Classifications

• • 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
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
  • G03F7/346—Imagewise removal by selective transfer, e.g. peeling away using photosensitive materials other than non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
  • B41M5/035—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B44—DECORATIVE ARTS
  • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
  • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
  • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
  • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
  • B44C1/17—Dry transfer
  • B44C1/1704—Decalcomanias provided with a particular decorative layer, e.g. specially adapted to allow the formation of a metallic or dyestuff layer on a substrate unsuitable for direct deposition
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B44—DECORATIVE ARTS
  • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
  • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
  • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
  • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
  • B44C1/17—Dry transfer
  • B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
  • B44C1/1716—Decalcomanias provided with a particular decorative layer, e.g. specially adapted to allow the formation of a metallic or dyestuff layer on a substrate unsuitable for direct deposition
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/003—Transfer printing
  • D06P5/004—Transfer printing using subliming dyes
• • 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
  • G03C1/66—Compositions containing chromates as photosensitive substances
• • 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]
  • Y10T428/31678—Of metal
  • Y10T428/31703—Next to cellulosic

Definitions

• the present invention relates to temporary supports and their use in the printing and dyeing of synthetic materials.
• the quality of the transfer that is to say the amount of dyestuff which passes effectively from the ice temporary support to the permanent support, depends largely on the nature of the temporary support.
• the present invention has, among other advantages, that of providing a very simple means of improving this quality.
• the latter have a layer in a single color or a design printed with one or more dyestuffs and/or optical bluing agents, all of which sublime or vaporize at between and 220 C. at atmospheric pressure.
• they differ from the known supports in that they also have at least one layer of material which is impermeable to the vapor of the dyestuffs or the optical bluing agents used, either in the form of an under-lacquer which separates the said print from the base of the support, or in the form of an over-lacquer which partially covers the colored layer.
• These new temporary supports thus comprise, on at least one of the two faces of a base sheet, tape or strip, which is inert and stable to heat, for example of paper optionally backed with an aluminium foil, in any order, at least two thin layers of organic materials (which completely or partially cover this face), the one comprising volatile or sublimable dyestuffs (and/or an optical bluing agent), which form the design to be transferred, and the other consisting of an albuminoid material or of another protein material which is stable to heat and soluble or able to be dispersed in water, or even in a mixture of water and organic solvents, for example alcohol.
• Gelatines from other sources can also be used, such as glue stock, fish glue, light-colored gelatines, or albumin, ovalbumin, and at times even casein or zein (the latter can be applied from anhydrous solutions) or their mixtures.
• the present invention also relates to a process for the preparation of temporary supports defined above.
• This process consists of coating, by any suitable means, at least one of the faces of a sheet or a tape which is inert and stable to heat, for example a strip of paper or cellophane, successively with a layer, with no breaks in it, of a substance which is impermeable to the vapors of dyestuffs and optical bluing agents, for example a layer of albuminoid material, and with a colored layer.
• colored layer there is to be understood in this context a layer containing, either in a uniform manner or in the form of a design, one or more dyestuffs or optical bluing agents which volatilize or sublime at between 160 and 220, preferably at between 180 and 210, at atmospheric pressure.
• this preparation process is used to apply a pre-lacquer (or under-lacquer), it results in the formation of a uniform varnish which is impermeable to the vapors of the dyestuffs and bluing agents used, located between the base of the support and these dyestuffs or bluing agents; it thus allows the dyeing yield to be substantially increased, any unevenness in the printing due to a possible lack of uniformity in the base of the temporary support to be avoided, which is a valuable advantage in the case of a uniform print and also permits cheaper papers to be used, and their quality, and thus their origin, to vary during manufacture, and certain disadvantages due to storage to be eliminated.
• the temporary support is stored in rolls, the back and the front face are in contact; it is thus possible for staining of the back to occur by dyestuff located on the front face, and, during the transfer, this blotch of dyestuff passes through the temporary support (if the latter does not comprise a backing aluminium foil), and is printed on the final support, thus causing a defect.
• the coating of the support before the design or the uniform layer of dyestuflf or optical bluing agent is printed on it can be carried out on the usual equipment. It is possible, for example, to carry out a pass on a separate varnisher, and thereafter to carry out the printing or the dyeing proper on a printing machine with ordinary cylinders. It is possible also to use only one printing machine equipped with an additional cylinder located in front of the engraved cylinders which print the design to be transferred, or in front of the inking cylinder which prints the uniform layer.
• albuminoid materials used are not soluble in anhydrous or nearly anhydrous solvents; thus it is necessary to use an aqueous solution and to apply it independently of the colored or whitening layer.
• the albuminoid material is applied to the paper in solution or dispersion preferably in water to which an organic solvent, for example, an alcohol, has optionally been added, at the rate of 0.5 to 6 and preferably 1 to 3.5 g. per square metre, yielding a coating fully impervious to the dyestuffs vapors.
