US3919450A - Color developing high impact polystyrene sheet and method of developing color images inside the same - Google Patents

Color developing high impact polystyrene sheet and method of developing color images inside the same Download PDF

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Publication number
US3919450A
US3919450A US37139573A US3919450A US 3919450 A US3919450 A US 3919450A US 37139573 A US37139573 A US 37139573A US 3919450 A US3919450 A US 3919450A
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Prior art keywords
sheet
acid
color developing
color
high impact
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Takuji Shimizu
Isao Ohara
Kenji Yasuda
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New Oji Paper Co Ltd
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Oji Paper Co Ltd
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    • 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
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2559/00—Photographic equipment or accessories
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/91—Product with molecular orientation
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • 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
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249978—Voids specified as micro
    • Y10T428/249979—Specified thickness of void-containing component [absolute or relative] or numerical cell dimension
    • 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
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/254—Polymeric or resinous material
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/268—Monolayer with structurally defined element
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
    • 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
    • Y10T428/31—Surface property or characteristic of web, sheet or block

Definitions

  • an acid-reactive colorless color forming dye solution in a non-volatile organic liquid capable of dissolving or swelling polystyrene into contact with an acid color developing high impact polystyrene sheet which comprises a substrate layer consisting of a high impact polystyrene film which has been stretched in at least one direction, at least one paper-like rough surface layer provided on the substrate layer by treating the surface portion of the high impact polystyrene film with an organic liquid capable of dissolving or swelling polystyrene. and having therein numerous microvoids, and acid color developing agent for the acid-reactive colorless color forming dye, the acid color developing agent being contained in the microvoids. whereby the colorless color forming dye solution penetrates into the microvoids and forms color images inside the sheet.
  • the present invention relates to a color developing high impact polystyrene sheet capable of developing color images having excellent resistances to the rays of the sun, water and rubbing. and a method of developing the color images inside the sheet.
  • acid reactive colorless color forming dyes for example. Crystal violet lactone, leuco Auramine type compounds, leuco Methylene Blue type compounds and leuco Fluorane type'compounds can be developedby bringing them into contact with an acid color developing agent.
  • Such acid-reactive colorless color forming dyes and the acid color developing agents are utilized in the fields of duplicating and printing.
  • the conventional pressure sensitive no carbon copying paper is composed of a combination of a top sheet carrying, on a surface thereof, a layer of microcapsules containing therein a colorless color forming dye and a bottom sheet carrying, on a surface thereof, a layer of color developing agent effective for the colorless color forming dye.
  • the color developing agent layer of the bottom sheet faces the microcapsule layer of the top sheet.
  • the microcapsules are composed of fine particles of a solution of the colorless color forming dye in a nonvolatile solvent and a thin shells covering the fine particles.
  • the thin shells are generally formed by a filmforming material. for example, gelatin.”
  • the bottom sheet of the pressure-sensitive copying paper may be utilized as a printing sheet for printing with a printing ink containing the colorless color forming dye. That is, when colorless images formed by the colorless printing ink on the printing plate are brought into contact with the color developing agent layer of the printing sheet, the colorless printing ink images are transferred onto the surface of the Lcolor-developing layer of the printing sheet and color images are formed thereon.
  • the acid-reactive colorless color forming dyes are electron donors and theacid color developing agents are electron acceptors. Accordingly, when the colorless color forming dyes are brought into contactwith the color developing agent, anelectron of the colorless color forming dye molecule transfers to the color developing agentmolecule so as to convert the colorless dye to'color "dye.”
  • the electron donor colorless dyes includes colorless triphenylmethane compounds, fore'xample, Crystal Vitional color developing sheet, the disadvantages as detailed below.
  • the triphenylmethane type coloring matters have an extremely low light fastness. That is, when exposed to the radiation of direct rays of the sun or ultraviolet ray for few hours, the color images of the triphenylmethane coloring matter are faded away and thereafter. disappear.
  • the triphenylmethane type colorless .color forming dye is mixed with a leuco Methylene Blue type colorless color forming dye and the mixture is used as the duplicating or printing dye.
  • the Methylene Blue type coloring matters have a high light fastness.
  • the Methylene Blue type coloring matters have the disadvantages of low color depth and high tendency to discoloration of the color images during storage over a long period of time. Accordinglygeven if the color images are formed by the coloring mixture of the triphenylmethane type coloring matter and the Methylene Blue type coloring matter. after fading away the color image of the triphenylmethane type coloring matter by the action of the rays of the sun. the remaining color images of the Methylene Blue type coloring matter are hard to read because of the low color depth thereof.
