JPH0283544A - Strippable photographic image receiving element for color diffusion transfer process - Google Patents

Abstract

PURPOSE:To improve the physical properties of an image receiving element as a film in both wet and dry states by adding a halotriazine hardening agent to a coating liq. for a first timing layer so that the agent is contained in the layer by 0.12-0.24g/m<2>. CONSTITUTION:A halotriazine-based hardening agent is added to a coating liq. for a first timing layer so that the agent is contained in the layer by 0.12-0.24g/m<2>. A soln. of a polyisocyanate compd. having two or more isocyanato groups in one molecule is applied between the first timing layer and a second timing layer so as to prevent the peeling of a film from an image receiving element when the element is separated from a photosensitive element after development. The above hardening agent contained in the first timing layer can prevent the exfoliation of a film at the time of printing. The physical properties of the image receiving element contg. a strippable layer as a film in both wet and dry states are remarkably improved and especially the printability is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a peelable color diffusion transfer photographic image receiving element.

(Prior Art) It is well known that in the color diffusion transfer method, after a diffusible dye or dye developer is transferred as a result of development with an aqueous alkaline developer, a neutralizing layer is provided to lower the surrounding pH. ing. However, due to the provision of a neutralizing layer, the pH
If the pH decreases early, development will be hindered, so to prevent this, it is well known that a layer to temporally control the pH decrease, a so-called "timing layer," is used in conjunction with the neutralization layer. There is.

In peel-apart (beer-apart) color diffusion transfer processes, an image-receiving element is used in combination with a light-sensitive element comprising at least one light-sensitive silver halide emulsion layer and an associated dye image-providing compound; After the photosensitive element has been imagewise exposed, it is processed (developed) with an alkaline processing composition. After the diffusible dye formed from the dye image-providing compound as a result of development diffuses imagewise into the image-receiving element, the image-receiving element is peeled (separated) from the photosensitive element. In this way, in the peel-off type color diffusion transfer method, compared to the non-peel type (for example, the so-called mono-sheet type), a stronger mechanical effect called "peeling" is applied, so the image-receiving element is subject to "more severe film physical properties". is required.

One of the required physical properties of the film is glabellar adhesion of each layer constituting the image receiving element. If the contact between the eyebrows is insufficient, a portion of the image receiving element may peel off when the image receiving element is separated from the photosensitive element, significantly impairing the value of the photograph.
For example, the timing layer of a peel-off type color diffusion transfer photographic image-receiving element is composed of two layers, a first timing layer and a second timing layer, and the first timing layer has a lower temperature as the temperature decreases.
If you design it so that it takes a long time for H to decrease,
Even when photographing and developing at low temperatures, a relatively high image density can be obtained, which is preferable in terms of reducing the development temperature dependence (expanding the development temperature latitude). However, when separating the image receiving element and the photosensitive element, The drawback is that the timing layers tend to peel off easily.

(Problem to be Solved by the Invention) In order to solve this problem, an intermediate layer is provided between the first timing layer and the second timing layer.
No. 232,548.

The provision of this intermediate layer can solve the problem of peeling of the film within the image receiving element when separating the image receiving element and the photosensitive element.
It has been found that when an image-receiving element (so-called print) on which an image is formed is engraved, the film becomes more likely to peel off. 2. Description of the Related Art In the field of identification documents such as passports and student ID cards, it is common practice to stamp predetermined information on each print.

When a print is engraved or during the storage period after being engraved, the print is rubbed and the film peels off, which is a serious problem that can impair the validity of the certificate. In an image receiving element without the above intermediate layer, film peeling due to marking can be reduced to some extent, but as described above, the film is likely to peel within the image receiving element when separating the image receiving element and the photosensitive element.

As a means for improving the adhesion between the first timing layer and the second timing layer without coating an intermediate layer, as described in JP-A-61-248041, the second timing layer and It is stated that a solution of a bifunctional or higher-functional isocyanate compound is applied between the first timing layer (this coating solution does not have enough film-forming ability and thickness to become a substantial intermediate layer after drying). It was found that this method does not cause the film to peel off within the image-receiving element when separating the image-receiving element and the photosensitive element, and also reduces film peeling to some extent when printing is engraved, but it is still at an insufficient level. be. The two problems we have to solve are 1) the film physics of the image-receiving element when separating the image-receiving element and the photosensitive element after development, i.e. in this case the image-receiving element absorbs the developer and swells and is in a weft state; 2) The physical properties of the film when marking a print, that is, the physical properties of the film when it is in a dry state.

As a result of our earnest efforts, we have found a means to solve the above two problems.

(Means for solving the problem) On the support, from the support, 1) a neutralization layer, 2) a second timing layer, 3) a layer that does not have the ability to form a film thereon, and has two layers in one molecule. In a peel-off color diffusion transfer photographic image-receiving element having an overcoat of the above polyisocyanate compound and having 4) a first timing layer, 5) a mordant layer, and 6) a release layer, a halotriazine hardener is added to .12g/M~0.2
The above objectives have been achieved by a peel-off laquer diffusion transfer photographic image receiving element characterized in that the first timing layer is contained in the first timing layer coating solution at an amount of 4 g/rd.

That is, as described in JP-A No. 61-248041, the second
A film of the image receiving element when the image receiving element and the photosensitive element are separated after development by applying a solution of a polyisocyanate compound having two or more isocyanate groups in one molecule between the timing layer and the first timing layer. To prevent peeling, apply 0.0% halotriazine hardener to the first timing layer.
By adding 12 g/r/~0.24 g/m, it was possible to prevent the film from peeling off when a print was engraved.

