US3920456A - Photographic elements containing a matt layer - Google Patents
Photographic elements containing a matt layer Download PDFInfo
- Publication number
- US3920456A US3920456A US475197A US47519774A US3920456A US 3920456 A US3920456 A US 3920456A US 475197 A US475197 A US 475197A US 47519774 A US47519774 A US 47519774A US 3920456 A US3920456 A US 3920456A
- Authority
- US
- United States
- Prior art keywords
- matt
- layer
- photographic material
- hydrophilic
- photographic
- 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.)
- Expired - Lifetime
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000006224 matting agent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- -1 silver halide Chemical class 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 abstract description 11
- 229920000159 gelatin Polymers 0.000 abstract description 8
- 235000019322 gelatine Nutrition 0.000 abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 7
- 239000011230 binding agent Substances 0.000 abstract description 6
- 239000001384 succinic acid Substances 0.000 abstract description 4
- 108010010803 Gelatin Proteins 0.000 abstract 1
- 239000008273 gelatin Substances 0.000 abstract 1
- 235000011852 gelatine desserts Nutrition 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 36
- 239000000126 substance Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000001828 Gelatine Substances 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000004808 2-ethylhexylester Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000004442 acylamino group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 235000011044 succinic acid Nutrition 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 1
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
-
- 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
- Y10S430/151—Matting or other surface reflectivity altering material
-
- 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
- Y10S430/155—Nonresinous additive to promote interlayer adhesion in element
Definitions
- This invention relates to a photographic material with a matt layer which contains inorganic matting agents which are introduced in the form of fine particles into hydrophilic binder layers with the aid of hydrophilic oil forming agents.
- matting agents are incorporated mainly in the uppermost layer of photographic materials.
- Inorganic pigments such as titanium dioxide and silica for example, have previously been added as matting agents to the photographic layers. These substances, however, are not entirely satisfactory for various reasons. They have a strong reflection, with the result that only medium grey tones are obtained instead of deep blacks.
- Another disadvantage is that the matting agents have a strong tendency to sediment in the casting solutions so that uniform matting is difficult to achieve.
- This invention relates to a photographic material with at least one matt layer which contains an inorganic matting agent in a hydrophilic binder, characterised in that the matt layer contains finely divided particles consisting of anhydrous silica enveloped in a hydrophilic oil-forming agent.
- the matting agent used according to this invention is preferably anhydrous silica (SiO of which various types are obtainable in powder form. It is immaterial whether the silica used is slightly acid or neutral.
- the average particle diameter should be between 1 and 5 pm.
- Oil forming substances are organic dispersing agents which have a relatively low melting point and which are capable of enveloping the dispersed substances, in this case silica particles, in the form of droplets.
- the oil forming substances are hydrophilic and contain at least one carboxyl group.
- Particularly suitable oil forming substances for embedding the silica particles are succinic acids with long chain substituents and derivatives thereof which still contain one free carboxyl group for each succinic acid group which carries a long chain substituent.
- the compounds may be represented by the following general formula in which R denotes a straight chain or branched chain alkyl or alkenyl group containing 12 to 20 carbon atoms,
- R hydrogen, straight chain or branched chain alkyl with preferably up to 10 C atoms which may be substituted, e.g. with hydroxyl, keto(oxo), alkoxy, cycloalkyl, amino, acylamino, cyano or heterocyclic groups; cycloalkyl such as cyclohexyl or decalyl; aralkyl such as benzyl; aryl such as phenyl; or a S-membered or 6-membered heterocyclic group, e.g. a pyridine, pyrimidine, triazole or 1,1-dioxothiolan group;
- R a group as defined for R a hydroxyl group or an amino group e.g.
- the acyl is derived from a carboxylic acid and preferably from a succinic acid having at one of its 01- and [3- carbon atoms a long chain aliphatic substituent.
- R and R may together denote the ring members required for completing a S-membered or 6-membered ring which contains nitrogen such as piperazine or triazole.
- the group iC H which frequently occurs is the l,l,3,5-tetramethylocten-(2)-yl group.
- the other long chain groups are not clearly defined as regards the degree of branching and, in the case of unsaturated groups, with regard to the position of the double bond.
- the compounds having the long chain groups are presumably mixtures of isomers.
- the compounds are prepared from succinic acid an hydrides having the long chain substituents by reacting them in known manner with alcohols, amines, hydrazine or hydroxylami'ne.
