JP2670843B2 - Color image recording method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a color image recording method. More specifically, a simple novel color image recording method in which a polymerizable compound finely dispersed in a binder is polymerized imagewise with a photopolymerization initiator to fix a coexisting color image forming substance, and a wash-off treatment is performed with an alkaline aqueous solution. Regarding

(Prior Art) Since an image forming method using a photopolymerization reaction involves chemical amplification by a chain reaction, it belongs to the highest sensitivity class among non-silver salt photographic methods.

Also, because a large physical change called polymerization can be used,
It is needless to say that the photopolymerization recording system has many uses and various studies have been made.

Uses of this photopolymerization recording system are roughly classified into two. One is an application that utilizes the physical properties (strength, dissolution, transmittance, water repellency, etc.) of the polymer image itself, such as a relief, a resist, and a PS plate. The other is to visualize a polymer image as a medium and use it as a color image, and a color proof is mentioned as an example.

The former is a feature not found in silver halide photography, and therefore has a great advantage even at low sensitivity, and has already been used in various industrially important applications.

However, the latter is limited in its use because of its low sensitivity, and many methods of using silver halide as a sensor have been studied.

However, from a different point of view, a color image forming method using a photopolymerization system is lower in cost because it does not use silver as compared with silver halide photography, and is moreover a process for removing silver halide or silver. Has the great advantage that it is unnecessary.

A photopolymerizable color image recording material and a color image recording method utilizing the above merits have been studied.

Except for special cases (for example, when the monomer itself has a color-forming function like an N-vinylcarbazole-carbon tetrabromide photosensitive material), a visible image can be directly formed by photopolymerization using a general photopolymerizable compound. Is difficult to form,
This is one of the reasons why the photopolymerization system is difficult to be applied to general color image recording.

To make the image visible, whether the exposed part or the unexposed part is colored by a method such as selective dyeing with a dye solution or adhering face amount powder depending on the difference in permeability or adhesiveness. Alternatively, after the photosensitive layer is colored in advance and imagewise exposed to form an image-like polymerized image, the difference in solubility between the cured part and the uncured part or the difference in physical properties such as the difference in adhesiveness is used. Therefore, physical treatment such as wash-off or peeling of the uncured portion was required.

A method for producing a visible image by a chemical reaction inside a photosensitive material directly using a photopolymerizable composition, that is, without performing any operation such as coloring from the outside or spatial separation of an exposed portion and an unexposed portion. Some have been proposed. JP52-8991
No. 5 proposes a method of forming a positive-positive visible image by thermal development using a photopolymerizable composition and a thermosensitive color developing material. However, this requires that the two components of the two-component thermosensitive coloring material be arranged separately inside and outside or on both sides of the photopolymerizable composition.

Further, JP-A-57-179836, JP-A-57-197538 and JP-A-58-23
No. 024 and No. 58-23025 describe a method of forming a visible image by pressure using a photopolymerizable composition and a heat-sensitive (pressure-sensitive) color-forming material. However, each of these requires a pressure treatment to microencapsulate one component of the two-component type color-forming substance together with the photopolymerizable composition and to break the uncured capsule.

As described above, the method of forming a dye by reaction has disadvantages in that the leuco dye to be used has a high restriction in molecular design, and the generated dye has low stability. Further, as described above, the composition of the composition becomes complicated, and various restrictions are added. For example, it becomes difficult to form a color image of two or more colors. In addition, there are various drawbacks such as generally poor image sharpness due to diffusion and transfer.

Many other improvements and improvements have been made, but a simple, stable, and sharp photopolymerizable color image forming material requires further research.

Further, application as a full-color image recording material using two or more colors, preferably three or more colors, is difficult.

In general, for each color, the polymerizable layer is previously colored with a pigment or the like, and after polymerization, a method of eluting an unpolymerized portion with a solvent,
A method of separating a polymerized portion and an unpolymerized portion onto a different sheet by peeling development, or a method of adhering a colored powder by utilizing the adhesiveness of the unpolymerized portion, or after washing off the unpolymerized portion, the remaining polymerized portion is removed. Although dyeing methods and the like have been developed and put into practical use, these methods require complicated steps such as coating, drying, polymerization, and treatment for the required number of colors. In particular, the necessity of precise alignment is added, so that the yield of the final color image is low and the cost is extremely high.

In order to slightly reduce the series of steps for each color, for example, Japanese Patent Application Laid-Open No. Sho 59-30537 and the like prepare a cyan, magenta, and yellow color image sheet, expose the sheet to a three-color separation image, A full-color image is formed by transferring the image three times. However, even in this case, the steps of exposure and transfer are complicated, and the problem of alignment cannot be solved.

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

The full color image forming material includes a photosensitive layer containing three sets of microcapsules.

Each set of microcapsules has a visible spectrum (400 to 7
It has a distinct sensitivity in the selected wavelength band up to (00 nm) and combines it with a cyan, magenta or yellow image forming agent to form a color by pressure transfer to form a full-color image.

The expansion of the color sensitivity to the visible region is very important for the photopolymerizable image recording method, but the microcapsule-coloring system has the drawbacks such as the sharpness and the image stability as described above.

On the other hand, in U.S. Pat.No. 3,579,339, a photopolymerizable composition containing a color coupler of the type used in a silver halide color film is bound with gelatin or the like, which is coated on a support to form a photopolymerizable droplet. Containing substances. A method has been proposed in which, as a photosensitive layer, a permeation of a liquid color former into an unpolymerized oily portion after exposure is developed by a coupling reaction.

JP-A-60-120353 also discloses a recording material in which a heterogeneous dispersion of a polymerizable monomer in a binder and a dye bleached by the monomer are combined.

These methods can be applied in multiple layers, and have the advantage that a full-color image can be formed with one shot if each monomer oil drop has different sensitivity. Further, since physical destruction such as transfer and removal of the monomer layer is not involved, the treatment is easy and the sharpness can be secured.

However, as described above, the dye formed by the color-forming reaction and the monomer bleaching dye have a great problem in the stability of the finally remaining color image, and the freedom of designing a dye having a good hue necessary for the color image is required. There is a drawback that the degree is narrow, and it has not reached practical use.

As described above, the photopolymerizable color image forming method described above has an extremely wide range of applications, but among these, the need for a "color filter" whose need has increased in recent years The application is notable.

With the development of microelectronic technology in recent years, the demand for visual information transmission has increased, and various visual devices have been developed. Among them, color filters play an important role for full-color visual information.

In particular, CCD and BB have recently been used in small home-use TV cameras.
Solid-state imaging devices such as D and MOS have come to be used. This solid-state imaging device has a large number of finely divided light-receiving parts and a drive circuit for taking out information from the light-receiving parts. To obtain a color image, a color filter is provided above the solid-state imaging device. It is necessary to place it in.

On the other hand, development of a small, thin, lightweight color display, which replaces the conventional color cathode-ray tube, is also in progress.
Various types of color displays using liquid crystal, plasma, fluorescent display tubes, electroluminescence, etc. have been proposed.

Among them, the liquid crystal display has attracted the most attention because it can be driven at low voltage and low power and can be made thin, lightweight and has a long life. There are various types of color display for liquid crystal displays. For example, a guest-host method (GH method; a dichroic dye mixed with liquid crystal is used), an ECB method (Electrically Controlled Birefringre)
nce method. And a light shutter system (using a combination of a liquid crystal cell and a color filter). Among these, the optical shutter system is considered to be most practically used at present because it can support full-color display.

The optical shutter system controls the amount of transmitted light by a liquid crystal cell and combines with a color filter for full color display. This makes it possible to display an arbitrary color in the color triangle of the CIE chromaticity diagram using the additive method.

The color filters used for full colorization are often composed of blue, green, and red (B, G, R) three primary colors arranged regularly (in a mosaic pattern or in a stripe pattern). It consists of hues of colors or more. For example, in a micro color filter for a solid-state imaging device, a black stripe is used to complete color separation between multi-color patterns, and in a color filter for a liquid crystal display, color separation is completely completed, and an optical shutter is turned on / off. A black stripe may be used for the purpose of blocking the TFT formed in the gap between the three primary color filters to control the light emission and lowering the on-current.

At present, as a method for manufacturing a color filter, a dyeing method, a vapor deposition method, an electrodeposition method, an interference film method, a printing method, a photographic method and the like are known.

Of these, the staining 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 and the dye-receiving layer (mordant layer)
Is formed, and a color element (pixel) is formed by using a coloring material such as a pigment.

Specifically, as described in U.S. Pat. No. 3,289,208, a gelatin layer made photosensitive by adding potassium dichromate is coated on a support, and after pattern exposure, this is washed with warm water to give a relief. An image is formed, and then a red dye is dyed to the gelatin layer remaining as this relief image using a red dye solution, and an intermediate layer is coated on the dyed layer, and then the same operation as described above is performed. Dye the green dye with the green dye solution, apply the intermediate layer on it, perform the same operation as above, dye the blue dye with the blue dye solution, and finally apply the protective layer. It is to apply.

However, the dyeing method has a drawback that it requires complicated steps as described above, and that the color filter thus obtained has a complicated structure, and pinholes and scratches are likely to occur.

Various techniques have been proposed to improve this disadvantage. For example, U.S. Pat. No. 4,236,098 describes a method of absorbing a dye from a dye solution into a gelatin layer through a window-like pattern formed using photoresist technology. U.S. Pat. Nos. 4,081,277 and 4,168,448 describe a technique for transferring a heat sublimable dye or a heat transferable dye to a dye receiving layer through a window pattern formed of a photoresist.

However, even in these techniques, it is necessary to repeat steps such as photoresist coating, development, and peeling, and there is a drawback that the heat is high and the yield is low.

Furthermore, recently, using this photoresist method, in order to reduce the number of steps for coating the intermediate layer for dye-proofing and increase the resistance of the dye,
A method using a pigmented photoresist has been developed. However, even with this method, application, drying,
Exposure and cleaning steps are required, and the complicated and poor yield points have not been solved yet.

