TW201305221A - Single-layer film and hydrophilic material constituted by the same - Google Patents

Abstract

The present invention provides a single-layer film containing hydrophilicity, and having not only excellent anti-fog, anti-fouling, anti-static, and anti-dewing properties, but also excellent transparency even when the film thickness is enlarged, while containing the tendency of excellent scratch resistance, and a laminated body containing the single-layer film. The present invention is to prepare a mixture, which contains a monomer composition and a solvent. The monomer composition is to contain a specific monomer and a multivalent monomer containing more than two (meth)acryl groups and not containing sulfo group, carboxyl group and phosphoryl group in a specific molar ratio, and the solvent is in a specific range of solubility parameter <sigma>; the mixture is coated onto a substrate, and then at least a part of solvent is removed and the monomer composition is polymerized, thereby preparing a single-layer film containing at least a anionic hydrophilic group selected from sulfo group, carboxyl group and phosphoryl group and with an anionic concentration ratio (Sa/Da) of the anionic concentration (Sa) of the external surface to the anionic concentration (Da) of the middle location of the internal surface and external surface of the contact substrate being a specific range.

Description

Monolayer film and hydrophilic material composed thereof

The present invention relates to a single layer film excellent in antifogging property, antifouling property, and antistatic property, and also excellent in transparency and scratch resistance, and a laminate having the single layer film.

In recent years, there has been an increase in demand for fogging and contaminants for improving a substrate formed of an inorganic material such as plastic or an inorganic material such as glass.

As a method for solving the problem of fogging, a method of improving hydrophilicity and water absorption through an antifogging paint containing a reactive surfactant or an acrylic oligomer has been proposed (for example, see Non-Patent Document 1). In addition, as a means of solving the problem of the contamination, it has been proposed to improve the hydrophilicity of the surface of the material, and to remove the dirt adhering to the external hydrophobic material such as the outer wall by spraying water or rain (for example, refer to the non-patent literature). 2 and 3).

A method of using a hydrophilic material such as a hydrophilic resin can be considered before solving problems such as fogging and soiling. As the hydrophilic resin, many resins having many hydroxyl groups in the molecule such as polyvinyl alcohol are known.

As another hydrophilic resin, for example, 3-sulfopropyl methacrylate ‧ potassium salt, 2-propenyl guanamine-2-methylpropane sulfonic acid ‧ sodium salt, and polyethylene glycol diacrylate are known to be polymerized The obtained resin (for example, refer to Patent Document 1); a resin obtained by polymerizing 3-sulfopropyl methacrylate ‧ sodium salt and long-chain urethane diacrylate (for example, refer to Patent Document 2); a resin obtained by polymerizing sulfoethyl ester, tetrahydrofurfuryl acrylate, trimethylolpropane acrylate, and snail glycol urethane diacrylate (for example, refer to Patent Document 3); a sulfoethyl ester and/or a resin obtained from a (meth) acrylate having a phosphate group and an epoxy resin (for example, refer to Patent Document 4); hydroxyethyl methacrylate or sulfoalkyl methacrylate (C6 to C10) A resin obtained by polymerizing an ester and methylene bis acrylamide (for example, see Non-Patent Document 4).

The hydrophilic resin of the above Patent Document 1 is transparent gel and can be used as a bioadhesive. The hydrophilic resin of the above-mentioned Patent Document 2 is excellent in ink absorbability and high in water resistance, and can be used as a recording material for a non-sticking ink jet recording method, and a hydrophilic resin of Patent Document 3 can be used for optical data. The metal protrusion for the disc drive is strongly bonded to the resin substrate. The hydrophilic resin of the above-mentioned Patent Document 4 can be used as an electrically conductive cured film which is excellent in mechanical properties, solvent resistance, film forming properties, adhesive properties, transparency, and abrasion resistance. In the above-mentioned Non-Patent Document 4, it is known that the hydrophilicity of the film composed of the micro-crosslinked hydrophilic resin formed on the glass is due to the use of the alkyl chain length of the sulfoalkyl methacrylate as a monomer (C6 to C10). And change (advancing contact angle and receding contact angle), and also due to hydration time.

However, most of the above hydrophilic resins have a low degree of cross-linking between molecules, and have high water solubility, and even if they are not water-soluble, they tend to absorb water and tend to be gel-like. Moreover, since the degree of cross-linking between molecules is small, the surface is soft and sometimes susceptible to damage.

Further, the hydrophilic resin of the above part is insufficient in hydrophilicity, and it cannot be said that it is sufficient as an antifogging material and an antifouling material.

On the other hand, in Patent Document 5, it is proposed to apply a cross-linkable polymerizable monomer composition to the surface of the substrate, control the amount of ultraviolet irradiation to form a cross-linked polymer which is incompletely polymerized, and secondly apply a hydrophilic monomer and irradiate it again. Ultraviolet rays, whereby the hydrophilic monomer is subjected to block or graft polymerization on the surface of the crosslinked polymer, and the obtained hydrophilic material having a two-layer structure is applied twice.

However, this two-time coating method is cumbersome and costly compared to the conventional one-layer structure method, and sometimes the surface smoothness is impaired.

As a means for solving the above problems, the inventors of the present invention have previously proposed a polymer obtained from a hydroxyl group-containing (meth) acrylamide (see Patent Document 6).

However, in consideration of the case of using as an antifouling film or an antifogging film, there is still room for further improvement in physical properties.

In addition, the inventors of the present invention have previously proposed a single-layer film in which a specific anionic hydrophilic group is present at a high concentration on the surface (see Patent Document 7).

However, in consideration of the case of using as an antifouling film or an antifogging film, there is still room for further improvement in physical properties.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2002-521140

Patent Document 2: Japanese Patent Laid-Open No. Hei 11-115305

Patent Document 3: Japanese Patent Laid-Open Publication No. Hei 08-325524

Patent Document 4: Japanese Patent Publication No. Sho 53-010636

Patent Document 5: Japanese Patent Laid-Open No. 2001-98007

Patent Document 6: International Publication No. 2004/058900

Patent Document 7: International Publication No. 2007/064003

[Non-patent literature]

Non-Patent Document 1: East Asian Synthetic Research Annual Report, TREND February 1999, 39~44

Non-Patent Document 2: Polymer, 44(5), page 307

Non-Patent Document 3: Future Materials, 2(1), 36-41

Non-Patent Document 4: Journal of Colloid and Interface Science, vol. 110(2), 468-476 (1986)

The present invention provides hydrophilicity, is excellent not only in antifogging property, antifouling property, antistatic property, and dew condensation property, but also has excellent transparency and excellent scratch resistance even when the film thickness is increased. A single layer film and a laminate having the single layer film are problems.

In order to solve the above problems, the inventors of the present invention have repeatedly found a single layer produced by mixing a monomer mixture containing a specific monomer and a specific polyvalent monomer with a specific solvent in a specific mixing ratio. The film is hydrophilic, and is excellent not only in antifogging property, antifouling property, antistatic property, and dew prevention property, but also has excellent transparency and excellent scratch resistance even when the film thickness is increased, and thus the film is completed. this invention.

That is, the single layer film of the present invention is a mixture comprising: a monomer (I) represented by the following general formula (1), and having two or more (meth)acryl fluorenyl groups and having no sulphur a polyvalent monomer (II) having an acid group, a carboxyl group and a phosphoric acid group, and a monomer having a monomer (I)/multivalent monomer (II) molar ratio of 1/1000 or more and less than 1/30. a composition; and a solvent containing a compound having a solubility parameter σ of 9.3 (cal/cm ³ ) or more; after applying the mixture to the substrate, removing at least a portion of the solvent, and containing the monomer (I) and the monomer ( The monomer composition of II) is obtained by polymerization, wherein at least one anionic hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxyl group and a phosphoric acid group, and an anion concentration (Sa) of the outer surface and contact with the substrate The anion concentration ratio (Sa/Da) of the anion concentration (Da) at the intermediate point between the inner surface and the outer surface is 1.1 or more.

[X] _s [M1] _l [M2] _m (1)

(In the above formula (1), s represents 1 or 2, and l and m represent integers satisfying s=l+m/2. M1 is at least one monovalent cation selected from hydrogen ions, ammonium ions and alkali metal ions. M2 is at least one divalent cation selected from the group consisting of alkaline earth metal ions, and X is at least one monovalent anion selected from the group represented by the following general formulas (1-1) to (1-4).

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4]

(In the above formulae (1-1) to (1-4), J and J' are each independently H or CH ₃ , n represents 0 or 1, and R is independently an aromatic group, an aliphatic cyclic group, or an ether group. And at least one selected from the group of esters is substituted with an aliphatic hydrocarbon group having 1 to 600 carbon atoms.)

The monomer (I) is preferably at least one selected from the group consisting of the compounds represented by the following general formula (1-1-1) and the general formula (1-1-2).

[Chemical 5]

[Chemical 6]

(In the formulae (1-1-1) and (1-1-2), J is H or CH ₃ , and R ₁ and R ₂ are each independently H, CH ₃ or C ₂ H _{3 .} n represents 1 to 20 An integer, 1 represents an integer from 2 to 10, and M is at least one monovalent cation selected from the group consisting of hydrogen ions, ammonium ions, and alkali metal ions, or at least one divalent cation selected from alkaline earth metal ions, and M is a valence of 1 In the case of a cation, m is 1, and when M is a divalent cation, m is 2.)

The polyvalent monomer (II) is preferably at least one monomer selected from the compounds represented by the following general formula (2-1) and general formula (2-2).

[Chemistry 7]

[化8]

(In the above formulae (2-1) and (2-2), R ₃ and R ₅ to R ₉ are each independently H or CH ₃ , and R ₁₂ and R ₁₃ are each independently H or CH ₃ , X ₁ , X _{2 .} , X ₃ , X ₄ and X ₅ are each independently O or S, a represents an integer from 2 to 30, b represents an integer from 0 to 2, c represents an integer from 0 to 30, d represents an integer from 0 to 20, and e represents An integer from 0 to 2, i represents an integer from 1 to 20, and k represents an integer from 1 to 10,

A indicates that

[Chemistry 9]

or

[化10]

One of the selected ones. Where * is the keying key,

R ₁₀ and R ₁₁ are each independently H or CH ₃ , and R ₁₀₀ and R ₁₀₁ are each independently H or an alkyl group having 1 to 6 carbon atoms; R ₂₀₀ and R ₂₀₁ are each independently H, CH ₃ or a phenyl group, and R is Hexamethylene, isophorone (1-methylene-3-ethylidene-3-methyl-5,5-dimethyl-cyclohexane), lower Alkyl dimethylene, dicyclohexylmethane, cyclohexane dimethylene or fluorenyl, R ₅₀ is hexamethylene, isophorone (1-methylene-3-ethylidene-3) -methyl-5,5-dimethyl-cyclohexane), drop Alkyl dimethylene, dicyclohexylmethane, cyclohexane dimethylene, extens a group, a diphenylmethane or a fluorenyl group, wherein V is OH or an oxygen atom having a bonding bond (*), and W1 to W3 are independently H, CH ₃ , OH or an oxygen atom having a bonding bond (*), Z represents OH, an oxygen atom having a bonding bond (*), COOH or a carboxyl group (COO) having a bonding bond (*), and V1 to V3 are independently H or a bonding bond (*), and n1 and n2 are independent, respectively. An integer representing 0~8, o1 and o2 respectively represent an integer from 1 to 3, f represents an integer from 1 to 20, g represents an integer from 0 to 3, m represents 0 or 1, and q represents an integer from 1 to 7, a1 Indicates an integer from 2 to 3, a2 represents an integer from 3 to 4, a3 represents an integer from 4 to 6, a4 represents an integer from 2 to 3, and a5 represents an integer from 2 to 4. )

As the polyvalent monomer (II), at least one monomer selected from the compounds represented by the following general formulas (3) to (8) and (10) to (33) is preferred.

[11]

(In the above formula (3), R ₃ and R ₄ are each independently H or CH ₃ , and R ₁₀₀ and R ₁₀₁ are each independently H or an alkyl group having 1 to 6 carbon atoms, and b1 and b2 each independently represent 0 to 2; Integer, n1 and n2 each represent an integer from 0 to 8.)

[化12]

(In the above formula (4), R ₃ to R ₆ are each independently H or CH ₃ , and R ₁₀₀ and R ₁₀₁ are each independently H or an alkyl group having 1 to 6 carbon atoms, and n1 and n2 each independently represent 0 to 8; Integer.)

[Chemistry 13]

(In the above formula (5), R ₃ to R ₆ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c1 represents an integer of 2 to 30.)

[Chemistry 14]

(In the above formula (6), R ₃ to R ₆ are each independently H or CH ₃ , and c2 and c3 each independently represent an integer of 1 to 5, and d1 represents an integer of 2 to 20.

[化15]

(In the above formula (7), R ₃ and R ₄ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, d1 represents an integer of 2 to 20, and m represents 0 or 1.

[Chemistry 16]

(In the above formula (8), R ₃ and R ₄ are each independently H or CH ₃ , and o1 and o2 each independently represent an integer of 1 to 3.)

[化17]

(In the above formula (10), R ₃ to R ₈ are each independently H or CH ₃ , and c4 and c5 each independently represent an integer of 0 to 5, and m represents 0 or 1.)

[化18]

(In the above formula (11), R ₃ and R ₄ are each independently H or CH ₃ , and m represents 0 or 1.)

[Chemistry 19]

(In the above formula (12), R ₃ to R ₇ are each independently H or CH ₃ .)

[Chemistry 20]

(In the above formula (13), * is a bonding bond, and R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , and c6 is an integer of 0 to 3.)

[Chem. 21]

(In the above formula (14), R ₃ to R ₈ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c7 and c8 each independently represent an integer of 0 to 5, and m represents 0 or 1. .)

[化22]

(In the above formula (15), R ₃ to R ₁₀ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c9 and c10 each independently represent an integer of 0 to 30.)

[化23]

(In the above formula (16), R ₃ to R ₁₀ are each independently H or CH ₃ , and c11 to c14 represent an integer of 1 or more, and satisfy c11+c12+c13+c14=4 to 30.)

[Chem. 24]

(In the above formula (17), R ₃ and R ₄ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2.)

