CA2029964A1 - Process for the preparation of optical color filters - Google Patents
Process for the preparation of optical color filtersInfo
- Publication number
- CA2029964A1 CA2029964A1 CA 2029964 CA2029964A CA2029964A1 CA 2029964 A1 CA2029964 A1 CA 2029964A1 CA 2029964 CA2029964 CA 2029964 CA 2029964 A CA2029964 A CA 2029964A CA 2029964 A1 CA2029964 A1 CA 2029964A1
- Authority
- CA
- Canada
- Prior art keywords
- light
- sensitive
- layer
- heat treatment
- color
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/28—Processing photosensitive materials; Apparatus therefor for obtaining powder images
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optical Filters (AREA)
Abstract
TITLE
PROCESS FOR THE PREPARATION OF OPTICAL COLOR FILTERS
ABSTRACT OF THE DISCLOSURE
A process for the preparation of a color filter is described utilizing an exposure step of a light-sensitive material, imagewise exposing, toning and heat treating.
PROCESS FOR THE PREPARATION OF OPTICAL COLOR FILTERS
ABSTRACT OF THE DISCLOSURE
A process for the preparation of a color filter is described utilizing an exposure step of a light-sensitive material, imagewise exposing, toning and heat treating.
Description
2 ~ 2 ~
~rT.E
PROCESS FOR THE PREPAR~TION OF OPTICAL COLOR FILTERS
~2~ 21!ND~ LMy~TION
The subject of the invention is a process for the preparation of any type of patterned, monochromatic or polychromatic, optical color fi.lter, such as is used, for e~ample, for color separation in devices for making color images or particularly in systems for the reproduction of such images (displays).
Most of such color filtercs are finely patterned, that is, the structural element:s are often only a few microns large. Depending on the use, these elements are in the form of stripes, circles or other geometric figures. Most are re~uired for filters with closely adjoining areas of different colors.
Many processes are known for the preparation of such color filters. The methods used include screen printing, color photography based on silver halides, diazo processes, the transfer of preformed polychromatic patterns onto a common substrate, imagewise ablation of color layers by laser, washoff after photocrosslinking, applying color to lithographically formed patterns from colorless binders, and others.
Similarly known are processes in which finely divided dyes or dyed compositions ars coated in the form of the desired pattern onto the substrate. Thus, European Patents 01 13 237 and 01 57 486 disclose the preparation first of a patterned~ conductive layer on an insulating substrate and then coating electro-phoretically on the conductive areas a dyed polymer layer from an aqueous solution containing a polymer and a dye. Various conductive areas insulated from one another can be provided successively with coatings of various colors in suitable electrophoretic baths. If 3 ~ ~
the conductive areas are later to serve as electrodes in liquid crystal cells, then the electrical field is partially shielded by the polymer layer, which decreases the sensitivity of the cell.
German Patents ~7 58 209 and 29 29 615 disclose negative-working light-sensitive layers, the exposed areas of which are tonable with a powdered color to produce an image. The layers described therein can also contain a plasticizer. The use of negative-working layers for polychromatic images offers the advantage that, in the first step, the unexposed and untoned areas retain their light-sensitivity and can be toned in a succeeding step with another color after exposure of another pattern. This process can be repeated until the entire layer is toned. However, patterns prepared by this process on transparent supports are not suitable as color filters, because they scatter too much light. In addi-tion, they are unstable to many solvents, so that further processing to liquid crystal cells, for example, the application of equalizing layers, is possible only with limitations.
The problem involved in the invention is the development of a process in which color filters with low light scatter and good stability to mechanical and chemical stresses can be prepared in a simple manner by the use of negative-working, light-sensitive, tonable layers.
The present invention is directed to a process for the preparation of a monochromatic or polychromatic color filter by (a) applying a negative-working, light-sensitive, tonable layer onto a transparent support, 3 2 0 2 ~
~b) imagewise exposing in a pattern corresponding to a spatial configuratLon of a filter element color, (c) toning the layer with a colored toner which is capable of being substantially completely volatilized in a heat treatment, (d) subjecting the toned layer to a heat treatment.
