JPH1073908A - Photographic element having temporary barrier layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photographic element having a temporary barrier layer excellent in temperature characteristic and stability during storage of a colored image by providing the temporary barrier layer containing a polymer containing a specified repeat unit. SOLUTION: This photographic element has at least one temporary barrier layer containing a polymer containing a repeat unit represented by the formula I. In the formula I, R represents hydrogen atom or methyl group. Q represents O or NH, L represents a substituted or non-substituted alkylene, arylene, or aralkylene group, wherein it represents an alkylene, arylene or aralkylene group having 4-20 carbon atoms in total when Q is O and having 7-20 carbon atoms in total when Q is NH, respectively. As a preferred example of this polymer, a polymer represented by the formula II is given. In the formula II, A represents a monomer unit (copolymerizing component) derived from a monomer having at least one copolymerizanble ethylenic unsaturated group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION This invention relates to photographic elements and, more particularly, to the diffusion (penetration) of alkaline processing compositions in photographic layers.
In contrast, the present invention relates to a photographic element having a layer forming a temporary barrier, wherein the temporary barrier layer comprises a high molecular polymer containing a novel monomer unit.

More particularly, it relates to a diffusion transfer photographic element having improved image storability.

[0003]

BACKGROUND OF THE INVENTION The placement of a temporary barrier layer between layers through which a processing composition penetrates in a photographic element is known in conventional photography and diffusion transfer photography.

[0004] In particular, in a diffusion transfer method photograph, a neutralizing layer is used for the purpose of stopping development and stabilizing an image. It is well known that a temporary barrier layer is used as a mechanism (timing layer) for neutralization timing in order to prevent the maximum concentration from decreasing too early.

Generally, the development reaction of silver halide photography is slow at low temperatures and fast at high temperatures. Therefore, when the diffusion transfer method is used as an instant photograph, the developing process is performed at various temperatures, not at a controlled temperature as in a normal photograph, so that a good image is obtained even when the developing temperature changes. The neutralization reaction of the developer depends on the temperature so that the neutralization reaction of the developer is carried out quickly at a high temperature because the development reaction is fast, and the neutralization reaction of the developer is carried out at a low temperature because the development reaction is slow. It is very important that the photographic element has a function of compensating for it.

US Pat. No. 4,423,14 discloses a timing layer having such a temperature compensation function.
No. 4,448,8 using a carboxy-ester-lactone polymer as proposed in US Pat.
No. 74, in which a copolymer of vinylidene chloride and an ethylenically unsaturated carboxylic acid is used in combination with a copolymer of maleic anhydride and a vinyl ester. A method using a copolymer containing an ethylenically unsaturated monomer having a group causing a β-elimination reaction in an alkaline environment as described in US Pat. No. 4,440,848. A method using a copolymer of a polybasic acid monovinyl ester, a hydrophobic aliphatic carboxylic acid vinyl ester and an aromatic carboxylic acid vinyl ester has been reported.

However, in the timing layers exemplified in these patents, temperature compensation of the neutralization reaction of the developing solution is possible, but the temperature range in which the compensation can be made is much larger than the temperature range actually used in instant photography. Therefore, only an unsatisfactory image can be obtained.

Further, the image formed by the processing, especially when stored under high temperature and high humidity, may be gradually faded even in a dark place, and the image may be remarkably deteriorated. The storage stability of an image is also one of the performances required for photographic performance, but the polymer exemplified in the above-mentioned patent did not provide an effect of improving the image storage stability.

Japanese Patent Application Laid-Open No. Sho 63-168648 discloses that a timing layer is provided with two layers, a first timing layer and a second timing layer, and further comprising an ethylenic compound having a substituted styrene and a hydrophobic carboxylic acid between the two layers. A method for improving the image storage stability by providing an auxiliary neutralizing layer comprising a copolymer with an unsaturated monomer is described. However, in this method, a sufficient effect of improving image storage stability has not been obtained, and the layer structure is complicated, and the burden on manufacturing costs and the like is large.

Another method of using the temporary barrier layer is to use the temporary barrier layer as an intermediate layer for controlling the development of a silver halide emulsion layer by layer. In this case, it is desirable to act as a barrier for a very short time only for developing each layer, and then to act so as not to hinder the diffusion of the dye.

As the intermediate layer, when a mordant layer and a silver halide emulsion layer are provided on the same support, for example, water is applied during storage so that the mordant layer does not affect the silver halide emulsion layer during storage. There is the use of an intermediate layer that acts as a barrier to penetration and does not hinder the diffusion of the dye after processing.

Further, in a photographic element for a diffusion transfer method in which an alkali processing composition is spread between two sheets, the alkali processing composition is prematurely absorbed by a sheet not containing a silver halide emulsion, whereby the halogenation is prevented. In some cases, the sheet may be provided with a temporary barrier layer for the alkali processing composition so that the development of the silver emulsion is not delayed and the alkali processing composition is not unnecessarily developed.

[0013]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a photopolymer having a temporary barrier layer comprising a novel polymer and having excellent temperature characteristics and excellent stability during storage of a color image. In providing the elements.

A second object of the present invention is to provide a photographic element for a diffusion transfer method which has excellent processing temperature characteristics and excellent stability during storage of a color image.

[0015]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object has been achieved by using a photograph having at least one temporary barrier layer containing a polymer containing a repeating unit represented by the following general formula (I). It has been found that it can be achieved by elements.

[0016]

Embedded image However, R represents a hydrogen atom or a methyl group, Q represents O or NH, L is a substituted or unsubstituted alkylene, arylene, or aralkylene group. When Q is O, the total carbon number is 4 or more and 20 or less. , Q represents NH, which represents an alkylene, arylene or aralkylene group having a total carbon number of 7 or more and 20 or less.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred examples of the polymer in the present invention include a polymer represented by the following general formula (II).

[0018]

Embedded image In the formula, A represents a monomer unit (copolymer component) derived from a monomer having at least one copolymerizable ethylenically unsaturated group.

