US3022169A - Matting of photographic layers - Google Patents
Matting of photographic layers Download PDFInfo
- Publication number
- US3022169A US3022169A US797059A US79705959A US3022169A US 3022169 A US3022169 A US 3022169A US 797059 A US797059 A US 797059A US 79705959 A US79705959 A US 79705959A US 3022169 A US3022169 A US 3022169A
- Authority
- US
- United States
- Prior art keywords
- polycarbonate
- layers
- layer
- particles
- matting
- 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
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- 239000004417 polycarbonate Substances 0.000 claims description 48
- 229920000515 polycarbonate Polymers 0.000 claims description 48
- 239000000839 emulsion Substances 0.000 claims description 14
- -1 SILVER HALIDE Chemical class 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical group OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 239000001828 Gelatine Substances 0.000 description 7
- 229920000159 gelatin Polymers 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 229940073584 methylene chloride Drugs 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229920001289 polyvinyl ether Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000006224 matting agent Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 229920001800 Shellac Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000005587 carbonate group Chemical group 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004208 shellac Substances 0.000 description 3
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 3
- 229940113147 shellac Drugs 0.000 description 3
- 235000013874 shellac Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 2
- 229940081735 acetylcellulose Drugs 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002160 Celluloid Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- 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
- Y10S430/162—Protective or antiabrasion layer
Definitions
- inorganic and also organic substances in finely divided form to photographic layers, especially silver halide emulsion layers, for the purpose of providing the layers with matted surfaces.
- examples of substances which have been used for this purpose are barium sulphate, silica gel, kaolin, starch and waxes. These substances, however, are deposited comparatively uickly during the casting of the layers and this results in an incomplete matting effect.
- an aqueous suspension of polystyrene or polyfluorethylene is incorporated into photographic layers for the purpose of providing the layers with matted surfaces.
- This proposal suffers from the disadvantage that particles of organic compounds frequently change in size during the drying process or on storage.
- the majority of the matting agents so far proposed have too coarse a grain size and consequently result in undesirable clouding on the surface of the photographic layer to which they are applied or show a broken line when retouching of the layer is carried out.
- Particularly preferred polycarbonates are those derived from di-(monohydroxyaryl)-alkanes, especially those derived from 4,4 di (monohydroxyaryl) alkanes. These polycarbonates may be prepared by the processes disclosed in British patent specification No. 772,627 and Smooth surfaces frequently French patent specification No. 1,141,261. Polycarbonates derived from dihydroxydiaryl sulphcnes or from mixtures of dihydroxydiaryl sulphones with other difunctiona1 hydroxy compounds, such as those obtained by the process disclosed in French patent specification No.
- High molecular weight polycarbonates derived from dihydroxydirayl ethers or dihydroxydiaryl thioethers or from mixtures of one or more of these compounds with other dihydroxy compounds are also suitable for employ- I ment in the process of the present invention. These high molecular weight polycarbonates can be prepared by the process disclosed in French patent specification No. 1,182,708.
- Suitable dihydroxydiaryl ethers are 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-2,2'-dimethy1 diphenyl ether and 4,4-dihydroxy-3,3-dimethyldiphenyl ether and homologues thereof.
- the two aryl radicals may be either the same or different and may carry substituents which will not react during the conversion of the dihydroxy compounds into the corresponding polycarbonates, for example halogen (chlorine, bromine, fluorine) alkyl groups, such as methyl, ethyl, propyl or tertiarybutyl groups or alkoxy groups.
- substituents which will not react during the conversion of the dihydroxy compounds into the corresponding polycarbonates, for example halogen (chlorine, bromine, fluorine) alkyl groups, such as methyl, ethyl, propyl or tertiarybutyl groups or alkoxy groups.
- the following substances may be used as layer formers: albumins such as gelatine and derivatives and mixtures thereof, polyvinyl alcohols, partially acetylated polyvinyl alcohols, methyl cellulose, salts of alginic acid, salts of polyacrylic acid, salts of copolymers of vinyl acetate and maleic acid and polyvinyl ethers such as polyvinylalkyl ethers, the alkyl groups of which have 1 to 12 carbon atoms.
- albumins such as gelatine and derivatives and mixtures thereof
- polyvinyl alcohols partially acetylated polyvinyl alcohols
- methyl cellulose salts of alginic acid
- salts of polyacrylic acid salts of copolymers of vinyl acetate and maleic acid
- polyvinyl ethers such as polyvinylalkyl ethers, the alkyl groups of which have 1 to 12 carbon atoms.