Pet a i le~l~s~:i}~;is~b~e~
Negative-working, light-3ensitive layers with 1,4-dihydropyridine compounds, as are described, for example, in German Patents 27 58 209 and 3g 29 615, are preferred for performing the process of the invention.
Compounds of 2'-nitrophenol-1,4-dihydropyridine, for example, the compounds cited on page 3, lines 51 to 60 of German Patent 34 29 615, are preferred. These compounds can be coated on transparent supports by a conventionai coating process, for example, spin coating, singly or as mutual mixtures, either as such or dissolved in a volatile solvent.
The light-sensitive layers can also be prepared from 1,4-dihydropyridines mixed with hexaaryl bisimidazoles. Suitable compounds are listed in Tables I and II of German Patent 27 58 209.
The li~ht-sensitive layer~ can contain plasticizers compatible with the toner binder. Examples of suitable plasticizers are esters of aliphatic or aromatic di-~
tri-, and tetracarboxylic acids with two to four carbon atoms and monofunctional alcohbls with 1 to 20 carbon atoms, esters of di-, tri-, and tetrafunctional alcohols with 2 to 20 carbon atoms and aliphatic or aromatic monocarboxylic acids with 4 to 12 carbon atoms, and ethers of any of the cited polyfunctional alcohols with the cited monofunctional alcohols. Examples are , ' . .
. ~, :
9 2~2~
diisohutyl phthalate, dibutyl adipate, dibutyl glycol, and trioctyl mellitate. The necessary quantity o~
plasticizer can be determined by test; it is generally between 2 and 15 percent by weight of the dry portion of the light-sensitive layer.
Satisfactory results are obtained without a particular plasticizer with cert:ain combinations of light-sensitive material and toner bindex, for example, dihydropyridine compounds, particularly 2'-nitrophenyl-1,5-dihydropyridine derivatives, preferably the ester of 2'-nitrophenyl-1,5-dihydropyrid~ne-3,5-dicarboxylic acid and cellulose acetate, polymethyl methacrylate or poly-alpha-methyl styrene. In this case, lt is assumed that the light-sensitive material itself or its photolysis products act simultaneously as plasticizers. Thus, the plasticizers are present in the layer only after imagewise exposure. Consequently, with such systems, the whole surface of the backside of the toned, light-sensitive layer is exposed through the transparent support to increase plasticizer concentration in the layer.
It is not absolutely necessary to add high molecular weight binders to the light-sensitive layers.
Adhesion of the filter areas o~ the invention to the support is generally adequate without a binder.
The thickness of the light-sensitive layer can be selected freely within certain limits. Consideration should be given to the fact that thicker layers have lower resolution capability, whereas thi~ner layers have lower color density. Good results are generally obtained with layers 0.5 to 5 microns thick.
The toners to be used in the in~ention contain requisite color agents (pigments or dyes), which can be selected according to the desired properties ~f the color filter. Suitable color agents are cited, for , , 2~2~
example, on page 5,lines 57 onwards ln German Patent 29 45 569. Furthermore, it is advantageou~ for the toners to contain a thermoplastic binder, which must be compatible with the plasticizer of the :Light-sensitive layer. Suitable examples thereof are polyvinyl chloride, polyvinyl alcohol, polystyrene, and vinyl chloride/vinyl acetate copolymers; cellulose acetate, poly-alpha-methyl styrene and polymethyl methacrylate are preEerred. If polyamide acids are used as binders for the toner, the subsequent heat treatment results in very resistant, chemically and mechanically, filter elements as a result of conversion to polyimides. If the color agent itself is fusible or is thermoplastic without decomposition, the toner does not need a binder.
The toners are used in the form of powders with a particle size between 0.2 and 30 microns and preferably with at least 50% of the particles having a spherical diameter between 2 and 10 microns. Use can also be made of toners specified for electrostatic copying processes with thermal fixing.
For the preparation of filters by the process of the invention, a pattern in the form of the desired filter element of one color is exposed through an appropriate mask on the light-sensitive layer of the transparent support and toned with the corresponding colored toner powder. This toning can be accomplished by various known methods, for example, with a pad or a brush, by strewing the powder and letting it trickle off, optionally with the support beiny vibrated, or by contact with an auxiliary surface on which the toner powder is loosely bonded. The pattern can also be toned with the aid of a color-bearing transfer layer, for example, in accordance with German Patents 29 49 ~62 or 36 25 01~. The light-sensitive layer is brought into contact with the transfer layer, optionally with the application of heat and pressure, and then peeled away.
