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WO2005121893A1 - Improvements in printing techniques - Google Patents

Improvements in printing techniques Download PDF

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Publication number
WO2005121893A1
WO2005121893A1 PCT/GB2005/001766 GB2005001766W WO2005121893A1 WO 2005121893 A1 WO2005121893 A1 WO 2005121893A1 GB 2005001766 W GB2005001766 W GB 2005001766W WO 2005121893 A1 WO2005121893 A1 WO 2005121893A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
gas
agent
substrate
image
Prior art date
Application number
PCT/GB2005/001766
Other languages
French (fr)
Inventor
David Malcolm Lewis
Peter Jeffrey Broadbent
Original Assignee
Inovink Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Inovink Limited filed Critical Inovink Limited
Publication of WO2005121893A1 publication Critical patent/WO2005121893A1/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
    • B41M5/50—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/06—Veined printings; Fluorescent printings; Stereoscopic images; Imitated patterns, e.g. tissues, textiles
    • 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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/41—Base layers supports or substrates

Definitions

  • the present invention relates to methods of manufacturing image articles, and image articles manufactured thereby.
  • Image articles which comprise embossed or Braille images on a substrate.
  • these image articles comprise a plain substrate on which a raised image has been applied by applying a three-dimensional material, image-wise over the coating, to produce the raised image.
  • a method of manufacturing an image article comprising:
  • raising of the polymer from the surface or expansion of the polymer is effected by generating a gas beneath, within or on the polymer.
  • Raising of the hydrophilic polymer may be effected by expansion of the polymer due to gas bubbles forming in the polymer matrix, thus causing the dimensions of the polymer to increase and form raised areas out of the plane of the coating.
  • raising of the polymer may be effected by stretching of the polymer due to formation of gas within or beneath the polymer coating and hence, the stretched polymer may be lifted away from the surface by gas. The stretched polymer spaced from the surface may then harden in that configuration.
  • the raising of the polymer may be effected by one or a mixture of bubbling of the polymer to effect expansion, or stretching or expansion of the polymer by "blowing out" the polymer with a gas .
  • the substrate is a sheet material, which may be planar or otherwise.
  • the substrate may comprise any suitable material, such as paper, card, wood, glass, metal
  • Suitable textile material includes leather, cotton, synthetic textiles such as polyester, nylon or rayon, linen, flax, hemp, jute and silk.
  • Preferred substrates are sheets of card, paper, plastics, textile materials or metal.
  • Suitable plastics materials include polyurethanes, polyesters, poly vinyl chlorides, polyamides, and mixtures and co-polymers thereof.
  • the hydrophilic polymer may be a water-soluble polymer or a water-dispersible polymer.
  • the polymer is a water-soluble polymer.
  • the hydrophilic polymer is present in an aqueous solution or as a dispersion in an aqueous medium.
  • the hydrophilic polymer may be a polymer selected from polyvinyl alcohol, polyvinylpyrrolidone, polyvinylacetate, polyacrylic acid, polyacrylates, active acrylic polymers, gelatins, carboxyalkylcelluloses, alginates, guar gum, locust bean gum, polymeric surfactants and polyols.
  • the hydrophilic polymer is polyvinylalcohol .
  • the hydrophilic polymer is laid down as a coating in an aqueous medium in step (b) , preferably as an aqueous solution or aqueous dispersion.
  • the coating is substantially dried, and may be dried by allowing the solvent to evaporate at ambient conditions, or by heating, for example.
  • the aqueous medium is printed onto the substrate, more preferably ink-jet printed, for example using a Hewlett Packard DeskJet series of printers.
  • the aqueous medium may include further ingredients such as, for example, humectants, fragrances, surfactants, dyes, pigments (or other colouring agents) , co-solvents, preservatives and the like.
  • a dye or pigment to present in the coating effects a coloured coating and subsequent raising of areas of the coating during or after step (c) may effect multi-tone images.
  • Step (c) may comprise applying an agent capable of generating a gas on application of a stimulus, to at least a portion of the coating.
  • the agent is image- wise applied.
  • the agent may comprise a compound, for example, diazo compounds, which generate a gas on application of heat as the stimulus.
