CA2025957A1 - Multilayer photographic elements having improved coating quality - Google Patents
Multilayer photographic elements having improved coating qualityInfo
- Publication number
- CA2025957A1 CA2025957A1 CA002025957A CA2025957A CA2025957A1 CA 2025957 A1 CA2025957 A1 CA 2025957A1 CA 002025957 A CA002025957 A CA 002025957A CA 2025957 A CA2025957 A CA 2025957A CA 2025957 A1 CA2025957 A1 CA 2025957A1
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- CA
- Canada
- Prior art keywords
- hydrophilic colloid
- photographic element
- multilayer photographic
- element according
- surface active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/38—Dispersants; Agents facilitating spreading
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/162—Protective or antiabrasion layer
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Laminated Bodies (AREA)
Abstract
Multilayer Photographic Elements Having Improved Coating Quality ABSTRACT OF DISCLOSURE
A multilayer photographic element comprising at least one light-sensitive emulsion layer comprising silver halide grains dispersed in a hydrophilic colloid and at least one auxiliary hydrophilic colloid layer, said plu-rality of layers of different composition being simultane-ously coated onto a hydrophobic support from aqueous hydrophilic colloid compositions, presents improved coat-ing quality if at least one auxiliary hydrophilic colloid layer comprises a) an anionic surface active agent, b) at least one of betaine, N-oxide or amide surface active agent the and c) at least one of dispersed droplets of a water-immiscible high-boiling organic solvent, a vinyl addition polymer latex ox a highly deionized gelatin.
All the layers can be simultaneously coated from said different hydrophilic colloid aqueous compositions while mantaining a distinct layer relationship and avoiding any coating defects.
A multilayer photographic element comprising at least one light-sensitive emulsion layer comprising silver halide grains dispersed in a hydrophilic colloid and at least one auxiliary hydrophilic colloid layer, said plu-rality of layers of different composition being simultane-ously coated onto a hydrophobic support from aqueous hydrophilic colloid compositions, presents improved coat-ing quality if at least one auxiliary hydrophilic colloid layer comprises a) an anionic surface active agent, b) at least one of betaine, N-oxide or amide surface active agent the and c) at least one of dispersed droplets of a water-immiscible high-boiling organic solvent, a vinyl addition polymer latex ox a highly deionized gelatin.
All the layers can be simultaneously coated from said different hydrophilic colloid aqueous compositions while mantaining a distinct layer relationship and avoiding any coating defects.
Description
44638CA~2A
202a~57 ~
Coatin~ Quality FIELI:) OF THE INVENTION
The present invention relates to multilayer photo-graphic elements, and more particularly ~o multilayer pho-tographic elements having improved coating quality.
BACKGROUND OF THE ART
Multilayer photographic elements comprise at least one hydrophilic layer (i. e. permeable to aqueous photo-graphic processing solutions) of an emulsion of silver halide gxains dispersed in an hydrophilic colloid and at least one auxiliary hydrophilic colloid layer (for exam-ple, a filter layer, an external protective layer, an in-termediate layer, an antihalation layer), said plurality of layers being coated over a hydrophobic support.
The art of multilayer coating of photographic ele-ments has been highly developed, particularly in the manu-facture of photographic elements which comprise a plurali-ty of hydrophilic layers of different composition coated on the hydrophobic support.
These composi~ions are commonly diluted with a low temperature boiling solvent, such as water, for reducing their viscosity and improving coating quality and speed, and they are coated with a multilayer slide bead coater, a multilayer cascade coater, a multilayer extrusion coater or the like onto a hydrophobic supportO This coating oper-ation is followed by a drying process in which the solvent is removed.
US Patents Nos. 2,761,791, 3,508,947 and 4,001,024 decribe methods of multilayer coating whereby a plurality of liquid coating compositions are simultaneously applîed to a moving support while mantaining a distinct layer re-lationship.
202a~57 ~
Coatin~ Quality FIELI:) OF THE INVENTION
The present invention relates to multilayer photo-graphic elements, and more particularly ~o multilayer pho-tographic elements having improved coating quality.
BACKGROUND OF THE ART
Multilayer photographic elements comprise at least one hydrophilic layer (i. e. permeable to aqueous photo-graphic processing solutions) of an emulsion of silver halide gxains dispersed in an hydrophilic colloid and at least one auxiliary hydrophilic colloid layer (for exam-ple, a filter layer, an external protective layer, an in-termediate layer, an antihalation layer), said plurality of layers being coated over a hydrophobic support.
The art of multilayer coating of photographic ele-ments has been highly developed, particularly in the manu-facture of photographic elements which comprise a plurali-ty of hydrophilic layers of different composition coated on the hydrophobic support.
These composi~ions are commonly diluted with a low temperature boiling solvent, such as water, for reducing their viscosity and improving coating quality and speed, and they are coated with a multilayer slide bead coater, a multilayer cascade coater, a multilayer extrusion coater or the like onto a hydrophobic supportO This coating oper-ation is followed by a drying process in which the solvent is removed.
US Patents Nos. 2,761,791, 3,508,947 and 4,001,024 decribe methods of multilayer coating whereby a plurality of liquid coating compositions are simultaneously applîed to a moving support while mantaining a distinct layer re-lationship.
- 2 - 202 3 ~ ~
A homogeneous coating quality is important for the production of high quality photographic materials, espe-cially for the production of large image areas wherein the worsening of the coating quality causes undesirable de-fects. This phenomenon of worsenlng of the ccating quality is particularly evident in multilayer photographic ele-ments due to the interaction between the commonly used anionic surface active agents and gelatin which is the generally used hydrophilic colloid. This interaction, which causes an increase of surface tension of the hydro-philic colloid composition, is particularly remarkable in the hydrophilic colloid auxiliary layers comprising at least one of highly deionized gelatins, disperesed drop-lets of water-immiscible high boiling organic solvents (oils) used to disperse hydrophobic photographic addenda in the auxiliary layer, or vinyl addition pol~mer latexes.
The action of water soluble salts, such as soluble Ca~+ salts, in decreasing the surface tension of the hydrophilic colloid photographic compositions wherein said salts are introduced, is known to the skilled in the art to reduce the coating defects of multilayer photographic elements when several hydrophilic layer forming composi-tions are coated simultaneously onto a moving support. The addition of water soluble salts, however, causes coales-cence of dispersed droplets of oils or vinyl addition pol-ymer latexes and tends to increase the residual moisture content of the photographic element thus causing sticking of the element itself.
US Patent No. 3,811,889 describes a light-sensitive material comprising a support having coated thereon at least one silver halide emulsion layer containing (a) an anionic polymer having a carboxyl group or an alkali metal salt thereof as a side chain thereof, and (b) at least one of a cationic surface active agent and a betaine-t~pe amphoteric surface active agent. This combination gives the film good antistatic properties.
_ 3 2~ 7 SUMMARY OF THE INVENTION
It has now been found that a multilayer photographic element comprising at least one light-sensitive emulsion layer comprising silver halide grains dispersed in a hydrophilic colloid and at least one auxiliary hydrophilic colloid layer,` said plurality of layers of different com-position being simultaneously coated onto a hydrophobic support from aqueous hydrophilic colloid compositions, pxesents improved coating quality if at least one auxilia-ry hydrophilic colloid layer comprises an anionic surface active agent, at least one of betaine, N-oxide or amide surface active agents and at least one of dispersed drop-lets of a water-immiscible high-boiling organic solvent, a vinyl addition polymer latex and a highly deioni7ed gela-tin.
According to this invention, all the layers can be simultaneously coated from said different hydrophilic col-loid aqueous compositions while mantaining a distinct lay-er relationship and avoiding any coating defects, such as relief patternings, repellencies or comets.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a multilayer photo-graphic element comprising a support having coated thereon a plurality of hydrophilic colloid layers comprising at least one hydrophilic colloid silver halide emulsion layer and at least one hydrophilic colloid auxiliary layer. At least one of said auxiliary hydrophilic colloid layers comprises an anionic surface active agent, at least one of which is betaine, N-oxide or amide surface activ agent.
