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
  • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
  • G03C1/7954—Polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
• • 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
  • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
  • G03C1/93—Macromolecular substances therefor
• • 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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
  • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2483/02—Polysilicates

Definitions

• a photosensitive drafting film comprising a polyester film with a subbing layer of a vinylidene chloride/methyl acrylate/itaconic acid copolymer having coated thereon a layer of methyl methacrylate polymer with a Tukon film hardness above KHN and containing a matting agent. This product is then coated with a wash-off gelatino-silver halide photographic emulsion which is bound to the hard matte-containing layer by the polymerization product of a vinyl monomer or mixtures of vinyl monomers polymerized in an aqueous gelatin solution.
• This invention relates to flexible film coated with a matted layer for drafting purposes. More particularly the invention relates to such drafting films having an extremely hard surface. Still more particularly, the invention is concerned with such a drafting film which may be overcoated, in turn, with an adhesive subbing layer and/or a photographic emulsion layer. The invention also relates to a process for making such films.
• Much of the prior art in the manufacture of drafting films describes processes which require that the layers for the drawing surfaces be coated on hydrophobic films from an organic solvent solution. This method of manufacture requires elaborate coating equipment including expensive solvent recovery systems.
• the prior art also describes processes that are used to prepare matted layers from polymer latices. However, the layers described are soft unless they contain cross-linking agents because the processes required the use of polymers known to be soft. These polymers normally form continuous films at low temperatures.
• a drafting film comprising a flexible, biaxially-oriented, highly polymeric 1 polyester film substantially composed of the polyesterification product of at least one dicarboxylic acid and at least one dihydric alcohol having on at least one surface, in order, .(1) a thin layer (e.g., 0.5-4 mg./dm.
• methyl methacrylate polymer layer is further characterized by the absence of any migratory gelatin cross-linking agent (.i.e., gelatin hardeners).
• the above drafting film is over-coated with a substratum comprised of a reaction product prepared by polymerizing, in the presence of a gelatin, at least one vinyl monomer selected from the class consisting of vinylidene chloride, methyl acrylate and ethyl acrylate.
• At least one surfactant preferably an amphoteric material such as N-coco- ,B-aminopropionate, c'etyl or other long chain betaine, etc. is normally present in the subbing formulation. This insures uniform coverage of the matte surface while the sub is drying.
• Light-sensitive, gelatino-silver halide emulsion layers may be applied over such a substratum with excellent anchorage.
• a gelatino-silver halide emulsion layer containing a tanning developing agent is applied over the above substratum in order to provide a wash-off film in which'the gelatin is unhardened prior to imagewise exposure and development steps.
• the invention also includes the process of preparing a drafting film on the above polymeric polyester film support, subcoated with the above thin layer of a vinylidene chloride copolymer, by (l) coating said support with an aqueous dispersion of a methyl methacrylate polymer having a Tukon film hardness greater than 10 KHN comprising heat-removable coalescent material and uniformly dispersed, finely-divided discrete particles of a water-insoluble, translucence-producing, solid matting agent having an average particle size from 0.1 micron to 10 microns, said aqueous dispersion being characterized by the absence of any migratory gelatin cross-linking agent, (2) drying the film at 60-125 C.
• glycols such as propylene glycol, ethylene glycol and diethylene glycol
• esters such as n-butoxy acetic acid, ethyl ester and n-butoxy-(2-ethoxy)acetic acid, ethyl ester, because they are less toxic, they yield mechanically stable (e.g., to pumping and ultrasonic deaeration) and pH stable dispersions and they act as anti-crazing or antimud-cracking agents.
• a dimensionally stable vinylidene chloride/methyl acrylate/itaconic acid copolymer coated polyethylene terephthalate film base as described in Example IV of Alles US. Patent 2,779,684 is coated to a dry thickness of about 0.4 mil with a continuous stratum comprised of a methyl methacrylate polymer having a Tukon film hardness greater than 10 KHN and about 0.2 to 1.0 part by weight per one part of polymer of matte (e.g., silicon dioxide of 1-10 micron particle size), to 0.05 part by weight of a thickener per 1 part of polymer and less than 0.01 part by weight dispersants per 1 part of polymer.
• matte e.g., silicon dioxide of 1-10 micron particle size
• other surfactants can be added to act as wetting agents.
• the polymer may approach 100% of the layer.
• the methyl methacrylate polymer is used in the form of a latex (aqueous dispersion) and the aqueous coating dispersion contains, in addition to the above ingredients, a certain amount of additional water and a coalescent, e.g., ethylene glycol, n-butoxy-(Z-ethoxy) acetic acid, ethyl ester, equal to more than about 40% by weight of the methyl/ methacrylate polymer.
• a coalescent e.g., ethylene glycol, n-butoxy-(Z-ethoxy) acetic acid, ethyl ester
• a hydrosol of silicon dioxide with the SiO equal to 3 to about- 25% by weight of the methyl methacrylate polymer to improve anchorage of subsequently overcoated layers to the matte layer.
• the SiO of the hydrosol is of much smaller particle size than that of the matte.
• the coating dispersion is advantageously treated mechanically, e.g., passed through a sand mill to disperse the pigments before or after adding the polymer latex, depending on the nature of the latex. After coating, the Water and the coalescent are partially removed by drying at a temperature above 60 C. to coalesce the polymer particles into a continuous water-resistant film and curing at 110 to 150 C. to remove the residual water and coalescent and thereby obtain maximum layer hardness.
