JPH02262663A - Color image recording method - Google Patents

Abstract

PURPOSE:To simplify processing and to improve performance by imagewise polymerizing a polymerizable compd. finely dispersed in a hydrophilic binder by a photopolymn. initiator, thereby immobilizing coexisting color image forming materials. CONSTITUTION:A photosensitive material formed by applying a compsn. contg. the photopolymn. initiator, the color image forming materials and the polymerizable compd. dispersed in the hydrophilic binder on a base is subjected to an exposing processing to polymerize the polymerizable compd. in the exposed part and to immobilize the color image forming materials contained therein; thereafter, the color image forming material contained in the unpolymerized polymerizable compd. in the unexposed part is eluted by an aq. alkaline soln. to form the dyestuff images. The color image recording material which is simple in the processing and has the high resolution, good hues and high stability of the formed dyestuff images is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color image recording method. For more details,
The present invention relates to a novel color image recording method in which a polymerizable compound finely dispersed in a binder is imagewise polymerized using a photopolymerization initiator to immobilize a coexisting color image forming substance, and a wash-off treatment is performed with an alkaline aqueous solution.

(Prior Art) An image forming method using a photopolymerization reaction includes chemical amplification by a chain reaction, and therefore belongs to the most complicated category among non-silver salt photographic methods.

In addition, since the large physical change of polymerization can be utilized, photopolymerization recording systems have a wide variety of uses, and needless to say, various studies have been conducted on them.

The uses of this photopolymerization recording system can be roughly divided into two types.

One is an application that utilizes the physical properties of the polymer image itself (strength, solubility, permeability, water repellency, etc.), and reliefs, resists, and PS plates are good examples. On the other hand, a polymer image is visualized as a medium and used as a color image, and color proofing is an example of this.

Since the former is a feature not found in silver halide photography, it has great advantages even at low sensitivity, and has already been used in various industrially important applications.

However, the latter has limited applications due to its low sensitivity, and many methods of using silver halide as a sensor are being considered.

However, from a different point of view, color image forming methods using photopolymerization systems are lower in cost than silver halide photography because they do not use silver, and they also require treatment to remove silver halide or silver. This has the great advantage that it is not necessary.

Photopolymerizable color image recording materials and color image recording methods that take advantage of the above advantages have been studied.

Except for special cases (for example, when the monomer itself has a color-forming function, such as N-vinylcarbazole-carbon tetrabromide-based photosensitive materials), direct visible light is produced by photopolymerization using a photopolymerizable compound. It is difficult to form an image, and this is one of the reasons why photopolymerization systems are difficult to be applied to -a color image recording.

In order to make the image visible, either the exposed or unexposed areas are colored by selective dyeing with a dye solution or by attaching pigment powder, depending on their permeability or tackiness. Alternatively, the photosensitive layer is colored in advance, imagewise exposed to form an image-like polymerized image, and then the difference in physical properties such as the difference in solubility or the difference in adhesiveness between the cured and uncured parts is used. Physical treatments such as washing off or peeling off uncured parts were required.

A method of creating a visible image by directly using a photopolymerizable composition, that is, by a chemical reaction inside the photosensitive material without external coloring or spatial separation of exposed and unexposed areas. Some have also been proposed. Unexamined Japanese Patent Publication 1989-1989
No. 915 proposes a method of forming a positive-positive visible image by heat development using a photopolymerizable composition and a thermosensitive coloring material.

However, this requires that the two components of the two-component thermochromic material be placed separately inside and outside the photopolymerizable composition, or on both sides.

Also, JP-A-57-179836 and JP-A No. 57-19753
No. 8, No. 58-23024 and No. 58-23025
No. 6, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 2003, No. 1, No. 2, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 2, No. 1, No. 1, No. 1, No. 2, and No. 2, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, 2003, 2003, and No. 2, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, 2003, 2003, and 2004, 2003, and describes a method of forming a visible image using a photopolymerizable composition and a heat-sensitive (pressure-sensitive) color-forming material.

However, these are all two-component coloring substances.
microencapsulating two components together with a photopolymerizable composition,
Additionally, pressure treatment is required to destroy uncured capsules.

The method of forming a dye by reaction as described above has disadvantages in that the leuco dye used has high restrictions in terms of molecular design and the stability of the produced dye is low. Further, as described above, the composition of the composition becomes complicated and various restrictions are added, making it difficult to form a color image of two or more colors, for example. Furthermore, since diffusion and transfer are involved, there are various drawbacks such as generally poor image sharpness.

Many other improvements and innovations have been made, but further research is needed to develop photopolymerizable color image forming materials that are simple, stable, and sharp.

Furthermore, it is difficult to apply it as a full-color image recording material using two or more colors, preferably three or more colors.

-M has a method in which the polymerizable layer for each color is colored in advance with a pigment, etc., and after polymerization, the unpolymerized part is eluted with a solvent, or the polymerized part and the unpolymerized part are placed on different sheets by peel development. Methods have been developed such as separating the polymer, using the adhesiveness of the unpolymerized part to attach colored powder, and washing off the unpolymerized part and then dyeing the remaining polymerized part.
Although they have been put into practical use, these methods are characterized by complex steps such as coating, drying, polymerization, and processing for the number of colors required, along with the need for particularly precise alignment, making it difficult to obtain the final color image. The yield is low and the cost is very high.

In order to reduce this series of processes for each color as much as possible, for example, in JP-A No. 59-30537, color image sheets of cyan, magenta, and yellow are prepared, and three-color separated images are exposed to light on these sheets and developed. A full-color image is formed by transferring the image to the sheet three times. However, even with this, the exposure and transfer steps are complicated and the alignment problem is not solved.

JP-A-62-143044 proposed a material and method capable of forming a full-color image by one-time exposure and one-time processing in a photopolymerization-based color image-forming method.

This full color imaging material includes a photosensitive layer containing three sets of microcapsules.

Each set of microcapsules has distinctly different sensitivities in selected wavelength bands extending into the visible spectrum (400-700 nm), and is combined with cyan, magenta or yellow imaging agents to develop color by pressure transfer, resulting in full-color images. form.

This expansion of color sensitivity into the visible range has a very important meaning in photopolymerizable image recording methods, but the microcapsule color development method has the aforementioned drawbacks such as sharpness and image stability.

On the other hand, U.S. Pat. No. 3,579,339 discloses that a photopolymerizable composition containing a color coupler of the type used in silver halide color films is bonded to gelatin or the like, coated on a support, and exposed to light. Contains polymerizable droplets. A method has been proposed in which a liquid coloring agent penetrates into an unpolymerized oily part after exposure to light as a photosensitive layer to form a color by a coupling reaction.

Furthermore, JP-A-60-120353 discloses a recording material that combines non-uniform dispersion of a polymerizable monomer in a binder and a dye that is bleached by the monomer.

These methods allow multilayer coating, and if each monomer oil droplet has a different sensitivity, they have the advantage of being able to form a full-color image in one shot, and they also avoid physical destruction such as transfer and removal of monomer layers. Processing is easy and sharpness can be ensured as there is no background noise.

However, as mentioned above, dyes produced by color-forming reactions and monomer bleaching dyes have a major problem in the stability of the final color image, and there is also freedom in designing dyes with good hue necessary for color images. It has the disadvantage of having a narrow range, so it is not practical.

As mentioned above, the photopolymerizable color image forming method described above has a wide range of applications, but among these, the need for it has been increasing in recent years.
Its application to color filters is noteworthy.

With the recent development of microelectronic technology, the demand for visual information transmission has increased, and various visual devices are being developed. Among these, color filters play an important role in converting visual information into full color.

In particular, CCD and B
Solid-state imaging devices such as BD and MOS have come into use. This solid-state image sensor has a large number of finely divided light-receiving sections and a drive circuit for extracting information from the light-receiving sections.In order to obtain a color image, a color filter is placed on the top of the solid-state image sensor. It is necessary to place the

On the other hand, it is a small, thin, and
Development of lightweight color displays is progressing, and various types of color displays using liquid crystals, plasma, fluorescent display tubes, electroluminescence, etc. have been proposed.

Among these, liquid crystal displays are attracting the most attention because they have advantages such as being able to be driven with low voltage and power, being thinner and lighter, and having a long lifespan. There are various methods for color display on liquid crystal displays.

For example, the guest-host method (GH method, which uses a dichroic dye mixed with liquid crystal), the ECB method (Elec
trically controlled biref
There are two types of optical shutters: a ringrence method (one that utilizes the birefringence of liquid crystals) and one-type optical shutter (one that utilizes a combination of a liquid crystal cell and a color filter). Among these, the one-type optical shutter is capable of supporting full-color display, and the current quantity is said to be close to practical use.

One type of light shutter uses a liquid crystal cell to control the amount of transmitted light and combines it with a color filter to display full color. This makes it possible to display any color within the color triangle of the CIE chromaticity diagram using the additive color method.

Most color filters used for full-color printing are composed of the three primary colors blue, green, and red (B, G, R) arranged regularly (in a mosaic or stripe pattern).
For example, micro color filters for solid-state image sensors use black stripes to completely separate the colors between multicolor patterns, and black stripes are used for liquid crystal displays. Black stripes are used to achieve complete color separation in color filters, and to control light shutter on/off by blocking light from the TPT formed in the gaps between the three primary color filters and lowering the on-state current. Sometimes.

Currently, known methods for manufacturing color filters include dyeing methods, vapor deposition methods, electrodeposition methods, interference film methods, printing methods, and photographic methods.

Among these, the dyeing method is most frequently used from the viewpoint of reliability. In the dyeing method, a polymer such as polyvinyl alcohol or gelatin is coated on a support to form a dye-receiving N (mordant layer), and a coloring substance such as a dye is applied to this to form a color element (
pixels).

Specifically, as described in U.S. Pat. No. 3,289,208, (1) a gelatin layer made photosensitive by adding potassium dichromate is coated on the support, pattern exposure is performed on this, and then washed with warm water. A relief image is formed, ■Then, the gelatin layer that remains as this relief image is dyed with a red dye using a red dye solution, ■After applying an intermediate layer on this dyed layer, ■Same as in the above ■. 1) Dye the green dye using a green dye solution, 2) Coat an intermediate layer on top of it, 2) Perform the same operations as above, 2) Dye the blue dye using a blue dye solution. Dyeing is carried out, and finally, a protective tJL layer is applied.

However, as described above, the dyeing method requires complicated steps, and the structure of the color filter obtained in this way is also complicated, which has the drawback of being susceptible to pinholes and scratches.