Said auxiliary layer also comprises at least one of dis-persed droplets of a water-immiscible high-boiling organic solvent, a vinyl addition polymer latex or a highly de-ionized gelatin.
Anionic surface active agents, normally used in 2a2~
photography, for example as coating, coagulant or dispers-ing agents, are surfactants of the type includiny a hydro-phobic group linked to an anionic hydrophilic group di-rectly or by means of a bridge consisting of a divalent organic residue, as expressed by the following formula:
R A -X
wherein R is an aliphatic, aromatic or a mixed hydrocarbon residue substituted or not substituted and preferably a linear or branched alkyl group having from 4 to 18 carbon atoms or an aryl group substituted with one or more alkyl groups altogether having from 4 to 18 carbon atoms~
A is a chemical bond or a divalent organic residue, preferably a carbonyl, a sulphonyl, an amino or an alkyl-ene group preferably having from 1 to 3 carbon atoms, an oxygen atom or groups consisting of two or more of the above-mentioned groups, such as for example carbonylamino, sulphonylamino, aminocarbonyl, aminosulphonyl, ester or polyoxyalkylene groups preferably containing from 2 to 40 oxyalkylene unities, and X is an anionic group of the sulphonate, carboxylate, phosphate and sulphate type.
Anionic surface active agents of this type are de-scribed for example in Schwarz et al. "Surface Active Agents and Detergents", Vol. I and II, Interscience Publ., in the US Pat. Nos. 2,992,108, 3,068,101, 3,201,152 and 3,165,409, in the French Pat. Nos. 1,556,~40 and 1,497,930 and in the British Pat. Nos~ 580,504 and 985,483.
With betaine, N-oxide or amide surface active agents, all those surfactants which present betaine, N-oxide or amide hydrophilic groups are hereby intended. These groups are preferably linked to a hydrophobic group R by means of a brid~e A, as expressed in the following formula:
R- A - Z
202~7 wherein R and A preferably represent a group of the above-defined type, and Z prPferably represents a betaine group, such as for example of the type comprising an ammonium cation and a carboxylate or sulphonate anion, an N-oxide group or an amide group, such as for example an hydroxyalkyleneamide group, such as those represented,for example, by the fol-lowing formulas:
- N - B - X
Rl R2 or B - X R~ or ~ N - R2 ~ R2~
or - C -, B - X or - C - N - B - OH
+ ~Ri'' '' wherein R1, R2 and R3 are hydrogen or alkyl group having from 1 to 10, preferably from 1 to 6 carbon atoms, wherein said alkyl group possibly can be substituted for example with an aryl group, preferably phenyl, R1 and R2 or R1, R2 and R3 altogether also represent the non-metallic atoms necessary to form a heterocyclic guaternized nitrogen nucleus, such as for example pyri-dinium and imidazolinium, B represents an alkylene group (possibly having a carbon atom replaced with a hetero atom such as a nitrogen atom, a sulfur atom, an oxygen atom, etc.), preferably having 1 to 6 carbon atoms, and X is a carboxylate or sulphonate anion.
Compounds of the anionic surface active agent type, 2 0 2 ~
-- 6 ~
as defined above, are for example: -1 Cl2H25S3Na ,CH3 C4Hg CIH C2H4 ~H C2H4 CH~
C2H5 SO4Na CH3 3~ C8H17- ~ SO3Na 4. C7H15- ~ -OSO3Na 5- C4H9 ~ -(OC2H4)n-SO3Na n = 2 - 40 6. Oleyl-CO-N-~CH2)2-S03Na 7- Stearyl ~C2H~)7 NHCO CH2S3Na 8. CH2-COO-CH2-CH-(CH2)3CH3 CH-COO-CH2-CH-(CH2)3CH3 ~: S03Na ::
A homogeneous coating quality is important for the production of high quality photographic materials, espe-cially for the production of large image areas wherein the worsening of the coating quality causes undesirable de-fects. This phenomenon of worsenlng of the ccating quality is particularly evident in multilayer photographic ele-ments due to the interaction between the commonly used anionic surface active agents and gelatin which is the generally used hydrophilic colloid. This interaction, which causes an increase of surface tension of the hydro-philic colloid composition, is particularly remarkable in the hydrophilic colloid auxiliary layers comprising at least one of highly deionized gelatins, disperesed drop-lets of water-immiscible high boiling organic solvents (oils) used to disperse hydrophobic photographic addenda in the auxiliary layer, or vinyl addition pol~mer latexes.
The action of water soluble salts, such as soluble Ca~+ salts, in decreasing the surface tension of the hydrophilic colloid photographic compositions wherein said salts are introduced, is known to the skilled in the art to reduce the coating defects of multilayer photographic elements when several hydrophilic layer forming composi-tions are coated simultaneously onto a moving support. The addition of water soluble salts, however, causes coales-cence of dispersed droplets of oils or vinyl addition pol-ymer latexes and tends to increase the residual moisture content of the photographic element thus causing sticking of the element itself.
US Patent No. 3,811,889 describes a light-sensitive material comprising a support having coated thereon at least one silver halide emulsion layer containing (a) an anionic polymer having a carboxyl group or an alkali metal salt thereof as a side chain thereof, and (b) at least one of a cationic surface active agent and a betaine-t~pe amphoteric surface active agent. This combination gives the film good antistatic properties.
_ 3 2~ 7 SUMMARY OF THE INVENTION
It has now been found that a multilayer photographic element comprising at least one light-sensitive emulsion layer comprising silver halide grains dispersed in a hydrophilic colloid and at least one auxiliary hydrophilic colloid layer,` said plurality of layers of different com-position being simultaneously coated onto a hydrophobic support from aqueous hydrophilic colloid compositions, pxesents improved coating quality if at least one auxilia-ry hydrophilic colloid layer comprises an anionic surface active agent, at least one of betaine, N-oxide or amide surface active agents and at least one of dispersed drop-lets of a water-immiscible high-boiling organic solvent, a vinyl addition polymer latex and a highly deioni7ed gela-tin.
According to this invention, all the layers can be simultaneously coated from said different hydrophilic col-loid aqueous compositions while mantaining a distinct lay-er relationship and avoiding any coating defects, such as relief patternings, repellencies or comets.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a multilayer photo-graphic element comprising a support having coated thereon a plurality of hydrophilic colloid layers comprising at least one hydrophilic colloid silver halide emulsion layer and at least one hydrophilic colloid auxiliary layer. At least one of said auxiliary hydrophilic colloid layers comprises an anionic surface active agent, at least one of which is betaine, N-oxide or amide surface activ agent.
Said auxiliary layer also comprises at least one of dis-persed droplets of a water-immiscible high-boiling organic solvent, a vinyl addition polymer latex or a highly de-ionized gelatin.
Anionic surface active agents, normally used in 2a2~
photography, for example as coating, coagulant or dispers-ing agents, are surfactants of the type includiny a hydro-phobic group linked to an anionic hydrophilic group di-rectly or by means of a bridge consisting of a divalent organic residue, as expressed by the following formula:
R A -X
wherein R is an aliphatic, aromatic or a mixed hydrocarbon residue substituted or not substituted and preferably a linear or branched alkyl group having from 4 to 18 carbon atoms or an aryl group substituted with one or more alkyl groups altogether having from 4 to 18 carbon atoms~
A is a chemical bond or a divalent organic residue, preferably a carbonyl, a sulphonyl, an amino or an alkyl-ene group preferably having from 1 to 3 carbon atoms, an oxygen atom or groups consisting of two or more of the above-mentioned groups, such as for example carbonylamino, sulphonylamino, aminocarbonyl, aminosulphonyl, ester or polyoxyalkylene groups preferably containing from 2 to 40 oxyalkylene unities, and X is an anionic group of the sulphonate, carboxylate, phosphate and sulphate type.
Anionic surface active agents of this type are de-scribed for example in Schwarz et al. "Surface Active Agents and Detergents", Vol. I and II, Interscience Publ., in the US Pat. Nos. 2,992,108, 3,068,101, 3,201,152 and 3,165,409, in the French Pat. Nos. 1,556,~40 and 1,497,930 and in the British Pat. Nos~ 580,504 and 985,483.