• the drying temperature required is inversely dependent on the amount of coalescent added to the coating medium.
• the uniformity (lack of crazing or mud-cracking) of rapidly dried layers is assured by either using ethylene, propylene, or diethylene glycol as the coalescents or by adding a copolymer of methyl vinyl ether and maleic anhy-dride to the system.
• Use of these glycols as coalescents also preserves the mechanical stability of the system.
• the drying and coalescing steps may be carried out very quickly; for example, adequate drying may be achieved in only 20 seconds, and adequate curing in one minute.
• the element may be used as a drafting film or may have additional coatings applied so as to become a lightsensitive photographic element.
• a subbing layer prepared by polymerizing a vinyl monomer, e.g., vinylidene chloride and/ or methyl or ethyl acrylate, in an aqueous gelatin solution, wherein there is a ratio of from 1 to 9 parts of gelatin to 1 part of total monomer on a dry weight basis or to use these polymers as a binder for the emulsion which is directly coated on the film.
• the reaction product is diluted considerably with water, and one or more surfactants is added, e.g., sodium N-coco-B-aminopropionate without which the subbing layer pulls away from the edges of the film or flows into rivulets before drying. It may also be desirable to add a hydrosol of silicon dioxide to the subbing composition to improve anchorage of the subsequently applied emulsion layer.
• one or more surfactants e.g., sodium N-coco-B-aminopropionate without which the subbing layer pulls away from the edges of the film or flows into rivulets before drying. It may also be desirable to add a hydrosol of silicon dioxide to the subbing composition to improve anchorage of the subsequently applied emulsion layer.
• a conventional gelatino-silver halide photographic emulsion layer a particularly useful emulsion being one of the wash-off variety, e.g., a gelatinosilver halide emulsion containing a tanning developing agent such as catechol, pyrogallol or hydroquinone, a hardener restrainer such as hydroxylamine, an antihalation dye, and various other additives such as stabilizers and conventional wetting agents.
• Excellent adhesion of the emulsion to the drafting layer may also be achieved with or without the use of a substratum by using the vinyl polymer-gelatin component as the emulsion binder.
• the subbing layer described above provides excellent anchorage to conventional gelatino-silver halide emulsions and the invention is by no means restricted to the use of the particularly-discussed wash-off type of emulsion. Certain combinations of normal gelatin with the gelatin reaction product may also provide the desired adhesion. Also, other surfactants may be used in place of those mentioned above. Although ordinarily not required, the adhesion provided by these formulations may be even improved further by heat treating the subbed acrylic layer at -150 C.
• This treatment may be accomplished advantageously by applying the sub to the drafting layer at the time between the drying and curing steps of the drafted layer.
• drafting films include doubly-coated drafting films. It would be preferred to use the same type of vinylidene chloride copolymer subbing layer on both sides of the polyester film support but the drafting layers themselves need not be identical. Thus, it is sometimes advantageous to provide one side of the drafting film with a very hard surface as described above while the opposite side may be considerably softer.
• matting agent is optional in preparing the drafting layer. For example, silicon dioxide is one of the most widely used matting agents in drafting films and gives excellent results when it is desired to draw on the film with a mechanical pencil. On the other hand, silicon dioxide is sufiiciently abrasive that it may cause damage to inking pens.
• the film may have a drafting layer on both sides of the support and either or both sides of the drafting surface will be overcoated.
• Material Parts by weight Distilled water 18 Silica hydrosol 30% by weight SiO an aqueous colloidal sol of alumina modified silica particles approximately 15 millimicrons diameter in size 15 Ethylene glycol 109 Titanium dioxide pigment (0.1 to microns particle size) 4.2 Silicon dioxide pigment (l to microns particle size) 55.8 Thickener, a copolymer of ethyl acrylate,
• composition was prepared for coating by first mixing the water, silica hydrosol, ethylene glycol, pigments, thickener and dispersant. The mixture was then passed through a sand mill to disperse the pigments and then admixed with the surfactant and the polymer latex. A small amount of NH OH was added to adjust the pH to 8.59.5 to stabilize the system.
• the matte-polymer mixture was coated on a dimensionally stable vinylidene chloride/methyl acrylate/itaconic acid copolymer coated polyethylene terephthalate film base as described in Example IV of Alles US. Patent 2,779,684, dried for 24 seconds at 1l0120 C., and cured for 3.5 minutes at 130-135" C. to remove the residual ethylene glycol coalescent.
• the coating mixture was stable to mechanical stresses encountered in pumping, milling, and ultrasonic deaeration.
• a continuous matted polymer film free of crazing also called alligatoring or mud-cracking
• the dry thickness of the layer was between .3 and .6 mil.
• the product was useful as a drafting film. It accepted drafting inks, and drafting pencil up to 9H without cutting, withstood wet erasure and did not discolor or flake upon prolonged exposure to ultraviolet light.
• Part of the matted polymer layer was then coated with a subbing composition comprised of the materials listed below and dried.
• the composition coated uniformly and remained uniformly spread over the surface of the matte layer throughout the drying period.
• the subbed layer was then coated with a gelatinosilver chloride emulsion containing catechol as a tanning developing agent, hydroxyl amine hydrochloride as a gelatin hardening restrainer, to prevent hardening of the gelatin by exterior agents, an antihalation dye, stabilizer, wetting agents and various other additives as conventionally used in photographic emulsions.