Various techniques have been proposed to improve this drawback.

For example, US Pat. No. 4,236,098 describes a method for absorbing dye from a dye solution into a gelatin layer through a window-like pattern formed using photoresist techniques. Also, US Patent Nos. 4081277 and 4168
No. 448 describes a technique in which a heat-sublimable dye or a heat-transferable dye is transferred to a dye-receiving layer through a window-like pattern formed with a photoresist.

However, these techniques also have the disadvantage of being complicated and having poor yields, as they require repeated steps such as photoresist coating, development, and peeling.

Furthermore, recently, a method using a pigment-containing photoresist has been developed using this photoresist method in order to reduce the process of coating the resist intermediate layer and increase the resistance of the dye.

However, even if this method is used, coating, drying, exposure, and cleaning steps are required for each color, and the problem of complexity and poor yield has not yet been solved.

Other methods of manufacturing color filters also have their own problems.

The dye vapor deposition method evaporates the dye and obtains pixels using the list-off method.It is a thin film that can be formed directly on a transparent electrode, but it is an inorganic vapor-deposited multilayer interference method that has the disadvantage of weak adhesion to the base. Color filters using films have good heat resistance, but it is difficult to control the thickness of the interference film, which poses problems in terms of cost and yield. In the electrodeposition method, a color filter is formed by forming an electrode and then electrodepositing a polymer thereon, but it has the disadvantage that it is difficult to arrange pixels freely and black stripes cannot be formed. Compared to the photoresist method mentioned above, the printing method allows for larger screens and easier mass production, but it has poor dimensional stability and is not satisfactory in terms of film uniformity and film surface smoothness. Although various photographic methods have been studied, the conventional method involves processing a coupler dispersed in a light-sensitive silver halide emulsion film with a color developing solution to form a non-diffusible dye.
Desilvering treatment is then applied to create a color filter, which requires a complex processing process, and the resulting color filter has a large film thickness and is insufficient in terms of quality such as sharpness and hue. Ta.

As mentioned above, color filters play an important role in converting visual information into full color, but the conventional method of manufacturing color filters is difficult in terms of the manufacturing process. 3
[It was crude, the yield was poor, and the quality of the manufactured color filters was not satisfactory. In particular, a method for manufacturing large-screen color filters with high quality through a simple process has been desperately desired.

(Object of the Invention) The object of the present invention is basically to provide a photopolymerizable color image recording material with good performance through simple processing.

A further object of the present invention is to provide a full-color image in one shot using the above color image recording material, and as a special object, to provide a method for manufacturing a micro color filter using this color image recording method. There is a particular thing.

(Structure of the Invention) The present inventor has discovered that it is possible to create multiple colors and full colors without requiring multiple steps, and that processing is simple, and above all, the resulting dye image has "high resolution" and "hue We investigated color image recording materials that have good stability and high stability, and color image recording methods using them.

In other words, there is no process such as physical destruction or transfer that deteriorates sharpness, and it is a new method that does not use color-developing or decolorizing color image forming methods, which narrow the freedom of dye design or have poor stability of the produced dye. The purpose of this research was to develop new materials and new color image recording methods using them.

In particular, we focused on the large difference in permeability of substances between photopolymerizable compounds (monomers) and macromolecules (polymers) produced by their polymerization. We considered combining breformed dyes that have a greater degree of freedom and can ensure hue and stability.

Specifically, in color photopolymerizable recording materials, parts that are included in polymerizable compounds and polymerized by exposure are fixed, whereas unpolymerized parts become water-soluble by treatment with an alkaline aqueous solution. , to design a stable, well-formed color image-forming material with good hue that has the ability to be easily eluted from a polymerizable compound; By designing a color image recording material in which a chemical compound is finely dispersed in a water-soluble binder, by using the above two points of ingenuity, a simple operation of exposure and alkaline aqueous solution treatment can produce sharp images with good color. We succeeded in forming color images with stable dye images.

That is, the present invention provides a photosensitive material in which a composition containing at least a photopolymerization initiator, a color image forming substance, and a polymerizable compound is dispersed in a hydrophilic binder and coated on a support.
The color image-forming substance contained therein is immobilized by exposure treatment and the polymerizable compound in the exposed area is polymerized, and then the color image-forming substance contained in the unpolymerized polymerizable compound in the unexposed area is immobilized with an alkaline aqueous solution. Regarding fixation and elution of color image forming substances, which are important elements of image formation, which is a color image recording method characterized by elution to form a dye image, see Photog'raphic 5cjen.
ceand Engineering No. 131! No. 2, pp. 84-89 (1969), the discrimination CDvaax /Dmin) of the color-forming system is not very good, and the fact that the discrimination in the photopolymerization system, as pointed out in JP-A No. 60-120354, etc. There is a problem in that it is difficult for the color image-forming materials described above to completely prevent mass transfer, and it is difficult for them to act as a sufficient barrier, making it difficult to increase the signal/noise (S/N) ratio. It has been found that color images with surprisingly good discrimination can be obtained by skillfully designing the molecules of the compound, selecting a combination with a polymerizable compound, etc., and extracting the color image-forming substance from the polymerizable compound using an alkaline aqueous solution. Ta.

In other words, in the cured part (Dmax part) of the polymerizable compound, there is almost no elution of the color image forming substance during treatment with an alkaline aqueous solution.
While maintaining a high D+*ax concentration, in the unpolymerized portion, the polymerizable compound was easily extracted and eluted from the aqueous phase by treatment with an alkaline aqueous solution, and a very low D+win concentration could be achieved.

It has also been found that sufficient gradation can be obtained depending on the degree of curing (degree of polymerization).

As a result, we succeeded in forming a color image with good sharpness, good S/N ratio, and excellent fastness.

Therefore, even with this technology alone, new image forming materials and image forming materials using the same can be provided.

However, by finely dispersing the polymerizable compound in a water-soluble binder, multicolor or full color can be easily achieved. The three-color, three-layer structure of yellow, magenta, and cyan made it possible to form a good full-color image.

This new color image forming method can be used for the same purposes as general silver halide photography, and also takes advantage of advantages such as high resolution, high stability, and high hue, and it also has the advantages of "continuous gradation", which was considered a drawback of photopolymerization systems. Rather, it is a binary (on-off) responsiveness.
Taking advantage of this feature, we discovered the great utility of being able to easily (at low cost) create high-quality "color filters," which are difficult to manufacture using regular silver halide color photography. It was also successful.

The present invention will be explained in more detail below.

First, the dye image-forming substance in the present invention will be described in detail.The dye image-forming substance refers to a dye that is breformed (colored from the beginning) and must have at least the following properties.

a) In compositions in which a polymerizable material is dispersed in a water-soluble binder, the color image-forming material is lipophilic and is included in the polymerizable material.

b) It does not significantly inhibit the polymerization of the polymerizable compound in the exposed area.

C) During treatment with an alkaline aqueous solution, the color image-forming substance easily becomes hydrophilic and is extracted and eluted from the aqueous layer by the uncured polymerizable compound, but is not eluted from the cured portion.

The color image-forming substance may be an organic compound or an inorganic compound as long as it has the above-mentioned properties, and may be dissolved or solid-dispersed in a polymerizable substance.

However, inorganic compounds have a small degree of freedom in molecular design and are difficult to exhibit necessary performance and properties. Therefore, it is desirable that the color image forming substance used in the present invention be an organic compound.

There are no particular restrictions on organic dyes, including azo, azomethine, azopyrazolone, indoaniline, indophenol, anthraquinone, triarylmethane, alizarin, nitro, quinoline, indigo, phthalocyanine, and bisazo. chelate dyes, styryls, xanthines, thiazines, aminoketones, methines, naphthalimides, benzopyrans, quinoneimines, xanthines, stilbenes, triazoles, cyanines, pyridines, etc. Dyes and pigments can be used.

However, in order for the dye image-forming organic dye to have the above-mentioned properties and performance, it is preferably an organic dye that becomes water-soluble through reaction and/or dissociation during washing with an alkaline aqueous solution.

Specifically, an organic dye that has a dissociative group with a PKa of 11 or less in the form of its precursor structure (including a conjugate acid) and becomes water-soluble when at least one dissociative group is generated by washing with an alkaline aqueous solution. It is preferable that

The dissociative group is -Cooe -POx e SOs' 5Ot
Ne--3Ot” 'Ce Sow' Co-
-NHCOO” -08-5 etc. tot'L4
゜Thus, in the photopolymerizable composition before exposure, these dissociable groups may have the structure of a precursor with a protected conjugate acid structure, or in some cases may be in a dissociable form, but cannot be hydrated like a pigment. It has the property of being insoluble in.

During post-treatment after polymerization, a deprotection reaction and/or deprotonation (dissociation), etc. occur, and the water-solubilized dye is eluted by the dissociated group.

Any reaction (e.g., hydrolysis reaction, substitution reaction, elimination reaction,
(oxidation reaction, reduction reaction, etc.) may be used, but it is necessary to design a molecule that allows for both stability in storage conditions and reaction activity during processing.

For example, taking carboxylic acid as an example, the conjugate acid is 1000H, and the deprotection reaction with the M retaining group is T, W.
, ProtectiveGrou by Greene
ps in Organic 5ynthesis
(1981 by John Wiley & 5ons
Chapter 5 from page 152 of , 1nc)
on for the carboxyl group
It is possible to use the items listed therein. Therefore, after forming a polymerization image, a deprotection reaction other than an alkali is allowed to proceed, and then the conjugate acid of the decomposed M group generated by the alkali treatment can be dissociated and eluted into an aqueous solution.

Among the dissociative groups mentioned above, in order to satisfy the degree of freedom in molecular design and the performance required for dyes, -COO@-SO□N@-
□Ia is particularly preferred, and it is most preferred to introduce a carboxyl group (-COOH) into the color image-forming dye in order to satisfy easy wash-off suitability during processing with an alkaline aqueous solution.

Typical examples of color image-forming dyes used in the present invention are listed below, but the present invention is not limited thereto.

+ H CHg CHt 0CHt CHg 0CHsHxOH CH! CN Ht CHI CHg OH CH.

Cm H+1 CHI CHI B "OOH ~ Hqc-'ゝC-H9 5HIff xHs Next, the polymerizable compound used in the present invention will be described in detail.

Examples of the polymerizable compound that can be used in the present invention include addition polymerizable monomers, oligomers, and polymers thereof. As addition polymerizable hexamer, carbon-
Compounds having one or more carbon unsaturated bonds can be used.

