JPS6057836A - Photographic element - Google Patents

Abstract

PURPOSE:To enhance light resistance and image density by forming a layer contg. a polymer contg. specified monomer units as a structural component and another polymer contg. another specified monomer units as a structural component. CONSTITUTION:A mordant layer contains as mordants a polymer having a structural component of monomer units represented by formula I and a polymer having a structural component of monomer units represented by formula II. The use of the mordants having these two various characteristics can form a mordant layer having both of good mordant performance for anionic dyes and performance of retaining the mordanted dyes stable at the same time, thus permitting light resistance and density of a dye image to be enhanced. In formulae I and II, A is a vinyl monomer unit having a tertiary amine; C is a vinyl monomer unit having none of tertiary amine and quaternary ammonium salt; (x) is 2-100mol%; (y) is 0-98mol%; B is a vinyl monomer unit having a quaternary ammonium salt; D is as C; (u) is 2-100mol%; and (v) is 0-98mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to photographic elements, and more particularly to novel polymer mixtures that are good mordants for dyes used in photographic elements, and photographic elements using the same. More particularly, the present invention relates to a mordant layer for fixing diffusible dyes formed on both edges, and a color photographic element using this novel mordant layer.

In the field of photography, it is well known to use various quaternary ammonium salt polymers in the mordant layer for the immobilization of anionic dyes.
Various polymer mordants are disclosed in U.S. Pat. However, this type of mordant does not have sufficient mordant properties for dyes, so it has drawbacks such as difficulty in increasing the density of dye images and the density of images decreasing over time.

To improve mordant properties, the water-insoluble polymeric mordants described by Cohen et al. in U.S. Patent J, 171.01t, or Campbell
U.S. Patent 3. Risr, yri! A water-dispersible polymer mordant was proposed as described in No. However, although this type of mordant exhibits good mordanting properties for dyes, it has another drawback in that it has a poor ability to retain mordanted dyes in a stable form. In other words, photographic systems containing dye images mordanted with this type of mordant have the disadvantage that the mordanted dye images are susceptible to chemical changes or decomposition when irradiated with fluorescent lights or sunlight.

Therefore, the first object of the present invention is to
The object of the present invention is to provide a photographic element that undergoes less chemical change or decomposition due to light.

A second object is to provide a photographic element that provides a highly concentrated dye image.

The above object is to produce a polymer having a monomer unit represented by the general formula (I) as a constituent component and a polymer having the general formula (I[)
This was achieved by using a photographic element in which a mixture of the monomer units represented by the formula with a non-polymer as a constituent is used as a mordant in the mordant layer.

General formula (I) -(-A+-+C x y [In general formula (I), A. represents a vinyl monomer unit having a tertiary amine. C has both a tertiary amine and a quaternary ammonium salt. Represents a vinyl monomer unit that is not present.
It is 1t morchi. ] General formula (n) +B-) -(-
D+ u v [In the general formula (■), B represents a vinyl monomer unit having a quaternary ammonium salt. D is the same as that represented by C in general formula (I). U is from 0 to 100 mol%, and v is from O to 100% by mole. ] In the above formula, A, B, C%D may contain two or more types of monomers as long as they each satisfy the definitions.

That is, when conventional quaternary ammonium salt polymers are used as mordants, good mordant properties for dyes are obtained, but the mordanted dye images are more susceptible to chemical alteration or decomposition.

On the other hand, tertiary amine polymers have extremely low mordanting properties for anionic dyes.

However, by combining these two types of mordants with different characteristics, the detailed reason for this is not clear, but at the same time it has good mordant properties for anionic dyes and the property of stably retaining the mordanted dyes. It was possible to obtain a mordant layer.

Vinyl monomer unit +A in general formula (I) of the present invention
Specifically, the following general formula (■) or the general formula (W
) is preferable.

(L)n [In the formula, R1 represents a hydrogen atom or a lower alkyl group having /-4 carbon atoms. L represents a divalent linking group having 1-2Q carbon atoms.

E represents a heterocycle containing as a constituent a nitrogen atom having a double bond with a carbon atom. n is O or l.

