TWI764989B - Hydrophilic structure and method for producing hydrophilic structure - Google Patents

Abstract

The present invention is a hydrophilic structure having a layered structure formed by sequentially laminating a substrate, an intermediate layer and a hydrophilic layer, wherein the intermediate layer is a film layer containing a siloxane-based polymer, and the hydrophilic layer is a film layer containing A film layer of a zwitterionic polymer having no silicon atom and containing no zwitterionic polymer having a silicon atom, and a method for producing the same. According to the present invention, a hydrophilic structure having a hydrophilic layer excellent in hydrophilicity, stain resistance, adhesion, and water resistance, and a method for producing the same are provided.

Description

Hydrophilic structure and method for producing hydrophilic structure

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.

A hydrophilic coating agent containing a polymer having a repeating unit derived from a polymerizable zwitterionic compound is conventionally known.

For example, Patent Document 1 describes the hydrophilicity of polymerizing a monomer component containing a betaine monomer and a compound containing an alkoxysilyl group to obtain a polymer containing an alkoxysilyl group A coating agent and a manufactured product having an anti-fogging layer formed using the hydrophilic coating agent on the surface.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] International Publication 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 exists on the surface of the substrate, a polymer containing an alkoxysilane group is chemically fixed. on the substrate surface. Therefore, by using this hydrophilic coating agent, a hydrophilic layer excellent in adhesion to a substrate having a reactive group on the surface can be effectively formed.

However, in the production of a hydrophilic coating agent (coating liquid) containing a polymer containing an alkoxysilane group, depending on the type of monomer used, solids may be precipitated during the polymerization reaction, resulting in an inability to A case where a coating liquid in which the components are completely dissolved or dispersed is obtained.

In order to stably manufacture a hydrophilic structure having a hydrophilic layer, the present inventors tried to form a hydrophilic layer using a coating liquid that does not contain a zwitterionic polymer having a silicon atom.

However, when such a coating liquid is used, it is difficult to form a hydrophilic layer excellent in adhesion to the base material layer.

Furthermore, depending on the components of the coating liquid, a hydrophilic layer having poor water resistance and contamination resistance may be formed, or the coating liquid may not be uniformly coated on the substrate.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a hydrophilic structure having a hydrophilic layer excellent in hydrophilicity, stain resistance, adhesion, and water resistance, and a method for producing the same.

As a result of intensive research to solve the above-mentioned problems, the present inventors found that a film layer containing a siloxane-based polymer is provided on the surface of a substrate, and a zwitterionic polymer containing no silicon atoms is formed on the film layer. A membrane layer containing a zwitterionic polymer having silicon atoms as a hydrophilic layer can stably produce a hydrophilic structure having a hydrophilic layer excellent in hydrophilicity, contamination resistance, adhesion, and water resistance. the present invention.

Therefore, according to the present invention, there are provided the following hydrophilic structures of [1] to [7], and methods of producing the hydrophilic structures of [8].

[1] A hydrophilic structure having a layered structure in which a substrate, an intermediate layer and a hydrophilic layer are sequentially laminated, wherein the intermediate layer is a film containing a siloxane-based polymer layer, and the hydrophilic layer is a film layer containing a zwitterionic polymer having no silicon atom and not having 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], wherein the siloxane-based polymer is a hydrolysis polycondensate of a hydrolyzable organosilicon compound.

[4] The hydrophilic structure according to [3], wherein the hydrolyzable organosilicon compound is a silicon compound represented by the following chemical formula (1) or a hydrolyzed polycondensate of a silicon compound represented by the following chemical formula (1). .

[Chemistry 1] Si(R ^a ) _q (R ^b ) _4-q (1)

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

[5] The hydrophilic structure according to [1], wherein the zwitterionic polymer having no silicon atom is a polymer having a repeating unit represented by the following chemical formula (2).

[In the chemical formula, 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 with or without an ether bond, with or without an ether bond A cyanoalkyl group with 2 to 11 carbon atoms, an alkenyl group with a carbon number of 2 to 10 with or without an ether bond, or an aromatic group with or without a substituent with a carbon number of 6 to 20 base. In addition, R ² and R ³ may be bonded to each other to form a ring. A ¹ represents a divalent group represented by any one of the following chemical formulae (3) to (5),

(In the chemical 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 each independently represent a hydrogen atom and an alkane having 1 to 6 carbon atoms. group, or an aromatic group with or without substituents having 6 to 20 carbon atoms. n represents an integer of 1 to 10. *1 represents a covalent bond with a carbon atom, and *2 represents a covalent bond with a nitrogen atom Valence bond.) m represents an integer from 2 to 5. ]

[6] The hydrophilic structure according to [1], wherein the zwitterionic polymer system having no silicon atom has a repeating unit derived from a zwitterionic monomer, and has a carboxyl group, a sulfo group, or the aforementioned groups A polymer of repeating units (but excluding repeating units derived from zwitterionic monomers) of groups obtained by reaction with bases.

[7] The hydrophilic structure according to [1], wherein the hydrophilic layer is a membrane layer further containing an ionic compound having a cation having 0 to 10 carbon atoms.

[8] A method for producing a hydrophilic structure, comprising the following steps (1) to (3) to produce the hydrophilic structure described in any one of [1] to [7], step (1): Coating a coating liquid containing a hydrolyzable organosilicon compound on a substrate, by hydrolyzing and polycondensing the hydrolyzable organosilicon compound in the obtained coating film, to form a coating film containing a siloxane polymer; step (2): In a state where the coating film containing the siloxane-based polymer is completely dried, or in a state where the solvent remains in the coating film, on the coating film, a bismuth compound containing no silicon atom is applied. A coating solution (A) of a zwitterionic polymer that does not contain a zwitterionic polymer having silicon atoms, so as to form a coating film of the aforementioned coating solution (A); In the structure of the obtained laminated structure, the coating film in the undried state was dried.

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

The hydrophilic structure of the present invention is a hydrophilic structure having a layered structure formed by sequentially laminating a substrate, an intermediate layer and a hydrophilic layer, wherein the intermediate layer is a film layer containing a siloxane-based polymer, The aforementioned hydrophilic layer is a film layer containing a zwitterionic polymer having no silicon atom and no 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 support the intermediate layer, the hydrophilic layer, and the like.

The shape of the base is not particularly limited, and any shape such as a cube, a rectangular parallelepiped, a spherical shape, a spindle shape, a plate shape, a film shape, and a fiber shape can be adopted.

The substrate can also be surface treated.

The surface treatment includes 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 base material include inorganic substances such as glass, pottery, porcelain, enamel, tiles, and ceramics; metals such as aluminum, stainless steel, and brass; various synthetic resins; cotton, silk, wool, and the like. fiber; etc.

Among these materials, a resin film is preferable as the substrate. By using a resin film as a base, a functional film such as an anti-fogging film can be obtained.

Examples of the raw material of the resin film include polyolefins such as polyethylene and polypropylene; polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate Polyesters such as ethylene glycol esters (poly naphthalene terephthalate), etc.; polyvinyl chloride; polycarbonates; acrylic resins; styrene resins;

The resin film may contain additives such as ultraviolet absorbers, light stabilizers, and antioxidants.

The thickness of the resin film is usually 20 to 1000 micrometers (μm), preferably 30 to 500 μm.

Furthermore, the resin film may be an elongated film or a short-striped film.

