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, comprising a layer support which is at least partially transparent to visible radiation, a light-sensitive layer on one side and a filter layer absorbing in the boring UV and short-wave, visible spectral range on the other side of the layer support and a Process for its production.
• the materials should therefore be such that the light-absorbing materials 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 is based on a recording material containing diazo compounds, in particular a microfilm, a layer support which is at least partially transparent to visible radiation, a light-sensitive layer on the one hand and a filter layer absorbing in the long-wave UV and short-wave, visible spectral range on the other hand of the layer support, which is characterized in that the filter layer is a polymer which is insoluble in acetone or an isopropanol / water mixture or is made less soluble by crosslinking in these solvents and at least one dye which is compatible with the constituents of the polymer and has an absorption in the range between 360 nm and 500 nm contains.
• 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 further tension shocks in the same work step.
• 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 to be 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-b13phenol A, isophthalic acid or neopentyl glycol.
• modified terephthalic acid ester as insoluble polymer, for example a terephthalic acid copolyester with a content of bisoxyethyl-b13phenol A, isophthalic acid or neopentyl glycol.
• polymers which are made less soluble by crosslinking in aggressive solvents those with suitable functional groups can be used.
• 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 less soluble by crosslinking are also intended to include poly
• 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 360 and 500 nm and the greatest possible light stability, it must be soluble in the coating solvent and sufficiently heat-stable. It must neither emerge or sublime from the filter layer as a result of exudation before nor after the copying process, nor can other film materials be transferred to the surface 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 layer support can furthermore 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 process for the preparation of the recording material containing diazo compounds, in particular a microfilm, by applying a filter layer absorbing in the boring UV and in the short-wave, visible spectral range to one side and by applying a solution and drying a light-sensitive layer to the other side layer carrier which is at least partially permeable to visible radiation, which is characterized in that first the filter layer is composed of a polymer which is insoluble in acetone or an isopropanol / water mixture or a polymer which is less soluble by crosslinking in these solvents and at least one, with the constituents of the polymer compatible dye with an absorption in the range between 360 nm and 500 nm and hardens and then provides the support on the other side with 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 which is less soluble 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 of great 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 and which, for reasons of mechanical strength, are less suitable for the production of film carrier materials. Because the filter layer is very thin is, measured on the total film thickness, the dye can also be incorporated more economically than when coloring the support. Furthermore, temperature / time ratios for the thin melt layer that are compatible with the decomposability of the dyes can be selected.
• the coating of the support with a colored lacquer requires an intermediate adhesive layer, as described for example in DE-B-1 694 534. 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 filter layer is additionally ratzif by the crosslinked structure is less K.
• the dry layer weight is generally 5 to 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, ensure that the filter layer is sufficiently hardened by heating, exposure to UV light or the like.
• a preferred embodiment for dyes with lower thermal stability is their use in a hardened filter layer which, if required, can also be advantageously printed with colored title strips. While in the case of uncured filter layers, printing can be difficult due to the partial or complete dissolution of the lacquer layer by the solvent of the printing ink, the printing of hardened filter layers without process engineering difficulties is much easier. The selection of a suitable base printing system is easier and less critical than with unhardened lacquer layers.
• the yellow layers of paint are each dried for 3 minutes at 100 ° C. and then 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, as a 20% solution in acetone / ethanol (72: 8), has a viscosity of 53-91 dPas.
• photosensitive yellow film samples A and B 1 are obtained.
• the dry layer weight of the photosensitive layer is 6 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 »diazomicrofilm 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 background image orange-yellow.
• the second generation of diazo films A 2 and B 2 cannot be produced from the diazo film copies A 1 and B 1 obtained, 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 is 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, except that the same weight amount 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 10-12dPas 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 20 parts by weight of water is used as the 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 E 1 in terms of solvent resistance and generation ability.
• 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 non-crosslinked 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 the solvent-treated diazo film copy E 1 is worse than that of D 1.
• the production of the second generation of diazo film E 2 is less 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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Publications (2)

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• 1979
  • 1979-10-29 DE DE19792943632 patent/DE2943632A1/de not_active Withdrawn
• 1980
  • 1980-10-07 CA CA000361686A patent/CA1148404A/en 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/de 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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