JPH01227145A - Optical image forming material and image recording method using said material - Google Patents

Abstract

PURPOSE:To improve image reproducibility, preservable property, etc., by using microcapsule and adding a specific phenolic compd. in addition to a leuco dye and photooxidizing agent into the microcapsule. CONSTITUTION:At least one kind selected from the oxidation-color formable leuco dyes and at one kind selected from the photooxidizing agents are included in the microcapsules. The phenolic compd. expressed by formula I is added into the microcapsules. In formula, R, R' denote a hydrogen atom. or alkyl group; R1-R4 denotes a hydrogen atom., aryl group, alkoxy group, etc. The respective components can, therefore, be microisolated on the inner side and outer side of the microcapsules. The influence of the external environment is decreased as far as possible and the included materials can be stably preserved by including the materials to the inner side. The revolutionary technique of improving the raw preservable property which does not undesirably affect the photosensitivity is thereby established.

Description

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

More specifically, the present invention relates to an optical image-forming material that can be used for proof paper, printout paper, overlay/if film, etc., and an image recording method using the same.

``Prior Art'' Conventionally, the photoimage-forming material of this plate has been used in many photographic applications, such as so-called free radical photography, in which the photosensitive area is visualized by exposing the image to light.

In this regard, what is effective for bamboo is a photo-oxidizing agent and one dose each.
This is a method of radical oxidation color development of leuco dye 1 to its corresponding dye 11 (for example, pl+oto).

Sci, Eng,,, L, Ta1-103 (/1
6/), Tokko Sho ≠ 3-. 2ri, Hiro 07, JP-A-13-
! r! J3! No., JP-A-57-60. J2, JP-A-62-tGA, JjIA). .

``Problem to be solved by the invention'' However, because they are sensitive to light, dyed diagonal images are exposed to normal indoor light, sunlight or white light even after they have been formed by exposure to light. Color formation occurs when such light [3! Handling of the forming material is difficult.

- In order to maintain a single image once formed, it is unavoidable to develop color in the unexposed areas during image exposure. It is known to preserve original images by applying a solution of a reducing agent, such as a free radical scavenger (such as hydroquinone), to the imaged material, for example by spraying or impregnating. Although this is advantageous for preserving or fixing the original image, going through a wet process has disadvantages in terms of workability and operability.
It will be forced to comply. Also, for example, Du Pont
The image is formed using UV light, like Dy1ux■ from the company.
There are commercially available materials that have an excellent characteristic of being processable only with light, such as fixing by activating a photogenic substance with visible light. However, this process monopolizes the device by using the light twice;
Moreover, since this requires work such as replacing spectral filters, the processing speed may be unsatisfactory depending on the intended use. Furthermore, the said Tokko Sho t
The specification of A3-λ, Hiro 07 describes whether a reducing heat fixing agent is contained in the binder solution together with a leuco dye and a photooxidizing agent, or whether the heat fixing agent is overcoated on the photosensitive layer. There is a description that heat fixing is performed after the image is OB-lighted. 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 5 manufacturing installations.
It requires explosion-proof measures such as FI, and has disadvantages in terms of safety and cost.

“Object of the Invention” The object of the present invention is to provide a photoimage-forming material having excellent image reproducibility, shelf life, and shelf life (fixing property), and to provide a photoimage-forming material that has excellent image reproducibility, shelf life, and shelf life (fixing property), and that is completely The purpose of the present invention is to provide a dry and simple recording method.

Another object of the invention is to provide a nine-component iron-forming material in which the handling of organic bath yarns, which is disadvantageous in terms of ease of manufacture, is reduced or made unnecessary.

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

(In the formula, `` and '' refer to a water atom or an alkyl atom, and may be the same or different from each other. R1, R2, 几3
and R4 are each a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an alkyl group, an acylamino group,
It represents a varicella group or all halogen atoms, which may be the same or different from each other. At least one of 0 and OR' may be bonded to any of R1 to R4 at these ortho positions to form a Y-membered or 6-membered ring, or at least one of R1 to R4 may be bonded to each other at ortho positions. At least one pair having the following relationship may be bonded to each other to form a j-membered ring or a 6-membered ring. ] The most characteristic feature of the uninvented light-forming material is that it uses microcapsules, and in the microcapsules, a specific phenolic compound of @VC dye and photooxidizing agent is added.
Cold 7) Ω.