  • step (c) comprises applying an agent capable of generating a gas on application of a stimulus
  • the method comprises step (d) of applying the stimulus to the agent.
  • the stimulus will depend on the agent used, but may for example, be heat, radiation, a chemical compound capable of reacting with the agent to form a gas, or any combination thereof.
  • Gas generation may be effected by the reaction of two or more agents applied in step (c) , or may be effected by reaction of an agent applied in step (c) with an agent present in the coating laid down in step (b) .
  • (b) may comprise coating both a hydrophilic polymer and a compound capable of reacting with another compound subsequently applied to the coating to generate a gas.
  • Suitable gases arranged to be generated include carbon dioxide, nitrogen, oxygen, sulphur dioxide, chloroform and the like, for example.
  • Step (b) may comprise coating a hydrophilic polymer and first agent capable of reacting with a second agent to form a gas to the substrate, and step (c) may comprise image-wise applying a second agent capable of reacting with the first agent to generate a gas, to the coating.
  • the first agent is an acid, more preferably a non-volatile acid
  • the second agent is an agent capable of reacting with the acid to generate a gas.
  • the acid may be any suitable acid, including organic acids, inorganic acids and the like.
  • the acid is an organic acid.
  • Suitable organic acids include citric acid, lactic acid, malic acid, maleic acid, oxalic acid, tartaric acid, and mixtures thereof.
  • the agent capable of reacting with the acid to generate a gas may comprise a water soluble salt, such as carbonate or bicarbonate, or a sulphite, for example.
  • Suitable carbonates include alkali metal carbonates, especially sodium and potassium carbonate, ammonium bicarbonate, and substituted amine carbonates.
  • the coating of hydrophilic polymer is dried after step (b) .
  • gas generation on, within or beneath the coating is effected such that different amounts of gas are generated at different areas of the coating.
  • this differential gas generation effects differential raising or expansion of the polymer to effect different elevation of raised polymer on different areas of the coating.
  • the image article is a printing form, an electronic part or a mask to a printing form or electronic part .
  • the differential generation of gas effects differential elevation of raised areas of the hydrophilic polymer to produce a 3-D image.
  • the degree of elevation can be incrementally changed to produce photographically equivalent images which vary according to viewing angle. For example, if viewed at a glancing angle to the substrate (preferably less than 45°) the image may be seen as a negative image, whereas if viewed at just off perpendicular to the substrate the image may be seen as positive; other viewing angles may reveal no image. If sufficient elevation occurs, then the degree of raising of the polymer is sufficient to enable a Braille reader to interpret the image by touch alone.
  • the method enables the manufacture of embossed, Braille and optically variable images .
  • the image article is allowed to stand for at least 12 hours, preferably 24 hours, more preferably 36 hours before use, in order that complete gas generation is achieved and thus, that the image areas may be completely raised.
  • the amount of gas generated in step (c) may be controlled by varying the amount of second agent applied to an area of the coating.
  • the second agent is preferably present in solution and the amount of second agent applied to the coating controlled by varying the amount of solution applied to the coating.
  • the amount of solution may be controlled image-wise, such that different amounts of solution are applied across different areas of the coating .
  • (c) is printed onto the coating, more preferably ink-jet printed, for example, using a Hewlett Packard DeskJet series of printers.
  • the substrate, hydrophilic polymer, first and second agents are as described hereinbefore.
  • a method of manufacturing an image article comprising:
  • hydrophilic polymer, substrate, agent capable of generating a gas upon contact with a stimulus and stimulus are as described hereinabove .
  • Card and paper substrates (white 160grrf 2 card supplied by Vanguard, UK, and white 80gdm ⁇ 2 paper, supplied by Niceday, UK) were coated with an aqueous solution containing poly (vinyl alcohol) (50gd ⁇ f 3 , supplied by Aldrich, UK) and citric acid (as a first agent capable of generating a gas by reaction with a second agent) (lOOgd ⁇ f 3 , supplied by Aldrich, UK) using a K-bar and allowed to dry at room temperature.
