KR19990007801A - Modified poly (maleic anhydride-co-styrene) and related polymers usable as substrates for color filters - Google Patents

Abstract

A method of manufacturing a color element for use in color filter arrangements and the like and a material for use in such a method are disclosed. The material can be a modified poly (maleic anhydride-co-styrene) and related polymers. The polymer may be used as a vehicle in a transparent or partially transparent form, such as a protective or barrier and leaching / antifouling coating. The polymer may also be combined with the dye to make each color element. The material can be used in combination with conventional photolithography.

Description

Modified poly (maleic anhydride-co-styrene) and related polymers usable as substrates for color filters

The manufacture of color flat panel displays and color video detectors uses an array of colored pixels, typically red, green and blue, for the flat panel display using colored polymer coatings (hereinafter color filters) and cyan, magenta for color video detectors. It depends on what constitutes an array of colors and yellow. In flat panel displays, color filters are arranged on a transparent substrate in a pattern that allows selective passage of light from a light source located behind the color filter array. The color video detector uses a filter array to pass ambient light of a predetermined wavelength into an addressed array of semiconductor light-cells located behind the color filter array.

The manufacture of color filter plates and color video detectors relies on the use of photolithography to define the arrangement of colored pixels. Two conventional conventional methods used to pattern pixels are wet etching (solvent etching) and dry etching (plasma or reactive ion etching). In both methods, the color filter is uniformly applied to the substrate to form a film typically having a color filter of 1 to 2 μm.

Application of the color filter is usually carried out by known methods such as spin coating, which places the color filter solution in the center of the spinning substrate and spreads evenly on the surface by centrifugal force.

Wet etching methods typically include 1) color filter application, 2) light baking to partially insoluble the coating, 3) application of photoresist, 4) exposure of photoresist, 5) exposed photoresist and underlying color. It is a multi-step process consisting of solvent removal of the filter, 6) solvent removal of the residual photoresist, and 7) final curing of the color filter. Subsequent color filters are first applied onto the treated color filters and repeated for each additional color filter used to be patterned by selective removal as described above.

Dry etching typically uses 1) application of color filters, 2) hard baking to cure the polymer, 3) application of photoresist, 4) solvent removal of exposed photoresist, 5) residual photoresist and reactive plasma. Thereby removing the area of the color filter which is not coated with the photoresist.

To produce a multicolor array, an additional color filter must first be coated on top of the treated color filter. When the color filter solution is coated onto the first treated color filter, a phenomenon called leaching may occur, in which the dye of the first treated color filter leaves the polymer matrix and diffuses into the solvent of the next layer to be applied. In addition, another phenomenon may occur, such as staining, in which the dye of the color filter solution to be applied is diffused into an already treated color filter. Both phenomena cause a mixture of dyes that can reduce the chromaticity of the color filter.

Applicants are described in US Pat. No. 4,822,718 and US Pat. Latham and D. Hawley, Color Filters From Dyed Polyimides, Solid State Technology, May 1988, the disclosures of which are incorporated herein by reference.

The effects of leaching and contamination have been reduced by using polyimide precursors (polyamic acid) as color filter matrix materials (as described, for example, in US Pat. No. 4,876,165 and US Pat. No. 4,822,718). The use of colored polyimides as color filters is also described in W. Latham and D. Hawley, Color Filters From Dyed Polyimides, Solid State Technology, May 1988}. According to Latham and Hawley, the colored polyimide cured at 230 ° C. for 1 hour provides substantial resistance to leaching and contamination for film thicknesses of 1 to 2 μm. However, the leaching and contamination resistance of the colored polyimide depends on the dye loading, ie the ratio of dye to polymer, the specific dye, curing time / temperature and the structure of the polyimide.

Care must be taken to uniformly produce the polyimide used in the color filter. As is known, the main factors affecting the preparation of the polyimide include monomer purity, order of monomer addition, rate of monomer addition, reaction temperature, stirring rate and time and ambient humidity. As is known, color filter formulations using polyimides require careful formulation / evaluation methods to produce products that meet established specifications.

Polyimides used in color filters also lose some of their optical clarity when heated at a sufficiently high temperature to adequately cure. This loss of optical clarity is evident in the yellow coloration of the cured film, which is believed to be due to the creation of charge transport complexes.

Polyimide based color filters also have a limited shelf life. Polyimide precursors (polyamic acid) undergo continuous linking / separation of amide bonds causing changes in molecular weight over time. Such molecular weight changes can cause changes in film thickness when coated at a given spin rate and may require process adjustments as is known.

Disclosure of the Invention

It is therefore an object of the present invention to provide a composition capable of forming a transparent polymer film which may not be contaminated from subsequent application of the dyed coating.

A further object of the present invention is to provide a composition containing an organic dye capable of withstanding leaching of the dye when the coating is brought into contact with the solvent in subsequent processing steps.

It is a further object of the present invention to provide a composition with a longer shelf life than the prior art which allows for the preparation of a final product which maintains processability within specified specifications for longer periods of time.

It is an object of the present invention to provide a coating that does not leach.

Another object of the present invention is to provide a composition that is not contaminated.

Yet another object of the present invention is to provide a photosensitive coating for use in information display devices and sensors.

It is an object of the present invention to provide an optically transparent barrier coating.

It is a further object of the present invention to provide a color filter substrate for embossed and negative photolithography with good electrical properties, including resistivity and dielectric strength.

It is an object of the present invention to provide a brightener / color contrast transmitting film with higher clarity in all colors as compared to the prior art. For example, the transmissive film produces a lighter blue than the blue of the prior art.

Another object of the present invention is to provide a composition that can be prepared to have consistent properties.

Yet another object of the present invention is to provide a composition with a longer shelf life than conventional materials.

It is an object of the present invention to provide a one component system.

It is an object of the present invention to provide compounds that can be securely fixed to glass or other substrates.

These and other aims are to combine polymer coatings with good solvent resistance, transparency and thermal stability by combining modified copolymers containing pendant anhydride groups and materials comprising two or more reactive functional groups capable of reacting with carboxylic acids into a single compound. It can be satisfied by the present invention to provide. According to the invention, a coating consisting of a copolymer containing pendant anhydride groups, grafted with a reactive crosslinking component and kneaded with a polyfunctional crosslinking component (preferably blocked polyisocyanate) capable of reacting with a carboxylic acid, has good transparency It has been found to exhibit thermal stability, solvent resistance, leaching resistance and fouling resistance.