[化25]

(In the above formula (18), R ₃ to R ₈ are each independently H or CH ₃ , and R ₂₀₀ and R ₂₀₁ are each independently H, CH ₃ or a phenyl group, and c4 and c5 each independently represent an integer of 0 to 5.)

[Chem. 26]

(In the above formula (19), R ₃ to R ₅ and R ₁₁ are each independently H or CH ₃ , and b1 to b3 each independently represent an integer of 0 to 2, and f represents an integer of 1 to 20.

[化27]

(In the above formula (20), * is a bonding bond, V is an OH or an oxygen atom having a bonding bond (*), and R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , and a1 represents 2 or 3 , b1 represents an integer from 0 to 2, and c15 represents an integer from 0 to 20.)

[化28]

(In the above formula (21), * is a bonding bond, W1 is H, CH ₃ , OH or an oxygen atom having a bonding bond (*), and R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , A2 means 3 or 4, and c16 means an integer from 0 to 20.)

[化29]

(In the above formula (22), * is a bonding bond, and W2 and W3 are each independently H, CH ₃ , OH or an oxygen atom having a bonding bond (*), and R ₃ , R ₅ and R ₆ are each independently H. Or CH ₃ , a3 represents an integer from 4 to 6, and c17 represents an integer from 0 to 3.)

[化30]

(In the above formula (23), R is hexamethylene, isophorone (1-methylene-3-ethylidene-3-methyl-5,5-dimethyl-cyclohexane), drop An alkane dimethylene group, a dicyclohexylmethane group, a cyclohexane dimethylene group or a fluorenyl group, and R ₃ to R ₁₀ are each independently H or CH ₃ , and e1 and e2 each independently represent an integer of 0 to 2. )

[化31]

(In the above formula (24), R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , b1 represents an integer of 0 to 2, c15 represents an integer of 0 to 20, and n100 represents an integer of 1 to 6.)

[化32]

(In the above formula (25), R ₃ to R ₁₀ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c9 and c10 each independently represent an integer of 0 to 5.)

[化33]

(In the above formula (26), R ₃ is H or CH ₃ , p1 represents an integer of 1 to 6, and a10 represents 3.)

[化34]

(In the above formula (27), R ₃ to R ₈ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c4 and c5 each independently represent an integer of 0 to 5.)

[化35]

(In the above formula (28), R ₃ to R ₈ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c4 and c5 each independently represent an integer of 0 to 5.)

[化36]

(In the above formula (29), R ₃ and R ₅ to R ₁₃ are each independently H or CH ₃ , and i1 represents an integer of 0 to 5.)

[化37]

(In the above formula (30), R ₃ and R ₅ to R ₉ are each independently H or CH ₃ , W1 is H, CH ₃ , OH or an oxygen atom having a bonding bond (*), and a2 represents 3 or 4. I1 represents an integer from 0 to 5.)

[化38]

(In the above formula (31), R ₃ to R ₉ are each independently H or CH ₃ , and W2 and W3 are independently H, CH ₃ , OH or an oxygen atom having a bonding bond (*), and a7 represents 1 to 6 The integer, a8 represents an integer from 0 to 5, and satisfies a7+a8=2~6.)

[39]

(In the above formula (32), R ₇₀ is a stretch Base, diphenylmethane, hexamethylene, isophorone (1-methylene-3-extended ethyl-3-methyl-5,5-dimethylcyclohexane), Alkyl dimethylene, dicyclohexylmethane, cyclohexane dimethylene, N,N',N"-fluorene (hexamethylene)-trimeric isocyanate, N,N,N'-叁 (six Methylene)urea, N,N,N',N'-fluorene (hexamethylene)urea or anthracene, R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , and W1 is H, CH ₃ , OH or an oxygen atom having a bond (*), a9 represents an integer from 1 to 4, a10 represents an integer from 2 to 4, b1 represents an integer from 0 to 2, and c4 represents an integer from 0 to 5.

[化40]

(In the above formula (33), R ₇₀ is a stretch Base, diphenylmethane, hexamethylene, isophorone (1-methylene-3-extended ethyl-3-methyl-5,5-dimethyl-cyclohexane), Alkyl dimethylene, dicyclohexylmethane, cyclohexane dimethylene, N,N',N"-fluorene (hexamethylene)-trimeric isocyanate, N,N,N'-叁 (six Methylene)urea, N,N,N',N'-fluorene (hexamethylene)urea or anthracene, R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , and W1 is H, CH ₃ , OH or an oxygen atom having a bond (*), a9 represents an integer from 1 to 4, a10 represents an integer from 2 to 4, b1 represents an integer from 0 to 2, and c4 represents an integer from 0 to 5.

The water contact angle of the above single layer film is preferably 30 or less.

The film thickness of the above single layer film is usually in the range of 0.5 to 100 μm.

The above single layer film can be used as an antifogging material, an antifouling material, an antistatic material, or the like.

The laminate of the present invention is characterized in that the above-mentioned single layer film is formed on at least one of the substrates.

The above laminated system forms a single layer film on one surface of the substrate, and may form an adhesive layer on the surface of the substrate on which the single layer film is not formed. Further, a peeling layer may be further formed on the surface of the adhesive layer.

In the laminate, a peelable coating material layer may be formed on the surface of the single layer film.

The method for producing a laminate of the present invention is characterized by comprising the step of producing a mixture comprising: a monomer (I) represented by the following general formula (1) and having two or more (meth) acrylonitriles. a polyvalent monomer (II) having no sulfonic acid group, carboxyl group or phosphoric acid group, and a monomer (I) / polyvalent monomer (II) molar ratio of 1/1000 or more and less than 1/30. a monomer composition comprising: a solvent comprising a compound having a solubility parameter σ of 9.3 (cal/cm ³ ) or more; a step of applying the mixture to at least one surface of the substrate; removing at least one of the coated mixture a step of a part of the solvent; and a step of polymerizing the monomer (I) and the monomer (II) contained in the mixture subjected to the above steps; thereby producing an anion concentration which forms an outer surface on at least one surface of the substrate (Sa An anion concentration ratio (Sa/Da) of an anion concentration (Da) at a position intermediate to an inner surface and an outer surface of the substrate is 1.1 or more, and at least one selected from the group consisting of a sulfonic acid group, a carboxyl group, and a phosphoric acid group A laminate of a single layer film of an anionic hydrophilic group.

[X] _s [M1] ₁ [M2] _m (1)

(In the above formula (1), s represents 1 or 2, and 1 and m represent integers satisfying s = 1 + m/2.

M1 is at least one monovalent cation selected from hydrogen ions, ammonium ions and alkali metal ions, and M2 is at least one divalent cation selected from alkaline earth metal ions.

X is at least one monovalent anion selected from the group represented by the following general formulas (1-1) to (1-4).

[化41]

[化42]

[化43]

[化44]

(In the above formulae (1-1) to (1-4), J and J' are each independently H or CH ₃ , and n represents 0 or 1, and R is independently an aromatic group or an aliphatic cyclic group. And an aliphatic hydrocarbon group having at least one substituent substituted for carbon of 1 to 600 carbon atoms, and an ether group and an ester group.)

According to the method for producing a laminate, it is preferable to produce a laminate having a single layer film having a water contact angle of 30 or less.

The single layer film of the present invention and the layered system having the single layer film are hydrophilic, and are excellent not only in antifogging property, antifouling property, antistatic property, and dew condensation property, but also have a large film thickness and transparency. It is also excellent and has a tendency to be excellent in scratch resistance.

The monolayer film of the present invention is obtained by polymerizing a specified monomer composition.

The monomer composition (1) represented by the following general formula (1) is contained in the above monomer composition.

[X] _s [M1] ₁ [M2] _m (1)

In the above formula (1), s represents 1 or 2, and 1 and m represent integers satisfying s = 1 + m/2.

M1 is at least one monovalent cation selected from the group consisting of hydrogen ions, ammonium ions, and alkali metal ions.

Further, the ammonium ion in the present invention is a cation obtained by binding a hydrogen ion to ammonia, a primary amine, a secondary amine or a tertiary amine. From the viewpoint of hydrophilicity, the ammonium ion is preferably a cation in which an amine having a small carbon number and a carbon number is bonded to a hydrogen ion, and an ammonium ion or a methylammonium formed by binding hydrogen ions to ammonia is more preferable.

Examples of the alkali metal include lithium, sodium, potassium, rubidium, and the like.

The above M1 is preferably an alkali metal ion, and more preferably a sodium ion, a potassium ion or a cesium ion.

M2 is at least one divalent cation selected from alkaline earth metal ions.

X is at least one monovalent anion selected from the group represented by the following general formulas (1-1) to (1-4).

[化45]

[Chem. 46]

[化47]

[48]

In the above general formulas (1-1) to (1-4), J and J' are each independently H or CH ₃ . n represents 0 or 1.

Each of R is independently an aliphatic hydrocarbon group having a carbon number of from 1 to 600, which may be substituted with at least one selected from the group consisting of an aromatic group, an aliphatic cyclic group, an ether group and an ester group. It is preferable that the R is substituted with at least one selected from the group consisting of an aromatic group, an aliphatic cyclic group, an ether group and an ester group, and an aliphatic hydrocarbon group having 2 to 100 carbon atoms. It is more preferable to substitute at least one group selected from the group consisting of an aromatic group, an aliphatic cyclic group, an ether group and an ester group with an aliphatic hydrocarbon group having 2 to 20 carbon atoms.

Among the above monomers (I), a monomer having m = 0 is preferred.

The amount of the above X is usually 50 to 18,000, preferably 100 to 1,000, more preferably 170 to 500.

Among the above monomers (I), those represented by the following general formula (1-1-1) and general formula (1-1-2) are preferred.

[化49]

[化50]

In the above formulae (1-1-1) and (1-2-1), J is H or CH ₃ .

R ₁ and R ₂ are each independently H, CH ₃ or C ₂ H ₅ . Among these R ₁ and R ₂ , H is preferable in terms of ease of synthesis.

n represents an integer of 1 to 20, and is preferably an integer of 2 to 10, and more preferably an integer of 2 to 4, in terms of ease of synthesis.

1 represents an integer of 2 to 10, preferably an integer of 2 to 6, more preferably an integer of 2 to 4.

M is at least one monovalent cation selected from hydrogen ions, ammonium ions, and alkali metal ions, or at least one divalent cation selected from alkaline earth metal ions.

In the case where M is a monovalent cation, m is 1, and M is a divalent cation, and m is 2.

The ammonium ion is a cation obtained by binding a hydrogen ion to ammonia, a primary amine, a secondary amine or a tertiary amine. From the viewpoint of hydrophilicity, the ammonium ion is preferably a cation in which a hydrogen atom is bonded to an amine having a small amount of carbon and a carbon atom, and an ammonium ion or a methylammonium formed by binding hydrogen ions to ammonia is more preferable.

Examples of the alkali metal include lithium, sodium, potassium, rubidium, and the like. Examples of the alkaline earth metal include barium, magnesium, calcium, barium, and the like.

Among these M, a monovalent cation is preferred, and an alkali metal ion is more preferable, and sodium ion, potassium ion and cesium ion are more preferable.

Among the monomers represented by the formulas (1-1-1) and (1-1-2), 2-sulfonyl (meth)acrylate, 3-sulfonate (meth)acrylate, and The alkali metal salts of the compounds are preferred.

The molecular weight of the above monomer (I) is usually 168 to 18,000, preferably 180 to 1,000, more preferably 200 to 500.

The monomer (I) may be used alone or in combination of two or more.

Further, the monomer composition of the present invention contains the monomer (I), but at least a part of the monomer (I) may be reacted in an oligomer form to be contained in the monomer composition. Further, the oligomer system herein usually contains 2 to 20 repeating units formed of the above monomer (I).

The above-mentioned monomer (I) can be produced according to a known method or a method known in the art. For example, Japanese Patent Publication No. Sho 49-36214, Japanese Patent Publication No. Sho 51-9732, and Japanese Patent Laid-Open No. SHO 63284157 It is produced by the method described in the specification of U.S. Patent No. 3024221.

For example, the single system represented by the above formula (1-1-1) can be produced by reacting with (meth)acrylic acid and propane sultone in the presence of an alkali metal carbonate, the above formula (1) -1-2) The single system shown can be obtained by halogenating a part of the hydroxyl group of the polyol with alkalized hydrogen, and then reacting the substituted halogen with an alkali metal sulfonate to synthesize an alkali metal sulfonate compound having a hydroxyl group. Finally, the hydroxyl group is produced by reacting a (meth)acrylic acid halide or (meth)acrylic acid.

The monomer composition further contains a polyvalent monomer (II) having two or more (meth)acrylonium groups and having no sulfonic acid group, carboxyl group or phosphoric acid group.

The form of the (meth)acryl fluorenyl group contained in the polyvalent monomer (II) is not particularly limited, and the (meth) acrylonitrile group may be, for example, (meth) propylene decyloxy group or (meth) propylene group. The thiol group or the benzylamino (meth) acrylate group is contained in the form of a polyvalent monomer (II), and is preferably contained in the form of a (meth) acryloxy group or a (meth) acryl thio group.

The polyvalent monomer (II) may, for example, be a compound having one or more hydroxyl groups and two or more (meth)acrylonium groups, having one or more ether bonds or thioether bonds, and two or more (meth) groups. a propylene fluorenyl compound, a compound having one or more ester bonds and two or more (meth) acryl fluorenyl groups, one or more aliphatic ring structures or an aromatic ring structure, and two or more (meth) acrylonitrile groups A compound having one or more heterocyclic structures and two or more (meth)acryl fluorenyl groups.

Among the polyvalent monomers (II), those represented by the following general formulas (2-1) and (2-2) are preferred.

[化51]

[化52]

(In the above formulae (2-1) and (2-2), R ₃ and R ₅ to R ₉ are each independently H or CH ₃ , and R ₁₂ and R ₁₃ are each independently H or CH ₃ , X ₁ , X _{2 .} , X ₃ , X ₄ and X ₅ are each independently O or S, a represents an integer from 2 to 30, b represents an integer from 0 to 2, c represents an integer from 0 to 30, d represents an integer from 0 to 20, and e represents An integer from 0 to 2, i represents an integer from 1 to 20, preferably from 1 to 10, more preferably from 1 to 5, and even more preferably from 1 to 3. The k represents an integer from 1 to 10, more preferably 2~ 8, then better to represent an integer from 2 to 6.

