Process for producing photochromic optical material

Patent metadata

Field	Value
Publication number	US-9605103-B2
Application number	US-201414909361-A
Country	US
Kind code	B2
Filing date	Aug 1, 2014
Priority date	Aug 2, 2013
Publication date	Mar 28, 2017
Grant date	Mar 28, 2017

Abstract

The process for producing photochromic optical materials of the present invention includes a step (i) of reacting at least one polymerizable monomer (A) having two or more ethylene-based unsaturated groups with at least one polythiol (B) having two or more mercapto groups to obtain a prepolymer; a step (ii) of mixing the prepolymer and a photochromic compound (C) to obtain a polymerizable composition; and a step (iii) of polymerizing the polymerizable composition, wherein, before the reaction of the step (i), the molar number of the mercapto groups included in the polythiol (B) is smaller than the molar number of the ethylene-based unsaturated groups included in the polymerizable monomer (A).

First claim

The invention claimed is:

1. A process for producing photochromic optical materials, comprising:
a step (i) of reacting at least one polymerizable monomer (A) having two or more ethylene-based unsaturated groups with at least one polythiol (B) having two or more mercapto groups to obtain a prepolymer;
a step (ii) of mixing the prepolymer and a photochromic compound (C) to obtain a polymerizable composition; and
a step (iii) of polymerizing the polymerizable composition,
wherein, before the reaction of the step (i), the molar number of the mercapto groups included in the polythiol (B) is smaller than the molar number of the ethylene-based unsaturated groups included in the polymerizable monomer (A).

2. The process for producing photochromic optical materials according to claim 1 ,
wherein, before the reaction of the step (i), the molar number of the mercapto groups included in the polythiol (B) is equal to or less than 0.3 times with respect to the molar number of the entirety of ethylene-based unsaturated groups included in the polymerizable monomer (A).

3. The process for producing photochromic optical materials according to claim 1 ,
wherein the polymerizable monomer (A) includes at least one ethylene-based unsaturated polymerizable monomer (a1) having two or more vinyl groups or isopropenyl groups and/or at least one ethylene-based unsaturated polymerizable monomer (a2) having two or more (meth)acrylic groups.

4. The process for producing photochromic optical materials according to claim 1 ,
wherein, in the step (i) or (ii), an ethylene-based unsaturated polymerizable monomer (D) having one (meth)acrylic group is included.

5. The process for producing photochromic optical materials according to claim 1 ,
wherein, in the step (i), the polymerizable monomer (A) reacts with the polythiol (B) in the presence of a phosphine-based compound.

6. The process for producing photochromic optical materials according to claim 1 ,
wherein the step (ii) is a step of mixing the prepolymer, the photochromic compound (C), and an azo-based compound.

7. The process for producing photochromic optical materials according to claim 6 ,
wherein the step (iii) is a step of polymerizing the polymerizable composition in the presence of an azo-based compound.

8. The process for producing photochromic optical materials according to claim 3 ,
wherein the polymerizable monomer (a1) is at least one selected from divinylbenzene, diisopropenylbenzene, trivinylbenzene, and divinylnaphthalene.

9. The process for producing photochromic optical materials according to claim 3 ,
wherein the polymerizable monomer (a2) is at least one selected from polymerizable monomers represented by the following general formula (4);

wherein, in formula (4), each of m and n is 0 or greater number, and m and n satisfy m+n=0 to 50; X 1 is a hydrogen atom or a methyl group, and a plurality of X 1 may be the same as or different from each other; X 2 is a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and a plurality of X 2 may be the same as or different from each other.

10. The process for producing photochromic optical materials according to claim 4 ,
wherein the ethylene-based unsaturated polymerizable monomer (D) is at least one selected from aromatic (meth)acrylic acid esters represented by the following general formula (5);

wherein, in formula (5), X 3 is a hydrogen atom or a methyl group.

11. The process for producing photochromic optical materials according to according to claim 1 ,
wherein the polythiol (B) is at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8, 4,7, or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptoethyl)sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane.

12. The process for producing photochromic optical materials according to claim 1 ,
wherein the photochromic compound (C) is represented by the following general formula (7) or (8);

wherein, in formulas (7) and (8),

R 1 and R 2 may be the same as or different from each other, and each of R 1 and R 2 independently represents
a hydrogen atom;
a linear or branched alkyl group having 1 to 12 carbon atoms;
a cycloalkyl group having 3 to 12 carbon atoms;
a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or a substituted or unsubstituted heteroaryl group having 4 to 24 carbon atoms,
wherein the substituted aryl group or the substituted heteroaryl group, as a substituent, has at least one substituent selected from a halogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched alkoxy group having 1 to 12 carbon atoms, a linear or branched haloalkyl group having 1 to 12 carbon atoms which is substituted with at least one halogen atom, a linear or branched haloalkoxy group having 1 to 12 carbon atoms which is substituted with at least one halogen atom, a phenoxy group or a naphthoxy group which is substituted with at least one linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, an —NH 2 group, an —NHR group, a —N(R) 2 group, wherein R is a linear or branched alkyl group having 1 to 6 carbon atoms, and in a case where two R's are present, the two R's may be the same as or different from each other,

a methacryloyl group, and an acryloyl group; or
an aralkyl or heteroaralkyl group which is formed by substituting a linear or branched alkyl group having 1 to 4 carbon atoms with an aryl group or a heteroaryl group,

R 3 's may be the same as or different from each other, and each R 3 's independently represents
a halogen atom;
a linear or branched alkyl group having 1 to 12 carbon atoms;
a cycloalkyl group having 3 to 12 carbon atoms;
a linear or branched alkoxy group having 1 to 12 carbon atoms;
a linear or branched haloalkyl group having 1 to 12 carbon atoms which is substituted with at least one halogen atom, a linear or branched halocycloalkyl group having 3 to 12 carbon atoms which is substituted with at least one halogen atom, a linear or branched haloalkoxy group having 1 to 12 carbon atoms which is substituted with at least one halogen atom;
an aryl group having 6 to 24 carbon atoms or a heteroaryl group having 4 to 24 carbon atoms which is substituted or unsubstituted,
wherein the substituted aryl group or the substituted heteroaryl group has at least one substituent selected from a halogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched alkoxy group having 1 to 12 carbon atoms, a linear or branched haloalkyl group having 1 to 12 carbon atoms which is substituted with at least one halogen atom, a linear or branched haloalkoxy group having 1 to 12 carbon atoms which is substituted with at least one halogen atom, a phenoxy group or a naphthoxy group which is substituted with at least one linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, and a

Assignees

• Mitsui Chemicals Inc

Inventors

• Ryu Akinori

Classifications

• C08F212/34

  Monomers containing two or more unsaturated aliphatic radicals · CPC title

• G02B1/04

  made of organic materials, e.g. plastics (G02B1/08 takes precedence) · CPC title

• C08F290/06 Primary

  Polymers provided for in subclass C08G · CPC title

• G02C7/102

  Photochromic filters · CPC title

• G02B1/041

  Lenses · CPC title