JPH01234842A - Photoimage forming material and method for recording image using same - Google Patents

Abstract

PURPOSE:To obtain the excellent reproducibility and preserving property (fixing property) of an image and the excellent preserving property of the raw photoimage forming material by encapsulating a leuco dyestuff capable of oxidation-coloring, and a photooxidizing agent in a microcapsule and sticking a reducing agent and an org. sulfonamide compd. on the exterior of the microcapsule. CONSTITUTION:A core substance contg. a reacting substance of the leuco dyestuff and the photooxidizing agent, etc., is emulsified, and then the wall of a polymer substance is formed around the oil drop of the core substance to form the microcapsule. In this case, a reactant capable of forming the polymer substance is incorporated in the interior or the exterior of the oil drop. Next, the reducing agent and the org. sulfonamide compd. are sticked on the exterior of the microcapsule. And, the image is fixed by allowing the photooxidant agent to contact with the reducing agent through the wall of the capsule by heating it. Thus, the excellent reproducibility and preserving property (fixing property) of the image and the excellent shelf-life of the raw photoimage forming material are obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a photoimage-forming material and an image recording method using the same.

More specifically, the present invention relates to a photoimage-forming material that can be used as proof paper, printout paper, opaque film, etc., and an image recording method using the same.

``Prior Art'' Conventionally, this photoimage-forming material has been used in many photographic applications, such as so-called free radical photography, in which photosensitive areas are visualized by imagewise exposure.

Particularly effective in this regard is the radical oxidative color development of six-moderate leuco dyes to their corresponding dyes using photooxidizing agents (e.g. Photo oxidation).

Sci, Eng,, Engineering, Ri r-103 (/91./),
Special Publication Sho≠3-22,1AO7, Japanese Patent Publication Shojj-1333
No. 5, Tokukai Shoj? No.-60,322, JP-A-Sho t2-At
, see Koj issue).

``Problem to be Solved by the Invention'' However, because they are sensitive to light pressure, even after forming a dye image by exposure, if exposed to normal indoor light, sunlight or white light, color formation occurs and therefore handling of such photoimageable materials is difficult.

- In order to retain the image after the feet are formed, it is unavoidable to develop color in the unexposed areas during image exposure. It is known to preserve the original image by applying a reducing agent solution, such as a free radical scavenger (such as hydroquinone), to the imaged material, for example by spraying or impregnating. Although it is advantageous for the wet process, the workability and operability are complicated due to the wet process.Also, for example, Du Pont's Dy1
There are commercially available materials that have the excellent feature of being photo-processable, such as U-, which forms an image with UV light and fixes with visible light by activating a photoreducing substance. However, in this process, the light is used twice, monopolizing the equipment for that time, and this requires work such as replacing the spectral filter, so the processing speed may be unsatisfactory depending on the usage. Furthermore, the above-mentioned Tokko Sho≠3−kota, ψ0
The specification of No. 7 discloses that images ('1
There is a description that heat fixing is performed after 8 lights. However, in reality, these methods are not preferable because the photosensitive portion (leuco dye and photooxidizing agent) and the fixing agent coexist in close proximity, resulting in deterioration of sensitivity over time.

On the other hand, photoimage-forming materials consisting of these leuco dyes and photooxidizing agents are usually uniformly dissolved in an organic solvent and applied (or dipped, cast, etc.) onto a support such as paper or plastic film, and the solvent is dried. Remove by evaporation. Therefore, the use of such volatile organic solvents requires explosion-proof measures for manufacturing equipment, etc., which has disadvantages in terms of both safety and cost.

``Object of the Invention'' The object of the present invention is to provide a photoimage-forming material having excellent *1iffi reproducibility, shelf life, and image preservation (fixability), and to provide a photoimage forming material having excellent reproducibility, shelf life, and image preservation (fixing properties), and in addition, in the image forming and fixing process. The purpose is to provide a completely dry and simple recording method.

Another object of the present invention is to provide a photoimage-forming material that reduces or eliminates the need for handling in an organic solvent system, which is disadvantageous in terms of manufacturing suitability.

