JPH0534908A - Production of microcapsule and photosensitive material - Google Patents

Abstract

PURPOSE:To produce a photosensitive microcapsule with the encapsulated material having a uniform composition and narrow grain diameter distribution. CONSTITUTION:An aq. soln. 3 contg. a halogen halide and an oily soln. 1 contg. a reducing agent, polymerizable compd. and color picture forming substance are continuously passed through a gap between the impeller 5 and stator relatively rotated and emulsified to form an water-in-oil emulsion (W/O). The W/O emulsion is emulsified in an aq. soln. 7 contg. a water-soluble polymer to form an oil-in-water emulsion (W/O/W). A microcapsule wall is then formed on the emulsion droplet to produce a photosensitive microcapsule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing photosensitive microcapsules and a photosensitive material using the same.

[0002]

2. Description of the Related Art A light-sensitive material comprising a silver halide, a reducing agent, a polymerizable compound and a color image-forming substance contained in microcapsules (photosensitive microcapsules) is disclosed in JP-A-61-161.
No. 275742. As a method for producing these microcapsules, an aqueous liquid such as a silver halide emulsion is used, and when a substance contained therein is contained in a capsule, the above aqueous liquid is added to an oily liquid containing a polymerizable compound. After emulsifying and dispersing to obtain a water-in-oil (W / O) emulsion, and then emulsifying and dispersing in another aqueous liquid to form an oil-in-water (W / O) emulsion containing the aqueous liquid,
A method of forming microcapsule walls around oil drops has been used.

These W / O emulsions and W / O /
As an emulsification process for forming a W emulsion, conventionally, the total amount of the oily liquid is put in a tank having an emulsifying blade inside, and the total amount of the aqueous liquid is added to the mixture to mix and stir W / O.
An emulsion was formed, and the total amount of the above-mentioned other aqueous liquid was added and further mixed and stirred to form a W / O / W emulsion. This step has been carried out by a batch-type emulsification method in which stirring is performed with a homogenizer, a dissolver or the like. When emulsifying and dispersing with such a device, the shearing force required for emulsification is limited to the very vicinity of the emulsifying blade, so the shearing force becomes non-uniform in the perspective of the emulsifying blade, and the silver halide emulsion is In the formation of a W / O emulsion in which an aqueous liquid containing the same is emulsified and dispersed in an oily liquid containing a polymerizable compound, the dispersion is likely to be inhomogeneous, and as a result, the composition of the inclusions of the photosensitive microcapsules is also inhomogeneous. I will end up. On the other hand, in the formation of the W / O / W emulsion by the batch type emulsification method, the particle size distribution of the dispersed droplets is widened, and as a result, the particle size distribution of the photosensitive microcapsules is also widened.

These photosensitive microcapsules require that the composition of the contents of the individual capsules be uniform between the capsules. When the composition of the encapsulated material is different among the capsules, the heat development rate tends to vary, resulting in uneven image density and stains. On the other hand, in these photosensitive microcapsules, the particle size is an important factor in determining the quality of the capsule, and therefore, as described in JP-A-63-5334, the particle size during the production of microcapsules is Is desired to be obtained uniformly and stably. That is, by making the particle diameter uniform, it is possible to improve the image density and reduce unevenness and stains. Further, when the photosensitive microcapsules are manufactured by the conventional batch type emulsifying machine, a large emulsification facility having a large-capacity emulsification tank is required and a large installation space is required.

[0005]

In the production of photosensitive microcapsules containing at least silver halide, a reducing agent, a polymerizable compound, and a color image-forming substance, the composition of the inclusions is uniform and the particle size is uniform. To provide a new emulsification method with excellent manufacturing suitability for obtaining a stable capsule.

[0006]

SUMMARY OF THE INVENTION The above problems include at least a silver halide in a method for producing a photosensitive microcapsule containing at least a silver halide, a reducing agent, a polymerizable compound, and a color image forming substance. A first emulsification step of emulsifying and dispersing an aqueous liquid in an oily liquid containing at least a polymerizable compound and a color image-forming substance to form a water-in-oil (W / O) emulsion, and the water-in-oil type emulsion. Secondly emulsified and dispersed in an aqueous liquid containing a water-soluble polymer to form an oil-in-water (W / O / W) emulsion containing the aqueous liquid.
And a wall forming step of forming microcapsule walls around the W / O / W emulsion droplets.
The first emulsification step is achieved by the step of emulsifying the aqueous liquid and the oily liquid by continuously passing them through the gap between the rotating blade and the stator that rotate relatively. Further, the second emulsification step is constituted by a step of emulsifying the water-in-oil emulsion and the aqueous liquid containing the water-soluble polymer by continuously passing them through the gap between the rotating blade and the stator that relatively rotate. Is more preferable, and further, in the first emulsification step and / or the second emulsification step, it is more preferable that the rotating blades that rotate relatively are formed of a cylinder and the stator is formed of an outer cylinder. On the other hand, in terms of manufacturing suitability, it is preferable that the second emulsification step is continuously performed in conjunction with the first emulsification step.

The point of the emulsification method of the present invention is to provide a uniform shearing force to the emulsion that continuously passes, as compared with the conventional batch type emulsification method in which an uneven shearing force acts on the emulsion (W / O emulsion). The point is to form a W / O emulsion upon application, whereby microcapsules having a uniform composition of the inclusions can be obtained. Furthermore, it is a point to form a W / O / W emulsion by giving a uniform shearing force to the W / O / W emulsion emulsion that continuously passes, whereby a desired particle size and a narrow particle size distribution are obtained. Further, photosensitive microcapsules having a uniform composition of the inclusions can be produced in a large amount with a relatively small emulsification facility. The outline of the method for producing microcapsules according to the present invention will be described below in the case where the second emulsification step is continuously performed in conjunction with the first emulsification step according to the configuration example shown in FIG. 1. In FIG. 1, an oily liquid containing a polymerizable compound and a color image forming substance, and an aqueous liquid containing silver halide are prepared in dissolution tanks 1 and 3 at appropriate ratios, and these liquids are mixed in a predetermined amount. The pumps 2a and 2b whose flow rates are adjusted to have a ratio are fed into the stator 4 through the first emulsifier inlet 11a. The stator 4 is provided with a rotary blade 5 which is rotated by a motor 6a, and the liquid fed into the stator 4 receives a uniform shearing force in a gap between the stator 4 and the rotary blade 5 to form a W / O emulsion. It is formed and sent to the second emulsifier inlet 12a through the outlet. On the other hand, the aqueous liquid containing the water-soluble polymer is prepared in the dissolution tank 7 and sent to the second emulsifier inlet 12a by the pump 2c whose flow rate is adjusted so that the mixing ratio with the W / O emulsion becomes a predetermined ratio. . This aqueous liquid is mixed with the W / O emulsion at the emulsifier inlet 12a and sent into the stator (outer cylinder) 8. A rotor (cylindrical) 9 that is rotated by a motor 6b is provided inside the stator (outer cylinder) 8, and the liquid sent into the stator (outer cylinder) 8 has the stator (outer cylinder) 8 and the rotor vane ( The W / O / W emulsion is formed while receiving a uniform shearing force in the gap of the inner cylinder 9 and the discharge port 12
It is sent to the encapsulation tank 10 through b and undergoes a wall forming treatment to obtain microcapsules.

The step of forming the W / O / W emulsion in the present invention is realized by using the first continuous emulsification equipment and the second emulsification equipment which are composed of a rotating blade and a stator which rotate relative to each other. In the above first emulsification equipment,
It is important to receive a relatively uniform shearing force when the liquid passes through the gap between the rotary blade 5 and the stator 4, and the structure thereof is not particularly specified. It may be a one-pass type, or may be a type that passes a plurality of times while circulating. The gap between the rotary blade and the stator is not particularly limited, but is preferably 0.03 to 5 mm, more preferably 0.1 to 2 mm. If the gap is narrower than this, galling is likely to occur between the rotor blade and the stator, causing a failure. On the other hand, when the gap is wide, in order to reduce the shearing force and obtain the target dispersibility and homogeneity, the rotation of the inner cylinder must be significantly increased, and a large capacity motor is required. Next, the time for the liquid to pass through the gap varies depending on the size of the gap, but is preferably 0.01 seconds to 10 minutes. If the time is shorter than this, a short pass phenomenon occurs, and the W / O emulsion particles not only become large, but also become inhomogeneous. On the other hand, when the time is longer than this, heat generation due to shearing energy is remarkable and causes polymerization of the polymerizable compound. Furthermore, the amount of processing per unit time decreases, and the productivity decreases.