Each of the other color filter manufacturing methods also has its own problems. The dye vapor deposition method is a method of evaporating a dye to obtain pixels by a wrist-off method, and is a thin film. Although it can be formed directly on a transparent electrode, it has a drawback that adhesion to a base is weak. A color filter using an inorganic vapor-deposited multilayer interference film has good heat resistance, but it is difficult to control the thickness of the interference film, and there are problems in terms of cost and yield. The electrodeposition method is to form an electrode and electrodeposit a polymer on it to form a color filter, but it is difficult to arrange pixels freely.
It has the drawback that black stripes cannot be inserted. Compared with the above-mentioned photoresist method, the printing method can have a large screen and is easy to mass-produce, but the dimensional stability is poor, and satisfactory performance is obtained in terms of film uniformity and film surface smoothness. Not obtained. Various photographic methods have been studied,
In the conventional method, a coupler dispersed in a photosensitive silver halide emulsion film is treated with a color developing solution to form a non-diffusible dye, and then desilvering treatment is applied to form a color filter. However, the color filter thus prepared has a large film thickness and is insufficient in terms of quality such as sharpness and hue.

As described above, the color filter plays an important role in realizing full color visual information.However, the conventional color filter manufacturing method has a complicated manufacturing process, a low yield, and a color The quality of the filters was also unsatisfactory. In particular, there has been a strong demand for a method of manufacturing a large-screen color filter with high quality in a simple process.

(Object of the Invention) An object of the present invention is basically to provide a photosensitive polymerizable color image recording material having good performance by simple processing.

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

(Constitution of the Invention) The inventor of the present invention has made it possible to realize multicolor and full-color images without requiring multiple steps, and furthermore, to simplify the processing. A color image recording material having "good" and "high stability" and a color image recording method using the same were studied.

In other words, there is no physical destruction or transfer that deteriorates the sharpness, the degree of freedom in dye design is narrowed, and the stability of the produced dye is not good. The research was carried out for the purpose of developing a new material and a new color image recording method using it.

In particular, attention is paid to a large difference in the permeability of a substance between a photopolymerizable compound (monomer) and a polymer (polymer) generated by the polymerization. We examined the combination of preformed dyes that have a high degree of design freedom and can secure hue and stability.

Specifically, it is included in the polymerizable compound in the color photopolymerizable recording material, and the portion polymerized by exposure is fixed, whereas the unpolymerized portion becomes water-soluble by the treatment with an alkaline aqueous solution. Designing a stable, good hue preformed color image forming substance having a function of changing and easily eluting from a polymerizable compound, and further, a lipophilic polymerization including the color image forming substance and a photopolymerization initiator. By designing a color image recording material in which a water-soluble compound is finely dispersed in a water-soluble binder, and by the simple idea of the above two points, exposure-treatment with an alkaline aqueous solution is performed, a sharp and good color is obtained. , Succeeded in forming a color image with a stable dye image.

That is, the present invention is to disperse a composition containing at least a photopolymerization initiator, a color image-forming substance and a polymerizable compound in a hydrophilic binder, and subject a photosensitive material coated on a support to an exposure treatment to form an exposed portion. By immobilizing the color image-forming substance contained therein by polymerizing the polymerizable compound of
Then, the color image recording method is characterized in that the dye image is formed by eluting the color image forming substance contained in the unpolymerized polymerizable compound in the unexposed portion with an alkaline aqueous solution. For fixation and elution of color image-forming substances, which are important elements of image formation, see Photograhpic Science and Enginee.
The fact that the coloring system discriminantion (Dmax / Dmin) described in ring Vol. 13, No. 2, pp. 84-89 (1969) is not very good, and is pointed out in JP-A-60-120354.
There is a problem that "the polymer generated in the photopolymerization system is difficult to completely prevent the mass transfer, it is difficult to form a sufficient barrier, and the signal / noise (S / N) ratio is not easily increased." However, the above-described color image-forming substance is well designed in a molecule, and a combination with a polymerizable compound is selected, and the color image-forming substance is extracted from the polymerizable compound with an alkaline aqueous solution. It has been found that a good color image can be obtained.

In other words, in the cured part (Dmax part) of the polymerizable compound, there is almost no elution of the color image-forming substance in the alkaline aqueous solution treatment, and the high Dmax concentration is maintained, whereas in the unpolymerized part, the alkaline compound is easily treated by the alkaline aqueous solution treatment. It was possible to achieve a very low Dmin concentration by extracting and eluting it into the aqueous phase.

It was also 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, a new image forming material and an image forming material using the same can be provided by using only this technique.

However, by further finely dispersing the polymerizable compound in a water-soluble binder, multicoloring and full-coloring could be easily achieved. For example, it was possible to easily make multi-color by forming a multi-layer by combining with a spectrally polymerized photopolymerization initiator, and it was possible to form a good full-color image by the three-color / three-layer constitution of yellow, magenta and cyan.

This new color image forming method can be used for the same purposes as general silver salt photography, it also has the advantages of high resolution, high stability, high hue, etc. Rather, the "color filter", which is said to be difficult to manufacture in ordinary silver salt color photography, is produced with high quality and easily (low We have also succeeded in finding a huge utility that can be created (at cost).

 Hereinafter, the present invention will be described in more detail.

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

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

b) It does not significantly hinder the polymerization of the polymerizable compound in the exposed portion.

c) Upon treatment with an alkaline aqueous solution, the color image-forming substance easily becomes hydrophilic, and the aqueous layer is extracted and eluted from the uncured polymerizable compound, but is not eluted in the cured part.

The color image-forming substance having the above properties may be an organic compound or an inorganic compound, and may be dissolved in the polymerizable substance or may be solid-dispersed.

However, the degree of freedom in the molecular design of inorganic compounds is small, and it is difficult to achieve the required performance and properties. Therefore, the color image-forming substance used in the present invention is preferably an organic compound.

The organic dye is not particularly limited, and may be azo, azomethine, azopyrazolone, indoaniline, indophenol, anthraquinone, triarylmethane, alizarin, nitro, quinoline, indigo, phthalocyanine, bisazo. System, chelate dye system, styryl system, xanthene system, thiazine system,
Many dyes and pigments such as aminoketone, methine, naphthalimide, benzopyran, quinoneimine, xanthene, stilbene, triazole, cyanine, and pyridine can be used.

However, dye image forming organic dyes have the aforementioned properties,
In order to have performance, during the alkaline aqueous solution cleaning treatment,
An organic dye that becomes an aqueous solution by reaction or / and dissociation is preferable.

Specifically, it is an organic dye that has a dissociating group of PKall or less in the form of its precursor structure (including a conjugate acid), and becomes water-soluble when at least one dissociating group is generated by an alkaline aqueous solution washing treatment. Preferably there is.

 The dissociating group is -COO , -PO_Three , -SO_Three , -S0_TwoN −, −SO_Two , −
C , -SO_Two CO-, -NHCOO , -O , -S Etc.
I can do it.

Therefore, in the photopolymerizable composition before exposure, these dissociative groups have the structure of the conjugate acid of the protected precursor structure or, in some cases, the dissociated form, but water like a pigment. It is insoluble in water. Depending on the post-treatment after the polymerization, a deprotection reaction and / or deprotonation (dissociation) or the like occurs, and the dye that is made water-soluble by the dissociated dissociation group elutes.

In order to easily generate the above-mentioned dissociating group by deprotection, any reaction (eg, hydrolysis reaction, substitution reaction, elimination reaction, oxidation reaction, reduction reaction, etc.) may be used. It is necessary to design a molecule that is compatible with the reaction activity during processing.

For example, taking the carboxylic acid as an example, the conjugate acid is -COOH, and the protecting group and the deprotection reaction are TWGree.
ne Protective Groups in Organic Synthesis (1981
by John Wiley & Sons, Inc) Chapter 152 P. 152
It is possible to use those listed in rotection for the carboxyl group. Thus, after forming an image of polymerization, a deprotection reaction other than alkali is allowed to proceed, and then the conjugate acid of the dissociative group generated by the alkali treatment can be dissociated and eluted into an aqueous solution.

 Among the aforementioned dissociating groups, the degree of freedom in molecular design and the dye
-COO to satisfy required performance , -SO_TwoN −,
-O Is particularly preferable, and when treating with an alkaline aqueous solution.
Color image-forming dyes to meet easy wash-off suitability.
It is most preferable to introduce a carboxyl group (-COOH) into
No.

Hereinafter, typical specific examples of the color image forming dye used in the present invention will be listed, but the present invention is not limited thereto.

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 an addition-polymerizable monomer, an oligomer thereof, and a polymer. Examples of the addition-polymerizable monomer include 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, styrenes , Vinyl ethers, vinyl esters, N-vinyl heterocycles and derivatives thereof.

Although these compounds are well known in the art and are useful in the present invention, it is desirable that they have an appropriate hydrophobicity (lipophilicity) 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 acid anilide, methacrylic acid anilide, styrene, vinyltoluene, chlorostyrene, methoxystyrene, chloromethylstyrene, 1-vinyl-2-methylimidazole, 1-vinyl-2-undecylimidazole, 1-vinyl-2 -Undecyl imidazoline, N-vinyl pyrrolidone, N-vinyl carbazole, vinyl benzyl ether, vinyl phenyl ether and the like.

In order to increase the S / N ratio of the obtained color image, it is desirable to use a crosslinkable compound having an effect of increasing the viscosity or the degree of curing of the produced polymer compound. The spontaneous compound referred to here is a so-called polyfunctional monomer having a plurality of vinyl groups or vinylidene groups in the formula.

In the present invention, a compound having two or more vinyl groups is particularly convenient, and may be used in combination as described above, or may be used alone or in combination of a plurality of such compounds having a plurality of vinyl groups. Is desirable.

