EP0094228B1 - Feuilles et recouvrements décoratifs contenant du chlorure de polyvinyle et des colorants cationiques - Google Patents

Feuilles et recouvrements décoratifs contenant du chlorure de polyvinyle et des colorants cationiques Download PDF

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Publication number
EP0094228B1
EP0094228B1 EP83302587A EP83302587A EP0094228B1 EP 0094228 B1 EP0094228 B1 EP 0094228B1 EP 83302587 A EP83302587 A EP 83302587A EP 83302587 A EP83302587 A EP 83302587A EP 0094228 B1 EP0094228 B1 EP 0094228B1
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EP
European Patent Office
Prior art keywords
substrate
sheet
set forth
dyestuff
image
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EP83302587A
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German (de)
English (en)
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EP0094228A3 (en
EP0094228A2 (fr
Inventor
Ronald Shaeffer Lenox
Moses Sparks, Jr.
Anne Louise Schwartz
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Armstrong World Industries Inc
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Armstrong World Industries Inc
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Priority to AT83302587T priority Critical patent/ATE54965T1/de
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Publication of EP0094228A3 publication Critical patent/EP0094228A3/en
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Classifications

    • 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
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/26—Printing on other surfaces than ordinary paper
    • B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
    • 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
    • B41M5/0355—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 characterised by the macromolecular coating or impregnation used to obtain dye receptive properties
    • 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
    • B41M5/0356—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 characterised by the inks used for printing the pattern on the temporary support or additives therefor, e.g. dyes, transferable compounds, binders or transfer promoting additives
    • 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
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
    • D06N7/0005—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface
    • D06N7/0028—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by colour effects, e.g. craquelé, reducing gloss
    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
    • B41M5/395—Macromolecular additives, e.g. binders
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the present invention relates to decorative sheets and coverings and more particularly to decorative sheets and coverings comprising polyvinyl chloride and cationic dyestuffs.
  • Substrates comprising polyvinyl chloride have come into wide use as decorative coverings and particularly as decorative floor coverings. In order for such materials to be aesthetically acceptable, they must be provided with a colored pattern or design.
  • Two general types of colorants have traditionally been available to provide such patterns; namely, dyes and pigments.
  • the Encyclopedia of PVC defined dyes to be colorants that are soluble in vinyl formulations, whereas pigments are colorants that are insoluble in vinyl formulations.
  • Dyes have primarily comprised disperse and solvent dyes; however, such dyes have been shown to have definite drawbacks which preclude their use in polyvinyl chloride systems.
  • Pigments are conventionally applied by means of printing inks, or by stencil deposition of pigmented particles. Nevertheless, pigmented products are not entirely satisfactory because, for example, the color selection is limited and through-color images cannot be obtained. Accordingly, industrial producers of products containing polyvinyl chloride have long sought ways to improve the color characteristics of such products.
  • flooring structures prepared in this fashion was the distinctiveness of detail which allegedly remained during the service life of the floor covering. It has been found, however, that when vinyl floor structures comprising a sublimable disperse dye are subjected to heat, migration of color and loss of pattern definition can be accelerated.
  • one objective of the present invention is to provide processes for preparing substrates comprising polyvinyl chloride whereby said substrates have a through-color image which will not fade or bleed with time or when exposed to high temperatures.
  • Yet another objective of the present invention is to provide decorative sheets and coverings having through-color images, said sheets and coverings being usable as flooring materials, wall coverings, and the like.
  • Still yet another objective of the present invention is to provide transfer sheets and ink compositions comprising cationic dyestuffs which will be useful to prepare decorative surfaces comprising polyvinyl chloride.
  • the present invention concerns our discovery that decorative sheets and coverings comprising polyvinyl chloride and having substantially non-migratable through-color images may be prepared using cationic dyestuffs.
  • These coverings may be prepared by providing a variety of polyvinyl chloride-containing dyestuffs and a suitable binder, and then treating these materials such that the cationic dyestuffs migrate into the substrate. Through-color images are obtained which are substantially non- migrating, even under severe conditions.
  • the present invention comprises a process for preparing a decorative sheet comprising polyvinyl chloride and a substantially non-migratable image, said process comprising the steps of
  • an image composition with a sheet substrate comprising polyvinyl chloride, said image composition comprising at least one cationic dyestuff and a binder of a type which will not substantially impede migration of said dyestuff,
  • composition being free from oxidizing agent and optionally containing a base, which is at most 5% by weight, based on the weight of the composition, of N,N,N',N'-tetramethylethylene diamine, and
  • the present invention comprises a decorative sheet comprising polyvinyl chloride and substantially non-migratable image comprising at least one cationic dyestuff, obtained by the above-mentioned process.
