Deprecated: The each() function is deprecated. This message will be suppressed on further calls in /home/zhenxiangba/zhenxiangba.com/public_html/phproxy-improved-master/index.php on line 456
EP0554370B2 - Revetement de reseaux interpenetrants hydrophiles - Google Patents
[go: Go Back, main page]

EP0554370B2 - Revetement de reseaux interpenetrants hydrophiles - Google Patents

Revetement de reseaux interpenetrants hydrophiles Download PDF

Info

Publication number
EP0554370B2
EP0554370B2 EP91920283A EP91920283A EP0554370B2 EP 0554370 B2 EP0554370 B2 EP 0554370B2 EP 91920283 A EP91920283 A EP 91920283A EP 91920283 A EP91920283 A EP 91920283A EP 0554370 B2 EP0554370 B2 EP 0554370B2
Authority
EP
European Patent Office
Prior art keywords
liquid
solution
materials
polymers
transparent
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
EP91920283A
Other languages
German (de)
English (en)
Other versions
EP0554370A1 (fr
EP0554370B1 (fr
Inventor
Mohammad Iqbal
Alan G. Miller
Terrance P. Smith
John J. Stofko, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=24412604&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0554370(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0554370A1 publication Critical patent/EP0554370A1/fr
Application granted granted Critical
Publication of EP0554370B1 publication Critical patent/EP0554370B1/fr
Publication of EP0554370B2 publication Critical patent/EP0554370B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose

