JPS60120353A - Recording material - Google Patents

Abstract

PURPOSE:To enhance gradation reproducibility, etc. by using a dye bleachable with polymerizable vinyl monomer, or the like, uniformly dispersed into a binder, or a dye precursor capable of producing such a dye upon heating. CONSTITUTION:When a photopolymerizable element-contg. layer 2 and a dye precursor-contg. layer 3 laminated on a sheet of a support 7 are imagewise exposed, photopolymn. is caused at the exposed parts, and the monomer is converted into a polymer 5. Next, upon heating, color is developed in all the layer 3 temporarily, but the nonpolymerized monomer in the unexposed parts of the layer 2 diffuses to the corresponding parts of the layer 3 and bleaches the dye there, and a reversal dye image 6 is formed in the exposed parts of the layer 3 contg. the dye precursor. The lamination order of the layers 2, 3 may be reversed, and a colored dye may be used in place of the dye precursor, and a barrier layer may be formed between the layer 2 and the layer 3.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a light and heat sensitive image recording material, particularly a highly sensitive recording material using a photopolymerization reaction. After exposing the image to light, it is developed by uniformly heating it, and it has the feature that an image can be obtained only by dry processing, and those using organic silver salts as photosensitive materials are well known.

On the other hand, many image recording methods using photopolymerization reactions are known and are applied to photoresists, printing plates, etc., but there are special cases (such as N-vinylcarbazole-carbon tetrabromide-based photosensitive materials). It is difficult to directly form a visible image by photopolymerization using general monomers, except when the monomer itself has a color-forming function. system) is one of the reasons why it is difficult to apply it to general photographic recording. To visualize the image, either the exposed or unexposed areas are selectively colored with a dye solution or Fi pigment powder depending on the difference in permeability or tackiness, or the photosensitive layer is colored in advance. After imagewise exposure and curing, physical development operations such as liquid development or peel development take advantage of differences in physical properties such as solubility or adhesiveness between the cured and uncured parts. It is necessary to spatially separate the exposed portion and the unexposed portion, and the processing is complicated, and a simpler 1iif# visualization method is desired.

Directly using a photopolymerizable composition (or photosensitive resin),
That is, several methods have been proposed in which a visible image is developed by a dry process using a chemical reaction inside the photosensitive material without external coloring or spatial separation of exposed and unexposed areas. Japanese Unexamined Patent Publication No. 2003-111002 describes a method of forming a visible image by heat development using a photopolymerizable composition (or a photocurable photosensitive resin) and a heat-sensitive coloring agent. This method uses a material in which the two components of a two-component thermosensitive coloring material are placed separately on the inside and outside of a photopolymerizable composition (or photosensitive resin), or on both sides, which is exposed to light and then heated. Then, in the part that has been cured by exposure, the heat-sensitive substance does not move and no color development occurs, but in the unexposed part, the material moves and reacts and develops color, showing a positive-positive recording response.

Also, JP-A-17-/7-ri r3t, same! 7-lri7131
, lt-230211 and jIr-230,21K
A method is described in which a photopolymerizable composition and a heat-sensitive (pressure-sensitive) color-forming material are developed to form a visible image under pressure. In both of these, one component of a two-component color-forming substance is microencapsulated together with a photopolymerizable composition, the material in which one component is placed outside the capsule is exposed to image light, and then pressure is applied. Since the hardened capsule is not destroyed, no color development occurs, but in the unexposed area, the capsule wall is destroyed by pressure, and the two component coloring substances come into contact and react, resulting in color development, and a positive-positive recording response is exhibited.

The photothermosensitive and photosensitive pressure-sensitive image recording methods using these photopolymerization reactions are all based on the principle of image-wise control of the coloring reaction by the difference in mass transfer and diffusivity between the polymer and the monomer.

However, the degree of curing caused by photopolymerization, that is, its property as a barrier against mass transfer, is generally not necessarily proportional to the polymerization rate; rather, when the polymerization rate reaches a certain value (gelling point), it rapidly gels and suddenly They tend to act as a barrier. Therefore, the above-mentioned image recording method has the disadvantage that the image density is difficult to be proportional to the amount of exposure, resulting in poor gradation reproducibility. Additionally, it is generally difficult to completely prevent mass transfer of polymers produced by photopolymerization;
In order to provide a sufficient barrier, a very large amount of exposure must be given, and therefore, fogging is likely to occur and the signal/noise ratio (S/N ratio) must be sufficiently high. The drawback is that it is difficult.

(Object of the Invention) The object of the present invention is basically to provide a non-silver salt image recording material capable of recording a color image by dry processing, and more specifically, to provide a non-silver salt image recording material capable of recording a color image by dry processing. It is an object of the present invention to provide a highly sensitive recording material with excellent gradation reproducibility and 8/N ratio. Another objective is to provide a recording material that is stable over a long period of time.

