JPS63274954A - Dye fixing element - Google Patents

Abstract

PURPOSE:To prevent curling and adhesion at the time of preservation by incorporating colloidal silica into at least one back layer which is disposed on the other face of a base provided with a dye fixed layer consisting of a mordant and base, etc., and into which hydrophilic colloid is incorporated. CONSTITUTION:At least one dye fixed layer contg. the mordant and the base and/or base precursor is provided on one face on the base and >=1 layers of the back layers into which the hydrophilic colloid is incorporated are disposed on the rear face thereof. Such colloidal silica-contg. layers are preferably formed as the layers in proximity to the base when the back layer consists of plural layers. The modulus of elasticity of the back layer is increased by incorporating the colloidal silica therein in such a manner. The back layer is then hardly elongatable and the curling thereof hardly arises if the layer thickness thereof is in a 1-20mum range. The adhesion of the front face to the rear face at the time of preservation in superposition on each other is prevented by such incorporation of the colloidal silica coupled with the addition of a matting layer into the back layer. In addition, the generation of uneven images by transfer of the base on the front face to the back layer is prevented.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to dye fixing elements for receiving and fixing mobile dyes formed by thermal development.

Prior art and its problems For information on how to obtain color images by heat development, see
Many methods have been proposed. Regarding the method of forming a color image by combining the oxidized form of a developer with a coupler, see
U.S. Pat. No. 3,531,286 uses a p-phenylene diamine reducing agent and a phenolic or active methylene coupler; U.S. Pat. No. 3,761,270 uses a p-aminophenol reducing agent; Belgian Patent No. 802, 51
No. 9 and Research Disclosure Magazine 1975 9
A sulfonamidophenol reducing agent is proposed on pages 31 and 32 of the same issue, and a combination of a sulfonamidophenol reducing agent and a 4-equivalent coupler is proposed in US Pat. No. 4,021,240.

However, in this method, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, resulting in a problem that the color image becomes cloudy.

To solve this problem, there are methods to remove the silver image by liquid processing or to transfer only the dye to another layer, such as a sheet with an image-receiving layer. It has the disadvantage that it is not easy to transfer.

Furthermore, the above-mentioned methods generally require a relatively long time for development, and the resulting images have the drawbacks of high fog and low image density.

In order to improve these drawbacks, there are methods in which a mobile dye is imagewise released by heating, and this mobile dye is transferred to a dye fixing element with a mordant using a solvent such as water, and a method in which the dye is transferred to a dye fixing element with a mordant using a solvent such as water. How to transfer to a fixed element,
A method has been proposed in which the dye is transferred to a dye-fixing element using a hydrophilic thermal solvent built into the dye-fixing element, and a method in which the mobile dye is heat-diffusible or sublimable and is transferred to a dye-receiving element such as a support. (U.S. Patent Nos. 4,463,079, 4,474,867, 4,478,927,
4,507.380, 4,500,626, 4,483,914; JP 58-14904
No. 6, No. 58-149047, No. 59-152440
No. 59-154445, No. 59-165054, No. 59-180548, No. 59-168439,
No. 59-174832, No. 59-174833, No. 59-174834, No. 59-174835, etc.).

In the above image forming method, receiving a mobile dye,
For fixing, a dye fixing element having at least one dye fixing layer is used.

However, under low humidity conditions, the dye fixing element may curl so that both ends are above the horizontal plane when the dye fixing layer is placed upward due to the shrinkage of the hydrophilic colloid contained in the dye fixing layer, or the dye fixing element may curl to a height above the horizontal plane. Under humidity, due to moisture absorption of the hydrophilic colloid contained in the dye fixing layer,
When the dye fixing layer is stretched and the dye fixing layer is placed downward,
It may be curled so that both ends are above the horizontal plane. Methods for preventing this curl include increasing the thickness of the support and making the material of the support harder. However, such a method has limitations because the thickness and material of the support are determined by the application and other factors.

In addition, as a method for improving curl prevention, a method is generally known in which a hydrophilic colloid layer (back layer) is coated on the back side of the dye fixing layer with an appropriate thickness to balance the curl.

In this case, as a method for preventing curling, there may be mentioned a method of adjusting the thickness of the dye fixing layer or the like provided on the front side of the support so that the thickness of the back layer is balanced with the thickness of the dye fixing layer. Moreover, since the thickness of the dye fixing layer is determined from a performance standpoint, even if the thickness of the back layer is adjusted to be comparable to the thickness of the dye fixing layer, it is still insufficient. Particularly, in the method of transferring the dye to the dye fixing element under heating, as the thickness of the back layer increases, curling toward the back layer becomes larger during heating, resulting in poor conveyance.

The above problem is particularly noticeable in dye fixing elements for OHP (over head projectors) which use transparent plastic films as supports. That is, when the dye-fixing element is placed on OH2 and observed, the upper surface (dye-fixing layer side) is heated and dried by the projection light, and as a result, it curls significantly toward the surface.

In order to promote the movement of the dye, the dye fixing element usually contains salts such as bases, base precursors, or reaction products thereof in the dye fixing layer or its adjacent layer. The shrinkage of the dye fixing layer becomes large. Furthermore, if a polysaccharide such as dextran or pullulan is included in the layer to prevent precipitation of these salts, the shrinkage on the OHP will further increase.

Therefore, improvement in this point is desired.

II. Purpose of the Invention The purpose of the present invention is to improve the physical properties of the film, to prevent curling toward the dye-fixing layer side especially at medium temperature and low humidity, and to prevent adhesion between the front and back surfaces when stored in layers. The object of the present invention is to provide a dye fixing element.

■Disclosure of invention These objects are achieved by the invention described below.

That is, the present invention provides at least one substrate containing a mordant and a base and/or a base precursor on one side on a support.
A dye-fixing element having a dye-fixing layer of layers and a back layer comprising at least one hydrophilic colloid on the opposite side thereof, wherein at least one of the back layers comprises colloidal silica. A dye fixing element characterized by containing.

■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

The dye fixing element of the present invention has at least one dye fixing layer containing at least one mordant and a base and/or base precursor on one side of the support, and on the opposite side. It has a back layer containing at least one hydrophilic colloid, and at least one of the back layers contains colloidal silica.

The colloidal silica used in the present invention has an average particle size of 7- to
120-, the main component is silicon dioxide, and may contain alumina, sodium aluminate, etc. as a minor component. Further, these colloidal silicas may contain an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, or an organic salt such as tetramethylammonium ion as a stabilizer. In particular, as a stabilizer for colloidal silica, colloidal silica made of potassium hydroxide or ammonium hydroxide is preferred.

For these colloidal silicas, e.g. Egon M
edited by atijevic, 5surface and Co1
Volume 6 of 1oidScience, pp. 3-100 (1
John Wiley & John Wiley, 973.

Specific examples of colloidal silica include E and I.

du Pant de Nemours & Go, (
USA) to Ludox 8M, L to dox 8S,
Ludox LS, Ludox TM, L
With product names such as udox H5, Snowtex 20 and Snowtex C are manufactured by Yassan Kagaku Co., Ltd. (Tokyo, Japan).
.

With product names such as Snowtex N and Snowtex 0, M
on5anto Go, 5yton from (USA)
With product names such as C-30,5yLon 200, and Na
1co Chem, Go.

(USA) Nalcoag 1030, Nalc
oag 1060, Nalcoag ID-21-64
Examples include those commercially available under trade names such as.

The preferred amount of colloidal silica used is 2 to 200 parts by weight/m2 of the binder in the back layer.
m2, preferably 5 to 100 parts by weight/m2, particularly preferably 10 to 70 parts by weight/m''.

If the amount of colloidal silica used is less than 2 parts by weight/m2, curling prevention effect cannot be obtained;
This is because if it exceeds m2, cracks in the coating film will become large.

By including colloidal silica in this manner, the elastic modulus can be increased, that is, it can be made harder, compared to the case where no silica is added, and the back layer becomes difficult to stretch.

When the back layer is composed of a plurality of layers, colloidal silica may be added to any one of the back layers, but it is preferably added to the back layer adjacent to the support.

In the present invention, it is preferable to provide a back layer containing a matting agent on the outside of the back layer containing colloidal silica described above for the purpose of improving adhesion as described later to form a two-layer structure. .

In the present invention, the thickness of the back layer containing colloidal silica is about 1 to 20 μs, preferably about 2 to 15 μs.

If the film thickness is less than 1 -, the curling improvement effect is insufficient, and if it exceeds 20 -, cracks are likely to occur and curling is likely to occur on the back layer side during heat development and/or heat transfer. This is because transport defects may occur.

In the present invention, a matting agent, especially a particle size of 1, is used in the back layer.
Those exceeding 0-, preferably 12-50-1, particularly preferably 12-30#m, have a total particle O, OO2cm.
"7m2 or more, preferably 0.005~0.5C1
l+31012, particularly preferably 0.01 to 0,3
It is preferable to contain a matting agent having an area of cm37m2.

By adding such a matting agent, image unevenness caused by transfer of the base or base precursor back layer when dye-fixing materials are stored in a layered state is significantly reduced, and adhesion is also improved.

Such a particle size is suitable for the total thickness of a typical backing layer (3 to 71
m), and adhesion failure is prevented.

It is preferable that such a matting agent is hard.

