DE3422455A1 - Thermally developable light-sensitive colour-photographic material - Google Patents

Abstract

A thermally developable light-sensitive colour-photographic material has a base and a photographic component layer which is applied thereto and contains at least (a) a silver halide, (b) an organic silver salt, (c) a reducing agent, (d) a binder and (e) a dye-donor substance which is a polymer prepared from a polymerisable compound of the formula (I): <IMAGE> in which R is a hydrogen atom or a methyl group, J is a divalent organic group or a single bond, P is a divalent organic group, Y is an alkylene group or arylene group, m and n are each the number 0 or 1 and Cp is a radical group providing a yellow, magenta or cyan dye, wherein a dye released by thermal development can be transferred to form a dye image, in particular a dye diffusion transfer image.

Description

► ♦ W ·

• ■ ι ·

T 54 558 June 15, 1984

Konishiroku Photo Industry Co., Ltd. No. 26-2 Nishishinjuku 1-chome Shinjuku-ku, Tokyo, Japan

Heat developable photosensitive color photo graphic material

The invention relates to a heat developable photosensitive A color photographic material in which a dye liberated therefrom by the application of heat development is transferred to form a color image; it relates in particular to the photosensitive material that can form a new thermal development type dye diffusion transfer image containing a dye Substance that can release or form a diffusible dye due to the development of heat.

Photosensitive materials that are a commonly known photosensitive silver halide are those other types in terms of their sensitivity, gradation, image retention and the like. Superior and so far most used in practice.

30th

However, there are many problems with these materials, including but not limited to: their treatment or development can take a long time and be very cumbersome; there is a risk that the treatment or development chemicals attack the human body or contaminate a work space or worker; further it may be necessary to take with you through the waste liquid

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pollution caused 'to get ready. Therefore, there is a great demand for the development of a photosensitive material in which a lichtempfindli- - ^ "ches -Silberhalogenid can be used and on a dry treatment or development can be applied.

There have already been many suggestions for photosensitive Materials from the above-mentioned dry treatment or. - ^. -development type made. It has been shown that under them 'the light-sensitive materials of the heat generation type, in which a heat treatment to carry out their Development process can be applied, the -above Condition are sufficient.

Regarding the light-sensitive materials from heat dissipation - · Winding types of this type are, for example, in the tested Japanese Patent Publications 4 921/1968 and 4 924/1968 describe photosensitive materials containing an organic Silver salt, a silver halide and a reducing agent contain.

There have been various methods of producing color images while improving the photosensitive ones Investigated materials of the aforementioned heat generation type.

They are already color photographic light-sensitive materials of the heat development type for the production of color images by reacting couplers with the oxidants a primary aromatic amine developing agent is known. These are, for example, in US Pat. No. 3,531,286, 3,761,270 and 3,764,328 and the like.

In Research Disclosure Nos. 15108 and 15127 are respectively other heat development type color photographic light-sensitive materials for producing color images by reacting couplers with the oxidants of the developer compound sulfonamidophenol derivative or sulfonamidoaniline

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ι 1 derivative described.

However, these photosensitive materials have a problem that the colors of the material become cloudy, because on a surface exposed to light, after the application of heat, a reduced silver image and a color image can be formed at the same time. To solve this problem, "some countermeasures · proposed, one of which is to remove the silver image by liquid treatment, and another is to just add dyes to another layer, for example an image-receiving sheet with a image-receiving layer applied thereon. However, the problem remains that it is not easy to ~~ to distinguish between non-reactants and the dyes, ι

Also in Research Disclosure No. 16966 is a photosensitive heat development type color photographic material described in which an organic imino silver salt containing dyes is used and the imino group is released in the areas exposed to the light by a heat development process and from which A color image is produced with a solvent on an image-receiving layer, which acts as transfer paper serves.

With this type of materials, however, there remains a problem that it is difficult to control the release of the dyes in to inhibit the unexposed areas so that a clear and sharp color image is not obtained can.

Also, in Japanese Patent Laid-Open Publications 105 821/1977, 105 822/1977 and 50 328/1981, in USHPS 4,235,957 and in Research Disclosure No. 14 448, 15 227 and 18 137 photosensitive color photographic Heat-generating-type materials for building

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formation of positive color images by a heat-sensitive silver dye bleaching process. . In this type.-.-- From materials, the problems that they ^to-one: must be sätzlichen BehandlungsÄtufe__unterworfen where. the films, each containing an activator to accelerate the fading of the dyes, are laid one on top of the other and then heated - and that an additional photographic component material must be used; - moreover, this type of material is gradually reduced and faded during storage for a long period of time due to the silver released at the same time.

U.S. Patents 3,180,732, 3,985,565, and 4,022,617 and 15 Research Disclosure No. 12,533 also disclose photosensitive heat development type color photographic materials described in each of them by using . Leuco dyes a color image is generated. With these materials however, the problem arises that the light-sensitive Material that can hardly contain leuco dyes in stable form. And that the material changes during storage gradually discolored.

Japanese Patent Laid-Open Publication 179 840 / 1982 is also a heat development type photosensitive material to form a dye using a dye releasing agent and a reduction-type dye-forming substance which releases a diffusion-type dye.

With this material, however, it is indispensable to use a dye releasing agent and this should be the so-called base or a basic precursor. In the case of a heat generation type photosensitive material, in which an organic silver salt oxidizing agent is used, on which the technique of use the aforementioned base or the aforementioned basic precursor

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runner is applied therein, there arises the problem that the fog increases in the presence of the base and that the maximum Density of an image decreases.

Also, in Japanese Laid-Open Patent Publication No. 186 744/1982, there is a light-sensitive color photographic one Thermal development type material for forming a color image using a dye-providing agent Described substance from which a diffusion-type dye is released in the heat generation process. The exemplary compounds of each of those in this specification However, the substances that supply a dye mentioned are not always checked to determine whether they are between the layers of material that is multilayered or thermally developed migrate. That type of material consequently, it has a defect that color clouding may occur.

The aim of the present invention is therefore to provide a photosensitive to provide heat development type color photographic material to which a new process for Formation of a color image can be applied, and to solve the problems associated with the conventional known light-sensitive materials occur. In other words, the present invention aims to provide a to indicate a heat generation type photosensitive material which is a new dye-providing substance contains.