In the second emulsification equipment, the rotary blade 9 is also used.
The gap between the stator 8 and the stator 8 is relatively narrow, and it is important that a relatively uniform shearing force is applied when the liquid passes through this gap, and the structure thereof is not particularly specified. It may be a one-pass type, or may be a type of passing a plurality of times while circulating. The point of the emulsifier of the third aspect is that, as described in Japanese Patent Application No. 3-50118, a cylinder is used as a rotary blade and an outer cylinder is used as a stator. The gap between the rotary blade and the stator is not particularly limited, but is preferably 0.05 to 5 mm, more preferably 0.1 to 2 mm. If the gap is narrower than this, the influence of the surface finish of the rotor and the stator on the gap and the influence of the runout of the rotor become large, the gap distribution becomes non-uniform, and the particle size distribution becomes wide. Moreover, the rotor and the stator may come into contact with each other, which may cause a failure when used for a long time. On the other hand, when the gap is wide, in order to apply the shearing force for obtaining the target particle size, the rotation speed of the rotary blade must be increased, but at this time, fine particles are generated in the vicinity of the rotary blade and the particle size distribution becomes wide. Next, the time for the liquid to pass through the gap is 0.02 seconds or longer, preferably 0.2 seconds or longer. If the time is shorter than this, a short-pass phenomenon occurs, coarse particles remain, and the distribution becomes wider.

The constitution of the emulsification equipment of the present invention is not limited to that shown in FIG. The main point of the emulsification and dispersion method of the present invention is that the first emulsification step continuously feeds the liquid to the gap between the relatively rotating rotor blade and the stator for emulsification, and further the second emulsification step. The emulsification step is also a point where the liquid is continuously fed to emulsify. Further, this is because the first emulsification method and the second emulsification method can remarkably reduce the equipment size as compared with the batch emulsification method. As described above, according to the emulsification method of the present invention, a uniform shearing force is applied to the emulsion that passes continuously to form a W / O emulsion,
A homogeneous W / O emulsion is obtained. Furthermore, the emulsion having a target particle size and a uniform particle size distribution is obtained by giving a uniform shearing history to the emulsion that continuously passes through the W / O emulsion and the aqueous liquid to form the W / O / W emulsion. Is formed, and then a wall film formation treatment is performed to produce a large amount of photosensitive microcapsules with a desired particle size, a narrow particle size distribution, and a uniform composition of the inclusions, using a relatively small emulsification facility. We can provide the possible equipment.

The silver halide, reducing agent, polymerizable compound, color image-forming substance, microcapsule, and support used in the light-sensitive material of the present invention will be described in detail below.

In the light-sensitive material of the present invention, any one of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide can be used as silver halide. Particles can also be used. The silver halide grains in the photographic emulsion are cubic,
Those having regular crystals such as octahedron, dodecahedron and tetradecahedron, those having an irregular crystal system such as spheres and plates, those having crystal defects such as twin planes, or A composite form of them may be used.

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

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
Engineering), Vol. 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent No. 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, the halogen composition,
Two or more kinds of silver halide grains having different crystal habits, grain sizes and the like can be used in combination.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and types"
, And ibid. 18716 (November 1979), 6
It can be prepared using the method described on page 48 and the like.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643 and No. 18716, and the corresponding portions 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 portions are shown in the following table.

[0018]         Additive type RD17643 RD18716         Chemical sensitizer page 23 page 648 right column         Sensitivity enhancer Same as above         Spectral sensitizer page 23-24 page 648 right column-         Supersensitizer, page 649, right column         Antifoggant page 24 to 25 page 649 right column ~         And stabilizers

Details of the above-mentioned silver halide emulsion and photographic additives are described in "Public Technology No. 5" (Aztec Co., Ltd., issued March 22, 1991), pages 2 to 17. The amount of silver halide used is 1
0.001 to 10 g, preferably 0.0 per m ^{2 in} terms of silver
It is 5 to 2 g. Further, in the present invention, an organic silver salt can be used together with silver halide. The organic silver salt is described on pages 17 to 18 of "Public Technology No. 5" mentioned above.

The reducing agent which can be used in the light-sensitive material of the present invention has a function of reducing silver halide and / or a function of accelerating (or suppressing) the polymerization of the polymerizable compound. Examples of the reducing agent having the above function include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones and 5-amino. Uracils, 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-sulfonamido-5
-Pyrazolones, 3-sulfonamidoindoles, sulfonamidepyrazolobenzimidazoles, sulfonamidepyrazolotriazoles, α-sulfonamidoketones, hydrazines and the like. The various reducing agents described above are described in detail on pages 18 to 35 of the above-mentioned known technology No. 5. The addition amount of the reducing agent can be widely varied, but it is generally 0.1 to 1500 mol%, preferably 10 to 300 mol% with respect to the silver salt.

The polymerizable compound used for the light-sensitive material is generally a compound having addition polymerization property or ring-opening polymerization property. The compound having an addition-polymerizable group includes a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable group includes a compound having an epoxy group. A compound having an ethylenically unsaturated group is particularly preferable. Details of the compound having an ethylenically unsaturated group which can be used in the light-sensitive material are described in "Known Technology No. 5", pages 51 to 55 and Japanese Patent Application No. 3-116667. The polymerizable compounds may be used alone or in combination of two or more. Regarding the photosensitive material in which two or more polymerizable compounds are used in combination,
It is described in JP-A-62-210445. In addition,
A substance obtained by introducing a polymerizable functional group such as a vinyl group or a vinylidene group into the chemical structure of the reducing agent described above can also be used as the polymerizable compound. The color image-forming substance that can be used in the light-sensitive material of the present invention is not particularly limited, and various types can be used. That is, the substance itself is colored (dye or pigment), or the substance itself is colorless or light-colored but external energy (heating, pressure, light irradiation, etc.) or another component (developing agent) A substance (color former) that develops a color upon contact with is also included in the color image forming substance. As the color image-forming substance of the present invention, as described in JP-A-62-187346, dyes and pigments which are excellent in image stability and colored themselves are preferable.

The dyes and pigments used in the present invention include
In addition to commercially available products, known products described in various documents can be used. Regarding literature, Color Index (CI) handbook, "Latest Pigment Handbook" edited by Japan Pigment Technology Association (1977), "Latest Pigment Application Technology" CMC Publishing (1986), "Printing Ink Technology" (CMC Publishing) ,
1984) etc. Details of the color image-forming substance that can be used in the present invention and the technique for using the same are described in the above-mentioned "Known Technique No. 5", pp. 35-50. In particular, the pigment is preferable because it has excellent light fastness and causes less blurring of an image during transfer. The pigment is preferably used in a proportion of 5 to 60 parts by weight with respect to 100 parts by weight of the polymerizable compound.

Various known techniques can be applied to the microcapsules that can be used in the present invention without any particular limitation, and they are described in detail in the above-mentioned "Known Technique No. 5", pp. 88-98. In the present invention, it is particularly preferable to use a melamine-formaldehyde resin, since a highly dense capsule can be obtained. Also, Japanese Patent Application No. 1-3
In order to obtain capsules having particularly excellent wall compactness, the specification of 7782 discloses that melamine is formed around a film composed of a reaction product of a water-soluble polymer having a sulfinic acid group and a polymerizable compound having an ethylenically unsaturated group. A microcapsule provided with a polymer wall of a high molecular compound such as formaldehyde resin is disclosed, which is preferable for the present invention.

When aminoaldehyde-based microcapsules are used, it is preferable that the amount of residual aldehyde is not more than a certain value, as in the light-sensitive material described in JP-A-63-32535. The method is disclosed in JP-A-63-14.
No. 2343, etc. The average particle size of the microcapsules is 1 to 50 μm, preferably 3 to 20 μm. The particle size distribution of the microcapsules is described in JP-A-63
As in the light-sensitive material described in JP-A-5334, it is preferable that the light-sensitive material is uniformly distributed over a certain value. The film thickness of the microcapsules is preferably within a certain range with respect to the particle diameter, as in the light-sensitive material described in JP-A-63-81336.

When the silver halide is contained in the microcapsules, the average grain size of the silver halide grains described above is preferably one fifth or less of the average size of the microcapsules, and preferably one tenth or less. More preferably, By setting the average grain size of the silver halide grains to be one fifth or less of the average size of the microcapsules, a uniform and smooth image can be obtained.
When the silver halide is contained in the microcapsules, it is preferable that the silver halide be present in the wall material that constitutes the outer shell of the microcapsules. Regarding a light-sensitive material containing silver halide in the wall material of the microcapsule, JP-A-62-62
No. 169147.

In the production of the photosensitive microcapsules of the present invention, when an oily liquid composed of a polymerizable compound containing a silver halide, a reducing agent and a color image-forming substance is dispersed in an aqueous medium to form capsule shells. , In an aqueous medium,
It is preferable to include a nonionic water-soluble polymer and an anionic water-soluble polymer. In this case, the oily liquid containing the polymerizable compound is mixed with the aqueous medium in an amount of 10
Is preferably 120 to 120% by weight, more preferably 20 to 90% by weight.

Examples of nonionic water-soluble polymers are polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-co-acrylamide, hydroxyethyl cellulose, hydroxy. Examples thereof include propyl cellulose and methyl cellulose. Examples of the anionic water-soluble polymer include polystyrene sulfinic acid, copolymer of styrene sulfinate, polystyrene sulfonate, copolymer of styrene sulfonate, polyvinyl sulfate ester salt, polyvinyl sulfonate, maleic anhydride. -Styrene copolymers, maleic anhydride / inbutylene copolymers and the like can be mentioned.

In this case, the concentration of the anionic water-soluble polymer in the aqueous medium is preferably 0.01 to 5% by weight, more preferably 0.1 to 2% by weight. In the above case, it is particularly preferable to use the nonionic water-soluble polymer in combination with the water-soluble polymer having a small amount of sulfinic acid groups.

