JP2014080471A - Monolayer film and hydrophilic material composed of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a monolayer film having high hydrophilicity and surface hardness which is excellent in antifogging properties, antifouling properties (self-cleaning properties) and antistatic properties (dust adhesion prevention properties) and further excellent in scratch resistance or the like, and to provide an antifogging material, antifouling material and antistatic material containing the monolayer film and a method for producing a laminate which is formed by providing the monolayer film on a substrate surface by heat polymerization.SOLUTION: There is prepared a laminate in which a monolayer film is formed and the method for producing the monolayer film comprises the steps of: producing a composition which contains a specific compound (I) and a compound (II) so that the molar ratio of the compound (I) to the compound (II) is in the range of 1/0.05 to 1/1000 and contains a peroxide (III) having one-hour half-life temperature Tof 40 to 100°C and a solvent (IV); forming a coated film composed of the composition on at least one surface of a substrate and then copolymerizing the coated film by heat to produce a monolayer film in which at least one anionic hydrophilic group selected from a sulfonic cid group, a carboxyl group and a phosphoric acid group is distributed so that the ratio (Sa/Da) of the anion concentration (Sa) on the outer surface to the anion concentration (Da) on the middle spot between the inner surface in contact with the substrate and the outer surface is 1.1 or more.

Description

  The present invention relates to a method for producing a monolayer film that is excellent in antifogging property, antifouling property, and antistatic property and in which anionic hydrophilic groups are distributed at a specific concentration ratio. More specifically, a monolayer film comprising a hydrophilic copolymer obtained by thermal polymerization of a composition containing a specific compound and a compound having two or more (meth) acryloyl groups in one molecule, Antifogging material comprising a layer film, antifouling material and antistatic material, antifogging coating, antifouling coating and antistatic coating, and production of a laminate in which these single layer films and coatings are provided on the substrate surface Regarding the method.

  Examples of the hydrophilic resin include 3-sulfopropyl methacrylate / potassium salt, 2-acrylamido-2-methylpropane-sulfonic acid / sodium salt, and polyethylene glycol diacrylate described in Patent Document 1. A polymer obtained by using 3-sulfopropyl methacrylate sodium salt and long-chain urethane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Oligo UA-W2A”) described in Patent Document 2; Polymer obtained by using 2-sulfoethyl acrylate, tetrahydrofurfuryl acrylate, trimethylolpropane acrylate, and spiroglycol urethane diacrylate described in Patent Document 3, 2-sulfoethyl methacrylate described in Patent Document 4 Les Polymer obtained by using (meth) acrylate having epoxy group and / or phosphate group and epoxy resin, hydroxyethyl methacrylate, sulfoalkylene (C6-C10) methacrylate described in Non-Patent Document 1, and methylenebisacrylamide There are known polymers obtained by using.

  Patent Document 1 describes that the obtained transparent gel is used as a bioadhesive, and Patent Document 2 describes an ink jet recording method in which the obtained polymer has excellent ink absorbability, high water resistance, and no blocking. Patent Document 3 describes that the polymer obtained is used as an adhesive that firmly bonds a metal hub for driving an optical information disk and a resin substrate. In Patent Document 4, a polymer obtained by crosslinking an ethylenically unsaturated bond and sulfonic acid group or phosphoric acid group by ionic reaction with an epoxy group has mechanical performance, solvent resistance, film-forming property, It is described that it can be used as an electrically conductive cured film excellent in adhesiveness, transparency and abrasion resistance.

  In Non-Patent Document 4, the hydrophilicity of the finely crosslinked film formed on the glass varies depending on the alkylene chain length (C6 to C10) of the sulfoalkylene methacrylate used as the monomer (advanced contact angle and receding contact angle), and It is described that it varies depending on the hydration time.

  In Patent Document 6, as a method for producing a hydrophilic molded product, a crosslinked polymerizable monomer composition is applied to the surface of a substrate to form an incompletely polymerized crosslinked polymer by controlling the amount of ultraviolet irradiation, A two-layer structure has been proposed in which a hydrophilic monomer is applied and irradiated again with ultraviolet rays to block or graft polymerize the hydrophilic monomer on the surface of a crosslinked polymer.

  However, according to the study of the present inventors, the polymers described in Patent Documents 1 to 4 have a low degree of cross-linking between molecules and high solubility in water or do not dissolve in water, but absorb water and form a gel. It was easy to become, easy to be scratched easily (easy), or insufficient in hydrophilicity, and could not be said to be sufficient for use as an antifogging material and antifouling material. The method of the above-mentioned Patent Document 6 is obviously complicated and expensive compared with a general method of a one-layer structure by a single coating in which a composition comprising a hydrophilic monomer and a crosslinking monomer is applied and polymerized by ultraviolet rays or the like. Further, the smoothness of the surface is easily lost, and it cannot be said to be a preferable method.

The present inventors previously proposed a polymer using a hydroxyl group-containing (meth) acrylamide compound as a method for solving the above problem (Patent Document 5).
In general, physical properties required for a resin for antifouling coating include high surface hardness and high hydrophilicity. The physical properties required for the resin for anti-fogging coating include relatively high surface hardness and hydrophilicity more than antifouling use.

  As methods for producing these polymers or resins, thermal polymerization (polymerization by heat), ultraviolet polymerization (polymerization by ultraviolet rays), etc. are known. Thermal polymerization is in contrast to ultraviolet polymerization. There are few restrictions, 2) The surface of the molded product is not limited to a flat surface, and it can handle complex shapes. 3) Since UV light is not used at the start, additives that have UV absorbing ability such as UV absorbers are more free. Has the advantage that it can be used at a high degree. For this reason, a method of polymerizing a hydrophilic film having high surface hardness and hydrophilicity by heat has been desired.

JP 2003-000000 A Special table 2002-521140 gazette JP-A-11-115305 Japanese Patent Laid-Open No. 08-325524 Japanese Examined Patent Publication No. 53-010636 International Publication No. 2004/058900 JP 2001-98007 A

Journal of Colloid and Interface Science, vol.110 (2), 468-476 (1986)

  The present invention is a single layer film having high hydrophilicity and surface hardness that is excellent in antifogging property, antifouling property (self-cleaning property) and antistatic property (anti-dust adhesion property), and also excellent in scratch resistance, etc. An object of the present invention is to provide a method for producing an antifogging material, an antifouling material and an antistatic material comprising the monolayer film, and further producing a laminate comprising the monolayer film on the surface of the substrate by thermal polymerization. .

According to the study by the present inventors, it has been found that when a hydrophilic single layer film is produced by thermal polymerization, the transparency and hydrophilicity of the resulting film may be lowered.
As a result of further studies to solve the above problems, the present inventors have
By performing thermal polymerization using an initiator having a specific decomposition temperature, the above problems can be prevented, and the resulting monolayer film has excellent antifogging properties, antifouling properties, antistatic properties and scratch resistance. As a result, the present invention was completed.

That is, the method for producing a laminate of the present invention includes:
Compound (I) represented by the following general formula (1) and compound (II) having two or more (meth) acryloyl groups (however, having no sulfonic acid group, carboxyl group and phosphoric acid group) The molar ratio (I) / (II) of compound (I) to (II) is in the range of 1 / 0.05 to 1/1000, and the one-hour half-life temperature T _1/2 is 40 to 100 ° C. A first step of preparing a composition comprising peroxide (III) and solvent (IV) in the range of
A second step of forming a coating film comprising the composition on at least one side of the substrate;
The coating film is copolymerized by heat so that at least one anionic hydrophilic group selected from a sulfonic acid group, a carboxyl group and a phosphoric acid group has an anion concentration (Sa) on the outer surface and an inner surface in contact with the substrate. The method includes a third step of forming a monolayer film distributed so that an anion concentration ratio (Sa / Da) with an anion concentration (Da) at an intermediate point with 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 = 1 + 2m. M1 represents at least one monovalent selected from a hydrogen ion, an ammonium ion, and an alkali metal ion. M2 is at least one divalent cation selected from alkaline earth metal ions, and X is at least one selected from groups represented by the following general formulas (1-1) to (1-4). It is a monovalent anion.)

（上記式（１−１）〜（１−４）中、Ｊ及びＪ'はそれぞれ独立にＨ又はＣＨ₃であり、ｎは０又は１を表し、Ｒはそれぞれ独立に、炭素数１〜６００の脂肪族炭化水素基であり、該脂肪族炭化水素基に含まれる任意のメチレン基は、２価の芳香族基、２価の脂肪族環状炭化水素基、−Ｏ−、−ＣＯＯ−、又は−ＯＣＯ−で置換されていてもよい。）

(In the above formulas (1-1) to (1-4), J and J ′ each independently represent H or CH ₃ , n represents 0 or 1, and R each independently represents 1 to 600 carbon atoms. Any methylene group contained in the aliphatic hydrocarbon group is a divalent aromatic group, a divalent aliphatic cyclic hydrocarbon group, -O-, -COO-, or (It may be substituted with -OCO-.)

The peroxide (III) contained in the composition produced in the first step is preferably at least one selected from peroxycarbonate and diacyl peroxide.
After the coating film is formed on the substrate in the second step, the solvent (IV) contained in the composition for forming the coating film is dried so that the content is 30% by weight or less, and then in the third step. It is preferable to perform copolymerization by heat of the coating film.
It is preferable that an ultraviolet absorber is further contained in the composition produced in the first step.

  According to the present invention, a hydrophilic monolayer film, a hydrophilic material containing them, for example, an antifogging material, an antifouling material and an antistatic material, an antifogging coating, an antifouling coating and an antistatic coating, and a basis thereof. It is possible to provide a method for producing a laminate formed by lamination on a material by thermal polymerization.

It is the schematic which shows the method of the sample preparation for a measurement of anion concentration ratio.

In the first step of the production method of the present invention, compound (I), compound (II) having two or more (meth) acryloyl groups in one molecule, 1 hour half-life temperature T _1/2 is in the range of 40 to 100 ° C. A composition comprising a peroxide (III) and a solvent (IV) is prepared.

Compound (I) contained in the composition is represented by the following general formula (1).
[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 = 1 + 2m.
M1 is at least one monovalent cation selected from a hydrogen ion, an ammonium ion, and an alkali metal ion.

  The ammonium ion in the present invention is a cation formed by bonding 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 hydrogen ions are bonded to ammonia and an amine having a small number of carbon atoms, more preferably an ammonium ion formed by bonding hydrogen ions to ammonia, or methylammonium. .

Examples of the alkali metal include lithium, sodium, potassium, rubidium, and the like.
Among the M1, alkali metal ions are preferable, and sodium ions, potassium ions, and rubidium ions are more preferable.

M2 is at least one divalent cation selected from alkaline earth metal ions.
X is at least one monovalent anion selected from the groups represented by the following general formulas (1-1) to (1-4).

