JPH01243048A - Light image forming material and image recording method using same - Google Patents

Abstract

PURPOSE:To ensure superior image reproducibility and image preservability by incorporating a specified phenol compd. into microcapsules. CONSTITUTION:A phenol compd. represented by formula I is incorporated into microcapsules contg. at least one kind of leuco dye capable of developing a color by oxidation and at least one kind of photooxidizing agent in a light image forming material further contg. at least one kind of reducing agent at the outside of the microcapsules. In formula I, each of R1 and R5 is H, alkyl or a heterocyclic group and each of R2-R4 is H, etc., but R1 and R2 are not simultaneously H. Superior image forming property and preservability are ensured.

Description

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

More specifically, the light that can be used for proofing paper, printout paper, overlay/if film, etc. relates to a forming material and an image recording method using the same.

[Prior Art J] Conventionally, this type of photoimage-forming material has been used in many photographic applications, such as so-called free radical photography, in which a photosensitive area is visualized by exposing one image to light.

Particularly effective in this regard is the radical oxidative color development of various leuco dyes using photooxidizing agents to dye their corresponding dyes (eg, pltoto.

Sci, Eng,,, L, Tal-103(/
? 1. /), Tokuko Showa 1tJ-27, ≠07, Tokuko Showa! -46335, JP-A-Sho Tough-1, 0, 3, 27,
(See JP-A-62-A&, No. 26μ).

[Problem to be Solved by the Invention] However, because of their sensitivity to light, even after forming a dye image by exposure, they cannot be exposed to normal indoor light, sunlight, or white light. Color formation occurs when such materials are used, and the handling of such optical bed-forming materials is therefore difficult.

- In order to hold an image on the floor after it has been 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 solution of a reducing agent, such as a free radical scavenger (such as hydroquinone), to an imaged material, for example by spraying or impregnating. Although this is advantageous for preserving or fixing the original image, it complicates workability and operability due to the wet process. Also, for example, Dy of Du PonL company
There are commercially available materials that have the excellent feature of being processable only with light, such as 1ux ■, which forms an image with UV light and fixes with visible light by activating a photoreducing substance. However, this process monopolizes the equipment by using the light once, and requires work such as replacing spectral filters, so the processing speed may be insufficient depending on the application. It has its drawbacks. Furthermore, the aforementioned Tokko Sho μ3-Kota,
The specification of No. 4L07 states that a reducing heat fixing agent is included in the binder solution together with a leuco dye and a photooxidizing agent, or the heat fixing agent is overcoated on the photosensitive layer.
There is a description that heat fixing is performed after image exposure. 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 a volatile tIM solvent requires explosion-proof measures for manufacturing equipment, etc., which is disadvantageous in terms of both safety and cost.

``Object of invention'' The purpose of non-invention is to improve l1bI image reproducibility, life insurance!・
It is an object of the present invention to provide a Kozosugi printing material having excellent storage properties (fixing properties), and also to provide a completely dry and simple E-recording method in the image forming and fixing process.

Another object of the invention is to provide an original image-form α-monthly material in which the handling of organic medium fibers, which is disadvantageous in terms of manufacturing suitability, is reduced or unnecessary.

"Means for Solving the Problem" The above-mentioned object of the present invention is to encapsulate at least one type of leuco dye capable of oxidative coloring and at least one type of leuco dye capable of forming an oxidative color in a microcapsule. and at least one kind selected from reducing agents is present on the outside of the microcapsules, and furthermore, a phenol compound represented by general formula (1) is added into the microcapsules. After forming an image by irradiating the characteristic light-forming material and the element 1* forming material with light, carrying out a constant process by bringing the nuclear oxidation reduction and the reducing agent into contact with each other.
This was achieved using a distinctive image recording method.

-Satsu (1) In the formula, R1 and R5 do not represent a hydrogen atom, an alkyl group, or a heterocyclic group, and R2, R3, and R4 may be the same or different, and each represents a hydrogen atom, an alkyl group, or an aryl group. group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, diacylamino group, sulfonamido group, alkylamino group, alkoxycarbonyl group, acyloxy group or halogen atom, provided that R1 and R5 are hydrogen at the same time It is never an atom.

The compound represented by general formula (1) will be explained in more detail.

General formula [! ] To describe R1 and R5 in more detail, R
1 and R5 each represent a hydrogen atom, an alkyl group (preferably an alkyl group having 20 or less carbon atoms, a linear or branched alkyl group, an aralkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, such as a methyl group) , n-butyl group, t-butyl group, n-octyl group, n-dodecyl group, n-hexadecyl group, benzyl group, allyl group, cyclopentyl group, cyclohexenyl group, etc.), heterocyclic group (
(for example, a tetrahydropyranyl group, etc.), however, R1 and R5 are not hydrogen atoms at the same time, and R
Preferably, 1 and R5 are a hydrogen atom or an alkyl group.

To describe R2, R6 and R4 in general formula [I] in more detail, R2, R3 and R4 are each a hydrogen atom, an alkyl group (preferably an alkyl group having 20 or less carbon atoms,
Represents a straight chain or branched alkyl group, aralkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, such as methyl group, ethyl group, i-propyl group, t-butyl group, t-octyl group, n-off , thyl group, t-hexadecyl group, benzyl group, allyl group, cyclopentyl group, cyclohexenyl group, etc.), aryl group (preferably an aryl group having 20 or less carbon atoms, such as phenyl group, p-methylphenyl group, P -methoxyphenyl group, p-octanamidophenyl group, 0-chlorophenyl group, α-naphthyl group, etc.), alkoxy group (preferably an alkoxy group having 20 or less carbon atoms, such as methoxy group, t-butoxy group, cyclo xyloxy group, n-dodecyloxy group,
n-octadecyloxy group, benzyloxy group, allyloxy group), aryloxy group (preferably an aryloxy group having 20 or less carbon atoms, such as phenoxy group,
p-methylphenoxy group, p-methoxyphenoxy group,
m-chlorophenoxy group, α-naphthoxy group, etc.), alkylthio group (preferably an alkylthio group having 20 or less carbon atoms, such as methylthio group, i-butylthio group, n-
hexylthio group, cyclohexylthio group, n-octadecylthio group), arylthio group (preferably an arylthio group having 20 or less carbon atoms, such as phenylthio group,
p-methylphenylthio group, 0-carboxylphenoxy group, m-methylphenylthio group, 0-methoxycarbonylphenylthio group, m-nitrophenylthio group, etc.)
, acylamino group (preferably an acylamino group having 20 or less carbon atoms, such as an acetylamino group, benzoylamino group, caproamino group, etc.), diacylamino group (preferably a diacylamino group having 30 or less carbon atoms, such as a succinimide group) , 3-hydantoinyl group, etc.), sulfonamide group (preferably a sulfonamide group having 20 or less carbon atoms, such as methanesulfonamide group, benzenesulfonamide group, etc.), alkylamino group (preferably alkylamino group having 30 or less carbon atoms) A group, such as ethylamino group, -butylamino group, dioctylamino group, n-
octadecylamino group, etc.), acyl group (preferably an acyl group having 20 or less carbon atoms, such as an acetyl group, caprylic group, p-methoxybenzoyl group, etc.), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 20 or less carbon atoms), , for example, methoxycarbonyl group, t-butoxycarbonyl group, n-octadecyloxycarbonyl group), acyloxy group (preferably an acyloxy group having 20 or less carbon atoms, such as acetoxy group, caproxy group, lauroxy group, benzoyloxy group, etc.) , represents a halogen atom (eg, chlorine atom, bromine atom, etc.). It is preferred that R3 and R+ are both hydrogen atoms.

Among the above definitions, the group having an alkyl moiety and an aryl moiety may be further substituted with a substituent, and some of the substituents are described in the definition of the general formula [T] above, but for example, an alkyl group , cycloalkyl group, alkenyl group, aryl group, benzyl group, halogen atom, nitro group, cyan group, hydroxyl group, alkyloxy group, cycloalkyloxy group, alkenyloxy group, aryloxy group, benzyloxy group, alkylthio group, arylthio group, amino group, alkylamino group, acylamino group, sulfonamide group, alkoxycarbonyl group, silyl group, acyl group, acyloxy group, sulfamoyl group, sulfonyl group, etc.

The most characteristic feature of the photoimage-forming material of the present invention is that microcapsules are used and a specific phenol compound is added to the microcapsules in addition to a leuco dye and a photooxidizing agent.

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

(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 removed 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 post-exposure heat fixing, and (4)
This function is used to improve manufacturing suitability.

In addition, the addition of a specific phenolic compound to the microcapsules is an innovative technology for improving shelf life that does not have a negative effect on sensitivity.The preferred capsules of the present invention are those in which the substance isolation of the microcapsule walls occurs at room temperature. This action prevents contact between substances inside and outside the capsule, and the permeability of the substance increases only when heated above a certain temperature.

The permeation start temperature of this phenomenon can be freely controlled by appropriately selecting the capsule wall material, capsule core material, and additives. In this case, the permeation start temperature is
It corresponds to the glass transition temperature of the capsule wall (e.g., Japanese Patent Application Publication No. 77゜U31, Japanese Patent Application Sho!
tit issue, Tokugan Shoj Tatata, Hirori 0 issue, etc.).

