JPH02275447A - Color diffusion transfer photographic sensitive material - Google Patents

Abstract

PURPOSE:To increase a transfer rate and to decrease the change in the density during green preservation by synthesizing any of specific compds. in an acid catalyst in an inert atmosphere of nitrogen, etc., and incorporating such polymer into the photosensitive material. CONSTITUTION:This photosensitive material has photosensitive silver halide emulsion layers combined with dyestuff donative compds. which can release diffusible dyestuffs, an image receiving layer which can mordant the diffusible dyestuffs and a neutral layer. The photosensitive material contains at least one kind of the polymers obtd. by the polycondensation of at least one kind respectively of formulas I and II in the presence of the acid catalyst. In the formula I, G denotes a hydroxyl group or a group which forms the hydroxyl group by an alkaline hydrolysis; n denotes >=2 integer; R1, R2 denotes a substituent on a benzene ring. In the formula II, R2 denotes a hydrogen atom, alkyl group, etc.; R4, R5 denote an alkyl group. Color mixing is prevented in this way and the time for perfection of images is short with the thin film thickness. The film strength is high and the adhesive strength to the adjacent layer is high to obviate the peeling near an intermediate layer.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color diffusion transfer photographic light-sensitive material, and particularly to a color diffusion transfer photographic light-sensitive material that can quickly complete an image and has strong film strength.

(Prior art) In a color diffusion transfer photographic light-sensitive material, the oxidized herbal medicine produced during development of one photosensitive layer diffuses to other color-sensitive photosensitive layers or layers containing dye-releasing compounds, causing color mixing. It is well known that the interlayer gold film is removed to prevent this from occurring. Therefore, it is well known that this intermediate layer contains a color mixing prevention agent (or color stain prevention agent).

Typical color mixture inhibitors include hydroquinone compounds, such as U.S. %FI-2,360.2yo, U.S. %FI-2,360.2yo, U.S. %FI-2,360.2yo, U.S. %FI-2,360.2yo, U.S. %FI-2,360.2yo, U.S. %FI-2,360.2yo, U.S. 3.940, No. 70, etc., mono-roalkylhydroquinones are disclosed in U.S. Pat. West German % revised publication col ≠ 7tL? Monobranched alkylhydroquinones are listed in U.S. Patent No. 2.721.619,
Same co, 732.300, same 31 ≠ 3.22 Hiro, same 3゜700, Hiro! No. 3, UK t￥j liver 7ta 2. /Hiroo No., JP-A-1989-/Taro μ3r No., Ta3-2 Tako R No.
The dialkyl-equipped hydroquine was installed on the Takoro Kotaro No. 37, the special public Kokoro Kokoro No. 2 in 1977, and the American hour hand 2. ≠
/I! , No. 6/3 contains arylhydroquinones, and US Pat. Nuclear-substituted hydroquinone, and U.S. Pat. In addition, hydroquinones substituted with sulfonamide groups are also disclosed in JP-A-Sho! No. 7-22, 237 propose hydroquinones containing an electron-withdrawing group, such as hydroquinone substituted with a carbamoyl group.

Sufficient diffusion resistance as a color mixture prevention agent! For example, in dialkyl hydroquinone yarn, the total number of carbon atoms in the dialkyl part must be greater than IQ, and such hydroquinone compounds become oil-like. There are many things. If a large amount of oily compound is contained in the intermediate layer, the film may become soft or seep out and be mixed into other polishing materials, so the binder that holds the film (e.g. gelatin)
It becomes necessary to use a large amount of , resulting in a thick film.

In order to increase the commercial value of the 10,000 color diffusion transfer photographic material, it is very important that the time from the start of processing to the completion of the image is short, that is, the completion of the image is quick. Therefore, various efforts have been made to speed up image completion, among them making the photosensitive material thinner (thinning the layer), that is, shortening the diffusion distance for the dye to reach the image-receiving layer. is the most important and effective. It is effective to reduce the amount of binder (e.g. gelatin) in each layer to make the layer thinner, but if the binder is completely destroyed, for example: 1) the strength of the film will decrease, 2) the adhesion with adjacent layers will decrease. It will peel off,
The holding power of emulsions, emulsions, etc. present in the 0 layer decreases, and during long-term storage, compounds migrate to the 1- layer at the @ contact, resulting in deterioration of film quality.

Among these disadvantages, (1) the strength of the film and (2) the adhesion with adjacent layers are particularly problematic in the case of photographic materials that are peeled off from the image-bearing partial sound film unit after the image is completed. In other words, if the intermediate layer (color mixing preventive agent) is peeled off from its adjacent layer with the same force as the peeling layer provided for peeling, or with a weaker force, the peeling layer will not be able to reliably peel off, and the intermediate layer will not peel off. It will come off. If the intermediate layer peels off, the image in the image-receiving layer will not be visible (this will result in a fatal failure).

Among the various peeling methods, an example in which the film quality of the intermediate layer is the most important is described in JP-A-63-221.6≠No.

The basic structure of this method includes: l) a white support, 2) an image-receiving layer,
3) Peeling layer, hiro) cyan coloring material layer, j) silver halide emulsion layer, 6) intermediate layer, 7) magenta coloring material layer, silver halide emulsion layer, ri) intermediate layer, IQ) yellow coloring material layer , //)
/S silver halogenide emulsion layer, /c) Since it is a protective layer, peeling a
You cannot even see the image unless you can reliably peel it off with T-. However, when a conventional intermediate layer is used, the intermediate layer often peels off, and it has been strongly desired to strengthen the film quality of the intermediate layer.

Further, even in the methods described in Japanese Patent Application Laid-open No. JP-A-JP-, J-co-Q-7-co-7, etc., peeling in the intermediate layer was a major defect.

10,000, Tokko Sho≠j-763! No., same≠r-j36F7
No., Japanese Patent Publication No. 10-130410 and British Special ff/,
330. In the product I-type (integrated type) described in No. 2≠, etc., and in the normal beer apartment method, there is a strong demand for increasing the image completion speed.
There was a need for an intermediate layer (color mixing prevention layer) that could be made thinner without degrading film quality.

It is effective not only to make the intermediate layer itself thinner, but also to make the intermediate layer such that it is possible to remove the isolation layer for preventing any mixing of the intermediate layer and the dye-providing compound layer. The purpose of the isolation layer described in Japanese Patent Publication No. 60/JLJ7 etc. is to improve the shelf life of photosensitive materials, and its purpose is to prevent the mixing of metals between the intermediate layer and the dye-providing compound layer during raw storage. If the intermediate layer is difficult to mix with the donor compound layer, the isolation layer becomes unnecessary, and it has also been desired to have such an intermediate layer that has good shelf life.

(Problems to be Solved by the Invention) The objects of the present invention are to prevent color mixing in a color diffusion transfer photographic light-sensitive material, to have a thin film, quick image completion time, strong film strength, and good adhesion to adjacent layers. An object of the present invention is to provide a color diffusion transfer photographic material that has strong adhesive properties and does not peel off near the intermediate layer.

(Means for Solving the Problems) The present inventors have discovered that the above object can be effectively achieved with the following photosensitive element.

That is, the object of the present invention is to provide a color diffusion transfer having at least a light-sensitive silver halide emulsion layer combined with a dye-providing compound capable of releasing all of the diffusible dye, an image-receiving layer capable of mordanting the diffusible dye, and a neutralizing layer. In a photographic light-sensitive material, a color diffusion transfer photographic light-sensitive material characterized by @ containing at least one kind of polymer obtained by polycondensing at least one kind of each of the following general formulas (I) and (11) under an acid catalyst can be used. achieved.

In the formula, G represents a hydroxyl group or a group capable of generating a hydroxyl group by alkaline hydrolysis, and n represents an integer of 2 or more. However, G may be the same or different, and Celsius may also be the same. Furthermore, RI R2 may be the same or different (representing a substituent group on the benzene ring).

In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a heterocyclic group, an acyl group, a carboxyl group, or a formyl group.

In the formula, RR represents an alkyl group, which may be the same and different in temperature. Further, RR may be connected to form a ring.

General formulas (1) and (it) will be explained in detail below.

G is a human mixi group or a group that generates a hydroxyl group by hydrolysis or the like. Examples of substituents of the human mixi group that generate hydroxyl L5 upon hydrolysis include acyl groups (such as acetyl groups and benzoyl groups), oxycarbonyl groups (such as ethoxycarbonyl groups, benzylox7carponyl groups, and tert-7thyroxy groups). carbonyl thread or phenoxycarbonyl group], carbamoyl group (e.g. N,N-dimethylcarbamoyl group, N,N-diethylcarbamoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, benzenesulfonyl group, etc.), 3-ketobutyl group , a substituted aminomethyl group (for example, N,N-dimethylaminomethyl tail or l).