The invention will be more fully understood by those skilled in the art through the accompanying drawings and the description of the preferred embodiments.

The present invention is typically used in information display devices and sensors with a coating containing an organic pigment that selectively passes (or blocks) the frequency band of the ultraviolet (UV), visible or infrared (IR) portion of the electromagnetic spectrum. To a polymeric material and optionally to a transparent barrier coating that provides leaching / fouling resistance.

1 is a graph demonstrating leaching resistance of a color filter element embodying the present invention.

2 is a graph demonstrating leach resistance of different color sets embodying the present invention.

3 is a process diagram showing the manufacture of a test color wheel embodying the present invention.

4 is a graph showing contamination of prior art coatings.

5 is a graph showing the protective effect of a transparent coating, which embodies the present invention.

6 is a process diagram showing the manufacture and use of a transparent coating according to the invention.

7 is a graph showing the protective effect of using a transparent photosensitive coating according to one embodiment of the present invention.

8 is a graph showing fouling resistance and leaching resistance of a coating protected by a transparent coating according to the invention.

9 is a graph showing leach resistance provided by a transparent photosensitive coating according to one embodiment of the invention.

FIG. 10 is a graph similar to FIG. 9 using a thinner protective coating.

11 is a process diagram showing a conventional color system according to the prior art.

12 is a process chart showing manufacture of a color system according to the invention.

Best way to carry out the invention

According to the present invention, a transparent polymer coating having leaching resistance and fouling resistance is a poly (maleic anhydride-co-styrene), for example Atochem Inc. under the trade name SMA® resin. Poly (maleic anhydride-co-styrene) and Aldrich and monomer-polymer Dazak Labs sold by Monsanto Company under the trade name Scripset® resin Commercially available poly (maleic anhydride-co-styrene), poly (maleic anhydride-co-methylvinyl ether), for example, ISP Technologies, is a Gantrez (R) AN copolymer. Poly (maleic anhydride-co-methylvinyl ether), or poly (maleic anhydride-co-ethylene) sold under the trade name, for example, Jiran Chemicals Inc. Certain copolymers containing pendant anhydride groups, preferably poly (maleic anhydride-co-styrene), such as poly (maleic anhydride-coethylene) commercially available from Zeeland Chemicals Inc., can react with anhydrides It can be prepared by reacting with one functional group and a multifunctional component having at least one functional group to enable thermal, optical or chemically induced polymerization. The multifunctional component (hereinafter reactive graft component) is preferably allylamine, diallylamine, 3-amino-1-propanol vinyl ether, allyl alcohol, 4-hydroxybutyl vinyl ether, glycerol dimethacrylate, 2-hydrate Hydroxyethyl methacrylate or 2-hydroxyethyl acrylate. The stoichiometry of the reactive graft component relative to the pendant anhydride may be in the range of 0.5 to 1.0, preferably 1.0. The reaction of the reactive graft component with the pendant anhydride is carried out by cleavage of the anhydride, and carboxylic acid (C═O stretch, 1706-1760 cm ⁻¹ ) and carboxylic acid when the functional group of the reactive graft component reacting with the anhydride is a hydroxyl group. If the functional group of the ester (C═O stretch, 1715-1770 cm ⁻¹ ), or reactive graft component, which reacts with anhydride is an amino group, will result in the subsequent production of amide (C═O stretch, 1630 − 1700 cm ⁻¹ ) Let's do it. Such infrared C = O stretching frequencies are described above as described in Silverstein, Rober M., Bassler, G. Clayton, Morrill, Terence C., Spectrometric Identification Of Oragnic Compounds, 4th edition, Wiley, NY. Intrinsic absorption frequency for one chemical functional group. The above infrared absorption frequency can be used as an indication of the reaction when grafting the reactive graft component onto an anhydride containing copolymer. The carboxylic acid resulting from the reaction of a hydroxy-containing or amino-containing compound with the anhydride functionality of the copolymer allows the grafted copolymer to be readily dissolved in dilute base aqueous solution. The increased rate of dissolution in dilute base aqueous solution relative to the dissolution rate of the grafted copolymer provides a quantitative indication of successful graft. A more quantitative measure of the degree of grafting is obtained by determining the acid value by titration with a base.

The grafted copolymer is then kneaded with a crosslinking component that can react with the pendant carboxylic acid groups or unreacted anhydride groups of the grafted copolymer. Crosslinking components are described, for example, by Sektec Industries Inc. It may be a melamine based curing agent or a polyfunctional isocyanate sold by Cytec Industries Inc. under the trade name Cymel®. The crosslinking component is preferably blocked diisocyanate or more preferably blocked polyisocyanate. This type of blocked polyisocyanate is Miles Inc. Is commercially available under the trade name Desmodur from Miles Inc. and Luxate from Olin Chemicals. Since blocked isocyanates do not react until heated to a predetermined temperature, this allows the preparation of some formulations with extended shelf life. Heating the blocked isocyanate to its deprotection temperature gives rise to free isocyanates that can react with the isocyanate typically.

The isocyanate groups blocked during the thermosetting process begin to deprotect at temperatures ranging from 60 ° C. to 200 ° C. depending on the type of blocking agent used to form free isocyanate groups. Free isocyanates generated in this way are described in K.J. Saunders, Organic Polymer Chemistry, Chapman and Hall, New York, 1973}, react with the carboxylic acid groups of the grafted copolymer to form amides. In addition to reacting with other isocyanate groups, there is also the possibility of secondary reactions of isocyanates with other functional groups, including unstable protons such as amides. The reaction of deprotected isocyanates as described above leads to prolonged crosslinking of the polymer matrix. If the reactive graft component is an unsaturated alkyl group, it is believed that the unsaturated bonds of the pendant reactive graft component at temperatures above 200 ° C. react to provide further crosslinking. The reactive graft component may also include photo-crosslinkable functional groups such as acrylate radicals.

The structure of the starting maleic anhydride copolymer is typically as described below.

Wherein R is H, -OCH ₃ , to be.

The structure of the grafted maleic anhydride copolymer is typically as described below.

Wherein X may be a straight or branched chain unsaturated alcohol or amine having 2 to 20 carbon atoms. Mixtures of straight or branched chain unsaturated alcohols and / or amines may also be used. m may be 0.2 to 1 and n may be 0.8 to 0.

The right (B) part is a maleic anhydride copolymer as described above and the left (A) part is a grafted component as described above which may comprise an amine or alcohol component. Substituents added to the reactive sites of the anhydride may include groups of greater complexity and functionality, such as those described below.