In order to control the inherent glass transition temperature of the capsule wall, it is necessary to change the group of capsule wall forming agents. Microcapsule wall materials that can be 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 may 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 preferable.

The microcapsules used in the present invention are produced by emulsifying a core material containing a reactive substance such as a leuco dye and a photo-oxidizing agent, and then forming a wall of a polymer material around the oil droplets to form microcapsules. is preferred, in which 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 U.S. Pat.
It is described in the specification of No. 626.

For example, when polyurethane urea is used as a capsule wall material, a polyvalent isocyanate and a second substance (e.g. polyol) that reacts with it to form the capsule wall are mixed into the water phase or an oily liquid to be encapsulated and emulsified and dispersed in water. By increasing the temperature, a polymer formation reaction occurs at the oil droplet interface, forming a microcapsule wall. If the second additive is added, for example a polyamine, or if nothing is added, a polyurea is formed.

In this case, the polyvalent incyanate used, the polyol to be reacted with it, and the polyamine are disclosed in US Pat. No. 321r/JlrJ, US Pat.
No. 2316r, special public Sho ψ♂-μ03≠7, same Kota l
tA/jri issue, JP-A-Sho g-roiyi issue, same g, r
-rq-ort, and they can also be used in Europe.

Examples of the polyvalent isocyanate include ■-phenylene diisocyanate, p-phenylene diisocyanate,
2.4-) Lylene diisocyanate, 214c-tolylene diisocyanate, naphthalene-l, μm diisocyanate, diphenylmethane-ψ, 4c'-diisocyanate, j, J'-dimethoxy-<c, tA, -hyphenylene diisocyanate, 3.3'-dimethyldiphenylmethane-μ, μ'-diisocyanate, xylylene-7゜μm diisocyanate, 1AIIA'-diphenylpro/ξ diincyanate, trimethylene diisocyanate, hexamethylene diisocyanate, bu/,
Diisocyanate such as 4cm diincyanate, μ,
4U, U"-triphenylmethane triisocyanate, toluene-2,ψ,4-) diisocyanate, ≠ p/-dimethyldiphenylmethane-2,J', J-,j'-tetraisocyanate, etc. Incyanate, adduct of hexamethylene diisocyanate and trimethylolpropane, adduct of co,l-tolylene diisocyanate and trimethylolpropane, adduct of xylylene diisocyanate and trimethylolpropane, addition of tolylene diisocyanate and hexanetriol Incyanate prepolymer is al.

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

The following polyols described in Japanese Patent Application Laid-Open No. 2003-110000-4Ly-Tata No. 1 can also be used. Ethylene glycol, l.

3-propanediol, /, u-butanediol, /,
j--? octanediol, l, 6-hexanediol, /, 7-hebutanediol, /, f-octanediol, propylene glyco-k, 2. ! l dihydroxybutane, 'l'l diedroxybutane, l,3-dihydroxybutane 1. Z,X-dimethyl-/,! -propanediol, co, μ-intanediol, λlj-hexanediol, 3-methyl-/, j-intanediol, l
, dicyclohexanedimethanol, dihydroxycyclohexane, diethylene glycol, /, , 2.4-
Trihydroxyhexane, λ-phenylpropylene glycol, /, /, /-)limethylolpronone, hexanetriol, pentaerythritol, pentaerythritol ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin, /, J-
Di(,2-hydroxyethoxy)benzene, condensation product of aromatic polyhydric alcohol such as resorcinol dihydroxyethyl ether and alkylene oxide, p-xylylene glycol, 111-xylylene glycol, α
, α'-dihydroxy-p-diisopropylbenzene,
μ, tA′-dihydroxy-diphenylmethane, no(
+'+p'-dihydroxydiphenylmethyl)benzyl alcohol, an adduct of ethylene oxide to bisphenol A, an adduct of propylene oxide to bisphenol A, and the like. In the polyol, the ratio of hydroxyl groups to 1 mole of incyanate groups is 0. It is preferable to use -2 mol of OJ for one cycle.

Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine/sif'mine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, In-phenylenediamine, piperazine, comethylbilazine, 2. ! ;-Dimethylpiperazine,! Examples include -hydroxytrimethylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, and amine adducts of epoxy compounds. Polyvalent isocyanates can also react with water to form polymeric materials.

phosphoric acid esters, phthalic acid esters, acrylic acid esters, methacrylic acid esters, other carboxylic acid esters, fatty amides, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, algylated naphthalenes, diarylethanes, etc. used. Specifically, rf opening θ−, 2 μ, l! , No. 074 and Japanese Patent Application No. 61-7, ≠07 can be used.

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 4M auxiliary solvent include ethyl acetate, inpropyl 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, it is possible to appropriately select and use an anionic or nonionic surfactant that does not interact with the medical colloid to cause precipitation or aggregation. can.

Preferred surfactants include sodium alkylbenzenesulfonate (eg, sodium lauryl sulfate), dioctyl sodium sulfosuccinate, polyalkylene glycol (eg, polyoxyethylene nonylphenyl ether '6).

In the present invention, the size of the microcapsule is /1
In-house solution f3S for 1. From the viewpoints of degree growth, storage stability, and handling, the volume average particle size is 20μ or less as measured by the measurement method described in, for example, Japanese Patent Application Laid-Open No. 2003-200100-2/4C, No. 270. is preferable, and particularly preferably not more than μμ. In addition, if the capsule is too small, there is a risk that it will disappear into the pores or fibers of the substrate, but this depends on the nature of the substrate or support, so it cannot be said with certainty, but it is 0. /μ or more is preferable.

Next, the leuco dye that constitutes one component of the photoimage-forming material of the present invention will be described. The leuco dyes used in the present invention are reduced type leuco dyes that have one or two hydrogen atoms, and which develop color and form a dye by removing them and, in some cases, adding additional electrons. dyes. These leuco dyes are essentially colorless, or in some cases have a weak color, so that when they develop color relative to the acid, they serve as a means of forming a notane.

This acid ratio is achieved in the present invention by the presence of at least one ray of light.

This photooxidant is activated by light irradiation and reacts with the leuco dye to produce a colored image against a background of unirradiated and therefore unchanged material.

Leuco dyes that easily develop color through oxidation due to the above mechanism are, for example, available in the United States! , ≠41.23ψ, and is included here for reference.

(a) Aminotriarylmethane.

(b) Aminoxanthine (C) Aminothioxanthine (d) Aminota, 10-dihydroacridine (e
) aminophenoxazine (f) aminophenothiazine (g) aminodihydrophenazine (II7 aminodiphenylmethane (i) leucomendamine (j) aminohydrocinnamic acid (cyanoethane, leucomethine) (k) hydrazine (υ leucoindigoid dye <m>Amino-2,3-dihydroanthraquinone (n)
Tetrahalo p,p'-biphenol(o)2(P-
Hydroxyphenyl)-4,5-diphenylimidazole (p > phenethylaniline Among these leuco dyes, (a) to (i) develop color by losing one hydrogen atom and become dyes, but ( The leuco dyes j) to (p) lose two hydrogen atoms to form the parent dye. Among these, aminotriarylmethane is preferred. - Generally preferred types of aminotriarylmethane are aryl at least two of the groups are (a) R1 and R2 are each hydrogen, 01-C
RIR2N- in the para position to the bond to the methane carbon atom, such as a group selected from 10 alkyl, 2-hydroxyethyl, 2-cyanoethyl, or benzyl;
a substituent and (b) phenyl having a group ortho to the methane carbon atom selected from lower alkyl (C 1 to 4), lower alkoxy (C 1 to 4), fluorine, chlorine, bromine, or hydrogen; and the third aryl group may be the same as or different from the first two, in which case (a) lower alkyl, lower alkoxy, chlorine, diphenylamino, cyano, (b) phenyl substituted with hydroxy, fluorine or bromine, alkylthio, arylthio, thioester, alkylsulfone, arylsulfone, sulfonic acid, sulfonamide, alkylamide, arylamide, etc.; (b) amino, di-lower alkylamino, alkyl; naphthyl which may be substituted with amino X; CC) pyridyl which may be substituted with alkyl; (dl
Quinolyl; (eJ Class 1 of aminotriarylmethane and its acid salts, characterized in that it is selected from indolinylidene substituted with alkyl. Preferably, 1 and R2 are hydrogen or 1-μ It is an alkyl of a carbon atom.

Most preferably all three aryl groups are the same.

Other leuco dyes are triarylmethane with the structure shown in 011. May undergo formative dark reactions.

However, these leuco dyes can be used in the new capsule-based material of the present invention.

This is because the color-forming dark reaction is prevented by the capsules having the same effect as storing the composition in the absence of air.

On the other hand, preferred photooxidizing agents that can be used in the photoforming materials of the present invention are inert 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 produces an acidic agent that oxidizes the color forming agent to its colored form.