Another object of the invention is to provide a photosensitive heat development type color photographic material capable of producing a clear and a sharp color image using a simple heat development process.

Another object of the invention is to provide a photosensitive heat development type color photographic material which enables the production of a color

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high density image even if it should be stored for a long period of time before exposure (hereinafter referred to as "storage before exposure").

Another object of the invention is to provide a photosensitive to create heat-developing-type color photographic material by lowering the haze and that allows a high maximum density to be achieved.

The aim of the invention is finally to provide a photosensitive To provide thermal development type color photographic material that requires the production of one substantially less cloudy, clear and sharp color image allowed.

The above objects of the invention can be achieved with a heat developable light-sensitive color photographic A material which is characterized by a support and a photographic component layer applied thereon which contains (a) a silver halide, (b) an organic silver salt, (c) a reducing agent, (d) a binder, and (e) a dye-providing agent (releasing) substance, wherein said dye-releasing (releasing) substance is a polymer is made from a polymerizable Compound of the general formula

I I

"2. ~" * * '' nT ^ ~ '~ ^T n where mean:

R represents a hydrogen atom or a methyl group; J is a divalent organic group such as -0-, -C-NH-, -CO-, \ jf ~ \ and the like, or a single-O O
binding;

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40 P is a divalent group, like 2.B.

-0-, -S-, -0-C-O-, (CpfO-C-NH-, (CpK) -C-,

1 Il ο

- ■ '-N = N-, (CpfNHCO-, (CPi-NHSO ₂ -, (CpK) -SO ₂ -,. Or a nitrogen-containing hetero ring, e.g.

Urazole diyl, hydantoinediyl and the like;

Y. an alkylene group such as a methylene, ethylene, • tetramethylene, octamethylene, benzylidene group and · the like, or an arylene group such as phenylene, naphthylene, bisphenylene, xylylene group and the like; and wherein the main chain of Y can also contain one or more linking groups selected from an oxy group, an imino group, a carbonyl group, an oxycarbonyl group, a carbamoyl group, a Thio group, a sulfonyl group, a sulfamoyl group and the like;

m and η each represent the number 0 or 1; and

Cp is a residual group that provides (donates) a yellow, purple or blue-green dye.

Below are some typical examples of the R component

given in formula (I):

(1) CH ₂ -CH-

(2) CH ₀ = C-

² I.

- ■ -CH

CH ₃

(3) CH ₂ = CH- (CH ₂₎ (4). CH ₂ = C- (CH ₂ ) CH, ³

-sr-

(S) CH ₂ = C-COO CH,

(6) ₂ CH = CHCH ₂ OCO

(7) CH ₀ = C-CONHCH-

² I -I CH ₃ CH ₃

(8) CH ₂ = CH

(9) CH ₀ = CH

CH ₀ NHCH-

² I.

(m-, p- object)

(10) CH ₂ = C-CONH ^

CH.

(11) CH ₀ = C-

² I CH ₂ COOCH ₃

(12) CH ₂ = CH-O- (CH ₂ ) ₂ -

(13) CH ₂ = CH-O-CH ₂

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1 Cp in the formula (I) is an organic group which, when an oxidant reacts with a reducing agent, formed by heat generation, a diffusible

■ "" can supply (surrender) dye. The organic groups 5 each have one of the following formulas:

Formula (II)

Formula (III)

OH

con:

Formula (IV) R ₁

N.

N \)

^R 2- ^ + ~ ^R 4

Formula (VI)

Formula * (V)

N N

Formula (VII)

N N-

—R.

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wherein R .., R ^ / R ₃ and R. each represent a group selected from a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, an acyl group , an er Acylamino group, an alkoxyalkyl group, an aryloxyalkyl group, an N-substituted carbamoyl group, an alkylamino group, an arylamino group, an acyloxy group, ... an acyloxyalkyl group and a cyano group. These groups can also be substituted by an alkyl group, an aryl group, a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a sulfamic group / a carbamoyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxy group, a Aryloxy group, an acyl group, an aralkyl group or the like.

An oxidant formed by the reaction of a reducing agent with an organic silver salt (oxidizing agent) is reacted with an organic group having one of the formulas (II) to (VII) given above, so that a diffusible Dye is released from it. The behavior of this dye release is roughly divided into two types: one is the type in which these dyes are formed (hereinafter referred to as "a dye-forming type" and the other is the type in which a dye is previously bonded to an active center via a cleavable group and which then diffuses (hereinafter referred to as "dye releasing type"). With that first named type is η = 1 and P is bound to the active center of Cp. On the other hand is in the case that a dye is previously bound in the molecule, as in the last-mentioned case of a dye-releasing type η = 1 and P are bound differently than in the active site of Cp.

35 "In-this case are examples of groups that uncouple can and can result in a bond between the dye (D) and the active center,

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the following: -0-, -S- / -0-C-O-,

0 ·

"(Di-OC-NH-, (DfO-C-, -N = N-, (DfNHCO-, (DfNHSO--, (DfO-SO ₉ -,

⁵ -A I

a divalent group of a nitrogen-containing hetero ring, such as urazole diyl, hydantoin diyl and the like. Among the dyes (D) previously bound in the molecules indulge yourself, include, for example, azo, azomethine, Anthraquinone, naphthoquinone, nitro, styryl, quino, phthalone, triphenylmethane, phthalocyanine and the like Dyes. -

The following compounds are typical examples of the present invention Links: *

1. Dye-releasing type compounds 20

(1-1)

I CH ₀ = C

Δ ι

CONH-Tj 1 N = N- / Vn =

SO ₃ Na

copy di

3Α22455

CH ₃ CH ₂ = C

CONH-

OH

OCH-

SO ₃ Na

CH ₀ = CH
2. ι

CONH

NH-CO-CH-COC (CH ₀ ), ι 3 3

NO.

OH

OH

CH ₉ = CH

SO ₂ CH ₃

NHCONHr CONH "T HO

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CH ^ OH

CH ₂ = C

NHCOCH.

OCH.

CH.

CH =

COO-f> CONH

OH

^N0

C ₂ H ₅ NHCOCH ₃

CH ₂ = CH- (CH ₂ CONH ₂ J

OH

OCH ₂ CONH

NHCOCH.

• CH.