Wherein X is an oxygen or nitrogen atom. R ₁ is a straight or branched chain divalent alkylene having about 1 to 6 carbon atoms or an oxyalkylated derivative thereof. R ₂ is a vinyl, acrylate or methacrylate radical. m may be 0.2 to 1 and n may be 0.8 to 0.

Applicants' grafted copolymer / blocked polyisocyanate blends can be applied directly to provide a barrier coating with a constant coating thickness that is optically clear, heat stable, chemically resistant and leach / fouling resistant. Applicants' grafted copolymer / blocked polyisocyanate blends can also be combined with pigments to provide a uniform colored film coating that is leach / fouling resistant for use as color filters for information displays and detectors.

Depending on the method and application, the thickness of the polymer coatings (with or without pigments) of the applicants can be several micrometers to several hundred millimeters. Conventional spin coating produces films having a thickness of typically 0.1 μm to 10 μm, depending on the molecular weight of the grafted copolymer and the rate at which the coating is spin coated. Typical speeds for spin coating of the polymer coating (with or without pigment) of the applicant are from 500 rpm to 6000 rpm depending on the type and size of the substrate being coated and the coating components as well as the molecular weight of the copolymer and crosslinker used. It can vary. Larger thickness films can be obtained by using polymers with higher molecular weight levels and / or higher molecular weights, as well as using other coating methods. Typical curing cycles for our polymer coatings range from 200 ° C. to 280 ° C. for a time between 10 minutes and 60 minutes.

Some specific applications of the Applicants' polymer coatings include binders for dyes or pigments to form color filter arrays for use in imaging systems such as charge-coupling devices for liquid crystal displays, electroluminescent displays, plasma displays and color video detectors. It includes. Applicants' polymer coatings may also be applied as a barrier coating applied over a coating lacking sufficient leach / fouling resistance to prevent contamination and leaching of the coating. Applicants' polymer coatings may also be used as intermediate dielectric layers in the manufacture of multilayer microcircuits. Applicants' polymer coatings may also be used in the fabrication of optical waveguides.

Example 1

The reaction vessel equipped with the stirrer, the nitrogen suction tube and the calcium chloride drying tube is filled with 800 parts of N-methyl-2-pyrrolidinone and 49.8 parts of allylamine. After washing the reactor with nitrogen for several minutes, 250.56 parts of a styrene-maleic anhydride copolymer having a number average molecular weight of about 350,000 (Aldrich 18,293-1) and an acid value of 473 are added in one charge with stirring. An additional 100 parts of N-methyl-2-pyrrolidinone is used to wash the inner wall of the reactor. Stirring is continued for about 48 hours. The infrared spectrum of the polymer shows a new absorption corresponding to the decrease in intensity of anhydride absorption at 1858 cm ^-1 and 1780 cm ^-1 and the C = O stretching vibrations of carboxylic acid and secondary amide at 1732 cm ^-1 and 1646 cm ^-1 , respectively. Show the band. The acid value of the product was 157.

Example 2

A reaction vessel equipped with a stirrer, a nitrogen suction tube, and a calcium chloride drying tube was prepared with 202.23 parts of styrene-maleic anhydride copolymer having a number average molecular weight of about 350,000 (Aldrich 18,293-1) and an acid value of 473 and N-methyl-2-pyrroli Fill with 500 copies of Dinon. After flushing the reactor with nitrogen for a few minutes, the reactor is heated to a temperature of 25 ° C. to 75 ° C. using an electrothermal mantle piece with stirring. Eventually, when the solid is dissolved, the solution is cooled to about 35 ° C. To the stirring solution is added dropwise a solution consisting of 48.50 parts of allylamine in 152.78 parts of N-methyl-2-pyrrolidone. Stirring is continued at room temperature for about 48 hours. The acid value of the product was 159.

Example 3

The reaction vessel equipped with the stirrer, the nitrogen suction tube and the calcium chloride drying tube is filled with 100 parts of N-methyl-2-pyrrolidinone. After washing the reactor with nitrogen for a few minutes, 46.71 parts of styrene-maleic anhydride copolymer (Monomer-Polymer Dajac Labs. Catalog # 9182) having a number average molecular weight of about 1600 to 2600 and an acid value of 475 are added. An additional 20 parts of N-methyl-2-pyrrolidinone is used to wash the inner wall of the reactor. To the stirring solution is added dropwise a solution consisting of 13.19 parts of allylamine in 20 parts of N-methyl-2-pyrrolidinone. Stirring is continued at room temperature for about 24 hours. The acid value of the product was 144.

Example 4

The reaction vessel equipped with the stirrer, the nitrogen suction tube and the calcium chloride drying tube is filled with 50 parts of N-methyl-2-pyrrolidinone, 50 parts of diethylene glycol dimethyl ether and 5.87 parts of allylamine. After flushing the reactor with nitrogen for a few minutes, 30 parts of styrene-maleic anhydride copolymer having a number average molecular weight of about 350,000 (Aldrich 18,293-1) and an acid value of 473 are added to the stirring solution. The inner wall of the reactor is washed with a mixture of 21.74 parts of N-methyl-2-pyrrolidinone and 21.74 parts of diethylene glycol dimethyl ether. Stirring is continued for about 48 hours. The acid value of the product was 172.

Example 5

A reaction vessel equipped with a stirrer, a nitrogen suction tube, and a calcium chloride drying tube was used to prepare 40.44 parts of a styrene-maleic anhydride copolymer having a number average molecular weight of about 350,000 (Aldrich 18,293-1) and an acid value of 473 and N-methyl-2-pyrroly Fill with 100 parts of dinon. After washing the reactor with nitrogen for several minutes, a solution consisting of 8.60 parts of allyl alcohol and 23.56 parts of N-methyl-2-pyrrolidinone was added, followed by 15.00 parts of triethylamine and 23.56 parts of N-methyl-2-pyrrolidinone. The solution is added with stirring. The reaction is heated to 50 ° C. to 65 ° C. with an electrothermal mantle. Stirring is continued for about 48 hours. The acid value of the product was 148.