Here, the "slender film" refers to a film having a length of 5 times or more of the width.

[middle layer]

The intermediate layer constituting the hydrophilic structure of the present invention is a film layer containing a siloxane-based polymer.

By providing a film layer containing a siloxane-based polymer as an intermediate layer, a hydrophilic layer excellent in adhesion can be formed without using a zwitterionic polymer having silicon atoms. This is considered to be caused by the entanglement of the siloxane-based polymer and the zwitterionic polymer having no silicon atoms at the interface between the intermediate layer and the hydrophilic layer.

Furthermore, when the coating liquid used for forming the hydrophilic layer is aqueous, the coating film may not be uniformly coated on the surface of the base.

On the other hand, as long as it is above the intermediate layer, even when an aqueous coating liquid is used, a uniform coating film can be effectively formed.

The siloxane-based polymer contained in the intermediate layer is a polymer having a siloxane bond (Si-O-Si). Siloxane-based polymers can generally be obtained by hydrolyzing and polycondensing hydrolyzable organosilicon compounds.

In addition, the siloxane-based polymer has substantially no hydrolytic polycondensation reactivity (that is, the hydrolytic polycondensation reaction of the hydrolyzable organosilicon compound, which is the raw compound, has ended).

Therefore, this siloxane-based polymer is used as a hydrolyzable organosilicon compound in terms of non-reactivity, and is different from the "partially hydrolyzed polycondensate of a silicon compound represented by the chemical formula (1)."

In the present invention, "hydrolyzable" refers to the property of forming a silanol group by reaction with water.

The degree of polymerization of the siloxane-based polymer is not particularly limited. The degree of polymerization of siloxane polymers is usually greater than 100.

A hydrolyzable organosilicon compound is an organosilicon compound having a hydrolyzable group in the molecule. Examples of the hydrolyzable organosilicon compound include a silicon compound represented by the following chemical formula (1), or a hydrolysis polycondensate (also referred to as a "partially hydrolyzed polycondensate") of a silicon compound represented by the following chemical formula (1). .

[Chemistry 4] Si(R ^a ) _q (R ^b ) _4-q (1)

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

Examples of the non-hydrolyzable organic group represented by R ^a include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, tert-amyl ( 1,1-dimethylpropyl), 1,1-dimethyl-3,3-dimethylbutyl, heptyl, octyl, nonyl, decyl and other alkanes having 1 to 10 carbon atoms cycloalkyl groups with 3 to 10 carbon atoms such as cyclopentyl and cyclohexyl; alkenyl groups with 2 to 10 carbon atoms such as vinyl and propenyl; ethylene and propylene groups with carbon atoms of 2 to 10 2-10 alkylene groups; phenyl, naphthyl, anthracenyl and other aromatic groups with 6-15 carbon atoms; etc.

The above-mentioned organic group may have a substituent. As a substituent, a (meth)acryloyloxy group, an epoxy group, an amino group, a mercapto group, a hydroxyl group, a halogen atom, an alkoxy group, a fluoroalkyl group, etc. are mentioned.

Examples of the hydrolyzable group represented by R ^b include alkoxy groups having 1 to 5 carbon atoms such as methoxy, ethoxy, and propoxy; Aloxy group; halogen atom such as chlorine atom, bromine atom, etc.; etc.

q represents an integer from 0 to 2, preferably 0 or 1, preferably 0.

Examples of the silicon compound represented by the chemical formula (1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraiso- Propoxysilane (tetraisopropoxysilane), tetra-n-butoxysilane (tetra-n-butoxysilane), tetraisobutoxysilane (tetraisobutoxysilane), tetra-s-butoxysilane (tetra-s-butoxysilane), Silicon compounds whose q is 0, such as tetra-t-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane Silane (methyltripropoxysilane), methyl triisopropoxy silane (methyl triisopropoxy silane), ethyl trimethoxy silane (ethyl trimethoxysilane), ethyl triethoxy silane (ethyltriethoxysilane), propyl trimethoxy silane (propyl trimethoxysilane) ), propyl triethoxysilane, butyl trimethoxysilane, butyl triethoxysilane, phenyltrimethoxysilane, phenyl trimethoxysilane Ethoxysilane (phenyltriethoxysilane), γ- (2,3-glycidoxypropyltrimethoxysilane), γ-glycidoxypropyltrimethoxysilane (γ-acryloyloxypropyltrimethoxysilane), γ -methacryloyloxypropyltrimethoxysilane (γ-methacryloyloxypropyltrimethoxysilane), vinyltrimethoxysilane (vinyltrimethoxysilane), vinyltriethoxysilane (vinyltriethoxysilane) and other silicon compounds whose q is 1; dimethyl Dimethoxysilane (dimethyl dimethoxysilane), dimethyl diethoxysilane (dimethyl diethoxysilane), dimethyl dimethoxysilane (die thyldimethoxysilane), dimethyldiethoxysilane (diethyldiethoxysilane), methylphenyldimethoxysilane (methylphenyldimethoxysilane), divinyl dimethoxysilane (divinyl dimethoxysilane), divinyldiethoxysilane ( Divinyldiethoxysilane) and other silicon compounds where q is 2; etc.

The above-mentioned silicon compounds may be used alone or in combination of two or more.

Furthermore, when using the above-mentioned silicon compounds, trimethylmethoxysilane, triethylmethoxysilane, triethylmethoxysilane, triethylmethoxysilane, and trimethylmethoxysilane can also be used together. Silicon compounds in which q is 3, such as triethyl ethoxysilane, trivinylmethoxysilane, and trivinyl ethoxysilane.

The hydrolysis polycondensate of the silicon compound represented by the above chemical formula (1), for example, in an organic solvent such as an ethanol solvent, in the presence of a specific amount of water and a condensation catalyst, or in the presence of a specific amount of water without a condensation catalyst, the The silicon compound represented by the chemical formula (1) is obtained by hydrolysis and polycondensation.

As a hydrolyzable organosilicon compound, the polymerization degree of the partially hydrolyzed polycondensate of the silicon compound represented by the above chemical formula (1) is not particularly limited. The degree of polymerization of this compound is usually 100 or less.

As a reaction liquid obtained by performing this reaction, known reaction liquids, such as alcoholic silica sol (alcoholic silica sol), are mentioned.

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- Commercially available products such as 485, SS-101, HAS-1, HAS-6, HAS-10, SS-C1, COLCOAT PX, COLCOAT N-103X, PC-291 (the above are manufactured by Colcoat Co., Ltd.).

The intermediate layer may contain components other than the siloxane-based polymer. Examples of components other than siloxane-based polymers include antistatic agents, surfactants, and polymer compounds other than siloxane-based polymers.

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 10-10,000 nanometers (nm), preferably 30-5,000 nm, and more preferably 50-500 nm.

As described later, the boundary between the intermediate layer and the hydrophilic layer may or may not be clear. By forming the hydrophilic layer after the intermediate layer is completely formed, a hydrophilic structure having a clear boundary between the intermediate layer and the hydrophilic layer can be obtained. Furthermore, by starting the formation of the hydrophilic layer in a state where the intermediate layer has not been completely formed, a hydrophilic structure in which the boundary between the intermediate layer and the hydrophilic layer is not clear can be obtained.

The formation method of the intermediate layer is not particularly limited. For example, the intermediate layer may be formed according to a method described later.

