Polymeric dye compound, photosensitive resin composition comprising same and use thereof

Patent metadata

Field	Value
Publication number	US-9683103-B2
Application number	US-201414570065-A
Country	US
Kind code	B2
Filing date	Dec 15, 2014
Priority date	Jun 3, 2014
Publication date	Jun 20, 2017
Grant date	Jun 20, 2017

Abstract

A polymeric dye compound, photosensitive resin composition comprising the same and use thereof are disclosed. The polymeric dye compound comprises three kinds of monomeric units. The photosensitive resin composition comprises a colorant, an alkali-soluble resin, a polymerizable monomer and a polymerization initiator, wherein the colorant comprises the polymeric dye compound and a pigment. The polymeric dye compound is prepared by copolymerization of styrenic monomer and other monomers, such that a colored layer having excellent heat resistance, light resistance and high transmittance can be formed.

First claim

The invention claimed is:

1. A polymeric dye compound useful for forming a colored layer of a color filter, comprising monomeric units (A), (B) and (C) represented by the following structural formulae:

wherein:
R 1 , R 2 , R 3 , R 8 , R 9 , R 10 and R 11 each independently represent hydrogen, halogen, C1-C12 alkyl, C3-C12 cycloalkyl, or C6-C12 aromatic hydrocarbyl;
R 4 is a group derived from a basic dye and connected to the monomeric unit (A) via a nitrogen atom, the basic dye is selected from the group consisting of Basic Red 9, Basic Red 29, Basic Blue 11, Basic Blue 17, Basic Blue 26, Basic Red 2 and Basic Violet 2;
R 5 , R 6 and R 7 each independently represent hydrogen, halogen, carboxyl, C1-C12 alkyl, or carboxyalkyl, and the carboxyl group contained in R 5 , R 6 or R 7 , if any, optionally forms a carboxylic anhydride structure with the carboxyl group present in the structural formula of the monomeric monomer (B); and
the sum of the monomeric units (A), (B) and (C) is in the range of 80-100 mol %, based on the total monomeric units of the polymeric dye compound, and
wherein the polymeric dye compound has a weight-average molecular weight (Mw) in the range of 7,000-9,000 and an acid value of 80-120 mg/g.

2. The polymeric dye compound according to claim 1 , characterized in that the molar ratio of the monomeric units (A):(B):(C) is 1:1-10:1-10.

3. The polymeric dye compound according to claim 1 , characterized in that the polymeric dye compound satisfies one or more selected from the group consisting of the following:
R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 each independently represent hydrogen, chlorine, methyl, ethyl, propyl or cyclohexyl;
R 4 is a group derived from Basic Red 9; and
the molar ratio of the monomeric units (A):(B):(C) is 1:1-7:1-5.

4. A method of preparing a polymeric dye compound useful for forming a colored layer of a color filter comprising monomeric units (A), (B) and (C) represented by the following structural formulae:

wherein:
R 1 , R 2 , R 3 , R 8 , R 9 , R 10 and R 11 each independently represent hydrogen, halogen, C1-C12 alkyl, C3-C12 cycloalkyl, or C6-C12 aromatic hydrocarbyl;
R 4 is a group derived from a basic dye and connected to the monomeric unit (A) via a nitrogen atom, the basic dye is selected from the group consisting of Basic Red 9, Basic Red 29, Basic Blue 11, Basic Blue 17, Basic Blue 26, Basic Red 2 and Basic Violet 2;
R 5 , R 6 and R 7 each independently represent a hydrogen, halogen, carboxyl, C1-C12 alkyl, or carboxyalkyl, and the carboxyl group contained in R 5 , R 6 or R 7 , if any, optionally forms a carboxylic anhydride structure with the carboxyl group present in the structural formula of the monomeric monomer (B); and
the sum of the monomeric units (A), (B) and (C) is in the range of 80-100 mol %, based on the total monomeric units of the polymeric dye compound, and
wherein the polymeric dye compound has a weight-average molecular weight (Mw) in the range of 7,000-9,000 and an acid value of 80-120 mg/g;
characterized in that the method comprises the following steps:
1) dissolving and reacting an acyl chloride group-containing ethylenically unsaturated monomer and the basic dye in a non-reactive organic solvent to produce an amide compound; and
2) mixing the amide compound obtained in step 1), an ethylenically unsaturated monomer having a carboxyl group or a carboxylic anhydride structure, an ethylenically unsaturated monomer having an aromatic functional group and a solvent under stirring, followed by the addition of a radical polymerization initiator to initiate a polymerization reaction, thereby producing the polymeric dye compound.

