol% or less, and adhesiveness with a to-be-coated object becomes favorable.
When the zwitterionic polymer (α) contains repeating units having a hydrophilic group, the amount of these repeating units is usually 0 to 50 mol%, preferably based on the total zwitterionic polymer (α), preferably It is 1-40 mol%, More preferably, it is 5-30 mol%.

  The zwitterionic polymer (α) can be used alone or in combination of two or more.

  The method for synthesizing the zwitterionic polymer (α) is not particularly limited. For example, in the presence of a radical polymerization initiator, by performing a polymerization reaction of the zwitterionic monomer (a) and, optionally, a monomer (monomer mixture) containing a monomer copolymerizable with the zwitterionic monomer (a), Zwitterionic polymer (α) can be synthesized.

Examples of the radical polymerization initiator include organic peroxides and azo compounds.
Examples of the organic peroxide include diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3,3 Peroxyketals such as 1,5-trimethylcyclohexane; peroxydicarbonates such as diisopropyl peroxydicarbonate and di-2-ethylhexyl peroxydicarbonate; t-butylperoxy-2-ethylhexanoate, t- And peroxyesters such as butyl peroxyisobutyrate.
Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2,2 '-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 2 , 2′-azobis (N-butyl-2-methylpropionamide), dimethyl 1,1′-azobis (1-cyclohexanecarboxylate) and other oil-soluble azo polymerization initiators; 4,4′-azobis (4-cyano Valeric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobi (2,4-dimethyl-4-methoxyvaleronitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloroide, 2,2′-azobis [2- (2- Imidazolin-2-yl) propane] disulfonate dihydrate, 2,2′-azobis (2-methylpropionamidine) dihydrochloroide, 2,2′-azobis [N- (2-carboxyethyl) -2-methyl Water-soluble azo polymerization initiators such as propionamidine] tetrahydrate, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide]; 4,4′-azobis (4-cyanovaleric acid) is particularly preferable.
These can be used singly or in combination of two or more.

  The amount of the radical polymerization initiator used is usually 0.0001 to 0.1000 mol, preferably 0.0005 to 0, based on 1 mol of the monomer used in the polymerization reaction (however, in the case of a copolymer, the total mol of monomers). .0050 mol.

  The reaction conditions for the radical polymerization reaction are not particularly limited as long as the target polymerization reaction proceeds. The heating temperature is usually 40 to 150 ° C., and the reaction time can be appropriately set within the range of 1 minute to 24 hours.

  The obtained reaction solution may be used as it is for the preparation of the hydrophilic resin composition, or may be used after isolating and purifying the zwitterionic polymer according to a conventional method.

The hydrophilic layer may contain an ionic compound (excluding the zwitterionic polymer (α)).
As the ionic compound, an ionic compound having a cation having 0 to 10 carbon atoms is preferable, and an ionic compound having a cation having 0 carbon atom is more preferable.

  Examples of the ionic compound having a cation having 0 to 10 carbon atoms include compounds represented by the following formulas (12) to (15).

  In formulas (12) to (15), M represents a monovalent cation having 0 to 10 carbon atoms, M ′ represents a divalent cation having 0 to 10 carbon atoms, and X represents a monovalent anion. X ′ represents a divalent anion.

Examples of M include alkali metal ions such as sodium ion and potassium ion; ammonium ion (NH ₄ ⁺ ); primary ammonium ion; secondary ammonium ion; tertiary ammonium ion; quaternary ammonium ion; It is done.
Examples of M ′ include alkaline earth metal ions such as calcium ions; magnesium ions;
Examples of X include halide ions such as chloride ions and bromide ions; bicarbonate ions; nitrate ions;
Examples of X ′ include carbonate ion and sulfate ion.

Examples of the ionic compound having a cation having 0 carbon atoms include NaCl, Na ₂ CO ₃ , NaHCO ₃ , Na ₂ SO ₄ , NaNO ₃ , KCl, K ₂ CO ₃ , KHCO ₃ , K ₂ SO ₄ , KNO _3. Alkali metal salts such as MgCl ₂ , MgSO _{4 and} other magnesium salts; CaCl _{2 and} other alkaline earth metal salts; NH ₄ Cl and other ammonium salts and the like.
Examples of the ionic compound having a cation having 1 to 10 carbon atoms include [(CH ₃ ) NH ₃ ] Cl, [(CH ₃ ) ₂ NH ₂ ] Cl, [(CH ₃ ) ₃ NH] Cl, [( CH ₃ ) ₄ N] Cl and the like.

