JPS60164741A - Image recording method - Google Patents

Abstract

PURPOSE:To form an image enhanced in gradation, reproducibility, and a signal/ noise ratio by allowing a vinyl monomer and/or a prepolymer in a photosensitive layer to be polymerized by imagewise exposing the photosensitive layer and heating it in contact with a developing layer or a barrier layer neighboring to the developing layer. CONSTITUTION:A photosensitive layer contains a polymerizable vinyl monomer and/or such a prepolymer, a photopolymerization initiator, and a color forming agent capable of producing a dye (bleachable with said monomer and/or prepolymer) by the action of a color developing agent, and a developing layer contains said a color developing agent. The photosensitive layer is imagewise exposed to polymerized said vinyl monomer and/or prepolymer. Then, the photosensitive layer is heated in contact with the developing layer or a barrier layer adjacent to the developing layer, and the dye developed with the developing agent is bleached with the nonpolymerized vinyl monomer and/or prepolymer remaining in the nonexposed or poorly exposed parts, and a dye image is formed on the exposed parts.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Application of the Invention) The present invention relates to a light and heat sensitive image recording method, particularly to a novel light and heat sensitive image recording method using a photopolymerization reaction.

(Prior Art) The light and heat sensitive image recording method involves developing an image by uniformly heating the image after exposure, and has the advantage that an image can be obtained only by dry processing.

On the other hand, many image recording methods using photopolymerized alloys are known, and are applied to photoresists, printing plates, etc.
Except for special cases (for example, when the 7-mer itself has a color-forming metal, such as in N-vinylcarbazole-carbon tetrabromide-based photosensitive materials), it is not possible to directly create a visible image by photopolymerization using a general 7-mer gold. It is difficult to form. To visualize the image, either the exposed or unexposed areas are selectively colored with a dye solution or pigment powder depending on the difference in permeability or tackiness, or the photosensitive layer is colored in advance.
After the image is cured by mist light, the liquid is
By physical development operations such as body development or peeling development,
It is necessary to spatially separate the exposed and unexposed areas.
Processing is complicated.

Several methods have been proposed for developing visible images in a dry process using photopolymerization and directly through chemical reactions.

Japanese Patent Application Laid-Open No. 2003-110002 describes a method of forming a visible image by heat development using a photopolymerizable composition and a heat-sensitive color forming material. This is because when the two components of a two-component heat-sensitive coloring material are placed separately inside and outside the photopolymerizable composition, or on both sides, when the material is exposed and heated, the heat-sensitive material does not move in the areas that are cured by exposure. Therefore, it does not develop color, but in unexposed areas it moves, reacts, and develops color to form an image, indicating a positive-positive recording response. Tokukai Akira again! 7-/7rirst, same! 7-7, 7z3r, etc., a method is described in which a material similar to the above is used and developed by pressure to form a visible image. This is because when one component of a two-component color-forming material is microencapsulated with a photopolymerizable composition and the other component is placed outside the capsule and the material is exposed to light and pressurized, the capsule hardened by exposure will not be destroyed. Although no color development occurs, the capsule wall is destroyed by pressure in the unexposed area, and an image is formed by color development, indicating a positive recording response.

These photothermosensitive and photosensitive pressure-sensitive image recording methods using photopolymerization are all based on the principle of image-wise control of the coloring reaction by the difference in substance diffusivity between the polymer and the monomer. However, the degree of curing due to photopolymerization, that is, the property as a barrier against diffusion of substances, is generally not proportional to the polymerization rate, and the polymerization rate is at a certain value (gel point) K.
When it reaches the desired level, it hardens rapidly and acts as a barrier, so that the image density is proportional to the exposure amount, resulting in poor gradation reproducibility. Furthermore, polymers produced by photopolymerization have the disadvantage of being susceptible to capri because it is generally difficult to completely prevent substance diffusion, and therefore having insufficient fixation against heat.

(Object of the Invention) The object of the present invention is to provide a light and heat sensitive image recording method suitable for forming images, particularly color images, with excellent gradation reproducibility and signal/noise ratio (S/N ratio) through dry processing. Our goal is to provide the following.