(Structure of the Invention) The object of the present invention is to heat a polymerizable vinyl monomer and/or a polymerizable prepolymer, a photopolymerization initiator, a binder, and a dye that can be bleached or a dye that can be bleached by the vinyl monomer and/or prepolymer. A recording material using the dye precursor produced below is characterized in that a polymerizable vinyl monomer and/or a polymerizable prepolymer (hereinafter monomer includes prepolymer) are dispersed in a non-uniform state in a binder. This was achieved using recording materials.

The image recording method using the recording material of the present invention is based on the phenomenon that polymerizable vinyl monomers bleach certain dyes, and when the monomers are polymerized to become polymers, the ability to bleach the dyes is lost. This method is based on a completely different and new principle. That is, in conventional photopolymerization image recording, the solubility in the solvent between the monomer and the polymer produced by its polymerization,
By utilizing differences in physical properties such as permeability, permeability, tackiness, adhesion, and light scattering properties of substances, exposed areas and unexposed areas can be spatially separated by wet or dry processing, or by light scattering. Development or image visualization was performed by optically distinguishing between the two.

Previously mentioned Tokukai Sho, T coat T Tata/j, same 17-/79
Even in dry visible image forming methods, such as those proposed in Publications No. 1rJt, j7-/ri7jJIr, sr-λ6-302≠, and No. 61-23021, The principle used was to control the color reaction by taking advantage of the difference in physical properties, that is, the difference in transmittance.

The adoption of the above-described principle of monomer dye bleaching by the present invention provides several important advantages in terms of process, application, and photographic properties in the image recording of the present invention.

As a feature of the process, just by heating after marking the image,
The visible image is developed, ie the light- and heat-sensitive image recording method is achieved, and at the same time the fixing is completed. Since the remaining unpolymerized upper layer was used for dye bleaching, it no longer polymerizes when exposed to light and therefore no longer produces capri on a white background. Furthermore, even when a material that develops color under heat, such as a two-component thermosensitive coloring material, rather than a ready-made dye is used as a visible image forming element, the white background has already been colored by heat and then bleached by the monomer. Since it is a part, even if it is heated further, it is unlikely that the color will develop and cause capri. That is,
In the method of the present invention, as the visible image is developed by heating, the image is simultaneously stabilized against light and heat, ie, fixed, and no additional processing for fixing is required. The superiority of this becomes clear when compared with other photothermography techniques. For example, in organic silver salt-based photothermography, the photosensitivity is generally not deactivated even after heat development, so if the image is exposed to light for a long time, capri will occur on the white background, and the image will be exposed to room light. If you accidentally heat it after exposure, a high concentration of capri will occur on the white background and the image will be lost. Also,
In the photothermography described in the above-mentioned Japanese Patent Laid-Open Publication No. 2003-120010, the image is fixed against light, but it cannot be said that it is completely fixed against heat. This is because even if the monomers are completely polymerized, such polymers generally have a relatively low softening point, and it is difficult to completely prevent the diffusion of the coloring substance and, therefore, the formation of capri due to the reaction.

An advantage of the application is that the method of the invention can be used not only for monochromatic (eg black and white) image formation, but also for color image recording. As described in detail later, the photopolymerization reaction enables selective spectral sensitization to red, green, and blue light, and each photosensitive layer is coated with cyan, magenta, and yellow dyes or If dye precursors that develop color when heated are combined and laminated to form a photosensitive material, a color image can be recorded by exposing and heating seven color light images.

The principle of monomer dye bleaching of the present invention also brings about the following advantages in terms of photographic properties. First, good tone reproduction is achieved. This is because the number of monomer molecules and the number of molecules of the dye bleached by it are proportional (or because they have a stoichiometric relationship), and the image density is determined by the amount of monomer consumed, that is, the conversion rate from monomer to polymer (polymerization rate). ) is exactly proportional to The conversion rate from monomer to polymer is generally proportional to the exposure amount, so the image density is (
At least the exposure amount before reaching the saturation density (Dmax) -? - (in the region), it was proportional to the exposure amount, and as a result, extremely good gradation reproduction was obtained. This means that when controlling image visualization using a polymer as a barrier to mass transfer, as in known methods, the amount of exposure and the amount of mass transfer (and therefore image density) are generally not proportional; When the value is exceeded, the amount of mass transfer tends to decrease rapidly.
It approaches a binary (on-off) response rather than a continuous gradation, making it difficult to reproduce gradations, but this is a major feature.
Ru.

Second, an image with less capri and a high S/N ratio can be obtained. This means that if the ratio of the 7-mer and the dye (or dye precursor) present in the light-sensitive material is set to an appropriate value (for example, the 7-mer is slightly excessive), the maximum image density can be substantially achieved. This is because it is possible to completely eliminate capri without degrading it. In this regard, in image visualization methods that use polymers as barriers, unless the ratio of mass transfer rates between the polymer and the monomer is very large, there is a paradox that if you try to increase the maximum image density, the fog also increases. It's better than there is.