Examples of such compounds include methylene-bis-acrylamide, trimethylene-bis-acrylamide,
Hexamethylene-bis-acrylamide, N, N'-diacryloylpiperazine, m-phenylene-bis-acrylamide, P-phenyle-bis-acrylamide, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate , Screw (4
-Acryloxypolyethoxyphenyl) propane, 1,5
-Pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol acrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, N-methylol acrylamide, diacetone acrylamide, Triethylene glycol dimethacrylate etc. are mentioned.

In addition, the following polymerizable prepolymers, for example,
Polybasic acids as described in 52-7361 (for example, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, malonic acid, succinic acid, adipic acid, etc.)
And polyhydric alcohols (eg, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, etc.)
An oligomer formed by the reaction of a hydroxy residue of a polyester produced by condensation with acrylic acid and acrylic acid, that is, polyester acrylate (or oligoester acrylate), an acrylic resin having a hydroxy group as described in JP-B-48-41708. Polyurethane acrylate obtained by reaction of acid ester and isocyanates,
An epoxy acrylate etc. are mentioned.

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

Various photopolymerization initiators can be used in the present invention. Photopolymerization initiators are roughly classified into radical polymerization initiators and cationic polymerization initiators according to the type of polymerization reaction. Which polymerization mode is used depends on the purpose and application. Naturally, the type of the polymerizable compound used in combination also differs. In the case of radical polymerization, various acrylates and methacrylates and unsaturated polyesters,
In the case of cationic polymerization, epoxy compounds and vinyl ethers are used.

Oster et al. "Chemi
cal Review, Vol. 68, pp. 125-151 (1968); Ko
sar "Light Seusitive Systems", pp. 158-193 (J
Ohn Wiley & Sons (1965), etc. have detailed description, but due to radical generation mechanism (1) direct cleavage type,
It can be roughly classified into (2) hydrogen extraction type and (3) two-component system.
The direct cleavage type is α, β, γ cleavage or Norr by photoexcitation.
ish Type I and II type radicals are generated through cleavage, benzoin ethers, benzyl ketals, α-hydroxyacetophenones, trihaloacetophenones, α-aminoacenophenones, acylphosphines. Representative examples thereof include oxides, α-dicarbonyl compounds, α-acyl oxime esters and the like. The hydrogen abstraction type is a type in which the excited triplet state of aromatic ketones undergoes a hydrogen abstraction reaction from a hydrogen donor to generate radicals. A combination of aromatic ketones and amines, thioxanthones and hydrogen donors, anthraquinones Representative examples are hydrogen donors, Michler's ketones, and the like. As the hydrogen donor, aromatic amines are the most common, but alcohols, alkylbenzoates and the like are also useful. The two-component system uses two kinds of compounds in combination, and when one of them is excited, an interaction occurs to cause electron transfer or proton transfer, and as a result, a radical is generated, which is a xanthene-based compound, a thioxanthene-based compound, Sensitizing dyes such as coumarin type and ketocoumarin type, peroxides as radical generators, loffins (bisimidazoles)
The combination of etc. is well known. The major feature of these systems is that the photosensitive 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,
No. 62-150,242 describes a combination of a triphenylalkylborate and a cationic dye, a combination of a pyrylium salt or diphenyliodonium salt and an anionic dye, whereby a salt is formed between the radical generator and the dye. Formed,
An efficient initiator system can be realized. By selecting a dye to be used, a high-sensitivity panchromatic photopolymerization system having photosensitivity up to 740 nm can be obtained, and this system is particularly useful in the present invention.

In addition, N-phenylglycines, phenylthioacetic acids, phenoxyacetic acids, and combinations of phenylacetic acids and electron-accepting dyes can also be efficient initiator systems. These are described in RS Davidsou et al., "Chem. Commun"., 1502.
Page (1971); RSDavidsou et al., "J. Chem. Soc.
(C) ", Page 1682 (1971); JLR Williams", Poly
m. Eng. Sci., vol. 23, p. 1022 (1983) and the like.

A combination of a polyhalogen compound and an amine is also useful. As the polyhalogen compound, trichloromethyltriazines are the most common, and they are used in combination with various aromatic amines. Trichloromethyltriazines having an aromatic amine structure in the molecule are also useful as a highly sensitive photopolymerization system. About these, Yamaoka et al.
"Circuit Technology", Volume 2, Page 50 (1987)
There is detailed description in.

Further, a system in which a photoreducing dye and a reducing agent or a hydrogen donor are combined is also useful in the present invention because it can sensitize to the visible region. As the photo-reducing dye, oxazine-based dyes such as oxazine-based, thiazine-based, and phenoxazine-based dyes; xanthene-based dyes such as rose bengal, eosin, erythrosine, and fluorescein; As the reducing agent, β-diketones, amines, sulfinic acid and salts thereof, ascorbic acid and the like are useful.

On the other hand, a cationic photopolymerization initiator generates an active species (specifically, a strong acid) that induces cationic polymerization by light, and is extremely limited as compared with a radical polymerization system. Among them, the most common ones are aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts and the like, all of which are useful in the present invention. About these
JVCrivrllo et al., "Ann. Rev. Mater. Sci.," Volume 13, p. 173 (1983). In addition, these photopolymerization initiators can be designed to be easily washed with water at the time of treatment by introducing an alkali-soluble group or to be easily decomposed at the time of post-treatment so that there is no residual color.

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

The binder used in the present invention can be contained alone or in combination. As the binder, a hydrophilic binder can be used. A typical example of the hydrophilic binder is a transparent or translucent hydrophilic binder, and a typical example thereof is gelatin. However, 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 derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives: polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid (or poly (meth) acrylic acid ester-bonded with glycidyl (meth) acrylate.), Polyacrylamide, polyvinylimidazole, polyvinyl. A wide variety of synthetic hydrophilic polymeric substances such as single or copolymers such as pyrazole can be used.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds are added to gelatin. What is obtained by reacting is used. Specific examples are U.S. Pat.Nos. 2,614,928, 3,132,945, and 3,186,846.
No. 3,312,553; British Patent Nos. 861,414, 1,033,189
No. 1,005,784 and JP-B No. 42-26845.

As the gelatin-grafted polymer, a single (homo) or copolymer of a vinyl monomer such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile and styrene is grafted onto gelatin. Can be used. In particular,
A graft polymer of a polymer having some degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, and hydroxyalkyl methacrylate is preferred. Examples of these are described in U.S. Pat. Nos. 2,763,625, 2,831,767, and 2,956,884. Representative synthetic hydrophilic polymeric substances are described, for example, in West German Patent Application (OLS) 2,312,708, U.S. Pat.
751, No. 3,879,205, and Japanese Patent Publication No. 437561.

The color image recording material of the present invention may contain as many additives as necessary in addition to the above-mentioned materials. Representative examples will be described below.

Since the polymerization of the polymerization-based material is inhibited or suppressed by oxygen, an autoxidizing agent may be effective in some cases.

Autooxidants are compounds that can absorb oxygen during the free radical chain process.

Examples of useful automatic curing agents are described in JP-A-62-143044 and the like.
N, N-dialkylaniline. Preferred examples of N, N-dialkylaniline include those in the ortho, meta or para position.
The above are dialkylanilines substituted with the following groups: methyl, ethyl, isopropyl, t-butyl, 3,4
-Tetromethylene, phenyl, trifluoromethyl, acetyl, ethoxycarbonyl, carbonyl, carboxylate, trimethylsilylmethyl, trimethylsilyl,
Triethylsilyl, trimethylgermanyl, triethylgermanyl, trimethylstannyl, triethylstannyl, n-butoxy, n-pentyloxy, phenoxy, hydroxy, acetyloxy, methylthio, ethylthio,
Isopropylpyrthio, thio (mercapto), acetylthio, fluoro, chloro, bromo and iodo.

Representative examples of N, N-dialkylanilines useful in the present invention are 4-cyano-N, N-dimethylaniline, 4-acetyl-N, N-dimethylaniline, 4-bromo-N, N-dimethylaniline, 4 -(N, N-dimethylamino) ethyl benzoate, 3-chloro-N, N-dimethylaniline, 4-chloro-N, N-dimethylaniline, 3-ethoxy-N, N-dimethylaniline, 4-fluoro- N, N-dimethylaniline, 4-methyl-N, N-dimethylmethylaniline, 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
-Acetamide-N, N-dimethylaniline and the like.

Preferred N, N-dialkylanilines are those in which the ortho position is substituted with an alkyl group and 2,6-diisopropyl-
N, N-dimethylaniline, 2,6-diethyl-N, N-dimethylaniline, N, N, 2,4,6-pentamethylaniline (RMA)
And pt-butyl-N, N-dimethylaniline.

It is known that these compounds act not only as an autoxidant but also to increase the efficiency of the initiation of polymerization.

In addition, it is possible to increase the polymerization efficiency to shorten the exposure time, and to introduce a polymerization accelerator that works to improve the S / N ratio by improving the degree of curing, which is sometimes very important. Have.

For example, a chain transfer agent for radical polymerization is useful. An example is J. Brandrop, EHImmergut, “Polymer Han
d book "(2nd edition) A.Wiley-Intersciencl pubbic
ation II-4, P57-104. Mercapto compounds are typical examples.
In addition, a compound for improving the efficiency at the time of radical generation for starting radical polymerization can be appropriately used.

Conversely, a polymerization inhibitor for improving the storage stability of the image recording material until exposure can be used. For example, it is selected from the compounds described as the Inhibitor of II-3 P53 to 56 in the above-mentioned document.

These materials involved in the polymerization are preferably used as needed according to the nature of the materials such as the polymerizable compound, the polymerization initiator and the color image forming substance, and the design of the image recording material.