Materials usable for the support include glass, paper, woodfree paper, baryta paper, coated paper, cast coated paper, synthetic paper, metal and its analogs, polyester, polyethylene, polypropylene, acetyl cellulose, cellulose. Ester, polyvinyl acetal,
Examples thereof include films such as polystyrene, polycarbonate, polyethylene terephthalate, and polyimide, and paper laminated with a resin material or a polymer such as polyethylene. For details, refer to “Public Technology No. 5” above.
No. "pp. 144-149. Among them, the preferred support of the present invention is a polymer film, and it is particularly preferred that it is a polymer film of 50 μm or less in view of the above-mentioned thermal conductivity.

Further, in order to coat the support with a photosensitive layer,
It is preferable to provide the undercoat layer described in JP-A-61-113058 on the polymer film, or to provide a metal vapor deposition film of aluminum or the like on the polymer film.
Therefore, as the support of the light-sensitive material of the present invention, 50 μm
A polymer film having a thickness of m or less and having an aluminum vapor deposition film is particularly preferable.

Other components that can be used in the light-sensitive material of the present invention will be described below. Details of these components are described in the above-mentioned "Known Technology No. 5", pp. 98-144 and 86-.
It is described on page 88.

The light-sensitive material of the present invention may further contain a base or a base precursor, a thermal solvent, an antioxidant having a function of removing oxygen, etc. as an image forming accelerator. As bases and base precursors that can be used in the light-sensitive material of the present invention, inorganic bases and organic bases, or base precursors thereof (decarboxylation type, thermal decomposition type, reaction type, complex salt forming type, etc.) can be used. 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 are polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-co-acrylamide, hydroxyethyl cellulose, hydroxy. Examples thereof include propyl cellulose and methyl cellulose. Further, as the amphoteric water-soluble polymer,
Mention may be made of gelatin.

The above water-soluble polymer is preferably contained in the base precursor in a proportion of 0.1 to 100% by weight, more preferably 1 to 50% by weight. The base precursor is preferably contained in the dispersion in an amount of 5 to 60% by weight, more preferably 10 to 50% by weight. Further, the base precursor is preferably contained in a proportion of 2 to 50% by weight with respect to the polymerizable compound,
It is more preferable that the content is 5 to 30% by weight. Details of these base precursors and the techniques for using them are described in "Public Technology No. 5," pages 55-86.

Preferred base precursors are JP-A 59-180549, 59-180537, 59-195237, 61-32844 and 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-
53638, 61-53639, 61-536.
40, 61-55644, 61-55645.
No. 61, No. 61-55646, No. 61-84640, No. 61-107240, No. 61-2119950, No. 6
1-251840, 61-252544, 61
-313431, 63-316740, 64-
No. 68746 and Japanese Patent Application No. 1-54452, salts of organic acids and bases that are decarboxylated by heating.
Further, JP-A-59-157637 and JP-A-59-1669.
The compounds described in JP-A-43-63 and JP-A-63-96159, which eliminate a base by heating, are mentioned.

The base precursor of the present invention is 50
It is preferable to release the base at ℃ to 200 ℃, 80
More preferably, the release is carried out at a temperature of 180 to 180 ° C. The base precursor used in the light-sensitive material of the present invention is housed in microcapsules.
As described in No. 59, a base precursor composed of a salt of a carboxylic acid and an organic base as described below, which has a solubility of 1% or less in water and a polymerizable compound at 25 ° C., is particularly preferable.

In the present invention, when the base precursor is contained in the microcapsules, a photosensitive composition in which the base precursor is directly solid-dispersed in a polymerizable compound may be used (Japanese Patent Application Laid-Open No. 64-32521). Kaihei 1-2
It is particularly preferable to use a photosensitive composition in which a base precursor is dispersed in water and emulsified in a polymerizable compound. (JP-A-63-21
No. 8964, Japanese Patent Application No. 1-182245, Japanese Patent Application No. 1-1
In addition, in order to reduce the solubility of the base precursor in the polymerizable compound, in the polymerizable compound, polyethylene glycol, polypropylene glycol, benzoic acid amide, cyclohexylurea, octyl alcohol, dodecyl alcohol,
-OH, such as stearyl alcohol and stearamide,
SO ₂ NH _2, -CONH _2, it is also possible to add a compound having a hydrophilic group such as -NHCONH _2.

In the present invention, in addition to the reducing agent, known antioxidants for preventing oxidative deterioration of the polymerizable compound and for preventing oxygen oxidation during heat development can be used together with the polymerizable compound. As such an antioxidant, 2,2 '
-Methylene-bis- (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, 2,
2'-butylidene-bis- (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4
-Methylphenyl acrylate, 4,4'-thio-bis- (3-methyl-6-t-butylphenol) and other phenolic antioxidants; diphenyldecyl phosphite,
Triphenyl phosphite, tris- (2,4-di-t
-Butylphenyl) phosphite, tris- (2-ethylhexyl) phosphite and other phosphite antioxidants; dilauryl-3,3'-thio-dipropionic acid ester, pentaerythritol-tetrakis- (β-lauryl-thio -Propionate), thio-dipropionic acid and other sulfur-based antioxidants; phenyl-1-naphthylamine, 6-ethoxy-2,2,4-trimethyl-
Examples include amine antioxidants such as 1,2-dihydroquinoline and dioctyliminodibenzyl.

The thermal solvent that can be used in the light-sensitive material will be described in the image forming accelerator described later. The binder that can be used in the light-sensitive material can be contained in the light-sensitive layer alone or in combination. It is preferable to mainly use a hydrophilic binder.
As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical. For example, natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, gum arabic, etc., and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, etc. Synthetic polymers such as water-soluble polyvinyl compounds. Other synthetic polymeric materials include dispersed polyvinyl compounds in the form of latices, which in particular increase the dimensional stability of photographic materials. In addition,
Regarding a light-sensitive material using a binder, Japanese Patent Laid-Open No. 61-
It is described in Japanese Patent No. 69062. A light-sensitive material using a binder together with microcapsules is described in JP-A-62-209525.

As the anti-smudge agent used in the light-sensitive material, a particulate material which is solid at room temperature is preferable. Specific examples thereof include starch particles described in British Patent No. 1232347, polymer fine powder described in U.S. Pat. No. 3,625,736, and microcapsule particles containing no color former described in British Patent No. 12359991. US Patent No. 2
Examples include cellulose fine powder described in No. 711375, talc, kaolin, bentonite, wax, inorganic particles such as zinc oxide, titanium oxide and alumina. The average particle size of the particles is preferably in the range of 3 to 50 μm in volume average diameter, and more preferably in the range of 5 to 40 μm. As described above, when the oil droplets of the polymerizable compound are in the microcapsule state, it is more effective that the particles are larger than the microcapsules. Various image formation accelerators can be used in the light-sensitive material.

The image forming accelerator has a function of accelerating the transfer of the base or the base precursor, accelerating the reaction of the reducing agent and the silver salt, and accelerating the immobilization of the dye-donor substance by polymerization. Are classified into the above-mentioned bases or base precursors, nucleophilic compounds, oils, thermal solvents, surfactants, compounds that interact with silver or silver salts, compounds having an oxygen scavenging function, and the like. However, these substance groups generally have a composite function and usually have some of the above-mentioned accelerating effects together. Details thereof are described in the specifications and publications of U.S. Pat. No. 4,678,739, columns 38 to 40, JP-A-62-209443 and the like. Further, the high-valent metal compounds described in Japanese Patent Application No. 2-272878 are also effective.

In the system for polymerizing the polymerizable compound in the portion where the latent image of silver halide is not formed,
A heat or photopolymerization initiator can be used for the purpose of initiating polymerization or for polymerizing an unpolymerized polymerizable compound after image transfer. Examples of thermal polymerization initiators include azo compounds, organic peroxides, inorganic peroxides, sulfinic acids and the like. Details thereof are described in pages 6 to 18 of “Addition Polymerization / Ring-Opening Polymerization” (1983, Kyoritsu Shuppan) edited by the Society for Polymer Science, Editorial Committee for Polymer Experiments.

Examples of the photopolymerization initiator include benzophenones, acetophenones, benzoins, thioxanthones and the like. Details thereof are described in "UV Curing System" (1989, Comprehensive Technical Center), pages 63 to 147, and the like. Various surface active agents can be used in the light-sensitive material for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173.
463, 62-183457 and the like.

An antistatic agent may be used in the light-sensitive material for the purpose of antistatic. As an antistatic agent, it is described in Research Disclosure Magazine, November 1978, No. 17643 (page 27). In the photosensitive layer of the photosensitive material,
Dyes or pigments may be added for the purpose of preventing halation or irradiation. A light-sensitive material containing a white pigment added to the light-sensitive layer.
It is described in the official gazette.

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

When a solvent for the polymerizable compound is used in the light-sensitive material, it is preferably used by enclosing it in a microcapsule different from the microcapsule containing the polymerizable compound.
A photosensitive material using an organic solvent miscible with a polymerizable compound encapsulated in microcapsules is disclosed in Japanese Patent Laid-Open No.
It is described in JP-A-2-209524.