- the succinic acid anhydride ring is thereby opened to form a carboxyl group and an ester, amide, hydrazide or hydroxamic acid group.
- Products in which the long chain group is in the a-position to the carboxyl this and those in which it is in the B-position to the carboxyl group are formed simultaneously but both isomers and the mixture thereof are equally suitable for the invention and for thesake of simplicity only one of these forms hasbeen shown in the above formulae and in the examples, butthe invention is in no way restricted to this one form.
- hydrophilic oil-forming substances according to the invention contain several succinic acid groups with long chain substituents, these are preferably identical groups although they may be different from each other.
- Compounds of ths kind be obtained from dihydroxy or diamino compounds by reacting them simultaneously or successively with various succinic acid anhydrides substituted with lon chain substituents. This reaction generally yields hydrophilic oil forming substances according to the invention which contain various succinic acid groups in statistical distribution.
- a dispersion of powdered anhydrous silica in the hydrophilic oil forming substances according to the invention is generally first prepared, optionally using at the same time a low boiling or water-soluble organic silvent which may be readily removed.
- This dispersion preferably contains 2 to 10 parts by weight of anhydrous silica.
- the dispersion is then added to the hydrophilic binder to prepare the casting solution .for the matt layer, eg to a 10% gelatine solution.
- the finished matt layer may contain between 5 and 30% by weight of matting agent.
- the uppermost emulsion layer is preferably prepared as the matt layer.
- This may be a light-sensitive layer or a protective layer.
- the matt layer contains a light-sensitive compound such as silver halide, optionally in combination with other conventional additives such as spectral sensitizers, dyes which can be bleached or color couplers, in addition to the matting agent and the hydrophilic oil forming substance.
- the matt layer of the invention is suitable for colorphotographic materials as well as for blackand-white photographic materials even if the matt layer according to the invention is a separate layer situated above the (uppermost) light sensitive layer, it may contain other compounds in addition to the emulsified matting agent, for example white couplers, white toner, UV absorbent substances, hardeners and thelike.
- the matt layer according to the invention may also be arranged on the back of the photographic material, especially if the support is polyester or polycarbonate.
- the matt layer serves not so much toimprove the optical impression but rather to perform a mechanical function in that it provides a hydrophilic structured surface on the back of the support, which has the effect of reducing the tendency of the photographic material to become electrostatically charged, especially if the material is rolled up.
- layers applied to the back in this way substantially improve the flat-lie of the photographic material.
- Photographic materials provided with matt layers according to the invention have the following advantages over comparable materials in which the matt layers also contain silica but no hydrophilic oil forming substance.
- the dull matt effect which is obtained with silica used without oil-forming substance is modified by the addition of oil forming substance to a silky matt finish.
- the image densities are hardly affected by the matting according to the invention.
- known matt layers containing pure silica reduce the black areas to medium grey due to the high degree of reflection.
- the ability to retouch the picture is fully preserved.
- the brittleness is greatly reduced.
- the tendency to roll up is also distinctly reduced, i.e. the flat lie is considerably improved. Further improvements can be achieved especially in this last respect if gelatine used as binder is partly replaced by other natural or synthetic hydrolulose sulfate as described 2,123,456.
- EXAMPLE 1 3 g of sulfosuccinic acid-bis-(2-ethylhexylester) and 100 g of compound 1 are dissolved in 160 ml of diethyl carbonate. 30 g of Syloid 72 (anhydrous silica product of Grace GmbH, Bad Homburg; average particle size 4 pm) are stirred in, using a high speed stirrer. The viscous mixture is emulsified in 100 ml of a aqueous gelatine solution at 60C. After the pH has been ad.- justed to 6.8-7.0 and hardener and 500 ml of water have been added, the solution is cast to form a protective layer on a color photographic material which is viewed by reflected light.
- Syloid 72 anhydrous silica product of Grace GmbH, Bad Homburg; average particle size 4 pm
- EXAMPLE 2 3 g of sulfosuccinic acid-bis-(2-ethylhexylester) and 100 g of compound 10 are dissolved in 100ml of ethanol and 300 ml of diethylcarbonate, and 30 g of Syloid 75 (anhydrous silica, average particle size 3 pm) are then stirred in, using a high speed stirrer. The viscous mixture is emulsified in 1000 ml of a 10% aqueous gelatine solution at 60C.