] General formula (■) R1 ■ +CH2-CCL>n to/\R4R5 [In the formula, R4, L, and n represent the same thing as in the general formula Cm). R4 and R5 each represent the same or different alkyl group having /-/2 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, R4% R5
may be interconnected to form a cyclic structure together with the nitrogen atom. n is 0 or /. ] In the general formula (III), R1 is a hydrogen atom or has a carbon number of l~
lower alkyl groups, such as methyl, ethyl, n
- Represents a propyl group, n-butyl group, n-amyl group, n-hexyl group, etc., and a hydrogen atom or a methyl group is particularly preferred.

L is a divalent linking group having from 7 to about 20 carbon atoms, such as an alkylene group (e.g., methylene, ethylene,
trimethylene group, hexamethylene force, etc.), 7A =
Ren group (e.g. O-)22dine or p-phenylene group,
m-7 enylene group represents an alkylene group of 7 to about 1/2. )・-CO2-CO2-IL3- (However, R3 represents an alkylene group, phenylene group, or arylene alkylene group.) -CONH-R3- (However, rt 3 represents the same as above y''.), -CON- 13 (however, R1 and R3 represent the same as above), -Co2-CH2
CH2-1-CO□-CH2CH2CH2-1:, -
CONHCH2-1-CONHC)I2CH2-1-C
ONHCH2CH2C)12- and the like are particularly preferred.

E is a heterocycle containing as a constituent a nitrogen atom having a double bond with a carbon atom, such as imidazo-1-13. ), and an imidazole ring is particularly preferred.

Specific examples of preferred monomer units represented by general formula (III) are shown below.

■-J General formula (■) R4 and R5 are alkyl groups having 7 to 12 carbon atoms, such as unsubstituted alkyl groups (methyl group,
Ethyl group, n-propyl group, n-butyl group, n-amyl group, hexyl group, n-nonyl group, n-decyl group, n-dodecyl group, etc. ), a substituted alkyl group (methquinethyl group, 3-cyanopropyl group, ethoxycarbonylethyl group, acetoxyethyl group, hydroxyethyl group, λ-butenyl group, etc.), or an aralkyl group having 7 to 0 carbon atoms. For example, unsubstituted aralkyl groups (Hensyl group, phenethyl group, diphenylmethyl group, naphthylmethyl group, etc.), substituted aralkyl groups (Hiro-methylbenzyl group, gooisopropylbenzyl group, Hiro-methoxybenzyl group, Hiro- methoxyphenyl)benzyl group,
3-chlorobenzyl group, etc. ) etc.

Further, as an example in which R 4 and R5 are interconnected to form a cyclic structure together with a nitrogen atom, specific examples of preferable monomer units represented by general formula (IV) are shown below.

H3 -CH2-Ca1- The vinyl monomer units +C+ and +D in the general formulas (I) and (It) of the present invention each represent a tertiary amine,
Any of the quaternary ammoniums represents a vinyl monomer unit that does not have a long shelf life, and among them, uncharged ones are preferable.

Preferred examples of the vinyl monomer unit +C are ethylene, propylene, l-butene, imbutene, styrene, α-methylstyrene, vinyltoluene, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate,
Allyl acetate. ), monoethylenically unsaturated amides of aliphatic acids (e.g. N-vinylacetamide, N-vinylpyrrolide 7, etc.), esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. methyl methacrylate, ethyl acrylate, n- Butyl acrylate, n-butyl methacrylate, benzyl acrylate, diethyl maleate, ethyl itaconate, etc.)
, ethylenically unsaturated monocarboxylic acid amides (e.g. acrylamide, dimethylacrylamide, methacrylamide, cyanoacrylamide, acryloylmorpholine, etc.), monoethylenically unsaturated compounds (e.g. acrylonitrile), or dienes (e.g. tutadiene, inoprene). etc., etc., and these styrene, ethylenically unsaturated carboxylic acid esters, ethylenically unsaturated carboxylic acid amides, etc. are particularly preferred.