(Structure of the Invention) As a result of intensive research, the present inventor has developed a polymerizable vinyl monomer and/or a polymerizable BR-1 photopolymerization initiator, and a color developer that can be bleached by the vinyl monomer and/or prepolymer. By imagewise exposing the photosensitive layer using a photosensitive layer containing a color forming agent that can be produced by a color forming agent and a developing layer containing a color developer, the vinyl monomer and/or the vinyl monomer in the photosensitive layer is exposed.
or by polymerizing the prepolymer and then heating the photosensitive layer and the developing layer in a foreground, either adjacent to each other or in contact through a single barrier layer, to remove the dye gold produced by the developer, either unexposed or at an insufficient exposure to polymerize. The object of the present invention can be achieved by an image recording method characterized in that a dye image is formed in the exposed area by bleaching the dye with unpolymerized vinyl monomer and/or prepolymer remaining in the exposed area. did it.

In the image recording method according to the present invention, a polymerizable vinyl monomer or a polymerizable prepolymer (hereinafter simply referred to as monomer) bleaches a dye produced from a two-component heat-sensitive coloring material, and a seven-component polymer is polymerized to form a polymer. This method is based on the phenomenon that the ability to bleach the dye t-□ is lost, and is based on a completely different principle from conventional image recording methods. This resulted in the following important features: First, a visible image is formed simply by heating after image exposure, and fixing is also completed at the same time. Since the 7-mer remaining in the unexposed areas was used to bleach the dye, it no longer polymerizes even when exposed to light, so it no longer produces capri on the white background. In addition, since the white part is the part where the dye that has already developed color due to heating has been bleached, no color development occurs even if the material is heated further, and no capri occurs. That is, the image obtained by heat development is
It is light and heat stabilized, ie, fixed, and no additional processing for fixing is required. Secondly,
Good gradation reproducibility is achieved. This is Nanatsuma,
As a result, the amount of dye bleached is proportional to the amount of dye consumed by polymerization, and the image density is
That is, it is exactly proportional to the polymerization rate, whereas the polymerization rate is generally proportional to the exposure amount, so that the image density is proportional to the exposure amount. Third, an image with less capri and a high SZN ratio can be obtained. This means that if the ratio of monomers and color-forming materials contained in the recording material is set appropriately (for example, by using a slight excess of monomer), fogging can be completely eliminated without substantially reducing the maximum image density. Because it can be done.

In all these respects, the above-mentioned Japanese Patent Application Laid-open No. 1
This method is superior to a method of forming an image using a polymer as a barrier for material diffusion, such as described in US Pat. No. 9,913. Furthermore, as a fourth feature, it is possible to form a color image, as will be described in detail later.

The image recording method of the present invention includes a photopolymerizable composition and a two-component thermosensitive coloring material, as disclosed in the above-mentioned Japanese Patent Application Laid-open No.
Co-j? At first glance, it is similar to the material described in R/J et al. However, when the image recording material according to the method of the present invention is used, an image is formed according to the novel principle described above, and it can be clearly distinguished from the above-mentioned materials. This is clear from the fact that the obtained images show a positive-positive recording response with the above-mentioned materials, whereas they show a negative-positive response with the recording material produced by the method of the present invention. .

The image recording material produced by the image recording method of the present invention can take several different forms, such as how each component is arranged, so it will be described in terms of dimensions using drawings.

FIG. 1(A) shows a photopolymerizable composition (seven polymer and photopolymerization initiator), a coloring agent, and generally 1. Furthermore, a photosensitive (and color forming) layer 3 containing a pigment is provided on the support j)/, and a developing layer V containing a color developer and generally also a binder is provided on the support 1/. 6 shows an image-recording material consisting of a set of two sheets of developed GITCO. Figure 1 CB) shows the state of the photosensitive sheet 1 after 9 days of image exposure, with 7 marks in the exposed area.

It polymerizes and becomes Polymer B. Note that exposure may be performed from the photosensitive layer side, contrary to the illustration. Alternatively, the developing sheet may be in close contact with the photosensitive sheet.

Figure 1 1) shows the exposed photosensitive sheet and developing sheet? f
- Shows the state after heat development in close contact. The color developer in the developing sheet is diffused into the photosensitive layer by heating and reacts with the color forming agent to develop color, but in unexposed areas, the dye formed by the remaining monomer is further bleached. As a result, a dye image 7 is formed in the exposed portion.

FIG. 2(A) shows an integrated image recording material in which a photosensitive layer t and a development layer similar to those described above are laminated on the same surface of a support IO. Note that the order of stacking may be reversed.

FIG. 2(B) shows the state after image exposure, and polymer // has been generated in the exposed area.

FIG. 2(C) further shows the state after heat development,
As in the case of FIG. 7, a dye image lλ is formed within the photosensitive layer.