- EXAMPLE 4 g of compound 19 and 3 g of sulfosuccinic acidbis(2-ethylhexylester) are dissolved in ml of ethanol, and 30 g of Syloid 72 are stirred in, using a high speed stirrer.
- the mixture is emulsified in 1000 ml of a 10% aqueous gelatine solution at 60C, and 400 ml of a 5% aqueous solution of carboxymethylcellulose are then stirred in.
- EXAMPLE 5 Test for brittleness and flat lie The brittleness and flat lie of the matt layers according to the invention are compared with those of a known matt layer prepared from pure silica and those of a pure protective gelatine layer.
- the casting solution for the matt layer prepared according to Example 1 is cast on polyethylene backed paper in a thickness corresponding to 25 g (i l g) per m
- the material prepared in this way is cut up into pieces 30 cm in length and 8 cm in width. The strips are passed over a drying drum heated to 90C by pressing them on with a cloth, the back of the material in contact with the surface of the drum. The time of contact with the drying drum is 6 minutes.
- the strips are pulled over movable rollers of various diameters. Each test sample is used only once.
- the diameter of the roller (in mm) at which cracks occur in the photographic material is taken as the measure of brittleness of the material and is given in column 2 in the table below. Since the time which elapses between the end of drying and end of the brittleness test is at the most 5 seconds, the material does not have time to adjust to the atmospheric moisture and consequently reproducible results are obtained.
- a photographic material comprising a light-sensitive composition layer on a photographic support and having at least one matt layer which contains in a hydrophilic binder finely distributed particles consisting of particles of anhydrous silica enveloped in a hydrophilic oil forming agent of the formula:
- I R represents alkyl or alkenyl containing 12 to 20 carbon atoms
- R represents hydrogen, alkyl, cycloalkyl, aralkyl, aryl or a S-membered or 6-membered heterocyclic group
- R represents a group as defined under R or a hydroxyl group, an amino group or an acylamino group
- R and R may together represent the ring members required for completing a S-membered or 6-membered ring which contains at least one nitrogen atom.
- a photographic material as claimed in claim 1, wherein the matting agent used is anhydrous silica with an average particle size of between 1 and 5 pm.
- a photographic material as claimed in claim 1 wherein the light-sensitive composition is a silver halide emulsion.
Abstract
A photographic material contains a matt layer, in which in a hydrophilic binder, f.e. gelatin there are distributed droplets of a hydrophilic oil-former envelopping particles of anhydrous silica. The hydrophilic oil-former is a derivative of a longchain substituted succinic acid having at least one free carboxyl group.
Description
United States Patent [191 Nittel et al. I
[451 Nov. 18,1975
[ PHOTOGRAPHIC ELEMENTS CONTAINING A MATT LAYER [75] Inventors: Fritz Nittel, Cologne; Karl Lohmer;
Helmut Kolberg, both of Leverkusen, all of Germany [73] Assignee: AGFA-Gevaert Aktiengesellschaft, Leverkusen-Bayerwerk, Germany;
[22] Filed: May 31, 1974 [21] Appl. No.: 475,197
[30] Foreign Application Priority Data June 6, 1973 Germany 2328781 [52] US. Cl 96/87 R; 96/67; 96/68;
96/84 R; 96/87 A [51] Int. Cl.'... G03C l/78; 603C l/96; GO3C l/76 [58] Field of Search 96/67, 84 R, 87 R, 87 A [56] References Cited UNITED STATES PATENTS 3,169,867 2/1965 Brandt 96/87 R 3,370,951 2/1968 I-lasenauer et al. 96/87 R 3,666,532 5/1972 Reedy et al. 96/87 R Primary ExaminerCharles L. Bowers, Jr. Assistant ExaminerJ. P. Brammer Attorney, Agent, or Firm-Connolly and Hutz ABSTRACT 3 .Claims, No Drawings PHOTOGRAPHIC ELEMENTS CONTAINING A MATT LAYER This invention relates to a photographic material with a matt layer which contains inorganic matting agents which are introduced in the form of fine particles into hydrophilic binder layers with the aid of hydrophilic oil forming agents.