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

(2) By packaging things inside the microcapsule,
The external environment (particularly moisture, oxygen, storage temperature, etc.) is reduced as much as possible, allowing the inclusions to be stored stably.

(3) Depending on the situation, 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 thread such as oil, the entire capsule dispersion system can be treated as an aqueous system.

etc. can be mentioned.

In order to improve the stability of functional gold thread in (1) and (2) above, we have added the functions of +11.131 to +41 as a means of post-exposure heat fixing and a simple recording method.
This function is used to improve manufacturing ease.

The addition of a specific phenolic compound to VC in microcapsules can be used as an innovative method for improving shelf life without adversely affecting sensitivity.

Preferred capsules in the present invention are: The material isolation action pressure of the microcapsule wall prevents contact between the inside and outside of 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 transmission Jnn humidity temperature, the glass transition of the capsule wall @ degree (corresponding to
Example: l? f Kaisho! Tar, ril.

'431 No. 431, special request Sho zy-tyo, txt No. 431, special request Sho zy-tyo, txt issue, special request Sho zy-tyo
Tatata, <cri No. 0, etc.).

In order to control the inherent glass transition temperature of 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 made by emulsifying a core material containing reactive substances such as leuco dye and photoacid ratio agent, and then forming a wall of a polymer material around the sled 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 about microcapsules that can be preferably used in the present invention, such as a preferred method for producing microcapsules, see U.S. Pat.
No. 626, Mei + T (tl f).

For example, when polyurethane urea is used as a capsule wall material, a multicylindrical isocyanate and a second substance (for example, a polyol) that reacts with it to form the capsule wall are used.
is mixed into an aqueous phase or an oily liquid to be encapsulated, emulsified and dispersed in water, and the temperature is raised to cause a polymer formation reaction at the oil droplet interface to form microcapsule walls.

If the second additive is, for example, a polyamine, or if nothing is added, a polyurea is formed.

In this case, the polyvalent incyanate used, the polyol to react with it, and the polyamine are described in US Pat.
7.2 No. Otsu, Tokuko Show ψ, Ryo-≠03≠7, same IA5
+', 2hiro i6ri, JP-A-4T (-J'0/ri1,
It is disclosed in the same pf-fu014, and they can also be used publicly.

Examples of the polyvalent isocyanate include nl-phenylene diisocyanate, p-phenylene diisocyanate, u,4-)lylene diisocyanate, 2. ≠-tolylene diisocyanate, naphthalene-7, ψ-diincyanate, diphenylmethane-ψ Hl-diisocyanate, J, J'-dimethoxy-u, IA, -hyphenylene diisocyanate, 3,3'-dimethyldiphenylmethane-μ 4C/ -Diisocyanate, xylylene-
7゜≠-diincyanate, 4c'-diphenylpropane diincyanate, trimethylene diisocyanate, hexamethylene diisocyanate, boo/! - Diisocyanates such as diisocyanates, μe"', ""
-Triphenyl meta/triisocyanate, toluene-
Triisocyanates such as λI''l'-triinocyanate, g, tA'-dimethyldiphenylmethane-λ
, 1', j, yo'-tetrine cyanates such as tetraisocyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, u,<4-) adducts of lylene diisocyanate and trimethylolpropane,
There are incyanate prepolymers such as adducts of xylylene diisocyanate and trimethylolpropane and adducts of tolylene diisocyanate and hexanetriol.

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

Ethylene glycol, l, which can also be used as the following polyol described in JP-A No. 1986-197-7-1.

