JPH04247230A - Production of microcapsule and photosensitive material using the same - Google Patents

Abstract

PURPOSE:To offer the production of photosensitive microcapsules which give picture images of good granularity and to offer a photosensitive material using these microcapsules. CONSTITUTION:Oil drops of different two or more colors containing polymerizable material and color image-forming material, as in a water-base medium, are settled. After removing the supernatant liquid, the oil drops are again dispersed in a water-base medium. Then, aminoaldehyde resinous walls are formed around the oil drops to form microcapsules.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for simultaneously producing two or more types of photosensitive microcapsules containing at least a color image-forming substance and a polymerizable compound, and a photosensitive material using the same.

0002

[Prior Art] A photosensitive material in which silver halide, a reducing agent, a color image forming substance, and a polymerizable compound are housed in microcapsules (photosensitive microcapsules) was disclosed in Japanese Patent Application Laid-open No. 61
-275742 and 61-278849.

[0003] As an image forming method using a photosensitive material having the above-described structure, first, the photosensitive material is imagewise exposed to form a latent image, and then this is thermally developed to improve the area on which the latent image was formed. Polymerizing the polymerizable compound, further superimposing the photosensitive material on an image receiving material having an image receiving layer, and applying pressure in this state,
A commonly used method is to transfer an unpolymerized polymerizable compound onto an image-receiving material to obtain a transferred image on the image-receiving material. On the other hand, regarding the method of polymerizing the polymerizable compound in the area where the latent image was not formed, Japanese Patent Application Laid-Open No. 62-70836
No. 62-81635, JP-A No. 2-141756, JP-A No. 2-141757, JP-A No. 2-207254, No. 2
It is described in publications and specifications such as No.-262662.

[0004] Various wall materials for microcapsules used in these photosensitive materials and image forming methods are known.
JP 64-91131, JP 1-154140, JP 2-89680, JP 62-209438, JP 6
No. 3-269146, No. 62-209440, No. 62
-209437, No. 62-209441, etc. Among these, microcapsules whose wall material is an amino aldehyde resin described in JP-A No. 62-209439 are particularly excellent in retaining core substances.

[0005] In addition to the above-mentioned amino aldehyde resin wall microcapsules, a method for manufacturing microcapsules is to emulsify and disperse oil droplets of a polymerizable compound in an aqueous medium, and then form a polymer resin wall around the oil droplets. A common method is to form After emulsifying and dispersing an oily liquid containing silver halide, a reducing agent, a color image forming substance, and a polymerizable compound in an aqueous medium, a capsule wall made of urea/formalin/resorcinol or melamine/formalin resin is formed around the oil droplets. In this case, the ability of the microcapsule wall to retain the core substance may be impaired depending on the conditions. In particular, JP-A-64-3
No. 2251, JP-A No. 1-263641, JP-A No. 2-1
46041 and Japanese Patent Application No. 1-160148, in order to speed up the development reaction,
This tendency was stronger when the base precursor was included in the microcapsules.

In order to solve this problem, the present inventor previously disclosed in Japanese Patent Application No. 02-405364 that an aqueous medium containing at least a color image forming substance and a polymerizable compound and having a density of 1.0 After emulsifying and dispersing a larger oily liquid, the resulting oil droplets are allowed to settle, and after removing some or all of the supernatant liquid, the oil droplets are redispersed in an aqueous medium, and then an amino acid is added around the oil droplets. We proposed a method to form capsule walls made of aldehyde resin.

[0007]

By the above method, the ability of the microcapsule wall to retain the core substance has been improved. However, two different color image-forming substances made by this method
When an image is formed using a photosensitive material in which more than one type of microcapsules are mixed and coated on a support, graininess worsens, especially in the hue area created by mixing two or more colorants. It was observed.

[0008]

[Means for Solving the Problems] The present invention provides an aqueous medium with:
comprising at least a color image forming substance and a polymerizable compound;
After emulsifying and dispersing an oily liquid with a density of more than 1.0, the resulting oil droplets are allowed to settle, and after removing some or all of the supernatant liquid, the oil droplets are redispersed in an aqueous medium, and then the oil droplets are A method for producing photosensitive microcapsules in which a capsule wall made of an amino aldehyde resin is formed around the photosensitive microcapsules, characterized in that two or more types of oil droplets having different color image forming substances are precipitated in a mixed state. This is a method for producing microcapsules.

According to research conducted by the present inventors, one of the causes of the deterioration of graininess is that microcapsules aggregate during encapsulation to form huge capsule aggregates of the same color. As a result, in a hue portion where two or more color materials are mixed, pixels become larger and graininess deteriorates.

[0010] It has also been found that the above-mentioned aggregation of microcapsules occurs not only in the process of forming microcapsule walls, but also in the process of settling emulsified oil droplets.

[0011] Then, it was discovered that the above problem can be improved by precipitating two or more types of oil droplets having different color image forming substances in a mixed state, and then encapsulating the mixture, and the present invention has been completed. It is. This is because oil droplets of different colors aggregate and become encapsulated even when they aggregate during sedimentation, resulting in smaller pixels than when oil droplets of a single color aggregate and become encapsulated. It seems likely that this is the case, but the details are unknown.

[0012] The microcapsules thus produced can be used as they are in photosensitive materials; however,
Silver sensor type microcapsules can be manufactured by containing silver halide and a reducing agent in the oily liquid. The present invention will be mainly explained using a silver sensor type.

[0013]
To mix two or more types of oil droplets, the first internal phase is dispersed in an aqueous medium to form the first oil droplets, and then the second internal phase is dispersed to form the second oil droplets. A method of generating the oil droplets may be used, or a method of generating the first oil droplets and the second oil droplets separately and then mixing them may be used. When sedimenting oil droplets, they may be diluted with water or an aqueous liquid containing a water-soluble polymer in order to increase the sedimentation rate. Generally, the higher the dilution ratio, the faster the sedimentation rate, but as mentioned above, the stability of the emulsion is impaired and it tends to aggregate, so it needs to be determined within an appropriate range. A preferred dilution ratio is 1.5 times to 50 times.

[0014] The sedimentation may be performed by natural sedimentation by standing still, or by centrifugation. A precipitating agent may be used, but it is necessary that it can be redispersed in a later step.

After sedimentation, after removing part or all of the supernatant, water or an aqueous liquid containing a water-soluble polymer is added if necessary to re-disperse the oil droplets in the aqueous medium, and then the amino aldehyde is dissolved according to the usual process. Microcapsules can be formed by forming resin-walled microcapsules.

The silver halide, reducing agent, color image forming substance, polymerizable compound, and
Microcapsules and supports will be explained in detail.

The light-sensitive material of the present invention may contain any one of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide as silver halide. Particles can also be used.

The silver halide grains in the photographic emulsion may have regular crystals such as cubic, octahedral, dodecahedral, or tetradecahedral, or irregular crystal systems such as spherical or plate-like. It may have crystal defects such as twin planes, or a composite form thereof.

The grain size of the silver halide may be as fine as about 0.01 micron or less, or as large as a projected area diameter of up to about 10 microns, or as a polydisperse emulsion as described in US Pat. No. 3,574,628. No. 3,655,394
Monodisperse emulsions such as those described in No. 1, British Patent No. 1,413,748 and the like may also be used.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
hic Science and Engineering
ng), Vol. 14, pp. 248-257 (1970);
U.S. Patent Nos. 4,434,226 and 4,414,31
No. 0, No. 4,433,048, No. 4,439,520
and British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. In addition, halogen composition,
Two or more types of silver halide grains having different crystal habits, grain sizes, etc. can also be used together.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) No.
．． 17643 (December 1978), pp. 22-23,
“I. Emulsion preparation
ion and types)” and No. 1
8716 (November 1979), p. 648, etc.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are listed in Research Disclosure No. 17643 and the same No. 18716
The relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Additive type RD1764
3 RD18716---
−−−−−−−−−−−−−−−−−−−−−−−−−
−−−−−−−−−−−−−−−−−−−−−
Chemical sensitizer page 23
Page 648 right column Sensitivity enhancer
Same as above Spectral sensitizer
Pages 23-24 Page 648 Right column ~
supersensitizer
Page 649 right column
Antifogging agent pages 24-25
Page 649 right column ~ and stabilizers

[0026] As the silver halide grains, as in the photosensitive material described in JP-A No. 63-68830,
It is preferable to use silver halide grains with relatively low fog values.