Various antifoggants or photographic stabilizers can be used in the present invention. For example,
Azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-168442.
Nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-111636, mercapto compounds and metal salts thereof described in JP-A-59-111636, and acetylene compounds described in JP-A-62-87957 are used. .

Various development stoppers can be used in the light-sensitive material for the purpose of always obtaining a constant image with respect to the processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction of a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. For further details, see JP-A-62-253159, pages (31) to (32), Japanese Patent Application No. 1-724.
No. 79, No. 1-3471, etc. are described.

In addition to the above, examples of optional components that can be contained in the photosensitive layer and the usage thereof are also described in the specification of the above-mentioned series of photosensitive materials and Research Disclosure Vol. 170, 197.
No. 17029 (pages 9 to 15), June 1996. As the layer that can be optionally provided in the photosensitive material,
Examples thereof include an image receiving layer, a heating element layer, an antistatic layer, an anti-curl layer, a peeling layer, a cover sheet or a protective layer, and an antihalation layer (colored layer).

A photosensitive material using a heating element layer is disclosed in JP-A-61-294434, and a photosensitive material provided with a cover sheet or a protective layer is disclosed in JP-A-62-2.
Japanese Patent Application Laid-Open No. 63-101842 discloses a light-sensitive material provided with a coloring layer as an antihalation layer.
Each of these is described in Japanese Patent Publication No. Further, examples of other auxiliary layers and usage modes thereof are also described in the specification of the series of photosensitive materials described above.

In the image forming method using the photosensitive material of the present invention, it is general to use the image receiving material together with the photosensitive material. The image receiving material will be described below. The details are described in "Public Technology No. 5", pages 149 to 178. The image receiving material may be only the support, but it is preferable to provide an image receiving layer on the support. The support of the image receiving material is not particularly limited, but like the support of the light-sensitive material, glass, paper, high-quality paper, baryta paper, coated paper, cast coated paper, synthetic paper, cloth, metal and its analogs. , Polyester, polyethylene, polypropylene, acetyl cellulose, cellulose ester, polyvinyl acetal,
Examples thereof include films such as polystyrene, polycarbonate and polyethylene terephthalate, and paper laminated with a resin material or a polymer such as polyethylene.

When a porous material such as paper is used as a support for the image receiving material, it is disclosed in JP-A-62-20953.
It is preferable that the image-receiving material described in JP-A-No. 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 voids between the particles of the white pigment enhance the receptivity of the polymerizable compound.

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

As the binder used in the image-receiving layer of the present invention, a water-soluble polymer, a polymer latex or a polymer soluble in an organic solvent can be used. As the water-soluble polymer, for example, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose derivatives such as methyl cellulose, gelatin, phthalated gelatin, casein, proteins such as ovalbumin, starches such as dextrin, etherified starch, polyvinyl alcohol,
Polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, synthetic polymers such as polyvinyl imidazole, polyvinyl pyrazole, polystyrene sulfonic acid, etc., locust bean gum, pullulan, gum arabic, alginic acid Examples include soda.

As the polymer latex, for example, a styrene-butadiene copolymer latex, a methyl methacrylate / butadiene copolymer latex, a polymer of acrylic acid ester and / or methacrylic acid ester, or a copolymer latex, ethylene / vinyl acetate copolymer is used. Polymer latex etc. are mentioned. Examples of the polymer soluble in an organic solvent include polyester resin, polyurethane resin, polyvinyl chloride resin, polyacrylonitrile resin and the like.

As for the method of using the above binders, two or more kinds can be used in combination, and the binders can also be used in a ratio such that the two kinds of binders cause phase separation. An example of such usage is described in JP-A-1-154789. The average particle size of the white pigment is 0.1
˜20 μ, preferably 0.1 to 10 μ, and the coating amount is 0.1 g to 60 g, preferably 0.5 g to 30 g.
Is the range. The weight ratio of the white pigment to the binder is preferably 0.01 to 0.4, more preferably 0.03 to 0.3, relative to 1 pigment.

The image-receiving layer may contain various additives as described below, in addition to the binder and the white pigment. For example, when a color-developing system comprising a color-developing agent and a color-developing agent is used, the image-receiving layer may contain the color-developing agent. Typical developers include phenols, organic acids or salts thereof, or esters, but when a leuco dye is used as a color image forming substance, a zinc salt of a salicylic acid derivative is preferable, Above all,
Zinc 3,5-di-α-methylbenzyl salicylate is preferred. The above color developer is preferably contained in the image receiving layer in a coating amount of 0.1 to 50 g / m ² . More preferably, it is in the range of 0.5 to 20 g / m ² .

The image receiving layer may contain a thermoplastic compound. When the image receiving layer contains a thermoplastic compound, it is preferable that the image receiving layer itself is formed as an aggregate of thermoplastic compound fine particles. The image-receiving layer having the above-described structure has an advantage that a transfer image can be easily formed and a glossy image can be obtained by heating after the image formation.
The thermoplastic compound is not particularly limited and can be arbitrarily selected and used from known plastic resins (plastics) and waxes. 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 the image-receiving layer containing the above-mentioned fine particles of a thermoplastic compound, Japanese Patent Application Laid-Open Publication No. 6-58242
2-280071 and 62-280739.

The image-receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator. In image formation using the image receiving material, the color image forming substance is transferred together with the unpolymerized polymerizable compound. Therefore, a photopolymerization initiator or a thermal polymerization initiator can be added to the image-receiving layer for the purpose of curing (fixing) the unpolymerized polymerizable compound. An image receiving material having an image receiving layer containing a photopolymerization initiator is disclosed in JP-A-62-161149, and an image receiving material having an image receiving layer containing a thermal polymerization initiator is disclosed in JP-A-62-161149.
Each of them is described in Japanese Patent Publication No. 210444.

In the following, the step of imagewise exposure in the image forming method of the present invention, the imagewise exposure, or after the imagewise exposure, the photosensitive material is heated from the surface of the support having no photosensitive layer coated thereon. And a series of steps such as a step of superposing the surface of the photosensitive material coated with the photosensitive layer and the image receiving material and pressurizing the same.

As the exposure method in the imagewise exposure step, various exposure means can be used, but in general, a latent image of silver halide is obtained by imagewise exposure of radiation including visible light. The type of light source and the amount of exposure depend on the photosensitive wavelength of silver halide (the wavelength sensitized when dye-sensitized)
Alternatively, it can be selected according to the sensitivity.

Typical light sources include low-energy radiation sources such as natural light, ultraviolet rays, visible light, infrared rays, fluorescent lamps, tungsten lamps, mercury lamps, halogen lamps, xenon flash lamps, laser light sources (gas laser, solid laser, Chemical lasers, semiconductor lasers, etc.), light emitting diodes, plasma arc tubes, FOTs and the like. In special cases, it is possible to use X-rays, γ-rays, electron beams, etc., which are high energy ray sources.

The light-sensitive material of the present invention, particularly in the case of a full-color light-sensitive material, is composed of microcapsules having photosensitivity in a plurality of spectral regions, and therefore it is necessary to perform image exposure with a plurality of corresponding spectral lines. Is. Therefore, the above light sources may be used alone or in combination of two or more. When selecting the light source,
It goes without saying that a light source suitable for the photosensitive wavelength of the photosensitive material is selected, but it can be selected in consideration of whether image information passes through an electric signal, the processing speed of the entire system, compactness, power consumption, and the like.

When the image information does not pass through an electric signal, for example, direct photography of landscapes and people, direct copying of original images,
In the case of exposing through a positive such as a reversal film, an exposure device for printing such as a camera, a printer or an enlarger, an exposure device for a copying machine or the like can be used. In this case, a two-dimensional image can be simultaneously exposed by so-called one shot, or scanning exposure can be performed through a slit or the like. You can also stretch or reduce the original image. In this case, the light source is 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 a plurality of monochromatic light sources.

When image information is recorded via an electric signal, as an image exposure device, a light emitting diode and various lasers may be used in combination according to 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 is an image signal obtained from a video camera or an electronic still camera, a television signal represented by Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels with a scanner or the like, or an image signal stored in a recording material such as a magnetic tape or a disk can be used.

When exposing a color image, LEDs, lasers, fluorescent tubes and the like are used in combination according to the color sensitivity of the light-sensitive material. However, the same materials may be used in combination or different kinds may be used in combination. May be. The color sensitivity of the light-sensitive material is R (red), G (green), B (blue) in the photographic field.
Photosensitivity is normal, but in recent years, it is often used in combination with UV, IR, etc., and the range of use of the light source is expanding. For example, the color sensitivity of the photosensitive material is (G, R, IR)
Or (R, IR (short wave), IR (long wave)),
(UV (short wave), UV (medium wave), UV (long wave)), (U
Spectral regions such as V, B, G) are utilized. The light source may also be a combination of different types such as a combination of two LED colors and a laser. The light emitting tube or element may be scanned and exposed by using a single tube or element for each color, or an array tube may be used to increase the exposure speed. Examples of usable arrays include an LED array, a liquid crystal shutter array, and a magneto-optical element shutter array.