Furthermore, when a crosslinked latex is made of a polymer having monomer units represented by general formula (I) or (II) as a constituent component, vinyl monomer units +C or (D+ have neither tertiary amine nor quaternary ammonium). Copolymerizable unsaturated bonds in vinyl monomer units /
Those having two or more in the molecule can be used. Preferred specific examples of the vinyl monomer unit are divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, methylene bisacrylamide, ethylene glycol diacrylate, etc. Among them, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, etc. is particularly preferred.

In the general formula (1), X is 0 to 100 mol, y is O to 1 mol, preferably X is 10 to 100
The mole ratio is Q or Hiro θ morti.

Preferred specific examples of the polymer having a monomer unit represented by the general formula (I) of the present invention as a constituent component are shown below.

T-/ (-CH2-CHsuT-λ +C1-12-CHsuT-hiro CH3 gi(-CH2-Csu'I'-t Cti3 (-CH2-CsuT-4(-C1-12- C) J S'l"-7 -1 'l'-//'l'-/λ +CI(2-CHS) Vinyl monomer unit +B in the general formula (■) of the present invention
Specifically, the following general formula (V) or the general formula (
Vl,) is preferable.

1 ■ General formula m (-CI-12-C nata [In the formula, R4% LSn represents the same as in general formula (01). G is a nitrogen atom that is quaternized and has a double bond with a carbon atom represents a heterocycle containing as a constituent component.Xo represents a monovalent anion.

n is O or l. J 1 General formula (Vl) -(-C1-12-Cs5 [In the formula, R1 and L%n represent the same as in general formula (III) -R4 and R5 represent the same as in general formula (IV) Table br
. R6 is selected from the same ones representing R4 and R5. Xe represents the same thing as in general formula (v). R4,
R5 and R6 may be interconnected to form a cyclic structure together with the nitrogen atom. 11 is.

or/is. ] In the general formula (■), G represents a quaternized petro ring containing a nitrogen atom having a double bond with carbon as a constituent, examples of which include imidazolium salts, among which imidazolium salts, Particularly preferred are pyridinium salts. Here, R4 represents the same thing as in general formula (N), and particularly preferably a methyl group, an ethyl group, or a pencil group.

Xe represents an anion, such as... rogane ion (e.g. chloride ion, odor ion, iodine ion), alkyl sulfate ion (e.g. methyl sulfate ion, ethyl sulfate ion), alkyl or aryl sulfonate ion (
Examples include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid λ#l: acid ions, sulfate ions, and especially chloride ions,
Preferred is p-toluenesulfonic acid ion.

Preferred vinyl monomer unit represented by general formula (V)+
Specific examples of B are shown below.

H3 -Cf-12-C)-1- Nawate (represents p-TsOe+!p-toluenesulfonic acid anion) In the general formula (■), R4 and R5 are connected to each other to form a cyclic structure with the nitrogen atom. Examples R4, R5,
Examples in which R6 forms a cyclic structure and specific examples of preferable vinyl monomer units +B represented by general formula (Vl) are shown below.

-CH2-CH- (Kokotep -T s Oθ represents p-) luenesulfonic acid anion. ) In the general formula (I[), U is from 1 to 100 molar,
■ is koaishiri g morchi, preferably U is HiroO or 7
00 mol%, v is O to 60 mol%.

Preferred specific examples of the polymer having a monomer unit represented by the general formula (II) of the present invention as a constituent component are shown below.

Q -/(-Cth -12-Cl-1-)-C1(3 Q-2(-CH2-CH+ -J -(Q-≠ [Q-IC)13 1 +CH2-C-7 Q-J 'Q-TACH3 ■ +CH2-Csu■ (Here, p-TSOe represents p-)toluenesulfonic acid anion.) The monomer units represented by the general formula (I) or (n) of the present invention are the constituent components. It is preferable that the molecular weight of the polymer Di9 is 70,000 or more from the viewpoint of photographic properties, coating suitability, etc. When using Mayuko's Polymer Di9 as a solution, the molecular weight teeth/ ,
000.000 or less, especially 3θo,o.

The vinyl monomer unit +
When using a vinyl monomer unit having λ or more copolymerizable unsaturated bonds in one molecule as C or +D, the molecular weight of the polymer becomes infinite, and from the viewpoint of coating properties, it is difficult to form a dispersion. used as.