! -diketopyrrolidinomethyl group, etc.) and phthalide group.

RR is a hydrogen atom, a hydroxyl group or a substitutable group. Examples of such 7"l include halogen atom, cyano group, sulfo group, carboxyl group, alkyl group, aryl group, aralkyl group, acylamino group, amino group, sulfonamide group, alkoxy group, alkylthio group, arylthio group, Carbamoyl group, sulfamoyl group, alkylsulfonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkoxysulfonyl group, aryloxysulfonyl group, carbamoylamino group, sulfamoylamino group, carbamoyloxy group, alkoxycarbonylamino group , aryloxycarnylamino group. Each of these groups may be independently substituted. Also, when R1 and R2 are adjacent to each other on a benzene ring, they are condensed to form a carbocyclic or heterocyclic ring. may be formed.

R3 is a linear, branched or cyclic alkyl group (including substituted alkyl groups), an aryl group such as a phenyl group (including an It-substituted phenol group), a benzyl group, an aralkyl group such as 7-enethyl, or an oxygen group. , nitrogen-containing ring, sulfur-containing ring, oxygen-containing -
Represents a nitrogen ring, a heterocyclic ring such as a sulfur-containing nitrogen ring, and an aful group such as an acetyl group or a benzoyl group.

RR represents a straight, branched, p- or cyclic alkyl group (including substituted alkyl groups) tl-; Further, R and R may be condensed via an alkyl group, an aryl group, a nityl group, a thioether group, etc. to form a complete carbocyclic ring.

Furthermore, a substituent is substituted with R-H.

Halogen atom, nitro group, alkoxy group (including substituted alkoxy group), -N)icOR6 group (R is alkyl group (including substituted alkyl group), phenyl group (including substituted phenyl group), aralkyl group (substituted (including Aralkyl Fund), -N) 1802 R6 (R6 has the same meaning as above), -8OR6 (R6 has the same meaning as above), -8
02R6 (16 has the same meaning as above), a group (RR may be the same or different, a hydrogen atom, an alkyl group <
(including W-substituted alkyl groups), phenyl groups (including substituted phenyl groups), aralkyl groups (including substituted aralkyl groups), amino groups (which may be substituted with alkyl groups), hydroxyl groups and hydrolyzable groups. Examples include groups that form a hydroxyl group.

In addition, examples of substituents for monosubstituted alkyl groups, substituted alkokene groups, substituted phenyl groups, and substituted aralkyl groups among the substituents substituted by R1 to R3 include hydroxyl groups, nitro groups,
Alkoxy group having 1 to about ≠ carbon atoms, -NH8O2E (8 represented by 6 (R6 has the same meaning as above), -het (group represented by COR (R6 (RR8 has the same meaning as above), -8O2
R (R has the same meaning as above), -CUR (R has the same meaning as above),
Examples include a halogen atom, a cyano group, and an amide group (which may be substituted with an alkyl group).

- maximum (I) °C Preferably G represents a hydroxyl group and n represents 1.

R1, RH may be the same or different and are preferably hydrogen atoms, hydroxyl, alkyl groups (including those with # substituents. Preferably carbon numbers /~/!. For example, methyl, ethyl, isopropyl, methyl , n-hexyl,
octyl, nonyl, dodecyl, comethoxyethyl, benzyl allyl), alkoxy group (2 groups having j substituents. Preferably carbon number /~/10, for example, methyl,
ethyl, isopropyl, n-methyl, n-hexyl, octyl, nonyl, dodecyl, λ-methoxyethyl, benzyl), aryl group (including gold as a substituent), preferably 6 to 1 carbon atoms, e.g. phenyl, p-toI
0-hydroxyphenyl, α-naphthol), sulfonamide group (including those in which all substituents meet. Preferably carbon number/-/2°, for example, methyl, ethyl, inpropyl, n-butyl, n-hexyl, nonyl, n)"decyl, phenyl, p-tolyl, p-methquinphenyl),
Acylamino group (including gold, having a substituent group) Preferably, the number of carbon atoms is 1 to 2°, such as acetyl, propionyl,
n-butyl, benzoyl, p-dolcle 1-fi.

Among the above general formula CI), preferred compounds have the general formula <II
I), (IV), and more preferred compounds are represented by C■).

In H (general formula <1ll), <IV), RU has the same meaning as above. ) In general formula (U), R is preferably a hydrogen atom or an alkyl group (including all substituents).

Preferably carbon number 1 to /10, for example, methyl, ethyl, impropyl, n-butyl, n-hebutyl, n-octyl, n-undecyl, n-dodecyl, aryl, benzyl, cinnacil), phenyl group (@substituent '!il- including those having 6 to 1 carbon atoms, preferably phenyl, p
-n-butylphenyl, p-cyanophenylt p-
chlorenyl, m-tolyl), heterocycle (with substituent η″
Including those who do.

Preferably 3 to 10 carbon atoms. For example, λ-pyridyl, coimidazolyl, cofuryl, λ-thiophene).

tt4R5 represents an alkyl group (including those having a substituent, including gold, preferably carbon number/~g, methyl, ethyl, isopropyl, butyl).

Specific examples of (1) and (11) are shown below, but of course the present invention is not limited thereto.

1-/　　　　　　　　　l-λ H ■−μ ■－／／ 1-/ko −j -A 1-/3 1-/Hiroshi ■-to 1-/ yo 1-/, G ■-ta 1-i.

H SuH H U1″i ■-77 1-/ri H ■−λ0 0t( H ■-ta 1-// ■-72 ■-/f ■-22 (Jl-1 -r 1-i.

■-23 1-/ 1-J ■-yo ■-/3 11-/Hiroshi 11-/G CH3/ ■−2≠ ■-2 ■−μ H-+ 1-i’y ■-／　r 1-/ri ■−λ0 1-2/ ■-22 ■-23 -24t ■-37 H ■-33 11-3 Hiro C) i30 ■-2! ■-26 ■-27 -2r -2F ■-3 ■-36 ■-37 1-31r 1-Jri ■-Hiro O The polymer of the present invention is synthesized by the following method.

That is, the polymer of the present invention can be obtained by stirring the compound of the general formula ( ) and the compound of -maximum (2) under an inert gas flow of nitrogen or the like in a homogeneous organic solvent in the presence of an acid catalyst and subjecting them to a condensation reaction under heating conditions. It will be done.

The method for synthesizing the polymer of the present invention will be described in detail below.

The usage ratio of (I) and (1) used in the present invention will be explained in detail.

The usage ratio of compound (n) used in the present invention is CI)
The molar ratio of the compound to the compound is preferably in the range of o,r to 2°0, more preferably in the range of 0.7 to i,r.

The molecular weight of the polymer of the present invention is that of the compound (1) and (II)
It depends on the usage ratio of the compound (It), and when you want to obtain a higher molecular weight product, the usage ratio of the compound (It) is
, r or more.

However, if the ratio of the compound (II) used is 7 or more, the substitution reaction with the hydroxyl group of the compound (1) tends to occur, and the resulting resin may have fewer hydroxyl groups. Not preferable.

Specific examples of acidic catalysts used when synthesizing the polymer of the present invention include sulfuric acid, hydrochloric acid, perchloric acid, nitric acid, phosphoric acid,
Various complexes of boron trifluoride with inorganic protic acids such as p-toluenesulfonic acid, memensulfonic acid, maleic acid, acetic acid, formic acid, etc., boron trifluoride, boron trifluoride ether complexes, etc. Among these acidic catalysts, it is preferable to use protonic acids.

Note that the amount of acidic catalyst used is o relative to the phenols mentioned above.
, i to 70 mole, but the amount used varies depending on the strength and type of acid used as a catalyst.

Solvents used when synthesizing the polymer of the present invention include alcohols, ethers, ketones, esters,
Organic solvents such as amides are used, and it is particularly necessary to select a solvent in which the polymer produced by the reaction can be dissolved.

The solvents in which the polymer is soluble are shown below. Alcohols include methanol, ethanol, propatool, 2-propanol, getanol, methoxyethanol, /-methoxy-coprobanol, λ-methquine-7-propanol, ethoxyethanol, ethoxyethanol, methoxyethoxyethanol, and ethers. Examples include dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diptyl ether, etc. Ketos include acetone, methyl ethyl ketone, methyl isopropyl ketone, etc. Esters include metochine ethyl acetate, ethoxyethyl acetate, butoxyethyl acetate Examples of the amides include iN, N-dimethylformamide, dimethylacetamide, and dimethylsulfoxide, but the present invention is not limited thereto.

Regarding the reaction concentration, it is preferable that the total charge weight of the compound (I) and the compound (n) is 10 to 70% by weight based on the amount of solvent used, and especially -〇 -10 times is preferable.