The ethylenically unsaturated monomer units in the preferred polymer used in the present invention are, for example, ethylene, propylene, 1-butene, isobutene, styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, vinylbenzylsulfonic acid Soda, N, N, N-trimethyl-N-vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-N-vinylbenzylammonium chloride, α-methylstyrene, vinyltoluene, 4-vinylpyridine,
2-vinylpyridine, benzylvinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone, 1-vinyl-2-methylimidazole, monoethylenically unsaturated esters of aliphatic acids (eg, vinyl acetate, allyl acetate), ethylenic Unsaturated monocarboxylic acids or dicarboxylic acids and salts thereof (for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate, potassium acrylate, sodium methacrylate), maleic anhydride, ethylenically unsaturated monocarboxylic acid Esters of acids or dicarboxylic acids (e.g., n-butyl acrylate, n-hexyl acrylate, hydroxyethyl acrylate, cyanoethyl acrylate, N, N-diethylaminoethyl acrylate, methyl methacrylate, n-butyl methacrylate Rate, benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl methacrylate, methoxyethyl methacrylate, N, N
-Diethylaminoethyl methacrylate, N, N, N-
Triethyl-N-methacryloyloxyethylammonium p-toluenesulfonate, N, N-diethyl-N
-Methyl-N-methacryloyloxyethylammonium p-toluenesulfonate, dimethyl itaconate, monobenzyl maleate), amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids (eg acrylamide, N, N-dimethylacrylamide, N
-Methylolacrylamide, N- (N, N-dimethylaminopropyl) acrylamide, N, N, N-trimethyl-N- (N-acryloylpropyl) ammonium p-toluenesulfonate, 2-acrylamide-2-
Sodium methylpropanesulfonate, acryloylmorpholine, methacrylamide, N, N-dimethyl-N'-acryloylpropanediaminepropionate betaine,
(N, N-dimethyl-N'-methacryloylpropanediamine acetate betaine).

A is arbitrarily selected for the purpose of controlling the properties (eg, solubility, glass transition point, ionicity, hydrophobicity, hydrophilicity, permeability of an alkali-treated composition, etc.) of the polymer used in the present invention. . A may contain two or more types of monomer units, and is useful for controlling the permeability and solubility of the alkali treatment composition. For example, when this polymer is used for a timing layer or the like, it is necessary to make the time serving as a temporary barrier relatively long, so that a hydrophobic monomer unit (for example, styrene, methyl methacrylate, butyl acrylate, etc.) should be used as A. Alternatively, when two or more monomer units are used for A, the proportion of hydrophobic monomer units may be increased. Conversely, when shortening the temporary barrier time as in the case where this polymer is used for an intermediate layer or the like, A is a hydrophilic monomer unit (for example, acrylic acid, acrylamide, etc.).
It is possible to achieve the purpose by using or increasing the ratio.

When the polymer used in the present invention is used as a crosslinked latex, A has at least two copolymerizable ethylenically unsaturated groups in addition to the above ethylenically unsaturated monomers. Monomers (for example, divinylbenzene, methylenebisacrylamide, ethylene glycol diacrylate, trimethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylene glycol dimethacrylate, neopentyl glycol dimethacrylate) are used.

R represents a hydrogen atom or a methyl group.

Q represents O or NH.

L represents a substituted or unsubstituted alkylene, arylene, or aralkylene group. When Q is O, L has a total carbon number of 4 to 20, preferably 7 to 20;
When Q is NH, it represents an alkylene, arylene or aralkylene group having a total carbon number of 7 or more and 20 or less, preferably 10 or more and 20 or less. When L is a substituted alkylene, arylene, or aralkylene group, examples of the substituent include a methyl group, an ethyl group, a butyl group, a phenyl group, and a benzyl group.

A and b represent weight percentages, and a is from 0 to 9
9, b is 1 to 100, preferably a is 50 to 95, b is 5 to 50, more preferably a is 75 to 90, b is 10
It takes a value of ２５25. a and b are arbitrarily selected according to the properties required for the polymer.

The polymer used in the present invention has a molecular weight of 3,0.
Those having a range of 00 to 1,000,000 can be used, preferably those having a range of 5,000 to 500,000, more preferably 10,000 to 300,000.

The preferred polymer represented by the general formula (II) of the present invention generally comprises the aforementioned ethylenically unsaturated monomer A and the ethylenically unsaturated monomer represented by the following general formula (III). It is obtained by polymerizing.

[0028]

Embedded image R represents a hydrogen atom or a methyl group.

Q represents O or NH.

L is a substituted or unsubstituted alkylene, arylene or aralkylene group. When Q is O, L has a total carbon number of 4 to 20, preferably 7 to 20;
When Q is NH, it represents an alkylene, arylene or aralkylene group having a total carbon number of 7 or more and 20 or less, preferably 10 or more and 20 or less. When L is a substituted alkylene, arylene, or aralkylene group, examples of the substituent include a methyl group, an ethyl group, a butyl group, a phenyl group, and a benzyl group.

Among the ethylenically unsaturated monomers represented by the general formula (III), typical useful monomers are listed below, but are not limited thereto.

When Q is O, the following monomers may be mentioned.

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image When Q is NH, the following monomers may be mentioned.

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image Hereinafter, specific synthesis examples of the monomer represented by the general formula (III) will be described. Synthesis Example 1 Synthesis of Monomer 1-1 δ-Valerolactone 30.0 g (300 mmol), 5
72 ml of a prescribed sodium hydroxide aqueous solution (360 mm
1) 5 g of p-methoxyphenol was added to acetonitrile 4
The mixture is heated to 65 ° C. with stirring and reacted for 1 hour. Then, after cooling with ice, 40.7 g (450 mmol) of acrylic acid chloride was added dropwise over 1 hour. After the temperature of the reaction solution was raised to 65 ° C. again, stirring was continued for another 1.5 hours. After filtering the reaction solution, acetonitrile in the filtrate was distilled off under reduced pressure, and the reaction solution was concentrated. Distillation (90-92 ° C./1.0 mmH) from the concentrated reaction solution
g) gave 28.4 g (55% yield) of the title compound. The structure was confirmed by NMR spectrum and IR spectrum. Synthesis Example 2. Synthesis of Monomer 2-1 47.8 g (300 mmol) of 8-aminocaprylic acid,
63.0 g (750 mmol) of sodium hydrogen carbonate, p
-Mix 5 g of methoxyphenol with 400 ml of acetone, cool on ice, and stir with acrylic acid chloride 40.7
g (450 mmol) was added dropwise over 1 hour. After the temperature of the reaction solution was raised to 65 ° C., stirring was further continued for 1.5 hours,
Thereafter, filtration was performed. The residue was added to 2 liters of aqueous hydrochloric acid solution to dissolve excess sodium hydrogen carbonate, and then filtered. The filtrate was air-dried overnight and recrystallized from 1 liter of acetonitrile to give the title compound 5.
4.4 g (85% yield) were obtained. NMR spectrum, I
The structure was confirmed by the R spectrum.

The polymerization of the ethylenically unsaturated monomer A with the ethylenically unsaturated monomer represented by the general formula (III) is carried out by a generally known radical polymerization method (for example, Takayuki Otsu and Masayoshi Kinoshita, “Polymer Experimental methods of synthesis ”, Kagaku Doujin, published in 1972, pages 124 to 154, etc.)
It should be done by.