- the grain size of the matting is controlled by suitable choice of solvent and concentration of polycarbonate emulsion or dispersion. If, for example, emulsified paraffin oil is incorporated into a polycarbonate emulsion or if a polycarbonate and parafiin oil are simultaneously emulsified, it is possible to obtain a surface layer which guarantees an absolutely uniform retouching stroke.
- the particle size of the polycarbonate matting agent amounts to about 0.1 to 5 microns.
- ing layer can be considerably reduced by the addition of a polyvinyl ether.
- the polycarbonate is precipitated on the support in a finely divided form and thus produces p, to remove from miniature films the tendency to form Newtons rings onthe glass plates of the diapositive frames during projection.
- Example 1 100 ccgof a 3 percent solution of a polycarbonate (such as the polycarbonic acid ester of 4,4-'di(hydroxyphenyl)dimethylmethane) in methylene chloride is 'incorporated at a temperature of 35 C. and with stirring into 1 litre of a' percent gelatine solution to which 7
- Example 2 A mixture of 1 litre of a 10 percent gelatine solution to which has been added a wetting agent and 100 cc. of a polycarbonate (such as the polycarbonic acid ester of 4,4-'di(hydroxyphenyl)dimethylmethane) in methylene chloride is 'incorporated at a temperature of 35 C. and with stirring into 1 litre of a' percent gelatine solution to which 7
- Example 2 A mixture of 1 litre of a 10 percent gelatine solution to which has been added a wetting agent and 100 cc. of
- a 3 percent solution of a polycarbonate (such as the polycarbonate of Example 1) in methylene chloride is emulsified at 32 C. with cc. of a 10 percent aqueous solution of a polyvinylether such as polyvinylmethylether, polyvinylethylether, polyvinylisobutylether, polyvinyldecalylether.
- a polyvinylether such as polyvinylmethylether, polyvinylethylether, polyvinylisobutylether, polyvinyldecalylether.
- Z stands for hydrocarbon groups necessary to complete a cycloaliphatic ring; it stands for a' whole number greater than 10 and preferably greater than R and R stand for hydrogen or at least one substituent which does not take part in the polyesterification process such as lower alkyl groups, alkoxy groups, halogen atoms.
- the mixed polycarbonates may contain the units represented by the above general formula and by the formulae:
- R stands for a phenylene radical and R for any bivalent radical which is different from R" and from the corresponding radicals of the first general formula, said bivalent radical being derived from a dihydroxy compound by subtraction of the two hydroxy groups, said two hydroxy groups being the sole groups capable of taking part in the polyesterification process.
- These mixed polycarbonates may either contain the polyvinylether to polycarbonate may vary from 10 to 100 g., and preferably 15 to 50 g. of polyvinylether per 100 g. of polycarbonate.
- toluene 95 cc. of toluene is applied as a thin layer to a glass plate and to both sides of a developed miniature film and then dried.
- thermoplastic polycarbonates may be represented by way of example by the following general formula:
- the mixed polycarbonates always contain units in which the O -o-i J-'-o group is bonded to an aromatic radical, said units being present in an amount corresponding to 20 to 99' molar percent.
- the polycarbonates may also be produced by the processes indicated in British patent specification 772,627, French patent specifications 1,149,261, 1,152,155, 1,152,- 156, 1,152,157, 1,152,158 and Belgian patent specifications 546,375 and 555,894.
- paraflin oils used for the production of the matted layers in addition to said polycarbonates may contain 10 to 25, preferably 15 to 22 carbon atoms. ,These paraffin oils may be applied in quantities of 20 to 206 g., and preferably 50 to 150 g., per 100 g. of polycarbonate.
- a light-sensitive photographic material comprising in combination a support, a light-sensitive silver halide emulsion layer and particles 0.1 to 5 microns in size of a thermoplastic linear polycarbonate of a dihydric phenol dispersed in a hydrophilic binding layer, said polycarbohate having a linear chain length of more than 10 carbonate units and the particles being present in amount that forms a matte surface on the binding layer;
- a light sensitive photographic material according to claim 1, wherein said polycarbonate particles are incorporated in a protective layer'coated on said silver halide emulsion layer.
- a light-sensitive photographic material wherein'a paraffin oil is dispersed in the hydrophilic binding layer along with the polycarbonate particles and the parafiin oil is present in an. amount of about 20 to 200 g. per 100 g. of polycarbonate.
