Claims
- 1. In a photographic assemblage comprising:
- (a) a support having thereon at least one photosensitive silver halide emulsion layer having associated therewith a dye image-providing material;
- (b) a dye image-receiving layer;
- (c) an alkaline processing composition and means for discharging same within said assemblage;
- (d) a neutralizing layer for neutralizing said alkaline processing composition; and
- (e) a timing layer disposed between said neutralizing layer and said photosensitive silver halide emulsion layer so that said processing composition must first permeate said timing layer before contacting said neutralizing layer;
- said neutralizing layer being located on the side of said timing layer which is farthest from said dye image-receiving layer, said assemblage containing a silver halide developing agent, the improvement wherein said assemblage contains a hydroquinone ester either in said timing layer or in a layer which is adjacent thereto, said adjacent layer being so located with respect to said timing layer that said processing composition must first permeate said timing layer before contacting said adjacent layer, said hydroquinone ester having the following formula: ##STR8## wherein: G is hydrogen, COR or SO.sub.2 R;
- G.sup.1 is COR or SO.sub.2 R;
- R is an alkyl group having from 1 to about 20 carbon atoms or an aryl group having from 6 to about 12 carbon atoms; and
- Z is hydrogen, an alkyl group having from 1 to about 6 carbon atoms, an alkoxy group having from 1 to about 6 carbon atoms, or an aryl group having from about 6 to about 8 carbon atoms;
- and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
- 2. The assemblage of claim 1 wherein:
- (a) said dye image-receiving layer is located between said support and said silver halide emulsion layer; and
- (b) said assemblage also includes a transparent cover sheet over the layer outermost from said support.
- 3. The assemblage of claim 2 wherein said transparent cover sheet is coated with said neutralizing layer and said timing layer, respectively.
- 4. The assemblage of claim 2 wherein said discharging means is a rupturable container containing said alkaline processing composition and an opacifying agent, said container being so positioned during processing of said assemblage that a compressive force applied to said container will effect a discharge of the container's contents between said transparent sheet and the layer outermost from said support.
- 5. The assemblage of claim 1 wherein said hydroquinone ester is hydroquinone diacetate, hydroquinone monoacetate, hydroquinone monohexanoate, 3-t-butyl-4-hydroxyphenyl acetate, hydroquinone monobenzoate, 2-methylhydroquinone monoacetate, 2-methoxyhydroquinone monoacetate, 2-methylhydroquinone monobenzoate, 2-methoxyhydroquinone monobenzoate, 2-ethoxyhydroquinone monoacetate, 2-ethoxyhydroquinone monobenzoate, p-methylsulfonyloxyphenol, and p-tolylsulfonyloxyphenol.
- 6. The assemblage of claim 1 wherein said hydroquinone ester is present at a concentration of from about 0.054 g/m.sup.2 to about 0.54 g/m.sup.2.
- 7. The assemblage of claim 1 wherein said timing layer comprises a polymeric latex comprising a polymer of from about 5 to about 35 percent by weight of polymerized ethylenically unsaturated monomer, from about 2 to about 10 percent by weight of polymerized ethylenically unsaturated carboxylic acid, and from about 55 to about 85 percent by weight of polymerized vinylidene chloride.
- 8. The assemblage of claim 1 wherein said timing layer comprises a polymeric latex comprising from about 5 to about 35 percent by weight of acrylonitrile, from about 2 to about 10 percent by weight of a member selected from the group consisting of acrylic acid and itaconic acid and from about 55 to about 85 percent by weight of vinylidene chloride.
- 9. The assemblage of claim 1 wherein said timing layer comprises a mixture of (1) from about 5 to about 95 percent by weight of a terpolymer comprising from about 55 to about 85 percent by weight of vinylidene chloride, from about 5 to about 35 percent by weight of an ethylenically unsaturated monomer, and from about 0 to about 20 percent by weight of an ethylenically unsaturated carboxylic acid, and (2) from about 5 to about 95 percent by weight of a polymeric carboxy-ester-lactone.
- 10. The assemblage of claim 1 wherein said hydroquinone ester is in a layer adjacent to said timing layer, said adjacent layer comprising a polymeric latex having an activation energy of penetration of the layer by an aqueous alkaline solution of less than 18 kcal/mole.
- 11. The assemblage of claim 10 wherein said adjacent layer comprises a mixture of cellulose acetate and a maleic anhydride copolymer, said mixture comprising about 5 to about 50 percent by weight of said copolymer.
- 12. The assemblage of claim 1 wherein said dye image-providing material is a ballasted sulfonamido compound which is alkali-cleavable upon oxidation to release a diffusible color-providing moiety from a benzene nucleus, said compound having the formula: ##STR9## wherein: (a) Col is a dye or dye precursor moiety;
- (b) Ballast is an organic ballasting radical of such molecular size and configuration as to render said compound nondiffusible in said photosensitive element during development in an alkaline processing composition;
- (c) G is OR.sub.2 or NHR.sub.3 wherein R.sub.2 is hydrogen or a hydrolyzable moiety and R.sub.3 is hydrogen or an alkyl group of 1 to 22 carbon atoms;
- (d) Y represents the atoms necessary to complete a benzene nucleus, a naphthalene nucleus, or a 5- to 7-membered heterocyclic ring; and
- (e) n is a positive integer of 1 to 2 and is 2 when G is OR.sub.2 or when R.sub.3 is hydrogen or an alkyl group of less than 8 carbon atoms.
