JPS59202463A - Photographic element - Google Patents

Abstract

PURPOSE:To obtain a photographic element having a temporary barrier layer with superior temp. characteristics by forming a layer contg. a polymer contg. monomeric units each having a specified group in the side chain on a photographic element. CONSTITUTION:A layer contg. a polymer contg. monomeric units each having a group represented by the general formula in the side chain is formed on a photographic element.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to photographic elements. Specifically, in a photographic element having a layer that forms a temporary barrier to diffusion (penetration) of an alkaline processing composition into the photographic layer, the temporary barrier layer comprises a polymeric polymer containing one unit of the novel monomer. The present invention relates to a photographic element characterized in that it consists of a combination.

It is known in conventional and diffusion transfer photography to provide temporary barrier layers in photographic elements between layers penetrated by processing compositions.

Particularly in diffusion transfer photography, a neutralizing layer is used for purposes such as stopping development and stabilizing the image. In order to prevent the maximum concentration from decreasing, it is well known to use the temporary barrier layer as a timing layer for neutralization timing.The temporary barrier layer used for this purpose is For example, U.S. Patent No. ≠, 07./
.

/Ari No. 2, Same No. +, 03t, 3? ',' No., Hiroshi.

20/,! ♂ No. 7, JP-A-33-72. It is disclosed in No. t22, Japanese Unexamined Patent Application Publication No. 37-1981/μ/A-Hiromu, etc.

The development reaction of silver halide photographs is generally slow at low temperatures and fast at high temperatures. Therefore, when using the diffusion transfer method as an instant photograph, the developing process is not carried out at a controlled temperature like in normal photography, but at various temperatures, so good images can be obtained even if the developing temperature changes. At high temperatures, the development reaction is fast, so the neutralization reaction of the developer is carried out quickly, and at low temperatures, the development reaction is slow, so the neutralization reaction of the developer is slowed down. It is extremely important to have the ability to compensate accordingly in the photographic element. Numerous examples of timing layers with such temperature compensation functions are disclosed in the aforementioned patents.

However, although it is possible to compensate for the temperature of the neutralization reaction of the developer using the timing layer exemplified in these patents, the range of temperatures that can be compensated is very narrow compared to the temperature range actually used in instant photography. In other words, if the neutralization reaction was controlled to have an appropriate speed to obtain a good image at a high temperature, the neutralization reaction could not be slowed down sufficiently at a low temperature. On the other hand, if you set the neutralization reaction speed to be appropriate for obtaining good images at low temperatures, the neutralization reaction will be too slow at high temperatures and the minimum density will increase. In any case, in the case of a wide temperature range in which instant photographs are actually used, the image quality of the resulting instant photographs would be significantly degraded.

Another use of the temporary barrier layer is as an intermediate layer for controlling the development of a silver halide emulsion in each layer in a photosensitive layer. In this case, it is desirable that the barrier act as a barrier for a very short period of time during layer-by-layer development, and then act so as not to inhibit the diffusion of the dye.

As an intermediate layer, when there is a mordant layer and a silver halide emulsion layer on the same support, for example, it should be coated to prevent water penetration 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 and does not impede the diffusion of the dye after processing.

Furthermore, in diffusion transfer photographic elements in which an alkaline processing composition is spread between two sheets, silver halide It may be advantageous to provide a temporary barrier layer to the alkaline processing composition on the core sheet to avoid delaying emulsion development and unnecessarily developing the alkali processing composition.

A first object of the present invention is to provide a photographic element having a temporary barrier layer of a novel polymer with excellent thermal properties.

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

A third object of the invention is to provide a photographic element for diffusion transfer with high image quality.

After extensive research, the inventors have discovered that the above objects can be achieved by photographic elements having at least one layer containing a polymer containing one monomer unit.

0 11] 1 However, J represents -C- or -S-, 1 X represents a plurality of atoms necessary to complete a heterocyclic nucleus having at least 7 j-membered rings or e-membered rings, O 111 Q represents -C-(J- or -S-, and R represents a hydrogen atom, an alkyl group, or an aryl group.

Preferred examples of the polymers in the present invention include polymers represented by the following general formula (I).

General formula (I) 1 The middle character represents a monomer unit (copolymerization component) derived from a monomer having at least one copolymerizable ethylenically unsaturated group.

Ethylenically unsaturated monomer units in preferred polymers of the invention include, for example, ethylene, propylene, /-phthene, isobutyne, styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, N ,N,
N-1-Dimethyl-N-vinylbenzylammonium chloride, N.

N-dimethyl-N-hen'zi-N-vinylbenzylammonium chloride, α-methylstyrene, vinyltoluene, ≠-vinylpyridine, covinylpyridine, benzylvinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone, /- Vinyl-2-methylimidazole, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate), ethylenically unsaturated mono- or dicarboxylic acids and their salts (e.g. acrylic acid, methacrylic acid, itaconic acid) ,
Maleic acid, Noda acrylate, Potassium acrylate,
(sodium methacrylate), maleic anhydride, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. han-) f k 7 acrylate, rhohexyl acrylate, hydroxyethyl acrylate, cyanoethyl acrylate), N, N-diethylaminoethyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl methacrylate, methoxyethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N,N-triethyl-N-methacryloyloxyethyl ammonium p-toluenesulfonate, N,, N-diethyl-N-methyl-N-methacryloyloxyethylammonium p-toluenesulfonate, dimethyl itaconate, maleic acid monobenzyl ester), ethylenically unsaturated monocarboxylic acid moiety or amides of dicarboxylic acids (e.g. acrylamide, N
, N-dimethylacrylamide, N-methylolacrylamide, N-(N,N-dimethylaminopropyl)acrylamide, N,N.