The following examples further illustrate specific examples of the invention.

Synthesis Example 1 Synthesis of Poly(N-vinylimidazole) T-7 Add N-vinylimidazole T-7 to a 300ml reaction vessel.
, 'Add DMF≠y, and replace thoroughly with nitrogen gas to
heated to oc. 2,2' when the temperature becomes constant
-Azobis(2,41-dimethylvaleronitrile) 1
．． 3g of 2hiro was added. Then, after 2 hours, 2,2'-azobis(,2,Hiro-dimethylvaleronitrile)/,2'
13fi was added and heating continued for an additional 2 hours. After the reaction solution was cooled to room temperature, it was added to acetone, and the precipitate was separated and dried under vacuum to obtain 20 g of a white polymer. Yield: 6% Synthesis Example 2 Synthesis of poly(N,N-dimethylaminopropyl acrylamide) T-6! N,N-dimethylaminopropylacrylamide ist, 2Ag, and ethanol are added to the reaction vessel of 00d. 2'-azobis(λ,≠-dimethylvaleronitrile), 2. t9 was added as an addition date.

Another hour later, do the same thing 1. After that, heating and stirring were continued for 1 hour and 30 minutes. The reaction sample was cooled to room temperature, 3 ooml of distilled water was added, and the mixture was placed in a cellulose dialysis chamber and dialysis was continued for λ days.The white polymer was obtained by freeze-drying.

Yield: 7. Synthesis Example 3: Synthesis of Poly(N-Pendylimidazol)ium Chloride) Q-2 Poly(N-vinylimidazole) λ HiroL obtained in Chemical Example 1
Mix DMP, z2og, and ethanol θ9, and
Heated to oC. Next (・Benzyl Chloride Hiroog
was gradually added dropwise and heated for 5 hours.

This reaction solution was added to 70% acetate of f3.11, and the precipitated crystals were separated and dried under vacuum to obtain a white polymer of tig. Yield: Octopus, Hirochi Synthesis Example 4 Synthesis of poly(styrene-N-methyl-N-vinylbenzylpiberidinium chloritol-co-divinylbenzene) Q-3 Synthesized by the method described in JP-A-J-30321.

Synthesis Example 5 Synthesis of poly(N-methyl-vinylbenzylmorpholinium chloride-co-divinylbenzene) Q-Hiro (i) Synthesis of poly(divinylbenzene-co-chloromethylstyrene) polymer dispersion 3! Pour 0 ml of distilled water, degas it with nitrogen gas, and add Triton 770 10 ml.
jl, 09 (0, J, S'mo/L/), Sihinylbenzene, tg (o, o, z moles) were added and heated to tOoC. Potassium persulfate/009 was added to θml of distilled water degassed with nitrogen gas, and 3tg of sodium bisulfite was added to 10ml of degassed distilled water, and the mixture was stirred for 4 hours. continued. Thereafter, the above mixture was cooled to room temperature and filtered to obtain a polymer dispersion (latex).

(il) To a quaternization reaction vessel, add 30 g of the above latex having a solid content concentration of 0% and distilled water sog, and add
Methylmorpholine //, 29 was added. Then 7o0
The temperature of the mixture was gradually raised to 100 mL, and the mixture was heated and stirred for 2 hours. After cooling to room temperature, the mixture was filtered to obtain a polymer dispersion mordant.

Solid content concentration: lg, ow. A polymer having a monomer unit represented by general formula (I) contained in the mordant layer of the present invention as a constituent component and a monomer unit represented by general formula (II) as a constituent component. The blending ratio ((I)/1ill) with the polymer having as a weight ratio is preferably 0. /~10, preferably 0.2~1
It is between.

The mixing ratio of the polymer mixture mordant and binder of the present invention and the coating amount of the polymer mixture mordant are determined depending on the amount of dye to be mordanted, the type and composition of the polymer mixture mordant, and the image forming process to be used. The mordant/gelatin ratio is 20/1, which can be easily determined by the manufacturer.
0-10/20 (weight ratio), mordant application amount is 0.2-l
Jg/m2, preferably 0.5 to 197 m2.