  • the Methylene Blue type coloring matter images tend to discolor and. the refore, the color images are changed in color tone.
  • the color developing agents to be applied on the color developing sheet surface are electron acceptor compounds.
  • the color 7 developing agent may be selected from inorganic acid solid materials, for example. attapulgite. bentonite. ka olin, zeolite and acid clay. These acid solid materials have a disadvantageous tendency to deteriorate and. therefore, to lose the capacity of developing the acidreactive colorless colorforming dyes when they are exposed to the atmosphere for more than about one month. While the basis of the deterioration of the acid solid materials is not quite clear, it is believed that the acid solidmaterials are deteriorated by absorbing water or reacting with carbon dioxide in atmosphere. From the above stated circumstances. it is clear that long storage of the color developing sheet carrying the inorganic acid solid material as the color developing agent. results in loss of practical usefulness thereof. I
  • phenol, phenol derivatives and condensation products of phenol are useful as the color developing agent for the acid-reactive colorless color forming dyes.
  • the phenolcompounds have the following defects.
  • the object of the present invention is to provide a color developing high impact polystyrene sheet capable of maintaining brilliant color images developed from an acid reactive colorless color forming dye over a long period of time while protecting the color images from the actions of the rays of the sun and moisture.
  • Another object of the present invention is to provide a color developing high impact polystyrene sheet capable of developing colorless reactive of acid ractive col orless color forming dye to brilliant deep color images even after storage over a long period of time.
  • a further object of the present invention is to provide a method of developing color images having excellent resistances to the rays of the sun. water and rubbing. inside a color developing sheet.
  • the color developing polystyrene sheet of the present invention which comprises a substrate layer consisting of a high impact polystyrene film which has been stretched in at least one direction. at least one rough surface layer provided on the surface of said substrate layer and having numerous microvoids formed therein. said rough surface layer being formed by treating the surface portion of the substrate film with a solvent capable of dissolving or swelling polystyrene. and an acid color developing agent contained in said microvoids. said acid color developing agent being effective for developing acid-reactive colorless color forming dyes.
  • a polystyrene-rubber blend contains uniformly dispersed fine particles of an elastic organic polymer selected from natural rubber and synthetic rubbers. for example. styrenegrafted and non-grafted styrenebutadiene. polybutadiene. and acrylonitrile-butadienestyrene rubbers.
  • the high impact polystyrene film comprises 80 to 98%. preferably. 92 to 96% by weight of polystyrene and 2 to preferably. 4 to 8% by weight of the rubber component as mentioned above. It is preferable that the fine rubber particles dispersed in the polystyrene have a mean size of about 1 to 7 1..
  • the polystyrene-rubber blend is shaped into a film or sheet by the conventional method. and the film or sheet is stretched in one or two directions. By the stretching. numerous fine particles of the rubber component dispersed in the polystyrene are elongated in one or more directions and fixed. in the elongated form. by the polystyrene component surrounding the rubber particles. Accordingly, the elongated and fixed rubber particles have a high potential for shrinkage.
  • the stretched high impact polystyrene film When at least one surface portion of the stretched high impact polystyrene film is treated with an organic liquid capable of dissolving or swelling the polystyrene. and allowing the stretched rubber particles to rapidly shrink the rubber particles are released from the fixation and elongation. Accordingly. the released rubber particles rapidly shrink.
  • the rapid shrinking of the rubher particles results in formation of microvoids in the treated portion of the film.
  • the formation of the microvids causes the formation of a rough surface layer on the non-treated film portion.
  • the microvoids thus formed contain the organic liquid.
  • the organic liquid in the microvoids are removed by a conventional method. for example. evaporation. replacement with a non-solvent or washing.
  • the high impact polystyrene sheet thus treated has one or two opaque or translucent rough surface layers provided with numerous microvoids therein. It is preferable that the microvoids have a mean size of about 3 to 20p.
  • the opaque or translucent rough surface layer is capable of absorbing therewithin writing ink. duplicating ink or printing ink. Accordingly. the high impact polystyrene sheet thus treated has at least one color developing rough surface layer provided with numerous microvoids and a non-treated substrate layer. It is preferable that the non-treated substrate layer has a mean thickness of about 50% based on the thickness of the original high impact polystyrene film.
  • the treated high impact polystyrene sheet can be utilized as the writing. duplicating and printing sheets.
  • the treating organic liquid for the high impact polystyrene may be selected from organic compounds capable of dissolving or swelling polystyrene.
  • the organic liquid may be selected from aliphatic hydrocarbons. for example. n-hexane. n-heptane and n-octane.
  • the rough surface layer formed by the treatment of the high impact polystyrene sheet includes therein numerous microvoids.
  • the microvoids in the rough surface layer include therein an acid color developing agent effective for developing the acid-reactive colorless color forming dyes.
  • the acid color developing agent is deposited in the microvoids in the high impact polystyrene sheet in an amount of 0.5 to 3 g/m". and substantially confined therein.
  • FIG. 1 is a photograph showing the cross-sectional view of the color developing polystyrene sheet of the present invention.