In the general formulas (1-1) to (1-4), J and J ′ are each independently H or CH ₃ . n represents 0 or 1. R each independently represents an aliphatic hydrocarbon group having 1 to 600 carbon atoms, and any methylene group contained in the aliphatic hydrocarbon group is a divalent aromatic group or a divalent aliphatic cyclic carbon group. It may be substituted with a hydrogen group, -O-, -COO-, or -OCO-.

  As R, any methylene group may be substituted with a divalent aromatic group, a divalent aliphatic cyclic hydrocarbon group, —O—, —COO—, or —OCO—. 100 aliphatic hydrocarbon groups are preferred, and any methylene group may be substituted with a divalent aromatic group, a divalent aliphatic cyclic hydrocarbon group, —O—, —COO—, or —OCO—. A good aliphatic hydrocarbon group having 2 to 20 carbon atoms is more preferred.

Among the compounds (I), compounds with m = 0 are preferable.
The formula amount of X is usually 50 to 18,000, preferably 100 to 1,000, and more preferably 170 to 500.

  Among the compounds (I), compounds represented by the following general formula (1-1-1) and general formula (1-1-2) are preferable.

In the above formulas (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 because of easy synthesis.
n represents an integer of 1 to 20, but is preferably an integer of 2 to 10 and more preferably an integer of 2 to 4 for ease of synthesis.

l 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.

When M is a monovalent cation, m is 1, and when M is a divalent cation, m is 2.
The ammonium ion is a cation formed 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 hydrogen ions are bonded to ammonia and an amine having a small number of carbon atoms, more preferably an ammonium ion formed by bonding hydrogen ions to ammonia, or methylammonium. .

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

Among these M, monovalent cations are preferable, alkali metal ions are more preferable, and sodium ions, potassium ions, and rubidium ions are more preferable.
Among these monomers represented by the formulas (1-1-1) and (1-1-2), 2-sulfonylethyl- (meth) acrylate, 3-sulfonylpropyl- (meth) acrylate, and these compounds Alkali metal salts are preferred.

The molecular weight of the compound (I) is usually 168 to 18,000, preferably 180 to 1,000, more preferably 200 to 500.
The said compound (I) may be used individually by 1 type, and may be used in mixture of 2 or more types.

  The monomer composition of the present invention contains the compound (I), but at least a part of the compound (I) reacts to form an oligomer and is contained in the monomer composition. It may be. In addition, an oligomer here contains the repeating unit formed from the said compound (I) normally 2-20. The molecular weight of the oligomer is usually in the range of 30,000 or less, preferably 10,000 or less, more preferably 5,000 or less.

  The compound (I) can be produced by a known method or a method according to a known method. For example, Japanese Patent Publication No. 49-36214, Japanese Patent Publication No. 51-9732, Japanese Patent Publication No. 6284157, or US Pat. No. 3,024,221 It can be produced by the method described in the book.

  The monomer represented by the above formula (1-1-1) can be produced, for example, by reacting (meth) acrylic acid with purpan sultone in the presence of an alkali metal carbonate. The monomer represented by the above formula (1-1-2) is, for example, a group in which a hydroxyl group of a polyol is partially halogenated with hydrogen halide, and then the substituted halogen is reacted with an alkali metal sulfonate. Can be produced by reacting the hydroxyl group with (meth) acrylic acid halide or (meth) acrylic acid.

  The composition prepared in the first step further includes a compound (II) having two or more (meth) acryloyl groups in one molecule. However, compound (II) does not have any of a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

  Although there is no restriction | limiting in particular about the form of the (meth) acryloyl group contained in this compound (II), For example, (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylthio group, or (meth) Although it is contained in the compound (II) in the form of an acrylamide group or the like, it is preferably contained in the form of a (meth) acryloyloxy group or a (meth) acryloylthio group.

  Examples of the compound (II) include compounds having one or more hydroxyl groups and two or more (meth) acryloyl groups, compounds having one or more ether bonds or thioether bonds and two or more (meth) acryloyl groups, A compound having one or more ester bonds and two or more (meth) acryloyl groups, a compound having one or more aliphatic ring structures or aromatic ring structures and two or more (meth) acryloyl groups, one or more heterocycles And a compound having a structure and two or more (meth) acryloyl groups.

  Among these compounds (II), compounds represented by the following general formulas (2-1) and (2-2) are preferable.

In the above formulas (2-1) and (2-2), R ₃ and R _{5 to} R ₉ are each independently H or CH ₃ , 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 of 2 to 30, b represents an integer of 0 to 2, c represents an integer of 0 to 30, d represents an integer of 0 to 20, and e represents an integer of 0 to 2. i represents an integer of 1 to 20, preferably 1 to 10, more preferably 1 to 5, and still more preferably an integer of 1 to 3. k represents an integer of 1 to 10, more preferably 2 to 8, and still more preferably an integer of 2 to 6.

  A represents one selected from the following chemical formula.

又は

Or

から選ばれる１種を表す。

1 type chosen from.

Here, * is a bond.
R ₅ , R ₆ , R ₇ , R ₉ , R ₁₀ and R ₁₁ are each independently H or CH ₃ ; 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. R is hexamethylene, isophorone (1-methylene-3-ethylene-3-methyl-5,5-dimethyl - cyclohexane), norbornane methylene, dicyclohexylene methane, cyclohexane dimethylene or xylylene, R ₅₀ is hexamethylene Methylene, isophorone (1-methylene-3-ethylene-3-methyl-5,5-dimethyl-cyclohexane), norbornane dimethylene, dicyclohexylenemethane, cyclohexanedimethylene, toluylene, diphenylmethane or xylylene.

V is an oxygen atom having OH or a bond (*), W _{1 to} W ₃ are independently oxygen atoms having H, CH ₃ , OH or a bond (*), and Z is OH, a bond An oxygen atom having (*), COOH, or a carboxyl group (COO) having a bond (*) is represented, and V _{1 to} V ₃ are each independently H or a bond (*).

  n1 and n2 each independently represent an integer of 0 to 8, o1 and o2 each independently represent an integer of 1 to 3, f represents an integer of 1 to 20, g represents an integer of 0 to 3, 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, and is preferably 3. a2 represents an integer of 3 to 4, and is preferably 3. a3 represents an integer of 4 to 6, preferably 5 or 6. a4 represents an integer of 2 to 3, and is preferably 3. a5 represents an integer of 2 to 4, and is preferably 3 or 4.

The compounds represented by the general formulas (2-1) to (2-2) can be produced by a known method or a method according to a known method. Moreover, it is available as a commercial item.
Among the compounds represented by the formula (2-1) and the general formula (2-2), compounds represented by the following general formulas (3) to (8) and (10) to (33) are preferable.

上記式（３）中、Ｒ₃及びＲ₄はそれぞれ独立にＨ又はＣＨ₃であり、Ｒ₁₀₀及びＲ₁₀₁はそれぞれ独立にＨ又は炭素数１〜６のアルキル基であり、ｂ１及びｂ２はそれぞれ独立に０〜２の整数を表し、ｎ１及びｎ２はそれぞれ独立に０〜８の整数を表す。

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

上記式（４）中、Ｒ₃〜Ｒ₆はそれぞれ独立にＨ又はＣＨ₃であり、Ｒ₁₀₀及びＲ₁₀₁はそれぞれ独立にＨ又は炭素数１〜６のアルキル基であり、ｎ１及びｎ２はそれぞれ独立に０〜８の整数を表す。

In the above formula (4), R _{3 to} R ₆ are each independently H or CH ₃ , R ₁₀₀ and R ₁₀₁ are each independently H or an alkyl group having 1 to 6 carbon atoms, and n1 and n2 are each Independently represents an integer of 0 to 8.

上記式（５）中、Ｒ₃〜Ｒ₆はそれぞれ独立にＨ又はＣＨ₃であり、ｂ１及びｂ２はそれぞれ独立に０〜２の整数を表し、ｃ１は２〜３０の整数を表す。

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

上記式（６）中、Ｒ₃〜Ｒ₆はそれぞれ独立にＨ又はＣＨ₃であり、ｃ２及びｃ３はそれぞれ独立に１〜５の整数を表し、ｄ１は２〜２０の整数を表す。

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

上記式（７）中、Ｒ₃及びＲ₄はそれぞれ独立にＨ又はＣＨ₃であり、ｂ１及びｂ２はそれぞれ独立に０〜２の整数を表し、ｄ１は２〜２０の整数を表し、ｍは０又は１を表す。

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 is 0 or 1 is represented.

上記式（８）中、Ｒ₃及びＲ₄はそれぞれ独立にＨ又はＣＨ₃であり、ｏ１及びｏ２はそれぞれ独立１〜３の整数を表す。

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.

上記式（１０）中、Ｒ₃〜Ｒ₈はそれぞれ独立にＨ又はＣＨ₃であり、ｃ４及びｃ５はそれぞれ独立に０〜５の整数を表し、ｍは０又は１を表す。

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

上記式（１１）中、Ｒ₃及びＲ₄はそれぞれ独立にＨ又はＣＨ₃であり、ｍは０又は１を表す。

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

上記式（１２）中、Ｒ₃〜Ｒ₇はそれぞれ独立にＨ又はＣＨ₃である。

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

上記式（１３）中、＊は結合手であり、Ｒ３、Ｒ５及びＲ６それぞれ独立にＨ又はＣＨ₃であり、ｃ６は０〜３の整数を表す。

In the above formula (13), * represents a bond, R3, R5 and R6 each independently H or CH _3, c6 represents an integer of 0 to 3.

上記式（１４）中、Ｒ₃〜Ｒ₈はそれぞれ独立にＨ又はＣＨ₃であり、ｂ１及びｂ２はそれぞれ独立に０〜２の整数を表し、ｃ７及びｃ８はそれぞれ独立に０〜５の整数を表し、ｍは０又は１を表す。

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

上記式（１５）中、Ｒ₃〜Ｒ₁₀はそれぞれ独立にＨ又はＣＨ₃であり、ｂ１及びｂ２はそれぞれ独立に０〜２の整数を表し、ｃ９及びｃ１０はそれぞれ独立に０〜３０の整数を表す。

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

上記式（１６）中、Ｒ₃〜Ｒ₁₀はそれぞれ独立にＨ又はＣＨ₃であり、ｃ１１〜ｃ１４は１以上の整数を表し、なおかつｃ１１＋ｃ１２＋ｃ１３＋ｃ１４＝４〜３０を満足する。

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

上記式（１７）中、Ｒ₃及びＲ₄はそれぞれ独立にＨ又はＣＨ₃であり、ｂ１及びｂ２はそれぞれ独立に０〜２の整数を表す。

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

上記式（１８）中、Ｒ₃〜Ｒ₈はそれぞれ独立にＨ又はＣＨ₃であり、Ｒ₂₀₀及びＲ₂₀₁はそれぞれ独立にＨ、ＣＨ₃又はフェニル基であり、ｃ４及びｃ５はそれぞれ独立に０〜５の整数を表す。

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

上記式（１９）中、Ｒ₃〜Ｒ₅及びＲ₁₁はそれぞれ独立にＨ又はＣＨ₃であり、ｂ１〜ｂ３はそれぞれ独立に０〜２の整数を表し、ｆは１〜２０の整数を表す。

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

上記式（２０）中、＊は結合手であり、ＶはＯＨ又は結合手（＊）を有する酸素原子であり、Ｒ₃、Ｒ₅及びＲ₆はそれぞれ独立にＨ又はＣＨ₃であり、ａ１は２又は３を表し、ｂ１は０〜２の整数を表し、ｃ１５は０〜２０の整数を表す。）

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

上記式（２１）中、＊は結合手であり、Ｗ₁はＨ、ＣＨ₃、ＯＨ又は結合手（＊）を有する酸素原子であり、Ｒ₃、Ｒ₅及びＲ₆はそれぞれ独立にＨ又はＣＨ₃であり、ａ２は３又は４を表し、ｃ１６は０〜２０の整数を表す。

In the above formula (21), * is a bond, W ₁ is H, CH ₃ , OH or an oxygen atom having a bond (*), and R ₃ , R ₅ and R ₆ are each independently H or is CH _3, a2 represents 3 or 4, c16 represents an integer of 0 to 20.