Example 6

30.00 parts 150 parts of allylamine grafted styrene-maleic anhydride copolymer solution as described in Example 1, 51 parts blocked polyisocyanate (Desmodur BL-3175A, Miles Inc.), N-methyl-2-pyrrolidinone Polymer blend of 10 parts and 25 parts of cyclohexanone

26.55 parts N-methyl pyrrolidinone

10.86 parts cyclohexanone

7.22 Part Solvent Blue 45

2.40 PART SOLVENT BLUE 67

A blue coating was prepared by stirring the mixture for about 12 hours using a coating formulation consisting of 10 parts Dowex® HCR-S-H ion exchange resin (manufactured by Dow Chemical Company). The mixture was then filtered to remove ion exchange resins and undissolved material. The coating can be used as a color filter in a multicolor pixel array for use in a full color flat panel display to selectively pass blue light from the light source behind the flat panel. The coating can also be used as a color filter in multicolor pixel arrays to selectively pass overwhelmingly blue light into a semiconductor photodetector array. This coating may be applied on a substrate by conventional spin or spray techniques and cured at 230 ° C. for 60 minutes or at 250 ° C. for 30 minutes. This coating can be patterned by conventional plasma etching techniques.

Example 7

30.00 parts of the polymer blend described in Example 6

26.55 parts N-methyl pyrrolidinone

10.86 parts cyclohexanone

5.61 Part Solvent Blue 38

4.03 Part Solvent Yellow 82

A green coating was prepared as described in Example 6 using a coating formulation consisting of 10 parts Dowex® HCR-S-H ion exchange resin (manufactured by Dow Chemical Company).

Example 8

30.00 parts of the polymer blend described in Example 6

26.55 parts N-methyl pyrrolidinone

10.86 parts cyclohexanone

4.50 Part Solvent Yellow 82

5.13 Part Solvent Red

A red coating was prepared as described in Example 6 using a coating formulation consisting of 10 parts Dowex® HCR-S-H ion exchange resin (manufactured by Dow Chemical Company).

Example 9

30.00 parts 150 parts of allylamine grafted styrene-maleic anhydride copolymer as described in Example 1, 75 parts blocked polyisocyanate (Desmour BL-4165, Miles Inc.), N-methyl-2-pyrrolidinone 10 Polymer blend consisting of 25 parts and 25 parts of cyclohexanone

28.42 parts N-methyl pyrrolidinone

11.30 parts cyclohexanone

7..47 Part Solvent Blue 45

2.49 Part Solvent Blue 67

A blue coating was prepared as described in Example 6 using a coating formulation consisting of 10 parts Dowex® HCR-S-H ion exchange resin (manufactured by Dow Chemical Company).

Example 10

30.00 parts of the polymer blend described in Example 9

28.42 parts N-methyl pyrrolidinone

11.30 parts cyclohexanone

5.80 parts Solvent Blue 38

4.16 Part Solvent Yellow 82

A green coating was prepared as described in Example 6 using a coating formulation consisting of 10 parts Dowex® HCR-S-H ion exchange resin (manufactured by Dow Chemical Company).

Example 11

30.00 parts of the polymer blend described in Example 9

28.42 parts N-methyl pyrrolidinone

11.30 parts cyclohexanone

4.65 Part Solvent Yellow 82

5.31 Part Solvent Red 119

A red coating was prepared as described in Example 6 using a coating formulation consisting of 10 parts Dowex® HCR-S-H ion exchange resin (manufactured by Dow Chemical Company).

Example 12

20.00 parts 100 parts of allylamine grafted styrene-maleic anhydride copolymer as described in Example 1, 18.5 parts of blocked polyisocyanate (Desmour BL-3175A, Miles Inc.), N-methyl-2-pyrrolidinone 28.68 Polymer blend consisting of 5 parts and 51.84 parts of cyclohexanone

22.06 parts N-methylpyrrolidinone

11.03 part cyclohexanone

3.36 Part Solvent Blue 38

A cyan coating was prepared as described in Example 6 using a coating formulation consisting of 10 parts Dowex® HCR-S-H ion exchange resin (manufactured by Dow Chemical Company).

Example 13

20.00 parts polymer blend as described in Example 12

17.78 parts N-methyl pyrrolidinone

8.89 parts cyclohexanone

2.40 Part Solvent Red

Magenta coatings were prepared as described in Example 6 using a coating formulation consisting of 10 parts Dowex® HCR-S-H ion exchange resin (manufactured by Dow Chemical Company).

Example 14

20.00 parts polymer blend as described in Example 12

24.89 parts N-methyl pyrrolidinone

12.44 parts cyclohexanone

4.00 Part Solvent Yellow 82

A yellow coating was prepared as described in Example 6 using a coating formulation consisting of 10 parts Dowex® HCR-S-H ion exchange resin (manufactured by Dow Chemical Company).

Example 15

5.00 parts 20.00 parts of allyl alcohol grafted styrene-maleic anhydride copolymer solution as described in Example 5, 5.41 parts of blocked polyisocyanate (Desmodur BL-3175A, Miles Inc.), 15.36 parts of N-methyl pyrrolidinone and Polymer blend of 10.00 parts of diethylene glycol dimethyl ether

1.00 parts N-methyl pyrrolidinone

1.38 Butadiethylene Glycol Dimethyl Ether

4.92 parts Dowex® HCR-SH ion exchange resin (Dow Chemical Company) 56.25 parts of Solvent Blue 45, stirred for 12 to 24 hours on 64 parts, then filtered to remove ion exchange resin and undissolved material A blue coating was prepared as described in Example 6 using a coating formulation consisting of 18.75 parts of Solvent Blue 67, 112.5 parts of N-methyl pyrrolidinone and 112.5 parts of diethylene glycol dimethyl ether.

Example 16

5.00 Polymer Blend as described in Example 15

1.00 parts N-methyl pyrrolidinone

1.38 Butadiethylene Glycol Dimethyl Ether

4.92 parts Dowex® HCR-SH ion exchange resin (manufactured by Dow Chemical Company) after stirring for 12 to 24 hours on 64 parts, filtered off to remove undissolved material, Solvent Blue 38 43.65 parts, Solvent Yellow 82 A green coating was prepared as described in Example 6 using a coating formulation consisting of a dye mixture consisting of 31.35 parts, 112.5 parts N-methyl pyrrolidinone and 112.5 parts diethylene glycol dimethyl ether.

Example 17

5.00 Polymer Blend as described in Example 15

1.00 parts N-methyl pyrrolidinone

1.38 Butadiethylene Glycol Dimethyl Ether

4.92 parts Dowex (R) HCR-SH ion exchange resin (manufactured by Dow Chemical Company) on 64 parts of solvent yellow 12 35 hours, and then filtered to remove ion exchange resin and undissolved material 82 35.03 parts A red coating was prepared as described in Example 6 using a coating formulation consisting of 39.97 parts of solvent red 119, 130 parts N-methyl pyrrolidinone and 130 parts diethylene glycol dimethyl ether.