The shape of the matting agent in the present invention may be any shape, such as amorphous or rounded, but rounded is more preferable than angular, and spherical is more preferable.

Further, the matting agent is preferably transparent or white, and more preferably transparent.

Further, it may be used in combination with a matting agent having a particle size of 1 to 10. The average particle size of all the matting agents in the present invention is 5-30-1, preferably 7-25-1, particularly preferably 10-20-1.

Matting agents are well known in the photographic art and can be defined as discrete solid particles of inorganic or organic material dispersible in a hydrophilic organic colloidal binder. Examples of inorganic matting agents include oxides (e.g. silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.);
Alkaline earth metal salts (e.g. sulfates and carbonates)
(Specifically, barium sulfate, calcium carbonate, magnesium sulfate, calcium carbonate, etc.), silver halide grains that do not form images (silver chloride, silver bromide, etc., and a small amount of iodine may be added as a halogen component) and glass.

Further, examples of organic matting agents include starch (eg, corn starch, rice starch, etc.), cellulose ester (eg, cellulose acetate propionate, etc.), cellulose ether (eg, ethyl cellulose, etc.), synthetic resin, etc. Examples of synthetic resins include water-insoluble or sparingly soluble synthetic polymers, such as alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycicilyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate), Acrylonitrile, olefins (e.g. ethylene), styrene, benzoguanamine formaldehyde condensates, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulfoalkyl ( Polymers containing a combination of meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used.

In addition, epoxy resin, nylon, polycarbonate, phenol resin, polyvinylcarbazole, polyvinylidene chloride, etc. can also be used.

Among them, benzoguanamine formaldehyde condensation polymers (benzoguanamine resin, specifically those shown by the following formula, such as the product Meiko Poster; manufactured by Nippon Shokubai Chemical Industry ■: Existing Chemical Trade 7-31, etc.), polyolefins (
For example, product names Flowbeads LE-1080, CL-20
80, HE-5023; manufactured by Tetsusei Kagaku or trade name Chemivar V-100: manufactured by Mitsui Petrochemical), polystyrene beads (manufactured by Moritex), nylon beads (manufactured by Moritex), AS resin beads (
(manufactured by Moritex), epoxy resin beads (manufactured by Moritex), polycarbonate resin (manufactured by Moritex)
etc. are preferred.

These matting agents may be used in combination.

The back layer in the present invention is formed by coating a hydrophilic colloid layer on the support opposite to the dye fixing layer and drying it. The hydrophilic colloid substance is preferably a hydrophilic organic polymer compound, and may be a commonly used hydrophilic natural or synthetic polymer, but preferably proteins such as gelatin and gelatin derivatives, cellulose derivatives, starch, Examples include natural substances such as polysaccharides such as gum arabic, water-soluble polyvinyl compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers. Among these, gelatin or gelatin derivatives are preferred. In addition to lime-processed gelatin, acid-processed gelatin and the Journal of the Photographic Society of Japan (Bul.
It is also possible to use enzyme-treated gelatin, gelatin hydrolysates, and enzymatically decomposed products as described in J. Soc. Phot, Japan), p. 16.30 (1966). Examples of gelatin derivatives include gelatin, acid halides, acid anhydrides, isocyanates, bromoacetic acid,
Those obtained by reacting numerous compounds such as alkanesultones, vinyl sulfonamides, maleimides, polyalkylene oxides, and epoxy compounds, and those obtained by reacting gelatin with acrylic acid, methacrylic acid, their esters, amides, etc. Derivatives, single or copolymers of vinyl monomers such as acrylonitrile and styrene can be graft-polymerized.

The number of back layers may be one, two or more. There is no limit to the thickness of the back layer, but it is preferably from 0.5 to 15-1, particularly from 1 to 10-1.

There is no particular limit to the amount of binder in the back layer, but the usual range of 0.5 g/m2 to 15 g/m2 is appropriate.

Other known additives may be added to the back layer of the present invention as described below.

In the present invention, the dye fixing layer is capable of fixing the mobile dye released by development.
To fix the dye, polymer mordants and JP-A-57-
Dye-receiving polymers such as those described in No. 198,458 can be used.

In the present invention, the dye-receiving polymer that can be used in the dye-fixing layer has a glass transition temperature of 40°C or higher, 2.
It is made of an organic polymer material that is heat resistant to temperatures below 50°C. In the present invention, there are many points that are not clear regarding the mechanism by which the dye released from the dye-donating substance enters the polymer. It is generally believed that at a treatment temperature above the glass transition point, the thermal motion of the polymer chains becomes large, and as a result, the dye can enter the gaps between the bundled chain molecules. Therefore, by using a layer made of an organic polymer substance with a glass transition temperature of 40°C or higher and 250°C or lower as the dye-fixing layer, the dye-donating substance and the dye can be distinguished, and only the dye can enter the dye-fixing layer. Clear images can be formed.

Examples of organic polymeric substances used in the present invention include the following. To list them, the molecular weight is 2000-8
5000 polystyrene, polystyrene conductors with substituents having up to 4 carbon atoms, polyacetals such as polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, polychloride Vinyl, chlorinated polyethylene, polytrichloride-butylene, polyacrylonitrile, poly-N, N-dimethylacrylamide, p-
cyanophenyl group, pentachlorophenyl group and 2.
Polyacrylate with 4-dichlorophenyl group, polyacryl chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly -2-cyano-
Polyesters such as ethyl methacrylate and polyethylene terephthalate, polysulfone, bisphenol A
Mention may be made of polycarbonate, polycarbonates, polyanhydrides, polyamides and cellulose acetates. In addition, Polymer Handbook 2nd edition J. Brandrup, E. H. Immergut (J, Brandrup, E. H. Immergut)
Also useful are synthetic polymers having a glass transition temperature of 40° C. or more and 250° C. or less, as described in John Wiley & Co., Ltd., edited by John Wiley & 5ons. These polymeric substances may be used alone or in combination, or may be used in combination as a copolymer. These polymers may also serve as a support applied to the photographic element described below, or may form a layer independent of the support.

In the present invention, the dye fixing element preferably has a dye fixing layer containing a mordant.

In the above case, the mordant can be arbitrarily selected from commonly used mordants, and among them, polymer mordants are particularly preferred. Here, the polymer mordant includes a polymer containing a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing these quaternary cation groups, and the like.

Preferred specific examples of homopolymers and copolymers containing one vinyl monomer unit having a tertiary amino group include the following. Numbers in thousands represent mol% (the same applies hereinafter).

Such.

Specific examples of homopolymers and copolymers containing one vinyl monomer unit having a tertiary imidazole group include U.S. Pat. Nos. 4,282,305 and 4,115,124;
No. 3,148゜061, JP-A-60-118834
The following may be mentioned, including the mordant described in No. 60-122941.

Such.

Preferred specific examples of homopolymers and copolymers containing one vinyl monomer unit having a quaternary imidazolium salt include British Patent No. 2,056.101, British Patent No. 2,093,
No. 041, No. 1,594,961, U.S. Patent No. 4,
No. 124.386, No. 4,115,124, No. 4
, No. 273,853, No. 4,450,224, JP-A No. 48-28325, and the like.

Shinn2-L, U2 LJt2-L+tl-L
;II 2 etc.

In addition, as preferred specific examples of homopolymers and copolymers containing one vinyl unit having a quaternary ammonium salt, U.S. Pat.
No. 98,088, No. 3,958,995, Japanese Unexamined Patent Publication No. 6
No. 0-57836, No. 60-60643, No. 60-1
No. 22940, No. 60-122942, No. 60-23
The following may be mentioned, including the mordant described in No. 5134.

shi8　r’l13 Such.

Others, U.S. Patent No. 2,548,564, U.S. Patent No. 2,4
No. 84,430, No. 3.148゜161, No. 3,
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in U.S. Pat. No. 756,814 and others - U.S. Pat.
59.096, British Patent No. 4,128,538, British Patent No. 1,277.453, etc., polymer mordants capable of crosslinking with gelatin, etc.; US Patent No. 3,9
No. 58,995, No. 2.721,852, No. 2,
No. 798,063, JP-A-54-115228, JP-A No. 54-115228, No. 5
Aqueous sol-type mordant disclosed in No. 4-145529, No. 54-26027, etc.; U.S. Patent No. 3.89
water-insoluble mordants as disclosed in US Pat. No. 8,088;
U.S. Patent No. 4,168°976 (Japanese Unexamined Patent Publication No. 54-137
No. 333) Reactive mordants capable of covalently bonding with the dyes disclosed in the specification; and US Pat. No. 3,709.
No. 690, No. 3,788,855, No. 3', 64
No. 2,482, No. 3,488,706, No. 3.5
No. 57,066, No. 3゜271.147, No. 3,
No. 271,148, JP-A-50-71332, JP-A No. 53
-30328, 52-155528, 53-1
The mordant disclosed in No. 25 and No. 53-1024 can be mentioned.

Others, U.S. Patent No. 2,675,316, U.S. Patent No. 2,8
Mention may also be made of the mordants described in US Pat. No. 82,156.

The molecular weight of the polymer mordant of the present invention is 1,000 to 1.0.
00,000 is suitable, especially 10,000 to 200
°000 is preferred.

The above polymer mordants are usually mixed with hydrophilic colloids.