The image display device described above is a CRT.
As described above, there are a color display and a monochrome display, but a method of performing exposure several times by combining filters of the monochrome display may be adopted. The existing two-dimensional image display device may be used by making it one-dimensional like FOT, or by dividing one screen into several pieces and using them in combination with scanning.

By the above imagewise exposure step, 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 the photosensitive material at the same time as the imagewise exposure or after the imagewise exposure to thermally develop the photosensitive material. Thermal development is preferably performed by heating from the surface of the support on which the photosensitive layer of the photosensitive material is not coated.

As this heating means, there is disclosed in JP-A-61-29.
As in the light-sensitive material described in Japanese Patent No. 4434, a heating element layer may be provided on the surface of the support on which the light-sensitive layer of the light-sensitive material is not coated to heat it. Further, as described in JP-A-61-147244, a hot plate, an iron, and a heat roller are used, or as described in JP-A-62-144166, a photosensitive material is sandwiched between a heat roller and a belt. You may use the method of heating.

That is, the photosensitive material may be brought into contact with a heating element having a surface area larger than the area of the photosensitive material to heat the entire surface at the same time, or a heating element having a smaller surface area (heating plate,
The entire surface may be heated over time by bringing it into contact with a heat roller, a heat drum, etc. and scanning it.
In addition to the heating method in which the heating element and the photosensitive material are brought into direct contact with each other as described above, electromagnetic waves, infrared rays, hot air or the like can be applied to the photosensitive material to heat it in a non-contact state.

In the image forming method of the present invention, thermal development is carried out by heating the photosensitive material from the surface of the support on which the photosensitive layer is not coated, and at this time, the photosensitive layer is coated. The surface that is marked may be in direct contact with the air,
It may be covered with a heat insulating material or the like in order to keep it warm so as not to release heat. In this case, it is preferable not to apply a strong pressure (10 kg / cm ² or more) to the photosensitive layer so as not to destroy the microcapsules contained in the photosensitive layer.

The thermal development by heating is carried out at the same time as the imagewise exposure or after the imagewise exposure, but it is preferable that the heating is carried out at least 0.1 seconds after the 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 and 20 seconds, preferably between 0.1 and 5 seconds.

The photosensitive material can be subjected to heat development as described above to polymerize the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image of silver halide is not formed. When a polymerization inhibitor is formed in the latent image-formed portion of silver halide by the reaction with a reducing agent, heat or photopolymerization initiation which has been added in advance in the photosensitive layer, preferably in the microcapsules. It is also possible to disperse the agent by heating or irradiating it with light to uniformly generate radicals and polymerize the polymerizable compound in a portion where a latent image of silver halide is not formed. In this case, in addition to the above-mentioned imagewise exposure step and heat development step, if necessary, a whole surface heating or whole surface exposure step is required, and the method is the same as the imagewise exposure step or the heat development step.

In the image forming method of the present invention, the unpolymerized polymerizable compound is transferred to the image receiving material by the step of applying pressure in the state where the photosensitive material having a polymer image and the image receiving material are superposed on the photosensitive layer, A color image can be obtained on the image receiving material. A conventionally known method can be used as the pressurizing method.

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 being conveyed using a pressure roller such as a nip roll. The pressure may be intermittently applied by a dot impact device or the like.
Further, high pressure air can be wiped with an air gun or the like, or can be pressurized with an ultrasonic generator, a piezoelectric element or the like. The pressure required for pressurization is 500 kg / cm ² or more,
It is preferably 800 kg / cm ² or more. However, 300 kg / cm when heating is also used at 40 ° to 120 ° C during pressurization
It may be ² or less.

The light-sensitive material of the present invention has many uses such as color photographing and printing light-sensitive materials, printing light-sensitive materials, computer graphic hard copy light-sensitive materials, and light-sensitive materials for copying machines. It is possible to make compact and inexpensive image forming systems such as copiers, printers, and simple printing machines.

[0077]

【Example】

Example 1 Preparation of silver halide emulsion (EB-1) 24 g of lime-processed inert gelatin was added to distilled water and 4
After dissolution 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.

After adding 10 mg of (AGS-1) to this solution, the solution I and the solution II were kept at 60 ° C. by the control double jet method while keeping pAg = 8.5 at the same time until solution I disappeared for 45 minutes. Added. After the addition is complete, p
H was adjusted to 6.0 with 1N NaOH and (AZ-1) 6.
4 mg and (AZ-2) 4.8 mg were added to 60 at 60 ° C.
Aged. After aging (SB-1), 480 mg was added, and 100 g of an aqueous solution containing 4.1 g of KI was added at an equal flow rate from 20 minutes to 3 minutes after the addition.

To this emulsion, 1.1 g of (CK-1) was added, precipitated, washed with water, desalted, and then added with 6 g of lime-processed gelatin to dissolve, and further a 3.5% aqueous solution of (ATR-3) 1. 5 cc was added to adjust the pH to 6.2. 550 g of a monodisperse silver iodobromide emulsion (EB-1) having an average grain size of 0.24 μm and a coefficient of variation of 20% was prepared.

Liquid I AgNO ₃ 120 g Distilled water 550 cc Liquid II KBr 85 g Distilled water 550 cc

Preparation of silver halide emulsion (EG-1) Same as silver halide emulsion (EG-1) except that
Solution II was added for 15 minutes, and 450 mg of (SG-1) was added instead of (SB-1). 550 g of a monodisperse silver iodobromide emulsion (EG-1) having an average grain size of 0.18 μm and a coefficient of variation of 20% was prepared.

Preparation of Silver Halide Emulsion (ER-1) Same as Silver Halide Emulsion (EB-1) except for Solution I and II.
The addition time of the liquid was set to 15 minutes, and instead of (SB-1), 450 mg of (SR-1) and 100 mg of (SR-2)
Was added. Average particle size 0.18 μm, coefficient of variation 2
550 g of a 2% monodisperse silver iodobromide emulsion (ER-1) was prepared.

[0083]

[Chemical 1]

[0084]

[Chemical 2]

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

Preparation of solid dispersion (KB-1) 5.4 of lime-processed gelatin in a 300 ml dispersion container.
% Aqueous solution 110 g, polyethylene glycol (average molecular weight 2000) 5% aqueous solution 20 g, base precursor (BG-1) 70 g, and glass beads 200 ml having a diameter of 0.5 to 0.75 mm are added, and 300 using a Dynomill.
Disperse at 0 rpm for 30 minutes, adjust to pH 6.5 with 2N sulfuric acid.
Adjusted to 1.0 μm or less and a base precursor (B
A solid dispersion (KB-1) of G-1) was obtained.

[0087]

[Chemical 3]

Preparation of Pigment Dispersion (GY-1) To 255 g of the polymerizable compound (MN-1), 45 g of Chromo Fine Yellow 5900 (trade name, manufactured by Dainichiseika Seiki Co., Ltd.) was mixed, and an Eiger Motor Mill (Eiger) was mixed. -Engineering company make) and it stirred at 5000 rpm for 1 hour, and the dispersion (GY-1) was obtained. Polymerizable compound (MN-
1) Compound described in Synthesis Example 1 of JP-A-64-68339 (manufactured by Nippon Kayaku Co., Ltd.)

Preparation of Pigment Dispersion (GM-1) Rubin F6B was added to 270 g of the polymerizable compound (MN-1).
(Product name, Hoechst) 30 g was mixed and stirred at 5000 rpm for 1 hour using an Eiger motor mill (Eiger Engineering) to obtain a dispersion (GM-
1) was obtained.

Preparation of Pigment Dispersion (GC-1) To 255 g of the polymerizable compound (MN-1), 45 g of copper phthalocyanine (CI Pigment 15) and 500 parts of Solsperse.
0 (manufactured by ICI) 1.13 g, Sols Perth 24000
3.37 g (manufactured by ICI) was mixed and stirred at 5000 rpm for 1 hour using an Eiger motor mill (manufactured by Eiger Engineering) to obtain a dispersion (GC-1).

Photosensitive microcapsule dispersion (CB-1
Preparation of a, CB-1b) Pigment dispersion (GY-1) 450 was added to the dissolution tank 1 shown in FIG.
90 g of (SV-1) 10% (wt%) solution of (1P-4), (RD-1) 23 g, (RD-3) 31 g,
An oily solution was prepared by adding 20 g of (SV-1) 0.5% (wt%) solution of (FF-3) and 5 g of (ST-1) and dissolving them while maintaining the temperature at 60 ° C. To the dissolution tank 2 shown in FIG. 1, 76 g of silver halide emulsion (EB-1) and 240 g of solid dispersion (KB-1) were added and dissolved while keeping the temperature at 40 ° C. to prepare an aqueous liquid. 40 g of a 15% aqueous solution of the polymer (2P-4) and 460 g of water were added to the dissolution tank 3 shown in FIG. 1, and the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid.
500 g of 10% aqueous solution of polymer (2P-2) in this liquid
Was added and mixed at 60 ° C. for 30 minutes to prepare an aqueous polymer solution. Next, the oil liquid and the aqueous liquid are respectively pumped by the pumps 2a and 2b at flow rates of 320 g / min and 163 g / min, respectively.
A W / O emulsion was obtained by passing through a gap between a rotor 5 and a stator 6 rotating at a clearance of 0.5 mm and a rotation speed of 10,000 rpm. At this time, in order to evaluate the uniformity of the composition, a small amount was sampled every 10 seconds. Further, this W / O emulsion is mixed with a polymer aqueous solution sent by a pump 2c at a flow rate of 517 g / min, and passed through a gap between an inner cylinder 9 and an outer cylinder 8 rotating at a clearance of 0.5 mm and a rotation speed of 5000 rpm to obtain W. A / O / W emulsion was obtained. Separately, 315 g of melamine and 37% formaldehyde
522 g of an aqueous solution and 1703 g of water were added, and the mixture was heated to 60 ° C. and stirred for 30 minutes to obtain a transparent aqueous solution of melamine-formaldehyde initial condensation product.