In the image recording materials shown above, the monomer -? - may be uniformly dispersed (molecularly dispersed) in the photosensitive layer, or may be non-uniformly dispersed as particles such as emulsions or microcapsules. In particular, in the present invention, a non-uniformly dispersed state is preferable because of the polymerization inhibiting effect of oxygen in the air, and a homogeneously dispersed state is also preferable because the photosensitivity is also high. In the case of a non-uniformly dispersed photosensitive layer, the color former may be present either inside or outside (in the binder, continuous phase) of the seven-dimensional particles. However, if the 7-mer particles exist only partially inside the 7-mer particle, the 7-mer will polymerize and become a polymer in the exposed area, but if heated sufficiently, the developer will diffuse into the polymer and react with the coloring agent to form on the dye. I can do it.

In addition, in the case of a non-uniformly dispersed photosensitive layer, the photopolymerization initiator may be present in the seven-layer particles, in the continuous phase of the binder, or at the interface between the seven-layer particles and the binder. Photopolymerization can be initiated as long as the ratio of the amount of the compound and the binder is within the range described below. The color developer in the developing layer may be uniformly dispersed in the binder or may be dispersed in particles.

IO- In the case of the integrated recording material shown in Figure 2, the color developer in the developing layer diffuses into the photosensitive layer at room temperature during manufacturing or storage of the recording material, reacts with the color forming agent, and develops color. Alternatively, polymerization may be inhibited or slowed down by contact with monomers. (For example, if the developer is a phenolic compound, this will generally reduce the rate of polymerization.) In such cases, a barrier layer may be provided at the interface of the two layers to prevent diffusion of the developer at room temperature; Alternatively, it is preferable to form monomers, color formers, or color developers into microcapsules so that the wall material acts as a barrier.

The image thus formed is already heat and light fixed and requires no additional processing for fixing.

Next, the case where the present invention is used for color image recording will be explained. As described in detail later, the photopolymerization reaction can be spectral sensitized by selecting a photopolymerization initiator to selectively sensitize each of the three primary colors of red, green, and blue. be. If three photosensitive layers are laminated for each photopolymerizable element using color formers that produce the three subtractive primary colors of cyan, magenta and yellow, the photosensitive layers shown in FIGS. 7 and 2 are constructed. A color image can be recorded by a single color light image exposure and thermal development. If necessary, a barrier layer may be provided at the interface of each photosensitive layer that allows the color developer to pass through but not the monomer, in order to prevent the monomer from diffusing into other layers and causing color mixing.

FIG. 3 and FIG. 1 show a color image recording material in which a combination of a photopolymerizable composition of three yuzu corresponding to the three primary colors and a coloring agent are dispersed in a binder to form a single photosensitive layer. Furthermore, the third
The figures and references correspond respectively to the two-sheet recording material of FIG. 7 and the monolithic recording material of FIG. 2. Photosensitive layer 13 in FIG. 3 and photosensitive layer 13 in FIG.
In , lj and 23 are binder continuous phases, /li and col are particles consisting of a monomer, a photoinitiator, and a color forming agent, and the photopolymerization initiator is sensitive only to red light and the cyan color is formed. Three types of particles that combine a color former that develops color, a photopolymerization initiator that is sensitive only to green light, a color former that develops magenta color, and a photopolymerization initiator that is sensitive only to blue light, and a color former that develops yellow color. are uniformly mixed and dispersed in the binder as pixels. The ratio of the amounts of the three types of particles is determined so that the image obtained by exposure to white light is neutral gray or black. This can vary depending on the sensitivity of the photopolymerization initiator to each color light and the concentration of color formed by the reaction of the color former with a certain color developer.
You can file a complaint accordingly. In the third and reference figures, /l and 21 are developing layers containing a color developer, l
j is a developing sheet, 17, /7/, λ is a support,
This is the same as in FIGS. 1 and 2. In the case of the integrated color image recording material shown in Figure 2, as in the case of the monochrome type material shown in Figure 2, the lamination order of the photosensitive layer and the developing layer may be reversed to that shown in the diagram, or if necessary. Depending on the requirements, a barrier layer may be provided at the interface of the two layers. The particles containing the monomer, photopolymerization initiator, and coloring agent in the third and reference figures are dispersed as emulsion particles or microcapsule particles. These recording materials are exposed to a color light image in exactly the same manner as in FIGS. 1 and 2, and a negative-positive color image is recorded by heat development.

