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
  • G03C1/52—Compositions containing diazo compounds as photosensitive substances
• • 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
  • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/08—Photoprinting; Processes and means for preventing photoprinting
• • 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
  • Y10S430/132—Anti-ultraviolet fading

Definitions

• the invention relates to a recording material containing diazo compounds, in particular a microfilm, consisting of a layer support which is at least partially transparent to visible radiation, a light-sensitive layer and a filter layer which absorbs in the long-wave UV and short-wave, visible spectral range, and a process for its production.
• the light-absorbing Arrange filter layer between layer support and light-sensitive layer.
• light-absorbing layers in this arrangement are only suitable if the curl of the film is not increased.
• care must be taken to prevent the light-absorbing material from diffusing into the light-sensitive layer.
• the materials should therefore be such that the light-absorbing substances cannot be removed. For example, they should no longer be separate from the layer support, or they should only be removable by partially destroying the layer support and reducing the information contained therein.
• the solution to this problem starts from a recording material containing diazo compounds, in particular a microfilm, from one for visible radiation at least partially permeable layer support, a light-sensitive layer and a filter layer arranged on the rear absorbing in the long-wave UV and short-wave, visible spectral range, which is characterized in that the filter layer is an insoluble or crosslinked polymer and at least one dye compatible with the constituents of the polymer with an absorption in the range of about 360 nm to about 500 nm.
• the filter layer preferably contains a yellow to orange dye.
• the filter layer offers the possibility of economically influencing the properties of the film by incorporating additional additives in the same operation.
• Suitable layer supports which are at least partially transparent to visible radiation are, for example, cellulose esters or polymers, mixed or copolymers which are processed from the melt into transparent films, such as polystyrene or polycarbonate. Films made from polyethylene terephthalate or from its copolymers or copolymers, which are selected essentially on the basis of their optical and mechanical properties, have proven particularly advantageous.
• the light-sensitive layers used are those based on diazo compounds.
• Photosensitive layers which contain at least one diazonium compound and at least one coupling component as the photosensitive substance are preferably used.
• the filter layer absorbing in the long-wave UV and short-wave visible spectral range contains modified terephthalic acid ester as insoluble polymer, for example a terephthalic acid copolyester with a content of bisoxyethyl-bisphenol A, isophthalic acid or neopentyl glycol.
• Polymers which are rendered insoluble by crosslinking can be used with suitable functional groups.
• cellulose esters can be used together with a curing agent such as urea or melamine-formaldehyde resins and a curing accelerator such as p-toluenesulfonic acid.
• the polymers made insoluble by crosslinking should also include polyamides, polyisocyanates, formaldehyde resins and suitable prepolymers.
• the dye compatible with the components of the polymer is colored yellow to orange.
• it In addition to the required spectral properties, such as absorption in the range between approximately 360 and 500 nm and the greatest possible light stability, it must be soluble in the coating solvent and sufficiently heat-stable. It must not come out of the filter layer before or after the copying process exiting or sublimating as a result of sweating can still be transferred to the surface of other film materials as a result of clapping.
• chemical compounds from the suitable dye and the polymer used are advantageous.
• the dye In the case of application by coextrusion or from the melt, the dye must also, in addition to the required spectral properties at the usual high temperatures, be well compatible with the polymer and so heat-stable that it does not change its spectral properties under extreme stress.
• Suitable dyes are, for example, mono- and bis-azo dyes such as Sudangelb GGN (C.I. Solvent Yellow 56), provided they meet the required solubility criteria, such as solubility in alcohols, ketones and / or ethers, or the required compatibility criteria.
• solubility criteria such as solubility in alcohols, ketones and / or ethers, or the required compatibility criteria.
• a layer applied to the back of the film may also contain conventional additives such as finely divided slip agents or commercially available antistatic agents.
• the filter layer according to the invention thus fulfills further important application requirements without additional work steps.