"Means for Solving the Problem" The above-mentioned object of the present invention is such that at least seven kinds of leuco dyes capable of color development by fR and at least one kind selected from photo-oxidizing agents are both encapsulated in microcapsules. In addition, a reducing agent and an organic sulfonamide compound should be present on the outside of the microcapsules! ? This is achieved by a stroke number recording method characterized by a photoimage-forming material having a characteristic characteristic, and a stroke number recording method characterized by irradiating the photoimage-forming material with light to form an image, and then bringing the photooxidizing agent and the reducing agent into contact to perform fixing. friend.

The most characteristic feature of the photoimage-forming material of the present invention is that microcapsules are used and an organic sulfonamide compound is added to the outside of the microcapsules.

In other words, the basic functions of microcapsules are (1)
Each ingredient inside and outside the microcapsule? Can be isolated microscopically.

(2) By encapsulating things inside microcapsules,
The influence of the external environment (particularly moisture, oxygen, storage temperature, etc.) is minimized, and inclusions can be stored stably.

(3) If necessary, the contents can be completely destroyed by external stimulation (for example, heat, pressure, etc.) or external additives can be introduced into the capsule to cause the components inside and outside the capsule to react.

(4) Even if the capsule core substance is based on an organic solvent such as oil, the entire capsule dispersion system can be treated as an aqueous system.

etc. can be mentioned.

In the present invention, the functions (1) and (2) above are used to improve system stability, the functions (1) and (3) are used as means for a simple recording method such as heat fixation after exposure, and (
The function 4) is utilized to improve manufacturing suitability.

Furthermore, the addition of an organic sulfonamide compound to the outside of the microcapsules can be used as an innovative low-temperature fixing technique that does not have any negative effects on raw storage stability.

In the present invention, preferred capsules are those in which at room temperature, the material isolation effect of the microcapsule walls prevents contact between the materials inside and outside the capsule, and the permeability of the material increases only when heated above a certain temperature.

The permeation starting temperature can be freely controlled by appropriately selecting the material for this phenomenon, the capsule wall material, the core material, and the additives. The transmission start temperature in this case corresponds to the glass transition temperature of the capsule wall (
Example: Tokukai Akira! Tata l.

A3R, Tokugan Sho B Tar/90.116, Tokkan Sho J Tartata, 4c Ri No. 0, etc.).

In order to control the glass transition temperature specific to the capsule wall, it is necessary to change the type of capsule wall forming agent. The wall materials of microcapsules used in the present invention include polyurethane, polyurea, polyester, polycarbonate, urea-formaldehyde resin, melamine-formaldehyde resin, polystyrene, styrene-methacrylate copolymer, gelatin, polyvinylpyrrolidone,
Examples include polyvinyl alcohol. Furthermore, two or more of these polymeric substances can also be used in combination.

In the present invention, among the above-mentioned polymeric substances, polyurethane, polyurea, polyamide, polyester, polycarbonate, etc. are preferable, and polyurethane and polyurea are particularly preferable.

The microcapsules used in the present invention are produced by emulsifying a core material containing reactive substances such as leuco dyes and photoreactive agents, and then forming a wall of polymer material around the oil droplets to form microcapsules. Preferably, in this case a reactant forming a polymeric substance is added to the interior of the oil droplet and/or to the exterior of the oil droplet.

For details about microcapsules that can be preferably used in the present invention, such as a preferred method for producing microcapsules, see the US patent! , No. 78.10μ, 3,726.6
It is described in the specification of No. 6.

For example, when polyurethane urea is used as a capsule wall material, a polyvalent incyanate and a second substance (e.g. polyol) that reacts with it to form the capsule wall are mixed into the aqueous phase or oily liquid to be encapsulated and emulsified in water. By dispersing and increasing the temperature, a polymer formation reaction occurs at the oil droplet interface to form a microcapsule wall.If the second additive is, for example, a polyamine, or if no additional examples are added, Polyurea is produced.

In this case, the polyvalent incyanate used, the polyol to be reacted with it, and the polyamine are disclosed in US Pat. No. 3,211,313, US Pat.
No. 261, Tokuko Sho<CZ-<CO3μ7, Same μtar 2
μ/! ri issue, JP-A-Sho ψr-roiyt issue, same u 1-
raott numbers are shown and can also be used.