  • FIGS. 2 through 5 are each a duplicating sheet including the color developing polystyrene sheet of the present invention.
  • a color developing polystyrene sheet 1 has a substrate layer 2 and rough surface layer 3 formed on both sides of the substrate layer 2.
  • the rough surface layer 3 is provided with numerous microvoids formed therein and having a complicated and non-fixed configuration. These microvoids contain the acid color developing agent.
  • the acid color developing agent usable for the present invention has to be selected in consideration of the acid-reactive colorless color forming dye to be developed by the acid color developing agent.
  • the acidreactive colorless color forming dye is selected from triphenylmethane type colorless color forming dyes, particularly. Crystal Violet lactone.
  • the color developing agent may be selected from the compounds capable of electron-acceptance from the above-stated colorless color forming dyes and color developing them. For example.
  • the color developing agent usable for the present invention may be selected from mono-carboxylic acids which may have one or more other radical than the carboxyl radical, for example, p-aminobenzoic acid, p-hydroxybenzoic acid and acetic acid; polycarboxylic acids which may have one or more other radical than the carboxyl radical, for example, succinic acid, maleic acid, citraconic acid, chloromaleic acid, itaconic acid, aconitic acid and phthalic acid; homopolymers of ethylenically unsaturated carboxylic acids.
  • mono-carboxylic acids which may have one or more other radical than the carboxyl radical
  • polycarboxylic acids which may have one or more other radical than the carboxyl radical, for example, succinic acid, maleic acid, citraconic acid, chloromaleic acid, itaconic acid, aconitic acid and phthalic acid
  • homopolymers of ethylenically unsaturated carboxylic acids for
  • polyacrylic acid and polymethacrylic acid for example, polyacrylic acid and polymethacrylic acid; copolymersof ethylenically unsaturated acid anhydrides, for example, maleic, chloromaleic, citraconic, itaconic and aconitic acid anhydrides with at least one of ethylene and styrene; phenol compounds, for example, p-cumylphenol, p-phenylphenol p-tert-butylphenol.
  • p-octylphenol and p-nonylphenol polyphenol compounds, for" example, gallic acid, bis-phenol A, bis-phenol B and cathecol; novolak type condensation products of a phenol compound, for example, novolak type condensation products of phenol, p-phenylphenol, p-cumylphenol, 'p-tert-butylphenol, p-octylphenol and p-nonylphenol with formaldehyde, preferably, having at most 3 of phenol units; and phenol-acetylene polymers.
  • the acid color developing agent is confined inside the microvoids of the rough surface layer, it is substantially isolated from atmosphere and, therefore, can be protected from deterioration thereof by the action of moisture in the atmosphere or the rays of the sun.
  • the color developing high impact polystyrene sheet of the present invention may be prepared by the method as detailed below.
  • a high impact polystyrene film is stretched in one or more directions, preferably, two directions.
  • the stretched film is treated with a solution of the acid color developing agent in an organic liquid capable of dissolving the acid color developing agent and of dissolving or swelling the polystyrene and allowing the stretched rubber particles to rapidly shrink.
  • the organic liquid may be selected from aliphatic hydrocarbons, for example, n-hexane, n-heptan and noctane.
  • the acid color developing agent may be selected from the compounds as stated hereinbefore.
  • the acid color developing agent may be dissolved direct into the organic solvent. Also, the acid color developing agent may be first dissolved into a solvent other than that to be used for dissolving or swelling the polystyrene, for instance, alcohols, for example, ethyl alcohol, n-butyl alcohol, ethers, ether, for example, tetrahydrofuran and 1,4-dioxane aliphatic hydrocarbons, for instance, alcohols, for example, ethyl alcohol, n-butyl alcohol, ethers, ether, for example, tetrahydrofuran and 1,4-dioxane aliphatic hydrocarbons, for
  • the first solution is mixed in a solvent for dissolving or swelling the polystyrene. Accordingly, the solvent for the polystyrene must be able to dissolve the acid color developing agent and the first solvent.
  • the high v impact polystyrene film is treated at its surface portion with the solution containing the acid color developing agent in the organic liquid, numerous microvoids are formed therein. The microvoids are impregnated with the solution. Thereafter, the organic solvent is removed so as to deposit the acid color developing agent inside the microvoids. After completely removing the organic solvent, the acid color developing agent is substantially confined within the microvoids.
  • the above-stated method has an advantage that the proposed color developing high impact polystyrene sheet can be prepared by only one step from the high impact polystyrene film.
  • the color developing polystyrene sheet of the present invention may also be prepared by the method as detailed below.
  • the stretched high impact polystyrene film is treated at its surface portions with the solvent capable of dissolving or swelling the polystyrene, so as to obtain the high impact polystyrene sheet having rough surface layers wherein numerous microvoids are formed.
  • the rough surface layer is treated with a solution of the acid color developing agent in a solvent.
  • This solvent may be selected from aliphatic hydrocarbons, for example n-heptane and n-octane; aromatic hydrocarbons.
  • ethers for example, toluene and xylene
  • ethers for example, ethyl ether and 1,4-dioxane
  • ether alcohols for example, B hydroxyethyl methyl ether and B-hydroxyethyl ether
  • carboxylic acids for example, acetic acid and methacrylic acid
  • ketones for example. acetone and methylisobutyl ketone
  • esters for example. ethyl acetate and methyl formate
  • halogenated hydrocarbons for example, tetrachloroethane
  • alcohols for example. methyl alcohol and ethyl alcohol
  • mixtures of two or more of the abovestated compounds for example, toluene and xylene
  • ethers for example, ethyl ether and 1,4-dioxane