CH ₂ = CH

OH

CONH

OH

N = N

OCH.

CIL

CH ₀ = C

² J OH

CONH

HO

ο- / Vn = N

(I-IO)

CH ₀ = CH

OH

CONH

HO

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422 455

2. Dye- forming type compounds

CH.

CH ₂ = C

CONH

OH

NHCOCII-

CH ₂ = CH

CONH

CH.

CH ₂ = C

CONH

O = CC (CH ₃ )

-CH CJl O = C-NH- /}>

COOH

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O = CC (CH ₃ J ₃

CH ₂ = CH- / Vo-CH

O = C-NH

CH.

CONH- / y

CH

CH ₂ = CH

COO-

OH

NHCOCH.

CH ₀ = CH

CH ₃ CL

CONH-

/ ~ Λ

NHCOCH.

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IO

CH ₂ = CH-O-CH ₂ Hf \ cONH- / \ n = N- | rr-NHCOCH.

CH ₀ = CH

² I.

CONH ■

JT \

CH.

CH ₂ = C

CONH-

/ T \

0 CJL

-CfL

Ci.

-NH

.Cl

Cl

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The compounds of the invention / can as in the following Examples given are synthesized.

Synthesis Procedure Example 1:

Synthesis of the Exemplified Compounds (1-1) Step 1

17 g sodium acetate and 25.5 g 3-amino-i- (4-sulfophenyl) -pyrazolo-5-one were added in 20.0 ml acetic acid and 11 mg methacryloyl chloride were added with stirring for 30 minutes

1.0 was added dropwise at a temperature not higher than 2O ⁰ C and then stirred for a further hour at room temperature. The resulting reaction mixture was poured into 2 l of ice water. A precipitate formed therein was filtered off, washed and dried. In this way, 28 g of crude products were obtained.

Level 2

13 g of i- (p-aminophenylazo) -2-naphthol were concentrated in 200 ml Hydrochloric acid and 400 ml of water were dispersed, and 3.5 g of sodium nitrate were added in portions at a Temperature of 0 to 5 ° C added to produce a diazonxum compound.

Separately, 18 g of the crude products obtained in step 1 were made into an aqueous solution, containing 4% sodium hydroxide was added and the temperature thereof was adjusted to a value of about 0 to 5 ° C. The acidic solution of the diazonium compound described was added dropwise over a period of 30 minutes and the mixture was stirred was continued for 1 hour at room temperature. The crystals which precipitated out were filtered and dried and then recrystallized from methanol. This gave 26 g of the desired compound. Your · structure was under Use of MS, IR and NMR methods confirmed. 35

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Example 2 of the synthetic procedures

Synthesis of Exemplified Compound (II-1) . step 1

- '"'" 30 g of 4- (p-nitrophenylthio) -2-acetamidophenol became 500 ml of ethanol was added, and there were also added 60 g of reduced iron, 10 ml of concentrated hydrochloric acid and 30 ml Water was added and the mixture was refluxed for 2 hours. After the completion of the reaction, sodium hydrogen carbonate was added to neutralize the solution. the The reaction solution was filtered with heating and then concentrated in vacuo, 24 g of the desired amino

t
Connection received.

Level 2

24 g of the amino compound obtained in Step 1 was added to 300 ml of acetonitrile, and further 2 g of pyridine was added. Then, 9.4 g of methacryloyl chloride under stirring for 2 hours was added dropwise at not higher than 20 ⁰ C. The reaction mixture obtained was poured into 1 l of ice water, a precipitate being formed. The precipitate was filtered off, and thus 28 g of the desired compound was obtained. Its structure was confirmed by using MS, IR and NMR methods.

In the case of the dye-supplying agents according to the invention (resulting) substances can either be a homopolymer that has been polymerized using of the specified polymerizable compounds with one another or around a copolymer which was prepared by Polymerizing with at least one of the other types of polymerizable unsaturated compounds. That guy of monomers includes, for example, a vinyl ester such as vinyl acetate and vinyl butylate; a vinyl amide, such as acrylamide, Methacrylamide, N-methylacrylamide and N-isopropyl methacrylamide; a vinyl nitrile such as acrylonitrile, methacrylonitrile and 3-butenenitrile; a vinyl ketone such as methyl vinyl ketone; a vinyl halide such as vinyl chloride and vinylidene chloride;

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monovinyl esters such as allyl methyl ester and allyl phenyl ester; an α, β-unsaturated acid or an ester thereof such as acrylic acid, methacrylic acid, methyl acrylate, butyl methacrylate, -2-dimethylaminoethyl methacrylate, 2-ethylhexyl acrylate and 2-hydroxyethyl methacrylate; an olefin or diolefin such as ethylene, propylene, butadiene, isoprene and 1,1-diphenyl-ethylene; a vinyl aromatic compound such as styrene, OC-methylstyrene and p-chlorostyrene; N-vinyl succinamide; N-vinyl phthalamide; N-vinylpyrazolidone; N-vinyl pyrrolidone; and the other polymerizable unsaturated ethylene compounds known in the art.

A hydrophilic monomer can also be copolymerized to improve the stability of the polymers that serve as dye-providing substances according to the invention. The hydrophilic monomers are those which each have at least one sulfonic acid, carboxyl, hydroxyl, amino, sulfonamido or epoxy group.

To hydrophilic monomers with sulfonic acid groups, according to the invention Usable include those disclosed, for example, in U.S. Patents 3,619,195, 3,926,436, and 4,215 and in Research Disclosure No. 18815.

Preferred concrete examples of these compounds are polymers each of which is a monomer represented by the following formula (VIII) contain:

R ₁ 0

I ¹ (I (viii)

CH ₂ = C — C — R ₂ —X — SO ₃ M-

where mean:

R _{1 is} a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
R ₂ -0- or -NR ₃ -;

R- * is a hydrogen atom or an alkyl group of 1 to 6

Carbon atoms;
X is a divalent aliphatic, alicyclic or

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5 M

aromatic group, preferably a hydrocarbon with 1 to 10 carbon atoms, which also has an ether bond or may contain a thioether bond in the middle of the carbon chains; and a hydrogen atom, an alkali metal atom such as sodium or potassium; Ammonium; an organic onium, such as tetramethylaitunonium; or the like

For examples of the type of polymerization of the invention Compounds include normal solution polymerization, suspension polymerization, and bulk polymerization and the like, each of which can be selectively applied according to the purpose of use.