  • the present invention provides a decorative floor covering comprising a backing and a substrate comprising polyvinyl chloride adhered to said backing, said substrate comprising a substantially non-migratable heat-stable through-color image comprising at least one cationic dyestuff.
  • the present invention provides a composite capable of forming a polyvinyl chloride-containing substrate comprising a substantially non-migratable through-color image, said composite comprising an image composition interfaced with a sheet substrate comprising polyvinyl chloride, said image composition comprising at least one cationic dyestuff, and a binder which will not substantially impede migration of said dyestuff, the composition being free from oxidizing agent and optionally containing a base, which is at most 5% by weight, based on the weight of the composition, of N,N,N',N'-tetramethylethylene diamine.
  • Basic dyes have long been of interest for dyeing various substrates, particularly fibrous textile substrates. Conventionally, these dyes were employed in dye baths in which the substrates were immersed. However, with the advent of transfer printing as a useful application technique for disperse dyes, many attempts were made to apply the same technology to basic dyestuffs. Basic dyes differ from disperse dyes because, as a general rule, they do not sublime at atmospheric pressure and even under reduced pressure they sublime only slightly. Therefore, difficulties were encountered relating to the proclivity to thermal degradation shown by many basic dyes. These problems, combined with the generally lower melting points of basic dyes, virtually precluded their use for transfer printing. Therefore, substantial effort was expended to find ways to overcome these problems.
  • the aforementioned transfer printing techniques which are applicable to basic and disperse dyes, are essentially directed to the printing of synthetic fibers, such as polyesters, acrylics, nylons and acetates. These materials readily permit the migration of dyes through the fiber matrix, presumably due to the high surface-area-to-volume ratio of the fibers. Conversely, sheet products present a different situation because they have a low surface-area-to-volume ratio, which tends to impede migration. The usual way to improve migration in such circumstances is by raising the temperature settings; however, this can lead to destruction of the dyes and can also damage the sheet material itself.
  • the present invention is applicable to a wide variety of sheet substrates derived from vinyl chloride.
  • Homopolymeric vinyl chloride substrates are preferred, although copolymers with vinylidene chloride, vinyl acetate, acrylic acid or other polymerizable materials also give good results.
  • Most vinyl chloride-containing copolymers that are in use today contain at least 70% vinyl chloride.
  • polyvinyl chloride as used herein to define various applicable substrates will be deemed to include copolymers of vinyl chloride with other monomers.
  • Polymeric materials derived from vinyl chloride monomer are essential because, as noted above, poor results are obtained with non-vinyl chloride-containing materials that are known to be transfer printable with cationic dyestuffs in the presence of migration-encouraging compounds, such as the oxidizing agents of Mizuno et al. While applicants do not wish to be bound by any particular theory of operability, it appears that cationic dyes have a particular affinity for polyvinyl chloride such that, when the dyes migrate by sublimation or otherwise into a sheet substrate comprising polyvinyl chloride, they interact with the polyvinyl chloride and become essentially non-migratable. Thus, even when subjected to solvents or prolonged, severe heat conditions, patterns prepared according to the present invention remain sharp and clear.
  • the physical character of the polyvinyl chloride-containing sheet substrate does not appear to be particularly significant. Suitable through-color images have been obtained by interfacing an image composition with gelled and ungelled plastisols (with or without chemical blowing agents), sintered dryblend resins, fused plastisols, and plasticized or unplasticized polyvinyl chloride film. In addition, it has been found that Saran * film, or like films which are copolymers of polyvinyl chloride, can be similarly treated.
  • the substrates may also comprise other common additives such as heat and light stabilizers, blowing agents, fire retardants, and the like, which are compatible with the objective of the present invention.
  • the cationic dyes in the image composition migrate into these substrates to give substantially non-migratable through-color images.
  • cationic dyes treated as described herein will maintain a color shade which remains essentially true throughout the dyeing process.
  • the present invention is decidedly superior to those prior art processes employing cationic dyestuffs in which the dyestuffs are treated such that they temporarily change or lose color.
  • the cationic dyestuffs of the present invention will be applied in combination with a binder that does not interfere with the subsequent migration of the dyestuff into the substrate.