The polymer used in the present invention is generally polymerized in a solvent such as an organic solvent.
It is also preferable to synthesize by emulsion polymerization. Next, an example of the polymerization reaction will be described. Other polymers can be easily synthesized according to this method. Synthesis Example 3 Synthesis of poly (methyl methacrylate-co-8-acrylamide-caprylic acid) 150 ml of methyl ethyl ketone, 35.2 g of methyl methacrylate, and 4.8 g of 8-acrylamide-caprylic acid were put into a reaction vessel, and degassed with nitrogen gas. '-Azobis (2,4-dimethylvaleronitrile) (2.0 g) dissolved in methyl ethyl ketone (15 ml) was added.
Heated to ° C. and continued stirring for 1 hour. Thereafter, 140.8 g of methyl methacrylate, 8-acrylamide-
19.2 g of caprylic acid in 240 ml of methyl ethyl ketone
A solution of 3.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 60 ml of methyl ethyl ketone was added dropwise over 2 hours. Two more
2'-azobis (2,4-dimethylvaleronitrile)
A solution prepared by dissolving 5.0 g in 20 ml of methyl ethyl ketone was added, and the mixture was heated to 75 ° C. and stirred for 5 hours, whereby the reaction solution became a colorless and transparent viscous liquid. After the reaction solution was cooled to room temperature, it was taken out of the reaction vessel. Yield 582
g, solid content concentration: 33.7% (polymer yield: 98.1%) Next, among the polymers represented by the general formula (II) of the present invention,
Representative examples of particularly useful polymers are listed below, but the present invention is not limited thereto.

The numbers in parentheses represent weight percentages. (1) Methyl methacrylate / monomer 1-1 copolymer (84/16), molecular weight: 30,000 (2) Methyl methacrylate / monomer 1-3 copolymer (84/16), molecular weight: 35,000 (3 ) Methyl methacrylate / monomer 1-5 copolymer (82/18), molecular weight: 30,000 (4) methyl methacrylate / monomer 1-10 copolymer (76/24), molecular weight: 40,000 (5) methyl methacrylate / Monomer 1-15 copolymer (82/18), molecular weight: 50,000 (6) methyl methacrylate / monomer 1-17 copolymer (82/18), molecular weight: 55,000 (7) n-butyl acrylate / Monomer 1-1 copolymer (84/16), molecular weight: 50,000 (8) n-butyl acrylate / monomer 1-6 copolymer (84/16), molecular weight: 45,000 (9) n-butyl Acrylate / monomer 1-13 copolymer (82/18), molecular weight: 75,000 (10) ethyl methacrylate / monomer 1-3 copolymer (84/16), molecular weight: 50,000 (11) ethyl methacrylate / Monomer 1-8 copolymer (80/20), molecular weight: 40,000 (12) methyl methacrylate / butyl acrylate / monomer 1-1 copolymer (50/34/16), molecular weight:
40,000 (13) Methyl methacrylate / butyl methacrylate /
Monomer 1-3 copolymer (50/34/16), molecular weight: 50,000 (14) methyl methacrylate / styrene / monomer 1
1 copolymer (50/34/16), molecular weight: 10,000 (15) ethyl methacrylate / styrene / monomer 1-
14 copolymer (50/34/16), molecular weight: 15,000 (16) methyl methacrylate / monomer 2-1 copolymer (82/18), molecular weight: 30,000 (17) methyl methacrylate / monomer 2- 2 copolymer (78/22), molecular weight: 40,000 (18) methyl methacrylate / monomer 2-5 copolymer (82/18), molecular weight: 45,000 (19) methyl methacrylate / monomer 2-7 copolymer Polymer (82/18), molecular weight: 45,000 (20) methyl methacrylate / monomer 2-15 copolymer (82/18), molecular weight: 40,000 (21) n-butyl acrylate / monomer 2-1 Polymer (82/18), molecular weight: 60,000 (22) n-butyl acrylate / monomer 2-4 copolymer (82/18), molecular weight: 70,000 (23) n-butyl acrylate / monomer 2-11 Polymer ( 0/20), molecular weight: 75,000 (24) ethyl methacrylate / monomer 2-3 copolymer (76/24), molecular weight: 50,000 (25) ethyl methacrylate / monomer 2-5 copolymer (82 / 18), molecular weight: 55,000 (26) Ethyl methacrylate / monomer 2-13 copolymer (78/22), molecular weight: 45,000 (27) methyl methacrylate / n-butyl acrylate / monomer 2-1 Polymer (50/32/18), molecular weight: 40,000 (28) methyl methacrylate / ethyl methacrylate /
Monomer 2-5 copolymer (50/32/18), molecular weight: 40,000 (29) methyl methacrylate / styrene / monomer 2
3 copolymer (50/26/24), molecular weight: 10,000 (30) ethyl methacrylate / styrene / monomer 2-
7 Copolymer (50/32/18), molecular weight: 20,000 The polymer represented by the general formula (II) of the present invention is dissolved in a suitable solvent for dissolving the polymer and coated on a support. It can optionally be incorporated into a photographic element as a temporary barrier layer comprising the polymer. This temporary barrier layer may contain other than the polymer used in the present invention. Suitable solvents for the polymer used in the present invention are, for example, organic solvents, and typical examples thereof include acetone, ethyl acetate, methyl ethyl ketone, alcohols such as methanol and ethanol, and diacetyl alcohol, and mixed solvents thereof. Can be. Further, depending on the type of the polymer, water can be used as the solvent.

The photographic element of the present invention can be a light-sensitive material, an image-receiving material or a cover sheet for a diffusion transfer method. The form of the photosensitive material may be a film unit for a diffusion transfer method in which a photosensitive element, an image receiving element and a processing element are combined. In any case, the light-sensitive material (hereinafter sometimes referred to as a light-sensitive material) has, as an essential component, at least one silver halide photographic emulsion layer provided on a support, and usually further comprises an intermediate layer and the like. including. The polymer of the general formula (II) of the present invention may be used as a layer for forming a temporary barrier against diffusion (permeation) of the treatment composition, for example, a neutralization timing layer in a cover sheet or an intermediate layer in a light-sensitive material. It is contained in a layer or a neutralization timing layer in an image receiving material (or an image receiving element), but is preferably contained in a timing layer of a cover sheet or an appropriate layer (for example, an intermediate layer) in a light-sensitive material. 0.5
-10 g / m ² (photosensitive material), preferably 1
-10 g / m ² , more preferably 2-8
g / m ² .

To reproduce a natural color by the subtractive color method, a silver halide emulsion having selective spectral sensitivity in a certain wavelength range and a dye image forming compound having selective spectral absorption in that wavelength range (hereinafter referred to as "color material") ) (Or a coloring material containing a group that forms such a dye) is used.