These process steps of exposure and toning are repeated for each color.
In many instances, it is necessary to have on the support, in addition to the color areas, achromatic, highly light-absorbing areas that form a so-called black matrix. Such a matrix can be prepared like the filter element by exposing a pattern and toning with a toner containing a black color agent. Preferably, this is done in a first step before the preparation of the color filter.
It is advantageous to treat light-sensitive layers containing dihydropyridines with a strong acid after each toning, as described in German Patent 35 40 804.
This prevents areas colored with a specific toner from being contaminated with other colors in subsequent toning steps.
Whenever all of the desired colors are applied, the system of support, light-sensitive layer, and toners that have been applied patternwise is subjected to a heat treatment. This accomplishes two objectives.
First, the light-sensitive layer's volatile portion, which is no longer needed and which could adversely affect the characteristics of the finished display, is volatilized. Second, the toner particles coalesce and the filter elements lose most o~ the disrupting property of high light scattering. In addition, the filter elements become significantly more stable to solvents used in further processing, for example, phenoxy ethanol or N-methyl pyrrolidone.
Heat treatment is accomplished at the lowest possible temperature, preferably below 240C. Its duration is preferably lO to 60 minutes. ~owever, duration and temperature should always be selected so .
' , .: .
that no visible decomposition of the support and toners occurs.
It is not completely clear why the heat treatment results }n such a sharp reduction of li~ht scattering in the toned filter elements. It is assumed that the number of scattering interfaces is drastically reduced by the coalescence of the toner particles. However, it is surprising that this effect doe snot occur if the toner particles actually melt. The effect of the invention is observed even if the toner contains only such color agents and binders that cannot melt at the temperature of the heat treatment, as well as if the polymer binder of the toner has a melting point lower than this temperature. It is similarly surpxising that performing the process of the invention does not produce a noticeable change in the form of the filter elements.
This applies independently of whether the toner contains components that melt at the temperature of the heat treatment.
In a particularly preferred embodiment o~ the process of the inven~ion, light scattering by the filter elements can be reduced even further. For this, the finished filter after heat treatment is placed in a solvent selected according to the characteristics of the toner binder. In the case of cellulose acetate toners, good results are obtained with acetone. Butanone and dichloromethane are also suitable. The solvent is used preferably in the vapor phase.
The color filters of the invention generally do not have completely ~lat surfaces, because the filters consist of individ~al, adjoining polychromatic areas adhering to the substrate. However, they can be coated by a simple method with an equali~ing layer of polyimide. A solution of the polyimide in a suitable solvent, for example, phenoxy ethanol, can be applied 8 2 ~
and dried. Such a coating is needed anyway as the so-called orientation coating in liquid crystal displays.
In another version, a patterned, conductive layer, for example, of indium tin oxide, can be coated on this layer to serve as the control electrode in the display.
The process of the invention is different from the state of the art in that it can be performed simply and inexpensively. Thus, for example, only one light-sensitive layer is required. Special measures to insure dimensional stability, like tho~se necessary with transfer layers, are eliminated, because the colored filter elements are produced directly on the support.
The hue of the filter elements can be matched to the goal value by choice of color agent or also by simple mixture of different toners. Color density can also be controlled in a simple manner, for exampler by the exposure.
The color filters prepared in the invention are outstandingly suitable for incorporation in liquid crystal displays. They have accurate dimensions, very uniform layer thickness, and are compatible with solvents and assembly materials. Pigments with improved aging stability can be used, because the type of color agent can be selected freely within wide limits. The ~5 low scattering of the filter elements requires high contrast in the finished display, because the light becomes only very slightly depolarized in the filter elements.
The invention can be used to prepare ~olor filter elements for devices that are specified for reproducing or recording monochromatic or polychromatic images, for example, video cameras. To further illustrate the present invention the following examples are presented.