The binders in the mordant layer used in the present invention can be contained alone or in combination.

A hydrophilic binder can be used for this binder. Hydrophilic binders are typically transparent or translucent hydrophilic colloids, such as gelatin, gelatin derivatives, polyvinyl alcohol, cellulose derivatives, and polysaccharides such as starch and gum arabic. Includes natural materials and synthetic polymeric materials such as polyvinylpyrrolidone, a water-soluble polyvinyl compound of an acrylamide polymer.

Among these, gelatin and polyvinyl alcohol can be particularly effectively used. As the gelatin used for the mordant layer, various known gelatins are used. For example, books on gelatin such as lime-treated gelatin, acid-treated gelatin, etc.
Alternatively, gelatin obtained by chemically modifying the obtained gelatin such as phthalation or sulfonylation can also be used. Further, if necessary, it can be used after being subjected to desalting treatment.

As the polyvinyl alcohol used for the mordant layer, various known polyvinyl alcohols are used.

Polyvinyl alcohols having various saponification degrees and polymerization degrees are used. The degree of saponification is preferably 70 or more, particularly preferably 10 or more. The degree of polymerization is preferably 300-2000, but materials having different degrees of saponification and polymerization may be used in combination.

Further, as for the saponification method, there are two methods, acid saponification method and alkali saponification method, and materials subjected to either saponification treatment can be used in the present invention.

As a material that satisfies these conditions, for example, (7) PVA-103, l'VA-/J Hiro, PV manufactured by Kuraray Co., Ltd.
A-C85PVA-IC (completely saponified), PVA-, :zo3, PVA = 4'20, L f
(The above are partially saponified).

The mordant layer containing the mordant of the present invention can contain various surfactants in order to improve coating properties.

For example, saponins (steroids), alkylene oxide derivatives (such as polyethylene glycol, polyethylene glycol/polypropynone glycol condensates, polyethylene glycol alkyl ethers, polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, Polyalkylene glycol alcohol-4-z+z amines or amides, silicone polyethylene oxide adducts, glycidol derivatives (
fc (e.g. alknylsuccinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc.Nonionic surfactants; rubenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfates, alkyl phosphate ester Q, N~ruacyl N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers,
Anionic surfactants containing acidic groups such as carboxyl, sulfo group, phosphor group, sulfate ester group, phosphate ester group, such as polyoxyethylene alkyl phosphate esters; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acids or amphoteric surfactants such as phosphoric acid esters, alkyl taurines, and amine oxides; alkyl amine salts; aliphatic or aromatic quaternary ammonium salts; and cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocycles.

Among the above-mentioned surfactants, it is preferable to include a polyethylene glycol type nonionic surfactant having a repeating unit of ethylene oxide in the molecule in the photosensitive material.

q′! j preferably has 5 or more repeating units of ethylene oxide.

Nonionic surfactants that meet the above conditions are widely used outside the field, and their structures, properties, and synthesis methods are well known. Representative known documents include 5urf
actant 5science seriesvolu
me 1. Nonjonic 5urfactants
(Edjted by Martin J, 5chic
k.

Marcel Dekker Inc, /ri47), 5
surface Active Ethylene 0x
ideAdducts (by Schoufeldt, N., Pergamon Pres., s/Fl.), and nonionic surfactants described in these documents that satisfy the above conditions are preferably used in the present invention.

These nonionic surfactants may be used alone or as a mixture of two or more.

The image-forming dyes to be mordanted in the mordanting layer of the present invention include the following. Namely, Phenolce 4: Azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, and carbonyl dyes having anionic groups such as hydroxyl groups, sulfo/amide groups, sulfonic acid groups, and carboxyl groups. and phthalocyanine/pigments, etc.

The mordant layer of the present invention is used to fix a dye in a color image forming method in which a diffusible dye is formed into an image, then diffused, and then fixed.

The above-mentioned color image forming methods include those that use a developing solution at a temperature around room temperature (for example, those described in Belgian Patent No. 7!7.2), and those that utilize heat development (for example, JP-A-5-118-1). j ni ≠ 3, same j doichi 772 hiro 7)
Although there are various forms such as, the mordant layer of the present application can be used in any of them.