In particular, a photosensitive element comprising a combination of a blue-sensitive silver halide emulsion and a yellow colorant, a combination of a green-sensitive silver halide emulsion and a magenta colorant, and a combination of a red-sensitive emulsion and a cyan colorant is useful. . These combination units of the emulsion and the colorant may be coated in layers in a face-to-face relationship in the light-sensitive material, or may be applied in the form of individual grains (the colorant and silver halide grains are present in the same grain). And may be mixed and applied as a single layer.

Hereinafter, a color material which releases a diffusible dye for forming a transferred image will be described as an example.

Hereinafter, each component included in the present invention will be sequentially described. 1. Components and Layers Constituting Photosensitive Sheet or Image Receiving Sheet A) Support The support of the photosensitive sheet used in the present invention is a smooth transparent or opaque support usually used for photographic photosensitive materials.

As the transparent support, for example, cellulose acetate, polystyrene, polyethylene terephthalate, polycarbonate and the like are used, and it is preferable to provide an undercoat layer. Preferably, the support usually contains a trace amount of a dye or a pigment such as titanium oxide to prevent light piping.

The thickness of the support is 50 to 350 μm, preferably 70 to 210 μm, more preferably 80 to 150 μm.
m.

As the opaque support, a baryta layer, α-
Paper coated or laminated with an olefin polymer (eg, polyethylene, polypropylene, polyester, ethylene-butene copolymer) or the like, or a transparent film containing a white pigment may be used.

If necessary, a layer for curl balance or an oxygen barrier layer described in JP-A-56-78833 may be provided on the back side of the support. B) Image receiving layer The dye image receiving layer used in the present invention contains a mordant in a hydrophilic colloid. This may be a single layer or a multilayer structure in which mordants having different mordant powers are applied in layers. This is described in JP-A-61-25255.
No. 1. As the mordant, a polymer mordant is preferable.

Polymer mordants include polymers containing secondary and tertiary amino groups, polymers having a nitrogen-containing heterocyclic moiety,
And a polymer containing a quaternary cation with a molecular weight of 5,
It is preferably from 000 to 500,000, particularly preferably from 10,000 to 300,000.

The coating amount of the mordant is generally 0.5 to 1
0 g / m ² is preferably particularly preferably 1.0 to 5.0 g / m ² is 2 to 4 g / m ^2.

As the hydrophilic colloid used in the image receiving layer, gelatin, polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone and the like are used, and gelatin is preferred.

In the image receiving layer, a discoloration preventing agent described in JP-A Nos. 62-30620, 62-30621 and 62-215272 can be incorporated. C) White reflective layer The white reflective layer forming the white background of the color image usually contains a white pigment and a hydrophilic binder.

As the white content for the white reflection layer, barium sulfate, zinc oxide, barium stearate, silver flake, silicates, alumina, zirconium oxide, sodium zirconium sulfate, kaolin, mica, titanium dioxide and the like are used. . Further, non-film-forming polymer particles made of styrene or the like are also used. These may be used alone or as a mixture as long as the desired reflectance is obtained.

A particularly useful white pigment is titanium dioxide.

The whiteness of the white reflective layer varies depending on the type of the pigment, the mixing ratio of the pigment and the binder, and the amount of the pigment applied, but the light reflectance is desirably 70% or more. In general, as the amount of the pigment applied increases, the whiteness improves.However, when the image forming dye diffuses through this layer, the pigment becomes resistant to the diffusion of the dye. Is desirable.

[0058] Titanium dioxide 5 to 40 g / m ^2, preferably 10 to 25 g / m ² was applied, light reflectance 540nm
A white reflective layer having 78 to 85% of light having a wavelength of is preferred.

Titanium dioxide can be selected from various commercially available brands.

Among them, it is particularly preferable to use rutile type titanium dioxide.

Many commercially available products are surface-treated with alumina, silica, zinc oxide, or the like. To obtain a high reflectance, the surface treatment amount is preferably 5% or more. Commercially available titanium dioxide includes, for example, those described in Research Disclosure No. 15162 in addition to Ti-pure R931 manufactured by DuPont.

As a binder for the white reflective layer, an alkali-permeable polymer matrix such as gelatin, polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose can be used.

A particularly preferred binder for the white reflective layer is gelatin. The ratio of white pigment to gelatin is 1/1 to 2
0/1 (weight ratio), preferably 5/1 to 10/1 (weight ratio).

The white reflective layer contains JP-B-62-3062.
It is preferable to incorporate an anti-fading agent such as No. 0 or No. 62-30621. D) Light-shielding layer A light-shielding layer containing a light-shielding agent and a hydrophilic binder is provided between the white reflective layer and the photosensitive layer.

As the light-shielding agent, any material having a light-shielding function can be used, but carbon black is preferably used. Degradable dyes described in U.S. Pat. No. 4,615,966 may be used.

The binder for coating the light-shielding agent may be any binder capable of dispersing carbon black, and is preferably gelatin.

As the carbon black raw material, for example, D
onnel Voet "Carbon Black" MarcelDekker, Inc. (1
Any production method such as a channel method, a thermal method and a furnace method described in 976) can be used. The particle size of the carbon black is not particularly limited, but is preferably 90 to 1800 angstroms (A). The addition amount of the black pigment as a light-shielding agent may be adjusted according to the sensitivity of the photosensitive sheet to be shielded from light, but is preferably about 5 to 10 in optical density. E) Photosensitive Layer In the present invention, a photosensitive layer comprising a silver halide emulsion layer combined with a dye image-forming substance is provided above the light-shielding layer. The components will be described below. (1) Dye image-forming substance The dye image-forming substance used in the present invention is a non-diffusible compound which releases a diffusible dye (may be a dye precursor) in association with the silver phenomenon, or has a diffusivity of itself. Is changing, and the theory of the photographic process (The The
ory of the Photographic Process), 4th edition. All of these compounds can be represented by the following general formula (IV).

Formula (IV) (DYE-Y) _n -Z ｛DYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, May cause a difference in diffusivity of the compound represented by (DYE-Y) _n -Z corresponding to or opposite to a photosensitive silver salt having a latent image in an image form, or release DYE and release (DYE-Y) _n -Z represents a group having a property that causes a difference in diffusivity, and n represents 1 or 2, and when n is 2, two DYE- Y may be the same or different.機能 By the function of Z, the compound is roughly classified into a negative type compound which becomes diffusible in a silver developed portion and a positive type compound which becomes diffusible in an undeveloped portion.

Specific examples of the negative type Z include those which are oxidized and cleaved as a result of development to release a diffusible dye.