  • binders such as polyvinyl alcohol or polyvinyl acetate, will cause this interference or impedence. Accordingly, a binder should be selected which does not cause this effect. Examples of binders which have given superior results are polyvinyl acetals, such as polyvinyl butyral; cellulose ethers, such as ethyl cellulose and methyl cellulose; and mixtures thereof.
  • Compositions comprising the cationic dyes and binders of the present invention will be referred to herein as "image compositions".
  • Image compositions may be applied to or interfaced with various surfaces by virtually any technique, such as transfer printing, conventional printing using rotogravure, flexographic, lithographic, screen, ink jet and other printing processes, hand application techniques such as those used by an artist, powder dispersion techniques and the like.
  • transfer printing conventional printing using rotogravure, flexographic, lithographic, screen, ink jet and other printing processes
  • hand application techniques such as those used by an artist, powder dispersion techniques and the like.
  • imaging the method of applying an image composition
  • interfacing the exposure of a substrate to an image composition
  • Transfer printing basically comprises the steps of imaging a transfer sheet, interfacing the sheet with the substrate such that the image is in contact, but preferably in intimate contact, with the substrate, and then applying heat to transfer the image.
  • transfer sheets are commercially available, and many of these are suitable to practice the present invention. Care must be taken in selecting an appropriate sheet, however, because certain sheets will become strongly adhered to the surface of the substrate during the transfer printing process. Consequently, even though a suitable image transfer may occur, adhesion of the transfer paper to the substrate may prevent a desirable product from being prepared. Especially good results have been obtained using foil or polyester transfer sheets; however, the most satisfactory results have been obtained using clay-coated kraft paper comprising a coating material between the clay coating and the image to facilitate release of the transfer sheet from the hot substrate.
  • coated transfer sheet is Frankote * Cover Bristol, a commercially available kaolin clay-coated white kraft paper, which has been coated with a 1-3 mil (0.025-0.076 mm) layer of polyvinyl alcohol, ethyl cellulose or methyl cellulose prior to use.
  • coated transfer papers also provide an exceptionally smooth surface for the image, as well as excellent contact of the image with the substrate. Furthermore, they have shown a remarkable ability to give immediate release from a hot (about 300°F or 150°C) vinyl substrate without causing picking, pitting or other damage to the substrate.
  • the binder cause the image composition after the dyestuff has migrated to the polyvinyl chloride substrate to remain adhered to the transfer sheet when the latter is separated from the substrate.
  • image compositions which adhere, in whole or in part, to the surface of the substrate may also have utility, they are not preferred because they usually must either be removed at a latter stage in the process, or be protected with a wear layer. It has been found that image compositions comprising the preferred binders set forth above also possess this desired attribute.
  • Transfer sheets When a dry powder is imaged to a transfer sheet, it will usually be applied as a pattern which preferably is then warmed to cause the binder to adhere to the sheet. Transfer sheets may be prepared in which the image composition is not adhered; however, they often lead to products having smeared images and, thus, are not preferred.
  • the inks When the image compositions are applied as inks, the inks will usually comprise one or more solvents for the dye and binder.
  • solvents for the dye and binder.
  • a wide variety of solvents have utility when incorporated into printable cationic dye systems. Examples of these may be found in U.S. Patent No. 4,272,292, another of the Mizuno et al. references. It is noted, however, that this reference places certain restrictions on the proportions of solvents
  • the solvent or solvents that are selected will be suitable to solubilize essentially all of the binder and dyestuff in order to obtain a uniform printing composition.
  • These compositions may also contain other compatible components, such as drying agents, hardening agents, emulsifiers, dispersants, thickeners, fillers and the like, all of which are well known in the art and which will be soluble or dispersable in the selected solvent system.
  • the ink compositions described above may be used without difficulty in the present invention when they are freshly prepared. Upon standing for several hours, however, a gelling reaction occurs which interferes with the applicability of the ink. The reason for the gelling is not apparent although it is believed to be due to an interaction of the dyestuff with the binder; nevertheless, gelling normally does not affect dye color.
  • the ink may be stabilized against gelation by including a basic stabilizer in the ink that does not substantially change the color of the dye, either immediately, or on long standing.
  • N,N,N',N'- tetramethylethylene diamine has given especially good results when included in the ink at levels of about 1 to about 5 percent of the total weight of the ink. If too much is used precipitation of the binder may occur.
  • the use of stabilizing base is purely optional.
  • Amines and bases have been used by others in formulating various cationic dye-containing compositions; however, the purposes for including these bases were entirely different.
