Monolayer film and hydrophilic material comprising the same

Patent metadata

Field	Value
Publication number	US-9238769-B2
Application number	US-201114234941-A
Country	US
Kind code	B2
Filing date	Jul 25, 2011
Priority date	Jul 25, 2011
Publication date	Jan 19, 2016
Grant date	Jan 19, 2016

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.

First claim

The invention claimed is:

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 (1) 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 σ of not less than 9.3 (cal/cm 3 ) 1/2 ;
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] l [M2] m   (1)

(in Formula (1), s indicates 1 or 2; l and m indicate integers satisfying s=1+2m; 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 CH 3 ; 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)).

2. 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 CH 3 ; R 1 and R 2 are each independently H, CH 3 or C 2 H 5 ; n indicates an integer of 1 to 20; l 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).

3. 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), 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;
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;
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 of 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), norbomanedimethylene, dicyclohexylenemethane, cyclohexanedimethylene or xylylene; R 50 is hexamethylene, isophorone (1-methylene-3-ethylene-3-methyl-5,5-dimethyl-cyclohexane), norbomanedimethylene, dicyclohexylenemethane, cyclohexanedimethylene, toluylene, diphenylmethane or xylylene; V is OH or an oxygen atom having a bonding hand (*); W1 to W3 are each independently H, CH 3 , 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; of 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).

4. 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), 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 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), 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 of 1 to 6 carbon atoms; and n1 and n2 each independently indicate an integer of 0 to 8)

(in Formula (5), R 3 to R 6 are each independently H or CH 3 ; b1 and b2 each independently indicate an integer of 0 to 2; and c1 indicates an integer of 2 to 30)

(in Formula (6), R 3 to R 6 are each independently H or CH 3 ; c2 and c3 each independently indicate an integer of 1 to 5; and dl indicates an integer of 2 to 20)

(in Formula (7), R 3 and R 4 are each independently H or CH 3 ; b1 and b2 each independently indicate an integer of 0 to 2; dl indicates an integer of 2 to 20; and m indicates 0 or 1)

(in Formula (8), R 3 and R 4 are each independently H or CH 3 ; and o1 and o2 each independently indicate an integer of 1 to 3)

(in Formula (10), R 3 to R 8 are each independently H or CH 3 ; c4 and c5 each independently indicate an integer of 0 to 5; and m indicates 0 or 1)

(in Formula (11), R 3 and R 4 are each independently H or CH 3 ; and m indicates

Assignees

• Okazaki Koju
• Mitsui Chemicals Inc

Inventors

• Okazaki Koju

Classifications

• C09D133/06

  of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical · CPC title

• C09D133/14

  of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen · CPC title

• B05D1/185

  applying monomolecular layers (B05D1/204 takes precedence) · CPC title

• C09D5/1668

  Vinyl-type polymers · CPC title

• Y10T428/2848

  Three or more layers · CPC title