EP0159493B1 - Beschichtetes fotografisches Trägermaterial - Google Patents
Beschichtetes fotografisches Trägermaterial Download PDFInfo
- Publication number
- EP0159493B1 EP0159493B1 EP85102318A EP85102318A EP0159493B1 EP 0159493 B1 EP0159493 B1 EP 0159493B1 EP 85102318 A EP85102318 A EP 85102318A EP 85102318 A EP85102318 A EP 85102318A EP 0159493 B1 EP0159493 B1 EP 0159493B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- support material
- material according
- photographic support
- substance
- hydroxyfunctional
- 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
Links
- 239000000463 material Substances 0.000 title claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 230000005855 radiation Effects 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 3
- -1 allyl ester Chemical class 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 3
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 150000001261 hydroxy acids Chemical class 0.000 claims 2
- 239000012463 white pigment Substances 0.000 claims 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical class OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- 150000002334 glycols Chemical class 0.000 claims 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 238000002845 discoloration Methods 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 29
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 13
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 9
- 238000010894 electron beam technology Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000010186 staining Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LGPAKRMZNPYPMG-UHFFFAOYSA-N (3-hydroxy-2-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OC(CO)COC(=O)C=C LGPAKRMZNPYPMG-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- BWDHJINUKACSDS-UHFFFAOYSA-N 2,3-bis(prop-2-enoxy)propan-1-ol Chemical compound C=CCOC(CO)COCC=C BWDHJINUKACSDS-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- CQHKDHVZYZUZMJ-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-prop-2-enoyloxypropyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CO)COC(=O)C=C CQHKDHVZYZUZMJ-UHFFFAOYSA-N 0.000 description 1
- TUOBEAZXHLTYLF-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CC)COC(=O)C=C TUOBEAZXHLTYLF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 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
- G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
- G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31794—Of cross-linked polyester
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31931—Polyene monomer-containing
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- the invention relates to a photographic support material which contains a coating on at least one side, the binder component of which is predominantly made from unsaturated compounds and which is cured by means of energy-providing radiation.
- a support material for photographic layers which can be used advantageously for both dry and wet development processes.
- a large number of substrates for photographic layers are known.
- the most common media include film materials and papers. Papers are usually additionally coated. Waterproof papers coated in particular with synthetic resin layers have found wide use as supports for photographic layers. Resin films and laminates coated with special layers are also known. Papers coated on both sides with polyolefin resin and film materials coated with pigmented layers (DAS 14 47 815, US 38 33 380, US 36 30 742, US 39 28 037) were most widespread.
- DOS 30 22 451 and DOS 30 22 709 which consist of base paper with at least one coating produced in situ with the aid of electron beam curing.
- the advantages of a coating hardened with electron beams are its scratch resistance, the high pigment absorption capacity and the higher surface smoothness compared to polyolefin coatings.
- Synthetic resin coatings are not only resistant to water, but also to acidic and alkaline photographic process solutions and thereby prevent these solutions from penetrating into any paper carrier underneath. As a result, the time-consuming washing process for paper or nonwoven base is significantly shortened.
- the common polyolefin resin coatings are generally less stable to heat because the coating material is thermoplastic.
- All resin coatings can contain pigments, dyes, optical brighteners, image stabilizers, antioxidants or other additives, insofar as this is desirable or necessary in view of the desired properties of an overlying photographic image.
- pigments and dyes are of the greatest importance for the visual impression of a photographic image on the coating. They determine the color character of color images and are decisive for the sharpness of the photographic images.
- the photographic layers are applied to the surface of the resin layer either directly or after previously applying an adhesion-promoting intermediate layer.
- These photographic layers are preferably layers which are known under the term silver salt photography and which are used either to produce black and white or color images.
- silver salt photography encompasses not only photographic layers which contain inorganic silver salts and are developed predominantly wet with so-called developer solutions or pastes, but also photographic layers which contain organic silver compounds and are predominantly dry, e.g. by exposure to heat.