Example 18

5.50 Grafted Copolymers as Described in Example 1

1.93 parts blocked polyisocyanate

(Desmodur BL-3175A, Miles Inc.)

1.19 Part Solvent Blue 67

1.64 parts Solvent Brown 44

11.31 parts cyclohexanone

4.13 parts N-methyl-2-pyrrolidinone

A black coating was prepared as described in Example 6 using a coating formulation consisting of 10 parts HCR-S-H ion exchange resin.

Example 19

6.37 Grafted Copolymers as described in Example 1

2.17 parts blocked polyisocyanate

(Desmodur BL-3175A, Miles Inc.)

3.56 parts cyclohexanone

A transparent coating was prepared by stirring the mixture for about 1 hour using a coating formulation consisting of 3.42 parts N-methyl-2-pyrrolidinone. The mixture was then filtered through a 0.2 μm filter. The coating is used as a transparent barrier layer on the color filter to prevent leaching of the dye from the color filter during subsequent processing steps and to prevent contamination of the color filter. It will be appreciated that various dyes can be added to produce a coating that is transparent at selected wavelengths and cloudy at other wavelengths. For example, the coating may be transparent in the spectrum used to determine alignment, but may be cloudy or colored at other wavelengths.

Example 20

The blue color filter formulation described in Example 6 was spin coated onto a glass substrate with a diameter of 7.62 cm (3 in) at 1000 rpm for 90 seconds and baked on a hot plate at 100 ° C. for 30 to 60 seconds and at 170 ° C. for 30 minutes. Bake preliminarily in reflux oven and hard (cure) in reflux oven at 250 ° C. for 30 minutes. The film thickness was 1.45 μm. The transmission spectrum of the cured color filter film is shown by line (a) in FIG. 1. The coated glass substrate was then dipped in N-methyl-2-pyrrolidinone for 30 seconds and then dried under a stream of dry nitrogen. The transmission spectra were recorded again, shown in line (b) in FIG. 1. The coated glass substrate was immersed in N-methyl-2-pyrrolidinone for a second time for 30 seconds and then dried under a stream of dry nitrogen. The transmission spectra were recorded again and shown as line (c) in FIG. 1.

Example 21

The green color filter formulation described in Example 7 was spin coated onto a glass substrate with a diameter of 7.62 cm (3 in) at 1000 rpm for 90 seconds and baked on a hot plate at 100 ° C. for 30 to 60 seconds and at 170 ° C. for 30 minutes. Bake preliminarily in reflux oven and hard (cure) in reflux oven at 250 ° C. for 30 minutes. The film thickness was 1.24 μm. The transmission spectrum of the cured color filter film is shown by line (d) in FIG. 1. The coated glass substrate was then dipped in N-methyl-2-pyrrolidinone for 30 seconds and then dried under a stream of dry nitrogen. The transmission spectra were recorded again, shown in line (e) in FIG. 1. The coated glass substrate was immersed in N-methyl-2-pyrrolidinone for a second time for 30 seconds and then dried under a stream of dry nitrogen. The transmission spectra were recorded again and shown as line (f) in FIG. 1.

Example 22

The red color filter formulation described in Example 8 was spin coated onto a glass substrate with a diameter of 7.62 cm (3 in) at 1000 rpm for 90 seconds and baked on a hot plate at 100 ° C. for 30 to 60 seconds and at 170 ° C. for 30 minutes. Bake preliminarily in reflux oven and hard (cure) in reflux oven at 250 ° C. for 30 minutes. The film thickness was 1.36 μm. The transmission spectrum of the cured color filter film is shown by line (g) in FIG. 1. The coated glass substrate was then immersed in N-methyl-2-pyrrolidinone for 30 seconds and then dried under a dry nitrogen stream. The transmission spectra were recorded again, shown in line (h) in FIG. 1. The coated glass substrate was immersed in N-methyl-2-pyrrolidinone for a second time for 30 seconds and then dried under a stream of dry nitrogen. The transmission spectra were recorded again and shown as line (i) in FIG. 1.

Example 23

The blue-green color filter formulation described in Example 12 was spin coated onto a glass substrate with a diameter of 7.62 cm (3 in) at 2000 rpm for 90 seconds, baked on a hot plate at 100 ° C. for 30 to 60 seconds and at 250 ° C. for 30 minutes. Bake tightly in a reflux oven (cure). The film thickness was 0.579 μm. The transmission spectrum of the cured color filter film is shown by line (a) in FIG. 2. The coated glass substrate was then immersed in N-methyl-2-pyrrolidinone for 30 seconds and then dried under a dry nitrogen stream. The transmission spectra were recorded again, shown in line (b) in FIG. 2. The coated glass substrate was immersed in N-methyl-2-pyrrolidinone for a second time for 30 seconds and then dried under a stream of dry nitrogen. The transmission spectra were recorded again and shown as line (c) in FIG. 2.

Example 24

The yellow color filter formulation described in Example 14 was spin coated onto a glass substrate with a diameter of 7.62 cm (3 in) at 2000 rpm for 90 seconds and baked on a hot plate at 100 ° C. for 30 to 60 seconds and at 250 ° C. for 30 minutes. Bake tightly in a reflux oven (cure). The film thickness was 0.585 μm. The transmission spectrum of the cured color filter film is shown by line (d) in FIG. 2. The coated glass substrate was then immersed in N-methyl-2-pyrrolidinone for 30 seconds and then dried under a dry nitrogen stream. The transmission spectra were recorded again, as shown in line (e) in FIG. 2. The coated glass substrate was immersed in N-methyl-2-pyrrolidinone for a second time for 30 seconds and then dried under a stream of dry nitrogen. The transmission spectra were recorded again and shown as line (f) in FIG. 2.

Example 25

The magenta color filter formulation described in Example 13 was spin coated onto a glass substrate with a diameter of 7.62 cm (3 in) at 2000 rpm for 90 seconds, baked on a hot plate at 100 ° C. for 30 to 60 seconds and 250 ° C. for 30 minutes. Bake hard at reflux oven (cured). The film thickness was 0.708 μm. The transmission spectrum of the cured color filter film is shown by line (g) in FIG. 2. The coated glass substrate was then immersed in N-methyl-2-pyrrolidinone for 30 seconds and then dried under a dry nitrogen stream. The transmission spectra were recorded again, shown in line (h) in FIG. 2. The coated glass substrate was immersed in N-methyl-2-pyrrolidinone for a second time for 30 seconds and then dried under a stream of dry nitrogen. The transmission spectrum was recorded again and shown in line (i) in FIG. 2.