- the hydrophilic layer that contains saidpolycarbonate also includes a poly-vinyl alkyl ether in an 100' g. of polycarbonate the alkyl groups of said poly-ether, having up to 12 carbon atoms.
- thermoplastic linear polycarbonate is a polycarbonic acid ester of a bis-(para-rnonohydroxyaryl)alkane.
- a photographic material comprising in combination a support, a layer containing a silver image and a layer of particles 0.1 to 5 microns in size of a thermoplastic linear polycarbonate of a dihydric phenol dispersed in a hydrophilic binding layer, said polycarbonate having a linear chain length of more than 10 carbonate units, and the particles being present in amount that forms a matte surface on the binding layer.
- a process for providing a matte photographic surface including the steps of providing a solution of a thermoplastic linear polycarbonate of a dihydric phenol having a linear chain length of more than 10 carbonate units, said polycarbonate being dissolved in a solution which is a mixture of components one of which is more volatile and by itself effectively dissolves the polycarbonate and another of which is less volatile and by itself does not effectively dissolve the polycarbonate;- applying the above polycarbonate References Cited in the file of this patent UNITED STATES PATENTS 2,322,037 Lindquist June 15, 1943 2,799,666 Caldwell July 16, 1957 2,831,831 Caldwell et a1 Apr. 22, 1958 2,874,046 Klockgether et al. Feb. 17, 1961
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Description
United States Patent Noprawing. Filed Mar. 4, 1959, Ser. No. 797,059 (Iianns priorit application Germany Mar. 5, 1958 9 Claims. (Cl. 96-67) 'lhe present invention relates to photographic materials which contain polycarbonates as matting agents.
It is known to apply inorganic and also organic substances in finely divided form to photographic layers, especially silver halide emulsion layers, for the purpose of providing the layers with matted surfaces. Examples of substances which have been used for this purpose are barium sulphate, silica gel, kaolin, starch and waxes. These substances, however, are deposited comparatively uickly during the casting of the layers and this results in an incomplete matting effect.
it has also been proposed to use finely divided cellulose or a derivative thereof as a matting agent. In this case, however, it is essential that the cellulose or derivative thereof is comminuted to the required grain size, either by mechanical or chemical means, prior to application to the photographic layer and this involves tedious additional measures.
It has also been proposed to apply alcoholic shellac solutions to photographic layers, for the purpose of providing the layers with a matted surface. In this method, however, the shellac easily flocculates and hence it is extremely difiicult to keep the size of the shellac particles within the necessary critical limits.
According to another proposal an aqueous suspension of polystyrene or polyfluorethylene is incorporated into photographic layers for the purpose of providing the layers with matted surfaces. This proposal, however, suffers from the disadvantage that particles of organic compounds frequently change in size during the drying process or on storage.
It is known that the nature of the surfaces of photographic layers plays a decisive part in the processing of most photographic films. lead to contact errors and consequently to the formation of Newtons rings, especially on magnification or projection when two smooth surfaces come into contact with each other. Other disadvantages of the surfaces of photographic layers being too smooth are that the possibility of retouching the layers is poor and the layers are too sensitive to scratches.
The majority of the matting agents so far proposed have too coarse a grain size and consequently result in undesirable clouding on the surface of the photographic layer to which they are applied or show a broken line when retouching of the layer is carried out.
Prior to the present invention no means .were known which prevented the formation of Newtons rings without producing an undesirable matting effect.
It has now been found that the aforementioned disadvantages in connection with the provision of matted surfaces on photographic layers can be obviated if emulsions or dispersions of polycarbonates are added either to the casting solutions employed in the production of the photographic silver halide emulsion layers themselves or to the auxiliary layers, for example the conventional protecL've gelatine layers.
Particularly preferred polycarbonates are those derived from di-(monohydroxyaryl)-alkanes, especially those derived from 4,4 di (monohydroxyaryl) alkanes. These polycarbonates may be prepared by the processes disclosed in British patent specification No. 772,627 and Smooth surfaces frequently French patent specification No. 1,141,261. Polycarbonates derived from dihydroxydiaryl sulphcnes or from mixtures of dihydroxydiaryl sulphones with other difunctiona1 hydroxy compounds, such as those obtained by the process disclosed in French patent specification No.
1,152,155, are also suitable.