Definitions

  • This invention relates to transparent materials that are capable of absorbing liquids, and, more particularly, to materials that can be used as ink-receptive layers for transparent imageable materials.
  • Transparent materials that are capable of absorbing significant quantities of liquid, while maintaining some degree of durability and transparency, are useful in contact lenses, priming layers for coatings coated out of aqueous solutions, fog-resistant coatings, and transparent imageable materials for use with mechanized ink depositing devices, such as pen plotters and ink-jet printers.
  • Transparent imageable materials are used as overlays in technical drawings and as transparencies for overhead projection. It is desirable that the surface of liquid absorbent materials for use in transparent graphical applications be tack free to the touch even after absorption of significant quantities of ink.
  • ink formulations typically utilize solvents of very low volatility, such as water, ethylene glycol, propylene glycol, and so on.
  • solvents of very low volatility such as water, ethylene glycol, propylene glycol, and so on.
  • aqueous inks Inks that contain water or water-miscible solvents are commonly referred to as aqueous inks, and the solvents for these inks are commonly referred to as aqueous liquids.
  • compositions useful as transparent liquid absorbent materials have been formed by blending a liquid-insoluble polymeric material with a liquid-soluble polymeric material.
  • the liquid-insoluble material is presumed to form a matrix, within which the liquid soluble material resides.
  • Examples of such blends are the transparent water-absorbent polymeric materials disclosed in U.S. Patent Nos. 4,300,820 and 4,369,229, and in European Patent Application No. 0 233 703.
  • Compatibility between two or more polymers in a blend can often be improved by incorporating into the liquid-insoluble matrix-forming polymer chains monomeric units that exhibit some affinity for the liquid-soluble polymer.
  • Polymeric materials having even a small amount of acid functionality are more likely to exhibit compatibility with polyvinyl lactams.
  • the compatibility of polymers being blended is improved if the polymers are capable of hydrogen bonding to one another.
  • a second form of incompatibility noted in using blends of liquid-absorbent polymers is the incompatibility of the matrix forming insoluble polymer with the liquid being absorbed.
  • the liquid being absorbed is water
  • the water-insoluble polymers are hydrophobic, some inhibition of water absorption ability can be expected.
  • One method of overcoming this difficulty is to utilize hydrophilic matrix polymers that are water-insoluble at the temperatures at which they are to be used, though they may be water-soluble at a different temperature.
  • ink-receptive coatings comprising either polyvinyl alcohol or gelatin blended with polyvinyl pyrrolidone are disclosed.
  • Both polyvinyl alcohol and gelatin being water-insoluble at room temperature, are able to act as matrix-forming polymers for these coatings, and the coatings are quite receptive to aqueous inks. However, the coatings do exhibit a tendency to become tacky, either because of imaging, or because of high humidity.
  • This invention provides a coatable composition capable of forming hydrophilic liquid-absorbent, semi-interpenetrating networks, hereinafter referred to as SIPNs.
  • SIPNs of this invention are formed from polymer blends comprising (a) at least one crosslinkable polymer, (b) at least one liquid-absorbent polymer comprising a water-absorbent polymer, and (c) optionally, a crosslinking agent. Substantially all crosslinking of the crosslinkable polymer takes place after the composition is coated onto a substrate and allowed to dry.
  • SIPNs are continuous networks wherein the crosslinked polymer forms a continuous matrix throughout the bulk of the material and through which the liquid-absorbent polymer is intertwined in such a way as to form a macroscopically homogeneous composition.
  • the SIPNS of this invention are capable of absorbing significant quantities of those liquids that are solvents or swelling agents of the uncrosslinked portion of the SIPN without loss of physical integrity and without leaching or other forms of phase separation.
  • the nature of the crosslinking used in the formation of the matrix component SIPN is such that it provides durability in the presence of the liquids encountered during use with compatibility toward the liquid-absorbent component.
  • the crosslinked matrix component and the liquid-absorbent component are miscible, exhibit little or no phase separation, and generate little or no haze upon coating.
  • the nature of the crosslinking should not cause phase separation or other inhomogeneity in the SIPN, or gelation of coating solutions before use or coating.
  • the present invention provides transparent compositions capable of providing improved ink absorption and durability, while at the same time retaining transparency and being amenable to the types of processing commonly used in producing transparent graphical materials.
  • the crosslinked portion of the SIPN will hereinafter be called the matrix component, and the liquid-absorbent portion will hereinafter be called the absorbent component.
  • hydrophilic is used to describe a material that is generally receptive to water, either in the sense that its surface is wettable by water or in the sense that the bulk of the material is able to absorb significant quantities of water. More specifically, materials that exhibit surface wettability by water are said to have hydrophilic surfaces, while materials that have surfaces not wettable by waterwill be said to have hydrophobic surfaces.
  • hydrophilic liquid-absorbing materials describes materials that are capable of absorbing significant quantities of water, blends of water and other liquids, including those materials that are water-soluble.
  • monomeric units When molecular structures are being discussed, monomeric units will be referred to as hydrophilic units if they have a water-sorption capacity of at least one mole of water per mole of monomeric unit. Sorption capacities of various monomeric units are given, for example, in D. W. Van Krevelin, with the collaboration of P. J. Hoftyzer, Properties of Polymers: Correlations With Chemical Structure Elsevier Publishing Company (Amsterdam, London, New York: 1972) pages 294-296. Monomeric units will be referred to as hydrophobic if they form water-insoluble polymers capable of absorbing only small amounts of water when polymerized by themselves.
  • the matrix component of the SIPN of the present invention comprises crosslinkable polymers that are either hydrophobic or hydrophilic in nature, and can be derived from the copolymerization of acrylic or other hydrophobic or hydrophilic ethylenically unsaturated monomeric units with monomers having acidic groups, or if pendant ester groups are already present in these acrylic or ethylenically unsaturated monomeric units, by hydrolysis.
