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WO2000071360A1 - Microporous ink-receptive sheet - Google Patents

Microporous ink-receptive sheet Download PDF

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Publication number
WO2000071360A1
WO2000071360A1 PCT/US2000/012315 US0012315W WO0071360A1 WO 2000071360 A1 WO2000071360 A1 WO 2000071360A1 US 0012315 W US0012315 W US 0012315W WO 0071360 A1 WO0071360 A1 WO 0071360A1
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WO
WIPO (PCT)
Prior art keywords
coating
microporous
ink
coating according
silane
Prior art date
Application number
PCT/US2000/012315
Other languages
French (fr)
Inventor
Armin J. Paff
Alan G. Miller
Original Assignee
3M Innovative Properties Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Publication of WO2000071360A1 publication Critical patent/WO2000071360A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • 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
    • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants

Definitions

  • the invention provides a microporous ink-receptive film useful for imaging with ink jet printers, such films having coated on a substrate a porous ink-receptive coating having a median pore diameter up to about 40 nanometers, wherein the coating has been formed out of a solution containing a substantial amount of at least one water miscible organic liquid having a boiling point greater than about 150°C.
  • Imaging devices such as ink jet printers are well known methods for printing various information including labels and multi-colored graphics. Presentation of such information has created a demand for transparent ink-receptive imageable receptors that are used as overlays in technical drawings and as transparencies for overhead projection. Imaging with either the ink jet printer or the pen plotter involves depositing ink on the surface of these transparent receptors. These imaging devices conventionally utilize inks that can remain exposed to air for long periods of time without drying.
  • the surface of these receptors be dry and non-tacky to the touch, even after absorption of significant amounts of liquid soon after imaging, transparent materials that are capable of absorbing significant amounts of liquid while maintaining some degree of durability and transparency, are useful as imageable receptors for imaging.
  • the receptors must have a rapid sorption rate to give uniform appearing images free from coalescence and banding.
  • Liquid-absorbent materials disclosed in U.S. Patent Nos. 5,134,198, 5,192,617, 5,219,928 and 5,241,006 attempt to improve drying and decrease tack time.
  • These materials comprise crosslinked polymeric compositions capable of forming continuous matrices for liquid absorbent semi-interpenetrating polymer networks.
  • These networks are blends of polymers wherein at least one of the polymeric components is crosslinked after blending to form a continuous network throughout the bulk of the material, and through which the uncrosslinked polymeric components are intertwined in such a way as to form a macroscopically homogeneous composition.
  • WO 8806532 discloses a recording transparency and an aqueous method of preparation.
  • the transparency is coated with one or more hydroxyethylcellulose polymer(s).
  • the coating solution may also contain a surfactant to promote leveling and adhesion to the surface, and hydrated alumina for surface properties.
  • U.S. Patent No. 5,120,601 discloses a recording sheet comprising an ink receiving layer containing highly water absorptive resin particles and a binder.
  • the resin particles include sodium, lithium and potassium polyacrylates: vinyl alcohol/acrylamide copolymers; sodium acrylate/acrylamide copolymer; cellulose polymers; starch polymers, and the like.
  • Useful binders include any hydrophilic resin.
  • US Patent No. 4,636,805 (Canon) discloses a recording medium comprising an ink receiving layer capable of fixing an ink within 3 minutes at 20°C and 65% R-H to the extent of 0.7ml/cm 2 .
  • Embodiments include various gelatins; polyvinyl alcohols; starches; cellulose derivatives; polyvinylpyrrolidone, polyethyleneimine; polyvinylpyridinium halide, sodium polyacrylate, SBR and NBR latexes; polyvinylformal; PMMA; polyvinylbutyral; polyacrylonitrile; polyvinylchloride; polyvinylacetate; phenolic resins and so on.
  • US Patent No. 4,701,837 discloses a light transmissive recording medium having an ink receiving layer formed mainly of a water soluble polymer and a crosslinking agent.
  • the crosslinked polymer has a crosslinking degree satisfying the water resistance of the receiving layer while giving the layer the ink receiving capacity of 0.2 microliters/square centimeter.