A specific example of Z is disclosed in US Pat. No. 3,928,312.
Nos. 3,993,638 and 4,076,529
Nos. 4,152,153 and 4,055,428
Nos. 4,053,312, 4,198,235
Nos. 4,179,291 and 4,149,892
No. 3,844,785, No. 3,443,943
Nos. 3,751,406 and 3,443,939
Nos. 3,443,940 and 3,628,952
Nos. 3,980,479 and 4,183,753
No. 4,142,891, No. 4,278,750
Nos. 4,139,379 and 4,218,368
No. 3,421,964, 4,199,355
No. 4,199,354, 4,135,929
No. 4,336,322, 4,139,389
No. JP-A-53-50736 and JP-A-51-104343.
No. 54-130122, No. 53-110827
Nos. 56-12642, 56-16131, 57-4043, 57-650, and 57-207
No. 35, No. 53-69033, No. 54-130927
Nos. 56-164342 and 57-119345.

Among the Z of the negative dye releasing redox compound, a particularly preferred group is an N-substituted sulfamoyl group (an N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). it can. Representative groups of Z are exemplified below, but are not limited thereto.

[0072]

Embedded image For positive-type compounds, see Angev. Hemi International Edition English.
Chem. Inst. Ed. Engl.), 22, 191 (1982).
It is described in.

Specific examples include compounds (dye developing agents) which are initially diffusible under alkaline conditions but are oxidized by development to become non-diffusible. As the effective Z for this type of compound, those described in U.S. Pat. No. 2,983,606 are representative.

Another type is a type in which a diffusible dye is released by, for example, self-ring closure under alkaline conditions, but the dye is not substantially released when oxidized during development. . Specific examples of Z having such a function are described in US Pat. No. 3,980,479,
-69033, 54-130927, U.S. Pat. Nos. 3,421,964 and 4,199,355.

Another type does not release the dye itself, but releases the dye when reduced.
Compounds of this type are used in combination with an electron donor,
The diffusible dye can be released imagewise by reaction with the remaining electron donor imagewise oxidized by silver development. For atomic groups having such a function, see, for example, US Pat. Nos. 4,183,753 and 4,142,891.
No. 4,278,750, 4,139,379
No. 4,218,368, JP-A-53-11082.
7, U.S. Pat. Nos. 4,278,750 and 4,356,
Nos. 249 and 4,358,525, JP-A-53-11
0827, 54-130927, 56-164
No. 342, published technical report 87-6199, European Patent Publication 2
20,746A2.

Specific examples are shown below, but the present invention is not limited to these.

[0077]

Embedded image When a compound of this type is used, it is preferably used in combination with a diffusion-resistant electron-donating compound (known as an ED compound) or a precursor thereof. E
Examples of D compounds include, for example, U.S. Pat. No. 4,263,39.
No. 3,4,278,750, JP-A-56-1387
No. 36, etc.

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

[0079]

Embedded image Details of this are disclosed in U.S. Pat.
No. 8,783.

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

Examples of yellow dyes: US Pat. No. 3,597,
No. 200, 3,309,199, 4,013,6
No. 33, No. 4,245,028, No. 4,156,60
No. 9, 4,139,383 and 4,195,992
No. 4,148,641, No. 4,148,643
No. 4,336,322: JP-A-51-11493
No. 0, No. 56-71072: Research Disclosure 1
7630 (1978) and 16475 (1977).

Examples of magenta dyes: US Pat. No. 3,453,453
No. 107, No. 3,544,545, No. 3,932,3
No. 80, No. 3,931,144, No. 3,932,30
No. 8, 3,954, 476, 4, 233, 237
Nos. 4,255,509 and 4,250,246
Nos. 4,142,891, 4,207,104
No. 4,287,292: JP-A-52-10672.
No. 7, No. 53-23628, No. 55-36804,
No. 56-73057, No. 56-71060, No. 55
-134.

Examples of cyan dyes: US Pat. No. 3,482,9
No. 72, No. 3,929,760, No. 4,013,63
No. 5, 4,268,625, 4,171,220
Nos. 4,242,435 and 4,142,891
Nos. 4,195,994 and 4,147,544
No. 4,148,642; British Patent 1,551,1
No. 38; JP-A-54-99431, JP-A-52-8827
No. 53-47823, No. 53-143323,
Nos. 54-99431 and 56-71061; European Patents (EP) 53,037 and 53,040;
Research Disclosure 17,630 (1978) and 16,475 (1977).

These compounds are disclosed in JP-A-62-2152.
No. 72, pages 144 to 146. These dispersions are described in JP-A-62-2152.
No. 72, pages 137 to 144 may be included. (2) Silver halide emulsion The silver halide emulsion used in the present invention may be a negative emulsion which mainly forms a latent image on the surface of silver halide grains,
An internal latent image type direct positive emulsion which forms a latent image inside silver halide grains may be used.

The internal latent image type direct positive emulsion may be, for example, a so-called “conversion type” emulsion prepared by utilizing a difference in solubility of silver halide, or may be doped with metal ions.
Or a "core / shell" emulsion in which at least the photosensitive sites of the silver halide inner nucleus (core) grains subjected to chemical sensitization or both are coated with an outer shell of silver halide. These are described in U.S. Pat. Nos. 2,592,250 and 3,206,313, British Patent 1,027,146, and U.S. Pat.
Nos. 6, 3,935,014 and 3,447,927
No. 2,297,875, No. 2,563,785
Nos. 3,551,662 and 4,395,478
No. 2,728,108, US Patent 4,43.
1,730 and the like.

When an internal latent image type direct positive emulsion is used, it is necessary to give a surface fog nucleus using light or a nucleating agent after image exposure.

As nucleating agents therefor, US Pat.
Hydrazines described in US Pat. Nos. 563,785 and 2,588,982; hydrazines and hydrazones described in U.S. Pat. No. 3,227,552; British Patent 1,28.
3,835, JP-A-52-69613, U.S. Pat. Nos. 3,615,615, 3,719,494, 3,734,738, 4,094,683, and 4,115. , A heterocyclic quaternary salt compound described in U.S. Pat. No. 3,122,470; a sensitizing dye described in U.S. Pat. Nos. 925, 4,031,127, 4,245,037, 4,255,511, 4,266,013, 4,276,364 and British Patent 2,012,443. Thiourea-bonded acylhydrazine-based compounds described in US Pat.
0,270, 4,278,748, British Patent 2,
Acylhydrazine-based compounds in which a thioamide ring or a heterocyclic group such as triazole or tetrazole described in 011, 391B or the like is bonded as an adsorptive group are used.