Example 26

6.37 Grafted Copolymers as described in Example 1

2.17 parts blocked polyisocyanate

(Desmodur BL-3175A, Miles Inc.)

3.56 parts cyclohexanone

The transparent coating was prepared by stirring the mixture for about 1 hour using a coating formulation consisting of 3.42 parts N-methyl-2-pyrrolidinone. The mixture was then filtered through a 0.2 μm filter. The coating can be used as a transparent barrier layer on the color filter to prevent leaching of the dye from the color filter and to prevent contamination of the color filter in subsequent processing steps.

Example 27

The fouling resistance evaluation of the formulation of Example 25 was carried out by making a three-color color wheel on a glass substrate with a diameter of 7.62 cm (3 in) as illustrated in FIG. 3 showing the processing steps used to produce the color filter plate. did. The manufacturing steps of the color wheel are as follows:

1) Spin coat the transparent barrier coating of Example 25 at 1220 rpm for 90 seconds, bake in a hot plate at 100 ° C. for 30 to 60 seconds, and bake in a reflux oven at 250 ° C. for 60 minutes. The film thickness was 1.1 μm. After this step the clear coating spectrum is shown by line (a) in FIG. 4.

2) Spin coat a red color filter (Brewer Science, Inc. PiC® Red 101) at 1200 rpm for 90 seconds and bake in a hot plate at 100 ° C. for 30 to 60 seconds and in a reflux oven at 164 ° C. for 30 minutes. Bake.

3) Spin coat the embossed photoresist (Shipley Microposit® 1400-27) at 5000 rpm for 30 seconds and bake on a hot plate at 100 ° C. for 30 seconds.

4) The sample was then exposed to actinic light (150 mJ / cm ² ) from the contact printer through a wedge shaped mask placed on the coated substrate.

5) The sample was soaked in 0.27 N tetramethylammonium hydroxide (TMAH) for 20 seconds and then washed with deionized water to remove the exposed resist and the underlying red 101 and left a semi-circle pattern of red 101. Unexposed resist remaining on top of Red 101 was removed with SafeStrip® (Brewer Science, Inc.). The remaining Red 101 was then hard baked (cured) in a reflux oven at 280 ° C. for 10 minutes. Red 101 film thickness was about 1.25 μm by proof of analysis. The spectra of Red 101 and the clear coating after this step are shown as lines (b) and (c) in FIG. 4, respectively.

6) Spin coat green color filter (Brewer Science, Inc. PiC® Green 02) at 1200 rpm for 90 seconds and bake on hot plate at 100 ° C. for 30 to 60 seconds, reflux oven at 170 ° C. for 30 minutes Bake in. Embossed photoresist (Shipley Microposit® 1400-27) is spin coated at 5000 rpm for 30 seconds and baked on a 100 ° C. hot plate for 30 seconds. The sample was then exposed to actinic light (150 mJ / cm ² ) from the contact printing machine through a wedge shaped mask placed on the coated substrate and rotated 90 degrees from its position in step 4.

7) The sample is soaked in 0.27 N tetramethylammonium hydroxide (TMAH) for 20 seconds and then washed with deionized water to remove the exposed resist and the underlying Green 02 and leave a semicircle pattern of Green 02. Unexposed resist remaining on top of Figure 02 is removed with SafeStrip® (Brewer Science, Inc.). The remaining Green 02 is then hardened (cured) in a reflux oven at 230 ° C. for 60 minutes. Green 02 film thickness was about 1.20 μm by proof of analysis. After this step, the spectra of Green 02, Red 101 and the clear coating are shown as lines (d), (e) and (f) in FIG. 4, respectively.

8) Spin coat a blue color filter (Brewer Science, Inc. PiC® EXP93004) at 1000 rpm for 90 seconds and bake on a hot plate at 100 ° C. for 30 to 60 seconds and in a reflux oven at 155 ° C. for 30 minutes. Bake. Embossed photoresist (Shipley Microposit® 1400-27) is spin coated at 5000 rpm for 30 seconds and baked on a 100 ° C. hot plate for 30 seconds. The sample was then exposed to actinic light (150 mJ / cm ² ) from the contact printing machine through a wedge shaped mask placed on the coated substrate and rotated 90 degrees from its position in step 6.

9) The sample was soaked in 0.27 N tetramethylammonium hydroxide (TMAH) for 20 seconds and then washed with deionized water to remove the exposed resist and the underlying EXP93004 and leave a semicircle pattern of EXP93004. Unexposed resist remaining on top of EXP93004 was removed with SafeStrip® (Brewer Science, Inc.). The remaining EXP93004 was then hard baked (cured) in a reflux oven at 230 ° C. for 60 minutes. Green 02 film thickness was about 1.00 μm by proof of analysis. After this step, the spectra of EXP93004, Green 02, Red 101 and the clear coating are shown as lines (g), (h), (i) and (j) in FIG. 4, respectively.

In FIG. 4, a slight decrease in the transmission of the transparent coating represented by lines (a), (c), (f) and (j) is the result of darkening by heat. There is no spectral evidence of contamination from any of the subsequent color filter processing steps. Line (g) of FIG. 4 shows the reduction of transmission of the red color filter due to contamination from the subsequent treatment of the blue color filter.

A second color wheel was prepared as described in steps 1-9 above except that a second application of the clear coating in Example 25 was applied after a red filter treatment as described in step 5. A second application of the clear coating was spin coated at 6000 rpm for 90 seconds and baked on a hot plate at 100 ° C. for 30 to 60 seconds and baked in a reflux oven at 250 ° C. for 60 minutes. The transmission spectra of the clear coating and each color filter were recorded after each hard baking as described in steps 1-9 for the first color wheel. Lines (a) to (j) in FIG. 5 correspond to the same processing steps as lines (a) to (j) in FIG. Line (g) in FIG. 5 indicates no contamination of the red color filter by subsequent application of the blue color filter. A slight decrease in the transmission of the red color filter, indicated by line (g) in FIG. 5, is due to the pyrolysis of the dye.