A indicates that

[化53]

or

[54]

One of the selected ones.

Among them, * is the key bond.

R ₁₀ and R ₁₁ are each independently H or CH ₃ , and R ₁₀₀ and R ₁₀₁ are each independently H or an alkyl group having 1 to 6 carbon atoms, and R ₂₀₀ and R ₂₀₁ are each independently H, CH ₃ or a phenyl group. R is hexamethylene, isophorone (1-methylene-3-ethylhexyl-3-methyl-5,5-dimethyl-cyclohexane), Alkyl dimethylene, dicyclohexylmethane, cyclohexane dimethylene or fluorenyl, R ₅₀ is hexamethylene, isophorone (1-methylene-3-ethylidene-3) -methyl-5,5-dimethyl-cyclohexane), drop Alkyl dimethylene, dicyclohexylmethane, cyclohexane dimethylene, extens Base, diphenylmethane or thiol.

V is OH or an oxygen atom having a bonding bond (*), and W1 to W3 are each independently H, CH ₃ , OH or an oxygen atom having a bonding bond (*), Z represents OH, and has a bonding bond (*) An oxygen atom, COOH or a carboxyl group (COO) having a bonding bond (*), and V1 to V3 are each independently H or a bonding bond (*).

N1 and n2 respectively represent integers from 0 to 8, and o1 and o2 independently represent integers from 1 to 3, f represents an integer from 1 to 20, g represents an integer from 0 to 3, and m represents 0 or 1. q represents an integer of 1 to 7, preferably an integer of 1 to 5, more preferably an integer of 1 to 3. A1 represents an integer of 2 to 3, preferably 3. A2 represents an integer of 3 to 4, preferably 3. A3 represents an integer of 4 to 6, preferably 5 or 6. A4 represents an integer of 2 to 3, preferably 3. A5 represents an integer of 2 to 4, preferably 3 or 4.

The polyvalent monomer represented by the above general formulas (2-1) to (2-2) can be produced by a known method or a known method. Moreover, it can be obtained in the form of a commercial product.

Among the polyvalent monomers represented by the above formula (2-1) and general formula (2-2), the polyvalent monomers represented by the following general formulas (3) to (8) and (10) to (33) It is better.

[化55]

In the above formula (3), R ₃ and R ₄ are each independently H or CH ₃ , and R ₁₀₀ and R ₁₀₁ are each independently H or an alkyl group having 1 to 6 carbon atoms, and b1 and b 2 each independently represent an integer of 0 to 2; , n1 and n2 independently represent integers from 0 to 8.

[化56]

In the above formula (4), R ₃ to R ₆ are each independently H or CH ₃ , and R ₁₀₀ and R ₁₀₁ are each independently H or an alkyl group having 1 to 6 carbon atoms, and n 1 and n 2 each independently represent an integer of 0 to 8 .

[化57]

In the above formula (5), R ₃ to R ₆ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c1 represents an integer of 2 to 30.

[化58]

In the above formula (6), R ₃ to R ₆ are each independently H or CH ₃ , and c2 and c3 each independently represent an integer of 1 to 5, and d1 represents an integer of 2 to 20.

[化59]

In the above formula (7), R ₃ and R ₄ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, d1 represents an integer of 2 to 20, and m represents 0 or 1.

[60]

In the above formula (8), R ₃ and R ₄ are each independently H or CH ₃ , and o1 and o2 each independently represent an integer of 1 to 3.

[化61]

In the above formula (10), R ₃ to R ₈ are each independently H or CH ₃ , and c4 and c5 each independently represent an integer of 0 to 5, and m represents 0 or 1.

[化62]

In the above formula (11), R ₃ and R ₄ are each independently H or CH ₃ , and m represents 0 or 1.

[化63]

In the above formula (12), R ₃ to R ₇ are each independently H or CH ₃ .

[化64]

In the above formula (13), * is a bonding bond, and R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , and c6 represents an integer of 0 to 3.

[化65]

In the above formula (14), R ₃ to R ₈ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c7 and c8 each independently represent an integer of 0 to 5, and m represents 0 or 1.

[化66]

In the above formula (15), R ₃ to R ₁₀ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c9 and c10 each independently represent an integer of 0 to 30.

[67]

In the above formula (16), R ₃ to R ₁₀ are each independently H or CH ₃ , and c11 to c14 represent an integer of 1 or more, and satisfy c11 + c12 + c13 + c14 = 4 to 30.

[化68]

In the above formula (17), R ₃ and R ₄ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2.

[化69]

In the above formula (18), R ₃ to R ₈ are each independently H or CH ₃ , and R ₂₀₀ and R ₂₀₁ are each independently H, CH ₃ or a phenyl group, and c4 and c5 each independently represent an integer of 0 to 5.

[化70]

In the above formula (19), R ₃ to R ₅ and R ₁₁ are each independently H or CH ₃ , and b1 to b3 each independently represent an integer of 0 to 2, and f represents an integer of 1 to 20. [71]

In the above formula (20), * is a bonding bond, V is an OH or an oxygen atom having a bonding bond (*), and R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , and a1 represents 2 or 3. B1 represents an integer from 0 to 2, and c15 represents an integer from 0 to 20. [化72]

In the above formula (21), * is a bonding bond, W1 is H, CH ₃ , OH or an oxygen atom having a bonding bond (*), and R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , a2 Indicates 3 or 4, and c16 represents an integer from 0 to 20. [化73]

In the above formula (22), * is a bonding bond, and W2 and W3 are each independently H, CH ₃ , OH or an oxygen atom having a bonding bond (*), and R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , a3 represents an integer from 4 to 6, and c17 represents an integer from 0 to 3. [化74]

In the above formula (23), R is hexamethylene, isophorone (1-methylene-3-ethylidene-3-methyl-5,5-dimethyl-cyclohexane), and An alkane dimethylene group, a dicyclohexylmethane group, a cyclohexane dimethylene group or a fluorenyl group, and R ₃ to R ₁₀ are each independently H or CH ₃ , and e1 and e2 each independently represent an integer of 0 to 2. [化75]

In the above formula (24), R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , b1 represents an integer of 0 to 2, c15 represents an integer of 0 to 20, and n100 represents an integer of 1 to 6. [化76]

In the above formula (25), R ₃ to R ₁₀ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c9 and c10 each independently represent an integer of 0 to 5. [化77]

In the above formula (26), R ₃ is H or CH ₃ , p1 represents an integer of 1 to 6, and a10 represents 3. [化78]

In the above formula (27), R ₃ to R ₈ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c7 and c8 each independently represent an integer of 0 to 5. [化79]

In the above formula (28), R ₃ to R ₈ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c7 and c8 each independently represent an integer of 0 to 5. [化80]

In the above formula (29), R ₃ and R ₅ to R ₁₃ are each independently H or CH ₃ , and i1 represents an integer of 0 to 5. [化81]

In the above formula (30), R ₃ and R ₅ to R ₉ are each independently H or CH ₃ , W1 is H, CH ₃ , OH or an oxygen atom having a bonding bond (*), and a2 represents 3 or 4, i1 Indicates an integer from 0 to 5. [化82]

In the above formula (31), R ₃ to R ₉ are each independently H or CH ₃ , and W2 and W3 are each independently H, CH ₃ , OH or an oxygen atom having a bonding bond (*), and a7 represents 1 to 6 Integer, a8 represents an integer from 0 to 5, and satisfies a7+a8=2~6. [化83]

In the above formula (32), R ₇₀ is a stretch Base, diphenylmethane, hexamethylene, isophorone (1-methylene-3-extended ethyl-3-methyl-5,5-dimethylcyclohexane), Alkyl dimethylene, dicyclohexylmethane, cyclohexane dimethylene, N,N',N"-fluorene (hexamethylene)-trimeric isocyanate, N,N,N'-叁 (six Methylene)urea, N,N,N',N'-fluorene (hexamethylene)urea or anthracene, R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , and W1 is H, CH ₃ , OH or an oxygen atom having a bond (*), a9 represents an integer from 1 to 4, a10 represents an integer from 2 to 4, b1 represents an integer from 0 to 2, and c4 represents an integer from 0 to 5. [Chem. 84 ]

In the above formula (33), R ₇₀ is a stretch Base, diphenylmethane, hexamethylene, isophorone (1-methylene-3-extended ethyl-3-methyl-5,5-dimethyl-cyclohexane), Alkyl dimethylene, dicyclohexylmethane, cyclohexane dimethylene, N,N',N"-fluorene (hexamethylene)-trimeric isocyanate, N,N,N'-叁 (six Methylene)urea, N,N,N',N'-fluorene (hexamethylene)urea or anthracene, R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , and W1 is H, CH ₃ , OH or an oxygen atom having a bond (*), a9 represents an integer from 1 to 4, a10 represents an integer from 2 to 4, b1 represents an integer from 0 to 2, and c4 is an integer from 0 to 5. The polyvalent monomer (II) represented by the formula (3) may, for example, be ethylene glycol di(meth)acrylate, 1,2-propanediol di(meth)acrylate or 1,3-propanediol di(a). Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl 1,2-ethyl-1,3-propanediol di(meth)acrylate, 1,2-bis{3-(methyl)propenyloxy-2-hydroxy-propoxy}ethane, 1, 2-bis{3-(methyl)propenyloxy-2-hydroxy-propoxy}propane, 1,3-double {3-(methyl) Propylene oxime-2-hydroxy-propoxy}propane, 1,4-bis{3-(methyl)propenyloxy-2-hydroxy-propoxy}butane, 1,6-double {3 - (meth) propylene oxime-2-hydroxy-propoxy} hexane, etc. As the polyvalent monomer (II) represented by the above general formula (4), for example, neopentyl glycol hydroxy trimethacrylate Diacetinic acid di(meth)acrylate and the like.

Examples of the polyvalent monomer (II) represented by the above general formula (5) include polyethylene glycol di(meth)acrylate, 1,2-polypropylene glycol di(meth)acrylate, and 1,3. - polypropylene glycol di(meth)acrylate, 1,4-polybutylene glycol di(meth)acrylate, polyethylene glycol-bis{3-(methyl)acryloxycarbonyl-2-hydroxy-propyl Ether, 1,2-polypropylene glycol-bis{3-(methyl)propenyloxy-2-hydroxy-propyl}ether, and the like. The polyvalent monomer (II) represented by the above general formula (6) may, for example, be 1,2-polypropylene glycol-bis{(methyl)acrylinyl-poly(oxyethylene)}ether. Examples of the polyvalent monomer (II) represented by the above general formula (7) include 1,3-polypropylene glycol di(meth)acrylate and 1,4-polybutylene glycol di(meth)acrylate. 1,4-polybutanediol-bis{3-(meth)acryloxy-2-hydroxy-propyl}ether. The polyvalent monomer (II) represented by the above general formula (8) may, for example, be bis{2-(methyl)propene sulfonium thioethyl}sulfide or bis{5-(methyl)propenesulfonylthio- 3-Thiopentyl} sulfur and the like. Examples of the polyvalent monomer (II) represented by the above general formula (10) include cyclohexanediol di(meth)acrylate and bis{(methyl)acryloxymethylol}cyclohexane. Double {7-(methyl)acryloxy-2,5-di Heptyl}cyclohexane, bis{(meth)acryloxy-poly(ethyleneoxy)-methyl}cyclohexane, and the like. The polyvalent monomer (II) represented by the above general formula (11) may, for example, be tricyclodecane dimethanol di(meth)acrylate or the like. The polyvalent monomer (II) represented by the above general formula (12) includes, for example, 2-acrylic acid {2-(1,1-dimethyl-2-{(1-oxy-2-propenyl)). Oxy}ethyl)-5-ethyl-1,3-di Alk-5-yl}methyl ester (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD R-604").

The polyvalent monomer (II) represented by the above general formula (13) may, for example, be N,N',N"-fluorene {2-(meth)acrylomethoxyethyl}trimeric isocyanate. The polyvalent monomer (II) represented by the general formula (14) may, for example, be xylene glycol di(meth)acrylate, bis{7-(methyl)propene oxime-2,5-di. Heptyl}benzene, bis{(meth)acryloxy-poly(ethyleneoxy)-methyl}benzene, and the like. Examples of the polyvalent monomer (II) represented by the above general formula (15) include bisphenol A di(meth)acrylate and bis{(methyl)acrylonitrile-oxyethyl}bisphenol A. Double {(meth)acryloyl-oxypropyl}bisphenol A, bis{(meth)acryloyl-poly(oxyethylene)}bisphenol A, bis{(methyl)acrylonitrile-poly( Oxy-1,2-propenyl)}bisphenol A, bis{3-(methyl)propenyloxy-2-hydroxy-propyl}bisphenol A, bis{3-(methyl)propenyloxy 2-hydroxy-propyl-oxyethyl}bisphenol A, bis{3-(methyl)propenyloxy-2-hydroxy-propyl-oxypropyl}bisphenol A, double {3-(A Acryloxy-2-hydroxy-propyl-poly(oxyethylene)}bisphenol A, bis{3-(methyl)propenyloxy-2-hydroxy-propyl-poly(oxy-1) , 2-propene)} bisphenol A and the like. The polyvalent monomer (II) represented by the above general formula (16) may, for example, be bis{(methyl)propenyl-oxyethyl-oxypropyl}bisphenol A or bis{(methyl)propene. Mercapto poly(oxyethylene)-poly(oxy-1,2-propene)}bisphenol A and the like. The polyvalent monomer (II) represented by the above general formula (17) may, for example, be naphthalenediol di(meth)acrylate or bis{3-(methyl)acryloxy-2-hydroxy-propyl Base-oxy}naphthalene and the like. Examples of the polyvalent monomer (II) represented by the above general formula (18) include 9,9-nonanediol di(meth)acrylate and 9,9-bis{4-(2-methyl). Propylene methoxy-ethyl-oxy}} fluorene, 9,9-bis{3-phenyl-4-(methyl) propylene oxy-poly(ethyleneoxy)} hydrazine, and the like. Examples of the polyvalent monomer (II) represented by the above formula (19) include a phenol novolac type epoxy (meth) acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "NK Oligo EA-6320, EA- 7120, EA-7420") and so on. The polyvalent monomer (II) represented by the above general formula (20) may, for example, be glycerol-1,3-di(meth)acrylate or 1-propenyloxy-2-hydroxy-3-methyl. Propylene oxime-propane, 2,6,10-trihydroxy-4,8-di Undecane-1,11-di(meth)acrylate, 1,2,3-叁{3-(methyl)propenyloxy-2-hydroxy-propyl-oxy}propane, 1,2 , 3-叁{2-(methyl)propenyloxy-ethyl-oxy}propane, 1,2,3-anthracene {2-(methyl)propenyloxy-propyl-oxy}propane 1,2,3-叁{(methyl)acryloxy-poly(ethyleneoxy)}propane, 1,2,3-叁{(meth)acryloxy-poly(1,2- Propylene oxy)}propane, etc.