  • Mizuno et al. in U.S. Patent No. 4,272,292, used strong bases to prevent long-term decomposition of the carbinol bases of the cationic dyes disclosed therein.
  • Defago et al. in U.S. Patent No. 4,042,545, disclosed a system in which organic or inorganic acid acceptors were used to free the cationic dyes from their salt form. These acid acceptors, which included amines, caused a color change or a loss of color, and the invention disclosed by Defago et al. taught the addition of an indicator dye so that this drawback could be circumvented.
  • the bases disclosed by Mizuno et al, and Defago et a/. were required for the operability of their respective inventions.
  • the cationic dyes maintain essentially a true color throughout the process and these colors remain constant in the presence or absence of a stabilizer.
  • Appropriate inks may be applied to the transfer paper by any of the techniques referred to above.
  • the ink is allowed to dry and the transfer sheet is interfaced with the substrate such that the image is in contact with the substrate.
  • the interfaced materials are then subjected to heat and perhaps pressure for a period of time.
  • the temperature and the residence time of the interfaced materials at that temperature are probably the two most important variables, the pressure being needed primarily to maintain good contact between the substrate and the image to be transferred. Suitable temperatures and residence times range from about 180° (82°C) to about 380°F (195°C) for from about 1 to about 300 seconds.
  • Preferred ranges are from about 270° (132°C) to about 350°F (177°C) for from about 1 to about 100 seconds, whereas most preferred ranges are from about 290° (143°C) to about 320°F (160°C) for from about 30 to about 90 seconds.
  • Pressures of from 0 to about 500 pounds per square inch (0 to 3447 kPa) may be used although pressures of from about 10 to about 50 pounds per square inch (68.9 to about 344.7 kPa) are preferred.
  • the best penetration is obtained using transfer printing.
  • moderate conditions such as 310°F (154°C) for 30 seconds
  • penetrations of about 3 to 5 mils (0.08 to 0.13 mm) are usually obtained, whereas, under more severe conditions, penetrations of about 8 to 10 mils (0.02 to 0.25 mm) can be obtained.
  • increased amounts of cationic dyes are used, penetrations of as much as perhaps 20 mils (0.5 mm) may be obtained. Nevertheless, increased levels of dyestuff cause loss of pattern definition and should be avoided.
  • dye penetration may also depend to a certain extent on dye color.
  • experiments conducted using red, black, blue and yellow dyestuffs at different temperatures for various times on a fused 30-mil (0.76 mm) thick plastisol showed varied results.
  • the red, black and blue dyes penetrated to a certain depth and stopped, whereas the yellow dye continued to penetrate until heating was stopped.
  • the red and black dyestuffs showed deeper penetration when the time of exposure was increased from 60 to 120 seconds, whereas the blue dyestuff showed no further penetration.
  • the yellow dyestuff showed continued penetration with continued heating, although it, too, eventually ceased migrating.
  • the migration characteristics of each individual dye should be considered by the artisan when practicing the present invention.
  • the color fastness of the various through color transfer-printed products was evaluated in a number of ways.
  • One method involved the subjection of samples, such as fused polyvinyl chloride sheets which had been transfer printed with a wood grain pattern, to thermal stability tests at 158°F and 180°F (70 and 82°C) for six weeks. No color migration or color change was observed during this time period and the dye colors also remained bright and unfaded.
  • a second method of testing stability involved the subjection of samples of several substrates dyed with different colors to various solvents, such as isopropyl alcohol, 5% acetic acid, 5% sodium hydroxide, 5% sulfuric acid, beef tallow, ASTM #1 oil, or cottonseed oil. No extraction of color was observed, even after 46 hours of testing. Furthermore, no crocking was observed when ethyl alcohol or water laden cloths were rubbed over the surfaces of the samples.
  • solvents such as isopropyl alcohol, 5% acetic acid, 5% sodium hydroxide, 5% sulfuric acid, beef tallow, ASTM #1 oil, or cottonseed oil.
  • a third test involved the subjection of several samples to a xenon fadeometer test, a severe test which measures the fading of the color when a sample is exposed to a xenon lamp for at least 100 hours.
  • the test indicated that samples of transfer printed polyvinyl chloride containing a plastisol had reasonably good color stability even after 100 hours.
  • cationic dyes in hydrophilic polymer systems such as cotton or nylon are known to have relatively poor color stability under these conditions.
  • imaging may also be achieved by interfacing the image composition with the substrate by applying the image composition directly on the surface of the substrate.