• the element was given an imagewise exposure to a carbon arc lamp and then developed for 1 minute at 68 F. in an aqueous solu- 6 tion comprising 5% by'weight sodium carbonate.
• the emulsion was tanned (hardened) in the image area; the non-image emulsion remained unhardened and was washed off in warm water leaving behind a relief image on the matted support.
• Such a process is useful in making reproductions of drawings, maps, etc., wherein the reproduction can be easily revised by drawing on the matte surface and/ or Wet erasing the relief image.
• Excellent adhesion was obtained between all layers before and after exposure and photographic processing of the element. Neither the matted acrylic polymer layer nor the substratum contributed to the hardness of the emulsion layer.
• Subcomposition 1 The gelatin-polymer component was prepared by copolymerizing 8 parts of vlnylidene chloride and 8 parts of methyl acrylate in the presence of 84 parts of gelatin. The polymerization was carried out in aqueous medium in the presence of a redox catalyst system, e.g., a mixture of ammonium persulfate and sodium metabisulfite, and an anionic surfactant, e.g., sodium lauryl sulfate.
• a redox catalyst system e.g., a mixture of ammonium persulfate and sodium metabisulfite
• an anionic surfactant e.g., sodium lauryl sulfate.
• Coco represents a mixture of the high molecular weight hydrocarbon radicals corresponding to those present in the esters in coconut oil including, in order of decreasing conciantlratiou, lauryl, myristyl, palmityl, caprylyl, capryl and o ey EXAMPLE II
• Part of the matted polymer layer prepared in Example I was coated with a subbing composition comprised of the materials listed below and dried.
• composition coated uniformly and remained uniformly spread over the surface of the matte layer throughout the drying period-
• the subbed layer was then coated with a litho-type gelatino-silver bromochloride emulsion comprising 30 mole percent silver bromide and 70 mole percent silver chloride, an orthochromatic optical sensitizing dye, formaldehyde hardener, gelatin and a polyethylacrylate resin latex equal to 33% of the gelatin on a dry weight basis.
• Excellent adhesion was obtained between all layers before and after developing and fixing of the exposed and unexposed emulsion.
• Subcomposition Material Parts by weight Water 14150 Gelatin-polymer component (dry wt.) Sodium salt of N-coco-fl-aminopropionate 3.6
• Example I Isooctyl phenoxy polyethoxy ethanol (containing 9-10 ethoxy groups) l5 Silica hydrosol (30% SiO as described in Example I 25 1
• the gelatimpolymer component was prepared by copolymerizmg 13 parts of vinylidene chloride and 7 parts of methyl acrylate 1n the presence of 75 parts of gelatin. Polymerization was carried out under conditions similar to those described for preparing the gelatinpolymer component of Example I except that the catalyst was hydrogen peroxide.
• EXAMPLE III 7 Subcomposition Material Parts by weight Water 14150 Gelatin-polymer component 1 (dry Wt.) 100 Sodium salt of N-coco-fl-aminopropionate 3.6 Isooctyl phenoxy polyethoxy ethanol (containing about 30 ethoxy groups) Silica hydrosol (30% SiO as described in Example I The gelatin-polymer component was prepared by polymerizing 35 parts of ethyl acrylate in the presence of 60 parts of gelatin. Polymerization was carried out similarly to that described in Example I except that bis-azoisobutyronitrile was used as the catalyst.
• EXAMPLE IV A matted acrylic composition comprising the following ingredients was prepared: Material: Parts by weight Silica hydrosol Si having silica particles approximately 15 millimicrons diameter 1 Specific viscosity is determined on a solution of 1 gram of the copolymer in 100 mls. of methylethyl ketone at 29 C.
• the composition was prepared for coating by first mixing the silica hydrosol, ethylene glycol and pigments, then passing the mixture through a sand mill to disperse the pigments. The dispersion was then admixed with an emulsified mixture of the coalescents, emulsifier and the latex. The thickener and a small amount of NaOH was added to stabilize the system.
• the matte-acrylic polymer mixture was coated on both sides of the polyester film support of Example I, dried for 30 seconds at 93 C. and cured for 2 minutes at 135 C. to remove the coalescents.
• a continuous matted polymer film free of cr-azing and having a dry thickness between 0.4 and 0.5 mils was obtained.
• the product was useful as a drafting film. It accepted drafting inks and at least 6H pencil without cutting, withstood wet erasure and the matte layer did not discolor or flake after prolonged exposure to ultraviolet light.
• a matted acrylic composition comprised of the following ingredients was prepared: Material: Parts by weight Silica hydrosol (30% SiO having a particle size approximately 7 millimicrons diameter in size 42 Ethylene glycol 17 Copolymer (1:1) of methylvinylether and maleic anhydride, specific viscosity range of 1.52.0, anticrazing agent and thickener 1.8 n-Butoxy acetic acid, ethyl ester, coalescent 10
• the composition was prepared for coating by first mixing the water, silica hydrosol, pigments, thickener and n-butoxy acetic acid, ethyl ester and then passing the mixture through a sand mill to disperse the pigments.
• the dispersion was then admixed with an emulsified mixture of the emulsifier, n-butoxy-(Z-ethoxy)acetic acid, ethyl ester and the latex. A small amount of NH OH was added to stabilize the system.
• the matte-acrylic polymer mixture was coated on a polyester film support similar to that of Example I, dried at C. and cured for 3.5 minutes at C. to remove the coalescent.