Regarding the reaction temperature, the compound of the polymer U(I) of the present invention and the compound of (11) are mixed in an inert atmosphere such as nitrogen in the presence of the acid catalyst,
It is produced in the above solvent under heating. The reaction temperature is preferably from 3o'c to iro'c or the boiling point of the solvent, particularly from ≠00c to 1ooo
It is preferable to react in the range 1 of 0c.

Polymers using at least one of each of general formulas (1) and (II) may be polymerized by condensation using (1) and (U), or several types of (I) and (II). May be used together.

Furthermore, in order to change the properties (solubility, molecular weight, etc.) of the polymer, any compound may be added during or after the polymerization.

Examples of such compounds that change the properties of polymers include the following, but of course they are not limited thereto.

Various solvents, acids (inorganic, organic), bases (inorganic, organic), phenols, salts (inorganic, organic), epichlorohydrin,
Melamine, licunin, chroman, indene, kalman,
Thiophene, polyamide compounds, fatty acid amides, polyvinyl alcohol, polyvinyl compounds, esters, acid nolides, /SO-genated acyalkyl rubonic acids Among the polymers used in the photographic light-sensitive material of the present invention, compounds represented by -maximum (I) The content is io~ri!
Weight percent is preferred.

When the polymeric antifouling agent used in the present invention contains a long chain alkyl (having 6 or more carbon atoms) in the polymer, it has a weighted average molecular weight of /, ooo-r, o.

Q is preferred. Moreover, when long-chain alkyl Kanakura is not used, a weight average molecular weight of i,ooo or more is preferable. Also, especially J,
000 or more is preferable. Furthermore, long-chain alkyl can also be introduced into the polymer obtained by condensation through a polymer reaction.

Next, a method for synthesizing a typical polymer of the present invention will be specifically described.

<Synthesis Example 1> Synthesis of Polymer 1 Cateryl 4tta, og<o, Hiro θ mol), n-octylaldehyde dimethyl acetal 12.7g (0,
4), and l-methoxy-2-propertool/
KoQI and Toluyev! 09 was placed in a reaction vessel under gxii and stirred at room temperature. There, 3. sulfuric acid is added as a catalyst. ri g<o
, o4L mol) was added, and heating was gradually started in a water bath. The reaction was carried out for 3 hours at a pass temperature≠Q0C.

300 ml of ethyl acetate was added to the reaction solution cooled to room temperature, and extraction and washing with water were performed three times. Thereafter, the ethyl acetate solution was dried over magnesium sulfate, passed through, concentrated, and dried using a vacuum pump.

Yield v] I, yield 5F 1.1% X average molecule Meng Yu, io.

Dispersion (MW/MN) J, / However, the coulometric average molecular weight was determined by gel/(-Miei 7 Yon chromatography (GPC).The measurement conditions for GPC were: Tosoh TSK-GEL as Tosoh HLCrOλθ type GPC1 separation column; 2 (≠, 0OOH, 2,0
OOH), T)iF (flow rate/, 0rnl as eluent)
The measurement was carried out by determining the absorption wavelength of UV absorption (2 nm) and the column temperature (o0c).

Polystyrene was used as the sample.

<Synthesis Example 2> Synthesis of Polymer 2 Hydroquino 733.09 (0.3 mol), n-dodecylaldehyde dimethyl acetal 6.

/fl (0.3 mol), and l-methoxy-cope o/
The mixture was placed in a reaction vessel under a nitrogen stream and stirred at room temperature. Then sulfuric acid is added as a catalyst.

(g<o, oi mol) was added, and the rest of the reaction was carried out in the same manner as in Example 2.

Further, the results of Examples 4 to 8 are shown in the table below, in which the ratio of n-dodecylaldehyde dimethyl acetal used relative to the molar ratio of no-hydroquinone was completely changed in the same manner as in Example 3.

(Table 1) Synthesis 1fll 3 > Synthesis of polymer r hydroquinone! 7.21ICo, zx mol), benzaldehyde dimethyl acetal 71, 1rjl (0,12 mol), and l-methoxycobro/enor iro,!
i! The mixture was placed in a container under a nitrogen atmosphere and stirred at room temperature.

Sulfuric acid is used as a catalyst! , /y(o, oz mol)'e was added, and heating was gradually started in a water bath. The bath temperature was set at ro0c, and the reaction was carried out over time and cooled to room temperature. l-methoxy-2-propatool 10 in the reaction solution
All 0 ml of the solution was added and dissolved, and the solution was reprecipitated into a water tank with stirring in an agitator. Separate all sediments and wash with water 2 times
After repeating ~3 times, drying was performed using a vacuum dryer.

Yield //717, Yield''4 Tat, Taty weight average molecule i
k, 2hiro, 200 Dispersion (MW/MN) J, / <Synthesis Example 4> Synthesis of Borimata Hydroquinone 33. Ni'! ! (0.31 mol), p
-n-butoxybenzaldehyde diethyl acetal 7
2. /17 (0.31 mol), and l-methoxy-2-
The mixture was placed in a reaction vessel under a nitrogen atmosphere and stirred at room temperature. There, sulfuric acid λ, ri(
0.03 mol) was added thereto, and heating was gradually started using a water bath. The temperature of the pass was set at ♂θ0C, and the reaction was carried out for a long time and then cooled to room temperature. l-methoxy7- in the reaction solution,
3. Add and dissolve 2-pro-ξnol in water and stir the solution with an agitator. Reprecipitated into OIl.

The precipitate was washed from door to door, and the washing sound was repeated 2 to 3 times, followed by drying in a vacuum dryer.

Yield tcoI, yield yt, rcs weight average molecular weight/P, 100 dispersion (MW/MN) 3. ≠ Synthesis Example 5> Synthesis of Polymer 1O Hyde a-Kino 7/6. j'/i (0,/!r mole), p
-nonylphenol 33/i (0,7! r mol), acetaldehyde diethyl acetal ir, zg (0,3 mol) and l-methoxy-coprobanol/! rOj;
The mixture was placed in a reaction vessel under a nitrogen stream and stirred at room temperature. Sulfuric acid λ, Pp (0.03 mol) was added there as a catalyst, and the reaction and post-treatment were carried out in the same manner as in Synthesis Example 3.

Similarly to Synthesis Example 5, the molar ratio of hydroquinone and p-nonylphenol was changed to
The results for /-/J are also shown in Table 2.

(Table 2) (Table 3) <Synthesis example 6> Polymer lμ~core was obtained according to the method described above.

Even when the compound of the present invention is added to a silver halide emulsion layer,
Although it may be added to the non-photosensitive layer, it is preferably added to the non-photosensitive layer. Furthermore, the same compound may be added to different layers, or two or more different compounds may be added to the same layer. The amount added is - converted to the unit derived from maximum (1), from /X10-6 to /X10-3 mol/m2, preferably from 10-5 to /0-3:Enyl/m2. The compound of the present invention is preferably used as a color mixing inhibitor, but may also be used as a color fogging inhibitor in the silver halide emulsion layer (in that case, the amount added is -maximum CI). Convert to l.

0xlO-7~1. QxlO-4 mol/m2, preferably i, oxio -t, oxio mol/m
The compound of the present invention can be introduced into a photosensitive material by various known dispersion methods, and typical examples include solid dispersion method, alkaline dispersion method, preferably latex dispersion method, and more preferably oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, after dissolving either a high-boiling organic solvent with a boiling point of 77,500 or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, water or an aqueous gelatin solution is added in the presence of a surfactant. finely dispersed in aqueous media.

Examples of high boiling point organic solvents are described in US Hour Hand No. 2, 3 Coco, No. 027, etc. Dispersion may be accompanied by phase inversion,
Further, if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, or ultrapure filtration before use for coating.

Examples of high-boiling organic solvents include phthalic acid esters (digityl phthalate, dicyclohexyl 7-talate,
esters of phosphoric or phosphonic acids (triphenyl phosphate, tri/resyl phosphate, etc.)
2-Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-λ-ethylhexyl phosphate, tridodecyl phosphate, tryptoki7
ethyl phosphate, trichloropropyl phosphate, sheath-ethylhexylphenyl phosphonate, etc.)
, benzoic acid esters (coethylhexylbenzoate, dodecylbenzoate, λ-ethylhexyl-p-
hydroxybenzoate, etc.), amides (diethyldodecanamide, hetetradecylpyrrolid, etc.), alcohols or phenols (stearyl alcohol, co, g')-tert-7milphenol°, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-digtylphtatoxyj-tert-octylaniline, etc.), hydrocarbons (paraffin, (Fulbenzene, diimpropylnaphthalene, etc.) 7'l
: and as an auxiliary solvent, the boiling point is about 30
0 to about /100c can be used, typically f
Examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Latex dispersion methods can be applied to the dispersion of the compounds of the invention,
The process, effects, and examples of latex bodies for impregnation are as follows:
U.S. Patent I@≠, l Tata, No. 363, OLS@co,! Group 1, 27th Hiro No. and OLS No. 1.