  • Hydrophobic monomeric units suitable for preparing crosslinkable matrix components are preferably selected from:
  • hydrophobic and hydrophilic monomeric units contain pendant ester groups that can readily be rendered crosslinkable by hydrolysis.
  • monomeric units containing acidic groups must be incorporated into the polymeric structure to render them crosslinkable. Polymerization of these monomers can be carried out by typical free radical solution, emulsion, or suspension polymerization techniques. Suitable monomeric units containing acidic groups include acrylic acid or methacrylic acid, other copolymerizable carboxydic acids, and ammonium salts.
  • the crosslinking agent is preferably selected from the group of polyfunctional aziridines possessing at least two crosslinking sites per molecule, such as trimethylol propane-tris-( ⁇ -(N-aziridinyl)propionate) penta erythritol-tris-( ⁇ -(N-aziridinyl)propionate) trimethylolpropane-tris-( ⁇ -(N-methylaziridinyl propionate) and so on.
  • Crosslinking can also be brought about by means of metal ions, such as provided by multivalent metal ion salts, provided the composition containing the crosslinkable polymer is made from 80 to 99 parts by weight of monomer and from 1 to 20 parts by weight of a chelating compound.
  • the metal ions can be selected from ions of the following metals: cobalt, calcium, magnesium, chromium, aluminum, tin, zirconium, zinc, nickel, and so on, with the preferred compounds being selected from aluminum acetate, aluminum ammonium sulfate dodecahydrate, alum, aluminum chloride, chromium (III) acetate, chromium (III) chloride hexahydrate, cobalt acetate, cobalt (II) chloride hexahydrate, cobalt (II) acetate tetrahydrate, cobalt sulfate hydrate, copper sulfate pentahydrate, copper acetate hydrate, copper chloride dihydrate, ferric chloride hexahydrate, ferric ammonium sulfate dodecahydrate, ferrous chloride, tetrahydrate, magnesium acetate tetrahydrate, magnesium chloride hexahydrate, magnesium nitrate hexahydrate, manganese acetate
  • the preferred chelating compounds can be selected from:
  • crosslinkable polymers suitable for the matrix component of the hydrophilic SIPNs of the present invention are polymers having crosslinkable tertiary amino groups, wherein said groups can be provided either as part of the monomeric units used in the formation of the polymer, or grafted onto the polymer after the formation of the polymeric backbone.
  • R 8 represents a member selected from the group consisting of substituted and unsubstituted alkyl groups, substituted and unsubstituted amide groups, and substituted and unsubstituted ester groups, the foregoing groups preferably having no more than ten carbon atoms, more preferably having no more than five carbon atoms, substituted and unsubstituted aryl groups, preferably having no more than 14 carbon atoms
  • R 9 and R 10 independently represent a member selected from the group consisting of substituted and unsubstituted alkyl groups, preferably having no more than ten carbon atoms, more preferably having no more than five carbon atoms, and substituted and unsubstituted aryl groups, preferably having no more than 14 carbon atoms.
  • R 9 and R 10 can be connected to form the substituted or unsubstituted cyclic structure -R 9 -R 10 -.
  • the symbol represents a plurality of unsubstituted or substituted -CH 2 - groups linked together to form the backbone of the chain.
  • Preferred substituents for R 11 are those capable of hydrogen bonding, including -COOH, -CN, and -NO 2 .
  • a particularly useful example of a crosslinkable matrix component is a copolymer of polymethyl vinyl ether and maleic anhydride, wherein these two monomeric units are present in approximately equimolar amounts.
  • This copolymer can be formed in the following manner: wherein R 9 , R 10 , and R 11 are as described previously, and s preferably represents a number from about 100 to about 600.
  • This reaction can be conveniently performed by dissolving the polymethyl vinyl ether/maleic anhydride copolymer, i.e., reactant (a), in methyl ethyl ketone, dissolving the amine, i.e., reactant (b), in an alcohol, such as methanol or ethanol, and mixing the two solutions. This reaction proceeds rapidly at room temperature, with agitation. The product of this reaction may begin to form a cloudy suspension, which can be cleared by the addition of water to the solution.
  • Crosslinking agents suitable for this type of polymer are multi-functional alkylating agents, each functional group of which forms a bond with a polymer chain through a tertiary amino group by quaternization of the trivalent nitrogen of the tertiary amino group.
  • Difunctional alkylating agents are suitable for this purpose.
  • this crosslinking reaction can be depicted as follows: where R 8 , R 9 , R 10 , and s are as described previously, R 12 can be the same as R 8 , R 9 , or R 10 , and Q - can be a halide, an alkyl sulfonate, preferably having no more than 5 carbon atoms, or any aryl sulfonate, preferably having no more than 14 carbon atoms.
  • crosslinkable polymers suitable for forming the matrix component of the SIPNs of the present invention include polymers having silanol groups, wherein the silanol groups can either be part of the monomeric units used in the formation of the polymer or be grafted onto the polymer after the formation of the polymeric backbone. If grafting is preferred, the polymeric backbones generally contain monomeric units of maleic anhydride, which can be converted into graftable sites by reaction with compounds having primary amino groups. Silanol side groups can be grafted onto these sites by heating a solution containing the backbone polymer with an aminoalkoxysilane. The alkoxysilane can subsequently be hydrolyzed by the addition of water.
  • reaction scheme can be depicted as follows: wherein A represents a monomeric unit preferably selected from the group consisting of acrylonitrile, allyl acetate, ethylene, methyl acrylate, methyl methacrylate, methyl vinyl ether, stilbene, isostilbene, styrene, vinyl acetate, vinyl chloride, vinylidene chloride, vinylpyrrolidone, divinylether, norbornene, and chloroethyl vinyl ether;
  • Suitable substituents for R 17 include alkoxy, -OH, -COOH, -COOR, halide, and -NR 2 , wherein R represents an alkyl group, preferably having up to five carbon atoms, more preferably having not more than three carbon atoms.
  • the relative amounts of the two types of side groups in polymer (d) are determined by the relative amounts of compounds (b) and (c) used in the grafting solutions.
  • the molar ratio of compound (c) to compound (b) in the reaction ranges from about 3 to about 6, preferably from about 4 to about 5.
  • the resulting polymer can be crosslinked by the removal of water and other solvents from the system without addition of further crosslinking agent, according to the reaction: Additionally, crosslinking can occur at more than one of the -OH groups attached to the silicon atom.