[Hydrophilic layer]

The hydrophilic layer constituting the hydrophilic structure of the present invention is a film layer containing a zwitterionic polymer having no silicon atom and no zwitterionic polymer having a silicon atom.

Here, the zwitterionic polymer is a polymer having repeating units derived from a zwitterionic monomer. Furthermore, the zwitterionic single system has a polymerizable carbon-carbon double bond in the molecule and a compound having a betaine structure having positive and negative charges.

Since the hydrophilic structure of the present invention contains a hydrophilic layer, it has excellent hydrophilicity.

As described above, the hydrophilic layer constituting the hydrophilic structure of the present invention contains a zwitterionic polymer having no silicon atom, and on the other hand, does not contain a zwitterionic polymer having a silicon atom.

Examples of the zwitterionic polymer having a silicon atom include zwitterionic polymers having a silicon atom-containing group such as an alkoxysilyl group. The hydrophilic layer containing such a zwitterionic polymer tends to be excellent in adhesion to other layers.

However, using a zwitterionic monomer having an alkoxysilyl group, such as a carboxyl group or a sulfo group, as a raw material monomer, in the synthesis process of a zwitterionic polymer having an alkoxysilyl group (polymerization reaction of the monomer) ) may occur in which solid precipitation fails to prepare a coating liquid for forming a hydrophilic layer in which the components are completely dissolved or dispersed.

On the other hand, since the hydrophilic layer constituting the hydrophilic structure of the present invention is a zwitterionic polymer having no silicon atoms, the above-mentioned problems do not occur when the hydrophilic structure of the present invention is produced.

In the hydrophilic layer constituting the hydrophilic structure of the present invention, a zwitterionic polymer having no silicon atom (hereinafter sometimes referred to as "zwitterionic polymer ( α )") contains a zwitterionic polymer having no silicon atom. One type or two or more types of repeating units derived from a zwitterionic 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 positive and negative charges in the molecule, but not having a silicon atom.

The mass average molecular weight of the zwitterionic polymer ( α ) is usually 50,000 to 3 million, preferably 100,000 to 2.5 million, and more preferably 200,000 to 2 million.

The mass average molecular weight of the zwitterionic polymer (α) can be measured according to the method described in the Examples.

As a repeating unit derived from a zwitterionic monomer (a), the polymer which has a repeating unit represented by following chemical formula (20) is mentioned.

In chemical formula (20), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms with or without an ether bond, with or without A cyanoalkyl group with 2 to 11 carbon atoms in an ether bond, an alkenyl group with 2 to 10 carbon atoms with or without an ether bond, or a 6 to 20 carbon atom with or without a substituent the aromatic group. R ² and R ³ may be bonded to each other to form a ring. "-G ^- " means -COO ^- or -SO ₃ ^- .

When R ² and R ³ represent an alkyl group having 1 to 10 carbon atoms with or without an ether bond, the number of carbon atoms of the alkyl group having 1 to 10 carbon atoms is preferably 1 to 8, preferably 1 to 5 is better.

As an alkyl group which does not have an ether bond, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, etc. are mentioned.

As an alkyl group which has an ether bond, the group etc. which are represented by following chemical formula (6) or (7) are mentioned.

[Chemistry 6] R ⁷ -OZ ¹ -* (6) R ⁸ -OZ ² -OZ ³ -* (7)

In chemical 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 sum of the carbon atoms of R ⁷ and Z ¹ is 3 to 3 10. * denotes a covalent bond.

In chemical 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 , and the total number of carbon atoms of R ⁸ , Z ² , and Z ³ is 5-10. * denotes a covalent bond.

When R ² and R ³ represent a cyanoalkyl group with or without an ether bond and having 2 to 11 carbon atoms, the carbon number of the cyanoalkyl group with 2 to 11 carbon atoms is preferably 2 to 9, and 2 ~6 is preferred.

As a cyanoalkyl group which does not have an ether bond, a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, a 4-cyanobutyl group, a 6-cyanohexyl group, etc. are mentioned.

As a cyano group which has an ether bond, the group etc. which are represented by the following chemical formula (8) or (9) are mentioned.

[Chemistry 7] R ⁹ -OZ ⁴ -* (8) R ¹⁰ -OZ ⁵ -OZ ⁶ -* (9)

In the chemical 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 sum of the carbon atoms of R ⁹ and Z ⁴ is 4 ~11. * denotes a covalent bond.

In chemical 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 The total number of carbon atoms of R ¹⁰ , Z ⁵ , and Z ⁶ is 6-11. * denotes a covalent bond.

When R ² and R ³ represent an alkenyl group having 2 to 10 carbon atoms with or without an ether bond, the number of carbon atoms of the alkenyl group having 2 to 10 carbon atoms is preferably 2 to 9, preferably 2 to 6 is better.

As an alkenyl group which does not have an ether bond, a vinyl group, a propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, etc. are mentioned.

As an alkenyl group which has an ether bond, the group etc. which are represented by following chemical formula (10) or (11) are mentioned.

[Chemistry 8] R ¹¹ -OZ ⁷ -* (10) R ¹² -OZ ⁸ -OZ ⁹ -* (11)

In chemical 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 sum of the carbon atoms of R ¹¹ and Z ⁷ is 4 to 4 10. * denotes a covalent bond.

In chemical 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 , and the total number of carbon atoms of R ¹² , Z ⁸ and Z ⁹ is 6-10. * denotes a covalent bond.

When R ² and R ³ represent an aryl group having 6 to 20 carbon atoms with or without a substituent, the aryl group having 6 to 20 carbon atoms preferably has 6 to 10 carbon atoms.

As an unsubstituted aryl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, etc. are mentioned.

Examples of the substituted aromatic group include alkyl groups having 1 to 6 carbon atoms such as methyl and ethyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; and fluorine atoms. , chlorine atom and other halogen atoms; and other aromatic groups.

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

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

In chemical formulae (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 and a carbon number. It is an alkyl group of 1 to 6, or an aryl group of 6 to 20 carbon atoms with or without a substituent. n represents an integer from 1 to 10. *1 represents a covalent bond with a carbon atom, and *2 represents a covalent bond with a nitrogen atom.

When A ² and A ³ represent an alkylene group having 1 to 10 carbon atoms, the number of carbon atoms is preferably 1 to 8, more preferably 1 to 6.

Examples of the alkylene group having 1 to 10 carbon atoms include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, and pentamethylene; propane-1, Branched alkylene such as 2-diyl, butane-1,3-diyl and the like.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁴ , R ⁵ and R ⁶ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl. base, n-pentyl, n-hexyl, etc.

When R ⁴ , R ⁵ and R ⁶ represent an aryl group having 6 to 20 carbon atoms with or without a substituent, the number of carbon atoms of the aryl group having 6 to 20 carbon atoms is preferably 6 to 10.

As an unsubstituted aryl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, etc. are mentioned.

Examples of the substituted aromatic group include alkyl groups having 1 to 6 carbon atoms such as methyl and ethyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; and fluorine atoms. , chlorine atom and other halogen atoms; and other aromatic groups.

n is an integer of 1-10, preferably an integer of 1-5.

In chemical formula (2), m is an integer of 2 to 5, preferably 3 or 4.

In the present invention, a compound having a repeating unit represented by the following chemical formula (2) is preferably used as the zwitterionic polymer (α) from the viewpoint of easiness of acquisition.