As the hydrophilic colloid, the same kind as the hydrophilic colloid for the back layer described above can be used, but gelatin is the most typical. The mixing ratio of the polymer mordant and gelatin and the coating amount of the polymer mordant can be easily determined by those skilled in the art depending on the amount of dye to be mordant, the type and composition of the polymer mordant, and the image forming process to be used. Yes, but the mordant/gelatin ratio is 20,780 to 80/2.
0 (weight ratio), mordant application amount is 0.2 to 15 g/rn
2 is suitable, preferably from 0.5 g/m'' to 8 g/m''.

The dye fixing layer may be composed of one layer, or may be composed of two or more layers. Further, an auxiliary layer other than the dye fixing layer may be provided above or below the dye fixing layer.
In particular, a protective layer is provided on top of the dye fixing layer containing a mordant,
It is preferred to improve the resistance of the image to mechanical manipulation.

The constituent layer on the dye fixing layer side of the dye fixing element of the present invention contains a base or a base precursor as described above.

The amount of base or base precursor added is 0.1 to 10
g/m2 is preferred.

In particular, when the photosensitive element contains a sparingly soluble metal compound as described later, the compound (complex-forming compound) that forms a complex with the metal ion constituting the sparingly soluble metal compound using water as a medium is used as a base precursor to form a dye-fixing element. A form in which it is added is preferable.

Complex-forming compounds tend to precipitate in the membrane when used as salts. To prevent precipitation, patent application 1876-1986
Polymers such as dextran and pullulan described in No. 00,
It is preferable to use a compound containing polyalkylene oxide described in Japanese Patent Application No. 60-206092.

Dextran and pullulan are types of polysaccharides and are polymers of D-glucose. The dextran used in the present invention preferably has a molecular weight of 20,000 to 2,000,000, particularly 100,000 to 2,000,000.
800,000 is preferable. Also, pullulan is 20,000 to 20
00,000 is preferable.

Examples of dextran and pullulan derivatives include those in which sulfinic acid groups, amino groups, etc. are introduced into dextran and pullulan so that they can easily react with hardening agents.

The polyalkylene oxide or its derivative preferably has a molecular weight of at least 600, and is preferably a C2-C4 realkylene oxide, such as ethylene oxide,
Propylene-1゜2-oxide, butylene-1,2-
a polyalkylene oxide consisting of at least 10 units of oxide, preferably ethylene oxide;
Water, aliphatic alcohols, aromatic alcohols, fatty acids,
It includes condensates with compounds having at least one active hydrogen atom, such as organic amines and hexitol derivatives, and block copolymers of two or more types of polyalkylene oxides. That is, polyalkylene oxide compounds, specifically polyalkylene glycols polyalkylene gelicol alkyl ethers polyalkylene gelyl aryl ethers polyalkylene glycol (alkylaryl) ethers polyalkylene gelicol esters polyalkylene glycol fatty acids Amides, polyalkylene gelicolaminos, polyalkylene gellicol block copolymers, polyalkylene gelicol graft polymers, and the like can be used.

The number of polyalkylene oxides is not limited to one, but may be two or more in the molecule. In that case, the exemplary polyalkylene oxides may consist of less than 10 alkylene oxide units, but the total number of alkylene oxide units in the molecule must be at least 10. When there is more than one polyalkylene oxide in the molecule, each of them may consist of different alkylene oxide units, such as ethylene oxide and propylene oxide. The polyalkylene oxide compound preferably contains from 14 to 100 alkylene oxide units.

The layer containing dextran, pullulan, derivatives thereof, or polyalkylene oxides may be any layer in the dye fixing element, but a layer containing a base and/or a base precursor is preferable, and in particular a layer containing a base and/or a base precursor is preferable. A layer containing a mordant is preferred.

The amount of dextran, pullulan and their derivatives or polyalkylene oxides used is 0.1-10g/
m2, preferably in the range 0.5-5 g/m2. This usage range is 0.1g/m
If it is less than 2, the present invention will not be effective, and if it exceeds 10 g/m2, the film quality will deteriorate.

Further, the (base and base precursor)/(dextran, pullulan and derivatives thereof or polyalkylene oxides) ratio (weight ratio) is preferably 0.1 to 10, preferably 0.2 to 5.

The bases used in the present invention include alkali metal or alkaline earth metal hydroxides, secondary
or tertiary phosphates, borates, carbonates, quinolates, metaborates; ammonium hydroxides; hydroxides of quaternary alkyl ammoniums; hydroxides of other metals, etc. Examples of bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines), aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted aromatic amines, and bis(p -(dialkylamino)phenyl)methanes), heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines, and those in which p has a of 8 or more are particularly preferred.

Also preferably used are salts of the above-mentioned organic bases and weak acids, such as carbonates, bicarbonates, borates, secondary and tertiary phosphates, quinolates, acetates, metaborates, and the like. In addition to these compounds, compounds described in JP-A-59-218443 are also preferably used.

Furthermore, there are various methods of generating a base using a base precursor, and all of the compounds used in these methods are useful as base precursors. For example, as described in Japanese Patent Application No. 60-169585, a base is formed by mixing a metal compound that is sparingly soluble in water and a compound (referred to as an fi-forming compound) that undergoes a complex-forming reaction with the metal ions constituting the sparingly soluble metal compound. How to generate it and the patent application in 1986
There is a method of generating a base by electrolysis as described in No. 74702.

The former method is particularly effective. Examples of poorly soluble metal compounds include carbonates, hydroxides, and oxides of zinc, aluminum, calcium, barium, and the like. Also,
Regarding complex-forming compounds, see, for example, N. E. Martell, R. M. Smith (A.E., Martell, R.
, M., 5IIIth) co-author, “Critical Stability Constant”
4, Volumes 4 and 5, Plenum Press. Specifically, aminocarboxylic acids, iminodiacetic acids, pyridylcarboxylic acids, aminophosphoric acids,
Carboxylic acids (mono, di, tri, and tetracarboxylic acids and compounds with substituents such as phosphohydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, and phosphino), hydroxamic acids, polyacrylates, polyphosphoric acids, etc. and salts with alkali metals, guanidines, amidines or quaternary ammonium salts.

In the present invention, it is desirable that the poorly soluble metal compound and the complex-forming compound be contained in at least one layer on separate supports.

For example, it is preferable that the poorly soluble metal compound be contained in the light-sensitive material and the complex-forming compound be contained in the image-receiving material. Slightly soluble metal compounds are disclosed in JP-A-59-174830 and JP-A-53-102.
Preferably, it is contained as a fine particle dispersion prepared by the method described in No. 733, etc., and the average particle size is 50 μm.
Below, 5 micrometers or less is especially preferable.

In the present invention, when a sparingly soluble metal compound or a complex-forming compound is contained in a layer on a support, the amount of the compound-like compound,
Although it depends on the particle size of the poorly soluble metal compound, the rate of complex formation reaction, etc., it is appropriate to use the coating film in an amount of 50% by weight or less, more preferably 0.01% to 40% by weight. % ranges are useful.

The content of the complex-forming compound in the present invention is 1/100 to 100 times the content of the poorly soluble metal compound in molar ratio.
It is preferably 1/10 to 20 times.

Other base precursors include salts of organic acids and bases that decarboxylate and decompose when heated, compounds that decompose and release amines through reactions such as intramolecular nucleophilic substitution reactions, Rossen rearrangement, and Beckmann rearrangement. Compounds that release a base by causing some kind of reaction, and compounds that generate a base by electrolysis or the like are preferably used.

Preferred base precursors of the former type that generate a base upon heating include salts of trichloroacetic acid described in British Patent No. 998.949, etc., and U.S. Patent No. 4,060,4.
Salt of α-sulfonylacetic acid described in No. 20, JP-A-59-
Salts of propiolic acids described in US Pat. No. 180537, 2-carboxycarboxamide derivatives described in US Pat. No. 4,088,496, thermally decomposable acids using an alkali metal or alkaline earth metal in addition to an organic base as the base component (JP-A-59-195237), hydroxamic carbamates described in JP-A-59-168440 using Rossen rearrangement, and JP-A-59 that produces nitriles by heating.
Examples include aldoxime carbamates described in No.-157637. Others, British Patent No. 988,94
No. 5, U.S. Patent No. 3゜220.846, Japanese Unexamined Patent Publication No. 1973-
Also useful are the base precursors described in British Patent No. 22625, British Patent No. 2,079,480, and the like.

The following compounds can be mentioned as compounds that generate bases by electrolysis.

For example, electrolysis of various fatty acid salts can be cited as a typical method using electrolytic oxidation.

Through this reaction, carbonates of alkali metals and organic bases such as guanidines and amidines can be obtained extremely efficiently.

In addition, methods using electrolytic reduction include the production of amines by reduction of nitro and nitroso compounds; production of amines by reduction of nitriles; nitro compounds, azo compounds,
Examples include the production of p-aminophenols, p-phenylenediamines, and hydrazines by reduction of azoxy compounds and the like. P-amine phenols, p-
In addition to being used as bases, phenylene diamines and hydrazines can also be used directly as color image forming substances.

Of course, it is also possible to generate an alkaline component by electrolyzing water in the coexistence of various inorganic salts.

Although the base can be supplied or generated by various methods as described above, the present invention is particularly effective when the base or base precursor is present in the form of a salt in the dye fixing layer or the layer adjacent thereto.