  • the liquid-absorbent component While it is the primary function of the matrix component of the SIPN to impart physical integrity and durability to the SIPN without adversely affecting the overall liquid absorbency of the SIPN, it is the primary function of the liquid-absorbent component to promote absorption of liquids.
  • the liquid-absorbent component When aqueous liquids are to be absorbed, as is in the case of most inks, the liquid-absorbent component must be capable of absorbing water, and preferably be water-soluble.
  • the liquid-absorbent component can be selected from polymers formed from the following monomers:
  • Polymerization of these monomers can be carried out by conventional typical free radical polymerization techniques as mentioned previously.
  • the liquid-absorbent component can be selected from commercially available water-soluble or water-swellable polymers such as polyvinyl alcohol, polyvinyl alcohol/poly(vinyl acetate) copolymer, poly(vinyl formal) or poly(vinyl butyral), gelatin, carboxy methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl starch, polyethyl oxazoline, polyethylene oxide, polyethylene glycol, polypropylene oxide, and so on.
  • the preferred polymers are polyvinyl lactams, especially polyvinyl pyrrolidone, and polyvinyl alcohol.
  • SIPNs of the present invention to be used for forming ink-receptive layers typically comprise from about 0.5 to 6.0% by weight of crosslinking agent, preferably from about 1.0 to 4.5% by weight, when crosslinking agents are needed.
  • the crosslinkable polymer can comprise from about 25 to about 99% by weight, preferably from about 30 to about 60% by weight, of the total SIPNs.
  • the liquid-absorbent component can comprise from about 1 to about 75% by weight, preferably from about 40 to about 70% by weight, of the total SIPNs.
  • Such ink-receptive layers are generally borne by a substrate, such as transparent polymeric sheet.
  • a composition for preparing such a layer to the substrate by means of a coating solution, which is subsequently dried to form a solid layer.
  • a coatable liquid composition can be prepared by dissolving polymers of the matrix component and the liquid-absorbent component in a common solvent, which can be water, or water-miscible solvents, in appropriate proportions depending on the solubility of the components. The appropriate crosslinking agent, if used, is then added, and mixed until a uniform solution is obtained.
  • Common solvents can be selected by making use of Hansen parameters, which are numerical values that characterize the individual contributions to cohesive energy density made by the intermolecular dispersion forces, dipole forces, and hydrogen bonding forces of a particular compound.
  • Hansen parameters are numerical values that characterize the individual contributions to cohesive energy density made by the intermolecular dispersion forces, dipole forces, and hydrogen bonding forces of a particular compound.
  • Soluble solid materials tend to be more readily dissolved by liquids having Hansen parameters within a specified range, this range being called the solubility envelope, and less readily dissolved by liquids having Hansen parameters outside of the solubility envelope. Because of this tendency, Hansen parameters can be used as a basis for selecting single solvents or for formulating solvent blends capable of dissolving a particular solid material or combination of solid materials.
  • Hansen parameters and solubility envelopes for a variety of solid materials along with Hansen parameters for many commonly used solvents, as well as formulae for mathematically estimating Hansen parameters of materials not listed, can be found in Barton, A.F.M. CRC Handbook of Solubility Parameters and Other Cohesion Parameters CRC Press, Inc., (Boca Raton: 1983), incorporated herein by reference.
  • SIPN solutions of the present invention may contain additional modifying ingredients such as adhesion promoters, particles, surfactants, viscosity modifiers, and like materials, provided that such additives do not adversely affect the liquid-absorbing capability of the invention.
  • Coating can be conducted by any suitable means, such as knife coating, rotogravure coating, reverse roll coating, or other conventional means. Drying can be accomplished by means of heated air. If preferred, an adhesion promoting priming layer can be applied to the substrate prior to coating. Such priming layers can include primer coatings, surface treatments such as corona treatment, or other appropriate treatment. Adhesion of the SIPN layer can also be promoted by providing a gelatin sublayer of the type used in photographic film backings between the priming layer and the SIPN layer. Film backings having both a priming layer and a gelatin sublayer are commercially available, and are frequently designated as primed and subbed film backings.
  • the backing of the film When the SIPNs of the present invention are to be used to form the ink absorbing layer of a film for use with an ink-jet printer, it is preferred that the backing of the film have a caliper in the range of about 50 to about 125 micrometers. Films having calipers below about 50 micrometers tend to be too fragile for graphic arts films, while films having calipers over about 125 micrometers tend to be too stiff for easy feeding through many of the imaging machines currently in use. Materials suitable for backings for graphic arts films include polyesters, e.g., polyethylene tetrephthalate, cellulose acetates, polycarbonates, poly(vinyl chlorides), polystyrenes, and polysulfones.
  • polyesters e.g., polyethylene tetrephthalate, cellulose acetates, polycarbonates, poly(vinyl chlorides), polystyrenes, and polysulfones.
  • the SIPN layer may further be overcoated with an ink-permeable, anti-tack protective layer, such as, for example, a layer comprising polyvinyl alcohol in which starch particles have been dispersed, or a semi-interpenetrating polymeric network in which polyvinyl alcohol is the absorbent component.
  • an ink-permeable, anti-tack protective layer such as, for example, a layer comprising polyvinyl alcohol in which starch particles have been dispersed, or a semi-interpenetrating polymeric network in which polyvinyl alcohol is the absorbent component.
  • overcoat layers can provide surface properties that help to properly control the spread of ink droplets so as to optimize image quality.
  • modifying ingredients such as surfactants, particles, or the like, can be added to the formulation for the overcoat layer to improve ink flow, dot spread, or other aspects of ink receptivity to improve image appearance.
  • a polymeric material suitable for the matrix of an SIPN was prepared by combining N-vinyl-2-pyrrolidone (75 parts by weight), N,N-dimethyl acrylamide (2 parts by weight), the ammonium salt of acrylic acid (5 parts by weight), azo-bis-isobutyronitrile (0.14 part by weight, "Vazo", available from E. I. DuPont de Nemours and Company), and deionized water (566 parts by weight) in a one-liter brown bottle. The mixture was purged with dry nitrogen gas for five minutes; polymerization was then effected by immersing the bottle for between 18 to 24 hours in a constant temperature bath maintained at a temperature of 60°C. The resulting polymerized mixture was then diluted with deionized water to give a 10% aqueous solution. The resulting solution will hereinafter be called Solution A.