The recording material of the present invention can take on several different aspects, such as how each component is arranged. Although different embodiments are shown in FIGS. 1 and 2, the present invention is not limited to these embodiments.

(In each figure, only the case where a dye precursor is used as a visible image forming element, which is colorless at room temperature and develops color after heating to form a dye, is shown, and the case where a dye is used is omitted.) The figure shows an example in which the photopolymerizable element-containing layer 3 and the dye precursor-containing layer 3 are laminated on a single support 7. On the other hand, when image exposure is performed, photopolymerization occurs at the exposed site and the monomer is converted to polymer j. Next, when heated, the dye precursor-Iv3 develops color, but the unpolymerized monomer in the unexposed area diffuses and the dye in that area is bleached, and the dye image t (negative-positive type) is deposited in the dye precursor-containing layer 3 in the exposed area. ) is formed. Note that the stacking order of layer λ and layer 3 may be reversed to that shown in FIG. Further, a colored dye may be used instead of the dye precursor. Also, a barrier layer can be provided between layer C and layer 3.

The purpose of providing a barrier layer is primarily when a dye precursor is used, and its components act as polymerization inhibitors for monomers (e.g., when a dye precursor is used as described below).
When is a two-component heat-sensitive color forming substance consisting of fluorans and phenols, the phenols have a polymerization inhibiting or decelerating effect. ) is to prevent contact between the monomer and the dye precursor in layer 3.
When a dye is used instead, the purpose is to prevent the monomer in layer 5 from diffusing and bleaching the dye in layer 3 during coating or during long-term storage after coating.

Note that in the photopolymerizable layer, the monomer is dispersed as particles in a continuous phase of the binder, and is in a non-uniform state.

FIG. 2 shows an example in which a photopolymerizable element and a dye precursor are mixed to form a single layer, and are provided on a single support 7 to form an integral structure. In this case, one of the two elements is a continuous phase and the other is a discontinuous phase and dispersed therein. In FIG. 3, the photopolymerizable element is a discontinuous phase in the dye precursor-containing layer 3. This shows the case where In this case, a pad 11 is provided at the interface. The barrier mass-encapsulated photopolymerizable elements are generally prepared as microcapsules;
Dispersed in the continuous phase. The purpose of providing a barrier (or microcapsule wall) is the same as in the case of Ryomachi's laminated type. When the image is exposed and then thermally developed, a negative-positive dye image t is formed as in the example shown in FIG.

In addition, in order to form a color image, the structure shown in Fig. 2 is laminated in three layers, each containing a photopolymerization initiator sensitive to red, green, and blue, and a cyan, magenta, and yellow dye or dye polymer 13 cursor, respectively. , a color image can be immediately recorded by exposing a color document to light and then thermally developing it. As another method, it is also possible to record a color image using a stack of three layers having the structure shown in FIG. In these cases, it is preferable to provide a barrier between each unit.

Image exposure can be performed using a light source with a pressure that includes the wavelength range to which the photopolymerization initiator is sensitive. For example, a tungsten lamp, a xenon lamp, a mercury layer, etc. are used.

l 3- Thermal development can be performed using a hot plate, a heat roller, an infrared heater, or the like. Thermal development OS degree is
Ir00C-K0O0C1 preferably 100°C
-/j00c. The development time is 3 seconds to 120 seconds, more preferably 10 seconds to 10 seconds.

The recording material of the present invention described above, in one embodiment, that is, when a two-component heat-sensitive (pressure-sensitive) color-forming substance is used, can be used in accordance with the above-mentioned JP-A-6.2-t Tata/j and JP-A-17-17-1. /7
At first glance, it is similar to the light-sensitive, heat-sensitive or light-sensitive pressure-sensitive recording materials described in No. t3 and other publications. However, in this case, considering the principle of image formation, that is, the polymer cured by photopolymerization is used to control the movement of the color-forming substance component (i.e., the color-forming reaction is suppressed in the hardened part), there are two problems. One of the components must be included inside the photopolymerizable composition, and the other components must be isolated and placed outside. On the other hand, in the present invention, since the polymer is not used to suppress the movement of the color-forming substance, there is no need to take such an arrangement. Since color must be developed, the color-forming substance must be placed outside the photopolymerizable composition of the two components so that they can easily develop color by contacting and reacting with each other under heating.

In the above points, the recording material of the present invention can be clearly distinguished from the above-mentioned known materials. This is clear from the fact that the image obtained is of a negative-positive type in the former (the present invention), whereas it is of a positive-positive type in the latter.