In order to uniformly contain silver halide in the microcapsules, it is preferred that a copolymer consisting of a hydrophilic repeating unit and a hydrophobic repeating unit be dissolved in the polymerizable compound. Details thereof are described in JP-A-62-209450, JP-A-63-287844, and JP-A-1-37782.

The reducing agent that can be used in the photographic material of the present invention has a function of reducing silver halide and/or a function of promoting (or suppressing) polymerization of a polymerizable compound. There are various types of reducing agents having the above functions. The reducing agents include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, 5-aminouracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-
Sulfonamidophenols, o- or p-sulfonamidonaphthols, 2,4-disulfonamidophenols, 2,4-disulfonamidonaphthols, o-
or p-acylaminophenols, 2-sulfonamide indanones, 4-sulfonamide-5-pyrazolones, 3-sulfonamide indoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α- These include sulfonamide ketones and hydrazines.

[0029] Regarding various reducing agents having the above-mentioned functions, please refer to Japanese Patent Application Laid-open Nos. 61-183640 and 61-1885.
35, 61-228441, and JP-A-62-70836, 62-86354, and 6
No. 2-86355, No. 62-206540, No. 62-
No. 264041, No. 62-109437, No. 63-2
No. 54442, JP-A No. 1-267536, JP-A No. 2-14
No. 1756, No. 2-141757, Patent Application No. 1-271
It is described in publications and specifications such as No. 75, No. 1-54101, No. 1-91162, and No. 1-90087. (Including those described as developing agents or hydrazine derivatives) Also, regarding the above-mentioned reducing agents, T. “The Theory of the Photog” by Jmames
4th edition, 291-3
34 pages (1977) Research Disclosure Vol. 170, June 1978, No. 17029 (pages 9-15), and the same magazine Vol. 176, 19
There is also a description in No. 17643 (pages 22-31) of December 1978. Furthermore, as in the photosensitive material described in JP-A No. 62-210446, a reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base may be used in place of the reducing agent. good. The reducing agents and reducing agent precursors described in each of the above-mentioned publications, specifications, and literature can also be effectively used in the photosensitive material used in this specification. Therefore,
The "reducing agent" in this specification includes the reducing agents and reducing agent precursors described in each of the above-mentioned publications and literature.

Among these reducing agents, those having basicity that form salts with acids can also be used in the form of salts with appropriate acids.

These reducing agents may be used alone, or as described in the above specifications, two or more reducing agents may be used in combination. When two or more types of reducing agents are used together, the interaction of the reducing agents is, first, to promote the reduction of silver halide (and/or organic silver salt) through so-called superadditivity; , causing polymerization of the polymerizable compound via a redox reaction with other reducing agents coexisting with an oxidized form of the first reducing agent generated by reduction of silver halide (and/or organic silver salt); (or suppressing polymerization), etc. However, in actual use, the reactions described above can occur simultaneously, so it is difficult to specify which effect is occurring. Specific examples of the above reducing agent are shown below.

[0032]

[Chemical formula 1]

[0033]

[Case 2]

[0034]

[Chemical formula 3]

[0035]

[C4]

The amount of the reducing agent added can vary widely, but is generally 0.1 to 1500 mol %, preferably 10 to 300 mol %, based on the silver salt. There are no particular restrictions on the color image-forming substance that can be used in the photosensitive material of the present invention, and various types can be used. In other words, substances that themselves are colored (dyes and pigments), and substances that are colorless or light in color but are exposed to external energy (heating, pressure, light irradiation, etc.) or other components (color developers). Color image-forming substances also include substances that develop color upon contact with (color formers).

As the color image-forming substance of the present invention, dyes and pigments which have excellent image stability and are themselves colored are preferred, as described in JP-A-62-187346.

[0038] Dyes and pigments used in the present invention include:
In addition to commercially available products, publicly known products described in various literature can be used. Regarding literature, see Color Index (C.I.) Handbook, "Latest Pigment Handbook" edited by Japan Pigment Technology Association (published in 1977), "Latest Pigment Application Technology" by CMC Publishing (published in 1986), "Printing Ink Technology" (CMC Publishing) , published in 1984).

The types of pigments are white pigments, black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymers. Examples include binding dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, and isoindolinone pigments. , quinophthalone pigments, dyeing lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, etc. can be used.

The pigment that can be used in the present invention may be the above-mentioned naked pigment, or may be a pigment that has been subjected to surface treatment. Surface treatment methods include methods of surface coating with resin or wax, methods of attaching surfactants, methods of bonding reactive substances (for example, silane coupling agents, epoxy compounds, polyisocyanates, etc.) to the pigment surface, etc. is considered and described in the following documents.

Properties and Applications of Metallic Soaps (Saiwai Shobo) Printing Ink Technology (CMC Publishing, 1984) Latest Pigment Application Technology (
CMC Publishing, 1986) The particle size of the pigment that can be used in the present invention is preferably in the range of 0.01 μ to 10 μ, more preferably in the range of 0.05 to 1 μ after being dispersed in the polymerizable compound. .

The pigment is preferably used in an amount of 5 to 60 parts by weight based on 100 parts by weight of the polymerizable compound. As a method for dispersing the pigment into the polymerizable compound, known dispersion techniques used in ink production, toner production, etc. can be used.

Examples of the dispersing machine include a sand mill, attritor, pearl mill, super mill, ball mill, impeller, desperser, KD mill, colloid mill, Dynatron, three-roll mill, and pressure kneader. For details, see "Latest Pigment Application Technology" (CMC Publishing, 1986)
) is stated.

The polymerizable compound used in the photosensitive material is generally a compound having addition polymerizability or ring-opening polymerizability. Examples of the compound having addition polymerizability include compounds having an ethylenically unsaturated group, and compounds having ring-opening polymerizability include compounds having an epoxy group, and compounds having an ethylenically unsaturated group are particularly preferred.

Compounds having ethylenically unsaturated groups that can be used in photosensitive materials include acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts, methacrylic esters, and methacrylamides. , maleic anhydride, maleic esters, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters, and derivatives thereof.

Specific examples of preferred polymerizable compounds that can be used in photosensitive materials include n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, and ethoxyethoxyethyl esters. Acrylate, tricyclodecanyloxyacrylate, nonylphenyloxyethyl acrylate, 1,3-dioxolane acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate,

Trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxyethylated bisphenol A diacrylate, 2-(2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-
5-ethyl-1,3-dioxane diacrylate, 2-
(2-hydroxy-1,1-dimethylethyl)-5,5
-dihydroxymethyl-1,3-dioxane triacrylate, triacrylate of propylene oxide adduct of trimethylolpropane, hexaacrylate of caprolactone adduct of dipentaerythritol, polyacrylate of hydroxy polyether, polyester acrylate, and polyurethane acrylate, etc. be able to.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate,
Examples include pentaerythritol tetramethacrylate and polyoxyalkylenated bisphenol A dimethacrylate.

The above polymerizable compounds may be used alone or in combination of two or more. For photosensitive materials containing two or more types of polymerizable compounds, please refer to JP-A No. 62-210445.
There is a description in the bulletin. In addition, a substance in which a polymerizable functional group such as a vinyl group or a vinylidene group is introduced into the chemical structure of the above-mentioned reducing agent can also be used as a polymerizable compound.