  • Solution A (8 g of a 10% aqueous solution) was mixed with surfactant (0.2 g of a 2% aqueous solution, "Triton X100", Rohm and Haas Co.), polyvinyl alcohol(8 g of a 5% aqueous solution, "Vinol 540", Air Products and Chemicals, Inc.), and polyfunctional aziridine crosslinking agent (0.5 g of a 10% aqueous solution, XAMA-7, Sanncor Ind. Inc.) in a separate vessel.
  • the resultant solution was coated onto a backing of polyethylene terephthalate film having a caliper of 100 micrometers, which had been primed with polyvinylidene chloride, over which had been coated a gelatin sublayer of the type used in photographic films for improving gelatin adhesion ("Scotchpar" Type PH primed and subbed film, available from Minnesota Mining and Manufacturing Company). Coating was carried out by means of a knife coater at a wet thickness of 200 micrometers. The coating was then dried by exposure to circulating heated air at a temperature of 90°C for five minutes to form a dear SIPN layer.
  • Printing was performed with an ink-jet printer and pen using ink containing Direct Blue 99 dye (3% solution in water). After six minutes, the imaged film was immersed in water and no dye was removed from image. The SIPN layer remained intact.
  • a solution of matrix component of the present invention was prepared by first dissolving 1.3 g of a copolymer of methyl vinyl ether and maleic anhydride ("Gantrez" AN-169, available from GAF Chemicals Corporation) in 24.6 g of methyl ethyl ketone. In a separate vessel, 1.3 g of aminopropyl morpholine (available from Aldrich Chemical Company, Inc.) were dissolved in 11.6 g of methanol. The previously prepared solution of copolymer was then added, dropwise, to the aminopropyl morpholine/methanol solution, after which 36.6 g of distilled water were added to the resulting combined solutions. The resulting solution will hereinafter be called matrix component Solution B.
  • blend Solution B In yet another vessel, 2.5 g of polyvinyl pyrrolidone (K90, available from GAF Chemicals Corporation) were dissolved in 22.1 g of distilled water. This solution was then added to matrix component Solution B and agitated until a uniform solution was obtained. The resulting solution, hereinafter called blend Solution B, was then divided into 5 samples of 20.0 g each.
  • K90 polyvinyl pyrrolidone
  • the dihalo compound 3,3-bis-(iodomethyl)-oxetane was prepared according to the procedure described in Sorenson, W.R., and Campbell, T.W., Preparative Methods of Polymer Chemistry, 2nd Edition, New York, Interscience Publishers, Inc., 1968, p. 376, incorporated herein by reference.
  • a solution of 10 parts by weight of this compound and 90 parts by weight of dimethyl formamide (DMF) was prepared for use as an alkylating agent for crosslinking the matrix component.
  • Crosslinkable solutions according to the present invention were prepared by adding 0.35 g of the 3,3-bis-(iodomethyl)-oxetane/DMF solution to one of the 20.0 g samples of blend Solution B, 0.70 g of the 3,3-bis-(iodomethyl)-oxetane/DMF solution to a second 20.0 g sample of blend Solution B, and 1.4 g of the 3,3-bis-(iodomethyl)-oxetane/DMF solution to a third 20.0 g sample of blend Solution B.
  • the polymeric material for the matrix of the SIPN was prepared by combining N-vinyl-2-pyrrolidone (28 parts by weight), N,N-dimethyl acrylamide (20 parts by weight), 2-acrylamido-2-methyl propanesulfonic acid (2 parts by weight of the ammonium salt), azo-bis-isobutyronitrile (0.07 part by weight, "Vazo", available from E. I. du Pont de Nemours and Company), and deionized water (280 parts by weight) in a one-liter brown bottle. After the mixture was purged with dry nitrogen gas for five minutes, polymerization was effected by immersing the bottle in a constant temperature bath maintained at 60°C for eight hours to give a very viscous clear solution (97.8% conversion). The resulting polymerized mixture was then diluted with deionized water to give a 10% solution in water, hereinafter called Solution C.
  • Solution C (21.94 g of a 10% aqueous solution) was thoroughly mixed with polyvinyl alcohol("Vinol 540", available from Air Products and Chemical, Inc., 28.6 g of a 5% aqueous solution), and chromium chloride crosslinking agent (0.29 g of a 10% aqueous solution) in a separate vessel.
  • the resultant solution was coated onto a backing of polyethylene terephthalate film having a caliper of 100 micrometers, which had been primed with polyvinylidene chloride, over which had been coated a gelatin sublayer of the type used in photographic films for improving gelatin adhesion ("Scotchpar" Type PH primed and subbed film, available from Minnesota Mining and Manufacturing Company). Coating was carried out by means of a knife coater at a wet thickness of 200 micrometers. The coating was then dried by exposure to circulating heated air at a temperature of 90°C for five minutes. After drying, a clear SIPN layer formed.
  • SIPN of the present invention is a single layer hydrophilic coating that is capable of absorbing aqueous ink.
  • a solution of the grafting material was prepared by first dissolving 0.07 g of 3-aminopropyltriethoxysilane (Aldrich Chemical Co., Inc.) and 0.22 g of 2-methoxyethylamine (Aldrich Chemical Co., Inc.) in 5.9 g of methanol.
  • a solution of the backbone polymer was prepared by dissolving 0.5 g of a copolymer of methyl vinyl ether and maleic anhydride ("Gantrez AN-169", GAF Chemicals Corporation) in 9.5 g of methyl ethyl ketone. The solutions of the grafting material and the backbone polymer were then combined and stirred to provide a clear, viscous liquid.
  • Asolution of absorbent component was prepared in a separate vessel by adding 1.5 g of polyvinyl pyrrolidone, (K-90, GAF Chemicals Corporation) to 13.5 g of deionized water and stirring the resulting mixture until a dear solution was formed.
  • An ink-receptive layer was formed by coating the solution so prepared onto a sheet of polyvinylidene chloride-primed and gelatin-subbed polyethylene terephthalate film having a caliper of 100 micrometers ("Scotchpar" Type PH primed and subbed film, available from Minnesota Mining and Manufacturing Company) by means of a knife coater adjusted so as to apply a liquid layer having a wet thickness of 125 micrometers. The liquid layer was dried in a forced air oven at a temperature of 90°C for a period of five minutes.
  • the ink receptivity of the dried coating was tested by writing on it with a pen which used an aqueous ink ("Expresso" brand pen, Sanford Corp. Bellwood, IL).
  • the ink image dried sufficiently in 10 seconds to be non-smearable when gently rubbed with the finger.
  • the SIPN layer tended to become tacky at relative humidities of about 90% or greater.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)