The heterogeneous state of the monomer used in the present invention can be obtained by incorporating the monomer as an emulsion or in microcapsule particles and dispersing the emulsion or microcapsules in a binder. When dispersed as an emulsion, / (It is generally applied by dispersing it in a binder solution as an oil-in-water type emulsion using a solvent, especially water, which dissolves the inder but not the tumbler, and a known surfactant.Also, it is applied as a microcapsule. When dispersing, the microcapsules of Nanatsuma can be dispersed using a known method, such as the coacervation method described in "Microcapsules" by Asashi Kondo (published by Nikkan Kogyo Shimbun, Showa ≠ J), or other methods. Either by making capsules and dispersing them in a binder solution, or by microencapsulating and applying the seven-mer particles in a binder solution.When the monomers are dispersed as emulsions or microcapsules, the photoinitiator is It may be present in one or both of the binder-continuous phase and the binder-continuous phase, depending basically on the solubility of the photoinitiator in the monomer and solvent. However, as long as the monomer to binder ratio is within the above-mentioned range, the radicals generated in the continuous phase can enter the monomer particles and photopolymerization will occur.

Photopolymerizable elements using monomers in a heterogeneous state have higher photosensitivity than those in which the monomers are dissolved in a solvent and uniformly dispersed (molecularly dispersed) in a binder.

The reason for this is not clear, but it is thought that it is less susceptible to the polymerization inhibiting effect of oxygen in the air, or that the local concentration of the monomer is high, which is advantageous for the growth of the polymerization reaction.

The polymerizable vinyl heptamer used in the present invention means at least 1
Compounds having 5 vinyl groups or vinylidene groups and capable of radical polymerization, known acrylic acid and methacrylic acid esters, acrylic acid metal salts (e.g. barium acrylate, calcium acrylate), Acrylamide, N,N-methylenebisacrylamide, vinyl ethers, N-vinyl compounds (for example, N-vinylcarbazole), vinyl acetates, and the like are used. 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. (Compounds in which one or all of these acryloyl groups are substituted with metadaryloyl groups,
That is, mixed esters of acrylic acid and methacrylic acid, mixed esters of methacrylic acid, and methacrylic acid esters can be used in the present invention in the same manner as acrylic acid esters, although specific examples are omitted. ) For example, monoacrylates such as methyl acrylate, ethyl acrylate, ethyl acrylate; polyethylene glycol diacrylate, polypropylene glycol diacrylate, hexanediol diacrylate, glycerin diacrylate)%)' Examples include diacrylates such as l-methylolprono-resistant diacrylate pentaerythritol diacrylate; tri- and tetraacrylates such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and the like.

Examples of polymerizable prepolymers used in the present invention include polybasic acids (e.g., phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, acids, malonic acid, succinic acid, adipic acid, etc.) and polyhydric alcohols (e.g., ethylene glycol, propylene glycol, polyethylene glycol, -/- polypropylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) Polyester acrylate (or oligoester acrylate), which is produced by the reaction of acrylic acid with the hydroxyl residue of polyester produced by condensation, is -≠/ As described in Publication No. 701, polyurethane acrylates and epoxy acrylates obtained by the reaction of acrylic esters having hydroxyl groups and incyanates can be mentioned. Hiko, in the present invention, two or more types of monomers can also be used in combination.

As the photopolymerization initiator used in the present invention, for example, 0s
ter% et al. Chemical Review No. t
Volume r (year 1r) / pages λj to pages lj and Kosa
rauthor rLight-8ensi order v e Sys te
As described in msJ (John W.Ey&, 5orls, /ri 35 years) izr page - lri page 3,
Carbonyl compounds (e.g. acetophenone, benzoins, benzyl, diacetyl, ketones such as benzophenone, anthraquinones, naphthoquinones, quinones such as phenanthrenequinone), organic sulfur compounds, peroxides, halogen compounds, optical semiconductors ( For example, zinc oxide, titanium dioxide, etc.), metal ions (for example, iron (I) ions, metal carbonyls, metal complexes, uranyl salts, etc.), silver halides, azo and diazo compounds, and photoreducible dyes are 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.

A photoinitiator using a photoreducible dye generally consists of a photoreducible dye and a reducing agent (or a hydrogen-donating compound), and the reaction between the photoexcited dye and the reducing agent generates a radical capable of initiating polymerization. is thought to occur. Photoreducible dyes include methylene blue, thionine, rose bengal, erythrosin-B, eosin, rhodamine, phloxine-B1 safranin, acriflavin, riboflavin,
Fluoretcein, uranine, benzoflavin, N.

N, N', N'-tetra-n-dutylthionine, N,
Examples include carbonyl compounds such as N, N', N'-tetramethyl-V'-dodecyl safranin, acridine orange, acridine yellow, 10-phenanthrenequinone, and 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-)luene. sulfinic acid,
Benzenesulfine e,p-(N-acetylamino)
Examples include sulfinic acids such as benzenesulfinic acid and salts thereof, N-phenylglycine, L-ascorbic acid, thiourea, allylthiourea, and the like. 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, varies considerably depending on the type of monomer. In the present invention, when an acrylic acid ester, which is a preferred heptamer, is used as a modifier, photoreducible dyes include methylene blue, methylene green, thionine, rose bengal, erythrosin-B, eosin, phloxine-B, safranin, phenosafranin, acriflavine, phenanthrenequinone as a reducing agent and dimedone or N-
It has been found that the highest photosensitivity is achieved when using phenylglycine. 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 in general, the reducing agent is 0,000 to 3 mol per 1 mol of the photoreducible dye. Preferably 0.0! ~1 mole. Furthermore, when a carbonyl compound such as 10-phenanthrenequinone is used as a photoreducible dye, it is not necessary to use a reducing agent because the binder acts as a hydrogen-donating compound.