• an organic solvent for example, an alcohol
• An intermediate drying carried out after the coating with the albuminoid material and before the printing or the dyeing, prevents the pre-lacquer from interfering with or having an influence on the subsequent transfer. This drying is facilitated in the case of a coating with a colloidal aqueous ink containing an organic solvent, for example an alcohol.
• the only modification to the equipment compared with the known process is thus the introduction of an additional coating cylinder or a varnisher, which covers the temporary support with a thin albuminoid layer, 0.5 to 50 microns (preferably 1 to 10 microns) thick.
• the dyeing or the pattern to be transferred is then printed according to the usual technique, which will be described later, directly on this layer.
• a considerable time interval can elapse between the two treatments.
• the paper, coated with the desired layer of albuminoid material for example, paper coated with gelatine, can even be stored, and the preparation proper of the temporary supports which are the subject of the present invention need not be carried out until much later by printing with the sublimable dyestuff or dyestuffs or optical bluing agent or agents.
• the process which is the subject of the present invention can also be used to apply an over-lacquer, because the albuminoid varnish forms a barrier to the vapors of the dyestuffs and to those of the optical bluing agents used, which is perfectly effective up to at least 220 C., the maximum temperature at which the transfer is carried out.
• this varnish is no longer applied over the entire surface of the support, which would have no sense, but instead is printed according to a given pattern, thus producing resists, in a simple, effective and economic way.
• the usual equipment can be used, by simply placing the corresponding coating cylinder after the inking cylinder or cylinders which print the colored layer on the paper, and by providing a drying device. It is also possible to use one of the numerous mechanical printing machines known such as the so-called air-bed machine, a machine used in photogravure, in rotogravure and the like. As in the case of the pre-lacquer, it is preferable to work on a machine independent of the equipment used for the printing or the dyeing to be transferred, taking account of the use of aqueous solutions to apply the resists of albuminoid materials. These solutions have the same composition as those which have been defined in the case of the pre-lacquer.
• resists can be printed on supports which already carry a pre-lacquer of albuminoid materials under the design or the uniform layer to be transferred.
• this process also offers the possibility of overprinting a colored pattern on the pattern of the overlacquer of albuminoid materials, which permits colored resists or patterns in color to be obtained on a white resist, thus making more flexible the production of the design to be transferred.
• this method of operating allows the sharpness of the printing of colored patterns on a light resist to be improved.
• the print, the resist and then the overprint can be applied at different times.
• a pattern already printed on the temporary support can subsequently be modified or completed, which is a valuable advantage for articles which must be adapted to the demands of fashion, and the production of Which must adapt rapidly to a demand which is often unforeseeable.
• a coating produced with gelatine containing 2 to 50% of potassium dichromate can be exposed to a light, the radiations of which are especially between 355 and 425 millimicrons, behind a plate on which the pattern to be reserved is produced as a transparency.
• the potassium dichromate can be combined with a ferric oxalate, or can be replaced by ammonium, quinoline or pyridine dichromate.
• the operation is preferably carried out in the presence of an organic acid or its salt, for example, potassium citrate.
• the drying is stopped preferably at a moisture content of about 14%, which removes the risk of having a brittle layer or a layer of reduced sensitivity or a layer which is less able to be stored.
• the patterns can equally well be a piece of textile as a film or a sheet of synthetic material such as a polyamide, a polyacrylonitrile or a polyester, which is preferably linear.
• the printing, on the temporary support, of a uniform layer or of a design using dyestuffs or optical bluing agents which sublime or vaporize at between 160 and 220 C. is carried out according to the known process, described, for example, in French Pats. 1,585,119, 1,574,- 528 and 1,223,330, preferably by application of anhydrous or almost anhydrous inks, that is to say, solutions, varnishes, emulsions or dispersions, completely or almost completely free of water, which contain, dissolved or very finely dispersed, a dispersion dyestuff which passes into the vapor state at between 160 and 220 C. at atmospheric pressure, an anhydrous or almost anhydrous organic solvent and a hinder or thickener which is stable to heat.
• anhydrous or almost anhydrous inks that is to say, solutions, varnishes, emulsions or dispersions, completely or almost completely free of water, which contain, dissolved or very finely dispersed, a dispersion dyes
• dyestuffs preferably dispersion dyestuffs, which pass into the vapor state at between 160 and 220 at atmospheric pressure; these dyestuffs can be, for example, sublimable azo or anthraquinone dyestuffs or nitroarylamines, styryl dyestuifs, derivatives of quinophthalone, perinones and the like.
• almost anhydrous organic solvents are used in order to prepare the inks intended to form the colored layer of the new supports according to the invention.
• almost anhydrous organic solvents there are understood in this context solvents or mixtures of solvents which are miscible or immiscible with water, and the boiling point of which is less than 120 and preferably less than 105 C. at atmospheric pressure. These solvents must contain less than 15% of water.
• halogenated or non-halogenated hydrocarbons of the aliphatic or aromatic series such as toluene, cyclohexane, petroleum ether, alcohols of low molecular weight such as methanol and ethyl, propyl and isopropyl alcohols, esters of aliphatic acids such as ethyl acetate, ketones such as methyl ethyl ketone and the like.