Typical photo-oxidizing agents include those described in U.S. Pat. 02. ≠7 Carbon tetrabromide, N-promosuccinimide, tribromomethylphenylsulfone and other halogen hydrocarbons, the azide polymer described on page J of the Abstracts of the Spring Research Presentation of the Photographic Society of Japan, U.S. Patent No. j, 212. azide compounds such as coazidobenzoxazole, benzoyl azide, and coazidobenzimidazole described in U.S. Pat. Compounds such as perchloride 1-, /-methoxycomethylhy+)dinium p-toluenesulfonate, Japanese Patent Publication No. 62-3
λ, Ge,! described in No. 7,721. - photooxidative rigid compounds from the group consisting of lophine dimer compounds such as triarylimidazole dimers, compounds such as benzophenones, p-aminophenyl ketones, polynuclear quinones, thioxanthenones, and mixtures of the above compounds; Among these, lophine dimer compounds and organic halogen compounds are preferred, and combination use of both is optimal because crystal sensitivity can be achieved.

The lophine dimer compound is prepared by the following formula. rf
When f is released, the field corresponds to =h'. 2. ≠, forming a j-triarylimidazolyl group.

/'7,''/'/ (wherein A, B and D are the same or different and are unsubstituted or provided with substituents that do not inhibit the dissociation of the dimorph into imidazolyl groups or the defeat of the leuco dye. Groups B and D representing an aryl group which may be carbocyclic or heterocyclic have an energizing Q to three substituents and are A
The group has θ to Hiro substituents. Useful lophine dimer compounds and methods for their preparation are disclosed in U.S. Pat.

The organic halogen compound is a solid compound in which the carbon content in the molecule is 4 cO or less.

Specifically, the compound shown by the formula % (in the formula, 几 is hydrogen, halogen, or aryl group, and X is halogen), Shiorie is shifunka ash, halitosis carbon Ie
, H)-nitrobenzotribromide, pro7trichloromethane, pencitrichloride, hexabromoethane, iodoform, /, /, /-tribromocotatyl-1-propatol, /, /.

Co, J-tetrabromoethane, Co, Co, λ-tribromoethanol, /, /, /-)lichlorocomethyl-4
-pro/f-nol, (2)-killing (in the formula 11 x is hydrogen or /- it on the 7 benzene ring
% represents a pendant group, and these substituents include a nitro group, a halokene group, an alkyl group, a haloalkyl group, an acetyl group, a haloacetyl group, and an alkoxy group. Compounds shown by , moe is 0
-Nitro-α,α.

α-Tribromoacetophenone, m-nitro α.

α α-trifluoroacetophenone, 9-nitro-α,
α, α-Tribromoacetophenone, α.

α, α-tribromoacetophenone, α, α, α-tribromo J, IA-7 chloroacetophenone, (3)-
Killing % Formula % [In the formula, R is an alkyl group, an aryl group (including those with !l substituents, and X is a halogen]),
For example, /, 3-benzenedisulfonyl chloride,
≠-dinitrobenzenesulfonyl chloride, O-nitrobenzenesulfonyl chloride, m-nitrobenzenesulfonyl chloride)', J, J'-diphenylsulfone disulfonyl chloride, ethanesulfonyl chloride F's p-bromobenzenesulfonyl chloride,
p-Nitrobenzenesulfonyl chloride% p-2 iodobenzenesulfonyl chloride, p-acetamidobenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride)', p-) L: L sulfonyl chloride, methanesulfonyl chloride, benzene Sulfonyl bromide, a compound represented by (41-mosquito formula % formula % [in the formula, R is an alkyl group, an aryl group (also referred to as having a substituent), and chloride, 0-nitrobenzenesulfenyl chloride, (5)-killing (in the formula, it is a directly substituted or unsubstituted aryl group, Xl, Compounds shown in Bromomethyl-p-nitrophenyl sulfone, λ-trichloromethylbenzothiazole sulfone, Hiroshi, 6-dimethylpyrimidyl-coated tribromomethyl sulfone, tetrabromodimethyl sulfone,
2.4'-dichlorophenyl-trichloromethylsulfone, λ-methyl-≠-chlorophenyl-trichloromethylsulfone, λ, 2-dimethyl-Hiro-kuchlorophenyl-trichloromethylsulfone, 44-dichlorophenyl-tribromomethylsulfone, (In the formula, 1L is The M-cyclic compound residue may have a substituent.Compounds represented by X, X2, and Xa are hydrogen, halogen, and are not all hydrogen at the same time, such as tribromoquinaldine, 2-tribromomethyl-4-methylquinoline, 4-tribromomethylpyrimidine, 4-
Phenyl-6-tribromomethylpyrimidine, 2-trichloromethyl-6-nitrobenzothiazole, 1-phenyl-3-trichloromethylpyrazole, 2゜5-ditribromomethyl-3,4-dibromothiophene, 2-trichloromethyl- 5-(p-butoxystyryl)-1,
Examples include organic halogen compounds such as 3,4-oxadiazole and 2,6-dydrichloromethyl-4-(p-methoxyphenyl)triazine.

Among these, compounds (2), (5), and (6) are preferred, and the halogen is preferably chlorine, bromine, or iodine.

In producing the photoimage-forming material of the present invention, the molar ratio of the leuco dye and the photooxidizing agent is about 10=1 to about 1:10.
Good results can be obtained by mixing at a ratio of . A more preferred ratio is 2:1 to 1:2.

-i Among the phenolic compounds of the present invention represented by the formula [1], the effects of the present invention are more effectively exhibited when those represented by the following formula [1a] are used.

General formula (la) In the formula, R5 and R7 represent a hydrogen atom and an alkyl group, respectively, provided that R6 and R7 are never hydrogen atoms at the same time.

The compound represented by the general formula [1] is disclosed in U.S. Patent No. 4.264.
．． It can be synthesized according to the method described in No. 720.

When carrying out the present invention, they can be used alone or in combination of two or more, and other known antifading agents can also be used in combination.

Known anti-fading agents include hydroquinones, phenols, chromanols, coumarans, hindered amines, and complexes, such as those disclosed in JP-A-59-83162, JP-A-58-24141, JP-A-52-152225, and U.S. Pat. Patent No. 3,698°909, Patent No. 4,268.593
British Patent No. 2.069,162 (A>, British Patent No. 2.069,162)
It is described in specifications such as No. 027.731.

Representative examples of compounds represented by -maximum [11 are shown below, but the compounds used in the present invention are not limited thereby.

21ts H Oll Shili3 H OC112(,:02(J(-112L,,112rishi113i) These compounds are microencapsulated together with the leuco dye and the photooxidant. The amount added is ioo parts of the photooxidant. It is preferably 7 to 100 parts, more preferably 3 to 0.
parts, most preferably from 7 to . This is the second part.

After the photoimage forming material of the present invention is exposed to light to form an image, a stable image can be reliably obtained by subjecting it to, for example, heat treatment. That is, the fixing mechanism of the photoimage-forming material of the present invention is that the photooxidizing agent and the reducing agent come into contact with each other through the capsule wall by heating, for example, so that even if the photooxidizing agent is subsequently activated, the reducing agent is no longer present. This is because the oxidizing agent acts to deactivate it.

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, in the specification of U.S. Pat. agents (e.g., hydroquinone, catechol,
resorcinol, hydroxyhydroquinone, pyrrologlycitur, and amine phenols such as 0-aminophenol and p-aminephenol), or cyclic phenylhydrazide compounds described in specification tK of the aforementioned Japanese Patent Publication No. 62-37゜721, such as l -Phenylpyrazo! J'
'7-J-one [phenidone A, the following formula (1)],
[l-phenyl-nomethylpyrazolidin-one [phenidone B, the following formula (,2)],]l-phenyl-ψ
≠-dimethylpyrazolidin-3-one [dimezone, the following formula (3)],] and 3-methyl-/-p-sulfophenyl-corbylazolin-one and 3-. 71-1-
One example is Ru-l-phenyl-corbylazoline.

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

0-, +1x- and p-methyl, p-trifluoromethyl, In- and p-chloro, m- and p-pro7, p-
Fluoro, 0-1■- and p-methoxy, p-ethoxy, p-benzyloxy, p-butoxy, p-phenoxy, co, <c, 1r-1 remethyl, 3°≠-dimethyl. The following substituents can be present at the μ position on the heterocyclic group of the cyclic phenyl hydrazide. bis-hydroxymethyl, hydroxymethyl and methyl, hydroxymethyl,
Dimethyl, diptyl, 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, /, 3-diphenylguanidine, /, 2. J-1-diphenylguanidine, /
, 2-dicyclohexylguanidine, /, 2. J-)
Licyclohexylguanidine, 113-di-0-tolylguanidine, 0-tolyldiphenylguanidine, In
-tolyldiphenylguanidine, pF') ludiphenylguanidine, N,N'-dicyclohexyl-Hiro-morpholinocarboxamidine, /, J-ditolyl-
Examples include 3-phenylguanidine, /, J-dicyclohexylphenylguanidine, /-0-)rilbiguanide, and N-benzylidene-guanidinoamine.

Examples of alkylenediamine cotton conductors include ethylenediamine, prozenediamine, nato-2-methylenediamine, hexamethylenediamine, octamethylenediamine,
/, /, 2-diaminododecane, tetrabenzylethylenediamine, and the like.