Dyes that can be bleached by vinyl monomers or dye precursors that produce dyes that can be bleached by vinyl monomers on heating for use in the present invention can be selected by the simple test method described below. That is, a dye or a dye precursor dissolved or dispersed in a 1% aqueous gelatin solution is applied onto a transparent film to a dry film thickness of about j .mu.m and dried. If the test sample is a dye precursor, add it to the ir.
Heat at 0C for 1 minute to develop color. The transmission optical density of the dye is /, 0 to /.

Adjust the coating amount of the dye or dye precursor so that it is between j. Next, 1 drop (approximately 0, ig) of a 30% aqueous solution of polyethylene glycol diacrylate (the number of -0CH2CH2- groups is arbitrary from 1 to /j) is dropped onto it and left at room temperature for 1 minute. . By this operation, the dye is bleached, and the transmitted optical density of the dropped center part is o,
If the dye or dye precursor is lower than i, the dye or dye precursor can be suitably used in the present invention. Those exceeding o61 are generally not preferred.

Dyes and dye precursors suitably used in the present invention
Generally, these are known two-component type color-forming substances (dye precursors) used in heat-sensitive or pressure-sensitive materials, and dyes obtained by heating them or developing color by solution reaction. A two-component color-forming substance consists of two components: a color-forming agent and a color developer.

When these two components come into contact, they generally react to form a dye even at room temperature. These two components dispersed in a binder so that they do not come into contact with each other form the dye precursor for visible image formation of the present invention. When heated, at least one of the two components melts and diffuses, and when it comes into contact with the other component, it reacts and develops color.

Specific examples of color formers for two-component color formers are given;
Triphenylmethane lactones (or triphenylmethane phthalide) described in Reference -1jλ2, such as crystal violet lactone, malachite I
J-nlactone; Tokko Sho≠2-ir7.2t, same Hirota/1727, same Hiroj-147g1 same≠j-≠70/, same value t-λri! 10. same≠t-dao, ti, sameat-g0
1λ, same da t-da 4/≠, same 41'r-17λ, same hiro r-4724. Same j2-/θt7i, same/-2320
3. V7-2ri tt2, Tokukai Sho! Fluorans described in Coat tλ2 Ko 3, for example, 3. t-dimethoxyfluorane, J-me-1) t-isopropylaminofluorane, λ-bromo 3-chloro 4-n-
10 % J-diethyl mino-7-dibenzylaminofluoran, 3-dimethylamino-7-methylaminofluoran, ≠, j, j.

7-titrachloro/1.21.31)limethyl-t
'-Diethylminofluorane, 3-diethylamino-
! , 6-benzfluorane, 3-diethylamino-7,
1-pentfluorane, --NN-ethyl-N-phenylamino&-diethylaminofluorane, J-N-phenylminnow 3-methyl-4-diethylminnowfluoran, co-N-phenylminnow 3-methyl-A- N
-ethyl-N-(p-)jl)aminofluorane, 3-diethylamino-7-phenylfluorane, 3
′.

z'-bis(N-methyl-N-phenylamino)-J
j-14Z, j, 4, 7-thitrachlorofluoran, λ-ethoxyethyl minnow 3-chloro-t-diethylaminofluoran: Tokkosho"r J'7λ7, 4
41-47.21. 4711-1729, 4A, r
-17JOk and the same $f-/1r72j, azaphthalide and diazapthalides, e.g.
-(μ'-diethylminophenyl)-3-(≠'-dimethylminorco'-chlorophenyl)-7-azaphthalide, 3,3-bis(pI-dimethylminophenyl)-IIL, 7-diasaphthalide; ≠7−kotaj
Fluorane-γ-lactams (rhodamine lactams) described in 4 Co., Doko 2-103710; JP-A-Shoa
t-<<tJ/9, 4'7-j41c4Z, 27
Fetchacins, such as penzoylleucomethylene, described in JP-A-7-41-010. British patent l.

/40,9≠O.
r, 3, spiropyrans described in JP-A-4'r-4jt4120; 2, special t- opening j/-ta 2λ07, same! Triphenylmethanes described in Reference-/4/jJ74c; JP-A-ShojJ-/11
10? ? , chromenoindoles described in the same zti-t2tllpK;
0. Same j≠-///j kot1 Same J-, 2-r+i3r,
13-902j1. The same reference is one λ 112, the same j/-/
21031. Same l-/ko103! , Tokko Sho ≠ 4-/2
3/7, same≠4-2130, same 11-7'173, same≠
j-λj6j Hiroshi, 4A Buichikota 112, Same≠Yoichi 22
Compounds described in 12 Hiromu and 22 from the same author.