  • poly (vinyl alcohol) 50gd ⁇ f 3 , supplied by Aldrich, UK
  • citric acid as a first agent capable of generating a gas by reaction with a second agent
  • the pre-coated papers produced were ink-jet printed with an aqueous solution containing sodium carbonate (as a second agent capable of generating a gas by reaction with the first agent) (lOOgdrrf 3 , supplied by Aldrich, UK) and N-methylmorpholine-N-oxide (250gdnf 3 , supplied by Aldrich, UK) and the printed sample allowed to stand at room temperature during which time the ink-jet printed areas gradually rose.
  • a photographic quality image was achieved, which gradually improved in quality over the next 2-3 days.
  • the resulting prints obtained exhibited optically variable image properties; the prints exhibiting a positive grey-scale image when viewed from one angle, a negative image when viewed from a second angle and finally disappeared from view when observed from a third angle.
  • Example 1 The process described in Example 1 was repeated, but in this case a series of dots corresponding to the Braille alphabet was printed. On standing, a raised series of dots was achieved, which could be readily detected by touch.
  • Example 1 The process described in Example 1 was repeated, but in this case sodium trichloroacetate (lOOgdm -3 , BASF) was incorporated in the paper pre-treatment solution in place of the citric acid originally present.
  • the coated papers were ink-jet printed with sodium carbonate and N- methylmorpholine-N-oxide, as in Example 1.
  • the ink-jet printed samples were dried at 100°C, during which time small amounts of chloroform and carbon dioxide were generated, which in turn created a raised ⁇ blown' image.
  • the prints were similar in quality and properties to those achieved in Example 1.
  • Paper was pre-treated as in Example 1, but in this case the citric acid was omitted.
  • An ink was prepared containing sodium trichloroacetate (lOOgdm -3 , BASF) and N- methylmorpholine-N-oxide (250gdm -3 , Aldrich) .
  • Ink-jet printing with sodium carbonate, followed by drying at 100°C produced small amounts of chloroform and carbon dioxide which created a raised blown' image. .
  • the prints were similar in quality and properties to those achieved in Example 1.
  • Example 5 A stabilised diazoamine compound was synthesised via the method described below. Sulphanilic acid (13.3g, O.lmole, Aldrich UK) was dissolved in distilled water (100ml), concentrated hydrochloric acid (30cm 3 ) was added and the resulting solution was cooled to 0-5°C. Sodium nitrite (7g, O.lmole, Aldrich UK) was dissolved in distilled water (50ml) and added dropwise to the sulphanilic acid solution over 20 minutes. After stirring for a further 20 minutes, sulphamic acid (Aldrich UK) was added until a negative result with starch iodide paper was obtained. This solution was added to a mixture of N-methyltaurine (16. lg, O.lmole, Aldrich UK) and sodium carbonate (30g, Aldrich UK) . The stabilised diazoamine was precipitated by the addition of sodium chloride and collected by filtration.
  • Sulphanilic acid (13.3g, O.lmol
  • Paper and card substrates were pre-coated and then ink-jet printed in a similar manner to the process described in Example 1, but in this case the stabilised diazoamine was used to replace the sodium carbonate present in the ink- jet ink formulation.
  • the diazoamine regenerated the original diazonium salt due to the acidic nature of the pre-coated paper and on heating decomposed to generate nitrogen gas, which in turn created a raised 'blown' image.
  • the prints achieved were similar in quality and properties to those achieved in Example 1.
  • the diazoamine generates a gas on application of a stimulus in the form of heat.
  • Example 6 The process described in Example 1 was repeated, but in this case the aqueous solution ink-jet printed onto the treated substrate contained sodium sulphite (lOOgdm -3 ) in place of the sodium carbonate present in the original solution of Example 1. Once printed, sodium sulphite decomposed due to the acidic nature of the pre-coated paper and liberated sulphur dioxide gas, which in turn created a raised ⁇ blown' image. The prints achieved were similar in quality and properties to those achieved in Example 1.
  • the pre-coated papers produced were ink-jet printed with an aqueous solution containing sodium nitrite (50gdm -3 , supplied by Aldrich, UK) and N- methylmorpholine-N-oxide (250gdm -3 , supplied by Aldrich, UK) and the printed sample allowed to stand at room temperature during which time the ink-jet printed areas gradually rose due to the generation of nitrogen gas.