• a continuous matted polymer film free of crazing and having a dry thickness between .30 and .46 mil was obtained.
• the product was useful as a drafting film. It accepted drafting inks and 6H pencil without cutting, withstood wet erasure and the matte layer did not discolor or flake after prolonged exposure to ultraviolet light.
• Example V was repeated except that between the drying and curing steps a sub was applied to the matted polymer layers and dried at 68 C.
• the sub was composed of:
• Gelatin-polymer components 1 (dry wt.) 100 Sodium salt of N-coco-fi-aminopropionate 2 Isooctyl phenoxy polyethoxy ethanol (containing about 40 ethoxy groups) 15 Silica hydrosol (30% SiO as in Example IV 26
• the gelatimpolymer component was prepared by copolymerizing 18 parts of vinylidene chloride and 7 parts of methyl acrylate in the presence of 75 parts of gelatin. Polymerization was carried out similarly to that described in Example I except that amornnium persulfate alone was used as the catalyst.
• composition coated uniformly and remained uniformly spread over the surface of the matte layer throughout the drying period.
• the subbed layer was then coated with a gelatinosilver halide emulsion. Excellent adhesion was obtained between all layers before and after developing and fixing of the exposed and unexposed emulsion. Neither the mated acrylic polymer layer nor the substratum contributed to the hardness of the emulsion layer.
• EXAMPLE VII The composition was prepared for coating by first mixing the water and pigments and thickener, then passing the mixture through a sand mill to disperse the pigments. The dispersion was then admixed with an emulsified mixture of water, the emulsifier and the coalescent and finally the latex. A small amount of NH OH was added to adjust the pH to 8.59.5 to stabilize the system.
• the matte-acrylic polymer mixture was coated on a polyester film support the same as in Example I, dried for 30 seconds at 79 C. and cured for 2 minutes at 134 C. to remove the coalescent.
• a continuous matted polymer film having a dry thickness between .30 and .36 mil was obtained.
• the prodnot was useful as a drafting film. It accepted drafting inks and 6H pencil without cutting, withstood wet erasure and the matte layer did not discolor or flake after prolonged exposure to ultraviolet light.
• Part of the matted polymer was then coated with a subbing composition comprised of the materials listed below and dried.
• the composition coated uniformly and remained uniformly spread over the surface of the matte layer throughout the drying period.
• the subbed layer was then coated with a gelatinosilver halide emulsion. Good adhesion was obtained between all layers before and after developing and fixing of the exposed and unexposed emulsion. Neither the matted acrylic polymer layer nor the substratum contributed to the hardness of the emulsion layer.
• Subcomposition Material Parts by weight Water 14000 Gelatin-polymer component 1 (dry wt.) 100 Sodium salt of N-coco-fl-aminopropionate 20 Silica hydrosol (30% SiO as in Example I 100 1
• the gelatin-polymer component was prepared by copolymerizing 18 parts of vinylidene chloride and 7 parts of methyl acrylate in the presence of 75 parts of gelatin. The polymerization process was similar to that described in Example I.
• Example I 263 Isooctyl phenoxy polyethoxy ethanol, emulsifier, as in Example I 1 n-Butoxy-(2-ethoxy) acetic acid, ethyl ester 40 Methyl methacrylate polymer latex (38% polymer) as in Example I 263
• the composition was prepared for coating by first mixing the water, silica hydrosol, pigments, thickener and n-butoxy acetic acid, ethyl ester and then passing the mixture through a sand mill to disperse the pigments.
• the dispersion was then admixed with an emulsified mixture of the emulsifier, n-butoxy-(Z-ethoxy)acetic acid, ethyl ester and the latex. A small amount of NaOH was added to stabilize the system.
• the matte-acrylic molymer mixture was coated on a polyester film support, the same as that of Example I, dried for 30 seconds at 93 C. and cured for 2 minutes at 130 C. to remove the coalescent.
• a continuous matted polymer film having a dry thickness between .35 and .60 mil was obtained.
• the product was useful as a drafting film. It accepted drafting inks and 6H pencil without cutting, withstood wet erasure and the matte layer did not discolor or flake after prolonged exposure to ultraviolet light.
• Part of the matted polymer layer was then coated with a subbing composition comprised of the materials listed below and dried.
• the composition coated uniformly and remained uniformly spread over the surface of the matte layer throughout the drying period.
• the subbed layer was then coated with a gelatinosilver halide emulsion. Excellent adhesion was obtained between all layers before and ater developing and fixing of the exposed and unexposed emulsion. Neither the matted acrylic polymer layer nor the substratum contributed to the harness of the emulsion layer.
• Subco mposition Material Parts by weight Water 14150 Gelatin-polymer component (dry wt.) Sodium salt of N-coco-B-aminopropionate 3.3
• Example I Isooctyl phenoxy polyethoxy ethanol as in Example I 15 Silica hydrosol (30% SiO as in Example I 25 1
• the gelatin-polymer component was prepared by copolymerizing 18 par-ts of vinylidene chloride and 7 parts of methyl acrylate in the presence of 75 parts of gelatin. The polymerization process was similar to that described in Example I.