! It is described in Hiroshi/, No. 230, etc.

In a preferred embodiment of the color diffusion transfer photographic light-sensitive material of the present invention, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer is used. A combination of layers, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye-providing compound, a magenta dye-providing compound and a cyan dye-providing compound in each of the above emulsion layers, respectively. (Here, the term "infrared light-sensitive emulsion layer" refers to an emulsion layer that is sensitive to light of 700 nm or more, particularly 7 hronm or more).

In the present invention, the silver halide emulsion layer combined with a dye-providing compound refers to a layer in which the dye-providing compound and the silver halide emulsion are added in the same layer or in a separate layer adjacent to each other. Color Diffusion A typical form of the film unit used in the transfer method is that an image-receiving element and a photosensitive element are laminated on a single transparent support, and after the transferred image is completed, the photosensitive element must be peeled off from the image-receiving element. There are forms that do not exist. The image-receiving element comprises at least one mordant layer, and between the mordant layer and the photosensitive layer or dye-providing compound-containing layer, a white reflective layer containing a solid pigment such as titanium oxide is provided so that the transferred image can be viewed through the transparent support. is provided.

A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the development process can be completed in a bright place. Further, if desired, a release layer may be provided at an appropriate position so that all or part of the photosensitive element can be released from the gold image-receiving element.
No., Canadian Watch 67≠, Or2. In another embodiment that does not require peeling, the photosensitive element described above is coated on one transparent support, a white reflective layer is coated thereon, and an image-receiving layer is further laminated thereon.

Regarding an embodiment in which an image receiving element, a white reflective layer, a peeling layer, and a photosensitive element are laminated on the same support, and the photosensitive element is intentionally peeled from the image receiving element, US Pat. No. 3,730.71
It is stated in No. r.

In addition, as described in JP-A No. 7-2266≠, an image receiving layer, a peeling layer, and a photosensitive layer'ft combined with a DRR compound are sequentially provided on a white reflective support, and a transparent layer having a neutralizing function is formed. The present invention also applies to a film unit in which an alkaline processing agent is spread between the cover plate and the photosensitive layer, and the white reflective support and the image-receiving layer are peeled off from the photosensitive layer at the peeling stage after processing. Preferably used.

On the other hand, there are two typical forms in which a photosensitive element and an image receiving element are separately coated on two supports.
One is a peelable type, and the other is a peelable type. To explain these in detail, in a preferred embodiment of the peelable film unit, there is an original reflective layer on the back side of the support, and at least one image-receiving layer is coated on the surface thereof. In addition, the photosensitive element is coated on a support having a light-shielding layer, and the surface coated with the photosensitive layer and the mordant layer do not face each other before the end of exposure, but after the end of exposure (for example, during development) the surface coated with the photosensitive layer does not face each other. It is devised so that it turns around and overlaps the image-receiving coated surface. Immediately after the transfer image is completed with the mordant layer, the photosensitive element is peeled off from the image receiving element.

In a preferred embodiment of the peel-free film unit, at least one mordant layer is coated on a transparent support, and a photosensitive element is coated on a support having a transparent or light-blocking layer, The surface coated with the photosensitive layer and the surface coated with the mordant layer are stacked facing each other.

The above-described color diffusion transfer system is usually further combined with a pressure-rupturable container (processing element) containing an alkaline processing liquid. In particular, in a peel-free film unit in which an image-receiving element and a photosensitive element are laminated on one support, the processing element is preferably disposed between the photosensitive element and a cover sheet overlaid thereon. Further, in the case where a photosensitive element and an image receiving element are separately coated on two supports, it is preferable that the processing element is placed between the photosensitive element and the image receiving element at the latest during development processing. Depending on the form of the film unit, the processing element preferably contains a light blocking agent (such as carbon black or a color-changing dye with PI-1) and/or a white pigment (such as titanium oxide). Furthermore, in a color diffusion transfer film unit, a neutralization timing mechanism comprising a combination of a neutralization layer and a neutralization timing layer is preferably incorporated into the cover sheet, the image receiving element, or the photosensitive element. .

The above film unit is No. 37427,
Japanese Patent Publication No. 4 Alr-'t33/7, same! 0-/1362
No. 1, same! , 2-/1027, J'6-ttrt,
As described in No. 22, it is generally processed into a monosheet using a mask material, a rail material, a surplus liquid trap material, etc.

In particular, in order to facilitate peeling after treatment, Re5ea
rch Di 5closure No. A623024 (
It is effective to make a slit as described in 15P13). The shape, depth, etc. of the slit are selected depending on the physical properties of the white support used.

The size of the film unit is arbitrary, but in addition to the size of instant films currently available on the market, more compact film sizes and larger film sizes can be used.

In order to take a photograph using the above-mentioned film unit, it is necessary to form a mirror image of the subject on the film. For this purpose, it is necessary to have mirror kumquats.

For these types of cameras, the US Percentage No. 3. ≠
≠ known as No. 7.4437.

In the present invention, a photosensitive layer consisting of a silver halide emulsion layer in combination with a dye-providing compound is provided.

Its components will be described below.

(1) Dye-donating compound The dye-donating compound used in the present invention is either a non-diffusible compound that releases a diffusible dye (which may also be a dye precursor) in association with a redox reaction, or its own diffusivity changes. It is a theory of photographic process.
he Theory of the Photog
It is described in the 1st edition of RAPHIC PROCESS. All of these compounds can be represented by the following - maximum CI).

DYE-Y Here, DYE represents a dye or its precursor, and represents a component that provides a compound having diffusivity different from that of the YU compound under alkaline conditions. Depending on the function of Y, silver is roughly divided into negative compounds that become diffusible in the silver developed area and positive compounds that become diffusible in the undeveloped area.

Specific examples of negative-type Y include those that oxidize and cleave as a result of development to release a diffusible dye.

A specific example of Y is #f house 3 in the United States. No. 21,372, 3.
Riyi, tit issue, same e, 076, 129, Mukaihiro, /j2. /No. 13, Douyu, oss, Kou 2 No., Dou +
1.0!3, 3/2 issue, same 4t, /rit.

23 evening issue, douu, /7ri, 2ri1 issue, mukai≠, l≠Y, I
r92 issue, same! , IIItlt, No. 711, 3゜μ弘3.9443, 3.7ri 1. ≠06 issue, Mukai 3.4 to Hiro 3.23P issue, 3, 4t4tJ, tag 0, same J, 621.912, same, ? , 910, Hiro 7
No. 7, same F, /13.713, same, /1fi2
．． lr 1st, 1fi, 271,710, 4t,
/3? .

37th issue, same μ, λ/l, 3 otsu j issue, same 3. Hiroλ/, ri6≠ issue, rotation, l tata, issue 315, same concern.

l Tata, 3yo Hirogo, Douan, /31. Takota, same≠, 3
3 Otsu, No. 122, 4t, /3ri,! ! No. 2, Tokukai Akira!
r3-j0736, same ll-70443 hiro 3, same!
Hiro-/10/ko λ issue, same! 3-//Q127, same jA
-/26μλ issue, jj-/4/3/ issue, j7-≠0
No. 413, same tough-No. 410, same! 7-2073! issue,
same! No. 3-62033, same zttt-iioy core issue,
Same jJ-/G Hiro 34t, No. 2, same j7-//ri 3 da! It is stated in the number etc.

Among Y of the negative dye-releasing redox compound, a particularly preferred group is a monosubstituted sulfamoyl group (the N-substituent is a group derived from an aromatic hydrocarbon ring or a heterocycle). Typical groups for Y are illustrated below, but are not limited to these.

H H H 0H For positive-type compounds, please refer to the Anguevante Hemi International Edition English
gev, Chem, In5t, Ed, Engl.).

λλ, /9/(/PIco).

A specific example is a compound (dye developer) that is initially diffusible under alkaline conditions but becomes non-diffusible after being oxidized during development. Typical examples of Y that are effective for this type of compound include those listed in US Pat. No. 2,913,606.

Another type is one that completely releases the diffusible dye by self-closing under alkaline conditions, but substantially no longer releases the dye when oxidized during development. For a specific example of Y having such a function, see US Patent 3. ri10゜hiro7ri, Tokukaisho! 3-toross,
Same j≠-130ri27, US time W3,4cl/,9tl
fi, intermediary.

l Tata, 3! ! etc. are listed.

Another type is one that does not itself release any pigment, but
Some of them release all of their dye when reduced.

This type of compound is used in combination with an electron donor,
@The diffusible dye can be totally released in a pattern by reaction with the remaining electron donor imagewise oxidized by development. For atomic groups awaiting such functions, see, for example, U.S. Patents u, /13.7j3, U.S. Patents
/, same II, J7r, 7!0. Same 4L, /3! P
, J7F, 4A + J/r, J+r, JP-A-13-10127, U.S. Pat.