Examples of these are acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamides, maleic anhydride, maleic esters, itaconic esters, and styrenes. , vinyl ethers, vinyl esters, N-vinyl heterocycles, and derivatives thereof.

These compounds are well known in the art, and while any are useful in the present invention, it is desirable that they have the appropriate hydrophobicity (a-oleaginousness) necessary for dispersion in a water-soluble binder.

Preferred examples of the polymerizable compound used in the present invention are shown below.

Acrylic acid, methacrylic acid, butyl acrylate, methoxyethyl acrylate, butyl methacrylate, acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-acryloylmorpholine, N
-acryloylpiperidine, glycidyl acrylate,
2-ethylhexyl acrylate, acrylic anilide, methacrylic anilide, styrene, vinyltoluene,
Chlorostyrene, methoxystyrene, chloromethylstyrene, 1-vinyl-2-methylimidazole, 1-vinyl-2-undecylimidacillin, 1-vinyl-2-undecylimidacillin, N-vinylpyrrolidone, N- Vinyl carbazole, vinyl benzyl ether, vinyl phenyl ether, etc.

In addition, in order to increase the S/N ratio of the obtained color image, it is desirable to use a crosslinking compound that has the effect of increasing the viscosity or degree of curing of the produced polymer compound. It is a so-called polyfunctional monomer that has a plurality of vinyl groups or vinylidene groups in it.

In the present invention, compounds having two or more vinyl groups are particularly advantageous, and it is possible to use them in combination as described above, or to use such compounds having a plurality of vinyl groups alone or in combination. desirable.

Examples of such compounds include methylene-bis-acrylamide, trimethylene-bis-acrylamide, hexamethylene-bis-acrylamide, N,N'-diacryloylpiperazine, m-phenylene-bis-acrylamide, P-phenylene-bis-acrylamide, - Acrylamide, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, bis(
4-acryloxypolyethoxyphenyl)propane, 1
, 5-bentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexane diol acrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, N-methylol acrylamide, diacetone Examples include acrylamide, triethylene glycol dimethacrylate, and the like.

In addition, the following polymerizable prepolymers, for example,
Polybasic acids such as those described in Publication No. 2-7361 (
For example, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, malonic acid, succinic acid, adipic acid, etc.) and polyhydric alcohols (such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, etc.)
Polyester acrylate (or oligoester acrylate), which is an oligomer produced by the reaction of acrylic acid with the hydroxyl residue of polyester produced by the condensation of
Examples include polyurethane acrylate and epoxy acrylate obtained by the reaction of an acrylic acid ester having a hydroxyl group with incyane 11, as described in Japanese Patent Publication No. 48-41708.

Next, the photopolymerization initiator used in the present invention will be explained in detail.

Various photoinitiators can be used in the present invention.

Photopolymerization initiators are broadly classified into two types, radical polymerization initiators and cationic polymerization initiators, depending on the mode of polymerization reaction. Which polymerization mode to use is selected depending on the purpose and use.

Naturally, the types of polymerizable compounds used in combination also differ. In the case of radical polymerization, various acrylates and methacrylates and unsaturated polyesters are used, and in the case of cationic polymerization, epoxy compounds and vinyl ethers are used.

Regarding radical photopolymerization initiators, see rc by Oster et al.
Chemical Review J Magazine, Volume 68 1
pages 25-151 (1968); Kosar
Author: LightSeusitive Systems
J+ pages 158-193 (John Wile
y & 5ons + 1965), etc., but it can be roughly divided into (11) direct cleavage type, (2) hydrogen abstraction type, and (3) two-component system depending on the radical generation mechanism. Direct cleavage type is α, β, T cleavage or N
orrish Type I, those that generate radicals through type II cleavage, such as benzoin ethers, benzyl ketals, α-hydroxyacetophenones,
Typical examples include trihaloacetophenones, α-aminoacetophenones, acylphosphine oxides, α-dicarbonyl compounds, α-acyloxime esters, and the like.

In the hydrogen abstraction type, the excited triplet state of aromatic ketones performs a hydrogen abstraction reaction from a hydrogen donor to generate radicals. Representative examples include hydrogen donors and Michler's ketones. Aromatic amines are the most common hydrogen donors, but alcohols, alkyl benzoates, etc. are also useful. Two-component systems use a combination of two types of compounds,
When one of them is excited, an interaction occurs, causing electron transfer and proton transfer, and as a result, radicals are generated. Peroxides as, Lofine R (bisimidazoles)
These combinations are well known. A major feature of these systems is that the sensitive wavelength range can be changed by selecting a sensitizing dye, and efficient radical generation is possible by electron transfer from the excited state of the dye.

In addition, the combination of a triphenyl alkyl borate and a cationic dye described in JP-A-62-150,242, or the combination of a pyrylium salt or diphenyliodonium salt and an anionic dye, can be used to combine a radical generator and a dye. A salt is formed between the two and an efficient initiator system can be realized.

Spun yarn is particularly useful in the present invention because by selecting the dye used, a highly sensitive panchromatic photopolymerization system having photosensitivity up to 740 nm can be obtained.

Also, N-phenylglycines, phenylthioacetic acids,
Phenoxyacetic acids and combinations of phenylacetic acids and electron-accepting dyes can also be efficient initiator systems. R,S for these.

Davtdsou et al., “Chem, Comwun.
+1502 pages (1971); R, S, D
avidsou et al., 'J.

Chem, Soc, (C)”, page 1682 (1971); J, L, R, Wi11iams″
+Polym,! ! ng, sci, + 23 volumes 1022
It is described in detail in Page (1983) and others.

Also useful are combinations of polyhalogen compounds and amines. Trichloromethyltriazines are the most common polyhalogen compounds, and are used in combination with various aromatic amines. Trichloromethyltriazines containing an aromatic amine structure in the molecule are also useful as highly sensitive photopolymerization systems. Regarding these, Yamama et al.
Circuit Technology, Volume 2, Page 50 (198
7) for detailed information.

Furthermore, a system in which a photoreducible dye is combined with a reducing agent or a hydrogen donor is also useful in the present invention in that it can be sensitized to the visible range. Common photoreducible dyes include azine dyes such as oxazine, thiazine, and phenoxazine; xanthine dyes such as rose bengal, eosin, erythrozine, and fluorescein; and acridine dyes such as acriflavine and acridine orange. , β as a reducing agent
-diketones, amines, sulfinic acids and their salts,
Ascorbic acid and the like are useful.

On the other hand, cationic photopolymerization initiators generate active species (specifically, strong acids) that induce cationic polymerization when exposed to light, and are extremely limited compared to radical polymerization initiators. The most common among them are aromatic diazonium salts,
These include aromatic iodonium salts and aromatic sulfonium salts, all of which are useful in the present invention. Regarding these, J.
V.

Cr1vrllo et al., “Ann, Rev. Mater.
A detailed description is given in Sci.

In addition, these photopolymerization initiators can be designed to be easily washed with water during processing by introducing an alkali-soluble group, or to be easily decomposed during post-processing so that there is no residual color.

The binder used in the present invention will be explained in detail.

The binders used in the present invention can be contained alone or in combination. A hydrophilic material can be used as the material.

The typical hydrophilic binder is a transparent or translucent hydrophilic binder, and gelatin is a typical example thereof, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose PJE forms such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, sodium alginate, starch derivatives, etc. Derivatives: polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid (or poly(meth)acrylic acid with glycidyl (meth)acrylate attached to an ester bond) polyacrylamide, polyvinyl Various synthetic hydrophilic polymeric substances such as single or copolymers of imidazole, polyvinylpyrazole, etc. can be used.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. Specific examples are U.S. Patent Nos. 2,614.928, 3,132.945, 3,186.846,
゜312.553, British Patent No. 861,414, same 1
, No. 033,189, No. 1.005,784, and Japanese Patent Publication No. 42-26845.

The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. can be used. Particularly preferred are graft polymers of gelatin with polymers that are to some extent compatible, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates, examples of which are described in U.S. Pat. No. 2,763,625. No. 2゜831.767,
No. 2,956,884, etc. 0 Typical synthetic hydrophilic polymer substances are, for example, West German patent application (OLS)
No. 2,312,708, U.S. Pat. No. 3,620.751, U.S. Pat.

In addition to the above-mentioned materials, the color image recording material of the present invention may contain many additives as required, and representative examples thereof will be described below.

Since the polymerization of polymeric materials is inhibited or suppressed by oxygen, autooxidizing agents may be effective.

Autooxidants are compounds that can absorb oxygen in a free radical chain process.

An example of an automatic curing agent that can be used is N,N-dialkylaniline described in JP-A-62-143044. Preferred examples of N,N-dialkylanilines are dialkylanilines substituted at one or more of the ortho-mimeta or para positions with the following groups: methyl, ethyl, isopropyl, t-
Butyl, 3゜4-tetramethylene, phenyl, trifluoromethyl, acetyl, ethoxycarbonyl, carbonyl, carboxylate, trimethylsilylmethyl, trimethylsilyl, triethylsilyl, trimethylgermanyl, triethylgermanyl, trimethylstannyl, triethylstannyl, n -butoxy, n-bentroxy, phenoxy, hydroxy, acetyloxy, methylthio,
Ethylthio, isopropylthio, thio (mercapto),
acetylthio, fluoro, chlor, bromo and iodo.

Representative examples of N,N-dialkylanilines useful in the present invention include 4-cyano-N,N-dimethylaniline, 4-acetyl-N,N-dimethylaniline, 4-bromo-N,N-
Dimethylaniline, ethyl 4-(N,N-dimethylamino)benzoate, 3-chloro-N, N-dimethylaniline, 4-chloro-NN-dimethylaniline, 3-ethoxy-NN-dimethylaniline, 4-fluoro-N .

N-dimethylaniline, 4-methyl-N,N-dialkylaniline, 4-ethoxy-N,N-dimethylaniline, N,N-dimethylaniline, N.

N-dimethylthioanisidine, 4-amino-N.

N-dimethylaniline, 3-hydroxy-N, N-
dimethylaniline, N, N, N'-tetramethyl-1,
4-Dianiline, 4-acetamido-N.

N-dimethylaniline and the like.

Suitable N,N-dialkylanilines are those substituted with an alkyl group in the ortho position, such as 2,6-diitupropyl-N,N-dimethylaniline, 26-dinithyl-N,N
-dimethylaniline, N.