  • ether alcohols for example, B hydroxyethyl methyl ether and B-hydroxyethyl ether
  • the solution of the acid color developing agent penetrates into the microvoids and is contained therein.
  • the ac'id color developing agent is deposited in the microvoids, and after completely removing the solvent, the acid color developing agent is substantially eonfined in the microvoids.
  • the color developing high impact polystyrene sheet of the present invention is prepared by any one of the methods stated above. It is preferable that the microvoids have a mean size of about 3 to 20,11, and that the non-treated substrate layer has a mean thickness of about 50% based on that of the originalfilm.
  • the colorless color forming dye should be transferred onto the rough surface layer of the developing sheet in accordance with the predetermined pattern.
  • the present invention includes a method of developing color images from an acid-reactive colorless color forming dye, inside the color developing high impact polystyrene sheet of the present invention.
  • a solution or ink containing an acid-reactive colorless color forming dye selected from leuco triphenylmethane type and leuco Fluorane type colorless color forming dyes is transferred onto the rough surface of the color developing sheet in accordance with the predetermined pattern.
  • the colorless color forming dyes are generally dissolved in an organic solvent selected from non-volatile liquids such as vegetable oils. for example, olive oil, castor oil. cotton seed oil and peanut oil; mineral oils, for example, various paraffin oils; synthetic oil, for example, chlorinated diphenyls, alkyl diphenyls. alkyl naphthalenes, aryl alkanes. chlorinated paraffins, dioctyl phthalate and tricresyl phosphate, and mixtures of two or more of the above-mentioned oils.
  • non-volatile liquids such as vegetable oils. for example, olive oil, castor oil. cotton seed oil and peanut oil; mineral oils, for example, various paraffin oils; synthetic oil, for example, chlorinated diphenyls, alkyl diphenyls. alkyl naphthalenes, aryl alkanes. chlorinated paraffins, dioctyl phthalate and tricresyl
  • the solution of the colorless color forming dye when the solution of the colorless color forming dye is applied onto the rough surface layer of the color developing sheet.
  • the solution can rapidly penetrate into the microvoids containing the acid color developing agent therewithin while dissolving or swelling the polystyrene.
  • the colorless color forming dye in the solution is brought into contact with the acid color developing agent in the microvoids. and converted to the coloring matter so as to form color images.
  • the solution containing the coloring matter thus developed further penetrates to the bottom portion of the rough surface layer. or sometimes to the substrate layer, and is fixed there in such a condition that the coloring matter is mixed with the polysty rene dissolved in the solvent.
  • the color images thus formed are absorbs the light radiated to the sheet and protects the color images from the radiation of light. Accordingly, even if the color images are formed by the triphenylmethane type dye which has essentially very low light fastness. the color images embedded in the high impact polystyrene sheet show an unexpected high light fastness.
  • the color developing high impact polystyrene sheet of the present invention may be utilized as a bottom sheet of a pressure sensitive no carbon duplicating sheet.
  • a no carbon duplicating sheet 21 is composed of a top sheet 22 and a bottom sheet 23.
  • the top sheet 22 comprises a base sheet 24 consisting of paper and a microcapsule layer 25 applied onto the lower surface of the base sheet 24 and consisting of numerous microcapsules and a binder incorporating the microcapsules into one layer.
  • the bottom sheet 23 is made of a color developing high impact polystyrene sheet of the present invention which comprises a substrate layer 26 and a color developing rough surface layer 27 facing the microcapsule layer 25.
  • the no carbon duplicating sheet 21 When the no carbon duplicating sheet 21 is pressed on the upper surface of the top sheet 22 in accordance with the predetermined pattern.
  • the microcapsules of the top sheet 22 are broken by the pressure in accordance with the pattern.
  • the duplicating ink flowed out from the broken microcapsules penetrates into the color developing rough surface layer of bottom sheet 23 while dissolving or swelling polystyrene thereof and contacts the color developing agent contained in the microvoids. Accordingly, the color images of the desired pattern are formed inside the rough surface layer 27 of the bottom sheet 23.
  • a no carbon duplicating sheet 30 is composed of a top sheet 31. an intermediate sheet 32 and a bottom sheet 33.
  • the top sheet 31 is composed of a base sheet 34 consisting of paper and a microcapsule layer 35 provided on the upper surface of the base sheet 34.
  • the interme diate sheet 32 is composed of a color developing high impact polystyrene sheet of the present invention having a substrate layer 36 and color developing rough surface layer 373 provided on the upper side of the substrate layer 36 and facing the microcapsule layer 35 of the top sheet 31, and a microcapsule layer 38 provided on the lower side of the substrate layer 36.
  • the bottom sheet 33 is made ofa color developing high impact polystyrene sheet of the present invention which has a substrate layer 39 and a color developing rough surface layer 37b provided on the upper side of the substrate layer 39 and facing the microcapsule layer 38 of the intermediate sheet 32.
  • the duplicating sheet may comprise two or more intermediate sheets as stated above.
  • the bottom and intermediate sheets carrying color images are separated from the top sheet and utilized as open air display sheets, labels and copying sheets to be kept over a long period of time.
  • a pressure sensitive no carbon duplicating sheet 41 is composed of a top sheet 42 and a bottom sheet 43.
  • the top sheet 42 consists of a base sheet 44 made of a paper or synthetic polymer. and a microcapsule layer 45 provided on the lower surface of the base sheet 44.
  • the bottom sheet 43 is composed of an adhesive duplicating sheet 46 and a releasable sheet 47 capable of being separated from the adhesive duplicating sheet 46.