Typical examples of polymers are given below,

· * Those using compounds according to the invention

(i.e. monomers) have been synthesized:

^CH

j CONH

SO ₃ Na

(χ = J7O % by weight)

(Y = 30% by weight)

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CH.

j X

CONH-

'ι Vn =

OH

OCH

SO ₃ Na

CONHC ₃ H ₇ (I)

(X = 70% by weight)

(Y = .30 wt%

(-CH

CONH- C-CH _o S0-, Na

I ²

CH.,

(X = 60% by weight) (Y = 40% by weight>

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Mm *

KiH ₀ -CH, _ν 2 ι X

CONH

NHCOCH.

OCIL

CONH-CH ₂ OH

(X = 50% by weight)

(Y = 50% by weight

(CH ₀ -V

C0NH

OCH ₂ CONH

\ CH ₂ -CH4y-

CONH-CH ₂ OH

(X = 75% by weight) (Y = 25% by weight.)

NHCOCH.

CH.

N (C ₂ H ₅ ) ₂

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ZL

CIL

OH NHCOCH.

Yo

2 ^C 4 ^H 9

(X = 60% by weight)

(Y = 40% by weight)

ONH

fCH ^ -

CO ₂ (CH ₂ ) ₃ SO 3 Na

(X = 40% by weight) (Y β 30% by weight) (Z = 30% by weight)

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CH-

O = CC (CH ₃ J ₃

CONH - // Vo-CH

O = C-NH

COOH

fCH ₂ -

CONHC ₃ H ₇ (I)

(X = 80% by weight) (Y = 20% by weight)

(P-9)

CIL

O = C-NH-

-C-CH _o -S0-, Na

I ²

(X = 70% by weight) (Y = 30% by weight)

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CH _n CL

COOK ⁷ V-OH

NHCOCH.

CH.

CONHC ₃ H ₇ (I)

(X = 50% by weight)

(Y = 50% by weight

(P-Il)

fOHo-

J ~ \

-CH.

■ /

₀
2

CO ₂ C ₄ H ₉

CO ₂ (CH ₂ J ₃ -SO ₃ Na

(X = 60% by weight) (Y = 10% by weight) (Z = 30% by weight)

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The above-mentioned polymer according to the invention can be synthesized, for example, as follows:

- Example 3 of the synthetic procedures

Synthesis of Exemplified Polymer (PI) A solution in which 7 g of Exemplified Compound (1-1), 3 g of butyl acrylate and 30 mg of 2,2'-azobis (2-methylpropionitrile) are dissolved in 50 ml of # J, N-dimethylformamide ^{was held at 60 °} C. for 10 hours while passing in high-purity nitrogen. The viscous polymer obtained in this way was added to ethyl ether for careful preparation by reprecipitation, the desired polymer (P-1) being obtained in the form of a brown powder.

Example 4 of the synthetic procedures

Synthesis of Exemplified Polymer (P-6) * 200 ml of distilled water, 6 g of Exemplary Compound (11-1), 4 g of butyl acrylate, and 0.2 g of dodecylbenzenesulfonic acid sodium salt were placed in a separable flask having a capacity of 500 ml and a suspension was obtained. ^{The reaction solution was then heated to 50 °} C., 0.12 g of potassium persulfate and 0.05 g of sodium sulfite were added and the mixture was stirred at the same temperature for 10 hours. After the polymerization, a precipitate was filtered off and 230 ml of latex were obtained (solids content: 15.2%). The latex thus obtained was dialyzed with distilled water for 2 days and then precipitated and concentrated by using an ultrafiltration film having a graduation molecular weight of 10,000 to obtain a latex having a solid concentration of 8.0%.

The above-mentioned polymer according to the invention as a Dye supplying (releasing) substance used can either individually or in the form of a combination of two or more of them can be used. The amount of the polymer used is not limited but may depend on the type of polymer or

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whether the polymer is used alone or in combination, or whether the photosensitive of the present invention is used Material a 1-layer material or a multi-layer -.- material with two or more layers is to be laid down. For example, it is recommended that the used The amount of the polymer is 0.01 to 5 times that of the organic silver salt, 0.05 to 1 times the same is particularly preferred.

Any method can be used with the aid of which the polymer according to the invention, the polymer according to the invention to be used as a dye providing (donating) substance in a photographic component layer can be incorporated. Examples of suitable

15. Process are the ultrasonic dispersing process, the is applied after the polymer is in a low-boiling solvent (e.g. in methanol, ethanol, ethyl acetate and the like) or in a high-boiling solvent (e.g. in dibutyl phthalate, dioctyl phthalate, tricresyl phosphate and the like) has been solved, the neutralization method in which with a mineral acid (e.g. with hydrochloric acid or nitric acid and the like) after dissolving the polymer in an aqueous alkali solution (e.g. in an aqueous Solution containing 10% sodium hydroxide and the like) is neutralized, or the method in which it is dispersed is combined with an aqueous solution containing the desired polymer (such as polyvinyl butyral, polyvinylpyrrolidone and the like) using a ball mill.

Examples of organic silver salts used in the invention Thermal development type color photographic material which can be used are silver salts of aliphatic carboxylic acids as disclosed in Examined Japanese Patent Publications 4 921/1968, 26 582/1969, 18 416 / - ' 1970, 12 700/1970 and 22 185/1970, in the published Japanese Patent Publications 56 626/1974, 31 728/1977, 137 321/1977, 141 222/1977, 36 224/1978, 37 610/1978 and U.S. Patents 3,330,633, 3,794,496, 4,105,451, 4,123,274

jrprv

-29-

and 4,168,980, such as silver laurate, silver myristate, Silver palmitate, silver stearate, silver arachidonate, Silver behenate and v- (1-phenyltetrazolthio) silver acetate, aromatic carboxylic acid silver salts such as silver benzoate and silver phthalate, and silver salts of an imino group such as in Japanese Patent Publications 26 582/1969, 12 700/1970, 18 416/1970 and -22 '185/1970, in laid-open Japanese Patent Publications 31 728/1977, 137 321/1977, 118 638/1983 and 118 639/1983 '

.10. described, such as the silver salt of benzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 5-methoxybenzotriazole, 4-sulfobenzotriazole, 4-hydroxybenzotriazole, 5-aminobenzotriazole, 5-carboxybenzotriazole, imidazole, Benzimidazole, 6-nitrobenzimidazole, pyrazole, urazole, 1,2,4-triazole, 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole, Saccharine, phthalazinone and phthalimido, and the silver salts of 2-mercaptobenzoxazole, mercaptooxadiazole, 2-mercaptobenzothiazole, 2-mercaptoberizimidazole, 3-mercapto-4-phenyl-1,2,4-triazole, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene and the like. Among the above-mentioned organic silver salts, preferred is the silver salt of the imino group and the silver salt the benzotriazole derivative is particularly preferred.