3-propanediol, /, 4L-butanediol, l
, j- is methanediol, l,6-hexanediol,
/, 7-hebutanediol, /, f-octanediol, propylene glycol, λ, 3-dihydroxybutane, /, U-dihydro as sibutane, /, 3-dihydroxybutane,! , 2-dimethyl-/, J-prononediol, λ, tA- is methanediol, λ, j-hexanediol, 3-methyl-1,yo-methanediol, /
, tA-cyclohexane dimetatool, dihydroxycyclohexane, diethylene glycol, /, 2.7
;-trihydroxyhexane, λ-phenylpropylene glycol, ll l, l-trimethylolpropane,
Hexanetriol, pentaerythritol, pentaerythritol ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin, /, 4C-
Di(+2-hydroxyethoxy)benzene, condensation product of aromatic polyhydric alcohol such as resorcinol dihydroxyethyl ether and alkylene oxide, p-xylylene glycol, m-xylylene glycol, α, α
'-dihydroxy-p-diisopropyl (nzen, μ,
IA'-dihydroxy-diphenylmethane, co-(po
Examples include p'-/hydroxydiphenylmethyl)benzyl alcohol, an adduct of ethylene oxide to bisphenol A, and an adduct of propylene oxide to bisphenol A. The polyol is preferably used in a proportion of hydroxyl groups of 0.02 to 2 moles per mole of incyanate groups.

Examples of polyamines include ethylene diamine, trimethylene diamine, tetramethylene diamine, hantamethylene diamine, hexamethylene diamine, p-phenylene diamine 7, m-phenylene diamine, piperazine, comethyl biradzine, λ, j-dimethyl piperazine, 2- 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.

-c-ki, phosphoric acid ester, phthalic acid ester, acrylic acid ester, methacrylic acid ester, other carboxylic acid ester, fatty acid amide, alkyl biphenyls, alkylated terphenyl, chlorinated mirafine, alkylated naphthalene, Diarylethane and the like are used.

Specifically, those described in Japanese Patent Application Laid-Open No. 2002-24-24cλIO, Japanese Patent Application No. 1s2-7, '1-02 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 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 water phase trap and a protective colloid 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 alkylbenzene sulfonic acids (eg, sodium lauryl sulfate), dioctyl sodium sulfosuccinate, polyalkylene glycols (eg, polyoxyethylene nonylphenyl ether), and the like. -'r3”6 can be done.

In the present invention, the size of the microcapsules is determined particularly from the viewpoint of image resolution, storage stability, and handling, as described in, for example, Japanese Patent Application Laid-open No. 1983-1989-λ/4C, Tata No. The size of the capsule is preferably 2 (7 μm or less, particularly μμ or less). Also, if the capsule is too small, there is a risk that it will disappear into the pores or fibers of the substrate; Although it cannot be generalized because it depends on the properties of the body, it is preferably 0.7μ or more.

Next, the leuco dye constituting one component of the photo-image forming material of the present invention will be described. The leuco dyes used in the present invention are those having one or two hydrogen atoms, whose removal and, in some cases, trapping results in the formation of a dye by the trapping of additional electrons. Contains reduced 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 miterns.

This oxidation is accomplished in the present invention by the presence of at least /fi of the photooxidizing agent 6.

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

The leuco dye that easily develops color by oxidation in the machine groove is disclosed in, for example, US Patent No. 3. Those described in the specification of ψHiroj, -27μ are included and are hereby incorporated by reference.

(a) Aminotriarylmethane (b) Aminoxanthine (C) Aminothioxanthin (d) Aminota, 10-dihydroacridine (e
) Aminophenoxazine (f) Aminophenothiazine (g) Aminodihydrophenazine (1 ly) Aminodiphenylmethane (i) Leucoindamine (jJ Aminohydrocinnamic acid (cyanoethane, leucometin (k)) Hydrazine (17 leucoindigoid mf+ (1 hair) Amino-co, 3-dihydroanthraquinone] Tetrahalo p* p'-biphenol (o)
λ-(p-hydroxyphenyl)-μ, j-diphenylimidazole ψ) Phenethylaniline Among these leuco dyes, (a) and (i) develop their color by losing one hydrogen atom. However, (jJ to (pJ leuco dye, I-) loses one hydrogen atom to produce a parent dye.Aminotriarylmethane is preferred among these.-General Preferred types of aminotriarylmethane include those having a small number of aryl groups (both of which are hydrogen, C1-C10 alkino, 1-hydroxyethyl, cocyanoethyl, or benzyl). rt1rt2N -11a in the para position to the bond to the methane carbon atom, such as a substituent and (b) lower alkyl (C'IJ"-/-Hiroshi), lower alkoxy (
Cb''-7-ψ), a phenyl group having a group ortho to the methane carbon atom selected from fluorine, chlorine, lambda or yg; and the third aryl group is the same as the first two or may be different, and if different, (a) lower alkino to lower alkoxy, chlorine, diphenylamino, cyano, nitro, hydroxy, fluorine or bromine, alkylthio, arylthio,
Phenyl which may be substituted with thioester, alkylsulfone, arylsulfone, sulfonic acid, sulfonamide, alkylamide, arylamide, etc.; (b) 7-tyl which may be substituted with amine, di-lower alkylamino, alkylamino X; (C) pyridyl substituted with alkyl; (d)
quinolyl; (e) r! of aminotriarylmethane and its acid salt, characterized in that it is selected from indolinylidene substituted with alkyl; It is a li class. Preferably, R□
and 几2 is hydrogen or alkyl of /-g carbon atoms. Most preferably all 30 aryl groups are the same.