The polyvalent monomer (II) represented by the above general formula (21) may, for example, be trimethylolpropane tri(meth)acrylate or trimethylolpropane-quinone {(meth)acryloxyloxy group. -ethyl-oxy}ether, trimethylolpropane-indole {2-(methyl)propenyloxy-propyl-oxy}ether, trimethylolpropane-indole {(meth)acrylonitrile Oxy-poly(vinyloxy)ether, trimethylolpropane-indole {(meth)acryloxy-poly(1,2-propenyloxy)} ether, pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, pentaerythritol-肆{(meth)acryloxy-ethyl-oxy}ether, pentaerythritol-肆{2-(meth)acryloxy-propyl-oxy }ether, pentaerythritol-肆{(methyl)acryloxy-poly(ethyleneoxy)} ether, pentaerythritol-肆{(methyl)propenyloxy-poly(1,2-propoxy)}ether Wait. Examples of the polyvalent monomer (II) represented by the above general formula (22) include di-trimethylolpropane tetra(meth)acrylate and di-trimethylolpropane-ruthenium ((methyl)). Propylene methoxy-ethyl-oxy}ether, di-trimethylolpropane-oxime {2-(meth)acryloxy-propyl-oxy}ether, di-trimethylolpropane-肆{(Methyl)acryloxy-poly(ethyleneoxy)} ether, di-trimethylolpropane-肆{(methyl)acryloxy-poly(1,2-propenyloxy)} Ether, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol-hexa{(methyl) propylene oxime-ethyl-oxy} ether, dipentaerythritol - six {2 -(Meth)acryloxy-propyl-oxy}ether, dipentaerythritol-hexa{(meth)acryloxy-poly(ethyleneoxy)} ether, dipentaerythritol-hexa{(methyl)propene Alkoxy-poly(1,2-propoxy)}ether and the like.

Examples of the polyvalent monomer (II) represented by the above general formula (23) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3- Reaction of hydroxypropyl (meth) acrylate with hexamethylene diisocyanate such as hydroxypropyl acrylate or 4-hydroxybutyl (meth) acrylate; hydroxyalkyl (meth) acrylate and isophorone diisocyanate Reactant; hydroxyalkyl (meth) acrylate and bis(isocyanomethyl) Alkane reactant; reaction of hydroxyalkyl (meth) acrylate with bis(4-isocyanatocyclohexyl)methane; hydroxyalkyl (meth) acrylate with 1,3-bis(isocyanatomethyl) a reactant of cyclohexane; a reaction product of a hydroxyalkyl (meth) acrylate with m-decyl diisocyanate, and the like. The molar ratio of the monomer (I) to the polyvalent monomer (II) contained in the monomer composition is 1/1000 or more and less than 1/30 of the monomer (I)/polyvalent monomer (II). . When the molar ratio of the monomer (I) to the polyvalent monomer (II) is within the above range, even when the film thickness of the obtained single layer film is increased, the transparency is excellent and the scratch resistance is excellent. Single layer film. The monomer (I)/polyvalent monomer (II) of the monomer (I) of the present invention and the polyvalent monomer (II) is 1/1000 or more and less than 1/30, preferably 1 /500 or more and less than 1/31, more preferably 1/300 or more and less than 1/32. Generally, the haze value is generally used as an index of transparency of a coating film, and in applications requiring high transparency such as optical use, the haze value must be less than 1%.

On the other hand, the single layer film described in Patent Document 7 is an excellent material such as an antifouling film or an antifogging film. However, when the haze value is 1% or more, the higher scratch resistance may not be sufficiently satisfied. . When the molar ratio of the monomer (I) to the polyvalent monomer (II) is in the above range, a single layer film having a haze value of less than 1% and excellent transparency can be obtained. Further, compared with Patent Document 7, there is a tendency to obtain a single layer film excellent in scratch resistance. The monomer (III) and the monomer (III) other than the monomer (II) may be contained in the monomer composition as long as the effects of the present invention are not impaired. Examples of the other monomer (III) include a monomer having a carboxyl group or a carboxylate group other than the monomer (I) such as (meth)acrylic acid; hydroxyethyl (meth)acrylate; a hydroxyalkyl (meth) acrylate such as hydroxypropyl acrylate or hydroxybutyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ( Methyl) acrylate An alkyl (meth)acrylate such as an ester; N,N-dimethyl-amine ethyl (meth)acrylate; N,N-dimethyl-amine ethyl ester hydrochloride (meth)acrylate; A monomer containing an amine group or an ammonium salt group; sodium vinyl sulfonate, styrene sulfonic acid, sodium styrene sulfonate, potassium styrene sulfonate, 2-propenylamine-2-methylpropane sulfonic acid, 2- a monomer containing a sulfonic acid group or a sulfonate group other than the monomer (I) such as potassium acrylamide-2-methylpropane sulfonate; allyl (meth) acrylate and diethylene glycol bis (carbonic acid) Allyl ester), diallyl phthalate, divinylbenzene, divinyl fluorene, glycidyl (meth)acrylate, 3-isopropenyl-α,α-dimethyl-benzyl isocyanate , (meth) propylene phthalate, isocyanate (meth) propylene oxirane ethyl ester, decyl diisocyanate, hexamethylene diisocyanate, bis (isocyanatomethyl) Alkane, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanato-cyclohexyl)methane, and the like.

Further, in the case where the refractive index value of the single layer film is to be increased, 2,5-bis(acryloylthiomethyl)-1,4-dithiane, 1,8-bis(propylene) can also be used.醯thio)-5-propylene sulfonylmethyl-3,6-dithiaoctane, 2,5-bis(propylene sulfonium thiomethyl)-1,4-dithiane, 1,11-bis(propylene A monomer having a sulfur atom such as thiol)-4,8-bis(propylenesulfonylthiomethyl)-3,6,9-trithiadecane or the like is used as the above monomer (III). The content of the monomer composition of the above monomer (III) is not particularly limited as long as the effect of the present invention is not impaired, and is usually 100 mol% based on the total of the monomer (I) and the monomer (II). The amount of the ear is less than or equal to, preferably 49% by mole or less, more preferably 40% by mole or less. When it is contained in the monomer composition at such a content, physical properties such as flexibility, toughness, and refractive index can be adjusted. In the present invention, the monomer composition is mixed with a solvent containing a compound having a solubility parameter σ of 9.3 (cal/cm ³ ) or more. The solubility parameter σ(cal/cm ³ ) can be calculated from the following values (1) to (4).

(1) Latent heat of evaporation per 1 mole Hb = 21 × (273 + Tb) [unit: cal / mol], Tb: boiling point of solvent (°C)

(2) Latent heat of evaporation per 1 mole at 25 ° C H25 = Hb × {1 + 0.175 × (Tb-25) / 100} [unit: cal / mol], Tb: boiling point of solvent (°C)

(3) Intermolecular binding energy E=H25-596 [unit: cal/mol]

(4) Intermolecular binding energy per 1 ml (cm ³ ) of solvent E1 = E × D / Mw [unit: cal / cm ³ ], D: density (g / cm ³ ), Mw: molecular weight of solvent

(5) Solubility parameter σ = (E1) ^1/2 [unit: cal / cm ³ ]

A solvent containing a compound having such a solubility parameter σ (cal/cm ³ ) of 9.3 or more is contained in a mixture with a monomer composition because of a certain interaction with an anionic hydrophilic group derived from the monomer (I) Therefore, when the mixture is applied to the substrate, and the solvent is removed from the mixture, the anionic hydrophilic group (monomer (I)) moves with the solvent on the surface of the applied mixture contacting the outside, and anionic The hydrophilic group is concentrated on the surface, and a structure (inclined structure) in which an anionic hydrophilic group is concentrated is formed on the outer surface of the monolayer film obtained by the present invention. On the other hand, if the solubility parameter σ (cal/cm ³ ) is less than 9.3, the above-described interaction becomes weak, and thus the above-described inclined structure cannot be sufficiently formed. From the viewpoint of more easily forming the inclined structure, the solubility parameter σ (cal/cm ³ ) is preferably 9.5 or more. Further, in the above solvent, the solvent having a boiling point of 30 to 170 ° C and a solvent having a boiling point of 50 to 140 ° C are more preferable, and the boiling point is 60 to 125 ° C. The solvent is better. Further, the solvent is a mixed solvent containing two or more compounds, and the highest boiling point of the mixed solvents may be the above range.

Examples of the compound which can be used as the solvent having a solubility parameter σ (cal/cm ³ ) of 9.3 or more and a boiling point of 30 to 170 ° C include methanol, ethanol, 2-methoxyethanol, cyclohexanol, and 1-propene. Alcohol, IPA (isopropanol), 2-ethoxyethanol, 1-butanol, isobutanol, 1-methoxy-2-propanol, 2-butanol, 1-pentanol, 2-methyl An alcohol such as 1-butanol or isoamyl alcohol (3-methyl 1-butanol); a ketone such as cyclohexanone, 2-methylcyclohexanone or acetone; a carboxylic acid such as formic acid, acetic acid or propionic acid. a carboxylic acid ester such as methyl acetate; An ether such as an alkane, anisole or THF (tetrahydrofuran); a decylamine such as DMF (N,N'-dimethylformamide) or DMAC (N,N'-dimethylacetamide); acetonitrile or the like Nitrile; and water.

Among these compounds, an alcohol is preferred, and the alcohol is methanol, ethanol, 1-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-butanol, 1-pentanol, 2-methyl A primary alcohol such as 1-butanol or isoamyl alcohol (3-methyl-1-butanol) is preferred. The above compound having a solubility parameter σ (cal/cm ³ ) contained in the solvent of 9.3 or more may be used singly or in combination. Moreover, when the solvent is a mixed solvent containing two or more compounds, at least one of them may satisfy the conditions of the solubility parameter. The solubility parameter of one of the compounds contained in the solvent satisfies the above conditions, since the anionic hydrophilic group derived from the monomer (I) has a certain interaction with one of the compounds, the mixture is applied to the substrate. And when the solvent is removed from the mixture, the anionic hydrophilic group (monomer (I)) does not change with the movement of one of the compounds on the surface of the applied mixture contacting the outside, and as a result, the anion The hydrophilic group is concentrated on the surface.

In the case of a mixed solvent containing two or more compounds, the compound having the highest boiling point tends to have an influence on the formation of the inclined structure. Therefore, the solubility parameter σ (cal/cm ³ ) of the compound having the highest boiling point contained in the mixed solvent is preferably 9.3 or more. Further, in the case of a mixed solvent containing two or more compounds, the compound having a solubility parameter σ (cal/cm ³ ) satisfying the above conditions: the weight ratio of the other compound is preferably 99.9:0.1 to 1:99, more preferably 99:1~10:90, and then the range of 98:2~30:70.

However, among the compounds having a solubility parameter σ (cal/cm ³ ) contained in the solvent of 9.3 or more, especially ethanolamine, diethanolamine, triethanolamine, N-ethyl-ethanolamine, N-(2-ethylhexyl)ethanolamine An ethanolamine compound having a hydroxyethylamine structure such as N-butyl-diethanolamine, N-hexyl-diethanolamine, N-lauryl-diethanolamine, N-cetyl, diethanolamine, etc. [NR _a R _b (CH ₂ CH ₂ OH): R _a and R _b independently of hydrogen, an alkyl group having 1 to 15 carbon atoms or a CH ₂ CH ₂ OH group are not preferred. Since the ethanolamine-based compound is too strongly interacted with the anionic hydrophilic group derived from the monomer (I), the ethanolamine-based compound and the anionic hydrophilic group form a state like a molecule (typically a salt), and an anion The molecular weight on the outer surface of the hydrophilic group is increased. This increase in molecular weight causes a decrease in the moving speed in the medium, so that when the solvent is coated on the substrate and the solvent is removed from the mixture with the monomer composition, the anionic hydrophilic group is difficult to move on the surface in contact with the outside. Further, even if the anionic hydrophilic group is accompanied by the movement of the ethanolamine-based compound on the surface contacting the outside, and the molecular weight of the anion interacting with the ethanolamine-based compound increases on the surface, the anion concentration per unit surface area is inevitably higher than that of the ethanolamine. The anion of the compound interaction is further reduced, and as a result, it is difficult to concentrate on the surface. Further, in addition to the above-described strong interaction, the ethanolamine compound has a high boiling point (about 170 ° C or higher) and is difficult to evaporate, so that even a free ethanolamine compound does not easily move toward the surface, and tends to remain inside. . Therefore, a substance produced by the interaction of an ethanolamine compound having a larger molecular weight with an anion tends to be more difficult to move toward the surface. In other words, when a solvent containing the above ethanolamine compound is used, the movement of the anion toward the surface contacting the outside is suppressed, and it is likely to remain in the mixture with the monomer composition (inside the single layer film), so that it is difficult to obtain the present invention. The outer surface of the single layer film tends to form a structure (inclined structure) in which an anionic hydrophilic group is concentrated, and the hydrophilicity and the like of the obtained single layer film tend to be lowered.

Further, when such an ethanolamine-based compound is used as a solvent, decomposition of an ester bond contained in the monomer (I) and the polyvalent monomer (II) (hydrolysis, alcoholysis, and ethanolamine-based compound level 1 or Direct decomposition by a secondary amine group, etc.), or a primary or secondary amine group of an ethanolamine compound directly reacts with a (meth)acryloyl group contained in the monomer (I) and the polyvalent monomer (II) ( Michael addition), there are cases where undesired side reactions such as poor polymerization of the monomer mixture and a decrease in crosslinking density in the monolayer film occur. In the mixture containing the above monomer composition and a solvent having a solubility parameter σ of 9.3 (cal/cm ³ ) or more, a polymerization initiator may be contained as needed. For example, in the case where the monomer composition contained in the above mixture is polymerized by radiation (for example, ultraviolet ray) on a substrate, a solvent containing the above monomer composition and a solubility parameter σ of 9.3 (cam/cm ³ ) or more may be used. The mixture contains a photopolymerization initiator, a photocationic polymerization initiator, a photoanion polymerization initiator, and the like.

