# US 2014/0154451 A1 · Monolayer film and hydrophilic material comprising the same

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- Number: US 2014/0154451 A1
- Document ID: US20140154451A1
- Status: Published application
- Kind: A1
- Application number: 14/234,941
- Filed: 2011-07-25
- Published: 2014-06-05
- Earliest claimed: 2011-07-25
- Assignees: Mitsui Chemicals, Inc.
- Inventors: Koju Okazaki
- Web page: https://patentgrep.com/patent/US20140154451A1

## CPC

- C09D 4/00: Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16}
- C09D 5/00: Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced {(electrically insulating plastics, resins or waxes H01B3/30)}; Filling pastes
- C09D 5/1668: {Vinyl-type polymers}
- C09D 133/06: of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D 133/14: of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09K 3/18: for application to surfaces to minimize adherence of ice, mist or water thereto (rendering particulate materials free flowing, in general, e.g. making them hydrophobic B01J2/30); Thawing or antifreeze materials for application to surfaces (used in liquids for heat-transfer, heat-exchange or heat-storage or for the production of heat or cold other than by combustion, e.g. radiator liquids, C09K5/00)
- C09K 8/16: characterised by the inorganic compounds other than clay
- B05D 1/185: {applying monomolecular layers (B05D1/204 takes precedence)}
- C08F 220/382: {and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate}
- Y10T 428/1462: Polymer derived from material having at least one acrylic or alkacrylic group or the nitrile or amide derivative thereof [e.g., acrylamide, acrylate ester, etc.]
- Y10T 428/263: Coating layer not in excess of 5 mils thick or equivalent
- Y10T 428/2848: Three or more layers
- Y10T 428/31938: Polymer of monoethylenically unsaturated hydrocarbon
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The invention provides monolayer films which not only have hydrophilicity and are excellent in such properties as antifogging properties, antifouling properties, antistatic properties and anti-condensation properties but also tend to exhibit excellent transparency even with a large film thickness and excellent scratch resistance, as well as stacks having the monolayer film. The monolayer film is obtained by preparing a mixture including a monomer composition and a solvent, the monomer composition including a specific monomer and a polyvalent monomer having two or more (meth)acryloyl groups and being free of sulfonic group, carboxyl group and phosphoric group in a specific molar ratio, the solvent having a specific solubility parameter σ; applying the mixture onto a substrate and removing at least part of the solvent; and polymerizing the monomer composition to produce a monolayer film having at least one anionic hydrophilic group selected from a sulfonic group, a carboxyl group and a phosphoric group and a specific anion concentration ratio (Sa/Da) of the anion concentration (Sa) at the outer surface to the anion concentration (Da) at the middle point between the inner surface in contact with the substrate and the outer surface.

## Claims

### Claim 1

A monolayer film disposed on a substrate, obtained by preparing a mixture including a monomer composition and a solvent, the monomer composition including a monomer (I) represented by General Formula (1) below and a polyvalent monomer (II) having two or more (meth)acryloyl groups and being free of sulfonic group, carboxyl group and phosphoric group in a monomer (I)/polyvalent monomer (II) molar ratio of 1/1000 to less than 1/30, the solvent including a compound with a solubility parameter a of not less than 9.3 (cal/cm3);
applying the mixture onto the substrate and removing at least part of the solvent; and
polymerizing the monomer composition including the monomer (I) and the monomer (II);
the monolayer film having at least one anionic hydrophilic group selected from a sulfonic group, a carboxyl group and a phosphoric group, the anion concentration ratio (Sa/Da) of the anion concentration (Sa) at the outer surface to the anion concentration (Da) at the middle point between the inner surface in contact with the substrate and the outer surface being not less than 1.1;
[X]s[M1]1[M2]m (1)
(in Formula (1), s indicates 1 or 2; 1 and m indicate integers satisfying s=l+m/2; M1 is at least one monovalent cation selected from hydrogen ion, ammonium ions and alkali metal ions; M2 is at least one divalent cation selected from alkaline earth metal ions; and X is at least one monovalent anion selected from groups represented by General Formulae (1-1) to (1-4) below:
(in Formulae (1-1) to (1-4), J and J′ are each independently H or CH3; n indicates 0 or 1; and Rs are each independently an aliphatic hydrocarbon group of 1 to 600 carbon atoms optionally substituted at a carbon atom with at least one group selected from aromatic groups, aliphatic cyclic groups, ether groups and ester groups)).