250 g of this initial condensate was added to the emulsion in the W / O / W emulsion state cooled to 40 ° C., and the pH was adjusted to 5.0 with 2N sulfuric acid while stirring at 1200 rpm with a propeller blade. Then add this solution to 3
The temperature was raised to 70 ° C. in 0 minutes, and the mixture was further stirred for 30 minutes. To this was added 103 g of a 40% aqueous solution of urea, the pH was adjusted to 3.5 with 2N sulfuric acid, and stirring at 70 ° C. was continued for another 40 minutes. This solution was cooled to 40 ° C., 90 g of a 3% aqueous solution of κ-carrageenan was added, and the mixture was stirred for 10 minutes and adjusted to pH 6.5 with a 2N aqueous sodium hydroxide solution to prepare a photosensitive microcapsule dispersion (CB- 1b) was prepared.

Separately, 100 g of the aqueous polymer solution prepared by the above method was added to 93.5 g of the W / O emulsion formed by the above method, and the mixture was mixed with a 40φ dissolver to give 6
The mixture was stirred at 0 ° C. at 6000 rpm for 20 minutes to obtain an emulsion in the state of W / O / W emulsion. This W / O / W emulsion was cooled to 40 ° C., 25 g of the melamine-formaldehyde initial condensate prepared by the above method was added, and the photosensitive microcapsule dispersion (CB-
1a) was obtained. When the W / O emulsions sampled above were observed under an optical microscope, they all had a uniform composition.

Photosensitive microcapsule dispersion (CG-1
a, CG-1b) 450 g of pigment dispersion (GM-1) and (SV-1) of (1P-4) were added to the dissolution tank 1 shown in FIG.
90 g of 10% (wt%) solution, 23 g of (RD-1),
(RD-3) 31 g, (FF-3) (SV-1) 0.
20 g of a 5% (wt%) solution and 5 g of (ST-1) were added and dissolved while keeping the temperature at 60 ° C. to prepare an oily solution. A silver halide emulsion (EG-
1) 76 g and 240 g of solid dispersion (KB-1) were added,
An aqueous liquid was prepared by dissolving the mixture while keeping it warm at 40 ° C. 40 g of a 15% aqueous solution of the polymer (2P-4) and 460 g of water were added to the dissolution tank 3 shown in FIG. 1, and the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid. Polymer (2P-2) in this liquid
10% aqueous solution (500 g) was added and mixed at 60 ° C. for 30 minutes to prepare an aqueous polymer solution. Next, except that the second emulsifier condition was set to a rotation speed of 5500 rpm, (CB-1
The treatment was carried out under the same conditions as in b) to obtain a W / O / W emulsion. Then, a photosensitive microcapsule dispersion liquid (CG-1b) was obtained in the same manner as in the preparation of (CB-1b).

Separately, 100 g of the polymer aqueous solution prepared by the above method was added to 93.5 g of the W / O emulsion formed by the above method, and the mixture was mixed by using a 40φ dissolver.
The mixture was stirred at 0 ° C. at 6000 rpm for 20 minutes to obtain an emulsion in the state of W / O / W emulsion. This W / O / W emulsion is cooled to 40 ° C., 25 g of the melamine-formaldehyde initial condensate prepared by the above method is added, and the photosensitive microcapsule dispersion (C
G-1a) was obtained. When the sampled W / O emulsions were observed with an optical microscope, they all had a uniform composition.

Photosensitive microcapsule dispersion (CR-1
a, CR-1b) Pigment dispersion (GC-1) 450 was added to the dissolution tank 1 shown in FIG.
90 g of (SV-1) 10% (wt%) solution of (1P-4), (RD-1) 23 g, (RD-3) 31 g,
An oily solution was prepared by adding 20 g of (SV-1) 0.5% (wt%) solution of (FF-3) and 5 g of (ST-1) and dissolving them while maintaining the temperature at 60 ° C. To a dissolution tank 2 shown in FIG. 1, 76 g of silver halide emulsion (ER-1) and 240 g of solid dispersion (KB-1) were added and dissolved while keeping the temperature at 40 ° C. to prepare an aqueous liquid. 40 g of a 15% aqueous solution of the polymer (2P-1) and 460 g of water were added to the dissolution tank 3 shown in FIG. 1, and the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid.
500 g of 10% aqueous solution of polymer (2P-2) in this liquid
Was added and mixed at 60 ° C. for 30 minutes to prepare an aqueous polymer solution. Next, the second emulsifying machine condition is set to the rotation speed of 4600 rp.
A W / O / W emulsion was obtained by treating under the same conditions as (CB-1b) except that m was used. Then
A photosensitive microcapsule dispersion liquid (CR-1b) was obtained in the same manner as in the preparation of (CB-1b).

Separately, 100 g of the above polymer aqueous solution was added to 93.5 g of the W / O emulsion formed by the above method, and a 40φ dissolver was used at 60 ° C. for 6000 minutes per minute.
The mixture was stirred by rotation for 20 minutes to obtain an emulsion in a W / O / W emulsion state. This W / O / W emulsion was cooled to 40 ° C., 25 g of the melamine-formaldehyde initial condensate prepared by the above method was added, and a photosensitive microcapsule dispersion (CR-1a) was obtained according to the above method. When the sampled W / O emulsions were observed with an optical microscope, they all had a uniform composition. The photosensitive microcapsule dispersion CB-1a,
The particle size distributions of CG-1a and CR-1a were measured with a Coulter Counter TA-II type, respectively, to obtain D50
= 12.7, 12.5, 12.1 μm, D90 / D10
= 2.11, 2.05, 2.08, the particle size distribution was highly uniform. Further, the particle size distributions of the photosensitive microcapsule dispersion liquids CB-1a, CG-1a, and CR-1b were measured by Coulter Counter TA-II type, respectively, and D50 = 12.3, 12.6, 11. 9
μm, D90 / D10 = 1.75, 1.79, 1.68
The particle size distribution was very uniform.

[0098]

[Chemical 4]

[0099]

[Chemical 5]

[0100]

[Chemical 6]

Polymer (2P-4) Polyvinylbenzenesulfinic acid potassium-co-acrylamide polymer (2P-2) Polyvinylpyrrolidone K-90

Preparation of Photosensitive Material 101 Photosensitive microcapsules (CB-1a) of the present invention
g, (CG-1a) 15g, (CR-1a) 15g
Were taken out, heated to 40 ° C. without stirring and melted, and then mixed, to prepare a 5% aqueous solution of a surfactant (WW-1).
5 g, 8% 1% aqueous solution of surfactant (WW-2), PV
16 g of 10% aqueous solution of A KL318 (manufactured by Kuraray, carboxy-modified PVA) and 10% aqueous solution of glycerin 9
g was added and mixed by stirring at 40 ° C. for 10 minutes. This solution was filtered with a filter cloth of 44 μ mesh to prepare a coating solution.

This coating solution was applied to the aluminum vapor deposition surface of a support obtained by vapor deposition of aluminum on a polyethylene terephthalate film having a thickness of 25 μm by an extrusion method so that the coating amount was 100 cc / m ² and dried at 60 ° C. The photosensitive material 101 of the present invention was prepared by winding the coated surface inside at 25 ° C. and 65%.

[0104]

[Chemical 7]

Preparation of Photosensitive Material 101b In the preparation of the photosensitive material 101a of the embodiment, instead of the photosensitive microcapsules (CB-1a), (CG-1a) and (CR-1a), (CB-1b), (CB-1b), CG-1
b) and (CR-1b) are used in the same manner,
A photosensitive material 101b was prepared.

Preparation of image receiving material (RS-1) Calcium carbonate (PC700, manufactured by Shiraishi Industry Co., Ltd.) 24
0 g, surfactant (Poise 520, manufactured by Kao Corporation) 5.
After stirring and mixing 6 g and 354.4 ml of water, a disperser (trade name: Ultra Disperser (LK-41
Type), manufactured by Yamato Scientific Co., Ltd.) and dispersed at 8000 rpm for 3 minutes. 52 g of this dispersion and 10% polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.) aqueous solution 4
0g and 1% of surfactant (WW-3)
An aqueous solution (4 ml) and water (22 ml) were added to prepare a coating solution for forming an image receiving layer.