Examples of the polyvalent incyanate include m-phenylene diisocyanate, p-phenylene diisocyanate,
2. A-) lylene diisocyanate), 'l''-tolylene diisocyanate, naphthalene-1,ψ-diisocyanate, diphenylmethane-μ, lA/-diisocyanate, J, J'-dimethoxy-μ, table, -hyphenyl diisocyanate ), JIJ'-dimethyldiphenylmethane-≠, 4c'-diincyanate, xylylene-7
゜Hiro-diisocyanate, Hiro, μ′-diphenylpropane diisocyanate, trimethylene diinocyanate,
Diisocyanates such as hexamethylene diisocyanate, boo/, ≠-diisocyanate, μ, ψ′, 4c“-
Triphenylmethane triisocyanate, toluene-2
, ≠, triisocyanates such as 6-dolyisocyanate, g, lLu-dimethyldiphenylmethane-2,
! ', r, 5/-tetraisocyanates such as tetraisocyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, 2.4L-) adducts of lylene diisocyanate and trimethylolpropane,
There are isocyanate prepolymers such as adducts of xylylene diisocyanate and trimethylolpro-Liao, and adducts of tolylene diisocyanate and hexanetriol.

Examples of polyols include aliphatic and aromatic polyhydric alcohols, hydroxy polyesters, and hydroxy polyalkylene ethers.

The following polyols described in JP-A-60-≠Tatata No. 1 are also used: ethylene glycol%'+3-propanediol, t,tA-7'tanediol,/,j-<methanediol, l,6-hexanediol , /l°7−
Hebutanediol, /, f-octanediol, propylene glycol, λ, 3-dihydroxybutane%'l'
-dihydroxybutane, l,3-dihydroxybutane,
Tips 2-dimethyl-/, 3-propanediol, 2. ≠
- is methanediol, ! -hexanediol, 3-
Methyl-/, j-intanediol, l, -cyclohexane dimetatool, dihydroxycyclohexane, diethylene glycol, t, 2. A-)! J) “Roxyhexane, λ-phenylpropylene glycol, t
, t, l-) IJ methio-rui lopan,
Hexanetriol, hantaerythritol, hantaerythritol ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin, /, tA-di(
2-hydroxyethoxy)yne, condensation products of aromatic polyhydric alcohols and alkylene oxides such as resorcinol dihydroxyethyl ether, p-xylylene glycol, m-xylylene glycol, α, α′-dihydroxy-p-diisopropyl ( Nzen, tA, tA
'-dihydroxy-diphenylmethane, co-(p+ I
-dihydroxydiphenylmethyl)benzyl alcohol, adducts of ethylene oxide to bisphenol A, adducts of propylene oxide to bisphenol A, etc. Polyols have a ratio of hydroxyl groups of 0.02 to 1 mole of incyanate groups. Preferably, 2 mol is used.

Examples of polyamines include ethylene diamine, trimethylene diamine, tetramethylene diamine, hantamethylene diamine, hexamethylene diamine, p-phinylene diamine, m-phinylene diamine, pi is butane, 2-methylbi is butane, 2. Examples of dimethyldiamine include butane, cohydroxytrimethylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenehantamine, and amine adducts of epoxy compounds. Polyvalent incyanates can also react with water to form polymeric materials.

phosphoric acid esters, phthalic acid esters, acrylic acid esters)
km ester, methacrylic acid ester, sono and other carboxylic acid esters, fatty acid amides, alkylated biphenyls,
Alkylated terphenyls, chlorinated paraffins, alkylated naphthalenes, diarylethanes, etc. are used. Specifically, Japanese Patent Application Publication No. 1987-2μ2,09, Japanese Patent Application No. 1987-
7. You can use the items listed in the μO number.

In the present invention, an auxiliary solvent may be added to the above-mentioned organic solvent as a low-boiling solubilizing agent. Particularly preferred examples of such auxiliary solvents include ethyl acetate, isopropyl acetate, butyl acetate, and methylene chloride.

On the other hand, the water-soluble polymer to be contained as a protective colloid in the aqueous phase to be mixed with the oil phase can be appropriately selected from known anionic polymers, nonionic polymers, and amphoteric polymers, but polyvinyl alcohol , gelatin, cellulose derivatives and the like are preferred.

Further, as the surfactant to be contained in the aqueous phase, one can be appropriately selected from anionic or nonionic surfactants that do not cause precipitation or aggregation by interacting with the above-mentioned protective colloid. .

Preferred surfactants include sodium alkylbenzenesulfonate (eg, sodium lauryl sulfate), dioctyl sodium sulfosuccinate, polyalkylene glycol (eg, polyoxyethylene nonylphenyl ether), and the like.