A polymer latex may be present in the constituent layer or back layer on the side of the dye fixing layer of the dye fixing element of the present invention for the purpose of improving the brittleness of the mordant layer and further improving the curl balance.

'I' constituting the polymer latex used in the present invention
Examples of -ff1 bodies include acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, acrylamides, methacrylamides, vinyl ethers, styrenes, etc. It will be done. More specific examples of these monomers include acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2- Ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate,
Examples include 2-methoxyacrylate, 2-ethoxyacrylate, 2-(2-methoxyethoxy)ethyl acrylate, and the like. Examples of methacrylic esters include styrene (acrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, ter
Examples include t-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate. Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate, and the like. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like. Examples of fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of itaconic acid diesters include diethyl itaconate, dimethyl itaconate, dibutyl itaconate, and the like. Acrylamides include acrylamide, methylacrylamide, ethyl acrylamide,
Propylacrylamide, n-butylacrylamide,
Examples include tert-butylacrylamide, cyclohexylacrylamide, 2-methoxyethylacrylamide, dimethylacrylamide, diethylacrylamide, and phenyl acrylamide. Methacrylamides include methylmethacrylamide, ethylmethacrylamide, n-butylmethacrylamide, tert-butylmethacrylamide, 2-methoxymethacrylamide,
Dimethyl methacrylamide, diethyl methacrylamide, etc. are mentioned. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like. Styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, chloromethylstyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromstyrene, and vinylbenzoin. Examples include acid methyl ester, 2-methylstyrene, and the like. These monomers may be homopolymers or copolymers, depending on the purpose of the invention.

Preferred are acrylic esters, copolymers of acrylic esters and methacrylic esters, and copolymers of acrylic esters and acrylic acid or methacrylic acid. The average molecular weight is preferably 100,000 or more, particularly 300,000 to 500,000.

Polymer latex can be produced in a variety of ways.

Free radical polymerization of ethylenically unsaturated solid monomers can be carried out by thermal decomposition of chemical initiators or by the action of reducing agents on oxidizing compounds (redox initiators) or by physical action such as ultraviolet light or other high-energy radiation, radiofrequency, etc. It is initiated by the addition of free radicals to monomer molecules that are formed. The main chemical initiators include persulfates (ammonium and potassium versalphate), hydrogen peroxide, 4゜4'-azobis(4-cyanovaleric acid), etc. (these are water-soluble), azoisobutyro Nitriles, benzoyl peroxide, chlorobenzoyl peroxide and other compounds which are insoluble in water.

Common redox initiators include hydrogen peroxide-iron(II)
Salt, potassium persulfate-potassium bisulfate, cerium salt alcohol, etc.

Examples of initiators and their effects are given by F. A. Bovey.
Emulsion Polymerization J
IntersciencePublishes Inc.
, New York, 1955, pp. 59-93.

As the emulsifier, a surface-active compound is used, and preferred examples include soaps, sulfonates and sulfates, cationic compounds, amphoteric compounds, and polymeric protective colloids. Examples of these groups and their effects are Be
lgischeChemische Industry
e Vol. 28, pp. 16-20 (1963).

Specific examples of the polymer latex used in the present invention are described below, but the present invention is not limited thereto.

(m, n; positive integer) The polymer latex used as the above additive is an aqueous dispersion of a water-insoluble polymer with an average particle size of 20 pn to 200 pn, and the preferable amount used is The weight ratio is 0.01 to 2.0, particularly preferably 0.1 to 1.0.

Further, among the above, those having a low glass transition point (especially 40° C. or lower) are preferable for improving the brittleness of the dye fixing layer.

The constituent layer or back layer on the side where the dye fixing layer of the dye fixing element of the present invention is located has improved slip properties, improved adhesion resistance, improved peelability between the dye fixing element and the photosensitive element, and improved brittleness of the mordant layer. , oil droplets may be present for the purpose of further improving curl balance.

In the present invention, oil droplets refer to liquid particles that are an oily independent system finely dispersed in a hydrophilic colloid and are substantially insoluble in water. The finer the size of the oil droplets, the better, preferably an average particle diameter of 3-3 or less, especially 1- or less, and even 0.
5- or less.

The oil droplets in the present invention are, for example, U.S. Pat. No. 2.322,
No. 027, No. 2,533,514, No. 2,882
, No. 157, Special Publication No. 46-23233, British Patent No. 9
No. 58,441, No. 1,222,753, Japanese Unexamined Patent Publication No. 1973
No. 0-82078, U.S. Patent No. 2,353°262,
JP 3,676.142, JP 3,600,454, JP 51-28921, JP 51-141623
Esters (e.g., phthalate esters, phosphoric acid esters, fatty acid esters, etc.), amides (e.g., fatty acid amides, sulfamides, etc.), and ethers described in Japanese Patent Application No. 148489/1989, etc. , alcohols, paraffins, silicone oil, and other high-boiling organic solvents that are liquid at room temperature and do not evaporate at heat treatment temperatures are preferred.

Furthermore, oil droplets also include those that are solid when used alone, but when two or more of them are used in combination, the melting point is lowered and the droplets become liquid in the coating film.

Oil droplets also include those that are solid at room temperature, but exist as liquid droplets when incorporated into a hydrophilic binder or when incorporated with various photographic additives.

Examples include stilbene, triazine, oxazole, and coumarin compounds used as whitening agents, and benzotriazole, thiazoline, and cinnamic acid ester compounds used as ultraviolet absorbers.

Oil droplets suitable for use in the present invention are saturated or unsaturated hydrocarbons having 10 or more carbon atoms (including those in which some or all of the hydrogen atoms are replaced with halogen atoms), or the following general formula (A ) to (G).

General formula (A) General formula (B) General formula (C) General formula (D) General formula (E) (R2a-0u-p=.

General formula (G) Ra -C00R-R32 (In the above general formula (A), RA represents an m + n-valent substituted or unsubstituted aliphatic hydrocarbon group, and R21 is a substituted or unsubstituted aliphatic hydrocarbon group , represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and m and n each represent an integer of 1 to 5.

In the above general formula (B), RB represents P+9-valent substituted or unsubstituted aliphatic hydrocarbon group or alicyclic hydrocarbon group, and R22 and RZI may be the same, and each is substituted or unsubstituted. represents an aliphatic hydrocarbon group or alicyclic hydrocarbon group, p represents 0.1.2 or 3, 9 represents 0.1.2 or 3, p+q represents 1
That's all.

In the above general formula (C), Re is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, acyl group, amino group, acyloxy group, carbamoyl group, ureido group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a cycloalkyloxycarbonyl group, or a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, or a cyan group.

R24 represents a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group.

r represents an integer of 1 to 5, S represents an integer of 1 to 4, and r+S is 6 or less.

When r is 2 or more, RCs may be the same or different.

When S is 2 or more, R24 may be the same or different.

In the above general formula (D), R" and R" each represent a substituted or unsubstituted alkyl group, a monocyclic to polycyclic alicyclic hydrocarbon group, an aryl group, or an aralkyl group.

R27 represents a substituted or unsubstituted alkyl group, aryl group, aralkyl group, or amino group, or a halogen atom. Z represents an atomic group for forming a carbon ring condensed to a benzene ring.

1 represents O or 1. (2) represents an integer from 0 to 2, W represents an integer from 0 to 7, and v+w is 7 or less.

R26Q- and/or R''- is substituted on the benzene ring and/or the fused carbon ring in the above general formula (D).

In the above general formula (E), R28 represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group or aryl group.

R28 may be the same or different.

In the above general formula (F), R29 is a hydrogen atom or n
' represents a substituted or unsubstituted aliphatic hydrocarbon group.

R'' and R'' each represent a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group or aromatic hydrocarbon group, and R'' and R'' may be the same or different.

R29 and R'' and R3° and R'' may be respectively connected to form a heterocycle.

n' represents 1 or 2.

In the above general formula (G), Ra represents a substituted or unsubstituted aliphatic hydrocarbon group, and Rx represents a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group. . ) Detailed explanations of the above general formulas (A) to (G) can be found in JP-A-59
-178455, 59-178454, 59-
No. 178452, No. 59-178453, No. 59-1
It is described in No. 78451, No. 59-178457, etc.

Specific examples of compounds used to form oil droplets are listed below.

(1) Liquid paraffin (2) Chlorinated paraffin 1=1On21 ca HI7 (12) (n-C1oH21)C-CH2COOC
2H5 Furthermore, as an example of the compound of formula (A) of the present invention,
Oil and Fat Chemistry Handbook (revised 2nd edition) 1971 (round neck), 108
~page 115, (Table 2-31.2-34.2-36.
2-39.2-47).

(13) CH3H2T COOCH8H37-is.

(32) (C4H9o←-p=.

(34) (Cs H1vo'j--P = 0(35
) (iso -Cog H21-)--P = 0
(36) (n−c+1llH33o−)−−p=.

(37) (n-CH8H3T O÷--p=.

(:19) C6Hj7CH=CH(CH2)11C
0NH2 (43) Leophos@50 (manufactured by Ajinomoto ■) (4
4) Leofos ■65 (manufactured by Ajinomoto ■) (45) Leofos ■95 (manufactured by Ajinomoto ■) (46) Leofos ■110 (
(manufactured by Ajinomoto Co., Ltd.) These compounds are known and can be easily synthesized manually as commercially available products or by known synthetic methods.