Among these coloring agents, those that provide a desired coloring agent and a coloring agent having 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 a color developer for a two-component coloring substance, phenol compounds (eg, bisphenol A1, bisphenol B, 2.
2-bis(hydroxyphenyl)n-hebutane, /
, /-bis(l-hydroxyphenyl)cyclohexane, coethyl-/, bisphenol AM such as /'-bis(≠-hydroxyphenyl)hexane, and t-7'
phenols such as tylphenol, ≠-phenylphenol), organic acids and their anhydrides and salts (e.g. citric acid, tartaric acid, succinic acid, maleic acid, heptalic acid, phthalic anhydride, tetrachlorophthalic anhydride% p) luenesulfonic acid and its sodium salt), inorganic salts (eg, aluminum sulfate, potassium alum, ammonium alum), [IE clay, activated clay, kaolin, zeolite, etc.]. Among these, bisphenols are particularly preferred in terms of color development density, speed, etc. The molar ratio of color forming agent and color developer used for forming a visible image is 0.
/~j1 More preferably 0. It is in the range of J to l.

Binders used in the present invention include water-soluble polymers such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, gum arabic, and casein, as well as polymethyl methacrylate, polyvinyl chloride, vinylidene chloride-vinyl chloride copolymer, and vinylidene chloride-vinyl chloride copolymer. Acrylonitrile copolymer, polyvinyl acetate, vinyl acetate-[vinyl acetate copolymer, styrene and acryl + 10 di) copolymer of 11, holJ ester, A
BS resin, polyamide, chlorinated polyethylene, tJiX
Polymers soluble in organic solvents such as polypropylene, polyvinyl butyral, polyvinyl formal, and acetyl cellulose are used.

When using dyes to form visible images of the present invention,
Any of the above polymers can be applied using either water or an organic solvent as a solvent, but when using a dye precursor, if an organic solvent is used, the color forming agent or color developer will be applied to it. Since there is a risk of color development immediately upon dissolution, it is generally preferable to use a water-soluble polymer as the binder and water as the solvent for coating. As the solvent other than the water plate, acetone, toluene, methylene chloride, ethylene dichloride, chloroform, methyl ethyl ketone, ethyl acetate dimethylformamide, dimethyl sulfoxide, etc. are used.

As the -λ ter support, it is preferable to use a sheet or film such as paper, polyethylene terephthalate, triacetyl cellulose, or waterproof paper with a layer of polymer material provided on both sides of the paper.

The quantitative ratio of each component is as follows.

In the embodiment shown in FIG. 1, the photopolymerizable element consists of a polymerizable vinyl monomer, a photoinitiator, and a binder. The weight ratio of monomer to binder is 0. /-70, preferably in the range of 0.3 to 3, and the amount of the photopolymerization initiator (when using a photoreducible dye and a reducing agent, the photoreducible dye) is determined based on its molecular extinction coefficient, radical generation. Although it can vary widely depending on the efficiency, etc., it is generally o, or to j moles of the monomer, and can be appropriately selected depending on the desired photosensitivity, etc. The M9 monomer is used in the range of Oo, 2 to -1097 m'', but preferably o, r to 70 g/TrL2.

On the other hand, the layer containing the dye or dye precursor preferably further contains a binder. The weight ratio of the color former of the dye or dye precursor to the binder is 0. /-20, preferably from 7 to 10. The dye or dye precursor is 0°01-109
/TrL2 more preferably 0. /-3g/m''. In the case of dyes, they are generally molecularly dispersed in a binder and may be dispersed in particles, but in the case of dye precursors, color development is prevented before image formation. In order to do this, the color forming agent and the color developer are generally dispersed in the form of particles in an insoluble solution (binder solution).

The pH in the photopolymerizable element and the visible imaging element is between λ and l
It is desirable to adjust it to λ, more preferably in the range of 3 to io. This is because bleaching of dyes by monomers during image formation is difficult to occur at low pH, and too much at high pH. The film thickness of each element is 0.3~30
It is preferably 1 to 10 μm.

When a barrier layer is provided, the polymer mentioned above is used as a binder, but it is necessary to select the polymer and solvent so that the binder is completely or almost insoluble in the liquid to be coated on the barrier layer. be. Particularly when the upper layer coating solution consists of a water-soluble binder and water, a water-insoluble polymer is used for the barrier layer. The thickness of the barrier layer can be determined by trial to avoid deterioration of photopolymerizability, but generally O,S~10
This is the range of ti@. It is necessary to properly determine the amount ratio of the monomer and the dye or dye precursor. If the monomer is in excess, bleaching will occur too much, the image density will decrease, and the dye (or dye precursor) This is because if it is in excess, it will not be sufficiently bleached and capri will occur.