In the present invention, the size of the microcapsules is determined particularly from the viewpoint of improving image resolution, storage stability, and ease of handling, for example, as described in Japanese Patent Application Laid-Open No. o-2itt, No. 220, the volume average particle size is preferably 20μ or less, and! It is preferable that it be less than μμ.

Furthermore, if the capsules are too small, there is a risk that they will disappear into the pores or fibers of the substrate, but this depends on the properties of the substrate or support, so it cannot be said in general, but it is preferably O1lμ or more.

Next, the leuco dye that constitutes one component of the photoimage-forming material of the present invention will be described. The leuco dyes that can be used in the present invention are reduced dyes that have one or two hydrogen atoms and that develop color upon removal of hydrogen atoms and, in some cases, addition of additional electrons, to form a dye. It includes. These leuco dyes are substantially colorless, or in some cases have a weak color, so that when they develop color relative to the acid, they can provide a means for forming patterns.

This oxidation is achieved in the present invention by the presence of a low (at least moderate) photooxidant.

This photo-oxidant is activated by light irradiation and reacts with the leuco dye to release the unirradiated and therefore unchanged material /ζ
Generates a colored image on the ground.

The leuco dye that easily develops color by oxidation due to a* is disclosed in, for example, the unopened patent J, tA4! J-, No. 23μ is included and is hereby incorporated by reference.

(al aminotriarylmethane (bJ aminoxanthine (c) aminothioxanthin (d) aminota, 10-dihydroacridine (,
e) Aminophenoxazine (f) Aminophenothiazine (g) Aminodihydrophenazine (h) Aminodiphenylmethane (i) Leucomendamine (j) Aminohydrocinnamic acid (cyanoethane, leucomethine) (k) Hydrazine (13 leucoindigoid dye (c) Amino-λ,3-dihydroanthraquinone (nl
y trahalo p+ p' -biphenol(0)co(p-hydroxyphenyl)-g, r-diphenylimidazole (p+ phenethylaniline Among these leuco dyes, those from (a) to /i) contain one hydrogen atom By losing , it develops a color and becomes a dye, but from (j) to ωJ, the dye loses two hydrogen atoms to produce a parent dye. Among these, aminotriarylmethane is preferred. - The type of aminotriarylmethane preferable for boat fishing has a small number of aryl groups (both of which have two aryl groups, (a) Rs and R2 are each hydrogen, C
1~C□. RIR in the para position to the bond to the methane carbon atom, such as a group selected from alkyl, 2-hydroxyethyl, 2-cyanoethyl, ma or benzyl;
2N-substituent and (b) lower alkyl (C is /-4
), lower alkoxy (C is l-ψ), a phenyl group having a group ortho to the methane carbon atom selected from fluorine, chlorine, or bromine;
The aryl group may be the same as or different from the first two, and if different, (a) lower alkyl, lower alkoxy, chlorine, diphnynylamino, cyan, nitro, hydroxy, fluorine or bromine, alkylthio, Phenyl which can be substituted with arylthio, thioester, alkyl sulfone, aryl sulfone, sulfonic acid, sulfonamide, alkylamide, orylamide, etc.; (b) Naphthyl substituted with amine, di-lower alkylamino, alkylamino; ( C) pyridyl which can be substituted with alkyl; (di
Quinolyl; (e) A class of aminotriarylmethanes and their acid salts, characterized in that they are selected from indolinylidenes which can be substituted with alkyl. Preferably R1 and R2 are hydrogen or alkyl of 1-μ carbon atoms. Most preferably all three aryl groups are identical.

Triarylmethane or other leuco dyes of the structure described above do not exhibit color-forming dark reactions that result in fogging or coloration when applied to photographic film, paper, or other systems as conventional photoimaging materials. You may receive it.

However, these leuco dyes can be used in new materials using capsules in the invention.

This is because the color-forming dark reaction can be prevented by the capsules achieving the same effect as storing such compositions in the absence of air.

On the other hand, preferred photooxidizing agents that can be used in the photoimaging materials of the present invention are inactive until exposed to actinic radiation, such as visible light, ultraviolet light, infrared radiation, X-rays, and the like. Various photooxidants have different peak sensitivities across the spectrum depending on the structure of the compound. As such, the particular photooxidizing agent selected will depend on the nature of the actinic radiation. When exposed to such radiation, the photooxidizing agent oxidizes the color former to its color forming form to form the oxidizing agent.