Silicone oils that are particularly preferably used in the present invention include all silicone oils, from dimethyl silicone oil to modified silicone oils in which various perforation groups are introduced into dimethylsiloxane.

A particularly preferred silicone oil used in the present invention is represented by the following general formula (I).

General formula (I) General formula (I) includes a linear siloxane having a siloxane unit represented by the following general formula (I-1) and a terminal group represented by the following general formula (I-2). .

General formula (I-13) General formula (I-2) In the formula, R1 is a hydrogen atom, an alkyl group, a substituted alkyl group,
represents a cycloalkyl group, aryl group, substituted aryl group, alkoxy group, substituted alkoxy group, alkoxycarbonyl group, or substituted alkoxycarbonyl group, 2 is O
or a number greater than or equal to 1, m is a number greater than or equal to 1, and LL+m is a number from 1 to 1000.

In general formula (I), R1 may be the same type or two or more different types. That is,
The silicone oil represented by general formula (I) may be composed of siloxane units of general formula (I-1) consisting of the same type of R1, or may be composed of two or more types of general formula (I-1) with different types of R1. -1) may be composed of the siloxane unit.

In general formula CI), R1 is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group, a cycloalkyl group, an aryl group, a substituted aryl group, an alkoxy group, a substituted alkoxy group, an alkoxycarbonyl group, or a substituted Represents an alkoxycarbonyl group. iL+
m is preferably 2-500.

Specific examples of R1 in the compound represented by general formula (I) include -CH3, -C5H1+, -C11H17, -C13
H2'l, -CI4R29, -CH2C82iD -(CI+2) 30(G2 H40)a (03H
s O) b R2 (where R2 is an alkyl group, a and b represent O or an integer of 1 or more), -(co2) 30H1-(CH2) 3 NR2,
-(ni112) 3 NHCH2CH2NR2, -(
C11□)30CII□Cl1-C) picture, -((:R2
) 3 5H1-([:R2)3 C00H5-(
CR2)s Cool, -(CR2)10 (OOH
.

-<CH2) 3 C0NHR2 (R2 has the same meaning as above)
, -C112CH2cps, -CH2CI(2C6
F 13, -((:R2) 3 CN, -(C))2 ) 3 <◇ -(C)+2 ) 30CH2() -(CH2) 30R2 (R2 has the same meaning as above), (wa,
iD −) I, −0CH3, = oc8 n, 7, −
0CH2CH20(C2H40)a(C3H60)bR
2 (a, b, R2 have the same meanings as above), and the like.

Among the silicone oils represented by the general formula (I), those represented by the following general formula (II) or (III) are particularly preferred.

General formula (II) General formula (III) In the formula, R1' is -CH3 or R1 of the general formula (I)
, p is 0 or a number greater than or equal to 1, q is 1
The above numbers represent the numbers a411 to 17.

In the above general formulas (II) and (m), the carboxyl equivalent (the value obtained by dividing the carboxyl equivalent and the molecular weight by the number of carboxyl groups contained therein) is 1.
20 to 6000 is preferable, particularly preferably 12
It is 0-4000.

Next, among the compounds represented by the general formula (I), typical examples used in the present invention will be listed, but the invention is of course not limited to these.

Knee 25 Knee 27 Knee 29 10t1 ga ■-30 Knee 31 Knee 32 to Knee 38 K -■-- Knee l-3291 I-36405 I -378010 I -38802 ■-39 ■-40 Compound of general formula (I) The manufacturing method is known, and many of the silicone oils used in the present invention are commercially available.

For example, the product names of Shin-Etsu Chemical ■ are F410 and KF41.
2, KF413, F351, KF945, F615, K851. X-22-819, FLlo
o, KF862, KF865, X-22-98
0, KFlooT, X-60-164, X-22-3
710, X-22-3715, KF-910, X-22
-160B etc.

Various known methods can be used to form oil droplets, but as a typical example, the above-mentioned compounds are dissolved in a low-boiling organic solvent such as methyl acetate or ethyl acetate as needed, and a surface-active An example of a method is to mix the agent with an aqueous solution of a hydrophilic colloid such as gelatin, stir to emulsify and disperse it, and then add this dispersion to a coating solution for a hydrophilic colloid layer and apply it.

The number of oil droplets is 5 to 60 with respect to the total amount of polymer components in the additive layer.
vol, %, especially 10-50 vol. It is preferable to add %.

There are no particular restrictions on the hardening agent used in the dye fixing layer, back layer, and other constituent layers of the dye fixing element of the present invention, and known hardeners such as aldehydes (formaldehyde,
daryoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,
3,5-Triacryloyl-hexahydro-5-triazine, bis(vinylsulfonyl)methyl ether, N,
N'-ethylene-bis(vinylsulfonylacetamide), N,N'-trimethylene-bis(vinylsulfonylacetamide), etc.), active halogen compounds (2,4-
dichloro-6-hydroxy-5-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), isoxazoles, dialdehyde starch,
1-chloro-6-hydroxytriazinylated gelatin,
Mention may be made of epoxy compounds such as, for example. The amount of the hardener to be added is arbitrary, but the appropriate amount is usually about 0.1 to 30 wt % of the hydrophilic colloid which is the binder and reacts with the hardener.

In addition, various additives can be used in the dye fixing element of the present invention. Examples include coating aids, antistatic agents, antifoggants, development stoppers, antifading agents, ultraviolet absorbers, and optical brighteners.

In addition, in order to prevent the transferred dye from being retransferred from the dye fixing element to the outside, a polymer having an anionic group (
For example, Sumikagel (trade name, manufactured by Sumitomo Chemical Co., Ltd.) may be added to the protective layer.

In addition, compounds such as higher alkyl sodium sulfate, higher fatty acids, higher alcohol esters, carbowaxes, higher alkyl phosphate esters, and silicone compounds are added to the protective layer and back layer for the purpose of improving slipperiness, peelability, and adhesion resistance. may also be used. Specifically, U.S. Patent No. 2,882,157
No. 3,121,060, No. 3,850.64
The compounds described in No. 0, JP-A-51-141623, etc. may be used alone or in combination of two or more.

Fluorosurfactants described in Japanese Patent Application No. 61-267492 can also be used for the same purpose.

It is also effective to use a fluorescent whitening agent described in JP-A-61-143752 and to adjust the amount of a white pigment such as titanium oxide to improve the whiteness.

The support used in the dye-fixing element of the invention is one that can withstand the processing temperatures. Common supports include glass, paper, metal and their analogs, as well as cellulose acetate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film,
Includes polyethylene terephthalate films and their related films or plastic materials.
A paper support laminated with a bomber such as polyethylene can also be used.

In the present invention, the effects of the present invention are exhibited when a plastic film having a thickness of 50 to 200 mm, particularly 80 to 150 mm, is used as the support. And 80~
This effect is particularly great when the plastic film is 150 mm thick and transparent and is used for over-the-top projectors (OHP).

In the present invention, the photosensitive element used in combination with the dye-fixing element described above has at least a photosensitive silver halide, a dye-donating substance, a binder, and, if necessary, an organic silver salt and a reducing agent on a support. .

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Alternatively, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide may be used.

Specifically, U.S. Patent No. 4,500,626, column 50, Research Disclosure June 1987 issue 9.
Pages - 10 (RD17029), JP-A-61-1072
No. 40, Patent Application No. 60-225176, No. 60-228
Any of the silver halide emulsions described in No. 267 and the like can be used.

The silver halide emulsion used in the present invention may be of the surface latent image type in which latent images are mainly formed on the grain surfaces, or may be of the internal latent image type in which the latent images are formed inside the grains. It may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. Further, in the present invention, a direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used.

Although the silver halide emulsion may be used unheated, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of nitrogen-containing heterocyclic compounds (JP-A-58-126526, JP-A-58-215644).
issue).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g/g in terms of silver.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver halide. In this case, the photosensitive silver halide and the organic metal salt need to be in contact or at a close distance.

Among such organic metal salts, organic silver salts are particularly preferably used.

Examples of organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include compounds described in JP-A-61-107240 and U.S. Pat. No. 4,500,626, columns 52 to 53. be.

Also useful are silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in Japanese Patent Application No. 113235/1982, and silver acetylene described in Japanese Patent Application No. 90089/1982. Two or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 50 mg to 10 g in terms of silver.
/rn” is appropriate.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, Japanese Patent Publication Nos. 59-180550 and 60-1
No. 40335, Research Disclosure Magazine 197
The sensitizing dyes described in June 1988 issue, pages 12-13 (RD17029), JP-A-60-111239, Japanese Patent Application No. 1983
Examples include heat-decolorizable sensitizing dyes described in Japanese Patent No. 172,967 and the like.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, the emulsion may contain a dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible or visible light and exhibits supersensitization (for example, as described in US Pat. No. 2,933.390, No. 3,635,7
No. 21, No. 3,743,510, No. 3,615,
No. 613, No. 3,615,641, No. 3゜617
．． No. 295, as described in No. 3,635,721)
.

These sensitizing dyes may be added to the emulsion during or before or after chemical ripening.
It may be carried out before or after nucleation of silver halide grains according to No. 756 and No. 4,225.666.

The amount added is generally about 10-8 to 10-2 mol per mol of silver halide.