Includes N,2,4.6-pentamethylaniline (RMA) and pt-butyl-N,N-dimethylaniline.

These compounds are known to work not only as an autoxidizer but also to improve the efficiency of polymerization initiation.

In addition, polymerization accelerators can be introduced that increase polymerization efficiency, shorten exposure time, and improve the S/N ratio by increasing the degree of curing, which is sometimes very important. ,
have meaning.

For example, chain transfer agents for radical polymerization are useful.

Examples include J., Brandrop, E., H.
, by Imsergut” Polymer Hand
book” (2nd edition) A.

WtIey-1interscientific, pub
selected from among the compounds described on pages 57 to 104 of I[-4 of ``bication''. Typical examples include mercapto compounds.

In addition, compounds for increasing efficiency in generating radicals that initiate radical polymerization can be appropriately used.

Conversely, a polymerization inhibitor can be used to enhance the storage stability of the image recording material until exposure.

For example, 1nh of 11-3 P53-56 of the above document
It is selected from among the compounds described as ibiLor.

The materials involved in these polymerizations include their polymerizable compounds,
It is preferable to use them as appropriate depending on the properties of materials such as polymerization initiators and color image forming substances and the design of the image recording material.

When the color image forming substance, photopolymerization initiator, etc. of the present invention are introduced into a polymerizable compound and emulsified and dispersed in a hydrophilic binder, an organic solvent is often used to assist the introduction.

For example, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol,
After dissolving in methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone acetone, toluene, ethylene dichloride dichloromethane, chloroform, N,N-dimethylformamidetetrohydrofuran, dimethyl sulfoxide, etc., homogenize with a polymerizable compound. and then dispersed in a hydrophilic colloid.

Examples of high boiling point a solvents include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricyclohexyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.) ), = citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesine Acid esters (e.g. tributyl trimesate) Carboxylic acids described in Japanese Patent Application No. 61-231500, JP-A-59-83154, JP-A-59-178451, JP-A-59
-178452, 59-178453, 59-
No. 178454, No. 59-178455, No. 59-1
Compounds described in No. 78457 can be used.

The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Furthermore, after dispersion, the low boiling point organic solvent can be removed by ultrafiltration or the like as required.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
A dispersion method using a polymer described in No. 3 can also be used. However, the addition of an auxiliary solvent greatly affects the properties of the oil droplets, especially the polymerization rate, degree of polymerization, degree of hardening, etc., so it must be used with caution.The particle size of the dispersed oil droplets can be freely controlled. For example, if high resolution is required, the particle size is made as small as possible without interfering with the resolution. Further, when preparing a dispersion such as mix durain or packet emulsion, a known method is used.

When dispersing a polymerizable compound in a hydrophilic colloid, it is necessary not only to control the dispersion, but also to use coating aids, antistatic agents,
Various surfactants can be used for various purposes such as improving slipperiness and preventing adhesion. For example, JP-A-59-157.
The surfactants listed on pages (37) to (38) of No. 636 can be used.

Furthermore, in order to promote the absorption of alkaline aqueous solutions during treatment,
When a super absorbent polymer is used in combination with a hydrophilic binder, it may be possible to adjust the viscosity of the coating liquid and improve the image quality by improving the water absorption capacity.

The color photosensitive material used in the present invention contains a color image-forming substance, and since the color image-forming substance is colored, an anti-irradiation or anti-halation substance or various dyes are added to the photosensitive element. Although it is not so necessary to contain it, in order to improve the sharpness of the image, Japanese Patent Publication No. 48-3692 and U.S. Pat.
．． It is possible to contain filter dyes, absorbent substances, etc., which are described in each Mei III, such as No. 253.921, No. 2,527,583, and No. 2.956,879. In addition, these dyes are preferably thermally decolorizable, such as those described in U.S. Pat. Nos. 3.769.019 and 3.
．． Dyes such as those described in US Pat. No. 745,009 and US Pat. No. 3,615,432 are preferred.

Even when the color image forming material is colored yellow, magenta, or cyan, it is necessary to prevent halation if it has an infrared RP layer, and an antihalation layer is provided using known dyes or pigments. Furthermore, it is advantageous to use an infrared absorber or carbon black to provide an antihalation layer to the infrared sensitive layer. The use of carbon black is particularly advantageous for preventing halation, and the base may be colored or a carbon black-containing layer may be provided separately. As for specific embodiments, those described in Japanese Patent Application No. 18963/1988 can be used.

In the method of the present invention, the material is treated with an alkaline aqueous solution as described below, but a base may be introduced into the material in the form of a precursor for the purpose of increasing the efficiency of this treatment or lowering the pH of the treatment solution.

The base precursors referred to here are those that release a base component upon heating or those that generate a base through a complex formation reaction, and the base component released may be an inorganic base or an organic base. Examples of preferred bases to be released include inorganic bases such as alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolates, metabolites. Acid salts; ammonium hydroxides; hydroxides of quaternary alkylammonium 5, hydroxides of other metals, etc.; polyamines, aromatic amines (N-alkyl substituted aromatic amines, N-hydroxylalkyl substituted aromatic amines and bis(p
-(dialkylamino)phenyl)methanes), heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines, and those with a pKa of 8 or more are particularly preferred.

Heating type base precursors include salts of organic acids and bases that decarboxylate and decompose when heated, intramolecular nucleophilic substitution reactions,
There are compounds that release amines by decomposition through reactions such as Rossen rearrangement, Beckmann rearrangement, etc., and some that release bases by causing some kind of reaction when heated. Preferred base precursors include the salts of notrichloroacetic acid described in British Patent No. 998,949, etc., the salts of α-sulfonylacetic acid described in U.S. Pat.
Salts of propiolic acids described in Sho 5s-ss, No. 700, 2-carboxycarboxamide derivatives described in U.S. Pat. salts with thermally decomposable acids (Japanese Patent Application No. 58-69.597), hydroxamic carbamates described in Japanese Patent Application No. 58-43.860 using Rossen rearrangement, and salts with thermally decomposable acids that produce nitriles by heating. Examples include aldoxime carbamates described in No. 58-31,614. Others, British Patent No. 998
．． No. 945, U.S. Patent No. 3,220°846, Japanese Patent Application Publication No. 50-22,625, British Patent No. 2,079,480
The base precursors described in No. 1, etc. are also useful.

These base precursors can be used alone or in combination.

In the present invention, a basic metal compound that is sparingly soluble in water and a metal ion constituting this basic metal compound contain a compound (hereinafter referred to as a complex-forming compound) that can undergo a complex-forming reaction using water as a medium, A base generation method can also be used in which the pH of the reaction system is raised by a reaction between these two compounds in the presence of water.

This base generation method, specific compounds, and specific dispersion method are detailed in US Pat. No. 474,044.

A preferred method is to introduce a water-resistant basic metal compound into the image forming material and supply water and a complex-forming substance from the processing solution.There are no particular restrictions on the hardening agent required when hardening a water-soluble binder. , known hardening agents such as aldehyde type (formaldehyde, glyoxal, geltaraldehyde, etc.), aziridine type (e.g. PB Report 19,
921, U.S. Patent No. 2,950,197, U.S. Patent No. 2,9
No. 64.404, No. 2,983,611, No. 3.
Specifications of No. 271,175, Japanese Patent Publication No. 46-40898
No. 50-91315)
, isoxazole series (e.g., U.S. Pat. No. 331,6
09), epoxy systems (for example, U.S. Patent No. 3,047,394, West German Patent No. 1,035,663, British Patent No. 1.833.5)
18, those described in Japanese Patent Publication No. 48-35495), vinyl sulfone examples (for example, 1,3.5
-) lyacryloyl-hexahydro-5-) riazine,
Bis(vinylsulfonyl)methyl ether, N, N'-
ethylene bis(vinylsulfonylacetamido)ethane,
NN′-trimethylene-bis(vinylsulfonylacetamide), etc. Also, for example, PB Report 19.920
, West German Patent No. 1,100,942, West German Patent No. 2,337,4
No. 12, No. 2,545,722, No. 2,635,51
No. 8, same 2. 742. No. 308, 2,749.2
No. 60, British Patent No. 1゜251.091, Patent Application No. 1973
-54236, U.S. Pat. No. 48-110996, U.S. Pat. , U.S. patent cylinder 3,640°720
2,938,892, US Pat. No. 4,043)
, No. 818, No. 4.061.499, Japanese Patent Publication No. 46-38715, Japanese Patent Application No. 15095-1983), triazine type (for example, 2,4
-dichloro-6-hydro, droxy-3-triazine, etc.
Also, for example, those described in the specifications of West German Patent No. 2,410,973, West German Patent No. 2.553.915, US Pat. -Methylol type (dimethylol urea, methylol dimethyl hydantoin, etc.), dioxane derivatives (2,
3,-dihydroxydioxane, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), dialdehyde starch, 1-chloro-6-hydroxytriazinylated gelatin, maleimides, acetylenes, methanesulfonic acid esters A hardening agent of the same type can be used.

Further, as a polymer hardening agent, for example, U.S. Patent No. 3.3
Polymers having aldehyde groups (e.g. copolymers of acrolein, etc.) described in No. 96.029, No. 3,36 of the same
No. 2.821, Research Disclosure 1733
3 (1978), polymers having epoxy groups as described in U.S. Pat. No. 3,623.878, Research Disclosure No. 16725 (1978), U.S. Patent No. 4.
No. 161,407, JP-A-54-65033, JP-A No. 56
Examples thereof include a polymer having an active vinyl group or a group that can be a precursor thereof, as described in Japanese Patent Application Laid-open No. 142524, and a polymer having an active ester group, as described in JP-A-56-66841.

The color image forming material of the present invention may contain an anti-fading agent in order to improve the light fastness of the dye image.The anti-fading agent may be, for example, a photographic antioxidant or an ultraviolet absorber. The materials used and metal complexes are effective.

These may be used alone or in combination of two or more (for example, an antioxidant and an ultraviolet absorber).

Antioxidants suitable for use in the present invention are, for example,
- Those described in detail on pages 207 to 294 of 3-205628 can be mentioned.

In addition, the color image forming materials of the present invention include oil droplets, polymer latex, organic fluoro compounds, matting agents, slipping agents, colloidal silica, antifoaming agents, antibacterial and antibacterial agents, antistatic agents, and fluorescent whitening agents. A water releasing agent, a thermal polymerization inhibitor, a thermal solvent, etc. can be used alone or in combination as appropriate.

Next, the binder in which the polymerizable compound is dispersed in the color image forming material used in the present invention is applied to the next support.