N-) Limethyl-N-(N-acryloylpropyl)ammonium p-toluenesulfonate, λ-acrylamide-comethylpropanesulfonate sodium, acryloylmorpholine, methacrylamide, N,N-dimethyl-N'-acryloylpropanediamine Propionate betaine %N.

It is derived from copolymerizable ethylenically unsaturated monomers such as N-dimethyl-N'-methacryloylpropanediamine acetate betaine).

The individual is optionally selected to control the properties of the polymers of the present invention, such as solubility, glass transition point, ionicity, hydrophobicity, hydrophilicity, permeability of alkaline processing compositions, etc. They may also contain more than one type of monomer unit and are useful in controlling the permeability and solubility of the alkaline treatment composition. For example, when using this polymer for a timing layer, etc., it is necessary to provide a relatively long period of time for it to act as a temporary barrier. or when one unit of two or more types of monomers is used for A, the proportion of one unit of a hydrophobic monomer may be increased. Conversely, when shortening the temporary barrier time, such as in an intermediate layer, the objective can be achieved by using a single hydrophilic monomer unit (for example, acrylic acid, acrylamide, etc.) as A, or by increasing its proportion. Is possible.

In addition, when the polymer of the present invention is used as a crosslinked latex, in addition to the above-mentioned ethylenically unsaturated monomers, at least two copolymerizable ethylenically unsaturated groups are used as A.
Monomers having more than 100% monomer (for example, divinylbenzene, methylene bisacrylamide, ethylene glycol diacrylate, trimethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, etc.) are used.

0 )111 J represents -〇- or -S-.

1 0 1 Hail multiple atoms needed to complete.

1 ma The best ones are as follows.

0 Q (In the formula, Y", Y, Y are each -〇-1-8-
or -N-, where z'' and z2 are 1.1 hydrogen atom, chlorine atom, bromine atom, 2) a group, carbamoyl group, sulfamoyl group, alkoxy group having preferably / to h carbon atoms (e.g. methoxy group, butoxy group, etc.)
, an alkyl group having preferably 7 to 2 carbon atoms (e.g. methyl group, isopropyl group, etc.), preferably having 4 carbon atoms
Represents an aralkyl group having ~72 carbon atoms (for example, a phenyl group), or an aralkyl group having preferably 7 to/λ carbon atoms (for example, a habenyl group, etc., R3 to R11 are hydrogen atoms,
An alkyl group having preferably /~ carbon atoms (e.g. methyl-N, isopropyl group, etc.), or an aryl group having preferably 2 to 7.2 carbon atoms (e.g. phenyl group, etc.)
, or an aralkyl group having preferably 7 to 2 carbon atoms (for example, a benzyl group). Q represents -CO- or -S-.

1 L represents a divalent organic group. Preferred examples are shown below, but the invention is not limited thereto.

0 11I CN R13, COR14- jl.

(In the above formula, R12 is a hydrogen atom, number of carbon atoms/~A pieces (
D 7 represents an alkyl group such as a methyl group or an isopropyl group, an aryl group having 4 to 7.2 carbon atoms such as a phenyl group, or an aralkyl group having 7 to 72 carbon atoms such as a benzyl group; It represents an alkylene group having 7 to 2 carbon atoms, such as a methylene group, a dimethylmethylene group, an inbutylene group, or a phenylene group. )
n represents O or /.

1 R represents a hydrogen atom or a methyl group.

R2 represents a hydrogen atom, an alkyl group preferably having /-J carbon atoms, or an aryl group preferably having 6 to /J carbon atoms; preferable.

a and b represent the molar fraction, a is θ~tata, and b is /~
10017) Take direct action. a, 1] are arbitrarily selected depending on the properties required for the polymer.

The combination of this light is generally a carboxyl group or a sulfinic acid residue and 14! Polymerized CFK1 in the ll chain Same as general formula (I), Q2 is -0H1-Br, -C/l
! represents. ) can be synthesized by reacting the compound shown in (1) in the presence of a suitable base or condensing agent. That is, taking a preferred polymer represented by general formula (I) as an example, it can be synthesized by reacting a polymer represented by general formula (I[) with a compound represented by general formula (III) as follows. Regarding the reaction mode, general formula C described in the next section
This is similar to the synthesis of the ethylenically unsaturated monomer represented by N).

General formula (1) 1 Q' General formula (1■) 1 (In the formula, A, J, X, L, n, R1, R2, a, b are the same as in general formula (I), and Ql is -COOH or -802I-f;
When Q is Q or -COOH, -OH.