With betaine, N-oxide or amide surface active agents, all those surfactants which present betaine, N-oxide or amide hydrophilic groups are hereby intended. These groups are preferably linked to a hydrophobic group R by means of a brid~e A, as expressed in the following formula:
R- A - Z
202~7 wherein R and A preferably represent a group of the above-defined type, and Z prPferably represents a betaine group, such as for example of the type comprising an ammonium cation and a carboxylate or sulphonate anion, an N-oxide group or an amide group, such as for example an hydroxyalkyleneamide group, such as those represented,for example, by the fol-lowing formulas:
- N - B - X
Rl R2 or B - X R~ or ~ N - R2 ~ R2~
or - C -, B - X or - C - N - B - OH
+ ~Ri'' '' wherein R1, R2 and R3 are hydrogen or alkyl group having from 1 to 10, preferably from 1 to 6 carbon atoms, wherein said alkyl group possibly can be substituted for example with an aryl group, preferably phenyl, R1 and R2 or R1, R2 and R3 altogether also represent the non-metallic atoms necessary to form a heterocyclic guaternized nitrogen nucleus, such as for example pyri-dinium and imidazolinium, B represents an alkylene group (possibly having a carbon atom replaced with a hetero atom such as a nitrogen atom, a sulfur atom, an oxygen atom, etc.), preferably having 1 to 6 carbon atoms, and X is a carboxylate or sulphonate anion.
Compounds of the anionic surface active agent type, 2 0 2 ~
-- 6 ~
as defined above, are for example: -1 Cl2H25S3Na ,CH3 C4Hg CIH C2H4 ~H C2H4 CH~
C2H5 SO4Na CH3 3~ C8H17- ~ SO3Na 4. C7H15- ~ -OSO3Na 5- C4H9 ~ -(OC2H4)n-SO3Na n = 2 - 40 6. Oleyl-CO-N-~CH2)2-S03Na 7- Stearyl ~C2H~)7 NHCO CH2S3Na 8. CH2-COO-CH2-CH-(CH2)3CH3 CH-COO-CH2-CH-(CH2)3CH3 ~: S03Na ::
9 . CH2 -CONH-C1 3H27 C~-COONa SO3Na Compounds of this type are sold under registered trade mark, such as for example TeepolTM, TergitolTM 4, : Nekal~M BX, AlrowetTM D65, MaprofixTM LK, HostapurTM SAS, .
, 202~7 AerosolT~ OT.
Compounds of the betaine, N-oxide and amide surface active agent type, as defined above, are for example:
, 202~7 AerosolT~ OT.
Compounds of the betaine, N-oxide and amide surface active agent type, as defined above, are for example:
10. cocco-CONH(C~2~3N ~CH3)2CH2COO
11. stearyl-N (CH3)2CH2COO
12. lauryl-N (CH3)2(CH2)3COO
13. stearyl-N (CH3)2(CH3)2S03 14. cocco-CONHtCH2)3N(CH3)2 5. lauryl-N(CH3)2 O
6 CH - NH+
CH2~ ~c-stearyl 17. ~N - CH2 C11~23 ~ N - CH2 CH2-CH2 CHzCH20H
COO
18. CH2COO
C12H25S02N-C3H6N (CH3)3 19. lauryl-CON ~
- 8 - 2~
20. Stearyl-CONHCH2CH2OH
*
cocco represents a mixed blend of groups derived from the reaction of coconut oils with amines. The nature of the resultant composition is about 65% C11H23 (lauric acid), 5% C13H27 ~mirystic acid), 15% C15H31 palmitic ac-id) and 15% C8H19 (capric acid).
The above listed compounds can be found on the market under registered trade mark, such as for example Tego-betaineTM L7, VelvetexTM, DeriphatTM, MyranolTM 2MCA, AminoxidTM W35, AmmonixTM LO, SuperamideTM L9 and L9C.
In the hydrophilic colloid auxiliary layer according to this invention, said anionic surface active agent is preferably contained in a quantity ranging from 2 to 5 g per 100 g of the hydrophilic colloid of the layer and said betaine, N-oxide or amide surface active agent is prefera bly contained in a quantity ranging from 1 to 4.5 g per 100 g of the hydrophilic colloid of the layer.
The auxiliary hydrophilic colloid layer according to this invention is formed by coating a hydrophilic colloid aqueous composition comprising in addition to the combina-tion of the above-mentioned surface active agents at least one of dispersed droplets of a water-immiscible high-boil-ing organic solvent, a vinyl addition polymer latex or a highly deionized gelatin.
The organic solvents which can be used in the auxil-iary hydrophilic colloid layer of this invention are de-fined as non-polymeric organic compounds having a boiling point higher than 200C and a water solubility lower than 0.5 g per liter at 25C, and are ordinarily used in dis-persing hydrophobic coupling agents and photographic addi-tives as described, for example, in US Patents Nos.
~,322,027, 2,501,170, 2,801,171, 2,801,171, 2,272,191, 2,304,940 and 3,748,141. Even though a wide variety of organic solvents can be used, those which are most prefer-able for the purpose of the present invention (because of the fact that they show no negative e~fects on the 9 2 ~ 7 photosensitive material, are easily obtainable and easy to handle because of their excellent stability) have been found to be organic solvents chosen from the class con-sisting of dibuthylphthalate r tricresylphosphate, triphen-ylphosphate, di-2-ethylhexylphthalate, di-n-octylphthal-ate, tris-2-ethylhexylphosphate, cetyltributylcitra~e, di-n-hexyladipate, dimethylsebacate, triethyleneglycol-di-2-ethylhexoa~e, ethylphthalylethylglycolate, quinitol-bis(2-ethylhexoate) and 1,4-cyclohexyldimethylene-bis-(2-hexylhexoate).
For the purpose of the present invention, said organ-ic solvents are dispersed in the ~orm of fine droplets (of a size from o.l to 1 ~m, more preferably from 0.15 to 0O3 ~m), which are produced by known methods, the most common-ly used method consisting of first dissolving the organic solvent, either alone or in mixture (two or more), in a low temperature boiling solvent (such as methylacetate, ethylacetate, propylacetate, butylacetate, butylpropion-ate, cyclohexanol, dimethyleneglycolemonoacetate, nitro-methane, carbontetrachloride, chloroform, cyclohexane, tetrahydrofuran, methylalcohol, ethylalcohol, propylalco-hol, acetonitrile, dimethylformamide, dioxane, acetone, methylethylketone, methylisobutylketone, and the like, used either alone or in combination) r then mixing the so-lution with an aqueous solution of a hydrophilic colloid containing one or more anionic dispersing agents of the type normally used in photography (such as dioctylsodium-sulphosuccinate, sodiumlaurylsulphate, sodiumalkyl~
naphthalenesulphate and others described in Schwarz et al.
"Surface Active Agents and Detergents", Vol. I and II, Interscience Publ., in the US Pat. Nos. 2,992,108, 3,068,101, 3,201,152 and 3,165,409, in the French Pat.
Nos. 1,556,240 and 1,497,930 and in the British Pat. Nos.
580,504 and 985,483) and finally dispersing the composi-tion obtained in this manner using a suitable means such as a colloidal mill, a high speed rotating mixer or ultra-sonic dispenser. Additionally the organic solvent droplets 2~5~7 could include photographic additives of a hydrophilic na ture, and more pxeferably of a hydrophobic nature such ~s W absorbers, anti-staining agents~ compounds which re-lease developing inhibitors, optical bleaches, anti-oxid-ants, dyes, color couplers and the like.
In the hydrophilic colloid coating composition used for forming the auxiliary hydrophilic colloid layer ac-cording to this invention, said organic solvent is present in proportion by weight of from 10 to 30%, preferably 15 to 20% with respect to the hydrophilic colloid of the coating composition.