An ionic compound can be used individually by 1 type or in combination of 2 or more types.
Content of the ionic compound in a hydrophilic layer is 0-70 mass% normally on the basis of the whole hydrophilic layer, Preferably it is 2-50 mass%, More preferably, it is 5-20 mass%.

The hydrophilic layer may contain a polymer other than the zwitterionic polymer (α).
Polymers other than the zwitterionic polymer (α) include polyester polymers, ethylene-vinyl alcohol copolymers, vinyl alcohol homopolymers, (meth) acrylic acid polymers, (meth) acrylic acid ester heavy polymers. Examples of the polymer include urethane polymer, acrylic-urethane polymer, polyamide resin, polyolefin resin, and cellulose resin.

The polymers other than the zwitterionic polymer (α) can be used alone or in combination of two or more.
When the hydrophilic layer contains a polymer other than the zwitterionic polymer (α), the content is usually 1 to 40% by mass, preferably 2 to 20% by mass, based on the entire hydrophilic layer. .

The hydrophilic layer may have a crosslinked structure. The crosslinked structure in the hydrophilic layer can be efficiently formed by using, for example, a crosslinking agent.
A crosslinking agent is a compound that can react with the polymer component in the hydrophilic layer to form a crosslinked structure. A hydrophilic layer having a crosslinked structure tends to be more excellent in water resistance.

  As crosslinking agents, epoxy crosslinking agents, isocyanate crosslinking agents, amine crosslinking agents, melamine crosslinking agents, aziridine crosslinking agents, hydrazine crosslinking agents, aldehyde crosslinking agents, oxazoline crosslinking agents, metal alkoxide crosslinking agents , Metal chelate crosslinking agents, metal salt crosslinking agents, ammonium salt crosslinking agents, and the like.

The hydrophilic layer may contain an additive as long as the effects of the present invention are not impaired.
Examples of the additive include a surfactant, a humectant, a viscosity modifier, and a dye.

The thickness of the hydrophilic layer is usually 1-1000 nm, preferably 2-800 nm.
The method for forming the hydrophilic layer is not particularly limited. For example, the hydrophilic layer can be formed according to a method described later.

[Hydrophilic structure]
The hydrophilic structure of the present invention is a structure having a layer structure in which the substrate, the intermediate layer, and the hydrophilic layer are laminated in this order.

The hydrophilic layer of the hydrophilic structure of the present invention is excellent in hydrophilicity.
After 2 μL of ion-exchanged water is dropped on the hydrophilic layer of the hydrophilic layer of the hydrophilic structure of the present invention, a water contact angle (measured for a water droplet 3 seconds after dropping) using a contact angle measuring device ( The pre-wash water contact angle is usually 70 ° or less, preferably 60 ° or less, more preferably 50 ° or less. Although there is no lower limit in particular, it is usually 3 ° or more.

  The hydrophilic layer of the hydrophilic structure of the present invention is excellent in stain resistance. In particular, the hydrophilic layer of the hydrophilic structure of the present invention is hard to adhere oily dirt.

The hydrophilic layer of the hydrophilic structure of the present invention is excellent in adhesion with the intermediate layer.
This is presumably because the siloxane polymer and the zwitterionic polymer (α) are intertwined at the interface between the intermediate layer and the hydrophilic layer.

The hydrophilic layer of the hydrophilic structure of the present invention is excellent in water resistance. In the present invention, water resistance means that the original hydrophilicity is maintained even after contact with water.
In particular, in the hydrophilic structure of the present invention, the hydrophilicity of the hydrophilic layer may be further increased by contact with water. This phenomenon is also considered to be caused by the entanglement between the siloxane-based polymer and the zwitterionic polymer (α).
That is, by removing the polymer chains that are hardly entangled on the surface portion of the hydrophilic layer by contact with water, a region in which the siloxane polymer and the zwitterionic polymer (α) are strongly entangled is formed. It is thought that it is exposed to the surface. And it is thought that the hydrophilicity of a hydrophilic layer increases more by exposing this area | region.
The surface of the hydrophilic layer of the hydrophilic structure of the present invention is washed with ion-exchanged water, and after drying, the water contact angle (water contact angle after washing) measured by the same method as above is usually 40 ° or less. , Preferably 30 ° or less, more preferably 10 ° or less. Although there is no lower limit in particular, it is usually 3 ° or more.