It is applied to flexible supports such as plastic films, paper, and cloth, which are commonly used in photographic materials, or to rigid supports such as glass, ceramics, and metals. Useful flexible supports include films made of semi-synthetic or synthetic polymers such as rulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and films related thereto. Alternatively, the paper may be coated or laminated with a resin material, or a baryta layer or an α-olefin polymer (for example, polyethylene, polypropylene, ethylene/butene copolymer). U.S. Patent 3,634.
Polyesters described in No. 089 and No. 3.725.070 are also preferably used. The support may be colored using dyes or pigments. For example, it may be black for the purpose of blocking light. It is desirable that the surface of these supports be primed to improve adhesion. The body surface may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the primer treatment.

The metal with a hydrophilic surface used in the present invention is suitably a metal such as aluminum (including aluminum alloys), zinc, iron, copper, etc., and these metals can be coated or coated on a plastic film. A vapor-deposited composite support may be formed or may itself be a support.

Among these supports, aluminum salt,
A composite sheet in which an aluminum sheet is bonded to a polyethylene tylphthalate film as described in Japanese Patent No. 18327 is preferred.

These supports are subjected to treatments such as surface treatment or formation of a hydrophilic layer, if necessary, in order to obtain a hydrophilic surface. Moreover, various known methods can be used for the hydrophilic treatment.

There are no particular restrictions on the support (although you can choose from materials other than those listed above, but there will be restrictions depending on the purpose of use of the color image, and an appropriate support will be selected).For example, when used as a color filter, stability , uniformity, dimensional stability, light transmittance, etc. To give a more specific example, for example, in the case of a color filter for a liquid crystal display, high heat (e.g. It is stable even when exposed to the effects of acids, organic solvents, etc. (heated to 300 degrees Celsius), and has certain conditions such as strength and light transmittance to withstand long-term use as a product even after forming a liquid crystal cell. Excellence is required.

Therefore, when used in liquid crystal displays, heat-resistant synthetic polymer films or glass are preferred.

In the case of synthetic polymer films, the usable range varies depending on the heating conditions for cell production, but in general, the synthetic polymers listed above for the support of photosensitive materials can be used.

Further, in some cases, after manufacturing the liquid crystal cell, a dye layer with a dye pattern formed thereon may be adhered to the front surface of the liquid crystal cell along with its support; in this case, heating is not required.

In the case of glass, any glass commonly used for forming liquid crystal cells can be used. In particular, it has a low coefficient of thermal expansion,
Glass with high smoothness is preferred.

Further, it is desirable that these glasses be pretreated in order to improve their adhesion with the coating dispersion liquid. There are various known pretreatments, and any of them can be used.

In addition, a transparent electrode layer (battered ITO) was applied to the support in advance.
etc.), or a transparent electrode may be applied to the support by sputtering or ion blasting after forming the color filter.

Furthermore, black stripes may be provided on the support in advance. There are various known ways to create black stripes, and any method may be used, such as chromium vapor deposition.By providing black stripes, a high-resolution color filter can be obtained even when the resolution of the transferred pixel image is low; Can produce black density.

As described above, it is desirable to select an appropriate support depending on the intended use of the formed color image.

When using glass as the support, roller coating is used.
Any method such as spin code, dip coating, curtain coating, etc. may be used, but it is necessary to select a coating method that provides a highly smooth coated surface and a uniform film.

Next, the relationship between the amounts of the main materials used in the color image recording material of the present invention, the dispersion method and coating method for preparing the material, and the aspects of the color image recording material will be described in detail.

The quantitative ratio of the main components can vary widely as it depends considerably on the mode of use, but when describing the polymerizable compound, photopolymerization initiator, color image forming substance, and binder, the polymerizable compound and binder weight ratio is 0
．． The range is about 1 to 10, more preferably 0.3 to 3. The amount of the photopolymerization initiator can vary widely depending on the absorption coefficient of the molecule, radical generation efficiency, influence of oxygen and other compounds, etc., but it is generally 0.05 to 10 mol% of the polymerizable compound, and it is sufficient to achieve the desired photosensitivity. etc., can be appropriately selected. Further, the photopolymerization initiator is normally used in a range of 0.1 to 40 g/cd, more preferably 0.1 to 40 g/cd. 2-2
0g/proof.

The range of color image-forming substances can vary widely depending on their absorption coefficient and molecular weight, but it is usually 0.1% to 50% by weight of the polymerizable compound, more preferably 1% to 20% by weight.

Also, preferably 0.05 g to 10 g/rd, 0.1
The zero-color image forming substance used in the range of g to 5 g/g is generally contained in a polymerizable compound and dispersed as fine particles in a water-soluble binder, but at this time, it is not necessarily dissolved in the polymerizable compound. It does not have to be in a solid state and may exist as a solid dispersion. However, in the case of solid dispersion, it is desirable to have fine dispersion in terms of concentration and elution efficiency during processing.Especially when using the created color image as a transparent image, it is desirable to have a fine dispersion that is sufficiently fine so as not to reduce the transmittance. Needs to be distributed. For the above reasons, it is preferable to use it in a dissolved state.

Furthermore, when the color image forming substance is dispersed in the water-soluble binder, it is preferable that the color image-forming substance is completely included in the polymerizable compound. D ring i due to elution
There is no need to worry about it becoming n, and it is not a problem.Dax can be ensured by increasing the amount of the color image forming substance to be distributed to the binder. In this respect as well, it can be said that the method of the present invention has a large degree of freedom in designing the color image forming substance.

Generally, a dispersion composition is prepared by directly dissolving or dispersing a color image forming material, a photopolymerization initiator, etc. in a polymerizable compound, or by dissolving or dispersing it using the above-mentioned auxiliary solvent, and then dissolving or dispersing it in a polymerizable compound. This can be carried out by mixing with a water-soluble binder solution in the presence of a dispersion aid such as a surfactant according to the conventional method for photographic emulsicone of -+a, and stirring using a suitable stirring device. The particle size of the dispersed particles can be controlled by the materials used, the amount ratio, stirring, etc.
Adapt, improve, and apply according to the purpose of use.

At the time of dispersion and in the image forming element, p) is generally 2 to 10, more preferably 3 to 8, although it cannot be determined unconditionally because it is closely related to the elution property of the color image forming substance, especially on the high pH side.
It is preferable to adjust it within the range of .

As described above, the method of applying the prepared dispersion is as follows:
Any application method may be used, such as roller coating, spin cord, dip coating, curtain coating, etc.

It is selected depending on the support, the form of the image forming material, and the purpose of use.

Next, aspects of the color image recording material will be explained.

The recording material of the present invention can take several forms with different arrangement of each component.For example, it can be freely designed and utilized from a simple monochrome single layer system to a full color multilayer system or a full color single layer system. Is possible.

Among these, a full-color system in which the usefulness of the present invention can be particularly demonstrated will be exemplified and explained. As a method for forming a full-color image, in order to obtain a wide range of colors in the chromaticity diagram using the subtractive method using the three primary colors of yellow, magenta, and cyan, the bright light material used in the present invention must contain at least three primary colors: yellow, magenta, and cyan. It is necessary to have a photopolymerization initiator (including an aggravating agent) that is sensitive to different spectral regions for each species.

A typical combination of at least three photosensitive photoinitiators that are sensitive to different spectral regions includes:
Blue sensitivity, combination of green sensitivity and red sensitivity, combination of green sensitivity, red sensitivity and infrared sensitivity, ultraviolet sensitivity, combination of blue sensitivity and green sensitivity, blue sensitivity, red sensitivity and infrared sensitivity combination, ultraviolet light sensitivity (1), ultraviolet light sensitivity (2)
) and ultraviolet light sensitivity (3), and combinations of ultraviolet light sensitivity (1), ultraviolet light sensitivity (2), and red sensitivity.

For example, when using a combination of a blue-sensitive polymerization initiator, a green-sensitive polymerization initiator, and a red-sensitive polymerization initiator, the blue-sensitive area contains a yellow image-forming substance and the green-sensitive area contains a magenta image-forming substance. The red-sensitive area may contain a cyan image-forming substance.

In this case, a mixture of a blue-sensitive polymerization initiator, a polymerizable compound, and a yellow image-forming substance, a mixture of a green-sensitive polymerization initiator, a polymerizable compound, and a magenta image-forming substance, and a mixture of a red-sensitive polymerization initiator, a polymerizable compound, and a cyan image-forming substance are used. It is desirable that mixtures of substances are separated from each other. As for the method of separation, each mixture is formed into a multilayer structure and placed on a support in two separate layers. Alternatively, each mixture may be made into packets or mixed gel layers and coated in the same layer.

Regarding the method of packetization, see Japanese Patent Application Laid-Open No. 58-40゜551.
There are detailed descriptions in the specification and can be used as a reference.

It is also effective to separate each combination element using microcapsules, and the burden of coating can be significantly reduced by layering. On the other hand, when the coating is divided into different layers, it is easy to separate each element. As a method, various layer arrangement orders known for ordinary color light-sensitive materials can be adopted, and each layer may be divided into two or more layers having different sensitivities, if necessary.

Alternatively, one type of color-sensitive polymerization initiator may be used, and two types of color image-forming substances may be used for each.

For example, a mixture of an ultraviolet-sensitive polymerization initiator, a polymerizable compound, and a yellow and magenta color image-forming substance, a mixture of a red-sensitive polymerization initiator, a polymerizable compound, and a yellow and cyan color image-forming substance, a green-sensitive polymerization initiator Various combinations such as a mixture of a polymerizable compound and a magenta and cyan color image forming substance are possible. Furthermore, it is also possible to use a three-color image-forming material of blue, green, and red.

Further, the number of colors may also be other than the above three colors, for example, black.

In addition to the photosensitive layers described above, the color image recording material used in the present invention may optionally include a smoothing layer, an oxygen barrier layer, an undercoat layer, and a protective layer. , intermediate layer, anti-halation layer, anti-static layer, anti-curl NC (mainly provided on the back surface)
, a release layer, a matting agent layer, and other auxiliary layers may be provided.

As an example, an antistatic layer can be applied to the back layer of a photosensitive material.
For the purpose of preventing static electricity, a cationic polymer or anionic polymer can be used. Preferably, a cationic polymer is used, specifically, 4
Polymers containing grade amine salts are effective. The polymer may be used dissolved in water or used as latex.

The above polymer may be added to the entire back layer, or 1
3! Alternatively, it may be added to two layers or only to the top layer.