Example 28

A reaction vessel equipped with a stirrer and a calcium chloride dry tube was prepared with SafeStrip® (Brewer Science, Inc. product added 40.00 parts of a styrene-maleic anhydride copolymer having a number average molecular weight of about 1900 (Atochem SMA3000A) and an acid value of 290. ) Fill it with 50.00 parts. After all solids are dissolved, 12.00 parts of 2-hydroxyethyl acrylate (HEA) (RohmTech AM-414) and 10 drops of triethylamine (Aldrich 23,962-3) are added. Stirring is continued at room temperature for about 24 hours.

Example 29

A 100 ml polyethylene beaker was prepared with 29.82 parts of the grafted polymer prepared in Example 27, 5.00 parts of dipentaerythritol penta- / hexa-acrylate (Aldrich 40,728-3) and SafeStrip® from Brewer Science, Inc. Fill with 8.69 wealth. The mixture is stirred for 1 hour at room temperature and stored for 14 days in an amber polyethylene screw cap bottle.

Example 30

Optically clear intaglio photoresist was prepared using 10.00 parts of the formulation prepared in Example 28, 1.90 parts of blocked polyisocyanate (Desmodur B1-3175A, Miles Inc.), 20.00 parts of SafeStrip®, isopropyl thioxanthone (ITX (First Chemical Corp.) 1.00 parts, octyl-para- (dimethylamino) benzoate (ODAB) (First Chemical Corp.) 0.50 parts and 1,4-diazabicyclo [2.2.2] octane (Aldrich D2,780) -2) Prepare by combining 0.025 parts. The mixture is stirred at room temperature for 1 hour and filtered through 0.2 μm.

Example 31

Evaluation of the formulation of Example 29 was carried out by making a three-color color wheel on a glass substrate with a diameter of 7.62 cm (3 in) as illustrated in FIG. 6 showing the processing steps used to produce the color filter plates. The manufacturing steps of the color wheel are as follows:

1) Spin coat a red color filter (Brewer Science, Inc. PiC® Red 02) at 1000 rpm for 90 seconds and bake in a hot plate at 100 ° C. for 30 seconds and in a reflux oven at 151 ° C. for 30 minutes.

2) Spin coat the transparent intaglio photoresist at 4000 rpm for 90 seconds and bake on a hot plate at 100 ° C. for 3 minutes.

3) The sample was then exposed to actinic light (150 mJ / cm ² ) from the contact printing machine through a wedge shaped mask placed on the coated substrate and then baked on a hot plate at 100 ° C. for 2 minutes.

4) The sample was soaked in 0.27 N tetramethylammonium hydroxide (TMAH) for 20 seconds and then washed with deionized water to remove the exposed resist and the underlying red 02 and the semicircle pattern of red 02 with the upper transparent resist layer. Left. The remaining Red 02 and clear resist were then baked (cured) in a reflux oven at 230 ° C. for 30 minutes. Red 02 film thickness was about 1.2 μm by proof of analysis. The thickness of the transparent resist film was about 0.35 μm. The spectrum of red 02 coated with transparent resist after this step is shown by line (a) in FIG. 7.

5) Spin coat green color filter (Brewer Science, Inc. PiC® Green 02) at 1100 rpm for 90 seconds and bake on hot plate at 100 ° C. for 30 seconds and bake at reflux oven at 165 ° C. for 30 minutes. . The transparent intaglio photoresist prepared in Example 29 is spin coated at 4000 rpm for 90 seconds and baked on a 100 ° C. hot plate for 3 minutes. The sample was then exposed to actinic light (150 mJ / cm ² ) from the contact printing machine through a wedge shaped mask placed on the coated substrate and rotated 90 degrees from its position in three steps.

6) The sample was soaked in 0.27 N tetramethylammonium hydroxide (TMAH) for 20 seconds and then washed with deionized water to remove the exposed resist and the underlying Green 02 and left a semicircle pattern of Green 02. The remaining Green 02 and clear resist were then hard baked (cured) in a reflux oven at 230 ° C. for 30 minutes. Green 02 film thickness was about 1.20 μm by proof of analysis. The transparent resist film thickness was about 0.35 μm. After this step, the spectra of green 02 coated with transparent resist and red 02 coated with transparent resist are shown as lines (b) and (c) in FIG. 7, respectively.

7) Spin coat the blue color filter (Brewer Science, Inc. PiC® EXP93004) at 1200 rpm for 90 seconds and bake on a hot plate at 100 ° C. for 30 seconds and bake in a reflux oven at 160 ° C. for 30 minutes. The transparent intaglio photoresist prepared in Example 29 is spin coated at 4000 rpm for 90 seconds and baked on a 100 ° C. hot plate for 3 minutes. The sample was then exposed to actinic light (150 mJ / cm ² ) from the contact printing machine through a wedge shaped mask placed on the coated substrate and rotated 90 degrees from its position in step 5.

8) The sample was soaked in 0.27 N tetramethylammonium hydroxide (TMAH) for 20 seconds and then washed with deionized water to remove the exposed resist and the underlying blue 10 and leaving a semi-circle pattern of blue 10. The remaining Blue 10 and clear resist was hard baked (cured) in a reflux oven at 230 ° C. for 30 minutes. Blue 10 film thickness was about 1.20 μm by proof of analysis. The transparent resist film thickness was about 0.35 μm. The spectra of blue 10 coated with transparent resist, green 02 coated with transparent resist and red 02 coated with transparent resist are shown by lines (d), (e) and (f) respectively in FIG. 7 after this step.

In Fig. 7, a slight decrease in the transmission of red 02 represented by lines (a), (c) and (f) and a slight decrease in the transmission of green 02 represented by lines (b) and (e) are followed by a color filter. It is the result of some contamination from any of the treatment steps and darkening by heat, but the impact is minimal.

A second color wheel was prepared as described above in steps 1-8 except blue 10 was developed in TMAH and not cured. Instead the color wheel was placed on the spinner and stretched at 2000 rpm while spraying with a stream of N-methyl-2-pyrrolidinone from the squeeze bottle for about 10 seconds. The color wheel was spun at 2000 rpm for an additional 80 seconds to help dry the wheel. FIG. 8 shows the spectra of red 02 and green 02 after curing and removing blue 10, respectively, where lines (a), (c) and (e) show transmission spectra of red 02, and lines (b) and (d ) Shows the transmission spectrum of Green 02. The spectrum shows a slight decrease in transmission for Red 02 and Green 02 due to the pyrolysis of the dye. Spectra showed that removal of Blue 10 using N-methyl-2-pyrrolidinone did not contaminate Green 02 and Red 02 and there was no leaching of dye from Green 02 and Red 02 during the Blue 10 removal step. To indicate.