Claims (4)

  1. Article transparent comprenant un substrat transparent comportant sur au moins une surface importante de celui-ci un réseau semi-interpénétrant, absorbant les liquides, hydrophile comprenant :
    a) au moins un polymère réticulé formant une matrice continue; et
    b) au moins un polymère absorbant les liquides comprenant un polymère absorbant l'eau, entremêlé dans ladite matrice,
    le polymère réticulé provenant d'un polymère réticulable qui est réticulé après qu'il a été appliqué audit substrat.
  2. Procédé de préparation de l'article transparent suivant la revendication 1, comprenant les étapes :
    (1) de mélange d'au moins le polymère réticulable avec au moins le polymère absorbant les liquides dans un milieu liquide pour former une solution applicable en couche et uniforme qui est essentiellement exempte de trouble et de gélification;
    (2) d'application de la solution au substrat transparent susdit; et
    (3) de séchage de ladite solution, de manière à ce que le polymère réticulable soit réticulé.
  3. Article transparent suivant la revendication 1, comprenant de plus un agent de réticulation.
  4. Procédé de préparation de l'article transparent suivant la revendication 3, comprenant les étapes :
    (1) de mélange d'au moins le polymère réticulable avec au moins le polymère absorbant les liquides et un agent de réticulation dans un milieu liquide pour former une solution applicable en couche et uniforme qui est essentiellement exempte de trouble et de gélification;
    (2) d'application de la solution au substrat transparent susdit; et
    (3) de séchage de ladite solution, de manière à ce que le polymère réticulable soit réticulé.
EP91920283A 1990-10-24 1991-09-13 Revetement de reseaux interpenetrants hydrophiles Expired - Lifetime EP0554370B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US60273890A 1990-10-24 1990-10-24
US602738 1990-10-24
PCT/US1991/006686 WO1992007722A1 (fr) 1990-10-24 1991-09-13 Revetement de reseaux interpenetrants hydrophiles