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

For example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone acetone, toluene, ethylene dichloride dichloromethane, chloroform, N, N -Dissolved in dimethylformamide tetrohydrofuran, dimethylsulfoxide, etc.,
It is homogenized with the polymerizable compound and then dispersed in a hydrophilic colloid.

As the high boiling point organic solvent, for example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphonate, triphenyl phosphonate, tricyclohexyl phosphonate, tricresyl phosphonate, tricresyl phosphonate, Dioctyl butyl phosphate), citric acid ester (eg tributyl acetyl citrate), benzoic acid ester (eg octyl benzoate), alkylamide (eg diethyl laurylamide), fatty acid esters (eg dibutoxyethyl succinate, dioctyl azetate) Rate), trimesic acid ester (eg, tributyl trimesate), carboxylic acids described in Japanese Patent Application No. 61-231500, JP-A-59-8315.
Nos. 4, 59-178451, 59-178452, 59-178453
No. 59-178454, No. 59-178455, No. 59-178457 and the like can be used.

The above-mentioned high-boiling organic solvent and low-boiling organic solvent may be mixed and used. Further, after the dispersion, if necessary, the low-boiling organic solvent may be removed by ultrafiltration or the like before use.

Further, a dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used. However,
The addition of the co-solvent greatly affects the properties of the oil droplets, particularly the polymerization rate, the degree of polymerization, the degree of curing, and the like. The particle size of the dispersed oil droplets can be freely controlled and selected according to the purpose. For example, when high resolution is required, the particle size is used as small as possible without affecting the resolution. A known method is used to prepare a dispersion of mixed grains, packet emulsion or the like.

When dispersing the polymerizable compound in the hydrophilic colloid, various surfactants may be used not only for controlling the dispersion but also for various purposes such as a coating aid, antistatic property, swell property improvement, and adhesion prevention. it can. For example, JP-A-59-1576
The surfactants listed on pages (37) to (38) of No. 36 can be used.

Further, when a superabsorbent polymer is used in combination with a hydrophilic binder in order to promote the absorption of an alkaline aqueous solution during processing, the viscosity of the coating solution may be adjusted and the image may be improved by improving the water absorbing ability.

The color light-sensitive material used in the present invention contains a color image-forming substance. Therefore, since the color image-forming substance is colored, an anti-irradiation or anti-halation substance or various dyes are further contained in the photosensitive element. Although it is not so necessary, in order to improve the sharpness of the image, Japanese Patent Publication No. 48-3692, U.S. Pat.
A filter dye, an absorptive substance or the like described in each specification such as No. 921, No. 2,527,583, No. 2,956,879 and the like can be contained. Further, as these dyes, those which are thermally decolorizable are preferable, for example, U.S. Patent No. 3,769,019.
And dyes described in JP-A Nos. 3,745,009 and 3,615,432 are preferred.

Even when the color image forming substance is colored yellow, magenta, and cyan, it is necessary to perform anti-halation when having an infrared-sensitive layer, and even if the anti-halation layer is provided using a known dye or pigment. Good. It is advantageous to use an infrared absorbing agent or carbon black to provide the antihalation layer on the infrared photosensitive layer. It is particularly advantageous to use a carbon black for preventing halation, and the base may be colored or a carbon black containing layer may be separately provided. As a specific embodiment, those described in Japanese Patent Application No. 61-18963 can be used.

In the method of the present invention, the material is treated with an alkaline aqueous solution after the post-treatment, but a base may be introduced into the material in the form of a precursor for the purpose of improving the efficiency of this treatment and lowering the pH of the treatment liquid.

The base precursor referred to here is one that releases a base component by heating or one that produces a base by a complex formation reaction, and the released base component may be an inorganic base or an organic base, and many are known. There is. Examples of preferred bases to be released include alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolinates, metaborates as inorganic bases. Ammonium hydroxide; quaternary alkylammonium hydroxide; hydroxides of other metals, etc., and organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic 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, cyclic guanidines, and particularly those having a pKa of 8 or more. Those are preferable.

The heating type base precursor is a salt of an organic acid and a base that is decarboxylated and decomposes by heating, a compound that decomposes by a reaction such as intramolecular nucleophilic substitution reaction, rotsene, rearrangement, and Beckmann rearrangement to release amines. , There is something that releases some base by causing some reaction by heating. Preferred base precursors include salts of trichloroacetic acid described in British Patent No. 998,949, salts of α-sulfonylacetic acid described in U.S. Pat.No. 4,060,420, salts of propiolic acids described in Japanese Patent Application No. 58-55,700, U.S. Pat. Patent No. 4,088,496, 2-carboxycarboxamide derivative, salt with a thermally decomposable acid using an alkali metal or alkaline earth metal in addition to an organic base as a base component (Japanese Patent Application No. 58-69,597); And the aldoxime carbamates described in Japanese Patent Application No. 58-31,614, which produce nitriles by heating, and the like. Others, British Patent No. 998,945,
Base precursors described in U.S. Pat. No. 3,220,846, JP-A-50-22,625, British Patent No. 2,079,480 and the like are also useful.

These base precursors can be used alone or in combination of several kinds.

In the present invention, with respect to the basic metal compound that is poorly soluble in water and the metal ion that constitutes this basic metal compound,
It is also possible to use a base generation method in which a compound capable of complex-forming reaction with water as a medium (hereinafter referred to as a complex-forming compound) is contained and the pH of the reaction system is increased by the reaction between these two compounds in the presence of water. .

This base generating method, specific compound, and specific dispersing method are described in detail in US Pat. No. 4,740,44.

A method in which a poorly water-soluble basic metal compound is introduced into the image-forming material and water and a complex-forming substance are supplied from the treatment liquid is preferable. There is no particular limitation on the hardener required for hardening the water-soluble binder, and known hardeners such as aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.) and aziridines (eg PB Report 19 , 9
21, U.S. Pat.Nos. 2,950,197, 2,964,404 and 2,
Nos. 983,611 and 3,271,175, JP-B-46-40
No. 898, those described in JP-A-50-91315), isoxazoles (for example, those described in U.S. Pat. No. 331,609), epoxys (for example, Also, for example, U.S. Pat.No. 3,047,394, West German Patent 1,03
5,663, UK Patent No. 1,033,518, JP-B-48
-35495), vinyl sulfone examples (for example, 1,3,5-triacryloyl-hexahydro-
s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-ethylene-bis (vinylsulfonylacetamide) ethane, N, N'-trimethylene-bis (vinylsulfonylacetamide), and the like, for example, PB Report 19,920, West German Patent Nos. 1,100,942, 2,337,412, and
2,545,722, 2,635,518, 2,742,308, 2,74
No. 9,260, UK Patent No. 1,251,091, Japanese Patent Application No. 45-54236
No. 48-110996, U.S. Patent Nos. 3,539,644 and 3,4.
90,911), acryloyl type (for example, Japanese Patent Application No. 48-27949, U.S. Pat.No. 3,640,720 described in each specification), carbodiimide type (e.g., U.S. Pat.No. 2,938,892). , No. 4,043,818, No. 4,061,
No. 499, Japanese Patent Publication No. 46-38715, Japanese Patent Application No. 49-
15095), triazines (eg, 2,4-dichloro-6-hydros-s-triazine, etc.), and, for example, West German Patents 2,410,973 and 2,553,915.
, U.S. Pat.No. 3,325,287, JP-A-52-127
No. 22), N-methylol type (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivative (2,3-dihydroxydioxane, etc.), mucohalogenic acid type (mucochloric acid, mucofenoxiclic acid, etc. ), Dialdehyde starch, 1-chloro-
A 6-hydroxytriazinylated gelatin, a maleimide type, an acetylene type, and a methanesulfonic acid ester type hardener can be used.

Further, as a polymer hardener, for example, U.S. Pat.
No. 6,029, polymers having an aldehyde group (for example, copolymers of acrolein and the like), No. 3,362,827,
Polymers having a dichlorotriazine group described in Research Disclosure No. 17333 (1978), polymers having an epoxy group described in US Pat. No. 3,623,878, Research Disclosure 16725 (1978),
U.S. Pat.Nos. 4,161,407, JP-A-54-65033, and JP-A-56-14
Polymers having an active vinyl group or a group which can be a precursor thereof as described in JP-A No. 2524, and JP-A-56-66.
Examples thereof include polymers having an active ester group described in Japanese Patent No. 841.

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. As the anti-fading agent, for example, an antioxidant for photography, an agent used as an ultraviolet absorber, and a metal complex 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 include, for example,
Mention may be made of those described in detail on pages 207 to 294 of 63-205628.

In addition, the color image-forming material of the present invention includes oil droplets, polymer latex, organic fluoro compounds, matting agents, sliding agents, colloidal silica, defoaming agents, antibacterial and antibacterial agents, antistatic agents, and fluorescence enhancers. Whitening agents, water-releasing agents, thermal polymerization inhibitors, thermal solvents and the like 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.

Plastic supports or glass, porcelain, etc., commonly used for photographic materials
It is applied to a rigid support such as metal. Useful as flexible supports are cellulose nitrate, cellulose acetate,
Cellulose acetate butyrate, polystyrene, polyvinyl chloride,
Films made of semi-synthetic or synthetic polymers such as polyethylene terephthalate and polycarbonate, and films or resin materials related thereto. Also, the baryta layer or the α-olefin polymer (for example, polyethylene,
Paper or the like coated or laminated with polypropylene, ethylene / butene copolymer) or the like. U.S. Patent 3,634,089
No. 3,725,070 are also preferably used. The support may be dyed or pigmented or colored. For example, it may be black for the purpose of shading. It is desirable that the surface of these supports be primed to improve adhesion. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoating treatment.

The metal having a hydrophilic surface used in the present invention is preferably a metal such as aluminum (including aluminum alloy), zinc, iron, copper, etc. These metals are laminated or vapor-deposited on paper or plastic film. The formed composite support may be formed, or may itself be the support.