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 photoimage-forming materials. may be received.

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 counteracted by the capsule achieving the same effect as having such a 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. Depending on the structure of the compound, various photooxidants have different peak sensitivities over the entire range of radiation.
, /depends on IK. When exposed to such radiation, the photooxidizer produces an acid ratio that oxidizes the color former to its color form.

A typical photo-oxidizing agent is 3.0≠λ, 5 for U.S. patents.
No. 15 and No. 3 of the same. ! 02. tA76 carbon tetrabromide, N-promosuccinimide, tribromomethylphenylsulfone and other halogen hydrocarbons, azide polymer described on page 11 of the Abstracts of the Spring Research Presentation of the Photographic Society of Japan, U.S. Patent J, 212 ．． Low azidobenzoxazole, benzoyl azide, described in A-3 No. 3!
-Azide compounds such as azidobenzimidazole, and 3'ethyl-1-methoxy-2-pyridothiacyanine verchlorate, l-methoxy-2-methylpyridinium p as described in U.S. Pat. - Compounds such as toluenesulfonate, 1. ≠, j-triarylimidazole tC
=t, compounds such as benzophenone, p-aminophenyl ketone, polynuclear quinone, thioxantenone, and mixtures of the foregoing compounds; It is not limited to this. Among these, lophine dimer compounds and organic halogen compounds are preferred;
Furthermore, the combination of both is optimal because it can achieve high sensitivity.

The lophine dimer compound is represented by the following formula. Upon dissociation, the dimer forms the corresponding λ,≠,j-triarylimidazolyl group.

(In the formula, A, B and D are the same 1'fc is different and is unsubstituted or substituted with a substituent that does not inhibit the dissociation of the dimer into an 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 O-Hiro substituents. Useful lophine dimer compounds and methods for their preparation are disclosed in U.S. Pat.

The organic halogen compounds include those in which the number of carbon atoms in the molecule is ≠O or less and are solid or waste.

Specifically, compounds represented by the general formula (1) (wherein R is hydrogen, halogen, or aryl group, and X is halogen), such as carbon tetranomide, carbon tetrabromide, p
-Nitrobenzotribromide, bromotrichloromethane, pencitrichloride, hexabromoethane, iodoform, /, /, /-)+7promo 2-methyl-λ
-propertool%'l'1λ, -1 tetrabromoethane, 2. ．． 2.2-) Libromoethanol, /, /, /-
Trichloro-1-methyl-copropanol, (2) General formula (wherein X is hydrogen or 7 to 5 straight groups on the benzene ring t
'', these substituents are nitro group, halogen group, alkyl group, haloalkyl group, acetyl group, haloacetyl group, alkoxy group, and there is no need to worry that all W radicals are the same), for example o −2) Rho α,
α.

α-) IJ-f romoacetophenone, m-nitro-α
.