In the present invention, silver can be used as the image forming material. Furthermore, when silver ions are reduced to silver under high temperature conditions, it is possible to use a compound that generates or releases a mobile dye in response to or inversely to this reaction, that is, a dye-donating substance. can. Also, silver can be used.

Examples of dye-donating substances that can be used in the present invention include:
Compounds that form pigments by oxidative coupling reactions (
couplers). This coupler is 4
It may be an equivalent coupler or a 2-equivalent coupler. Also,
Two-equivalent couplers that have a diffusion-resistant group as a leaving group and form a mobile (diffusible) dye through an oxidative coupling reaction are also preferred. Specific examples of developers and couplers can be found in "The Theory of the Photographic Process" by James, 4th edition (T.

11.James “The Theory”
of the PhotographicProc
ess”) pages 291-334 and pages 354-361, JP-A-58-123533, JP-A No. 5B-149046
No. 58-149047, No. 59-111148, No. 59-124399, No. 59-174835,
No. 59-231539, No. 59-231540, No. 60-2950, No. 60-2951, No. 60-14
No. 242, No. 60-23474, No. 60-66249
Details are given in the issue.

Another example of the dye-donating substance is a compound that has the function of releasing or diffusing a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula (LI).

(Dye-X). -Y (LI)Dye
represents a dye group, a temporarily shortened dye group or a dye precursor group, X represents a simple bond or a connecting group,
Y corresponds to or inversely corresponds to the photosensitive silver salt having a latent image in image form (Dye Dye and (Dye
e-X may be the same or different.

As a specific example of the dye-donating substance represented by the general formula (LI), for example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in US Pat. No. 3,134,764.
No. 3,362.819, No. 3,597,20
No. 0, No. 3,544,545, No. 3,482,9
It is described in No. 72, etc. In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction is disclosed in U.S. Patent No. 3,
No. 980,479, etc., and JP-A-49-111.628, etc., disclose substances that release diffusible dyes through an intramolecular rewinding reaction of isoxacilone rings.

Another example is to make a dye-releasing compound into an oxidized form without dye-releasing ability, coexist with a reducing agent or its precursor, and after development, reduce it with the reducing agent that remains unoxidized to produce a diffusible dye. A method of releasing dye has also been devised, and a specific example of the dye-donating substance used therein is disclosed in Japanese Patent Application Laid-Open No. 53
-110,827, 54-130,927, 5
It is described in No. 6-164,342 and No. 53-35.533. Japanese Patent Application No. 60-244,873 describes a compound that releases a diffusible dye when the N-0 bond is cleaved by a remaining reducing agent as a dye-donating substance that releases a diffusible dye using a similar mechanism. has been done.

Furthermore, as described in JP-A-59-185333, a donor-acceptor reaction occurs in the presence of a base and releases a diffusible dye, but when it reacts with an oxidized form of a reducing agent, dye release does not substantially occur. Non-diffusible compounds (LDA compounds) can also be used.

In all of these methods, the diffusible dye is released or diffused in areas where development has not occurred, and the dye is neither released nor diffused in areas where development has occurred.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, it is a coupler that has a diffusible dye as a leaving group and that releases a diffusible dye by reaction with an oxidized form of a reducing agent (DDR coupler). However, British Patent No. 1,330,52
No. 4, Special Publication No. 48-39,165, British Patent No. 3゜4
No. 43.940, etc., and is preferably used in the present invention.

In addition, in methods using these reducing agents, image contamination due to oxidative decomposition products of the reducing agent may become a problem. Dye-releasing compounds (DRR compounds) have also been devised and are also advantageously used in the present invention. Typical examples are U.S. Pat. No. 3,928,312, U.S. Pat.
No. 053,312, No. 4,055゜428, No. 4
, No. 336, 322, JP-A No. 59-65839, No. 5
No. 9-69839, No. 53-3819, No. 51-10
No. 4,343, Research Disclosure Magazine 174
No. 65, U.S. Patent No. 3,725,062, U.S. Patent No. 3.7
No. 28,113, No. 3,443,939, Japanese Unexamined Patent Publication No. 1973
It is a dye-donating substance described in No. 8-116,537, No. 57-179840, U.S. Pat. Specific examples of this type of dye-donating substance include the compounds described in columns 22 to 44 of the above-mentioned U.S. Pat. No. 4,500,626; Compounds (1) to (3),
(10) - (13), (16) - (19), (28)
〜(30),(33)〜(35),(38)〜(40)
, (42) to (64) are preferred. Also, JP-A-61-
Compounds described in No. 124941 are also useful. In addition, as dye-donating substances other than those mentioned above, dye silver compounds in which organic silver salts and dyes are combined (Research Disclosure magazine, May 1978 issue, pp. 54-58, etc.), heat-developable silver dye bleaching, etc. Azo dye used in the method (U.S. Patent No. 4
, No. 235.957, Research Disclosure Magazine, April 1976 issue, pp. 30-32), leuco dyes (
U.S. Patent Nos. 3,985,565 and 4,022,61
No. 7 etc.) can also be used.

The amount of the dye-donating substance added is 0.02 to 10 mmol/
m2, preferably 0.03 to 5 mmol/m2, is suitable.

Hydrophobic additives such as the dye-providing compounds described above and the imaging promoters described below are described in U.S. Pat. No. 2,322.02.
They can be incorporated into the layers of the photosensitive element by known methods such as the method described in No. 7. In this case, JP-A-59
No. -83154, No. 59-178451, No. 59-1
No. 78452, No. 59-178453, No. 59-17
No. 8454, No. 59-178455, No. 59-178
A high boiling point organic solvent such as that described in No. 457 may be used in combination with a low boiling point organic solvent having a boiling point of 50° C. to 160° C., if necessary.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing substance used.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used.

In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above.

Various surfactants can be used when dispersing hydrophobic substances into hydrophilic colloids.

For example, Nos. (37) to (3) of JP-A No. 59-157636.
The surfactants listed on page 8) can be used.

In the present invention, it is desirable to contain a reducing substance in the photosensitive element. Reducing substances include those generally known as reducing agents, as well as the aforementioned dye-donating substances having reducing properties.

Also included are reducing agent precursors that do not themselves have reducing properties but develop reducing properties through the action of nucleophiles and heat during the development process.

Examples of reducing agents used in the present invention include U.S. Pat.
, No. 500,626, columns 49-50, same No. 4,483
, No. 914, No. 30-31, JP-A-60-14033
No. 5, pages (17) to (18), JP-A-1284-1984
No. 38, No. 60-128436, No. 60-12843
Reducing agents described in No. 9, No. 60-128437, etc. can be used. Also, JP-A-56-138736 and JP-A-57
Reducing agent precursors described in US Pat. No. 4,330,617 and the like can also be used.

Combinations of various reducing agents can also be used, such as those disclosed in US Pat. No. 3,039,869.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 01 to 20 mol, particularly preferably 0.1 to 10 mol.

In the present invention, a compound that activates development and simultaneously stabilizes images can be used in the photosensitive element. For specific compounds preferably used, see U.S. Patent Nos. 4 and 5.
No. 00,626, columns 51-52.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples include Research Disclosure magazine, December 1978 issue 24-2.
Azoles and azaindenes described on page 5, JP-A-59
Nitrogen-containing carboxylic acids and phosphoric acids described in Japanese Patent Application No. 168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, Japanese Patent Application No. 60-22
Acetylene compounds described in No. 8267 are used.

In the present invention, the photosensitive element may contain an image toning agent if necessary. Specific examples of effective toning agents include compounds described in JP-A-61-147244. In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, it is necessary to use a light-sensitive element having at least three silver halide emulsion layers each sensitive to a different spectral region. good. For example, a combination of three layers: a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, a green-sensitive layer,
There are combinations of red-sensitive layers and infrared-sensitive layers. Each of these photosensitive layers may be divided into two or more layers, if necessary.

The photosensitive element used in the present invention may contain various additives known for use in heat-developable photosensitive elements and layers other than the photosensitive layer, such as a protective layer, an intermediate layer, an antistatic layer, an antihalation layer, and a dye fixing layer. It can have a release layer, a matte layer, etc. to facilitate peeling off from the element. Various additives are listed in Research Disclosure Magazine, 1978, 6.
Plasticizers, matting agents, sharpness-improving dyes, antihalation dyes, surfactants, optical brighteners, anti-slip agents, etc. described in Japanese Patent Application Laid-open No. 61-88256, pages 9 to 15 of the Monthly issue, There are additives such as antioxidants and anti-fading agents.

In particular, the protective layer usually contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant and an ultraviolet absorber. Each of the protective layer and the intermediate layer may be composed of two or more layers.

Further, the intermediate layer may contain a reducing agent to prevent color fading and color mixing, an ultraviolet absorber, and a white pigment such as titanium dioxide. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of improving sensitivity.

In the present invention, an image formation accelerator can be used in the photosensitive element and/or the dye fixing element. Image formation promoters include promoting redox reactions between silver salt oxidizing agents and reducing agents;
It has functions such as promoting reactions such as generation of dye from dye-donating substance, decomposition of dye, and release of diffusible dye, and promotion of movement of dye from the light-sensitive element layer to the dye fixing layer. The functions include bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents,
It is classified as a surfactant, a compound that interacts with silver or silver ions, etc. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. For details on these, please refer to JP-A No. 6
No. 1-93451.