  • a photographic quality image was achieved, which gradually improved in quality over the next 2-3 days.
  • the resulting prints obtained exhibited optically variable image properties; the prints exhibiting a positive grey-scale image when viewed from one angle, a negative image when viewed from a second angle and finally disappeared from view when observed from a third angle.

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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Vascular Medicine (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

The invention provides a method of manufacturing an image article, the method comprising: (a) providing a substrate; (b) coating at least a portion of a surface of the substrate with a hydrophilic polymer; and (c) effecting raising or expansion of at least a portion of the hydrophilic polymer from the surface of the substrate to create one or more raised image areas.

Description

IMPROVEMENTS IN PRINTING TECHNIQUES
Field of the invention
The present invention relates to methods of manufacturing image articles, and image articles manufactured thereby.
Background to the invention
Image articles are known which comprise embossed or Braille images on a substrate. Generally, these image articles comprise a plain substrate on which a raised image has been applied by applying a three-dimensional material, image-wise over the coating, to produce the raised image.
These image articles are generally manufactured by specialist companies, utilising relatively expensive apparatus and techniques. The manufacture of embossed or Braille image articles in smaller premises, or even domestically, is rare due to the prohibitive expense of commercially available equipment.
Furthermore, the three-dimensional materials used in known Braille and embossed image manufacturing are relatively expensive, and require specialist apparatus to cut or mould into the desired image before application to a substrate .
It would be advantageous to provide a method of manufacturing embossed and Braille images, which utilises domestic and commercially available printing equipment. It would furthermore be advantageous to provide a method of manufacturing Braille and embossed images which does not utilise solid three-dimensional material to provide the raised images.
It would furthermore be advantageous to provide a method of manufacturing a raised image on an image article, in which the image effects an optically variable image, which when viewed from one angle is a negative of the image, and when viewed from a second angle is a positive of the image, with viewing angles in between revealing no image.
It is therefore an aim of preferred embodiments of the present invention to overcome or mitigate at least one problem in the prior art, whether expressly disclosed here or not.
Summary of the invention
According to a first aspect of the present invention there is provided a method of manufacturing an image article, the method comprising:
(a) providing a substrate; (b) coating at least a portion of a surface of the substrate with a hydrophilic polymer; and (c) effecting raising or expansion of at least a portion of the hydrophilic polymer from the surface of the substrate to create one or more raised image areas.
Suitably, raising of the polymer from the surface or expansion of the polymer, is effected by generating a gas beneath, within or on the polymer. Raising of the hydrophilic polymer may be effected by expansion of the polymer due to gas bubbles forming in the polymer matrix, thus causing the dimensions of the polymer to increase and form raised areas out of the plane of the coating. Alternatively or additionally raising of the polymer may be effected by stretching of the polymer due to formation of gas within or beneath the polymer coating and hence, the stretched polymer may be lifted away from the surface by gas. The stretched polymer spaced from the surface may then harden in that configuration. In effect, the raising of the polymer may be effected by one or a mixture of bubbling of the polymer to effect expansion, or stretching or expansion of the polymer by "blowing out" the polymer with a gas .
Suitably, the substrate is a sheet material, which may be planar or otherwise. The substrate may comprise any suitable material, such as paper, card, wood, glass, metal
(including alloy) , ceramic, stone, mineral, including mineral-based paper, plastics, hair and keratinous substances, composite, polymeric, or textile material, for example. Suitable textile material includes leather, cotton, synthetic textiles such as polyester, nylon or rayon, linen, flax, hemp, jute and silk.
Preferred substrates are sheets of card, paper, plastics, textile materials or metal.
Suitable plastics materials include polyurethanes, polyesters, poly vinyl chlorides, polyamides, and mixtures and co-polymers thereof. The hydrophilic polymer may be a water-soluble polymer or a water-dispersible polymer. Preferably the polymer is a water-soluble polymer.
Suitably the hydrophilic polymer is present in an aqueous solution or as a dispersion in an aqueous medium.