上記式（２２）中、＊は結合手であり、Ｗ₂及びＷ₃はそれぞれ独立にＨ、ＣＨ₃、ＯＨ又は結合手（＊）を有する酸素原子であり、Ｒ₃、Ｒ₅及びＲ₆はそれぞれ独立にＨ又はＣＨ₃であり、ａ３は４〜６の整数を表し、ｃ１７は０〜３の整数を表す。

In the above formula (22), * is a bond, W ₂ and W ₃ are each independently an oxygen atom having H, CH ₃ , OH or a bond (*), and R ₃ , R ₅ and R ₆ Are each independently H or CH ₃ , a3 represents an integer of 4 to 6, and c17 represents an integer of 0 to 3.

上記式（２３）中、Ｒ₃₀はヘキサメチレン、イソホロン（１−メチレン−３−エチレン−３−メチル−５，５−ジメチル−シクロヘキサン）、ノルボルナンジメチレン、ジシクロヘキシレンメタン、シクロヘキサンジメチレン、又はキシリレンであり、Ｒ₃〜Ｒ₁₀はそれぞれ独立にＨ又はＣＨ₃であり、ｅ１及びｅ２はそれぞれ独立に０〜２の整数を表す。

In the above formula (23), R ₃₀ is hexamethylene, isophorone (1-methylene-3-ethylene-3-methyl-5,5-dimethyl-cyclohexane), norbornane dimethylene, dicyclohexylenemethane, cyclohexanedimethylene, or Xylylene, 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.

上記式（２４）中、Ｗ₄はＨ、ＣＨ₃、ＯＨ又は結合手（＊）を有する酸素原子であり、Ｒ₃、Ｒ₅及びＲ₆はそれぞれ独立にＨ又はＣＨ₃であり、ｂ１は０〜２の整数を表し、ｃ１５は０〜２０の整数を表し、ａ６は１〜６の整数を表し、ｎ１００は１〜６の整数を表す。

In the above formula (24), W ₄ is H, CH ₃ , OH or an oxygen atom having a bond (*), R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , and b1 is N represents an integer of 0 to 2, c15 represents an integer of 0 to 20, a6 represents an integer of 1 to 6, and n100 represents an integer of 1 to 6.

上記式（２５）中、Ｒ₃〜Ｒ₁₀はそれぞれ独立にＨ又はＣＨ₃であり、ｂ１及びｂ２はそれぞれ独立に０〜２の整数を表し、ｃ９及びｃ１０はそれぞれ独立に０〜５の整数を表す。

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

上記式（２６）中、Ｒ₃はＨ又はＣＨ₃であり、ｐ１は１〜６の整数を表し、ａ１０は３を表す。

In the above formula (26), R ₃ is H or CH _3, p1 is an integer of 1 to 6, a10 represents 3.

上記式（２７）中、Ｒ₃〜Ｒ₈はそれぞれ独立にＨ又はＣＨ₃であり、ｂ１及びｂ２はそれぞれ独立に０〜２の整数を表し、ｃ７及びｃ８はそれぞれ独立に０〜５の整数を表す。

In the above formula (27), R _{3 to} R ₈ are each independently H or CH ₃ , b1 and b2 each independently represent an integer of 0 to 2, and c7 and c8 are each independently an integer of 0 to 5 Represents.

上記式（２８）中、Ｒ₃〜Ｒ₈はそれぞれ独立にＨ又はＣＨ₃であり、ｂ１及びｂ２はそれぞれ独立に０〜２の整数を表し、ｃ７及びｃ８はそれぞれ独立に０〜５の整数を表す。

In the above formula (28), R _{3 to} R ₈ are each independently H or CH ₃ , b1 and b2 each independently represent an integer of 0 to 2, and c7 and c8 are each independently an integer of 0 to 5 Represents.

上記式（２９）中、Ｒ₃及びＲ₅〜Ｒ₁₃はそれぞれ独立にＨ又はＣＨ₃であり、ｉ１は０〜５の整数を表す。

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

上記式（３０）中、Ｒ₃及びＲ₅〜Ｒ₉はそれぞれ独立にＨ又はＣＨ₃であり、Ｗ₁はＨ、ＣＨ₃、ＯＨ又は結合手（＊）を有する酸素原子であり、ａ２は３又は４を表し、ｉ１は０〜５の整数を表す。

In the above formula (30), R ₃ and R _{5 to} R ₉ are each independently H or CH ₃ , W ₁ is H, CH ₃ , OH or an oxygen atom having a bond (*), and a2 is 3 or 4 is represented, and i1 represents an integer of 0 to 5.

上記式（３１）中、Ｒ₃〜Ｒ₉はそれぞれ独立にＨ又はＣＨ₃であり、Ｗ₂及びＷ₃はそれぞれ独立にＨ、ＣＨ₃、ＯＨ又は結合手（＊）を有する酸素原子であり、ａ７は１〜６の整数を表し、ａ８は０〜５の整数を表し、なおかつａ７＋ａ８＝４〜６を満足する。

In the above formula (31), R _{3 to} R ₉ are each independently H or CH ₃ , and W ₂ and W ₃ are each independently an oxygen atom having H, CH ₃ , OH, or a bond (*). , A7 represents an integer of 1-6, a8 represents an integer of 0-5, and a7 + a8 = 4-6 is satisfied.

上記式（３２）中、Ｒ₇₀はトルイレン、ジフェニルメタン、ヘキサメチレン、イソホロン（１−メチレン−３−エチレン−３−メチル−５，５−ジメチル−シクロヘキサン）、ノルボルナンジメチレン、ジシクロヘキシレンメタン、シクロヘキサンジメチレン、Ｎ，Ｎ‘，Ｎ“−トリス（ヘキサメチレン）−イソシアヌレート、Ｎ,Ｎ,Ｎ’−トリス（ヘキサメチレン）−ウレア、Ｎ,Ｎ,Ｎ‘,Ｎ’−テトラキス（ヘキサメチレン）−ウレア、又はキシリレンであり、Ｒ₃、Ｒ₅及びＲ₆はそれぞれ独立にＨ又はＣＨ₃であり、Ｗ₁はＨ、ＣＨ₃、ＯＨ又は結合手（＊）を有する酸素原子であり、ａ９は２〜３の整数を表し、ａ１０は２〜４の整数を表し、ｂ１は０〜２の整数を表し、ｃ４は０〜５の整数を表す。

In the above formula (32), R ₇₀ is toluylene, diphenylmethane, hexamethylene, isophorone (1-methylene-3-ethylene-3-methyl-5,5-dimethyl - cyclohexane), norbornane methylene, dicyclohexylene methane, cyclohexane Dimethylene, N, N ', N "-tris (hexamethylene) -isocyanurate, N, N, N'-tris (hexamethylene) -urea, N, N, N', N'-tetrakis (hexamethylene) -Urea or xylylene, R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , W ₁ is H, CH ₃ , OH or an oxygen atom having a bond (*), a9 Represents an integer of 2 to 3, a10 represents an integer of 2 to 4, b1 represents an integer of 0 to 2, and c4 represents an integer of 0 to 5.

上記式（３３）中、Ｒ₇₀は、トルイレン、ジフェニルメタン、ヘキサメチレン、イソホロン（１−メチレン−３−エチレン−３−メチル−５，５−ジメチル−シクロヘキサン）、ノルボルナンジメチレン、ジシクロヘキシレンメタン、シクロヘキサンジメチレン、Ｎ，Ｎ‘，Ｎ“−トリス（ヘキサメチレン）−イソシアヌレート、Ｎ,Ｎ,Ｎ’−トリス（ヘキサメチレン）−ウレア、Ｎ,Ｎ,Ｎ‘,Ｎ’−テトラキス（ヘキサメチレン）−ウレア、又はキシリレンであり、Ｒ₃、Ｒ₅及びＲ₆はそれぞれ独立にＨ又はＣＨ₃であり、Ｗ₂及びＷ₃はそれぞれ独立にＨ、ＣＨ₃、ＯＨ又は結合手（＊）を有する酸素原子であり、ａ９は３〜５の整数を表し、ａ１０は２〜４の整数を表し、ｂ１は０〜２の整数を表し、ｃ４は０〜５の整数を表す。

In the above formula (33), R ₇₀ is toluylene, diphenylmethane, hexamethylene, isophorone (1-methylene-3-ethylene-3-methyl-5,5-dimethyl-cyclohexane), norbornane dimethylene, dicyclohexylenemethane, Cyclohexanedimethylene, N, N ′, N ″ -tris (hexamethylene) -isocyanurate, N, N, N′-tris (hexamethylene) -urea, N, N, N ′, N′-tetrakis (hexamethylene) ) -Urea or xylylene, R ₃ , R ₅ and R ₆ are each independently H or CH ₃ , and W ₂ and W ₃ are each independently H, CH ₃ , OH or a bond (*). A9 represents an integer of 3 to 5, a10 represents an integer of 2 to 4, b1 represents an integer of 0 to 2, and c4 represents an integer of 0 to 5.

  Examples of the compound (II) represented by the general formula (3) include ethylene glycol di (meth) acrylate, 1,2-propanediol di (meth) acrylate, and 1,3-propanediol di (meth) acrylate. 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 1,2-bis { 3- (meth) acryloyloxy-2-hydroxy-propyloxy} ethane, 1,2-bis {3- (Meth) acryloyloxy-2-hydroxy-propyloxy} propane, 1,3-bis {3- (meth) acryloyloxy-2-hydroxy-propyloxy} propane, 1,4-bis {3- (meth) acryloyloxy -2-hydroxy-propyloxy} ptane, 1,6-bis {3- (meth) acryloyloxy-2-hydroxy-propyloxy} hexane, and the like.

Examples of the compound (II) represented by the general formula (4) include neopentyl glycol hydroxypivalic acid di (meth) acrylate.
Examples of the compound (II) represented by the 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- (meth) acryloyloxy-2-hydroxy-propyl} ether, 1,2-polypropylene glycol-bis {3- (meth) acryloyl And oxy-2-hydroxy-propyl} ether.