A photographic element using the mordant layer of the present invention will be described in more detail below.

Photographic elements containing mordants of the present invention typically include 1) a support, 2)
It consists of a photosensitive element and 3) an image receiving element, and development can be done by heating or spreading a developer.

In either case, after exposing the photographic element in a double-sided manner,
. . develops the rogens, during which a diffusible dye is correspondingly produced image-wise, and this dye migrates to the image-receiving element (.

The photographic element described above may optionally be further provided with a developer, an auxiliary developer, and an auxiliary developer.
It can contain illustrative agents and processing elements.

One of the preferred specific embodiments of the above embodiment is Belgian Patent No. 7
This is disclosed in No. j7.2. Another preferred embodiment in which the mordant of the present invention can be used is described in US Pat. Hirois, Hiro V, same 3. l/l/j,
Hiroj No. 3. Hirois.

6 hiro 6, same j, 4 hiro, ≠ryo 7, and same 3゜1J3
No. 3,707, German Patent Application (OLS), 2°gλt
, RI No. 10, etc.

Another preferred embodiment using the mordant of the present invention is disclosed in JP-A-Sho! l-1g! 4t3, same! This is an embodiment in which the phenomenon occurs by heating as described in g-7 Takohiro 7, Japanese Patent Application No. 77-3/1976, j7-j2 ≠7, and is particularly preferred.

Example 1 This article describes how to make a silver iodobromide emulsion.

Gelatin Hiroshi θI and K B r , 2 A jl and water 30
Dissolve in 00ml. This solution is kept at jooC and stirred.

Next, a solution prepared by dissolving 3 kg of silver nitrate in 200 g of water is added to the above solution over a period of 70 minutes.

After that, 100ml of 3゜3g of KI! Add the IIC solution over 2 minutes.

Adjusting p ti 1 of the silver iodobromide emulsion thus prepared,
Allow to settle and remove excess salt.

After that, p i-i was 4, OVC combined yield l1-O
A silver iodobromide emulsion of O& was obtained.

Next, we will discuss how to make a benzotriazole silver emulsion.

Gelatin 219 and benzotriazole/3°2g to water 3
Dissolve in 000vdl. The solution is kept at ≠0°C and stirred. A solution of silver nitrate/79 dissolved in 10 ml of water was added to this solution over 2 minutes.

The pH of the benzotriazole silver emulsion is adjusted, and excess salt is removed by settling. Thereafter, p)1 was adjusted to t.O to obtain a benzotriazole with a yield of θog.

Next, we will describe how to make a gelatin dispersion of a dye-donating substance.

5 g of a cyan dye-donating substance with the following structure: 1 co-phosphoric acid
Sodium 2-ethylhexyl ester sulfonate o,t
9. Tree resin phosphate (TCP)t,!
Weigh i', add 30 ml of ethyl acetate, and add about tθ0C.
Heat to dissolve and make a homogeneous solution. After stirring and mixing this solution and 100y of a 70% solution of lime-treated gelatin,
Disperse in a homogenizer for 70 minutes at 10.00 ORPM.

This dispersion is called a dye-donating substance (cyanne dispersion).

Zero cyan dye-donating substance C4t(9(11 Next, we will discuss how to make a photosensitive coating.

The following materials were mixed and dissolved, and then coated on a polyethylene terephthalate film to a wet film thickness of 30 It m, and dried.

(a) Silver benzotriazole emulsion 109 (b) Silver iodobromide emulsion 209 (c) Dispersion of the dye-providing substance (cyan) 33
ji (e) 70% ethanol solution of guanidine trichloroacetic acid lλ,! - (f) H2N502N(CH3) 2/1% aqueous solution
1 (g) Water 7. ! Further, on top of this, the following composition was applied as a protective layer to a film thickness of 2J μm.
I applied it and let it dry.