• Example I Parts by weight Methyl methacrylate polymer latex 38% polymer) as in Example I 263 Silica hydrosol (30% SiO as in Example IV l5 Silicon dioxide pigment as in Example I 55.8 Titanium dioxide pigment as in Example I 4.2 Thickener as in Example I (solids) 0.65
• Propylene glycol, coalescent 75 The composition was prepared for coating by first mixing the latex, silica hydrosol, pigments and thickener. A small amount of NaOH was added to adjust the pH to 9.1 to stabilize the system. The mixture was then passed through a sand mill to disperse the pigments. The propylene glycol coalescent was then added and the resulting mixture was coated on a polyester film support similar to that of Example I, dried for 30 seconds at C. and cured for 2 minutes at C. to remove the coalescent. The coating mixture was stable to mechanical stresses encountered in pumping and milling. A continuous matted polymer film free of crazing was obtained. The dry thickness of the layer was between .3 and .5 mil. It accepted drafting ink and drafting pencil up to 9H without cutting, withstood wet erasure and did not discolor or flake after exposure to ultraviolet light.
• Part of the matted polymer layer was then coated with a subbing composition comprised of the materials listed below and dried.
• the composition coated uniformly and remained uniformly spread over the surface of the matte layer throughout the drying period.
• the subbed layer was then coated with a gelatino-silver halide emulsion. Excellent adhesion was obtained between all layers before and after developing and fixing of the exposed and unexposed emulsion. Neither the matted acrylic polymer layer nor the substratum contributed to the hardness of the emulsion layer.
• Subcomposition Material Parts by weight Water 14150 Gelatin-polymer component (dry wt.) 100 Sodium salt of N-cocmfi-aminopropionate 6.8
• Example I Isooctyl phenoxy polyethoxy ethanol as in Example I 15 Silica hydrosol (30% SiO as in Example I 25 1
• the gelatin-polymer component was prepared by Copolymerizing 18 parts of vinylidene chloride and 7 parts of methyl acrylate in the presence of 75 parts of gelatin. The polymerization process was similar to that described in Example I.
• composition was prepared for coating by first mixing the water, starch and pigment and then ball milling to effect dispersion. The dispersion was then admixed with the latex coalescent and thickener. A small amount of NaOH was added to stabilize the system.
• the matte-polymer mixture was coated on a polyester film support, the same as Example I, dried for 30 seconds at 110 C. and cured for 2 minutes at 135 C. to remove the coalescent.
• the coating mixture was stable to mechanical stresses encountered in pumping and milling.
• a continuous matted polymer film free of crazin-g was obtained.
• the dry thickness of the layer was between .2 and .4 mil.
• the product was useful as a drafting film. It caused less wear on drafting pens than layers containing a higher percentage of SiO pigment. It accepted drafting ink and drafting pencils up to 9H without cutting, withstood wet erasure, and did not flake upon exposure to ultraviolet light.
• Part of the matted polymer layer was then coated with a subbing composition comprised of the materials listed below and dried.
• the composition coated uniformly and remained uniformly spread over the surface of the matte layer throughout the drying period.
• the subbed layer was then coated with a gelatino-silyer halide emulsion. Good adhesion was obtained between all layers before and after developing and fixing f the exposed and unexposed emulsion. Neither the matted acrylic polymer layer nor the substratum contributed to the hardness of the emulsion layer.
• Subcomposition Material Parts by weight Water 14150 Gelatin-polymer component 1 (dry wt.) 10 0 Sodium salt of N-coco-B-aminopropionate 6. 8 Isooctyl phenoxy polyethoxy ethanol as in Example I I.
• Silica hydrosol (30% SiO as in Example I 1
• the gelatin-polymer component was prepared by copolyrnerizing 18 parts of vinylidene chloride and 7 parts of methyl acrylate in the presence of 75 parts of gelatin. The polymerization process was similar to that described in Example L.
• composition was prepared for coating by first mixing the water, starch and. pigment and then ball milling to effect dispersion. The dispersion was then admixed with the latex coalescent, and thickener. A small amount of NaOI-I was added to stabilize the system.
• the matte-polymer mixture was then coated on a polyester film support the same as Example I, dried for 12 seconds at C. and cured for 2 minutes at 135 C. to remove the coalescent.
• the coating mixture was stable to mechanical stresses encountered in pumping, milling, etc.
• a continuous matted polymer film free of crazing was obtained.
• the dry thickness of the layer was between .3 and .5 mil.
• the product was useful as a drafting film. It caused less wear on drafting pens than layers containing a higher percentage of SiO pigment. It accepted drafting ink and drafting pencils up to 9H without cutting, withstood wet erasure and did not flake upon exposure to ultraviolet light.
• the composition was prepared for coating by first mixing the water, silica hydrosol, ethylene glycol, pigments, thickener and dispersant. The mixture was then passed through a sand mill to disperse the pigments and then admixed With the polymer latex. A small amount of NH OH was added to adjust the pH to 8.59.5 to stabilize the system.
• the matte-polymer mixture was coated on a polyester film support the same as in Example 1, dried for 30 seconds at 110-120 C. and cured for 2 minutes at C. to remove the ethylene glycol coalescent.
• the coating mixture was stable to mechanical stresses encountered in pumping.
• a continuous matted polymer film free of crazing also called alligatoring or mud cracking
• the dry thickness of the layer ranged from .2 to .6 mil.
• the product was useful as a drafting film. It accepted drafting inks, and drafting pencil up to 9H Without cutting, withstood wet erasure and did not discolor or flake upon prolonged exposure to ultraviolet light.
• the composition was prepared for coating by first mixing the water and pigments and thickener, then passing the mixture through a sand mill to disperse the pigments. The dispersion was then admixed with an emulsified mixture of water, the emulsifier and the coalescent and finally adding the latex. A small amount of NaOH was added to adjust the pH to 8.59.5 to stabilize the system.