Examples of the hydrophilic structure of the present invention include functional films such as an antifogging film and an antifouling film.
Moreover, the hydrophilic structure of the present invention is not limited to a film-like product. For example, the hydrophilic structure of the present invention is used as a product that requires hydrophilicity, such as a mirror, a display, a signboard, a guide plate, a road sign, a building outer wall, and a window glass.

The manufacturing method of the hydrophilic structure of the present invention is not particularly limited. For example, the hydrophilic structure of the present invention can be produced by a method having the following steps (1) to (3).
Step (1): Applying a hydrolyzable organosilicon compound-containing coating solution (hydrolyzable organosilicon compound-containing coating solution) on the substrate, and hydrolyzing the hydrolyzable organosilicon compound in the resulting coating film. Step (2) of forming a coating film containing a siloxane polymer by decomposing polycondensation: In a state where the coating film containing the siloxane polymer is completely dried or in the coating film In the state which remained, the coating liquid (A) which contains the zwitterionic polymer which does not have a silicon atom, and does not contain the zwitterionic polymer which has a silicon atom is apply | coated on the said coating film, A) Step (3) of forming the coating film: A step of drying the undried coating film in the structure having the laminated structure obtained in the step (2).

  In the step (1), a coating liquid containing the hydrolyzable organosilicon compound is applied onto the substrate, and the hydrolyzable organosilicon compound in the obtained coating film is subjected to hydrolysis polycondensation. A coating film containing a siloxane polymer is formed.

The solvent contained in this coating solution is not particularly limited as long as it can dissolve or disperse components such as a hydrolyzable organosilicon compound.
Examples of the solvent include water and organic solvents miscible with water.
Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ethers; lactams such as N-methyl-2-pyrrolidone, and the like.
These solvents can be used alone or in combination of two or more.
Among these, the solvent is preferably a mixed solvent of water and alcohols.
The content of the solvent is preferably adjusted so that the solid content concentration of the hydrolyzable organosilicon compound-containing coating solution is 0.1 to 30.0% by mass, more preferably 0.5 to 10.0% by mass. preferable.

  The method for applying the coating solution is not particularly limited. For example, the coating solution can be applied onto the substrate using a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like.

The method for hydrolytic polycondensation of the hydrolyzable organosilicon compound is not particularly limited. The hydrolysis polycondensation reaction can be promoted by using a catalyst or heating as necessary.
The reaction temperature in the hydrolysis polycondensation reaction is usually 40 to 110 ° C, preferably 50 to 100 ° C.
The reaction time (heating time) is usually 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes.

  When the hydrolysis polycondensation reaction is performed by heating, drying of the coating film usually proceeds by the heat treatment. As will be described later, after the coating film is completely dried, the next step (2) may be performed, or the coating film is not completely dried (the state in which the solvent remains in the coating film). Then, the next step (2) may be performed. The degree of entanglement between the siloxane polymer and the zwitterionic polymer (α) can be adjusted by controlling the dry state of the coating film when performing the step (2).

  In the step (2), the coating film containing the siloxane polymer is completely dried, or the solvent remains in the coating film, and does not have the silicon atom on the coating film. A coating liquid (A) containing a zwitterionic polymer and not containing a zwitterionic polymer having a silicon atom is applied to form a coating film of the coating liquid (A).