Examples of hydroxyamine derivatives include diethanolamine, triethanolamine, 3-β-f7 thyloquine/-N,N dimethylamine-prononol, and the like.

The above reducing agents that act as free radical extractants can be used alone or in combination, but are limited to these if they are reducing substances that have the ability to act on so-called oxidizing agents. It is not something that will be done.

In the source-forming material of the present invention, both the pre-BC leuco dye and the photooxidizing agent are encapsulated in microcapsules, but the reducing agent, which is not encapsulated, has a concentration of λ to 30% in the case of solid dispersion. water mt+: dispersed in a polymer solution,
The preferred dispersed particle size is ioμ or less. Preferred water-soluble polymers include water-soluble polymers used when making microcapsules. Regarding emulsification and dispersion, see Japanese Patent Application No. 4.2-73. This can be done by referring to the method and materials described in the specification of Koori No.

The preferred reducing agent bran is based on the moles of the photooxidizing agent component.
The amount is 100 times the molar amount, but in order to obtain the desired result with as little amount as possible, a range of t- to io times the molar amount is more preferable.

Incidentally, image fixation in the present invention is effectively achieved by contacting the photo-oxidizing agent with the reducing agent through the capsule wall as described above, but it goes without saying that (the capsule may be destroyed by pressurization). It is also possible to bring out similar effects by doing so. Also, by performing heating and pressurization at the same time, a synergistic effect can be expected.

Furthermore, in order to impart fixing properties to a photoforming material consisting of a leuco dye capable of oxidative color development and a photooxidizing agent, it is also possible to encapsulate only a reducing agent, or in an embodiment of the present invention, a reducing agent in addition, in microcapsules. It is possible.

In the present invention, a known sensitizer can also be used as an additional component of the photooxidizing agent. For example, "Sensitizer" edited by Katsumi Tokuku and Makoto Okawara, published by Kodansha, 1964, 7th year.
Compounds described on pages t to 7j can also be used. Specifically, aromatic ketones, a7tophenones, diketones,
carbonyl compounds such as acyloxime esters,
Aromatic compounds such as aromatic thiols, mono- and disulfides, thioureas, dithiocarbonates and bamates, peroxides such as benzoyl peroxide, and azo compounds such as azobisisobutyronitrile. , halides such as N-promosuccinimide, and the like. In addition, Fr dyes that increase in the visible range include amidinium ion type, carboxyl ion type, as described on pages 704 to 723,
Examples include dyes having a dipolar amide chromophore. Specifically, cyanine-based, phthalein-based, and oxonol-based dyes are representative. In the present invention, stabilizers such as known antioxidants may also be added to the capsule. . Although the purpose of use of the stabilizer is different, it goes without saying that the stabilizer is a substance that has the same function as the reducing agent, so it is necessary to keep the amount used to the minimum necessary. Specifically, in addition to the above-mentioned free radical scavenging substances, compounds described in specification 1 of U.S. patents ψ, Q6 O, and μJ, and 2 described in specification 1 of JP-A No. 11-11-F, 33-T. .g-
Dihydroxyaldoxime etc. can be mentioned, but
The amount of these stabilizers to be used is based on the photo-oxidizing agent [2 and about 0
゜Q1 is preferably used in an amount of about 25 mol% from θ. The range of 1 mol% to 10 mol 6G is J! I also like L7.

The photo-image-forming material of the present invention can be applied to a support as a dispersion of microcapsules containing such a leuco dye and a photooxidizing agent, and a reducing agent, or impregnated with the support to form a self-supporting layer. You can make it.

At this time, binders that can be added to the above dispersion include polyvinyl alcohol, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, gum arabic, gelatin, polyvinylpyrrolidone, casein, styrene/-butadiene latex, acrylonitrile-butadiene latex, polyacetic acid. Various emulsions such as vinyl, polyacrylic ester, ethylene-vinyl acetate copolymer, etc. can be used. The amount used is converted to solid content: Q, evening p/tn 2~j//nt
It is 2.

The coating amount of the light-forming material in the present invention is 3 jl/m2 to jOp/nt2 in terms of solid content, especially! ! ! It is preferable that it is between /m2 and 20 p/m.

Below J ji / m, sufficient 0 degrees cannot be obtained,
3°! ! /m or more will not improve the quality and will be disadvantageous in terms of cost.

Suitable materials for the support include papers ranging from tissue paper to thick balls and ttEK, regenerated cellulose,
Cellulose acetate, cellulose nitrate, polyethylene di1/
Phthalates, vinyl polymers and copolymers, polyethylene, polyvinyl acetate, polymethyl methacrylate, polyvinylpyrrolidone; woven fabrics; materials commonly used in graphic arts and decorative applications such as glass, wood and metal scraps includes.

In coating the support, generally known coating methods such as dip coating, air knife coating, curtain coating, roller coating, doctor coating, wire barcoding, slide coating, and gravure coating are used. Coat method, spin code method or US patent 2.
It can be coated by the extrusion coating method using the hopper described in 1ii1 in the specification of IG, S'/, J5'μ, etc.

Any convenient light source can be used in the present invention for activating the photooxidant and forming the Leuco Dye H image. The light 91 may be natural or artificial, monochromatic or non-coherent or coherent, and suitable light must be of sufficient density for activation of the forming composition.

Conventional light sources include fluorescent, mercury, metal doped and arc lamps. A coherent light source is a pulsed nitrogen laser whose emission is within or overlaps the UV or visible absorption bands of the photooxidant. These are xenon lasers, argon ion lasers and ionized neon lasers. 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. The negative may be silver on a film of cellulose acetate or polyester or such that its opacity results from agglomeration of regions with different refractive indices. The image is formed using conventional diazo printing equipment,
In graphic art exposure or; latching apparatus, and US Patent J, 461. It may also be performed by the projection described in ≠t1. Exposure time depends on the density of the light and the vector energy distribution, its distance from the composition, and the composition used! l: may vary from a fraction of a second to a few minutes depending on the quality and quantity and density of color in the desired image.

After the image is exposed, the image can be fixed by combining a photooxidizing agent and a reducing agent. A gentle method can be applied to bring the two into contact.

For example, there is a method of heating. In this method, the temperature of the microcapsule wall is raised to a temperature above its glass transition point so that the photooxidant and the reducing agent pass through the softened microcapsule wall and come into contact with each other. The glass transition point of the microcapsule wall varies depending on the material used, and therefore, the heat treatment conditions necessary for fixing can be appropriately selected in consideration of these factors.

Another method is to destroy the microcapsules by mechanical force and bring them into contact. This method also uses materials with a high glass transition point.

The force required to break may vary depending on the material and particle size, but can be easily determined by one skilled in the art.

The photoimage-forming material of the present invention is used as a photoimage-forming 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" indicating the amount added indicate "parts by weight."

Example 1 The photoimage forming material shown below was prepared.

Sample (1): Leuco dye leuco crystal violet 3.0 parts/photooxidant 2,2-bis-(0-chlorophenyl)-
4,4,5,5-Tetraphenylbiimidazole 3.0 parts Tribromomethylphenylsulfone 0.6 parts Compound [E-2] 0.4 parts Methylene chloride 22 parts Tricresylpos Fate ko≠parttakene)L)−
/l0N (7 parts by weight ethyl acetate m liquid) (Narita Pharmaceutical Co., Ltd. (cleavage (trade name)) - particulate was mixed, and a water bath solution consisting of tJ parts of polyvinyl alcohol 1% water bath solution and 100 parts of distilled water was prepared. After adding 6 inside, 2
The mixture was emulsified and dispersed at 0°C to obtain an emulsion having an average particle size of lμ. Furthermore, the obtained emulsion was heated at Hiro 00C for 3 hours (jt t4!
L continued. Thereafter, it was returned to xb and filtered to obtain an aqueous capsule dispersion.

Next, 30 parts of polyvinyl alcohol≠n''% water-drinking ljO part reducing agent l-phenylpyrazolidin-3-one (Phenidone) were mixed, and Dynomil (Willie AΦ Bacophene) was mixed.
Dispersed with A.G. Co., Ltd. (trade name) to achieve an average particle size of 3.
A phenidone A osseous fluid of μ was obtained.

The above capsule surface 7 parts and phenidone A dispersion WAtiti
Mix and use super calendering U-quality paper (Tsubo BAt
, tW/m2) to give a solid n1 fabric/θ2/m2, and dried under heat.
Two Bull (11) (Uta.

Run 4ijIJ, 2-j 夷b=91J/Compounds [E-/], [IE-J), (E-j
] and (E-//) were carried out in exactly the same manner as Meigarasu Example 1, and sample (2), sample 1; Jl,
A sample (4) and a twin (5) were obtained.

Comparative Example/Middle 1+Th 1+lI / was carried out in the same manner as Meishi Series/, except that the compound [E-co] was not used, and a comparison sample (Ratio-/) was scooped out.