[Chemistry 10]

[In chemical formula (2), R ¹ , R ² , R ³ , A ¹ and m have the same definitions as described above, respectively. ]

The zwitterionic monomer (a) used for synthesizing the zwitterionic polymer ( α ) can be appropriately determined according to the desired zwitterionic polymer.

For example, a zwitterionic polymer having a repeating unit represented by the chemical formula (2) can be synthesized by using the zwitterionic monomer represented by the following chemical formula (2A).

In the chemical formula (2A), R ¹ , R ² , R ³ , A ¹ , m and " ^-G- " have the same definitions as above, respectively.

The synthesis method of the zwitterionic monomer represented by the chemical formula (2A) is not particularly limited.

In the above chemical formula (2A), " ^-G- " represents a zwitterionic monomer of -COO- ^, for example, it can be obtained by combining the corresponding amine compound [the following chemical formula (2b)] with the molecular formula: hal-(CH ₂ ) _m -COOH (hal represents a halogen atom, and m represents the same definition as above.) It is obtained by a known method for preparing a carboxybetaine compound such as a method for reacting a halogenated carboxylic acid represented by (Japanese Patent Laid-Open Hei 2) No. 8-99945, Japanese Patent Laid-Open No. 7-278071, Japanese Laid-Open No. 2006-143634, Japanese Laid-Open No. 2006-143635, etc.).

Furthermore, in the above chemical _formula (2A), " ^-G- " represents a zwitterionic monomer of ^-SO3- [a compound represented by the following chemical formula (2a)], and as shown in the following reaction formula, it can be It can be obtained by reacting the corresponding amine compound (2b) with a sultone compound (2c).

In the above chemical formula, R ¹ to R ³ , A ¹ and m have the same definitions as above, and p is (m-2).

The amine compound (2b) can be prepared and obtained in a known manner.

Examples of the sultone compound (2c) include 1,2-ethane sultone, 1,3-propane sultone, 1,4-butane sultone, and 2,4-butane sultone , 1,5-pentane sultone.

These are known compounds and can be prepared and obtained by known methods. Furthermore, in the present invention, commercially available products can also be used as these sultone compounds.

In the reaction between the amine compound (2b) and the sultone compound (2c), the amount of the sultone compound (2c) used is preferably 0.8 to 1.2 equivalents, preferably 0.9 to 1.1 equivalents, relative to the amine compound (2b). is better. By making the usage-amount of a sultone compound (2c) into the said range, the process of removing an unreacted material can be abbreviate|omitted, or the time required for removal can be shortened.

The reaction of the amine compound (2b) and the sultone compound (2c) may be carried out without a solvent or in the presence of an inert solvent.

Examples of the inert solvent to be used include water; ether solvents such as tetrahydrofuran and diglyme; nitrile solvents such as acetonitrile and propionitrile; acetone and methyl ethyl ketone (methyl ethyl ketone). ethyl ketone) and other ketone solvents; toluene, xylene and other aromatic hydrocarbon solvents; chloroform and other halogenated hydrocarbon solvents; and other inert solvents.

When an inert solvent is used, the usage amount thereof is not particularly limited, but is usually 0.1 to 100 parts by mass, preferably 1 to 100 parts by mass, relative to 1 part by mass of the amine compound (2b).

The reaction temperature is not particularly limited, but is usually 0 to 200°C, preferably 10 to 100°C, and preferably in the range of 20 to 60°C. In addition, the reaction may be carried out under normal pressure (atmospheric pressure) or under pressurized conditions.

The reaction time is not particularly limited, but is usually 12 to 332 hours, preferably 24 to 168 hours.

This reaction is carried out under an inert gas atmosphere such as nitrogen gas, argon gas, etc., from the viewpoint of preventing a decrease in yield due to oxidation by oxygen or hydrolysis of the sultone compound (2c) by moisture in the air. good.

The progress of this reaction can be confirmed by general analytical methods such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR (nuclear magnetic resonance), and IR (infrared spectroscopy).

After the reaction is completed, general post-processing steps in organic synthetic chemistry can be carried out. According to requirements, purification can be carried out by known purification methods such as recrystallization and column chromatography to separate the desired amphoteric ionic monomer.

Among the zwitterionic monomers represented by the above-mentioned chemical formula (2A), in the present invention, sulfobetaine represented by the following chemical formula (2a) is used from the viewpoint of ease of acquisition and the like The structured compound is preferably used as a zwitterionic monomer.

[In chemical formula (2a), R ¹ , R ² , R ³ and m have the same definitions as described above, respectively. ]

In addition, in the present invention, as a commercial product of the zwitterionic monomer represented by the chemical formula (2A), it may be used as it is, or it may be used after purification as required.

The zwitterionic polymer (α) may have a repeating unit derived from a monomer which may be copolymerized therewith, in addition to the repeating unit derived from the zwitterionic monomer (a).

In the zwitterionic polymer (α), repeating units derived from monomers which may be copolymerized with the zwitterionic monomer (a) include repeating units derived from (meth)acrylic acid, (maleic) acid-derived repeating unit, repeating unit derived from crotonic acid, repeating unit derived from itaconic acid, etc. repeating unit having a carboxyl group; (Meth)acrylamide t-butylsulfonic acid-derived repeating unit having a sulfo group; repeating unit derived from (meth)acrylate such as methyl (meth)acrylate, ethyl methacrylate, etc.; Repeating units derived from (meth)acrylamide, etc. Here, (meth)acrylic acid means acrylic acid or methacrylic acid (the same applies hereinafter).

Among these materials, it is preferable to have a hydrophilic group as a repeating unit derived from a monomer which may be copolymerized with the zwitterionic monomer (a). Since the zwitterionic polymer (α) has these repeating units, the storage stability of the coating liquid tends to be further improved, and it becomes easier to obtain a hydrophilic layer with better hydrophilicity.

Examples of the hydrophilic group include a sulfo group (-SO ₃ H), a carboxyl group (-CO ₂ H), a phosphonic acid group (-PO ₃ H ₂ ), a hydroxyl group (-OH), and the above-mentioned groups react with bases Anionic hydrophilic groups such as formed groups; cationic hydrophilic groups such as substituted or unsubstituted amino groups, substituted or unsubstituted nitrogen-containing heterocyclic groups, and groups formed by the reaction of the above groups with acids; Wait.

Among these materials, as the hydrophilic group, an anionic hydrophilic group is preferred, and -SO ₃ H, -CO ₂ H, -PO ₃ H ₂ , or a group formed by reacting the above-mentioned groups with a base group is preferred.

Examples of the base for forming "the group formed by the reaction between the above-mentioned group and the base" include hydroxides or amine compounds of metals of Group 1 or Group 2 of the periodic table. Therefore, the repeating unit having "a group formed by the reaction of the above-mentioned group with a base" usually has an ion or ammonium ion of a metal of Group 1 or Group 2 of the periodic table, and is located in the entire zwitterionic monomer. electrically neutral state

From the viewpoint of obtaining more excellent effects of the present invention, the zwitterionic polymer (α) contained in the hydrophilic resin composition of the present invention has a molecule composed of the zwitterionic monomer (a) in the molecule. Preferred are copolymers of repeating units derived, and repeating units derived from monomers that may be copolymerized with the zwitterionic monomer (a).