By applying the coating liquid (A) in a state where the coating film containing the siloxane polymer is completely dried, a hydrophilic structure having a clear boundary between the intermediate layer and the hydrophilic layer (that is, the siloxane polymer) And a hydrophilic structure having a thin region in which the zwitterionic polymer (α) is entangled with each other.
On the other hand, by applying the coating liquid (A) with the solvent remaining in the coating film containing the siloxane-based polymer, a hydrophilic structure in which the boundary between the intermediate layer and the hydrophilic layer is not clear (that is, A hydrophilic structure having a thick region where the siloxane polymer and the zwitterionic polymer (α) are intertwined can be obtained.
As described above, the degree of entanglement between the siloxane polymer and the zwitterionic polymer (α) affects the adhesion and water resistance of the hydrophilic layer.
Therefore, by appropriately controlling the dry state of the coating film containing the siloxane polymer at the start of the step (2), a hydrophilic layer having the desired characteristics can be efficiently formed.

The solvent contained in the coating liquid (A) is not particularly limited as long as it can dissolve or disperse components such as a zwitterionic polymer having no silicon atom.
Examples of the solvent include water and organic solvents miscible with water.
Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n-propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; alkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; methyl cellosolve and ethyl Alkyl ethers such as cellosolve; lactams such as N-methyl-2-pyrrolidone; and the like.
These solvents can be used alone or in combination of two or more.
Among these, the solvent is preferably a mixed solvent of water and alcohols.
The content of the solvent is preferably adjusted so that the solid content concentration of the coating liquid (A) is 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass.

  The method for applying the coating solution is not particularly limited. For example, the coating solution (A) can be applied by the same method as that shown as the coating method of the hydrolyzable organosilicon compound-containing coating solution.

  In the step (3), the undried coating film in the structure having the laminated structure obtained in the step (2) is dried.

  Here, the undried coating film refers to “coating film derived from the coating liquid (A)” when the step (2) is performed in a state where the coating film containing the siloxane polymer is completely dried. When the step (2) is performed in a state where the solvent remains in the coating film containing the siloxane polymer, the “coating film containing the siloxane polymer” and the “coating film derived from the coating liquid (A)” Say.

The method for drying the coating film is not particularly limited. For example, conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be used.
The drying conditions can be appropriately determined according to the state of the intermediate layer and the like.
A drying temperature is 60-130 degreeC normally, Preferably it is 70-120 degreeC.
The drying time (heating time) is usually from 10 seconds to 3 minutes, preferably from 30 seconds to 2 minutes.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Unless otherwise indicated, the part and% in each example are based on mass.

[Mass average molecular weight (Mw)]
The mass average molecular weight (Mw) of the zwitterionic polymer was determined by performing gel permeation chromatography (GPC) under the following conditions.

Apparatus: HLC-8320GPC / UV-8320 (manufactured by Tosoh Corporation)
Column: TSKgel GMPW _XL (manufactured by Tosoh Corporation) x 2
Detector: RI detector with built-in HLC-8320GPC / UV-8320 (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample concentration: 1.0 g / L (polymer component concentration)
Injection volume: 100 μL
Eluent: 0.2 M NaNO ₃ aqueous solution Flow rate: 1.0 mL / min Molecular weight marker: Standard polyethylene oxide, polyethylene glycol

[Production Example 1] Synthesis of zwitterionic monomer (1) In a reaction vessel equipped with a stirrer, 100 parts of N- [3- (dimethylamino) propyl] acrylamide, 0.4 part of dibutylhydroxytoluene, and 383 parts of acetone were added. While stirring the contents, 72 parts of propane sultone was slowly added dropwise. Thereafter, the content was stirred at 25 ° C. for 24 hours, and the precipitated white solid was collected by filtration and dried to give zwitterionic monomer (1) (N-acryloylaminopropyl-N, N-dimethylammoniumpropyl). -Α-sulfoxybetaine) was obtained.

[Production Example 2] Synthesis of zwitterionic monomer (2) In a reaction vessel equipped with a stirrer, N- [3- (dimethylamino) propyl] methacrylamide 100 parts, dibutylhydroxytoluene 0.4 parts, acetone 383 parts Then, 72 parts of propane sultone was slowly added dropwise while stirring the contents. Thereafter, the content was stirred at 25 ° C. for 24 hours, and the precipitated white solid was collected by filtration and dried to give zwitterionic monomer (2) (N-methacryloylaminopropyl-N, N-dimethylammoniumpropyl). -Α-sulfoxybetaine) was obtained.