  • the adhesive duplicating sheet 46 is composed of a color developing high impact polystyrene sheet 48 of the present invention which has a substrate layer 49 and a color developing rough surface layer 50, facing the microcapsule layer 45 of the top sheet 42, and an adhesive layer 51 provided on the lower surface of the high impact polystyrene sheet 48.
  • the releasable sheet 47 is composed of a base sheet 52 made of paper or a synthetic polymer sheet and a layer 53 of releasing material facing the adhesive layer 51 of the duplicating sheet 46 and being adhered to the adhesive layer 51 at such a very small adhesiveness that the releasable sheet 47 can be easily separated from the duplicating sheet 46.
  • the releasable sheet 47 is separated from the duplicating sheet 46 and the duplicating sheet 46 carrying the desired color images is adhered to a desired article or material through the adhesive layer 51.
  • a no carbon duplicating sheet is composed of a top sheet 61, an intermediate sheet 62 and bottom sheet 63.
  • the top sheet 61 is composed of a base sheet 64 made of paper or a synthetic polymer film and a microcapsule layer 65 provided on the lower surface of the base sheet 64.
  • the intermediate sheet 62 is composed of an adhesive duplicating sheet 66 and a releasable sheet 67.
  • the adhesive duplicating sheet 66 consists of a color developing high impact polystyrene sheet 68 having a substrate layer 69 and a color developing rough surface layer 70 facing the microcapsule layer 65 of the top sheet 61, and an adhesive layer 71 provided on the lower surface of the high impact polystyrene sheet 68.
  • the releasable sheet 67 consists of a base sheet 72 made of paper or a synthetic polymer sheet, and a layer 73 of a releasing agent provided on the upper surface of the base sheet 72, and a microcapsule layer 74 provided on the lower surface of the base sheet 72.
  • the releasing agent layer 73 adheres to the adhesive layer 71 of the duplicating sheet'66 with a very small adhesive strength and, therefore, is easily peeled off from the adhesive layer 71.
  • the bottom sheet 63 consists of a color developing high impact polystyrene sheet of the present invention having a substrate layer 75 and a color developing rough surface layer 76 facing the microcapsule layer 74 of the intermediate layer 62.
  • the duplicating sheet 66 of the intermediate sheet 62 is separated from the releasable sheet 67 and adhered to a desired article or material, and the bottom sheet 63 is kept as a record.
  • two or more intermediate sheets may be inserted between the top and bottom sheets.
  • the color developing high impact polystyrene sheet of the present invention possesses the advantages detailed below.
  • the colorless color forming dye having a low resistance to water and a poor light fastness such as triphenylmethane type colorless dyes
  • the color images formed on the color developing sheet of the present invention have an excellent light fastness and resistance to water. Therefore, the triphenylmethane type colorless dye does not need to be mixed with the Methylene Blue type colorless dye which has been conventionally used to enhance the light fastness of the I color images formed by the triphenylmethane type dye. This is effective to lower the color image formingcost and eliminate the problem that the Methylene Blue type coloring matter readily discolors during storage.
  • the Methylene Blue type colorless dye is used in the form of mixture with the triphenylmethane type colorless dye, it is necessary to dissolve the Methylene Blue type colorless dye in a strong non-volatile solvent such as polychlorobenzenes which has a high toxicity, because of the difficulty of dissolving it.
  • a strong non-volatile solvent such as polychlorobenzenes which has a high toxicity
  • the color developing sheet of the present invention does not need the Methylene Blue type colorless dye mixed with the triphenylmethane type colorless dye, there is the advantage that the solvent to be used to dissolve the colorless dye is non-toxic.
  • the color developing sheet of the present invention has a larger advantage in practical use than that of the conventional color developing paper. 7
  • the,color developing agent may be a volatile or sublimatable solid or liquid.
  • the color developing sheet of the present invention can be utilized as a recording sheet to be kept over a long period of time, because the color image developed on the color developing sheet has an excellent light fastness and resistances to water and rubbing.
  • the color developing sheet of the present invention can be utilized as an indicating sheet to be used in the open air or chit sheet for delivery without cover sheet. Compared with this, the indicating sheet and the chit sheet carrying color images developed on the conventional color developing sheet need to be covered by a clear film, because the color images have a poor light fastness and low resistance to water.
  • the present invention can provide a very thin color developing sheet which is effective to obtain clear color images on a plurality of color developing sheets even if they are simultaneously superimposed and subjected to duplication.
  • the color developing sheet used as a printing sheet for the conventional printing processes for example. typographic, lithographic and intaglio printings. has the following advantages. Since the printing ink penetrates into the inside of the sheet, the printed sheets do not adhere to each other. Further, since the color images are formed inside the sheet, the color images have a very high resistance to abrasion.
  • EXAMPLE 1 Preparation of top sheet A mixture of 2 g of gelatin and 2 g of gum arabic was dissolved in 1 litre of pure water, and the solution was adjusted to a pH of 10.0 by adding 10% sodium hydroxide aqueous solution. To the solution was added 20 g of a dye solution which has been prepared by dissolving 6 parts of Crystal Violet lacton in 100 parts of hexylnaph- ,lthalene. The mixture was emulsifiedby using a homogenizer at a temperature of C. The emulsion was adjusted to a pH of 4.0 by adding 10% acetic acid.