High molecular weight polycarbonates derived from dihydroxydirayl ethers or dihydroxydiaryl thioethers or from mixtures of one or more of these compounds with other dihydroxy compounds are also suitable for employ- I ment in the process of the present invention. These high molecular weight polycarbonates can be prepared by the process disclosed in French patent specification No. 1,182,708.
Suitable dihydroxydiaryl ethers are 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-2,2'-dimethy1 diphenyl ether and 4,4-dihydroxy-3,3-dimethyldiphenyl ether and homologues thereof.
In the dihydroxy compounds the two aryl radicals may be either the same or different and may carry substituents which will not react during the conversion of the dihydroxy compounds into the corresponding polycarbonates, for example halogen (chlorine, bromine, fluorine) alkyl groups, such as methyl, ethyl, propyl or tertiarybutyl groups or alkoxy groups.
The following substances may be used as layer formers: albumins such as gelatine and derivatives and mixtures thereof, polyvinyl alcohols, partially acetylated polyvinyl alcohols, methyl cellulose, salts of alginic acid, salts of polyacrylic acid, salts of copolymers of vinyl acetate and maleic acid and polyvinyl ethers such as polyvinylalkyl ethers, the alkyl groups of which have 1 to 12 carbon atoms.
The grain size of the matting is controlled by suitable choice of solvent and concentration of polycarbonate emulsion or dispersion. If, for example, emulsified paraffin oil is incorporated into a polycarbonate emulsion or if a polycarbonate and parafiin oil are simultaneously emulsified, it is possible to obtain a surface layer which guarantees an absolutely uniform retouching stroke. The particle size of the polycarbonate matting agent amounts to about 0.1 to 5 microns.
Other properties of the film can also be favourably influenced by incorporating a polycarbonate emulsion into gelatine layers. In this way it is possible to improve considerably the adhesion of the film to the support, the
. ing layer can be considerably reduced by the addition of a polyvinyl ether.
By applying a solution of a polycarbonate in a suitable solvent such as methylene chloride to which has been added one or more liquids in which the polycarbonate is insoluble or only sparingly soluble, to a smooth support such as Celluloid or glass or to gelatine or gelatino silver halide emulsion layers, there is obtained on the support after the evaporation of the solvent a surface which, with little visible matting, does not produce any disturbing Newtons n'ngs when brought into contact with another smooth surface. If desired, other film-forming agents, such as acetyl cellulose, may be added to the polycarbonate solution. In this embodiment of the invention on evaporation of the liquid components of the polycarbonate solution the polycarbonate is precipitated on the support in a finely divided form and thus produces p, to remove from miniature films the tendency to form Newtons rings onthe glass plates of the diapositive frames during projection.
In order that the invention may be more clearly understood the following examples are given by way of illustration only:
Example 1 100 ccgof a 3 percent solution of a polycarbonate (such as the polycarbonic acid ester of 4,4-'di(hydroxyphenyl)dimethylmethane) in methylene chloride is 'incorporated at a temperature of 35 C. and with stirring into 1 litre of a' percent gelatine solution to which 7 Example 2 A mixture of 1 litre of a 10 percent gelatine solution to which has been added a wetting agent and 100 cc. of
a 3 percent solution of a polycarbonate (such as the polycarbonate of Example 1) in methylene chloride is emulsified at 32 C. with cc. of a 10 percent aqueous solution of a polyvinylether such as polyvinylmethylether, polyvinylethylether, polyvinylisobutylether, polyvinyldecalylether. On adding this emulsion to gelatine or emulsion layers there is formed a surface which is very insensitive to scratching and the developed film maintains almost complete clarity. The proportion of 4, Z stands for hydrocarbon groups necessary to complete a cycloaliphatic ring; it stands for a' whole number greater than 10 and preferably greater than R and R stand for hydrogen or at least one substituent which does not take part in the polyesterification process such as lower alkyl groups, alkoxy groups, halogen atoms.
The mixed polycarbonates may contain the units represented by the above general formula and by the formulae:
(II) t;
-R"oo-o (-R -O-ii-Q) in which R stands for a phenylene radical and R for any bivalent radical which is different from R" and from the corresponding radicals of the first general formula, said bivalent radical being derived from a dihydroxy compound by subtraction of the two hydroxy groups, said two hydroxy groups being the sole groups capable of taking part in the polyesterification process.