- Resin coatings hardened with electron beams in accordance with DOS 30 22 451 or DOS 30 22 709 are produced by applying a flowable mixture to the surface of a paper or other base support, distributing it uniformly there and then solidifying it under inert gas or other covering with high-energy electron beams.
- the mixtures contain as a crucial component at least one substance with ethylenically unsaturated double bonds, which have the ability to polymerize with one another when this is initiated by radiation.
- Suitable substances with ethylenically unsaturated double bonds are all vinyl or vinylidene compounds.
- the mixture should preferably contain at least one substance which contains two or more double bonds.
- non-reactive substances without double bonds can also be contained in a mixture to a limited extent.
- Substances containing acrylate or methacrylate groups are primarily used as reactive components. However, esters of maleic acid, fumaric acid, mesaconic acid, citraconic acid or itaconic acid, other derivatives of these acids, allyl compounds and linear and cyclic dienes or trienes are also suitable as reactive mixture components. Those esters of the acids mentioned which are derived from polyhydric alcohols are preferred. Examples are hexanediol diacrylate, trimethylolpropane triacrylate, polyester acrylates, polyurethane acrylates, polyether acrylates, polyepoxy acrylates, alkyd resin acrylates or the methacrylates corresponding to the acrylates mentioned.
- the flow properties of curable mixtures are adjusted by mixing components of higher molecular weight with low molecular weight substances.
- the hardness and flexibility of the hardened layers is determined by the ratio of double bonds to the molecular size in the starting material and can be varied widely by mixing different substances.
- the layers hardened with electron beams now have many advantages compared to polyolefin layers, but so far they have also had disadvantages. Despite the wide range of variations in the composition of radiation-hardened layers, it was not possible to produce a layer that showed equally good behavior in all photographic process solutions. Rather, it was found that the layers hardened with electron beams behave differently towards different process solutions. There are commercially available color developer preparations which, in combination with subsequent exposure to oxygen, lead to a yellowish discoloration of the surface of the radiation-hardened layer. This discoloration is true low, but clearly visible and cannot be prevented by the stop bath or fixing bath or by thorough washing.
- the trend towards yellowing is no longer visible if the determination of the optical density according to DIN 4512, measured with a yellow filter over a white background, shows changes that are smaller than 0.03.
- the measurement is first carried out on the freshly hardened coatings and then repeated after bath treatment and four days of exposure to air. The difference between these two measured values marks the discoloration.
- the coating composition contains at least one unsaturated monomeric, oligomeric or polymeric hydroxyl functional substance before curing and the molar concentration of the hydroxyl groups in the coating is equal to or greater than 2.
- the preferred positions of the OH group in relation to the developer staining according to the invention are a ⁇ or y position relative to the ester or ether group. Accordingly, allyl alcohol was found to be as ineffective as allyl alcohol / styrene copolymer or vinyl alcohol copolymer.
- Effective and suitable substances are, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, glycerol diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, incompletely esterified sugar acrylates as well as polyester acrylates, polyether acrylates, epoxy resin acrylates with OH-acrylates or the group acrylates corresponding to the OH-acrylates or PU-acrylates here, respectively.
- Suitable substances are also OH-containing allyl ethers of polyhydric alcohols, e.g. Pentaerythritol triallyl ether, glycerol diallyl ether and other substances of similar structure. Even with allyl ethers, an OH molality of greater than 2 is required in order to obtain layers which do not give visible color with color developer.
- the layers hardened with electron beams contain further additives as are customary in such photographic supports.
- additives include, in particular, pigments of all types as well as pigment dispersants, dyes and other substances which have a favorable effect on the image quality and which are known to the person skilled in the art and e.g. are described in DOS 30 22 451.
- the coating layers according to the invention can be on paper, precoated paper, film or various types of laminates. They can be produced in any way according to one of the known processes and have different surface structures, which range from shiny to very matt. This includes such symmetrical surface structures as described in DP 25 15 261. A particularly suitable method for producing the coatings according to the invention is described in DOS 30 22 709.