A known example of adding a hardening agent to the first timing layer is JP-A-61-20036.
The known example uses various types of hardening agents to strengthen the interlayer adhesion of each layer, and uses a polymer with high hydrophilicity and film-forming ability as an intermediate layer between the first timing layer and the second timing layer. It states that it is preferable.

We have found, as shown in the Examples below, that the print passability of the print is not improved at all in the presence of an interlayer.

Furthermore, even in the absence of an intermediate layer, halotriazine hardeners and glutaraldehyde are effective in improving the engraving suitability of prints, but no improvement effect was found with hardeners such as dimethylol compounds and carbodiimides.

Although glutaraldehyde was effective in improving the engraving suitability, it was found to have an adverse effect on photographic performance, as shown in the Examples below. In the end, the solution described above is a system that does not degrade photographic performance, does not cause film peeling within the image receiving element when the photosensitive element and image receiving element are separated after development, and does not cause film peeling when a print is engraved. It turns out that this is the system that can be described.

Is the amount of halotriazine hardener added 0.12g/n? It was found that in smaller areas, the effect of improving the engraving suitability of the print is very small, and even in the area of more than 0.24 g/tri, the effect of improving the engraving suitability of the print is small and the photographic performance is impaired.

The neutralizing layer used in the present invention is a layer containing an acidic substance in an amount sufficient to neutralize the alkali carried over from the treatment composition. Preferred acidic substances are those containing an acidic group with a pKa of 9 or less (or a precursor group that provides such an acidic group upon hydrolysis), and more preferably oleic acid as described in U.S. Pat. No. 2,983,606. higher fatty acids, polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in U.S. Pat. No. 3,362,819; Copolymers of acrylic acid and acrylic esters as disclosed in U.S. Pat. No. 4,139,383 and Research Disclosure ml 6
102 (1977).

In addition, U.S. Patent No. 4,088,493, Japanese Patent Application Laid-open No. 1987-
No. 153,739, No. 53-1,023°, No. 53-
4.540, 53-4,541, 53-4,5
Acidic substances disclosed in No. 42 and the like can also be mentioned.

Specific examples of acidic polymers include ethylene, vinyl acetate,
Copolymers of vinyl monomers such as vinyl methyl ether and maleic anhydride and their n-butyl esters, copolymers of butyl acrylate and acrylic acid, cellulose,
These include acetate and hydrogen phthalate.

The polymeric acid can be used in combination with a hydrophilic polymer. Examples of such polymers include polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polymethyl vinyl ether, and the like. Among these, polyvinyl alcohol is preferred.

Furthermore, a polymer other than a hydrophilic polymer, such as cellulose acetate, may be mixed with the polymeric acid.

The amount of polymeric acid applied is controlled by the amount of alkali developed on the photosensitive element. The equivalent ratio of polymer acid to alkali per unit area is preferably 0.9 to 2.0. If the amount of polymeric acid is too small, the hue of the transferred dye may change or staining may occur in the white background area, and if it is too large, problems such as a change in hue or a decrease in light resistance may occur. A more preferable equivalent ratio is 1.0 to 1.3. If the amount of hydrophilic polymer mixed is too large or too small, the quality of the photograph will deteriorate. The weight ratio of hydrophilic polymer to polymeric acid is from 0.1 to 10, preferably from 0.3 to 3.0.

The thickness of the neutralizing layer is generally 5 to 30 microns.

Additives can be incorporated into the neutralizing layer of the present invention for various purposes. For example, hardening agents known to those skilled in the art can be added to harden this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. can be added to improve the brittleness of the film. Other antioxidants, fluorescent brighteners,
It is also possible to add dyes, development inhibitors, precursors thereof, etc. for blue tinting.

As the second timing layer, for example, Research Disclosure + -rResearch Disclosure
e J Magazine 11h12331 (vol. 123, July 1974)
), U.S. Pat. No. 3,753,764, 4. 029
．． Examples include blends of cellulose acetate and maleic anhydride copolymers, as described in No. 849.

The degree of acetylation of cellulose acetate (% by weight of acetic acid produced by hydrolyzing 100 g of cellulose acetate) is suitably about 45 to 60%, preferably 50 to 55%. When a maleic anhydride-based copolymer is blended with cellulose acetate, it is appropriate to use from about 1 to about 20% by weight of the copolymer based on the cellulose acetate, preferably from 2 to 10% by weight.

The thickness of the second timing layer is suitably between about 1 and 20 mm;
Preferably it is 2 to 10μ.

The second timing layer is dissolved in an organic solvent such as acetone or cyclohexanone (either alone or in combination) and coated on the neutralization layer.

The second timing layer can incorporate a development inhibitor or its precursor.

The polyisocyanate compound used in the present invention may be an aliphatic isocyanate, an aromatic isocyanate, or a mixture of both. Moreover, the number of isocyanate groups in the molecule may be two or more, and there is essentially no limit to the number.

Specific preferred examples of compounds are listed below, but the invention is not limited thereto.

(Compound 1) OCN(CHz)JCO (Compound 3) CH! 0CONH(CIri 6NCO CHsCHxC-CHzOCONH(CIlz) hN
c.

C1l gOcONII (C1l□)hNCO (compound 8) (compound 6) 0CN (CHz)JCNH (CHz)JCOC-NO(
CHz) JCO (Compound 10) (Compound 7) GO Book 0CN (CI!hCH C-0(CHi)tNc.

(Compound 11) (Compound 12) CN (Compound 13) GO The amount of application required for the polyisocyanate mentioned above to have the effect of strengthening the adhesive force between the eyebrows is 0.001
g/ffr~1. Og / rdka good* Shii,
Sarani preferably 0.01 g/M to 0.4 g
/rd coating amount. The polyisocyanate applied at this time may be one type or a mixture of two or more types.