• the invention also relates to a method for producing the recording material containing diazo compounds, in particular a microfilm, from a layer support which is at least partially transparent to visible radiation, a light-sensitive layer and a filter layer which absorbs in the long-wave UV and short-wave, visible spectral range, which is characterized in that the filter layer of an insoluble or to be rendered insoluble by crosslinking and a dye compatible with the constituents of the polymer with an absorption in the range between about 360 nm and about 500 nm is applied to a surface of the support and then on the opposite surface of the Layer supports the photosensitive layer.
• the filter layer is preferably applied using an adhesion-promoting intermediate layer with the aid of a lacquer solution which contains the polymer to be made insoluble by crosslinking together with the dye, and is then dried and cured.
• the recording material according to the invention can be produced by coextrusion of the support and filter layer or by melt coating on the stretched or undrawn support.
• the layer support material and the colored filter layer material are simultaneously coextruded and brought together from a multi-slot die. This process is therefore very large This is an advantage because it usually does not require an additional intermediate layer to improve adhesion.
• the application after the melt coating is preferably carried out on the stretched substrate.
• melt containing dye can be prepared separately, for example also via a color masterbatch. It is also possible to use polymers which are more easily meltable or more miscible with the dye . which are less suitable for the production of film carrier materials for reasons of mechanical strength. Since the filter layer is only very thin, measured in terms of the total film thickness, the dye can also be incorporated more economically than when the support is colored. Furthermore, temperature / time ratios for the thin melt layer which are compatible with the decomposability of the dyes can be selected.
• the coating of the substrate with a colored lacquer requires an adhesive intermediate layer, as described for example in DE-AS 16 94 534. After the coating solution has been applied, it is dried and, as a result of a heat treatment, the filter layer is inseparably connected to the correspondingly subbed surface of the support.
• the cross-linked structure also makes the filter layer less sensitive to scratches.
• the dry layer weight is generally about 5 to about 20 g / m 2 .
• the light-absorbing filter layers as far as they are processed as lacquer, can be applied by printing, casting or other known methods. After the solvent has evaporated, heating, exposure to UV light or the like to ensure that the filter layer is sufficiently hardened.
• a preferred embodiment for dyes with lower thermal stability is their use in a hardened filter layer which, if required, can advantageously also be printed with colored title strips. While printing on non-hardened filter layers can be difficult due to partial or complete dissolution of the lacquer layer by the solvent of the printing ink, the printing of hardened filter layers is possible much more easily without procedural difficulties.
• the selection of a suitable base printing system is easier and less critical than with unhardened lacquer layers.
• a 125 / um thick, clear polyethylene terephthalate film which is provided on both sides with an adhesive layer, a 10 cm wide die coater of 0.15 mm gap width by means of one side with yellow colored clear coats coated.
• the yellow lacquer layers are dried for 3 minutes at 100 ° C and then post-cured for up to 5 minutes by heating. During the drying and curing phase, the coated film samples lie on an aluminum plate as a flat surface.
• the dry layer weights are about 7 g / m 2 .
• a 7% solution of cellulose acetopropionate in a solvent mixture of acetone, methanol, n-butanol and ethylene glycol monomethyl ether serves as the basecoat.
• the crosslinkable, yellow-colored lacquer is obtained from the non-crosslinkable lacquer by adding so much hexamethoxymethylmelamine that a ratio of cellulose ester to melamine resin of 9: 1 is obtained.
• P-Toluenesulfonic acid serves as a curing accelerator.
• the yellow film pattern B is produced with this crosslinkable, yellow lacquer.
• the cellulose acetopropionate used here contains 3.6% acetyl groups, 44.7% propionyl groups and 1.8% hydroxyl groups and has a viscosity of 53-91 poise as a 20% solution in acetone / ethanol (72: 8).
• the photosensitive yellow film samples A 1 and B 1 are obtained.
• the dry layer weight of the photosensitive layer is 6-7 g / m 2 .
• the light-sensitive layer of the yellow film patterns A1 and B1 is exposed in contact under a transparent silver image template and then the latent copy of the diazo film is developed in a humid ammonia atmosphere. Exposure and development takes place in a commercially available "diazo microfilm duplicating device". High-contrast two-color copies of the original are obtained, with a blue dye image on one side and an orange-yellow background on the other side of the film. When viewed in transmitted light, the image parts of the copies appear black, the image background orange-yellow. Of the Diazo film copies A 1 and B 1 obtained, the 2nd generation of diazo film A 2 and B 2 cannot be produced, since it is no longer possible to differentiate between image and non-image areas. The diazo film copies A 1 and B 1 cannot be duplicated.