### Claim 2 (depends on 1)

The monolayer film according to claim 1, wherein the monomer (I) is at least one monomer selected from compounds represented by General Formula (1-1-1) and General Formula (1-1-2) below:
(in Formulae (1-1-1) and (1-1-2), J is H or CH3; R1 and R2 are each independently H, CH3 or C2H5; n indicates an integer of 1 to 20; 1 indicates an integer of 2 to 10; M is at least one monovalent cation selected from hydrogen ion, ammonium ions and alkali metal ions, or is at least one divalent cation selected from alkaline earth metal ions; and m is 1 when M is a monovalent cation, and m is 2 when M is a divalent cation).

### Claim 3 (depends on 1)

The monolayer film according to claim 1, wherein the polyvalent monomer (II) is at least one monomer selected from compounds represented by General Formula (2-1) and General Formula (2-2) below:
(in Formulae (2-1) and (2-2), R3 and R5 to R9 are each independently H or CH3; R12 and R13 are each independently H or CH3;
X1, X2, X3, X4 and X5 are each independently O or S;
the letter a indicates an integer of 2 to 30; b indicates an integer of 0 to 2; c indicates an integer of 0 to 30; d indicates an integer of 0 to 20; e indicates an integer of 0 to 2; i indicates an integer of 1 to 20; k indicates an integer of 1 to 10; and
the letter A indicates an atom or group selected from:
or from:
wherein * indicates a bonding hand;
R10 and R11 are each independently H or CH3; R100 and R101 are each independently H or an alkyl group of 1 to 6 carbon atoms; R200 and R201 are each independently H, CH3 or a phenyl group; R is hexamethylene, isophorone (1-methylene-3-ethylene-3-methyl-5,5-dimethyl-cyclohexane), norbornanedimethylene, dicyclohexylenemethane, cyclohexanedimethylene or xylylene; R50 is hexamethylene, isophorone (1-methylene-3-ethylene-3-methyl-5,5-dimethyl-cyclohexane), norbornanedimethylene, dicyclohexylenemethane, cyclohexanedimethylene, toluylene, diphenylmethane or xylylene; V is OH or an oxygen atom having a bonding hand (*); W1 to W3 are each independently H, CH3, OH or an oxygen atom having a bonding hand (*); Z is OH, an oxygen atom having a bonding hand (*), COOH or a carboxyl group having a bonding hand (*) (COO); V1 to V3 are each independently H or a bonding hand (*);
n1 and n2 each independently indicate an integer of 0 to 8; o1 and o2 each independently indicate an integer of 1 to 3; f indicates an integer of 1 to 20; g indicates an integer of 0 to 3; m indicates 0 or 1; q indicates an integer of 1 to 7; a1 indicates an integer of 2 to 3; a2 indicates an integer of 3 to 4; a3 indicates an integer of 4 to 6; a4 indicates an integer of 2 to 3; and a5 indicates an integer of 2 to 4).