- 13. An integral photographic assemblage comprising:
- (a) a photosensitive element comprising a transparent support having thereon the following layers in sequence: a dye image-receiving layer; an alkaline solution-permeable, light-reflective layer; an alkaline solution-permeable, opaque layer; a red-sensitive, direct positive silver halide emulsion layer having a ballasted redox cyan dye releaser associated therewith; a green-sensitive, direct positive silver halide emulsion layer having a ballasted redox magenta dye releaser associated therewith; and a blue-sensitive, direct positive silver halide emulsion layer having a ballasted redox yellow dye releaser associated therewith;
- (b) a transparent sheet superposed over said blue-sensitive silver halide emulsion layer and comprising a transparent support coated with, in sequence, a neutralizing layer and a timing layer; and
- (c) a rupturable container containing an alkaline processing composition and an opacifying agent, said container being so positioned during processing of said assemblage that a compressive force applied to said container will effect a discharge of the container's contents between said transparent sheet and said blue-sensitive silver halide emulsion layer;
- said assemblage containing a silver halide developing agent, the improvement wherein said assemblage contains a hydroquinone ester either in said timing layer or in a layer which is adjacent thereto, said adjacent layer being so located with respect to said timing layer that said processing composition must first permeate said timing layer before contacting said adjacent layer, said hydroquinone ester having the following formula: ##STR10## wherein: G is hydrogen, COR or SO.sub.2 R;
- G.sup.1 is COR or SO.sub.2 R;
- R is an alkyl group having from 1 to about 20 carbon atoms or an aryl group having from 6 to about 12 carbon atoms; and
- Z is hydrogen, an alkyl group having from 1 to about 6 carbon atoms, an alkoxy group having from 1 to about 6 carbon atoms, or an aryl group having from about 6 to about 8 carbon atoms;
- and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
- 14. The assemblage of claim 13 wherein each said redox dye releaser is a ballasted sulfonamido compound which is alkali-cleavable upon oxidation to release a diffusible color-providing moiety from a benzene nucleus, said compound having the formula: ##STR11## wherein: (a) Col is a dye or dye precursor moiety;
- (b) Ballast is an organic ballasting radical of such molecular size and configuration as to render said compound nondiffusible in said photosensitive element during development in an alkaline processing composition;
- (c) G is OR.sub.2 or NHR.sub.3 wherein R.sub.2 is hydrogen or a hydrolyzable moiety and R.sub.3 is hydrogen or an alkyl group of 1 to 22 carbon atoms;
- (d) Y represents the atoms necessary to complete a benzene nucleus, a naphthalene nucleus, or a 5- to 7-membered heterocyclic ring; and
- (e) n is a positive integer of 1 to 2 and is 2 when G is OR.sub.2 or when R.sub.3 is hydrogen or an alkyl group of less than 8 carbon atoms.
- 15. The assemblage of claim 14 wherein each said silver halide emulsion is an internal-image silver halide emulsion, and said timing layer comprises a polymeric latex comprising a polymer of from about 5 to about 35 percent by weight of polymerized ethylenically unsaturated monomer, from about 2 to about 10 percent by weight of polymerized ethylenically unsaturated carboxylic acid, and from about 55 to about 85 percent by weight of polymerized vinylidene chloride.
- 16. The assemblage of claim 14 wherein each said silver halide emulsion is an internal-image silver halide emulsion; said timing layer comprises a mixture of (1) from about 5 to about 95 percent by weight of a terpolymer comprising from about 55 to about 85 percent by weight of vinylidene chloride, from about 5 to about 35 percent by weight of an ethylenically unsaturated monomer, and from about 0 to about 20 percent by weight of an ethylenically unsaturated carboxylic acid, and (2) from about 5 to about 95 percent by weight of a polymeric carboxy-ester-lactone; and said hydroquinone ester is located in said timing layer.