It is known to improve the optical impression of photographic materials by means of matt layers which reduce the surface glare. For this purpose matting agents are incorporated mainly in the uppermost layer of photographic materials. Inorganic pigments such as titanium dioxide and silica for example, have previously been added as matting agents to the photographic layers. These substances, however, are not entirely satisfactory for various reasons. They have a strong reflection, with the result that only medium grey tones are obtained instead of deep blacks. Another disadvantage is that the matting agents have a strong tendency to sediment in the casting solutions so that uniform matting is difficult to achieve.
Furthermore, it is found that if photographic materials are matted with organic pigments by conventional methods, they have an increased tendency to roll up and to crack.
It has now been found that matt layers which have satisfactory properties and do not impair the black densities or the flat lie or other mechanical properties of the photographic materials are obtained if silica is added as matting agent to the matt layers with the aid of hydrophilic organic oil forming substances.
This invention relates to a photographic material with at least one matt layer which contains an inorganic matting agent in a hydrophilic binder, characterised in that the matt layer contains finely divided particles consisting of anhydrous silica enveloped in a hydrophilic oil-forming agent.
The matting agent used according to this invention is preferably anhydrous silica (SiO of which various types are obtainable in powder form. It is immaterial whether the silica used is slightly acid or neutral. The average particle diameter should be between 1 and 5 pm.
Oil forming substances are organic dispersing agents which have a relatively low melting point and which are capable of enveloping the dispersed substances, in this case silica particles, in the form of droplets. According to this invention, the oil forming substances are hydrophilic and contain at least one carboxyl group. Particularly suitable oil forming substances for embedding the silica particles are succinic acids with long chain substituents and derivatives thereof which still contain one free carboxyl group for each succinic acid group which carries a long chain substituent.
The compounds may be represented by the following general formula in which R denotes a straight chain or branched chain alkyl or alkenyl group containing 12 to 20 carbon atoms,
n 1 or 2,
R hydrogen, straight chain or branched chain alkyl with preferably up to 10 C atoms which may be substituted, e.g. with hydroxyl, keto(oxo), alkoxy, cycloalkyl, amino, acylamino, cyano or heterocyclic groups; cycloalkyl such as cyclohexyl or decalyl; aralkyl such as benzyl; aryl such as phenyl; or a S-membered or 6-membered heterocyclic group, e.g. a pyridine, pyrimidine, triazole or 1,1-dioxothiolan group;
R a group as defined for R a hydroxyl group or an amino group, e.g.
or an acylamino group;
In the acylamino groups contained in R represented by R the acyl is derived from a carboxylic acid and preferably from a succinic acid having at one of its 01- and [3- carbon atoms a long chain aliphatic substituent.
R and R may together denote the ring members required for completing a S-membered or 6-membered ring which contains nitrogen such as piperazine or triazole.
Compounds of the above formula also include those which contain two or three groups of succinic acid with long chain substituents. In these compounds, R or R denotes a group which contains at least one other group of the following formula:
l ca -coo 36) C B -CH COOH cm-coo c1 Other examples of hydrophilic oil forming substances of the above formula have been described in German OS Nos. 1,772,192; 2,042,659 and 2,049,689.
The group iC H which frequently occurs is the l,l,3,5-tetramethylocten-(2)-yl group. The other long chain groups are not clearly defined as regards the degree of branching and, in the case of unsaturated groups, with regard to the position of the double bond. The compounds having the long chain groups are presumably mixtures of isomers.
The compounds are prepared from succinic acid an hydrides having the long chain substituents by reacting them in known manner with alcohols, amines, hydrazine or hydroxylami'ne. The succinic acid anhydride ring is thereby opened to form a carboxyl group and an ester, amide, hydrazide or hydroxamic acid group. Products in which the long chain group is in the a-position to the carboxyl this and those in which it is in the B-position to the carboxyl group are formed simultaneously but both isomers and the mixture thereof are equally suitable for the invention and for thesake of simplicity only one of these forms hasbeen shown in the above formulae and in the examples, butthe invention is in no way restricted to this one form. In cases where the hydrophilic oil-forming substances according to the invention contain several succinic acid groups with long chain substituents, these are preferably identical groups although they may be different from each other. Compounds of ths kind be obtained from dihydroxy or diamino compounds by reacting them simultaneously or successively with various succinic acid anhydrides substituted with lon chain substituents. This reaction generally yields hydrophilic oil forming substances according to the invention which contain various succinic acid groups in statistical distribution. i
To prepare the matt layers according to the invention, a dispersion of powdered anhydrous silica in the hydrophilic oil forming substances according to the invention is generally first prepared, optionally using at the same time a low boiling or water-soluble organic silvent which may be readily removed. This dispersion preferably contains 2 to 10 parts by weight of anhydrous silica. The dispersion is then added to the hydrophilic binder to prepare the casting solution .for the matt layer, eg to a 10% gelatine solution. The finished matt layer may contain between 5 and 30% by weight of matting agent.