The microcapsules used in the present invention have amino aldehyde resin as a wall material, and the method thereof is described, for example, in US Pat. No. 4,001,140 and US Pat.
No. 087376, No. 4089802 and No. 402
No. 5455, JP-A-62-209439, JP-A-64
-91131, Japanese Patent Application Laid-Open No. 1-154140, and Japanese Patent Application No. 63-241635. Examples of amino aldehyde resins include urea-formaldehyde resin, urea-formaldehyde-resorcinol resin, melamine-formaldehyde resin, acetoguanamine-formaldehyde resin, benzoguanamine-formaldehyde resin, and the like.

[0051] In the present invention, it is particularly preferable to use melamine-formaldehyde resin, since it is possible to obtain highly dense capsules. Also, patent application No. 1-377
In the specification of No. 82, in order to obtain capsules with especially excellent wall density, melamine is added around a membrane made of a reaction product of a water-soluble polymer having a sulfinic acid group and a polymerizable compound having an ethylenically unsaturated group. - Microcapsules provided with a polymer wall of a high molecular compound such as formaldehyde resin have been disclosed and are preferred for the present invention. In addition, JP-A-63
As in the photosensitive material described in Japanese Patent No. 32535, it is preferable that the amount of residual aldehyde is kept below a certain value.

[0052] The average particle diameter of the microcapsules formed by the method of the present invention is preferably 5 to 25 μm. The particle size distribution of microcapsules was determined by Japanese Patent Application Laid-open No. 6
As in the photosensitive material described in Publication No. 3-5334, it is preferable that the distribution is uniform over a certain value. Further, the film thickness of the microcapsules is preferably within a certain value range with respect to the particle diameter, as in the photosensitive material described in JP-A-63-81336.

[0053] When silver halide is contained in microcapsules, it is preferable that the average grain size of the silver halide grains described above is one-fifth or less, and one-tenth or less of the average size of the microcapsules. It is more preferable that A uniform and smooth image can be obtained by setting the average particle size of the silver halide grains to one-fifth or less of the average size of the microcapsules.

When silver halide is contained in microcapsules, it is preferable that silver halide be present in the wall material constituting the outer shell of the microcapsules. A photosensitive material containing silver halide in the wall material of microcapsules is described in JP-A-62-169147.

In the production of the photosensitive microcapsules of the present invention, when an oily liquid containing at least silver halide, a reducing agent, a color image forming substance, and a polymerizable compound is dispersed in an aqueous medium, the aqueous medium contains , a nonionic water-soluble polymer and an anionic water-soluble polymer are preferably included. In this case, the oily liquid containing the polymerizable compound is preferably 10 to 120% by weight, more preferably 20 to 90% by weight, based on the aqueous medium.

Examples of nonionic water-soluble polymers include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-coacrylamide, hydroxyethylcellulose, hydroxypropyl. Examples include cellulose and methylcellulose.

Examples of anionic water-soluble polymers include polystyrene sulfinic acid, styrene sulfinate copolymers, polystyrene sulfonates, styrene sulfonic acid copolymers, polyvinyl sulfate ester salts, polyvinyl sulfonates, Examples include maleic anhydride/styrene copolymer and maleic anhydride/isobutylene copolymer. In this case, the concentration of the anionic water-soluble polymer in the aqueous medium is preferably in the range of 0.01 to 5% by weight, more preferably in the range of 0.1 to 2% by weight. In the above case, it is particularly preferable to use a nonionic water-soluble polymer and a water-soluble polymer having a small amount of sulfinic acid groups together.

[0058] When a water-soluble polymer is included in the aqueous liquid added after emulsification, dilution and sedimentation, and removal of the supernatant,
Preference is given to using the nonionic and anionic polymers mentioned above. As the support for the photosensitive material of the present invention, it is preferable to use a material with good thermal conductivity.

Materials that can be used for the support include glass, paper, wood-free paper, baryta paper, coated paper, cast coated paper, synthetic paper, metals and their analogues, polyester, polyethylene, polypropylene, acetylcellulose, and cellulose. Examples include films of ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, polyimide, etc., and papers laminated with resin materials and polymers such as polyethylene. Among these, the preferred support of the present invention is a polymer film, and from the above-mentioned thermal conductivity, a polymer film of 50 μm or less is particularly preferred.

That is, the image forming method of the present invention requires at least a series of steps such as imagewise exposure, heating, and pressing, and the photosensitive material is used in the form of a continuous strip. is particularly preferable in terms of efficiency. Therefore, since the photosensitive material is subjected to operations such as conveyance, heating, pressurization, and rolling as a continuous band, it is required to have mechanical or thermal properties to withstand such operations. From this point of view, the support is preferably a polymer film from the viewpoint of mechanical properties (tensile strength, modulus of elasticity, stiffness, etc.), and among these, one with good thermal conductivity and a thickness of 50 μm or less is particularly preferred. If the thickness exceeds 50 μm, the thermal conductivity is poor and it is difficult to shorten the heat development time. Moreover, those having a thickness of 10 μm or less have problems in transportability in terms of mechanical strength.

Furthermore, in order to coat the photosensitive layer on the support,
It is preferable to provide an undercoat layer as described in JP-A-61-113058 on the polymer film, or to provide a metal vapor deposited film such as aluminum on the polymer film. Therefore, as a support for a photosensitive material for carrying out the image forming method of the present invention, a polymer film having a thickness of 50 μm or less and having an aluminum vapor-deposited film is particularly preferable.

Other components that can be used in the photosensitive material of the present invention will be explained below. In the present invention, it is preferable to use a base precursor in order to cause the heat development reaction to proceed rapidly. As the base precursor that can be used in the photosensitive material of the present invention, base precursors of inorganic bases and organic bases (decarboxylation type, thermal decomposition type, reaction type, complex salt forming type, etc.) can be used.

Preferred base precursors include JP-A-59-180549, JP-A-59-180537, JP-A-59-195237, JP-A-61-32844, and JP-A-61.
-36743, 61-51140, 61-52
No. 638, No. 61-52639, No. 61-53631
No. 61-53634, No. 61-53635, No. 61-53636, No. 61-53637, No. 61-
No. 53638, No. 61-53639, No. 61-536
No. 40, No. 61-55644, No. 61-55645, No. 61-55646, No. 61-84640, No. 6
No. 1-107240, No. 61-219950, No. 61
-251840, 61-252544, 61-
No. 313431, No. 63-316740, No. 64-6
8746 and Japanese Patent Application No. 62-209138, salts of organic acids and bases that are decarboxylated by heating, and JP-A Nos. 59-157637 and 59-166.
Examples include compounds that eliminate bases upon heating as described in Japanese Patent No. 943 and No. 63-96159.

The base precursor of the present invention is 50
It is preferable to release the base at a temperature between 80°C and 200°C.
It is more preferable to release at a temperature of 180°C to 180°C. In the present invention, in order to make the heat development reaction proceed more rapidly, it is preferable to accommodate the base precursor in microcapsules. In that case, the following base precursor consisting of a salt of a carboxylic acid and an organic base having a solubility in water and a polymerizable compound at 25° C. of 1% or less is preferred.

(a) The base precursor consists of a salt of a carboxylic acid and an organic base, and the organic base has the following formula (1).
It is a diacid to tetraacid base consisting of two to four partial structures corresponding to an atomic group obtained by removing one or two hydrogen atoms from amidine represented by the formula, and a structural group of the partial structure.

[0066]

[C5]

[In the above formula (1), R11, R12
, R13 and R14 each represent a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, and a heterocyclic residue (each group is may have one or more substituents), and R11, R12,
Any two groups selected from R13 and R14 may be bonded to each other to form a five- or six-membered nitrogen-containing heterocycle]

(b) A partial structure in which the base precursor is composed of a salt of a carboxylic acid and an organic base, and the organic base corresponds to an atomic group obtained by removing one or two hydrogen atoms from guanidine represented by the following formula (2). It is a diacid to tetraacid base consisting of two to four of these and a linking group of the partial structure.