In order to accelerate the reaction rate of isocyanate groups, tertiary amines such as triethylamine, diazabicyclooctane, triethanolamine, N-methylformoline, etc.
or dibutyltin laurate, cobalt octenoate,
Approximately 0.1 to 7 mol% of metal salts such as lead octenoate, tin octenoate, and zinc octenoate to polyisocyanate.
May be added.

In order to shorten the drying time, it is important to reduce the amount of polyisocyanate solution applied as mentioned above, but it is also better to increase the amount of drying air to the extent that it does not cause uneven air flow immediately after application. It is desirable to raise the drying temperature to an extent that does not cause deformation of the support.

The timing of applying the polyisocyanate solution applied to improve the adhesion between the eyebrows should be after the lower layer (e.g. neutralization layer) has been applied and dried.For example, when applying to a continuously running web. After the web is sent out and the lower layer is applied, it is dried and then wound up. Then, the polyisocyanate solution for improving adhesion may be applied again and dried, or the polyisocyanate solution may be applied and dried continuously after the lower layer is applied and dried.

There is no particular restriction on the method of applying polyisocyanate, but for example, gravure, bar code, extrusion hopper type, slide hopper type, etc. can be applied.

As a solvent for polyisocyanate, any inert and highly soluble organic solvent that does not react with isocyanate groups may be used, such as aliphatic or aromatic hydrocarbons, ketones, ethers, esters, etc. For example, acetone 2 methyl ethyl ketone, benzene, Toluene, tetrahydrofuran, dichloromethane, ethyl acetate, etc. can be used as solvents.

The first timing layer is, for example, Research Disclosure.
e J Magazine 15162 (Volume 151, November 1976)
, U.S. Patent No. 4,056,394, JP 53-726
Examples include polymer latex films described in No. 22 and the like. Specific examples of these polymer latexes include methyl acrylate, itaconic acid, and vinylidene chloride.
Original copolymer, ternary copolymer of acrylonitrile/acrylic acid/vinylidene chloride, ternary copolymer of styrene/butyl acrylate/acrylic acid, ternary copolymer of methyl acrylate/acrylic acid/vinylidene chloride, styrene/butyl acrylate/acrylic acid/N- Examples include a quaternary copolymer of methylol acrylamide, a ternary copolymer of methyl methacrylate/acrylic acid/N-methylol acrylamide, and the like. The average particle diameter of these latexes is suitably about 0.05 to about 0.4 microns, preferably 0.1 to 0.2 microns. The acid monomer content is preferably between 2 and 10 mol%.

Furthermore, instead of a water-dispersed polymer latex film, a film obtained by coating a polymer dissolved in an organic solvent can be used as the first timing layer.

Such polymers include copolymers in which one or more ethylenically unsaturated monomers copolymerizable with ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid) are combined; , JP-A No. 59-202463, and U.S. Pat. No. 4,297,431;
, 288゜523, 4,201,587, 4,
No. 229.516, JP-A No. 55-121438, No. 5
No. 6-166212, No. 55-41490, No. 55-
No. 54341, No. 56-102852, No. 57-14
No. 1644, No. 57-173834, No. 57-179
No. 841, West German Patent Application Publication (OLS) 2,910,2
No. 71, European Patent Application Publication EP 31957 A I
5Research Disclosure184
Examples include those described in No. 52, etc.

Examples of ethylenically unsaturated monomers include ethylene,
Propylene, l-butene, isobutyne, styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, vinylbenzylsulfonic acid sort, N,N,N-trimethyl-N-vinylbenzylammonium chloride, N,N-dimethyl -N-benzyl-N-vinylbenzylammonium chloride, α
- Methylstyrene, vinyltoluene, 4-vinylpyridine, 2-vinylpyridine, benzylvinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone, l-vinyl-2-methylimidazole, monoethylenically unsaturated aliphatic acids esters (e.g. vinyl acetate, allyl acetate), maleic anhydride, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. n-butyl acrylate, n-hexyl acrylate, nitroxyethyl acrylate, cyanoethyl acrylate, N , N-diethylaminoethyl acrylate, methyl methacrylate, n-butyl methacrylate,
Benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl methacrylate, methoxyethyl methacrylate, N.

N-diethylaminoethyl methacrylate, N.

N,N-)diethyl-N-methacryloyloxyethylammonium p-toluenesulfonate, N,N-diethyl-N-methyl-N-methacryloyloxyethylammonium p-)toluenesulfonate, dimethyl itaconate, monobenzyl maleate esters), amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. acrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, N-(N.

N-dimethylaminepropyl)acrylamide, N,N
, N-trimethyl-N-(N-acryloylpropyl)
Ammonium p-)luenesulfonate, sodium 2-acrylamido-2-methylpropanesulfonate, acryloylmorpholine, methacrylamide, N,N-dimethyl-N'-acryloylpropanediamine probionate betaine, N,N-dimethyl-N' -methacryloylpropanediamine acetate vequin), etc.

Preferred specific examples of the polymer for the neutralization timing layer will be given, but the invention is not limited thereto. (Copolymerization ratio is molar ratio) fi+ H3 H3 C)13 CH.

CH3 COOCI(3 COOCJ40tl ool COOCJs C00CxHaOHC0OH Preferably, the above (1) to (8) are preferred, and (1) to (3) and (8) are particularly preferred.

In addition, for timing layers made of these materials, for example, U.S. Patent No. 4,009,029, West German Patent @ (OLS)
2,913,164, 3,014.672, JP-A-54-155837, JP-A-55-138745, etc., and the development inhibitors and/or precursors thereof, as well as U.S. Pat. It is also possible to incorporate the hydroquinone precursor disclosed in No. 201,578, other additives useful for photography, or their precursors.