In the photographic materials according to this invention, the uppermost emulsion layer is preferably prepared as the matt layer. This may be a light-sensitive layer or a protective layer. In the former case, the matt layer contains a light-sensitive compound such as silver halide, optionally in combination with other conventional additives such as spectral sensitizers, dyes which can be bleached or color couplers, in addition to the matting agent and the hydrophilic oil forming substance. Thus the matt layer of the invention is suitable for colorphotographic materials as well as for blackand-white photographic materials even if the matt layer according to the invention is a separate layer situated above the (uppermost) light sensitive layer, it may contain other compounds in addition to the emulsified matting agent, for example white couplers, white toner, UV absorbent substances, hardeners and thelike.
The matt layer according to the invention may also be arranged on the back of the photographic material, especially if the support is polyester or polycarbonate. In that case, the matt layer serves not so much toimprove the optical impression but rather to perform a mechanical function in that it provides a hydrophilic structured surface on the back of the support, which has the effect of reducing the tendency of the photographic material to become electrostatically charged, especially if the material is rolled up. In addition, layers applied to the back in this way substantially improve the flat-lie of the photographic material.
Photographic materials provided with matt layers according to the invention have the following advantages over comparable materials in which the matt layers also contain silica but no hydrophilic oil forming substance. The dull matt effect which is obtained with silica used without oil-forming substance is modified by the addition of oil forming substance to a silky matt finish. The image densities are hardly affected by the matting according to the invention Whereas known matt layers containing pure silica reduce the black areas to medium grey due to the high degree of reflection. The ability to retouch the picture is fully preserved. The brittleness is greatly reduced. The tendency to roll up is also distinctly reduced, i.e. the flat lie is considerably improved. Further improvements can be achieved especially in this last respect if gelatine used as binder is partly replaced by other natural or synthetic hydrolulose sulfate as described 2,123,456.
EXAMPLE 1 3 g of sulfosuccinic acid-bis-(2-ethylhexylester) and 100 g of compound 1 are dissolved in 160 ml of diethyl carbonate. 30 g of Syloid 72 (anhydrous silica product of Grace GmbH, Bad Homburg; average particle size 4 pm) are stirred in, using a high speed stirrer. The viscous mixture is emulsified in 100 ml of a aqueous gelatine solution at 60C. After the pH has been ad.- justed to 6.8-7.0 and hardener and 500 ml of water have been added, the solution is cast to form a protective layer on a color photographic material which is viewed by reflected light.
EXAMPLE 2 3 g of sulfosuccinic acid-bis-(2-ethylhexylester) and 100 g of compound 10 are dissolved in 100ml of ethanol and 300 ml of diethylcarbonate, and 30 g of Syloid 75 (anhydrous silica, average particle size 3 pm) are then stirred in, using a high speed stirrer. The viscous mixture is emulsified in 1000 ml of a 10% aqueous gelatine solution at 60C.
EXAMPLE 3 UV Matt layer 3 g of sulfosuccinic acid-bis-(2-ethylhexylester), 100 g of compound 5 and 30 g of a UV absorbent of the following formula (tert.)
C H (sec) 8 are dissolved in 150 ml of diethylcarbonate and 30 g of Syloid are stirred in, using a high speed stirrer. The viscous mixture is emulsified in 1000 ml ofa 10% aqueous gelatine solution at 60C and the solution is cast as protective layer over a color photographic material which is to be viewed by reflected light.
EXAMPLE 4 g of compound 19 and 3 g of sulfosuccinic acidbis(2-ethylhexylester) are dissolved in ml of ethanol, and 30 g of Syloid 72 are stirred in, using a high speed stirrer. The mixture is emulsified in 1000 ml of a 10% aqueous gelatine solution at 60C, and 400 ml of a 5% aqueous solution of carboxymethylcellulose are then stirred in.