-Br, -α, and when Ql is -8O2H, -B
r, represents -. ) Moreover, the preferred polymer represented by the general formula (1) of the present invention generally comprises: - the previously mentioned ethylenically unsaturated monomer A and the ethylenically unsaturated monomer represented by the following general formula (IV); It can be obtained by copolymerizing.

General formula (rυ 1 C) i 2: C 0 (However, 1. ■, X, Q, L, n, R, R are general formula (I)
Same as. ) Among the ethylenically unsaturated monomers represented by the general formula (IV), typical monomers useful for If\ are listed below, but the monomers are not limited to these.

-Sen U Tadashi
Q Medium A W Monomer 7 Monomer 8 Seven Monomers 9 The ethylenically unsaturated phase monomer represented by the general formula (iv'') of the present invention can be easily synthesized by the following various general synthesis methods.

(However, J, X, Q, L%n, , R, R are general formula (I)
Same as. ) Specific synthesis examples of some of the above monomers are shown below.

Synthesis example 1. Synthesis of Monomer 1 Mix acrylic acid chloride sjml, N-methylol phthalimide/00ji with 00ml of tetrahydrofuran, and add 1ml of diisopropylethylamine with stirring while cooling on ice and keeping the internal temperature at 5-7°C. The mixture was added dropwise over 1 hour. After continuing to stir for another 3 hours, the reaction solution was cooled on ice! % acid acetic acid aqueous solution. 1, crystals precipitated. After drying this crystal at night,
The title compound was obtained by recrystallization from ethanol 1.2.371 containing hydroquinone monomethyl ether jI91.

Bone collection, 23g, t♂% of theoretical value, m, p/33-/3g
'C, the structure was confirmed by NMR spectrum and IR spectrum.

Synthesis Example 2 Synthesis of Monomer 3 Acrylic acid 2om1. N-methylol dimethadione≠t
, 2g1 ≠-dimethylaminopyridine O0! A solution of g in methylene chloride (300 ml) was cooled with water and brought to an internal temperature of 5-5.
While keeping the temperature at 7°C, 62g of N,N'-synchrohexylcarbodiimide and methylene chloride (300g of
rrtl) was added dropwise over 30 minutes. After returning to room temperature and stirring thoroughly for 3 hours, the precipitated crystals were filtered out, and the mother liquor was further concentrated under reduced pressure. 3 g of Irganox 10IO (Ciba Geigy) was added to the remaining oily liquid, and the mixture was distilled under reduced pressure to obtain the title compound. Yield 3jjq, J-7% of theoretical value, bp/ri 0-20
The structure was confirmed by NMR and IR spectra at 0°c//mmHg.

Synthesis example 3. Synthesis of monomers N-bromomethylphthalimide 10I, potassium styrene sulfinate r, tg, nitrobenzene 0.1ml,
Add a mixture of 2 ml of acetic acid, ethanol, and 20 rnl to 70
The mixture was heated and stirred at 0.00 C for 3 hours. After cooling to room temperature, the precipitated crystals were collected. The crystals were dried to obtain the title compound. The yield was 36% of the theoretical value, the mp20 temperature was 210'C, and the structure was confirmed by NMR spectrum and IR spectrum.

The polymerization of the ethylenically unsaturated monomer A and the ethylenically unsaturated monomer represented by the general formula (■) is carried out by the generally well-known radical polymerization method (for example, in the book "Experiments on Polymer Synthesis" co-authored by Tsuyoshi Otsu and Masayoshi Kinoshita). Law” Kagaku Doujin, published in Showa≠7,
/26~/jl/- pages etc. for details. ), but a polymerization example will be shown next.

Synthesis example 4. Poly-(N-acryloyloxymethyl 7
Methyl ethyl ketone som13. monomer i
3. og, acrylic acid (Toagosei Chemical) 3゜0g,
Methyl methacrylate (Mitsubishi Gas Chemical) 2hiro.

After degassing with nitrogen gas, add 2'-azobis(
, 2,+-dimethylvaleronitrile) was added, and the mixture was heated to Jj'C and stirred for 3 hours. Then further λ,27-azobis(2,≠-dimethylpareronitrile)0. /jjj was added and heated and stirred for 3 hours, and the reaction solution became a colorless and transparent viscous liquid. After the reaction solution was returned to room temperature, it was added to hexane (AOOml) with stirring to precipitate a white polymer. The precipitated polymer is
After separation, the mixture was dried at room temperature under reduced pressure for an hour to obtain the title compound. Yield 2jg [13=0. /, 2u (30°C1 ethyl acetate solution).

Representative specific examples of preferable copolymers used for coating the neutralization timing layer of the present invention are listed below, but the invention is not limited thereto.

;ki ;ki ′:S
;ki =ki ;ki
=ki =ki11111111 ;ki =ki =ki nido =to;ki ;to;kihe
to to to to to
to λ to 1 to 6
o h 611
k k 6゜1 ＼ 1
\ 1 \ 1 \ 1 \ 1 \ 1 \
1 to brown)
b to car
−− no ri ω
ω Medium Q Medium Q Ya ν Ko! Instep
V inside V inside ψ A The polymer represented by the general formula (I) of the present invention is dissolved in an appropriate solvent that dissolves it,
The polymer can be incorporated as a temporary barrier layer into photographic elements by coating it on a support. This temporary barrier layer may contain other than the polymer of the present invention. Suitable solvents for the polymers of the present invention include, for example, organic solvents, representative examples of which are acetone,
Examples include alcohols such as ethyl acetate, methyl ethyl ketone, methanol, ethanol, diacetin alcohol, and mixed solvents thereof. Furthermore, depending on the type of polymer, water can also be used as a solvent.