  • a support surface may be imaged and then interfaced with a later-applied substrate into which the dye will migrate.
  • the support surface may be imaged by any of the application techniques previously described. If printing inks are used, the solvent is evaporated and the substrate bearing the design is heated as previously described. Nevertheless, although through-color images may be obtained by such direct application techniques, product quality is often not as satisfactory because the images normally are not as sharp or as deep as those obtained by transfer printing. This may be illustrated as follows.
  • Each of these particles can serve as a source from which the individual dye molecules can migrate in all directions when heated.
  • dye molecules can continue to migrate from these particles, causing a fuzziness of pattern.
  • these molecules also interact with the polyvinyl chloride, as suggested earlier, and become essentially fixed in place.
  • the flooring can be constructed by sequentially applying to a backing a plurality of individually dyed polyvinyl chloride-containing layers, thereby giving a three-dimensional color effect.
  • a transfer sheet of the present invention can have a polyvinyl chloride-containing substrate applied to it in order to provide the substrate with a transferred, through-color image. This substrate could then be used as a wear layer which is subsequently adhered to a floor structure.
  • a further advantage resides in the light-stability of these cationic dye-containing products.
  • the plastisol used in the following examples was composed of the following components:
  • the plastisol was coated at various thicknesses on a standard permanent floor backing and fused at about 375°F (191°C) for 3-5 minutes. Plastisols of this type are referred to herein as "backed fused plastisols”. Samples were also prepared by drawing down coatings of the plastisol on a glass plate, similarly fusing them, and removing the resulting film from the plate. Plastisols of this type are referred to herein as "clear fused plastisols".
  • Examples I-IV illustrate the transfer printing of clear fused plastisols with various dyes at various temperatures to measure dye penetration.
  • Example I comprised 6 parts of Basic Yellow 13 dye for every 100 parts of Ink Base A;
  • Example II comprised 6 parts of Basic Blue 26 dye for every 100 parts of Ink Base A;
  • Example III comprised 6.2 parts of Basic Red 12 dye for every 100 parts of Ink Base B;
  • Example IV comprised 6.2 parts of Maxilon * Super Black OLN dye for every 100 parts of Ink Base B.
  • the inks of Examples I and II were found to be stable for weeks, whereas the inks of Examples III and IV, which contained no stabilizer, gelled after a few hours.
  • samples of Mylar O polyester film were transfer printed with the same image compositions. Virtually no coloration of the film occurred, other than a faint coloration of the surface. This coloration was readily removed by wiping with a dry cloth.
  • Examples V through VIII backed fused plastisol pieces having a plastisol layer about 30 mils (0.76 mm) thick were directly printed with the ink compositions of Examples I, II, III and IV, respectively.
  • the samples were placed in a forced air oven at temperatures of 270° or 370°F (132° or 188°C) for times ranging from 30 to 120 seconds. After each sample had cooled, it was checked for wet and dry crocking, an indication of incomplete dye absorption, and the depth of penetration was measured.
  • Dry crocking was measured by using a white cloth and rubbing vigorously; wet crocking was measured by similarly rubbing with room temperature solutions of water or a laboratory cleaning solution containing ammonia and an anionic surfactant. The cloth in each case was examined for any color which might have been removed, and the sample was examined for any change in appearance. The following results were obtained.
  • This example illustrates the heat stability of color patterns produced according to the present invention.
  • These samples were prepared utilizing three ink compositions containing about 100 parts of Ink Base B and about 6 parts of Basic Blue 26, Basic Red 12 or Basic Yellow 11, respectively.
  • the respective inks were rotogravure printed onto transfer sheets, as described for Examples I-IV, which were then used to individually transfer print different samples of backed fused plastisol at 300°F (149°C) for 60 seconds under a pressure of 10 psi.
  • the individual samples were placed in an oven at 158°F (70°C) for six weeks, during which time they were examined for color fastness. Essentially no loss of pattern definition or color fading was detected.
  • a comparative sample of a backed fused plastisol transfer printed with a disperse dye pattern was prepared as follows.
  • a commercially available transfer paper printed with a geometric design was obtained from Sublistatic Corporation of America. This paper was interfaced with a sample of backed fused plastisol which was then transfer printed to give a through-color pattern comprising several colors, including yellow, red, orange, green and purple.
  • the printed sample was placed in an oven at 158°F (70°C) and changes were apparent after four days. These changes included blurring of the pattern edges and merging of the colors into one another to give new color combinations. After six weeks the pattern had markedly degraded and several of the colors had faded significantly.