• the matte-acrylic polymer mixture was coated on a polyester film support the same as Example I, dried for 30 seconds at 80 C. and cured for 2 minutes at 125 C. to remove the coalescent.
• a continuous matted polymer film having a dry thickness ranging from .2 to .36 mil was obtained.
• the product 13 was useful as a drafting film. It accepted drafting inks and 6H pencil without cutting, withstood wet erasure and the matte layer did not discolor orflake after prolonged exposure to ultraviolet light.
• Part of the mated acrylic layer was then coated with a wash-off type emulsion of the same composition as that used in Example I except that the gelatin binder was replaced by a gelatin-polymer component prepared by copolymerizing, 12 parts of vinylidene chloride and 4 parts of methyl acrylate in the presence of 84 parts of gelatin.
• the polymerization was carried out in an aqueous system in the presenceof a redox catalyst system, e.g., a mixture of ammonium persulfate and sodium metabisulfite, an ionic surfactant, e.g., sodium lauryl sulfate.
• Excellent adhesion was obtained between all layers before and after photographic processing of the exposed and unexposed emulsions.
• Neither thejmatted polymer layer nor the emulsion itself contained any material that contributed to the hardness of the emulsion layer prior to exposure and tanning development.
• a good wash-off relief image was obtained-according to the process
• EXAMPLE XIV Part of the matted acrylic polymer layer prepared in Example XIII was coated with an emulsion of the same composition as that used in Example I except that the gelatin binder was replaced by a gelatin-polymer component prepared by copolymerizi-ng 18 parts of vinylidene chloride and 7 parts of methyl acrylate in the presence of 75 parts of gelatin. Polymerization was carried out under conditions similar to those described for preparing the gelatin-polymer component of Example I, except that the catalyst was hydrogen peroxide. Excellent adhesion was obtained between all layers before and after photographic processing of the exposed and unexposed emulsion. Neither the matted polymer layer or the emulsion itself contained any material that contributed to the hardness of the emulsion layer prior to exposure and tanning development. A good wash-off relief image was obtained according to the process of Example I.
• EXAMPLE XV -Part of the matted acrylic polymer layer prepared in Example XIII was coated with an emulsion of the same composition as that used in Example I except that the gelatinbinder was replaced by a gelatin-polymer component prepared by copolymerizing 8 parts of vinylidene chloride and 8 parts of methyl acrylate in the presence of 84 parts of gelatin.
• the polymerization was carried out in aqueous medium in the presence of a redox catalyst system, e.g., a mixtureof ammonium persulfate and sodium me'tabisulfite, and an anionic surfactant e.g., sodium lauryl sulfate.
• a redox catalyst system e.g., a mixtureof ammonium persulfate and sodium me'tabisulfite
• an anionic surfactant e.g., sodium lauryl sulfate.
• Example XVI Part of the matted acrylic polymer layer prepared in Example XIII was coated with an emulsion of the same composition as that used in Example I except that the gelatin binderwasreplaced by a gelatin-polymer composure and tanning development. A good wash-off relief image was obtained according to the process of Example I.
• EXAMPLE XVII Part of the matted acrylic polymer layer prepared in Example XIII was coated with a subbing composition comprised of the materials listed below and dried at approximately C. The subbed layer was then coated with a wash-off type emulsion like that used in Example I. Good adhesion was obtained between all layers before and after photographic processing of the exposed and unexposed emulsion. Neither the polymer layer nor the substratum contributed to the hardness of the emulsion layer.
• Subcomposition Material Parts by weight Water 14140 Gelatin-polymer component 1 100 Silica hydrosol (30% SiO 28 Isooctyl phenoxy polyethoxy ethanol (containing 9-l0 ethoxy groups) 16 Dispersant, (optional) ammonium salt of a carboxylated polyelectrolyte (Amberlac).
• the gelatin polymer component was prepared by copolymerizing 18 parts of vinylidene chloride and 7 parts of methyl acrylate in the presence of 75 parts of gelatin. Polymerization was carried out under conditions similar to those described for preparing the gelatin-polymer component of Example I except that the catalyst was hydrogen peroxide.
• Methyl methacrylate polymer latex as in Example I 263
• the composition was prepared by first mixing the water, silica hydrosol, pigments, dispersant and propylene glycol. The mixture was then passed through a sand mill to disperse the pigments and then admixed with the copolymer and the latex. A small amount of NH OH was added to adjust the pH to 8.5-9.5 to stabilize the system.
• the matte polymer mixture was coated on the polyester film support of Example I, dried and cured for 5 minutes at C. to remove the water and coalescent, propylene glycol.
• a continuous matted polymer film free of crazing was obtained.
• the product was useful as a drafting film. It accepted ink and 7H drafting pencil without cutting, withstood wet erasure and did not discolor or flake after exposure to ultraviolet light.
• Hardness of polymer films is best determined by means of a Tukon Microhardness Tester as described in the Resin Review, vol. -6, pp. 12-14, December 1962, published by Rohm and Haas Company. A load of 25 grams is used in making the reported hardness measurements since, as described in the above reference the Knoop Hardness Numbers, KHN, vary with the load.
• samples of a matted acrylic layer were exposed to a G.E., 100 watt, S4, mercury vapor sun lamp for 24 hours at a distance of 3 /2 inches.