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

α, α-tribromoacetophenone, α, α, α-tribromo3. Hiro-cycloacetophenone, (3) a compound represented by the general formula % formula % [wherein R is an alkyl group (including those having a substituent) and X is a halogen], for example /, 3-benzene Disulfonyl chloride, Ko, Hiro-
Dinitrobenzenesulfonyl chloride, 0-nitrobenzenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, 3. J'-diphenylsulfonedisulfonyl chloride, ethanesulfonyl chloride,
p-Flomobenzenesulfonyl chlorite, p-nitrobenzenesulfonyl flora (do, p-iodobenzenesulfonyl chloride, p-acetamidobenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, p-toluenesulfonyl chloride, methanesulfonyl chloride, benzenesulfonyl bromide,(
4) Compounds represented by the general formula [the middle hole is an alkyl group, an aryl group (including those having a substituent), and X is...logen], such as co, Hiro-dinitrobenzenesulfenyl chloride,
o-Nitrobenzenesulfenyl chloride, (5) general formula (in the formula, R is a direct or unsubstituted aryl group, xl, x2, and (never hydrogen), such as hexabromodimethyl sulfoxide, pentabromodimethyl sulfoxide, hexabromodimethyl sulfone, trichloromethylphene, nyl sulfone, trifuromomethylphenylsulfone, trichloromethyl-pτ dichlorohenyl Sulfone, tribromomethyl-p-nitrophenyl sulfone, λ-trichloromethylbenzothiazole sulfone, ≠, 6-dimethylpyrimidyl-2-tribromomethyl sulfone, tetrabromodimethyl sulfone, λ, Hiro-dichlorophenyl-trichloromethyl sulfone , λ-methyl-≠-chlorophenyl-trichloromethylsulfone, λ, t-dimethyl-≠-chlorophenyl-
Trichloromethylsulfone, λ, ≠-dichlorophenyl-tribromomethylsulfone, (wherein R may carry a substituent on the residue of a cyclocyclic compound vlJ. Xl, Xl, and X3 are all hydrogen and halogen. At the same time, it is not hydrogenated), and the chemical compound indicated by ``Shiosue'' is tribromoquinaldine, tribromomethyl-≠
-Methylquinoline, Hiro-) IJ Bromomethylpyrimidine, ≠-phenyl-6-dribromomethylpyrimidine, coated dichloromethyl-nitrorobenzothiazole, l-phenyl-3-trichloromethylpyrazole 1.
2゜j-ditribromomethyl-3,≠-dibromothiophene, -1-trichloromethyl-3-(p-butoxystyryl)-/, J, 44-oxadiazole, 2,6-ditrichloromethyl-4'- (p-methoxyphenyl)-
Examples include organic halogen compounds such as triazine.

Among these, the preferred bet is 121, +51. In the +61 compound, the halogen is preferably chlorine, bromine, or iodine.

In producing the volatile cedar sole material of the present invention, the leuco dye and photooxidizing agent are mixed in a molar ratio of approximately /0:/7? Good results can be obtained by mixing in a ratio of about 1:1 to 1:2. A more preferred ratio is 2:2 to 1:2.

-ff Among the phenolic compounds of the present invention represented by the formula CII, those in which 01t' is at the ortho or para position of OR are preferred from the viewpoint of the effects of the present invention, and those of the general formula CI-/
L"[1-,1, (1-3'l, (1-4') or (1
-j] is historically preferred.

Cl-1) In the compounds represented by the general formulas CI-/) to (I-j), R', R, R2, R3 and R4 are the same as in the general formula [C1]. R5, 几6, 几7, R8, 几9 and kLx
o may be the same or different, and each represents a hydrogen atom, an alkyl group (a linear, branched, or cyclic alkyl group with 5/-20 carbon atoms; for example, a methyl group, an ethyl group, an n-
butyl group, n-octyl group, cycloheΦyl group, etc.), aryl group (aryl group with 6 to 7 carbon atoms: e.g. phenyl group, naphthyl group, etc.), alkoxy group (7 to 20 carbon atoms)
Alkoxy group: e.g. methoxy group, n-butoxy group,
n-octyloxy group, etc.), heterocyclic group (?lle is morpholinyl group), alkylamino group (alkylamino group with carbon number/~20: file is diethylamino group, dibutylamino group, n-octylamino group, etc. ), alkoxycarbonyl group < an alkoxycarbonyl group having carbon x number/~20, such as ethoxycarbonyl group, n-hexyloxycarbonyl group).

When carrying out the present invention, these compounds can be used alone or in combination of 25 or more, and other known anti-fading agents can also be used in combination.