Photographic elements of the invention can be light-sensitive materials, image-receiving materials, or cover sheets for diffusion transfer processes. The form of the photosensitive material may be a film unit for diffusion transfer method in which a photosensitive element, an image receiving element, and a processing element are combined. In any case, the above-mentioned photographic material has at least one silver halide photographic emulsion layer coated on a support as an essential component, and usually further includes an intermediate layer etc. The polymer of general formula (I) can be used as a layer for forming a temporary barrier against the diffusion (penetration) of a processing composition, such as a neutralization timing layer in a cover sheet or an intermediate layer in a sensitive material. It is contained in a neutralization timing layer or the like in an image-receiving material (or image-receiving element), but it is preferably contained in a timing layer of Kapaanto or a suitable layer (for example, an intermediate layer) in a light-sensitive material.

To reproduce natural colors by the subtractive color method, a silver halide emulsion with selective spectral sensitivity in a certain wavelength range and a dye image-forming compound (hereinafter referred to as "coloring material") with selective spectral absorption in that wavelength range (or colorants containing such pigment-forming groups)
A photosensitive material consisting of at least two combinations of is used.

Particularly useful are light-sensitive elements comprising a combination of a blue-sensitive silver halide emulsion and a yellow colorant, a combination of a green-sensitive emulsion and a magenta colorant, and a combination of a red-sensitive emulsion and a cyan colorant.

These combination units of emulsion and coloring material may be coated in a layered manner in a face-to-face relationship in a light-sensitive material, or they may be coated in the form of individual grains (coloring material and silver halide grains are present in the same grain). ) may be mixed and applied as a single layer.

Hereinafter, a coloring material that releases a diffusible dye for forming a transferred image will be explained as an example.

The colorants preferably used in the present invention are substantially immobile under alkaline processing conditions and can generally be represented by the following formula.

(Ballast)-(redox cleavage group+-+D
ye) In the formula, (Ballast) is a group for substantially immobilizing this compound under alkaline treatment conditions, but ÷
This group is not necessary if the redox cleavage group →Φye) alone is substantially immobile. (Dye) is a dye group or its skeleton that, when separated from this compound, can move into the photosensitive element under at least alkaline processing conditions, and (redox cleavage group) It has the property of being cleaved by oxidation or reduction.

As a redox cleavage atomic group, US Patent Application Publication US
83j/, No. 473, U.S. Permit-q z y, 2g
, No. 37, Japanese Patent Publication No. 3-j'0.73, US Patent No. 0.1! ,≠2r issue, same 1f,, Or3.3/ko issue, same g, 33t, 3.22 issue, JP-A-Sho! l-/01
13'A3, same Ta 3-Hirot 730, same! ≠-/3
0. /Coλ, US Patent 3. Google 3. ri No. 30, ri No. 3
, F4'J, Taj5', same 3. t, 21゜ri5
No. 2, 3.1≠≠, 7g! No. 3,4t≠3,
F4',? No. 3, ? l'0, ≠7P issue, same≠.

No. 271.7g0, JP-A No. 33-/10♂27, U.S. Pat.

No. 372, 4≠, 2/za, No. 36♂, same≠, lzaJ,
No. 713, 41. /112. Iri No. 1, same 3゜≠2/
, ri 2≠ issue, same ≠, / Tata, 3! Examples include those listed in item j. The dyes released from the colorants used in this invention may be ready-made dyes or alternatively dye precursors that can be converted into dyes in photographic processing steps or additional processing steps (the final image dye is Typical dye structures of coloring materials useful in the present invention include metal-complexed or metal-complexed azo dyes, azomethine dyes, anthraquinone dyes, and phthalocyanine dyes. Among these, cyan, magenta and yellow dyes are of particular importance.

Example of yellow dye: US Patent 3. 77.200, 3.30.

No. 722, same≠, 0/3, No. 133, rotation, 2≠3.0
No. 2, same≠, /j Otsu, toy No., same≠.

/3ri, 3j/3 issue, same≠, /rij, 9F2 issue, same t,
/≠f, JIIL/issue, same≠, l hong, 6 hong 3;
Unexamined Japanese Patent Publication No. 31-1973/≠730, t+-1ti No. 30,
Same number j4-71072; Re5earch Disclo
sure / 7A30 (/ri 7F), 76≠7
5 (/ri77).

Example of magenta dye: US Patent 3. ≠! 3, / No. 07, same j, t44
Gu.

! ≠! No. 3,732,310, No. 3. ri3/,/
≠≠ No. 3. ri32.30za issue, 3゜rij≠,≠7
No. 3,732.310, ≠, 2! j,! 0ri issue, same≠, 2 evening 0, 2≠ issue, samehiro, l≠2. Zari No. 1, Dohiro, No. 207.10≠, No. II, No. 217, 2 Octopus; Tokukai Sho! 2-10&, No. 727, z2-1047
No. 27, same! 3-23. t21, same jj-31. ．． I
No. O'1, No. A-73,037, No. jA-7101
, No. 0, No. 11-/3≠.