In order to examine the fresh shelf life of samples (1) to (5) and (ratio-7) of IL et al. The skin W degree (Turnip IJ) was measured with a Macbeth reflection densitometer, and the change in the Capri woman degree was added by 611.

Further, the fresh sample was irradiated with light using a jet light (ultra-high pressure mercury lamp, manufactured by Oak Co., Ltd.) through the line drawing original 3, and the image density of the exposed area was measured using a Macbeth reflection densitometer.

The results are shown in Table 1.

Table 1 Sample Fresh Dry Thermo T & Exposure Section (1)
0.068 0.070 1.23(2)
0.069 0.073 1.20 (3)
0.067 0.071 1.21 (4)
0.070 0.074 1.22(5) 0
．． 068 0.070 1.21 (ratio -1) 0.0
68 0.921 1.20 From these results, it can be seen that by adding the specific compound of the present invention, an epoch-making technique for improving raw shelf life that does not have an adverse effect on sensitivity has been established.

Next, the samples (1) to (5) after image formation are passed through a heating roller at a temperature of 120 °C at a speed of 450 mm/min to promote the permeability of the capsule wall by heat and to fix the materials inside and outside the capsule. contact).

As a result, even though the entire surface of these samples was irradiated with light five times as much as the image exposure using a jet light, no change in the image was observed.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment form) ■, Small case indication 1985 Patent Application No. 7θJ! ≠ No. 2, Title of the invention: Photoimage-forming material and recording method using it 3, Relationship with the person making the amendment case Patent application location: Naka, Minamiashigara City, Kanagawa Prefecture? G? No. 210 4, Date of amendment order 1967 (Monday - 2) (shipment date) 5. Subject of amendment Pages 1 to JJ of the specification, μ! ~j
Page 6, a separate sheet with the contents of the amendment.

Description 1, Title of the Invention Photoimage-forming material and image recording method using the same 2, Claims (1) At least one selected from leuco dyes capable of oxidative color development and at least one selected from photo-oxidizing agents A photoimage-forming material in which a species is encapsulated in a microcapsule, and at least one kind selected from reducing agents is present on the outside of the microcapsule. A photoimage-forming material characterized by adding a phenol compound represented by (1).

- Sapporo (I) (In the formula, R, Miyo and R2 each represent a hydrogen atom, an alkyl group, or a heterocyclic group; Rz, Rs, and R4 are the same or different; each represents a hydrogen atom, an alkyl group, represents an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acylamino group, a diacylamino group, a sulfonamido group, an alkylamino group, an alkoxycarbonyl group, an acyloxy group, or a halogen atom, provided that R1 and R8 are simultaneously (2) At least one selected from leuco dyes capable of color development by oxidation and at least one selected from photo-oxidizing agents are both encapsulated in microcapsules, and At least one reducing agent selected from reducing agents is provided on the outside of the microcapsule.
In a photoimage-forming material in which a species is present, a phenol compound represented by general formula (1) is added to microcapsules.After forming an image by irradiating the photoimage-forming material with light, An image recording method characterized by bringing a photooxidizing agent into contact with the reducing agent.

3. 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 for applications such as blue paper, printout paper, and overlay films, and an image recording method using the same.

"Prior Art" Conventionally, this type of 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 various leuco dyes to their corresponding dyes using photo-oxidizing agents (eg Photo.

Sci, Eng-+ 5.98-103 (1961
), Special Publication No. 43-29,407, Japanese Patent Publication No. 55-55,
No. 335, JP-A-57-60, 329, JP-A-62-
66.254).

``Problem to be Solved by the Invention'' However, because they are sensitive to light, even after exposure to form a dye image, 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 once it has been formed, it is unavoidable to develop color in the unirradiated areas during image exposure. Although this is advantageous, it requires complicated workability and operability due to the wet process.Also, for example, DuP
There are commercially available materials, such as Dy1ux from onL, which have the excellent feature of being processable only with light, such as forming an image with UV light and fixing 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 it has the disadvantage that the processing speed may be unsatisfactory depending on the usage. have. Furthermore, the specification of the above-mentioned Japanese Patent Publication No. 43-29.407 describes leuco dyes,
There is a description that a reducing heat fixing agent is contained in the binder solution together with a photooxidizing agent, or the heat fixing agent is coated with -L on the photosensitive layer to carry out heat fixing after image exposure. 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 to each other, resulting in sensitivity deterioration 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.

"Objective of the Invention The object of the present invention is to provide a photoimage forming material having excellent image reproducibility, raw storage stability, and image storage stability (fixing performance), and to provide a completely dry and fixing process in the image forming and fixing process. The purpose is to provide a 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 aqueous solvent system, which is disadvantageous in terms of manufacturing suitability.

"Means for Solving the Problem" The above object of the present invention is that at least one kind selected from leuco dyes capable of developing color by oxidation and at least one kind selected from photo-oxidizing agents are both encapsulated in microcapsules. , and at least one type selected from reducing agents is present on the outside of the microcapsule, and a phenol compound represented by general formula (1) is further added to the microcapsule. This was achieved by an image recording method characterized in that an image forming material is irradiated with light to form an image, and then the photooxidizing agent and the reducing agent are brought into contact with each other to perform fixing.

-Salt (1) In the formula, R and R3 each represent a hydrogen atom, an alkyl group, or a heterocyclic group, R, R5, and R4 may be the same or different, and each represents a hydrogen atom, an alkyl group,
It represents an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acylamino group, a diacylamino group, a sulfonamido group, an alkylamino group, an alkoxycarbonyl group, an acyloxy group, or a halogen atom. However, R+ and R3 are never hydrogen atoms at the same time.

The compound represented by general formula (1) will be explained in more detail.

-S To describe R, , R, in formula (1) in more detail, R
, R, respectively represent a hydrogen atom, an alkyl group (preferably an alkyl group having 20 or less carbon atoms, a straight chain or branched alkyl group, an aralkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, such as methyl group, n-butyl group, t-butyl group, n-octyl group, n-dodecyl group, n-hexadecyl group, benzyl group, allyl group, cyclopentyl group, cyclohexenyl group, etc.), heterocyclic group (
(e.g., tetrahydropyranyl group, etc.), provided that
R1 and R are not hydrogen atoms at the same time, and it is preferable that R1 and R3 are hydrogen atoms or alkyl groups.

To describe Rt, Rs and R4 in general formula (1) in more detail, Rz, Rs and R4 are each a hydrogen atom, an alkyl group (preferably an alkyl group having 20 or less carbon atoms,
Represents a straight-chain or branched alkyl group, aralkyl group, alkenyl group, cycloalkyl group, or cycloalkenyl group, such as a methyl group, ni-f-114, i-propyl group, t-
Butyl group, 1-. 1-ctyl group, n-octyl group, t-hexadecyl group, benzyl group, allyl group, cyclopentyl group, cyclohexenyl group, etc.), aryl group (preferably an aryl group having 20 or less carbon atoms, such as phenyl group,
p-methylphenyl group, P-methoxyphenyl group, p-
Octanemidophenyl group, 0-chlorophenyl group <α
-naphthyl group, etc.), alkoxy group (preferably an alkoxy group having 20 or less carbon atoms, such as methoxy group, t-butoxy group, dichlorooxy group, etc.), aryloxy group (preferably an aryloxy group having 20 or less carbon atoms, For example, phenoxy group, p-methylphenoxy L p-methoxyphenoxy L m-chlorophenoxy group, α-naphthoxy group, etc.), alkylthio group (preferably an alkylthio group having 20 or less carbon atoms, such as methylthio group, i
-butylthio group, n-hexylthio group, cyclohexylthio group, n-octadecylthio group, etc.), arylthio group (preferably an arylthio group having 20 or less carbon atoms, such as phenylthio group, p-methylphenylthio group, 〇-
carboxylphenoxy group, m-methylphenylthio group, 0-methoxycanibonylphenylthio group, m-nitrophenylthio group), acylamino group (preferably an acylamino group having 20 or less carbon atoms, such as acetylamino group, benzoyl amino group, caproamino group, etc.), diacylamino group (preferably a diacylamino group having 30 or less carbon atoms, such as succinimide group, 3-hydantoinyl group, etc.), sulfonamide group (preferably 2 carbon atoms).
0 or less sulfonamide group, such as methanesulfonamide group, benzenesulfonamide group, etc.), alkylamino group (preferably an alkylamino group having 30 or less carbon atoms, such as ethylamino group, L-butylamino group, dioctylamino group) group, n-octadecylamino group, etc.), acyl group (preferably an acyl group having 20 or less carbon atoms, such as acetyl group, caprylic group, p-methoxybenzoyl group, etc.), alkoxycarbonyl group (preferably 2 carbon atoms)
0 or less alkoxycarbonyl group, such as methoxycarbonyl 4, t-butoxycarbonyl group, n-octadecyloxycarbonyl group, etc.), acyloxy group (preferably an acyloxy group having 20 or less carbon atoms, such as acetoxy group, caproxy group, lauroxy group) It is preferable that R2 and Ra, which represent a halogen atom (eg, a chlorine atom, a bromine atom, etc.), are both hydrogen atoms.