This coating solution was weighed 80 g / m ^{2 on} a paper support (as a fiber length distribution defined by JIS-P-8207, the sum of the weight% of the 24 mesh residue and the weight% of the 42 mesh residue was 30). A paper support having a fiber length distribution such that the fiber length distribution is from 60 to 60% [JP-A 63-18623]
No. 9)]) was uniformly coated on the surface of the plate at 65 g / m ² and dried at 60 ° C. to prepare an image receiving material (RS-1).

[0108]

[Chemical 8]

Image forming photosensitive materials 101a and 101b are continuously changed by using a halogen lamp whose color temperature is adjusted to 3100K.
5000 lux through a wedge with a transmission density of 0, 1
It was exposed under the exposure condition of 2 seconds. Two seconds after the exposure, the opposite side of the coated surface of the photosensitive material was brought into close contact with a drum heated to 150 ° C. and heat-developed for 1.5 seconds. The sheets were superposed and passed through a pressure roller (surface temperature 70 ° C.) having a diameter of 3 cm and a pressure of 250 kg / cm ² at a speed of 2 cm / sec. When the image receiving material was peeled off from the light-sensitive material immediately after passing, a clear positive image was obtained on the image receiving material. When the density of the image obtained by the light-sensitive material 101a was measured by X-Rite310, the maximum density was 1.2.
8 and the minimum concentration was 0.08. Further photosensitive material 101b
When the density of the image was measured in the same manner, the maximum density was 1.3.
It was 0 and the minimum concentration was 0.07. Furthermore, no spot color development was observed in the lowest density portion of any of the images. In addition, D1
0, D50 and D90 are percent particle diameters obtained from the cumulative volume distribution. That is, D10: cumulative 10% particle diameter D50: cumulative 50% particle diameter D90: cumulative 90% particle diameter.

Comparative Example 1 Preparation of Photosensitive Microcapsules (CB-2) 45 g of pigment dispersion (GY-1) was added to (S) of (1P-4).
V-1) 9 g of 10% (wt%) solution, (RD-1)
2.3 g, (RD-3) 3.1 g, (FF-3) (S
V-1) 20 g of 0.5% (wt%) solution and (ST-
1) 0.5 g was added and dissolved while keeping the temperature at 60 ° C. to prepare an oily solution. Silver halide emulsion (E
B-1) 7.6 g and solid dispersion (KB-1) 24 g were added, and the mixture was stirred at 10000 rpm for 5 minutes using a 40φ dissolver while keeping the temperature at 40 ° C. A composition (PB-2) was obtained. This W / O
In order to evaluate the homogeneity of the composition of the emulsion, a small number of samples were sampled at multiple points. Next, 46 g of water was added to 4 g of a 15% aqueous solution of the polymer (2P-4), and the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid. To this solution, 50 g of a 10% aqueous solution of the polymer (2P-2) was added, mixed at 60 ° C. for 30 minutes, and the mixed solution was added to the photosensitive composition (PB-2). Stir for 20 minutes at 6000 rpm and W / O
An emulsion in the form of a / W emulsion was obtained. Using this, the same treatments as those in the example were performed thereafter to prepare a photosensitive microcapsule dispersion liquid (CB-2) for comparison. When each sampled W / O emulsion was observed with an optical microscope, nonuniform composition was observed depending on the sampling location. Furthermore, when the particle size distribution of this capsule was measured with a Coulter Counter TA-II type, D50 =
The particle size distribution was wide with 13.1 μm and D90 / D10 = 2.87.

Preparation of Photosensitive Microcapsules (CG-2) 45 g of pigment dispersion (GM-1) was added with (S) of (1P-4).
V-1) 9 g of 10% (wt%) solution, (RD-1)
2.3 g, (RD-3) 3.1 g, (FF-3) (S
V-1) 20 g of 0.5% (wt%) solution and (ST-
1) 0.5 g was added and dissolved while keeping the temperature at 60 ° C. to prepare an oily solution. Silver halide emulsion (E
G-1) 7.6 g and solid dispersion (KB-1) 24 g were added, and the mixture was stirred at 10000 rpm for 5 minutes using a 40φ dissolver while keeping the temperature at 60 ° C. A composition (PG-2) was obtained. This W / O
In order to evaluate the homogeneity of the composition of the emulsion, a small number of samples were sampled at multiple points. Next, 46 g of water was added to 4 g of a 15% aqueous solution of the polymer (2P-4), and the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid. To this solution, 50 g of a 10% aqueous solution of the polymer (2P-2) was added, mixed at 60 ° C. for 30 minutes, and the mixed solution was added to the photosensitive composition (PG-2). Stir for 20 minutes at 6000 rpm and W / O
An emulsion in the form of a / W emulsion was obtained. Using this, the same treatments as those in the examples were performed to prepare a photosensitive microcapsule dispersion liquid (CG-2) for comparison. When each sampled W / O emulsion was observed with an optical microscope, nonuniform composition was observed depending on the sampling location. Furthermore, when the particle size distribution of this capsule was measured with a Coulter Counter TA-II type, D50 =
The particle size distribution was wide with 12.9 μm and D90 / D10 = 2.94.

Preparation of photosensitive microcapsules (CR-2) 45 g of pigment dispersion (GC-1) was added with (S) of (1P-4).
V-1) 9 g of 10% (wt%) solution, (RD-1)
2.3 g, (RD-3) 3.1 g, (FF-3) (S
V-1) 20 g of 0.5% (wt%) solution and (ST-
1) 0.5 g was added and dissolved while keeping the temperature at 60 ° C. to prepare an oily solution. Silver halide emulsion (E
R-1) 7.6 g and solid dispersion (KB-1) 24 g were added, and the mixture was stirred at 10000 rpm for 5 minutes using a 40φ dissolver while keeping the temperature at 60 ° C. A composition (PR-2) was obtained. This W / O
In order to evaluate the homogeneity of the composition of the emulsion, a small number of samples were sampled at multiple points. Next, 46 g of water was added to 4 g of a 15% aqueous solution of the polymer (2P-4), and the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid. To this solution, 50 g of a 10% aqueous solution of the polymer (2P-2) was added, mixed at 60 ° C. for 30 minutes, and the mixed solution was added to the photosensitive composition (PR-2). Stir for 20 minutes at 6000 rpm and W / O
An emulsion in the form of a / W emulsion was obtained. Using this, the same treatments as those in the example were performed thereafter to prepare a photosensitive microcapsule dispersion liquid (CR-2) for comparison. When each sampled W / O emulsion was observed with an optical microscope, nonuniform composition was observed depending on the sampling location. Furthermore, when the particle size distribution of this capsule was measured with a Coulter Counter TA-II type, D50 =
The particle size distribution was 12.1 μm and D90 / D10 = 2.95, and the particle size distribution was wide.

Preparation of Photosensitive Material 102 Photosensitive Material 1 of Example
In the preparation of 01, photosensitive microcapsules (CB-
Photosensitive material 102 was prepared in the same manner except that (CB-2), (CG-2) and (CR-2) were used instead of 1), (CG-1) and (CR-1). An image was formed using the image forming photosensitive material 102 in the same manner as in the example. The density of this image was 1.12 at the maximum and 0.14 at the minimum. In addition, several spot colors per square millimeter were observed in the lowest density area.

[Brief description of drawings]

FIG. 1 is a schematic view of an apparatus used in the present invention.

[Explanation of symbols]

1 ・ ・ ・ ・ ・ ・ ・ ・ Oil liquid dissolution tank 2a, 2b, 2c ... Pump 3 ... Aqueous liquid dissolution tank 4 ... stator 5: Rotating blade 6a, 6b ... ・ Motor 7 .... Aqueous liquid dissolution tank 8: Stator (outer cylinder) 9: Rotating blade (inner cylinder) 10: Encapsulation tank 11a ... Liquid inlet 11b ... Liquid outlet 12a: Liquid injection port 12b ... Liquid outlet

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 26, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction content]

[0002]

2. Description of the Related Art A light-sensitive material comprising a silver halide, a reducing agent, a polymerizable compound and a color image-forming substance contained in microcapsules (photosensitive microcapsules) is disclosed in JP-A-61-161.
No. 275742. As a method for producing these microcapsules, an aqueous liquid such as a silver halide emulsion is used, and when a substance contained therein is contained in a capsule, the above aqueous liquid is added to an oily liquid containing a polymerizable compound. After emulsifying and dispersing to obtain a water-in-oil (W / O) emulsion, emulsifying and dispersing in another aqueous liquid to form an oil-in-water (W / O / W) emulsion containing the aqueous liquid, A method of forming microcapsule walls around oil drops has been used.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

The step of forming the W / O / W emulsion in the present invention is realized by using the first continuous emulsification equipment and the second emulsification equipment which are composed of a rotating blade and a stator which rotate relative to each other. In the above first emulsification equipment,
It is important to receive a relatively uniform shearing force when the liquid passes through the gap between the rotary blade 5 and the stator 4, and the structure thereof is not particularly specified. It may be a one-pass type, or may be a type that passes a plurality of times while circulating. The gap between the rotary blade and the stator is not particularly specified, but is preferably 0.03 to 5 mm, more preferably 0.1 to 2 mm. If the gap is narrower than this, galling is likely to occur between the rotor blade and the stator, causing a failure. On the other hand, when the gap is wide, the shearing force is reduced, and in order to obtain the target dispersibility and homogeneity,
The rotation of the rotor blade must be increased significantly, and a large capacity motor is required. Next, the time taken for the liquid to pass through the gap varies depending on the size of the gap, but is 0.01 second to 1 second.
0 minute is desirable. If the time is shorter than this, a short pass phenomenon occurs, and the W / O emulsion particles not only become large, but also become inhomogeneous. On the other hand, when the time is longer than this, heat generation due to shearing energy is remarkable and causes polymerization of the polymerizable compound. Furthermore, the amount of processing per unit time decreases, and the productivity decreases.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