271.7JrO, same p, irt, xuy, same≠.

3! T,! 2! , JP-A-Shoj-3-/10127, same! ≠
-/30P core, same jA-/6≠3+L core, public technical report r
7-4/Tata, European Patent Publication No. 2, No. 7, Hiro AAJ, etc.

All specific examples are shown below, but the invention is not limited to these.

52Hzs l-13 When compounds of this type are used, they are preferably used in combination with diffusion-resistant electron donor compounds (known as ED compounds) - or their precursors.

An example of an ED compound is US Patent ≠, 263.3.
No. 23, Intermediate, No. 271゜710, JP-A-74-731
It is described in No. 716, etc.

Further, as examples of other types of dye image-forming substances, the following can also be used.

C16 Day 31 (wherein DYE represents a dye or a precursor thereof as defined above) Details of this can be found in US Pat. No. 3,7/'? , Hiroirigoya and staff, Q
It is described in R.R., No. 713.

On the other hand, examples of the dye represented by the general formula DYE are described in the following literature.

Examples of yellow dyes: US patent j, r? No. 7,200, 3,302°/PP
Issue, same≠, oii, ti3 issue, same IA, Kohiro! ,02r
No., same a, irt, to? No., same≠.

iiy, its issue, maid, liri! , Tata No. 2, 44
, /1AIr, 4 Hiro/No., 4 (, / Hiro, 6 Hiro 3, 4t, j3t, J Coco; JP-A Showj I-//≠
? 3Q No. 16-7/θ7, 2; Re5earc
hDisclosure / 7430 (/ri7J
r), direction l≦4A7j (/5'77).

Example of magenta dye: U.S. Pat. No. 31, No. 3.107, 3. Yo Guru.

Rihiro! No. J, No. 532.310, No. 3. ri3/,
/Hiroshi 41, same! , No. 132, 101r, 31P! Hiroshi, ≠ 7, room clerk, 233.237, Mukahiro, co! the law of nature,
Rori No., same≠, λj0. Kohiro No., same 1t, /QL2
．． Lr 1 No. 1, 1.207, 10 IA No. 1, 1.207, 10 IA No. 1, 1.207, 10 IA No. 7.2 Octopus: JP-A No. 12-10 Otsu, 7.27 No.
same! λ-106727, j3-co3. Bu2r, Tatar 34.10≠, Tj-73. Oj No.7, Mukaij
No. 4-77040, same! What is described in J-7141.

Examples of cyan dyes: US%1'fJ, 4t1.2, No. 972, 3. Ri2ri.

7tO, IA, 0/3, 63! No., Intermediate, 26r
, txr issue, 11. /7/, No. 220, Intermediate.

O-, ≠ 3 issue, intermediary, l ≠ J, ruri 1 issue, doujinshi, /?
! , Tata number, same number, /Hiro 7.74, Mukai 41-
, /4tI, &u2; UK ##'F/, evening l
.

/3r issue: Unexamined Japanese Patent Publication Showa J4cm25'4ZJ / issue, same number 2
-1127, same j! -1t7r23, Mukai 73-/Hiroshi 3323, same! Hiro - Tata Hiro 31, Tata Hiro 7106
No. 7; Yorotsu 7g special! 'f(RPC)! 3゜037, same! j, 0140; Re5earchDisc
losure / 7.630 (/ri 7Ir) issue,
and direction/6. IAy! (i-77).

(2) Silver halide emulsion The silver halide emulsion used in the present invention may be a negative emulsion that mainly forms a latent image on the surface of silver halide grains, or
It may be an internal latent image type direct positive emulsion in which a latent image is entirely formed inside the silver halide grains.

Internal latent image type direct positive emulsions include, for example, so-called "conversion type" emulsions that are made by taking advantage of the difference in solubility of silver halides, and emulsions that are fully doped with metal ions, chemically sensitized, or both. There are "core//L type" emulsions in which at least the photosensitive area l-' of coated inner core grains of silver halide are coated with an outer shell of silver halide. US time FF, 2.
jriλ, 2 to 0. 3.206, 3/3, British Patent I.

Q core, /4! Otsu, U.S. Patent 3.7t/, Core 6, Same 3
．． Riis, oihiro, same 3 Mamoru 47. Pλ7, same J, 4
tP7, 171, same! t3.7rjr.

Dou 3, 11/, 662, Douu, 3 Tata, ≠7r.

West German Patent Co., 72r, ior, US Patent Guru 317
30 etc.

Further, when using an internal latent image type direct positive emulsion, it is necessary to provide fog nuclei on the surface by using light after image exposure or by using a nucleating agent.

The nucleating agent for this purpose is a US patent! , rt! , 71
! Saletahydrazines described in , Ibid., 2, jl#, tar2, American Hour Hand J, 227. r! Hydrazides, hydrazones, and British watches described in Co., 213, I
r3! , Japanese Patent Publication Showa RX-696/3, American Watch 3. T/!
, t/jT, 3,71 ri, Hiro911, 3, 731
1, 731. doti, oytt, tr3, douu, ii
Heterocyclic 4LI&salt compounds described in r, /λ co, etc., sensitizing dyes having a substituent with a nucleating effect in the dye molecule, described in U.S. ff3, 7ir, Ko 70, U.S. hour hand g, 030.92! , Dou, 03/, /27, Douu,, 2
Hiroj, 037, Intermediate, 2rr, rii, Intermediate, 26t,
0/3, same≠, 27 Otsu, 36≠, British% swindler, 0/2.
≠ Thiourea-bonded acylhydrazine compounds described in Kou 3, etc., and U.S. ff4t, 010,270, same/
I-, 271.7tll, British special n2. oii, 3ri/
An acylhydrazine thread compound having a thioamide ring or a hetero ring &' such as triazole or tetrazole bonded as an adsorption group as described in No. 13, etc., is used.

In the present invention, a spectral sensitizing dye is used in combination with these negative emulsions and internal latent image type direct positive emulsions.

For specific examples, see JP-A-Shory-ivoryO,
Same 1GO-/Hiro033! Issue, Research Disclosure (RD)/7Q, 2nd edition, US time it'F/.

rtt, 3oo, 2,07r, 233, same.

01rF, /2F, same 2, its,! 31. Same guy.

23/,l,! lr, direction 2. ri/7. ! /l, same 3゜3
12.117, 3,4t//, YI&, 2゜2F1
．． 27t, same J, 4 (Ir/, 451'f, direction λ.

trr, rtir, same, ri, 2/, 067, same 3゜212.933, same 3.3F7.01rO1 same 3゜66
0, 103, 3.33! , 0/θ, 3°3r2.
410. 3,31rlt, 4#6, 3゜623,
lrr/, Id. J, 7/I, 4470, Id.≠.

0! , 34t, etc.

(3) Configuration of 1m exposure To reproduce natural colors by the subtractive color method, the dye image-forming substance provides a dye having selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized with the above-mentioned spectral sensitizing dye. The emulsion and the dye image-forming substance may be stacked as separate layers to form a face, or they may be mixed to form a single layer and coated in one coat. If the dye image-forming material has absorption in the spectral sensitivity range of the combined emulsion in the coated state, a separate layer is preferred.

The single emulsion layer may consist of a plurality of emulsion layers with different sensitivities (and an arbitrary layer may be provided between the emulsion layer and the dye image forming material layer. For example, JP-A-Sho JO-/ 7jj
A layer containing a nucleating development accelerator described in ≠/, Tokko Sho AO
It is also possible to increase the color image density by providing a barrier layer as described in -/l Colo 7, or to increase the sensitivity of the photosensitive element by providing a reflective layer as described in JP-A-60-1989-T/3J-Hiroshi. .

In a preferred multilayer structure, a combination unit of a blue-sensitive emulsion, a combination unit of a green-sensitive emulsion 4j, and a combination unit of a red-sensitive emulsion are arranged in this order from the exposure side.

Any layers can be provided between each emulsion layer unit as required. Particularly, in order to prevent unfavorable effects caused by the development effect of one emulsion layer on other emulsion layer units, all intermediate layers containing all the compounds of the present invention are provided.

In the present invention, an irradiation prevention layer, an isolation layer, a protective layer, etc. are applied as necessary.

Examples of the support for the color photosensitive material of the present invention include paper and synthetic polymers (films). In terms of K, polyethylene terephthalate, polycarbonate,
Polyvinyl chloride, polystyrene, polypropylene, polyimide, cellulose (e.g. triacetyl cellulose) or cholera films containing all pigments such as titanium oxide, film method synthetic paper made from polypropylene, etc. Mixed paper made from synthetic resin/ξ loop and natural bulb, Yankee paper, baryta paper, coachite paper (cast coated paper for #!f), metal, cloth, glass, etc. are used.