The polymerizable vinyl heptamer used in the present invention means at least 1
It is a compound capable of radical polymerization and has 2 vinyl or vinylidene groups, including known esters of acrylic acid and methacrylic acid, acrylic acid metal salts (e.g. barium acrylate, calcium acrylate), acrylamide, N , N-methylenebisacrylamide, vinyl ethers, N-vinyl compounds (for example, N-vinylcarbazole), vinyl acetate, and the like. Among these, esters of acrylic acid and methacrylic acid are particularly suitable for the present invention. Specific examples thereof are shown below using acrylic esters. (One of those acryloyl groups
Compounds in which all the linkages are substituted with methacryloyl groups, that is, acrylic acid and methacrylic acid mixed esters and methacrylic acid di/4! - Although specific examples of sters are omitted, they can be used in the present invention in the same manner as acrylic esters. ) For example, methyl acrylate, ethyl acrylate, butyl acrylate,
Monoacrylates such as; polyethylene glycol diacrylate, polypropylene glycol diacrylate,
Diacrylates such as hexanediol diacrylate, glycerin diacrylate, trimethylolpronodiacrylate, pentaerythritol diacrylate, tri- and tetraacrylates such as nitrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, etc. .

Examples of the polymerizable prepolymers used in the present invention include polybasic acids (e.g., phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, malonic acid, A polyester produced by the condensation of polyhydric alcohols (e.g., ethylene glycol, tetrahylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) Oligomers produced by the death of hydroxyl residues and acrylic acid, that is, polyester acrylates (or oligoester acrylates), reactions between acrylic esters with hydroxyl groups and isocyanates, as described in Japanese Patent Publication No. 4 At-piZotr Examples include polyurethane acrylate, epoxy acrylate, etc. obtained from In addition, in the present invention, two or more kinds of 7mers can also be used together.

As the photopolymerization initiator used in the present invention, for example, Os
ter, my book “Chemjcal ReviewW
J Volume 6 ()ytt year) No j pages ~ /j/ pages and K
Written by osar [Light-8 intensive 8ys
temaJ (John W eye & 5ons, /ri4j)/! As described on page 3,
Carbonyl compounds (e.g., ketones such as a7tophenone, benzoins, benzyl, diacetyl, benzophenone, anthraquinones, naphthoquinones, quinones such as phenanthrenequinone), organic sulfur compounds, peroxides, haμ photo-semiconductors (e.g. zinc oxide, titanium dioxide, etc.), metal ions (e.g. iron(1) ions, metal carbonyls, metal complexes, uranyl salts, etc.), halogenated chains, azo and diazo compounds, photoreducible dyes is used.

Among these, photoreducible dyes are particularly preferably used in the present invention in that they are capable of spectral sensitization of photopolymerization to any wavelength region in the visible light region and are useful for color image recording.

Photoinitiators using photoreducible dyes generally consist of a photoreducible dye and a reducing agent (or a hydrogen-donating compound), and upon photoexcitation, the reaction between the dye and the reducing agent generates radicals capable of initiating polymerization. It is believed that. Photoreducible dyes include methylene blue, thionin, rose bengal, erythrosin-B1 eosin, rhodamine, phloxine-B1 safranin, acriflavin, riboflavin,
Fluoretcein, uranine, benzoflavin, N.

77- N, N/, N/-tetra-n-butylthionine, N,
Examples include carbonyl compounds such as N, N/, N/-tetramethyl-dodecylsafranine, acridine orange, acridine yellow, and IO-phenanthrenequinone, penzanthrone. Examples of reducing agents include β-diketones such as dimedone and acetylacetone, amines such as triethanolamine, jetanolamine, monoethanolamine, dimethylamine, diethylamine, tetramethylethylenediamine, triethylamine, and phenylhydrazine, and p-toluenesulfine. acids, benzenesulfuric acid, p-(N-acetylamino)benzene/insulfinic acid and other sulfinic acids and their salts, N-phenylglycine, L-ascorbic acid,
Examples include thiourea and allylthiourea. In general, when a photopolymerization initiator consisting of a photoreducible dye and a reducing agent is used, the efficiency of photopolymerization initiation, and therefore the sensitivity of photopolymerization, vary considerably depending on the type of hexamer. In the present invention, when an acrylic acid ester, which is a preferred heptamer, is used as a monomer, photoreducible dyes include methylene blue, methylene green, thionine, rose bengal, erythrosin-B, eosin, phloxine-B1, safranin, and phenol. It has been found that the highest photosensitivity is achieved when safranin, acriflavine, acridine yellow, and phenanthrene quinone are used with dimedone or N-phenylglycine as the reducing agent. The molar ratio of the photoreducible dye and the reducing agent used in the photopolymerizable element varies depending on their solubility in the coating solvent, etc., but generally the photoreducible dye is o.ooz to 3 moles per mole of the reducing agent. More preferably 0.0. It is in the range of t-1 mole. Again, 10
When a carbonyl compound such as -7 enanthrenequinone is used as a photoreducible dye, a reducing agent is not necessarily used because the binder acts as a hydrogen-donating compound.