The vinyl addition polymers which can be used in the auxiliary hydrophilio colloid layer of this invention are obtained by polymerizing suitable monomers in an emulsion.
The preferred monomers axe ethylene-unsaturated monomers of the acrylic or methacrylic acid ester type, such as ethylacrylate, methylmethacrylate, methylacrylate, butyl-methacrylate, etc., alkyl-substituted acrylamides such as N,N-dibutylacrylamide, N-octylacrylamide, etc., vinyl ester such as vinylacetate, vinylbutyrate, etc., dienes such as butadiene, isoprene, dimethylbutadiene, chloro-prene, fluoroprene, etc., aromatic compounds such as styrene, vinyltoluene, etc., vinylhalides such as vinyl-chloride and vinylidenechloride, acrylonitrile, meth-acrylonitrile, vinylpyridine, vinylquinoline and other commonly known similar monomers.
These polymers are dispersed in the auxiliary layer of the present invention in the form of very small parti-~les of a size between 0.03 and 0.4 ~m, and more prefera-bly between 0.04 and 0.1 ~m. Said aqueous dispersions of polymers (latexes) are usually prepared by dispersing one or more of the aforesaid monomers in water in the presence of a dispersing or surface active agent of the type al-ready described heretofore for dispersing the oil, and carrying out polymerization by the use of a water-soluble initiator which is generally a per-compound (ammonium or potassium persulphate, hydrogen peroxide, sodium perborate, etc.), or a redox system such as persulphate-bisulphite, or a compound of the a,a'-azo-bisisobutyro-amidine hydrochloride type and a,a'-azo-bis-4-cyano-psntanoic acid (US Pat. Nos. 2,739,137 and 2,599,300 and UK Pat. No. 759,409), or a water-insoluble initiator (such as azo-bis-isobutyronitrile, benzoylperoxide, or cumene-hydroperoxide). In preparing the latex, it is often advan-tageous to use, together with the aforesaid monomers, smaller quantities of water-soluble monomers such as acrylic or methacrylic acid, acrylamide, N-methylacryl-amide, methacrylamide, vinylpyrrolidone, vinyloxazolidone~
potassium vinylbenzenesulphonate, sodium 3-acryloyloxy-propane-l-sulphonate sodium 3-methacryloyloxypropane-1-methylsulphonate or sodium 2-acrylamido-2-methylpropane-sulphonate, as described, for example, in BE Pat. No.
869,816.
Preferably, the vinyl addition polymers should have a glass transtion temperature of less than 25C (the term "glass transition" referring to the characteristic change in the polymer properties ~rom those of a relatively hard, fragile, viteous material to those of a softer, more flex-ible substance similar to rubber when the temperature is increased beyond the glass transition temperature), the most preferable being the acrylic acid esters chosen from the class comprising polymethylacrylate, polyethylacryl-ate, polybutylacrylate, polyethoxyethylacrylate, polyhexyl acrylate, polyethylhexylacrylate, polybutylmethacrylate and polyethoxyethylmethacrylate.
In the hydrophilic colloid coating composition used for forming the auxiliary hydrophilic colloid layer ac-cording to the present invantion, said vinyl addition pol-ymer is present in a weight proportion of from 20 to 50 %, preferably 30 to 40 % with respect to the hydrophilic col-loid of the coating composition.
The highly deionized gelatin which can be used in the auxiliary hydrophilic colloid layer of the present inven-tion is characterized by a higher d~ionization with 2 ~ 2 ~ ~ ~ 7 respect to the commonly used photographic gelatins. Pref-erably, said highly deionized gelatin is almost completely deionized, which i5 defined as meaning that it presents less than 50 ppm lparts per million) of Ca~+ ions and is practically absent (less than 5 ppm) of other ions such as chlorides, sulphates, phosphates and nitrates, compared with commonly used gelatins having up to 5,000 ppm of Ca ions and a significant presence of other ions.
In the hydrophilic colloid aqueous compositions used for forming the auxiliary hydrophilic colloid layer, sai~
highly deionized gelatin is present in a weight proportion of at least 30%, preferably at least 50% with respect to the total hydrophilic colloid content of said coating com-position.
The hydrophilic colloid of the coating composition is preferbly the gelatin commonly used in photographic mate-rials, but other hydrophilic colloids can be used such as protein derivatives, cellulose derivatives, poly-saccharides such as starch, sugars such as dextran, syn-thetic polymers such as polyvinyl alcohol, polyacrylamide and polyvinylpyrrolidone, and other suitable hydrophilic colloids such as those described in US Pat. No. 3,297,446.
More preferably said highly deionized gelatin represents at least 90% or all the hydrophilic colloid of the coating composition.
Several hydrophilic colloid photographic compositions including the auxiliary hydrophilic colloid composition according to this invention can be coated simultaneously using processes known in the art, such as those described in US Pat. Nos. 2,761,791 and 4,001,024. Fig. 1 of said patents shows a four slide bead coater by use of which four separate layers of different composition may be si-multaneously applied onto a hydrophobic support. In this device, the first coating composition is continously pumped at a given rate into a cavity from which it is ex-truded through a narrow vertical slot out onto a downward-ly inclined surface over which it flows by gravity to form ~ ~3 ~
a layer of that composition. Likewise other coating compo-sitions may be con~inously pumped into chambers and may be extruded from narrow vertical slots onto slide surfaces down which they flow by gravity to form separate layers of different composition. The four slide surfaces are co-planar so that as the layers of different coating composi~
tions flow down their respective slide suraces they are brought together in overlapping relation and by the time the four layers reach the coating bead, they are combined in the desired laminated relationship. This distinct layer relationship is mantained throughout the bead so that as said hydrophobic support is moved across and in contact with the bead by means of a roll, it takes up on its sur-face the four layers of coating in the desired orienta-tion. There is no limit as to the number of separate lay-ers of coating compositions which may be laid down on said hydrophobic support with this type of apparatus as regard to its potentiality.
In the practice of the present invention, various types of photographic supports may be used to prepare the photographic elements. Suitable supports include polymeric films, such as cellulose nitrate films, cellulose acetate film, polystyrene film, polyvinyl acetal film, polycarbon-ate film, polyethylene terephthalate film and other poly~
ester films, paper, glass, cloth and the like.
The present invention is suitable for conventional silver halide photographic materials which include at least one silver halide emulsion layer and at least one auxiliary layer~ The invention is particularly suitable for conventional color photographic elements of negative or reversal type designed for camera exposure. Sai~ color photographic elements generally include silver halide emulsion layers naturally sensitive (or sensitized) to-wards blue, and associated with non-diffusing coupling agents ~orming yellow dyes (with aromatic diamine color development after exposure), silver halide emulsion layers sensitized towards green and associ~ted with non-diffusing ~2~7 coupling agen~s forming magenta (blue-red) dyes, and sil-ver halide emulsion layers sensitized towards red and as-sociated with non-diffusing coupling agents forming cyan (blue-green) dyes.
Although the invention is particularly suitable for conventional color photographic materials of negative and reversal type, it can be also useful for other color pho-tographic materials characterized by a different arrange-ment of sensitive layers, such as positive materials for cinema, printing, duplicating, etc. as well as for black and white photographic materials.
The photographic element can also contain chemical sensitizers, spectral sensitizers and desensitizers, opti-cal bleaches, antifoggants and stabilizing agents, cou-pling agents, screening and antifog dyes, hydrophilic col-loid and gelatin substituents, hardeners, spreading agents, plasticizers, antistatic agents and matting agents as known to the expert o the art, and treated in various treatments as described in Research Disclosure 17643, De-cember 1978, which is incorporated herein by reference.
The present invention will be better described and illustrated by the following example of its practice.
EXAMPLE
A multilayer color photographic element tFilm A) was prepared by coating the following layers over a subbed cellulose triacetate support in the indicated order.
First layer:
An auxiliary antihalation layer of 1.5 g/m2 of gela-tin A (described below), containing 0.25 g/m2 of dispersed black colloidal silver, 0.116 g/m2 of the HostapurTM SAS93 surface active agent (a C12 14 alkyl sodium sulphonate manufactured by Hoechst Co., West Germany) and 14.5 g/m2 of the dispersion 1 (described below).