- the opposite side must generally also be waterproof. This can also be done with a mixture according to the invention. However, the opposite side can also be given a polyolefin coating or another waterproof coating. Several similar or different types of coatings can also be placed on top of one another.
- a photographic support provided with one or more coatings according to the invention can be coated with photographic layers in a known manner and after customary pretreatment and is suitable for processing in all commercial photographic process solutions without any disturbing discoloration, as well as for thermal or other dry development processes.
- the curable coatings arranged on any carrier material are preferably cured by means of electron beams.
- this is not a limiting element of the invention. Rather, the coatings can be cured with any type of radiation that provides enough energy to trigger the polymerization reaction on which the curing is based. Accordingly, X-rays or y-rays are just as suitable as UV light or visible light, light generally requiring the addition of special initiators.
- the characteristic element of the invention is solely the presence in a radiation-curable layer of a sufficient amount of at least one hydroxyl-functional unsaturated compound, for example a hydroxyl-functional ester of an unsaturated acid or a hydroxyl-functional allyl ether or allyl ester.
- Example 1 is to be seen as a comparative example, which shows the large number of possible substances for radiation-hardened layers, all of which show a more or less strong coloring of the layer after the action of color developer.
- Examples 2, 3 and 4 show the effect of mixtures according to the invention, further comparisons being built in with experiments 2d, e, I and 3c and d, in which the OH molality is below the limit of 2. This illustrates in a special way the importance of this limit value for the present invention.
- test data in Tables 1 to 4 are based on discolorations which were obtained with a commercially available color developer from Kodak. Other developers gave different values for the discoloration, but showed the same tendency and confirmed that the OH molality of two should not be undercut.
- the hardened coatings were then treated with commercially available photographic developer for color paper, washed and the samples were stored for four days at room temperature with access to air.
- the resulting discoloration of the layer was determined as a change in optical density in accordance with DIN 4512 and is listed in the last column of the table.
- Table 1 includes all curable substances described in examples or used in practice to date, as well as an example of a selection of other substances from the large number of substances examined.
- the test results show that after curing, all have the property of visibly staining with a commercially available color developer, methacrylates behaving worse than corresponding acrylates or allyl compounds. Another clear trend cannot be seen from these comparative examples according to the prior art.
- alkyl acrylates, alkyl methacrylates and glycidyl compounds such as, for example, allyl glycidyl ether, etc. were not included in Table 1.
- these compounds always showed increased developer staining, which increases both in proportion to the length of the alkyl group and in proportion to the amount used.
- Example 2 samples of a paper coated with polyethylene were coated on one side with in each case approximately 20 g / m 2 of radiation-curable mixtures which contained pentaerythritol triacrylate as the characteristic constituent.
- the coatings were cured as in Example 1 and then subjected to the color test with color developer solution described there.
- the relevant data are summarized in Table 2.
- Example 3 samples of a paper coated with polyethylene were coated on one side with 20 g / m 2 each of radiation-curable mixtures which contained hydroxyethyl acrylate as a characteristic constituent. The coatings were cured as in Example 1 and then subjected to the color test with color developer solution described there. The relevant data are summarized in Table 3.
- Example 2 samples of a paper coated with polyethylene were coated on one side with 20 g / m 2 each of radiation-curable mixtures which contained various hydroxyl compounds in addition to other curable components. The coatings were cured as in Example 1 and then subjected to the color test with color developer solution described there. The data are summarized in Table 4.