  Examples of the compound (II) represented by the general formula (6) include 1,2-polypropylene glycol-bis {(meth) acryloyl-poly (oxyethylene)} ether.

  Examples of the compound (II) represented by the general formula (7) include 1,3-polypropylene glycol di (meth) acrylate, 1,4-polybutylene glycol di (meth) acrylate, and 1,4-polybutylene. And glycol-bis {3- (meth) acryloyloxy-2-hydroxy-propyl} ether.

  Examples of the compound (II) represented by the general formula (8) include bis {2- (meth) acryloylthio-ethyl} sulfide and bis {5- (meth) acryloylthio-3-thiapentyl} sulfide. Can be mentioned.

  Examples of the compound (II) represented by the general formula (10) include cyclohexanediol di (meth) acrylate, bis {(meth) acryloyloxy-methyl} cyclohexane, and bis {7- (meth) acryloyloxy-2. , 5-dioxaheptyl} cyclohexane, bis {(meth) acryloyloxy-poly (ethyleneoxy) -methyl} cyclohexane, and the like.

Examples of the compound (II) represented by the general formula (11) include tricyclodecane dimethanol di (meth) acrylate.
As the compound (II) represented by the general formula (12), for example, 2-propenoic acid {2- (1,1, -dimethyl-2-{(1-oxo-2-propenyl) oxy} Ethyl) -5-ethyl-1,3-dioxane-5-yl} methyl ester (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD R-604”).

Examples of the compound (II) represented by the general formula (13) include N, N ′, N ″ -tris {2- (meth) acryloyloxy-ethyl} isocyanurate.
Examples of the compound (II) represented by the general formula (14) include xylylenediol di (meth) acrylate, bis {7- (meth) acryloyloxy-2,5-dioxaheptyl} benzene, bis { (Meth) acryloyloxy-poly (ethyleneoxy) -methyl} benzene and the like.

  Examples of the compound (II) represented by the general formula (15) include bisphenol A di (meth) acrylate, bis {(meth) acryloyl-oxyethyl} bisphenol A, bis {(meth) acryloyl-oxypropyl} bisphenol. A, bis {(meth) acryloyl-poly (oxyethylene)} bisphenol A, bis {(meth) acryloyl-poly (oxy-1,2-propylene)} bisphenol A, bis {3- (meth) acryloyloxy-2 -Hydroxy-propyl} bisphenol A, bis {3- (meth) acryloyloxy-2-hydroxy-propyl-oxyethyl} bisphenol A, bis {3- (meth) acryloyloxy-2-hydroxy-propyl-oxypropyl} bisphenol A, screw {3- (meta Examples include acryloyloxy-2-hydroxy-propyl-poly (oxyethylene)} bisphenol A, bis {3- (meth) acryloyloxy-2-hydroxy-propyl-poly (oxy-1,2-propylene)} bisphenol A, and the like. It is done.

  Examples of the compound (II) represented by the general formula (16) include bis {(meth) acryloyl-oxyethyl-oxypropyl} bisphenol A, bis {(meth) acryloyl poly (oxyethylene) -poly (oxy-). 1,2-propylene)} bisphenol A and the like.

  Examples of the compound (II) represented by the general formula (17) include naphthalenediol di (meth) acrylate, bis {3- (meth) acryloyloxy-2-hydroxy-propyl-oxy} naphthalene, and the like. .

  Examples of the compound (II) represented by the general formula (18) include 9,9-fluorenediol di (meth) acrylate, 9,9-bis {4- (2- (meth) acryloyloxy-ethyl). -Oxy)} fluorene, 9,9-bis {3-phenyl-4- (meth) acryloyloxy-poly (ethyleneoxy)} fluorene, and the like.

  Examples of the compound (II) represented by the general formula (19) include a phenol novolac type epoxy (meth) acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade names “NK Oligo EA-6320, EA-7120, EA-7420”). ) And the like.

  Examples of the compound (II) represented by the general formula (20) include glycerin-1,3-di (meth) acrylate, 1-acryloyloxy-2-hydroxy-3-methacryloyloxy-propane, 2,6 , 10-trihydroxy-4,8-dioxaundecane-1,11-di (meth) acrylate, 1,2,3-tris {3- (meth) acryloyloxy-2-hydroxy-propyl-oxy} propane, 1,2,3-tris {2- (meth) acryloyloxy-ethyl-oxy} propane, 1,2,3-tris {2- (meth) acryloyloxy-propyl-oxy} propane, 1,2,3- Tris {(meth) acryloyloxy-poly (ethyleneoxy)} propane, 1,2,3-tris {(meth) acryloyloxy-poly (1, - propylene oxy)} propane.

  Examples of the compound (II) represented by the general formula (21) include trimethylolpropane tri (meth) acrylate, trimethylolpropane-tris {(meth) acryloyloxy-ethyl-oxy} ether, trimethylolpropane- Tris {2- (meth) acryloyloxy-propyl-oxy} ether, trimethylolpropane-tris {(meth) acryloyloxy-poly (ethyleneoxy)} ether, trimethylolpropane-tris {(meth) acryloyloxy-poly ( 1,2-propyleneoxy)} ether, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol-tetrakis {(meth) acryloyloxy-ethyl-oxy} ether, Intererythritol-tetrakis {2- (meth) acryloyloxy-propyl-oxy} ether, pentaerythritol-tetrakis {(meth) acryloyloxy-poly (ethyleneoxy)} ether, pentaerythritol-tetrakis {(meth) acryloyloxy-poly (1,2-propyleneoxy)} ether and the like.

  Examples of the compound (II) represented by the general formula (22) include ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane-tetrakis {(meth) acryloyloxy-ethyl-oxy} ether, ditrimethylolpropane- Tetrakis {2- (meth) acryloyloxy-propyl-oxy} ether, ditrimethylolpropane-tetrakis {(meth) acryloyloxy-poly (ethyleneoxy)} ether, ditrimethylolpropane-tetrakis {(meth) acryloyloxy-poly ( 1,2-propyleneoxy)} ether, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol-hexa {(meth) acryloylo Cy-ethyl-oxy} ether, dipentaerythritol-hexa {2- (meth) acryloyloxy-propyl-oxy} ether, dipentaerythritol-hexa {(meth) acryloyloxy-poly (ethyleneoxy)} ether, dipenta And erythritol-hexa {(meth) acryloyloxy-poly (1,2-propyleneoxy)} ether.

  Examples of the compound (II) represented by the general formula (23) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxy Reaction product of hydroxylalkyl (meth) acrylate and hexamethylene diisocyanate such as butyl (meth) acrylate, reaction product of hydroxylalkyl (meth) acrylate and isophorone diisocyanate, hydroxylalkyl (meth) acrylate and bis (isocyanate) Reaction product of natomethyl) norbornane, reaction product of hydroxylalkyl (meth) acrylate and norbis (4-isocyanatocyclohexyl) methane, hydroxylalkyl (meth) acrylate and 1,3-bis (isocyanato) Chill) a reaction product of cyclohexane, and the like hydroxyalkyl (meth) reaction product of acrylate and m- xylylene diisocyanate.

  The molar ratio (I) / (II) of the compound (I) to the compound (II) contained in the composition is usually in the range of 1 / 0.05 to 1/1000, preferably 1/1 to 1/1000. More preferably, the range is from 1/5 to 1/1000, and particularly preferably from 1/5 to 1/500. Even when the film thickness of the resulting monolayer film is increased because the molar ratio of (I) / (II) is within the above range, it is excellent in hydrophilicity and scratch resistance. A layer film is obtained.

The composition prepared in the first step may contain a polymerizable compound (VI) other than the compound (I) and the compound (II) as long as the effects of the present invention are not impaired.
As said other polymeric compound (VI), carboxyl group or carboxylate group containing monomers other than compound (I), such as (meth) acrylic acid; hydroxyethyl (meth) acrylate, hydroxypropyl (meth), for example Hydroxyalkyl (meth) acrylates such as acrylate and hydroxybutyl (meth) acrylate; alkyl mono (meta) such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobornyl (meth) acrylate ) Acrylate; amino group or ammonium base-containing monomer such as N, N-dimethyl-aminoethyl- (meth) acrylate, N, N-dimethyl-aminoethyl- (meth) acrylate hydrochloride; sodium vinyl sulfonate, styrene Sulfonic acid, sodium styrene sulfonate Potassium styrene sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methyl compounds such as propane potassium acid (I) other than the sulfonic acid group or sulfonate group-containing monomers;
Allyl (meth) acrylate, diethylene glycol bis (allyl carbonate), diallyl phthalate, divinylbenzene, divinyl sulfone, glycidyl (meth) acrylate, 3-isopropenyl-α, α-dimethyl-benzyl isocyanate, (meth) acryloyl isocyanate , (Meth) acryloyloxyethyl isocyanate, xylylene diisocyanate, hexamethylene diisocyanate, bis (isocyanatomethyl) norbornane, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, bis (4- And isocyanato-cyclohexyl) methane.

  When it is desired to increase the refractive index value of the single layer film, 2,5-bis (acryloylthiomethyl) -1,4-dithiane, 1,8-bis (acryloyl) is used as the monomer (III). Thio) -5-acryloylthiomethyl-3,6-dithiaoctane, 2,5-bis (acryloylthiomethyl) -1,4-dithiane, 1,11-bis (acryloylthio) -4,8-bis (acryloylthio) A monomer having a sulfur atom such as methyl) -3,6,9-trithiaundecane may be used.

  The content of the polymerizable compound (VI) in the composition is not particularly limited as long as the effect of the present invention is not impaired, but is usually 100 mol% with respect to 100 mol% in total of the compound (I) and the compound (II). In the following, it is preferably used in an amount of 49 mol% or less, more preferably 40 mol% or less, still more preferably 20 mol% or less, usually 1 mol% or more, preferably 3 mol% or more. By including the monomer composition in such a content, physical properties such as flexibility, toughness, and refractive index can be adjusted.

The composition prepared in the first step includes peroxide (III) having a one-hour half-life temperature T _{1/2 in} the range of 40 to 100 ° C. When such a peroxide (III) is contained in the composition, the hydrophilicity and scratch resistance of the monolayer film obtained by copolymerization with heat are excellent. Although the detailed mechanism by which such a single layer film is formed on the substrate is unknown, if the decomposition of the peroxide is slow, the copolymerization (curing) of the composition forming the single layer film is slow. Therefore, it is considered that phase separation is likely to occur in the composition, and as a result, the hydrophilic group on the surface of the single layer film is not fixed and the hydrophilicity is lowered, or the scratch resistance is lowered due to insufficient curing. .