The thickness of the first timing layer is suitably between about 0.5 and about lOμ, preferably between 1 and 5μ.

The mordant layer used in the image receiving element of the present invention is preferably a gelatin layer containing a polymeric mordant.

Polymer mordants used in the present invention include secondary and tertiary mordants.
Polymers containing primary amino groups, polymers having nitrogen-containing heterocyclic moieties, polymers containing these quaternary cation groups, etc., with molecular weights of s, ooo to 200,000, especially io,
ooo~50,000.

For example, U.S. Patent Section 2,548,564;
No. 4,430, No. 3,148.061, No. 3,7
Vinyl polydine polymers and vinyl pyridinium cationic polymers disclosed in JP-A-56,814, etc.; JP-A-55-48210, JP-A-55-129346, U.S. Pat. Nos. 4.282.305 and 4.273 ,85
No. 3, No. 4.193,796, No. 4,228,257
No. 3,625,694, No. 3,859,096, No. 4.12838, British Patent Section 1,277 Polymer mordant crosslinkable with gelatin etc. disclosed in U.S. Patent No. 3,958,995, U.S. Pat. No. 54-115228, No. 54-145529, No. 54-126027,
Latex-type mordant or aqueous sol-type mordant disclosed in Japanese Patent Application No. 107411/1983; water-insoluble mordant disclosed in U.S. Patent No. 3,898,088; U.S. Patent No. 4,168 No. 976 (Unexamined Japanese Patent Publication No. 1983)
-137333) A reactive mordant capable of forming a covalent bond with the dye disclosed in the specification, etc.;
No. 09,690, No. 3,788,855, No. 3,
642゜482, same No. 3,488.706, same No. 3
557.066, 3.271,147, 3,271,148, JP 50-71332, 53-30328, 52-155528, 53
Examples include mordants disclosed in Japanese Patent No. 125 and No. 53-1024.

Other U.S. Patent Nos. 2,675,316 and 2.88
Mention may also be made of the mordants described in No. 2,156.

Among these mordants, those that are difficult to migrate from the mordant layer to other layers are preferred; for example, those that crosslink with a matrix such as gelatin, water-insoluble mordants, and latex dispersion (or aqueous sol) type mordants are preferred. .

The release layer used in the present invention is a layer for easily separating the photosensitive element and the image-receiving element after development processing while maintaining glossiness.Layer structure of the present invention from 1) neutralization layer to 5) mordant layer It has been found that layers to which gelatin or carboxymethylcellulose are added tend to become "cloudy" after development, or the processing solution tends to stick and remain partially.

However, it has been found that if a layer coated with a polymer represented by the general formula (1) described below is used for the purpose of peeling off, such drawbacks can be overcome.

Polymers for the release layer that form a uniform and good film even when applied in a thin layer are useful.

This film exhibits good adhesion to adjacent layers (for example, image-receiving layer) in a dry state before being developed.

In addition, this polymer is hydrophilic and alkali-swellable, and swells and softens when an alkaline processing solution is developed during development, freeing image-forming substances that accompany or diffuse in the processing solution. Because it is transparent, it does not interfere with image formation.After image formation (stable), when the image-receiving sheet is peeled off from the photosensitive sheet, it exhibits good peelability over a wide processing temperature range, and images that have often been a problem in the past. Remaining processing liquid on the top, so-called "powdering", cloudiness, uneven images,
Various points such as temperature lowering/lowering and color tone changes are improved.

Furthermore, since the polymer for the release layer of the present invention is a synthetic polymer, it has excellent stability over time during manufacture and storage.

Since the peeling layer can be applied using an organic solvent such as alcohol, one of the features of the present invention is that the drying load during film formation is small.

The release layer of the present invention may contain other substances, such as color toning agents, image stabilizers, antistatic agents, fluorescent whitening agents, matting agents, antifoggants, etc., as long as they do not impede the effects of the invention. You may.

If the film thickness of the release layer of the present invention is too thick, "clouding" will easily occur during low-temperature development processing, and if the film thickness is too thin, it will be difficult to process during long-term development processing. Approximately 0.001 g/nf ~ 1 due to increased liquid adhesion failure
．． Approximately Og/rrf is appropriate, preferably 0.
01 g/if to 0.5 g/rrf.

This coating amount is also important in that it does not substantially reduce the alkalinity of the processing solution. Therefore, the release layer used in the present invention should be clearly distinguished from a neutralization layer (a layer that neutralizes the high pH of the processing solution to a neutral state) often used in the diffusion transfer method.

A preferred example of the copolymer used in the release layer of the present invention can be represented by the following general formula (1).

General formula (1) % formula %) In the formula, X represents a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted alkyl group.

Y is a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, a -C-0-R1 group (where R1 is a substituted or unsubstituted alkyl group having 2 or more carbon atoms, or a substituted or unsubstituted alkyl group) aryl group), -0-C-R'' group (where Rz is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), -0-N-R' group, is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group (R3 and R4 may be the same or different), and A is the same as the ethylenically unsaturated monomer. Represents a repeating unit (monomer unit) derived from a polymerizable ethylenically unsaturated monocarboxylic acid or monocarboxylic acid salt.

X and y are the mole percentages of the monomer components in the copolymer, and have the following relationship:

x+y-100, O<x<60.40≦3+<100 Substituents for the above-mentioned substituted alkyl groups and substituted aryl groups include hydroxyl group, halogen atom (preferably chlorine atom), cyano group, alkyl group, aryl group, etc. can be mentioned.

Among the copolymers represented by the general formula (1), the following are more preferable. That is, in the formula, 2-12 substituted or unsubstituted alkyl group), -0-C-R" group (here, R1 is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms and r!), or R3R3 General formula (n) CHg -CHC0OR' and R4 are both hydrogen atoms or substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, and R3 and R4 may be the same or different. ).