In the present invention, a spectral sensitizing dye is used in combination with the negative emulsion and the internal latent image type direct positive emulsion.
For specific examples, see JP-A-59-180550,
No. 60-140335, Research Disclosure (RD) 17029, U.S. Patent 1,846,300
No. 2,078,233 and 2,089,129
Nos. 2,165,338 and 2,231,658
No. 2,917,516, 3,352,857
No. 3,411,916, 2,295,276
No. 2,481,698, 2,688,545
Nos. 2,921,067 and 3,282,933
Nos. 3,397,060 and 3,660,103
Nos. 3,335,010 and 3,352,680
Nos. 3,384,486 and 3,623,881
Nos. 3,718,470 and 4,025,349. (3) Composition of photosensitive layer To reproduce a natural color by the subtractive color method, the dye image-forming substance which provides a dye having selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the spectral sensitizing dye. And a photosensitive layer composed of at least two of the following combinations. The emulsion and the dye image-forming substance may be coated as separate layers,
Alternatively, they may be mixed and applied as a single layer. When the dye image-forming substance is coated and has absorption in the spectral sensitivity range of the emulsion combined therewith, a separate layer is preferred. The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image forming substance layer. For example, a layer containing a nucleation development accelerator described in JP-A-60-173541, JP-B-60-1
It is also possible to increase the color image density by providing a partition layer described in No. 5267, or to enhance the sensitivity of a photosensitive sheet by providing a reflective layer.

The reflection layer is a layer containing a white pigment and a hydrophilic binder. Preferably, the white pigment is titanium oxide and the hydrophilic binder is gelatin. The coating amount of titanium oxide ^{0.1g / m 2 ~8g / m 2} , and preferably from ^{0.2g / m 2 ~4g / m 2} . Examples of the reflective layer are described in JP-A-60-91354.

In a preferred multilayer structure, a combination unit of a blue-sensitive emulsion, a combination unit of a green-sensitive emulsion, and a combination unit of a red-sensitive emulsion are sequentially arranged from the exposure side.

An optional layer can be provided between the emulsion layer units as needed. In particular, to prevent the undesired effect of the development effect of one emulsion layer on other emulsion layer units,
Preferably, an intermediate layer is provided.

When a developer is used in combination with a non-diffusible dye image-forming substance, the intermediate layer preferably contains a non-diffusible reducing agent to prevent diffusion of the oxidized developer. Specific examples thereof include non-diffusible hydroquinone, sulfonamidophenol, and sulfonamidonaphthol, and more specifically, JP-A-50-21249, and JP-A-50-21249.
No. 0-23813, JP-A-49-106329, and JP-A-49-106329.
No. 9-129535, U.S. Pat. No. 2,336,327,
2,360,290, 2,403,721, 2,544,640, 2,732,300, 2,782,659, 2,937,086, and 3 637,393, 3,700,453, British Patent 557,750, JP-A-57-24949, and 58-21249. The dispersing methods are described in JP-A-60-238831 and JP-B-60-18978.

In the case of using a compound capable of releasing a diffusible dye by silver ions as described in JP-B-55-7576, it is preferable to include a compound that captures silver ions in the intermediate layer.

In the present invention, an anti-irradiation layer, a UV absorber layer, a protective layer and the like are provided as required. F) Release Layer In the present invention, a release layer can be provided, if necessary, to peel off the photosensitive sheet in the unit at an arbitrary place after the treatment. Therefore, this release layer must be easily peelable after the treatment. Materials for this purpose include, for example, JP-A Nos. 47-8237, 59-220727 and 5
Nos. 9-229555 and 49-4653, U.S. Pat. Nos. 3,220,835 and 4,359,518, JP-A-49-4334, JP-A-56-65133, and JP-A-45-465.
No. 24075, U.S. Pat. Nos. 3,227,550, 2,759,825, 4,401,746, and 4,366,227 can be used. One specific example is a water-soluble (or alkali-soluble) cellulose derivative. Examples include hydroxyethyl cellulose, cellulose acetate phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate, carboxymethyl cellulose, 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 can also be used. Still another example is a water-soluble synthetic polymer. For example, polyvinyl alcohol, polyacrylate, polymethyl methacrylate, polybutyl methacrylate, or a copolymer thereof, or the like.

The release layer may be a single layer or a plurality of layers as described, for example, in JP-A-59-220727 and JP-A-60-60642. II. Neutralization timing layer G) Layer having a neutralization function The layer having a neutralization function comprises a neutralization layer and a timing layer containing the polymer used in the present invention. Are disposed above or below (directly or indirectly) above or below the neutralizing layer in such a positional relationship as to reach the neutralizing layer via the above. The layer having a neutralizing function may be disposed on any of the photosensitive sheet, the image receiving sheet, and the cover sheet,
Also, a plurality may be arranged.

The neutralizing layer used in the present invention is a layer containing a sufficient amount of an acidic substance to neutralize the alkali introduced from the treatment composition. A preferred acidic substance is pKa9
A higher fatty acid such as oleic acid described in U.S. Pat. No. 2,983,606, which is a substance containing the following acidic groups (or precursor groups that provide such acidic groups by hydrolysis): US Patent 3,362
No. 819, polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or anhydrides; acrylic acid and acrylic as disclosed in French Patent 2,290,699 Acid ester copolymers; U.S. Pat. No. 4,139,383 and Research Disclosure;
re) No. 16102 (1977).

In addition, US Pat. No. 4,088,493,
JP-A Nos. 52-153739, 53-1023, 53-4540, 53-4541 and 53-45.
No. 42 and the like can also be mentioned.

Specific examples of the acidic polymer include ethylene,
Copolymers of vinyl monomers such as vinyl acetate and vinyl methyl ether with maleic anhydride and their n-butyl esters, copolymers of butyl acrylate and acrylic acid, cellulose, acetate hydrogendiene phthalate and the like.

The above-mentioned polymer acid can be used by mixing with a hydrophilic polymer. Such polymers include:
Examples include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol, carboxymethylcellulose (including partially saponified products), hydroxymethylcellulose, hydroxyethylcellulose, and polymethylvinylether. Among them, polyvinyl alcohol is preferred.

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

The amount of the polymer acid applied is adjusted in accordance with the amount of the alkali spread on the film unit. The equivalent ratio of polymer acid and alkali per unit area is 0.9 to 2.0
Is preferred. If the amount of the polymer acid is too small, the hue of the transfer dye is changed or stain is generated on a white background portion. If the amount is too large, inconveniences such as a change in hue and a decrease in light resistance are caused. A more preferred equivalent ratio is 1.0-1.
3. If the amount of the hydrophilic polymer to be mixed is too large or too small, the quality of the photograph is deteriorated. The weight ratio of the hydrophilic polymer to the polymer acid is from 0.1 to 10, preferably from 0.3 to 3.0.