[Production Example 3] to [Production Example 8] Synthesis of zwitterionic polymer In a reaction vessel equipped with a stirrer, each monomer was charged so as to have a molar ratio as shown in Table 1, and the total amount of each monomer. 100 parts per 100 parts of polymerization initiator (Wako Pure Chemical Industries, Ltd., product name “V-501”, 4,4′-azobis (4-cyanovaleric acid)) 0.19 parts, shown in Table 1 The diluted solvent was added and stirred at 25 ° C. for 30 minutes while introducing nitrogen into the reaction vessel. Then, the inside of the system was raised to 80 ° C., and the polymerization reaction was carried out by stirring for 16 hours as it was to obtain a solution having a solid content concentration of 30% containing each zwitterionic polymer. The mass average molecular weight of each zwitterionic polymer obtained is shown in Table 1. Abbreviations and the like in Table 1 are as follows.
In addition, about the zwitterionic polymer of the manufacture example 7 and the manufacture example 8, since precipitation was produced at the time of a polymerization reaction as mentioned later, the measurement of molecular weight was abbreviate | omitted.

<Monomer>
SBAAm: (N-acryloylaminopropyl-N, N-dimethylammoniumpropyl-α-sulfoxybetaine)
SBMAAm: (N-methacryloylaminopropyl-N, N-dimethylammoniumpropyl-α-sulfoxybetaine)
ATBS: Acrylamide t-butylsulfonic acid AAc: Acrylic acid VTMS: Vinyltrimethoxysilane <diluent>
Water: Distilled water TFE: Trifluoroethanol

In the following Examples and Comparative Examples, hydrophilic structures were produced using the raw materials shown below in addition to the zwitterionic polymer solutions prepared in Production Examples 3-8.
(Substrate)
Substrate (1): manufactured by Toyobo Co., Ltd., product name “Cosmo Shine A4100”, thickness 50 μm
Base (2): manufactured by Toray Industries, Inc., product name “Lumirror 50T60”, thickness 50 μm

(Alcoholic silica sol)
Alcoholic silica sol (1): manufactured by Colcoat Co., Ltd., product name “N-103X”, solid content concentration 2.0%
Alcoholic silica sol (2): manufactured by Colcoat Co., Ltd., product name “PC-291”, solid content concentration 2.5%

(Water-based polyester resin)
Aqueous polyester resin (1): An aqueous polyester resin having a repeating unit represented by the following formula (16). Mass average molecular weight (Mw) 16,000
Aqueous polyester resin (2): An aqueous polyester resin comprising a copolymer having a repeating unit represented by the following formula (16) and a repeating unit derived from methyl acrylate.

[Example 1]
To 100 parts of zwitterionic polymer solution prepared in Production Example 3 (solid content), add 5% sodium chloride aqueous solution with the amount adjusted so that the solid content of sodium chloride becomes the value described in Table 2. Then, distilled water was mixed to obtain a hydrophilic layer forming coating solution having a solid content concentration of 3%.
Separately from this, the alcoholic silica sol (1) was applied to the easy adhesion surface of the substrate (1) using a wire bar so that the thickness after drying was 100 nm. The resulting laminate was heated at 80 ° C. for 1 minute. After heating, the coating film in the laminate was not completely dried.
Next, the hydrophilic layer forming coating solution was applied thereon to obtain a structure having a laminated structure. Subsequently, this structure was heated at 120 ° C. for 1 minute to dry the undried coating film in the structure, thereby obtaining a hydrophilic structure.

[Examples 2 to 11]
A hydrophilic structure was obtained in the same manner as in Example 1 except that the hydrophilic structure was produced under the conditions shown in Table 2.

[Comparative Example 1]
100 parts (solid content) of the zwitterionic polymer solution prepared in Production Example 5 and 500 parts of trifluoroethanol (TFE) were mixed to obtain a coating solution for forming a hydrophilic layer.
The hydrophilic layer-forming coating solution was applied to the easy-adhesion surface of the substrate (1) to obtain a structure having a laminated structure. Subsequently, this structure was heated at 100 ° C. for 1 minute to dry the coating film, thereby obtaining a hydrophilic structure.

