# US 4,376,162 A · Heat-developable photosensitive material with antihalation layer

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- Number: US 4,376,162 A
- Document ID: US4376162A
- Status: Granted
- Kind: A
- Application number: 06/313,705
- Filed: 1981-10-19
- Granted: 1983-03-08
- Earliest claimed: 1980-10-17
- Assignees: Fuji Photo Film Co., Ltd.
- Inventors: Ken Kawata; Isamu Itoh; Misao Awata; Takao Masuda
- Web page: https://patentgrep.com/patent/US4376162A

## CPC

- G03C 1/498: Photothermographic systems, e.g. dry silver
- G03C: PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES (for photomechanical purposes G03F); PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY (photographic processes characterised by the use or manipulation of apparatus classifiable per se in subclass G03B, see G03B; photomechanical production of textured or patterned surfaces G03F; electrophotography, magnetography G03G)

## Abstract

A heat-developable photosensitive material is disclosed having a high image sharpness. The material is comprised of a heat-developable photosensitive layer which includes an organic silver salt, a photocatalyst, and a reducing agent. An antihalation layer is provided on the opposite face of the material with respect to the side intended for imagewise exposure. The antihalation layer contains a photosensitive halogen-containing compound which reduces the pH of the antihalation layer by photolysis and is colored with a dye which causes a change of color when the pH of the antihalation layer is reduced.

## Claims

### Claim 1

A heat-developable photosensitive material comprising:
a heat-developable photosensitive layer comprised of an organic silver salt, a photocatalyst, and a reducing agent; and
an antihalation layer provided on the opposite side of said heat-developable photosensitive layer with respect to the side intended for imagewise exposure, wherein said antihalation layer is comprised of a photosensitive halogen-containing compound capable of reducing the pH of said antihalation layer by photolysis, said antihalation layer being colored with a dye which changes color when the pH of said antihalation layer is reduced.

### Claim 2 (depends on 1)

A heat-developable photosensitive material, as claimed in claim 1, wherein said photosensitive halogen-containing compound is a compound represented by the formula (I): ##STR78## wherein X represents a halogen atom, R.sub.1, R.sub.2 and R.sub.3, are independently hydrogen, a halogen atom, a nitro group, an alkyl group having from 1 to 10 carbon atoms, an aryl group having from 6 to 14 carbon atoms, an alkylcarbonyl group having from 2 to 11 carbon atoms, and arylcarbonyl group having from 7 to 15 carbon atoms, an amido group substituted with an alkyl group having from 1 to 10 carbon atoms or an aryl group having from 6 to 14 carbon atoms, or a sulfonate group substituted by an alkyl group having from 1 to 10 carbon atoms or an aryl group having from 6 to 14 carbon atoms, and R.sub.1 and R.sub.2 together can also form a cycloalkyl ring by linking to each other.

### Claim 3 (depends on 1)

A heat-developable photosensitive material, as claimed in claim 1, wherein said photosensitive halogen-containing compound is a compound of formula (II): ##STR79## wherein A is a heterocyclic ring, B.sub.1, B.sub.2 and B.sub.3 are independently, hydrogen, chlorine or bromine, provided that one of B.sub.1, B.sub.2 or B.sub.3 is a chlorine atom or a bromine atom.

### Claim 4 (depends on 1)

A heat-developable photosensitive material, as claimed in claim 1, wherein said photosensitive halogen-containing compound is a compound having the formula (III): ##STR80## wherein D is an alkyl group having from 1 to 5 carbon atoms, and may be substituted by halogen atoms or an aryl group having from 6 to 10 carbon atoms, X is a halogen atom, and n is an integer selected from the group consisting of 1, 2 and 3.

### Claim 5 (depends on 1)

A heat-developable photosensitve material, as claimed in claim 1, wherein said photosensitive halogen-containing compound is a compound having the formula (IV): ##STR81## wherein W is a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, and wherein said phenyl group may be substituted with halogen atoms, a nitro group, a cyano group, an alkyl group having from 1 to 3 carbon atoms or an alkoxy group having from 1 to 4 carbon atoms, X is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, and Y is a halogen atom.

### Claim 6 (depends on 1, 2, 3, 4, 5)

A heat-developable photosensitive material as claimed in any of claims 1, 2, 3, 4 or 5, wherein said photosensitive halogen-containing compound is contained in an amount of from about 0.1 mol to about 100 mols per mol of said dye.

### Claim 7 (depends on 6)

A heat-developable photosensitive material as claimed in claim 6, wherein said photosensitive halogen-containing compound is contained in an amount of 0.5 mol to 10 mols per mol of said dye.

### Claim 8 (depends on 7)

A heat-developable photosensitive material, as claimed in claim 7, wherein said dye is contained in an amount sufficient to make the transmission optical density of the antihalation layer at least 0.1, and to make the reflection optical density at least 0.05.

### Claim 9 (depends on 8)

A heat-developable photosensitive material, as claimed in claim 8, wherein said transmission optical density is at least 0.3 and the reflection optical density is at least 0.1.

### Claim 10 (depends on 1)

A heat-developable photosensitive material, as claimed in claim 1, wherein said dye is a dye which has an absorption in the sensitive wavelength range of the heat-developable photosensitive layer in an ordinary state before thermal development, but has a property that the maximum wavelength thereof shifts in a shorter wavelength side or a longer wavelength side to cause the change of color when the pH of the antihalation layer is reduced.