[0069]

[C6]

[In the above formula (2), R21, R22
, R23, R24 and R25 each represent a monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, and a heterocyclic residue (each (the group may have one or more substituents), and R21,
Any two groups selected from R22, R23, R24 and R25 may be bonded to each other to form a five- or six-membered nitrogen-containing heterocycle. The base precursors are described in detail in JP-A-63-31670 and JP-A-64-68746, respectively. Specific examples of these base precursors are shown below, but are not limited thereto.

[0071]

[C7]

[0072]

[Chemical formula 8]

[0073]

[Chemical formula 9]

[0074]

[Chemical formula 10]

[0075]

[Chemical formula 11]

[0076]

[Chemical formula 12]

In the present invention, when the base precursor is contained in microcapsules, a photosensitive composition in which the base precursor is directly solid-dispersed in a polymerizable compound may be used. Kaihei 1-2
63641), it is particularly preferable to use a photosensitive composition in which a base precursor is dispersed in water and emulsified in a polymerizable compound. (Unexamined Japanese Patent Publication No. 63-21
No. 8964, Japanese Patent Application No. 1-182245, Japanese Patent Application No. 1-1
60148 and the specification) Here, when dispersing the base precursor in water, it is preferable to use a nonionic or amphoteric water-soluble polymer.

Examples of nonionic water-soluble polymers include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-co-acrylamide, hydroxyethyl cellulose, hydroxy Examples include propylcellulose and methylcellulose. Moreover, gelatin can be mentioned as an amphoteric water-soluble polymer.

The above water-soluble polymer is preferably contained in an amount of 0.1 to 100% by weight, more preferably 1 to 50% by weight, based on the base precursor. Further, the base precursor is preferably contained in an amount of 5 to 60% by weight, more preferably 10 to 50% by weight, based on the dispersion. In addition, the base precursor is 2 for polymerizable compounds.
It is preferably contained in a proportion of ~50% by weight, and 50% by weight.
More preferably, it is contained in a proportion of 30% by weight.

In addition, in order to reduce the solubility of the base precursor in the polymerizable compound, polyethylene glycol, polypropylene glycol, benzoic acid amide, cyclohexyl urea, octyl alcohol, dodecyl alcohol, stearyl alcohol, stearamide, etc. are added to the polymerizable compound. -OH,
-SO2 NH2 , -CONH2 , -NHCONH
A compound having a hydrophilic group such as 2 can also be added.

The binders that can be used in the photosensitive material can be contained in the photosensitive layer alone or in combination. It is preferable to use a mainly hydrophilic binder. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, gum arabic, etc., and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, etc. synthetic polymeric materials such as water-soluble polyvinyl compounds. Other synthetic polymeric substances include dispersed vinyl compounds in the form of latexes, which increase the dimensional stability of photographic materials, among others. Incidentally, a photosensitive material using a binder is described in JP-A-61-69062. Furthermore, a photosensitive material using a binder together with microcapsules is described in JP-A-62-209525.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the organic silver salt oxidizing agents described above include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 626, columns 52-53. Also, JP-A-60-1
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A No. 13235, and JP-A No. 6
Acetylene silver described in the publications No. 1-249044 and No. 64-57256 is also useful. Two or more types of organic silver salts may be used in combination.

The above organic silver salt is photosensitive silver halide 1
per mole, from 0.01 to 10 moles, preferably 0.01 to 10 moles.
01 to 1 mole can be used in combination. The total coating amount of photosensitive silver halide and organic silver salt is suitably 1 mg to 10 g/m 2 in terms of silver.

The anti-smudge agent used in the photosensitive material is preferably a particulate material that is solid at room temperature. As a specific example,
Starch particles described in UK Patent No. 1,232,347, polymer fine powders described in US Pat. No. 3,625,736, etc., microcapsule particles containing no coloring agent described in UK Patent No. 1,235,991, etc., US Pat. No. 271
Inorganic particles such as cellulose fine powder described in No. 1375, talc, kaolin, bentonite, waxite, zinc oxide, titanium oxide, and alumina can be mentioned. The average particle size of the particles is preferably in the range of 3 to 50 μm, more preferably in the range of 5 to 40 μm in volume average diameter. As mentioned above, when the oil droplets of the polymerizable compound are in the form of microcapsules, it is more effective if the particles are larger than the microcapsules. Various image formation accelerators can be used in the photosensitive material.

The image forming accelerator has functions such as: (1) promoting the movement of the base or base precursor; (2) promoting the reaction between the reducing agent and the silver salt; and (2) promoting the immobilization of the dye-donating substance through polymerization. In terms of physicochemical functions, they are classified into the aforementioned bases or base precursors, nucleophilic compounds, oils, heat solvents, surfactants, compounds that interact with silver or silver salts, and compounds that have an oxygen removal function. . However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Details of these are described in publications and specifications such as U.S. Pat.

In the photosensitive material, in a system in which a partially polymerizable compound that does not form a silver halide latent image is polymerized, it is necessary to initiate polymerization or to polymerize the unpolymerized compound after image transfer. A thermal or photopolymerization initiator can be used for this purpose. Examples of thermal polymerization initiators include azo compounds, organic peroxides, inorganic peroxides, sulfinic acids, and the like. Details of these are described in pages 6 to 18 of "Addition Polymerization/Ring-Opening Polymerization" (Kyoritsu Shuppan, 1983), edited by the Society of Polymer Science and Technology, Editorial Committee of Polymer Experimental Science.

Examples of photopolymerization initiators include benzophenones, acetophenones, benzoins, and thioxanthone. Details of these are described in "Ultraviolet Curing System" (1989, General Technology Center), pages 63 to 147. Various surfactants can be used in photosensitive materials for the purposes of coating aids, improving peelability, improving slipperiness, preventing electrification, promoting development, and the like. Specific examples of surfactants are given in JP-A-62-1734.
No. 63, No. 62-183457, etc.

An antistatic agent can be used in the photosensitive material for the purpose of preventing static electricity. Researched as an antistatic agent
Disclosure Magazine, November 1978, No. 1764
No. 3 (page 27), etc. A dye or pigment may be added to the photosensitive layer of the photosensitive material for the purpose of preventing halation or irradiation. JP-A-63-297 regarding a photosensitive material with a white pigment added to the photosensitive layer
There is a description in Publication No. 48.

A dye having the property of being decolored by heating or light irradiation may be contained in the microcapsules of the photosensitive material. The dye having the property of being decolored by heating or light irradiation can function as a yellow filter in conventional silver salt photography. A photosensitive material using a dye having the property of being decolored by heating or light irradiation as described above is described in JP-A-63-974940.

When a solvent for a polymerizable compound is used in a photographic material, it is preferable to encapsulate it in a microcapsule separate from the microcapsule containing the polymerizable compound. Regarding photosensitive materials using organic solvents that are miscible with polymerizable compounds encapsulated in microcapsules, Japanese Patent Laid-Open No. 6
There is a description in Publication No. 2-209524. A water-soluble vinyl polymer may be adsorbed onto the silver halide grains described above. A photosensitive material using a water-soluble vinyl polymer as described above is described in JP-A-62-91652.

In addition to those mentioned above, examples of optional components that can be included in the photosensitive layer and their usage can be found in the application specifications related to the above-mentioned series of photosensitive materials, and in Research Disclosure Magazine Vol. 170,
It is described in No. 17029, June 1978 (pages 9-15). Examples of layers that can be optionally provided on the photosensitive material include an image-receiving layer, a heating layer, an antistatic layer, an anti-curl layer, a peeling layer, a cover sheet or protective layer, an anti-halation layer (colored layer), etc. can.