• This lamp emits 500600 micro watts per square centimeter between 2600-3700 Angstroms.
• the matting agents are present in amounts of about 0.3 to 0.8 part by weight of matte per 1 part of methyl methacrylate polymer.
• Titanium dioxide can act in more than one capacity, e.g., as a matting agent and/ or opacifying pigment and/ or coloring agent.
• Other materials which may be used in one or more of these capacities are, for example, silica, ground glass, chalk, talc, diatomaceous earth, magnesium carbonate, starch, barytes, clay, Monastral Fast Blue (C.I. Pigment Blue) and other pigments and dyes.
• the average particle size of these materials can vary from about 0.1 to 10 microns but preferably have an average particle size of 1 to 10 microns.
• the copolymer coated polyester film used to make the drafting film has a thickness from 3 to 10 mils and is dimensionally stable
• copolymer-coated polyester films of the foregoing type are described in Alles U.S. Patent 2,779,684 and in the patents referred to therein.
• the preferred films have a polyethylene terephthalate base and a vinylidene chloride copolymer layer wherein the addition copolymer contains at least 35 by Weight of vinylidene chloride.
• the dispersions can be supplied from a gravity-fed or pressure-fed hopper or they can be applied by dip-coating techniques or by means of bead coating or applicator rolls.
• the thickness of the coating can be controlled by means of doctor blades or by means of air streams, e.g., air-doctor knives.
• the oriented polyester film base has a vinylidene chloride/ acrylic ester/ itaconic acid copolymer layer container such components in amounts by weight of 35 to 96.0%, 3.5 to 64.5% and 0.5 to 2.5% on one or both surfaces of the oriented polyester base and the drafting layer is coated over the copolymer.
• the copolymer layer is exceedingly thin, about 0.5-4 mg./dm. and is usually applied to the polyester base prior to orienting it and rendering it dimensionally stable.
• This vinylidene chloride copolymer coated base preferably a polyethylene terephthalate film, can be made after the manner described in Alles et a1.
• U.S. Patent 2,627,088 and Alles US. Patent 2,779,684 will exhibit shrinking of not more than 0.2% in both longitudinal and lateral directions when not under tension and heated to a temperature of 120 C. for a period of 5 minutes.
• the various vinyl esters (including acrylonitrile) which can be used in making the vinylidene chloride copolymers are those disclosed in the Alles et al. patent.
• a suitable copolymer may be composed of 75-90% vinylidene chloride, 4 to methyl acrylate and 1 to 5% itaconic acid.
• the support need not necessarily be 4-mi1 polyethylene terephthalate film but may be composed of other di mensionally stable polyester films such as are disclosed in Carothers U.S. Patent 2,071,250, andbearing a thin layer of an adherent film-forming essentially hydrophobic copolymer as disclosed in Alles et al. U.S. 2,627,088 and Alles U.S. 2,779,684 and the patents referred to in the specifications of these patents.
• Suitable supports are the polyethylene terephthalate/isophthalates of British Patent 766,290 and Canadian 562,672 and those obtainable by condensing terephthalic acid or dimethyl terephthalate with propylene glycol, diethylene glycol, tetramethylene glycol or cyclohexane 1,4 dimethanol (hexahydro-p-xylene alcohol).
• Other high molecular weight, oriented polyesters such as polycarbonates are also useful.
• U.S. Patent 2,698,235 discloses, as aparticular useful subbing layer for the films disclosed above,- a very thin layer of a tri-component copolymer of vinylidene chloride, an acrylic ester, and itaconic acid. coated under controlled conditions.
• Other subbing compositions suitable for use on polyester films are those disclosed tive humidity.
• the matting coat is flexible while having an excellent drafting surface, is resistant to abrasion and does not become brittle or flake ofl during tough han1-- dling.
• An acrylic polymer such as used as a binding material in the examples of this application is particularly advantageous because, in addition to its great hardness, it has little or no tendency to discolor or deteriorate upon exposure to ultraviolet radiation or after prolonged aging.
• a drafting layer comprising such a binding material is extremely resistant to flaking.
• a particularly unique advantage of this invention is the absence of migratory chemicals in the drafting layer which can cause dimensional change in the drafting layer with age or which would be capable of causing the hardening or cross-linking of gelatin in subsequently applied subbing layersor light-sensitive layers. It is because of this absence of cross-linking agents that it is possible to overcoat the drafting film with a wash-off gelatino-silver halide emulsion which can be preferentially hardened under the action of light and subsequent development. Still further advantages will be apparent from the above description of the invention.
• a dimensionally stable drafting film comprising (1) a biaxially-oriented polyester film of at least one dicarboxylic acid and at least one dihydric alcohol having on at least one surface, in order (2) an essentially hydrophobic vinylidene chloride copolymer containing atleast 35 by weight of vinylidene chloride and (3) a hydrophobic film layer of methyl methacrylate polymer havinga Tukon film hardness above 10 KHN, said film containing up to 1 part by weight of matting agents per 1 part of said acrylate polymerand a silica hydrosol having about 3 to 25% of silicon dioxide based upon the weight of said acrylate polymer.