In addition, regarding the molar percentage of the monomer component, y is 60 to
The case of 99 is preferable, and the case of 70 to 90 is more preferable.

Among Y, particularly preferred are -C-0-R' groups (where R1 is a substituted or unsubstituted alkyl group in which the alkyl residue has 2 to 6 carbon atoms, more preferably 3 to 5 carbon atoms);
, or -0-C-R1 group (R in 22 is a substituted or unsubstituted alkyl group in which the alkyl residue has 1 to 6 carbon atoms).

As a monomer that provides component A, the monomer represented by the following general formula (%) may be used in the form of a salt, and the cations forming the salt include alkali metal ions, alkaline earth ions, Examples include metal ions and ammonium ions.

Specific examples of this monomer are listed below representatively in the form of free acid.

Co,H cot.

cug=cn ■ C(hCHzCHgOCCHgCHiCOJcHz=c
-cus C(hcHzcHxOccl(tcHtcoMushroomH) Specific examples are listed (copolymerization ratios in compound examples represent mole percentages).

l.

(CHzCH-tn- -fCIItCHhrr- 7g 66.9℃ Cot-n-CJq CO□Na 2゜ )ChzCll - Masu Low C0z-n-CJq CH.

1+C■2ChT CO,ll -0,27°C Among the above monomers, it is particularly preferable to use acrylic acid and methacrylic acid.

-M formula) In addition to the above monomer components, as long as the Tg of the copolymer is less than 90'C, other copolymerizable monomer components (such as styrenes, specifically styrene, α - methylstyrene, 4-methylstyrene, etc.).

3゜ of the copolymer represented by the general formula (1) below. 1+CHzCH-tn- Cog-n-C4Hg 4゜ CH.

1+CH2C-)-TT- Cog-n-C,H.

(CHzCHh-r- CO□C1□CIl□OCCII□CIl□CO, 11
(C11□CH) Loaf 9.1°C CogH (C)ItCH-h-5-icozcn 6° 7° 8° To create a release layer using these copolymers, alcohols (e.g. methanol, ethanol, propatool, ethylene glycol, etc.), acetone, methyl ethyl ketone, acetonitrile, dioxane, formamide,
It may be dissolved in an organic solvent such as tetrahydrofuran or ethyl acetate alone or in a mixed solvent thereof, or in a mixed solvent with water and coated on a support by a conventional method.

In addition, the color diffusion transfer photographic unit is patented in West Germany under patent number 111.
(OLS) No. 3753970, for example, Japanese Patent Applications No. 63-22526 and No. 63-234.
93, 63-76859, 63-76860. Same 6
3-84666, Kentoku 7094, etc., are used.

Halotriazine hardeners include, for example, Japanese Patent Publication No. 47-6
No. 151, Japanese Patent Publication No. 47-33380, Japanese Patent Publication No. 48-3
No. 1937, Japanese Patent Publication No. 53-2726, Japanese Patent Publication No. 52-1
No. 27229, Special Publication No. 58-33542, Special Publication No. 1983
-12903, JP-A No. 60-205443, and U.S. Pat. No. 4,670°377, etc.; A water-soluble halotriazine hardener is applied, and if the first timing layer is prepared from a polymer solution dissolved in an organic solvent, a halotriazine hardener that is soluble in the solvent is applied.

The light-sensitive element used in combination with the image-receiving element of the present invention can be any conventionally known one, and generally comprises a support coated with at least one silver halide emulsion layer combined with a dye-providing compound. It is.

A compound that provides a diffusible dye (or a precursor thereof) to the mordant layer is used in combination with the silver halide emulsion. The compound may be any compound that releases or forms a diffusible dye or its precursor imagewise as a result of development, such as a dye developer that becomes diffusible in an alkaline solution or a compound that releases a diffusible dye as a result of coupling. Dye-releasing redox compounds, such as non-diffusible couplers that release dyes and dye-releasing redox compounds that release dye as a result of a redox reaction, can be either negative working or positive working.
positive working).

The dye-releasing redox compound that can be used in the present invention can be represented by the following general formula.

-DD Typical examples of the diffusible dye represented by D are cyan, magenta or yellow ab dyes.

Specific examples of Y include U.S. Pat. No. 3,928.312 and U.S. Pat.
No. 93,638, No. 4.076.529, No. 4.15
No. 2,153, No. 4,055,428, No. 4,053
, No. 312, No. 4,198゜235, No. 4.179,
No. 291, No. 4,149.892, No. 3,844,7
No. 85, No. 3゜443.943, No. 3,751,40
No. 6, No. 3.443.939, No. 3,443,940
No. 3,628.952, No. 3,980,479, No. 4,183,753, No. 4,142,891,
4,278,750, 4,139°379, 4,218,368, 3,421.964, 4
, No. 199,355, No. 4゜199.354, No. 4,
135.929, 4.336,322, 4.1
No. 39,389, JP-A-53-50736, JP-A No. 51-
No. 104343, No. 54-130122, No. 53-1
No. 10827, No. 56-12642, No. 56-161
No. 31, No. 57-4043, No. 57-650, No. 5
No. 7-20735, No. 53-69033, No. 54-1
No. 30927, No. 56-164342, No. 57-11
It is described in No. 9345, etc.

Among Y of the negative dye-releasing redox compound, a particularly preferred group is an N-substituted sulfamoyl group (the N-substituent is a group derived from an aromatic hydrocarbon ring or a heterocycle).

The coating amount of the dye-providing compound used in the present invention is approximately 1Xl.
A range of 0-' to 1X10-'' mol/rf is suitable, preferably 2 XIO''' to 2 X10-' mol/rrf.