[0092] For photosensitive materials using a heating layer, see JP-A No. 61-294434, and for photosensitive materials provided with a cover sheet or protective layer, see JP-A No. 62-2.
No. 10447 discloses a photosensitive material provided with a colored layer as an antihalation layer, and Japanese Patent Application Laid-Open No. 63-101842.
They are described in the respective publications. Furthermore, examples of other auxiliary layers and their usage are also described in the applications relating to the above-mentioned series of light-sensitive materials.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples include azoles and azaindenes described in RD17643 (1978) pages 24-25, and JP-A-59-16844.
Nitrogen-containing carboxylic acids and phosphoric acids described in No. 2, mercapto compounds and metal salts thereof described in JP-A-59-111636, acetylene compounds described in JP-A-62-87959, etc. are used. It will be done.

Various development stoppers can be used in the photosensitive material in order to always obtain a constant image regardless of the processing temperature and processing time during development. The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that Specific examples thereof include acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction of coexisting bases when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and precursors thereof. For more details, see JP-A-6
No. 2-253159 (31)-(32), Patent Application No. 1-
It is described in No. 72479, No. 1-3471, etc.

In the image forming method of the present invention, an image-receiving material is generally used together with a photosensitive material. The image receiving material will be explained below. The image-receiving material may be only a support, but it is preferable to provide an image-receiving layer on the support. Supports for image-receiving materials are not particularly limited, but like the supports for photosensitive materials, glass, paper, high-quality paper, baryta paper, coated paper, cast-coated paper, synthetic paper, cloth, metal, and their analogs can be used. Examples include films of polyester, polyethylene, polypropylene, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, etc., and papers laminated with resin materials and polymers such as polyethylene.

In addition, when using a porous material such as paper as a support for the image-receiving material, Japanese Patent Laid-Open No. 62-20953
It is preferable that the image-receiving material has a certain level of smoothness like the image-receiving material described in Japanese Patent No. 0. Further, an image receiving material using a transparent support is described in JP-A-62-209531. The image-receiving layer of the image-receiving material is composed of a white pigment, a binder, and other additives, and the white pigment itself or the voids between the particles of the white pigment increase the receptivity of the polymerizable compound.

Examples of the white pigment used in the image-receiving layer include inorganic white pigments such as oxides such as silicon oxide, titanium oxide, zinc oxide, magnesium oxide, and aluminum oxide, magnesium sulfate, barium sulfate, calcium sulfate, and magnesium carbonate. , barium carbonate, calcium carbonate,
Alkaline earth metal salts such as calcium silicate, magnesium hydroxide, magnesium phosphate, and magnesium hydrogen phosphate, as well as aluminum silicate, aluminum hydroxide, zinc sulfide, various clays, talc, kaolin, zeolite, acid clay, and activated clay. Examples include white clay and glass. Examples of organic white pigments include polyethylene, polystyrene, benzoguanamine resin, urea-formalin resin, melamine-formalin resin, polyamide resin, and the like. These white pigments may be used alone or in combination, but those with high oil absorption to polymerizable compounds are preferred.

Further, as the binder used in the image-receiving layer of the present invention, water-soluble polymers, polymer latexes, polymers soluble in organic solvents, etc. can be used. Examples of water-soluble polymers include cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, and methyl cellulose, proteins such as gelatin, phthalated gelatin, casein, and ovalbumin, starches such as dextrin and etherified starch, polyvinyl alcohol, and polyvinyl alcohol moieties. Synthetic polymers such as acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, polystyrene sulfonic acid,
Other examples include locust bean gum, pullulan, gum arabic, and sodium alginate.

Examples of the polymer latex include styrene-butadiene copolymer latex, methyl methacrylate-butadiene copolymer latex, acrylic acid ester and/or methacrylic acid ester polymer or copolymer latex, and ethylene-vinyl acetate copolymer latex. Examples include polymer latex. Examples of polymers soluble in organic solvents include polyester resins, polyurethane resins, polyvinyl chloride resins, polyacrylonitrile resins, and the like.

[0100] The above-mentioned binders can be used in combination of two or more types, and furthermore, two types of binders can be used in combination in such a ratio that phase separation occurs. An example of such usage is JP-A-1-154789.
There is a description in the bulletin. The average particle size of the white pigment is 0.
The thickness is 1 to 20μ, preferably 0.1 to 10μ, and the coating amount is in the range of 0.1g to 60g, preferably 0.5g to 30g. The weight ratio of the white pigment to the binder is preferably in the range of 0.01 to 0.4 of the binder to 1 of the pigment;
．． The range of 0.03 to 0.3 is more preferable.

[0101] In addition to the binder and the white pigment, the image-receiving layer can contain various additives as described below. For example, when using a coloring system consisting of a color former and a color developer, the image receiving layer can contain the color developer. Typical color developers include phenols, organic acids or their salts, and esters, but when leuco dyes are used as color image forming substances,
Zinc salts of derivatives of salicylic acid are preferred, especially 3,
Zinc 5-di-α-dimethylbenzylsalicylate is preferred. The color developer is preferably contained in the image-receiving layer in a coating amount ranging from 0.1 to 50 g/m<2>. More preferably, it is in the range of 0.5 to 20 g/m2.

A thermoplastic compound for the image-receiving layer may be included. When the image-receiving layer contains a thermoplastic compound, it is preferable that the image-receiving layer itself is constituted as an aggregate of thermoplastic compound fine particles. The image-receiving layer having the above structure has the advantage that it is easy to form a transferred image, and that a glossy image can be obtained by heating after image formation. The above thermoplastic compound is not particularly limited and can be arbitrarily selected from known plastic resins (plastics), waxes, and the like. However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 200° C. or lower. Regarding the image-receiving material having an image-receiving layer containing thermoplastic compound fine particles as described above,
It is described in No. 2-280071 and No. 62-280739.

The image-receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator. In forming images using image-receiving materials, color image-forming substances are transferred along with unpolymerized polymerizable compounds. Therefore, a photopolymerization initiator or a thermal polymerization initiator can be added to the image-receiving layer for the purpose of curing treatment (fixing treatment) of the unpolymerized polymerizable compound. Regarding an image receiving material having an image receiving layer containing a photopolymerization initiator, see JP-A-62-161149, and regarding an image-receiving material having an image-receiving layer containing a thermal polymerization initiator, see JP-A-62-2.
Each of these is described in Publication No. 10444.

[0104] In the image forming method of the present invention, the photosensitive material is heated from the surface of the support on which the photosensitive layer is not coated, either simultaneously with the imagewise exposure or after the imagewise exposure. A series of steps will be described, including the step of overlapping the surface of the photosensitive material coated with the photosensitive layer and the image-receiving material and applying pressure.

Various exposure means can be used as the exposure method in the imagewise exposure step, but generally a latent image of silver halide is obtained by imagewise exposure to radiation including visible light. The type of light source and the amount of exposure can be selected depending on the wavelength at which the silver halide is sensitive (in the case of dye sensitization, the sensitized wavelength) and sensitivity.

Typical light sources include natural light, ultraviolet light, visible light, infrared light, fluorescent light, tungsten lamp, mercury lamp, halogen lamp, xenon flash lamp, laser light source (gas laser,
solid state lasers, chemical lasers, semiconductor lasers, etc.)
Examples include light emitting diodes, plasma arc tubes, FOTs, and the like. In special cases, high-energy ray sources such as X-rays, γ-rays, and electron beams can also be used.

[0107] The photosensitive material of the present invention, especially in the case of a full-color photosensitive material, is composed of microcapsules that are sensitive to multiple spectral regions, and therefore requires image exposure using multiple corresponding spectral lines. It is. Therefore, one type of the light source may be used or a combination of two or more types may be used. When choosing a light source,
In addition to choosing a light source that is suitable for the sensitive wavelength of the photosensitive material, the choice can also be made by taking into consideration whether image information is transmitted via electrical signals, the processing speed of the entire system, compactness, power consumption, etc.