I These mixed polycarbonates may either contain the polyvinylether to polycarbonate may vary from 10 to 100 g., and preferably 15 to 50 g. of polyvinylether per 100 g. of polycarbonate.
, v Example 3 A mixture of 8 cc. of a 3 percent-solution of a polycarbonate in meth ylene chloride 165 cc. of methylene chloride 30 cc. of a5 percent solution; of acetyl cellulose in methylene chloride, and
95 cc. of toluene is applied as a thin layer to a glass plate and to both sides of a developed miniature film and then dried.
'The glass plate thus treated in contact with a strip of normal color miniature film prevents the formation of disturbing Newtons rings on projection. The treated miniature film no longer produced any disturbing Newtons rings during projection when in contact with normal glass plates.
The present film-forming thermoplastic polycarbonates may be represented by way of example by the following general formula:
wherein X stands for a bivalent substituent selected from the group consisting of in which substituents R and R stand'for hydrogen,
unbranched and branched monovalent aliphatic hydrocarbon radicals having 1 to 10 carbon atoms, monovalent cycloaliphatic radicals, monovalent araliphatic radicals,.
the alkyl groups of which contain 1 to 4 carbon atoms,
- amount of 10 to 100 g. per
radicals of the Formula I and of the. Formula II or of the Formula I and the Formula 111 or of the Formula II and of the Formula III or of all three groups. In other words the mixed polycarbonates always contain units in which the O -o-i J-'-o group is bonded to an aromatic radical, said units being present in an amount corresponding to 20 to 99' molar percent.
The polycarbonates may also be produced by the processes indicated in British patent specification 772,627, French patent specifications 1,149,261, 1,152,155, 1,152,- 156, 1,152,157, 1,152,158 and Belgian patent specifications 546,375 and 555,894.
The paraflin oils used for the production of the matted layers in addition to said polycarbonates may contain 10 to 25, preferably 15 to 22 carbon atoms. ,These paraffin oils may be applied in quantities of 20 to 206 g., and preferably 50 to 150 g., per 100 g. of polycarbonate.
What is claimed is:
1. A light-sensitive photographic material comprising in combination a support, a light-sensitive silver halide emulsion layer and particles 0.1 to 5 microns in size of a thermoplastic linear polycarbonate of a dihydric phenol dispersed in a hydrophilic binding layer, said polycarbohate having a linear chain length of more than 10 carbonate units and the particles being present in amount that forms a matte surface on the binding layer;
2. A light-sensitive photographic material according to claim 1, wherein said polycarbonate particles are incorporated in said silver halide emulsion layer.
3. A light sensitive photographic material according to claim 1, wherein said polycarbonate particles are incorporated in a protective layer'coated on said silver halide emulsion layer. a
'4. A light-sensitive photographic material according to claim 1, wherein said polycarbonate containing layer is coated on one face of said support, and said silver halide emulsion is coated on the opposite face.
5. A light-sensitive photographic material according to claim 1, wherein'a paraffin oil is dispersed in the hydrophilic binding layer along with the polycarbonate particles and the parafiin oil is present in an. amount of about 20 to 200 g. per 100 g. of polycarbonate. 6. A light-sensitive photographic material according to claim 1, wherein the hydrophilic layer that contains saidpolycarbonate also includes a poly-vinyl alkyl ether in an 100' g. of polycarbonate the alkyl groups of said poly-ether, having up to 12 carbon atoms.
7. A light-sensitive photographic material according to claim 1, wherein said thermoplastic linear polycarbonate is a polycarbonic acid ester of a bis-(para-rnonohydroxyaryl)alkane.
8. A photographic material comprising in combination a support, a layer containing a silver image and a layer of particles 0.1 to 5 microns in size of a thermoplastic linear polycarbonate of a dihydric phenol dispersed in a hydrophilic binding layer, said polycarbonate having a linear chain length of more than 10 carbonate units, and the particles being present in amount that forms a matte surface on the binding layer.