The molar ratio of the monomer to the dye (or the color former of the dye P11 cursor) is o, ii, o, preferably 0. j-
j, a range of 0 is appropriate. This can be set by adjusting the quantity ratio of the 7-mer, dye, etc. in the photopolymerizable element and the visible image forming element, or by adjusting the film thickness of each layer.

In the embodiment of FIG. 2, the monomer is then generally microencapsulated and dispersed in the binder along with the dye or dye precursor. Preferably, the same polymer as the barrier described above is used as the wall material of the microcapsule. The quantitative ratio of each component, etc. are the same as in the embodiments of FIGS. 1 and 2.

The thickness of the layer provided on the support is o3~J OB? FL
It is preferably in the range of /-10 μm.

This will be specifically explained using examples.

Example The dispersion Azg and the dispersion Biog shown below were mixed uniformly and coated on a polyethylene terephthalate film (thickness 100 μTrL) using a bar coater so that the dry film thickness was approximately 100 μm, and dried to coat the pigment. A precursor-containing layer was provided.

(Dispersion A) λ-ethoxyethyl minnow 3-chloro-bu-diethylaminofluorane iog, gelatin IO weight % aqueous solution iog, p-dodecylbenzenesulfonate sodium 5 weight % aqueous solution 0. ．． 29 and water pog were mixed and dispersed together with glass beads using a homogenizer for 1 hour to obtain a dispersion liquid A.

33- (Dispersion B) Coethyl-i, i'-bis(Hiro-hydroxyphenyl)hexane iog, gelatin lO weight fA water fa liquid/
0.29 of a 5 wt % aqueous solution of 11 um of sodium g, p-dodecylbenzenesulfonate and water ginseng were mixed and dispersed together with glass beads in a homogenizer for 1 hour to obtain a dispersion B.

Next, a 10% solution of polymethyl methacrylate (average molecular weight: about 30,000) + methylene tetrachloride was applied onto the dye precursor-containing layer and dried to form a barrier layer with a dry film thickness of 3 μm. Furthermore, the following photopolymerizable composition was coated on the barrier layer so that the dry film thickness was approximately JbIH, and dried to provide a photopolymerizable layer to prepare a recording material.

(Photopolymerizable composition) 10% by weight aqueous solution of polyvinyl alcohol (average degree of polymerization 100) 10f1. A homogeneous solution consisting of 1 g of a 5% by weight aqueous solution of sodium p-dodecylbenzenesulfonate and 1 g of methylene blue was added to a mixture of 1 g of dichlorinated tyrene and Dimedone 01139. Ultrasonic emulsification was performed in a dark place for 1 hour to obtain a photopolymerizable composition.

A black and white step wedge (the step is A) is used as the mourning record material obtained.
og [transmission density] of 0.3) and a red filter and exposed through it to a halogen lamp at 10,000 lux for 30 seconds. When heated uniformly for 30 seconds on a hot plate heated to 200C, a negative-positive 7-level black image was obtained on the original (step wedge). The maximum transmission density of the image is i, z, and the minimum transmission density is O0/.
At a value of 0 g (exposure amount), gradations over approximately /, j) were recorded. The resulting image was uniformly exposed to room light for about -0 hours, but no change in texture was observed.

Further, when the recording material was stored unexposed in a dark place for 60 days and then subjected to image gI exposure and heat treatment in the same manner, the same black image as when the recording material was completed was obtained.

Comparative Example A uniform photopolymerizable layer was used in place of the non-uniform photopolymerizable layer in the example, using the photopolymerizable composition shown below, and was carried out in exactly the same manner as in the example except that it was provided with the same thickness.

(Photopolymerizable composition) A homogeneous solution consisting of

Exposure and heat development were performed, but no image was obtained, and the dye was bleached over the entire surface. That is, no polymerization has occurred.

Next, a polyethylene terephthalate film was tightly adhered to the photopolymerizable layer of the same recording material, and imagewise exposure was carried out with air blocked, followed by thermal development. A 5-stage black image was obtained, with a Dmax of 1. Ko, Dmin were o, i.

Furthermore, on the photopolymerizable layer of the same recording material, use a bar coater to apply an io weight % water bath solution of polyvinyl alcohol (average degree of polymerization of about 200) as a surface layer to prevent oxygen permeation! 11
It was applied and dried to the same dry film thickness as the fan.

When this was exposed in air and thermally developed, a one-stage black image was obtained, and Dmax was ' -1b Dm 1 n was o
, i. .

As is clear from the above, a non-uniformly dispersed photopolymerizable layer is less affected by oxygen in the air and has higher photosensitivity than a uniformly dispersed photopolymerizable layer.