These can be used alone, or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition to this, there are also
/) can be used.

The surface of these supports may be coated with a hydrophilic binder, alumina sol, a semiconductive metal oxide such as tin oxide, carbon black or other antistatic agent gold.

In the present invention, a light-shielding layer may be provided for the purpose of completely shielding the photosensitive layer from external light during development processing, thereby enabling processing under daylight. Specifically, a layer containing a light shielding agent is coated on the back side of the support or between the emulsion layer and the support, or
Alternatively, a layer containing a light shielding agent may be provided in the support. Although any material having a light blocking function can be used, carbon black is preferably used.

As the binder for applying the light shielding agent, any binder that can disperse carbon black may be used, and gelatin is a suitable binder.

In the present invention, a release layer may be provided between the emulsion layer combined with the dye image-forming material and the dye image-receiving layer, and the emulsion layer may be peeled off after processing. In an untreated state, this release layer is
In addition to maintaining the density of the emulsion layer, it must also be easy to peel off after processing. Materials for this purpose include, for example, Japanese Patent Publication No. 7-1237, same evening? -220727,
j2-22L? J! , ≠7-≠l, 13, US Patent 32 or 3! , Same sorrow 3! ri r/r, Tokukai Sho ≠ 2-Hiroshi 3
3 Hiro, same evening 4-Ari/JJ, same 1LLj-2≠071,
US time FF J 227! r O1 same 27 times rko! , 4AO/7 Hiroshi 6, 366227, etc. can be used. One example of the member is a water-soluble (or alkali-soluble) cellulose derivative. Examples include hydroxyethylcellulose, cellulose acetate-phthalate, plasticized methylcellulose, ethylcellulose, cellulose nitrate, carboxylmethylcellulose, and the like. Other examples include various natural polymers, such as alginic acid, pectin, gum arabic, and the like. Various modified gelatins, such as acetylated gelatin and phthalated gelatin, may also be used. Further examples include water-soluble synthetic polymers. For example, polyvinyl alcohol, polyacrylate, polymethyl methacrylate, butyl methacrylate, or copolymers thereof.

The release layer may be a single layer or may consist of multiple layers, for example, JP-A-Sho! Tar220727, same +0
-+0+≠λ etc.

The image receiver J11i used in the present invention contains a mordant in a hydrophilic colloid. Even if this is a single layer,
It may also have a multilayer structure in which mordants having different mordant powers are coated one on top of the other. Regarding this, please refer to JP-A-67-Koj2! It is described in l. As the mordant, a polymer mordant is preferred.

The polymer mordants used in the present invention are polymers containing secondary and tertiary amino groups, polymers having nitrogen-containing heterocyclic moieties, polymers containing these high class cation groups, and those having a molecular weight of z, ooo or more are particularly preferable. io, oo
o or more.

For example, US patent λ,! Hiro r, rt (I-No., mukoko.

Vinyl pyridine polymers and vinyl pyridinium cationic polymers disclosed in Hiro Ir44, 4t30, 3,71, 1,06/, i, 'yrtr, ri≠ specifications, etc.; US eP! jl? f hiro, l co hiro, 31
Vinylimidazolium cationic polymer disclosed in Specification No. 6, etc.;
Same 3. r Tata, No. 026, same≠, /2! .

No. 1311, UK %: ff/, Polymer mordant capable of crosslinking with gelatin etc. disclosed in No. 277.1 AjE Specification etc.: US % Total 3. Tata-t, ta-ta! No. 2.72/
, Ir No. 12, Ir. 2.791r, O6J No., JP-A-Shora-//j, No. 221, Mukai ru-ittr.

No. 62Y, same! Hiro-/No. 26,027, same j Hiro-/ri!
, t3! Aqueous sol type mordant disclosed in No. 2, J4-/7.7, etc.;
Water-insoluble mordants disclosed in the specifications of US Pat.
A reactive mordant capable of forming a covalent bond with the dye disclosed in No. O et al.
No. 0, No. 3.7rr, No. rrr, No. 1gJ, 61A
2, 4#2 No. J, 4Llrl, 70! No. a, No. 3. jj7.06, same No.3. λ7/ , /I
It No. 7, No. 3.27/.

/≠r issue, JP-A-13-30321, the same taco/! j
jtJt issue, 63-/2 evening issue, 3-10241 issue, same! 3-107. r3 evening issue, British hour hand, 06 Hiro, 1
Examples include mordants disclosed in No. 02, Ministry of Specification, etc.

Other US Pat.

Mention may also be made of the mordants described in No. RR, IRT.

In the present invention, a system for neutralizing the pH of the alkaline processing liquid can be provided in the cover sheet, the layer adjacent to the image receiving layer, etc. By providing neutralization 1-1 neutralization timing n4, a neutralization system can be achieved. This timing layer is disposed between the processing solution and the neutralization layer in such a positional relationship that the alkaline processing solution passes through the entire timing m and reaches the neutralization l-C, and the higher the pR gold is, the more After being maintained for a period of time, p)l rapidly decreases (a pH decreasing process called an inverted S-shape). Preferably, the peeling is performed at a pH of 70 and under an evening breeze. During this period of high pH maintenance, the components of the neutralization timing layer,
Adjusted by composition, amount of application, etc.

Such polymers include ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. acrylic acid,
methacrylic acid, itaconic acid) and one or more types of ethylenically unsaturated monomers that can be copolymerized, polymers such as those described in JP-A No. 20241T No. 1I, 297. lt
3/ issue, douan, cor rr, r, x3 issue, same't, 20/,
! No. 17, Intermediate.

22ri, No. 116, Tokukai Sho! ! -/2/1431, 74-/l, 62/2, jj-44/μri 0, 137-jlA31A/, ? No. 4-102112,
same! 7-/l+/Ag44, direction j7-/731r3'
No. 4, Mukai J7-/7 Rihiro/No., West German %ken application publication (O
LS) λ, 10.27/issue, European Patent Application Publication EP3/, Tata 7A/, Re5earchDisclo
Examples include those described in Sure A/Iiliri et al. Examples of ethylenically unsaturated monomers include ethylene, propylene, l-butene, isobutyne,
Styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, N,N,N-trimethyl-vinylbenzylammonium chloride, N,N-dimethyl-hebenzyl-vinylbenzylammonium Chloride, α-methylstyrene, vinyltoluene,
≠-vinylpyridine, λ-vinylpyridine, benzylvinylpyridinium chloride, hevinyl acetamide, hevinylpyrrolidone, /-vinyl-comethylimidazole, monoethylenically unsaturated esters of fatty acids (e.g. vinyl acetate, allyl acetate), anhomalein acids, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. n-butyl acrylate, n-hexyl acrylate, human mixyethyl acrylate, cyanoethyl acrylate, N,N-diethylaminoethyl acrylate, methyl methacrylate, n- Butyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl methacrylate, methoxy7ethyl methacrylate-1-,N,N-diethylaminoethyl methacrylate, N,N,N-triethyl-
methacryloyloxyethylammonium p-toluenesulfonate, N-diethyl-hemonomethyl-methacryloyloxyethylammonium p-toluenesulfonate, dimethyl itaconate, maleic acid monobenzyl ester), ethylenically unsaturated monocarboxylic acid or amides of dicarboxylic acids (e.g. acrylamide, N,N-dimethylacrylamide, hemethylol acrylamide, he(he,hedimethylami/papyl)acrylamide, N,N,N-1 dimethyl-(N
- acryloylpropyl) ammonium p-toluene,! -7 IJ Ruamide-comethylpropanesulfonic acid, acryloylmorpholine, methacrylamide, to.

Hedimethyl-to'-acryloylpC1zendiaminepropionatebetaine, N,N-dimethyl-to'-
Examples include methacryloyl diamine acetate betaine).

The neutralization timing layer may be a single layer or multiple layers.

In addition, for timing layers made of these materials, for example, US Pat.
)! , 5'/l, 74≠ issue, 3, 0/44, 4
No. 72, Tokukai Sho! 'fi-/No. 11137, same! ! −／
317 Hiro! development inhibitors and/or precursors thereof, as well as hydroquinone precursors disclosed in U.S. Pat. It is also possible to incorporate money such as

As the acidic substance for the neutralization layer, conventionally known acidic substances can be used, and there are no particular limitations. Preferred acidic substances have pKa
is 2 or less acidic groups (or a precursor group that provides such an acidic group upon hydrolysis), more preferably oleic acid as described in U.S. Clock No. 2, Rixi, tot. Higher fatty acids such as
．． Polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in No. 31,2°rl; French Hour Hand No. 2,220.
Copolymers of acrylic acid and acrylic esters as disclosed in No. 6 Tata;
issue and [(esearchDisclosure 4/
It/0λ (/!P77), latex type acidic polymers can be mentioned.