Example of cyan dye: US Patent 3. ≠♂λ, ri No. 72, same 3. riλri.

No. 740, u + (' Z J y 6 J No. 1, No. 1, 2t♂, &, lt, No. 11./7/, 22
0@, Dohiro.

2≠λ, ≠3j issue, same≠, /≠2, 19/ issue, same g, /
9! , Tata ≠ issue, same 4! , /4A7, jf
No. 1, same +, /≠t, 6≠No. 2; British patent/, 3j/
.

/3Ir issue; Tokkai Shoj! -991t3/issue, same j2-8
'127, jf3-47za23, jf3-7≠3
No. 323, J Hiro-Tata Hiro 3/No., J6-710t/
No.: European Patent (E'pc) j3゜037, same j
f3.0IAO issue; Re5earch Disclos
ure /7. A30 (/ri7J'), same/l, a
7s (iri71) and the same/4. ≠Things described in 7j (/ri77) issue.

Also useful as a type of dye precursor are those having a dye moiety that temporarily shifts light absorption in photosensitive elements.

Other colorants useful in the present invention include couplers that release diffusible dyes (such as those described in US Pat. No. 3,227J!0) and dye developers.

In the photographic emulsion used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide. Preferred silver halide is silver bromide, silver iodobromide or silver iodochlorobromide having an iodide content of 2.0 mol% or less and a chloride content of 30 mol% or less. Particularly preferred is silver iodobromide containing from λ mol % to 13 mol % iodide.

Silver halide emulsions are internal latent image type emulsions in which latent images are mainly formed inside silver halide grains.

Preferably, those that directly form a positive image when used in combination with a nucleating agent (direct reversal photographic emulsion).

Internal latent image type: Silver halide emulsions are exposed to light and the maximum density achieved when developed with an "internal type" developer is greater than the maximum density achieved when developed with a [surface type] developer. This allows for a clear definition. The internal latent image type emulsion according to the present invention is obtained by coating the silver halide emulsion on a transparent support and exposing it to light for a fixed time of 0-01 to 7 seconds using the following developer A (internal type developer). The maximum density measured by the usual photographic density measurement method when developed at 200C for 3 minutes was the same as above. At least the maximum density obtained when developing for φ minutes at It has twice the concentration.

The internal latent image type silver halide emulsion used in the present invention is a hydrophilic colloidal dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or a mixture thereof. And,
The halogen composition is selected depending on the intended use of the photosensitive material and processing conditions, but the iodide content is /I! 7 mole% or less,
Silver bromide, silver iodobromide or silver chloroiodobromide having a chloride content of 30 mole % or less is particularly preferred. Specifically, in addition to the emulsions described in U.S. Pat. No. J72.230, British Pat. /Ill, No. 3, U.S. Pat. 2OA
.

3/3 issue, same 3. j//, Atλ No. 3. ≠Hiroshi 7,
No. 227, 3,737, 3/3, 3゜71, /,
271. No. 3. Examples include conversion type emulsions, core/shell type emulsions, emulsions doped with different metals, etc., as described in No. 3, No. 0/≠, and the like. However, it is not limited to these.

Various photographic supports can be used in the light-sensitive material of the present invention.

The image-receiving element in the image-receiving material or film unit of the invention includes a small mordant layer (image-receiving layer), which mordant layer preferably consists of a polymer mordant. The polymer mordant includes secondary and tertiary amino groups. Polymers containing nitrogen-containing heterocyclic moieties, polymers containing these diurnal cation groups, etc. with a molecular weight of 3,000 or more,
Particularly preferred is 10,000 or more.

For example, US patents λ, j≠r, s6≠, and the same.

p, ra, tt3o, same 3. /1llr, Ot1, 3.7j6. Vinyl pyridine polymers and vinyl pyridinium cationic polymers disclosed in US Pat. ．． Otsu jj, A tag number, same 3. rz9,0
No. 94, ibid. a, i, 2g.

Yo3/issue, British Patent l, Core 7, Gu! A polymer mordant capable of crosslinking with gelatin, etc., disclosed in Specification No. 3, etc.;
US Patent 3. rij♂, No. 225, same J, 72/, 1
3; No. 2, same, No. 2.791.01, No. 3, Tokukai Sho! Hiroshi
//! , Coco g issue, same≠-l≠! .

Aqueous sol type mordant disclosed in No. 122, lij]jll-/, 24, 027, j't-1rr, r3s, j4-/7, 3, etc.; US Patent 3
Water-insoluble mordants disclosed in , 1 tr, orr specifications, etc.; U.S. Pat. , No. 27, Same Gu, Koi, ♂ Gu. A reactive mordant capable of forming a covalent bond with the dye disclosed in the specification, etc.;
tP. No. 3, 7♂za, t! ! No. J, 4≠2.
l1g-No. 3, G♂1,70z No. J,
! 17, No. 06, No. 3 of the same. λ7/, /Gua No. j, 27/.