[Comparative Example 2]
To 100 parts of zwitterionic polymer solution prepared in Production Example 3 (solid content), add 5% sodium chloride aqueous solution with the amount adjusted so that the solid content of sodium chloride becomes the value described in Table 2. Then, distilled water was mixed to obtain a hydrophilic layer forming coating solution having a solid content concentration of 3%.
When the hydrophilic layer-forming coating solution was applied to the easy-adhesion surface of the substrate (1), the coating solution bounced on the substrate (1) and could not be applied.

[Comparative Example 3]
The alcoholic silica sol (1) was applied to the easily adhesive surface of the substrate (1) using a wire bar so that the thickness after drying was 100 nm. The obtained laminate was heated at 120 ° C. for 1 minute to obtain a hydrophilic structure.

[Comparative Example 4]
For the purpose of forming a layer containing a zwitterionic polymer having a silicon atom, an attempt was made to synthesize a zwitterionic polymer having a silicon atom by the method of Production Example 7.
However, precipitation occurred during the polymerization reaction, and a coating solution could not be obtained.

[Comparative Example 5]
For the purpose of forming a layer containing a zwitterionic polymer having a silicon atom, an attempt was made to synthesize a zwitterionic polymer having a silicon atom by the method of Production Example 8.
However, precipitation occurred during the polymerization reaction, and a coating solution could not be obtained.

[Comparative Example 6]
To 100 parts of zwitterionic polymer solution prepared in Production Example 6 (solid content), add 5% sodium chloride aqueous solution with the amount adjusted so that the solid content of sodium chloride becomes the value described in Table 2. Then, distilled water was mixed to obtain a hydrophilic layer forming coating solution having a solid content concentration of 3%.
Separately from this, a coating solution containing the aqueous polyester resin (1) was applied to the easily adhesive surface of the substrate (1) using a wire bar so that the thickness after drying was 100 nm. The resulting laminate was heated at 80 ° C. for 1 minute. After heating, the coating film in the laminate was not completely dried.
Next, the hydrophilic layer forming coating solution was applied thereon to obtain a structure having a laminated structure. Subsequently, this structure was heated at 100 ° C. for 1 minute to dry the undried coating film in the structure, thereby obtaining a hydrophilic structure.

[Comparative Example 7]
A hydrophilic structure was obtained in the same manner as in Comparative Example 6 except that the coating liquid containing the aqueous polyester resin (2) was used instead of the coating liquid containing the aqueous polyester resin (1).

(Water contact angle measurement)
On the hydrophilic layer of the hydrophilic structure obtained in Examples and Comparative Examples, 2 μL of ion exchange water was dropped. Using a fully automatic contact angle measurement device (DM-701, manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle (water contact angle before washing) was measured for water droplets 3 seconds after dropping.

(Water resistance evaluation)
The surface of the hydrophilic layer of the hydrophilic structure obtained in Examples and Comparative Examples was washed with ion-exchanged water, and after drying, the water contact angle (water contact angle after washing) was measured by the same method as above, The water resistance was evaluated according to the following criteria.
A: The water contact angle after washing is equal to or less than the water contact angle before washing.
B: The water contact angle after washing is larger than the water contact angle before washing.

[Evaluation of adhesion of hydrophilic layer]
After attaching cello tape (registered trademark) manufactured by Nichiban Co., Ltd. to the hydrophilic layer of the hydrophilic structure obtained in Examples and Comparative Examples, it was peeled off. The surface of the hydrophilic structure after peeling was observed, and the adhesion of the hydrophilic layer was evaluated. The evaluation criteria are shown below.
A: No peeling of the hydrophilic layer B: The hydrophilic layer was partially peeled off.
C: The hydrophilic layer was completely peeled off.

[Evaluation of stain resistance of hydrophilic layer]
The hydrophilic layers of the hydrophilic structures obtained in Examples and Comparative Examples were colored with an oil pen (Mckey) manufactured by Zebra Corporation, and this was used as a test piece. This test piece was immersed in distilled water and shaken, and then the distilled water was wiped off with a non-woven wiper (product name “Bencot” manufactured by Asahi Kasei Corporation). After this operation was repeated twice, the surface condition was observed to evaluate the stain resistance. The evaluation criteria are shown below.
A: The ink of the oil-based pen is completely removed.
B: The ink of the oil-based pen is removed, but a part remains.
C: More than half of the oil pen ink is not removed.