The hydrophilic polymer may be a polymer selected from polyvinyl alcohol, polyvinylpyrrolidone, polyvinylacetate, polyacrylic acid, polyacrylates, active acrylic polymers, gelatins, carboxyalkylcelluloses, alginates, guar gum, locust bean gum, polymeric surfactants and polyols.
Preferably the hydrophilic polymer is polyvinylalcohol .
Preferably the hydrophilic polymer is laid down as a coating in an aqueous medium in step (b) , preferably as an aqueous solution or aqueous dispersion. Preferably the coating is substantially dried, and may be dried by allowing the solvent to evaporate at ambient conditions, or by heating, for example.
Suitably the aqueous medium is printed onto the substrate, more preferably ink-jet printed, for example using a Hewlett Packard DeskJet series of printers.
The aqueous medium may include further ingredients such as, for example, humectants, fragrances, surfactants, dyes, pigments (or other colouring agents) , co-solvents, preservatives and the like. A dye or pigment to present in the coating effects a coloured coating and subsequent raising of areas of the coating during or after step (c) may effect multi-tone images. Preferably raising or expansion of the hydrophilic polymers effected by contacting the coating with a gas.
Step (c) may comprise applying an agent capable of generating a gas on application of a stimulus, to at least a portion of the coating. Preferably the agent is image- wise applied. The agent may comprise a compound, for example, diazo compounds, which generate a gas on application of heat as the stimulus. Thus when step (c) comprises applying an agent capable of generating a gas on application of a stimulus, preferably the method comprises step (d) of applying the stimulus to the agent. The stimulus will depend on the agent used, but may for example, be heat, radiation, a chemical compound capable of reacting with the agent to form a gas, or any combination thereof.
Gas generation may be effected by the reaction of two or more agents applied in step (c) , or may be effected by reaction of an agent applied in step (c) with an agent present in the coating laid down in step (b) . Thus step
(b) may comprise coating both a hydrophilic polymer and a compound capable of reacting with another compound subsequently applied to the coating to generate a gas.
Suitable gases arranged to be generated include carbon dioxide, nitrogen, oxygen, sulphur dioxide, chloroform and the like, for example.
Step (b) may comprise coating a hydrophilic polymer and first agent capable of reacting with a second agent to form a gas to the substrate, and step (c) may comprise image-wise applying a second agent capable of reacting with the first agent to generate a gas, to the coating.
Preferably the first agent is an acid, more preferably a non-volatile acid, and the second agent is an agent capable of reacting with the acid to generate a gas.
The acid may be any suitable acid, including organic acids, inorganic acids and the like. Suitably the acid is an organic acid. Suitable organic acids include citric acid, lactic acid, malic acid, maleic acid, oxalic acid, tartaric acid, and mixtures thereof.
The agent capable of reacting with the acid to generate a gas may comprise a water soluble salt, such as carbonate or bicarbonate, or a sulphite, for example. Suitable carbonates include alkali metal carbonates, especially sodium and potassium carbonate, ammonium bicarbonate, and substituted amine carbonates.
Preferably the coating of hydrophilic polymer is dried after step (b) .
Suitably, gas generation on, within or beneath the coating is effected such that different amounts of gas are generated at different areas of the coating. Thus, this differential gas generation effects differential raising or expansion of the polymer to effect different elevation of raised polymer on different areas of the coating.
Suitably the image article is a printing form, an electronic part or a mask to a printing form or electronic part . The differential generation of gas effects differential elevation of raised areas of the hydrophilic polymer to produce a 3-D image. The degree of elevation can be incrementally changed to produce photographically equivalent images which vary according to viewing angle. For example, if viewed at a glancing angle to the substrate (preferably less than 45°) the image may be seen as a negative image, whereas if viewed at just off perpendicular to the substrate the image may be seen as positive; other viewing angles may reveal no image. If sufficient elevation occurs, then the degree of raising of the polymer is sufficient to enable a Braille reader to interpret the image by touch alone.
The method enables the manufacture of embossed, Braille and optically variable images .
Preferably the image article is allowed to stand for at least 12 hours, preferably 24 hours, more preferably 36 hours before use, in order that complete gas generation is achieved and thus, that the image areas may be completely raised.