Examples of the peroxide (III) having a one-hour half-life temperature T _{1/2 in} the range of 40 to 100 ° C. include peroxydicarbonates such as di (4-t-butylcyclohexyl) peroxydicarbonate (RO- (C ═O) —O—O— (C═O) —OR ′: R and R ′ represent a hydrocarbon group.); Diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide (R— (C═ O) -O-O- (C = O) -R ': R and R' represent a hydrocarbon group.); Peroxyesters such as t-butylperoxy-2-ethylhexanoate (R- ( C═O) —O—O—R ′ or R—O— (C═O) —O—O—R ′: R and R ′ represent a hydrocarbon group))); alkyl peroxyester (R— (C═O) —O—O—R ′: R and R ′ each represents a hydrocarbon group.

  Among these peroxides (III), peroxycarbonate and diacyl peroxide are preferable from the viewpoint of high hydrophilicity of the film obtained and excellent scratch resistance. Di (4-t-butylcyclohexyl) peroxydi Carbonate and dibenzoyl peroxide are more preferable.

The said peroxide (III) may be used individually by 1 type, and may be used in combination of 2 or more type.
If the peroxide (III) is contained as a thermal polymerization initiator in the composition prepared in the first step, other peroxides, azo compounds, etc., as long as the effects of the present invention are not impaired. The thermal polymerization initiator may be contained. When a thermal polymerization initiator other than such peroxide (III) is contained in the composition, at least one kind of one-hour half-temperature among the peroxides contained in the thermal polymerization initiator However, it is preferable that it exists in the range of 40-100 degreeC.

  The composition prepared in the first step includes a solvent (IV). Examples of the solvent (IV) include alkyl monoalcohols, alkoxyethanols represented by alkoxyethanol and alkoxypropanol, alcohols such as alkylene glycol and glycerin, alkylene glycol alkyl ethers such as alkylene glycol methyl ether, ketones, carboxylic acids, and carboxylic acids. Examples thereof include polar solvents such as acid esters, ethers, amides, nitriles, water, and mixtures of these compounds such as water and alcohol. These solvents (IV) may be used alone or in combination of two or more.

  Among these solvents (IV), from the viewpoint of increasing the anion concentration ratio (Sa / Da) in the obtained monolayer film (making it easier to concentrate anions on the surface of the monolayer film), the solvent (IV) The boiling point is preferably in the range of 30 to 170 ° C, more preferably 50 to 140 ° C, and still more preferably 60 to 125 ° C. In addition, when solvent (IV) is a mixture of a some compound, it is preferable that the boiling point of the compound with the highest boiling point contained in the mixture exists in the said range.

Examples of the solvent (IV) within the above boiling range include methanol, ethanol, cyclohexanol, 1-propanol, isopropanol (IPA), 1-butanol, isobutanol, 2-butanol, 1-pentanol, 2-methyl- Alkyl monoalcohols such as 1-butanol and isopentanol (3-methyl-1-butanol); Alcohol alkyl alcohols such as 2-methoxyethanol, 2-ethoxyethanol and 1-methoxy-2-propanol; Alcohol compounds such as cyclohexanone , Ketones such as 2-methylcyclohexanone and acetone;
Carboxylic acids such as formic acid, acetic acid, propionic acid;
Carboxylate esters such as methyl acetate;
Ethers such as dioxane, anisole, tetrahydrofuran (THF);
Amides such as N, N′-dimethylformamide (DMF), N, N′-dimethylacetamide DMAC;
Nitriles such as acetonitrile;
And water.
Among these solvents (IV), alcohol and a mixture of alcohol and ketone are preferable.

  Among alcohols, primary alkyl monoalcohols such as methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 2-methyl-1-butanol, isopentanol (3-methyl-1-butanol) and the like A linear alkoxyalkyl alcohol which is a reaction product of a primary alkyl monoalcohol such as 2-methoxyethanol and 2-ethoxyethanol and a linear alkylene glycol tends to be preferable.

Of the mixture of alcohol and ketone, a mixture of methanol and acetone is preferred.
The amount of the solvent (IV) used is not particularly limited as long as the laminate of the present invention is obtained, and the amount used can be appropriately determined in consideration of economy and the like.

  When using the monolayer film obtained in the present invention as, for example, an antifouling material, an antifogging material or the like, in order to prevent deterioration even when exposed to the outside for a long period of time, the above-mentioned produced in the first step It is desirable to add a UV absorber or a hindered amine light stabilizer to the composition to obtain a weather-resistant composition.

  Examples of the UV absorber include benzotriazole UV absorbers, triazine UV absorbers, benzophenone UV absorbers, benzoate UV absorbers, propanedioic acid ester UV absorbers, and oxanilide UV absorbers. Various common ultraviolet absorbers can be used. When a single layer film is formed by ultraviolet polymerization, the ultraviolet absorber absorbs the ultraviolet rays, and in the case of remarkable, the polymerization may be inhibited. However, in the production method of the present invention, thermal polymerization is performed. Such a problem is unlikely to occur because a single layer film is formed as a main body.

Examples of the ultraviolet absorber include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4-tert-butylphenol, 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-benzotriazole- 2-yl) -4- (3-one-4-oxa-dodecyl) -6-tert-butyl-phenol, 2- {5-chloro (2H) -benzotriazol-2-yl } -4- (3-one-4-oxa-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-tert-pentylphenol, 2- {5-chloro (2H) -benzotriazol-2-yl} -4,6- Di-tert-butylphenol, 2- (2H-benzotriazol-2-yl) -4-tert-octylphenol, 2- (2H-benzotriazol-2-yl) -4-methyl-6-n-dodecylphenol, methyl -3- {3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl} propionate / polyethylene glycol Benzotriazole ultraviolet absorbents such as reaction products of Lumpur 300;
2- (4-phenoxy-2-hydroxy-phenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-oxa-hexadecyloxy) -4,6-di ( 2,4-dimethyl-phenyl) -1,3,5-triazine, 2- (2-hydroxy-4-oxa-heptadecyloxy) -4,6-di (2,4-dimethyl-phenyl) -1,3 5-triazine, 2- (2-hydroxy-4-iso-octyloxy-phenyl) -4,6-di (2,4-dimethyl-phenyl) -1,3,5-triazine, trade name Tinuvin 400 (Ciba Specialty Chemicals Co., Ltd.), trade name Tinuvin 405 (Ciba Specialty Chemicals Co., Ltd.), trade name Tinuvin 460 (Ciba Specialty Chemicals Co., Ltd.) , Triazine-based UV absorbers such as trade name Tinuvin 479 (manufactured by Ciba Specialty Chemicals Co., Ltd.);
Benzophenone ultraviolet absorbers such as 2-hydroxy-4-n-octoxybenzophenone;
Benzoate UV absorbers such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; and propanedioic acid-{(4-methoxyphenyl) -methylene}- Propanediocic acid ester-based ultraviolet absorbers such as dimethyl ester, trade name hostabin PR-25 (manufactured by Clariant Japan KK), trade name hostabin B-CAP (manufactured by Clariant Japan KK);
Oxanilide ultraviolet absorbers such as 2-ethyl-2′-ethoxy-oxanilide and trade name Sanduvor VSU (manufactured by Clariant Japan Co., Ltd.) and the like can be mentioned.

Among these ultraviolet absorbers, triazine ultraviolet absorbers tend to be preferable.
The amount of the ultraviolet absorber used is usually 0 with respect to 100 parts by weight of the total of the compound (I), the compound (II) contained in the monomer composition and the polymerizable compound (VI) contained if necessary. 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight.

  When the usage-amount of a ultraviolet absorber is less than the said lower limit, it exists in the tendency for the improvement effect of the weather resistance of the single layer film obtained to become small. Moreover, even if the usage-amount of a ultraviolet absorber exceeds the said upper limit, the weather-resistant improvement effect may not become large any more.

  The hindered amine light stabilizer (HALS) is a general term for a compound having a 2,2,6,6-tetramethylpiperidine skeleton, generally abbreviated as HALS, and has a low molecular weight. Molecular weight HALS, medium molecular weight HALS, high molecular weight HALS, and reactive HALS are roughly divided.

  Examples of the HALS include trade name Tinuvin 111FDL (manufactured by Ciba Specialty Chemicals Co., Ltd.), bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name Tinuvin 123). (Ciba Specialty Chemicals Co., Ltd.)), trade name Tinuvin 144 (Ciba Specialty Chemicals Co., Ltd.), trade name Tinuvin 292 (Ciba Specialty Chemicals Co., Ltd.), trade name Tinuvin 765 (Ciba Specialty Chemicals Co., Ltd.) Ciba Specialty Chemicals Co., Ltd.), trade name Tinuvin 770 (Ciba Specialty Chemicals Co., Ltd.), N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl -N- (1,2,2,6,6-pentamethyl-4-pipe Lysyl) amino] -6-chloro-1,3,5-triazine condensate (trade name CHIMASSORB 119FL (Ciba Specialty Chemicals Co., Ltd.)), trade name CHIMASSORB 2020FDL (Ciba Specialty Chemicals Co., Ltd.), Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (trade name CHIMASSORB 622LD (manufactured by Ciba Specialty Tea Chemicals)), poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) Imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino ] (Trade name CHIMASSORB944FD (manufactured by Ciba Specialty Chemicals Co., Ltd.)), the trade name Sanduvor3050 Liq. (Manufactured by Clariant Japan Co., Ltd.), trade name Sanduvor 3052 Liq. (Manufactured by Clariant Japan Co., Ltd.), trade name Sanduvor 3058 Liq. (Manufactured by Clariant Japan Co., Ltd.), trade name Sanduvor 3051 Powder. (Manufactured by Clariant Japan Co., Ltd.), trade name Sanduvor 3070 Powder. (Manufactured by Clariant Japan Co., Ltd.), product name VP Sanduvor PR-31 (manufactured by Clariant Japan Co., Ltd.), product name Hostabin N20 (manufactured by Clariant Japan Co., Ltd.), product name Hostabin N24 (manufactured by Clariant Japan Co., Ltd.) , Brand name Hostabin N30 (manufactured by Clariant Japan KK), brand name Hostabin N321 (manufactured by Clariant Japan KK), brand name Hostabin PR-31 (manufactured by Clariant Japan KK), brand name HOSTABIN 845 (Clariant Japan KK) And Niro stub S-EED (manufactured by Clariant Japan Co., Ltd.).

  The amount of HALS used is usually 0.01 with respect to a total of 100 parts by weight of the compound (I), the compound (II) and the polymerizable compound (VI) contained as necessary in the monomer composition. -10 parts by weight, preferably 0.05-5 parts by weight, more preferably 0.05-3 parts by weight.

  When the amount of HALS used is less than the lower limit, the effect of improving the weather resistance of the resulting single layer film tends to be small. Moreover, even if the usage-amount of HALS exceeds the said upper limit, the improvement effect of a weather resistance may not become large any more.