Typical photo-oxidizing agents include U.S. Patent No. 3. Qu2.
Jlta No. 3,102. Carbon tetrabromide, N-promosuccinimide, and tribromomethylphenylsulfone halogenated hydrocarbons of No. tA7, azide polymers described on page 5 of the Abstracts of the 961 Spring Research Conference of the Photographic Society of Japan, and U.S. Patent No. 3. 12. Azide compounds such as 2-azidobenzoxazole, benzoyl azide, and 2-azide (zuimidazole) described in U.S. Pat. f-hybrid compounds such as pyridotheacyanine verchlorate, l-methoxy-cortacylpyridinium p-toluenesulfonate,
No. 721 (7), 2. g, lophine dimer compounds such as J--triarylimidazole dimer, benzophenone, p-aminophenyl lactone, polynuclear quinone,
At least one photooxidation side compound from the group consisting of compounds such as thioxanthenone and mixtures of the above compounds!
It includes, but is not limited to.

In producing the photoimage-forming material of the present invention, good results are obtained when the leuco dye and the photooxidizing agent are mixed in a molar ratio of about 10:/ to about 1:10. A more preferred ratio is 2:/ to 1:2.

The photoimage-forming material of the present invention can be exposed to light to form an image, and then subjected to, for example, heat treatment to obtain a stable image. That is, as a mechanism for fixing the photoimage forming material of the present invention, for example, a photooxidizing agent and a reducing agent are brought into contact with each other through a capsule wall from a heating trap! ! ! By doing so, even if the photo-oxidizing agent is subsequently activated, the reducing agent acts to deactivate the oxidizing agent.

Such reducing agents typically act as so-called free radical traps that trap the free radicals of the activated photooxidant.

All known free radical scavenging substances can be used, and specifically include the following.

For example, the United States! Existence j, O1A, 2. ．． Organic reducing agents having a hydroxyl group on the benzene ring and at least another hydroxyl group or an amino group at another position on the benzene ring described in the specification of No. J-/j (for example) - hydroquinone, catechol,
resorcinol, hydroxyhydroquinone, pyrrologlycitur, and amine phenols such as O-amine phenol and p-aminophenol), or the aforementioned Japanese Patent Publication No. 1983-3.

72r4i7, such as l-phenylpyrazolidin-3-one [
Phenidone A, the following formula (1)), /-phenyl-ψ
-Methylvirazolidi/-3-one [Phenidone B, below 17] Formula (-211, /-phenyl-μ).

μm dimethylpyrazolidin-3-one [dimezone, the following formula (3)], and 3-methyl-/-p-sulfophenyl)-2-pyrazoline-! -one and h-3-methyl-7-
Examples include phenyl-2-virasorin-j-one.

However, the following substituents can be present on the phenyl group of the cyclic phenyl hydrazide.

Q-, m- and p-methyl, p-trifluoromethyl,
m- and tFp-chloro, m- and p-furomo, p-fluoro, 0-lm- and p-methoxy, p-ethoxy,
p-benzyloxy, p-butoxy, p-phenoxy,
Co, μ, is one trimethyl, 3゜μm dimethyl. The following substituent can be present at the 4-position on the heterocyclic group of the cyclic phenyl hydrazide. bis-hydroxymethyl, hydroxymethyl and methyl, hydroxymethyl, dimethyl,
dibutyl, ethyl, benzyl. The following substituents can be present at the 5-position on the heterocyclic group of the cyclic phenyl hydrazide: dimethyl, methyl, phenyl.

Furthermore, guanidine derivatives, alkylene diamine derivatives,
Compounds selected from hydroxyamine derivatives can be used. Specifically, the guanidine derivatives include:
For example, phenylguanidine, /, J-diphenylguanidine, /, 2. ! -I7 phenylguanidine, /,
2-dicyclohexylguanidine, /, 2. J-tricyclohexylguanidine, l,3-di-0-tolylguanidine, 0-)lyldiphenylguanidine, m-tolyldiphenylguanidine, p-)'J-diphenylguanidine, N,N'-dicyclohexyl-≠- Morpholinocarboxamidine, l,3-ditolyl-3-phenylguanidine, /, -1dicyclohexylphenylguanidine, /-o-tolylbiguanide, N-benzylidene-
Examples include guanidinoamine.