In the zwitterionic polymer (α), the amount of repeating units derived from the zwitterionic monomer (a) is usually 50 to 100 mol % based on the entire zwitterionic polymer (α), with 60 mol % ~99 mol% is preferred, and 70-95 mol% is preferred. In the zwitterionic polymer (α), when the amount of the repeating unit derived from the zwitterionic monomer (a) is 50 mol % or more, the hydrophilicity increases. In addition, when it is 99 mol% or less, it becomes easier to introduce a crosslinking point, and the adhesion to a to-be-coated object is improved.

When the zwitterionic polymer (α) contains repeating units having a hydrophilic group, the amount of these repeating units is usually 0 to 50 mol % based on the entire zwitterionic polymer (α), with 1 to 40 mol % is preferred, and 5 to 30 mol % is preferred.

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

The synthesis method of the zwitterionic polymer (α) is not particularly limited. For example, by conducting a zwitterionic monomer (a), and a monomer comprising a monomer that may be copolymerized with the desired zwitterionic monomer (a) in the presence of a radical polymerization initiator The polymerization reaction of (monomer mixture) can synthesize a zwitterionic polymer (α).

As a radical polymerization initiator, an organic peroxide, an azo (azo) type compound, etc. are mentioned.

The organic peroxides include diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; 1,1-bis(tert-butyl) peroxy)cyclohexane (1,1-bis(t-butylperoxy)cyclohexane), 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane(1,1- Peroxy ketal (peroxy ketal) such as bis(t-butylperoxy)3,3,5-trimethylcyclohexane); diisopropyl peroxydicarbonate (diisopropyl peroxydicarbonate), di-2-ethylhexyl peroxydicarbonate Peroxydicarbonate (peroxydicarbonate) such as ester (di-2-ethylhexyl peroxydicarbonate); t-butylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate peroxyesters such as t-butylperoxyisobutyrate; etc.

As the azo compound, 2,2'-azobisisobutyronitrile (2,2'-azobisisobutyronitrile), 2,2'-azobis(2-methylbutyronitrile) (2,2'-azobis(2-methylbutyronitrile) )), 1,1'-azobis(cyclohexane-1-carbonitrile)(1,1'-azobis(cyclohexane 1-carbonitrile)), 2,2'-azobis(2,4-dimethylene) valeronitrile) (2,2'-azobis(2,4-dimethylvaleronitrile)), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) 2,2'- azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate) (dimethyl 2,2'-azobis(2-methylpropionate)), 2, 2'-azobis(N-butyl-2-methylpropionamide) (2,2'-azobis(N-butyl-2-methylpropionamide)), dimethyl 1,1'-azobis( Oil-soluble azo polymerization initiators such as 1-cyclohexanecarboxylate (dimethyl 1,1'-azobis(1-cyclohexanecarboxylate)); 4,4'-azobis(4-cyanovaleric acid) ( 4,4'-azobis(4-cyanovaleric acid)), 2,2'-azobis(2-hydroxymethylpropionitrile), 2,2'-azobis[2-(2-imidazoline-2 -yl)propane](2,2'-azobis[2-(2-imidazolin-2-yl)propane]), 2,2'-azobis(2,4-dimethyl-4-methoxy Valeronitrile) (2,2'-azobis(2-hydroxymethylpropionitrile)), 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (2,2'- azobis(2,4-dimethyl-4-methoxyvaleronitrile)), 2,2'-azobis[2-(2-imidazolin-2-yl)propane]disulfonate dihydrate (2,2'- azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride), 2,2'-azobis(2-methylpropionamidine) dihydrochloride (2,2'-azobis(2-methylpropionamidine) dihydrochloride), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate (2,2'-azobis [N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamidine](2,2'-azobis [2-methyl-N-(2-hydroxyethyl)propionamide]) and other water-soluble azo polymerization initiators; etc.

The above-mentioned materials may be used alone or in combination of two or more.

The amount of the radical polymerization initiator to be used is usually 0.0001 to 0.1000 mol relative to 1 mol of the monomer used in the polymerization reaction (however, in the case of a copolymer, it is the total mol of the monomer) , preferably 0.0005~0.0050 mol.

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

The obtained reaction solution can be directly used to prepare a hydrophilic composition, or the zwitterionic polymer can be separated and purified according to a general method.

The hydrophilic layer may contain an ionic compound (however, zwitterionic polymer (α) is excluded).

As the ionic compound, an ionic compound having a cation having 0 to 10 carbon atoms is preferred, and an ionic compound having a cation having 0 carbon atoms is preferred.

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

[Chemistry 14] MX (12) M'X ₂ (13) M ₂ X' (14) M'X' (15)

In the chemical formulae (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, X represents a monovalent anion, and X represents a monovalent cation. ' represents a divalent anion.

Examples of M include alkali metal ions such as sodium ions and potassium ions; ammonium ions (NH ₄ ⁺ ); primary amine ions; secondary amine ions; tertiary amine ions;

Examples of M' include alkaline earth metals such as calcium ions; magnesium ions; and the like.

Examples of X include halide ions such as chloride ions and bromide ions; hydrogen carbonate ions; nitrate ions; and the like.

Examples of X' include carbonate ions, sulfate ions, and the like.

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 , Alkali metal salts such as _KNO3 ; magnesium salts such as _MgCl2 , _MgSO4 ; alkaline earth metals such as _CaCl2 ; ammonium salts such as _NH4Cl ;

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, etc.

The ionic compound may be used alone or in combination of two or more.

The content of the ionic compound in the hydrophilic layer is usually 0 to 70% by mass, preferably 2 to 50% by mass, and more preferably 5 to 20% by mass, based on the entire hydrophilic layer.

The hydrophilic layer may contain polymers other than the zwitterionic polymer (α).

Examples of polymers other than the zwitterionic polymer (α) include polyester-based polymers, ethylene-vinyl alcohol copolymers, vinyl alcohol monomers, and (meth)propylene ((meth)acrylic) acid polymer, (meth)acrylate polymer, urethane polymer, acrylic-urethane polymer, polyamide resin, polyolefin resin, Cellulose (cellulose) resins, etc.

Polymers other than the zwitterionic polymer (α) may 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 thereof is usually 1 to 40% by mass, preferably 2 to 20% by mass, based on the entire hydrophilic layer.

The hydrophilic layer may also form a cross-linked structure. The cross-linked structure in the hydrophilic layer can be effectively formed, for example, by using a cross-linking agent.

The crosslinking agent refers to a compound that reacts 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.

Examples of the crosslinking agent include epoxy-based crosslinking agents, isocyanate-based crosslinking agents, amine-based crosslinking agents, melamine-based crosslinking agents, aziridine-based crosslinking agents, Hydrazine-type cross-linking agent, aldehyde-type cross-linking agent, oxazoline-type cross-linking agent, metal alkoxide-type cross-linking agent, metal chelate-type cross-linking agent , metal salt crosslinking agent, ammonium salt type crosslinking agent, etc.

The hydrophilic layer may contain additives within a range that does not impair the effects of the present invention.

As an additive, a surfactant, a moisturizing agent, a viscosity modifier, a dye, etc. are mentioned.

The thickness of the hydrophilic layer is usually 1 to 1000 nm, preferably 2 to 800 nm.

The method of forming the hydrophilic layer is not particularly limited. For example, the hydrophilic layer may be formed according to a method described later.

[Hydrophilic structure]

The hydrophilic structure system of the present invention has a hydrophilic structure of a layered structure formed by sequentially laminating the aforementioned substrate, the aforementioned intermediate layer, and the aforementioned hydrophilic layer.