Among the above definitions, the group having an alkyl moiety and an aryl moiety may be further substituted with a substituent (some of the substituents are described in the definition of the general formula (1) above, but for example, an alkyl group, cycloalkyl group, alkenyl group, aryl group, benzyl group, halogen atom, nitro group, cyano group, hydroxyl group, alkyloxy group, cycloalkyloxy group, alkenyloxy group, aryloxy group, benzyloxy group, alkylthio group, Examples include arylthio group, amino group, alkylamino group, acylamino group, sulfonamide group, alkoxycarbonyl group, silyl group, acyl group, acyloxy group, sulfamoyl group, and sulfonyl group.

The most characteristic feature of the photoimage-forming material of the present invention is that microcapsules are used and a specific phenol compound is added to the microcapsules in addition to a leuco dye and a photooxidizing agent.

The basic functions of microcapsules are (1)
Each component can be isolated microscopically inside and outside the microcapsule.

(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 removed 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 an organic solvent system 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) described above are used to improve the stability of the system, the functions (1) and (3) are used as means for a simple recording method such as heat fixing after exposure, and (4) )
This function is used to improve manufacturing suitability.

Furthermore, the addition of a specific phenol compound into microcapsules has been utilized as an innovative technique for improving raw shelf life without adversely affecting sensitivity.

/ / / Preferred capsules in the present invention 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 start temperature of this phenomenon can be freely controlled by appropriately selecting the capsule wall material, capsule core material, and additives. In this case, the permeation start temperature is
It corresponds to the glass transition temperature of the capsule wall (e.g., Japanese Patent Application Laid-Open No. 59-91゜438, Japanese Patent Application No. 59-190,
No. 886, Japanese Patent Application No. 59-99,490, 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. Microcapsule wall materials that can be 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 photo-oxidizing agents, and then forming a wall of polymer material around the oil droplets to form microcapsules. In this case, it is preferable to form a polymeric substance or add an actant to the inside of the oil droplet and/or to the outside of the oil droplet.

For details on microcapsules that can be preferably used in the present invention, such as preferred methods for producing microcapsules, see U.S. Pat.
It is described in the specification of No. 696.

For example, when polyurethane urea is used as a capsule wall material, a polyvalent isocyanate and a second substance (e.g. polyol) that reacts with it to form the capsule wall are mixed into the water phase or an oily liquid to be encapsulated and emulsified and dispersed in water. By increasing the temperature, a polymer formation reaction occurs at the oil droplet interface, forming a microcapsule wall. If the second additive is, for example, a polyamine, or if nothing is added, a polyurea is formed.

In this case, regarding the polyvalent isocyanate to be used and the polyol and polyamine to be reacted with it, US Pat.
No. 268, Special Publication No. 48-40347, No. 49-241
No. 59, JP-A-48-80191, JP-A No. 4B-8408
No. 6, and they can also be used.

Examples of polyvalent isocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate,
2.6-1-lylene diisocyanate, 2.4-)lylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3.3'-dimethoxy-4,4'-biphenyl-diisocyanate, 3.3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylylene-1゜4-
diisocyanate), 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1, Diisocyanates such as 4-diisocyanate, 4.4',4"-triphenylmethane triisocyanate, triisocyanates such as toluene-2,4,6-1-diisocyanate, 4,4'-dimethyldiphenylmethane-2,2' , tetraisocyanates such as 5,5'-tetraisocyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, adducts of 2,4-tolylene diisocyanate and trimethylolpropane, adducts of xylylene diisocyanate and trimethylolpropane, There are isocyanate prepolymers such as adducts of tolylene diisocyanate and hexatriol.

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

The following polyols described in JP-A-60-49991 can also be used. Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-bentanediol, 1,6-hexanediol, 1. ,? -hebutanediol, 1°8-octanediol, propylene glycol, 2.3-dihydroxybutane, 1.2-
dihydroxybutane, l,3-dihydroxybutane, 2
゜2-dimethyl-1,3-propanediol, 2゜4-
Bentanediol, 2,5-hexanediol, 3-methyl-1,5-bentanediol, 1゜4-cyclohexane dimetatool, dihydroxycyclohexane, diethylene glycol, 1,2゜6-trihydroxyhexane, 2-phenylpropylene glycol ,1,1.1-
Aromatic polyhydric alcohols such as trimethylolpropane, hexanetriol, pentaerythritol, pentaerythritol ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin, 1,4-di(2-hydroxyethoxy)benzene, resorcinol dihydroxyethyl ether, etc. Condensation products with alkylene oxide, p-xylylene glycol, m-xylylene glycol, α, α'-dihydroxy-p-diisopropylbenzene, 4,4'-dihydroxy-diphenylmethane, 2-(p, p'-dihydroxy Examples include diphenylmethyl)benzyl alcohol, an adduct of ethylene oxide to bisphenol A, and an adduct of propylene oxide to bisphenol A. The ratio of hydroxyl groups to 1 mole of isocyanate groups in polyols is 0.02 to 1.
Preferably, 2 mol is used.

Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, and 2-hydroxytrimethylene. Diamine, diethylene 1 rear mini/,
Polyvalent isocyanates, such as triethylenetriamine, triethylenetetramine, diethylaminoprobylamine, tetraedylenebentamine, and amine adducts of epoxy compounds, can also react with water to form polymeric substances.

Here, as an i solvent for forming oil droplets, -m
can be selected from among high boiling point oils, including phosphoric acid esters, phthalic acid esters, acrylic esters,
methacrylic acid esters, other carboxylic acid esters,
Fatty acid amides, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, alkylated naphthalenes,
Diarylethane and the like are used. Specifically, those described in Japanese Patent Application Laid-Open No. 60-242.094 and Japanese Patent Application No. 62-75.409 can be used.

In the present invention, an auxiliary solvent may be further added to the above organic solvent as a low boiling point 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 alkylhenzenesulfonate (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 to be 20 μm in volume average particle size as measured by the measurement method described in JP-A No. 60-214,990, particularly from the viewpoint of improving image resolution, storage stability, and handling properties. It is preferably less than or equal to 4μ, particularly preferably less than 4μ, and
If the capsule is too small, there is a risk that it will disappear into the pores or fibers of the substrate, but this depends on the properties of the substrate or support and cannot be definitively determined, but it is preferably 0.1μ or more.

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

This oxidation is achieved in the present invention by the presence of at least one photooxidizing agent.

This photooxidant is activated by light irradiation and reacts with the leuco dye to produce a colored image against a background of unirradiated and therefore unchanged material.

Leuco dyes that can readily develop color upon oxidation by the above mechanism include, for example, those described in US Pat. No. 3,445,234, which is hereby incorporated by reference.

(a) Aminotriarylmethane (1)) Aminoxanthine (C) Aminothioxanthin (d) Amino-9,1O-dihydroacridine (e
) aminophenoxazine (f) aminophenothiazine (powder aminodihydrophenazine (b) aminodiphenylmethane (i) leucomendamine 0) aminohydrocinnamic acid (cyanoethane,
Leucomethine) (g) Hydrazine (1) Leucoidigoid dye (e) Amino-2,3-dihydroanthraquinone (n
) Tetrahalo p,p'-biphenol(o)2
-(p-Hydroxyphenyl)-4,5-diphenylimidazole (p) Phenethylaniline Among these leuco dyes, (a) to (i) develop color by losing one hydrogen atom and become dyes. However, the leuco dyes (j) to Φ) lose two hydrogen atoms to form the parent dye. Among these, aminotriarylmethane is preferred. - The preferred type of aminotriarylmethane for boat fishing is at least two aryl groups.
(a) R and Rz are hydrogen, C, and XC, respectively
+. R in the para position to the bond to the methane carbon atom, such as a group selected from alkyl, 2-hydroxyethyl, 2-cyanoethyl, or benzyl, Rg
N-substituent and (b) a group ortho to the methane carbon atom selected from lower alkyl (C 1 to 4), lower alkyl (C 1 to 4), fluorine, chlorine, bromine or hydrogen; and the third aryl group may be the same as or different from the first two, and if different, (a) lower alkyl, lower alkoxy, chlorine, diphenylamino, cyano, nitro, Phenyl which may be substituted with hydroxy, fluorine or bromine, alkylthio, arylthio, thioester, alkylsulfone, arylsulfone, sulfonic acid, sulfonamide, alkylamido, arylamido, etc.; (b) substituted with amino, di-lower alkylamino, alkylamino Naphthyl which can be substituted with: (C) Pyridyl which can be substituted with alkyl; (dl
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 R8 are hydrogen or alkyl of 1 to 4 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 the new capsule-based material of the present 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 demons across the spectrum, depending on the structure of the compound. For this reason, the particular photo-oxidizing agent chosen will depend on the nature of the actinic radiation. When exposed to such radiation, the photooxidizing agent produces an oxidizing agent that oxidizes the color forming agent to its colored form.