EXAMPLE 5 Test for brittleness and flat lie The brittleness and flat lie of the matt layers according to the invention are compared with those of a known matt layer prepared from pure silica and those of a pure protective gelatine layer. For this purpose, the casting solution for the matt layer prepared according to Example 1 is cast on polyethylene backed paper in a thickness corresponding to 25 g (i l g) per m To test the brittleness, the material prepared in this way is cut up into pieces 30 cm in length and 8 cm in width. The strips are passed over a drying drum heated to 90C by pressing them on with a cloth, the back of the material in contact with the surface of the drum. The time of contact with the drying drum is 6 minutes. Immediately thereafter, the strips are pulled over movable rollers of various diameters. Each test sample is used only once. The diameter of the roller (in mm) at which cracks occur in the photographic material is taken as the measure of brittleness of the material and is given in column 2 in the table below. Since the time which elapses between the end of drying and end of the brittleness test is at the most 5 seconds, the material does not have time to adjust to the atmospheric moisture and consequently reproducible results are obtained.
To determine the flat lie, circular samples with a diameter of 7.5 cm are punched out of the cast materials and stored for 3 days at 20C and 20% relative humidity. The chord of the arc is measured and entered in columns 3 and 4 in the following table as a measure of the flatness (in mm). In column 4 are entered the values which are obtained if the material has been color processed before the three days storage. All the samples were curved with the emulsion layer facing inwards.
For further tests, a color photographic material for viewing by reflected light was prepared on polyethylene backed paper and the uppermost protective layer was replaced by a matt layer (thickness 3 gm) according to this invention. The results are shown in Table 2.
1. A photographic material comprising a light-sensitive composition layer on a photographic support and having at least one matt layer which contains in a hydrophilic binder finely distributed particles consisting of particles of anhydrous silica enveloped in a hydrophilic oil forming agent of the formula:
wherein I R represents alkyl or alkenyl containing 12 to 20 carbon atoms,
R represents hydrogen, alkyl, cycloalkyl, aralkyl, aryl or a S-membered or 6-membered heterocyclic group;
R represents a group as defined under R or a hydroxyl group, an amino group or an acylamino group;
R and R may together represent the ring members required for completing a S-membered or 6-membered ring which contains at least one nitrogen atom.
2. A photographic material as claimed in claim 1, wherein the matting agent used is anhydrous silica with an average particle size of between 1 and 5 pm.
3. A photographic material as claimed in claim 1 wherein the light-sensitive composition is a silver halide emulsion.
Claims (3)
1. A PHOTOGRAPHIC MATERIAL COMPRISING A LIGHT-SENSITIVE COMPOSITION LAYER ON A PHOTOGRAPHIC SUPPORT AND HAVING AT LEAST ONE MATT LAYER WHICH CONAINS IN A HYDROPHILIC BINDER FINELY DISTRIBUTED PARTICLES CONSISTING OF PATICLES OF ANHYDROUS SILICA ENVELOPED IN A HYDROPHILIC OIL FORMING AGENT OF THE FORMULA:
2. A photographic material as claimed in claim 1, wherein the matting agent used is anhydrous silica with an average particle size of between 1 and 5 Mu m.