In the present invention, various development stoppers can be used in the photosensitive element and/or dye fixing element in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that Specifically, examples include acid precursors that release acids when heated, electrophilic compounds that undergo a substitution reaction with coexisting bases when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors (for example, No. 60-108837, No. 60-1
No. 92939, No. 60-230133 or No. 60-
Compounds described in No. 230134 and the like. ) Compounds that release mercapto compounds upon heating are also useful; for example, JP-A-61-67851, JP-A-61-61-
No. 147244, No. 61-124941, No. 61-1
No. 85743, No. 61-182039, No. 61-18
No. 5744, No. 61-184539, No. 61-188
There are compounds described in No. 540 and No. 61-53632.

A hydrophilic binder can be used for the photosensitive element and/or dye fixing element of the present invention. As the hydrophilic binder, the aqueous colloid mentioned for the back layer can be used.

In the present invention, the binder is applied in an amount of 20 g or less per bag, preferably 10 g or less, more preferably 7 g or less.
g or less is appropriate.

The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is 1 cc or less of solvent per 1 g of binder, preferably 0.
．． A suitable amount is 5 cc or less, more preferably 0.3 cc or less.

The constituent layers (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive element and/or dye fixing element of the present invention may contain an inorganic or organic hardening agent.

Specific examples of hardening agents include those described in JP-A-61-147244 and JP-A-59-157636, page (38), and these can be used alone or in combination.

Further, in order to promote dye transfer, a hydrophilic thermal solvent that is solid at room temperature and soluble at high temperature may be incorporated into the photosensitive element or dye fixing element.

The hydrophilic thermal solvent may be incorporated into either the photosensitive element or the dye fixing element, or may be incorporated into both. Further, the layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto. Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alnyls, oximes, and other heterocycles. Further, in order to promote dye transfer, a high boiling point organic solvent may be contained in the photosensitive element and/or the dye fixing element.

The support used in the photosensitive element in this invention is one that can withstand processing temperatures. Common supports include glass, paper, polymer films, metals and their analogues, as well as JP-A-61-14
7244 as a support can be used.

The photosensitive element and/or the dye fixing element may be in the form of an electrically conductive heating layer as a heating means for thermal development or diffusion transfer of the dye.

The transparent or opaque heating element in this case can be made using conventionally known techniques for producing resistive heating elements.
As a resistance heating element, there are two methods: a method using a thin film of an inorganic material exhibiting semiconductivity, and a method using a thin film of an organic material in which conductive fine particles are dispersed in a binder. Materials that can be used in these methods include those described in Japanese Patent Application No. 151,815/1984.

In the present invention, the method of coating the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer, dye fixing layer, and other layers is described in columns 55 to 56 of U.S. Pat. No. 4,500,626. method can be applied.

Radiation, including visible light, can be used as a light source for imagewise exposure to record an image on the photosensitive element. In general, light sources used for normal color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, light emitting diodes (LEDs), etc.
No. 244 and U.S. Pat. No. 4.500.626, No. 56J.
The light source described in 1 can be used.

In the present invention, the steps of thermal development and dye transfer may be performed independently or simultaneously. Further, it may be continuous in the sense that development is followed by transfer in one step.

For example, (1) after imagewise exposing and heating the photosensitive element,
There are two methods: (2) a method in which the dye-fixing elements are stacked and heated if necessary to transfer the mobile dye to the dye-fixing element; and (2) a photosensitive element is imagewise exposed, and the dye-fixing elements are stacked and heated.

The methods (1) and (2) above can be carried out in the substantial absence of water or in the presence of a trace amount of water.

The heating temperature in the heat development step can be developed at about 0°C to about 250°C, and particularly useful is about 0°C to about 180°C. When heating in the presence of a trace amount of water, the upper limit of the heating temperature is below the boiling point. When the transfer process is performed after the heat development process, the heating temperature in the transfer process can be in the range from the temperature in the heat development process to room temperature, but in particular, it is 50°C or higher, which is about 10°C lower than the temperature in the heat development process. More preferably up to temperature.

A preferred image forming method in the present invention involves heating in the presence of a trace amount of water and a base and/or a base precursor after or simultaneously with image exposure, and at the same time as development, diffusion is generated in a portion corresponding to or inversely corresponding to a silver image. The coloring matter is transferred to the dye fixing layer. According to this method, the production or release reaction of the diffusible dye proceeds extremely quickly, and the movement of the diffusible dye to the dye fixing layer also proceeds rapidly, so that a high-density color image can be obtained in a short time.

The amount of water used in this embodiment is at least 0.1 times, preferably 0.1 times or more, the weight of the total coating film of the light-sensitive element and dye fixing element, and the amount of solvent is equivalent to the maximum swelling volume of the total coating film. A small amount of less than the weight (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film) may be sufficient.

The state of the film during swelling is unstable, and depending on the conditions, there is a risk of local bleeding.To avoid this, use water equivalent to the volume at maximum swelling of the total coating film thickness of the photosensitive element and dye fixing element. It is preferable that the amount is less than or equal to . Specifically, 1g per square meter of the total area of the photosensitive element and dye fixing element.
A range of 50 g to 35 g, particularly 2 g to 35 g and even 3 g to 25 g is preferred.

The base and/or base precursor used in this embodiment can be incorporated into both the photosensitive element and the dye fixing element.
It can also be supplied dissolved in water.

In the above embodiment, the image forming reaction system contains, as a base precursor, a basic metal compound that is sparingly soluble in water, and a compound that undergoes a complex formation reaction with a metal ion constituting the sparingly soluble metal compound using water as a medium; Preferably, the pH of the system is raised by reaction of these two compounds upon heating.

Here, the image reaction system means a region where an image forming reaction occurs. Specifically, layers belonging to both the photosensitive element and the dye fixing element can be mentioned. If two or more layers are present, any of the layers may be used.

The poorly soluble metal compound and the complex forming compound need to be added at least in separate layers in order to prevent them from reacting before the development process. For example, in a so-called monosheet material in which a photosensitive element and a dye-fixing element are provided on the same support, it is preferable that the above-mentioned two additive layers are separate layers, with one or more layers interposed between them. A more preferred embodiment is one in which the poorly soluble metal compound and the complex-forming compound are contained in layers provided on separate supports. for example,
It is preferable that the poorly soluble metal compound is contained in the photosensitive element and the complex-forming compound is contained in the dye fixing element having a support separate from the photosensitive element. In the present invention, the complex-forming compound may be supplied in the form of being dissolved in water, which is present in addition to the dye-fixing element. Slightly soluble metal compounds are disclosed in JP-A-56-17483.
It is desirable to contain it as a fine particle dispersion prepared by the method described in No. 0, No. 53-102733, etc., and the average particle size thereof is preferably 50 microns or less, particularly 5 microns or less. The poorly soluble metal compound may be added to any layer of the photosensitive element, such as the photosensitive layer, intermediate layer, or protective layer.
It may be added by dividing into more than one layer.

When the poorly soluble metal compound or complex-forming compound is contained in the layer on the support, the amount added is as described above.

The method for adding water to the photosensitive layer or dye fixing layer is as follows:
For example, there is a method described in JP-A-61-147244.

As a heating means in the development and/or transfer process, a hot plate, an iron, a hot roller, etc. are used.
There is a method described in No. 7244. In addition, layers of conductive materials such as graphite, carbon black, metals, etc. are applied to the photosensitive element and/or the dye fixing element,
This conductive layer may be heated directly by passing an electric current through it.

The pressure conditions and method of applying pressure when overlapping the photosensitive element and the dye fixing element and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 1472-1986.
The method described in No. 44 can be applied.

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, JP-A No. 59-75247,
Apparatuses described in Japanese Patent No. 59-177547, No. 59-181353, No. 60-18951, Japanese Utility Model Application No. 116734-1980, etc. are preferably used.

(2) Specific effects of the invention According to the invention, the film properties of the dye fixing element can be improved. In particular, it is possible to prevent curling, which is concave toward the dye fixing layer, at medium temperature and low humidity.

Such an effect becomes remarkable when applied to a dye fixing element for OHP, which is made of a transparent plastic film having a thickness of 80 to 150 mm. In other words, OHP
This is to prevent the dye fixing layer (surface) side from being heated and dried by the projection light and curling toward the surface side when observing with a dye fixing element placed thereon. Furthermore, such curling may occur when the dye fixing layer or its adjacent layer contains salts such as bases or base precursors, or polysaccharides such as dextran and pullulan to prevent precipitation of the salts, especially when both are contained. However, by applying the present invention, curling can be prevented.

This effect is due to the inclusion of colloidal silica, which increases the elastic modulus of the back layer film (that is, makes it hard), and even if the front film shrinks and tries to curl toward the front side on the OHP, the back layer film will not This is thought to be due to the fact that it is difficult to stretch.

Conventionally, the occurrence of curling has been dealt with by increasing the thickness of the back layer, but in dye fixing elements that have a dye fixing layer containing bases, base precursors, etc., and polysaccharides such as dextran, Insufficient effects can be obtained, and furthermore, when the film thickness is increased, curling toward the back side becomes large and poor conveyance becomes noticeable, but the present invention solves this problem.

Furthermore, when dye-fixing elements are stored in layers, transfer of bases, base precursors, etc. from the front surface to the back surface due to contact between the front and back surfaces of the dye-fixing element is suppressed.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown, and the effects of the present invention will be explained in further detail.

Example The method for making the first layer emulsion will be described.