As the coloring agent used in the present invention, which can produce a dye that can be bleached with a 7-mer by reaction with a color developer, known coloring agents used in two-component heat-sensitive (pressure-sensitive) coloring materials are suitable. used for.

Here are some specific examples of color formers; US patent! ≠t.

JtA, Doko, 101 Goshi, Tokukai Sho! J-j6
Triphenylmethane lactones (or triphenylmethane phthalide) described in 2≠, such as crystal violet lactone, malachite green lactone; equity lI8≠ter/r726, same reference 2-/17
27, same≠5=4Lt,yr.

Same≠j-pi70/, same≠t-λrizso, sameda t-≠0
11. Same rig-3〇j, 2, same≠ 1st j/3, same 1
fir-1721, fir 4ct-1724, fir-10
17/, Ill-23203, Id. 7-KotajAλ, JP-A-Sho I Togoko, fluorans described in 2≠3,
For example, 3. t-dimethoxyfluorane, cortacyl-
4-isozolopylaminofluorane, coprom-3-
Chloro-6-n-propylaino-7-bromofluorane, 3-diethylamine-7-cybenzylaminofluorane, 3-dimethylamino-7-methylanofluorane, 44. J, 4.7-tet>chloro-7/.

λ', 3'-trimethyl-4'-diethylaminofluorane, 3-diethylamino-! , t-benzfluoran, 3-diethylamino-7, r-benzfluoran, co-N-ethyl-N-phenylamino-4-diethylaminofluoran, 2-N-phenylamino-3-methyl-
4-diethylaminofluorane 1.2-N-phenylamino-3-methyl-j-N-ethyl-N-(1)-)lyl)aminofluorane, 3-diethylamino-7-phenylfluorane 3/, 4 /-BisCN-MefruN-
phenylamino) -4C, j, J,? -Tetrachlorofluoran, λ-ethoxyethylamino-3-nichloro-t-diethylaminofluoran: Tokko Sho≠t-4
727, same reference t-17kot1 same≠r-4729, same 'l
azaphthalide and diazapthalides, such as j-(4C'-diethylaminophenyl)-j-(dan-dimethylamino-,2/-chlorophenyl)-7-azaphthalide, as described in ll-1730 and +r-ir'ysz. , 3.3-bis(4!/-dimethylaminophenyl)2l-1μ,7-diazaphthalide;
Fluorane-r described in Opener 103710
-Lactams (rhodamine lactams); JP-A-Sho≠I -
4j j /ri, phenothiazines described in 7-3≠≠17, such as benzoylleucomethylene blue; JP-A-4T7-4'AD10. British patent /, /4
0. Indolyl phthalides described in Japanese Patent Publication No. 34-/≠173, 7-10713; spiropyrans 1 described in Japanese Patent Publication No. 1997-17-10713; ko, JP-A Show xi-y coco 07, same j
Triphenylmethanes described in Reference-1t1437; JP-A-Sho! λ-1proy, same! Q-/24//I
Chromenoindoles described in JP-A-10-1989/J No. 2301 Ibid. j≠-1itz, 2r, Ibid.! Toysanko II, 13-40211. Same≠t−λri!
! λ, same! l-i, ziosz, same j/-/210Jj
, Tokuko Sho 4cj-/23/7, Sho 4I4-2130, Sho zz-7≠73, Sho 11j-coztz reference, Sho ≠t-22
! -λ λ - jko, the same 4 (j-λztzp, the compound described in the same t data j takota, etc.).

Among these color formers, those that provide a dye having a desired hue and weather resistance can be selected and used in the present invention. Moreover, λ or more color formers can be used at the same time.