  • This example illustrates the preparation of a sample having a layered or three-dimensional image.
  • a standard permanent backing material of a type conventionally used in flooring structures was directly imprinted with a design according to the procedure described in Examples V-VIII.
  • An ink was used which contained about 6 parts by weight of Basic Yellow 13 dye for every 100 parts of Ink Base B. After the solvent had evaporated, the backing was coated with a 0.25 mm (10-mil) layer of plastisol which was fused at 375°F (191°C) for 3 minutes in the absence of pressure. This caused the dye to migrate upwardly into the plastisol.
  • the plastisol When the plastisol had cooled, it was transfer printed at 300°F (149°C) for 60 seconds under a pressure of 10 psi (68.9 kPa) using a transfer paper imprinted with an image composition containing about 6 parts of Basic Blue 26 dye for every 100 parts of Ink Base B.
  • the resulting structure had an upper blue layer and a lower yellow layer, thus giving a three-dimensional effect.
  • Example XVI illustrates the application of a transfer printed design to a polyvinyl chloride-containing tile base.
  • a tile base comprising 37 parts of a vinyl chloride-vinyl acetate copolymer resin, 5 parts of a hydrocarbon resin, 14.5 parts of plasticizer, 2.4 parts of stabilizer, 235.1 parts of limestone and 6 parts of fiber was prepared and transfer printed using the Frankote paper described for Examples I-IV.
  • the transfer sheet had been rotogravure printed with a Basic Yellow 13 ink as set forth in Example I. Even under severe conditions, such as 380°F (193°C) for 10 minutes at 1,000 psi (6894 kPa) very poor penetration of the color into the tile was observed. Unfortunately, the transfer paper was difficult to release from the tile.
  • a preferred method of providing a tile substrate with a through-color image according to the present invention is illustrated in the following two examples.
  • Example XVII illustrates the simultaneous application and transfer printing of a polyvinyl chloride wear layer to the tile base of Example XVI.
  • a 0.1 mm (4-mil) plastisol layer was applied to the transfer sheet which had been rotogravure printed with a Basic Yellow 13 ink composition as set forth in Example XV.
  • the plastisol was gelled at 250°F (121°C) for 3 minutes and then interfaced with a tile substrate as set forth in Example XVI.
  • the interfaced composite materials were then subjected to 69 kPa (10 psi) pressure at 320°F (160°C) for 60 seconds, after which the transfer paper was separated from the plastisol.
  • a tile having a through-color fused wear layer was produced.
  • This example illustrates the interfacing of a tile base, a vinyl film and a transfer paper printed with a design to produce a tile having a through-color wear layer.
  • a tile base as set forth in Example XVI was interfaced with a 4-mil (0.102 mm) commercially available vinyl film containing about 20% butyl benzyl phthalate plasticizer.
  • the exposed surface of the vinyl film was then interfaced with an image carried by a transfer paper prepared as described in Examples I-IV, the image on the transfer paper having been rotogravure printed using an ink composition as set forth in Example XV.
  • the interfaced materials were subjected to a temperature of 300°F (149°C) and a pressure of 10 psi (68.9 kPa) for 1 minute. After separating the transfer paper, the tile had a fused, through-color vinyl wear layer.
  • This example illustrates the use of a powder dispersion technique to image a transfer sheet, after which the dye is migrated into a substrate.
  • a powdered image composition comprising 46% polyvinyl butyral binder, 3% Basic Blue 26 dye and 51 % inorganic material was randomly sprinkled on the surface of a piece of Frankote paper prepared as described in Examples I-IV.
  • the transfer sheet was warmed to 300°F (149°C) to tack the image composition to the surface of the sheet.
  • the imaged transfer sheet was then interfaced with a backed fused plastisol and heated under about 10 pounds (68.9 kPa) pressure for 30 seconds at 300°F (149°C).
  • the transfer sheet was separated and the image composition was removed with the transfer sheet.
  • the resulting dyed substrate had a through-color image corresponding to the random distribution of the image composition.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Duplication Or Marking (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Claims (25)

1. Procédé de préparation d'une feuille décorative comprenant du chlorure de polyvinyle et une image qui n'est pratiquement pas susceptible de migration, ce procédé consistant:
à exposer à une composition formant une image un substrat en feuille comprenant du chlorure de polyvinyle, cette composition formant image comprenant au moins un colorant cationique soluble et un
liant d'un type qui n'empêche pratiquement pas la migration de ce colorant soluble,
la composition étant exempte d'agent oxydant et contenant d'une manière facultative une base qui est, au plus à 5% en poids rapporté au poids de la composition, de la tétraméthyléthylène-N,N,N',N' diamine et
à élever la température de ce substrat exposé et de cette composition formant image de façon à faire migrer dans le substrat le colorant soluble.