According to a second aspect of the present invention there is provided a method of manufacturing an image article, the method comprising:
(a) providing a substrate; (b) coating at least a portion of a surface of the substrate with a hydrophilic polymer and a first agent capable of generating a gas by reaction with a second agent; and (c) image-wise applying a second agent capable of reacting with the first agent to generate a gas, to the coating .
The amount of gas generated in step (c) may be controlled by varying the amount of second agent applied to an area of the coating. The second agent is preferably present in solution and the amount of second agent applied to the coating controlled by varying the amount of solution applied to the coating. The amount of solution may be controlled image-wise, such that different amounts of solution are applied across different areas of the coating .
Suitably the second agent applied to the coating in step
(c) is printed onto the coating, more preferably ink-jet printed, for example, using a Hewlett Packard DeskJet series of printers.
Suitably the substrate, hydrophilic polymer, first and second agents are as described hereinbefore.
According to a third aspect of the invention there is provided a method of manufacturing an image article, the method comprising:
(a) providing a substrate;
(b) coating at least a portion of a surface of the substrate with a hydrophilic polymer; (c) image-wise applying an agent capable of generating a gas upon contact with a stimulus, to the coating; and
(d) applying the stimulus to the agent capable of generating a gas. According to a fourth aspect of the invention there is provided an image article manufactured by the method of the first, second or third aspects of the invention.
Suitably the hydrophilic polymer, substrate, agent capable of generating a gas upon contact with a stimulus and stimulus are as described hereinabove . EXAMPLES
The various aspects of the invention will now be described by way of example.
Example 1
Card and paper substrates (white 160grrf2 card supplied by Vanguard, UK, and white 80gdm~2 paper, supplied by Niceday, UK) were coated with an aqueous solution containing poly (vinyl alcohol) (50gdπf3, supplied by Aldrich, UK) and citric acid (as a first agent capable of generating a gas by reaction with a second agent) (lOOgdπf 3, supplied by Aldrich, UK) using a K-bar and allowed to dry at room temperature. The pre-coated papers produced were ink-jet printed with an aqueous solution containing sodium carbonate (as a second agent capable of generating a gas by reaction with the first agent) (lOOgdrrf3, supplied by Aldrich, UK) and N-methylmorpholine-N-oxide (250gdnf3, supplied by Aldrich, UK) and the printed sample allowed to stand at room temperature during which time the ink-jet printed areas gradually rose. A photographic quality image was achieved, which gradually improved in quality over the next 2-3 days. The resulting prints obtained exhibited optically variable image properties; the prints exhibiting a positive grey-scale image when viewed from one angle, a negative image when viewed from a second angle and finally disappeared from view when observed from a third angle.
Example 2
The process described in Example 1 was repeated, but in this case a series of dots corresponding to the Braille alphabet was printed. On standing, a raised series of dots was achieved, which could be readily detected by touch.
Example 3
The process described in Example 1 was repeated, but in this case sodium trichloroacetate (lOOgdm-3, BASF) was incorporated in the paper pre-treatment solution in place of the citric acid originally present. The coated papers were ink-jet printed with sodium carbonate and N- methylmorpholine-N-oxide, as in Example 1. The ink-jet printed samples were dried at 100°C, during which time small amounts of chloroform and carbon dioxide were generated, which in turn created a raised λblown' image. The prints were similar in quality and properties to those achieved in Example 1.
Example 4
Paper was pre-treated as in Example 1, but in this case the citric acid was omitted. An ink was prepared containing sodium trichloroacetate (lOOgdm-3, BASF) and N- methylmorpholine-N-oxide (250gdm-3, Aldrich) . Ink-jet printing with sodium carbonate, followed by drying at 100°C produced small amounts of chloroform and carbon dioxide which created a raised blown' image. . The prints were similar in quality and properties to those achieved in Example 1.
Example 5 A stabilised diazoamine compound was synthesised via the method described below. Sulphanilic acid (13.3g, O.lmole, Aldrich UK) was dissolved in distilled water (100ml), concentrated hydrochloric acid (30cm3) was added and the resulting solution was cooled to 0-5°C. Sodium nitrite (7g, O.lmole, Aldrich UK) was dissolved in distilled water (50ml) and added dropwise to the sulphanilic acid solution over 20 minutes. After stirring for a further 20 minutes, sulphamic acid (Aldrich UK) was added until a negative result with starch iodide paper was obtained. This solution was added to a mixture of N-methyltaurine (16. lg, O.lmole, Aldrich UK) and sodium carbonate (30g, Aldrich UK) . The stabilised diazoamine was precipitated by the addition of sodium chloride and collected by filtration.