5. The method according to claim 4 , characterized in that step 1) satisfies one or more selected from the group consisting of the following:
reacting the acyl chloride group-containing ethylenically unsaturated monomer and the basic dye at a molar ratio in the range of 3:1-1:3;
the acyl chloride group-containing ethylenically unsaturated monomer is selected from acryloyl chloride, methacryloyl chloride, or derivatives thereof;
the non-reactive organic solvent is triethylamine;
the reaction is performed at a temperature in the range of 5-20° C.;
the reaction is performed for 2-5 hours; and
filtration and rotary evaporation are performed after completion of the reaction.

6. The method according to claim 4 , characterized in that the polymerization reaction of step 2) satisfies one or more selected from the group consisting of the following:
the molar ratio of the amide compound: the ethylenically unsaturated monomer having a carboxyl group or a carboxylic anhydride structure: the ethylenically unsaturated monomer having an aromatic functional group is in the range of 1:1-10:1-10;
the ratio of the volume of the solvent to the total weight of the amide compound, the ethylenically unsaturated monomer having a carboxyl group or a carboxylic anhydride structure and the ethylenically unsaturated monomer having an aromatic functional group ranges from 10:1 to 1:10 ml/g;
the weight ratio of the radical polymerization initiator to the total of the amide compound, the ethylenically unsaturated monomer having a carboxyl group or a carboxylic anhydride structure and the ethylenically unsaturated monomer having an aromatic functional group ranges from 0.1% to 5%;
the radical polymerization initiator is added as a solution in the solvent;
the polymerization reaction is performed at a temperature in the range of 50-120° C.;
the polymerization reaction is performed for 5-10 hours;
washing and filtration are performed after completion of the polymerization reaction;
the ethylenically unsaturated monomer having a carboxyl group or a carboxylic anhydride structure is an ethylenic monocarboxylic acid, an ethylenic dicarboxylic acid or anhydride thereof, or an ethylenic polycarboxylic acid or anhydride thereof;
the ethylenically unsaturated monomer having an aromatic functional group is styrene, α-methyl styrene, o-vinyl toluene, p-vinyl toluene or m-vinyl toluene;
the solvent is one selected from ethylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate and ethyl 3-ethoxypropionate, or a mixture of at least two thereof; and
the radical polymerization initiator is 2,2′-azobisisobutyronitrile or dibenzoyl peroxide.

7. The method according to claim 4 , characterized in that the polymerization reaction of step 2) satisfies one or more selected from the group consisting of the following:
the molar ratio of the amide compound: the ethylenically unsaturated monomer having a carboxyl group or a carboxylic anhydride structure: the ethylenically unsaturated monomer having an aromatic functional group is in the range of 1:1-7:1-5;
the ethylenically unsaturated monomer having a carboxyl group or a carboxylic anhydride structure is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid or anhydride thereof, fumaric acid or anhydride thereof, itaconic acid or anhydride thereof, and citraconic acid or anhydride thereof;
the solvent is ethyl 3-ethoxypropionate;
the initiator is added in 2-5 batches; and
after completion of the polymerization reaction, the method further comprises washing with toluene, followed by filtration.

8. A photosensitive resin composition, characterized in that the compositio

Assignees

• Boe Technology Group Co Ltd

Inventors

• Xin Yangyang
• Liu Chen
• Lun Jianchao

Classifications

• G03F7/0007

  Filters, e.g. additive colour filters; Components for display devices · CPC title

• G03F7/033

  the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers · CPC title

• G02B1/04

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

• G03F7/105

  having substances, e.g. indicators, for forming visible images · CPC title

• G03F7/027

  Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence) · CPC title