The compound of general formula (I) used in the present invention is disclosed in U.S. Patent No.
, 360, 3t issue, same issue ≠, λ73゜Ryo6hiro issue, JP-A-1989-3! -jθ2≠≠ No. 3-λQ327, No. 33
- No. 77326, same name / No. 0 #37, Tokuko Akira! 7
-37ξj It can be easily synthesized by the method described in No. O, etc., or according to that method.

Specific examples of the compound represented by the general formula [I] are shown below, but the invention is not limited thereto.

E-r E-ta E-i.

E-// E-/j These compounds are microencapsulated together with a leuco dye and a photooxidizing agent. The amount of added VO is preferably /-100 parts with respect to ioo parts of photooxidant, more preferably 3 to 100 parts.
O parts, most preferably 7 to λj parts.

The light cone forming material of the present invention is exposed to light and after image formation, for example, v0
A stable image can be reliably obtained by performing heat treatment. That is, as for the mechanism of constant evaluation of the Motoken-forming material of the present invention, for example, when the photo-oxidizing agent and the reducing agent come into contact through the capsule wall due to DO heat, the reduction is no longer possible even if the photo-oxidizing agent is subsequently activated. This is because the stimulant acts to deactivate the stimulant.

Such reducing agents typically act as so-called 17-radical scavengers that trap the free radicals of the activated photooxidant.

All known free radical traps can be used, and specific examples include the following.

For example, US Patent 3.0≠2. An organic reducing agent 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 amine phenols such as -amine phenol and p-amine phenol; Zolidine-3
-one [Phenidone A, formula (1) below],] l-phenyl-μm methylpyrazolidin 3-one [Phenidone B
, the following formula (λ1'), t-phenyl-≠.

Hiro-dimethylpyrazolidin-3-one [dimezone, the following formula (3)], also 3-methyl-/-p-sulfophenyl)-2-pyrazolin-ion and 3-methyl-1-
Examples include phenyl-λ-pyrazoline.

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

0-1111- and p-methyl, p-)lifluoromethyl, m- and p-chloro, m- and p-bromo, p-fluoro, 0-lm- and p-methoxy, p-ethoxy,
p-benzyloxys p-butoxy, p-phenoxy, co, lA, A-) dimethyl, 3゜hiro-dimethyl. The following substituents can be present at the ψ position on the heterocyclic group of the cyclic phenyl hydrazide. bis-hydroxymethyl,
Hydroxymethyl and methyl, hydroxymethyl, dimethyl, dibutyl, ethyl, benzyl. On the heterocyclic group of cyclic phenylhydrazide! The following substituents can be present in the position: 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, 3-triphenylguanidine, /, J-
dicyclohexylguanidine, /, 2. J-) dicyclohexylguanidine, / , J-cy o-tolylguanidine, 0-1 lyldiphenylguanidine, m-)'+.
lyldiphenylguanidine, p-)lyldiphenylguanidine, N,N'-dicyclohexyl-≠-morpholinocarboxamidine, /, J-ditolyl-3-phenylguanidine, l, codicyclohexylphenylguanidine, /-0- ) Rilbiguanide, N-benzylidene-
Examples include guanidinoamine.

Examples of the alkylene diamine conductor include ethylene diamine, propylene diamine, tetramethylene diamine, hexemedele diamine, octamethylene diamine,
/, I, cordiaminododecane, tetrabenzylethylenediamine, and the like.

Examples of the hydroxyamine conductor include jetanolamine, triethanolamine, 3-β-7thyloxy-t-N, N-dimethylamino-coprobanol, 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 light forming material of the present invention, both the leuco dye and the photo-oxidizing agent described in J3iJ are encapsulated in microcapsules, but the reducing agent, which is not encapsulated, has a solid dispersion in the amount of The preferred dispersed particle size is ioμ 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. 1973-7J-, Ko0ri.

The preferred reducing agent degree is /- on a mole basis of the photooxidant component.
/%/(7 times the molar amount is used, but in order to obtain the desired result with as little amount as possible, a range of /%/(7 times the molar amount is more preferable).