9. A process for providing a matte photographic surface, said process including the steps of providing a solution of a thermoplastic linear polycarbonate of a dihydric phenol having a linear chain length of more than 10 carbonate units, said polycarbonate being dissolved in a solution which is a mixture of components one of which is more volatile and by itself effectively dissolves the polycarbonate and another of which is less volatile and by itself does not effectively dissolve the polycarbonate;- applying the above polycarbonate References Cited in the file of this patent UNITED STATES PATENTS 2,322,037 Lindquist June 15, 1943 2,799,666 Caldwell July 16, 1957 2,831,831 Caldwell et a1 Apr. 22, 1958 2,874,046 Klockgether et al. Feb. 17, 1959
Claims (1)
1. A LIGH-SENSITIVE PHOTOGRAPHICH MATERIAL COMPRISING IN COMBINATION A SUPPORT, A LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER AND PARTICLES 0.1 TO 5 MICRONS IN SIZE OF A THERMOPLASTIC LINEAR POLYCARBONATE OF A DIHYDRIC PHENOL DISPERSED IN A HYDROPHILLIC BINDING LAYER, SAID POLYCARBONATE HAVING A LINEAR CHAIN LENGTH OF MORE THAN 10 CARBONATE UNITS AND THE PARTICLES VEING PRESENT IN AMOUNT THAT FORMS A MATTE SURFACE ON THE BINDING LAYER.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3022169X | 1958-03-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3022169A true US3022169A (en) | 1962-02-20 |
Family
ID=8084554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US797059A Expired - Lifetime US3022169A (en) | 1958-03-05 | 1959-03-04 | Matting of photographic layers |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3022169A (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3212920A (en) * | 1960-09-20 | 1965-10-19 | Du Pont | Delustering of glossy surfaces by the use of a non-particle containing coating composition |
| US3238043A (en) * | 1961-07-06 | 1966-03-01 | Levy Marilyn | Viscous processing solution |
| US3253926A (en) * | 1962-01-08 | 1966-05-31 | Paul Desire Van Pee | Light-sensitive silver halide material containing hydrophobic starch derivatives |
| US3411907A (en) * | 1965-03-04 | 1968-11-19 | Eastman Kodak Co | Photographic compositions containing combination of soft and hard matting agents |
| US3503743A (en) * | 1966-05-26 | 1970-03-31 | Diagravure Film Mfg Corp | Protection of hydrophilic films,layers,and products thereof |
| US3632342A (en) * | 1969-03-03 | 1972-01-04 | Eastman Kodak Co | Photographic element containing acrylic latex polymers |
| US3656954A (en) * | 1969-03-17 | 1972-04-18 | Agfa Gevaert Nv | Photographic material with improved surface properties |
| US3850640A (en) * | 1972-02-29 | 1974-11-26 | Eastman Kodak Co | Coating quality and reducing static simultaneously |
| US4238560A (en) * | 1978-08-30 | 1980-12-09 | Fuji Photo Film Co., Ltd. | Photosensitive printing plate forming material having a novel matting layer composition |
| FR2467421A1 (en) * | 1979-10-15 | 1981-04-17 | Fuji Photo Film Co Ltd | SILVER HALIDE-SENSITIVE ELEMENT AND METHOD OF FORMING A LASER-EXPOSED IMAGE |
| US4592976A (en) * | 1984-12-07 | 1986-06-03 | N. Peter Whitehead | Identification card |
| 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 |
| JPH0650375B2 (en) | 1985-09-04 | 1994-06-29 | 富士写真フイルム株式会社 | Photographic material |
| EP1593523A1 (en) | 2004-05-06 | 2005-11-09 | Konica Minolta Medical & Graphic, Inc. | Printing plate material, printing plate and printing process |
| US20060003272A1 (en) * | 2004-06-09 | 2006-01-05 | Konica Minolta Medical & Graphic, Inc. | Photothermographic material, development method and thermal development device thereof |
| EP1628156A1 (en) | 2004-08-12 | 2006-02-22 | Konica Minolta Medical & Graphic, Inc. | Method of manufacture of photosensitive material packaging body and photosensitive material packaging body |
| EP1630609A1 (en) | 2004-08-23 | 2006-03-01 | Konica Minolta Medical & Graphic, Inc. | Printing plate material and printing plate |
| EP1700710A1 (en) | 2005-03-08 | 2006-09-13 | Konica Minolta Medical & Graphic, Inc. | Printing method, sheet material and mounting method of printing plate |