2. Procédé suivant la revendication 1, selon lequel on réalise la migration en élevant la température à une valeur de 82° à 195°C pendant 1 à 300 secondes et à une pression de 0 à 3 447 kPa.
3. Procédé suivant la revendication 1 ou 2, selon lequel le liant comprend au moins un acétal polyvinylique, notamment un butyral polyvinylique, au moins un éther de cellulose, notamment l'éthylcellulose ou la méthylcellulose, ou un mélange de ceux-ci.
4. Procédé suivant l'une quelconque des revendications 1 à 3, selon lequel le colorant soluble a une charge ionique relativement délocalisée.
5. Procédé suivant l'une quelconque des revendications 1 à 4, selon lequel on applique directement une image sur le substrat à l'aide de la composition formant image.
6. Procédé suivant l'une quelconque des revendications 1 à 5, selon lequel on obtient l'image en réalisant une impression par transfert sur le substrat.
7. Procédé suivant la revendication 6, comprenant les opérations consistant:
à appliquer une image sur une feuille de transfert à l'aide de la composition formant image,
à exposer le substrat à une image à l'aide de la feuille de transfert sur laquelle l'image a été appliquée, de manière que la composition formant image soit pratiquement au contact du substrat et
à séparer du substrat la feuille de transfert une fois que la migration du colorant soluble est pratiquement complète.
8. Procédé suivant la revendication 7, selon lequel le résidu de la composition formant image qui reste après la migration du colorant soluble vers le substrat en chlorure de polyvinyle reste sur la feuille de transfert après la séparation.
9. Procédé suivant la revendication 7, selon lequel la feuille de transfert comprend un papier kraft revêtu d'argile, qui est revêtu d'une matière qui facilite la séparation de la feuille de transfert par rapport au substrat.
10. Procédé suivant l'une quelconque des revendications 1 à 4, selon lequel le substrat est exposé à une image à l'aide d'une surface de support sur laquelle une image a été appliquée à l'aide de la composition formant image.
11. Procédé suivant l'une quelconque des revendications 1 à 10, selon lequel le substrat est un plastisol non gélifié, gélifié ou fondu.
12. Feuille décorative comprenant du chlorure de polyvinyle et une image qui n'est pratiquement pas susceptible de migration, comprenant au moins un colorant soluble cationique, cette feuille étant obtenue:
en exposant à une composition formant une image un substrat comprenant du chlorure de polyvinyle, cette composition formant image comprenant au moins un colorant cationique soluble et un liant d'un type qui n'empêche pratiquement pas la migration de ce colorant soluble,
la composition étant exempte d'agent oxydant et contenant d'une manière facultative une base qui est, au plus à 5% en poids rapporté au poids de la composition, de la tétraméthyléthylène-N,N,N',N' diamine et
en élevant la température de ce substrat exposé et de cette composition formant image de façon à faire migrer dans le substrat le colorant soluble.
13. Feuille décorative suivant la revendication 12, cette feuille comprenant un homopolymère de chlorure de vinyle.
14. Feuille décorative suivant la revendication 12, cette feuille comprenant un copolymère de chlorure de vinyle, avantageusement avec au moins un composé choisi dans le groupe constitué du chlorure de vinylidène, de l'acétate de vinyle et de l'acide acrylique.
15. Feuille décorative suivant l'une quelconque des revendications 12 à 14, cette feuille comprenant une image dont la couleur la traverse pratiquement de part en part, ou "image à couleur dans l'épaisseur".
16. Feuille décorative suivant l'une quelconque des revendications 12 à 15, cette feuille étant un revêtement de sol comprenant un matériau de support.
17. Feuille décorative suivant l'une quelconque des revendications 12 à 16, cette feuille comprenant plusieurs couches pratiquement à couleur dans l'épaisseur, cette feuille offrant un aspect pratiquement tridimensionnel.
18. Feuille décorative suivant l'une quelconque des revendications 12 à 17, dans laquelle le substrat est obtenu à partir d'un plastisol.