As the color developer used in the present invention, phenol compounds (e.g. bisphenol A1, bisphenol B,
z, λ-bis(≠-hydroxyphenyl)n-hebutane, /,/-bis(≠-hydroxyphenyl)cyclohexane, Koe 5-ni-7-/, /'-bis(≠-hydroxyphenyl)hexane, etc. bisphenol A, and phenols such as t-butylphenol and daphenylphenol), organic acids (e.g. citric acid, tartaric acid,
succinic acid, maleic acid, 7-thalic acid, phthalic anhydride, tetrachloro-7-thalic anhydride, salicylic acid, p-)luenesulfonic acid, etc.) and their salts, inorganic salts (for example, aluminum sulfate, potassium alum, ammonium alum, etc.), etc. Among the known color developers that are generally used in two-component thermosensitive coloring materials, substances that are easily melted or move in molecular form through the binder upon heating are used. The dyes produced by the reaction of these color developers with color formers are generally easily bleached by the above-mentioned dyes, but depending on the color developer, they may be difficult to bleach. In such a case, an alkaline substance (
For example, bleaching can be caused by appropriately adding caustic soda, caustic potash, salts of these with organic carboxylic acids, basic phosphates, etc.). Furthermore, in order to facilitate the diffusion of the color developer into the binder under heating, a low melting point compound that melts under heating and can serve as a solvent for the color developer, that is, a hot solvent, is added to the developing layer and/or the photosensitive layer. It can also be included. Specific examples of heat solvents include sorbitol, dulcitol, pentaerythritol, trimethylolpropane, trimethylolethane,
Examples include acetamide, methylurea, dimethylurea, etc.

As binders, water-soluble polymers such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, gum arabic, and casein, as well as polymethyl methacrylate, polyvinyl chloride, vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-vinyl chloride copolymer, and polyacetic acid. Vinyl, vinyl acetate-vinyl chloride copolymer, styrene-acrylonitrile copolymer, polyester, AB8 resin, polyamide,
Polymers soluble in organic solvents such as chlorinated polyethylene, chlorinated polypropylene, polyvinyl butyral, polyvinyl formal, and acetyl cellulose are used.

Particularly when the 7-mer is dispersed in the form of particles as an emulsion or microcapsule in the photosensitive layer, water-insoluble monomers are prepared as an oil-in-water emulsion, so water is used as the solvent and a water-soluble polymer is used as the binder. is preferable. Organic solvents include acetone, methanol, ethanol, methylene chloride, ethylene dichloride, chloroform, methyl ethyl ketone, methyl acetate, ethyl acetate, and dimethyl chloride! - Lumamito, dimethyl sulfoxide, etc. are used.

A polymer similar to the binder is preferably used as the wall material of the microcapsule for the barrier layer, but if a water-soluble polymer is used, 1. After applying using a known method (
or after capsule formation) is preferably hardened.

As the support, paper, water-resistant paper provided with a polymer layer, sheets or films of polyethylene terephthalate, triacetylcellulose, etc. are used.

The combined amount ratio of each component contained in the image recording material of the present invention is as follows. The monomer is 00J-2o y/m
2, more preferably 0. The photopolymerization initiator (photoreducible dye when using a photoreducible dye and reducing agent) is used in the range of 117 m''. Although the amount may vary, it is generally preferably in the range of 0.0001 to 0.0 j mol per 1 mol of hexamer.

The amount of coloring agent is determined by the desired image density, coloring property (dye amount - λ
The ratio of the amount of the dye to the dye to be formed can vary widely depending on the coloring agent (extinction coefficient), and the amount ratio of the dye to be produced is completely bleached by the dye in the unexposed area and does not cause fogging. I have to decide. It is preferable to determine this by trial and error, but in general, 1 mole of monomer or more,
The amount of the color former is preferably in the range of 0.07 to 3 moles. The amount of binder per monomer lf in the photosensitive layer is 0.0! t
The range of 0.2 to 3t is more preferable than -10f1. The amount of color developer in the developing layer is preferably sufficient to diffuse into the photosensitive layer under heating and develop almost all of the color developer, and is generally 0.0l-20f/m.
”, more preferably in the range of 0.1 to j f /m 2 .The amount of binder per developer If in the developing layer is 0.0 l to 10 f.

More preferably, it is in the range of 0.7 to 3f. The amount of thermal solvent is q-- per 1V of binder for both the photosensitive layer and the developing layer.
A range of V is preferred.

The film thickness of the photosensitive layer and the developing layer (in the case of a nine-color recording material in which the photosensitive layer is stacked in three layers, the film thickness of each layer) is 0.1-10.
μm, more preferably in the range of /~1101J. The thickness of the barrier layer depends on the type of polymer used, but it is generally in the range of 0.1-10 μm, and the desired barrier effect at room temperature and the diffusion rate (current rate) of the color developer upon heating are desired. It can be determined by trial and error to fall within the range of .