Examples of alkylene diamine derivatives include ethylene diamine, propylene diamine, tetramethylene diamine, hexamethylene diamine, octamethylene diamine,
Examples include /, /, J-diaminododecane, and tetrabenzylethylenediamine.

Examples of hydroxyamine derivatives include jetanolamine, triethanolamine, 3-β-7teroxy/-N,N dimethyl 7minor-propanol, and the like.

The above-mentioned reducing agents that act as free radical extractants can be used alone or in combination of two or more, but the reducing agents that have the function of acting on so-called oxidizing agents are limited to these. It's not a thing.

In the photoplaton-forming feather of the present invention, both the leuco dye and the photocatalytic agent described ifJ are encapsulated in microcapsules, but the reducing agent that is not encapsulated is solid-dispersed by sand milling or oil. It is best to use it after dispersing it into a hole.

In the case of solid dispersion, the particles are dispersed in a water-soluble polymer solution having a concentration of 1 to 10 g L*, and the preferred dispersed particle size is 10 μm or less. Preferred water-soluble polymers include water-soluble polymers used when making microcapsules.

Emulsification and dispersion can be carried out by referring to the method and materials described in the specification of Japanese Patent Application No. 1AoP, No. 1986-7.

The preferred amount of reducing agent is between 7 and 1 on a mole basis of photooxidation series components.
Although it can be used in an amount of 00 times the molar amount, a range of 7 to 10 times the molar amount is more preferable in order to obtain the desired result with as little amount as possible.

The fixation of the lotus in the present invention can be effectively achieved by bringing the photooxidizing agent and the reducing agent into contact with each other through the capsule wall by heating as described above.

It is believed that the organic sulfonamide compound of the present invention, which is added to the outside of the microcapsule together with the reducing agent, lowers the melting point of the reducing agent and further improves the thermal permeability of the microcapsule wall, thereby enabling low-temperature fixing. .

Specific examples of organic sulfonamides include the following compounds. That is, p-toluenesulfonamide, o-toluenesulfonamide, benzenesulfonamide, p-toluenesulfonanilide, N(p-methoxyphenyl)-p-toluenesulfonamide, N-(o-
methoxyphenyl)-p-)luenesulfonamide, N
-(p-chlorophenyl)-p-)luenesulfonamide, N-(0-chlorophenyl)-p-toluenesulfonamide)'', N(p)lyl)p-toluenesulfonamide)', N-(o-toluenesulfonamide)'', N-(o-hydroxyphenyl)-p-)toluenesulfonamito, N-bensyl-p-
) luenesulfonamide, N-(2-phenethyl)-p
-) luenesulfonamide, N-(2-hydroxyethyl)-p-) luenesulfonamide, N-(J-methoxypropyl)-p-toluenesulfonamide, methanesulfonani IJ)", N-(p-) tolyl) sulfonamide, N-(0-tolyl) sulfonamide, N-(p-
methoxyphenyl)sulfonamide, N-(o-methoxy)sulfonamide, N-(p-chlorophenyl)sulfonamide, N-(o-chlorophenyl)sulfonamide, N-(J,≠-xylyl)sulfonamide, N-
(p-ethoxyphenyl)sulfonamide, N-benzylmethanesulfona.

Mido, N-(2-phenoxyethyl)methanesulfonamide, /, 3-bis(methanesulfonylamino)benzene, 113-bis(p-toluenesulfonylamino)benzene, p-ethylbenzenesulfonamide, etc. is not limited to these.

The amount of the organic sulfonamide compound of the present invention used is the reducing agent/
0.0/~IO per part by weight! if part, preferably 0.
/~! Parts by weight.

In the present invention, a known sensitizer can also be used as an additional component of the photooxidizing agent. For example, compounds described in "Sensitizer" edited by Katsumi Tokumaru and Makoto Okawara, Kodansha/yJ'7, pages 6q to 7j can be mentioned. Specifically, aromatic ketones, acetophenones, diketones, carbonyl compounds such as acyloxime esters, aromatic thiols, sulfur compounds such as mono- and disulfides, thioureas, dithiocarbamates,
These include organic peroxides such as benzoyl peroxide, azo compounds such as azobisisobutyronitrile, and halides such as N-promosuccinimide. Further, as sensitizing dyes in the visible range, there may be mentioned dyes having amidinium ion-based, carboxyl ion-based, or dipolar amide-based chromophores described in the same book, pages 6 to 1.23 of IO. Specifically, cyanine-based, phthalein-based, and oquinnol-based dyes are representative.