Among these supports, aluminum salts, Japanese Patent Publication No. 48-
A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film described in JP 18327 is preferable.

These supports are subjected to a surface treatment or a treatment such as providing a hydrophilic layer, if necessary, to obtain a hydrophilic surface.
Various known substances can be used for the hydrophilic treatment.

The support is not particularly limited and may be selected from those other than those mentioned above, but an appropriate one is selected depending on the intended use of the color image. For example, when used as a color filter, performances such as stability, uniformity, dimensional stability, and light transmission are required. Further specific examples include, for example, in the case of a color filter for liquid crystal display, a manufacturing process of a liquid crystal cell. It is stable even under the influence of high heat (for example, heated to 150 to 300 ° C. at the time of forming the alignment film) or an acid or an organic solvent. It is required to have excellent conditions such as strength and light transmittance.

Therefore, when used in a liquid crystal display, a heat resistant synthetic polymer film or glass is preferable.

In the case of a synthetic polymer film, its usable range varies depending on the heating conditions for producing the cell. In general, the synthetic polymer mentioned for the support of the photosensitive material can be used.

In some cases, after the liquid crystal cell is manufactured, a dye layer on which a dye pattern is formed may be adhered to the front surface of the liquid crystal cell together with the support. In this case, heating is not required.

In the case of glass, any glass generally used for forming liquid crystal cells can be used. In particular, a glass having a low coefficient of thermal expansion and a good smoothness is preferable. Further, it is desirable that these glasses have been pre-treated in advance to improve the adhesion to the coating dispersion. Various pretreatments are known, and any of them can be used.

In addition, a transparent electrode layer (patterned ITO
Etc.) may be provided, or a transparent electrode may be provided on the support by sputtering or ion plating after the color filter is formed.

Further, a black stripe may be provided on the support in advance. There are various known methods for forming the black stripe, and any method such as installation by chromium vapor deposition may be used. By providing the black stripe, a high-resolution color filter can be obtained and a black density can be obtained even when the resolution of the transferred pixel image is low.

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

When glass is used for the support, the coating may be performed by any of roller coating, spin coating, deep coating, curtain coating, etc., but the smoothness of the coated surface is high,
It is necessary to select a coating method that can provide a uniform film.

Next, the relationship between the amount of the main material used in the color image recording material of the present invention, a dispersion method for preparing the material, a coating method,
Further, embodiments of the color image recording material will be described in detail.

Although the ratio of the main components is considerably dependent on the mode according to the purpose of use, a wide range is possible, but a polymerizable compound,
When describing the photopolymerization initiator, the color image forming substance, and the binder, the weight ratio of the polymerizable compound to the binder is
It is about 0.1 to 10, more preferably 0.3 to 3.
The amount of the photopolymerization initiator can vary greatly depending on the extinction coefficient of the molecule, radical generation efficiency, the influence of oxygen and other compounds, but is generally 0.05 to 10 mol% of the polymerizable compound, and depends on the desired photosensitivity and the like. It can be selected appropriately. The photopolymerization initiator is usually used in the range of 0.1 to 40 g / m ² , and more preferably 0.2 to 20 g / m ² .

The range of the color image-forming substance may vary widely depending on its extinction coefficient and molecular weight, but is usually 0.1% by weight to 50% by weight and more preferably 1% by weight to 20% by weight of the polymerizable compound.

Further, it is used in a range of 0.05 g to 10 g / m ^2, more preferably 0.1 g to 5 g / m ² . The color image-forming substance is generally contained in the polymerizable compound and is dispersed as fine particles in the water-soluble binder. At this time, the color image-forming substance does not necessarily need to be in a dissolved state in the polymerizable compound and exists as a solid dispersion. May be. However, in the case of solid dispersion, it is desirable that fine dispersion is performed from the viewpoint of obtaining the concentration and the elution efficiency during treatment. In particular, when using the created color image as a transparent image, it is necessary to finely disperse the color image sufficiently so as not to reduce the transparency. For the above reasons, use in a dissolved state is preferred.

The color image-forming substance is preferably completely contained in the polymerizable compound when the polymerizable compound is dispersed in the water-soluble binder. There is no concern that it will become Dmin due to the elution, so this is not a problem. Dmax can be secured by increasing the amount of the color image forming substance by the amount distributed to the binder. In this respect, it can be said that the method of the present invention has a high degree of freedom in designing a color image forming substance.

The dispersion composition is generally prepared by directly dissolving or dispersing a color image-forming material, a photopolymerization initiator, or the like in a polymerizable compound, or by dissolving or dispersing using the above-mentioned auxiliary solvent, and then the polymerizable compound. It 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 a conventional method for ordinary photographic emulsion and stirring with a suitable stirring device. . The particle size of the dispersed particles can be controlled by the material used, the ratio by volume, stirring, etc.
It is suitable for the purpose of use, and is improved and applied.

During dispersing, the pH in the image forming element is adjusted to a range of generally 2 to 10, more preferably 3 to 8, although it cannot be explicitly shown since the high pH side is closely related to the dissolution property of the color image forming substance. Is preferred.

As described above, the method for applying the prepared dispersion liquid may be any application method such as roller coating, spin coating, deep coating, or curtain coating.

The choice is made depending on the support, the mode of the image forming material, and the purpose of use.

 Next, an embodiment of the color image recording material will be described.

The recording material of the present invention can take several different modes such as the arrangement of each component. For example, it is possible to design and use freely from a simple mono-color single-layer system to a full-color multi-layer system or a full-color single-layer system.

Among these, the full-color system which can exert the usefulness of the present invention will be described as an example. As a method for forming a full-color image, in order to obtain a wide range of colors in a chromaticity diagram using the three primary colors of yellow, magenta, and cyan of the subtractive color method, the photosensitive material used in the present invention must have at least 3 It is necessary to have photoinitiators (think including sensitizers) that are sensitive to different spectral regions of the species.

Typical combinations of at least three photosensitive photopolymerization initiators having photosensitivity in mutually different spectral regions include a combination of blue-sensitive, green-sensitive and red-sensitive, a combination of green-sensitive, red-sensitive and infrared-sensitive. , A combination of ultraviolet light sensitivity, blue sensitivity and green sensitivity, a combination of blue sensitivity, red sensitivity and infrared light sensitivity, ultraviolet light sensitivity (1), ultraviolet light sensitivity (2) and ultraviolet light sensitivity (3 ), And the combination of UV photosensitivity (1), UV photosensitivity (2), and red sensitivity.

For example, when a combination of a blue-sensitive polymerization initiator, a green-sensitive polymerization initiator and a red-sensitive polymerization initiator is used, the blue-sensitive portion contains a yellow image-forming substance, the green-sensitive portion contains a magenta image-forming substance, and The photosensitive section may contain a cyan image forming substance.

In this case, a mixture of a blue-sensitive polymerization initiator and a polymerizable compound and a yellow image-forming substance, a mixture of a green-sensitive polymerization initiator and a polymerizable compound and a magenta image-forming substance, and a red-sensitive polymerization initiator and a polymerizable compound and a cyan image forming substance Desirably, the mixture of substances is separate. As a method of separating, there is a method of coating each mixture as a multi-layered structure in separate layers on a support, or a method of forming each mixture into a packet or mixed grain and coating them in the same layer.

The packetization method is described in detail in JP-A-58-40,551, which can be referred to.

It is also effective to separate each combination element with a microcapsule, and by further increasing the number of layers, the burden of application can be significantly reduced. Conversely, when the coating is performed in different layers, the components are easily separated. As a method, various layer arrangement orders known for ordinary color light-sensitive materials can be adopted, and if necessary, each layer may be divided into two or more layers having different sensitivities.

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

For example, a mixture of an ultraviolet light-sensitive polymerization initiator and a polymerizable compound and a color image-forming substance of yellow and magenta, a mixture of a red-sensitive polymerization initiator and a polymerizable compound and a mixture of a color image-forming substance of yellow and cyan, a green-sensitive polymerization initiator And polymerizable compounds and mixtures of magenta and cyan color image-forming substances. Further, three color image forming products of blue, green and red can also be used.

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

In the color image recording material used in the present invention, a smoothing layer, an oxygen blocking layer, if necessary, in addition to the photosensitive layer described above,
Undercoat layer, protective layer, intermediate layer, anti-halation layer, antistatic layer, anti-curl layer (mainly provided on the back surface),
An auxiliary layer such as a peeling layer or a matting agent layer can be provided.

As an example, the antistatic layer is a backing layer of a light-sensitive material, a cationic polymer or
An anionic polymer can be used. Preferably, a cationic polymer is used, and specifically, a polymer containing a quaternary amine salt is effective. The polymer may be dissolved in water and used, or may be used as a latex.

The polymer may be added to all layers of the back layer,
It may be added to one or two layers. It may be added only to the uppermost layer.

Other antistatic agents are British Patent No. 1,466,600, Research Disclosure 158
No. 40, No. 16258, No. 16630, U.S. Pat.No. 2,327,828
Nos. 2,861,056, 3,206,312, 3,245,833,
3,428,451, 3,775,126, 3,963,498, 4,0
No. 25,342, No. 4,025,463, No. 4,025,691, No. 4,025, 70
The compounds described in No. 4 and the like can be mentioned, and these can be preferably used.

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

 First, the exposure will be described.

In the present invention, various exposure means can be used.

Generally, commonly used light sources such as sunlight, strobes, flash lamps, tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser beams, and CRT light sources, plasma light sources, fluorescent tubes, light-emitting diodes, etc. are used as light sources. be able to. Also,
It is also possible to use an exposure means in which a micro-shutter array using an LCD (liquid crystal) or PLZT (lanthanum-doped lead zirconate titanate) and a linear or planar light source are combined. The type of light source and the amount of exposure can be selected according to the photosensitive wavelength and the sensitivity due to dye sensitization of silver halide.