  • a large variety of water soluble polymers are disclosed, including gelatin, casein, starch, gum arabic, sodium alginate, hydroxyethyl cellulose, carboxyethyl cellulose and the like; polyvinyl alcohols; saponified products of vinylacetate and other monomers; homopolymers or copolymers with other monomers of unsaturated carboxylic acids; copolymers or homopolymers with other vinyl monomers of sulfonated vinyl monomers; copolymers or homopolymers with other vinyl monomers of (meth)acrylamide; copolymers or homopolymers with other vinyl monomers of ethylene oxide, and so on.
  • 5.277.965 discloses a recording medium comprising a base sheet with an ink receiving layer on one surface, and a heat absorbing layer on the other, and an anti-curl layer coated on the surface of the heat absorbing layer.
  • the materials suitable for the ink-receptive layer can include hydrophilic materials such as binary blends of polyethylene oxide with one of the following group: hydroxypropyl methyl cellulose (Methocel®), hydroxyethyl cellulose; water-soluble ethylhydroxyethyl cellulose, hydroxybutylmethyl cellulose, hydroxypropyl cellulose, methyl cellulose, hydroxyethylmethyl cellulose; vinylmethyl ether/maleic acid copolymers; acrylamide/acrylic acid copolymers; salts of carboxymethylhydroxyethyl cellulose; cellulose acetate; cellulose acetate hydrogen phthalate, hydroxypropyl methyl cellulose phthalate: cellulose sulfate; PVA; PVP; vinyl alcohol/vin
  • US Patent No. 5,118.570 discloses a transparency comprising a hydrophilic coating and a plasticizer.
  • the coating is comprised of a ternary mixture of hydroxypropyl cellulose, carboxymethyl cellulose, polyethylene oxide and a plasticizer. This coating can also have dispersed therein additives such as colloidal silica.
  • U.S. Patent No. 5,068,140 discloses a transparency comprised of a supporting substrate and an anticurl coating or coatings thereunder.
  • the transparency is comprised of an anticurl coating comprising two layers.
  • the ink receiving layer in one embodiment is comprised of blends of poly(ethylene oxide), mixtures of poly(ethylene oxide) with a cellulose derivative such as sodium carboxymethyl cellulose, hydroxymethyl cellulose, and another component selected from a large variety of polymers and copolymers.
  • U.S. Patent 5,567,507 discloses an ink-jet receptive sheet comprising a multilayered ink-receptive coating having a thin upper layer comprising a high viscosity binder selected from the group consisting of methylcellulose, hydroxypropyl methylcellulose, and blends thereof, and further comprises an organic salt of polyethyleneimine.
  • a high viscosity binder selected from the group consisting of methylcellulose, hydroxypropyl methylcellulose, and blends thereof, and further comprises an organic salt of polyethyleneimine.
  • 4,460,637 discloses an ink-jet recording sheet comprising one or more layers, having a uppermost layer with a pore radius distribution showing a peak between 0.2 and 10 ⁇ m, and that the pore distribution radius of all ink receptive layers shows a peak in the same range and at least one other peak at 0.05 ⁇ m.
  • the patent teaches that colloidal particles of silica, aluminum hydroxide, alumina, etc., are useful if agglomerated into particles having an average size of 1 to 5 ⁇ m.
  • U.S. Patent 5,372,884 discloses an ink jet recording sheet comprising an ink receiving layer containing a cation-modified non-spherical colloidal silica.
  • the cation modifier is preferably hydrous aluminum oxide, hydrous zirconium oxide or hydrous tin oxide.
  • the sheet is disclosed to be quick drying and superior in water resistance.
  • U.S. Patent 4,816,333 discloses a continuous gelled network of silica particles useful as a coating for film. A polymeric binder may also be present.
  • U.S. Patent 5.002,825 discloses a surface porous film useful for offset printing and ink-jet recording.
  • the porous layer is prepared by mixing a water-dispersible polymer and specific colloidal silica containing a plurality of linearly connected primary particles to generate undulation in the layer.