9 ~ J~!~
E~lQl A glass plate was coated with a solution of 3.75 g dimethyl ester of 2,6-dimethyl-9-~2'-nitrophenyl)-1,4-- dihydropyridine-3,5-dicarboxylic acid and 11.25 g diethyl ester of 2r6-dimethyl~4-~2'-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid in 190 ml methyl ethyl ketone and dried. The dried layer was 1.2 microns thick. It was exposed at 160 mJ/cm2 through a mask with clear, square areas of 250 microns in size by means of a 1000 watt mercury vapor lamp provided with a filter having maximum transparency at 360 nm. Because the light-sensitive layer was sliyhtly tacky, direct contact with the mask was avoided.
The exposed layer was toned with a cellulose acetate powder 154% acetylated, two microns average particle size) incorporating 30 percent by weight particles of Perylene Pigment Red 123 (CAS Number 24108-83-2), and excess tonex was wiped off with a dust cloth.
For the determina~ion of scattering behavior, the glass plate with the filter element pattern was laid on the stage of an o~erhead projector. The filter elements appeared black in the projection without a noticeable polychromatic portion.
Now, the glass plate was heated in an oven for 60 minutes at 225C. After the plate was cooled, the test was repeated with the overhead projector. The filter elements now appeared brown in the projection.
Finally, the plate was placed in a covered beaker for 10 minutes over acetone at a temperature of 50C.
The test in the projector now showed a slightly blackened red color.
~=m~
Example 1 was repeated, except that the toner was a preparation from 18 parts by weight Pigment Blue 15:4 ~CAS Number 147-14-8) and 8~ parts by weight polymethyl .
~ ' ' 2~6~
methacrylate with a glass transition temperature of 105~C ("Elvacite" 2008 from the Du Pont Company).
Although testing the freshly prepared filter element in the overhead projector showed a black image, a pure blue green projection was observed after a heat treatment for 60 minutes at 225C.
~xamplQ_~, Example 2 was repeated, except that the toner contained poly-alpha~methyl styrene as a polymeric binder, instead of polymethyl methacrylate. Here, too, a pure blue green image was observed in the projection after the heat treatment.
~m~
Example 2 was repeated, except that, instead of polymethyl methacrylate, the toner contained a binder of a copolymer of alpha-methyl styrene and vinyl toluene with a softening temperature of 100C.
E~m~l~ 5 Example 4 was repeated, except that the exposure was at 240 mJ/cm2. Color filter elements were obtained with a visually obvious, higher color density. This was also shown by a 65% transmission at 500 nm (instead of 75% as in Example 4), as measured by a spectrophotometer.
Exa 1Q ~
Example 3 was repeated, except that, before the heat treatment, the light-sensitive, toned layer was exposed through the glass plate at 500 mJ/cm2. After the heat treatment, the filter;elements showed a pure, blue green image on projection.
, -' .
~rT.E
PROCESS FOR THE PREPAR~TION OF OPTICAL COLOR FILTERS
~2~ 21!ND~ LMy~TION
The subject of the invention is a process for the preparation of any type of patterned, monochromatic or polychromatic, optical color fi.lter, such as is used, for e~ample, for color separation in devices for making color images or particularly in systems for the reproduction of such images (displays).
Most of such color filtercs are finely patterned, that is, the structural element:s are often only a few microns large. Depending on the use, these elements are in the form of stripes, circles or other geometric figures. Most are re~uired for filters with closely adjoining areas of different colors.
Many processes are known for the preparation of such color filters. The methods used include screen printing, color photography based on silver halides, diazo processes, the transfer of preformed polychromatic patterns onto a common substrate, imagewise ablation of color layers by laser, washoff after photocrosslinking, applying color to lithographically formed patterns from colorless binders, and others.
Similarly known are processes in which finely divided dyes or dyed compositions ars coated in the form of the desired pattern onto the substrate. Thus, European Patents 01 13 237 and 01 57 486 disclose the preparation first of a patterned~ conductive layer on an insulating substrate and then coating electro-phoretically on the conductive areas a dyed polymer layer from an aqueous solution containing a polymer and a dye. Various conductive areas insulated from one another can be provided successively with coatings of various colors in suitable electrophoretic baths. If 3 ~ ~
the conductive areas are later to serve as electrodes in liquid crystal cells, then the electrical field is partially shielded by the polymer layer, which decreases the sensitivity of the cell.