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

As an original picture, let alone line images such as drafting,
A photographic image having a gradation may be used. It is also possible to photograph a person image or a landscape image using a camera. The printing from the original image may be performed by adhesion printing with the original image, by reflection printing, or by enlarging and printing.

In addition, it is also possible to directly print out the image captured by video color or the image information sent from the TV station to the CRT or FOT, form this image on the photosensitive material with contact or a lens, and print it. .

Recently, LEDs (light emitting diodes), which have made great progress, are being used as exposure means or display means in various devices. It is difficult to make this LED that emits blue light effectively. In this case, in order to reproduce a color image, three types of LEDs that emit green light, red light, and infrared light are used as LEDs, and the photopolymerization initiators sensitive to these lights are yellow, magenta, and cyan image forming substances, respectively. What is necessary is just to design so that it may contain.

That is, the green photosensitive portion may contain a yellow image forming material, the red photosensitive portion may contain a magenta image forming material, and the infrared photosensitive portion may contain a cyan image forming material. Other combinations are possible as required.

Other than the method of directly contacting or projecting the above original drawing,
The original image irradiated by the light source is read by a light receiving element such as a photoelectric tube or CCD and is stored in a memory such as a computer, and after this image information is processed to process this information as necessary, this image information is reproduced on a CRT, There is also a method of using this as an image-like light source or exposing three kinds of LEDs directly to emit light based on processed information.

The color light-sensitive material used in the present invention, particularly in the case of a full-color light-sensitive material, is composed of polymerizable compound oil droplets containing a photopolymerization initiator having photosensitivity in a plurality of spectral regions, so that a plurality of corresponding spectral It is necessary to image-expose with lines. Therefore, the above light sources may be used alone or in combination of two or more.

Considering, for example, the case of producing a color filter by the color image forming method of the present invention, when selecting a light source, it goes without saying that a light source suitable for the photosensitive wavelength of the color photosensitive material is selected, but the image information is an electrical signal. It can be selected in consideration of whether to pass through, the processing speed of the entire process system, compactness, power consumption, and the like.

When the image information does not pass through an electric signal, that is, when the exposure is performed through a photomask necessary for forming a target color mosaic, an exposure device for printing such as a camera, a printer or an enlarger, and a copying machine. Exposure apparatus or the like can be used. In this case, a two-dimensional image can be simultaneously exposed with a so-called one shot,
Scanning exposure can also be performed through a slit or the like. It can be stretched or shrunk with respect to the photo mask. Of course, it is common that the exposure is performed in close contact with the photomask for the purpose of actual size. In this case, the close contact greatly affects the resolution of the color image to be generated. For example, close contact using a vacuum is effective. At this time, a light source such as a tungsten lamp is usually used instead of a monochromatic light source such as a laser.

When image information is recorded via an electric signal, as an exposure device, a light emitting diode and various lasers may be used in combination according to the color sensitivity of a color photosensitive material, or known as an image display device. Various devices (CRT, liquid crystal display, electroluminescence display, electrochromic display, plasma display, etc.) can also be used. In this case, the mosaic image information is obtained by dividing 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 into a large number of pixels with a scanner or the like. Image signal,
Image signals stored in recording materials such as magnetic tapes and disks can be used.

When exposing the color mosaic pattern, LEDs, lasers, fluorescent tubes, etc. are used in combination according to the color sensitivity of the light-sensitive material, but the same thing may be used in combination or different kinds may be used in combination. Good. The color sensitivity of the photosensitive material is R (red), G (green), B (blue) in the field of photography.
Photosensitivity is normal, but in recent years it is often used in combination with UV, IR, etc., and the range of use of light sources is expanding. For example, when the color sensitivity of a color light-sensitive material used for a micro color filter is (G, R, IR), (R,
It may be in various spectral regions such as IR (short wave), IR (long wave)), (UV (short wave), UV (medium wave), UV (long wave)). Although the spectral sensitivity range is selected depending on the purpose, for example, short wave is advantageous in terms of resolution. The light source may be another type such as a combination of two colors of LED and laser. The light emitting tube or element may be scanned and exposed by using a single tube or element for each color, or an array tube may be used to increase the exposure speed. Examples of usable arrays include LED arrays, liquid crystal shutter arrays, and magneto-optical element shutter arrays.

As the image display device described above, there are a color display device and a monochrome display device such as a CRT, but it is also possible to employ a system in which a monokura display device is combined with a filter and exposed several times. The existing two-dimensional image display device may be used in a one-dimensional manner like FOT, or one screen may be divided into several screens and used in combination with scanning.

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

It goes without saying that the performance of the photomask has a great influence on the performance of the product color filter. The photopolymerization initiator functions by exposure, and the curing of the polymerizable compound proceeds.At this time, in order to promote the polymerization, to heat and heat the color image recording material, or to remove the influence of oxygen. Performing under deoxygenation (for example, in a vacuum, in a nitrogen atmosphere, under an argon stream, etc.) can greatly affect the polymerization rate, curing degree, gradation, S / N ratio, etc., and is sometimes very effective. It is also effective to simply stack transparent sheets (which do not adversely affect the light at the time of exposure) having oxygen blocking ability and expose them.

In addition, since the influence of light scattering affects the resolution, some measures should be taken to prevent irradiation and halo.

For example, it is effective to apply an anti-halation layer (for example, carn bomb 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 anti-irradiation dye.

 Next, a processing method and a processing liquid used therein.

The treatment liquid used in the present invention is an alcal aqueous solution, and its composition is appropriately selected depending on the color image recording material.

The alkali is sufficient to adjust the pH of the treatment solution to 9 to 14. As the base, a hydroxide of an alkali metal or an alkaline earth metal (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide) is used as an inorganic base. ), A secondary or tertiary phosphate (eg potassium phosphate), borate, carbonate, quinolinate, metaborate; ammonium hydroxide; quaternary alkylammonium hydroxide (eg tetrahydroxide). Methylammonium); hydroxides of other metals, and the like, and organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines); aromatic amines (N-alkyl-substituted) Aromatic amines, N-hydroxylalkyl-substituted aromatic amines and bis [p- (dialkylamino) phenyl] methanes), heterocycle Amines, amidines, cyclic amidines, guanidines, and cyclic guanidines.

Also, salts of the above organic bases and weak acids, for example, carbonates, bicarbonates, borates, second and third phosphates, quinophosphates, acetates, metaborates and the like can be used. Besides these, the compounds described in JP-A-59-218443 can be used. The base to be used is appropriately selected according to the purpose. For example, in the case of a color filter, the content of an alkali metal becomes a problem, so it is desirable to use a base other than this. However, in this case, it can be avoided by treating with a base containing an alkali metal and thoroughly washing with water.

It may also contain the complex-forming compound of the above-mentioned complex-forming chlorinated precursor.

Specifically, aminocarboxylic acids, iminodiacetic acid and its derivatives, anilinecarboxylic acids, pyridinecarboxylic acids, aminophosphoric acids, carboxylic acids (mono-, di-, tri-, tetracarboxylic acids and further phosphono, hydroxy, oxo, ester, amide, alkoxy) , Compounds having a substituent such as mercapto, alkylthio and phosphino), alkali metals such as hydroxamic acids, polyacrylates and polyphosphoric acids, and salts such as guanidines, amidines and quaternary ammonium salts.

In some cases, the above base or base precursor is dissolved in water to obtain a treatment liquid, and in addition to water, in order to promote the penetration into the image recording material or to elute the color image forming substance from the polymerizable compound. Auxiliary agents, solvents, and additives may be mixed for the purpose of promoting or improving the stability of the treatment liquid itself.

In general, the treatment liquid often uses water as a solvent, but this water is not limited to so-called “pure water”,
Includes water in a widely used and customary sense.

For example, a thickener is used for uniformly developing the processing liquid and for facilitating the elution of the color image forming substance from the photosensitive material. For example, polyvinyl alcohol, hydroxyethyl cellulose, alkali metal salts of carboxymethyl cellulose and the like are used, and preferably, hydroxyethyl cellulose and sodium carboxymethyl cellulose are used.

Various surfactants are effective as the wetting improver.

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Nonionic interfaces such as alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkyl phenol polyglyceride), fatty acid esters of polyhydric alcohols, etc., and alkyl esters Activator: alkyl carboxylate, alkyl sulfonate,
Alkylbenzene sulphonate, alkyl naphthalene sulphonate, alkyl sulphates, alkyl phosphates, N-acyl-N-alkyl taurines, sulphosuccinates, esfoalkyl polyoxyethylene alkyl phenyl ethers Anionic surfactants containing acidic groups such as carboxoxy groups such as polyoxyethylene alkyl eicosanoic acid esters, sulfo groups, phospho groups, sulfuric acid ester groups and phosphoric acid ester groups; amino acids, aminoalkyl sulfonic acids, Amphoteric surfactants such as aminoalkyl sulfuric acid or phosphoric acid esters, alkylbetaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium such as pyridinium and imidazolium salt And it can be used cationic surfactants such as phosphonium or sulphonium salts containing aliphatic or heterocyclic ring. Organic fluorine-containing surfactants, Japanese Patent Application Nos. 61-14826 and 61-24113,
Surfactants such as Japanese Patent Application No. Sho 60-232625 are also effective. An antifoaming agent may be added to suppress the generation of bubbles in the processing liquid.

As the defoaming agent, silicone oil (polymethylsiloxane), a nonionic activator such as Suban (US Atlas,
Powder Company's trade name), Sorbone (Toho Kagaku Kogyo Co., Ltd. trade name), Sorgen (Daiichi Kogyo Agricultural Co., Ltd. trade name), etc. can be used, but they are chemically stable and have excellent effects. Is preferably silicone oil. Further, a bactericidal / antibacterial agent may be added to prevent rot.