Example 32

Three glass substrates with a diameter of 7.62 cm (3 in) were coated by spin coating at 800 rpm for 90 seconds using a blue color filter material (EXP94056, Brewer Science, Inc.). Each sample was baked on a hot plate for 30 seconds. Sample 1 was baked in a reflux oven at 250 ° C. for 30 minutes, sample 2 was baked in a reflux oven at 230 ° C. for 60 minutes, and sample 3 was baked in a reflux oven at 165 ° C. for 30 minutes. Sample 2 was spin coated with a 1: 1 dilution of the transparent resist described in Example 29 and SafeStrip® (Brewer Science, Inc.). The diluted transparent resist was spin coated at 1000 rpm for 90 seconds and then baked on a hot plate at 100 ° C. for 3 minutes. Samples were flood exposed on a contact press (150 mJ / cm ² ) and placed in a reflux oven at 230 ° C. for 30 minutes. The film thickness was determined to be 0.39 μm from the spin curve. Sample 3 was coated by spin coating at 5000 rpm for 90 seconds using a transparent resist diluted as described above and then baked on a hot plate at 100 ° C. for 3 minutes. Samples were flood exposed on a contact press (150 mJ / cm ² ) and placed in a reflux oven at 230 ° C. for 30 minutes. The film thickness was measured to be 0.1 μm from the spin curve. Evaluation of solvent resistance was performed by soaking each sample in N-methyl-2-pyrrolidinone. Spectra of each sample were recorded before and after dipping in N-methyl-2-pyrrolidinone. Sample 1 was stripped from the substrate while soaked in N-methyl-2-pyrrolidinone. Line (a) of FIG. 9 shows the transmission spectrum of the blue color filter of Sample 2 before application of the transparent resist. Line (b) of FIG. 9 shows the transmission spectrum of Sample 2 in which the transparent resist was baked. Line (c) of FIG. 9 shows the transmission spectrum of Sample 2 after soaking in N-methyl-2-pyrrolidinone for 30 seconds and baking the transparent resist thereon.

Line (a) in FIG. 10 shows the transmission spectrum of the blue color filter of Sample 3 after application and curing of the transparent resist. In FIG. 10, line (b) shows the transmission spectrum of Sample 3 which was soaked in N-methyl-2-pyrrolidinone for 30 seconds and then baked transparent resist thereon.

It will be appreciated that the above examples can also be shown for the use of separate vehicles and soluble dyes, while the dyes can be part of the vehicle polymer, for example attached to the polymer as additional compounds. The polymer may also be one having the desired filtering properties which emit light of the desired wavelength and exclude other wavelengths.

Those skilled in the art will appreciate that variations of the invention disclosed herein are possible without departing from the spirit of the invention disclosed. The invention is not limited by the specific embodiments disclosed herein, but only by the claims appended hereto.

Claims (10)

Applying a substantially non-particulate filter coating layer to the filter substrate, applying a photoresist to the filter coating layer on the filter substrate, imaging with photolithography and developing the photoresist to form a pattern with the photoresist, patterning By etching the photoresist, the pattern is transferred to the filter coating material, the color filter element pattern is formed on the color filter material, and the color filter element is cured to substantially insoluble the color element. In the manufacturing method, the filter coating comprises a vehicle and a soluble dye introduced therein, which is heat stable and, in combination with the vehicle, is effective in producing high color contrast and gloss even with a reduced level of halo. Stable, the cured filter element being effective to consistently transmit and split colored light with high gloss And a dye, wherein the cured color filter element comprises a stable dye that is highly resistant to leaching and contamination from neighboring applications of subsequent filters. The method of claim 1, wherein the substrate is coated in a substantially flat array of multicolor filter elements. 3. The method of claim 2, comprising orienting the filter coating in the color filter element to provide alignment. The method of claim 3 comprising applying a liquid crystal material to the oriented filter coating. The method of claim 1, wherein the vehicle comprises an anhydride modified copolymer grafted with a reactive crosslinking component and kneaded with a multifunctional crosslinking component. Applying a layer of filter coating material substantially non-particulate to the filter substrate, etching to form a pattern on the color filter material and forming a color filter element, curing the color filter element to substantially insoluble the color element, and coloring A method for producing a microelectronic filter element by microphotographic flat plate application, wherein the filter coating material is applied to a vehicle and the soluble introduced therein, wherein the barrier coating is applied to the prepared filter element and the barrier coating is cured to substantially insoluble the barrier coating. Dyes, wherein the soluble dye is heat stable and, in combination with the vehicle, is effective in producing high color contrast and gloss at a reduced level of halo, wherein the cured filter element consistently transmits colored light with high gloss and It contains a stable dye that is effective for partitioning, and the cured barrier coating is applied to the neighboring application of subsequent filters. To provide high resistance to leaching and contamination. Applying a substantially non-particulate filter coating layer to the filter substrate, applying a photosensitive barrier coating to the color filter coating layer on the filter substrate, patterning the photosensitive barrier coating into photography, developing and etching the pattern of the barrier coating Microelectronics by microphotolithography, which transfers the pattern to the filter coating by forming a color filter element covered with a oxidized barrier coating and hardens the color filter element and barrier coating by curing the color filter element and the barrier coating. A method of making a filter element, said filter coating comprising a vehicle and a soluble dye introduced therein, wherein the soluble dye is heat stable and in combination with the vehicle produces high color contrast and gloss at a reduced level of halo. It is effective for the cured filter element to transmit colored light consistently with high gloss. And a stable dye effective to partition, wherein the cured barrier coating provides high resistance to leaching and contamination from neighboring application of subsequent filters. A vehicle comprising a copolymer grafted with a reactive crosslinking component and modified with an anhydride kneaded with a multifunctional crosslinking component, and when thermally stable and combined with the vehicle introduced therein, high contrast and high contrast at a reduced level of halo; A light absorbing coating for photolithography comprising a soluble light absorbing dye effective to produce a gloss. Adjacent filters comprising a vehicle and a substantially non-particulate filter coating, comprising a soluble dye introduced therein that is thermally stable and effective in combination with the vehicle to produce high color contrast and gloss at a reduced level of halo. A color filter substrate on which a patterned filter element is highly resistant to leaching and contamination from the substrate. The filter substrate of claim 9, wherein the vehicle comprises a copolymer grafted with a reactive crosslinking component and modified with anhydrides kneaded with the multifunctional crosslinking component.