  In the method for producing a laminate of the present invention, a single layer film is formed by thermal polymerization, but in addition to thermal polymerization, a part may be further polymerized by radiation. As the radiation, energy rays 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, X rays, electron beams, ultraviolet rays, and visible light. When partially polymerizing with ultraviolet rays, an ultraviolet polymerization initiator such as an ultraviolet radical polymerization initiator, an ultraviolet cationic polymerization initiator, or an ultraviolet anionic polymerization initiator may be contained in the composition. In addition, when a part of the mixture is polymerized by ultraviolet rays, an ultraviolet polymerization accelerator may be further contained in the mixture in addition to the ultraviolet polymerization initiator.

  In addition, the composition prepared in the first step further includes an infrared absorber, a radical scavenger, an antioxidant, a polymerization inhibitor, a dye, a binder, an internal mold release agent, a leveling agent, and a catalyst as necessary. Other additives such as various metal oxides, metals, metal salts, iodine, and iodonium salts may be included.

  Metals or metal oxides such as silica and titanium oxide can be added for the purpose of improving mechanical strength or thermal stability and for the purpose of imparting photoresponsiveness or bactericidal properties. For the purpose of imparting bactericidal or antibacterial properties, metal salts such as silver salts and lithium salts, iodine, iodonium salts, and the like can be added.

  The addition amount of these other additives can be appropriately set according to the purpose, but is the total of compound (I), compound (II) contained in the monomer composition and polymerizable compound (VI) contained if necessary. The range is usually 0.01 to 200 parts by weight, preferably 0.1 to 100 parts by weight with respect to 100 parts by weight.

In the second step of the production method of the present invention, a coating film is formed from the composition obtained in the first step on at least one side of the substrate.
Examples of the material used as the substrate include crystalline or amorphous inorganic materials such as silica, metal, and metal oxide; polymethyl methacrylate, polycarbonate, polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyurethane resin, epoxy Examples thereof include polymer materials such as resins, vinyl chloride resins and silicone resins, organic materials such as paper and pulp, and hybrid materials of inorganic materials and organic materials typified by a mixture of glass filler and polyethylene terephthalate.

  Examples of the material used as the base material of the present invention include the above-mentioned materials, but the base material used in the present invention is obtained by applying a paint or the like on the surface of a base material made of an inorganic material, an organic material, or the like. Also good.

  Further, the surface of the substrate may be subjected to a surface treatment such as a physical or chemical treatment, a primer treatment, or the like, if necessary. This surface treatment is performed for the purpose of, for example, activating the surface of the base material in order to improve the adhesion (adhesion) between the base material and the single layer film.

  Examples of physical or chemical treatment include corona treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, and the like.

The primer treatment is performed by applying and drying a coating agent called a so-called primer coating agent, undercoat agent, or anchor coating agent on the substrate surface.
Examples of the coating agent include polyesters, polyamides, polyurethanes, epoxy resins, phenolic resins, (meth) acrylic resins, polyolefins such as polyvinyl acetate, polyethylene and polypropylene, polymers such as modified polyolefins and cellulose resins. Examples thereof include a polymer composition having a vehicle as a main component.

  Examples of the coating agent include a solvent type coating agent obtained by dissolving the polymer in a solvent, and a latex type or dispersion type aqueous type coating agent obtained by dispersing the polymer in an aqueous solvent such as water.

  Polymers contained in the aqueous coating agent include polyurethanes such as polyolefin, polyethylene vinyl alcohol, polyethylene imine, polybutadiene, urethane acrylic resin and polyester polyurethane, polyvinyl chloride, silicon acrylic resin, vinyl acetate acrylic resin, acrylic resin. Styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, methyl methacrylate-butadiene copolymer, rubber such as chloroprene rubber, polybutadiene, polyacrylic acid ester, polyvinylidene chloride, and these resins with carboxylic acid, etc. Examples thereof include modified polymers.

  Among these coating agents, a coating agent containing polyurethane is preferable. The polyurethane may have a urethane bond in either the main chain or the side chain of the polymer, and is obtained, for example, by reacting a polyol such as polyester polyol, polyether polyol or acrylic polyol with an isocyanate compound. Polyurethane can be used.

  In addition, as the coating agent containing polyurethane, a two-component coating agent that coats a solution containing a polyol and a solution containing an isocyanate compound on the spot can also be used. In the case of this two-pack type coating agent, as long as a primer is formed on the substrate, the mixing method of the liquid containing the polyol and the liquid containing the isocyanate compound is not particularly limited. Further, as long as the primer is formed on the substrate, the blending ratio of the polyol and the isocyanate compound is not particularly limited, but the value of (OH group contained in the polyol) / (NCO group contained in the isocyanate compound) is equivalent. In terms of conversion, it is usually in the range of 2/1 to 1/40.

  Among these coating agents containing polyurethane, polyester polyols such as condensed polyester polyols and lactone polyester polyols are used as the isocyanate compounds because they have excellent adhesion between the substrate and the single layer film and high peel strength. A coating agent containing polyurethane using tolylene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate or the like is preferable.

Examples of the method for applying the coating agent to the substrate include a gravure coating method, a reverse roll coating method, a knife coating method, and a kiss coating method. The coating amount of the coating agent, in the dry state, typically ^{0.01g / m 2 ~10g / m 2} , preferably from ^{0.05g / m 2 ~5g / m 2} .

  Thus, the composition produced at the 1st process is apply | coated to the base material which processed as needed, and a coating film is formed. The method for applying the composition is not particularly limited, and examples thereof include a bar coating method, a gravure coating method, a roll coating method, a reverse roll coating method, a knife coating method, and a kiss coating method.

  The coating film formed in the second step is usually dried, and at least a part of the solvent (IV) is removed from the composition forming the coating film. If the removal of the solvent is insufficient, the transparency of the obtained monolayer film tends to be lowered.

  Therefore, the content of the solvent (IV) contained in the composition immediately before copolymerizing the composition forming the coating film is preferably 30% by weight or less, more preferably 10% by weight or less, and further preferably 5%. % By weight or less, particularly preferably 1% by weight or less.

  The method for removing the solvent from the mixture is not particularly limited, for example, a method for allowing the solvent to spontaneously evaporate and remove from the mixture by leaving at room temperature, a method for removing the solvent from the mixture by heating, and standing at room temperature. A method of removing the solvent from the mixture by a draft, a method of removing the solvent from the mixture by reducing the pressure, a method of removing the solvent from the mixture by reducing and heating, and a method of removing the solvent from the mixture by heating and wind. The method etc. are mentioned.

  Among these methods, representative examples include a method of removing the solvent from the mixture applied to the substrate with hot air, and a method of removing the solvent from the mixture with hot air while heating the substrate coated with the mixture. The method of removing a solvent from the said mixture with the heating and wind which are performed is preferable.

When removing the solvent with heating, the heating temperature is usually room temperature or higher, and the upper limit is preferably set to the 10-hour half-life temperature of the peroxide from the viewpoint of suppressing the decomposition of the peroxide.
The atmosphere for removing the solvent may be air or an inert gas such as nitrogen. However, a lower atmospheric humidity tends to be preferable. The humidity of the atmosphere is preferably 60% or less, more preferably 50% or less, and still more preferably 40% or less.

  When removing the solvent with heating, adding air increases the evaporation rate, reducing the residual amount of solvent, shortening the drying time, lowering the drying temperature, etc., and from the base material when removing the solvent. Film peeling (adhesion degradation), cracks (film cracking) and the like tend to be suppressed.

  The wind speed when adding 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 still more preferably in the range of 0.2 m / sec to 5 m / sec. It is a range. When the wind speed exceeds the above upper limit, a uniform coated surface tends to be difficult to obtain. On the other hand, if it is less than the lower limit, the effect of adding wind tends to be insufficient.

The pressure at the time of solvent removal is not particularly limited, but it is relatively preferable to remove the solvent under normal pressure or reduced pressure. The solvent removal may be performed under slight pressure.
Although the time for removing the solvent can be appropriately set from the viewpoint of a preferable residual amount of the solvent, it is usually preferably about 5 to 30 minutes.

In the third step of the production method of the present invention, the coating film formed in the second step is copolymerized by heat to form a single layer film, and a laminate including the single layer film and the substrate is produced.
The temperature at which the copolymerization with heat is performed is usually room temperature or higher and lower than the heat resistant temperature of the substrate used. The temperature is preferably not less than the one-hour half-life temperature of the peroxide, more preferably not less than the one-hour half-life temperature + 20 ° C., more preferably not less than the one-minute half-life temperature. The higher the copolymerization temperature, the shorter the heating time, which is preferable from the viewpoint of productivity.

  The polymerization may be performed in the air, but it is preferably performed in an inert gas atmosphere such as nitrogen from the viewpoint of shortening the polymerization time (avoiding the inhibition of polymerization by oxygen). Furthermore, the polymerization may be carried out under reduced pressure.

  Although the time required for heating depends on the copolymerization temperature, a shorter one is preferable from the viewpoint of productivity. It is preferably within 12 hours, more preferably within 6 hours, further preferably within 4 hours, and particularly preferably within 2 hours.

  For the purpose of avoiding polymerization inhibition due to oxygen, after applying the above mixture to a substrate and removing at least a part of the solvent, the coating layer of this mixture is coated with a coating material such as a film and then polymerized. May be performed. When the coating layer is coated with the coating material, it is desirable that the coating layer and the coating material are in close contact so as not to include air (oxygen). By avoiding air, especially oxygen, when performing polymerization by radiation, the radiation dose may be reduced, and the amount of polymerization initiator such as peroxide (III) may be reduced. Can do.

  As the covering material, various materials can be used in various forms without particular limitation as long as oxygen is blocked, but a film is preferable from the viewpoint of operability, and when polymerization is performed by radiation, radiation that does not inhibit the polymerization. A transparent film having a high transmittance is preferred.

  Examples of the material for the covering material include vinyl alcohol polymers such as polyvinyl alcohol (PVA) and ethylene-vinyl alcohol copolymer, polyacrylamide, polyisopropylacrylamide, polyacrylonitrile, polycarbonate (PC), polymethyl methacrylate ( PMMA), polyethylene terephthalate (PET), polystyrene (PS), biaxially oriented polypropylene (OPP), and the like.

The thickness of the covering material, typically a film, is usually 3 to 200 μm, preferably 5 to 100 μm, more preferably 10 to 50 μm.
In the single-layer film of the present invention and a laminate in which the single-layer film is formed on at least one surface of the base material, the above-described covering material may be covered as it is. When the covering material is formed on the single-layer film, the single-layer film or the laminate can be prevented from being damaged or soiled during transportation, storage, display, or the like.

The monolayer membrane of the present invention thus obtained has at least one anion selected from a sulfonic acid group (SO ₃ ⁻ ), a carboxyl group (CO ₂ ⁻ ), and a phosphoric acid group (PO ₄ ⁻ ). Hydrophilic organic monolayer film having a hydrophilic hydrophilic group, preferably a sulfonic acid group (SO ₃ ⁻ ).

  The anion concentration ratio (Sa / Da) between the anion concentration (Sa) of the outer surface in contact with the outside air of the monolayer film and the anion concentration (Da) at the intermediate point between the inner surface and the outer surface in contact with the substrate is 1. .1 or more.