Examples of silver halides that are suitable for the inventive Thermal development type light-sensitive color photographic materials that can be used are silver chloride, Silver bromide, silver iodide, silver chloride bromide, silver chloride iodobromide, silver chloride iodide and silver iodobromide as well as mixtures thereof.

These can be used individually or in ·. Form of a combination of two or more thereof can be used. The silver halide can be made using a single jet process or a double jet process well known in the photographic art. The photosensitive silver halide can be chemically sensitized are made using any process,

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as is well known in the photographic art. Examples of such sensitization methods, various types of methods, such as bilisierung the Goldsensi- '''', the sulfur sensitization, Gdldschwefelsensibilisierung ™ ürfd the ~ reduction sensitization. A component of the light-sensitive material of the invention can be prepared by adding a previously in the above described manner produced photosensitive silver halide.

'

Another possible manufacturing method is to cause the formation of a photosensitive silver halide on part of the organic silver salt by causing a photosensitive silver salt-forming component to be present together with the above-mentioned organic silver salt. As a photosensitive silver salt-forming components, in In the manufacturing process, inorganic halides such as halides represented by the formula M (X) ₁ (wherein M is a hydrogen atom, the NH. group or a metal atom, X is a Cl, Br or I atom, and 1 is the number) are used 1 when M = H or -NH., While when M is a metal atom, 1 represents its valence and the metal atom includes, for example: lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, magnesium, Calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, lead, antimony, bismuth, chromium, Molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum or cerium); Metal complexes containing halogen (such as "K ₂ PtCl ₆ , K ₂ PtBr ₆ , HAuCl ₄ , (NH ₄ J ₃ IrCl ₆ , (NH ₄ J ₃ -IrCl ₆ , (NH ₄ J ₂ RuCl ₆ , (NH ₄ J ₃ RuCl ₆ , (NH ₄ J ₃ RhCl ₅ or (NH ₄ ) -RhBr ₆ and the like); the onium halide includes quaternary ammonium halide, such as tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, such as, for example, trimonateethylammonium bromophosphorus, such as, for example, tetra-methylthiazolium bromophosphorus, such as trimonate methyl benzoic bromide ammonium, such as trimonate methyl bromide phosphide ammonium halide, such as trimonate ethyl benzoic bromide ammonium halide includes quaternary ammonium halide, such as, e.g. ; a tertiary sulfonium

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halide such as benzylethylmethylsulfonium bromide and 1-ethylthiazolium bromide; a halogenated hydrocarbon, such as iodoform, bromoform, carbon tetrabromide, and 2-bromo-2-methylpropane; an N-halogen compound, such as e.g. N-chlorosuccinimide, N-bromosuccinimide, N-brornophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, Ν, Ν-dibromobenzenesulfonaraid and 1,3-dibromo-4,4-dimethylhydantoin; and other halogen-containing compounds such as triphenylmethyl chloride, triphenylmethyl bromide, - 2-bromobutyric acid and 2-bromoethanol.

These photosensitive silver salts and a photosensitive one Silver salt forming components can be used in combination in various processes and they can be used in an amount of 0.001 to 4.0 moles per mole of the organic silver salt, the range being from 0.01 to 1.0 mole is preferred.

Examples of reducing agents in the invention color photographic light-sensitive material from The type of heat build-up that can be used are developer compounds having a p-phenylenediamine group and a p-aminophenol group, developer compounds having a phosphoramidophenol group and a sulfonamidophenol group and color developing agents having a hydrazo group, as disclosed in US 5,499,399 U.S. Patents 3,531,286, 3,761,270, and 3,764,328, Research Disclosure Nos. 12,146, 15,108, and 15,127, and U.S. Patent Laid-Open Japanese Patent Publication 27 132/1981. Color developing agent precursors can also be used and others such as those disclosed in U.S. Patents 3,342,599 and 3,719,492 and Japanese Patent Laid-Open Patent Publications 135 628/1978 and 79 035/1979 are described.

In addition to the above, the following reducing agents can also be used:

Namely phenols such as p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, N-methyl-p-aminophenol and the like '; Sulfonamidophenols such as 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6 ~ dibromo-4- (p-toluenesulfonamidophenol) and the like; Polyhydroxybenzenes such as hydroquinone, tert-butyl hydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxypyrocatechol, and the like; Naphthols such as of-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol and the like; Hydroxybinaphthyls and methylenebisnaphthols, such as 1,1'-dihydroxy-2,2'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6'-dinitro-2, 2'-dihydroxy-1,1'-binaphthyl, ^{4,4'-Dirnethoxy-1,11-dihydroxy-1} 2, 2-binaphthyl, bis (2-hydroxy-1-naphthyl) methane, etc .; Methylenebisphenols, such as 1,1-bis- (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane, 1,1-bis- (2-hydroxy-3-tert-butyl-5- methylphenyl) methane, 1,1-bis- (2-hydroxy-3,5-di-tert-butylphenyl) methane, 2,6-methylenebis (2-hydroxy-3-tert-butyl-5-methylphenyl) -4-methylphenol, O (-Phenyl-öi, <X.-bis- (2-hydroxy-3, 5-di-tert-butylphenyl) methane, oC-phenyl-tfVoi-bis- (2-hydroxy-3 tert-butyl-5-methylphenyl) methane, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane, 1,1,5,5-tetrakis- (2-hydroxy-3 , 5-dimethylphenyl) -2, 4-ethylpentane, 2,2-bis- (4-hydroxy-3, 5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-methyl-5-tert.- butylphenyl) propane, 2,2-bis- (4-hydroxy-3,5-di-tert-butylphenyl) propane and the like; ascorbic acids; 3-pyrazolidones; hydrazones; paraphenylenediamines,

These reducing agents can be used either singly or in combination of two or more thereof. The amount in which the reducing agent is used is usually within the range of 0.05 to 10 moles per mole of the organic silver salt, with a range of 0.1 to 3 moles being preferred, although it depends on the kind of the organic acid silver salt used , depends on the type of photosensitive silver salt and the type of other additives _f

- ■ ■ - EPOCOPY Q

. As a binder in the photosensitive according to the invention heat development type color photographic material synthesized substances or natural high polymers such as polyvinyl butyral, polyvinyl acetate, ethyl cellulose, Polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin and phthalated Gelatin, ·. ^

can be used singly or in combination of two or more thereof. Is particularly preferred Combination of gelatin or its derivative and a hydrophilic polymer such as polyvinylpyrrolidone or the like.