Paper and card substrates were pre-coated and then ink-jet printed in a similar manner to the process described in Example 1, but in this case the stabilised diazoamine was used to replace the sodium carbonate present in the ink- jet ink formulation. Once printed, the diazoamine regenerated the original diazonium salt due to the acidic nature of the pre-coated paper and on heating decomposed to generate nitrogen gas, which in turn created a raised 'blown' image. The prints achieved were similar in quality and properties to those achieved in Example 1. Thus the diazoamine generates a gas on application of a stimulus in the form of heat.
Example 6 The process described in Example 1 was repeated, but in this case the aqueous solution ink-jet printed onto the treated substrate contained sodium sulphite (lOOgdm-3) in place of the sodium carbonate present in the original solution of Example 1. Once printed, sodium sulphite decomposed due to the acidic nature of the pre-coated paper and liberated sulphur dioxide gas, which in turn created a raised λblown' image. The prints achieved were similar in quality and properties to those achieved in Example 1.
Example 7
Card (white, 160gm-2, supplied by Vanguard, UK) and paper (white, 80gm-2, supplied by Niceday, UK) substrates were coated with an aqueous solution containing poly (vinyl alcohol) (50gdm-3, supplied by Aldrich, UK) , citric acid (lOOgdm-3, supplied by Aldrich, UK) and urea (200gdm-3, supplied by Aldrich, UK) using a K-bar and allowed to dry at room temperature. The pre-coated papers produced were ink-jet printed with an aqueous solution containing sodium nitrite (50gdm-3, supplied by Aldrich, UK) and N- methylmorpholine-N-oxide (250gdm-3, supplied by Aldrich, UK) and the printed sample allowed to stand at room temperature during which time the ink-jet printed areas gradually rose due to the generation of nitrogen gas. A photographic quality image was achieved, which gradually improved in quality over the next 2-3 days. The resulting prints obtained exhibited optically variable image properties; the prints exhibiting a positive grey-scale image when viewed from one angle, a negative image when viewed from a second angle and finally disappeared from view when observed from a third angle. The reader's attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.
All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive.
Each feature disclosed in this specification (including any accompanying claims, abstract and drawings) , may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
The invention is not restricted to the details of the foregoing embodiment (s ) . The invention extend to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed .

Claims

1. A method of manufacturing an image article, the method comprising :
(a) providing a substrate; (b) coating at least a portion of a surface of the substrate with a hydrophilic polymer; and
(c) effecting raising or expansion of at least a portion of the hydrophilic polymer from the surface of the substrate to create one or more raised image areas.
2. A method as claimed in Claim 1 wherein raising of the polymer from the surface or expansion of the polymer is effected by generating a gas beneath, within or on the polymer .
3. A method as claimed in Claim 1 or 2 wherein the substrate is a sheet material.
4. A method as claimed in any one of Claims 1 to 3 wherein the substrate comprises card, paper, plastics, textile materials or metal.
5. A method as claimed in any preceding claim wherein hydrophilic polymer is a water-soluble polymer or a water- dispersible polymer.
6. A method as claimed in any preceding claim wherein the hydrophilic polymer is present in an aqueous solution or as a dispersion in an aqueous medium.
7. A method as claimed in any preceding claim wherein the hydrophilic polymer is a polymer selected from polyvinyl alcohol, polyvinylpyrrolidone, polyvinylacetate, polyacrylic acid, polyacrylates, active acrylic polymers, gelatins, carboxyalkylcelluloses, alginates, guar gum, locust bean gum, polymeric surfactants and polyols.
8. A method as claimed in Claim 7 wherein the hydrophilic polymer is polyvinylalcohol .
9. A method as claimed in any preceding claim wherein the hydrophilic polymer is laid down as a coating in an aqueous medium in step (b) .