The silver halide emulsions used in the present invention are hydrophilic colloidal dispersions of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide or mixtures thereof.

Photographic emulsions use sensitizing dyes to capture relatively long-wavelength blue light.
It may also be spectrally sensitized to green, red or infrared light.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, styryl dye,
Hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used.

Examples of developers that can be used to develop exposed silver halide are as follows.

Hydroquinones, aminophenols, phenylenediamines, pyrazolidinones [e.g., l-phenyl-3-pyrazolidinone, dimezone, 1-p-tolyl-4,4-dihydroxymethyl- 3-pyrazolidinone, 1-p-)dyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidinone,
1-(4'-methoxyphenyl)-4-methyl-4-hydroxymethyl-3-pyrazolidinone, l-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidinone] and the like.

Of those listed herein, black and white developers (among them pyrazolidinones) are particularly preferred as they generally have properties that reduce stain formation in the image receiving layer more than color developers such as phenylene diamines.

The processing liquid contains a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium phosphate, and has a pH of 9.
It preferably has an alkali strength of 11.5 or more.

The processing solution may contain antioxidants such as sodium sulfite, ascorbate, piperidinohexose reductone, and may also contain silver ion concentration regulators such as potassium bromide. It may also contain viscosity increasing compounds such as hydroxyethyl cellulose and sodium carboxymethyl cellulose.

The alkaline processing solution may also contain a compound that promotes development or dye diffusion (for example, a compound such as benzyl alcohol).

In addition, the alkaline processing liquid contains a white pigment (for example, Ti0z or Z) for forming the background (white reflective layer) of the transferred image.
nO, etc.), or it may contain a black pigment (carbon black, etc.) or a compound that exhibits a black color under alkalinity and changes to colorless when the pH decreases so that development can be completed in a bright place. good.

Preferably, the alkaline treatment is contained in a pressure rupturable container.

Supports for photographic elements that can be used in the present invention are preferably those that do not undergo significant dimensional changes during processing.

Examples of such supports include plastic films and laminated films thereof such as cellulose acetate, cellulose acetate butyrate, polyethylene terephthalate, polystyrene, and polypropylene used in ordinary photographic materials, synthetic paper, baryta, and polyethylene. Resin-coated paper coated on both sides with such α-olefin polymers is used, and among them, polyolefin-coated paper, which is particularly inexpensive, is preferably used.

In particular, this support is generally used with an image-receiving layer provided thereon, but when polyolefin-coated paper is used because heat resistance is required during the coating and drying process of the image-receiving layer, the surface The polyolefin resin layer used is preferably polypropylene, a blend of polypropylene and polyethylene, high-density polyethylene, or a blend of high-density polyethylene and low-density polyethylene. In particular, from the viewpoint of cost and suitability for lamination, high-density polyethylene and low-density polyethylene are preferred. Most preferred is a blend with

The blend ratio of high-density polyethylene and low-density polyethylene is 1/9 to 9/1, preferably 2/8 to 8/1.
2, most preferably used in 3/7 to 7/3. Although there is no particular restriction on the molecular weight of the polyethylene, it is desirable that both high-density polyethylene and low-density ethylene have a melt index of 1.0 to 40 g/10 minutes and have extrusion suitability.

Examples of white pigments used in the surface polyolefin resin layer include titanium dioxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, lithopone, alumina white, zinc oxide, silica, antimony trioxide, and titanium phosphate. It will be done. These can be used alone or in combination.

Titanium dioxide is particularly preferred because it has a large hiding power.Titanium dioxide may be of the rutile type or anatase type, and these may be used alone or in combination.

Further, it may be made by a sulfuric acid method or a chlorine method.

In addition, titanium oxide can be treated with inorganic surfaces such as hydrous alumina treatment and/or hydrous silicon dioxide treatment, or with organic surface treatments such as trimethylolmethane, trimethylolethane, trimethylolpropane, and 2,4-dihydroxy-2-methylpentane. A coating-treated material or a siloxane-treated material such as polydimethylsiloxane can be used as appropriate.

The filling rate of titanium oxide is preferably 10% by weight to zO% by weight from the viewpoint of hiding power.

The coating thickness of the polyolefin layer is about 15μ to 100μ, preferably about 25μ to 50μ.

Coloring dyes, pigments, fluorescent whitening agents, etc. are used in the polyolefin layer as necessary.

Regarding the base paper used in the present invention, paper made of natural valves, paper made of synthetic valves made of polyethylene or polypropylene, paper made by mixing natural valves and synthetic valves, or paper made from a mixture of natural valves and synthetic valves. Various materials can be conveniently used, such as paper made by combining paper.

Since the polyolefin-coated paper used in the present invention is required to have good smoothness, a base paper made of bulb fibers having a fiber length distribution disclosed in JP-A No. 58-68037 is conveniently used.

The basis weight of the base paper is preferably 50 g/rrl to 250 g/nf, especially 100 g/m2 to 180 g/rrf, and the thickness is preferably 50 μ to 250 μ, especially 100 μ to 180 μ. .

It is also desirable to use base paper that has been made even smoother by applying a thermal calender during the papermaking process.

Furthermore, the water content of the base paper is preferably 5% to 9% by weight, preferably 6% to 7.5% by weight.

To enable development in a bright room, the support may be laminated with polyethylene containing a light-shielding agent such as carbon black, or a water-soluble polymer (gelatin or polyvinyl The amount of the light-shielding agent added may be adjusted depending on the sensitivity of the light-sensitive material to be light-shielded.

(Example) Example 1 As an example of the present invention, image receiving sheets (A) to (
E) was created.