(h) 10% gelatin and high water solution 3! g (i) 10% ethanol solution of guanidine trichloroacetic acid 5 ml (j) Aqueous solution of 2-ethyl-hexyl succinate sulfonic acid 1 (k) Water! Next, we will describe how to make the dye fixing material. The aforementioned T-/,
Add J, Q-2, 3, and Da as shown in the table below, and make 2QOml.
of distilled water was added, and 10% lime-treated gelatin ioog was added and mixed uniformly. This mixed solution was uniformly applied onto a paper support laminated with polyethylene in which titanium dioxide was dispersed to a wet film thickness of 0 μm.

This sample was dried and used as a dye fixing material.

Using a tungsten bulb on the above photosensitive coating,
Imagewise exposure was carried out for 10 seconds at 0 lux. After that/300C
The mixture was heated uniformly for 30 seconds on a heat block heated to . Next, 10 ml of water per 7 m 2 was supplied to each film side of the dye fixing material, and after fc, the photosensitive coating material that had been heat treated and the dye fixing material to which the water had been supplied were placed so that the film sides were in contact with each other. Superimposed on. ? After heating for 1 second on a heat block at 00C, the dye-fixing material was peeled off from the light-sensitive material, and a negative cyan dye was obtained on the dye-fixing material. The densities of these negative images were measured using a Macbeth reflection densitometer (RD-t).

Next, a transparent film with an ultraviolet absorbing layer was placed on the film surface of the dye fixing material with these negative images, and xenon light (700,000 lux) was irradiated onto the color image for 3 days using an Atlas Cl5j weatherometer. did. The density of the color image before and after irradiation with xenon light was measured to evaluate the fastness of the color image to light.

Each maximum thickness and reflection density 1. Table 7 shows the dye residual rate at θ.

As shown in Table 1, by using a tertiary amine polymer and a quaternary ammonium salt polymer together in the mordant layer for cyan dye, the high transfer density exhibited by the quaternary ammonium polymer alone can be maintained. It was found to improve the light fastness of color images.

Example 2 The same operations and treatments as in Example 1 were carried out except that the cyan dye-donating substance in the dispersion of dye-providing substance in the photosensitive coating of Example 1 was replaced with a dye-donating substance having the following structure. I did it. The results are shown in Table 2.

*Magenta dye-donating substance H Also, as shown in Table 2, for the magenta dye, by using a tertiary amine polymer and a quaternary ammonium salt polymer together in the mordant layer, the quaternary ammonium salt polymer can be used alone. Next we find that the high transfer density.

Example 3 The same operations and treatments as in Example 1 were carried out, except that the cyan dye-providing substance in the dispersion of the dye-providing substance in the photosensitive coating of Example 1 was replaced with a dye-providing substance having the following structure. .

The results are shown in Table 3.

*Yellow dye-donating substance CH3 Table 3 Regarding the yellow dye, by using a tertiary amine polymer and a quaternary ammonium salt polymer together in the mordant layer, the high transfer density exhibited by the quaternary ammonium polymer alone was maintained. It was found to improve the light fastness of the dye.

As is clear from Examples 1 to 3 above, when a quaternary ammonium salt is used alone in the mordant layer, a high transfer density can be obtained, but it is difficult to stably maintain the transferred color image. However, by adding a tertiary amine polymer to this mordant layer, it is possible to increase the light fastness of the dye image while maintaining a high transfer density.

Therefore, it is shown that the present invention provides a mordant layer with high transfer density and excellent light fastness of the transferred dye image.

Example 4 A photosensitive sheet coated on a polyethylene terephthalate transparent support as follows: (1) A mordant consisting of the same polymer composition as used in Example 10 dye fixing material 1~/7 3°Oy/rn
2 and a mordant layer containing 3.0 g/m2 of gelatin. (Mordant layer 1~/7) (2) Titanium oxide 20 g/m 2 and gelatin λ
.

White reflective layer containing o g/m2.

(3) Carbon black λ, 3j! /m2 and gelatin 3, /y/m2.

(4) The following cyan dye image donor O0, Aji/m and λ, tertiary t-butylhydro Φnon 0゜o3g
Dissolve 7m2 fc/, 4. A layer containing @/m2 of N,N-diethyl laurylamide and/or 697 m2 of gelatin.