1lit issue, JP-A-13-30,321, same j2-/
33. jλ♂ issue, 33-/2j issue, same! 3-/,
No. 02!44, No. j3-107,133, British Patent 2
, 06≠2go2 and the like.

Other US patents 2. , t7j, 3/ issue, same co.

l♂2. Mention may also be made of the mordants described in No. ljt.

The image-receiving layer that mordants an azo dye having a chelating group is preferably one in which a polymer capable of immobilizing transition metal ions and a transition metal ion are incorporated in the mordant layer or in a layer adjacent thereto. An example of a polymer that can immobilize such transition metal ions is 1% Kaisho! ! -171210, 33-
/2?311t, US Patent No. 11,273. I! ; No. 3 and No. 41,212.301, Dohiro, / 3, 7, 4l.

, 2♂r, ti1 issue, Dohiro, 2≠/, /13 issue.

The processing composition used to process the photosensitive material of the present invention preferably contains a base such as IJ hydroxide, potassium hydroxide, sodium carbonate, or sodium phosphate, and has a pH of about 100% or higher. (preferably with an alkaline strength of 1 or more, the treatment composition is sulfite) IJ
It may contain antioxidants such as chloride, ascorbate, piberidinohequinose retactant, and silver ion concentration regulators such as potassium bromide. It may also contain viscosity increasing compounds such as hydroquine ethyl cellulose and sodium carboxymethyl cellulose.
Also, the present alkaline processing composition has the effect of accelerating development or promoting dye diffusion. For example, compounds such as benzyl alcohol may be included. The developing agent may be added to the processing composition, or at least a portion of the developing agent may be added to the processing composition.
or a film unit) may be contained in an appropriate layer (for example, a silver halide emulsion layer, a colorant-containing layer, an intermediate layer, an image-receiving layer, etc.) ('-0 Specific examples of such a developing agent include: Hydroquinone compounds such as hydroquinone, co,j-dichlorohydroquinone and co-chlorohydroquinone; aminophenol compounds and eva, ≠-aminephenol, N-
Methylaminophenol, j-methyl-≠-aminophenol and 3,! -dibromoaminophenol; catechol compounds such as catechol, ≠ -7 chlorohexylcatechol, 3-methoxydicatecol and + -(
N-octadecylamino)catechol; phenylenediamine compounds such as N,N-diethyl-p-phenylenediamine, 3-methyl-N,N-diethyl-p-phenylenediamine, 3-methoxy N-x f-N
-ethoxy-p-phenylenediamino and N,N,N
', N'-tetramethyl-p-phenylenediamino;
3-pyrazolidone compounds such as /-phenyl-3-pyrazolidone, /-phenyl-≠, dag-methyl-3-pyrazo')ton, ≠-hydroxymethyl-≠-methyl-l
-phenyl-3-pyrazolidone;/-m-tolyl-3-
Pyrazolidone, /-p-tolyl-≠-methyl-derhydroxymethyl-3-pyrazolidone, /-phenyl-≠-
Methyl-3-pyrazolidone, /-phenyl-1-methyl-3-pyrazolidone, /-phenyl-Hiro, ≠-bis(
Hydroxymethyl)-3-pyrazolidone, l, ≠-dimethyl-3-pyrazolidone, ≠-methyl-3-pyrazolidone, Hiroshi.

≠-dimethyl-3-pyrazolidone, /-(m-chlorophenyl)-μmmethyl-3-pyrasolitone, /-(p-
chlorophenyl)-+-methyl-3-hirame')ton,
/-(m-chlorophenyl)-3-birasoliton, /-
(p-chlorophenyl)-3-pyrazolitone, /-(
p-tolyl)-gumethyl-3-pyrazolidone, / −
(o-)lyl)-gumethyl-3-pyrazolidone, /
-(p-tolyl)-3-pyrazolidone, / -(m -
tolyl)-g, ≠-dimethyl-3-pyrazolidone, /-
(2-trifluoroethyl)-p,p-dimethyl-3-
Examples include pyrazolidone and termethyl-3-pyrazolidone. Among these, 3-pyrazolidone compounds are preferred.

Various herbal medicines can be used in combination, as disclosed in US Pat. No. 3,033, No. ♂t.

A cover sheet for a diffusion transfer method is usually a neutralization film having at least a neutralization layer and a neutralization timing layer (a layer that forms a temporary barrier against diffusion (penetration) K of a processing composition) coated on a support. It has a system.

Preferred acidic substances used in the neutralization layer include pKa2
A substance containing an acidic group (or a precursor group that provides such an acidic group upon hydrolysis), more preferably a higher oleic acid such as the oleic acid described in U.S. Pat. Fatty acids, polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in U.S. Pat. , <2
Acrylic acid and acrylic 10 as disclosed in No. 2
Examples include latex-type acidic polymers as disclosed in No. 2 (/77).

The photographic element of the present invention can be used as a diffusion transfer film unit I-
When it is a peeling (beer apartment) type or JP-A-4T4-11336, the same type - JJI-RI No. 7, JP-A-Sho! θ-/j04tθ and British Patent/, 330.
It is possible to take the structure of an integrated type film unit as described in No. 2ψ, or a film unit that does not require peeling as described in JP-A-Sho Tough-//ri No. 3≠j. .

