Single layer film and hydrophilic material comprising the same

Patent metadata

Field	Value
Publication number	US-9034464-B2
Application number	US-201113812779-A
Country	US
Kind code	B2
Filing date	Jul 25, 2011
Priority date	Jul 29, 2010
Publication date	May 19, 2015
Grant date	May 19, 2015

Abstract

There is stably provided a hydrophilic cured product, such as a single-layer film, in which anionic hydrophilic groups are concentrated at a surface that is in contact with the air and which is excellent in transparency and adhesion to a substrate and tends to be rarely cracked. The hydrophilic cured product or single-layer film comprising a resin composition is produced by applying a mixture containing a polyvalent monomer (II) having two or more (meth) acryloyl groups and a compound (IV) having a specific group and a sulfonic acid group to a substrate or the like, drying the mixture if necessary, and then performing polymerization.

First claim

The invention claimed is:

1. A hydrophilic cured product obtained by polymerizing a mixture containing:
a polyvalent monomer (II) having two or more (meth)acryloyl groups, and
a compound (IV), wherein the compound (IV) contained in the mixture is at least one compound selected from a group of compounds represented by the following general formulas (100), (200) and (300):

wherein D 1 is a mercapto group, an amino group, a methylamino group or an ethylamino group, Z is a hydrogen ion, an ammonium ion, an amine ion, an alkaline metal ion or ½ equivalent of an alkaline earth metal ion, R 1 and R 2 are each independently H, a methyl group, an ethyl group, a methoxy group or an ethoxy group, and nn is an integer of 1 to 10,

wherein D 2 , R 3 and SO 3 Z are each a group bonded to carbon on a ring contained in the above formula, each D 2 is independently a mercapto group, an amino group, a methylamino group, an ethylamino group or a hydroxyl group, Z is a hydrogen ion, an ammonium ion, an amine ion, an alkaline metal ion or ½ equivalent of an alkaline earth metal ion, each R 3 is independently H, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, k is an integer of 0 to 10, l and m are each independently an integer of 1 to 11, k, l and m are numbers satisfying the condition of k+l+m=2 to 6+2n, and n is an integer of 0 to 3,

wherein D 2 , R 3 and SO 3 Z are each a group bonded to carbon on a ring contained in the above formula, each D 2 is independently a mercapto group, an amino group, a methylamino group, an ethylamino group or a hydroxyl group, Z is a hydrogen ion, an ammonium ion, an amine ion, an alkaline metal ion or ½ equivalent of an alkaline earth metal ion, each R 3 is independently H, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, r is an integer of 0 to 6, q and p are each independently an integer of 1 to 7, and p, q and r are numbers satisfying the condition of p+q+r=an integer of 2 to 8,
and the amount of the compound (IV) added based on 100 parts by weight of the polyvalent monomer (II) is in the range of 0.01 to 200 parts by weight.

2. The hydrophilic cured product as claimed in claim 1 , wherein the mixture further contains a mono(meth)acrylate (I) having at least one anionic hydrophilic group selected from a sulfonic acid group, a carboxyl group and a phosphoric acid group, wherein the mono(meth)acrylate (I) is a mono(meth)acrylate represented by the following general formula (1):
[X] s [M1 ]l [M2 ]m   (1)

wherein s is 1 or 2, l is 1 or 2, m is 0 or 1, M1 and M2 are each a monovalent cation selected from a hydrogen ion, an ammonium ion, an amine ion and an alkaline metal ion, or an alkaline earth metal ion that is a divalent cation, and they may be the same or different, X is a hydrophilic anion represented by any one of the following general formulas (1-1) to (1-3):

wherein J is H or CH 3 and may be the same or different, and n is 1, R is a hydrocarbon group of 1 to 600 carbon atoms which may contain an aromatic group, an alicyclic hydrocarbon group, an ether group or an ester group.

3. The hydrophilic cured product as claimed in claim 2 , wherein the amount of the compound (IV) added based on 100 parts by weight of the total amount of the mono(meth)acrylate (I) and the polyvalent monomer (II) is in the range of 0.01 to 30 parts by weight.

4. A single-layer film formed from the hydrophilic cured product as claimed in claim 1 .

5. The single-layer film as claimed in claim 4 , wherein the degree of inclination (anion concentration ratio) (Sa/Da) of a surface concentration (Sa) of sulfonic acid groups, carboxyl groups and phosphoric acid groups that are anionic hydrophilic groups in the single-layer film to a deep part concentration (Da) of these anionic hydrophilic groups at the position of ½ of the film thickness of the single layer film is not less than 1.1.

6. The single-layer film as claimed in claim 4 , which has a water contact angle of not more than 30°.

7. The single-layer film as claimed in claim 4 , which has a water contact angle of not more than 10°.

8. The single-layer film as claimed in claim 4 , which has a film thickness of 0.05 to 500 μm.

9. A process for producing a laminate including a single-layer film having an anionic hydrophilic group and formed on at least one surface of a substrate, comprising:
a step of preparing a mixture containing

a polyvalent monomer (II) having two or more (meth)acryloyl groups, and
a compound (IV), wherein the compound (IV) contained in the mixture is at least one compound selected from a group of compounds represented by the following general formulas (100), (200) and (300):

wherein D 1 is a mercapto group, an amino group, a methylamino group or an ethylamino group, Z is a hydrogen ion, an ammonium ion, an amine ion, an alkaline metal ion or ½ equivalent of an alkaline earth metal ion, R 1 and R 2 are each independently H, a methyl group, an ethyl group, a methoxy group or an ethoxy group, and nn is an integer of 1 to 10,

wherein D 2 , R 3 and SO 3 Z are each a group bonded to carbon on a ring contained in the above formula, each D 2 is independently a mercapto group, an amino group, a methylamino group, an ethylamino group or a hydroxyl group, Z is a hydrogen ion, an ammonium ion, an amine ion, an alkaline metal ion or ½ equivalent of an alkaline earth metal ion, each R 3 is independently H, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, k is an integer of 0 to 10, l and m are each independently an integer of 1 to 11, k, l and m are numbers satisfying the condition of k+l+m=2 to 6+2n, and n is an integer of 0 to 3,

wherein D 2 , R 3 and SO 3 Z are each a group bonded to carbon on a ring contained in the above formula, each D 2 is independently a mercapto group, an amino group, a methylamino group, an ethylamino group or a hydroxyl group, Z is a hydrogen ion, an ammonium ion, an amine ion, an alkaline metal ion or ½ equivalent of an alkaline earth metal ion, each R 3 is independently H, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, r is an integer of 0 to 6, q and p are each independently an integer of 1 to 7, and p, q and r are numbers satisfying the condition of p+q+r=an integer of 2 to 8,
and the amount of the compound (IV) added based on 100 parts by weight of the polyvalent monomer (II) is in the range of 0.01 to 200 parts by weight,
and contains a solvent containing a compound having a solubility parameter σ of not less than 9.3 (cal/cm 3 ),
a step of applying the mixture to at least one surface of a substrate,
a step of removing at least a part of the solvent from the mixture applied, and
a step of polymerizing the mixture h

Assignees

• Okazaki Koju
• Mitsui Chemicals Inc

Inventors

• Okazaki Koju

Classifications

• C08J7/0427

  with only one layer of a composition containing a polymer binder (with more layers C08J7/042) · CPC title

• C09D4/00

  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} · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F222/1006

  of polyhydric alcohols or polyhydric phenols · CPC title

• C08J7/047

  Chemistry & Metallurgy · mapped topic