Other antistatic agents include British Patent No. 1,466°600 and Research Disclosure.
Disclosure) No. 15840, No. 16258
No. 16630, U.S. Patent No. 2,327°828, U.S. Patent No. 2,861,056, U.S. Pat.
No. 3,775,126, No. 3.963.498, No. 4,025,342, No. 4,025,463, No. 4
, No. 025.691, No. 4,025,704, etc., and these can be preferably used.

Next, a color image recording method using the above-mentioned color image recording material will be described in detail.

First, exposure will be explained.

Various exposure means can be used in the present invention.

In general, commonly used light sources such as sunlight, strobes,
A flash, a tungsten lamp, a halogen lamp such as a mercury lamp, an iodine lamp, a xenon lamp, a laser lamp, a CRT light source, a plasma light source, a fluorescent tube, a light emitting diode, etc. can be used as the light source. Also, L
It is also possible to use an exposure means that combines a microshack array using CD (liquid crystal) or PLZT (lanthanum-doped lead titanium zirconate) with a linear light source or a planar light source. The type of light source and the amount of exposure can be selected depending on the wavelength to which silver halide is sensitive by dye sensitization and the sensitivity.

The original image used in the present invention may be a black and white image or a color image.

The original image may be a line image such as a drawing, or a photographic image with gradation. It is also possible to photograph portraits of people and landscapes using a camera. The printing from the original may be carried out by contact printing over the original, reflection printing, or enlarging printing.

It is also possible to output images taken by a video camera or the like or image information sent from a television station directly to a CRT or FOT, and then form this image on a poor light material using a close contact or a lens and print it. be.

Furthermore, LEDs (light emitting diodes), which have recently seen great progress, are being used as exposure means or display means in various devices. It is difficult to make an LED that effectively emits blue light, so in this case,
To reproduce color images, green light, red light,
Three types of photopolymerization initiators that emit infrared light may be used, and the photopolymerization initiators sensitive to these lights may be designed to contain yellow, magenta, and cyan image forming substances, respectively.

That is, the green-sensitive area may contain a yellow image-forming substance, the red-sensitive area may contain a magenta image-forming substance, and the infrared-sensitive area may contain a cyan image-forming substance. Other combinations may be used as required. It is possible.

In addition to the above-mentioned method of directly attaching or projecting the original image, so-called image processing involves reading the original image illuminated by a light source using a light-receiving element such as a phototube or CCD, storing it in the memory of a computer, etc., and processing this information as necessary. There is also a method of reproducing this image information on a CRT and using it as an image-like light source, or directly causing the three types of LEDs to emit light based on the processed information for exposure.

The color photosensitive material used in the present invention, especially in the case of a full color photosensitive material, is composed of oil droplets of a polymerizable compound containing a photopolymerization initiator that is sensitive to multiple spectral regions. It is necessary to imagewise expose the line. Therefore, the above-mentioned light sources may be used alone or in combination of two or more types.

For example, if we consider the case of creating a color filter using the color image forming method of the present invention, when selecting a light source, it goes without saying that one should choose a light source that is suitable for the photosensitive wavelength of the color photosensitive material. You can choose whether or not to go through it, taking into consideration the processing speed, compactness, power consumption, etc. of the entire process system.

If the image information does not go through electrical signals, that is, if the image information is exposed through a photomask necessary to form the desired color mosaic, a camera, exposure device for printing such as a printer or enlarger, or a copying machine is used. You can use the machine's exposure equipment, etc. In this case, the two-dimensional image can be simultaneously exposed in so-called 1 shots, or can be scanned and exposed through a slit or the like. It is also possible to stretch or reduce the photomask. Of course, it is common to expose the image in close contact with a photomask for the purpose of actual size. In this case, close contact has a large effect on the resolution of the generated color image9.For example, close contact using a vacuum is effective. Also, the light source at this time is not a monochromatic light source such as a laser (usually a light source such as a tungsten lamp is used).

When recording image information via electrical signals, a light emitting diode or various lasers may be used in combination as an exposure device depending on the color sensitivity of the color photosensitive material, or a known image display device may be used. Various devices (C
(RT, liquid crystal display, electroluminescent display, electrochromic display, plasma display, etc.) can also be used. In this case, the mosaic image information is an image signal obtained from a video camera or an electronic still camera, a television signal represented by the Nippon Television Signal Standard (NTSC), or a photomask that is further divided into many pixels using a scanner or the like. It is possible to use image signals obtained by using a magnetic tape, image signals stored on recording materials such as magnetic tapes, disks, etc.

When exposing a color mosaic pattern, a combination of LEDs, lasers, fluorescent tubes, etc. is used depending on the color sensitivity of the photosensitive material, but it is also possible to use a combination of multiple types of the same type, or a combination of different types. Good, the color sensitivity of photosensitive materials is R (red), G (green), and B (blue) in the photographic field.
Usually, they are photosensitive, but in recent years they are often used in combination with UV, IR, etc., and the range of use of light sources is expanding. For example, the color sensitivity of the color photosensitive material used in micro color filters may be (G, R, IR), (RIR (short wave), IR (long wave)) 1, (UV (short wave), UV (medium wave)). The spectral sensitivity range may be selected depending on the purpose, but the light source may also be L E. D2
Different types of light emitting tubes or elements, such as a combination of colors and lasers, may be combined.The above-mentioned arc tubes or elements may be used for scanning exposure using a single tube or element for each color, or an array may be used to speed up the exposure speed. Available arrays that may be used include LED arrays, liquid crystal shutter arrays, magneto-optic shutter arrays, and the like.

The image display devices described above include those with color display such as a CRT and those with monochrome display, but a method may be adopted in which a monochrome display is combined with a filter and exposed several times.

Existing two-dimensional image display devices may be used in a one-dimensional manner like FOT, or one screen may be divided into several parts and used in combination with scanning.

In the above case, when the light-sensitive material is depressurized and absorbed during pattern image exposure, it is effective to use a light-sensitive material having a smooth back surface as described in Japanese Patent Application No. 60-232188. In addition, in the case of exposure through a photomask, the photomask used must be designed to match the light source and photosensitive material used, taking into account its spectral absorption, size, precision (edge sharpness), uniformity, etc. No.

It goes without saying that the performance of the photomask greatly affects the performance of the product's color filter.

When exposed to light, the photopolymerization initiator functions and the curing of the polymerizable compound progresses. At this time, in order to accelerate the polymerization, the color image recording material is heated, or to remove the influence of oxygen. , under deoxidized conditions (e.g. in vacuum, nitrogen atmosphere,
It is sometimes very effective to carry out the process under an argon stream (eg under an argon stream) as it can have a great effect on the polymerization rate, degree of curing, gradation, S/N ratio, etc. It is also effective to simply stack transparent sheets (which have no adverse effect on the light during exposure) that have oxygen blocking ability and expose them to light.

In addition, since resolution is affected by light scattering, measures are taken to prevent irradiation and halation as necessary.

For example, it is effective to apply an antihalation layer (for example, carbon black) to prevent halation, to color the support, or to place it on a material that absorbs light during exposure (for example, black paper).

It is also effective to design a system in which the color image-forming substance functions as an irradiation-preventing dye.

Next, we will discuss the treatment method and the treatment liquid used therein.

The processing liquid used in the present invention is an alkaline aqueous solution,
Its composition is appropriately selected depending on the color image recording material.

Al and potassium are sufficient to adjust the pH of the treatment solution to 9 to 14, and as bases, alkali metal or alkaline earth metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, hydroxide, Lithium oxide), secondary or tertiary phosphates (e.g. potassium phosphate), borates, carbonates, quinolates, metaborates; ammonium hydroxides; hydroxides of quaternary alkylammoniums (e.g. (tetramethylammonium oxide) ; hydroxides of other metals, etc., and organic bases include aliphatic amines If (realkylamines, hydroxylamines, aliphatic polyamines); aromatic amines ( N-alkyl substituted aromatic amines, N-hydroxylalkyl substituted aromatic amines and bis(p-(dialkylamino)phenylcomecune M), heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines Examples include:

Salts of the above-mentioned organic bases and weak acids, such as carbonates, bicarbonates, borates, secondary and tertiary phosphates, quinolates, acetates, metaborates, etc., can also be used.

In addition to these, compounds described in JP-A-59-218443 can also be used. The base used is appropriately selected depending on the purpose.For example, in the case of a color filter,
Since the content of alkali metals poses a problem, it is desirable to use bases other than these. In this case, it can also be avoided by thoroughly washing with water after treatment with a base containing an alkali metal.

It may also contain a complex-forming compound of the complex-forming base precursor described above.

Specifically, aminocarboxylic acids, iminodiacetic acid and its derivatives, aniline carboxylic acids, pyridine carbon MR, aminophosphoric acids, carboxylic acids (mono, di, tri, tetracarboxylic acids, and also phosphono, hydroxy, oxo, ester, amide) , alkoxy, mercapto, alkylthio, phosphino, etc.), alkali metals such as hydroxamic acids, polyacrylates, polyphosphoric acids, guanidines, amidines, or salts such as quaternary ammonium salts.

The above base or base precursor may be dissolved in water to form a processing solution, but in addition to water, it may also be used to promote permeability into image recording materials and to elute color image forming substances from polymerizable compounds. Auxiliary agents, solvents, and additives may be mixed for the purpose of accelerating the treatment or improving the stability of the treatment liquid itself.

Further, the above-mentioned treatment liquid generally often uses water as its solvent, but this water is not limited to so-called "pure water", but includes water in the widely customary sense.

For example, thickeners are used to spread the processing solution uniformly and to make it easier for color image-forming substances to be eluted from the light-sensitive material. Examples of thickeners include polyvinyl alcohol, hydroxyethyl cellulose, and alkali metal salts of carboxymethyl cellulose. Hydroxyethylcellulose and sodium carboxymethylcellulose are preferably used.

Various surfactants are also effective as wettability improvers.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene glycols) Alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols,
Nonionic surfactants such as alkyl esters such as;
Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurate, sulfosuccinate, esphoalkyl Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as polyoxyethylene alkylphenyl ethers and polyoxyethylene alkyl eicosanoic acid esters; amino acids amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts,
Cationic surfactants such as heterocyclic quaternary ammonium salts such as pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. Fluorinated surfactants containing
Surfactants such as those disclosed in Japanese Patent Application No. 60-232625 are also effective. Further, an antifoaming agent may be added to suppress the generation of foam in the processing liquid.