Table 3 shows the following.
The hydrophilic layers of the hydrophilic structures of Examples 1 to 11 were excellent in hydrophilicity, stain resistance, adhesion, and water resistance.
In the hydrophilic structures of Comparative Examples 1 and 2, an attempt was made to form a hydrophilic layer directly on a substrate. However, in Comparative Example 1, a hydrophilic layer having the same performance as that of the example could not be formed. Further, in Comparative Example 2, it was not possible to uniformly coat the substrate, and a hydrophilic layer could not be formed.
Moreover, the hydrophilic structure of Comparative Example 3 has the intermediate layer of the present invention on the surface. This layer was not hydrophilic enough.
In Comparative Examples 4 and 5, the zwitterionic polymer could not be synthesized as described above.
The hydrophilic structures of Comparative Examples 6 and 7 are obtained by forming an intermediate layer containing an aqueous polyester resin and forming a hydrophilic layer thereon. However, this hydrophilic layer was inferior in water resistance.

Claims (8)

A hydrophilic structure having a layer structure in which a substrate, an intermediate layer and a hydrophilic layer are laminated in this order,
The intermediate layer is a layer containing a siloxane polymer,
The hydrophilic structure, wherein the hydrophilic layer is a layer containing a zwitterionic polymer not having a silicon atom and not containing a zwitterionic polymer having a silicon atom.   The hydrophilic structure according to claim 1, wherein the substrate is a resin film.   The hydrophilic structure according to claim 1 or 2, wherein the siloxane-based polymer is a hydrolyzed polycondensate of a hydrolyzable organosilicon compound. The hydrophilic structure according to claim 3, wherein the hydrolyzable organosilicon compound is a silicon compound represented by the following formula (1) or a hydrolyzed polycondensate of a silicon compound represented by the following formula (1). body.

(In the formula, R ^a represents a hydrogen atom or a non-hydrolyzable organic group, R ^b represents a hydrolyzable group, and q represents an integer of 0 to 2.) The hydrophilic structure according to any one of claims 1 to 4, wherein the zwitterionic polymer having no silicon atom is a polymer having a repeating unit represented by the following formula (2).

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an ether bond with or without an ether bond. Or a C2-C11 cyanoalkyl group which does not have, a C2-C10 alkenyl group which has or does not have an ether bond, or a C6-C20 aryl group which has or does not have a substituent. R ² and R ³ may be bonded to each other to form a ring. A ¹ represents the following formulas (3) to (5)

(In the formula, A ² and A ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Or an aryl group having 6 to 20 carbon atoms with or without a substituent, n represents an integer of 1 to 10, * 1 represents a bond with a carbon atom, and * 2 represents a nitrogen atom. (Represents a bond.)
Represents a divalent group represented by any of the above. m represents an integer of 2 to 5. ]   The zwitterionic polymer having no silicon atom is a repeating unit derived from a zwitterionic monomer, and a repeating unit having a carboxy group, a sulfo group, or a group obtained by reacting these groups with a base (however, a zwitterionic polymer) The hydrophilic structure according to any one of claims 1 to 5, which is a polymer having a repeating unit derived from a cationic ion monomer.   The hydrophilic structure according to claim 1, wherein the hydrophilic layer further contains an ionic compound having a cation having 0 to 10 carbon atoms. The manufacturing method of the hydrophilic structure in any one of Claims 1-7 which has following process (1)-(3).
Step (1): A coating liquid containing a hydrolyzable organosilicon compound is applied on a substrate, and the hydrolyzable organosilicon compound in the obtained coating film is hydrolyzed and polycondensed to obtain a siloxane polymer. Step (2) of forming a coating film containing: In a state where the coating film containing the siloxane polymer is completely dried or in a state where a solvent remains in the coating film, A step of applying a coating solution (A) containing a zwitterionic polymer not having a silicon atom and not containing a zwitterionic polymer having a silicon atom to form a coating film of the coating solution (A) ( 3): The process of drying the undried state coating film in the structure which has the laminated structure obtained at the process (2).