- 17. In a process for producing a photographic transfer image in color from an imagewise-exposed photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer having associated therewith a dye image-providing material, said process comprising treating said element with an alkaline processing composition in the presence of a silver halide developing agent to effect development of each of said exposed silver halide emulsion layer, said processing composition contacting said emulsion layer prior to contacting a neutralizing layer; whereby an imagewise distribution of dye image-providing material is formed as a function of development and at least a portion of it diffuses to a dye image-receiving layer to provide said transfer image, whereby a timing layer associated with said neutralizing layer is permeated by said alkaline processing composition after a predetermined time, said timing layer being disposed between said neutralizing layer and said photosensitive silver halide emulsion layer so that said processing composition must first permeate said timing layer before contacting said neutralizing layer, said neutralizing layer being located on the side of said timing layer which is farthest from said dye image-receiving layer; whereby said alkaline processing composition is neutralized by means of said neutralizing layer associated with said photographic element after said predetermined time; the improvement wherein a hydroquinone ester is employed either in said timing layer or in a layer adjacent thereto, said adjacent layer being so located with respect to said timing layer that said processing composition must first permeate said timing layer before contacting said adjacent layer, said hydroquinone ester having the following formula: ##STR12## wherein: G is hydrogen, COR or SO.sub.2 R;
- G.sup.1 is COR or SO.sub.2 R;
- R is an alkyl group having from 1 to about 20 carbon atoms or an aryl group having from 6 to about 12 carbon atoms; and
- Z is hydrogen, an alkyl group having from 1 to about 6 carbon atoms, an alkoxy group having from 1 to about 6 carbon atoms, or an aryl group having from about 6 to about 8 carbon atoms;
- and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
- 18. The process of claim 17 wherein said hydroquinone ester is hydroquinone diacetate, hydroquinone monoacetate, acetate, hydroquinone monohexanoate, 3-t-butyl-4-hydroxyphenyl acetate, hydroquinone monobenzoate, 2-methylhydroquinone monoacetate, 2-methoxyhydroquinone monoacetate, 2-methylhydroquinone monobenzoate, 2-methoxyhydroquinone monobenzoate, 2-ethoxyhydroquinone monoacetate, 2-ethoxyhydroquinone monobenzoate, p-methylsulfonyloxyphenol, and p-tolylsulfonyloxyphenol.
- 19. The process of claim 17 wherein said hydroquinone ester is present at a concentration of from about 0.054 g/m.sup.2 to about 0.54 g/m.sup.2.
- 20. The process of claim 17 wherein said timing layer comprises a polymeric latex comprising a polymer of from about 5 to about 35 percent by weight of polymerized ethylenically unsaturated monomer, from about 2 to about 10 percent by weight of polymerized ethylenically unsaturated carboxylic acid, and from about 55 to about 85 percent by weight of polymerized vinylidene chloride.
- 21. The process of claim 17 wherein said timing layer comprises a mixture of (1) from about 5 to about 95 percent by weight of a terpolymer comprising from about 55 to about 85 percent by weight of vinylidene chloride, from about 5 to about 35 percent by weight of an ethylenically unsaturated monomer, and from about 0 to about 20 percent by weight of an ethylenically unsaturated carboxylic acid, and (2) from about 5 to about 95 percent by weight of a polymeric carboxy-ester-lactone.
- 22. In a dye image-receiving element comprising a support having thereon, in sequence, a neutralizing layer, a timing layer and a dye image-receiving layer, the improvement wherein a hydroquinone ester is employed in a layer between said dye image-receiving layer and said support, said hydroquinone ester having the following formula: ##STR13## wherein: G is hydrogen, COR or SO.sub.2 R;
- G.sup.1 is COR or SO.sub.2 R;
- R is an alkyl group having from 1 to about 20 carbon atoms or an aryl group having from 6 to about 12 carbon atoms; and
- Z is hydrogen, an alkyl group having from 1 to about 6 carbon atoms, an alkoxy group having from 1 to about 6 carbon atoms, or an aryl group having from about 6 to about 8 carbon atoms;
- and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
- 23. In a cover sheet comprising a transparent support having thereon, in sequence, a neutralizing layer and a timing layer, the improvement wherein said cover sheet contains a hydroquinone ester having the following formula: ##STR14## wherein: G is hydrogen, COR or SO.sub.2 R;
- G.sup.1 is COR or SO.sub.2 R;
- R is an alkyl group having from 1 to about 20 carbon atoms or an aryl group having from 6 to about 12 carbon atoms; and
- Z is hydrogen, an alkyl group having from 1 to about 6 carbon atoms, an alkoxy group having from 1 to about 6 carbon atoms, or an aryl group having from about 6 to about 8 carbon atoms;
- and wherein said timing layer has an activation energy of penetration of the layer by an aqueous alkaline solution of greater than 18 kcal/mole.
- 24. The cover sheet of claim 23 wherein said timing layer comprises a polymeric latex comprising a polymer of from about 5 to about 35 percent by weight of polymerized ethylenically unsaturated monomer, from about 2 to about 10 percent by weight of polymerized ethylenically unsaturated carboxylic acid, and from about 55 to about 85 percent by weight of polymerized vinylidene chloride.
- 25. The cover sheet of claim 23 wherein said timing layer comprises a mixture of (1) from about 5 to about 95 percent by weight of a terpolymer comprising from about 55 to about 85 percent by weight of vinylidene chloride, from about 5 to about 35 percent by weight of an ethylenically unsaturated monomer, and from about 0 to about 20 percent by weight of an ethylenically unsaturated carboxylic acid, and (2) from aout 5 to about 95 percent by weight of a polymeric carboxy-ester-lactone.
Parent Case Info
This application is a continuation-in-part of my copending U.S. application Ser. No. 848,061, filed on Nov. 3, 1977, now abandoned.
US Referenced Citations (4)
Non-Patent Literature Citations (1)
Entry |
"Photographic Processes and Products," Research Disclosure No. 15162 Nov. 1976 pp. 76-89. _ |
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
848061 |
Nov 1977 |
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