  • U.S. Patent 5,612,281 discloses a recording sheet for ink-jet recording, electrographic recording or thermal transfer recording comprises a transparent colorant receptive layer having a void volume of 50% to 80% in which the network is formed from silica fine particles having a mean primary particle diameter of 10 nm or less and a water soluble resin wherein the weight of the silica particles to the resin is
  • U.S. Patent 5.679,451 discloses a recording medium providing an ink receptive layer containing a pigment having an aggregated particle diameter of from 0.5 to 50 ⁇ m and a binder.
  • U.S. Patent 5.639,546 discloses a coated product comprising a thermoplastic sheet support bearing on at least one surface an adhesion promoting cured layer comprising 30-80% individually dispersed colloidal metal oxide particles having average particle size 10-100 nm, and 20-70% crosslinked polymer matrix derived from one or more ethyleneically unsaturated monomers and a photoinitiator. Silica particles are disclosed as one of the preferred embodiments.
  • U.S. Patent 5,397,827 discloses thermoplastic polyester compositions containing special colloidal silica particles having a straight chain or a branched shape for use in films, particularly for magnetic tape. Preferred embodiments of this invention also have reduced image bleeding, improved shelf life, even when it is exposed to elevated temperature and high humidity, or in cases where solvent is prevented from leaving the coating, e.g., when stored in a transparency protector, and also display excellent drytimes.
  • the present invention discloses a coating which has been formed from a coating solution containing a high boiling point organic liquid.
  • the coating contains a colloidal silica and has a small median pore size.
  • the coating provides a superior ink- receptor for use with ink-jet imaging devices exhibiting both quick drying and low haze properties.
  • the invention provides a coating solution capable of forming a microporous coating onto a substrate, such solution containing a) a substantial amount of at least one water miscible organic liquid having a boiling point greater than 150°C, b) a colloidal silica comprising particles having a median particle size of up to 200 nm, and c) at least one polymeric binder. wherein said microporous coating has a median pore diameter up to 40 nm.
  • the invention further provides a microporous coating, such coating containing a colloidal silica comprising particles having a median particle size of up to 200 nm. at least one polymeric binder, wherein the microporous coating has a median pore diameter up to 40 nm, and was formed from a solution further comprising at least 3 % of at least one water miscible organic liquid having a boiling point of at least about 150°C.
  • Preferred microporous coatings of the invention comprise an elongated colloidal silica, although spherical colloidal silica of small particle size is also useful.
  • the invention further provides a coated ink-receptive sheet comprising a substrate having two surfaces, at least one surface having a microporous coating comprising a colloidal silica sol comprising particles having a median particles size of up to 200 nm, at least one polymeric binder, wherein said microporous coating has a median pore diameter up to 40 nm, said microporous coating having been formed from a solution further comprising at least 3% of at least one water miscible organic liquid having a boiling point of at least 150°C.
  • high boiling organic liquid means an organic solvent having a boiling point of at least about 150°C.
  • miscible means capable of mixing in any ratio without separation into two phases.
  • microporous means a porous material whose majority of pore diameters are less than 100 nm. All parts, percents, and ratios herein are by weight unless otherwise specifically stated.
  • High boiling organic liquids or solvents useful in formulations and microporous coatings of the materials of the invention include those organic solvents which are liquids at room temperature and which have a boiling point of at least about 150°C, preferably at least about 200°C. Examples include di(ethylene glycol) methyl ether, di(propylene glycol) methyl ether, tri(propylene glycol) methyl ether, and N- methylpyrrolidone. and the like.
  • Useful commercial embodiments include Dowanol TPM Glycol Ether, available from Dow Chemicals, and M-pyrol. available from I.S.P. Technologies Inc., Wayne. NJ. While not wishing to be bound by theory, it is believed that the slow evaporation of the high boiling liquid contributes to the even drying and the minimizing of cracking of the coating surface.
  • the amount of high boiling liquid in the solution is up to 30% of the coating solution, preferably from 5 to 15%.
  • the coating is allowed to dry, or is dried by introduction of heat or light, much of the liquid evaporates, and subsequent to such drying, less than 10% of the coating is high boiling organic liquids.