19. Revêtement de sol décoratif, ce revêtement comprenant:
un support et
un substrat en feuille comprenant du chlorure de polyvinyle fixé par adhérence sur le support, ce substrat comprenant une image à couleur dans l'épaisseur, qui est stable à la chaleur et n'est pratiquement pas susceptible de migration, cette image comprenant au moins un colorant soluble cationique.
20. Revêtement de sol suivant la revendication 19, constituant un revêtement continu en feuille ou un dallage de sol.
21. Revêtement de sol suivant l'une des revendications 19 et 20, qui comprend une couche d'usure à couleur dans l'épaisseur.
22. Composite capable de former un substrat, contenant du chlorure de polyvinyle, qui comporte une image pratiquement à couleur dans l'épaisseur qui n'est pratiquement pas susceptible de migration, ce composite comprenant
une composition formant une image à laquelle est exposé un substrat en feuille comprenant du chlorure de polyvinyle, cette composition formant image comprenant au moins un colorant cationique soluble et un liant qui n'empêche pratiquement pas la migration de ce colorant soluble,
la composition étant exempte d'agent oxydant et contenant d'une manière facultative une base qui est, au plus à 5% en poids rapporté au poids de la composition, de la tétraméthyléthylène-N,N,N',N' diamine.
23. Composite suivant la revendication 22, dans lequel le liant est tel que défini à la revendication 3, ou le colorant soluble tel que défini à la revendication 4, ou dans lequel le liant et le colorant soluble sont tels que définis respectivement aux revendications 3 et 4.
24. Composite suivant l'une quelconque des revendications 22 et 23, dans lequel le substrat est un plastisol non gélifié, gélifié ou fondu.
EP83302587A 1982-05-10 1983-05-09 Feuilles et recouvrements décoratifs contenant du chlorure de polyvinyle et des colorants cationiques Expired - Lifetime EP0094228B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83302587T ATE54965T1 (de) 1982-05-10 1983-05-09 Polyvinylchlorid sowie kationische farbstoffe enthaltende dekorative schichten und beschichtungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US37655082A 1982-05-10 1982-05-10
US376550 1982-05-10

Publications (3)

Publication Number Publication Date
EP0094228A2 EP0094228A2 (fr) 1983-11-16
EP0094228A3 EP0094228A3 (en) 1985-11-27
EP0094228B1 true EP0094228B1 (fr) 1990-07-25

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Application Number Title Priority Date Filing Date
EP83302587A Expired - Lifetime EP0094228B1 (fr) 1982-05-10 1983-05-09 Feuilles et recouvrements décoratifs contenant du chlorure de polyvinyle et des colorants cationiques

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Country Link
EP (1) EP0094228B1 (fr)
JP (2) JPS58199186A (fr)
AT (1) ATE54965T1 (fr)
AU (1) AU562300B2 (fr)
CA (1) CA1198857A (fr)
DE (1) DE3381756D1 (fr)

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Publication number Priority date Publication date Assignee Title
JPS61102491A (ja) * 1984-10-24 1986-05-21 東ソー株式会社 着色材およびその製造法
FR2676966A1 (fr) * 1991-05-30 1992-12-04 Telimmed Procede d'impression de matieres polymeriques.
JPH06142923A (ja) * 1992-10-30 1994-05-24 Matsumoto Kikai Kk 金属帯板材料の端面接合方法及びその装置
FR2702416B1 (fr) * 1993-03-10 1995-06-09 Lecomte Roger Materiau imprime a base de pvc et procede de fabrication.
CN105415907A (zh) * 2015-11-06 2016-03-23 河南圣美阳光装饰材料有限公司 一种木塑材料的热转印方法
KR102506728B1 (ko) * 2018-01-09 2023-03-06 주식회사 쿠라레 가식 성형용 시트, 프리폼 성형체, 및 가식 성형체

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Publication number Priority date Publication date Assignee Title
JPS526431B2 (fr) * 1971-10-05 1977-02-22
JPS5423287B2 (fr) * 1973-03-20 1979-08-13

Also Published As

Publication number Publication date
EP0094228A3 (en) 1985-11-27
JPS58199186A (ja) 1983-11-19
CA1198857A (fr) 1986-01-07
DE3381756D1 (de) 1990-08-30
AU9158982A (en) 1983-11-17
EP0094228A2 (fr) 1983-11-16
JPS6183092A (ja) 1986-04-26
ATE54965T1 (de) 1990-08-15
AU562300B2 (en) 1987-06-04

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