German Patents ~7 58 209 and 29 29 615 disclose negative-working light-sensitive layers, the exposed areas of which are tonable with a powdered color to produce an image. The layers described therein can also contain a plasticizer. The use of negative-working layers for polychromatic images offers the advantage that, in the first step, the unexposed and untoned areas retain their light-sensitivity and can be toned in a succeeding step with another color after exposure of another pattern. This process can be repeated until the entire layer is toned. However, patterns prepared by this process on transparent supports are not suitable as color filters, because they scatter too much light. In addi-tion, they are unstable to many solvents, so that further processing to liquid crystal cells, for example, the application of equalizing layers, is possible only with limitations.
The problem involved in the invention is the development of a process in which color filters with low light scatter and good stability to mechanical and chemical stresses can be prepared in a simple manner by the use of negative-working, light-sensitive, tonable layers.
The present invention is directed to a process for the preparation of a monochromatic or polychromatic color filter by (a) applying a negative-working, light-sensitive, tonable layer onto a transparent support, 3 2 0 2 ~
~b) imagewise exposing in a pattern corresponding to a spatial configuratLon of a filter element color, (c) toning the layer with a colored toner which is capable of being substantially completely volatilized in a heat treatment, (d) subjecting the toned layer to a heat treatment.
Pet a i le~l~s~:i}~;is~b~e~
Negative-working, light-3ensitive layers with 1,4-dihydropyridine compounds, as are described, for example, in German Patents 27 58 209 and 3g 29 615, are preferred for performing the process of the invention.
Compounds of 2'-nitrophenol-1,4-dihydropyridine, for example, the compounds cited on page 3, lines 51 to 60 of German Patent 34 29 615, are preferred. These compounds can be coated on transparent supports by a conventionai coating process, for example, spin coating, singly or as mutual mixtures, either as such or dissolved in a volatile solvent.
The light-sensitive layers can also be prepared from 1,4-dihydropyridines mixed with hexaaryl bisimidazoles. Suitable compounds are listed in Tables I and II of German Patent 27 58 209.
The li~ht-sensitive layer~ can contain plasticizers compatible with the toner binder. Examples of suitable plasticizers are esters of aliphatic or aromatic di-~
tri-, and tetracarboxylic acids with two to four carbon atoms and monofunctional alcohbls with 1 to 20 carbon atoms, esters of di-, tri-, and tetrafunctional alcohols with 2 to 20 carbon atoms and aliphatic or aromatic monocarboxylic acids with 4 to 12 carbon atoms, and ethers of any of the cited polyfunctional alcohols with the cited monofunctional alcohols. Examples are , ' . .
. ~, :
9 2~2~
diisohutyl phthalate, dibutyl adipate, dibutyl glycol, and trioctyl mellitate. The necessary quantity o~
plasticizer can be determined by test; it is generally between 2 and 15 percent by weight of the dry portion of the light-sensitive layer.
Satisfactory results are obtained without a particular plasticizer with cert:ain combinations of light-sensitive material and toner bindex, for example, dihydropyridine compounds, particularly 2'-nitrophenyl-1,5-dihydropyridine derivatives, preferably the ester of 2'-nitrophenyl-1,5-dihydropyrid~ne-3,5-dicarboxylic acid and cellulose acetate, polymethyl methacrylate or poly-alpha-methyl styrene. In this case, lt is assumed that the light-sensitive material itself or its photolysis products act simultaneously as plasticizers. Thus, the plasticizers are present in the layer only after imagewise exposure. Consequently, with such systems, the whole surface of the backside of the toned, light-sensitive layer is exposed through the transparent support to increase plasticizer concentration in the layer.
It is not absolutely necessary to add high molecular weight binders to the light-sensitive layers.
Adhesion of the filter areas o~ the invention to the support is generally adequate without a binder.
The thickness of the light-sensitive layer can be selected freely within certain limits. Consideration should be given to the fact that thicker layers have lower resolution capability, whereas thi~ner layers have lower color density. Good results are generally obtained with layers 0.5 to 5 microns thick.