Second layer:
An auxiliary layer of 0.64 g/m2 of gelatin A, 2 ~ 7 containing 1.6 g/m2 of the dispersion 2 (described below) and 0.025 g/m2 of the anionic surface active agent HostapurTM SAS93.
Third layer:
A layer of a red sensitive silver bromoiodide emul-sion in gelatin A, containing 3.5 g/m~ of gelatin A, the cyan couplers A and B (described below) dispersed into fine droplets of dibutylphthalate (oil) in a coupler amount of 0.8 g/m2 and an oil amount of 0.3 g/m2, and the anionic surface active agent NekalTM BX (a di-isopropyl-naphthalene sulphonate manufactured by BASF Co., West Ger-many).
A second multilayer color photographic element (Film B) was prepared in a like manner to film A~ but with the difference that the second layer coated over the subbed support had the following composition:
An auxiliary layer of 0.64 g/m2 of gelatin A~ 1.6 g/m2 of the dispersion 2 and 0.025 g/m2 of the anionic surface active agent AerosolTM OT75 (a sodium di-isooctyl-sulphosuccinate manufactured by Cyanamid Co., USA).
A third multilayer color photographic element (Film C~ was prepared in a like manner to film A, but with the difference that the second layer coated over the subbed support had the following composition:
An auxiliary layer of 0.64 g/m2 of gelatin A, 1.6 y/m2 of the dispersion 2, 0.016 g/m2 of the anionic sur face active agent HostapurTM SAS93 and 0.009 g/m2 of the betaine type surface active agent TegobetaineTM L7 manu-factured by Tego-Tenside Co~, West Germany (corresponding to the following formula:
R-CO-NH-(CH2)2-N -CH2-COO
R=C~ 7) A fourth multilayer color photographic element (Film 2~2~
6 CH - NH+
CH2~ ~c-stearyl 17. ~N - CH2 C11~23 ~ N - CH2 CH2-CH2 CHzCH20H
COO
18. CH2COO
C12H25S02N-C3H6N (CH3)3 19. lauryl-CON ~
- 8 - 2~
20. Stearyl-CONHCH2CH2OH
*
cocco represents a mixed blend of groups derived from the reaction of coconut oils with amines. The nature of the resultant composition is about 65% C11H23 (lauric acid), 5% C13H27 ~mirystic acid), 15% C15H31 palmitic ac-id) and 15% C8H19 (capric acid).
The above listed compounds can be found on the market under registered trade mark, such as for example Tego-betaineTM L7, VelvetexTM, DeriphatTM, MyranolTM 2MCA, AminoxidTM W35, AmmonixTM LO, SuperamideTM L9 and L9C.
In the hydrophilic colloid auxiliary layer according to this invention, said anionic surface active agent is preferably contained in a quantity ranging from 2 to 5 g per 100 g of the hydrophilic colloid of the layer and said betaine, N-oxide or amide surface active agent is prefera bly contained in a quantity ranging from 1 to 4.5 g per 100 g of the hydrophilic colloid of the layer.
The auxiliary hydrophilic colloid layer according to this invention is formed by coating a hydrophilic colloid aqueous composition comprising in addition to the combina-tion of the above-mentioned surface active agents at least one of dispersed droplets of a water-immiscible high-boil-ing organic solvent, a vinyl addition polymer latex or a highly deionized gelatin.
The organic solvents which can be used in the auxil-iary hydrophilic colloid layer of this invention are de-fined as non-polymeric organic compounds having a boiling point higher than 200C and a water solubility lower than 0.5 g per liter at 25C, and are ordinarily used in dis-persing hydrophobic coupling agents and photographic addi-tives as described, for example, in US Patents Nos.
~,322,027, 2,501,170, 2,801,171, 2,801,171, 2,272,191, 2,304,940 and 3,748,141. Even though a wide variety of organic solvents can be used, those which are most prefer-able for the purpose of the present invention (because of the fact that they show no negative e~fects on the 9 2 ~ 7 photosensitive material, are easily obtainable and easy to handle because of their excellent stability) have been found to be organic solvents chosen from the class con-sisting of dibuthylphthalate r tricresylphosphate, triphen-ylphosphate, di-2-ethylhexylphthalate, di-n-octylphthal-ate, tris-2-ethylhexylphosphate, cetyltributylcitra~e, di-n-hexyladipate, dimethylsebacate, triethyleneglycol-di-2-ethylhexoa~e, ethylphthalylethylglycolate, quinitol-bis(2-ethylhexoate) and 1,4-cyclohexyldimethylene-bis-(2-hexylhexoate).
For the purpose of the present invention, said organ-ic solvents are dispersed in the ~orm of fine droplets (of a size from o.l to 1 ~m, more preferably from 0.15 to 0O3 ~m), which are produced by known methods, the most common-ly used method consisting of first dissolving the organic solvent, either alone or in mixture (two or more), in a low temperature boiling solvent (such as methylacetate, ethylacetate, propylacetate, butylacetate, butylpropion-ate, cyclohexanol, dimethyleneglycolemonoacetate, nitro-methane, carbontetrachloride, chloroform, cyclohexane, tetrahydrofuran, methylalcohol, ethylalcohol, propylalco-hol, acetonitrile, dimethylformamide, dioxane, acetone, methylethylketone, methylisobutylketone, and the like, used either alone or in combination) r then mixing the so-lution with an aqueous solution of a hydrophilic colloid containing one or more anionic dispersing agents of the type normally used in photography (such as dioctylsodium-sulphosuccinate, sodiumlaurylsulphate, sodiumalkyl~
naphthalenesulphate and others described in Schwarz et al.
"Surface Active Agents and Detergents", Vol. I and II, Interscience Publ., in the US Pat. Nos. 2,992,108, 3,068,101, 3,201,152 and 3,165,409, in the French Pat.
Nos. 1,556,240 and 1,497,930 and in the British Pat. Nos.
580,504 and 985,483) and finally dispersing the composi-tion obtained in this manner using a suitable means such as a colloidal mill, a high speed rotating mixer or ultra-sonic dispenser. Additionally the organic solvent droplets 2~5~7 could include photographic additives of a hydrophilic na ture, and more pxeferably of a hydrophobic nature such ~s W absorbers, anti-staining agents~ compounds which re-lease developing inhibitors, optical bleaches, anti-oxid-ants, dyes, color couplers and the like.
In the hydrophilic colloid coating composition used for forming the auxiliary hydrophilic colloid layer ac-cording to this invention, said organic solvent is present in proportion by weight of from 10 to 30%, preferably 15 to 20% with respect to the hydrophilic colloid of the coating composition.
The vinyl addition polymers which can be used in the auxiliary hydrophilio colloid layer of this invention are obtained by polymerizing suitable monomers in an emulsion.
The preferred monomers axe ethylene-unsaturated monomers of the acrylic or methacrylic acid ester type, such as ethylacrylate, methylmethacrylate, methylacrylate, butyl-methacrylate, etc., alkyl-substituted acrylamides such as N,N-dibutylacrylamide, N-octylacrylamide, etc., vinyl ester such as vinylacetate, vinylbutyrate, etc., dienes such as butadiene, isoprene, dimethylbutadiene, chloro-prene, fluoroprene, etc., aromatic compounds such as styrene, vinyltoluene, etc., vinylhalides such as vinyl-chloride and vinylidenechloride, acrylonitrile, meth-acrylonitrile, vinylpyridine, vinylquinoline and other commonly known similar monomers.