Publications (3)

Publication Number Publication Date
EP0554370A1 EP0554370A1 (fr) 1993-08-11
EP0554370B1 EP0554370B1 (fr) 1994-08-17
EP0554370B2 true EP0554370B2 (fr) 2002-01-09

Family

ID=24412604

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91920283A Expired - Lifetime EP0554370B2 (fr) 1990-10-24 1991-09-13 Revetement de reseaux interpenetrants hydrophiles

Country Status (9)

Country Link
EP (1) EP0554370B2 (fr)
JP (1) JPH06502358A (fr)
KR (1) KR930702162A (fr)
AU (1) AU653757B2 (fr)
BR (1) BR9107009A (fr)
CA (1) CA2093514A1 (fr)
DE (1) DE69103534T3 (fr)
ES (1) ES2060416T5 (fr)
WO (1) WO1992007722A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5474843A (en) * 1993-12-16 1995-12-12 Labelon Corporation Acceptor material for inks
US5656378A (en) * 1993-12-16 1997-08-12 Labelon Corporation Ink acceptor material containing an amino compound
US5733672A (en) * 1993-12-16 1998-03-31 Labelon Corporation Ink acceptor material containing a phospholipid
DE4433077C1 (de) 1994-09-16 1995-11-16 Renker Gmbh & Co Kg Aufzeichnungsmaterial für Tintenstrahldruck
JPH08230313A (ja) * 1994-12-12 1996-09-10 Arkwright Inc インクジェット媒体用ポリマーマトリックスコーティング
AU7157396A (en) * 1995-10-26 1997-05-15 Minnesota Mining And Manufacturing Company Ink-jet recording sheet
ID20411A (id) 1997-01-23 1998-12-10 Daicel Chem Bagian permukaan perekaman dan proses produksi daripadanya
JP2002503763A (ja) * 1998-02-23 2002-02-05 ミネソタ マイニング アンド マニュファクチャリング カンパニー インクジェット記録シート
US6514600B1 (en) 2000-05-18 2003-02-04 Isp Investments Inc. Color inkjet receptive films having long term light stability
US6555213B1 (en) 2000-06-09 2003-04-29 3M Innovative Properties Company Polypropylene card construction
US6979480B1 (en) 2000-06-09 2005-12-27 3M Innovative Properties Company Porous inkjet receptor media
DE60228930D1 (de) 2002-01-22 2008-10-30 Fujifilm Corp Tintenstrahlaufzeichnungsblatt