[0108] When image information does not pass through electrical signals, for example, direct photography of landscapes or people, direct copying of original images,
In the case of exposure through a positive such as a reversal film, a camera, an exposure device for printing such as a printer or an enlarger, an exposure device of a copying machine, etc. can be used. In this case, the two-dimensional image can be exposed simultaneously in a so-called one shot, or can be scanned and exposed through a slit or the like. You can also enlarge or reduce the original image. In this case, the light source is usually not a monochromatic light source such as a laser, but a light source such as a tungsten lamp or a fluorescent lamp, or a combination of multiple monochromatic light sources.

[0109] When image information is recorded via electric signals, a light emitting diode or various lasers may be used in combination as the image exposure device in accordance with the color sensitivity of the heat-developable color photosensitive material; Various devices known as image display devices (CRT, liquid crystal display, electroluminescent display, electrochromic display, plasma display, etc.) can also be used. In this case, the image information includes an image signal obtained from a video camera or an electronic still camera, a television signal typified by the Nippon Television Signal Standard (NTSC),
Image signals obtained by dividing an original image into many pixels using a scanner or the like, or image signals stored on recording materials such as magnetic tapes or disks can be used.

[0110] When exposing a color image, LEDs, lasers, fluorescent tubes, etc. are used in combination according to the color sensitivity of the photosensitive material, but it is also possible to use a combination of multiple types of the same type, or to use a combination of different types. It's okay. In the photographic field, the color sensitivity of photosensitive materials is R (red), G (green), and B (blue).
Usually, they are photosensitive, but in recent years they are often used in combination with UV, IR, etc., and the range of use of light sources has been expanding. For example, the color sensitivity of a photosensitive material is (G, R, IR)
or (R, IR (short wave), IR (long wave)), (
UV (short wave), UV (medium wave), UV (long wave)), (UV
, B, G) etc. are utilized. The light source may also be a combination of different types, such as a combination of two-color LED and a laser. The above-mentioned arc tube or element may be used for scanning exposure using a single tube or element for each color, or an array may be used to increase the exposure speed. Arrays that can be used include LED arrays, liquid crystal shutter arrays, magneto-optic shutter arrays, and the like.

[0111] As the image display device described above, CRT
There are color displays and monochrome displays, as shown in Figure 2. However, a method of combining a monochrome display with a filter and performing several exposures may be adopted. Existing two-dimensional image display devices may be used in a one-dimensional manner like FOT, or one screen may be divided into several parts and used in combination with scanning.

By the imagewise exposure step described above, a latent image is obtained on the silver halide contained in the microcapsules. The image forming method of the present invention includes a step of heating in order to thermally develop the photosensitive material simultaneously with or after the imagewise exposure. Preferably, thermal development is carried out by heating the surface of the support on which the photosensitive layer of the photosensitive material is not coated.

[0113] As this heating means, Japanese Patent Application Laid-Open No. 61-29
As in the photosensitive material described in Japanese Patent No. 4434, a heating layer may be provided on the surface of the support on which the photosensitive layer of the photosensitive material is not coated and heated. Furthermore, as described in JP-A-61-147244, a hot plate, an iron, or a heated roller is used, or as described in JP-A-62-144166, a photosensitive material is sandwiched between a heated roller and a belt. A heating method may also be used.

That is, the photosensitive material may be brought into contact with a heating element having a surface area larger than that of the photosensitive material to heat the entire surface at the same time, or the entire surface of the photosensitive material may be heated simultaneously (heating plate, heat plate, etc.) with a smaller surface area.
The entire surface may be heated over time by scanning with a heated roller, heated drum, etc.). In addition to the above heating method in which the heating element and the photosensitive material are brought into direct contact, it is also possible to heat the photosensitive material in a non-contact manner by applying electromagnetic waves, infrared rays, hot air, etc. to the photosensitive material.

In the image forming method of the present invention, thermal development is carried out by heating the surface of the photosensitive material on which the photosensitive layer is not coated. The coated surface may be in direct contact with the air, but
It may be covered with a heat insulating material to keep the heat from escaping. In this case, it is preferable not to apply strong pressure (10 kg/cm2 or more) to the photosensitive layer so as not to destroy the microcapsules contained in the photosensitive layer.

[0116] Thermal development by heating may be carried out simultaneously with or after imagewise exposure, but heating is preferably carried out after 0.1 second or more has elapsed after imagewise exposure. The heating temperature is generally 60°C to 250°C, preferably 80°C to 180°C, and the heating time is between 0.1 seconds and 5 seconds.

The photosensitive material can be thermally developed as described above to polymerize the polymerizable compound in the areas where the silver halide latent image is formed or the areas where the silver halide latent image is not formed. In addition, if a polymerization inhibitor is generated in the area where a latent image of silver halide is formed by reaction with a reducing agent, the polymerization inhibitor may be added to the photosensitive layer in advance, preferably in microcapsules, to initiate thermal or photopolymerization. It is also possible to decompose the agent by heating or irradiating it with light, uniformly generating radicals, and polymerizing the polymerizable compound in the portion where the silver halide latent image is not formed. In this case, in addition to the imagewise exposure step and heat development step described above, a step of heating or exposing the entire surface is required if necessary, but the method is the same as the imagewise exposure step or the heat development step.

[0118] According to the image forming method of the present invention, the unpolymerized polymerizable compound is transferred to the image-receiving material by the step of pressing the photosensitive material and the image-receiving material in a superimposed state, on which a polymer image is formed on the photosensitive layer. Color images can be obtained on the material. As the above-mentioned pressurizing method, a conventionally known method can be used.

For example, the photosensitive material and the image-receiving material may be sandwiched between press plates such as a presser, or pressure may be applied while conveying them using a pressure roller such as a nip roll. Pressure may be applied intermittently using a dot impact device or the like. Alternatively, highly pressurized air can be blown with an air gun or the like, or the pressure can be applied with an ultrasonic generator, a piezoelectric element, or the like. The pressure required for pressurization is 500 kg/cm2
It is preferably 800 kg/cm2 or more. However, if heating is also used at 40° to 120° C. during pressurization, the pressure may be 300 kg/cm 2 or less.

The photosensitive material of the present invention has many uses such as color photographing and printing photosensitive materials, printing photosensitive materials, computer graphics hard copy photosensitive materials, and copying machine photosensitive materials. Compact and inexpensive image forming systems such as copying machines, printers, and simple printing machines can be created.

[0121]

[Example] Example 1 Preparation of silver halide emulsion (EB-1) 24 g of lime-treated inert gelatin was added to distilled water,
After dissolving at 0° C. for 1 hour, 3 g of NaCl was added, and 1N sulfuric acid was added to adjust the pH to 3.2.

[0122] Add the following solutions I and II to this solution for 60 minutes.
pAg = 8 using the controlled double jet method at °C.
．． The solution was added over 45 minutes while maintaining the temperature at 5, until the I solution disappeared. After the addition is complete, adjust the pH to 6 with 1N NaOH.
．． Further, 4.8 mg of (ATR-1) and (
480 mg of SB-1) was added, and 100 g of an aqueous solution containing 4.1 g of KI was added at an equal flow rate over 20 minutes to 3 minutes after the addition.

To this emulsion, 1.1 g of (CK-1) was added and precipitated, washed with water and desalted, 6 g of lime-treated gelatin was added and dissolved, and a 72% aqueous solution of (ATR-1) 3
cc was added to adjust the pH to 6.2. Average particle size 0
．． 550 g of a monodispersed tetradecahedral silver iodobromide emulsion (EB-1) having a diameter of 24 μm and a coefficient of variation of 20% was prepared.

[0124]

Preparation of silver halide emulsion (EG-1) Same as silver halide emulsion (EG-1) except that liquid I and liquid II were
The addition time of the liquid was set to 15 minutes, and 450 mg of (SG-1) was added instead of (SB-1). Monodispersed silver iodobromide emulsion with an average grain size of 0.18 μm and a coefficient of variation of 22% (
EG-1) 550g was prepared.