These polymers are dispersed in the auxiliary layer of the present invention in the form of very small parti-~les of a size between 0.03 and 0.4 ~m, and more prefera-bly between 0.04 and 0.1 ~m. Said aqueous dispersions of polymers (latexes) are usually prepared by dispersing one or more of the aforesaid monomers in water in the presence of a dispersing or surface active agent of the type al-ready described heretofore for dispersing the oil, and carrying out polymerization by the use of a water-soluble initiator which is generally a per-compound (ammonium or potassium persulphate, hydrogen peroxide, sodium perborate, etc.), or a redox system such as persulphate-bisulphite, or a compound of the a,a'-azo-bisisobutyro-amidine hydrochloride type and a,a'-azo-bis-4-cyano-psntanoic acid (US Pat. Nos. 2,739,137 and 2,599,300 and UK Pat. No. 759,409), or a water-insoluble initiator (such as azo-bis-isobutyronitrile, benzoylperoxide, or cumene-hydroperoxide). In preparing the latex, it is often advan-tageous to use, together with the aforesaid monomers, smaller quantities of water-soluble monomers such as acrylic or methacrylic acid, acrylamide, N-methylacryl-amide, methacrylamide, vinylpyrrolidone, vinyloxazolidone~
potassium vinylbenzenesulphonate, sodium 3-acryloyloxy-propane-l-sulphonate sodium 3-methacryloyloxypropane-1-methylsulphonate or sodium 2-acrylamido-2-methylpropane-sulphonate, as described, for example, in BE Pat. No.
869,816.
Preferably, the vinyl addition polymers should have a glass transtion temperature of less than 25C (the term "glass transition" referring to the characteristic change in the polymer properties ~rom those of a relatively hard, fragile, viteous material to those of a softer, more flex-ible substance similar to rubber when the temperature is increased beyond the glass transition temperature), the most preferable being the acrylic acid esters chosen from the class comprising polymethylacrylate, polyethylacryl-ate, polybutylacrylate, polyethoxyethylacrylate, polyhexyl acrylate, polyethylhexylacrylate, polybutylmethacrylate and polyethoxyethylmethacrylate.
In the hydrophilic colloid coating composition used for forming the auxiliary hydrophilic colloid layer ac-cording to the present invantion, said vinyl addition pol-ymer is present in a weight proportion of from 20 to 50 %, preferably 30 to 40 % with respect to the hydrophilic col-loid of the coating composition.
The highly deionized gelatin which can be used in the auxiliary hydrophilic colloid layer of the present inven-tion is characterized by a higher d~ionization with 2 ~ 2 ~ ~ ~ 7 respect to the commonly used photographic gelatins. Pref-erably, said highly deionized gelatin is almost completely deionized, which i5 defined as meaning that it presents less than 50 ppm lparts per million) of Ca~+ ions and is practically absent (less than 5 ppm) of other ions such as chlorides, sulphates, phosphates and nitrates, compared with commonly used gelatins having up to 5,000 ppm of Ca ions and a significant presence of other ions.
In the hydrophilic colloid aqueous compositions used for forming the auxiliary hydrophilic colloid layer, sai~
highly deionized gelatin is present in a weight proportion of at least 30%, preferably at least 50% with respect to the total hydrophilic colloid content of said coating com-position.
The hydrophilic colloid of the coating composition is preferbly the gelatin commonly used in photographic mate-rials, but other hydrophilic colloids can be used such as protein derivatives, cellulose derivatives, poly-saccharides such as starch, sugars such as dextran, syn-thetic polymers such as polyvinyl alcohol, polyacrylamide and polyvinylpyrrolidone, and other suitable hydrophilic colloids such as those described in US Pat. No. 3,297,446.
More preferably said highly deionized gelatin represents at least 90% or all the hydrophilic colloid of the coating composition.
Several hydrophilic colloid photographic compositions including the auxiliary hydrophilic colloid composition according to this invention can be coated simultaneously using processes known in the art, such as those described in US Pat. Nos. 2,761,791 and 4,001,024. Fig. 1 of said patents shows a four slide bead coater by use of which four separate layers of different composition may be si-multaneously applied onto a hydrophobic support. In this device, the first coating composition is continously pumped at a given rate into a cavity from which it is ex-truded through a narrow vertical slot out onto a downward-ly inclined surface over which it flows by gravity to form ~ ~3 ~
a layer of that composition. Likewise other coating compo-sitions may be con~inously pumped into chambers and may be extruded from narrow vertical slots onto slide surfaces down which they flow by gravity to form separate layers of different composition. The four slide surfaces are co-planar so that as the layers of different coating composi~
tions flow down their respective slide suraces they are brought together in overlapping relation and by the time the four layers reach the coating bead, they are combined in the desired laminated relationship. This distinct layer relationship is mantained throughout the bead so that as said hydrophobic support is moved across and in contact with the bead by means of a roll, it takes up on its sur-face the four layers of coating in the desired orienta-tion. There is no limit as to the number of separate lay-ers of coating compositions which may be laid down on said hydrophobic support with this type of apparatus as regard to its potentiality.
In the practice of the present invention, various types of photographic supports may be used to prepare the photographic elements. Suitable supports include polymeric films, such as cellulose nitrate films, cellulose acetate film, polystyrene film, polyvinyl acetal film, polycarbon-ate film, polyethylene terephthalate film and other poly~
ester films, paper, glass, cloth and the like.
The present invention is suitable for conventional silver halide photographic materials which include at least one silver halide emulsion layer and at least one auxiliary layer~ The invention is particularly suitable for conventional color photographic elements of negative or reversal type designed for camera exposure. Sai~ color photographic elements generally include silver halide emulsion layers naturally sensitive (or sensitized) to-wards blue, and associated with non-diffusing coupling agents ~orming yellow dyes (with aromatic diamine color development after exposure), silver halide emulsion layers sensitized towards green and associ~ted with non-diffusing ~2~7 coupling agen~s forming magenta (blue-red) dyes, and sil-ver halide emulsion layers sensitized towards red and as-sociated with non-diffusing coupling agents forming cyan (blue-green) dyes.
Although the invention is particularly suitable for conventional color photographic materials of negative and reversal type, it can be also useful for other color pho-tographic materials characterized by a different arrange-ment of sensitive layers, such as positive materials for cinema, printing, duplicating, etc. as well as for black and white photographic materials.
The photographic element can also contain chemical sensitizers, spectral sensitizers and desensitizers, opti-cal bleaches, antifoggants and stabilizing agents, cou-pling agents, screening and antifog dyes, hydrophilic col-loid and gelatin substituents, hardeners, spreading agents, plasticizers, antistatic agents and matting agents as known to the expert o the art, and treated in various treatments as described in Research Disclosure 17643, De-cember 1978, which is incorporated herein by reference.
The present invention will be better described and illustrated by the following example of its practice.
EXAMPLE
A multilayer color photographic element tFilm A) was prepared by coating the following layers over a subbed cellulose triacetate support in the indicated order.
First layer:
An auxiliary antihalation layer of 1.5 g/m2 of gela-tin A (described below), containing 0.25 g/m2 of dispersed black colloidal silver, 0.116 g/m2 of the HostapurTM SAS93 surface active agent (a C12 14 alkyl sodium sulphonate manufactured by Hoechst Co., West Germany) and 14.5 g/m2 of the dispersion 1 (described below).
Second layer:
An auxiliary layer of 0.64 g/m2 of gelatin A, 2 ~ 7 containing 1.6 g/m2 of the dispersion 2 (described below) and 0.025 g/m2 of the anionic surface active agent HostapurTM SAS93.
Third layer:
A layer of a red sensitive silver bromoiodide emul-sion in gelatin A, containing 3.5 g/m~ of gelatin A, the cyan couplers A and B (described below) dispersed into fine droplets of dibutylphthalate (oil) in a coupler amount of 0.8 g/m2 and an oil amount of 0.3 g/m2, and the anionic surface active agent NekalTM BX (a di-isopropyl-naphthalene sulphonate manufactured by BASF Co., West Ger-many).
A second multilayer color photographic element (Film B) was prepared in a like manner to film A~ but with the difference that the second layer coated over the subbed support had the following composition:
An auxiliary layer of 0.64 g/m2 of gelatin A~ 1.6 g/m2 of the dispersion 2 and 0.025 g/m2 of the anionic surface active agent AerosolTM OT75 (a sodium di-isooctyl-sulphosuccinate manufactured by Cyanamid Co., USA).