Antifoaming agents include silicone oil (polymethylsiloxane), nonionic surfactants such as Span (product name of Atlas Co., Ltd., Powder Co., Ltd., USA), and Tsurupon (product name of Toho Kagaku Kogyo Co., Ltd.).
, Solgen (trade name of Dai-Kogyo Nohyaku Co., Ltd.), etc. can be used, but silicone oil is preferred as it is chemically stable and has excellent effects, and an antibacterial and anti-bacterial agent is added to prevent spoilage. It's okay.

The antibacterial and antibacterial agent used in the present invention may be any water-soluble agent, but specific examples include thiazolylbenzimidazole compounds, isothiazolone compounds, chlorophenol compounds, bromophenol compounds, and thiocyanic acid. and isothyanic acid compounds, acid azide compounds, diazine and triazine compounds, thiourea compounds, alkylguanidine compounds, quaternary ammonium salts,
Organic tin and organic zinc compounds, cyclohexylphenol compounds, imidazole and benzimidazole compounds, sulfamide compounds, chlorinated isocyanuric acid, active halogen compounds such as sodium, chelating agents, sulfite compounds, antibiotics such as penicillin, etc. There are various antibacterial and antifungal agents. And others, E,
West (L.

E, West) ,Water Quality Cr1t
eria”) Phot, Sci.

and Eng,, Vol 9m6 (1965)
Disinfectant described; JP-A-57-8542, JP-A No. 58-10
No. 5145, No. 59-126, 533, No. 55-11
Various antifungal agents described in No. 1.942 and No. 57-157244; antibacterial and antifungal agents described in "Chemistry of Antibacterial and Antifungal" by Hiroshi Horiguchi (Sankyo Publishing, 1980), etc. can be used.

Further, these antifoaming agents, antibacterial and antibacterial agents, etc. are also effective when added to the image recording material as described above. The solvent is not limited to water, but commonly used water-soluble alcohols (methanol, ethanol, isopropyl alcohol, benzyl alcohol, ethylene glycol, polyethylene glycol, methylcellosolve, etc.), ketones W4 (acetone, methyl ethyl ketone,
acetylacetone, etc.), esters (methyl acetate, ethyl acetate, butyl phosphate, etc.), amides [(N,N-dimethylformamide, N,N-dimethylacetamide, etc.),
Ureas (tetramethylurea, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), sulfoxide i
(dimethyl sulfoxide, sulfolane, etc.), acetonitrile nitrogen-containing compounds (pyridine, picoline, methylamine, etc.)
It may be a mixed system with many organic solvents added, such as, or a compound normally used to create a buffer solution may be added to maintain the buffering capacity at the pH of the alkaline processing solution. For example, carboxylic acids, boric acids, carbonic acid, phosphoric acid, etc. are added, but it is thought that the above-mentioned salts are formed in the processing liquid.

In addition, if the elution of the color image-forming material is accompanied by the generation of dissociative groups through hydrolysis, a promoter or nucleophile that promotes the hydrolysis reaction may be introduced. For example, 0R (R; alkyl group, aryol group, etc.)
, hydroxamic acid, anions such as 5Off'',
Examples include primary or secondary amines, hydrazines, hydroxylamines, thiols, organic selenium compounds, lithium ions, cyan ions, silyl compounds, and fluorine ions.

If the color image-forming product generates a dissociative group from the dissociative group precursor structure by some reaction other than hydrolysis and becomes soluble in the alkaline aqueous solution, it is a matter of course that a reagent involved in the reaction is added. It is necessary to do so. In this case, the additive used varies widely depending on the type of reaction and the reaction substrate, so it cannot be explained in a general way, but for example, when deprotection progresses due to a reduction reaction and a dissociating group is generated, the addition of a reducing agent is necessary. It becomes necessary. In this case, the reducing agent may be an inorganic compound or an organic compound, and may be hydrogenated by a catalyst or reduced by energization, and may be used in combination of two or more, or may itself be a reducing agent. It is also possible to use a precursor that does not have any properties but exhibits reducing properties by the action of heat or the like.

Examples of reducing agents include columns 49-50 of U.S. Pat. No. 4,500,626 and columns 30-3 of U.S. Pat. No. 4,483,914.
Column 1, No. 4,330,617, No. 4,590,152
No. (17) to (18) of JP-A-60-140335
) page, No. 57-40245, No. 56-138736, JP-A-60=128438, No. 60-128436
The reducing agents and reducing agent precursors described in European Patent No. 220,746A2, pages 78 to 96, etc. be.

Combinations of various reducing agents can also be used, such as those disclosed in US Pat. No. 3,039,869.

Furthermore, as will be discussed later in the post-processing section, effective antifading agents, ultraviolet absorbers, antioxidants, etc. may be added to improve the stability of the color image forming material. It is also possible to add compounds to improve the properties. The additives can also be added appropriately depending on the purpose.

When performing elution treatment of color image-forming substances from uncured polymerizable compounds using the processing liquids described above, the image recording material after polymerized image formation is usually immersed in the processing liquid, left to stand, stirred, or subjected to ultrasonic waves. The treated liquid is extracted into the aqueous phase through treatments such as these. At this time, the temperature of the treatment liquid is above the freezing point and below the boiling point of the treatment liquid, but is generally 5 to 40°C. However, in order to increase the efficiency of elution, high temperature treatment (40° C. or higher) may be used.

Although immersion in a treatment liquid is common, for example,
Roller coating method or wire bar coating method as described in JP-A-59-1813
A method of applying a processing liquid to a photographic material using a water-absorbing member as described in No. 54, JP-A-59-18134
As described in No. 8, a method of applying a processing liquid by forming a bead between a water-repellent roller and an image material, other methods include a dip method, an extrusion method, and a method of applying by jetting from pores. Various methods can also be used, such as a method of applying the material by crushing the bod.

Further, the processing liquid may be used alone or in combination of two or more types, and the elution process of the color image forming substance may be performed once or multiple times. In addition, a pretreatment step (for example, a swelling treatment to facilitate alkaline wash-off, a protection treatment to prevent damage caused by alkali, etc.) may be added.

Alternatively, for example, the color image-forming substance can be deprotected by pretreatment under acid conditions to form a conjugate acid with a dissociating group, and then dissociated with an alkaline processing solution to make it water-soluble and then washed off. Further, another treatment as described above may be performed between a plurality of alkaline wash-off treatments. There are no particular restrictions on these processes, and they can be appropriately selected depending on the purpose. Post-processing will be explained.

After the above-mentioned wash-off treatment with an alkaline aqueous solution is performed, cleaning is usually performed to remove unnecessary components (base, additives, etc.).

Of course, it is possible to use "ordinary water" as the cleaning solvent used here, but additives and other water-soluble organic solvents may be added to improve the cleaning effect and the performance of color images. Good too.

Examples of additives include those listed above for the processing liquid. Conversely, "pure water" is sometimes used for purposes such as reducing the ion content of color image recording materials. It is also effective to change the membrane pH by controlling the water washability and the pI of water.Furthermore, an organic solvent can be used as a cleaning solvent in order to remove unnecessary lipophilic components in the image recording material. The organic solvent may be used alone or in a mixture of two or more types, and water may be included in it.The temperature and method of the cleaning treatment are based on the elution treatment described above.In addition, various post-treatments have been formed. Appropriately selected depending on the purpose of use of the color image.

For example, it is also effective to improve film quality. For example, when gelatin is used as a binder, various commonly known methods for improving film quality can be used. Using a hardening agent to further harden the film and make it a strong film is effective in increasing the resistance of the dye and the resistance of the layer itself. As the hardening agent in this case, those mentioned above can be used. A dichromate gelatin hardening method can also be used.

In addition, stabilizers, ultraviolet absorbers,
It is also possible to introduce various additives into the material, such as anti-fading agents, antioxidants, anti-bacterial agents and the like. Further, in order to improve the stability of the uncured polymerizable compound in the recording material, curing treatment is also effective. The curing (polymerization) method may be performed by only front exposure if the photopolymerization initiator remains effectively, but it can also be carried out by introducing the polymerization initiator from the outside. In addition to photopolymerization, thermal polymerization by front heating is also effective. This heat can be used not only for post-processing, but also for promoting polymerization during exposure, or as a pre-treatment after exposure.

Furthermore, it is further protected on the color image recording layer or the protective layer thereon! ! Providing a layer can obtain a lot of hardening of the ring, improving durability as well as smoothness.

For example, in the case of a color filter, it is particularly effective in preventing the eluate from flowing out from the color image recording layer and in making the color filter smoother.

Of course, it is also effective for protecting color filters.
For example, when forming a liquid crystal cell, it is important to protect the color image recording layer because it is exposed to various harsh conditions such as heat, solvents, and acids.

As a method for protection, methods used in general color filter manufacturing methods such as a dyeing method and a pigment resist method can also be used.

The photosensitive recording material of the present invention and the color image forming method using the same will be specifically described below using Examples.

<Example 1> Color image forming substance D-1150iv, dichloromethane 5m
l, polymerizable compound R-12,5g, photopolymerization initiator P-1
80■ A homogeneous solution of P-280■ was kept at 45℃ 10
% gelatin aqueous solution with stirring, and further added 1 ml of a 2% aqueous solution of surfactant -1, and then emulsified and dispersed using a homogenizer (15,000 rps).

5 minutes, 40°C). Add 5% of a 2% aqueous solution of hardener H-1 to this.
．． 5g was added and stirred for 1 minute at 40°C to prepare a dispersion.

When the above dispersion was observed under a microscope, the oil droplet size was 1
The dye (D-1) was completely present in the oil droplets below μ.

The above dispersion was applied to a polyethylene terephthalate film (gelatin undercoat) to a wet film thickness of 60 μm.
Sample 78-1 was prepared by drying and hardening at 0° C. for 40 minutes and at 20° C. for 24 hours.

Sample S-1 was placed in vacuum contact with a chromium-deposited resolution mask, and then heated with a high-pressure mercury lamp (ozone-less, 120
After exposure for 1000 counts (approximately 4 minutes) at
0.1N-sodium hydroxide (3% methanol, 0.1
% Cr t Ht s・CM)! , ・SO3Na
After soaking in an aqueous solution containing water and cleaning with an ultrasonic cleaner for 5 minutes,
Washed with water and dried. The entire surface of this sample was exposed again using the above exposure conditions to harden the uncured areas. As shown in Table 1, the completed sample had a good S/N ratio between exposed and unexposed areas.