### Claim 4 (depends on 1)

The monolayer film according to claim 1, wherein the polyvalent monomer (II) is at least one monomer selected from compounds represented by General Formulae (3) to (8) and (10) to (33) below:
(in Formula (3), R3 and R4 are each independently H or CH3; R100 and R101 are each independently H or an alkyl group of 1 to 6 carbon atoms; b1 and b2 each independently indicate an integer of 0 to 2; and n1 and n2 each independently indicate an integer of 0 to 8)
(in Formula (4), R3 to R6 are each independently H or CH3; R100 and R101 are each independently H or an alkyl group of 1 to 6 carbon atoms; and n1 and n2 each independently indicate an integer of 0 to 8)
(in Formula (5), R3 to R6 are each independently H or CH3; b1 and b2 each independently indicate an integer of 0 to 2; and c1 indicates an integer of 2 to 30)
(in Formula (6), R3 to R6 are each independently H or CH3; c2 and c3 each independently indicate an integer of 1 to 5; and d1 indicates an integer of 2 to 20)
(in Formula (7), R3 and R4 are each independently H or CH3; b1 and b2 each independently indicate an integer of 0 to 2; d1 indicates an integer of 2 to 20; and m indicates 0 or 1)
(in Formula (8), R3 and R4 are each independently H or CH3; and o1 and o2 each independently indicate an integer of 1 to 3)
(in Formula (10), R3 to R8 are each independently H or CH3; c4 and c5 each independently indicate an integer of 0 to 5; and m indicates 0 or 1)
(in Formula (11), R3 and R4 are each independently H or CH3; and m indicates 0 or 1)
(in Formula (12), R3 to R7 are each independently H or CH3)
(in Formula (13), * represents a bonding hand; R3, R5 and R6 are each independently H or CH3; and c6 indicates an integer of 0 to 3)
(in Formula (14), R3 to R8 are each independently H or CH3; b1 and b2 each independently indicate an integer of 0 to 2; c7 and c8 each independently indicate an integer of 0 to 5; and m indicates 0 or 1)
(in Formula (15), R3 to R10 are each independently H or CH3; b1 and b2 each independently indicate an integer of 0 to 2; and c9 and c10 each independently indicate an integer of 0 to 30)
(in Formula (16), R3 to R10 are each independently H or CH3; c11 to c14 indicate integers of 1 or above and satisfy c11+c12+c13+c14=4 to 30)
(in Formula (17), R3 and R4 are each independently H or CH3; and b1 and b2 each independently indicate an integer of 0 to 2)
(in Formula (18), R3 to R8 are each independently H or CH3; R200 and R201 are each independently H, CH3 or a phenyl group; and c4 and c5 each independently indicate an integer of 0 to 5)
(in Formula (19), R3 to R5 and R11 are each independently H or CH3; b1 to b3 each independently indicate an integer of 0 to 2; and f indicates an integer of 1 to 20)
(in Formula (20), * represents a bonding hand; V is OH or an oxygen atom having a bonding hand (*); R3, R5 and R6 are each independently H or CH3; a1 indicates 2 or 3; b1 indicates an integer of 0 to 2; and c15 indicates an integer of 0 to 20)
(in Formula (21), * represents a bonding hand; W1 is H, CH3, OH or an oxygen atom having a bonding hand (*); R3, R5 and R6 are each independently H or CH3; a2 indicates 3 or 4; and c16 indicates an integer of 0 to 20)
(in Formula (22), * represents a bonding hand; W2 and W3 are each independently H, CH3, OH or an oxygen atom having a bonding hand (*); R3, R5 and R6 are each independently H or CH3; a3 indicates an integer of 4 to 6; and c17 indicates an integer of 0 to 3)
(in Formula (23), R is hexamethylene, isophorone (1-methylene-3-ethylene-3-methyl-5,5-dimethyl-cyclohexane), norbornanedimethylene, dicyclohexylenemethane, cyclohexanedimethylene or xylylene; R3 to R10 are each independently H or CH3; and e1 and e2 each independently indicate an integer of 0 to 2)
(in Formula (24), R3, R5 and R6 are each independently H or CH3; b1 indicates an integer of 0 to 2; c15 indicates an integer of 0 to 20; and n100 indicates an integer of 1 to 6)
(in Formula (25), R3 to R10 are each independently H or CH3; b1 and b2 each independently indicate an integer of 0 to 2; and c9 and c10 each independently indicate an integer of 0 to 5)
(in Formula (26), R3 is H or CH3; p1 indicates an integer of 1 to 6; and a10 indicates 3)
(in Formula (27), R3 to R8 are each independently H or CH3; b1 and b2 each independently indicate an integer of 0 to 2; and c4 and c5 each independently indicate an integer of 0 to 5)
(in Formula (28), R3 to R8 are each independently H or CH3; b1 and b2 each independently indicate an integer of 0 to 2; and c4 and c5 each independently indicate an integer of 0 to 5)
(in Formula (29), R3 and R5 to R13 are each independently H or CH3; and i1 indicates an integer of 0 to 5)
(in Formula (30), R3 and R5 to R9 are each independently H or CH3; W1 is H, CH3, OH or an oxygen atom having a bonding hand (*); a2 indicates 3 or 4; and i1 indicates an integer of 0 to 5)
(in Formula (31), R3 to R9 are each independently H or CH3; W2 and W3 are each independently H, CH3, OH or an oxygen atom having a bonding hand (*); a7 indicates an integer of 1 to 6; a8 indicates an integer of 0 to 5; and a7+a8=2 to 6)
(in Formula (32), R70 is toluylene, diphenylmethane, hexamethylene, isophorone (1-methylene-3-ethylene-3-methyl-5,5-dimethyl-cyclohexane), norbornanedimethylene, dicyclohexylenemethane, cyclohexanedimethylene, N,N′,N″-tris(hexamethylene)-isocyanurate, N,N,N′-tris(hexamethylene)-urea, N,N,N′,N′-tetrakis(hexamethylene)-urea or xylylene; R3, R5 and R6 are each independently H or CH3; W1 is H, CH3, OH or an oxygen atom having a bonding hand (*); a9 indicates an integer of 1 to 4; a10 indicates an integer of 2 to 4; b1 indicates an integer of 0 to 2; and c4 indicates an integer of 0 to 5)
(in Formula (33), R70 is toluylene, diphenylmethane, hexamethylene, isophorone (1-methylene-3-ethylene-3-methyl-5,5-dimethyl-cyclohexane), norbornanedimethylene, dicyclohexylenemethane, cyclohexanedimethylene, N,N′,N″-tris(hexamethylene)-isocyanurate, N,N,N′-tris(hexamethylene)-urea, N,N,N′,N′-tetrakis(hexamethylene)-urea or xylylene; R3, R5 and R6 are each independently H or CH3; W1 is H, CH3, OH or an oxygen atom having a bonding hand (*); a9 indicates an integer of 1 to 4; a10 indicates an integer of 2 to 4; b1 indicates an integer of 0 to 2; and c4 indicates an integer of 0 to 5).