Example 1 The following layers (1) and (2) were sequentially coated on a transparent polyethylene terephthalate support to prepare a force/glue sheet.

(1) Copolymer of acrylic acid and butyl acrylate at a ratio of 10 to λO (weight ratio) (l1g/rrL2) and l, goobis(2,3-epoxypropoquine)-butane (00,
2,2j9/m2).

(2) The above-mentioned exemplary copolymers (1) to (9) (≠, op/m
2) and development inhibitor precursor, j-(/-methyl-2-
A layer containing 7anoethylthio)-1-phenyltetrazole (2°A mmol/m), which was prepared by adding a solution of the above copolymer and a development inhibitor precursor in acetone/diacetone alcohol (weight ratio 3/m). Apply on the Japanese layer, 1
Obtained by drying at r00C for 70 minutes.

Comparative cover sheets were also prepared by coating one to three layers on a transparent polyethylene terephthalate support in the following manner.

(1') Neutralization layer same as layer (1) (2') Acetylcellulose (hydrolyzes ioog acetylcellulose to generate 3A, tg acetyl groups) (≠, 3i/rn) and styrene methanol ring-opening of a copolymer (molecular weight approximately J 0,000) of 6o to ≠ O < X amount ratio of maleic anhydride and
and the same development inhibitor precursor as layer (2) (2゜lp m
mo II /rn 2)-containing sul layer.

(3') Styrene-n-butyl acrylate-acrylic fit-N-methylolacrylamide getter.

A copolymer latex of 7:≠2.3:3:j and a 23:g:3 (weight ratio) copolymer latex of methyl methacrylate-acrylic acid-N-methylolacrylamide were combined into a solid mixture of the former latex and the latter latex. A layer of 1μ thick was mixed and applied at a ratio of 6:g.

The neutralization timing time of each cover sheet was measured by the following method.

The neutralization timing time of the cover note was measured as follows.

pH indicator-coated film A pH indicator-coated filter was prepared by coating a polyethylene terephthalate transparent support as follows.

(1'utymolphthalein (0,2fJ/rn)
and an indicator mulberry layer containing gelatin (,7 g/m2).

White reflective layer containing (2' titanium oxide (-2097 m2) and gelatin -29/m2).

(3 (same designated prefecture layer as 1).

Processing liquid A processing liquid consisting of

Each cover sheet faced the pH indicator-coated film, and the treatment solution was spread out to a thickness of goμ between them. Next, pE (the time required for the high pH color (blue) reflection density of thymolphthalein to be reduced by neutralization and halved by measuring the concentration from the side of the indicator-coated film (this time is called the "neutralization timing time") ) was measured at 1j0C and -zs0c.

The results are shown in Table 1.

Table 1 As is clear from the comparison of the values in Table 1, the temperature compensation ability (T1.5/T2 s) of the alkali permeability at timing j using the copolymer of the present invention is higher than that of a single layer coating. Despite this, it turns out to be a big deal. Furthermore, it is shown that both the timing time and temperature dependence can be freely changed by changing the composition of the copolymer.

Example 2 On a polyethylene terephthalate transparent support, the following (
Each layer was coated to make a photosensitive sheet.

(1) Mordant layer containing 3.0 g/rn of gelatin and 3.0 g/7 m2 of the following polymer latex mordant.

(2) Titanium dioxide/Zag/Door 2, Gelatin λ, Og/
, 2. A white reflective layer containing .

(3) A light-shielding layer containing carbon black, Oi/rn2, and gelatin/097m2.

(4) The following cyan dye-releasing redox compound 0°11
ujq/m, ) IJ cyclohexyl phosphate o, ori 97m, 2. ! -D-t-pentadecylhydroquinone 0.001jq/m”, and gelatin 0
．． Layer containing 1 g/m2.

(5) Red-sensitive internal temperature direct positive silver bromide emulsion (according to the amount of silver/
0! p/m2), gelatin/, 2i/m2, the following nucleating agent 0.0um9/m2 and λ-sulfoj-n-pentadecylhydroquinone sodium salt 0.0um9/m2. /3ji/
A red-sensitive emulsion layer containing m2.

(6) J, t-di-t-pentadecylhydroquinone θ
, ≠ 3 g/m , ), 17 hexyl phosphate 0
, / g/yn,” and gelati 70,4L9/m2
A layer containing.

(7) Magenta dye-releasing redox compound of the following structural formula (C0,2/I/m2), magenta dye-releasing redox compound of the structural formula (2) (0, / / 97m2), tri7chlorohexylphos7ate (o.

org7m2), u, t-di-t-pentadecylhydroquino7 (0,0099/rn”) and gelatin (0
, 2g/-2).

Structural formula 1 % Formula % Structural formula■ (8) Green-sensitive endothermic direct positive bromide chain hole 'R1j (silver amount 0.1r2g/vn2), gelatin 7 (O,2g/rI
L2), the same nucleating agent as layer (5) (0, 0,3 my/m2
) and λ-sulfo-t-n-pentadecylno-1-hydroquinone sodium salt <o, or17m2).

(9) Same layer as (6).