Examples of a support which can be used in the heat development type color photographic light-sensitive material of the present invention are synthesized plastic films such as a polyethylene film _; a cellulose acetate film, a polyethylene terephthalate film and a polyvinyl chloride film, and the like, and a paper support such as a base paper for photographic use, a printing paper, a baryta paper and a resin-coated paper, and others.

Examples of a component other than that mentioned above in the light-sensitive color photography of the present invention Heat development type material usable are various known additives such as a spectral sensitizing dye, an antihalation agent, an antifoggant, and a development accelerator, which can be added without any limitation.

Examples of spectral sensitizing dyes are certain-type thereof which succeeds in a silver halide emulsion such as cyanine, merocyanine, rhodacyanine, and styryl dyes can be used.

As an additive, for example, a development accelerator or the like, a dicarboxylic acid and phthalazine and the like ..

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as described in Japanese Patent Publication 93 396/1981, a thioether-containing carboxylic acid and carboxamide as in Japanese Patent Publication J-- 1 064/1982, triazoles with a mercapto group, as described in Japanese Patent Publications 64 513/1982 and 65 388/1982, and a polyhydroxy compound, as described in Japanese Patent Publication 82 064/1982 can be used.

Any of the above components that are iii a photographic Component layer of the heat development type color photographic light-sensitive material of the present invention is used together with a binder and a suitable solvent applied in the form of a layer to the above-mentioned support. The layer thickness according to the drying is 1 to 1000 μΐη, preferably 3 to 20 μm. Preferably these components are in a single one photographic component layer obtained, if necessary but can also have several layers, each of which can contain the above-mentioned components, in a multi-layer arrangement or each layer of the group of layers can contain or contain any component there can be intermediate layers, backing layers and top layers be formed. '

The heat development type light-sensitive color photographic material of the present invention prepared in this way can usually be developed after imagewise exposure by heating it at a temperature within the range of 80 to 200 ^° C. for only 1 to 60 seconds. Erforderli- • chenfalls -can also a water-impermeable material for the development to be attached thereto or may be a pre- läufiges · heating to a temperature within the range are carried out of 70 to 180 ⁰ C prior to exposure.

Examples "of one suitable for imagewise exposure Light sources are a tungsten lamp, a fluorescent lamp (fluorescent tube), a mercury lamp, an iodine lamp,

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-35-

a xenon lamp, a CRT light source, and a laser light source and these light sources can be applied through an optical fiber.

The 'using the in Research Disclosure No. 15 108 and 15,127 described method prepared dye. pictures (color pictures) are brought into close contact with a transfer paper such as an image receiving layer, a solvent from the group consisting of methanol, ethanol, tributyl phosphate and the like. Or a thermal one Solvent (thermal development transfer accelerating substance), such as acetamide, 1,10-decanedioyl, succinimide, 1,6-hexanedicarboxylic acid, 1,8-ethylene naphthalene, Methyl anisate, benzophenone, methyl stearate, methoxynaphthalene or biphenyl, and the transfer paper is heated as needed and then it is deducted *, whereby color images are obtained on the transfer paper. The above-mentioned thermal solvent can of course also be used in included in the photosensitive material of the present invention be. The above-mentioned transfer paper is preferably one having an image-receiving layer containing a mordant used on its carrier and the mordant is a polymer that contains an ammonium salt, and preferably such as is described in US Pat. No. 3,709,690. The pickling agent is, for example to poly (styrene-co-NjN / N-tri-n-hexyl-N-vinylbenzylammonium chloride) and the ratio of styrene to vinylbenzylammonium chloride is about 1: 4 to about 4: 1 and the preferred ratio is 1: 1. The typical image receiving layer for use in diffusion transfer can be prepared by mixing the one containing an ammonium salt Polymers with gelatin and applied in the form of a layer on the support.

The light-sensitive color photographic of the present invention Heat generation type material is characterized in that it is obtained from the combination of the above-mentioned general Formula (I) prepared polymers therein as a

a dye-supplying (forming) substance is used, whereby a leakage of the polymer from a certain Layer which is selected in advance after the application of the multilayer coating and during the heat development averted "~ is ~, ~ so that clear color images with excellent shelf life, low fog density and a high maximum density can be easily obtained.

Examples

The invention is illustrated in more detail by the following examples, but without being limited to it.

example 1

Silver nitrate in an amount of 16.9 g was dissolved in 200 ml of pure water, and it became 29% aqueous ammonia added in an amount of 35 ml. On the other hand, 4-sulfobenzotriazole was used in an amount of 20.1 g in 50 ml dissolved in pure water. An aqueous solution of 4-sulfobenzotriazole was turned into an aqueous ammoniacal one with stirring Silver nitrate solution was added at room temperature, followed by stirring for 30 minutes. That formed in this way The ammonium salt of 4-sulfobenzotriazole silver was filtered off and then washed with water to obtain the ammonium salt of 4-sulfobenzotriazole silver in an amount of 21.5 g. 150 ml of an aqueous solution containing 3% polyvinylpyrrolidone was added to the ammonium salt of 4-sulfobenzotriazole silver added in an amount of 16.2 g and dispersed in a ball mill for 24 hours, dispersing one Liquid (hereinafter referred to as Dispersed Liquid I).