In the present invention, a stabilizer such as a known antioxidant may also be added to the capsule. Needless to say, the function of the stabilizer here is a substance that has a similar function to the reducing agent, although its purpose is different, so its use must be kept to the minimum necessary. Therefore,
Specifically, in addition to the above-mentioned free radical scavenging substances, compounds described in the specifications of US Pat. Examples include λ,≠-dihydroxyaldoxime described in the specification of No. JJj, but the amount of these stabilizers used is about θ,01
It is preferable to use about 2J molti from molti, and 0
．． Most preferred is a range of 1 molti to 10 molti.

The photoimage-forming material in the present invention is a leuco dye and a photooxidizing agent. It can be prepared by coating, impregnating, or forming a self-supporting layer on a support as a dispersion of encapsulated microcapsules, a reducing agent, and an organic sulfonamide compound.

At this time, binders that can be added to the dispersion include polyvinyl alcohol, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, gum arabic, gelatin, polyvinylpyrrolidone, casein, styrene-butadiene latex, acrylonitrile-butadiene latex, and polyacetic acid. Various emulsions such as vinyl, polyacrylic ester, ethylene-vinyl acetate copolymer, etc. can be used. The amount used is 0.0 in terms of solid content. jll 7m~! l 7m
It is.

The coating amount of the light-forming material in the present invention is preferably between 3///m and JOF/nl, particularly 11/m2 and 207/m2 in terms of solid content.

j / / m 2 or less, sufficient C degree cannot be obtained, and 3
Even if more than 0.017 m is coated, no improvement in quality will be seen, so it will be disadvantageous in terms of cost.

Suitable materials for the support include papers ranging from tissue paper to heavy cardboard, regenerated cellulose, cellulose acetate, cellulose nitrate, polyethylene terephthalate, vinyl polymers and copolymers, polyethylene, polyvinyl acetate, polymethyl Films of plastic and polymeric materials such as methacrylates, polyvinyl chloride; woven fabrics; materials commonly used in graphic arts and decorative applications such as glass, wood and metal.

When coating the support, generally well-known coating methods such as dip coating, air knife coating, curtain coating, roller coating, doctor coating, wire barcoding, slide coating, and gravure coating can be used. method, spin code method or U.S. Patent No.
It can be coated by the extrusion coating method using a hopper described in the specification of No. 1, r/, 27ψ.

Any convenient light source can be used in the present invention to activate the photooxidant and form the image of the leuco dye. The radiation may be natural or artificial, monochromatic or non-coherent or coherent light (and must be of sufficient density for proper activation of the photoimaging composition).

Conventional light sources include fluorescent, mercury, metal doped and arc lamps. Coherent light sources include pulsed atom-lasers, xenon lasers, argon ion-lasers, and ion-ratio neon lasers whose emission is within or overlaps the UV or visible absorption bands of the photooxidant. − is. Also useful in the subject compositions are UV and near visible light illumination-emitting cathode ray tubes, which are widely used in printout systems for writing on photosensitive materials.

The image may be formed by writing with a beam of activating light or by exposing selected areas behind a negative, stencil or other relatively opaque pattern to such light. Negatives are +! ): It may be silver on a film of cellulose or polyester or such that its opacity arises due to agglomeration of regions with different refractive indices. Image formation can be done using conventional diazo printing equipment, graphic art exposure or electronic flash.
and U.S. Patent J, T61,174.
It may also be performed by the projection described in No. 1. The exposure time depends on the density and spectral energy distribution of the light, its distance from the composition, the nature and amount of the composition used, and the density of the colors in the desired image.
It may change within a few minutes after extraction.

After surface exposure, a photo-oxidizing agent and a reducing agent can be brought into contact with each other by heating to carry out a single phase i'e.

The photopolymerization material of the present invention is used as a photopolymerization composition that has excellent manufacturing suitability and excellent image forming properties and storage stability.

Examples are shown below, but the present invention is not limited thereto. Note that "parts" shown in addition fk indicate "parts by weight."

"Example" Example 1 Prepare the photoimageable materials shown below.