The toners to be used in the in~ention contain requisite color agents (pigments or dyes), which can be selected according to the desired properties ~f the color filter. Suitable color agents are cited, for , , 2~2~
example, on page 5,lines 57 onwards ln German Patent 29 45 569. Furthermore, it is advantageou~ for the toners to contain a thermoplastic binder, which must be compatible with the plasticizer of the :Light-sensitive layer. Suitable examples thereof are polyvinyl chloride, polyvinyl alcohol, polystyrene, and vinyl chloride/vinyl acetate copolymers; cellulose acetate, poly-alpha-methyl styrene and polymethyl methacrylate are preEerred. If polyamide acids are used as binders for the toner, the subsequent heat treatment results in very resistant, chemically and mechanically, filter elements as a result of conversion to polyimides. If the color agent itself is fusible or is thermoplastic without decomposition, the toner does not need a binder.
The toners are used in the form of powders with a particle size between 0.2 and 30 microns and preferably with at least 50% of the particles having a spherical diameter between 2 and 10 microns. Use can also be made of toners specified for electrostatic copying processes with thermal fixing.
For the preparation of filters by the process of the invention, a pattern in the form of the desired filter element of one color is exposed through an appropriate mask on the light-sensitive layer of the transparent support and toned with the corresponding colored toner powder. This toning can be accomplished by various known methods, for example, with a pad or a brush, by strewing the powder and letting it trickle off, optionally with the support beiny vibrated, or by contact with an auxiliary surface on which the toner powder is loosely bonded. The pattern can also be toned with the aid of a color-bearing transfer layer, for example, in accordance with German Patents 29 49 ~62 or 36 25 01~. The light-sensitive layer is brought into contact with the transfer layer, optionally with the application of heat and pressure, and then peeled away.
These process steps of exposure and toning are repeated for each color.
In many instances, it is necessary to have on the support, in addition to the color areas, achromatic, highly light-absorbing areas that form a so-called black matrix. Such a matrix can be prepared like the filter element by exposing a pattern and toning with a toner containing a black color agent. Preferably, this is done in a first step before the preparation of the color filter.
It is advantageous to treat light-sensitive layers containing dihydropyridines with a strong acid after each toning, as described in German Patent 35 40 804.
This prevents areas colored with a specific toner from being contaminated with other colors in subsequent toning steps.
Whenever all of the desired colors are applied, the system of support, light-sensitive layer, and toners that have been applied patternwise is subjected to a heat treatment. This accomplishes two objectives.
First, the light-sensitive layer's volatile portion, which is no longer needed and which could adversely affect the characteristics of the finished display, is volatilized. Second, the toner particles coalesce and the filter elements lose most o~ the disrupting property of high light scattering. In addition, the filter elements become significantly more stable to solvents used in further processing, for example, phenoxy ethanol or N-methyl pyrrolidone.
Heat treatment is accomplished at the lowest possible temperature, preferably below 240C. Its duration is preferably lO to 60 minutes. ~owever, duration and temperature should always be selected so .
' , .: .
that no visible decomposition of the support and toners occurs.
It is not completely clear why the heat treatment results }n such a sharp reduction of li~ht scattering in the toned filter elements. It is assumed that the number of scattering interfaces is drastically reduced by the coalescence of the toner particles. However, it is surprising that this effect doe snot occur if the toner particles actually melt. The effect of the invention is observed even if the toner contains only such color agents and binders that cannot melt at the temperature of the heat treatment, as well as if the polymer binder of the toner has a melting point lower than this temperature. It is similarly surpxising that performing the process of the invention does not produce a noticeable change in the form of the filter elements.
This applies independently of whether the toner contains components that melt at the temperature of the heat treatment.
In a particularly preferred embodiment o~ the process of the inven~ion, light scattering by the filter elements can be reduced even further. For this, the finished filter after heat treatment is placed in a solvent selected according to the characteristics of the toner binder. In the case of cellulose acetate toners, good results are obtained with acetone. Butanone and dichloromethane are also suitable. The solvent is used preferably in the vapor phase.