Here, the intermediate point between the inner surface and the outer surface in contact with the substrate is 1/2 of the inner surface portion in contact with the substrate and the outer surface portion in contact with the outside air when viewed in the film thickness direction of the single layer film. The point of.
The anion concentration ratio is obtained by obliquely cutting a single layer film provided on a substrate, and an anion concentration on the outer surface in contact with the outside air of the single layer film and an anion concentration at an intermediate point between the inner surface and the outer surface, Measurement is performed using a time-of-flight secondary ion mass spectrometer (TOF-SIMS).

  In such a monolayer film of the present invention, the above-mentioned anions in the monolayer film are distributed with a concentration difference from the inner surface portion on the substrate side to the outer surface portion in contact with the outside air, and the outer layer in contact with the outside air is distributed. The anion concentration difference is such that the most anions are distributed on the surface portion. It is estimated that the reason why such anion concentration difference occurs in the film thickness direction is that the hydrophilic anions described above are self-assembled on the surface in contact with the outside air in the process of forming a coating film or a single layer film. In the single layer film of the present invention, since the anion of the highly hydrophilic group is present in a high concentration on the outer surface of the single layer film, antifogging property, antifouling property or self-cleaning property, antistatic property, dust Excellent adhesion prevention.

  The anion concentration ratio (Sa / Da) is preferably 1.2 or more, more preferably 1.3 or more. When the anion concentration ratio is not less than the above value, the antifogging property, antifouling property or self-cleaning property, antistatic property, dust adhesion preventing property and the like tend to be excellent. The anion concentration ratio (Sa / Da) is usually about 20.0 or less.

  The water contact angle of the monolayer film of the present invention is usually 30 ° or less, preferably 20 ° or less, more preferably 10 ° or less. A single layer film having a water contact angle of not more than the above upper limit has high hydrophilicity and is easily blended (wet) with water and is excellent as a hydrophilic material. Thus, for example, antifogging materials, antifogging coatings (hereinafter also referred to as antifogging coatings), antifouling materials, antifouling coatings or self-cleaning coatings, antistatic materials, quick drying materials or quick drying coatings, and antistatic coatings or dust. Useful for anti-adhesion coats.

  For example, when used as an anti-fogging coat, water droplets spread on the film surface and a water film can be formed, so it is excellent in an anti-fogging effect, and when used as a self-cleaning coat, water enters between the dirt and the coating surface to float dirt. Since it can be removed, the antifouling effect is excellent.

  In addition, the monolayer film having an anionic hydrophilic group of the present invention is superior in antistatic properties as compared with a film having a conventional anionic hydrophilic group, and can be used as an antistatic material, an antistatic film, or an anti-dust coating. Is also useful.

The thickness of the monolayer film can be appropriately set depending on the application, but is usually in the range of 0.1 to 100 μm, preferably 0.5 to 20 μm, more preferably 1 to 10 μm.
The monolayer film of the present invention can be made into various forms of monolayer films by devising the shape of the substrate.

An adhesive layer may be provided on the other surface of the base material on which the single layer film of the laminate is not formed.
Thus, the laminate provided with the adhesive layer is, for example, an antifogging film and an antifouling film, glass, a mirror such as a bathroom, a display, the surface of a display material such as a television, a signboard, an advertisement, a guide plate such as a guide plate, It can be easily attached to signs such as railways and roads, outer and inner walls of buildings, and window glass.

  The pressure-sensitive adhesive layer can be formed on the base material by applying a pressure-sensitive adhesive to the other surface of the base material on which the monolayer film is not formed, and further removing the solvent as necessary. This pressure-sensitive adhesive can be used without particular limitation. Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, rubber pressure-sensitive adhesives, vinyl ether polymer pressure-sensitive adhesives, and silicone pressure-sensitive adhesives. The thickness of the pressure-sensitive adhesive layer is generally 2 to 50 μm, preferably 5 to 30 μm.

A release layer may be further provided on the adhesive layer.
Moreover, the laminated body of this invention may be further provided with the coating | coated material layer which can peel on the surface of the said single layer film.

  The laminate of the present invention can be made into laminates of various forms by devising the shape of the substrate. For example, the monolayer film and laminate of the present invention can be used in the form of a film, a sheet, a tape and the like. The single layer film of the present invention can also be used as a primer layer.

  The monolayer film and laminate obtained in the present invention are excellent in hydrophilicity and are useful as antifogging materials, antifouling materials, antistatic materials and the like. For example, a laminate in which a single layer film of the present invention is laminated on a substrate made of a transparent material such as transparent resin and glass has transparency, hydrophilicity, antifogging property, antifouling property, and further antistatic property, speed It can be used as a laminate excellent in dryness and anti-condensation properties.

  Therefore, the single-layer film and the laminate of the present invention are materials for transportation equipment represented by automobiles, ships, aircrafts such as bodies, wheels, exterior materials, and interior materials; outer wall materials, inner wall materials, floor materials, furniture materials, Building materials such as bathroom materials, toilet materials, kitchen materials such as ventilation fans, toilet materials, piping materials, etc .; construction materials such as sound insulation boards installed on highways, etc .; clothes, cloth, fibers, etc. Materials for clothing; optical materials such as window materials, mirrors, optical films, optical disks, glasses, contact lenses, goggles, reflective films, and reflectors; lighting materials such as lamp materials and light materials; industrial materials such as cooling fins; Product materials, wiring materials, display materials such as touch panel flat panels, and electrical and electronic materials such as photoresists; ink jet recording plates, printing and printing plastics Printing materials such as Ma; can be used in applications such as daily necessities timber, such as cosmetic containers.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited only to these Examples. In the present invention, the physical properties of the coating were evaluated as follows.
<Appearance>
The surface of the single-layer membrane was scrubbed with Kimwipe (Wiper S-200, manufactured by Crecia Co., Ltd.) while flowing tap water, and the appearance after the membrane surface was dried by air blow was visually evaluated.

<Measurement of water contact angle>
The surface of the monolayer membrane is washed with Kimwipe (Wiper S-200, manufactured by Crecia Co., Ltd.) while flowing water with tap water, and the membrane surface is dried by air blow, and then a water contact angle measuring device manufactured by Kyowa Interface Science Three places were measured at room temperature (25 ° C.) using a CA-V type, and the average value was described.

<Steel Wool Abrasion Test>
Steel wool # 0000 was used and rubbed back and forth 10 times with a load of 1 Kgf.

<Measurement of anion and cation concentration ratio>
The sample is cut obliquely as shown in the sample preparation shown in FIG. 1, and using a time-of-flight secondary ion mass spectrometer (TOF-SIMS), the anion concentration (Sa) on the surface of the single layer film and the inside of the single layer film (membrane) The anion concentration (Da) at the intermediate point between the inner surface and the outer surface was measured, and the anion concentration ratio (Sa / Da) was determined from the value.

(Analyzer and measurement conditions)
TOF-SIMS; TOF-SIMS ⁵ manufactured by ION-TOF
Primary ion; Bi ₃ ²⁺ (acceleration voltage 25 kV)
Measurement area: 400 μm ²
Measurement uses an electron gun for charge correction

(Sample preparation etc.)
As shown in FIG. 1, a sample having a single-layer film 20 provided on the surface of a base material 10 is subjected to precision oblique cutting in the cutting direction 30 and then cut into a size of about 10 × 10 mm ² and measured. A single-layer film surface 40 and a single-layer film inside 50 that are in contact with the outside air and a single-layer film inside 50 (a point at a thickness of 1/2, an inner surface of the single-layer film that contacts the base material 10 and a single-layer film) In the middle of the surface), the anion concentration was measured using a time-of-flight secondary ion mass spectrometer (TOF-SIMS).

(Evaluation)
Evaluation was performed by the following calculation formula. The relative intensity (relative to the total detected ions) was used as the ion concentration at each measurement point.
Sa / Da (anion concentration ratio, gradient) = anion concentration at the monolayer film surface 40 / anion concentration within the monolayer film 50

[Production Example 1] Preparation of liquid mixture 1 A uniform liquid mixture 1 having a solid content of 50 wt% was prepared according to the mixing ratio shown in Table 1 below.

The compounds indicated by symbols are as follows.
SPA-K; 3-sulfopropyl acrylate potassium salt P-2M; 2-methacryloxyethyl acid phosphate (light ester P-2M; manufactured by Kyoeisha Chemical Co., Ltd.)
A-GLY-9E; ethoxylated glycerin triacrylate (NK ester A-GLY-9E; manufactured by Shin-Nakamura Chemical Co., Ltd.)
A9300-1CL; ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate (NK ester A9300-1CL; manufactured by Shin-Nakamura Chemical Co., Ltd.)
U-15HA; polyfunctional urethane acrylate (NK ester U-15HA; Shin-Nakamura Chemical Co., Ltd.)
S-EED; 1,3-benzenedicarboxamide-N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) (Nyrostub S-EED; manufactured by Clariant Japan KK)

[Example 1-1]
In a glass screw tube, mixed solution 1 (10.0 g) prepared in Production Example 1 and di (4-t-butylcyclohexyl) peroxydicarbonate (Perroyl TCP; manufactured by NOF Corporation) as a polymerization initiator 0.075g was added and it stirred at room temperature for 1 hour using the magnetic stirrer, and prepared the uniform coating liquid. This coating solution was applied to a polycarbonate sheet (hereinafter abbreviated as PC board) as a base material under a low humidity condition (26 ° C.-20% RH) using a bar coater # 10, and a nitrogen gas atmosphere in an oven. Then, it was dried at a furnace temperature of 30-35 ° C. for 30 minutes. Next, the temperature was raised to 100 ° C. (temperature raising time: 5 minutes), followed by thermosetting at 100 ° C. for 2 hours to form a coating film having a thickness of about 6.8 μm on the PC plate. The results are shown in Table 2 below.

[Example 1-2]
In Example 1-1, Example 1 was used except that 0.075 g of dilauroyl peroxide (Perroyl L; manufactured by NOF Corporation) was used instead of 0.075 g of Perloyl TCP as a polymerization initiator. The same operation as 1 was performed, and a coating film having a film thickness of about 6.8 μm was formed on the PC plate. The results are shown in Table 2 below.

[Example 1-3]
In Example 1-1, Example 1-1 was used except that 0.075 g of dibenzoyl peroxide (Niper BW; manufactured by NOF Corporation) was used instead of 0.075 g of perloyl TCP as a polymerization initiator. The same operation was performed to form a coating film having a film thickness of about 6.8 μm on the PC plate. The results are shown in Table 2 below.

[Example 1-4]
In Example 1-1, instead of using 0.075 g of Parroyl TCP as a polymerization initiator, 0.025 g of Parroyl TCP and t-butylperoxy-2-ethylhexanoate (Perbutyl O; manufactured by NOF Corporation) ) The same operation as in Example 1-1 was performed except that 0.025 g was used, and a coating film having a thickness of about 6.8 μm was formed on the PC plate. The results are shown in Table 2 below.