### Claim 11 (depends on 1, 10)

A heat-developable photosensitive material, as claimed in claim 1 or 10, wherein said dye is a pH indicator.

### Claim 12 (depends on 1)

A heat developable photosensitive material, as claimed in claim 1, or 10, wherein said dye is
(1) Cyanine
(2) Quinaldine Red
(3) Neutral Red
(4) Curcumin
(5) Haematoxylin
(6) Alizarin
(7) Methyl Orange
(8) Ethyl bis-2,4-dinitrophenyl acetate
(9) o-Cresolphthalein
(10) Phenolphthalein
(11) Thymolphthalein
(12) Tetrabromophenolsulfonphthalein
(13) Dibromodichlorophenolsulfonphthalein
(14) Thymolsulfonphthalein
(15) 1,4-Dimethyl-5-hydroxybenzenesulfonphthalein
(16) m-Cresolsulfonphthalein
(17) o-Cresolsulfonphthalein or
(18) Dibromo-o-cresolsulfonphthalein.

### Claim 13 (depends on 1)

A heat developable photosensitive material, as claimed in claim 1, or 10, wherein said dye is a compound represented by formula (V): ##STR82## wherein Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4 and Z.sub.5, which may be identical or different, each represents hydrogen, a halogen atom, a cyano group, --CH.dbd.N--OH, a carboxy group, a sulfo group, an alkyl group, an acyl group, an alkoxy group, an amido group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an aryl group or a nitro group, provided that at least one of Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4 and Z.sub.5 is a nitro group; and Z.sub.1 and Z.sub.2, or Z.sub.2 and Z.sub.3 together may form a ring by linking to each other.

### Claim 14 (depends on 1)

A heat developable photosensitive material, as claimed in claim 1, or 10, wherein said dye is a compound represented by formula (VI): ##STR83## wherein Z.sub.6, Z.sub.7, Z.sub.8, Z.sub.9 and Z.sub.10 which may be identical or different, each represents hydrogen, a halogen atom, a cyano group, --CH.dbd.N--OH, a carboxyl group, a sulfo group, an alkyl group, an acyl group, an alkoxy group, an amido group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an aryl group or a nitro group, provided that at least one of Z.sub.6 and Z.sub.8 represents a phenylazo group.

### Claim 15 (depends on 1)

A heat developable photosensitive material, as claimed in claim 1, wherein said antihalation layer further contains a cationic polymer mordant.

### Claim 16 (depends on 15)

A heat developable photosensitive material, as claimed in claim 15, wherein said cationic polymer mordant is a polymer containing quaternary cationic groups and has a molecular weight of 5,000 to 200,000.

### Claim 17 (depends on 15, 16)

A heat developable photosensitive material, as claimed in claim 15 or 16, wherein said cationic polymer mordant is a polymer having quaternary ammonium groups and groups capable of linking to the binder.

### Claim 18 (depends on 15, 16)

A heat developable photosensitive material, as claimed in claim 15 or 16, wherein said cationic polymer mordant is a reaction product of a copolymer composed of a repeating unit of the monomer represented by the following formula and a repeating unit of another ethylenically unsaturated monomer, and a cross-linking agent: ##STR84## R.sub.1 : H or an alkyl group R.sub.2 : H, an alkyl group or an aryl group
Q: a divalent group
R.sub.3, R.sub.4 and R.sub.5 : an alkyl group, an aryl group, or at least two of R.sub.3, R.sub.4 and R.sub.5 may form a heterocyclic ring by linking to each other
X: an anion.

### Claim 19 (depends on 15, 16)

A heat developable photosensitive material, as claimed in claim 15 or 16, wherein said cationic polymer mordant is a polymer represented by the following formula: ##STR85## x: about 0.25 to about 5% by mol y: about 0 to about 90% by mol
z: about 10 to about 99% by mol
A: monomer having at least two ethylenically unsaturated bonds
B: copolymerizable ethylenically unsaturated monomer
Q: N or P
M: an anion
R.sub.1, R.sub.2 and R.sub.3 : an alkyl group, a cyclic hydrocarbon group, and at least two of R.sub.1, R.sub.2 and R.sub.3 may form a ring by linking to each other.

### Claim 20 (depends on 15, 16)

A heat developable photosensitive material, as claimed in claim 15 or 16, wherein said cationic polymer mordant is a copolymer composed of (a), (b) and (c): ##STR86## X: a hydrogen atom, an alkyl group or a halogen atom, (b) Acrylic acid ester, and
(c) Acrylonitrile.

### Claim 21 (depends on 15, 16)

A heat developable photosensitive material, as claimed in claim 15 or 16, wherein said cationic polymer mordant is a water insoluble polymer, more than 1/3 of which is composed of a repeating unit represented by the following formula: ##STR87## R.sub.1, R.sub.2 and R.sub.3 : an alkyl group, respectively, wherein the total of carbon atom numbers in R.sub.1, R.sub.2 and R.sub.3 is 12 or more.

### Claim 22 (depends on 15)

A heat developable photosensitive material, as claimed in claim 15, wherein said cationic polymer mordant is used in a range of from 1 wt% to 4000 wt% based on the dye.

### Claim 23 (depends on 16)

A heat developable photosensitive material, as claimed in claim 16, wherein said polymer has a molecular weight of 10,000 to 50,000.