The color filters of the invention generally do not have completely ~lat surfaces, because the filters consist of individ~al, adjoining polychromatic areas adhering to the substrate. However, they can be coated by a simple method with an equali~ing layer of polyimide. A solution of the polyimide in a suitable solvent, for example, phenoxy ethanol, can be applied 8 2 ~
and dried. Such a coating is needed anyway as the so-called orientation coating in liquid crystal displays.
In another version, a patterned, conductive layer, for example, of indium tin oxide, can be coated on this layer to serve as the control electrode in the display.
The process of the invention is different from the state of the art in that it can be performed simply and inexpensively. Thus, for example, only one light-sensitive layer is required. Special measures to insure dimensional stability, like tho~se necessary with transfer layers, are eliminated, because the colored filter elements are produced directly on the support.
The hue of the filter elements can be matched to the goal value by choice of color agent or also by simple mixture of different toners. Color density can also be controlled in a simple manner, for exampler by the exposure.
The color filters prepared in the invention are outstandingly suitable for incorporation in liquid crystal displays. They have accurate dimensions, very uniform layer thickness, and are compatible with solvents and assembly materials. Pigments with improved aging stability can be used, because the type of color agent can be selected freely within wide limits. The ~5 low scattering of the filter elements requires high contrast in the finished display, because the light becomes only very slightly depolarized in the filter elements.
The invention can be used to prepare ~olor filter elements for devices that are specified for reproducing or recording monochromatic or polychromatic images, for example, video cameras. To further illustrate the present invention the following examples are presented.
9 ~ J~!~
E~lQl A glass plate was coated with a solution of 3.75 g dimethyl ester of 2,6-dimethyl-9-~2'-nitrophenyl)-1,4-- dihydropyridine-3,5-dicarboxylic acid and 11.25 g diethyl ester of 2r6-dimethyl~4-~2'-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid in 190 ml methyl ethyl ketone and dried. The dried layer was 1.2 microns thick. It was exposed at 160 mJ/cm2 through a mask with clear, square areas of 250 microns in size by means of a 1000 watt mercury vapor lamp provided with a filter having maximum transparency at 360 nm. Because the light-sensitive layer was sliyhtly tacky, direct contact with the mask was avoided.
The exposed layer was toned with a cellulose acetate powder 154% acetylated, two microns average particle size) incorporating 30 percent by weight particles of Perylene Pigment Red 123 (CAS Number 24108-83-2), and excess tonex was wiped off with a dust cloth.
For the determina~ion of scattering behavior, the glass plate with the filter element pattern was laid on the stage of an o~erhead projector. The filter elements appeared black in the projection without a noticeable polychromatic portion.
Now, the glass plate was heated in an oven for 60 minutes at 225C. After the plate was cooled, the test was repeated with the overhead projector. The filter elements now appeared brown in the projection.
Finally, the plate was placed in a covered beaker for 10 minutes over acetone at a temperature of 50C.
The test in the projector now showed a slightly blackened red color.
~=m~
Example 1 was repeated, except that the toner was a preparation from 18 parts by weight Pigment Blue 15:4 ~CAS Number 147-14-8) and 8~ parts by weight polymethyl .
~ ' ' 2~6~
methacrylate with a glass transition temperature of 105~C ("Elvacite" 2008 from the Du Pont Company).
Although testing the freshly prepared filter element in the overhead projector showed a black image, a pure blue green projection was observed after a heat treatment for 60 minutes at 225C.
~xamplQ_~, Example 2 was repeated, except that the toner contained poly-alpha~methyl styrene as a polymeric binder, instead of polymethyl methacrylate. Here, too, a pure blue green image was observed in the projection after the heat treatment.
~m~
Example 2 was repeated, except that, instead of polymethyl methacrylate, the toner contained a binder of a copolymer of alpha-methyl styrene and vinyl toluene with a softening temperature of 100C.
E~m~l~ 5 Example 4 was repeated, except that the exposure was at 240 mJ/cm2. Color filter elements were obtained with a visually obvious, higher color density. This was also shown by a 65% transmission at 500 nm (instead of 75% as in Example 4), as measured by a spectrophotometer.
Exa 1Q ~
Example 3 was repeated, except that, before the heat treatment, the light-sensitive, toned layer was exposed through the glass plate at 500 mJ/cm2. After the heat treatment, the filter;elements showed a pure, blue green image on projection.