[Comparative Example 1-1]
In Example 1-1, instead of using 0.075 g of perloyl TCP as a polymerization initiator, t-butyl peroxylaurate (Perbutyl L; manufactured by NOF Corporation; T _1/2 = 118 ° C.) Except that 075 g was used, the same operation as in Example 1-1 was performed to form a coating film having a thickness of about 6.8 μm on the PC plate. The results are shown in Table 2 below.

[Example 1-5]
In Example 1-1, the same operation as in Example 1-1 was performed except that 0.025 g of Parroyl TCP was used instead of 0.075 g of Perloyl TCP as a polymerization initiator, and the film thickness was formed on the PC plate. A coating film of about 6.8 μm was formed. The results are shown in Table 3 below.

[Example 1-6]
In Example 1-1, the same operation as in Example 1-1 was carried out except that 0.050 g of Parroyl TCP was used instead of 0.075 g of Peroyl TCP as a polymerization initiator, and the film thickness was formed on the PC plate. A coating film of about 6.8 μm was formed. The results are shown in Table 3 below.

[Example 1-7]
In Example 1-1, except that perloyl TCP 0.150 g was used instead of 0.075 g as a polymerization initiator, the same operation as in Example 1-1 was performed, and the film thickness was formed on the PC plate. A coating film of about 6.8 μm was formed. The results are shown in Table 3 below.

[Example 1-8]
In Example 1-1, the same operation as in Example 1-1 was performed, except that the film was thermally cured at 100 ° C. for 0.5 hour instead of being thermally cured at 100 ° C. for 2 hours. A coating film of about 6.8 μm was formed. The results are shown in Table 3 below.

[Example 1-9]
In Example 1-1, the same operation as in Example 1-1 was performed except that heat curing was performed at 100 ° C. for 1 hour instead of heat curing at 100 ° C. for 2 hours. A coating film of 8 μm was formed. The results are shown in Table 3 below.

[Example 1-10]
In Example 1-1, except that Perloyl TCP 0.150 g was used instead of Perloyl TCP 0.075 g as a polymerization initiator, and coating was performed using Bar Coater # 2 instead of Bar Coater # 10. The same operation as in Example 1-1 was performed to form a coating film having a thickness of about 1.4 μm on the PC plate. The results are shown in Table 4 below. In Table 4 below, the results of Example 1-1 are also shown.

[Example 1-11]
In Example 1-1, the same operation as in Example 1-1 was performed, except that bar coater # 5 was used instead of bar coater # 10, and a coating having a thickness of about 3.4 μm was formed on the PC plate. A film was formed. The results are shown in Table 4 below.

[Example 1-12]
In Example 1-1, a coating film having a film thickness of about 20 μm was formed on the PC plate by performing the same operation as in Example 1-1 except that bar coater # 30 was used instead of bar coater # 10. Formed. The results are shown in Table 4 below.

[Production Example 2] Preparation of Mixed Liquid 2 A uniform mixed liquid 2 having a solid content of 50 wt% was prepared according to the blending ratio shown in Table 5 below. The compounds indicated by symbols are the same as those in Production Example 1.

[Example 2-1]
Mixing solution 2 (10.0 g) prepared in Production Example 2 and 0.075 g of Parroyl TCP as a polymerization initiator were added to a glass screw tube, and stirred at room temperature for 1 hour using a magnetic stirrer to form a uniform coating A liquid was prepared. This coating solution was applied to a PC plate under low humidity conditions (26 ° C.-20% RH) using a bar coater # 10, and the oven temperature was 30 to 35 ° C. in a nitrogen gas atmosphere for 30 minutes. Dried. Next, the temperature was raised to 100 ° C. (temperature raising time: 5 minutes), and thermosetting was performed at 100 ° C. for 2 hours to form a coating film having a thickness of about 6.8 μm on the PC plate. The results are shown in Table 6 below.

[Example 2-2]
In Example 2-1, the same operation as in Example 2-1 was performed, except that 0.075 g of Nyper BW was used instead of 0.075 g of Parroyl TCP as the polymerization initiator, and the film thickness was formed on the PC plate. A coating film of about 6.8 μm was formed. The results are shown in Table 6.

[Production Example 3] Preparation of liquid mixture 3 A uniform liquid mixture 3 having a solid content of 50 wt% was prepared according to the blending ratio shown in Table 7 below. The compounds indicated by symbols are as follows.
PE-3A; Petol triacrylate (NK ester A-TMM-3L; Shin-Nakamura Chemical Co., Ltd.)

[Example 3-1]
To the glass screw tube, add the mixed solution 1 (5.0 g) prepared in Production Example 1, the mixed solution 3 (5.0 g) prepared in Production Example 3, and 0.075 g of Parroyl TCP as a polymerization initiator. The mixture was stirred for 1 hour at room temperature using a tic stirrer to prepare a uniform coating solution. This coating solution was applied to a PC plate under low humidity conditions (26 ° C.-20% RH) using a bar coater # 10, and the oven temperature was 30 to 35 ° C. in a nitrogen gas atmosphere for 30 minutes. Dried. Next, the temperature was raised to 100 ° C. (temperature raising time: 5 minutes), followed by thermosetting at 100 ° C. for 2 hours to form a coating film having a thickness of about 6.8 μm on the PC plate. The results are shown in Table 8 below.

[Example 3-2]
In Example 3-1, instead of using liquid mixture 1 (5.0 g) and liquid mixture 3 (5.0 g), liquid mixture 1 (3.3 g) and liquid mixture 3 (6.7 g) were used. Otherwise, the same operation as in Example 3-1 was performed to form a coating film having a thickness of about 6.8 μm on the PC plate. The results are shown in Table 8 below.

[Example 3-3]
In Example 3-1, instead of using the mixed solution 1 (5.0 g) and the mixed solution 3 (5.0 g), the mixed solution 1 (2.8 g) and the mixed solution 3 (7.2 g) were used. Otherwise, the same operation as in Example 3-1 was performed to form a coating film having a thickness of about 6.8 μm on the PC plate. The results are shown in Table 8 below.

[Production Example 4] Preparation of mixed solution 4 According to the blending ratio shown in Table 9 below, a uniform mixed solution 4 having a solid content of 50 wt% was prepared. The compounds indicated by symbols are the same as those in Production Examples 1 to 3.

[Example 4-1]
To a glass screw tube, add the mixed solution 4 (5.0 g) prepared in Production Example 4, the mixed solution 3 (5.0 g) prepared in Production Example 3, and 0.075 g of Parroyl TCP as a polymerization initiator. The mixture was stirred for 1 hour at room temperature using a tic stirrer to prepare a uniform coating solution. This coating solution was applied to a PC plate under low humidity conditions (26 ° C.-20% RH) using a bar coater # 10, and the oven temperature was 30 to 35 ° C. in a nitrogen gas atmosphere for 30 minutes. Dried. Next, the temperature was raised to 100 ° C. (temperature raising time: 5 minutes), followed by thermosetting at 100 ° C. for 2 hours to form a coating film having a thickness of about 6.8 μm on the PC plate. The results are shown in Table 10 below.

[Example 4-2]
In Example 4-1, instead of using the mixed solution 4 (5.0 g) and the mixed solution 3 (5.0 g), the mixed solution 4 (2.5 g) and the mixed solution 3 (7.5 g) were used. Except for the above, the same operation as in Example 4-1 was performed to form a coating film having a thickness of about 6.8 μm on the PC plate. The results are shown in Table 10 below.

[Example 4-3]
In Example 4-1, instead of using the mixed solution 4 (5.0 g) and the mixed solution 3 (5.0 g), the mixed solution 4 (1.7 g) and the mixed solution 3 (8.3 g) were used. Except for the above, the same operation as in Example 4-1 was performed to form a coating film having a thickness of about 6.8 μm on the PC plate. The results are shown in Table 10 below.

[Example 4-4]
In Example 4-1, instead of using the mixed solution 4 (5.0 g) and the mixed solution 3 (5.0 g), the mixed solution 4 (1.3 g) and the mixed solution 3 (8.7 g) were used. Except for the above, the same operation as in Example 4-1 was performed to form a coating film having a thickness of about 6.8 μm on the PC plate. The results are shown in Table 10 below.

以下、実施例１−１で得られた単層膜について、膜切削面の相対イオン強度比（アニオン及びカチオン濃度の分布）を、ＴＯＦ−ＳＩＭＳにより分析した。結果を表９に示す。

Hereinafter, for the monolayer film obtained in Example 1-1, the relative ionic strength ratio (anion and cation concentration distribution) of the membrane cutting surface was analyzed by TOF-SIMS. The results are shown in Table 9.

  Since the monolayer film obtained by the present invention has high hydrophilicity and high hardness, a film having antifogging property, antifouling property, and antistatic property and a laminate in which the surface of the substrate is coated are obtained. Useful for.

10: base material, 20: single layer film, 30: cutting direction, 40: single layer film surface, 50: single layer film inside

Claims (4)

Compound (I) represented by the following general formula (1) and compound (II) having two or more (meth) acryloyl groups (however, having no sulfonic acid group, carboxyl group and phosphoric acid group) The molar ratio (I) / (II) of compound (I) to (II) is in the range of 1 / 0.05 to 1/1000, and the one-hour half-life temperature T _1/2 is 40 to 100 ° C. A first step of preparing a composition comprising peroxide (III) and solvent (IV) in the range of
A second step of forming a coating film comprising the composition on at least one side of the substrate;
The coating film is copolymerized by heat so that at least one anionic hydrophilic group selected from a sulfonic acid group, a carboxyl group and a phosphoric acid group has an anion concentration (Sa) on the outer surface and an inner surface in contact with the substrate. A method for producing a laminate comprising a third step of forming a monolayer film distributed so that an anion concentration ratio (Sa / Da) with an anion concentration (Da) at an intermediate point with 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 = 1 + 2m. M1 represents at least one monovalent selected from a hydrogen ion, an ammonium ion, and an alkali metal ion. M2 is at least one divalent cation selected from alkaline earth metal ions, and X is at least one selected from groups represented by the following general formulas (1-1) to (1-4). It is a monovalent anion.)

(In the above formulas (1-1) to (1-4), J and J ′ each independently represent H or CH ₃ , n represents 0 or 1, and R each independently represents 1 to 600 carbon atoms. Any methylene group contained in the aliphatic hydrocarbon group is a divalent aromatic group, a divalent aliphatic cyclic hydrocarbon group, -O-, -COO-, or (It may be substituted with -OCO-.)   The method for producing a laminate according to claim 1, wherein the peroxide (III) is at least one selected from peroxycarbonate and diacyl peroxide.   After the coating film is formed on the substrate in the second step, the solvent (IV) contained in the composition for forming the coating film is dried so that the content is 30% by weight or less, and then in the third step. The manufacturing method of the laminated body of Claim 1 or 2 which performs copolymerization with the heat | fever of a coating film.   The manufacturing method of the laminated body of any one of Claims 1-3 in which the ultraviolet absorber is further contained in the composition produced at said 1st process.

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