As mentioned above, the standard image of the present invention is that the contact between the photooxidizing agent and the reducing agent can be effectively achieved by itself through the capsule wall due to head heat, but it goes without saying that the capsule can be brought into contact with the reducing agent by applying pressure. It is also possible to obtain a similar effect by destroying the . 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 photo-1 non-forming material consisting of a leuco dye capable of acid-specific color development and a photo-oxidizing agent, only a reducing agent is required.
Alternatively, in an embodiment of the present invention, it is also possible to further encapsulate a reducing agent in microcapsules.

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 Tokumaru and Shin Okawara, Kodansha 121r7 year 6
Compounds described on pages tA 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, dyes having amidinium ion-based, carboxyl ion-based, and dipolar amide-based chromophores described on pages 106 to 2j of the same publication may be mentioned. Specifically, cyanine-based, phthalein-based, and oquinol-based (
Qg is a typical example.

In the present invention, a stabilizer such as a known antioxidant may also be added to the capsule. Although the purpose of use of the stabilizer is different, it goes without saying that the stabilizer functions as a reducing agent and a shellfish, so it is necessary to keep the amount used to the minimum necessary. ,
Specifically, in addition to the above-mentioned free radical scavenging substances, US patents QL, Q&4. Compounds described in the specification of Hiroyori issue and JP-A-6-Yo! , 2,4cm dihydroxyaldoxime described in the specification of No. 33j, etc., but the amount of these stabilizers used is based on the photooxidizing agent (approximately
Preferably, from i mol % to about λ mol %,
Most preferred is a range of 0.1 mol% to lo mol%.

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

At this time, in addition to the above dispersion, binders include polyvinyl alcohol, methyl cellulose carboxymethyl cellulose, hydroxyzorobyl cellulose, gum arabic, gelatin, polyvinylpyrrolidone, casein,
Styrene-butadiene latex, acrylonitrile-
Various emulsions such as butadiene latex, polyvinyl acetate, polyacrylic ester, and ethylene-vinyl acetate copolymer can be used. The amount used is o, r: g7m2 to r1/nt2 in terms of solid content.

The coating amount of the light-forming material in the present invention is 31/nl to 3097m in terms of solid content, IF%Kjl/m2
Preferably it is between ~20 l/nt.

j! ! / m or less, sufficient C degree cannot be obtained, and 3
Even if more than 0jj/nt is coated, no improvement in quality will be observed, which will be disadvantageous in terms of cost.

Suitable materials for the support include a wide variety of materials ranging from paperboard to thick cardboard, regenerated cellulose,
Films of plastic and polymeric materials such as cellulose acetate, cellulose nitrate, polyethylene terephthalate, vinyl polymers and copolymers, polyethylene, polyvinyl acetate, polymethyl methacrylate, polyvinyl chloride; woven fabrics; such as glass, wood and metal. Includes materials commonly used in graphic arts and decorative applications.

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 1, spin code method or U.S. Patent No. 1
．． It can be coated by the extrusion coating method using a hopper described in the Meiji No. t8"l, 2?mu.

Any convenient light source can be used in the present invention for the activation of the photooxidant and the formation of the leuco dye. The lrt UJ may be natural or artificial, monochromatic or non-coherent or coherent light, and suitable light must be of sufficient density for activation of the forming composition.

Conventional light sources include full lamps, mercury, metal addition and arc lamps. Coherent light sources include pulsed nitrogen 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. It is. Also useful in the subject compositions are Uv-O6 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 scanning 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 formation of the ridge is done using conventional diazo printing equipment,
In graphic art exposure or liquid flashing apparatus, and in U.S. Patent J, 47. It may also be performed by the projection described in .mu./, μ61. The exposure time is a fraction of a second depending on the density and intensity of the light/l/energy distribution, its distance from the composition, the nature and amount of the composition used, and the color variation in the desired image. It can vary from a few minutes to a few minutes.

After exposure, the image can be fixed by bringing a photooxidizing agent into contact with a reducing agent. 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 8 points on the glass surface of the microcapsule wall vary depending on the material used, so the heat treatment required for fixing is determined by taking these into account.
It can be selected as appropriate.

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

The force required for breaking may vary depending on the material and grain size, but can be easily determined by those skilled in the art.