A typical photooxidizing agent is U.S. Patent No. 3,042.5.
Halogen hydrocarbons such as carbon tetrabromide, N-promosuccinimide, and tribromomethylphenylsulfone described in No. 15 and No. 3.502,476, and halogenated hydrocarbons such as carbon tetrabromide, N-promosuccinimide, and tribromomethylphenylsulfone described in No. 15 and No. 3.502,476; Azide polymer, 2- as described in U.S. Pat. No. 3,282.693
Azide compounds such as azidobenzoxazole, benzoyl azide, 2-azidobenzimidazole, and 3'ethyl-1 as described in U.S. Pat. No. 3,615,568.
-methoxy-2-pyridothiacyanine verchlorate,
Compounds such as 1-methoxy-2-methylpyridinium P-1 lienesulfonate, lophine dimer compounds such as 2.4.5-triarylimidazole dimer described in Japanese Patent Publication No. 62-39.728, benzophenone, p-amino including, but not limited to, at least one photooxidant compound from the group consisting of compounds such as phenylketones, polynuclear quinones, thioxanthenones, and mixtures of the foregoing compounds; Dimer compounds and organic halogen compounds are preferred, and combination use of both is optimal because high sensitivity can be achieved.

The lophine dimer compound is represented by the following formula. Upon dissociation, the dimer forms the corresponding 2,4.5-)arylimidazolyl group.

(wherein A, B and D are the same or different aryl which may be a carbocyclic or heterocyclic ring which is unsubstituted or substituted with a substituent which does not inhibit the dissociation of the dimer to the imidazolyl group or the oxidation of the leuco dye) The groups B and D usually have 0 to 3 substituents and A
The group has 0 to 4 substituents. Useful lophine dimer compounds and methods for their preparation are described in U.S. Pat. No. 35,529.
No. 73 Specification No. 4+rj! It is disclosed from line 22 to column 6, line 3.

Organic halogen compounds include those having 40 or less carbon atoms in the molecule and are either solid or liquid.

Specifically, (1) a compound represented by the formula (wherein R is hydrogen, halogen, or aryl group, and X is halogen), such as carbon tetrachloride, carbon tetrabromide, p
-Nitrobenzotribromide, bromotrichloromethane, pencitrichloride, hexabromoethane, iodoform, 1,1.1-tribromo-2-methyl-2-
Propatool, ■, 1゜2.2-tetrabromoethane,
2.2.2-) Libromoethanol, i, 1. i-Trichloro-2-methyl-2-propertool, (2)-carlicide (in the formula, Rx represents hydrogen or 1 to 5 substituents on the benzene ring, and these substituents include a nitro group, a halogen group, an alkyl compounds represented by O-nitro-α, α
.

α-Tribromoacetophenone, m-nitro-α.

α, α-tribromoacetophenone, p-nitro-α,
α, α-Tribromoacetophenone, α.

α, α-tribromoacetophenone, α, α, α-tribromo 3.4-dichloroacetophenone, (3)-killing% formula% [In the formula, R is an alkyl group or an aryl group (including those with substituents) X is halogen], such as I, 3-benzenedisulfonyl chloride, 2,4-dinitrobenzenesulfonyl chloride, 0-nitrobenzenesulfonyl chloride,
m-Nitrobenzenesulfonio.

3,3'-diphenylsulfonyl chloride, ethanesulfonyl chloride, p-bromobenzenesulfonyl chloride, p-nitrobenzenesulfonyl chloride)', p-iodobenzenesulfonyl chloride, p-acetamidobenzenesulfonyl chloride , P-chlorobenzenesulfonyl chloride, P-t)Ii:Lsulfonyl chloride, methanesulfonyl chloride, benzenesulfonyl bromide,
(4) - Compounds represented by the formula (where R is an alkyl group or an aryl group (including those having a substituent) and X is a halogen), such as 2,4-dinitrobenzenesulfenyl chloride, 0-nitrobenzenesulfenyl Chloride, (5) - Compound represented by (in the formula, R is a substituted or unsubstituted aryl group, X+, Xs, and Xs are hydrogen and halogen in the heterocyclic ring residue, but not all are hydrogen at the same time) , for example, hexabromodimethyl sulfoxide, pentabromodimethyl sulfoxide, centrobromodimethyl sulfone, trichloromethyl phenyl sulfone, tribromomethyl phenyl sulfone, tricumeromethyl-p-chlorophenyl sulfone, tribromomethyl-p-nitrophenyl sulfone, 2-trichloromethylbenzothiazole sulfone, 4,6-dimethylpyrimidyl-2-tribromomethyl sulfone, tetrabromodimethyl sulfone, 2
, 4-dichlorophenyl-trichloromethylsulfone,
2-Methyl-4-chlorophenyl-trichloromethylsulfone, 2,5-dimethyl-4-chlorophenyl-trichloromethylsulfone, 2,4-dichlorophenyl-tribromomethylsulfone, (6)-saccharide (wherein R is a heterocyclic compound Compounds represented by -X+, Xs, Xs may be hydrogen or halogen, but not all are hydrogen at the same time), such as tribromoquinaldine, 2-tribromomethyl- 4-
Methylquinoline, 4-tribromomethylpyrimidine, 4
-Phenyl-6-tribromomethylpyrimidine, 2-trichloromethyl-6-nitrobenzothiazole, ■-phenyl-3-trichloromethylpyrazole, 2゜5-ditribromomethyl-3,4-dibromothiophene, 2-
Trichloromethyl-5-(P-7'toxystyryl)-
Examples include organic halogen compounds such as 1,3,4-oxadiazole and 2,6-dydrichloromethyl-4-(p-methoxyphenyl)triazine.

Among these, compounds (2), (5), and (6) are preferred, and the halogen is preferably chlorine, bromine, or iodine.

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 1O:1 to about 1:10. A more preferred ratio is 2:1 to 1:2.

Among the phenol compounds of the present invention represented by the general formula (1), the effects of the present invention are more effectively exhibited when those represented by the following formula (Ia) are used.

General Formula (Ia) In the formula, R& and R'l represent a hydrogen atom and an alkyl group, respectively, provided that R4 and R1 are not hydrogen atoms at the same time.

The compound represented by general formula (1) is disclosed in U.S. Patent No. 4゜264.
．． It can be synthesized according to the method described in No. 720.

When carrying out the present invention, they can be used alone or in combination of two or more, and other known antifading agents can also be used in combination.

Known anti-fading agents include hydroquinones, phenols, chromanols, coumarans, hindered amines, and complexes, such as those disclosed in JP-A-59-83162, JP-A No. 5B-24141, JP-A No. 52-152225, and U.S. Pat. No. 3,698°909, No. 4,268,593
British Patent No. 2.069.162 (A), British Patent No. 2.069.162 (A),
It is described in specifications such as No. 027,731.

Representative examples of the compound represented by -Tsuriyoshi (1) are shown below, but the compounds used in the present invention are not limited thereby.

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 (e.g., hydroquinone, catechol, resorcinol, hydroxyhydroquinone, pyrrologlycitur, and O-amino phenol, aminophenols such as p-aminophenol, etc.), or cyclic phenylhydrazide compounds described in the specification of Japanese Patent Publication No. 62-39゜728, such as 1-phenylpyrazolidine-3
-one [Phenidone A, the following formula (1)],]1-phenyl-4-methylpyrazolidin-3-one [Phenidone B
, the following formula (2)], 1-phenyl-4,4-dimethylpyrazolidin-3-one [dimezone, the following formula (3)]
, 3-methyl-1-(p-sulfol3CI+3phenyl)-2-pyrazolin-5-one and 3-methyl-1-phenyl-2-pyrazolin-5-one.

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

0-lm- and P-methyl, P-)lifluoromethyl,
m- and p-chloro, m- and p-bromo, p-fluoro, 0-2m- and p-methoxy, p-ethoxy, p-
Benzyloxy, P-butoxy, P-phenoxy, 2,
The following substituents can be present at the 4-position on the heterocyclic group of 4.6-trimethyl, 3°4-dimethyl, and 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 cyclic phenylhydrazide: dimethyl, methyl, Phenyl Yu/Furthermore, guanidine derivatives, alkylene diamine derivatives,
Compounds selected from hydroxyamine derivatives can be used. Specifically, the guanidine derivatives include:
For example, phenylguanidine, 1,3-diphenylguanidine, 1,2,3-triphenylguanidine, 1,2-
Dicyclohexylguanidine, 1,2.3-tricyclohexylguanidine, 1,3-di0-tolylguanidine, 0-)lyldiphenylguanidine, m-tolyldiphenylguanidine, p-tolyldiphenylguanidine,
N,N'-dicyclohexyl-4-morpholinocarboxamidine, 1,3-ditolyl-3-phenylguanidine, 1,2-dicyclohexylphenylguanidine, 1
-0-) rilbiguanide, N-benzylidene-guanidinoamine, and the like.

Examples of alkylene diamine derivatives include ethylene diamine, propylene diamine, tetramethylene diamine, hexamethylene diamine, octamethylene diamine,
Examples include 1,1,2-diaminododecane and tetrabenzylethylenediamine.

Examples of hydroxyamine derivatives include jetanolamine, triethanolamine, 3-β-naphthyloxy-1-N, N-dimethylamino-2-propatol, and the like.

The above-mentioned reducing agents that act as free radical trapping substances can be used alone or in combination of two or more, but are limited to these reducing substances that have the function of acting on so-called oxidizing agents. isn't it.