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Laminated Bodies (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT85102318T ATE47921T1 (de) | 1984-04-21 | 1985-03-01 | Beschichtetes fotografisches traegermaterial. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3415215 | 1984-04-21 | ||
DE3415215A DE3415215A1 (de) | 1984-04-21 | 1984-04-21 | Gegen fotografische baeder resistentes fotografisches traegermaterial |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0159493A2 EP0159493A2 (de) | 1985-10-30 |
EP0159493A3 EP0159493A3 (en) | 1988-06-01 |
EP0159493B1 true EP0159493B1 (de) | 1989-11-08 |
Family
ID=6234242
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP85102318A Expired EP0159493B1 (de) | 1984-04-21 | 1985-03-01 | Beschichtetes fotografisches Trägermaterial |
Country Status (8)
Country | Link |
---|---|
US (1) | US4663236A (ja) |
EP (1) | EP0159493B1 (ja) |
JP (1) | JPH0648363B2 (ja) |
AT (1) | ATE47921T1 (ja) |
DE (2) | DE3415215A1 (ja) |
ES (1) | ES542336A0 (ja) |
GR (1) | GR850904B (ja) |
PT (1) | PT80153B (ja) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3518113C2 (de) * | 1985-05-21 | 1987-03-19 | Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück | Trägermaterial für thermisch entwickelbare fotografische Aufzeichnungsmaterialien |
KR960015658B1 (ko) * | 1988-01-28 | 1996-11-20 | 하이페리온 캐탈리시스 인터내쇼날 | 탄소 미소섬유(Carbon Fibrils) |
DE4302678A1 (de) * | 1993-02-01 | 1994-08-04 | Schoeller Felix Jun Papier | Recyclierbarer Schichtträger |
US5425980A (en) * | 1994-02-22 | 1995-06-20 | Eastman Kodak Company | Use of glow discharge treatment to promote adhesion of aqueous coats to substrate |
US5618659A (en) * | 1995-03-01 | 1997-04-08 | Eastman Kodak Company | Photographic element containing a nitrogen glow-discharge treated polyester substrate |
US20050032464A1 (en) * | 2003-08-07 | 2005-02-10 | Swisher Robert G. | Polishing pad having edge surface treatment |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4866182A (ja) * | 1971-12-15 | 1973-09-11 | ||
DE2324590A1 (de) * | 1973-05-16 | 1974-12-05 | Agfa Gevaert Ag | Material und verfahren zur herstellung sichtbarer bilder durch diffusionsuebertragung |
JPS5033279A (ja) * | 1973-07-24 | 1975-03-31 | ||
DE3022451A1 (de) * | 1980-06-14 | 1982-01-07 | Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück | Wasserfestes fotografisches papier |
DE3022709A1 (de) * | 1980-06-18 | 1982-01-07 | Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück | Wasserfestes fotografisches papier und verfahren zu seiner herstellung |
-
1984
- 1984-04-21 DE DE3415215A patent/DE3415215A1/de active Granted
-
1985
- 1985-03-01 EP EP85102318A patent/EP0159493B1/de not_active Expired
- 1985-03-01 AT AT85102318T patent/ATE47921T1/de not_active IP Right Cessation
- 1985-03-01 DE DE8585102318T patent/DE3574188D1/de not_active Expired
- 1985-03-22 PT PT80153A patent/PT80153B/pt unknown
- 1985-04-10 GR GR850904A patent/GR850904B/el unknown
- 1985-04-11 US US06/722,732 patent/US4663236A/en not_active Expired - Fee Related
- 1985-04-17 ES ES542336A patent/ES542336A0/es active Granted
- 1985-04-19 JP JP60082731A patent/JPH0648363B2/ja not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
GR850904B (ja) | 1985-11-25 |
PT80153A (de) | 1985-04-01 |
ES8603089A1 (es) | 1985-12-16 |
ATE47921T1 (de) | 1989-11-15 |
DE3415215A1 (de) | 1985-10-24 |
US4663236A (en) | 1987-05-05 |
EP0159493A2 (de) | 1985-10-30 |
DE3574188D1 (en) | 1989-12-14 |
PT80153B (de) | 1986-10-23 |
ES542336A0 (es) | 1985-12-16 |
JPH0648363B2 (ja) | 1994-06-22 |
DE3415215C2 (ja) | 1988-07-14 |
JPS6111740A (ja) | 1986-01-20 |
EP0159493A3 (en) | 1988-06-01 |
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