Examples of the photoradical polymerization initiator include diphenyl ketone, 4-phenyl diphenyl ketone, and 2,4-diethyl 9-oxo sulphide. IRUGACURE 651 (manufactured by Ciba Specialty Chemicals Co., Ltd.), IRUGACURE 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.), DAROCURE 1173 (manufactured by Ciba Specialty Chemicals Co., Ltd.), IRUGACURE 500 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and IRUGACURE 2959 (manufactured by Ciba Specialty Chemicals Co., Ltd.) IRUGACURE 127 (manufactured by Ciba Specialty Chemicals Co., Ltd.), IRUGACURE 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.), IRUGACURE 369 (manufactured by Ciba Specialty Chemicals Co., Ltd.), IRUGACURE 1300 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and IRUGACURE 819 (manufactured by Ciba Specialty Chemicals Co., Ltd.) IRUGACURE 1800 (manufactured by Ciba Specialty Chemicals Co., Ltd.), DAROCURE TPO (manufactured by Ciba Specialty Chemicals Co., Ltd.), DAROCURE 4265 (manufactured by Ciba Specialty Chemicals Co., Ltd.), IRUGACURE OXE 01 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and IRUGACURE OXE02 (manufactured by Ciba Specialty Chemicals Co., Ltd.) ), ESACURE KT55 (manufactured by Lanbelty Co., Ltd.), ESACURE K1P150 (manufactured by Lanbelty Co., Ltd.), ESACURE KIP100F (manufactured by Lanbelty Co., Ltd.), ESACUREKT37 (manufactured by Lanbelty Co., Ltd.), ESACURE KTO46 (manufactured by Lanbelty Co., Ltd.), ESACURE 1001M (manufactured by Lanbelty Co., Ltd.), ESACURE KIP/EM ( Lanbelty Co., Ltd., ESACURE DP250 (manufactured by Lanbelty Co., Ltd.), and ESACURE KB1 (manufactured by Lanbelty Co., Ltd.). Among these photo-radical polymerization initiators, IRUGACURE 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.), DAROCURE 1173 (manufactured by Ciba Specialty Chemicals Co., Ltd.), IRUGACURE 500 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and IRUGACURE 819 (Ciba Specialty Chemicals Co., Ltd.) are also used. It is preferable that TAROCURE TPO (manufactured by Ciba Specialty Chemicals Co., Ltd.), ESACURE KIP100F (manufactured by Lanbelty Co., Ltd.), ESACURE KT37 (manufactured by Lanbelty Co., Ltd.), and ESACURE KTO46 (manufactured by Lanbelty Co., Ltd.) are preferable.

Examples of the photocationic polymerization initiator include IRUGACURE 250 (manufactured by Ciba Specialty Chemicals Co., Ltd.), IRUGACURE 784 (manufactured by Ciba Specialty Chemicals Co., Ltd.), ESACURE 1064 (manufactured by Lanbelty Co., Ltd.), and CYRAURE UV 16990 (manufactured by Union Cabite Japan Co., Ltd.). ADEKAOPTOMER SP-172 (made by Asahi Kasei Co., Ltd.), ADEKAOPTOMER SP-170 (made by Asahi Kasei Co., Ltd.), ADEKAOPTOMER SP-152 (made by Asahi Kasei Corporation), and ADEKAOPTOMER SP-150 (made by Asahi Kasei Co., Ltd.). Among the above photopolymerization initiators, a photoradical polymerization initiator is preferred. The amount of the photopolymerization initiator to be used is 100 parts by weight based on the total of the monomer (I), the polyvalent monomer (II), and, if necessary, the monomer (III) contained in the monomer composition. It is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, still more preferably 1 to 5 parts by weight. In the above mixture, the photopolymerization initiator may further contain a photopolymerization accelerator.

The photopolymerization accelerator may, for example, be 2,2-bis(2-chlorophenyl)-4,5'-tetraphenyl-2'H-<1,2'>bisimidazolyl, fluorene (4- Dimethylaminophenyl)methane, 4,4'-bis(dimethylamino)diphenyl ketone, 2-ethyl hydrazine, camphorquinone, and the like. Further, a mixture containing the monomer composition and a solvent having a solubility parameter σ of 9.3 (cal/cm ³ ) or more may also contain a UV absorber and a hindered amine light stabilizer (HALS). The single layer film of the present invention is used as an antifouling material or an antifogging material which does not deteriorate even when exposed to the outside for a long period of time, and an ultraviolet absorber or a hindered amine light stabilizer (HALS) may be added to the above mixture. ), improving the weather resistance of the obtained single layer film. As the above ultraviolet absorber, a benzotriazole-based ultraviolet absorber, three can be used. Various kinds of general ultraviolet absorption such as ultraviolet absorber, diphenyl ketone ultraviolet absorber, benzoate ultraviolet absorber, malonate ultraviolet absorber, and oxanilide ultraviolet absorber Agent.

Examples of the ultraviolet absorber include 2-(2H-benzotriazol-2-yl)-p-cresol and 2-(2H-benzotriazol-2-yl)-4-t-butyl group. Phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-butylphenol, 2-(2H-benzotriazol-2-yl)-4,6-bis ( 1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethyl-butyl)-6- (1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(3-one-4- -dodecyl)-6-tert-butyl-phenol, 2-{5-chloro(2H)-benzotriazol-2-yl}-4-(3-one-4- -dodecyl)-6-tert-butyl-phenol, 2-{5-chloro(2H)-benzotriazol-2-yl}-4-methyl-6-tert-butyl-phenol , 2-(2H-benzotriazol-2-yl)-4,6-di-third amyl phenol, 2-{5-chloro(2H)-benzotriazol-2-yl}-4 ,6-di-tert-butylphenol, 2-(2H-benzotriazol-2-yl)-4-thanooctylphenol, 2-(2H-benzotriazol-2-yl)-4 -methyl-6-n-dodecylphenol, methyl-3-{3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl}propionic acid a benzotriazole-based ultraviolet absorber such as a reaction product of a methyl ester/polyethylene glycol 300; 2-(4-phenoxy-2-hydroxy-phenyl)-4,6-diphenyl-1, 3,5-three , 2-(2-hydroxy-4- -hexadecaneoxy)-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-three , 2-(2-hydroxy-4- -heptadecenyloxy)-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-three , 2-(2-hydroxy-4-isooctyloxy-phenyl)-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-tri Trade name: TINUBIN 400 (manufactured by Ciba Specialty Chemicals Co., Ltd.), trade name TINUBIN 405 (manufactured by Ciba Specialty Chemicals Co., Ltd.), trade name TINUBIN 460 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and trade name TINUBIN 479 (Ciba Specialty) Chemicals Co., Ltd.) a UV absorber; a diphenyl ketone ultraviolet absorber such as 2-hydroxy-4-n-octyloxydiphenyl ketone; 2,4-di-t-butylphenyl-3,5-di- a benzoate-based ultraviolet absorber such as tributyl-4-hydroxybenzoate; and malonic acid-{(4-methoxyphenyl)methylene}-dimethyl ester, trade name HOSTABIN PR- a malonate-based ultraviolet absorber such as 25 (manufactured by Clarient Japan Co., Ltd.), trade name HOSTABIN B-CAP (manufactured by Clarent ‧ Japan Co., Ltd.); 2-ethyl-2'-ethoxy oxalate oxalate An amine benzene, a urethane phthalic acid ultraviolet absorber such as Sanduror VSU (manufactured by Clarient ‧ Japan Co., Ltd.), or the like.

Among these ultraviolet absorbers, three Ultraviolet absorbers are preferred. The amount of the ultraviolet absorber to be used is usually 0.1 to 100 parts by weight based on 100 parts by weight of the monomer (I), the polyvalent monomer (II) and, if necessary, the monomer (III) contained in the monomer composition. It is a range of 20 parts by weight, preferably 0.5 to 10 parts by weight. When the amount of use of the ultraviolet absorber is less than the above lower limit, the effect of improving the weather resistance of the obtained single layer film tends to be small. Further, when the amount of the ultraviolet absorber used exceeds the above upper limit, the polymerization may be insufficient. Hindered Amin Light Stabilizers (HALS) are generally referred to as HALS, generally referred to as compounds of the 2,2,6,6-tetramethylpiperidine skeleton, and can be roughly classified into low molecular weights according to molecular weight. HALS, medium molecular weight HALS, high molecular weight HALS and reactive HALS.

For example, the product name: TINUBIN 111FDL (manufactured by Ciba Specialty Chemicals Co., Ltd.), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacic acid Ester (trade name: TINUBIN123 (manufactured by Ciba Specialty Chemicals Co., Ltd.)), trade name TINUBIN 144 (manufactured by Ciba Specialty Chemicals Co., Ltd.), trade name TINUBIN 292 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and trade name TINUBIN 765 (Ciba Specialty Chemicals) Co., Ltd.), trade name TINUBIN770 (manufactured by Ciba Specialty Chemicals Co., Ltd.), N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1) ,2,2,6,6-pentamethyl-4-piperidinyl)amino]-6-chloro-1,3,5-three A condensate (trade name: CHIMASSORB 119FL (manufactured by Ciba Specialty Chemicals Co., Ltd.)), trade name CHIMASSORB2020FDL (manufactured by Ciba Specialty Chemicals Co., Ltd.), dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy- 2,2,6,6-tetramethylpiperidine polycondensate (trade name: CHIMASSORB622LD (manufactured by Ciba Specialty Chemicals Co., Ltd.)), poly[{6-(1,1,3,3-tetramethylbutyl) Amino-1,3,5-three -2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethylene {(2,2,6,6-tetramethyl-) 4-piperidinyl)imine}] (trade name: CHIMASSORB 944FD (manufactured by Ciba Specialty Chemicals Co., Ltd.)), trade name Sanduvor 3050Liq. (manufactured by Clarient ‧ Japan Co., Ltd.), trade name Sanduvor 3052Liq. (Clarient ‧ Japan Co., Ltd. , product name: Sanduvor 3058Liq. (manufactured by Clarient ‧ Japan Co., Ltd.), trade name Sanduvor 3051 Powder (manufactured by Clarient ‧ Japan Co., Ltd.), trade name Sanduvor 3070 Powder (manufactured by Clarient ‧ Japan Co., Ltd.), trade name VP Sanduvor PR -31 (manufactured by Clarient Japan Co., Ltd.), trade name HOSTABIN N20 (manufactured by Clarient Japan Co., Ltd.), trade name HOSTABIN N24 (manufactured by Clarient Japan Co., Ltd.), and trade name HOSTABIN N30 (limited by Clarient Japan) Company name), product name HOSTABIN N321 (manufactured by Clarient Japan Co., Ltd.), product name HOSTABIN PR-31 (manufactured by Clarient Japan Co., Ltd.), product name HOSTABIN 845 (manufactured by Clarient Japan Co., Ltd.), trade name NYLOSTAB S-EED (Cl Arient ‧ Japan Co., Ltd.) and so on. The amount of the HALS used is usually 0.1 to 10 by weight based on 100 parts by weight of the total of the monomer (I), the polyvalent monomer (II), and the monomer (III) optionally contained in the monomer composition. The portion is preferably in the range of 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight.

When the amount of use of the HALS is less than the above lower limit value, the effect of improving the weather resistance of the obtained single-layer film tends to be small. Further, when the amount of use of the HALS exceeds the above upper limit, the polymerization may be insufficient. Further, in the mixture containing the monomer composition and a solvent containing a compound having a solubility parameter σ of 9.3 (cal/cm ³ ) or more, an infrared ray absorbing agent, a radical replenisher, an antioxidant, or the like may be further contained as needed. Polymerization inhibitors, pigments, binders, internal mold release agents, leveling agents, catalysts, various metal oxides, metals, metal salts, iodine, and phosphonium salts. A metal such as cerium oxide or titanium oxide or a metal oxide may be added for the purpose of imparting light responsiveness, bactericidal property, etc., such as mechanical strength and thermal stability. Further, a metal salt such as a silver salt or a lithium salt, an iodine or a phosphonium salt or the like may be added for the purpose of imparting bactericidal properties, antibacterial properties and the like. The amount of the other additives to be added may be appropriately set according to the purpose, and the total amount of the monomer (I), the polyvalent monomer (II), and the monomer (III) optionally contained in the monomer composition may be 100. The parts by weight are usually in the range of 0.01 to 200 parts by weight, preferably 0.1 to 100 parts by weight. In the present invention, a mixture containing a solvent of the above monomer composition and a compound having a solubility parameter σ of 9.3 (cal/cm ³ ) or more is prepared and applied to a substrate. Examples of the material to be used as the substrate include inorganic materials such as crystallinity or amorphousness such as cerium oxide, metals, and metal oxides; polymethyl methacrylate, polycarbonate, and polyethylene terephthalate; Polymer materials such as diester, polyethylene, polypropylene, polystyrene, polyurethane resin, epoxy resin, vinyl chloride resin, polyoxyxylene resin, organic materials such as paper, wood pulp; and glass A composite material of an inorganic material and an organic material represented by a mixture of a filler and polyethylene terephthalate. The material to be used as the substrate of the present invention can be exemplified as the above-mentioned material, and the substrate used in the present invention may be coated with a coating material or the like on the surface of a substrate composed of an inorganic material or an organic material.