Image-receiving sheet (A) Paper support: 150μ thick paper laminated with 30μ polyethylene on both sides.

The polyethylene on the image-receiving layer side is 10% nitrogen oxide by weight based on ethylene Tan is added in a dispersed manner.

Back side: (a) Light shielding layer of carbon black 4.0g/nf and gelatin 2.0g/nf.

(b) Titanium oxide 8.0 g / a, gelatin 1.0 g
/rrf white layer.

(C) Protective layer of gelatin 0.6 g/I.

They are coated in the order of (a) to (C).

Image-receiving layer side: (1) Neutralization layer containing 22 g/nf of acrylic acid-butyl acrylate (mole ratio 8:2) copolymer having an average molecular weight of 50,000.

(2) Cellulose acetate with an acetylation degree of 51.3% (the weight of acetic acid released by hydrolysis is 0.513 g per 1 g of sample) and styrene-maleic anhydride (molar) with an average molecular weight of about 10,000. comparison
:1) A second timing layer containing 4.5 g/i of copolymer in a weight ratio of 95:5.

(3) Interlayer containing 0.4 g/I of poly-2-hydroxyethyl methacrylate.

(4) Polymer latex obtained by emulsion polymerization of styrene-butyl acrylate-acrylic acid-N-methylol acrylamide in a weight ratio of 49.7/42.3/4/4, and methyl methacrylate/acrylic acid/N-methylol. A first timing layer comprising a polymer latex emulsion polymerized with acrylamide at a weight ratio of 93:3:4 and a solid content ratio of 6:4, with a total amount of 1.6 g/rd. .

(5) As a coating aid (n・30) with the following repeating unit using Polymer mordant 3.0g/n (and gelatin) Image-receiving layer coated with 3.0, /Po.

x+y:zsets:s:9°(6) Release layer containing 0.04 g/ml of butyl methacrylate/acrylic H (molar ratio 15:85) copolymer.

Image-receiving sheet (B) 2-hydroxy 4,6-
0.16 Na salt of dichloro-1,3,5-)riazine
The image-receiving sheet (A) was prepared in the same manner as the image-receiving sheet (A) except that g/% was added.

Image-receiving sheet (C) Except for layer (3) of image-receiving sheet (A), and in layer (4), 0.16 g of Na salt of 2-hydroxy-4,6-dichloro-1,3°5-triazine was added. The image receiving sheet (A) was prepared in the same manner as the image receiving sheet (A) except that rrl was added.

Image-receiving sheet (D) Except for the layer (3) of the image-receiving sheet (A), 0.05 g/r of polyisocyanate compound 3 without film properties was added instead.
The image receiving sheet (A) was prepared in the same manner as the image receiving sheet (A) except that rr coating was performed.

Image-receiving sheet (E) Except for the layer (3) of the image-receiving sheet (A), 0.05 g/rd* of polyisocyanate compound 3 without film properties was added instead.
0.16 g/i of Na salt of 2-hydroxy-4゜6-dichloro-1,3,5-)riazine was added to the layer (4).
It was prepared in the same manner as image-receiving sheet (A) except that f was added.

Polyisocyanate compound 3 CHtOCONH (CIri6NCO CHsCHtC-CHtOCONH4(CHt) hN
c.

CHxOCONH (CHt) 68CO 1-L A photosensitive sheet was prepared by coating each layer on a polyethylene terephthalate transparent support as follows.

Back side: (a) Carbon black 4.0g/nf
and a light-shielding layer containing 2.0 g/rrf of gelatin.

Emulsion layer side: (1) 0.44 g/nr of the following cyan dye-releasing redox compound, 0.09 g/nr of tricyclohexyl phosphate, 0.008 g/nr of 2.5-di-pentadecylhydroquinone, and gelatin. 0
．． A layer containing 8g/rd.

(2) Red-sensitive red-sensitive inscribed positive silver bromide emulsion (silver amount 1.03g/resistant, gelatin 1.28/m2), the following nucleating agent 0°04mg/n
(and a red-sensitive emulsion layer containing 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.13 g/rd.

Structural formula (3) A layer containing 0.43 g/rrl of 2,5-di-t-pentadecylhydroquinone, 0.1 g/rrl trihexyl phosphate, and 0.4 g/rrl gelatin.

(4) Magenta dye-releasing redox compound of the following structural formula I (0,218/m2), magenta dye-releasing redox compound of structural formula H (0,11 g/m2), tricyclohexyl phosphate (0,08 g/m2), 2. 5-layer containing one pentadecyl hydroquinone (0,009 g/l) and gelatin (0,9 g/l).

Structural formula■ (5) Green-sensitive inner layer type direct positive silver bromide emulsion (silver content: 0.82 g/po, gelatin: 0.9 g/po)
nf), a green-sensitive emulsion layer containing the same nucleating agent as layer (2) (0.03 g/A) and 2-sulfo-5-n-pentadecylhydroquinone sodium salt (0.08 g/E).

(6) Same layer as layer (3).

(7) Yellow dye-releasing redox compound with the following structure (0,53g/nf), tricyclohexyl phosphate (0,13g/nf), 2,5-di-pentadecylhydroquinone (0,014g/nf) and gelatin A layer containing (0.7 g/a).

Ho 5-n-pentadecylhydride Rokinone sodium salt (0.07g /if).

(9) Layer containing 1.0 g/rri of gelatin.