The i1m-forming material of the present invention can be used as a photoimage-forming composition that has excellent manufacturability, positive formation properties, and storage stability. Examples are shown below, but the present invention is not limited to these. Naofu DI] "Parts" indicating the amount are "parts by weight"
shows.

"Example" Example/ The following Motona formation system #+ was made by V@.

Sample (1): Leuco dye Leuco Crystal Violet 3.0 parts Photooxidizer λ, 2'-bis(0-chloro7enyl)
-arrow, l, j, yo'- tetraphenylbiimidazole 3.0 parts) IJ-i lomomethylphenylsulfone
0.1 part Compound MNE-2 exemplified in this specification] o, 4 parts methylene 22 parts tricresyl phosphate, 2 parts Lt mechenate D-//θN
(7% it% ethyl acetate bath solution) (manufactured by Ota Pharmaceutical Co., Ltd.) (
(Product name)) - μ parts were mixed and soaked in a water bath solution consisting of 63 parts of polyvinyl alcohol J heavy'jk'A water solution and 100 parts of distilled water, and then emulsified and dispersed with 20" (: , emulsification g with average particle size lμ
attended. Furthermore, the obtained emulsion was continuously stirred for 3 hours in a Hiro OuC. Thereafter, the mixture was returned to room temperature and filtered to obtain an aqueous capsule dispersion.

Next, polyvinyl alcohol≠Jyusagi% water bath liquid/! Mix 30 parts of θ part reducing agent /-phenylpyrazolidin-3-one (phenidone A),
Manufactured by A.G. Co., Ltd. (trade name)
A phenidone octadispersion of μ was obtained.

2 parts of capsule liquid on Ju and 6 parts of phenidone A dispersion! ts
The super calender hanger is made of high quality paper (tsubo QA4
Z″//m2) K solid coating ii / 09 / z 2
Apply it so that
Sample fi+ was obtained.

Example λ~! In place of compound [E-λ] in Example 1, compounds [E-/], (E-1), (E-♂] and (E-
Sample (2), sample 13), and sample (4) were carried out in exactly the same manner as in Example 1 except that //) was used.
and sample (5) was obtained.

Comparative Example 1 All procedures were carried out in Example 9111 and IKIJ T, * except that the compound [E-λ] was not used, and a comparative sample (ratio-7) was also used.

In order to examine the fresh storage properties of these samples (1) to (5) and (ratio-7), we tested the fresh skin ffl& and the skin degree after daytime storage ( Fog) was measured using a Macbeth reflection densitometer, and changes in fog density were measured.

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

The results are shown in Table 7.

Section / Table Sample Fresh After dry thermostat Brightening part i
lI O,01,Y 0.072
/, 20+21 0.070 0.0rl
k / , /1 (31o, ob de 0.1
01 /,,2)141 0.07/
0.09za /, 20f51 0.
070 0.077 / ,,! λ(ratio-/
) 0.06 completed O02, 2 reference /, λ
/ From these results, it can be seen that by adding the provisional compound of the present invention, an epoch-making technique for improving the raw storage stability that does not have an adverse effect on the 4-rings has been established.

Next, the samples (1) to (5) after image formation were applied to a 710 heat roller at a temperature of 1 O'C at a speed of 1 minute to determine the permeability of the capsule wall due to heat. Promote fixed eyebrows (
contact between one member inside and outside the capsule). As a result, even though these samples were then irradiated with a jet light to the full surface of the image, no change was observed in the images.

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 and R' represent a hydrogen atom or an alkyl group, and may be the same or different. R_1, R_2, R
_3 and R_4 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylthio group, an acylamino group, a hydroxyl group, or a halogen atom, and these may be the same or different. At least one of OR and OR' is R_1 to R_4 at these ortho positions.
may be bonded to each other to form a 5- or 6-membered ring, or at least one pair of R_1 to R_4 in the ortho position may be bonded to each other to form a 5- or 6-membered ring. You may. ) (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 the photoimage-forming material in which a species is present, the photoimage-forming material is characterized in that a phenol compound represented by the general formula [I] is added to the microcapsules. An image recording method characterized by carrying out fixing by bringing a photooxidizing agent into contact with the reducing agent.