In addition, US Patent No. V, orr, Ko 23, and JP-A-Sho! Ko/jJ73rd issue, same ta! -1023, same j3-
4AjltO issue, same Ta 3-Hiro! Hiro, number 3 - Hiro! Acidic substances disclosed in No. λ and the like can also be mentioned.

Specific examples of acidic polymers include ethylene, vinyl acetate,
These include 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 acetate hydrogen heptatalate, and the like.

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

The amount of polymeric acid applied is controlled by the amount of alkali developed on the photosensitive element. The equivalent ratio of the polymeric acid to the alkali per unit area is preferably O1-Q. If the amount of polymer acid is too small, the hue of the transferred dye may change or staining occurs in the colored area, and if it is too large, problems such as a change in hue or a decrease in light fastness occur. A more preferable equivalent ratio is /,Q~/,3. Too much or too little of the hydrophilic polymer in the mixture will reduce the quality of the photograph. The weight ratio of the hydrophilic bo+)-r- to the polymeric acid is o, i to IO1, preferably from 0°3 to 3.0.

Additives can be incorporated into the layer having a neutralizing function 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 additives such as antioxidants and dyes can also be added as necessary.

The color sensitivity f of the present invention, the processing composition used when wet processing the material is uniformly spread on the photosensitive element after exposure of the photosensitive element, completely shields the photosensitive layer from external light, and at the same time contains the The photosensitive layer is developed using the components. For this, the composition contains alkalis, thickeners,
Contains a developer and a light shielding agent as essential components, and also includes a development accelerator, a development inhibitor, an antioxidant to prevent the deterioration of the developer, and a cover sheet to protect the dye generated in the image. Contains white pigment to enable previewing from the side.

The alkali is sufficient to make the pi ('i/J~l≠) of the liquid, and the alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide, lithium hydroxide), alkali metal phosphates (e.g. (potassium phosphate), guanidines, and quaternary amine hydroxides (eg, tetramethylammonium hydroxide), among which potassium hydroxide and sodium hydroxide are preferred.

The thickener is necessary to spread the processing solution uniformly and to maintain close contact between the photosensitive layer and the cover sheet when peeling off the used photosensitive layer together with the metal bar sheet. For example, alkali metal salts of polyvinyl alcohol, hydroxyethylcellulose, and carboxymethylcellulose are used, preferably L<H, hydroxyethylcellulose,
NaI-IJ lamb carboxymethyl cellulose is used.

As the light shielding agent C, any dye or pigment, or a combination thereof, can be used as long as it does not diffuse into the dye image-receiving layer and cause staining, and carbon black is preferably used.

The amount of light shielding agent added is sufficient to sufficiently shield the photosensitive element during processing under strong external light, and is 3 oy per 5 J of processing solution.
~2009. Preferably it is Hiroo1~/Coop.

Any white pigment can be used as long as it does not have a photographic sensitizing effect. For example, inorganic titanium white pigments as well as hollow polymer beads (e.g. Rohm a
It is also possible to use 0P-ra■) published by ND Hass.

The content of white pigment is from toy to hirooo per treatment liquid iKy.
g, preferably 1009 to 3009.

Preferred staining agents are any that cross-oxidize the entire dye image-forming material and do not substantially stain when oxidized.

These developers can be used alone or in combination of two or more.
C may also be used, and may also be used in the form of a precursor. These developing agents may be included in the appropriate II of the photosensitive element or may be included in the alkaline processing solution. Examples of mediating compounds include amine phenols and pyrazolidinones, and among these, pyrazolidinones are particularly preferred because they cause less staining.

For example /-phenyl-3-pyrazolidinone, /-p
-Tolyl-Hiro, ≠-dihydroxymethyl-3-pyrazolidinone, /-(J'-methyl-phenyl)-Koichi methyl-≠-hydroquinemethyl-3-birasolidinone, /-phenyl-Hiro-methyl-Hiro-hydroxymethyl- Examples thereof include 3-pyrazolidinone, 1-p-tolyl-Hiro-methyl-Hiro-hydroquinemethyl-3-pyrazolidinone, and the like.

When applied to a heat-developable photosensitive material, these developers are preferably incorporated into the photosensitive material.

Examples of the contents of the present invention are shown in the following examples, but the present invention is not limited thereto. In particular, various formats and layer configurations are possible, and the present invention can be effectively utilized as long as it has a one-color mixing prevention layer, and all useful effects can be achieved.

(Example) Example 1 Image-receiving photosensitive sheet A carbon black layer (
Carbon black 3', Oji/m2 gelatin μ, 11
77 m) and titanium oxide layer (titanium oxide 3.
0ji/m, gelatin/QgZm) was applied.

Next, the following layers were sequentially coated on the opposite side of the light-shielding layer of this support to prepare an image-receiving photosensitive sheet.

(1) An image-receiving layer containing the following polymer latex mordant kE&/m and gelatin 397m2.

(2) A first release layer consisting of the following compound 0,797m.

H3 (3) Degree of acetylation 1% cellulose acetate 0.7/
A second release layer consisting of i7 m2.

(4) Ethyl acrylate latex'frI9/m2
2. Gelatin. The layer includes 97m.

(5) The following cyan dye-releasing redox compound O8≠4
49/m tricyclohexyl phosphate o
, ori97m2. Ko,! -G-t-pentadenlehydroquinone o, oorg7m, carbon black o
, oz17m and gelatin O0r, jil/m
A layer containing.

(6) Titanium oxide 2i/m2 and gelatin O6j
A light reflecting layer containing 9/m.

(Grain size f, octahedral internal latent image type direct positive silver bromide emulsion with grain size f, 0 μm (silver fraction o, iz97m), red-sensitive sensitizing dye, gelatin O6≠N/m, the following nucleating agent ( NA)/, /μ97m, and 2-sulfo-!-
n-pentadecylhydroquinone.

Low red-sensitive emulsion layer containing sodium salt 0.02/i/m f.

Highly sensitive red-sensitive emulsion layer containing NA sodium salt 0.0 hg/m2, t-.

(9) Color mixture prevention layer having the contents shown in Table 1.

(lI Layer containing 0.3 g/mf of gelatin.

αυ The following magenta dye-releasing redox compound 0゜1
197m, tricyclohexyl phosphate 0
．． 197m 2. Targe-t-pentadecyl hydroquino: yo, 00Yg/m and gelatin O9ri! j/m Containing layer.

(8) Octahedral internal latent image type direct positive silver bromide emulsion with a size of 7.4 μm (0.197 m in silver), red-sensitive sensitizing dye, gelatin θ, 19/m, m (1υ same residual agent (NA) 7.0 μN/m and λ-sulfo J-n-pentadecylhydroquinone.

(12+ titanium oxide/, !i'/m2 and gelatin O1λ!fj/m).

(13 grain size/, 0 μm octahedral internal latent image type direct positive silver bromide emulsion (0.1297 m in silver), green-sensitive sensitizing dye, gelatin Q, λ1 g/m, same nucleation as layer αυ agent (NA)/, /μg/rn 2 and cosulfo t-n-pentadecylhydroquinone sodium salt 0
．． A low-speed green-sensitive emulsion layer containing 029/m'c.

α Xu grain size/, 4 μm octahedral internal latent image type direct positive silver bromide emulsion (0.3!97 m at the silver platform), green-sensitive sensitizing dye, gelatin 0.797 m, same nucleation as layer qυ agent (A)/, 7 μg/m and 2-sulfo-r
, a high-sensitivity green-sensitive emulsion layer containing 0.04 #/mk of 6-ntadecylhydroquinone sodium salt.

+15) Same color mixture prevention layer as layer (9) with the contents shown in Table/.

(IQ layer containing 70.3 g/m2 of gelatin.

・αη Yellow dye-releasing redox compound with the following structure <0. Evening 397m ), tricyclohexyl phosphate (0,1327m ), Ko,! - di-t-pentadecylhydroquinone o, oi≠g/m 2 ) and gelatin (0,7117 m 2 ).

Q8 Titanium oxide 0.7g/m and gelatin Q
.

A light reflective layer containing 7197m.

fil Octahedral internal latent image type direct positive silver bromide emulsion with grain size /, / μm (0.2!177 m in silver amount), blue-sensitive sensitizing dye, gelatin 0.4 Ljl/m , layer (1
The same nucleating agent (NA) λμ as in 1),! i'/m, and a low-speed blue-sensitive emulsion layer containing 0.0 μ3 g/m of λ-sulfo r-n 6-tadecyl hydride a-quinone sodium salt.