Microcapsules can be prepared using known methods such as "
Microcapsules" (published by Nikkan Kogyo Shimbun, Showa pt.), coacervation method or other method.

The photosensitive layer and the developing layer can be provided on the support by a known coating method. 1iii) Any light source including the wavelength range to which the photopolymerization initiator is sensitive, such as a tungsten lamp, a xenon lamp, a mercury lamp, a laser beam,
This can be done using a light emitting diode, CRT, or the like.

Thermal development can be performed using a hot plate, a heat roller, an infrared heater, or the like. The temperature of heat development is
to"c~kooo'c, more preferably 100"C~/
The developing time is preferably in the range of 3 seconds to 1-0 seconds, preferably 10 seconds to 10 seconds.

Examples 1 to 4 (Preparation of photosensitive sheets) To a homogeneous solution consisting of the following, were added the amounts of monomers shown in Table 7, ethylene dichloride iy, and dimedone (frozen confection-providing compound) 0. A mixture of If was added thereto, and ultrasonic emulsification was performed in a dark place for 1 hour to prepare an emulsion in which hepatoma was dispersed in an aqueous polyvinyl alcohol solution. on the other hand,
Coethoxyethylamino-3-chloroa-4-diethylaminofluorane (color former) 1Of - 1 weight polyvinyl alcohol (average degree of polymerization 100) aqueous solution j17
In addition to V, the dispersion liquid If was dispersed with glass beads in a homogenizer for 1 hour was mixed with the above emulsion, and this was coated on a polyethylene terephthalate film (gioμm) using a percoater and dried to form a photosensitive sheet. Created.

The thickness of the photosensitive layer was approximately j μm.

(Preparation of developer sheet) Add λ-ethyl/,//-his(Hiro-hydroxyphenyl)hexane (color developer) ioy to a 1% by weight polyvinyl alcohol (average degree of polymerization 200) aqueous solution jof, and add it together with glass beads. A developed sheet was prepared by dispersing the dispersion using a homogenizer for 1 hour and applying it onto a polyethylene terephthalate film (thickness: 100 μm) using a percoater and drying it. The thickness of the developing layer was approximately j μm.

(Image recording) A black and white step wedge (step 30 - 0.3 in Log (transmission density)) and filters of the colors listed in Table 7 were layered on the photosensitive sheet, and a halogen lamp was passed through the wedge to record images using a halogen lamp. This was then exposed to light for 120 seconds on a hot plate heated to 1.200C in close contact with a developing sheet. A black image with good tonal reproducibility was developed.The sensitivity of the image (number of step wedges) is shown in the table.The maximum transmission density of the image (D
max) are all approximately 2.01 minimum transmission density (DmIn)
were all below O0l. Note that when a filter of a color other than those shown in the table (for example, a green or blue filter in the case of Example 1) was used, no or almost no image was formed.

(Fixing property test) The two sheets of all the images obtained were peeled off, the photosensitive sheet on which the images were formed was divided into two parts, and the following test was conducted on each part.

(1) By the same light source used for image exposure! million lu
When uniformly irradiated with light for 5 minutes at x, Dmax, D
There was no change at all with min.

(2) When the support side was placed in close contact with a hot plate heated to 10°C and heated for 70 minutes, Dmin did not change at all, but Dmax slightly decreased.

Examples 5 to 6 When the same procedure as in Example 1 was carried out except that the same amount of the compound listed in Table 1 was used as the color former, negative-positive images of the colors listed in the table were obtained. Ta. The values of sensitivity, gradation reproducibility, Dmln, and Dmax were almost the same as in the case of the black image of Example 1.

Table 1 Example 7 When the same procedure as in Example 1 was carried out except that the same amount of bisphenol was used as the color developer, a negative-positive black image was obtained, and the sensitivity and gradation reproducibility were improved. ,Dmin,
The value of Dmax was almost the same as in Example 1.

A mixed solution consisting of was added to a homogeneous solution consisting of, and the mixture was ultrasonically emulsified for 1 hour in the dark.
Using a bar coater, it was coated on the same support as in Example 1 and dried to produce a photosensitive sheet.