  • bottom sheet 250 g of a commercial 2.2'-methylene-bis(4-chlorophenol) was dissolved in a uniform mixture of4.9 litres of n-heptane and 0.1 litre of ,B-hydroxyethyl ether while heating. and the solution was maintained at a temperature of 50C.
  • a stretched high impact polystyrene film of a thickness of 100 p. was immersed in the solution for 2 seconds and dried in the atmosphere A polystyrene sheet having both upper and lower rough surfaces was obtained.
  • the thickness of the resultant sheet was 120 The rough surfaces were provided with numerous microvoids containing therein the 2.Z'-methylene-bis(4- chlorophenol) as a color developing agent. and a mean size of about 5 [.L.
  • the color images formed on the bottom sheet of the present invention did not run or flow away even when immersed in water.
  • the rough surface carrying the color images of the bottom sheet of the present invention was moistened and rubbed. However. the color images did not bleed. Compared with this. when the conventional bottom sheet (I) was immersed in water. the color images thereon rapidly ran. Also. when the conventional bottom sheets (I) and (II) were moistened and rubbed. the color images thereon did bleed and dis appear.
  • A. Preparation of color developing agent A mixture of 170 parts of p-phenylphenol. parts of 37% aqueous solution of formaldehyde. 1 part of oxalic acid anhydride and 50 parts of 77 aqueous solution of hydrochloric acid. was charged into a flask with a reflux condenser. and heated at the boiling point thereof to react them. After 4 to 6 hours the heating was stopped. and water in the mixture was removed. The resultant product had a molecular weight of 270 to 400. The flask was reduced in pressure by using an aspirator and. thereafter. the product was distilled under the reduced pressure at a temperature of 100C. The resultant product had a melting point of l00C.
  • the light fastness of the color developing agent contained in the bottom sheet was determined by exposing it, using a xenon type fading meter. for "hours and duplicating in the same manner as in Example 1.
  • the same tests as stated above were applied to the same conventional bottom sheets (1) and (11) as used in Example 1.
  • the results of the tests are shown in bottom sheet ()2 From Table 2. It is obvious that the color images and the color developing agent in the bottom sheet of the present invention had a remarkably higher light fastness than those of the conventional bottom sheets. Further, it was observedthat the color images formed in the bottom sheet of the present invention had a remarkably higher resistance to water and rubbing than those of the conventional bottom sheets.
  • Color developing agent A commercial p-aminobenzoic. acid was used as the color developing agent.
  • Example II E. Testing of color images
  • The'ligh t fastness of the color images formed in the bottom sheet was tested in the same manner as in Example I. Also. the light fastness of the color developing agent contained in the bottom sheet was determined in the same manner as in Example 1.
  • the same conventional bottom sheets l and (2) as used in Example 1 were put under the same top sheets used in Example 1. and the same procedures were repeated for the conventional duplicating sheets 1 and (2) prepared above.
  • EXAMPLE 4 The same bottom sheet as in Example 1 was used as a printing sheet. Predetermined images of a printing colorless-ink consisting of 5% of Rhodamine B lactam 40% of volume pigment. of varnish and 25% of diarylethane. were printed on the rough surface of the printing sheet (25 -cm) using a typographic printing' testing machine. The colorless ink rapidly penetrated'into the rough layer and brilliantred images were immediately formed therein. Even after superimposing the printed sheets over a week under a weight of 10 kg/cm there was no adhering of the sheets to each other. v
  • the color images thus formed had excellent high fastness and resistance to water and rubbing.
  • the images of the same colorless ink as in Example 4 was printed on 500 printing sheets under a printing pressure of about l2 kg/cm using a rotary offset press at a velocity of 120 sheets/minute.
  • the printing ink was absorbed immediately by the rough surface layer of the printing sheet and brilliant blue images were formed therein. No blocking of the printed sheet was observed.
  • the light fastness of the color images was determined by exposing them for 24 hours to artificial light of a fading meter.
  • the color im ages were faded by an amount of 5%.
  • 500 pieces of the conventional printing sheets (25 X cm) were prepared by the following method.
  • a color developing high impact polystyrene sheet comprising:
  • a substrate layer consisting essentially of a high impact polystyrene film which has fine particles of a rubber component uniformly dispersed in the polystyrene and which has been stretched in at least one direction.
  • microvoids being formed by treating the surface portion of the high impact polystyrene film with an organic liquid capable of dissolving or swelling the polystyrene and capable of allowing the stretched particles of said rubber component to rapdily shrink.
  • an acid color developing agent contained in said microvoids. said acid color developing agent being capable of developing acid-reactive colorless color forming dye.
  • a color developing sheet as claimed in claim 2, wherein said monocarboxylic acid is selected from the group consisting of p-aminobenzoic acid. p-hydroxybenzoic acid and acetic acid.
  • a color developing sheet as claimed in claim 2, wherein said polycarboxylic acid is selected from the group consisting of succinic acid. maleic acid. citra- 16 conic acid. chloromaleic acid. itaconic acid. aconitic acid and phthalic acid.
  • a color developing sheet as claimed in claim 2, wherein said novolak type condensation product of a phenol compound is selected from the group consisting of novolak type condensation products of phenol. pphenylphenol. p-cumylphenol. p-tert-butylphenol. poctylphenol and p-nonylphenol with formaldehyde. each having 3 or less phenolic components.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
  • Laminated Bodies (AREA)
US37139573 1972-06-24 1973-06-19 Color developing high impact polystyrene sheet and method of developing color images inside the same Expired - Lifetime US3919450A (en)