(Table 1) S-4 density is 1 to 2 μm for transmission density and resolution measured with a Macbeth densitometer, which is sufficient for application not only to general photographic image formation but also to color filters that require high resolution. It turned out that it can be used.

In addition, the polymerizable compound R-1 of sample S-1 was replaced with R-2, R
Sample S-2 replaced with -3, R-4, and R-5, respectively.
, S-3, S-4, and S-5 were prepared and subjected to similar exposure processing.

(CH2-CHCooCHz)-3ccz HsCH
xC) IzOCC-CHtl; CH3 As shown in Table 2, good discrimination was obtained between exposed and unexposed areas in samples using various polymerizable compounds.

(Table 2) Transmission density after wash-off CHiCHxOCCH-CHt Next, the color image forming substance D-1 of sample S-1 was converted to the compound 1.2,6°+1.26.
Samples S-6 to 5-16 were prepared by replacing 37,45,51,73.89 with Compound D-2 in which the dissociative carboxyl group of Compound 6 was an ester group, and the same exposure and
processed.

Table 3 Transmission density after wash-off Tab
As shown in le 3, it can be seen that good discrimination can be obtained between exposed and unexposed areas even in samples using various color image forming materials.

In addition, D-
It can be seen that in sample 5-16 using Sample No. 2, almost no dye elution was observed even in the unexposed area, and no S/N image was obtained.

<Example 2> A sample was prepared in the same manner as in Example 1 except that dye D-3 was used and aniline compound A-150 was added.

The completed sample was prepared as shown in 7able 4. The above sample was exposed to 2000 counts in the same manner as in Example 1 using Step Uni Fuji. First, the sample was thoroughly cleaned with Treatment/&A, treated with ultrasonic waves at room temperature for 3 minutes, further immersed in treatment solution B, treated with ultrasonic waves at room temperature for 3 minutes, washed with water, and then dried.

A positive image with ischemia was obtained.

For comparison, only the processing B step was performed without the processing liquid A step, and an image with almost no S/N was obtained.

This indicates that deprotection progresses through a reduction reaction at the stage of treatment A, and a dissociable group is formed.

(Table 4) <Example 3> (Preparation of dispersion I) D-4200■, ethyl acetate JLt 5 ml
, 3 g of polymerizable compound R-6', photoinitiator p-1
20mg, P-220tt, 3-tinoyl-7-ethylaminocoumarin 30■, pentamethylaniline 50
■, After adding a homogeneous solution of 20■ of 2.6-diitubropylaniline to 25 g of 10% gelatin aqueous solution at 45°C with stirring, add 4 mA of 1% aqueous solution of -1 to the surfactant and using a homogenizer. 13000rps, 5 minutes, 4
After dispersion at 0° C., 5 g of a 2% aqueous solution of a 3:1 mixture of hardeners H-1 and H-2 was added and stirred for 1 minute to prepare Dispersion I.

(Preparation of dispersion liquid ■) D-5200w, ethyl acetate 6ml, polymerizable compound 91R
-63g, photoinitiator P-330■, sensitizer S-11
A dispersion liquid (2) was prepared under the same conditions as above using a homogeneous solution of 0.0cm, S-210g, and 20g of pentamethylaniline.

/'-3O□/'VCONH-HEHA\NHCO□S cLα狽11 A test element was prepared by sequentially coating the above dispersions (1) and (II) on a polyethylene terephthalate support (ceratin undercoat), and further providing gelatin paste 31FJ (1.5 μm film thickness) thereon. .

First, a mask corresponding to the yellow image was attached to this sample under reduced pressure, and exposed using a high-pressure mercury lamp under a nitrogen atmosphere. Then, a mask corresponding to the magenta image was attached in the same manner, and white light was exposed through a yellow cut filter. exposed. The sample after two exposures was 0. It was immersed in an IN-sodium hydroxide aqueous solution and washed using ultrasonic waves for 3 minutes, then immersed in a 5% ammonia aqueous solution, washed for 2 minutes, and washed with running water for 2 minutes. The resulting image was a three-color image with a good S/N ratio of yellow, magenta corresponding to each mask, and red formed by both.

(Table 5) (Reflection density) <Example 4> The following [BL,
RL, GL and gelatin protective layer (1°0g/rrr)
were applied sequentially and the test elements were adjusted.

(1) BL (to 1.5/r/) a) Magenta image forming substance D-51,98gb) Cyan image forming substance D-61,32gd) e) Polymerization initiator (C 6 sensitizer H %) Koso C4 H.

0.

g 0, 6g 0, 6g 0, 3g C) Polymerizable compound 0g (CIIghO CO/Hepef) Pentamethylaniline 1.0gg
) 1% aqueous solution of surfactant K-1 3 Q m j
! h) 10% gelatin 300gi
) Hardeners H-1 and H-2 (3:1) mixture of 2
% aqueous solution (II) RL (to a) Yellow image forming substance D-4 b) Magenta image forming substance D-5 0) Polymerizable compound R-3 d) Polymerization initiator P-5 0ml 1.4 /rrD 1 .93g 1,38 g 0g 0,7g (ch Hs)t♀C6 e) Sensitizer 0,3g 0,3g C4H9C宕 H4 (C&Hri3 8C4He 0OH 0,8g e) Sensitizer S-1 f ) to i) are the same as the BL layer (III) GL (1.6 nr)a) Yellow image forming substance D-42,31gb) Cyan image forming substance D-61,0ggC) Polymerizable compound R-
330g d) Polymerization initiator p-60,5g f) to i) As with the BL layer, a negative original was brought into close contact with the sample under reduced pressure and exposed to white light.

After exposure, immerse in the next processing solution, treat with ultrasound for 5 minutes, then immerse in dilute salt M (IN-HCJ! aqueous solution) for 5 minutes, and after washing with water, immerse in 10% potassium hydroxide aqueous solution for 5 minutes. After washing thoroughly with water, it was dried. The completed sample gave a full-color positive image that corresponded to the negative original.

<Example 5> A test element in which the support was made of glass in the same way as the test element of Example 4 was created.

Using a tungsten bulb for this color photosensitive material, Y, M
, C and a colorless stripe mosaic filter (a photomask with each pixel of 100 μm x 150 μm and a stripe width of 40 μm) were vacuum-adhered and exposed at 5000 lux at 50° C. for 10 minutes. Place black paper on the back of the glass,
Prevented halation. This exposed photosensitive material is
After leaving at 0°C for 30 seconds, it was immersed in treatment solution A (0.5N sodium hydroxide aqueous solution), treatment solution B (IN-hydrochloric acid aqueous solution), and treatment solution C (2% aqueous ammonia) for 5 minutes (soaked for more than 2 minutes). When treated at room temperature for 1 minute with sonic waves and 2 minutes with ultrasonic waves, and then washed with running water for 10 minutes, a mosaic color filter of B, G, R, and black was obtained on the glass substrate. After that, the entire surface was exposed to light to complete the sample.

Each vixel had sufficient spectral absorption of B, G, and R as a color filter, and there were no particular unevenness or defects.

The results of measuring each concentration (transmission) of B, G, and R are shown in the following table.

The polymer particles forming this vixel had an average particle size of 0.6 μm, and the edge resolution of the vixel was satisfactory as a filter. Distance L of the transient part (from the vixel edge to the density 1/1 of the center)
The results expressed as distance to 0 are shown in the table below.

Next, this filter was washed with pure water at 25°C for 10 minutes, then dry-smoked and further preserved! Polymerizable compound R-3 on the membrane surface of the membrane
A strong protective film was formed as a cured film (thickness: 1.2 μm).

Next, the upper part of this color filter was coated with indium tin oxide (ITO) to serve as a common electrode.

The formation method used ion blating.

Next, the ITO layer was covered with a polyimide film, and after curing, a rubbing treatment was performed to obtain a liquid crystal alignment film.

On the other substrate constituting the liquid crystal cell, electrodes having a pattern similar to that of the color filter were formed by a well-known method, wired, and further covered with an alignment film.

The above two types of substrates were glued together, liquid crystal was injected, and a polarizing film was adhered to produce a liquid crystal cell.

The liquid crystal cell produced in this manner was sufficiently satisfactory in brightness and durability as a display, compared to a liquid crystal cell using a dyed color filter.

Preferred embodiment B of the present invention is listed below.

(υ) The color image recording method according to claim 1, wherein the color image forming substance is an organic dye that becomes water-soluble by reaction and/or dissociation during washing with an alkaline aqueous solution.

(2) The image-forming substance has a dissociative group with a pKall of 0 or less in the form of its precursor structure (including a conjugate acid), and becomes water-soluble through reaction and/or dissociation during alkaline aqueous cleaning treatment. The color image recording method of (11) above, characterized in that it is an organic dye.

(3) It has at least two combination elements of a polymerization initiator, a polymerizable compound, and a color image-forming substance, and the spectral sensitivity of the photopolymerization initiator and the spectral absorption of the color image-forming substance are different among the combination elements. A color image recording method according to claim 1, characterized in that:

(4) A photosensitive composition in which a dispersion of a polymerizable compound containing at least two or more types of photopolymerization initiators having different spectral sensitivities and a color image forming substance having different spectral absorptions is coated in multiple layers. (3) above characterized by using
color image recording method.

(5) The color image recording method according to (3) or (4) above, wherein the color image forming substance is comprised of cyan, magenta, yellow, or a combination of blue, green, and red.

(6) At least one of the photopolymerization initiators is 60Qn
(3) above, characterized by having a spectral sensitivity of m or more;
Or the color image recording method (4).

(7) A multicolor image made of two or more color image-forming substances is formed by exposing the photosensitive composition multiple times to light of two or more different wavelengths. The color image recording method according to (3) or (4) above.

(8) A full-color positive image is formed by exposing the photosensitive composition in one shot through a negative color original image, or (3) above, or (
4) Color image recording method.

(9) The method for producing a color filter according to (3) or (4) above, characterized in that a multicolor color mosaic is formed by exposing the photosensitive composition to light through a color mosaic mask.

Claims (1)

[Claims] (1) A composition containing at least a photopolymerization initiator, a color image forming substance, and a polymerizable compound is dispersed in a hydrophilic binder, and a photosensitive material coated on a support is exposed to light, and the exposed areas are By polymerizing the polymerizable compound, the color image-forming substance contained therein is immobilized, and then the color image-forming substance contained in the unpolymerized polymerizable compound in the unexposed area is eluted with an alkaline aqueous solution to form a dye image. A color image recording method characterized by forming a color image.