3. A photographic material as claimed in claim 1 wherein the light-sensitive composition is a silver halide emulsion.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2328781A DE2328781A1 (en) | 1973-06-06 | 1973-06-06 | PHOTOGRAPHIC MATERIAL WITH A MATT LAYER |
Publications (1)
Publication Number | Publication Date |
---|---|
US3920456A true US3920456A (en) | 1975-11-18 |
Family
ID=5883194
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US475197A Expired - Lifetime US3920456A (en) | 1973-06-06 | 1974-05-31 | Photographic elements containing a matt layer |
Country Status (5)
Country | Link |
---|---|
US (1) | US3920456A (en) |
BE (1) | BE815384A (en) |
DE (1) | DE2328781A1 (en) |
FR (1) | FR2232773B1 (en) |
GB (1) | GB1438259A (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4029504A (en) * | 1976-04-14 | 1977-06-14 | Eastman Kodak Company | Photographic image transfer elements containing neutralizing layers comprising particulate materials |
DE2900542A1 (en) * | 1978-01-09 | 1979-07-19 | Konishiroku Photo Ind | LIGHT SENSITIVE PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL |
US4235959A (en) * | 1978-02-03 | 1980-11-25 | Huyghebaert Paul Administrator | Photographic matt layers or surfaces |
US4376159A (en) * | 1977-05-09 | 1983-03-08 | Keuffel & Esser Company | Method of preparing matte finish color-proofing surprints |
US4464464A (en) * | 1981-07-30 | 1984-08-07 | Agfa-Gevaert Aktiengesellschaft | Color photographic recording material |
JPS63151343A (en) * | 1986-11-22 | 1988-06-23 | バイエル・アクチエンゲゼルシヤフト | Bifunctional emulsifier using perhydrobisphenol and carboxylic acid anhydride as base |
US4777113A (en) * | 1984-12-12 | 1988-10-11 | Fuji Photo Film Co., Ltd. | Silver halide photographic material containing a silica containing overlayer and specific hydrazine derivatives |
US4912023A (en) * | 1985-09-04 | 1990-03-27 | Fuji Photo Film Co., Ltd. | Photographic light-sensitive materials having an oil component and a block copolymer |
US5208139A (en) * | 1990-12-11 | 1993-05-04 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials |
US5223372A (en) * | 1988-09-27 | 1993-06-29 | Somar Corporation | Chemical mat film and a photosensitive film comprising an o-naphthoquinine diazide compound and a binder coated over the chemical mat film |
US5288598A (en) * | 1992-10-30 | 1994-02-22 | Eastman Kodak Company | Photographic light-sensitive elements |
US5378577A (en) * | 1992-10-30 | 1995-01-03 | Eastman Kodak Company | Photographic light-sensitive elements |
US5498510A (en) * | 1991-10-17 | 1996-03-12 | Fuji Photo Film Co., Ltd. | Method for simultaneously coating at least two layers to make a photographic light-sensitive element |
US5554496A (en) * | 1994-03-02 | 1996-09-10 | Fuji Photo Film Co., Ltd. | Silver halide photographic material comprising emulsion layer and backing layer provided on support |
US6136520A (en) * | 1997-12-18 | 2000-10-24 | Konica Corporation | Silver halide photographic element and a processing method of the same |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5399928A (en) * | 1977-02-10 | 1978-08-31 | Konishiroku Photo Ind Co Ltd | Preparation of silver halide photosensitive material |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3169867A (en) * | 1962-07-07 | 1965-02-16 | Kalle Ag | Manufacture of photo-sensitive films |
US3370951A (en) * | 1962-08-22 | 1968-02-27 | Eastman Kodak Co | Matte-surfaced polyester sheeting |
US3666532A (en) * | 1968-01-22 | 1972-05-30 | Eastman Kodak Co | Dimensionally stable matte-surfaced polyester drafting film |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3502473A (en) * | 1965-05-05 | 1970-03-24 | Eastman Kodak Co | Photographic elements containing a synthetic surface active material and inert particles |
-
1973
- 1973-06-06 DE DE2328781A patent/DE2328781A1/en active Pending
-
1974
- 1974-05-22 BE BE1005979A patent/BE815384A/en unknown
- 1974-05-30 GB GB2394074A patent/GB1438259A/en not_active Expired
- 1974-05-31 US US475197A patent/US3920456A/en not_active Expired - Lifetime
- 1974-06-06 FR FR7419614A patent/FR2232773B1/fr not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3169867A (en) * | 1962-07-07 | 1965-02-16 | Kalle Ag | Manufacture of photo-sensitive films |
US3370951A (en) * | 1962-08-22 | 1968-02-27 | Eastman Kodak Co | Matte-surfaced polyester sheeting |
US3666532A (en) * | 1968-01-22 | 1972-05-30 | Eastman Kodak Co | Dimensionally stable matte-surfaced polyester drafting film |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4029504A (en) * | 1976-04-14 | 1977-06-14 | Eastman Kodak Company | Photographic image transfer elements containing neutralizing layers comprising particulate materials |