As the antibacterial and antifungal agent used in the present invention, any water-soluble agent may be used, and specifically, thiazolylbenzimidazole compounds, isothiazolone compounds, chlorophenol compounds, bromophenol compounds,
Thiocyanic acid and isothianoic acid compounds, acid azide compounds, diazine and triazine compounds, thiourea compounds, alkylguanidine compounds, quaternary ammonium salts,
Organotin and organozinc compounds, cyclohexylphenol compounds, imidazole and benzimidazole compounds, sulfamide compounds, chlorinated isocyanuric acid, active halogen compounds such as sodium, chelating agents, sulfite compounds, antibiotics typified by penicillin, etc. There are various antibacterial and antifungal agents. Also LEWest, Water Quality Criteria Phot.Sci.and En
Disinfectant described in g., Vol 9 No. 6 (1965); JP-A-57-8542
No. 58, No. 105-145145, No. 59-126,533, No. 55-111,942.
And various anti-fungal agents described in No. 57-157244; Hiroshi Horiguchi, "Antibacterial and antifungal chemistry" (Sankyo Publishing, 1982) and the like 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. In addition, the solvent is not limited to water, and commonly used water-soluble alcohols (methanol, ethanol, isopropyl alcohol, benzyl alcohol, ethylene glycol, polyethylene glycol, methyl cellosolve, etc.), ketones (acetone, Methyl ethyl ketone, acetylacetones), esters (methyl acetate, ethyl acetate, butyl phosphate, etc.), amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), ureas (tetramethylurea, etc.), ether Even in a mixed system containing many organic solvents such as compounds (tetrahydrofuran, 1,4-dioxane, etc.), sulfoxides (dimethyl sulfoxide, sulfolane, etc.), acetonitrile nitrogen-containing compounds (pyridine, picoline, methylamine, etc.) Good. Further, a compound usually used for preparing a buffer solution may be added so as to maintain the buffer capacity at the pH of the alkaline processing solution. For example, carboxylic acid, boric acid, carbonic acid, phosphoric acid and the like are added, and it is considered that the above-mentioned salt is formed in the treatment liquid.

 Elution of color image forming products is also dissociation due to hydrolysis
If it involves generation of a group, accelerates the hydrolysis reaction
Such accelerators and nucleophiles may be introduced. Nucleophilic
Examples of agents(R; alkyl group, aryl group, etc.), hydroxamic acid, SO
_Three ^Two Anions such as, primary or secondary amines, hydr
Radins, hydroxylamines, thiols, organic salts
Len compounds, lithium ions, cyan ions, silylation
Examples thereof include compound and fluorine ions.

Here, if the color image-forming product generates a dissociating group from the precursor structure of the dissociating group by some reaction other than hydrolysis and becomes soluble in an alkaline aqueous solution, it is natural that
It is necessary to add a reagent involved in the reaction. In this case, the additives are extremely diverse depending on the type of reaction and the reaction substrate, and therefore cannot be explained unconditionally.However, for example, when deprotection proceeds due to the reduction reaction and a dissociative group is generated,
It is necessary to add a reducing agent. In this case, the reducing agent may be an inorganic compound or an organic compound, may be hydrogenated by a catalyst, may be reduced by energization, or may be used in combination of two or more. In addition, a precursor which does not itself have a reducing property but exhibits a reducing property by the action of heat or the like can be used.

Examples of reducing agents include U.S. Pat.
Column 0, columns 4,483,914, columns 30-31, columns 4,330,617,
4,590,152, JP-A-60-140335 (17) to (18)
Pp. 57-40245, 56-138736, JP-A-60-12843.
No. 8, No. 60-128436, No. 60-128439, No. 60-128437
No. 62-131253 to 62-131256, European patents
There are reducing agents and reducing agent precursors described on pages 78 to 96 of No. 220,746A2.

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

Further, as will be discussed in the post-treatment described later, a discoloration inhibitor, an ultraviolet absorber, an antioxidant, and the like effective for improving the stability of the color image forming substance may be added. Further, a compound for improving the film quality may be added. The additives can be appropriately added according to the purpose.

When performing the elution treatment from the uncured polymerizable compound of the color image forming substance using the treatment liquid described above, usually, the image recording material after the formation of the polymerized image is immersed in the treatment liquid, left standing, stirred,
Extract into the aqueous phase of the treatment liquid by treatment such as ultrasonic waves. At this time, the temperature of the processing liquid is generally higher than the freezing point and lower than the boiling point of the processing liquid, but generally 5 to 40 ° C. However, high temperature treatment (40 ° C or higher) may be used to improve the elution efficiency.
Immersion in the treatment liquid is common, but for example, Japanese Patent Laid-Open No.
Roller coating method or wire bar coating method as described in JP-A-181353, JP-A-59-181354, a method for coating a processing liquid on a photographic material using a water-absorbing member, JP-A- As described in 59-181348, a method of forming a bead between a water repellent roller and an image material to apply a processing liquid, other methods such as a day method, an extrusion method, and jetting from a fine hole to eject. It is also possible to use various methods such as a method of applying, a method of crushing the pot, and the like.

The treatment liquid may be used alone or in combination of two or more kinds. The elution step of the color image forming substance may be performed once or plural times. Furthermore, before performing the elution treatment of the color image-forming substance with the alkaline treatment liquid, a pretreatment step (for example, a swelling treatment for facilitating the alkaline wash-off, a protective treatment for preventing alkali damage, etc.) is added. May be.

Alternatively, for example, the color image-forming substance may be deprotected by a pretreatment under an acid condition to form a conjugate acid of a dissociating group, and then dissociated with an alkaline treatment liquid to be water-soluble to be washed off. Further, another treatment as described above may be inserted between the alkaline wash-off treatments performed plural times. These processes are not particularly limited and can be appropriately selected depending on the purpose. The post processing will be described.

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

As the washing solvent used here, of course, “general water” can be used. However, even if an additive or other water-soluble organic solvent is added for the purpose of improving the washing effect or improving the performance of the color image, the like. Good.

Examples of the additives include those mentioned in the above-mentioned processing liquid.
Conversely, "pure water" may be used for the purpose of reducing the ion content of the color image recording material. It is also effective to change the membrane pH by controlling the washability and the pH of water. Further, an organic solvent can be used as a washing solvent in order to remove lipophilic unnecessary components in the image recording material.
The organic solvent may be used alone or as a mixture of two or more kinds, and may contain water. The temperature and method of the washing treatment are the same as those of the above-mentioned elution treatment. In addition, various post-processing is appropriately selected depending on the purpose of use of the formed color image.

For example, improvement of film quality is also effective. For example, when gelatin is used as a binder, various generally known film quality improving methods can be used. It is effective to further advance the hardening by using a hardening agent to form a strong film in order to increase the resistance of the dye and the resistance of the layer itself. As the hardener in this case, those described above can be used. A dichromated gelatin hardening method can also be used.

In addition, various additives such as stabilizers, ultraviolet absorbers, anti-fading agents, antioxidants, and antibacterial agents are used for the purpose of improving the resistance of color images and improving the stability of image recording materials. A process of introducing an object into a material can also be performed. In order to improve the stability of the uncured polymerizable compound in the recording material, a curing treatment is also effective. Curing (polymerization) method, if the photopolymerization initiator remains effectively,
Although only front exposure is required, it can be carried out by introducing a polymerization initiator from the outside. Further, not only photopolymerization but also thermal polymerization by heating the front surface is effective. The use of this heat can be used not only for post-processing but also during exposure to promote polymerization, or after exposure as a pre-treatment to promote polymerization.

Further, by providing a protective layer on the protective layer on the color image recording layer, it is possible to obtain many hardenings such as improvement in smoothness and durability. For example, in the case of a color filter, the effect of preventing the eluate from flowing out from the color image recording layer and further smoothing the color filter is great.

Of course, it is effective also for the purpose of protecting the color filter, and when it is formed into a liquid crystal cell, for example, it is important to protect the color image recording layer because it is subjected to various severe conditions such as heat, solvent and acid.

As a protecting method, a method used in a general color filter manufacturing method such as a dyeing method and a pigment-containing resist method can also be used.

Hereinafter, the photosensitive recording material of the present invention and a color image forming method using the same will be described in detail with reference to Examples.

<Example 1> Color image-forming substance D-1 150 mg, dichloromethane 5 ml,
Polymerizable compound R-1 2.5 g, photoinitiator P-1 80 mg
P-2 80 mg of a homogeneous solution was added to 26 g of 10% gelatin aqueous solution kept at 45 ° C with stirring, and the surfactant K-
After adding 1 ml of a 2% aqueous solution of No. 1, the mixture was emulsified and dispersed using a homogenizer (15000 rps, 5 minutes, 40 ° C.). 5.5 g of a 2% aqueous solution of the hardener H-1 was added thereto, and the mixture was stirred at 40 ° C. for 1 minute to prepare a dispersion liquid.

_{K-1 C 12 H 25 -C} 6 H 4 -SO 3 Na Observation of the above dispersion with a microscope revealed that the oil droplet size was 1 μm or less, and the dye (D-1) was completely present in the oil droplets.

The above dispersion was applied to a polyethylene rephthalate film (gelatin undercoat) with a wet film thickness of 60 μm, and the temperature was 50 ° C.
40 minutes, dried at 20 ° C. for 24 hours, and hardened to prepare sample S-1.

After bringing the sample S-1 into close contact with a chromium deposition resolution mask in vacuum, a high-pressure mercury lamp (ozone-less, 120 w
/ cm) after exposure to 1000 counts (about 4 minutes)
Sodium hydroxide (3% _{methanol, 0.1% C 12 H 25 ·} C
_After immersion in an aqueous solution (containing ₆ H ₄ · SO ₃ Na), washing with an ultrasonic cleaner for 5 minutes, washing with water, and drying. The entire surface of the sample was exposed again using the above exposure conditions, and the uncured portion was cured. As shown in Table 1, the finished sample showed good S / N in the exposed and unexposed areas.