(8) Blue-sensitive blue-sensitive inscribed positive silver bromide emulsion (silver amount 1.09 g/I, gelatin 1.1 g/I), same nucleating agent as layer (2) (0,0
After exposing the photosensitive sheet to light from the emulsion layer side through a color test chart, the clearance between the photosensitive sheet and the image receiving sheet was 100.
Spacers were placed on both sides of the image-receiving sheet so that the distance was .mu.. The unfolding was carried out with the help of a pressure roller, and the stacked sheets were pulled out at an angle closer to the side (about 3 m when actually measured) than when they passed through the roller. The developing process was carried out at 15°C, and the photosensitive sheet and image receiving sheet were peeled off 3 minutes after the process. Image receiving sheet) All of (A) to (E) had problems (they could be peeled off).

The obtained prints were left at 23°C and 60% RH for 6 hours, and then stamped using a motorized automatic embossing stamping machine model M-4 (manufactured by Yamakoshi Kosakusho Co., Ltd.). The results are shown in Table 1. has been done.

Table 1. Suitability for engraving prints. Table 2 shows the situation when the print was pulled diagonally downward at an angle of 40 degrees, the development process was carried out at 15°C, and the photosensitive sheet and image receiving sheet were peeled off 3 minutes after processing. ing.

Table 2 Peeling status when pulled diagonally at 40° From Tables 1 and 2, it is clear that a polyisocyanate compound without film properties is applied between the first timing layer and the second timing layer, and the first timing It can be seen that in image receiving sheet 1-(E) in which a halotriazine hardener was added to the layer, the film did not peel off when peeled off after the development process, and the suitability for printing was significantly improved.

Example 2 Image receiving sheets (E) to (H) having the following configurations were prepared.

Image receiving sheet) (E) Image receiving sheet of Example 1 (E)
Image-receiving sheet (F) 2-hydroxy-4,6 in layer (4) of image-receiving sheet (E)
A sample was prepared in the same manner as in (E) except that 0.16 g/day of glutaraldehyde was added instead of the Na salt of -dichloro-1,3,5-)riazine.

Image receiving sheet (G) 2-hydroxy-4,6 on the eyebrows (4) of the image receiving sheet (E)
An image-receiving sheet (E) was prepared in the same manner as the image-receiving sheet (E) except that 0.16 g/rl'f of N,N'-dimethylol urea was added instead of the Na salt of -dichloro-1,3,5-) riazine.

Image-receiving sheet (H) 2-hydroxy-4,6 in layer (4) of image-receiving sheet (E)
-0.16g/n' of dicyclohexylcarbodiimide instead of Na salt of dichloro-1,3,5-1-riazine
It was prepared in the same manner as image-receiving sheet (E) except that f was added.

Exposure was carried out in the same manner as in Example 1, and the photosensitive sheet and processing solution were combined.
It was pulled diagonally at an angle of 40° and developed.

The development process was carried out at 25°C, and the photosensitive sheet and image-receiving sheet were peeled off after 90 seconds. All of the image receiving sheets (E) to (H) could be peeled off without any problem.

Also, pull it out through the rollers at an angle close to the side, and
Color density (so-called Dsin) of the white part of the print obtained by peeling off the photosensitive sheet and image-receiving sheet after 90 seconds at 5°C
The measurement results are shown in Table 3.

Table 3: Color density of white area (Dmin) In addition, the sample for which the above Dmin was measured was measured at 25°C and 45%RH.
After standing for 3 hours, the stamping was performed using the same equipment as in Example 1, and the results are shown in Table 4.

Table 5 Addition of hardener! (Continued) The exposed photosensitive sheet, processing liquid, and image receiving sheet were combined and pulled out through rollers at an almost horizontal angle. Each development process was performed at 23°C. After 100 seconds at 23°C, the photosensitive sheet and image receiving sheet were peeled off and the resulting print was
Table 6 shows the results of a marking test after being left at 3°C and 145% RH for 2 hours.

From Tables 3 and 4, the image receiving sheet (E) is DiIII.
It can be seen that ll is low and the suitability for printing is improved.

Example 3 Image receiving sheets (E) and (1) to (N) were created.

Image-receiving sheet (E) Image-receiving sheet (E) of Example 1 Image-receiving sheets (I) to (N) 2-hydroxy-4,6 in layer (4) of image-receiving sheet (E)
-Dichloro-1,3,5-) Recipients were prepared in the same manner as in (E) except that Na salt of riazine was added in the amount shown in Table 5.

Table 5: Amount of hardener added Table 6: Suitability for engraving prints From Table 6, the amount of halotriazine hardener added is o, x2
It can be seen that the marking suitability is significantly improved in the range of g/d to 0.24 g/nf.

(Effects of the Invention) The structure of the present invention, especially the image receiving element including the release layer, has significantly improved film physical properties in both wet and dry states, and particularly improves the suitability for marking.

In the present invention, a neutralization layer, a second timing layer,
In an image-receiving element formed by applying a first timing layer, a mordant layer and a release layer in this order, particularly in an image-receiving element in which the release layer is made of the above-mentioned specific polymer, the second timing layer is applied thereon. It is characterized in that all of the above-mentioned problems with film physical properties are solved by coating a specific polyisocyanate compound and further containing a specific range of halotriazine in the coating solution for the first timing layer. .

Patent Applicant: Fuji Photo Film Co., Ltd. Ending month 1, 1988, Indication of the case 2, Title of the invention 3, Person making the amendment Relationship to the case 1988 Patent Application No. 23J-60

Claims (1)

[Claims] On the support, in order from the support, 1) a neutralization layer, 2) a second timing layer, 3) overcoating thereon with two or more polyisocyanate compounds in one molecule, which do not have the ability to form a film, In a peel-off color diffusion transfer photographic image-receiving element having a 4) first timing layer, 5) a mordant layer, and 6) a release layer, a halotriazine hardener was added at 0.12 g/m^2 to 0.
．． A peel-off type laquer diffusion transfer photographic image-receiving element, characterized in that the first timing layer is contained in the coating solution at a concentration of 24 g/m^2.