Further, the surface of the substrate may be subjected to a surface treatment such as physical or chemical treatment or primer treatment as needed. This surface treatment can be carried out for the purpose of, for example, improving the adhesion (adhesion) of the substrate to the single layer film to activate the surface of the substrate. Examples of the physical or chemical treatment include corona treatment, ozone treatment, low-temperature plasma treatment using oxygen or nitrogen, glow discharge treatment, oxidation treatment using chemicals, and the like. In the primer treatment, a coating agent such as a primer coating agent, an undercoating agent, or an anchor coating agent may be applied to the surface of the substrate and dried. Examples of the coating agent include polyester, polyamide, polyurethane, epoxy resin, phenol resin, (meth)acrylic resin, polyvinyl acetate, polyethylene, and polypropylene. A polymer composition such as a polyolefin, a modified polyolefin, or a cellulose resin is used as a polymer component of a carrier main component. The coating agent may, for example, be a solvent-type coating agent in which the polymer is dissolved in a solvent, or a latex-type or dispersion-type aqueous coating agent in which the polymer is dispersed in an aqueous solvent such as water.

Examples of the polymer contained in the aqueous coating agent include polyolefin, polyvinyl vinyl alcohol, polyethylenimine, polybutadiene, urethane acrylate resin, and polyester polyamine group. Polyurethane such as acid ester, polyvinyl chloride, polyoxyn acrylate resin, vinyl acetate acrylate resin, acrylic resin, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, methyl A rubber such as a methyl acrylate-butadiene copolymer, a chloroprene rubber or a polybutadiene, a polyacrylate, a polyvinylidene chloride, or a polymer modified with a carboxylic acid or the like. Among these coating agents, a coating agent containing a polyurethane is preferred. The polyurethane may have a urethane bond in either the main chain or the side chain of the polymer, and for example, a polyester polyol, a polyether polyol or an acrylic polyol may be used. A polyvalent carbamate obtained by reacting a plurality of compounds with an isocyanate compound.

Further, as the coating agent containing the above-mentioned polyurethane, a two-liquid type coating agent in which a liquid containing a polyol and a liquid containing an isocyanate compound are mixed and applied in the field may be used. In the case of the two-coat type coating agent, the method of mixing the liquid containing the polyol and the liquid containing the isocyanate compound is not particularly limited as long as the primer can be formed on the substrate. Further, the blending ratio of the polyol and the isocyanate compound is not particularly limited as long as the primer can be formed on the substrate, and the value of (the OH group contained in the polyol) / (the NCO group contained in the isocyanate compound) is equivalent. The conversion is usually in the range of 2/1 to 1/40. Among these coating agents containing a polyurethane, a condensed polyester polyol or a lactone polyester is used in terms of excellent adhesion between a substrate and a single layer film and high peel strength. As the polyhydric alcohol, a polyester polyol such as a polyhydric alcohol is used, and a polyurethane such as toluene diisocyanate, hexamethylene diisocyanate or decyl diisocyanate is preferably used as a coating agent for the isocyanate compound. Examples of the method of applying the coating agent to the substrate include a gravure coating method, a reverse roll coating method, a knife coating method, and a contact coating method. The coating amount of the coating agent is usually from 0.01 g/m ² to 10 g/m ² , preferably from 0.05 g/m ² to 5 g/m ² in a dry state. Thereafter, at least a portion of the solvent is removed from the above mixture coated on the substrate. When the solvent removed from the above mixture is insufficient, the anion tilt of the obtained single layer film is insufficient, so that the hydrophilicity is lowered, and the adhesion between the single layer film and the substrate tends to be lowered. Therefore, the residual amount of the solvent contained in the above mixture before the polymerization of the monomer composition on the substrate is usually less than 20% by weight, preferably less than 10% by weight, more preferably less than 5% by weight. More preferably, it is less than 2% by weight, and most preferably less than 1% by weight. The method for removing the solvent from the above mixture is not particularly limited, and examples thereof include a method of allowing to stand at room temperature and allowing the solvent to evaporate naturally in the mixture, and a method of removing the solvent from the mixture by heating, and allowing to stand at room temperature. And removing the solvent from the above mixture by means of a wind, a method of removing the solvent from the above mixture under reduced pressure, a method of removing the solvent from the above mixture under reduced pressure and heating, and removing the solvent from the mixture by heating and blowing. Method, etc. In these methods, a method of removing a solvent from the mixture coated with a substrate by warm air, a method of removing a solvent from the mixture by heating in a warm air while heating a substrate to which the mixture is applied, and the like are represented by Heating and wind are preferably carried out by removing the solvent from the above mixture.

The heating temperature at the time of removing the solvent with heating is usually room temperature or more and 200 ° C or less, preferably 30 ° C or more and 150 ° C or less, more preferably 40 ° C or more and 100 ° C or less. The environment in which the solvent is removed may be an inert gas such as the atmosphere or nitrogen gas, and may be any. However, the humidity of the environment is preferably lower. The humidity of the environment is preferably 70% or less, more preferably 60% or less, and still more preferably 55% or less. When the solvent is removed by heating, if the air is added, the evaporation rate is increased, the amount of solvent remaining can be reduced, the drying time can be shortened, the drying temperature can be lowered, and the like, and the film can be peeled off from the substrate when the solvent is removed (the adhesion is lowered). The tendency of cracks (membrane splitting). The wind speed at the time of applying the wind is preferably in the range of 0.1 m/sec to 30 m/sec, more preferably in the range of 0.1 m/sec to 10 m/sec, and more preferably 0.2 m/sec to 5 m/sec. The scope of the clock. When the wind speed exceeds the above upper limit, it tends to be difficult to obtain a uniform coated surface. On the other hand, if the lower limit is not satisfied, the effect of the wind addition tends to be insufficient. The pressure at which the solvent is removed is not particularly limited, but it is preferred to carry out the solvent removal under normal pressure or reduced pressure. Alternatively, the solvent can be removed under slight pressure. The time for removing the solvent may be appropriately set from the viewpoint of a preferable solvent residual amount, etc., and it is preferable to use it in a short period of time in consideration of productivity, for example, 5 minutes or less, typically 3 minutes or less, more typically 2 minutes. The solvent was removed at the following times.

After the coating to the substrate is carried out and at least a part of the solvent is removed, the monomer composition containing the monomer (I) and the monomer (II) is polymerized. The polymerization method of the monomer composition is not limited, and the monomer composition can usually be polymerized by heat or radiation, or both heat and radiation. The polymerization may be carried out in the atmosphere, but it is preferably carried out in an inert gas atmosphere such as nitrogen from the viewpoint of shortening the polymerization time. When the polymerization is carried out by heat, a thermal radical initiator such as an organic peroxide is added to the monomer composition as needed, and it is usually polymerizable by heating at a temperature of from room temperature to 300 ° C. In the case of polymerization by radiation, as the radiation, an energy line having a wavelength region of usually 0.0001 to 800 nm can be used. Examples of such radiation include α rays, β rays, γ rays, electron beams, ultraviolet rays, visible light, and the like. These radiations can be appropriately selected and used depending on the composition of the above monomer composition and, if necessary, a photopolymerization initiator or a photopolymerization accelerator. Among these radiations, ultraviolet rays having a wavelength region of 200 to 450 nm are preferred. In a mixture containing a monomer composition and a solvent containing a compound having a solubility parameter σ of 9.3 (cal/cm ³ ) or more, after adding an ultraviolet absorber or HALS, the monomer composition is polymerized by radiation to produce a single layer of the present invention. In the case of a film, it is preferable to use a radiation lamp having a peak output power in the range of 240 to 270 nm or 370 to 430 nm. Further, although the apparatus is expensive, if the polymerization is carried out by an electron beam having an output power peak in the range of 0.01 to 0.002 nm, the polymerization can be completed in a short time, which is also preferable.

Further, in order to avoid the polymerization inhibition by oxygen, the coating may be applied to the mixture and at least a part of the solvent may be removed, and then the coating layer of the mixture may be coated with a coating material such as a film. When coating a coating layer with a coating material, it is desirable to adhere to the coating layer and the coating material so that air (oxygen) is not contained. When the polymerization is carried out by radiation without containing air (especially oxygen), the amount of radiation irradiation may be reduced, and polymerization of a polymerization initiator such as a photopolymerization initiator may be used to reduce the polymerization starting dose. . The above-mentioned coating material is not particularly limited as long as it does not block oxygen, and various materials can be used in various forms, and in terms of workability, a film is preferably used, and polymerization is carried out by radiation so as not to inhibit polymerization and radiation wear. A transparent film having a high transmittance is preferred. Examples of the material of the coating material include a vinyl alcohol polymer such as polyvinyl alcohol (PVA) and an ethylene-vinyl alcohol copolymer, polypropylene decylamine, polyisopropyl acrylamide, polyacrylonitrile, and polycarbonate. Ester (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polystyrene (PS), biaxially oriented polypropylene (OPP), and the like. The above-mentioned coated material typically has a thickness of the film of usually 3 to 200 μm, preferably 5 to 100 μm, more preferably 10 to 50 μm. Further, in the single layer film of the present invention and the laminate in which the single layer film is formed on at least one of the substrate faces, the above-mentioned coated material may be directly coated. When the covering material is formed on the single layer film, damage or contamination of the single layer film when the single layer film or the laminated body is transported, stored, arrayed, or the like can be prevented.

The monolayer film formed on the substrate of the present invention thus obtained has at least one anionic hydrophilic group selected from the group consisting of a sulfonic acid group (SO ₃ ^- ), a carboxyl group (CO ₂ ^- ) and a phosphate group (PO ₄ ^- ) Further, the anion concentration ratio (Sa/Da) of the anion concentration (Sa) of the outer surface and the anion concentration (Da) at the intermediate point between the inner surface and the outer surface of the substrate is 1.1 or more. Here, the contact between the inner surface and the outer surface of the substrate means that the inner surface portion of the substrate is in contact with the outer surface portion of the outer layer and the outer surface portion of the outer layer when facing the film thickness direction of the single layer film. The above anion concentration ratio is obtained by obliquely cutting a single layer film provided on a substrate, and using a time-of-flight secondary ion mass spectrometer (TOF-SIMS) to measure the anion concentration and the inner surface of the surface of the single layer film contacting the outside. Determined from the anion concentration at the middle of the outer surface. In the monolayer film of the present invention, the anion in the monolayer film has a concentration difference distribution on the inner surface portion of the substrate side to the outer surface portion contacting the outside, and has the most distribution of the surface portion in contact with the outside. The anion concentration is poor. The reason why such an anion concentration difference occurs in the film thickness direction is presumed to be due to the fact that the above-mentioned anions of hydrophilicity self-assemble on the surface contacting the outside in the process of forming a single layer film. The monolayer film of the present invention has an anion having a high hydrophilic group at a high concentration on the outer surface of the monolayer film, so that it is excellent in antifogging property, antifouling property, self-cleaning property, antistatic property, and dust adhesion resistance. .

The anion concentration ratio (Sa/Da) is preferably 1.2 or more, more preferably 1.3 or more. When the anion concentration ratio is at least the above value, the antifogging property, the antifouling property, the self-cleaning property, the antistatic property, and the dust adhesion prevention property are more excellent. Further, the anion concentration ratio (Sa/Da) is usually about 20.0 or less. The water contact angle of the single layer film of the present invention is usually 30 or less, preferably 20 or less, more preferably 10 or less. The single layer film having a water contact angle of not less than the above lower limit is highly hydrophilic, and is excellent as a hydrophilic material which is easily compatible with water (wet). Therefore, for example, it can be used for an antifogging material, an antifogging film (hereinafter also referred to as antifogging coating), an antifouling material, an antifouling film or a self-cleaning coating, an antistatic material, a quick-drying material, or a quick-drying coating, and Antistatic film or dust adhesion coating. For example, if it is used as an anti-fog coating, since water droplets can spread on the surface of the film to form a water film, the anti-fogging effect is excellent, and if it is used as a self-cleaning coating, the contamination between the sewage and the coated surface can be caused. The object is floated and removed, so that the antifouling effect is excellent. Further, the monolayer film having an anionic hydrophilic group of the present invention is excellent in antistatic property as compared with a film having a conventional anionic hydrophilic group, and can also be used for an antistatic material and an antistatic coating or to prevent adhesion of dust. Wait. The thickness of the above-mentioned single layer film can be appropriately set depending on the application, and is usually in the range of 0.1 to 100 μm, preferably 0.5 to 20 μm, more preferably 1 to 10 μm. The single layer film of the present invention can be formed into a single layer film of various forms by working on the shape of the above substrate. The single layer film of the present invention can also be used in a laminate type in combination with its substrate. The laminate of the present invention can be produced by forming a single layer film on at least one side of the substrate by the above method.

An adhesive layer may be provided on the other surface of the substrate on which the single layer film is not formed. The laminated body in which the adhesive layer is provided, for example, in the form of an antifogging film and an antifouling film, can be easily attached to an indication of a surface of a display material such as a mirror of a glass, a bathroom, a display, a television, or the like, a billboard, an advertisement, an indicator board, or the like. Marks for boards, railways, roads, etc., exterior and inner walls of buildings, window glass, etc. The adhesive layer is formed by applying an adhesive to the other surface of the substrate on which the single layer film is not formed, and further removing the solvent as needed. This adhesive can be used without particular limitation. Examples of the above-mentioned adhesive include an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a vinyl ether polymer-based pressure-sensitive adhesive, and a polyoxynoxy adhesive. The thickness of the adhesive layer is usually in the range of 2 to 50 μm, preferably 5 to 30 μm. Further, a peeling layer may be further provided on the adhesive layer. Further, in the laminate of the present invention, a peelable coating material layer may be further provided on the surface of the single layer film. The laminate of the present invention can be formed into a laminate of various forms by working on the shape of the substrate. For example, the single layer film and the laminate of the present invention can be used in the form of a film, a sheet, a belt or the like. Further, the single layer film of the present invention can also be used as a primer layer. The single layer film and the laminate of the present invention are excellent in hydrophilicity and can be used as an antifogging material, an antifouling material, an antistatic material, and the like. For example, a laminate of the single layer film of the present invention is laminated on a substrate made of a transparent material such as a transparent resin or glass, and can be used for transparency, hydrophilicity, antifogging property, antifouling property, antistatic property, and speed. A laminate that is dry and has excellent dew condensation.