(5) Red spectrally sensitized silver iodobromide internal latent image type direct reversal emulsion containing 1 g/m2 of silver (emulsion of Example 1 of JP-A-2-3-3-2012), o , o4′.

1/m2 of 3-(2-formylethyl)-comethyl-benzothiazolium bromide and/or ji'/
A red-sensitive emulsion layer containing m” of gelatin.

(613,31/m Seratin, 0,030ji/m
2 liters of sodium bisulfite. Dissolved in both g/m2 of tricresyl phosphate and 0.77 I/m2 of dibutyl phthalate L/, 2 & 7 rn 2. j-
An intermediate layer containing di-t-octyl.hydroquinone.

(7) / -j g/m2 of gelatin, 0. Ij'
A magenta dye image donor having the following structure of g/m2 and 0.030ji/m (1)2. ! -Dissolved both di-t-butylhydroquinone/,! g/rn of N,N-diethyl laurylamide.

Magenta dye image donor holiday: 0H (8)/. Green spectrally sensitized silver iodobromide internal latent image type direct reversal emulsion containing 4'& / m 2 of silver (Patent Application No. 6)
Emulsion of Example 1 of No. 0-79193), 0,010 g/m
2-3-(2-formylethyl)-comethyl-penzothiazolium bromide 6 and/.

Green-sensitive emulsion layer containing 0 &/m2 gelatin.

(9) 3-7.9/m2 cellar yarn, 0,02
317/m Sodium Bisulfite, 0.2” 9
/m2 of Co,j-di-tert-octylhydroquinone dissolved in an intermediate containing 7'C/,j g/m2 of tricundyl phosphate (solvent) and 0.4/,9An2 of dibutyl phthalate (solvent). layer.

(102°/g 7 m 2 of gelatin, yellow dye image donor/, j, 9/J and co, !-G-t-
i-thylhydroquinone 0.0≠, 2777 m (7) A layer containing 2,5 g 7 m2 of N,N-diethyl laurylamide in which both were dissolved.

Yellow dye image donor: Blue-sensitive internal latent image type silver iodobromide direct reversal emulsion containing silver of αη 2.2 y 7m 2 (Japanese Patent Application Laid-Open No. 2002-23492-34', ! Emulsion layer of Example 1) , 3-(2-
formylethyl)-2-methyl-benzothiazolium bromide and 1. ．． 7! A blue-sensitive emulsion layer containing j7rJ gelatin.

Gelatin protective layer of α g/m 2. The following processing solution was spread between the coated cover sheet and the above photosensitive sheet on a polyethylene terephthalate transparent support, and the results shown in Table 1 were obtained. (Example 1)
The fastness to light was evaluated using the same method. ) Cover sheet: polyacrylic acid as a neutralized acidic polymer layer on a polyethylene terephthalate support (viscosity approximately / 000 (p) / j ji / m in a 10 wt.
Hydrolyze 100jJ of acetylcellulose and
Produces acetic acid of Hiro I) 3. g/m and poly(styrene-co-maleic anhydride) Cmi ratio, styrene-maleic anhydride = 4B; o: Hiro θ, molecular weight approximately 50,000)'-
-i! , 97m2 was applied.

Dye Remaining Rate Even in the form of a diffusion transfer type color photosensitive material that uses a developer at a temperature around room temperature, as shown in the table, the mordant layer contains a tertiary amine polymer and a quaternary ammonium salt polymer. It has been found that the light fastness of color images can be improved by using them in combination.

Claims (1)

[Scope of Claims] At least one layer containing both a polymer having a monomer unit represented by the following general formula (I) as a constituent and a polymer having a monomer unit represented by the general formula (If) as a constituent. Photo element with. General formula (I), -+A+--(-C+x y , [General formula (I) [where A represents a ruhinyl monomer unit having a tertiary amine; C represents either a tertiary amine or a quaternary ammonium salt; Represents a vinyl monomer unit that does not have any mol.
D~ [In the general formula CI[), B represents a vinyl monomer unit having a quaternary ammonium salt. D is general formula (1)
is the same as that represented by C. ・U is λ to 100 mol%, and v is 0 to 100 mol%. ]