Then 200 ml of an aqueous solution containing 3% polyvinylpyrrolidone contained, to 7.6 g of N- / 4- (N, N-diethylamino) -2-methylphenyl / sodium sulfamate and 20 g of the polymer according to the invention (P-I) were added and placed in a ball mill

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• Dispersed for 24 hours, making a dispersed liquid obtained (hereinafter referred to as Dispersed Liquid II).

Using the same procedure, with the exception that 20 g of the polymer according to the invention (P-2) instead of the polymer according to the invention (P-1), as for the Dispersed Liquid II was used, another dispersed liquid (hereinafter referred to as dispersed liquid III).

The following components were added sequentially to the aqueous solution, wherein a 6% aqueous gelatin solution in an amount of 20 ml and a 3% aqueous polyvinylpyrrolidone solution in an amount 'of 50 ml were mixed while stirring the aqueous solution to obtain the coating liquid.

(Component-1) dispersed liquid I 30 ml (component-2) dispersed liquid II 40 ml (Component-3) Silver bromide emulsion (emulsion,

in the 3,3'-Di - (^ - SuIfOPrOPyI) -

9-methylthia-dicarbocyanine-na-

—4

trium salt in an amount of 4x10 Moles per mole of silver are added to a cubic emulsion having an average grain size of 0.06 μπι, the 60 g of gelatin and "0.35 mol of silver in 1 kg of emulsion

contains) 10 ml

(Component-4) 3% aqueous S-amino-S-mercapto-

1,2,4-triazole solution 2.5 ml

(Component-5) Ν, Ν-dimethylurea. 5 g

This coating liquid was applied in the form of a layer on the ethylene terephthalate support in an amount of 0.60 g of silver per 1 m ^a , and thus the

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-ie- -

first layer made.

Then an aqueous solution would be, in which a 6% aqueous Gelatin solution in an amount of 20 ml and a 6% aqueous polyvinylpyrrolidone solution in an amount of 50 ml were mixed together, applied in the form of a layer on the first layer, being the intermediate layer received.

The components indicated below were then added one after the other to the aqueous solution with stirring, in which a 6% aqueous gelatin solution in an amount of 20 ml and a 6% aqueous polyvinylpyrrolidone solution were mixed together in an amount of 50 ml to obtain the coating liquid:

(Component-1) dispersed liquid I 30 ml

(Component-2) dispersed liquid III 40 ml

(Component-3) Silver bromide emulsion (emulsion,

wherein 3,3'-di (γ-sulfopropyl) -5,5'-

diphenyl-9-ethylcarbocyanine-natri-

-4 umsalz in an amount of 4x10

Mol per mol of silver were added to a cubic emulsion with a

² ^ n of the average grain size

of 0.0 6 μια, which contained 60 g of gelatin and 0.35 mol of silver in 1 kg of emulsion) 10 ml (component-4) 3% aqueous S-amino-S-mercapto-1,2,4-triazole -Solution 2.5 ml (component-5) N, N ¹ -Dimethylurea 5 g

This coating liquid was in the form of a layer applied to the intermediate layer to obtain the second layer.

Using the procedure described above, Photosensitive Material (A) was prepared.

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For comparison, the following steps were also carried out.

Using the same procedure, with the exception that 20 g of the comparative compound I given below instead of the polymer according to the invention (PtD as used for the dispersed liquid II were used, a dispersed liquid was obtained Liquid (hereinafter referred to as dispersed liquid IV).

In addition, using the same procedure except that 20 g of the comparative compound II were used instead of the polymer (P-1) according to the invention used for the dispersed liquid II, a dispersed liquid is obtained (hereinafter referred to as dispersed liquid V).

In addition, using exactly the same procedure, but with the exception that 40 ml of the dispersed liquid IV instead of the (component-2) -dispersed Liquid II of the coating liquid from which the first layer was made and 40 ml of the dispersed one Liquid V instead of the (component-2) -dispersed liquid III of the coating liquid from which the second layer was used, a photosensitive material (B) was prepared.

(Comparison compound I) ³⁰ ,

SO ₃ Na

COPY

(Comparison compound II)

OCH ₃

The photosensitive materials thus produced (A) and (B) were with 1600 CMS (Candela. m. s) using white light, red light and green light each exposed through a step wedge (gray wedge).

Each of the photosensitive materials thus exposed was placed on an image receiving paper and ^{heated at 160 °} C. for 30 seconds to develop them, and after the development was completed, the image receiving paper was peeled off.

In the image receiving paper used on this occasion Was it a baryta paper for photograph! - see uses, to which a 10% vinylidene chloride-tetrahydrofuran solution was applied in the form of a layer so that the dry layer thickness was 50 μm.

The results obtained are shown in Tables 1-1, 1-2 and 1-3 below ^

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Table 1-1 (area exposed to white light)

° y ^D M Photosensitive
ches material A 1.47 1.58 Photosensitive
ches mater ial__. B 1.30 1.42

Table 1-2 (area exposed to red light)

1.47 ^D M Photosensitive
: hes material A 1.30 0.28 Photosensitive
ches material B 0.41

Table 1-3 (area exposed to green light)

^D y ^D M Photosensitive
ches material A 0.31 1.58 Photosensitive
ches material B 0.53 1.42

35 in the tables above, D _y stands for the maximum density,

which was obtained in the measurement for blue light through the reflection _{density, and D M} stands for the maximum density which was obtained in the measurement for green light through the reflection

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1 on density was determined.

As apparent from Tables 1-2 and "apparent 1-3, the ■ - '''using the eririndurigsgemäßen polymers prepared light-sensitive material A excellent properties mxjf a lower" + Färb tr exercise, compared to the one used for comparison purposes, photosensitive material B , on. ^ "~;"

Example 2. , -

The photosensitive ones shown below became Materials (C), (D), (E) and (F) are made.

/ Photosensitive material (C) /

The first layer of this photosensitive material (C) was prepared by applying 50 ml of an I / a'tex,. ' of the inventive polymer (P-6) instead of the inventive Polymer (P-1), which was contained in the dispersed j - <, liquid II, which was used as component 2 of the, first layer of photosensitive material (A) in "ν Example 1 was used, in the form of a layer and. the first layer was provided with a protective layer underneath ■ Use of an aqueous solution in, cier 20 ml of a 12% aqueous gelatin solution and 50 ml of a 12% strength aqueous polyvinylpyrrölidonlösung mixed together became.