Preparation of silver halide emulsion (ER-1) Same as silver halide emulsion (EG-1) except (SG-1)
instead of (SR-1) 450 mg and (SR-3
) 100 mg was added. Average particle size 0.18μm
, monodispersed silver iodobromide emulsion (ER-1) 5 with a coefficient of variation of 22%
50g was prepared.

[0127]

[Chemical formula 13]

[0128]

[Chemical formula 14]

(CK-1) Poly(isobutylene-co-monosodium maleate)

Preparation of solid dispersion (KB-1) 300ml
110 g of a 5.4% aqueous solution of lime-processed gelatin, polyethylene glycol (average molecular weight 200
0), 20 g of a 5% aqueous solution of base precursor (BG-1
) and 200 ml of glass beads with a diameter of 0.5 to 0.75 mm were added, and the mixture was heated at 3000 rpm using a Dyno Mill.
p. m. Disperse for 30 minutes and adjust the pH to 6.5 with 2N sulfuric acid.
Base precursor (B) with a particle size of 1.0 μm or less
A solid dispersion (KB-1) of G-1) was obtained.

[0131]

[Chemical formula 15]

Preparation of pigment dispersion (GY-1) Microlith Yellow 4GA was added to 265 g of the polymerizable compound (MN-2).
(trade name, manufactured by Ciba Geigy) and stirred for 1 hour at 5000 revolutions per minute using an Eiger motor mill (manufactured by Eiger Engineering).
Y-1) was obtained.

Preparation of pigment dispersion (GM-1) Microrethread 3RA was added to 270 g of the polymerizable compound (MN-2).
(trade name, manufactured by Ciba Geigy) and stirred for 1 hour at 5000 revolutions per minute using an Eiger motor mill (manufactured by Eiger Engineering).
M-1) was obtained.

Preparation of pigment dispersion (GC-1) Copper phthalocyanine (CI) was added to 262 g of the polymerizable compound (MN-1).
Pigment 15) 45g, Solsperse 5000
(manufactured by ICI) 1.13g, Solsperse 24000 (
(manufactured by ICI) were mixed and stirred for 1 hour at 5000 revolutions per minute using an Eiger motor mill (manufactured by Eiger Engineering) to obtain a dispersion (GC-1).

Preparation of photosensitive composition (PB-1) Copolymer (1P-1) (S
V-1) 9 g of 20% (wt%) solution, (RD-1) 2
．． (SV of 5g, (RD-2) 5.8g, (FF-3)
-1) 1 g of 0.5% (wt%) solution and (ST-1
) was added and dissolved to prepare an oily solution.

Silver halide emulsion (EB-1) was added to this solution.
Add 3.8g and 23g of solid dispersion (KB-1),
The mixture was stirred for 5 minutes at 10,000 revolutions per minute using a 40φ dissolver while keeping the temperature at ℃, to obtain a W/O emulsion photosensitive composition (PB-1).

Preparation of photosensitive composition (PG-1) 45 g of pigment dispersion (GM-1) was mixed with (S) of copolymer (1P-1).
V-1) 8 g of 20% (wt%) solution, (RD-1) 2
．． (SV of 3g, (RD-2) 3.1g, (FF-3)
-1) 1 g of 0.5% (wt%) solution and (ST-1
) was added and dissolved to prepare an oily solution.

Silver halide emulsion (EG-1) was added to this solution.
Add 3.8g and 24g of solid dispersion (KB-1),
While keeping the temperature at 0° C., the mixture was stirred for 5 minutes at 10,000 revolutions per minute using a 40φ dissolver to obtain a W/O emulsion photosensitive composition (PG-1).

Preparation of photosensitive composition (PR-1) 45 g of pigment dispersion (GC-1) was mixed with (S) of copolymer (1P-1).
V-1) 6g of 20% (wt%) solution, (RD-1)2
．． (SV of 3g, (RD-2) 6.2g, (FF-3)
-1) 1 g of 0.5% (wt%) solution and (ST-1
) was added and dissolved to prepare an oily solution.

Silver halide emulsion (ER-1) was added to this solution.
Add 3.8g and 24g of solid dispersion (KB-1),
While keeping the temperature at 0° C., the mixture was stirred for 5 minutes at 10,000 revolutions per minute using a 40φ dissolver to obtain a W/O emulsion photosensitive composition (PR-1).

[0141]

[Chemical formula 16]

[0142]

[Chemical formula 17]

[0143]

[Chemical formula 18]

Photosensitive microcapsule dispersion (C-1)
Preparation: Add 10 g of water to 12 g of a 15% aqueous solution of polymer (2P-1).
8 g was added, and the mixed liquid was adjusted to pH 5.0 with 2N sulfuric acid. Add 18% of a 10% aqueous solution of polymer (2P-2) to this solution.
0g was added and mixed for 30 minutes at 60°C. The above-mentioned photosensitive composition (PB-1) was added to this mixed solution, and the mixture was stirred at 60° C. and 7000 revolutions per minute for 20 minutes using a 40φ dissolver to obtain an emulsion in the form of a W/O/W emulsion. Next, (PG-1) was added and stirred at 5000 rpm for 20 minutes to obtain an emulsion in which two types of W/O/W emulsions were mixed. Next, (PR-1) was added and stirred at 4000 rpm for 20 minutes to obtain an emulsion in which three types of W/O/W emulsions were mixed.

[0145] 1710 g of distilled water was added to the above emulsion and stirred with a stirrer for 5 minutes. Thereafter, the emulsion was allowed to stand for 1 hour to settle, and then 2052 g of the upper layer was removed. Add 114 g of a 6% aqueous solution of polymer (2P-2) to the residue,
The emulsion was redispersed. Separately, add 52.2 g of a 37% formaldehyde aqueous solution to 31.5 g of melamine and 170 g of water.
．． 3 g was added, heated to 60° C., and stirred for 30 minutes to obtain a transparent aqueous solution of melamine/formaldehyde initial condensate.

[0146] 50 g of this initial condensate was added to the above emulsion sedimentation redispersion cooled to 25°C, and stirred with a propeller blade for 120 g.
pH 5.0 using 2N sulfuric acid while stirring at 0 rpm.
Adjusted to. Next, the temperature of this liquid was raised to 70° C. over 30 minutes, and the mixture was further stirred for 30 minutes. Add to this 40% of urea.
% aqueous solution was added, the pH was adjusted to 3.5 with 2N sulfuric acid, and stirring was continued at 70°C for an additional 40 minutes. After cooling this liquid to 25°C, the pH was adjusted to 6.5 using a 2N aqueous sodium hydroxide solution to prepare a photosensitive microcapsule dispersion (C-1) in which the capsule walls were made of melamine formaldehyde resin. . Polymer (2P-1) Potassium polyvinylbenzenesulfinate polymer (2
P-2) Polyvinylpyrrolidone K-90

Preparation of photosensitive material 101 50 g of photosensitive microcapsule dispersion (C-1), 0.5 g of surfactant (WW-1), and surfactant (WW-2)
1.3 g of a 10% aqueous solution of PVA and 25 g of a 10% aqueous solution of PVA KL318 (manufactured by Kuraray, carboxy-modified PVA) were added and mixed at 40°C.

[0148] This coating solution was applied to the aluminum-deposited surface of a support made of a polyethylene terephthalate film having a thickness of 12μ with aluminum deposited thereon, using an extrusion method to give a coating amount of 120cc/m2, and after drying at 60°C, The film was wound up at 65% Celsius so that the coated surface was on the inside. This photosensitive material was sealed in a moisture-proof bag laminated with aluminum under conditions of 25° C. and 55%.