[Brief explanation of the drawing]

7 and 2 each show different embodiments of the image forming method of the present invention. In each figure, (5) is before exposure, 0
3) indicates the state after exposure, (q indicates the state after heat development. In each figure, / indicates the recording material, λ indicates the photopolymerizable element-containing layer, λ' indicates the photopolymerizable element-containing material, and 3 indicates the dye plate 37. - Recursor-containing layer, 3 is a barrier layer, j is a polymer produced by photopolymerization, O is a dye image, and 7 is a support. Patent applicant: Fuji Photo Film Co., Ltd. 3 T-111 Procedural Amendment Letter Commissioner of the Patent Office 1, Display of the incident Showa! 2nd patent application No. 2.
Title of the invention Recording material 3, Relationship with the case of the person making the amendment Patent applicant name (520) Fuji Photo Film Co., Ltd. 4, Subject of the amendment 1. Detailed explanation of the invention in the specification column 5, Details of the content of the amendment The description in the "Detailed Description of the Invention" section of the book is amended as follows. 1) Delete the lines from "in this case" in the it line of the first page to "in FIG. 3" in the 20th line. 2) On the 13th page, line C, amend ``indicates the case'' to ``distributed.'' 3) On page 14, lines l to /j, "described above" is corrected to "described later." Procedural amendment document, February 2-7, 1930, Mr. Tsutomu, Commissioner of the Patent Office, 1, Indication of the case, Showa SR, Patent Application No. 22T Co. 2, 2,
Name of the invention Recording material 3, Relationship with the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52
0) Fuji Photo Film Co., Ltd. 4. Subject of the amendment The description in the "Detailed Description of the Invention" column 5 of the description and the "Detailed Description of the Invention" section of the description of the amendment will be amended as follows. (1) Correct “photoreducible dye” in line 10 of this page to “reducing agent”. (2) Correct “reducing agent” in line 1 of page 11 to “photoreducible dye”. Procedural amendment book Showa! 2nd year 4th Mr. Commissioner of the Japan Patent Office 1, Indication of the case 1975 Patent Application No. 221222 2
, Title of the invention Recording material 3, Relationship with the person making the amendment Patent applicant 4, Subject of the amendment "Detailed description of the invention" column 5 of the specification, Contents of the amendment "Detailed description of the invention" of the description ” has been amended as follows. (1) On page 33, the line "Example" is corrected to read "Example 1." (2) After rfc, j on page 31, line 20, apply the following photopolymerizable composition on the dye precursor-containing layer of Example 1 to a dry film thickness of about IOμ. Apply as shown,
A photopolymerizable layer was formed by drying, and a recording material was produced. (Photopolymerizable composition) / of polyvinyl alcohol (average degree of polymerization 200), 0% by weight aqueous solution log, P-dodecyl-/- of sodium benzenesulfonate! Weight% aqueous solution o
, zg, methylene blue JWLg and sorbitol/
A mixture of 1 pentaerythritol tetraacrylate 211 and dimedone 00JII was added to a homogeneous solution consisting of 1i, and ultrasonic emulsification was performed in a dark place for 1 hour to obtain a photopolymerizable composition. The obtained recording material was subjected to mfII formation in the same manner as in Example 1 except that the exposure time and heating time were changed to 30 seconds and 40 seconds in the image forming method of Example 1, respectively, and the maximum transmission density of the image was / , J, and the minimum transmission density is 0. In l,
During this time, the wedge's j-stage CIolC exposure amount] is approximately 1.
．． A wide range of gradations are recorded. The 1 m image obtained was stable, and the unexposed recording material could also be stored in primary stability. ” is inserted. 11 Procedural Amendments dated July 17, 1944, 1, Indication of the case, Showa JT, Japanese Patent Application No. 2212-ta No. 2,
Title of the invention Recording material 3, Relationship with the person making the amendment Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Target of the amendment ``Detailed description of the invention'' column of the specification & Description of the contents of the amendment The description in the "Detailed Description of the Invention" section is amended as follows. (11, page 30, line 77, change "i." to "ku, the amount of binder applied is o, i-ko0f/m.
", more preferably 0.j-10f/m2." (2) From "dye again" in the JON/F line to "Used" in the ≠ line on page 37, the coating amount of the coloring agent is 0. λ~-〇f/m2, more preferably o, j-
jf/m2, and the coating amount of the binder is 0.0 to f/m21, more preferably o, i to it/@2. The amount of comb binder per -/- color former/f of the dye or dye precursor is in the range of 0.01 to It, more preferably a,/-/f. ” he corrected. (3) Correct [o, i~i, oJ of Jth page/Jth line to [0, l~ioJ]. 11

Claims (1)

[Claims] polymerizable vinyl monomer and/or polymerizable prepolymer,
A photopolymerization initiator, a binder, and a dye precursor that produces a dye that can be bleached or a dye that can be bleached by the vinyl monomer and/or prepolymer under heating.
A recording material using a binder, characterized in that a polymerizable vinyl monomer and/or a polymerizable prepolymer are non-uniformly dispersed in a binder.