The constitution of the emulsification equipment of the present invention is not limited to that shown in FIG. The main point of the emulsification and dispersion method of the present invention is that the first emulsification step continuously feeds the liquid to the gap between the relatively rotating rotor blade and the stator for emulsification, and further the second emulsification step. The emulsification step is also a point where the liquid is continuously fed to emulsify. Further, this is because the first emulsification method and the second emulsification method can remarkably reduce the equipment size as compared with the batch emulsification method. As described above, according to the emulsification method of the present invention, a uniform shearing force is applied to the emulsion that passes continuously to form a W / O emulsion,
A homogeneous W / O emulsion is obtained. Furthermore, an emulsion having a target particle size and a uniform particle size distribution is obtained by applying a uniform shearing force to an emulsion liquid consisting of a W / O emulsion and an aqueous liquid that pass continuously to form a W / O / W emulsion. Is formed, and then a wall film formation treatment is performed to produce a large amount of photosensitive microcapsules with a desired particle size, a narrow particle size distribution, and a uniform composition of the inclusions, using a relatively small emulsification facility. We can provide the possible equipment.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

Various development stoppers can be used in the light-sensitive material for the purpose of always obtaining a constant image with respect to the processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction of a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. For further details, see JP-A-62-253159, pages (31) to (32), JP-A-1.
No. 72479, No. 1-3471, etc.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0081

[Correction method] Change

[Correction content]

Preparation of Silver Halide Emulsion (EG-1) Same as silver halide emulsion (EB-1) except that the addition time of Solution I and Solution II was 15 minutes and instead of (SB-1). 450 mg of (SG-1) was added. 550 g of a monodisperse silver iodobromide emulsion (EG-1) having an average grain size of 0.18 μm and a coefficient of variation of 20% was prepared.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0110

[Correction method] Change

[Correction content]

Comparative Example 1 Preparation of Photosensitive Microcapsules (CB-2) 45 g of pigment dispersion (GY-1) was added to (S) of (1P-4).
V-1) 9 g of 10% (wt%) solution, (RD-1)
2.3 g, (RD-3) 3.1 g, (FF-3) (S
V-1) 2 g of 0.5% (wt%) solution and (ST-
1) 0.5 g was added and dissolved while keeping the temperature at 60 ° C. to prepare an oily solution. Silver halide emulsion (E
B-1) 7.6 g and solid dispersion (KB-1) 24 g were added, and the mixture was stirred at 10000 rpm for 5 minutes using a 40φ dissolver while keeping the temperature at 40 ° C. A composition (PB-2) was obtained. This W / O
In order to evaluate the homogeneity of the composition of the emulsion, a small number of samples were sampled at multiple points. Next, 46 g of water was added to 4 g of a 15% aqueous solution of the polymer (2P-4), and the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid. To this solution, 50 g of a 10% aqueous solution of the polymer (2P-2) was added, mixed at 60 ° C. for 30 minutes, and the mixed solution was added to the photosensitive composition (PB-2). Stir for 20 minutes at 6000 rpm and W / O
An emulsion in the form of a / W emulsion was obtained. Using this, the same treatments as those in the example were performed thereafter to prepare a photosensitive microcapsule dispersion liquid (CB-2) for comparison. When each sampled W / O emulsion was observed with an optical microscope, nonuniform composition was observed depending on the sampling location. Furthermore, when the particle size distribution of this capsule was measured with Coulter Counter TA-II type, D50
= 13.1 μm and D90 / D10 = 2.87, the particle size distribution was wide.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0111

[Correction method] Change

[Correction content]

Preparation of Photosensitive Microcapsules (CG-2) 45 g of pigment dispersion (GM-1) was added with (S) of (1P-4).
V-1) 9 g of 10% (wt%) solution, (RD-1)
2.3 g, (RD-3) 3.1 g, (FF-3) (S
V-1) 2 g of 0.5% (wt%) solution and (ST-
1) 0.5 g was added and dissolved while keeping the temperature at 60 ° C. to prepare an oily solution. Silver halide emulsion (E
G-1) 7.6 g and solid dispersion (KB-1) 24 g were added, and the mixture was stirred at 10000 rpm for 5 minutes using a 40φ dissolver while keeping the temperature at 60 ° C. A composition (PG-2) was obtained. This W / O
In order to evaluate the homogeneity of the composition of the emulsion, a small number of samples were sampled at multiple points. Next, 46 g of water was added to 4 g of a 15% aqueous solution of the polymer (2P-4), and the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid. To this solution, 50 g of a 10% aqueous solution of the polymer (2P-2) was added, mixed at 60 ° C. for 30 minutes, and the mixed solution was added to the photosensitive composition (PG-2). Stir for 20 minutes at 6000 rpm and W / O
An emulsion in the form of a / W emulsion was obtained. Using this, the same treatments as those in the examples were performed to prepare a photosensitive microcapsule dispersion liquid (CG-2) for comparison. When each sampled W / O emulsion was observed with an optical microscope, nonuniform composition was observed depending on the sampling location. Furthermore, when the particle size distribution of this capsule was measured with Coulter Counter TA-II type, D50
= 12.9 μm and D90 / D10 = 2.94, the particle size distribution was wide.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0112

[Correction method] Change

[Correction content]

Preparation of photosensitive microcapsules (CR-2) 45 g of pigment dispersion (GC-1) was added with (S) of (1P-4).
V-1) 9 g of 10% (wt%) solution, (RD-1)
2.3 g, (RD-3) 3.1 g, (FF-3) (S
V-1) 2 g of 0.5% (wt%) solution and (ST-
1) 0.5 g was added and dissolved while keeping the temperature at 60 ° C. to prepare an oily solution. Silver halide emulsion (E
R-1) 7.6 g and solid dispersion (KB-1) 24 g were added, and the mixture was stirred at 10000 rpm for 5 minutes using a 40φ dissolver while keeping the temperature at 60 ° C. A composition (PR-2) was obtained. This W / O
In order to evaluate the homogeneity of the composition of the emulsion, a small number of samples were sampled at multiple points. Next, 46 g of water was added to 4 g of a 15% aqueous solution of the polymer (2P-4), and the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid. To this solution, 50 g of a 10% aqueous solution of the polymer (2P-2) was added, mixed at 60 ° C. for 30 minutes, and the mixed solution was added to the photosensitive composition (PR-2). Stir for 20 minutes at 6000 rpm and W / O
An emulsion in the form of a / W emulsion was obtained. Using this, the same treatments as those in the example were performed thereafter to prepare a photosensitive microcapsule dispersion liquid (CR-2) for comparison. When each sampled W / O emulsion was observed with an optical microscope, nonuniform composition was observed depending on the sampling location. Furthermore, when the particle size distribution of this capsule was measured with Coulter Counter TA-II type, D50
= 12.1 μm and D90 / D10 = 2.95, the particle size distribution was wide.

Claims (5)

[Claims] 1. A method for producing a photosensitive microcapsule containing at least silver halide, a reducing agent, a polymerizable compound, and a color image-forming substance, wherein an aqueous liquid containing at least silver halide is at least polymerizable. It is emulsified and dispersed in an oily liquid containing a compound and a color image-forming substance, and water drops in oil (W /
O) a first emulsification step of forming an emulsion, and the water-in-oil emulsion is emulsified and dispersed in an aqueous liquid containing a water-soluble polymer to form an oil-in-water droplet (W / O / W) containing the aqueous liquid.
A second emulsification step of forming an emulsion, said W / O /
The W emulsification step comprises a wall forming step of forming microcapsule walls around the emulsion droplets, and the first emulsifying step continuously passes an aqueous liquid and an oily liquid through a gap between a rotating blade and a stator that relatively rotate. A process for producing photosensitive microcapsules, which comprises a step of emulsifying and emulsifying. 2. The second emulsification step comprises a step of continuously passing a water-in-oil emulsion and an aqueous liquid containing a water-soluble polymer through a gap between a rotating blade and a stator, which relatively rotate, to emulsify the same. The method for producing photosensitive microcapsules according to claim 1, wherein 3. In the first emulsification step and / or the second emulsification step, the relatively rotating rotor blades are cylindrical,
The method for producing a photosensitive microcapsule according to claim 1 or 2, wherein the stator comprises an outer cylinder. 4. The production of photosensitive microcapsules according to claim 1, wherein the second emulsification step is continuously performed in conjunction with the first emulsification step. Method. 5. A substrate made at least by the method of claim 1 or claim 2 or claim 3 or claim 4 on a support.
A photosensitive material comprising photosensitive microcapsules of one kind or a plurality of kinds coated with a binder.