In the present invention, the layer having a neutralizing function includes:
Additives can be incorporated for various purposes. For example,
To harden this layer, hardeners well known to those skilled in the art can be added, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin and the like can be added to improve the brittleness of the film. In addition, if necessary, an antioxidant, a fluorescent whitening agent, a development inhibitor and a precursor thereof may be added.

In the present invention, the timing layer is provided between the neutralizing layer and the dye-providing compound layer when the photosensitive sheet has a neutralizing layer, and when the image receiving sheet has a neutralizing layer, the neutralizing layer and the image receiving layer, and the cover sheet. When there is a neutralizing layer, it is preferable to provide the neutralizing layer between the neutralizing layer and the layer in contact with the alkali treatment composition.

When the polymer-containing layer used in the present invention is used as a timing layer, for example, gelatin, polyvinyl alcohol, a partially acetalized product of polyvinyl alcohol, or the like in the same timing layer or in another timing layer.
Polymers that reduce alkali permeability, such as cellulose acetate, partially hydrolyzed polyvinyl acetate, and the like;
Latex polymers made by copolymerizing a small amount of a hydrophilic comonomer such as an acrylic acid monomer to increase the activation energy of alkali permeation; and polymers having a lactone ring can also be used.

Among them, JP-A-54-136328,
U.S. Pat. Nos. 4,267,262 and 4,009,030
No. 4,029,849 and the like, a timing layer using cellulose acetate;
No. 335, No. 56-69629, No. 57-6843
No. 4,056,394 and 4,061,4
Nos. 96, 4,199,362, 4,250,24
No. 3, 4,256, 827, 4,268,604
And the like. A latex polymer made by copolymerizing a small amount of a hydrophilic comonomer such as acrylic acid;
A polymer having a lactone ring disclosed in U.S. Pat. No. 4,229,516;
Nos. 56-97346 and 57-6842, European Patent (EP) 31,957A1, 37,724A
No. 1, No. 48,412 A1 and the like are particularly useful.

In addition, those described in the following documents can also be used.

US Pat. Nos. 3,421,893 and 3,4
55,686, 3,575,701, 3,77
8,265, 3,785,815, 3,84
7,615, 4,088,493, 4,12
3,275, 4,148,653, 4,20
1,587, 4,288,523, 4,29
7,431, West German Patent Application (OLS) 1,622,9
No. 36, No. 2, 162, 277, Research
Disclosure 15, 162 No. 151 (1
976) The timing layer using these materials can be used as a single layer or as a combination of two or more layers.

The timing layers made of these materials are used, for example, in US Pat. No. 4,009,029, West German Patent Application (OLS) No. 2,913,164, and US Pat.
No. 72, JP-A Nos. 54-155837 and 55-138.
No. 745, and the like, and a development inhibitor and / or a precursor thereof disclosed in US Pat.
Hydroquinone precursor disclosed in No. 78,
Other useful photographic additives or precursors thereof can be incorporated. H) Others In addition to the layer having a neutralizing function, a layer having an auxiliary function may include a back layer, a protective layer, a filter dye layer, and the like.

The back layer is provided for adjusting the curl and imparting a slipperiness. Filter dyes may be added to this layer.

The protective layer is mainly used for preventing adhesion to the back surface of the cover sheet and adhesion to the protective layer of the photosensitive sheet when the photosensitive sheet and the cover sheet are overlapped.

The sensitivity of the photosensitive layer can be adjusted by incorporating a dye into the cover sheet. The filter dye may be added directly to the support of the cover sheet or to a layer having a neutralizing function, further to the back layer, the protective layer, or the like, or a single layer may be provided. III. Alkali treatment composition The treatment composition used in the present invention is an alkaline solution sufficient to adjust the pH to 12 to 14, and includes a hydroxide of an alkali metal (for example, sodium hydroxide, potassium hydroxide,
Lithium hydroxide), alkali metal phosphates (eg, potassium phosphate), guanidines, and quaternary amine hydroxides (eg, tetramethylammonium hydroxide, etc.). Sodium is preferred.

The thickener is used in order to spread the treatment liquid uniformly.
Further, it is necessary to maintain the close contact between the photosensitive sheet and the cover sheet or between the photosensitive sheet and the image receiving sheet. For example, alkali metal salts of polyvinyl alcohol, hydroxyethyl cellulose, and carboxymethyl cellulose are used, and preferably, hydroxyethyl cellulose and sodium carboxymethyl cellulose are used.

As the light-shielding agent, any dye or pigment, or a combination thereof, can be used as long as it does not diffuse to the dye image-receiving layer and produce stain. A typical example is carbon black.

As the preferred developing agent, any one can be used as long as it cross-oxidizes the dye image-forming substance and does not substantially generate stain even when oxidized. Such developing agents may be used alone or in combination of two or more, and may be used in a precursor form. These developing agents may be contained in an appropriate layer of the photosensitive sheet or in an alkaline processing solution. Specific examples of the compound include aminophenols and pyrazolidinones, and among them, pyrazolidinones are particularly preferable because they generate less stain.

For example, 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3
-Pyrazolidinone, 1- (3'-methyl-phenyl)-
4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-
4-hydroxymethyl-3-pyrazolidinone.

The processing composition used in the peeling-free type film unit is uniformly spread on the photosensitive sheet after exposing the photosensitive sheet, and is disposed on the back surface of the support or on the side opposite to the processing solution of the photosensitive layer to form a light-shielding layer. As a pair, the photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed by the components contained therein. For this purpose, the composition contains an alkali, a thickener, a light-blocking agent, a developer, and further, a development accelerator for controlling the development, a development inhibitor, and an antioxidant for preventing the deterioration of the developer. Etc. The composition always contains a light-shielding agent.

A photosensitive sheet, an image receiving sheet, a cover sheet, or an alkali treatment composition is disclosed in JP-A-62-2.
No. 15272, pages 72 to 91, development accelerators;
Hardeners described on page 155, surfactants described on pages 201 to 210, fluorine-containing compounds described on pages 210 to 222, 225
To 227 to 230, an antistatic agent to 227 to 230, a polymer latex to 230 to 239,
Matting agents described on page 240 can be included.

[0118]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. Example 1 Cover Sheet A cover sheet 1-1 was prepared in the following order on a polyethylene terephthalate support containing a light-piping preventing dye and subbed with gelatin. (A) 10.4 g / m ² of acrylic acid-n-butyl acrylate (molar ratio 8: 2) copolymer having an average molecular weight of 50,000 and 1,4-bis (2,3-epoxypropoxy) -butane as 0 Neutralizing layer containing 1 g / m ² . (B) A neutralization timing layer containing 5.0 g / m ^{2 of the} above-mentioned exemplary copolymer (1).