Applications Claiming Priority (1)

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JP6282972A JPS5122413B2 (de) 1972-06-24 1972-06-24

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US (1) US3919450A (de)
JP (1) JPS5122413B2 (de)
AU (1) AU470053B2 (de)
BE (1) BE801317A (de)
CA (1) CA992314A (de)
DE (2) DE2331963C3 (de)
FR (1) FR2190064A5 (de)
GB (1) GB1434586A (de)
IT (1) IT989401B (de)
NL (1) NL7308778A (de)

Cited By (6)

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US4037004A (en) * 1972-11-09 1977-07-19 Sekisui Kagaku Kogyo Kabushiki Kaisha Method for producing thermoplastic resin films or sheets for chelate color printing
FR2350205A1 (fr) * 1976-05-07 1977-12-02 Mead Corp Procede de fabrication de feuilles d'enregistrement sans carbone sensible a la pression a l'aide de systemes " hot melt ", systemes " hot melt " utilises pour la mise en oeuvre de ce procede et produits ainsi obtenus
US4956309A (en) * 1988-12-06 1990-09-11 The Mead Corporation Microroughened developer sheet for forming high density images
US6042945A (en) * 1997-10-02 2000-03-28 Sumitomo Chemical Company Limited Light diffusing laminated resin sheet
ES2199089A1 (es) * 2003-09-03 2004-02-01 Signe Sa Papel autocopiativo de seguridad.
US8912119B2 (en) 2011-10-31 2014-12-16 Intertape Polymer Corp. Pressure-chromic tape and methods of making same

Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
JPS6018384A (ja) * 1983-07-12 1985-01-30 Mitsubishi Paper Mills Ltd 減感インキ
JPS60124284A (ja) * 1983-12-09 1985-07-03 Lion Corp 減感剤組成物
US4927971A (en) * 1988-05-11 1990-05-22 Mitsubishi Paper Mills Ltd. Desensitizer composition