The hydrophilic layer of the hydrophilic structure of the present invention has excellent hydrophilicity.

On the hydrophilic layer of the hydrophilic structure of the present invention, after dropping 2 μL of ion-exchanged water, the contact angle of water droplets after dropping for 3 seconds (water before washing) was measured using a contact angle measuring device. Contact angle), the water contact angle is usually 70° or less, preferably 60° or less, more preferably 50° or less. There is no specific lower limit, but it is usually 3° or more.

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

The hydrophilic structure of the present invention has excellent adhesion between the hydrophilic layer and the intermediate layer. This is considered to be due to the entanglement of the siloxane-based polymer and the zwitterionic polymer (α) at the interface between the intermediate layer and the hydrophilic layer.

The hydrophilic layer of the hydrophilic structure of the present invention has excellent water resistance. In the present invention, the term "water resistance" means that the initial 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 enhanced by contact with water. As described above, it is considered that this phenomenon is also caused by the entanglement of the siloxane-based polymer and the zwitterionic polymer (α).

That is, it is considered that the siloxane-based polymer and the zwitterionic polymer (α) are strongly entangled because the polymer chains that are hardly entangled in the surface portion of the hydrophilic layer are removed by contact with water. The area is exposed from the surface. Then, it is considered that the hydrophilicity of the hydrophilic layer is further improved due to the exposure of this region.

The surface of the hydrophilic layer of the hydrophilic structure of the present invention is washed with deionized water and dried, and then the water contact angle (water contact angle before washing) is measured by the same method as above. The water contact angle is usually 40° or less. , preferably below 30°, more preferably below 10°. There is no specific lower limit, but it is usually 3° or more.

As the hydrophilic structure of the present invention, functional films such as antifogging films and antifouling films can be exemplified.

In addition, the hydrophilic structure of this invention is not limited to a film layer product. For example, the hydrophilic structure of the present invention can be used for products that require hydrophilicity, such as mirrors, displays, signboards, guide boards, road signs, outer walls of buildings, and window glass.

The manufacturing method of the hydrophilic structure of this invention is not specifically limited. For example, the hydrophilic structure of the present invention can be produced by a method including the following steps (1) to (3).

Step (1): Coating a coating solution containing a hydrolyzable organosilicon compound (a coating solution containing a hydrolyzable organosilicon compound) on a substrate, by applying the hydrolyzable organic The silicon compound is hydrolyzed and polycondensed to form a coating film containing siloxane-based polymers; step (2): in the state where the coating film containing the siloxane-based polymer is completely dried, or the solvent remains in the coating film In this state, on the aforementioned coating film, a coating solution (A) containing a zwitterionic polymer having no silicon atoms and a zwitterionic polymer having no silicon atoms is applied to form the aforementioned coating solution (A). The coating film of A); step (3): drying the coating film in the undried state in the structure having the laminated structure obtained in the step (2).

In step (1), the coating solution containing the hydrolyzable organosilicon compound is applied on the substrate, and the hydrolyzable organosilicon compound in the obtained coating film is hydrolyzed and polycondensed to form a hydrolyzable organosilicon compound. Alkane polymer coating.

The solvent contained in the coating liquid is not particularly limited as long as it can dissolve or disperse components such as a hydrolyzable organosilicon compound.

As a solvent, water, a water-miscible organic solvent, etc. are mentioned.

Examples of the water-miscible organic solvent include alcohols such as methanol, ethanol, n-propanol, and isopropanol; ketones such as acetone and methyl ethyl ketone; Polyalkylene glycols such as ethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycols; N-methyl-2-pyrrolidone ) etc. of lactams; etc.

These solvents may be used alone or in combination of two or more.

Among these materials, a mixed solvent of water and alcohol is preferable as the solvent.

The content of the solvent is preferably adjusted to the solid content concentration of the coating liquid containing the hydrolyzable organosilicon compound to be 0.1 to 30.0 mass %, more preferably 0.5 to 10.0 mass %.

The coating method of the said coating liquid is not specifically limited. For example, bar coat method, knife coat method, roll coat method, blade coat method, die coat method, gravure coat method can be used (gravure coating) method, etc., the coating liquid is applied on the substrate.

The method of hydrolyzing and polycondensing the hydrolyzable organosilicon compound is not particularly limited. The hydrolysis polycondensation reaction can be accelerated by using a catalyst or heating as required.

In the hydrolysis polycondensation reaction, the reaction temperature 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 carried out by heating, drying of the coating film is usually also performed by this heat treatment. As described later, the next step (2) may be performed after the coating film is completely dried, or the next step (2) may be performed in a state where the coating film is not completely dried (a state in which the solvent remains in the coating film). . The degree of entanglement between the siloxane-based polymer and the zwitterionic polymer ( α ) can be adjusted by controlling the drying state of the coating film during the step (2).

In step (2), in a state in which the coating film containing the siloxane-based polymer is completely dried, or in a state in which the solvent remains in the coating film, on the coating film, a coating film containing no silicon atom is applied. The coating liquid (A) of the zwitterionic polymer which does not contain the zwitterionic polymer having a silicon atom is used to form the coating film of the aforementioned coating liquid (A).

By applying the coating solution (A) in a state where the coating film containing the siloxane-based polymer is completely dried, a hydrophilic structure (that is, a silicon A hydrophilic structure in which the oxane-based polymer and the zwitterionic polymer ( α ) are entangled with each other in a thin region).

On the other hand, by applying the coating solution (A) with the solvent remaining in the coating film containing the siloxane-based polymer, a hydrophilic structure (also known as a hydrophilic structure) having no clear boundary between the intermediate layer and the hydrophilic layer can be obtained. That is, the siloxane-based polymer and the zwitterionic polymer ( α ) are entangled with each other in a thick hydrophilic structure).

As described above, the degree of entanglement between the siloxane-based polymer and the zwitterionic polymer ( α ) affects the adhesion and water resistance of the hydrophilic layer.

Therefore, by appropriately controlling the drying state of the coating film containing the siloxane-based polymer at the beginning of the step (2), a hydrophilic layer having 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.

As a solvent, water, a water-miscible organic solvent, etc. are mentioned.

Examples of the water-miscible organic solvent include alcohols such as methanol, ethanol, n-propanol, and isopropanol; ketones such as acetone and methyl ethyl ketone; ethylene glycol, diethylene glycol, propylene glycol, and the like. polyalkylene glycols; alkyl ethers of polyalkylene glycols; lactamides such as N-methyl-2-pyrrolidone; etc.

These solvents may be used alone or in combination of two or more.

Among these materials, a mixed solvent of water and alcohol is preferable as the solvent.

The content of the solvent is preferably adjusted to 0.1 to 20 mass %, more preferably 0.5 to 10 mass %, by adjusting the solid content concentration of the coating liquid (A).

The coating method of the said coating liquid is not specifically limited. For example, the coating liquid (A) can be applied by the same coating method shown as the coating liquid containing the hydrolyzable organosilicon compound.

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

Here, the coating film in the undried state is referred to as "the coating film obtained from the coating liquid (A)" when the step (2) is performed in a state where the coating film containing the siloxane-based polymer is completely dried. , and in the case of performing step (2) in a state where the solvent remains in the coating film containing the siloxane-based polymer, it is called "the coating film containing the siloxane-based polymer" and "the coating solution (A) ) obtained coating film”.

The method of drying the coating film is not particularly limited. For example, previously 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.

The drying temperature is usually 60~130℃, preferably 70~120℃.

The drying time (heating time) is usually 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples in any way.

Unless otherwise specified, the parts and % in each example are based on mass.

[Mass average molecular weight (Mw)]

The mass average molecular weight (Mw) of the zwitterionic polymer can be obtained by gel permeation chromatography (GPC) under the following conditions.

Device: HLC-8320 GPC/UV-8320 (manufactured by Tosoh Co., Ltd.)

Column: TSKgel GMPW _XL (manufactured by Tosoh Co., Ltd.) × 2

Detector: HLC-8320 GPC built-in RI detector/UV-8320 (made by Tosoh Co., Ltd.)

Column temperature: 40℃

Sample concentration: 1.0g/L (polymer component concentration)

Injection volume: 100 μL

Eluent: 0.2M _NaNO in water

Flow rate: 1.0mL/min

Molecular weight markers: standard polyethylene oxide, polyethylene glycol

[Production Example 1] Synthesis of Zwitterionic Monomer (1)

100 parts of N-[3-(dimethylamino)propyl]acrylamide, 0.4 parts of dibutylhydroxytoluene, and 383 parts of acetone were added to a reaction vessel with a stirring device, and the contents were put aside. While stirring, 72 parts of propane sultone was gradually added dropwise. After that, the contents were stirred at 25° C. for 24 hours, and the precipitated white solid was collected by filtration and dried to obtain zwitterionic monomer (1) (N-acrylamidopropyl-N,N- Dimethylammoniumpropyl-α-sulfinylbetaine).

[Production Example 2] Synthesis of Zwitterionic Monomer (2)

100 parts of N-[3-(dimethylamino)propyl]methacrylamide, 0.4 parts of dibutylhydroxytoluene, and 383 parts of acetone were added to a reaction vessel with a stirring device, and the contents were mixed. 72 parts of propane sultone was slowly dropped into the mixture while stirring. After that, the contents were stirred at 25° C. for 24 hours, and the precipitated white solid was collected by filtration and dried to obtain zwitterionic monomer (2) (N-methacrylamidopropyl-N, N-dimethylammoniumpropyl-α-sulfinylbetaine).

[Production Example 3] to [Production Example 8] Synthesis of Zwitterionic Polymer

Each monomer was put into a reaction vessel equipped with a stirring device so as to have the molar ratio shown in Table 1, and the total amount of each monomer was 100 parts, and a polymerization initiator (Wako Pure Chemical Industries, Ltd. Manufacturing, product name is "V-501", 0.19 part of 4,4'-azobis(4-cyanovaleric acid)) was added, the diluting solvent shown in Table 1 was added, and nitrogen gas was introduced into the reaction vessel while the Stir at 25°C for 30 minutes. Then, the temperature of the reaction system was raised to 80° C., and the polymerization reaction was carried out by stirring for 16 hours, and a solution containing each zwitterionic polymer with a solid content concentration of 30% was obtained. Table 1 shows the mass average molecular weight of each zwitterionic polymer obtained. Abbreviations and the like in Table 1 are as follows.

In addition, regarding the zwitterionic polymers of Production Example 7 and Production Example 8, since precipitation occurred during the polymerization reaction, the measurement of molecular weight was omitted, as described later.

<single body>

SBAAm: (N-acrylamidopropyl-N,N-dimethylammoniumpropyl-α-sulfinylbetaine)

SBMAAm: (N-methacrylamidopropyl-N,N-dimethylammoniumpropyl-α-sulfinylbetaine)

ATBS: acrylamide tert-butylsulfonic acid

AAc: Acrylic

VTMS: Vinyltrimethoxysilane

<Dilution solvent>

Water: Distilled water

TFE: trifluoroethanol

In the following Examples and Comparative Examples, in addition to the zwitterionic polymer solutions prepared in Production Examples 3 to 8, hydrophilic structures were produced using the raw materials shown below.

(base)

Substrate (1): manufactured by Toyobo Co., Ltd., product name "COSMOSHINE A4100", thickness 50 μm .

Substrate (2): manufactured by Toray Co., Ltd., product name "LUMIRROR 50T60", thickness 50 μm .

(Alcoholic Silica Sol)

Ethanol-based silica sol (1): manufactured by Colcoat Co., Ltd., product name "N-103X", and solid content concentration of 2.0%.

Ethanol-based silica sol (2): manufactured by Colcoat Co., Ltd., product name "PC-291", and solid content concentration of 2.5%.

(Aqueous polyester resin)

Aqueous polyester resin (1): an aqueous polyester resin having a repeating unit represented by the following chemical formula (16). The mass average molecular weight (Mw) was 16,000.

Aqueous polyester resin (2): An aqueous polyester resin composed of a copolymer having a repeating unit represented by the following chemical formula (16) and a repeating unit derived from methyl acrylate.

[Example 1]

To 100 parts (solid content) of the zwitterionic polymer solution prepared in Production Example 3, a 5% sodium chloride aqueous solution was added to adjust the solid content of sodium chloride to the value described in Table 2, and Distilled water was mixed to obtain a coating liquid for forming a hydrophilic layer with a solid content concentration of 3%.

Separately from the above, the ethanolic silica sol (1) is coated on the easy-adhesion surface of the substrate (1) with a wire bar to a thickness of 100 nm after drying. The obtained laminate was heated at 80°C for 1 minute. After heating, the coating film in the laminate was not completely dried.

Next, the aforementioned coating liquid for forming a hydrophilic layer is applied thereon to obtain a structure having a laminated structure. Next, by heating this structure at 120 degreeC for 1 minute, the coating film in the undried state in this structure was dried, and a hydrophilic structure was obtained.

[Examples 2 to 11]

The preparation of the hydrophilic structure was carried out in the same manner as in Example 1 except that the conditions described in Table 2 were used to obtain a hydrophilic structure.

[Comparative Example 1]

100 parts (solid content) of the zwitterionic polymer solution prepared in Production Example 5 was mixed with 500 parts of trifluoroethanol (TFE) to obtain a coating solution for forming a hydrophilic layer.

On the easy-adhesion surface of the substrate (1), the aforementioned coating liquid for forming a hydrophilic layer is applied to obtain a structure having a laminated structure. Next, by heating this structure at 100 degreeC for 1 minute, the said coating film was dried, and a hydrophilic structure was obtained.

[Comparative Example 2]

To 100 parts (solid content) of the zwitterionic polymer solution prepared in Production Example 3, a 5% sodium chloride aqueous solution was added to adjust the solid content of sodium chloride to the value described in Table 2, and Distilled water was mixed to obtain a coating liquid for forming a hydrophilic layer with a solid content concentration of 3%.

When the aforementioned coating liquid for forming a hydrophilic layer is applied to the easy-adhesion surface of the substrate (1), the coating liquid is blocked on the substrate (1) and cannot be applied.

[Comparative Example 3]

The ethanolic silica sol (1) is coated on the easy-adhesion surface of the substrate (1) by using a coating rod to a thickness of 100 nm after drying. The resulting laminate was heated at 120° C. for 1 minute to obtain a hydrophilic structure.

[Comparative Example 4]

For the purpose of forming a film layer containing a zwitterionic polymer having a silicon atom, by the method of Production Example 7, an attempt was made to synthesize a zwitterionic polymer having a silicon atom.

However, precipitation occurred during the polymerization reaction, and thus a coating liquid could not be obtained.

[Comparative Example 5]

For the purpose of forming a film layer containing a zwitterionic polymer having a silicon atom, by the method of Production Example 8, an attempt was made to synthesize a zwitterionic polymer having a silicon atom.

However, precipitation occurred during the polymerization reaction, and thus a coating liquid could not be obtained.

[Comparative Example 6]

To 100 parts (solid content) of the zwitterionic polymer solution prepared in Production Example 6, a 5% sodium chloride aqueous solution was added to adjust the solid content of sodium chloride to the value described in Table 2, and Distilled water was mixed to obtain a coating liquid for forming a hydrophilic layer with a solid content concentration of 3%.

Separately from the above, the coating liquid containing the aqueous polyester resin (1) was applied on the easy-adhesion surface of the substrate (1) using a coating bar to a thickness of 100 nm after drying. The obtained laminate was heated at 80°C for 1 minute. After heating, the coating film in the laminate was not completely dried.

Next, the aforementioned coating liquid for forming a hydrophilic layer is applied thereon to obtain a structure having a laminated structure. Next, by heating the structure at 100° C. for 1 minute, the coating film in the undried state in the structure was dried to obtain 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 hydrous polyester resin (2) was used instead of the coating liquid containing the hydrous polyester resin (1).

[Measurement of water contact angle]

On the hydrophilic layer of the hydrophilic structures obtained in Examples and Comparative Examples, 2 μL of ion-exchanged water was dropped. Using an automatic contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., DM-701), the water contact angle of the water droplet (water contact angle before washing) was measured 3 seconds after dropping.

[Evaluation of water resistance]

The surfaces of the hydrophilic layers of the hydrophilic structures obtained in the Examples and Comparative Examples were washed with ion-exchanged water and dried, and then the water contact angle (water contact angle after washing) was measured by the same method as above. Water resistance was evaluated according to the following criteria.

A: The water contact angle after cleaning is equal to or smaller than the water contact angle before cleaning.

B: The water contact angle after cleaning is greater than the water contact angle before cleaning.

[Evaluation of Adhesion of Hydrophilic Layer]

Cellophane (registered trademark) manufactured by NICHIBAN Co., Ltd. was stuck to the hydrophilic layer of the hydrophilic structure obtained in the Example and the comparative example, and it 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 as follows.

A: The hydrophilic layer was not peeled off.

B: The hydrophilic layer is partially peeled off.

C: The hydrophilic layer was completely peeled off.

[Evaluation of contamination resistance of hydrophilic layer]

The hydrophilic layers of the hydrophilic structures obtained in Examples and Comparative Examples were colored with an oil-based pen (Mackie) manufactured by Zebra Co., Ltd., and used as experimental samples. This experimental sample was immersed in distilled water and shaken, and then the distilled water was wiped off using a non-woven wiper (manufactured by Asahi Kasei Co., Ltd., trade name "Bemcot"). After repeating this operation 2 times, the surface state was observed and the stain resistance was evaluated. The evaluation criteria are as follows.

A: The ink of the oil-based pen is completely removed.

B: The ink of the oil-based pen was removed but partially remained.

C: More than half of the ink of the oil-based pen was not removed.

The following points can be learned from Table 3.

The hydrophilic layers of the hydrophilic structures of Examples 1 to 11 had excellent hydrophilicity, stain resistance, adhesion, and water resistance.

The hydrophilic structures of Comparative Examples 1 to 2 are hydrophilic structures that attempt to form a hydrophilic layer directly on a substrate. However, in Comparative Example 1, a hydrophilic layer having the same performance as the Example could not be formed. Furthermore, in Comparative Example 2, the substrate could not be uniformly coated, and thus the hydrophilic layer could not be formed.

In addition, the hydrophilic structure of Comparative Example 3 has the intermediate layer of the present invention on the surface. The hydrophilicity of this layer is insufficient.

In Comparative Examples 4 and 5, as described above, the zwitterionic polymer could not be synthesized.

In the hydrophilic structures of Comparative Examples 6 and 7, an intermediate layer containing a hydrous polyester resin was formed, and a hydrophilic layer was formed thereon. However, the water resistance of this hydrophilic layer is poor.

Claims (7)

A hydrophilic structure, which is a hydrophilic structure with a layered structure formed by sequentially laminating a substrate, an intermediate layer and a hydrophilic layer, wherein the intermediate layer is a film layer containing siloxane-based polymers, and the The hydrophilic layer is a film layer that contains a zwitterionic polymer without silicon atoms and does not contain a zwitterionic polymer with silicon atoms, wherein the aforementioned zwitterionic polymer without silicon atoms has the following chemical formula (2) Polymers of repeating units shown:

In the chemical formula, 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 with or without an ether bond, and a group with or without an ether bond. A cyanoalkyl group with 2 to 11 carbon atoms, an alkenyl group with 2 to 10 carbon atoms with or without an ether bond, or an aryl group with 6 to 20 carbon atoms with or without a substituent , in addition, R ² and R ³ can also be bonded to each other to form a ring, and A ¹ represents a divalent group represented by any one of the following chemical formulas (3) to (5):

(In the chemical 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 each independently represent a hydrogen atom and an alkane having 1 to 6 carbon atoms. base, or, with or without a substituent, an aromatic group with 6 to 20 carbon atoms, n represents an integer from 1 to 10, * 1 represents a covalent bond with a carbon atom, and * 2 represents a covalent bond with a nitrogen atom Valence bond) m represents an integer from 2 to 5. The hydrophilic structure according to claim 1, wherein the substrate is a resin film. The hydrophilic structure according to claim 1, wherein the siloxane-based polymer is a hydrolyzable polycondensate of a hydrolyzable organosilicon compound. The hydrophilic structure described in claim 3, wherein the hydrolyzable organosilicon compound is a silicon compound represented by the following chemical formula (1), or a hydrolyzed polycondensate of a silicon compound represented by the following chemical formula (1). : Si(R ^a ) _q (R ^b ) _4-q (1) (In the chemical formula, R ^a represents a hydrogen atom or a non-hydrolyzable organic group, R ^b represents a hydrolyzable group, and q represents 0~2 integer.) The hydrophilic structure according to claim 1, wherein the zwitterionic polymer having no silicon atom has repeating units derived from zwitterionic monomers, and has a carboxyl group, a sulfo group, or the aforementioned groups A polymer of repeating units (but excluding repeating units derived from zwitterionic monomers) of groups obtained by reaction with bases. The hydrophilic structure according to claim 1, wherein the hydrophilic layer is a membrane layer further containing an ionic compound having a cation having 0 to 10 carbon atoms. A manufacturing method of a hydrophilic structure, comprising the following steps (1) to (3), to manufacture the hydrophilic structure as described in any one of items 1 to 6 of the patent application scope: step (1): on a substrate A coating solution containing a hydrolyzable organosilicon compound is applied on top, and a coating film containing a siloxane-based polymer is formed by hydrolyzing and polycondensing the hydrolyzable organosilicon compound in the obtained coating film; step (2) ): apply a zwitter ion containing no silicon atom on the coating film in a state where the coating film containing the siloxane-based polymer is completely dried, or in a state where the solvent remains in the coating film A coating solution (A) of polymer and no zwitterionic polymer having silicon atoms to form a coating film of the aforementioned coating solution (A); The coating film in the undried state in the structure of the laminated structure dries.