(Yellow dye-releasing redox compound with the following structure of 1 (
o,! 31/m2), tricyclohexyl phosphate (0,/3.9/m2), 2.1-di-t'phtadecyl/1-hydroquinone <0.0/44,97m2)
and a layer containing gelatin (0,797 m).

(11) Blue-sensitive internal temperature direct positive silver bromide emulsion (according to the amount of silver/
, 02g/m2), gelati y (/ , / 9/yn
2), a blue-sensitive emulsion layer containing the same nucleating agent as layer (5) (0, Oumy/m2) and hycosulfo j-n-1 ntadecylhydroquinone sodium salt (0.07 g/m2).

(12) A layer containing gelatin/, all/rn''.

After exposing the above photosensitive sheet through a color test chart, the cover sheet of Example 1 was overlapped to form one car.
- Apply the following treatment solution to a thickness of 10 μm between the
°C and 2s0C (the development was carried out with the help of a pressure roller). The maximum concentration at each treatment temperature is shown in Table 2 of the treatment solution. The maximum concentration at low temperatures is high without increasing the maximum lJ-concentration compared to that for use. To some extent, the difference in maximum concentration between high and low temperatures is small (・.

That is, it suggests that the temperature compensation ability is excellent. 9), (1
5)) and comparative power/g-1 on the sheet.
1), /N sodium hydroxide! p when dropping Oμl
Changes in H over time were measured using a planar composite electrode connected to a recorder. Measurements were carried out at 2!0C. The /ξ millameter shown in the following formula was used as a measure of pH reduction, and the results are shown in Table 3.

Table 3 Cover sheet Galo S for comparison 2. ≠3 3/,! ;1 5 / , A7 9 / , 110 15 / , λ As is clear from the results in Table 3, the pH of the inventive sheet was more rapid than that of the comparative sheet.

In other words, the cover sheet of the present invention has a feature that the period during which high pH water remains in the cover sheet is longer than that of the comparative cover sheet (and then the pH changes rapidly when it starts to decrease). be.

Example 4 The following polymers having various compositions were obtained in the same manner as in Synthesis Example 4.

Monomer 1/methyl methacrylate/acrylic acid copolymer (mole ratio 167♂j-C/C) Example except that the obtained copolymer was used in layer (2), except that the development inhibitor precursor 1 was omitted. Create a cover sheet in the same way as 1, and /! When the neutralization timing was measured at 0C and 2!0C, the relationship between the acrylic acid composition (mol %) and the temperature dependence of the neutralization timing (Tl 5 /T2 s ) was as shown in Table 1.

That is, the polymer of the present invention is characterized in that its temperature compensation ability can be freely controlled within the range of about 3 to 7 in terms of 'r15/T25 by changing its copolymer composition.

Furthermore, even if the methyl methacrylate/acrylic acid binary copolymer does not contain monomer 1, an appropriate composition (acrylic acid 1
2-1≠mai1%) showed a certain degree of temperature compensation ability, but the value of T15/T25 was constant at about 3, and the temperature compensation ability by the copolymer composition was poor and could not be controlled.

Table j j 7. P! , 3 7 lI , 'f
l, 0 ta 3, j/
Q3. Preferred embodiments of the present invention are listed below, but the present invention is not limited thereto.

l) Within the scope of the claims, it is derived from monomer unit m 1 in the polymer represented by general formula (I).

2. In the claims, one of the monomer units +A+ in the polymer represented by general formula (I) is derived from acrylate or methacrylate.

3) In embodiment (2), one of the monomer units is
It must be derived from methyl methacrylate.

4) One monomer unit +A+ in the polymer represented by general formula (I) is derived from a monomer having a carboxylic acid group within the range of % tolerance.

5) In embodiment 4), one monomer unit is derived from acrylic acid.

6) The claimed photographic element is a cover sheet.

7) The claimed photographic element comprises a photosensitive sheet consisting of an image-receiving element and a photosensitive element coated in sequence on a support, a cover sheet having a neutralization system, and a cover sheet spread between the photosensitive element and the cover sheet. (However, if necessary, these elements may be made removable.) Laminated integrated film.
Being a unit.

8) In embodiment 7, the photosensitive element has at least one silver halide photographic emulsion layer in combination with a dye image-providing compound.

9) In embodiment 8, the dye image-providing compound is contained in a layer adjacent to the photographic emulsion layer.

10) In embodiment 8, the dye image-providing compound is a compound that releases a diffusible dye when oxidized by an oxidation product of a developing agent.

11) In embodiment 8, the photographic emulsion is a direct reversal photographic emulsion.

12) In Embodiment 11, the direct reversal photographic emulsion is an internal latent image type direct reversal photographic emulsion.

13) In embodiment 12, the internal latent image type emulsion is a core/
It must be a shell-type internal latent image emulsion.

14) In the scope of the claims, the polymer represented by general formula (I) is contained in the photosensitive material.

15) The claimed polymer is a polymer represented by general formula (I).

Claims (1)

Claims: 1. A photographic element having at least one layer containing a polymer containing one unit of a monomer. OO 111 However, J represents -C- or -S-. 1 X completes a heterocyclic nucleus having at least 7 j-membered rings or e-membered rings (C represents the necessary plural atoms, 1 where R represents a hydrogen atom, an alkyl group or an aryl group.