A well-stirred gelatin aqueous solution (20 g of gelatin and 3 g of sodium chloride in 10,100 O of water)
An aqueous solution 600111 containing sodium chloride and potassium bromide and an aqueous silver nitrate solution (0.59 mol of silver nitrate dissolved in water 600) were simultaneously added at equal flow rates for 40 minutes. Added.
In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a were added.

Chemical sensitization was performed at 60° C. by adding 20 mg of 7-chitrazaindene. The yield of emulsion was 600 g.

Next, I will talk about how to make the emulsion for the third layer.

Add 600 ml of an aqueous solution containing sodium chloride and potassium bromide to a well-stirred aqueous gelatin solution (20 g of gelatin and 3 g of sodium chloride in 1,000 ml of water kept at 75°C) and an aqueous solution of silver nitrate (600 ml of water). (in which 0.59 mol of silver nitrate was dissolved) and the following dye solution (I) were simultaneously added at equal flow rates over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % of bromine) having a dye adsorbed thereon with an average grain size of 0.35 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a were added.

Chemical sensitization was performed at 60° C. by adding 20 mg of 7-chitrazaindene. The yield of emulsion was 600 g.

methanol
400m1 Next, we will explain how to make a silver halide emulsion for the fifth layer.

A well-stirred aqueous gelatin solution (20 g of gelatin and ammonia dissolved in 1000 ref of water and kept at 50°C) was mixed with an aqueous solution 1000111 containing potassium iodide and potassium bromide and an aqueous silver nitrate solution (in 1000 ml of water). (1 mole of silver nitrate dissolved in the solution) was added at the same time while keeping the pAg constant.

In this way, a monodispersed silver iodobromide octahedral emulsion (5 mol % of iodine) with an average grain size of 0.5 μm was prepared.

After washing with water and desalting, 5 mg of chloroauric acid (tetrahydrate) and 2 mg of sodium thiosulfate were added to perform gold and sulfur sensitization at 60°C. The yield of emulsion was 1.0 kg.

This article describes how to make organic silver salts.

Organic silver salt (1) This article describes how to make benzotriazole silver emulsion.

28 g of gelatin and 13.2 g of benzotriazole were dissolved in 300 g of water. Add this solution to 40
The mixture was kept at ℃ and stirred. Add 17g of silver nitrate to this solution and 10g of water.
011M solution was added over 2 minutes.

The pH of the benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Then the pH was adjusted to 6.30.
Accordingly, a benzotriazole silver emulsion with a yield of 400 g was obtained.

Organic silver salt (2) 20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were mixed with 10 g of 0.1% aqueous sodium hydroxide solution.
00 ml and 200 ml of ethanol.

This solution was kept at 40°C and stirred.

A solution prepared by dissolving 4.5 g of silver nitrate in 200 ml of water was added to this solution over 5 minutes.

The pH of the dispersion was adjusted and excess salt was removed by settling. Thereafter, the pH was adjusted to 6.3 to obtain a dispersion of organic silver salt (2) in a yield of 300 g.

Next, how to make a gelatin dispersion of a dye-donating substance will be described.

5g of yellow dye-donating substance (A), auxiliary developer (
0.2 g of D), 0.2 g of antifoggant (E), and 0.2 g of sodium succinate 2-ethyl-hexyl ester sulfonate as a surfactant. sg, triisononyl phosphate was weighed out, 15 ml of ethyl acetate was added thereto, and the mixture was heated and dissolved at about 60° C. to form a homogeneous solution.

After stirring and mixing this solution and 40 g of a 10% solution of lime-treated gelatin, the mixture was heated to 10,000 g for 10 minutes using a homogenizer.
Dispersion was performed at rpm. This dispersion is called a yellow dye-providing substance dispersion.

A dispersion of a magenta dye-providing substance and a dispersion of a cyan dye-providing substance were prepared in the same manner as above, except that the magenta dye-providing substance (B) or the cyan dye-providing substance (C) was used. Had made.

(C) Auxiliary developer (D) Antifoggant (E) Color light-sensitive materials having a multilayer structure as shown in Table 1 were prepared using these materials.

Next, a dye fixing material having the structure shown in Table 2 was prepared.

In addition, when adding colloidal silica to the first layer of the back layer, Snowtex C (manufactured by Shirataki Kagaku) was used. The amounts of gelatin and colloidal silica added are shown in Table 3. Colloidal silica was added as a solid. The amount added is expressed in parts by weight based on 100 parts by weight of gelatin.

The film thickness of the first layer of the back layer is also shown.

Table 2 *1) Surfactant A *2) Surfactant B Shi+13 *3) Mordant *4) Oil phase compound Nireofusu 95 (manufactured by Ajinomoto ■) 11
1-! I = and Δ 5 of sodium dodecylbenzenesulfonate to 100 g of 10% gelatin aqueous solution
% aqueous solution was added, and 20 g of Rheophos [Co., Ltd.] 95 (manufactured by Ajinomoto ■) was added, and the mixture was blended with a homoblender.

A dispersion of oil droplets prepared by emulsifying and dispersing for 6 minutes in Orpm was added to the coating liquid of the dye fixing layer (first layer).

*5) Hardener A *6) Surfactant C *7) Silicone oil droplets *4) The same except that Rheophos 95 (manufactured by Ajinomoto) was replaced with silicone oil (dimethylpolysiloxane). It was prepared as follows.

*8) Benzoguanamine resin (JIS-7215/Durometer D hardness >90, average particle size 5.6-110-
The size of the photosensitive material prepared as described above was larger than A4, and the size of the dye fixing material was A4.

This dye fixing material was heated and dried with a hair dryer at 25°C.
Curling was measured after conditioning at 25% RH overnight.

Curling was measured when the sample was left at 25° C. and 20% R) for one day, and when it was then placed on an OHP and observed.

In addition, curling was measured by placing the dye-fixing material on a horizontal surface with the dye-fixing layer (front) side facing up, and measuring the height from the horizontal surface with upward curl as + and downward curl as -. For upward curls, the average value of the heights at both ends was taken as the average value.

On the other hand, these dye-fixing materials were passed through an actual thermal development transfer device to test their transportability.

The thermal development transfer device used in the test of this example will be explained with reference to FIG.

As shown in FIG. 1, the photosensitive material 3 is stored in a photosensitive material storage section 4, and the photosensitive material 3 is sent out as needed.
This photosensitive material 3 may be in the form of a roll or a cut sheet, but if it is in the form of a roll, it is cut into the required length by a cutter 5.

Thereafter, it is sent to the exposure section 6, wound around the exposure drum 6E, and conveyed to the exposure source 62 by rotation.

The exposed photosensitive material 3 rotates in the opposite direction to the rotation when being wound around the exposure drum 61, and is sent to the development transfer section 7. Next, the photosensitive material 3 is transferred to an exposure section 6 and a development transfer section 7.
Water application (12g/m
2) To be done.

Then, a sensor (
(not shown), the pickup roller 12 of the dye-fixing material supply device 1 starts rotating, and the dye-fixing material 2 is sent to the development and transfer section 7 by the transport rollers 13 to 16 and the guide plates 17 to 19.

In this case, as shown in FIG. 2, the dye fixing materials 2 are stored in a stacked state in the storage section 11. When the sensor detects that the photosensitive material 3 has come to a predetermined position as described above, the pickup roller 12 rotates in the direction of the arrow shown in the figure based on this signal. sent from.
The dye fixing material 2 sent out in this manner is superimposed on the photosensitive material 3 that has been transported as described above in the development and transfer section 7, and is heated and developed and transferred while being transported by the heat rollers 21 to 26. The photosensitive material 3 is transported to a post-peeling section 9 and is peeled off from the dye-fixing material 2.

The dye fixing material 2 on which the image has been formed is then transported to a drying section 10.
transported to and dried. Further, the photosensitive material 3 is disposed of in a photosensitive waste box 30 via the photosensitive material transport section 20.

Put the dye fixing materials 101 to 107 into the tray 11,
This was installed in the dye fixing element supply device 1 of the thermal development transfer device shown in FIG.

The apparatus shown in FIG. 1 was operated in a room adjusted to conditions of 25° C. and 5 to 10% RH.

When processing through a thermal development transfer device, troubles in transporting some of the heat rollers in the device were investigated.

These results are shown in Table 3.

From the results in Table 3, it can be seen that when the dye fixing material of the present invention is used, curling is prevented, and the tip folding observed in dye fixing materials 106 and 107 with increased film thickness does not occur.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of a thermal development transfer device, and FIG. 2 is a sectional view of a dye fixing material storage section. Explanation of symbols 1...Dye fixing material supply device, 2...Dye fixing material, 3...Photosensitive material, 4...Photosensitive material storage section, 5...Cutter, 6...Exposure section,
7...Development transfer section, 8...Water application section,
9...Peeling part, 10-...Drying part,
11-... Storage section 12-... Pick up roller, 13-16... Conveying roller, 17-19... Guide plate, 20... Sensitive material conveying section, 30... Sensitive material disposal box, 21-26...heat roller,

Claims (1)

[Claims] On one side of the support, there is at least one dye fixing layer containing a mordant and a base and/or a base precursor, and on the opposite side there is a back layer containing at least one hydrophilic colloid. A dye fixing element having
A dye fixing element characterized in that at least one of the back layers contains colloidal silica.