US4376159A (en) * | 1977-05-09 | 1983-03-08 | Keuffel & Esser Company | Method of preparing matte finish color-proofing surprints |
DE2900542A1 (en) * | 1978-01-09 | 1979-07-19 | Konishiroku Photo Ind | LIGHT SENSITIVE PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL |
US4399213A (en) * | 1978-01-09 | 1983-08-16 | Konishiroku Photo Industry Co., Ltd. | Silver halide photosensitive photographic material |
US4235959A (en) * | 1978-02-03 | 1980-11-25 | Huyghebaert Paul Administrator | Photographic matt layers or surfaces |
US4464464A (en) * | 1981-07-30 | 1984-08-07 | Agfa-Gevaert Aktiengesellschaft | Color photographic recording material |
US4777113A (en) * | 1984-12-12 | 1988-10-11 | Fuji Photo Film Co., Ltd. | Silver halide photographic material containing a silica containing overlayer and specific hydrazine derivatives |
US4912023A (en) * | 1985-09-04 | 1990-03-27 | Fuji Photo Film Co., Ltd. | Photographic light-sensitive materials having an oil component and a block copolymer |
JPS63151343A (en) * | 1986-11-22 | 1988-06-23 | バイエル・アクチエンゲゼルシヤフト | Bifunctional emulsifier using perhydrobisphenol and carboxylic acid anhydride as base |
JP2701033B2 (en) | 1986-11-22 | 1998-01-21 | バイエル・アクチエンゲゼルシヤフト | Bifunctional emulsifiers based on perhydrobisphenol and carboxylic anhydride |
US5223372A (en) * | 1988-09-27 | 1993-06-29 | Somar Corporation | Chemical mat film and a photosensitive film comprising an o-naphthoquinine diazide compound and a binder coated over the chemical mat film |
US5208139A (en) * | 1990-12-11 | 1993-05-04 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials |
US5498510A (en) * | 1991-10-17 | 1996-03-12 | Fuji Photo Film Co., Ltd. | Method for simultaneously coating at least two layers to make a photographic light-sensitive element |
US5288598A (en) * | 1992-10-30 | 1994-02-22 | Eastman Kodak Company | Photographic light-sensitive elements |
US5378577A (en) * | 1992-10-30 | 1995-01-03 | Eastman Kodak Company | Photographic light-sensitive elements |
US5554496A (en) * | 1994-03-02 | 1996-09-10 | Fuji Photo Film Co., Ltd. | Silver halide photographic material comprising emulsion layer and backing layer provided on support |
US6136520A (en) * | 1997-12-18 | 2000-10-24 | Konica Corporation | Silver halide photographic element and a processing method of the same |
Also Published As
Publication number | Publication date |
---|---|
DE2328781A1 (en) | 1975-01-09 |
FR2232773A1 (en) | 1975-01-03 |
FR2232773B1 (en) | 1979-05-25 |
BE815384A (en) | 1974-11-22 |
GB1438259A (en) | 1976-06-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3920456A (en) | Photographic elements containing a matt layer | |
US2816028A (en) | Polymeric gentisamide antistain agents for color photography | |
AU622920B2 (en) | Hydrophilic colloid compositions for photographic materials | |
DE2930627A1 (en) | DIRECT POSITIVE RECORDING MATERIAL | |
US4657846A (en) | Silver halide photographic printing paper | |
JPS62180361A (en) | Image forming method | |
JPS5855928A (en) | Method for processing direct positive silver halide photosensitive material | |
US3128180A (en) | Hardened high-contrast photographic silver chloride emulsions and method of processing | |
JPS61170733A (en) | Silver halide photographic sensitive material | |
EP0349274B1 (en) | Photographic dot enhancing compositions and methods for their use | |
DE3842091A1 (en) | IMAGING PROCESS | |
US4144071A (en) | Photographic light-sensitive material | |
JPS6332538A (en) | Silver halide photographic sensitive material | |
US3782955A (en) | Photographic material | |
GB1563004A (en) | Process of forming an amplified dye image | |
EP0241107A2 (en) | Silver halide photograhic material that is resistant to fogging during storage | |
US3529965A (en) | Irradiation-sensitive material adapted for development by aqueous developer solution | |
US3877946A (en) | Photographic element | |
JPH05165149A (en) | Silver halide photographic sensitive material | |
JPH0627588A (en) | Photographic material | |
GB1593751A (en) | Light-sensitive silver halide photographic material | |
US4840889A (en) | High whiteness silver halide photographic paper for direct positives | |
JPS62131248A (en) | Production of silver halide photographic sensitive material | |
JP2663350B2 (en) | Silver halide photographic materials containing antifoggants | |
JPS63163337A (en) | Silver halide photographic sensitive material preventing generation of fog |