• the thickening agents or binders which are stable to heat are available commercially and are widely used for the direct printing of textiles, but it is expedient to choose them from amongst those which have a low content of solid substances. They must be capable of drying to give a non-sticky film which holds the dyestuif or dyestuffs used. Inert binders, which have relatively little or no tendency to decompose, and which only hold the sublimable substances used onto the paper without modifying the substances are preferably used.
• binders which are particularly suitable, esters (acetates or acetobutyrates, for example) will be mentioned, and above all celluloseethers soluble in the organic solvents present in the inks used to form the colored layer such as hydroxypropyl-, propyl-, benzyland ethoxy-ethyl-celluloses as well as their mixtures, and more especially ethyl-cellulose and the mixtures of cellulose ethers containing ethylor hydroxypropyl-cellulose.
• the supports obtained allow synthetic materials to be dyed or printed.
• This dyeing or printing which is also the subject of the present invention consists of placing the temporary support, printed as has just been described, at least locally in contact with the material to be dyed, which is preferably brought, during this placing in contact, to a temperature of the same order of magnitude as that at which the dyestuffs pass into the vapor state, in order that the latter do not simply condense on the surface.
• the dyeing or printing is thus reduced to pass over a hot plate or over a hot calender or on any other apparatus which allows the temporary support and the material to be dyed to be placed in contact, and to be brought to the required temperature for the necessary length of time.
• the present process is suitable for dyeing synthetic materials such as polyamides (polymers of e-caprolactam or of hexamethylene-diamine adipate), polyesters, especially linear polyesters, such as polyethylene terephthalates, polyacrylonitriles and the like.
• the materials to be dyed can be in the most varied forms, for example in the form of sheets or films.
• EXAMPLE 1 Printing of a multi-colored design on one face of a sheet of an ethylene terephthalate polymer: a strip of paper is coated with a thin layer of bone gelatin (about 2 grams per m?) using one or morecylinders and a solution of 10 parts of gelatine in parts of a mixture of 5 parts of ethyl alcohol and 100 parts of water, and is dried.
• Yellow, red and blue inks are prepared by dispersing 6 parts of each of the dyestuffs OH on co NH ⁇ C/ Q -0 oo with 6 parts of ethyl-cellulose in 88 parts of isopropyl or ethyl alcohol.
• the face of the paper coated with bone gelatine is printed, by photogravure printing, with these inks and several inking cylinders, in such a way as to obtain a multicolored design, and is dried.
• a film or a web of ethylene terephthalate polymer is placed on the sheet of paper which has been printed in this way, and the whole is passed over a metal plate, heated electrically to 200 C.
• a second, unheated, plate ensures even contact.
• the time of contact whilst hot is 1 minute.
• a faithful reproduction of the design, of which the lines remain sharp, is thus obtained on the polymer.
• the dyeing yield is thus considerably greater than that of the process in which a paper which does not carry gelatin is used.
• Example 2 The procedure of Example 1 is followed, but on a single printing machine, the first cylinder of which coats the paper over its entire width with a solution of 12 parts of bone gelatine in 100 parts of water. After an intermediate drying, the paper passes over the other cylinders of the machine which print a multi-colored design using the yellow, red and blue inks indicated in Example 1.
• the temporary support thus obtained also allows the printing of polyester or polyamide surfaces with a remarkable sharpness.
• ovalbumin can also be used.
• EXAMPLE 3 A green ink is prepared by dispersing, in 88 parts of isopropyl'alcohol, 7 parts of a preparation containing 50% of ethylcellulose and 50% of a blue dyestuff consisting of a mixture of dyestuffs of the formula HO O NH:
• an orange ink is prepared by dispersing respectively 6.5 and 6 parts of preparations containing 50% of ethylcellulose and 50% of the yellow dyestutf or the red dyestufi mentioned in Example 1 (respectively, 3-hydroxy-quinophthalone and 1-hydroxy-4-amino-3-phenoxy-anthraquinone), in parts of isopropyl alcohol.
• a uniform green print is produced on a temporary paper support by printing with a cylinder engraved with a helix usually employed in this technique.
• the support is dried.
• a pattern for example in the form of a flower, is then printed on this uniform green print, with a preparation containing Parts Bone gelatine 5 Potassium dichromate 0.2 Water Ethyl alcohol 5
• the support is dried, and then a circle is printed with another inking cylinder in the centre of the flowers with orange ink.
• the support is dried.
• the temporary support thus obtained allows a print of remarkable sharpness to be produced, by dry transfer in the vapor phase, on polyester, polyacrylonitrile or polyamide white surfaces, yielding white flowers with an orange heart on a green ground.
• EXAMPLE 4 A uniform red print is produced on a paper support ,using the following ink:
• the support prepared in this way allows a satisfactory dry transfer in the vapor phase onto any polyester, polyamide or polyacrylonitrile surface.
• a strip, sheet or tape of flexible, heat-stable material having one of the faces thereof completely or partially covered in any order with at least two thin layers of organic materials said layers being (a) a colored layer consisting essentially of (1) at least one dyestutr", at least one optical bluing agent or mixtures thereof which pass into the vapor state at between 160 and 220 C.
• a binder which is stable in the indicated temperature range and is soluble in the organic solvents present in the inks used to form the colored layer
• a layer consisting of an albuminoid material which is stable to heat in the indicated temperature range, and which is capable of being sensitized to light when it is placed over a colored layer and which is preferably non-hardened when it is between the surface of the said flexible heat-stable material and a colored layer.
• a support according to claim 11 wherein the colored layer or layers comprise at least one anthraquinone dyestufl'.
• n is an integer equal to 3 or 4.
• a support according to claim 1 wherein the colored layer or layers comprise ethyl or hydroxypropyl cellulose as a binder.