Therefore, the single-layer film and the laminate of the present invention can be used for conveying machine materials represented by automobiles, ships, and aircraft, such as blanks, wheels, exterior materials, and interior materials; outer wall materials, inner wall materials, and bed materials. , materials for the use of materials such as furniture materials, bathroom materials, bathroom materials for washing and dressing, ventilating fans, building materials, materials for building materials, and materials for housing; construction materials for sound-absorbing panels such as highways; clothes and cloth And materials for clothing such as fibers; optical materials such as window materials, mirrors, optical films, optical disks, glasses, contact lenses, frog mirrors, reflective films, and reflectors; lighting materials for electric lamps and light materials; cooling fans, etc. Industrial materials; materials for electrification products, wiring materials, display materials such as touch panel, and electrical and electronic materials such as photoresist; printing materials such as inkjet recording boards, printing and printing primers; cosmetics containers, etc. Use of daily necessities, etc.

[Examples]

Hereinafter, the present invention will be described in further detail based on examples, but the present invention is not limited to the examples.

Further, the physical property evaluation of the film in the present invention is carried out as follows.

<Measurement of water contact angle>

Using the water contact angle measuring device CA-V type manufactured by Kyowa Interface Science Co., Ltd., three samples were measured, and the average value of the equivalent values was regarded as the value of the water contact angle.

<Measurement of fog value>

Four samples were measured for one sample using a Haze Meter NDH 2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the average value of the equivalent values was regarded as a haze value.

<Scratch resistance test>

Use Steel Wool #0000 to wipe back and forth 10 times with a certain load.

The case where no damage is caused is ○, and the case of 1 to 5 damages is △, and the case of 6 to countless damages is ×.

<Evaluation of anti-fog property>

The case where fogging is not caused by exhalation is regarded as ○, and the case where fogging is caused is regarded as ×.

<Evaluation of antifouling properties>

The oily marker "Maki Very Fine" (black, model MO-120-MC-BK) made by Zebra was used, and water drops were placed on it and left for 30 seconds, and wiped with a paper towel. The case where the mark can be erased is ○, and the case where it is not wiped off remains x.

<Evaluation of Adhesion>

It was evaluated by a checkerboard peel test.

<Measurement of anion and cation concentration ratio>

The sample prepared by the sample shown in Fig. 1 was cut obliquely, and the anion concentration (Sa) of the outer surface and the anion concentration of the intermediate point (Da) were measured using a time-of-flight secondary ion mass spectrometer (TOF-SIMS). From this value, the anion concentration ratio (Sa/Da) of the outer surface of the single layer film contacting the outside and the inner surface and the outer surface of the single layer film is determined.

(analytical device and measurement conditions)

TOF-SIMS; TOF-SIMS ⁵ made by IDN‧TOF

1st ion: Bi ₃ ²⁺ (acceleration voltage 25kV)

Measuring area; 400 μm ²

Neutralization gun for charging correction used in the measurement

(sample preparation, etc.)

As shown in Fig. 1, the sample having the coating layer 20 on the surface of the substrate 10 is oriented in the cutting direction 30, and after precise oblique cutting, a size of about 10 × 10 mm ^{2 is} cut out, and the measurement surface is contacted to the sample holder. Using a time-of-flight secondary ion mass spectrometer (TOF-SIMS), the surface of the coating layer 40 which is in contact with the outside and the interior of the coating layer 50 inside the single-layer film (the film thickness is 1/2, the substrate 10 is bonded) The inner surface of the coating layer was measured for the anion concentration.

(assessment)

The evaluation is performed by the following calculation formula. In addition, the ion concentration at each measurement point is relative intensity (relative to all detected ions).

Anion concentration ratio = anion concentration of the coating layer surface 40 / anion concentration at the film thickness 1/2 of the coating layer 20

[Reference Example 1~5] (modulation of solution 1)

According to the compounding ratio of Table 1, a solution 1 containing a uniform monomer composition of 80% by weight of a solid content (NV) was prepared.

[化85]

(Formation of a mixture 1 for forming a single layer film)

Initiation initiator IRUGACURE 127 (2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropenyl)benzyl]phenyl}-2-methyl-propan-1-one To 0.3 g of methanol, 7.8 g of methanol was added and dissolved, and then 12.5 g of a solid portion of 80 wt% of the above solution 1 was added and dissolved to obtain a monolayer film-forming mixture 1 having a solid content of 50% by weight.

(formation of a single layer film)

The single layer film mixture 1 was formed and applied to a polycarbonate sheet (manufactured by TAKIRON Co., Ltd.) as a substrate by a bar coater. In addition, in order to evaluate the film thickness of the single layer film of Reference Examples 1 to 5, the number of the bar coater coated in each of Reference Examples 1 to 5 was changed and applied as follows.

Reference Example 1: #03 (single layer film thickness: 2 μm is dry)

Reference Example 2: #05 (single layer film thickness: 3 μm is dry)

Reference Example 3: #08 (single layer film thickness: 5 μm is dry)

Reference Example 4: #12 (single layer film thickness: 8 μm is dry)

Reference Example 5: #20 (single layer film thickness: 14 μm is dry)

Immediately after coating, it is dried by a 45 to 50 ° C warm air dryer. After drying, it was passed through a UV conveyor belt (Fusion UV Systems ‧ Japan Co., Ltd., electrodeless discharge lamp H Bulb, conveyor speed 18 m/min) 3 times (integrated light amount 900 Mj/cm ² ) on a polycarbonate plate A single layer film of each of the film thicknesses of Reference Examples 1 to 5 was formed. Finally, the water was washed for the purpose of removing contaminants from the outer surface of the single-layer film which was in contact with the outside, and the surface of the film was dried with a hair dryer to evaluate the single-layer film. The results are shown in Table 2.

When the molar ratio of the monomer (I)/polyvalent monomer (II) is outside the range specified in the present invention, when the scratch resistance is further improved and the film thickness is increased, the fog value tends to increase, and the transparency is improved. Sex has a tendency to decrease.

[Example 1] (modulation of solution 2)

According to the compounding ratio of Table 3, a solution 2 containing no hydrophilic monomer SPA-K and containing a uniform monomer composition of 80% by weight of a solid content was prepared.

(Formation of the mixture 2 for forming a single layer film)

Initiation initiator IRUGACURE 127 (2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)benzyl]phenyl}-2-methyl-propane-1- Ketone) 0.24 g of methanol was added and dissolved, and then 5.9 g of a solid portion of 80 wt% of solution 1, and 4.1 g of a solid portion of 80 wt% of solution 2 were added and dissolved to obtain a solid content of 50 wt% for forming a monolayer film. Mixture 2.

(formation of a single layer film)

The single layer film mixture 2 was formed and applied to a polycarbonate plate (manufactured by TAKIRON Co., Ltd.) as a substrate by a bar coater #12. Immediately after coating, it was dried by a 45-50 ° C warm air dryer for 2 minutes. After drying, it was formed on a polycarbonate plate by a UV conveyor belt (Fusion UV Systems ‧ Japan Co., Ltd., electrodeless discharge lamp H Bulb, conveyor speed of 18 m/min) three times (integrated light amount: 900 Mj/cm ² ) A single layer film having a film thickness of about 8 μm. Finally, the water was washed for the purpose of removing contaminants from the outer surface of the single-layer film which was in contact with the outside, and the surface of the film was dried with a hair dryer to evaluate the single-layer film. The results are shown in Table 4.

[Examples 2 to 3]

A single layer film was produced in the same manner as in Example 1 except that the mixing ratio of the solution 1 and the solution 2 was changed to the mixing ratio described in Table 4. The results are shown in Table 4.

[Examples 4 to 6]

The same as Example 1 except that the mixing ratio of the solution 1 and the solution 2 was the mixing ratio described in Table 5, and the number of the bar coater was changed from #12 to #20 (single layer film thickness: 14 μm was dry). A single layer film was made and evaluated. The results are shown in Table 5.

It is understood that the monomer (I) / polyvalent monomer (II) is compared to the scope of the invention, and transparency and scratch resistance are improved.

[Reference Example 6~9] (modulation of solution 3)

According to the mixing ratio of the following Table 6, a solution 3 containing a uniform monomer composition of 50% by weight of the solid content was prepared.

[化86]

(Modulation of polymerization initiator solution 3)

IRUGACURE 127 (2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propan-1-one) 50 50 g of methanol and methanol were mixed and dissolved to obtain a solid content of 50 wt% of a polymerization initiator solution 3.

(Formation of a single layer film mixture 3)

10.0 g of the solution 3 was mixed with 0.3 g of the polymerization initiator solution 3 to obtain a solid layer 50% by mass to form a monolayer film mixture 3.

(formation of a single layer film)

The single layer film mixture 3 was formed and applied to a polycarbonate plate (manufactured by TAKIRON Co., Ltd.) as a substrate by a bar coater. In order to evaluate the single-layer film in which the film thickness was changed in Reference Examples 6 to 9, the number of the bar coater coated in each of Reference Examples 6 to 9 was changed and applied as follows, and a single-layer film was produced in the same manner as Reference Examples 1 to 5 after coating. And carry out its evaluation. The results are shown in Table 7.

Reference Example 6: #02 (single layer film thickness: 1 μm is dry)

Reference Example 7: #03 (single layer film thickness: 2 μm is dry)

Reference Example 8: #05 (single layer film thickness: 3 μm is dry)

Reference Example 9: #08 (single layer film thickness: 5 μm is dry)

In the same manner as in Reference Examples 1 to 5, when the monomer (I)/polyvalent monomer (II) is outside the range specified in the present invention, it is understood that the haze value is increased when the film thickness is increased, and the transparency tends to be lowered.

[Embodiment 7] (modulation of solution 4)

According to the compounding ratio of Table 8, a solution 4 containing no hydrophilic monomer SPA-K and containing a uniform monomer composition of 50% by weight of solid content was prepared.

(Formation of the mixture 4 for forming a single layer film)

The solution 3 5.0 g, the solution 4 5.0 g, and 30.3 g of a polymerization initiator solution were mixed and dissolved to obtain a solid layer 50% by mass to form a monolayer film mixture 4.

(formation of a single layer film)

The single layer film mixture 4 was formed and applied to a polycarbonate sheet (manufactured by TAKIRON Co., Ltd.) as a substrate by a bar coater #05, and immediately dried in a warm air dryer at 45 to 50 ° C for 2 minutes. After drying, it was formed on a polycarbonate plate by a UV conveyor belt (Fusion UV Systems ‧ Japan Co., Ltd., electrodeless discharge lamp H Bulb, conveyor belt speed 18 m/min) 3 times (integrated light amount 900 mJ/cm ² ) A single layer film having a film thickness of about 3 μm. Finally, the water was washed for the purpose of removing contaminants from the outer surface of the single-layer film which was in contact with the outside, and the surface of the film was dried with a hair dryer to evaluate the single-layer film. The results are shown in Table 9.

[Examples 8 to 10]

A single layer film was produced in the same manner as in Example 7 except that the mixing ratio of the solution 3 and the solution 4 was changed to the mixing ratio described in Table 9, and the evaluation was carried out (the thickness of the single layer film: drying was 3 μm).

The results are shown in Table 9.

Comparing the monomer (I) / polyvalent (II) to the scope of the invention, the transparency can be greatly improved.

Hereinafter, regarding the single layer films obtained in Example 4 and Example 10, the relative ionic strength ratio (distribution of anion and cation concentration) of the cut surface of the film was analyzed by TOF-SIMS. The results are shown in Table 10.

[Example 11] (modulation of solution 5)

According to the mixing ratio of Table 11 below, a solution 5 containing a uniform monomer composition of 80% by weight of the solid content was prepared.

[化87]

(Formation of a single layer film mixture 5)

0.3 g of methanol was added to 0.3 g of the polymerization initiator IRUGACURE 127 and mixed and dissolved, and then 5 12.5 g of a solution of 80 wt% of the solid portion was added, and then 6.0 g of the dilution solvent described in Table 12 was added and mixed to obtain a solid content of 52% by weight. Mixture 5 for a single layer film.

(formation of a single layer film)

The single layer film mixture 5 was formed and applied to a polycarbonate sheet as a substrate by a bar coater #18, and immediately dried in a warm air dryer at 45 to 55 ° C for 2 minutes. After drying, it was formed on a polycarbonate plate by a UV conveyor belt (Fusion UV Systems ‧ Japan Co., Ltd., electrodeless discharge lamp H Bulb, conveyor belt speed 18 m/min) once (integrated light amount 300 mJ/cm ² ) A single layer film having a film thickness of about 13 μm. Finally, the water was washed for the purpose of removing contaminants from the outer surface of the single-layer film which was in contact with the outside, and the surface of the film was dried with a hair dryer to evaluate the single-layer film. The results are shown in Table 12.

(Formation of a single layer film mixture 6)

Add 0.9 g of methoxyethanol to 0.6 g of the polymerization initiator IRUGACURE 127 and mix and dissolve, and then add 5 25.0 g of a solution of 80 wt% of solid content, and then add 5.0 g of methanol as a dilution solvent and 10.0 g of methoxyethanol. The mixture was dissolved in a mixture to obtain a mixture 6 of a single-layer film having a solid content of 50% by weight.

(formation of a single layer film)

The single layer film mixture 6 was formed, and after applying the bar coater #20 to the polycarbonate sheet as the substrate, the wind speed was changed at a temperature of 43 to 47 ° C and dried at the time indicated in Table 13. . However, the drying of the wind speed of 0 m/sec (no wind) was carried out by an IR (infrared) dryer. After drying, a film was formed on a polycarbonate plate by a UV conveyor belt (Fusion UV Systems ‧ Japan Co., Ltd., electrodeless discharge lamp HBulb, conveyor speed of 18 m/min) once (integrated light amount: 300 mJ/cm ² ) A single layer film having a thickness of about 13 μm. Finally, the water was washed for the purpose of removing contaminants from the outer surface of the single-layer film which was in contact with the outside, and the surface of the film was dried with a hair dryer to evaluate the single-layer film. The results are shown in Table 13.

10. . . Substrate

20. . . Coating layer

30. . . Cutting direction

40. . . Coating surface

50. . . Coating interior

Fig. 1 is a schematic view showing a method of preparing a sample for measurement of an anion concentration ratio.