• the non-crosslinked yellow filter layer of the diazo film copy A 1 can be removed in a few seconds with a cotton ball soaked in acetone, for example. Those parts of the image of the diazo film copy A 1 which are opposite the detached filter layer on the other side of the film can be duplicated again. The production of the second generation diazo film A 2 has become possible by removing the yellow filter layer.
• the comparative experiment shows that a hardened yellow filter layer considerably increases the security of a non-duplicable microfilm, even if an aggressive solvent such as acetone is used for detachment.
• the procedure for producing the diazo film copy C 1 is as described in Example 1, but the same amount by weight of a butylated urea-formaldehyde resin is used as the cross-linking component for the cellulose acetopropionate.
• the urea resin used is a commercial product with an acid number of less than 3.
• a 65% solution of this resin in isobutanol has a viscosity of 1000-1200 cP at 20 ° C.
• the solvent resistance of the crosslinked yellow filter layer of the diazo film copy C 1 is again compared with the non-crosslinked yellow filter layer of the diazo film copy A 1 of Example 1.
• a mixture of 80 parts by weight of isopropanol and 2 0 parts by weight of water is used as solvent in this experiment.
• a duplication attempt is then carried out.
• Example 1 the superiority of the crosslinked yellow filter layer of the diazo film copy C 1 over the uncrosslinked of the diazo film copy A 1 is evident both in the solvent treatment and in the subsequent duplication attempt. While A 1 shows the known results, the diazo film copy C 1 can only be duplicated with significant loss of information. The production of the second generation of diazo film C 2 is considerably more difficult here.
• Example 2 The procedure is as in Example 1, except that dimethyl yellow (C.I. Solvent Yellow 2) is used as the dye for the yellow filter layer. To produce the yellow colored absorbent filter layer, 8.75 g of dimethyl yellow are dissolved in 700 g of basecoat.
• dimethyl yellow C.I. Solvent Yellow 2
• the non-crosslinked yellow filter layer of the diazo film copy D 1 is compared with the crosslinked of the diazo film copy Er 1 with regard to solvent resistance and generation capability.
• a mixture of 80 parts by weight of isopropanol and 20 parts by weight of water is used as the solvent, as described in Example 2.
• the uncrosslinked yellow filter layer of the diazo film copy D 1 is easier to remove at the same time than the crosslinked one of the diazo film copy E 1.
• the duplicability of those treated with solvent Dia film copy E 1 is worse than D 1.
• the production of the second generation dia film E 2 is significantly more difficult than D 2.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Testing Or Measuring Of Semiconductors Or The Like (AREA)
• Luminescent Compositions (AREA)
• Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

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• 1979
  • 1979-10-29 DE DE19792943632 patent/DE2943632A1/de not_active Withdrawn
• 1980
  • 1980-10-07 CA CA000361686A patent/CA1148404A/fr not_active Expired
  • 1980-10-22 AT AT80106437T patent/ATE5673T1/de not_active IP Right Cessation
  • 1980-10-22 DE DE8080106437T patent/DE3065953D1/de not_active Expired
  • 1980-10-22 EP EP80106437A patent/EP0028003B1/fr not_active Expired
  • 1980-10-23 PT PT71960A patent/PT71960B/pt unknown
  • 1980-10-27 US US06/201,040 patent/US4317875A/en not_active Expired - Lifetime
  • 1980-10-27 ZA ZA00806588A patent/ZA806588B/xx unknown
  • 1980-10-27 FI FI803357A patent/FI67964C/fi not_active IP Right Cessation
  • 1980-10-27 BR BR8006914A patent/BR8006914A/pt unknown
  • 1980-10-28 ES ES496357A patent/ES8207358A1/es not_active Expired
  • 1980-10-28 DK DK456080A patent/DK456080A/da not_active Application Discontinuation
  • 1980-10-29 JP JP15088780A patent/JPS5674243A/ja active Granted

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