Sample (1): Leuco dye Leuco Crystal Violet 3.0 parts Photoemitting agent λ,2'-bis-(0-?lorophenyl)
-Hiro, l, r, r'- 3.0 parts of tetraphenylbiimidazole 0.1 part of trifluoromethylphenylsulfone
θ, μ part methylene chloride
2 Part tricresyl phosphate
Two parts of Takenate D-/10N (77% by weight ethyl acetate solution) (manufactured by Takeda Pharmaceutical Co., Ltd. (trade name)) were mixed together, and polyvinyl alcohol was mixed with 63 parts of an aqueous solution and 10 parts of distilled water. After adding into the aqueous solution, 2
Emulsification and dispersion was carried out at 00C to obtain an emulsion having an average particle size/μ. (
The emulsion obtained was kept stirring for 3 hours at ≠0°CK. After that, it was returned to room temperature and filtered to obtain an aqueous capsule dispersion.

Next K.

Polyvinyl alcohol ≠ heavy! t% aqueous solution iro part R light train /-phenylpyrazolidin-3-one (phenidone A) 30 parts p-toluenesulfonamide 3Ofm
Dispersed using A.G. Co., Ltd. (product name)), with an average particle size of 3.
A reducing agent-containing dispersion of μ was obtained.

Mix the above capsule liquid part and reducing agent-containing dispersion liquid, and use high-quality paper (basis weight i→/m2) for super calendering.
Apply it so that the solid application amount is / Of / Wind 2,
Heat and dry at RO 0C for 1 minute to obtain sample (1).

Comparative Example 1 The same procedure as in Example 1 was carried out except that p-)rue/sulfonamide was not used in Example 1, and comparative sample (
Ratio-7) was obtained.

The obtained friend samples (1) and (ratio-7) were irradiated with jet light (ultra-high pressure mercury lamp, orc I! light) through the line drawing manuscript to form a negative impression, and then Samples (1) and (ratio -7) after gap formation,
'fijO' on heating rollers at temperatures of 0°C and 720°C
A through-fixing operation was performed at a speed of tx1 minute.

Thereafter, these samples were exposed to jet light and the entire surface was irradiated with light five times the amount of exposure, and the background density (Cub IJ) was measured using a Macbeth reflection densitometer. The results are shown in Table 1.

No. 1 My sample shop Fixing operation Temperature after full surface light irradiation
Skin density (1) tao 0c o, otty
12θ o, otri (ratio -/) ta0 0, j7//koo
o, oty Is there a fresh shelf life for samples (1) and (ratio-7)?
To see, fresh skin density and dry thermo t0
The skin density after storage at 0c for 217 hours was measured using a total Macbeth reflection densitometer. The results are shown in Table 2.

Table λ Sample store Fresh dry skin density after dry skin density (1) 0. O400,07/ (ratio -/) 0. From the results of O & T 0.072 or higher, it is clear that by adding the organic sulfonamide compound of the present invention, an innovative low-temperature fixing technology that does not adversely affect raw storage stability can be established.

Example 2.3 51M9'lJ/ K o -) luenesulfonamide or id p instead of nop-1-luenesulfonamide
Sample (2) and Sample (3) were prepared in the same manner as in Example/, except that the sulfonate was used.
) created seven.

We evaluated these in the same way as sample (1),
Obtained similar results.

Example ≠ Tris-(2-methyl-≠-diethylaminophenyl)-methane was used instead of leuco crystal violet as the leuco dye, and 2λ,6-dydolychloro was used instead of the photooxidant trifuromomethylphenylsulfone. Sample <4L) 1 was prepared using methyl-≠-(p-methoxyphenyl)-triazine in the same manner as in Example except for the following.

It was evaluated in the same way as Sample (1), and the same results were obtained.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment (spontaneous) May q, 1986

Claims (2)

[Claims] (1) At least one type selected from leuco dyes capable of oxidative color development and at least one type selected from photo-oxidizing agents are both encapsulated in microcapsules, and a reducing agent and an organic A photoimage-forming material characterized by the presence of a sulfonamide compound. (2) At least one kind selected from leuco dyes capable of oxidative color development and at least one kind selected from photo-oxidizing agents are both encapsulated in microcapsules, and a reducing agent and an organic 1. An image recording method, which comprises forming an image by irradiating a photoimage forming material containing a sulfonamide compound with light, and then fixing the image by bringing the photooxidizing agent into contact with the reducing agent.