Photosensitive material (D)

The first layer of the photosensitive material (D) was prepared using 70 ml of a latex of a polymer according to the invention (P-7) instead of (P-6) in the above photosensitive material (C) and on the crute layer v / iude ahm ßfjfruUSfMoIiI.

with an identical composition as in the photosensitive one Material (C) applied.

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HS

-4 * 3-

Photosensitive material (E) * The first layer and the protective layer of the photosensitive material (E) were prepared in the same manner as in

. Example 1 prepared, but this time 20 g of the Comparative compound ~~ III with the one given below Structural formula instead of the polymer according to the invention (P-1), which is in the dispersed liquid II of the component 2 in the first layer of photosensitive material (A) of Example 1 were used.

~~

(Comparison compound III)

Photosensitive material (F)

The first layer and the protective layer of the photosensitive Materials (F) were prepared using Comparative Compound IV in place of the Comparative Compound III of the above photosensitive material (E).

(Comparison compound IV)

nhcoc ₈ h ₁₇

The light-sensitive materials (C), (D), (E) and (F) produced in this way were treated with 1600 CMS (Candela. M. S) exposed using white light through a step wedge (gray wedge). Then each of the thus prepared light-sensitive materials on an image receiving card

pier set that was used dem''in identical to Example 1 and 30 s heated at 160 ⁰ C in order to develop them, and after completion-of development, the image-receiving paper was peeled off.

On the other hand, the above-mentioned light-sensitive materials -24 hours under the conditions of an ordeal test, for example a temperature of 50 ° C and relative humidity of 50%. After the torture test, they were exposed and developed.

The results obtained on the image receiving paper are given in Table II below. The numbers that are in the Table representing the density were obtained "by Measure the reflection density on the cyan negative images obtained for red light. The numbers of the relative sensitivity in the table represent the relative sensitivity values based on the value 100, which is the sensitivity of the photosensitive Material (C) acts before the deterioration of the same.

Table II

photosensitive
material before the ordeal
test relative
Sensitivity after the ordeal
test relative
Sensitive!* (C) maximum
density 100 maximum
t density 95 (D) 1.81 95 1.62 82 (E) 1.75 110 1.56 68 (F) 1.81 98 1.20 67 1.72 1.14

EPOCOPY Jf

As can be seen from Table II, 'it is noteworthy that that the photosensitive materials (C) and (D), in each of which a polymer according to the invention is used "had an extremely better shelf life as raw film than the light-sensitive materials (E) and (F) in which comparative compounds were used. The reason for this is how it is believed that the substances supplying (releasing) a dye are polymerized - and thereby in the same Layer can also be fixed under the conditions of the ordeal test. On the other hand is with the photosensitive Materials (E) and (F) are the reason for their lower shelf life, it is believed, that the dye-supplying (releasing) substances under the conditions of the torture test to the protective layer have hiked.

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Claims (11)

-Si · - T 54 558 - -__ Patent claims' "" ^ 1. Heat developable light-sensitive color photography Material characterized by a carrier with at least one applied thereon photographic component layer that contains at least (a) a silver halide, (b) an organic silver salt, (c) a reducing agent, (d) a binder, and (e) a a dye-supplying substance, the dye-supplying substance being a polymer, which was prepared from a polymerizable compound of the general formula AO St. where mean: R represents a hydrogen atom or a methyl group; J is a divalent organic group or a single bond;
ρ is a divalent organic group; Y is an alkylene group or an arylene group; m and η each represent the number 0 or 1; and Cp is a residual group which provides a yellow, magenta or cyan dye.
35
2. Heat developable, photosensitive color photographic Material according to claim 1, characterized in that COPY M ¹ that the polymer, which is the substance providing a dye, contains a monomer of the general formula. . · R, 0 .5 '"1 Il ~ ij where mean: i R _{1 is} a hydrogen atom or an alkyl group having 1 to 8 I 10 carbon atoms; -4 R ₂ -0- or -NR ₃ -; . ". • VR _{3 is} a hydrogen atom or an alkyl group with 1 to 6 ■ jß. Carbon atoms; - ■; ":, ·· ■ · X is a divalent aliphatic, alicyclic or aro- ', 15 matic group; and ί; M is a hydrogen atom, an alkali metal atom, ammonium or an organic onium. j 3. Heat developable, photosensitive color photo J; 20 graphic material according to claim 2, characterized in that that it is represented by X in formula (VIII); sent divalent group around a hydrocarbon with 1 to 10 carbon atoms, which is an ether bond ■ ~ formation or a thioether bond in the middle of its carbon .; 25 may contain a fuel chain. ~ 4. Heat developable photosensitive color photographic ,, ·: phical material according to any one of claims 1 to 3, characterized . "indicates that the amount of one dye used · '30 supplying substance 0.05 part to 1 part per part of the organic Silver salt is. 5. Heat developable photosensitive color photographic Material according to one of Claims 1 to 4, characterized 35 characterized in that the organic silver salt is one having an imino group. 6. Heat developable photosensitive color photogra-ί .. ■ EPO COPY phical material according to claim 5, characterized that the organic silver salt is one with a benzotriazole derivative. 7. · Heat Developable "light-sensitive color photographic Material according to one of Claims 1 to 6, characterized / that the respective amount of the light-sensitive Silver salt and the component for the * formation of the _ photosensitive silver salt used for the manufacture of a silver halide is to be used is 0.01 to 1 mole per mole of the organic silver salt. 8. Heat developable photosensitive color photographic Material according to one of Claims 1 to 7, characterized in that the amount of reducing agent used Is 0.1 to 3 moles per mole of the organic silver salt. 9. Heat developable photosensitive-color photographic Material according to any one of claims 1 to 8, characterized characterized in that the binder is made from a combination of gelatin or a derivative thereof and a hydrophilic polymer such as polyvinyl pyrrolidone. 10. Heat developable photosensitive color photographic Material according to one of Claims 1 to 9, characterized in that the thickness of the photosensitive component layer after drying is 3 to 20 µm. 11. Heat developable color photosensitive photographic Material according to one of Claims 1 to 10, characterized in that each of the components (a), silver halide, (b) organic silver salt, (c) reducing agent, Containing (d) binder and (e) dye-providing substance in a single photographic component layer is. EPO COPY