### Claim 5 (depends on 1)

The monolayer film according to claim 1, wherein the water contact angle of the monolayer film is not more than 30°.

### Claim 6 (depends on 1)

The monolayer film according to claim 1, wherein the film thickness of the monolayer film is 0.5 to 100 μm.

### Claim 7 (depends on 1)

An antifogging material comprising the monolayer film described in claim 1.

### Claim 8 (depends on 1)

An antifouling material comprising the monolayer film described in claim 1.

### Claim 9 (depends on 1)

An antistatic material comprising the monolayer film described in claim 1.

### Claim 10 (depends on 1)

A stack wherein the monolayer film described in claim 1 is disposed on at least one surface of a substrate.

### Claim 11 (depends on 10)

The stack according to claim 10, wherein the monolayer film is disposed on one surface of the substrate and a pressure-sensitive adhesive layer is disposed on the surface of the substrate on which the monolayer film is not disposed.

### Claim 12 (depends on 11)

The stack according to claim 11, wherein a peel layer is further disposed on the surface of the pressure-sensitive adhesive layer.

### Claim 13 (depends on 11)

The stack according to claim 11 wherein a peelable cover layer is disposed on the surface of the monolayer film.

### Claim 14

A method for producing stacks, comprising:
a step of preparing a mixture including a monomer composition and a solvent, the monomer composition including a monomer (I) represented by General Formula (1) below and a polyvalent monomer (II) having two or more (meth)acryloyl groups and being free of sulfonic group, carboxyl group and phosphoric group in a monomer (I)/polyvalent monomer (II) molar ratio of 1/1000 to less than 1/30, the solvent including a compound with a solubility parameter a of not less than 9.3 (cal/cm3);
a step of applying the mixture onto at least one surface of a substrate;
a step of removing at least part of the solvent from the mixture applied; and
a step of polymerizing the monomer (I) and the monomer (II) present in the mixture resulting from the above steps;
the method thus producing a stack having a monolayer film on at least one surface of the substrate, the monolayer film having at least one anionic hydrophilic group selected from a sulfonic group, a carboxyl group and a phosphoric group, the anion concentration ratio (Sa/Da) of the anion concentration (Sa) at the outer surface of the monolayer film to the anion concentration (Da) at the middle point between the inner surface in contact with the substrate and the outer surface being not less than 1.1;
[X]s[M1]1[M2]m (1)
(in Formula (1), s indicates 1 or 2; 1 and m indicate integers satisfying s=l+m/2;
M1 is at least one monovalent cation selected from hydrogen ion, ammonium ions and alkali metal ions; M2 is at least one divalent cation selected from alkaline earth metal ions; and
X is at least one monovalent anion selected from groups represented by General Formulae (1-1) to (1-4) below:
(in Formulae (1-1) to (1-4), J and J′ are each independently H or CH3; n indicates 0 or 1; and Rs are each independently an aliphatic hydrocarbon group of 1 to 600 carbon atoms optionally substituted at a carbon atom with at least one group selected from aromatic groups, aliphatic cyclic groups, ether groups and ester groups)).

### Claim 15 (depends on 14)

The method for producing stacks according to claim 14, wherein the water contact angle of the monolayer film is not more than 30°.