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US3244549A (en) * 1961-08-31 1966-04-05 Burroughs Corp Manifold sheets coated with lactone and related chromogenous compounds and reactive phenolics and method of marking
US3515567A (en) * 1966-01-26 1970-06-02 Kaneyasu Tani Method of surface treating polymer film to produce paper-like article
US3540911A (en) * 1967-01-30 1970-11-17 Ncr Co Pressure sensitive record sheets employing 3 - (phenyl) - 3-(indol - 3 - yl)-phthalides
US3634121A (en) * 1969-03-17 1972-01-11 Ncr Co Acid-sensitized record sheet
US3663256A (en) * 1964-08-27 1972-05-16 Ncr Co Mark-forming record material
US3681390A (en) * 1970-11-16 1972-08-01 Ncr Co Dialkylamino fluoran chromogenic compounds
US3741860A (en) * 1969-11-28 1973-06-26 Oji Yuka Goseishi Kk Synthetic paperlike film suitable for writing and printing and its preparation
US3767449A (en) * 1970-09-28 1973-10-23 Fuji Photo Film Co Ltd Recording sheet
US3769302A (en) * 1969-01-21 1973-10-30 T Hoover Aliphatic amino-substituted flourans
US3799828A (en) * 1968-03-26 1974-03-26 Mitsubishi Petrochemical Co Synthetic papers and the method of making the same

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Publication number Priority date Publication date Assignee Title
US3244549A (en) * 1961-08-31 1966-04-05 Burroughs Corp Manifold sheets coated with lactone and related chromogenous compounds and reactive phenolics and method of marking
US3663256A (en) * 1964-08-27 1972-05-16 Ncr Co Mark-forming record material
US3515567A (en) * 1966-01-26 1970-06-02 Kaneyasu Tani Method of surface treating polymer film to produce paper-like article
US3540911A (en) * 1967-01-30 1970-11-17 Ncr Co Pressure sensitive record sheets employing 3 - (phenyl) - 3-(indol - 3 - yl)-phthalides
US3799828A (en) * 1968-03-26 1974-03-26 Mitsubishi Petrochemical Co Synthetic papers and the method of making the same
US3769302A (en) * 1969-01-21 1973-10-30 T Hoover Aliphatic amino-substituted flourans
US3634121A (en) * 1969-03-17 1972-01-11 Ncr Co Acid-sensitized record sheet
US3741860A (en) * 1969-11-28 1973-06-26 Oji Yuka Goseishi Kk Synthetic paperlike film suitable for writing and printing and its preparation
US3767449A (en) * 1970-09-28 1973-10-23 Fuji Photo Film Co Ltd Recording sheet
US3772052A (en) * 1970-09-28 1973-11-13 Fuji Photo Film Co Ltd Recording sheet and color developer therefor
US3681390A (en) * 1970-11-16 1972-08-01 Ncr Co Dialkylamino fluoran chromogenic compounds

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4037004A (en) * 1972-11-09 1977-07-19 Sekisui Kagaku Kogyo Kabushiki Kaisha Method for producing thermoplastic resin films or sheets for chelate color printing
FR2350205A1 (fr) * 1976-05-07 1977-12-02 Mead Corp Procede de fabrication de feuilles d'enregistrement sans carbone sensible a la pression a l'aide de systemes " hot melt ", systemes " hot melt " utilises pour la mise en oeuvre de ce procede et produits ainsi obtenus
US4063754A (en) * 1976-05-07 1977-12-20 The Mead Corporation Process for the production of pressure sensitive carbonless record sheets using novel hot melt systems and products thereof
US4956309A (en) * 1988-12-06 1990-09-11 The Mead Corporation Microroughened developer sheet for forming high density images
US6042945A (en) * 1997-10-02 2000-03-28 Sumitomo Chemical Company Limited Light diffusing laminated resin sheet
ES2199089A1 (es) * 2003-09-03 2004-02-01 Signe Sa Papel autocopiativo de seguridad.
US8912119B2 (en) 2011-10-31 2014-12-16 Intertape Polymer Corp. Pressure-chromic tape and methods of making same

Also Published As

Publication number Publication date
IT989401B (it) 1975-05-20
GB1434586A (en) 1976-05-05
CA992314A (en) 1976-07-06
DE2331963B2 (de) 1975-03-20
BE801317A (fr) 1973-10-15
DE7323369U (de) 1976-06-03
DE2331963C3 (de) 1975-11-27
JPS4923008A (de) 1974-03-01
NL7308778A (de) 1973-12-28
AU5731973A (en) 1975-01-09
JPS5122413B2 (de) 1976-07-09
FR2190064A5 (de) 1974-01-25
AU470053B2 (en) 1976-03-04
DE2331963A1 (de) 1974-01-10

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