The thickness of the photosensitive layer was approximately j μm. This photosensitive sheet and
Image recording was carried out in exactly the same manner as in Example 1 using the developing sheet of Example 1, and a negative-positive black image was obtained. The sensitivity and gradation reproducibility are exactly the same as in Example 1, and Dmax is /, j, Dminij
It was O,/.

Example 9 A diethanolic solution of polyvinyl butyral (average molecular weight approximately 50,000) was coated on the developing sheet prepared in Example 1 using a percoater to form a barrier layer with a dry film thickness of 3 μm. Thereafter, the same coating liquid as that used for the photosensitive sheet of Example 1 was applied and wire was applied to produce an integrated image recording material. Feeling.

The film thicknesses of the optical layer and the developing layer are the same as in Example 1. After exposing this image in the same manner as in Example/,
When heated uniformly for 30 seconds on a hot plate heated to C, a negative-positive black image almost the same as in Example 1 was obtained.

[Brief explanation of drawings]

FIG. 7 and FIG. 2 respectively show two images of the image recording material of the present invention. An example of the embodiment of type II is shown below. A, B:; and C are
The states before exposure, after no light, and after heat development are shown, respectively. In No. 711, l is a photosensitive sheet, c is a developing sheet,
3 is a photosensitive layer, 3 is a developing layer, j and j/ are a support, t is a polymer produced by photopolymerization, and 7 is a dye image. ;Second
In the figure, t is a photosensitive layer, ri is a developing layer, IO is a support,
1/ indicates a polymer produced by photopolymerization, and 1 indicates a dye image. FIG. 3 and FIG. μ each show two examples of embodiments of color image recording materials. In Figure 3, 13 is 34
- light sheet, /F is a developing sheet, /j is a photosensitive layer, 16 is a developing layer, 17 and /7' are a support, /l is a binder,
/ indicates pixels corresponding to the three primary colors. In FIG. 1, reference numeral 20 indicates a photosensitive layer, Co/ indicates a developing layer, Co/λ indicates a support, λ3 indicates a binder, 1. 2≠ indicates pixels corresponding to the three primary colors. Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendments, Showa J, 2013, Hirotsuki Z, 2, Title of the invention: Method of recording one image per image 3, Relationship with the person making the amendment: Patent applicant's identity: Address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52
0) Fuji Photo Film Co., Ltd. Contact information: 2-26-30 Nishi-Azabu, Minato-ku, Tokyo 106 Fuji Photo Film Co., Ltd. Tokyo Head Office Telephone: (406) 2537 Hiroshi, Subject of amendment ``Scope of Claims'' column in Specification Co. “Detailed description of the invention” column! , the statement in the "Claims" section of the description of the amendment is amended as shown in the attached sheet. The description in the "Detailed Description of the Invention" section of the specification is amended as follows. (1) No. 1! "Adjacent" in line 13 of the page is corrected to "contact." (2) Number! Insert "from the beginning" after "or" on the 13th line of the page. (3) Insert “or without” after “through” on page j, line 13. 1/- (4) Correct "dye" in line 17 of page j to "pigment". (5) 〆4% Page 3j/line 2, “Autumn Vinyl” to page 34, line 1, “After installation,
' Delete up to '. 1 No. Attached Claims Polymerizable vinyl monomer and/or polymerizable prepolymer,
Using a photosensitive layer containing a photopolymerization initiator and a color forming agent capable of producing a bleachable dye with the vinyl monomer and/or prepolymer by a color developer, and a current layer containing the color developer, The vinyl monomer and/or prepolymer in the photosensitive layer is superimposed by imagewise exposure of the photosensitive layer, and then the photosensitive layer is brought into contact with the developer r-, or even initially through one barrier r@. (○ 1 fic heating in a state of high vibration [7. 9. An image recording method characterized by forming a dye image on exposed areas by bleaching the dye.

Claims (1)

[Claims] polymerizable vinyl monomer and/or polymerizable prepolymer,
A photosensitive layer containing a photopolymerization initiator, a color former capable of producing a dye that can be bleached by the vinyl monomer and/or prepolymer, and a developing layer containing a color developer are used to form a photosensitive layer. The f-nyl monomer and/or prepolymer in the photosensitive layer is polymerized by imagewise exposure, and then the photosensitive layer and the developing layer are heated adjacent to each other or in contact with each other through a barrier layer, and the color is formed by a color developer. Bleaching the dye with the unpolymerized vinyl monomer and/or prepolymer remaining in the unexposed area or the exposure amount insufficient to polymerize the dye to completely form a dye image in the exposed area (t%) Image recording method used as a signature.