The same as the cover sheet 1-1 except that the copolymer (1) of the cover sheet 1-1 was changed to copolymers (3), (4), (5) and (6), respectively. The coated cover sheets 1-2, 1-3, 1-4 and 1-5 were produced.

Further, the copolymer (1) of the cover sheet 1-1 was replaced with the copolymers (16), (17) and (1), respectively.
8), (19) and (20), except that the cover sheets 2-1 and 2-
2, 2-3, 2-4 and 2-5 were produced.

As a cover sheet for comparison, the copolymer (1) of the cover sheet 1-1 was prepared using the following polymers (i), (ii) and (i).
ii) Alternatively, cover sheets 3-1, 3-2, 3-3 coated in the same manner as cover sheet 1-1, except that the following polymer (iv) described in U.S. Pat. No. 4,440,848 was used. ,
3-4 was produced.

(I) Methyl methacrylate / 2-carboxyethyl acrylate copolymer (weight percentage 92/8) (ii) Methyl methacrylate / 5-acrylamide-caproic acid copolymer (weight percentage 86/14) (iii) Methyl Methacrylate / acrylic acid copolymer (weight percentage 94/6) (iv) Vinyl acetate / vinyl benzoate / monovinyl adipate copolymer (weight percentage 52/34/14) Further, as a cover sheet for comparison, cover sheet 1-
On the same support as in No. 1, coating was performed in the following order to prepare a cover sheet 4-1. (A ') The same neutralized layer as the layer (a). (B') 4.3% cellulose acetate having an oxidation degree of 55%.
g / m ² and a layer containing 0.2 g / m ² of a methyl half ester of a methyl vinyl ether-maleic anhydride copolymer (molar ratio: 50/50). (C ′) 1.7 g / m ^{2 of} styrene-n-butyl acrylate-acrylic acid-N-methylolacrylamide copolymer latex (weight percentage: 49.7 / 42.3 / 4.0 / 4.0) and methyl methacrylate Acrylic acid
A layer containing 1.1 g / m ^{2 of} N-methylolacrylamide copolymer latex (weight percentage: 93.0 / 3.0 / 4.0).

The neutralization timing time of each cover sheet was measured as follows.

[0124] pH indicator coating film transparent polyethylene terephthalate onto a thymolphthalein support 0.2 g / m ² and gelatin 7.0 g / m ²
Was applied to prepare a pH indicator coated film.

The alkali treatment liquid for neutralization timing time measurement The formulation of the alkali treatment liquid is shown below.

0.8 g of a treatment liquid having the following composition was filled in a container which can be broken under pressure.

Carboxymethylcellulose Na salt 58 g Potassium hydroxide (28% aqueous solution) 200 cc Water 830 cc Each of the transparent cover sheets was opposed to the above-mentioned pH indicator coated film, during which the alkali treatment liquid for measuring the neutralization timing time was applied to the liquid thickness. Expanded to 75 μm.
The predetermined time "neutralization timing time" required for the reflection density of the high pH color (blue) of thymolphthalein to be reduced and reduced to half by neutralization was measured at 15 ° C and 25 ° C.

The results are summarized in Table 1.

[0129]

[Table 1] As is clear from the comparison of the values in Table 1, the cover sheet 1 using the copolymer represented by the general formula (II) of the present invention was prepared.
Nos. 1 to 1-5 and 2-1 to 2-5 have a higher temperature-compensating ability (T ₁₅ / T ₂₅ ) of alkali permeability than the comparative cover sheet despite the single coating. Example 2 Image-Receiving Photosensitive Sheet A photosensitive sheet was prepared by coating a 90 μm-thick transparent polyethylene terephthalate film support with a layer structure as shown in Table-A.

[0130]

[Table 2]

[0131]

[Table 3]

[0132]

[Table 4]

[0133]

[Table 5] The chemical structural formulas and the like of the compounds used in the image receiving photosensitive sheet are shown below.

[0134]

Embedded image

[0135]

Embedded image

[0136]

Embedded image

[0137]

Embedded image

[0138]

Embedded image

[0139]

Embedded image Alkali treatment solution The formulation of the composition of the alkali treatment solution is shown below.

1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 10.0 g methylhydroquinone 0.18 g 5-methylbenzotriazole 3.0 g sodium sulfite (anhydrous) 0.2 g benzyl alcohol 1.5 cc carboxymethylcellulose Na salt 58 g carbon black 150 g potassium hydroxide (28% aqueous solution) 200 cc water 680 cc 0.8 g of the treatment liquid having the above composition was filled into a "pressure-disruptable container".

After the photosensitive sheet was exposed from the emulsion layer side through a color test chart, the photosensitive sheet was superposed on the cover sheet, and the above-mentioned alkali treatment composition was placed between the two sheets.
Use a pressure roller to a thickness of 2 μm and use a 25 ° C
Unfolded in.

One hour after the developing solution was developed, the green density of the formed image of each film unit was measured. Further, each film unit was placed in a dark place at a temperature of 60 ° C. (dry) and at a temperature of 45 ° C.
After storing each in a dark place at 80 ° C.-80% relative humidity (wet) for 3 days, the green density of the image was measured again. Change from the maximum density (D ^G _max ) of the green density part after one hour (Δ
^DG _max ) was determined as a measure of image storability. ΔD ^G
_If the value of _max is positive, it means increasing color, and if it is negative, it means fading. The smaller the absolute value of ΔD ^G _max , that is, the smaller the movement of D ^G _max after one hour, the more preservation of the image. Is superior. Table 2 shows the results.

[0143]

[Table 6] As is clear from the comparison of the values in Table 2, the cover sheet 1 using the copolymer represented by the general formula (II) of the present invention.
Film unit with 1～1-5,2-1～2-5, as compared to a film unit using a comparative coversheet "dry", "wet" both small decrease in D ^G _max, image storage It turns out that it is excellent.

[0144]

By using the polymer represented by the general formula (II) of the present invention, a photographic element having a temporary barrier layer having excellent temperature characteristics and excellent stability during storage of a color image can be obtained. be able to.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tetsuya Asakura 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (2)

[Claims] 1. A photographic element having at least one temporary barrier layer containing a polymer containing a repeating unit represented by the following general formula (I). Embedded image However, R represents a hydrogen atom or a methyl group, Q represents O or NH, L represents a substituted or unsubstituted alkylene, arylene, or aralkylene group. When Q is O, the total carbon number is 4 or more and 20 or less. , Q represents NH, which represents an alkylene, arylene or aralkylene group having a total carbon number of 7 or more and 20 or less. 2. A diffusion transfer photographic element having at least one neutralization timing layer containing the polymer of claim 1.