Claims (15)

A single layer film is obtained by applying the following mixture, after applying the mixture to a substrate, removing at least a part of the solvent, and polymerizing the monomer composition containing the monomer (I) and the monomer (II). The mixture contains: a monomer composition having the monomer (I) represented by the following general formula (1), and having two or more (meth)acryl fluorenyl groups and having no sulfonic acid group or carboxyl group. And a polyvalent monomer (II) having a phosphate group, which is contained in a monomer (I) / polyvalent monomer (II) molar ratio of 1/1000 or more and less than 1/30; and a solvent containing solubility a compound having a parameter σ of 9.3 (cal/cm ³ ) or more; wherein, at least one anionic hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxyl group and a phosphoric acid group, and an anion concentration (Sa) and a contact-based group on the outer surface The anion concentration ratio (Sa/Da) of the anion concentration (Da) at the intermediate point between the inner surface and the outer surface of the material is 1.1 or more; [X] _s [M1] _l [M2] _m (1) (the above formula (1) Wherein s represents 1 or 2, and l and m represent integers satisfying s=l+m/2; M1 is at least one monovalent cation selected from hydrogen ion, ammonium ion and alkali metal ion, and M2 is composed of alkaline earth Metal separation At least one divalent cation selected from the group; X is at least one monovalent anion selected from the groups represented by the following general formulas (1-1) to (1-4); [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] (In the above formulae (1-1) to (1-4), J and J' are each independently H or CH ₃ , and n represents 0 or 1, and R is independently an aromatic group or an aliphatic cyclic group. And at least one selected from the group consisting of an ether group and an ester group is substituted with an aliphatic hydrocarbon group having a carbon number of from 1 to 600 carbon atoms)). The single layer film of the first aspect of the invention, wherein the monomer (I) is selected from the compounds represented by the following general formula (1-1-1) and general formula (1-1-2). At least 1 monomer; [Chemical 5] [Chemical 6] (In the formulae (1-1-1) and (1-1-2), J is H or CH ₃ , and R ₁ and R ₂ are each independently H, CH ₃ or C ₂ H ₃ ; n represents 1 to 20 An integer, l represents an integer from 2 to 10, and M is at least one monovalent cation selected from hydrogen ions, ammonium ions, and alkali metal ions, or at least one divalent cation selected from alkaline earth metal ions, M is In the case of a monovalent cation, m is 1, and when M is a divalent cation, m is 2). The monolayer film according to claim 1 or 2, wherein the polyvalent monomer (II) is selected from the compounds represented by the following general formula (2-1) and general formula (2-2). At least 1 monomer; [Chem. 7] [化8] (In the above formulae (2-1) and (2-2), R ₃ and R ₅ to R ₉ are each independently H or CH ₃ , and R ₁₂ and R ₁₃ are each independently H or CH ₃ , X ₁ , X _{2 .} , X ₃ , X ₄ and X ₅ are each independently O or S, a represents an integer from 2 to 30, b represents an integer from 0 to 2, c represents an integer from 0 to 30, d represents an integer from 0 to 20, and e represents An integer from 0 to 2, i represents an integer from 1 to 20, k represents an integer from 1 to 10, and A represents one of the following: [Chemical 9] Or [10] Wherein * is a bonding bond; R ₁₀ and R ₁₁ are each independently H or CH ₃ , and R ₁₀₀ and R ₁₀₁ are each independently H or an alkyl group having 1 to 6 carbon atoms; R ₂₀₀ and R ₂₀₁ are each independently H, CH ₃ or phenyl, R is hexamethylene, isophorone (1-methylene-3-extended ethyl-3-methyl-5,5-dimethyl-cyclohexane), Alkyl dimethylene, dicyclohexylmethane, cyclohexane dimethylene or fluorenyl, R ₅₀ is hexamethylene, isophorone (1-methylene-3-ethylidene-3) -methyl-5,5-dimethyl-cyclohexane), drop Alkyl dimethylene, dicyclohexylmethane, cyclohexane dimethylene, extens (toluylene) group, diphenylmethane or hydrazine group; V is OH or an oxygen atom having a bonding bond (*), and W1 to W3 are independently H, CH ₃ , OH or have a bonding bond (*) An oxygen atom, Z represents OH, an oxygen atom having a bonding bond (*), COOH or a carboxyl group (COO) having a bonding bond (*), and V1 to V3 are independently H or a bonding bond (*); n1 and N2 independently represents an integer from 0 to 8, and o1 and o2 independently represent integers from 1 to 3, f represents an integer from 1 to 20, g represents an integer from 0 to 3, m represents 0 or 1, and q represents 1 to 7. Integer, a1 represents an integer from 2 to 3, a2 represents an integer from 3 to 4, a3 represents an integer from 4 to 6, a4 represents an integer from 2 to 3, and a5 represents an integer from 2 to 4. The monolayer film of claim 1 or 2, wherein the polyvalent monomer (II) is a compound represented by the following general formulas (3) to (8) and (10) to (33); Select at least one monomer; [Chem. 11] (In the above formula (3), R ₃ and R ₄ are each independently H or CH ₃ , and R ₁₀₀ and R ₁₀₁ are each independently H or an alkyl group having 1 to 6 carbon atoms, and b1 and b2 each independently represent 0 to 2; Integer, n1 and n2 respectively represent integers from 0 to 8;) [12] (In the above formula (4), R ₃ to R ₆ are each independently H or CH ₃ , and R ₁₀₀ and R ₁₀₁ are each independently H or an alkyl group having 1 to 6 carbon atoms, and n ₁ and n ₂ each independently represent 0 to 0. An integer of 8;) [Chem. 13] (In the above formula (5), R ₃ to R ₆ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c1 represents an integer of 2 to 30;) [Chemical 14] (In the above formula (6), R ₃ to R ₆ are each independently H or CH ₃ , c2 and c3 each independently represent an integer of 1 to 5, and d1 represents an integer of 2 to 20;) [Chemical 15] (In the above formula (7), R ₃ and R ₄ are each independently H or CH ₃ , b1 and b2 each independently represent an integer of 0 to 2, d1 represents an integer of 2 to 20, and m represents 0 or 1; 16] (In the above formula (8), R ₃ and R ₄ are each independently H or CH ₃ , and o1 and o2 each independently represent an integer of 1 to 3;) [Chem. 17] (In the above formula (10), R ₃ to R ₈ are each independently H or CH ₃ , and c4 and c5 each independently represent an integer of 0 to 5, and m represents 0 or 1;) [Chem. 18] (In the above formula (11), R ₃ and R ₄ are each independently H or CH ₃ , and m represents 0 or 1;) [Chem. 19] (In the above formula (12), R ₃ to R ₇ are each independently H or CH ₃ ;) [Chemical 20] (In the above formula (13), * is a bonding bond, R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , and c6 represents an integer of 0 to 3;) [Chem. 21] (In the above formula (14), R ₃ to R ₈ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c7 and c8 each independently represent an integer of 0 to 5, and m represents 0 or 1. ;)[化22] (In the above formula (15), R ₃ to R ₁₀ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c9 and c10 each independently represent an integer of 0 to 30;) [Chem. 23] (In the above formula (16), R ₃ to R ₁₀ are each independently H or CH ₃ , and c11 to c14 represent an integer of 1 or more, and satisfy c11+c12+c13+c14=4 to 30;) [Chem. 24] (In the above formula (17), R ₃ and R ₄ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2;) [Chem. 25] (In the above formula (18), R ₃ to R ₈ are each independently H or CH ₃ , and R ₂₀₀ and R ₂₀₁ are each independently H, CH ₃ or a phenyl group, and c4 and c5 each independently represent an integer of 0 to 5; [Chem. 26] (In the above formula (19), R ₃ to R ₅ and R ₁₁ are each independently H or CH ₃ , and b1 to b3 each independently represent an integer of 0 to 2, and f represents an integer of 1 to 20;) [27] (In the above formula (20), * is a bonding bond, V is an OH or an oxygen atom having a bonding bond (*), and R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , and a1 represents 2 or 3 , b1 represents an integer from 0 to 2, and c15 represents an integer from 0 to 20;) [28] (In the above formula (21), * is a bonding bond, W1 is H, CH ₃ , OH or an oxygen atom having a bonding bond (*), and R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , A2 means 3 or 4, and c16 means an integer of 0~20;)[29] (In the above formula (22), * is a bonding bond, and W2 and W3 are each independently H, CH ₃ , OH or an oxygen atom having a bonding bond (*), and R ₃ , R ₅ and R ₆ are each independently H. Or CH ₃ , a3 represents an integer from 4 to 6, and c17 represents an integer from 0 to 3;) [Chem. 30] (In the above formula (23), R is hexamethylene, isophorone (1-methylene-3-ethylidene-3-methyl-5,5-dimethyl-cyclohexane), drop Alkyl dimethylene, dicyclohexylmethane, cyclohexane dimethylene or fluorenyl, R ₃ ~ R ₁₀ are each independently H or CH ₃ , and e1 and e2 each independently represent an integer of 0 to 2; [化31] (In the above formula (24), R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , b1 represents an integer of 0 to 2, c15 represents an integer of 0 to 20, and n100 represents an integer of 1 to 6;) [ 32] (In the above formula (25), R ₃ to R ₁₀ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c9 and c10 each independently represent an integer of 0 to 5;) [Chem. 33] (In the above formula (26), R ₃ is H or CH ₃ , p1 represents an integer of 1 to 6, and a10 represents 3;) [Chem. 34] (In the above formula (27), R ₃ to R ₈ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c4 and c5 each independently represent an integer of 0 to 5;) [Chem. 35] (In the above formula (28), R ₃ to R ₈ are each independently H or CH ₃ , and b1 and b2 each independently represent an integer of 0 to 2, and c4 and c5 each independently represent an integer of 0 to 5;) [Chem. 36] (In the above formula (29), R ₃ and R ₅ to R ₁₃ are each independently H or CH ₃ , and i1 represents an integer of 0 to 5;) [Chem. 37] (In the above formula (30), R ₃ and R ₅ to R ₉ are each independently H or CH ₃ , W1 is H, CH ₃ , OH or an oxygen atom having a bonding bond (*), and a2 represents 3 or 4. I1 represents an integer from 0 to 5;) [Chem. 38] (In the above formula (31), R ₃ to R ₉ are each independently H or CH ₃ , and W2 and W3 are independently H, CH ₃ , OH or an oxygen atom having a bonding bond (*), and a7 represents 1 to 6 The integer, a8 represents an integer from 0 to 5, and satisfies a7+a8=2~6;)[39] (In the above formula (32), R ₇₀ is a stretch Base, diphenylmethane, hexamethylene, isophorone (1-methylene-3-extended ethyl-3-methyl-5,5-dimethyl-cyclohexane), Alkyl dimethylene, dicyclohexylmethane, cyclohexane dimethylene, N,N',N"-fluorene (hexamethylene)-trimeric isocyanate, N,N,N'-叁 (six Methylene)urea, N,N,N',N'-fluorene (hexamethylene)urea or anthracene, R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , and W1 is H, CH ₃ , OH or an oxygen atom having a bond (*), a9 represents an integer from 1 to 4, a10 represents an integer from 2 to 4, b1 represents an integer from 0 to 2, and c4 represents an integer from 0 to 5; 40] (In the above formula (33), R ₇₀ is a stretch Base, diphenylmethane, hexamethylene, isophorone (1-methylene-3-extended ethyl-3-methyl-5,5-dimethyl-cyclohexane), Alkyl dimethylene, dicyclohexylmethane, cyclohexane dimethylene, N,N',N"-fluorene (hexamethylene)-trimeric isocyanate, N,N,N'-叁 (six Methylene)urea, N,N,N',N'-fluorene (hexamethylene)urea or anthracene, R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , and W1 is H, CH ₃ , OH or an oxygen atom having a bond (*), a9 represents an integer from 1 to 4, a10 represents an integer from 2 to 4, b1 represents an integer from 0 to 2, and c4 represents an integer from 0 to 5. The single layer film according to any one of claims 1 to 4, wherein the single layer film has a water contact angle of 30 or less. The single layer film according to any one of claims 1 to 5, wherein the single layer film has a film thickness of 0.5 to 100 μm. An anti-fogging material comprising the single layer film of any one of claims 1 to 6. An antifouling material comprising the single layer film of any one of claims 1 to 6. An antistatic material comprising the single layer film of any one of claims 1 to 6. A laminate comprising a single layer film of any one of claims 1 to 6 formed on at least one side of a substrate. The laminate according to claim 10, wherein a single layer film is formed on one surface of the substrate, and an adhesive layer is formed on the surface of the substrate on which the single layer film is not formed. The laminate of claim 11, wherein a release layer is further formed on the surface of the adhesive layer. The laminate according to any one of claims 11 to 13, wherein a peelable coating material layer is formed on the surface of the single layer film. A method for producing a laminate, the laminate system forming a single layer film on at least one surface of the substrate, the anion concentration (Sa) of the outer surface of the single layer film and the contact between the inner surface and the outer surface of the substrate The anion concentration (Da) has an anion concentration ratio (Sa/Da) of 1.1 or more, and has at least one anionic hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxyl group, and a phosphoric acid group; and the production method includes: preparing a monomer-containing composition And a step of mixing a solvent, the monomer composition is a monomer (I) represented by the following general formula (1) and having two or more (meth)acryl fluorenyl groups and having no sulfonic acid group or carboxyl group And the polyvalent monomer (II) having a phosphate group is contained in such a manner that the monomer (I) / polyvalent monomer (II) molar ratio is 1/1000 or more and less than 1/30, and the solvent contains solubility. a compound having a parameter σ of 9.3 (cal/cm ³ ) or more; a step of applying the mixture to at least one surface of the substrate; a step of removing at least a portion of the solvent from the coated mixture; and a mixture of the above steps a step of polymerizing the monomer (I) and the monomer (II); [X] _s [M1] _l [M2] _m (1) ( In the above formula (1), s represents 1 or 2, and l and m represent integers satisfying s=l+m/2; M1 is at least one monovalent cation selected from hydrogen ions, ammonium ions and alkali metal ions, M2 is at least one divalent cation selected from the group consisting of alkaline earth metal ions; and X is at least one monovalent anion selected from the group represented by the following general formulas (1-1) to (1-4); 41] [化42] [化43] [化44] (In the above formulae (1-1) to (1-4), J and J' are each independently H or CH ₃ , and n represents 0 or 1, and R is independently an aromatic group or an aliphatic cyclic group. And at least one selected from the group consisting of an ether group and an ester group is substituted with an aliphatic hydrocarbon group having a carbon number of from 1 to 600 carbon atoms)). The method for producing a laminate according to claim 14, wherein the single layer film has a water contact angle of 30 or less.