A third multilayer color photographic element (Film C~ was prepared in a like manner to film A, but with the difference that the second layer coated over the subbed support had the following composition:
An auxiliary layer of 0.64 g/m2 of gelatin A, 1.6 y/m2 of the dispersion 2, 0.016 g/m2 of the anionic sur face active agent HostapurTM SAS93 and 0.009 g/m2 of the betaine type surface active agent TegobetaineTM L7 manu-factured by Tego-Tenside Co~, West Germany (corresponding to the following formula:
R-CO-NH-(CH2)2-N -CH2-COO
R=C~ 7) A fourth multilayer color photographic element (Film 2~2~
D) was prepared in a like manner to film A, but with the difference that the second layer coated over the subbed support had the following composition:
An auxiliary layer of 0.64 g/m2 of gelatin B, and O.02 g/m2 of the anionic surface active agent HostapurTM
SAS93.
A fifth multilayer color photographic element (Film E) was prepared in a like manner to film A, but with the difference that the second layer coated over the subbed support had the following composition:
An auxiliary layer of 0.64 g/m2 of gelatin B, 0.01 g/m2 of the anionic surface active agent HostapurTM SAS93 and 0.01 g/mZ of the betaine type surface active agent TegobetaineTM L7.
Gelatine A was a commonly used photographic gelatin having a viscosity in water (at 40C and 6.66% concentra-tion by weight) of 7.5 mPA/s and a concentration of Ca++
ions of 4,000 ppm.
Gelatine B was a highly deionized gelatin having a viscosity in water ~at 40C and 6.66% concentration by weight) of 6.5 mPA/s and a concentration of Ca++ ions of 40 ppm.
Preparation of dispersion 1:
5.26 g of the W absorber having the following formula:
4- ~ \X ~~ ~ -C4~9 C4Hg and 1.12 g of the W absorber having the following formu-la:
2 a ~ 7 3 3 Cl 6 ~ CN
N- CH=CH- CH=C~
were dissolved in 8.26 g of tricresylphosphate and 4.5 g ethylacetate at 40~C. The obtained solution was added un-der stirring to 45 cc of an aqueous solution of gelatin A
at 10% by weight containing 0.7 g of the anionic surfac-tant HostapurTM S~S93, the mixture then being dispersed by means of a rotatory homogenizer to give 100 g of disper-sion 1.
Preparation of dispersion 2:
2 g of the cyan dye having the following formula:
o ~ 5H
( 2)4 N
N
were dissolved in 5.94 g of N,N-dibutylacetanilide and 7.2 g ethylacetate at 40C. The obtained solution was added under stirring to 45 cc of an aqueous solution of gelatin A at 10% by weight containing 0.4 g of the anionic surfac-tant NekalTM BX, the mixture ~hen being dispersed by means of a rotatory homogenizer to give 100 g of dispersion 2.
An auxiliary layer of 0.64 g/m2 of gelatin B, and O.02 g/m2 of the anionic surface active agent HostapurTM
SAS93.
A fifth multilayer color photographic element (Film E) was prepared in a like manner to film A, but with the difference that the second layer coated over the subbed support had the following composition:
An auxiliary layer of 0.64 g/m2 of gelatin B, 0.01 g/m2 of the anionic surface active agent HostapurTM SAS93 and 0.01 g/mZ of the betaine type surface active agent TegobetaineTM L7.
Gelatine A was a commonly used photographic gelatin having a viscosity in water (at 40C and 6.66% concentra-tion by weight) of 7.5 mPA/s and a concentration of Ca++
ions of 4,000 ppm.
Gelatine B was a highly deionized gelatin having a viscosity in water ~at 40C and 6.66% concentration by weight) of 6.5 mPA/s and a concentration of Ca++ ions of 40 ppm.
Preparation of dispersion 1:
5.26 g of the W absorber having the following formula:
4- ~ \X ~~ ~ -C4~9 C4Hg and 1.12 g of the W absorber having the following formu-la:
2 a ~ 7 3 3 Cl 6 ~ CN
N- CH=CH- CH=C~
were dissolved in 8.26 g of tricresylphosphate and 4.5 g ethylacetate at 40~C. The obtained solution was added un-der stirring to 45 cc of an aqueous solution of gelatin A
at 10% by weight containing 0.7 g of the anionic surfac-tant HostapurTM S~S93, the mixture then being dispersed by means of a rotatory homogenizer to give 100 g of disper-sion 1.
Preparation of dispersion 2:
2 g of the cyan dye having the following formula:
o ~ 5H
( 2)4 N
N
were dissolved in 5.94 g of N,N-dibutylacetanilide and 7.2 g ethylacetate at 40C. The obtained solution was added under stirring to 45 cc of an aqueous solution of gelatin A at 10% by weight containing 0.4 g of the anionic surfac-tant NekalTM BX, the mixture ~hen being dispersed by means of a rotatory homogenizer to give 100 g of dispersion 2.
- 18 - 2~
Cyan coupler A:
OH~5H
~CONH(CH2)4-O-Cyan coupler B:
¦ CONH- ~
NCo CllH23 p 2 ~ ~
The dinamic and static surface tension of the coat-ing composition forming, after coating, the second layer of each film was measured according to Communication No.
1851~ form Kodak Research laboratories published under the title " A direct reading electrically operated balance for static and dynamic surface tension measurement".
The estimate of the degree of overall coating quality was graded into 3 steps as follows:
: 4 coating to be rejected 6 coating acceptable but with scraps 8 coating 100% acceptable : The following Table 1 reports the values of static and dynamic surface tension of the coating composition ~2~
expressed in N/m (Newton/ meter) and the estimate of the coating quali~ of each film.
Table 1 ._.__________________ _~____________________________ Film Surface Tension Coating Quality static dynamic ____________________________________________________ A (comparison) 34 34 4 B (comparison) 32 32.5 4 C (invention) 29 29.5 8 - D (comparison) 39 39 4 E (invention) 29 30 8 _______________________ ______________________ _____ As is evident from Ta~le 1, the combination of sur-face active agents according to this invention allows a reduction of surface tension of the coating composition and improves the coating quality of the film. The same results as those of films C and E were obtained using in-stead of TegobetaineTM L7 the following sur~ace active agents in combination with the anionic sur~ace active agent:
stearyl-N+(cH3)2(cH3)2so3- or cocco-CONH(CH2)3~(CH3)2 or O
~ CH2C~20H
lauryl-CON
Cyan coupler A:
OH~5H
~CONH(CH2)4-O-Cyan coupler B:
¦ CONH- ~
NCo CllH23 p 2 ~ ~
The dinamic and static surface tension of the coat-ing composition forming, after coating, the second layer of each film was measured according to Communication No.
1851~ form Kodak Research laboratories published under the title " A direct reading electrically operated balance for static and dynamic surface tension measurement".
The estimate of the degree of overall coating quality was graded into 3 steps as follows:
: 4 coating to be rejected 6 coating acceptable but with scraps 8 coating 100% acceptable : The following Table 1 reports the values of static and dynamic surface tension of the coating composition ~2~
expressed in N/m (Newton/ meter) and the estimate of the coating quali~ of each film.
Table 1 ._.__________________ _~____________________________ Film Surface Tension Coating Quality static dynamic ____________________________________________________ A (comparison) 34 34 4 B (comparison) 32 32.5 4 C (invention) 29 29.5 8 - D (comparison) 39 39 4 E (invention) 29 30 8 _______________________ ______________________ _____ As is evident from Ta~le 1, the combination of sur-face active agents according to this invention allows a reduction of surface tension of the coating composition and improves the coating quality of the film. The same results as those of films C and E were obtained using in-stead of TegobetaineTM L7 the following sur~ace active agents in combination with the anionic sur~ace active agent:
stearyl-N+(cH3)2(cH3)2so3- or cocco-CONH(CH2)3~(CH3)2 or O
~ CH2C~20H
lauryl-CON
Claims (12)
1. A multilayer photographic element comprising a support having coated thereon a plurality of hydrophilic colloid layers comprising at least one hydrophilic colloid silver halide emulsion layer and at least one hydrophilic colloid auxiliary layer, characterized in that at least one hydrophilic colloid auxiliary layer comprises at least three components, a) an anionic surface active agent, b) at least one of betaine, N-oxide or amide surface active agents, and c) at least one of dispersed droplets of a water-immiscible high-boiling organic solvent, a vinyl addition polymer latex and a highly deionized gelatin.