10. A method as claimed in Claim 9 wherein the coating is substantially dried.
11. A method as claimed in Claim 10 wherein the aqueous medium is printed onto the substrate.
12. A method as claimed in Claims 10 or 11 wherein the aqueous medium further includes a dye or pigment.
13. A method as claimed in any preceding claim wherein step (c) comprises applying an agent capable of generating gas on application of a stimulus to at least a portion of the coating.
14. A method as claimed in Claim 13 wherein gas generation is effected by the reaction of two or more agents applied in step (c) .
15. A method as claimed in Claim 13 wherein gas generation is effected by the reaction of an agent applied in step (c) with an agent present in the coating laid down in step (b) .
Figure imgf000017_0001
16
16. A method as claimed in any one of Claims 13 to 15 wherein step (b) comprises coating a hydrophilic polymer and a first agent capable of reacting with a second agent to form a gas to the substrate, and step (c) may comprise image-wise applying a second agent capable of reacting with the first agent to generate a gas.
17. A method as claimed in Claim 16 wherein the first agent is an acid and the second agent is an agent capable of reacting with the acid to generate a gas.
18. A method as claimed in any preceding claim wherein the coating of hydrophilic polymer is dried after step (b) .
19. A method as claimed in any preceding claim wherein gas generation on, within or beneath the coating is effected such that different amounts of gas are generated at different areas of the coating.
20. A method of manufacturing an image article, the method comprising :
(a) providing a substrate;
(b) coating at least a portion of a surface of the substrate with a hydrophilic polymer and a first agent capable of generating a gas by reaction with a second agent; and
(c) image-wise applying a second agent capable of reacting with the first agent to generate a gas, to the coating.
21. A method as claimed in Claim 20 wherein the amount of gas generated in step (c) is controlled by varying the amount of the second agent applied to an area of the coating .
22. A method as claimed in Claims 20 or 21 wherein the second agent applied to the coating in step (c) is printed onto the coating.
23. A method of manufacturing an image article, the method comprising :
(a) providing a substrate;
(b) coating at least a portion of a surface of the substrate with a hydrophilic polymer;
(c) image-wise applying an agent capable of generating a gas upon contact with a stimulus, to the coating; and
(d) applying the stimulus to the agent capable of generating a gas.
24. An image article manufactured by any one of Claims 21 to 23.
PCT/GB2005/001766 2004-06-10 2005-05-10 Improvements in printing techniques WO2005121893A1 (en)

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WO2007142788A3 (en) * 2006-05-30 2008-05-22 Eastman Kodak Co Laser ablation resist
US7831178B2 (en) 2007-07-13 2010-11-09 Eastman Kodak Company Printing of optical elements by electrography
US7965961B2 (en) 2007-07-13 2011-06-21 Eastman Kodak Company Printing of raised multidmensional toner by electography
US8358957B2 (en) 2006-12-27 2013-01-22 Eastman Kodak Company Selective printing of raised information by electrography
US9358578B2 (en) 2006-02-10 2016-06-07 Inovink Limited Printing

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US2601161A (en) * 1948-08-19 1952-06-17 Louis S Sanders Medium for use in making camera copy and method of preparing the same
US4459344A (en) * 1970-12-21 1984-07-10 Ezekiel Jacob J Method for producing raised images by xerographic means
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US5639540A (en) * 1994-07-21 1997-06-17 Brother Kogyo Kabushiki Kaisha Thermal expansile sheet
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9358578B2 (en) 2006-02-10 2016-06-07 Inovink Limited Printing
WO2007142788A3 (en) * 2006-05-30 2008-05-22 Eastman Kodak Co Laser ablation resist
US7867688B2 (en) 2006-05-30 2011-01-11 Eastman Kodak Company Laser ablation resist
US8358957B2 (en) 2006-12-27 2013-01-22 Eastman Kodak Company Selective printing of raised information by electrography
US7831178B2 (en) 2007-07-13 2010-11-09 Eastman Kodak Company Printing of optical elements by electrography
US7965961B2 (en) 2007-07-13 2011-06-21 Eastman Kodak Company Printing of raised multidmensional toner by electography

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