■ Same nucleating agent as the grain size/7 μm octahedral internal latent image type direct positive silver bromide emulsion (silver amount O6μλ97m>, blue-sensitive sensitizing dye, gelatin 0.≠jg/m2, layer Ql) (NA) 3.31ti/m, and 10-bentadenlehytroquinone sodium salt o
, oxrg7m+ high-speed blue-sensitive emulsion layer.

Qυ All of the following ultraviolet absorption layers, each II x 10”-
UV-absorbing layer containing 'mol/m and 0.6 g/m of gelatin.

(c) A protective layer containing a matting agent and gelatin o, rg/m 2 .

Cover Sheet If was prepared by coating in the following order on a polyethylene telemerate support containing cover foot light piping prevention dye and undercoated with gelatin.

(a) Average molecular weight! 10,000 acrylic acid-butyl acrylate (molar ratio r:, 2) copolymer is io, ≠,! iI
/m2 and /,44-bis(2,3-epoxypropoxy)-butane0, /i7m2(b) Neutralized timing layer (cl gelatin/,0117m) containing ≠9/m of polymer with structure below and structure below: A layer processing solution consisting of a polymer/, OEl/m2 Each of the above film units was exposed to light from the cover sheet side using a gray wedge, and then the processing solution was developed to a thickness of 70 μm using a suppressor at 2!0C and developed. After each film unit was developed with the gold treatment solution, 1 minute and 30 seconds later, 2 minutes later, 2 minutes and 30 seconds later, μ minute diameter, io minutes later, and to
The yellow image forming density at each peeling time was defined as the image completion rate, where the yellow image forming density (Bo) of the peeling after to minutes was set as floo.

On the other hand, the releasability was examined for both an untreated sample (ie, dry sample) and a developed sample (ie, wet sample). The releasability of the dry sample was determined by scratching (cutting) the image-receiving photosensitive sheet with a cutter knife.
Cellophane tape is pasted on the surface of the photosensitive layer side (protective layer side), and when the cellophane tape is peeled off, it is checked which layer and how much has been peeled off.
It is necessary that the film can be peeled off between 3) and 3).

The removability of the wet sample is determined by t of the above-mentioned development treatment.

The covernte and the photosensitive sheet i were peeled off from each other, and the extent to which the cover was peeled off was examined.

Again, it is necessary that all the layers can be peeled off between the peeling layers (layer (2) and layer (3)).

Hydroquinone A 0H Polymer A Average molecular weight to, oo.

Table 1 shows that in the photosensitive sheet using the polymer hydroquinone compound of the present invention, the intermediate layer (
It is clear that the film has a strong film quality that does not peel off due to color mixing prevention 1-).

Furthermore, since the coating film thickness can be made thinner than conventional ones, it has the excellent effect of increasing the transfer speed (speed of image completion). It is surprising that the film is faster (and has stronger film quality) than the conventional color mixing prevention layer.

In addition, there was no color mixing in any of the samples, and color separation was good.

Example 2 A laminated integrated color diffusion transfer photosensitive sheet and a cover sheet were prepared as follows.

Preparation of photosensitive sheets Photosensitive sheets 7 to i32 were prepared by coating each layer in the following order on a polyethylene terephthalate transparent support.

(1) Copoly [styrene-vinylbenzyl-methyl-piperidinium chloride]3. O,! i'
/m2, gelatin 3.0/i/m total containing image-receiving layer.

(2) Titanium dioxide θ, 9/m2, gelatin 2°Op
/ m Totally Contains White Reflection J-0 (3) Carbon Plastic Co., Ofl/m and Gelatin /,! ,!
A light shielding layer containing 111m.

(4) The following cyan dye-releasing redox compound O0
≠μg/m ToIJ cyclohexylphosphate 0
．． 029/m Ko! - di-t-pentadecylhytroquinone o, oorg7rn, and gelatin O
．． Layer containing r9/m2ft.

(6) Color mixture prevention layer having the contents shown in Table 2.

(Force the following magenta dye-releasing redox compound f0.
397m tricyclohexyl phosphate (o,
01177m2), Ko,! -G-tert-intertadefluhydroquinone (0,009'/i/m2) and gelatin (0-j, S'/m2).

(5) Red-sensitive internal temperature direct positive silver bromide emulsion (according to the amount of silver/
0Jfl/m2), gelatin/297m2 Nucleating agent below 0,0 urI! 9/m2 and 2-sulfo-
t-n- is a red-sensitive emulsion layer containing 0.1397 m2f of sodium salt of tadecylnohydroquinone.

(8) Green-sensitive endothermic direct positive bromide chain hole j! r11 (0.1297 m2 in silver amount), gelatin y (o, ri11/m2
), a green-sensitive emulsion layer containing the same nucleating agent as layer (5) (0.03 .mu./m.sup.2) and cosulfo t-n-pentadecylhydroquinone sodium salt (0,Or,!iI/m.sup.2)t".

(9) Same layer as (6).

00+ Yellow dye-releasing redox compound with the following structure (0,63 g/m ), tricyclohexyl phosphate (0,1397 m ), co,! -dit-intadenylhydroquinone (0,0/Hiro, 9/m2) and gelatin (0,7j!/m2>f.

Containing layer.

Contains a UV absorbing layer.

αυ Blue-sensitive Utsumi type direct positive silver bromide emulsion (in the silver world/,
0 Yll/m), gelatin (/-/ &/m Same nucleating ax as in 5th layer (5) (0,0≠η/m2), courseluho!-n-<nmedenruhyde aki/n sodium salt<o , o7j!/rn).

α2 Each ultraviolet absorbing layer gold with the following structure≠×10mo
l/m2, and gelati 70.70g7m2 (13)
Polymethyl methacrylate latex (average particle size μμ, 0.109/m), gelatin (0, rg/m
) and triacroyltriazine (0
,0λ1! Protective layer containing /m >k.

Composition of Cover Sheet A A cover sheet was prepared by sequentially coating the following layers (l') to (Hiro') on a transparent napolyethylene terephthalate support.

(/') Acrylic acid-butyl acrylate (weight ratio, r:, Z) copolymer with average molecular weight to, ooo is 109
/m2 and /,4(-bis(2,3-epoxyp-a-boxy)-butane 0.coF/m).

The second timing layer was coated with 7.197 m of cellulose acetate and methyl vinyl ether-i-leic acid monomethyl ester alternating copolymer with a degree of J'lization!/! of 0% and a weight ratio of 1!/!.

(3') Methyl vinyl ether-anofomaleic acid alternating copolymer 7.0!777m, and! -(λ-anor/-methylthio)-7-phenyltetrazole fO,
Auxiliary neutralization layer containing rmmot/m2.

(Hiro') Styrene-n-butyl acrylate-acrylic acid-hemethylolacrylamide μ9°7 vs. 4c2
．． 3 to 3! P3 to French to J (weight ratio) copolymer latex and methyl methacrylate-acrylic acid-to-methylol acrylamide were mixed so that the solid content ratio of the former latex to the latter latex was 6 to μ. A first timing layer of thickness μ was mixed and applied.

Photosensitive sheets 7 to ii2 produced in this way room temperature (F
resh), 60°CDryJ day, +t'c10%RH
After being stored for j days, each was exposed to light using a rust wedge.
At Jj'C, the combination of the treatment solution and the cover sheet was passed through a pair of pressure rollers for development treatment. After 1 hour, the density was measured using a color densitometer, and the Dmaxt shown in Table 2 was obtained.

Further, changes in Dmax were measured every j seconds immediately after development at 2j0C, and the time required to reach 1/2 of the concentration (])max) after 60 minutes was read. This indicates the overall transfer speed; the faster the better.

As is clear from Table 2, when the photosensitive sheet of the present invention is used, the transfer speed becomes faster. It also has the effect of improving storage stability by reducing changes in density during raw storage. It is clear that photosensitive sheets using inhibitors have a crushing effect.

In addition, there was no color mixing in any of the samples (color separation was good).

hour hand applicant Fuji Photo Film Co., Ltd.

Claims (1)

[Scope of Claims] Color diffusion transfer comprising at least a light-sensitive silver halide emulsion layer in combination with a dye-providing compound that releases or produces a diffusible dye, an image-receiving layer capable of mordanting the diffusible dye, and a neutralizing layer. 1. A color diffusion transfer photographic material comprising at least one polymer obtained by polycondensing at least one of each of the following general formulas (I) and (II) under an acid catalyst. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) In the formula, G represents a hydroxyl group or a group that can generate a hydroxyl group by alkaline hydrolysis, and n is Represents an integer greater than or equal to 2. However, G may be the same or different. Further, R^1 and R^2 may be the same or different and represent substituents on the benzene ring. In the formula, R^3 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a heterocyclic group, an acyl group, or a carboxyl group. In the formula, R^4 and R^5 may be the same or different and represent an alkyl group. Further, R^4 and R^5 may be connected to form a ring.