2. A multilayer photographic element according to claim 1, wherein said anionic surface active agent corre-sponds to the formula wherein R represents a hydrocarbon group, A is a chemical bond or a divalent organic residue, and X represents an anionic group.
3. A multilayer photographic element according to claim 1, wherein said betaine, N-oxide or amide surface active agent corresponds to the formula wherein R represents a hydrocarbon group, A is a chemical bond or a divalent organic residue, and Y represents a hydrophilic betaine, N-oxide or amide group.
4. A multilayer photographic element according to claim 1, wherein said anionic surface active agent is con-tained in said hydrophilic colloid auxiliary layer in a quantity ranging from 2 to 5 g per 100 g of hydrophilic colloid.
5. A multilayer photographic element according to claim 1, wherein said betaine, N-oxide or amide surface active agent is contained in said hydrophilic colloid aux-iliary layer in a quantity ranging from 1 to 4.5 g per 100 g of hydrophilic colloid.
6. A multilayer photographic element according to claim 1, wherein said organic solvent has a boiling point exceeding 200°C and a water solubility of less than 0.5 g per liter at 25°C.
7. A multilayer photographic element according to claim 1, wherein said organic solvent is chosen from the class consisting of dibuthylphthalate, tricresylphosphate, triphenylphosphate, di-2-ethylhexylphthalate, di-n-octyl-phthalate, tris-2-ethylexylphosphate, cetyltributyl-citrate, di-n-hexyladipate, dimethylsebacate, triethylene-glycol-di-2-ethylhexoate, ethylphthalylethylglycolate, quinitol-bis(2-ethylhexoate) and 1,4-cyclohexyldimethyl-ene-bis-(2-hexylhexoate).
8. A multilayer photographic element according to claim 1, wherein said dispersed droplets have an average size of between 0.1 and 1 µm.
9. A multilayer photographic element according to claim 1, wherein said vinyl addition polymer has a glass transition temperature of less than 25°C.
10. A multilayer photographic element according to claim 1, wherein said vinyl addition polymer is chosen from the class comprising polymethylacrylate, polyethyl-acrylate, polybutylacrylate, polyethoxyethylacrylate, polyhexyl acrylate, polyethylhexylacrylate, polybutyl-methacrylate and polyethoxyethylmethacrylate.
11. A multilayer photographic element according to claim 1, wherein said vinyl addition polymer latex com-prise particles having an average size of between 0.03 and 0.4 µm.
12. A multilayer photographic element according to claim 1, wherein said highly deionized gelatin has a Ca++
content lower than 50 ppm.
content lower than 50 ppm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT21815-A/89 | 1989-09-25 | ||
| IT8921815A IT1232339B (en) | 1989-09-25 | 1989-09-25 | MULTI-LAYER PHOTOGRAPHIC ELEMENTS HAVING IMPROVED OUTDOOR QUALITY. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2025957A1 true CA2025957A1 (en) | 1991-03-26 |
Family
ID=11187249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002025957A Abandoned CA2025957A1 (en) | 1989-09-25 | 1990-09-21 | Multilayer photographic elements having improved coating quality |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5037729A (en) |
| EP (1) | EP0421162B1 (en) |
| JP (1) | JPH03164734A (en) |
| CA (1) | CA2025957A1 (en) |
| DE (1) | DE69029636T2 (en) |
| IT (1) | IT1232339B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5310637A (en) * | 1992-04-14 | 1994-05-10 | Eastman Kodak Company | Minimization of ripple by controlling gelatin concentration |
| JPH0695281A (en) * | 1992-09-10 | 1994-04-08 | Konica Corp | Silver halide photographic sensitive material |
| EP2197996B1 (en) | 2007-10-11 | 2012-12-05 | Promega Corporation | Cleavable surfactants |
| EP2551024B1 (en) | 2011-07-29 | 2017-03-22 | 3M Innovative Properties Co. | Multilayer film having at least one thin layer and continuous process for forming such a film |
| EP2735595A1 (en) | 2012-11-23 | 2014-05-28 | 3M Innovative Properties Company | Multilayer pressure-sensitive adhesive assembly |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE487024A (en) * | 1948-01-24 | |||
| US3502473A (en) * | 1965-05-05 | 1970-03-24 | Eastman Kodak Co | Photographic elements containing a synthetic surface active material and inert particles |
| DE1547721A1 (en) * | 1965-08-16 | 1969-12-18 | Eastman Kodak Co | Use of sulfobetaines as coating aids in the production of photographic layers |
| US3547644A (en) * | 1966-01-03 | 1970-12-15 | Du Pont | Photographic drafting film with a polyethylene terephthalate base containing silica |
| BE712297A (en) * | 1967-03-17 | 1968-07-15 | ||
| US3573049A (en) * | 1967-10-02 | 1971-03-30 | Eastman Kodak Co | Photographic materials and processes for developing photographic compositions having a zwitterionic and anionic elements |
| US3607291A (en) * | 1968-04-08 | 1971-09-21 | Eastman Kodak Co | Dimethylamine oxides as coating aids for photographic elements |
| GB1274523A (en) * | 1968-08-22 | 1972-05-17 | Fuji Photo Film Co Ltd | Incorporating colour couplers into colour-photographic light-sensitive materials |
| US4146398A (en) * | 1974-09-05 | 1979-03-27 | Mitsubishi Paper Mills, Ltd. | Color photographic material comprising acid-treated gelatin |
| JPS5399928A (en) * | 1977-02-10 | 1978-08-31 | Konishiroku Photo Ind Co Ltd | Preparation of silver halide photosensitive material |
| JPS55149938A (en) * | 1979-05-11 | 1980-11-21 | Konishiroku Photo Ind Co Ltd | Photographic coating fluid |
| US4347308A (en) * | 1980-02-15 | 1982-08-31 | Fuji Photo Film Co., Ltd. | Photographic materials |
| IT1129033B (en) * | 1980-09-17 | 1986-06-04 | Minnesota Mining & Mfg | COLOR PHOTOGRAPHIC ELEMENTS WITH IMPROVING MECHANICAL PROPERTIES |
| DE3217020A1 (en) * | 1982-05-06 | 1983-11-10 | Agfa-Gevaert Ag, 5090 Leverkusen | PHOTOGRAPHIC RECORDING MATERIAL |
| JPS63253351A (en) * | 1987-04-09 | 1988-10-20 | Mitsubishi Paper Mills Ltd | Production of photographic material |
| US4891308A (en) * | 1987-11-30 | 1990-01-02 | E. I. Du Pont De Nemours And Company | Photographic film antistatic backing layer with auxiliary layer having improved properties |
-
1989
- 1989-09-25 IT IT8921815A patent/IT1232339B/en active
-
1990
- 1990-09-12 EP EP90117564A patent/EP0421162B1/en not_active Expired - Lifetime
- 1990-09-12 DE DE69029636T patent/DE69029636T2/en not_active Expired - Fee Related
- 1990-09-19 US US07/584,901 patent/US5037729A/en not_active Expired - Lifetime
- 1990-09-21 CA CA002025957A patent/CA2025957A1/en not_active Abandoned
- 1990-09-25 JP JP2255009A patent/JPH03164734A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0421162A3 (en) | 1992-03-11 |
| EP0421162B1 (en) | 1997-01-08 |
| IT8921815A0 (en) | 1989-09-25 |
| EP0421162A2 (en) | 1991-04-10 |
| US5037729A (en) | 1991-08-06 |
| DE69029636T2 (en) | 1997-05-07 |
| DE69029636D1 (en) | 1997-02-20 |
| IT1232339B (en) | 1992-01-28 |
| JPH03164734A (en) | 1991-07-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |