Composite of polymer and tungstic acid and/or molybdic acid

Patent metadata

Field	Value
Publication number	US-10131777-B2
Application number	US-201314408519-A
Country	US
Kind code	B2
Filing date	Jun 17, 2013
Priority date	Jun 18, 2012
Publication date	Nov 20, 2018
Grant date	Nov 20, 2018

Abstract

A method produces a composite of a polymer and tungstic acid and/or molybdic acid; and the composite obtained by the method has high transparency and a desired refractive index. This composite contains tungstic acid and/or molybdic acid and a polymer that has a number average molecular weight of 1,000-10,000,000 and an ether bond and/or an ester bond. The content of tungstic acid and/or molybdic acid in the composite is 0.01-95% by weight.

First claim

The invention claimed is:

1. A transparent film comprising a composite comprising a uniform dispersion of one or more acids and one or more polymers formed from a solution containing the one or more acids and the one or more polymers dissolved in the solution;
wherein the one or more acids is selected from the group consisting of phosphotungstic acid, phosphomolybdic acid, and silicomolybdic acid,
wherein the one or more polymers has a number average molecular weight of 1,000 to 10,000,000, the one or more polymers consists of repeating units obtained by polymerizing one or more compounds selected from the group consisting of compounds represented by the following formula 1, and the one or more polymers has one or more bonds selected from the group consisting of ester bonds and ether bonds,
wherein the content of the one or more acids in the composite is 10% by weight to 95% by weight,
wherein the total amount of the one or more acids and the one or more polymers in the composite is 90% by weight or more, and

where, X represents a single bond or a linking group represented by —COO—, —CONR3- or —NHCO—,
R1 and R3 respectively and independently represent: (i) a hydrogen atom, (ii) an alkyl group having 1 to 18 carbon atoms in which an arbitrary hydrogen may be substituted with a hydroxyl group or an alkenyl group having 1 to 18 carbon atoms, (iii) an aryl group having 6 to 18 carbon atoms in which an arbitrary hydrogen may be substituted with a methyl group, (iv) an aralkyl group having 7 to 18 carbon atoms, (v) a heterocyclic group having 3 to 18 carbon atoms, (vi) an alicyclic hydrocarbon group having 3 to 18 carbon atoms, (vii) polyethylene oxide having a degree of polymerization of 2 to 20 or (viii) a glycidyl group,
R2 represents a hydrogen atom or a methyl group, and
R1 and R3 may be linked through an ether bond, and
when X is —COO— and R1 is the alkyl group, the compound represented by formula 1 is one or more compounds selected from the group consisting of methyl (meth)acrylate, butyl (meth)acrylate, norbornyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid, and 2-hydroxyethyl (meth)acrylate.

2. The transparent film comprising the composite according to claim 1 , wherein the compound represented by formula 1 is one or more compounds selected from the group consisting of methyl (meth)acrylate, butyl (meth)acrylate, norbornyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, and styrene.

3. The transparent film comprising the composite according to claim 1 , wherein the one or more polymers is selected from the group consisting of poly(methyl (meth)acrylate), and poly(meth)acrylic acid, and poly(2-hydroxyethyl methacrylate).

4. The transparent film comprising the composite according to claim 1 , wherein a transmittance reduction rate of the composite is 10% or less when the transparent film has a thickness of 5 μm.

5. A method for producing a transparent film comprising:
obtaining a solution by dissolving one or more acids and one or more polymers in a solvent; and
distilling off the solvent from the solution to form the film;
wherein the one or more acids is selected from the group consisting of phosphotungstic acid, phosphomolybdic acid and silicomolybdic acid,
wherein the one or more polymers has a number average molecular weight of 1,000 to 10,000,000, the one or more polymers consists of repeating units obtained by polymerizing one or more compounds selected from compounds represented by the following formula (I) and the one or more polymers has one or more bonds selected from the group consisting of ester bonds and ether bonds,
wherein the content of the one or more acids in the film is 10% by weight to 95% by weight,
wherein the total amount of the one or more polymers and the one or more acids in the film is 90% by weight or more, and
wherein the solvent is one or more compounds selected from the group consisting of ester-based compounds, alcohol-based compounds, ketone-based compounds, lactone-based compounds, glycol monoether monoester-based compounds, and glycol diester-based compounds;

wherein, X represents a single bond or a linking group represented by —COO—, —CONR 3 — or —NHCO—,
R 1 and R 3 respectively and independently represent: (i) a hydrogen atom, (ii) an alkyl group having 1 to 18 carbon atoms in which an arbitrary hydrogen may be substituted with a hydroxyl group or an alkenyl group having 1 to 18 carbon atoms, (iii) an aryl group having 6 to 18 carbon atoms in which an arbitrary hydrogen may be substituted with a methyl group, (iv) an aralkyl group having 7 to 18 carbon atoms, (v) a heterocyclic group having 3 to 18 carbon atoms, (vi) an alicyclic hydrocarbon group having 3 to 18 carbon atoms, (vii) a polyethylene oxide having a degree of polymerization of 2 to 20 or (viii) a glycidyl group,
R 2 represents a hydrogen atom or methyl group, and
R 1 and R 3 may be linked through an ether bond, and
when X is —COO— and R1 is the alkyl group, the compound represented by formula (I) is one or more compounds selected from the group consisting of methyl (meth)acrylate, butyl (meth)acrylate, norbornyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid, and 2-hydroxyethyl (meth)acrylate.

6. The method according to claim 5 , wherein the one or more polymers is selected from the group consisting of poly(methyl (meth)acrylate) and poly(meth)acrylic acid.

7. The method according to claim 5 , wherein the distilling off the solvent from the solution is carried out on a base material coated with the solution.

8. The method according to claim 5 , wherein the solvent is one or more selected from the group consisting of ethyl acetate, methanol and ethanol.

9. The transparent film of claim 1 , wherein the content of the one or more acids in the composite is 16% by weight to 92% by weight.

Assignees

• Univ Kumamoto Nat Univ Corp

Inventors

• Ihara Hirotaka
• JINTOKU Hirokuni

Classifications

• C09D133/14

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

• C09D129/04

  Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids · CPC title

• C08L2201/10

  Transparent films; Clear coatings; Transparent materials · CPC title

• C08F120/20

  of polyhydric alcohols or {polyhydric} phenols {, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate} · CPC title

• C08K2003/328

  Phosphates of heavy metals · CPC title