, -' .
Claims (16)
1. A process for the preparation of a monochromatic or polychromatic color filter by (a) applying a negative-working, light-sensitive, tonable layer onto a transparent support, (b) imagewise exposing in a pattern corresponding to a spatial configuration of a filter element color, (c) toning the layer with a colored toner which is capable of being substantially completely volatilized in a heat treatment, (d) subjecting the toned layer to a heat treatment.
2. The process of claim 1 wherein steps (b) and (c) are repeated with a pattern corresponding to a spatial configuration of a filter element of another color prior to the heat treatment.
3. The process of claim 2 wherein the colored toner is a fusible powder, a thermoplastic or a colored agent in combination with a thermoplastic binder.
4. The process of claim 2 with the heat treatment performed at a temperature below 290°C.
5. The process of claim 4 with the duration of the heat treatment in a range from 10 to 60 minutes.
6. The process of claim 2 with light sensitive, toned layer containing a plasticizer.
7. The process of claim 2 with the light-sensitive, tonable layer containing a dihydropyridine compound.
8. The process of claim 2 with the light-sensitive, tonable layer containing a 2'-nitrophenyl-dihydropyridine derivative.
9. The process of claim 2 with the light-sensitive, tonable layer is treated after each toning step with a strong acid.
10. The process of claim 2 with the light-sensitive, tonable layer containing an ester of a polyfunctional carboxylic acid or alcohol as a plasticizer.
11. The process of claim 2 with the toner containing a cellulose acetate, poly-alpha-methyl styrene or polymethyl methacrylate as a binder.
12. The process of claim 2 with toning accomplished by contact with a transfer layer carrying the toner.
13. The process of claim 2 with the exposed and toned layer treated with a solvent after the heat treatment.
14. The process of claim 13 with acetone, butanone, or dichloromethane used as the solvent.
15. The process of claim 23 with the treatment accomplished with a vapor phase of the solvent.
16. The process of claim 2 with the light-sensitive, toned layer exposed overall through a support before the heat treatment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19893938112 DE3938112A1 (en) | 1989-11-16 | 1989-11-16 | METHOD FOR PRODUCING OPTICAL COLOR FILTERS |
| DEP3938112.9 | 1989-11-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2029964A1 true CA2029964A1 (en) | 1991-05-17 |
Family
ID=6393654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2029964 Abandoned CA2029964A1 (en) | 1989-11-16 | 1990-11-14 | Process for the preparation of optical color filters |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0432465A3 (en) |
| JP (1) | JPH03210502A (en) |
| CA (1) | CA2029964A1 (en) |
| DE (1) | DE3938112A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10336352B4 (en) * | 2003-08-08 | 2007-02-08 | Schott Ag | Method for producing scattered light structures on flat light guides |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3429615C1 (en) * | 1984-08-11 | 1985-12-12 | Du Pont de Nemours (Deutschland) GmbH, 4000 Düsseldorf | Process for producing patterns consisting of powders |
| US4650734A (en) * | 1986-06-09 | 1987-03-17 | Eastman Kodak Company | Color filter elements and electrophotographic method of making same |
| DE3625014C1 (en) * | 1986-07-24 | 1987-10-29 | Du Pont Deutschland | Process for the production of images on tonable photosensitive layers |
| DE3642855C1 (en) * | 1986-12-16 | 1988-06-23 | Du Pont Deutschland | Photosensitive mixture |
-
1989
- 1989-11-16 DE DE19893938112 patent/DE3938112A1/en active Granted
-
1990
- 1990-11-10 EP EP19900121533 patent/EP0432465A3/en not_active Withdrawn
- 1990-11-14 CA CA 2029964 patent/CA2029964A1/en not_active Abandoned
- 1990-11-16 JP JP2311265A patent/JPH03210502A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03210502A (en) | 1991-09-13 |
| DE3938112C2 (en) | 1991-08-29 |
| EP0432465A2 (en) | 1991-06-19 |
| DE3938112A1 (en) | 1991-05-29 |
| EP0432465A3 (en) | 1992-07-08 |
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