| WO2007052470A1 (en) | 2005-11-01 | 2007-05-10 | Konica Minolta Medical & Graphic, Inc. | Lithographic printing plate material, lithographic printing plate, method for preparing lithographic printing plate, and method for printing by lithographic printing plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2322037A (en) * | 1939-07-07 | 1943-06-15 | Eastman Kodak Co | Photographic film |
| US2799666A (en) * | 1956-01-26 | 1957-07-16 | Eastman Kodak Co | Linear polycarbonates from bis (hydroxyethoxy) aromatic compounds |
| US2831831A (en) * | 1954-08-04 | 1958-04-22 | Eastman Kodak Co | Copolyesters containing aromatic amino acid derivatives |
| US2874046A (en) * | 1955-06-25 | 1959-02-17 | Agfa Ag | Process for the retreatment of foils consisting of highly polymeric substances for the application of hydrophilic colloids |
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1959
- 1959-03-04 US US797059A patent/US3022169A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2322037A (en) * | 1939-07-07 | 1943-06-15 | Eastman Kodak Co | Photographic film |
| US2831831A (en) * | 1954-08-04 | 1958-04-22 | Eastman Kodak Co | Copolyesters containing aromatic amino acid derivatives |
| US2874046A (en) * | 1955-06-25 | 1959-02-17 | Agfa Ag | Process for the retreatment of foils consisting of highly polymeric substances for the application of hydrophilic colloids |
| US2799666A (en) * | 1956-01-26 | 1957-07-16 | Eastman Kodak Co | Linear polycarbonates from bis (hydroxyethoxy) aromatic compounds |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3212920A (en) * | 1960-09-20 | 1965-10-19 | Du Pont | Delustering of glossy surfaces by the use of a non-particle containing coating composition |
| US3238043A (en) * | 1961-07-06 | 1966-03-01 | Levy Marilyn | Viscous processing solution |
| US3253926A (en) * | 1962-01-08 | 1966-05-31 | Paul Desire Van Pee | Light-sensitive silver halide material containing hydrophobic starch derivatives |
| US3411907A (en) * | 1965-03-04 | 1968-11-19 | Eastman Kodak Co | Photographic compositions containing combination of soft and hard matting agents |
| US3503743A (en) * | 1966-05-26 | 1970-03-31 | Diagravure Film Mfg Corp | Protection of hydrophilic films,layers,and products thereof |
| US3632342A (en) * | 1969-03-03 | 1972-01-04 | Eastman Kodak Co | Photographic element containing acrylic latex polymers |
| US3656954A (en) * | 1969-03-17 | 1972-04-18 | Agfa Gevaert Nv | Photographic material with improved surface properties |
| US3850640A (en) * | 1972-02-29 | 1974-11-26 | Eastman Kodak Co | Coating quality and reducing static simultaneously |
| US4238560A (en) * | 1978-08-30 | 1980-12-09 | Fuji Photo Film Co., Ltd. | Photosensitive printing plate forming material having a novel matting layer composition |
| FR2467421A1 (en) * | 1979-10-15 | 1981-04-17 | Fuji Photo Film Co Ltd | SILVER HALIDE-SENSITIVE ELEMENT AND METHOD OF FORMING A LASER-EXPOSED IMAGE |
| US4592976A (en) * | 1984-12-07 | 1986-06-03 | N. Peter Whitehead | Identification card |
| 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 |
| JPH0650375B2 (en) | 1985-09-04 | 1994-06-29 | 富士写真フイルム株式会社 | Photographic material |
| EP1593523A1 (en) | 2004-05-06 | 2005-11-09 | Konica Minolta Medical & Graphic, Inc. | Printing plate material, printing plate and printing process |
| US20060003272A1 (en) * | 2004-06-09 | 2006-01-05 | Konica Minolta Medical & Graphic, Inc. | Photothermographic material, development method and thermal development device thereof |
| US7445884B2 (en) | 2004-06-09 | 2008-11-04 | Konica Minolta Medical & Graphic, Inc. | Photothermographic material, development method and thermal development device thereof |
| EP1628156A1 (en) | 2004-08-12 | 2006-02-22 | Konica Minolta Medical & Graphic, Inc. | Method of manufacture of photosensitive material packaging body and photosensitive material packaging body |
| EP1630609A1 (en) | 2004-08-23 | 2006-03-01 | Konica Minolta Medical & Graphic, Inc. | Printing plate material and printing plate |
| EP1700710A1 (en) | 2005-03-08 | 2006-09-13 | Konica Minolta Medical & Graphic, Inc. | Printing method, sheet material and mounting method of printing plate |
| WO2007052470A1 (en) | 2005-11-01 | 2007-05-10 | Konica Minolta Medical & Graphic, Inc. | Lithographic printing plate material, lithographic printing plate, method for preparing lithographic printing plate, and method for printing by lithographic printing plate |
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