In the photoimage-forming material of the present invention, both the leuco dye and the photooxidizing agent are encapsulated in microcapsules, but the reducing agent that is not encapsulated is solid-dispersed using a sand mill or the like, or after being dissolved in oil. It is best to use it in a porous and dispersed manner.

In the case of solid dispersion, it is dispersed in a water-soluble polymer solution having a concentration of 2 to 30% by weight, 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 with reference to the method and materials described in the specification of Japanese Patent Application No. 1982-75.409.

The preferred amount of reducing agent is from 1 to 1 on a mole basis of the photooxidant component.
Although it can be used in an amount of 1 to 10 times the molar amount, in order to obtain the desired result with as little amount as possible, a range of 1 to 10 times the molar amount is more preferable.

Incidentally, image fixation in the present invention can be effectively achieved by contacting the photo-oxidizing agent with the reducing agent through the capsule wall by heating as described above, but needless to say, fixing of the image can be achieved by destroying the capsule by applying pressure. It is also possible to derive similar effects. Further, a synergistic effect can be expected by performing heating and pressurization at the same time.

Furthermore, in order to impart fixing properties to a photoimage-forming material composed of a leuco dye capable of forming oxidative color and a photooxidizing agent, it is also possible to encapsulate only a reducing agent, or in an embodiment of the present invention, a reducing agent in addition, in microcapsules. It is possible.

In the present invention, a known aggravating agent may be added as an additional component to the photo-oxidizing agent.
Compounds described on pages 1 to 75 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, and benzoyl peroxide. These include organic peroxides, azo compounds such as azobisisobutyronitrile, and halides such as N-promosuccinimide. Further, examples of sensitizing dyes in the visible range include dyes having amidinium ion-based, carboxyl ion-based, and dipolar amide-based chromophores described on pages 106 to 123 of the same book. Specifically, cyanine-based, phthalein-based, and oxonol-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 having a similar function to that of the reducing agent, although the purpose of use is different, so the amount used must be kept to the minimum necessary. 9th,
Specifically, in addition to the above-mentioned free radical scavenging substances, compounds described in the specification of U.S. Pat. etc., but the amount of these stabilizers used is preferably about 0.01 mol% to about 25 mol%, based on the photo-oxidizing agent, and 0.01 mol% to about 25 mol%, based on the photo-oxidizing agent.
Most preferred is a range of 1 mol% to 10 mol%.

The photoimage-forming material of the present invention can be prepared by coating, impregnating, or forming a self-supporting layer on a support as a dispersion of microcapsules containing such a leuco dye and a photooxidizing agent and a reducing agent.

At this time, binders that can be added to the above dispersion include polyvinyl alcohol, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, gum arabic, gelatin, polyvinylpyrrolidone, casein, styrene-butadiene latex, acrylonitrile-butadiene latex, polyvinyl acetate. Various emulsions such as polyacrylic acid ester, ethylene-vinyl acetate copolymer, etc. can be used. The amount used is 0.5 g/rrf to 5 g/nf in terms of solid content.

The coating amount of the photoimage-forming material in the present invention is 3 g/n to 30 g-n, particularly 5 g/n (to 20 g-nf) in terms of solid content.
It is preferable that it be between. If it is less than 3 g/ni, a sufficient concentration cannot be obtained, and even if it is applied twice or more than 30 g/rrf, no improvement in quality will be seen, resulting in a cost disadvantage.

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 methacrylate, Includes films of plastic and polymeric materials such as polyvinyl chloride; woven fabrics; materials commonly used in graphic arts and decorative applications such as glass, wood and metal.

For coating on the support, generally well-known coating methods such as date coat method, air knife coat method, curtain coat method, roller coat method, drutter coat method, wire bar code method, slide coat method, and gravure method can be used. coat method, spin code method or U.S. Patent No. 2,
It can be coated by the extrusion coating method using a hopper as described in Japanese Patent No. 681,294.

Any convenient light source can be used in the present invention for activating the photooxidant and forming 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 lamps, mercury, metal doped and arc lamps. Coherent light sources include pulsed nitrogen lasers, xenon lasers, argon ion lasers, and ionized neon lasers whose emission is within or overlaps the UV or visible absorption bands of the photooxidant. Also useful in the subject compositions are UV and near-visible radiation-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 of the rear of the negative, stencil or other relatively opaque pattern with such light, the negative being formed on cellulose acetate or polyester. The opacity may be due to the agglomeration of silver or regions with different refractive indices on the film. The image is formed using conventional diazo printing equipment,
The light time depends on the density and spectral energy distribution of the light, its distance from the composition, the use The time may vary from a fraction of a second to several minutes depending on the nature and amount of the composition used and the density of color in the desired image.

After image exposure, the image can be fixed by bringing the photooxidizing agent and the reducing agent into contact with each other. Various methods can be applied to bring the two into contact.

For example, there is a method of heating. In this method, the temperature of the microcapsule wall is raised to a temperature above its glass transition point so that the photooxidant and the reducing agent pass through the softened microcapsule wall and come into contact with each other. The glass transition point of the microcapsule wall varies depending on the material used, and therefore, the heat treatment conditions necessary for fixing can be appropriately selected in consideration of these factors.

Another method is to destroy the microcapsules by mechanical force and bring them into contact. In this method, materials with high glass transition points can also be used.

The force required to break may vary depending on the material and particle size, but can be easily determined by one skilled in the art.

The photoimage-forming material of the present invention is used as a photoimage-forming 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" indicating the amount added indicate "parts by weight."

Example 1 The photoimage forming material shown below was prepared.

Sample (1): Leuco dye Leuco Crystal Violet 3.0 parts Photooxidizer 2.2'-bis-(0-chlorophenyl)
-4,4',5.5' - Tetraphenylbiimidazole 3.0 parts Tribromomethylphenylsulfone 0. 6 parts Compound (E-2) exemplified herein 0.4 parts Methylene chloride 22 parts Tricresyl phosphate 24 parts Takenate D-1
After mixing 24 parts of 1ON (75% ethyl acetate solution) (manufactured by Narita Pharmaceutical Co., Ltd. (trade name)) and adding it to an aqueous solution consisting of 63 parts of an 8% by weight aqueous solution of polyvinyl alcohol and 100 parts of distilled water, 2
Emulsification and dispersion was carried out at 0°C to obtain an emulsion having an average particle size of lμ. The resulting emulsion was further stirred at 40°C for 3 hours.

Thereafter, the temperature was returned to room temperature and filtered to obtain an aqueous capsule dispersion.

Next, 150 parts of a 4% by weight aqueous solution of polyvinyl alcohol were mixed with 30 parts of a reducing agent 1-phenylpyrazolidin-3-one (phenidone A), and Dynomil (Willy A. Bacofen.
Dispersed with A.G. Co., Ltd. (trade name) to achieve an average particle size of 3.
A phenidone A dispersion of μ was obtained.

Mix 9 parts of capsule liquid and 6 parts of phenidone A dispersion, and use high-quality paper (basis weight 64 g/n) for super calendering.
f) to a solid coating amount of 10 g/rrf,
The sample (1) was obtained by heating and drying at 50°C for 1 minute.

Examples 2 to 5 Compounds (E-1), rE-3), (E-5] and (E-5) were used instead of compound (E-2) in Example 1, respectively.
Sample (2), sample (3), and sample (4) were prepared in exactly the same manner as in Example 1, except that Sample 11)
and sample (5) was obtained.

Comparative Example 1 A comparative sample (ratio-1) was obtained in the same manner as in Example 1 except that compound (E-2) was not used.

In order to examine the fresh storage properties of these samples (1) to (5) and (ratio -1), we calculated the fresh skin density and the skin density (fog) after storage at 60°C for 124 hours using a dry thermometer as the Macbeth reflection density. The change in Capri concentration was measured using a meter.

Claims (2)

[Claims] (1) At least one kind selected from leuco dyes capable of developing color by oxidation and at least one kind selected from photo-oxidizing agents are both encapsulated in microcapsules, and outside of the microcapsules, at least one selected from reducing agents selected from among reducing agents are included. at least 1
A photoimage-forming material in which a phenol compound represented by the following general formula [I] is added to microcapsules in the photoimage-forming material in which seeds are present. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_5 each represent a hydrogen atom, an alkyl group, and a heterocyclic group,
4 may be the same or different, and each represents a hydrogen atom,
Represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acylamino group, a diacylamino group, a sulfonamido group, an alkylamino group, an alkoxycarbonyl group, an acyloxy group, or a halogen atom, provided that R_1 and R_5 is never a hydrogen atom at the same time. ) (2) At least one selected from leuco dyes capable of oxidative color development and at least one selected from photo-oxidizing agents are both encapsulated in microcapsules, and outside of the microcapsules, at least one selected from reducing agents is provided. at least 1
In a photoimage-forming material in which a species is present, a phenol compound represented by the general formula [I] is added to microcapsules.After forming an image by irradiating the photoimage-forming material with light, An image recording method characterized by bringing a photooxidizing agent into contact with the reducing agent.