• a dimensionally stable drafting film comprising (1) a biaxially-oriented polyester film of at least one dicarboxylic acid and at least one dihydric alcohol havingon at least one surface in order (2) an essentially hydrophobic vinylidene chloride copolymer containing at least 35% by weight of vinylidene chloride and (3) a hydrophobic film layer of methyl methacrylate polymer having a Tukon film hardness above 10 KHN, said film containing a silica hydrosol having about 3 to 25% of silicon dioxide based upon the weight of said acrylate polymer and up to 1 part by weight of matting agents per 1 part 'of said acrylate polymer, the matting agentshavingv a particle size of about 0.1 to 10 microns.
• a dimensionally stable drafting film comprising (1) a biaxially-oriented polyester film of a dicarboxylic acid and a dihydric alcohol having on at least one surface, in order (2) an essentially hydrophobic vinylidene chloride copolymer containing at least 35% by weight of vinylidene chloride (3) a hydrophobic film layer of methyl methacrylate polymer having a Tukon film hardness above KHN, said film containing up to 1 part by weight of matting agents per 1 part of said acrylate polymer and (4) a gelatino-silver halide photographic emulsion, said emulsion being bound to said acrylate polymer layer by the polymerization product of a member selected from the group consisting of a single vinyl monomer and mixtures of vinyl monomers polymerized in an aqueous gelatin solution.
• a dimensionally stable drafting film comprising (1) a biaxially-oriented polyester film of a dicarboxylic acid and a dihydric alcohol having on at least one surface, in order (2) an essentially hydrophobic vinylidene chloride copolymer containing at least 35% by weight of vinylidene chloride (3) a hydrophobic film layer of methyl methacrylate polymer having a Tukon film hardness above 10 KHN, said film containing up to 1 part by weight of matting agents per 1 part of said acrylate polymer and (4) a wash-off gelatino-silver halide photographic emulsion containing a tanning developing agent, said emulsion being bound to said acrylate polymer layer by the polymerization product of a monomer selected from the group consisting of methyl acrylate, ethyl acrylate, vinylidene chloride and mixtures of said monomers polymerized in an aqueous solution of gelatin, said polymerization product being free from gelatin hardeners.
• a process for preparing a drafting film having a biaxially-oriented polymeric polyester base covered with a thin layer of a vinylidene chloride copolymer which comprises (1) coating said layer with an aqueous dispersion containing a methyl methacrylate polymer having a Tukon hardness of greater than 10 KHN, a matting agent and a heat-removable coalescent material and (2) heating the film above 60 C. to remove said coalescent.
• a process for preparing a drafting film having a biaxially-oriented polymeric polyester base covered with a thin layer of a vinylidene chloride copolymer which comprises (1) coating said layer with an aqueous dispersion containing -a methyl methacrylate polymer having a Tukon hardness of greater than 10 KHN, a matting agent and a heat-removable coalescent material (2) heating the film above 60 C.
• a subbing layer upon said acrylate polymer, comprising of a surfactant and the polymerization product of a member selected from the group consisting of vinyl monomers and mixtures of said monomers polymerized in an aqueous gelatin solution and (4) covering said subbing layer with a photographic gelatino-silver halide emulsion.
• a process for preparing a drafting film having a biaxially-oriented polymeric polyester base covered with a thin layer of a vinylidene chloride copolymer which comprises (1) coating said layer with an aqueous dispersion containing a methyl methacrylate polymer having a Tukon hardness of greater than 10 KHN, a matting agent and a heat-removable coalescent material (2) heating the film above 60 C. to remove said coalescent, and (3) applying a layer having a gelatino-silver halide photographic emulsion, and the polymerization product of a member selected from the group consisting of vinyl monomers and mixtures of said monomers polymerized in an aqueous gelatin solution.
• thermoplastic material is ethylene glycol, propylene glycol or diethylene glycol.
• a dimensionally stable drafting film comprising (1) a biaxially-oriented polyester film of a dicarboxylic acid and a dihydric alcohol having on at least one surface, in order (2) an essentially hydrophobic vinylidene chloride copolymer containing at least 35% by Weight of vinylidene chloride (3) a hydrophobic film layer of methyl methacrylate polymer having a Tukon film hardness above 10 KHN, said film containing up to 1 part by weight of matting agents per 1 part of said acrylate polymer and (4) a wash-off silver-halide photographic emulsion having as its binder the polymerization product of a member selected from the group consisting of a single vinyl monomer and mixtures of vinyl monomers polymerized in an aqueous gelatin solution, said emulsion additionally containing a tanning developing agent.
• a dimensionally stable drafting film comprising (1) a biaxially-oriented polyester film of a dicarboxylic acid and a dihydric alcohol having on at least one surface, in order (2) an essentially hydrophobic vinylidene chloride copolymer containing at east 35% by weight of vinylidene chloride (3) a hydrophobic film layer of methyl methacrylate polymer having a Tukon film hardness above 10 KHN, said film containing up to 1 part by weight of matting agents per 1 part of said acrylate polymer (4) a substratum comprised of a reaction product prepared by polymerizing a monomer selected from the group consisting of methyl acrylate, ethyl acrylate, vinylidene chloride and mixtures thereof and an aqueous solution of gelatin, and (5) a wash-off gelatino-silver halide photographic emulsion containing a tanning developing agent.

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• 1964
  • 1964-01-24 US US339849A patent/US3353958A/en not_active Expired - Lifetime
• 1965
  • 1965-01-22 BE BE658724A patent/BE658724A/xx unknown
  • 1965-01-22 FR FR2978A patent/FR1422579A/fr not_active Expired
• 1967
  • 1967-09-25 GB GB2785/65A patent/GB1121859A/en not_active Expired

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