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• Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Textile Engineering (AREA)
• Printing Methods (AREA)
• Coloring (AREA)

Applications Claiming Priority (2)

Publications (1)

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ID=25688392

Family Applications (1)

Country Status (12)

Cited By (9)

Families Citing this family (9)

• 1972
  • 1972-03-06 CA CA136,272A patent/CA999192A/en not_active Expired
  • 1972-03-06 IL IL3890772A patent/IL38907A/xx unknown
  • 1972-03-07 FR FR7207903A patent/FR2129481A5/fr not_active Expired
  • 1972-03-07 US US00232507A patent/US3813218A/en not_active Expired - Lifetime
  • 1972-03-07 DE DE2210956A patent/DE2210956C3/de not_active Expired
  • 1972-03-08 IT IT4883272A patent/IT952157B/it active
  • 1972-03-09 ES ES400575A patent/ES400575A1/es not_active Expired
  • 1972-03-09 BE BE780427A patent/BE780427A/xx unknown
  • 1972-03-09 GB GB1102972A patent/GB1391012A/en not_active Expired
  • 1972-03-09 NL NL7203158A patent/NL7203158A/xx unknown
  • 1972-03-10 JP JP2462572A patent/JPS5338622B1/ja active Pending
  • 1972-03-10 AR AR24088772A patent/AR192916A1/es active

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