[0149]

[Chemical formula 19]

Preparation of image-receiving material (RS-1) 240 g of calcium carbonate (PC700, manufactured by Shiraishi Kogyo Co., Ltd.), 5.6 g of surfactant (Poise 520, manufactured by Kao Corporation), and 354.4 ml of water were stirred. After mixing, the mixture was dispersed for 3 minutes at 8000 revolutions per minute using a dispersing machine (trade name: Ultra Disperser (LK-41 model), manufactured by Yamato Scientific). 52 g of this dispersion and 10% polyvinyl alcohol (PV
A-117, manufactured by Kuraray Co., Ltd.) was mixed with 52 g of an aqueous solution, and 4 ml of a 1% aqueous solution of the following surfactant and 22 ml of water were added to prepare a coating solution for forming an image-receiving layer.

[0151] The fiber length distribution of this coating liquid is defined by the paper support (JIS-P-8207) with a basis weight of 80 g/m2, and the sum of the weight % of the 24 mesh residue and the weight % of the 42 mesh residue is Paper support using base paper having a fiber length distribution of 30 to 60% [JP-A-63-1862
39]) at a density of 65 g/m 2 and dried at 60° C. to prepare an image-receiving material (RS-2).

[0152]

[C20]

Image Formation The following experiments were carried out at 25° C. and 50%. Using a halogen lamp whose color temperature was adjusted to 3100K, the photosensitive material 101 taken out from the moisture-proof bag was heated to continuously change color temperature from 0 to
Exposure at 20,000 lux for 1 second through a three-color separation wedge with a transmission density of 4.0, an ND filter with a density of 1.0, and a yellow and magenta CC filter (manufactured by Fujifilm) to match the gray balance. did. After 10 seconds of exposure, heat development was carried out for 1 second from the side opposite to the coated side of the photosensitive material in a heat developing machine equipped with an exhaust device heated to 160°C.

[0154] Next, the image-receiving material (RS-1) and the photosensitive material, the coated surfaces of which were overlapped, were heated at a speed of 2 cm/sec for 70 minutes.
The sample was passed through a pressure roller heated to 0.degree. C. with a diameter of 3 cm and a pressure of 300 kg/cm2. When the image-receiving material was peeled off from the photosensitive material immediately after passing, a clear positive image was obtained on the image-receiving material. When this image was viewed from a distance of 30 cm, no noticeable graininess was observed in the red, green, and blue areas.

Comparative Example 1 Preparation of Photosensitive Microcapsule Dispersion (CB-1) 36 g of water was added to 4 g of a 15% aqueous solution of polymer (2P-1), and the pH of the mixed solution was adjusted to 5.0 with 2N sulfuric acid. 60 g of a 10% aqueous solution of polymer (2P-2) was added to this liquid and mixed at 60°C for 30 minutes. The above photosensitive composition (PB-1) was added to this mixed solution, stirred for 20 minutes at 60°C and 7000 rpm using a 40φ dissolver, and
An emulsion in the form of a /O/W emulsion was obtained. Two of the above emulsions were prepared, and 2250 g of distilled water was added to 250 g of the mixture, and the mixture was stirred with a stirrer for 15 minutes. After that, the emulsion was allowed to settle for 1 hour, and then 2400 g of the upper layer was removed. Polymer in the residue (2P-2)
50 g of a 6% aqueous solution of was added to redisperse the emulsion.

[0156] The same melamine material as the cloth made in Example 1 was used.
16.7 g of formaldehyde initial condensate was added to the above emulsion sedimentation redispersion cooled to 25°C, and 16.7 g of formaldehyde initial condensate was added to
pH 5 using 2N sulfuric acid while stirring at 200 rpm.
．． Adjusted to 0. Next, the temperature of this liquid was raised to 70° C. over 30 minutes, and the mixture was further stirred for 30 minutes. Add 6.7g of 40% aqueous solution of urea to this and adjust the pH to 3.5 with 2N sulfuric acid.
Stirring was continued at 70° C. for an additional 40 minutes. After cooling this liquid to 25°C, the pH was adjusted to 6.5 using a 2N aqueous sodium hydroxide solution to prepare a photosensitive microcapsule dispersion (CB-1) in which the capsule walls were made of melamine formaldehyde resin. .

Photosensitive microcapsule dispersion (CG-1
) Preparation Add 36 g of water to 4 g of a 15% aqueous solution of polymer (2P-1).
The pH of the mixed solution was adjusted to 5.0 with 2N sulfuric acid. 60 g of a 10% aqueous solution of polymer (2P-2) was added to this liquid and mixed at 60°C for 30 minutes. The above photosensitive composition (PG-1) was added to this mixed solution, stirred at 60°C for 20 minutes at 5000 rpm using a 40φ dissolver, and
An emulsion in the form of a /O/W emulsion was obtained.

Two of the above emulsions were prepared, and 1250 g of distilled water was added to 250 g of the mixture and stirred with a stirrer for 15 minutes. After that, the emulsion was allowed to settle for 1 hour, and then 1400 g of the upper layer was removed. 50 g of a 6% aqueous solution of polymer (2P-2) was added to the residue to redisperse the emulsion. Next, in the same manner as in the preparation of (CB-1), a melamine/formaldehyde initial condensate was added and encapsulated to obtain a photosensitive microcapsule dispersion (
CG-1) was prepared.

Photosensitive microcapsule dispersion (CR-1
) Preparation Add 36 g of water to 4 g of a 15% aqueous solution of polymer (2P-1).
The pH of the mixed solution was adjusted to 5.0 with 2N sulfuric acid. 60 g of a 10% aqueous solution of polymer (2P-2) was added to this liquid and mixed at 60°C for 30 minutes. The above photosensitive composition (PB-1) was added to this mixed solution, stirred at 50°C for 20 minutes at 4000 rpm using a 40φ dissolver, and
An emulsion in the form of a /O/W emulsion was obtained.

Two of the above emulsions were prepared, and 750 g of distilled water was added to 250 g of the mixture and stirred for 15 minutes using a stirrer. After that, the emulsion was allowed to settle for 1 hour, and then 900 g of the upper layer was removed. 50 g of a 6% aqueous solution of polymer (2P-2) was added to the residue to redisperse the emulsion. Next, in the same manner as in the preparation of (CB-1), a melamine/formaldehyde initial condensate was added and encapsulated to obtain a photosensitive microcapsule dispersion (CR
-1) was prepared.

Preparation of photosensitive material 201 16.7 g of photosensitive microcapsules (CB-1) (CG
-1) After mixing 16.7 g of surfactant (WW-1) and 16.7 g of (CR-1), 0.5 g of surfactant (WW-1) and 16.7 g of surfactant (CR-1) were mixed.
1.3 g of 10% aqueous solution of WW-2), PVA KL3
25 g of a 10% aqueous solution of No. 18 (manufactured by Kuraray, carboxy-modified PVA) was added and mixed at 40°C.

[0162] This coating solution was applied to the aluminum-deposited surface of a support made of a polyethylene terephthalate film with a thickness of 12 μm to a coating amount of 120 cc/m2 by an extrusion method, and after drying at 60°C, The film was wound up at 65% Celsius so that the coated surface was on the inside. This photosensitive material was sealed in a moisture-proof bag laminated with aluminum under conditions of 25° C. and 55%.

Image Formation An image was formed in the same manner as in Example 1 using photosensitive material 201 and image receiving material (RS-1). In this image, visible graininess was observed in the green and red areas.

Claims (3)

[Claims] Claim 1: Emulsifying and dispersing an oily liquid containing at least a color image-forming substance and a polymerizable compound and having a density of more than 1.0 in an aqueous medium, and then sedimenting the generated oil droplets to obtain a supernatant liquid. In a method of manufacturing photosensitive microcapsules, the oil droplets are redispersed in an aqueous medium after removal of some or all of the oil droplets, and then a capsule wall made of amino aldehyde resin is formed around the oil droplets. A method for producing photosensitive microcapsules, which comprises sedimenting oil droplets of two or more different substances in a mixed state. 2. The method for producing photosensitive microcapsules according to claim 1, wherein the oily liquid contains silver halide and a reducing agent. 3. A photosensitive material comprising a support and a photosensitive layer containing at least the photosensitive microcapsules produced by the method according to claim 1 and a binder.