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4935307A (en) * 1988-10-21 1990-06-19 Minnesota Mining And Manufacturing Company Transparent coatings for graphics applications

Also Published As

Publication number Publication date
ES2060416T5 (es) 2002-05-01
DE69103534T2 (de) 1995-03-09
KR930702162A (ko) 1993-09-08
JPH06502358A (ja) 1994-03-17
AU8905191A (en) 1992-05-26
CA2093514A1 (fr) 1992-04-25
EP0554370A1 (fr) 1993-08-11
BR9107009A (pt) 1993-08-24
EP0554370B1 (fr) 1994-08-17
ES2060416T3 (es) 1994-11-16
WO1992007722A1 (fr) 1992-05-14
DE69103534T3 (de) 2002-08-29
DE69103534D1 (de) 1994-09-22
AU653757B2 (en) 1994-10-13

Similar Documents

Publication Publication Date Title
US5376727A (en) Polymeric bland of a matrix resin and absorbent resin and a multivalent metal ion crosslinking agent
EP0482836B1 (fr) Matériaux transparents absorbant les liquides
EP0688265B1 (fr) Feuille a imprimabilite amelioree
EP0482838B1 (fr) Matériaux transparents absorbant les liquides pour fabriquer des couches réceptrices d'encre
EP0482837B1 (fr) Matériaux transparents absorbant les liquides
CA2052178C (fr) Materiaux transparents absorbents pour encrage direct
EP0365307B1 (fr) Révêtements transparents pour applications graphiques
US5192617A (en) Transparent liquid absorbent materials
EP0554370B2 (fr) Revetement de reseaux interpenetrants hydrophiles
JP2001508713A (ja) インキジェット記録用シート
US20040071900A1 (en) Binding substrate for inkjet inks

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19930518

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE ES FR GB IT LI NL SE

17Q First examination report despatched

Effective date: 19931006

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 69103534

Country of ref document: DE

Date of ref document: 19940922

ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2060416

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
EAL Se: european patent in force in sweden

Ref document number: 91920283.8

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: CANON INC. CORPORATE INTELLECTUAL PROPERTY AND LEG

Effective date: 19950516

NLR1 Nl: opposition has been filed with the epo

Opponent name: CANON INC. CORPORATE INTELLECTUAL PROPERTY AND LEG

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: CANON INC. CORPORATE INTELLECTUAL PROPERTY AND LEG

Effective date: 19950516

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

NLR1 Nl: opposition has been filed with the epo

Opponent name: CANON INC. CORPORATE INTELLECTUAL PROPERTY AND LEG

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

27A Patent maintained in amended form

Effective date: 20020109

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): BE CH DE ES FR GB IT LI NL SE

REG Reference to a national code

Ref country code: CH

Ref legal event code: AEN

Free format text: MAINTIEN DU BREVET DONT L'ETENDUE A ETE MODIFIEE

NLR2 Nl: decision of opposition
NLR3 Nl: receipt of modified translations in the netherlands language after an opposition procedure
REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Kind code of ref document: T5

Effective date: 20020125

ET3 Fr: translation filed ** decision concerning opposition
APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20070926

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20070924

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20070926

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20070927

Year of fee payment: 17

Ref country code: DE

Payment date: 20071031

Year of fee payment: 17

Ref country code: NL

Payment date: 20070923

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20071025

Year of fee payment: 17

Ref country code: SE

Payment date: 20070926

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070917

Year of fee payment: 17

BERE Be: lapsed

Owner name: *MINNESOTA MINING AND MFG CY

Effective date: 20080930

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20080913

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090401

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20090401

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20090529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090401

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080913

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080930

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080930

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080930

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20080915

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080913

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080915

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080914