The density was 1 to 2 μm in terms of transmission density or resolution measured by a Macbeth densitometer, and it was found that it can be used not only for general photographic image formation but also for application to a color filter or the like which requires resolution.

Further, the polymerizable compound R-1 of Sample S-1 was R-2,
Sample S- replaced with R-3, R-4 and R-5 respectively
2, S-3, S-4 and S-5 were prepared and the same exposure process was performed.

_{R-2 (CH 2 = CHCOOCH} 2 3 CC 2 H 5 As shown in Table 2, even in the samples using various polymerizable compounds, good discriminant was obtained in the exposed and unexposed areas.

Next, the color image forming substance D-1 of the sample S-1 was replaced with the compounds 1,2,6,11,26,37,45,51,7 shown in the specific compound examples above.
Samples S-6 to S-16 in which 3,89 and Compound D-2 in which the carboxyl group of Compound 6 was used as an ester group were replaced.
Was prepared, and similar exposure and processing were performed.

As shown in Table 3, it can be seen that even in samples using various color image-formed products, good discriminant can be obtained in the exposed and unexposed areas.

In addition, D does not form a dissociative group when treated with an alkaline aqueous solution.
In Sample S-16 using Sample-2, elution of the dye was hardly observed even in the unexposed portion, and it was found that no S / N image was obtained.

<Example 2> A sample was prepared in the same manner as in Example 1 except that 50 mg of aniline compound A-1 was further added using Dye D-3.

The above sample was exposed for 2000 counts in the same manner as in Example 1 using a step wedge. First, immerse in treatment liquid A,
After ultrasonic treatment for 3 minutes at room temperature, it was further immersed in treatment liquid B, subjected to ultrasonic treatment for 3 minutes at room temperature, washed with water and dried.

As shown in Table 4, the finished sample gave a positive image with discriminant. For comparison, when only the treatment B step was performed without passing through the treatment liquid A step, only an image having almost no S / N was obtained.

This indicates that the deprotection progressed by the reduction reaction at the stage of treatment A, and a dissociative group was formed.

<Example 3> (Preparation of dispersion liquid I) D-4 200 mg, ethyl acetate 5 ml, polymerizable compound R-6 3 g, photopolymerization initiator P-1 20 mg, P-2 20
mg, 3-teinoyl-7-diethylaminocoumarin 30m
g, pentamethylaniline 50 mg, 2,6-diisopropylaniline 20 mg homogeneous solution in 10% gelatin aqueous solution 25 g at 45 ° C.
Then, 4 ml of a 1% aqueous solution of surfactant K-1 was added thereto, and the mixture was added at 13000 rps, 5 using a homogenizer.
After dispersion under the conditions of 40 ° C. for 5 minutes, 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 II) D-5 200 mg, ethyl acetate 6 ml, polymerizable compound R-6
3g, photopolymerization initiator P-3 30mg, sensitizer S-1 10m
Using a uniform solution of g, S-2 (10 mg) and pentamethylaniline (20 mg), a dispersion liquid II was prepared under the same conditions as above.

The above dispersions (I) and (II) were sequentially coated on a polyethylene terephthalate support (gelatin subbing), and a gelatin protective layer (1.5 μm film thickness) was further provided thereon to prepare a test element.

A mask corresponding to the yellow image was first adhered to this sample under reduced pressure, and exposed under a nitrogen atmosphere using a high-pressure mercury lamp.After that, a mask corresponding to the magenta image was adhered in the same manner, and white light was passed through a yellow cut filter. Exposed. The sample which has been exposed twice is dipped in a 0.1N sodium hydroxide aqueous solution, washed with ultrasonic waves for 3 minutes, then dipped in a 5% ammonia aqueous solution, washed for 2 minutes and washed with running water for 2 minutes. did. The finished image was an image with good S / N ratio of yellow, magenta corresponding to each mask, and the red formed by both.

<Example 4> The following layer BL on a polyethylene terephthalate support,
RL, GL and a gelatin protective layer (1.0 g / m ² ) were sequentially applied to prepare test elements.

(I) BL layer (dispersion of the following compound: 1.5 g / m ² ) a) Magenta image forming substance D-5 1.98 g b) Cyan image forming substance D-6 1.32 g c) Polymerizable compound R-3 30 g d) Polymerization initiator R-4 0.8 g e) Sensitizer S-1 0.6 g S-2 0.6 g S-3 0.3 g f) Pentamethylaniline 1.0 g g) Surfactant 1% aqueous solution of K-1 30 ml h) 10% gelatin 300 g i) 2% aqueous solution of a mixture of hardeners H-1 and H-2 (3: 1). 50 ml (II) RL layer (dispersion of the following compound 1.4 g / m ² ) a) Yellow image forming substance D-4 1.93 g b) Magenta image forming substance D-5 1.38 g c) Polymerizable compound R-3 30 g d) Polymerization initiator P-5 0.7 g e) Sensitizer S-1 0.8 g f) to i) are the same as BL layer. (III) GL layer (dispersion of the following compound 1.6 g / m ² ) a) Yellow image forming substance D-4 2.31 g b) Cyan image forming substance D-6 1.00 g c) Polymerizable compound R-330 g d) Polymerization initiator P-6 0.5 g P-6 e) Sensitizer S-3 0.3 g S-4 0.3 g In f) to i), the negative original image was brought into close contact with the above-described sample under reduced pressure and exposed using white light, as in the BL layer.

After exposure, immersed in the next processing solution and treated with ultrasonic waves for 5 minutes, Next, it was immersed in dilute hydrochloric acid (1N-HCl aqueous solution) for 5 minutes, washed with water, then immersed again in a 10% aqueous potassium hydroxide solution for 5 minutes, washed sufficiently with water, and dried. The completed sample provided a full color positive image corresponding to the negative original.

<Example 5> A test element in which the support was made of glass in the test element of Example 4 was produced.

Using a tungsten light bulb for this color photosensitive material, Y, M,
C and a colorless stripe mosaic filter (a photo mask having a pixel width of 100 μm × 150 μm and a stripe width of 40 μm) were vacuum-deposited and exposed at 50 ° C. and 5000 lux for 10 minutes. Black paper was adhered to the back of the glass to prevent halation. After exposing this exposed light-sensitive material at 90 ° C. for 30 seconds, a treatment liquid A (0.5N-sodium hydroxide aqueous solution), a treatment liquid B (1N-hydrochloric acid aqueous solution), a treatment liquid C (2% aqueous ammonia) were sequentially added for 5 minutes ( Immersion, ultrasonic wave for 2 minutes, ultrasonic wave for 1 minute, ultrasonic wave for 2 minutes at room temperature, and then washing with running water for 10 minutes to obtain B, G, R and black mosaic color filters on the glass substrate. Was given. Thereafter, the entire surface was exposed to complete a sample.

Each pixel was B, G, and R with sufficient spectral absorption as a color filter, and there was no unevenness or defect.

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

The polymer particles forming this pixel had an average particle size of 0.6 μm, and the edge resolution of the pixel was satisfactory as a filter. The results are shown in the following table, expressed as the distance L of the transient part (the distance from the pixel edge to the point where the density becomes 1/10 of the central part).

Next, this filter was washed with pure water at 25 ° C. for 10 minutes and then dried, and a strong protective film of a cured film of the polymerizable compound R-3 (film thickness 1.2 μm) was formed on the film surface of the protective film. .

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

 The formation method used ion plating.

Next, the ITO layer was covered with a polyimide film, and rubbing treatment was performed after curing 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 known method, wiring was performed, and the electrodes were further covered with an alignment film. The two substrates were bonded together, a liquid crystal was injected, and a polarizing film was adhered to produce a liquid crystal cell.

The liquid crystal cell thus manufactured was sufficiently satisfactory in freshness and durability as a display, as compared with a liquid crystal cell using a color filter by a dyeing method.

 Hereinafter, preferred embodiments of the present invention will be listed.

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

(2) The image-forming substance has a dissociative group having a pKa of 11.0 or less in the form of its precursor structure (including a conjugate acid), and during the alkaline aqueous solution washing treatment, by reaction or / and dissociation,
The color image recording method according to (1) above, which is an organic dye which becomes water-soluble.

(3) It has at least two kinds of combination elements of a polymerization initiator, a polymerizable compound and a color image forming material, and the spectral sensitivity of the photopolymerization initiator and the spectral absorption of the color image forming material are different between the combination elements. The color image recording method according to claim 1.

(4) A photosensitive composition in which a dispersion of a polymerizable compound containing at least two or more photopolymerization initiators having different spectral sensitivities and a color image-forming substance having different spectral absorption is applied in layers (3) The color image recording method described above.

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

(6) At least one of the above photopolymerization initiators is 600 nm
The color image recording method as described in (3) or (4) above, which has spectral sensitivity.

(7) A multicolor color image composed of two or more types of color image-forming substances is formed by exposing the photosensitive composition described above a plurality of times with light having two or more different wavelengths. The color image recording method according to (3) or (4) above.

(8) The color image recording method according to (3) or (4) above, wherein a positive full-color image is formed by exposing the photosensitive composition through a negative color original image with a one shot.

(9) The method of (3) or (4) above, wherein the photosensitive composition is exposed through a color mosaic mask to form a multi-color mosaic.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 60-129707 (JP, A) JP 60-120353 (JP, A) JP 60-120354 (JP, A) JP 62- 78552 (JP, A)

Claims (1)

(57) [Claims] 1. A photosensitive material, comprising a composition containing at least a photopolymerization initiator, a color image forming substance, and a polymerizable compound dispersed in a hydrophilic binder, coated on a support, and subjected to exposure treatment. By immobilizing the color image-forming substance contained therein by polymerizing the part of the polymerizable compound, and then eluting the color image-forming substance contained in the unexposed part of the unpolymerized polymerizable compound with an alkaline aqueous solution, a dye A color image recording method comprising forming an image.