  • the coating solution and microporous coating contain a significant amount of a colloidal silica.
  • the silica comprises from 5 to 35% of the coating solution, and at least 65% of the coating formed therefrom.
  • Useful colloidal silicas have median particle sizes of up to 200 nanometers
  • the particles can be spherical or elongated, with elongated being preferred. Both spherical and elongated colloidal silicas are commercially available from companies such as Nalco Chemical Company, E.I. DuPont de Nemours Co, Inc., and as Snowtex. from Nissan Chemical Industries, Ltd.
  • the microporous coatings also contain a polymeric binder. Most conventional polymeric binders are useful.
  • the binder may be in the form of a water soluble resin or a non-water soluble dispersion.
  • Useful water soluble resins or nonwater soluble dispersions include various gelatins, including reaction products of gelatins with anhydrides of dibasic organic acids, starches such as oxidized or cation-modified starches, vinyl acetate polymer latexes such as polyvinyl acetate, vinyl acetate-maleate copolymer, vinyl acetate- acrylate copolymers, (meth)acrylate polymers, ethylene-acrylate copolymers, styrene- acrylate copolymers, salts of acrylic acid-methacrylic acid copolymers; glycols such as polyethylene glycol, polypropylene glycol, polyvinyl ethers, synthetic polymers such as polyvinylpyrrolidones, and modified polyvinylpyrrolidones such as
  • NVP/vinyl acetate copolymers e.g., those available commercially from as “S-630" and “W735"
  • NVP DMAEMA copolymers available as Gafquat® 755, NVP/acrylic acid copolymers. available as ACRYLIDONE®
  • NVP/MEAHEMA/AA copolymers such as "copolymer 958", all of which are available from I.S.P. Technologies Inc.. Wayne, NJ
  • modified polyvinylalcohols include polyvinylalcohols having various percentages of vinylacetate, methylcellulose polymers, and the like.
  • Useful polymeric binders also include cellulose binders such as methylcellulose, hydroxypropylmethylcellulose and hydroxyethyl-methylcellulose hydroxyethyl cellulose, hydroxymethyl cellulose, and carboxymethyl cellulose, ethylcellulose, ethylhydroxyethyl cellulose and hydroxybutyl cellulose, and the like.
  • Useful dispersions include polyester dispersions and polyurethane dispersions.
  • Examples include hydrophilic urethane resins having a polyester urethane backbone prepared by reaction of a monocarboxylic acid having two hydroxyl groups per molecule or a dicarboxylic acid with a diol. and subsequently reacting the terminal hydroxyl groups with an aromatic or aliphatic isocyanate.
  • the polymeric binder can also contain or consist of a crosslinked semi- interpenetrating network, or "SIPN".
  • the SIPN for this ink-receptive coating would be formed from polymer blends comprising (a) at least one crosslinkable polyethylene-acrylic acid copolymer, (b) at least one hydrophilic liquid absorbent polymer, and (c) a crosslinking agent.
  • the SIPNs are continuous networks wherein the crosslinked polymer forms a continuous matrix, as disclosed in U.S. Patents 5,389,723, 5,241,006, 5,376,727, and 5.208,092.
  • the material may also comprise additives in addition to the binders that can improve dry times, color quality, tack, haze and the like, in such amounts as do not effect the overall properties of the coated material.
  • additives include such as catalysts, thickeners, adhesion promoters, glycols, defoamers, surfactants, thickeners, silane coupling agents and the like, so long as the addition does not negatively impact the drying time.
  • a preferred additive is a silane coupling agent; especially preferred are amino functional silane coupling agents.
  • Some useful silane coupling agents are selected from (3 chloropropyl) trimethoxysilane, ⁇ -methacryloxypropyltrimethoxy silane, ⁇ -aminopropyltrimethoxy silane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxy silane, triamino functional silane, and N- ⁇ -(aminoethyl)- ⁇ -aminopropylmethyldimethoxy silane. and the like.
  • Preferred amounts of coupling agent comprise less than 1% of the solution and less than 10% of the final coating.
  • the solution capable of forming the microporous ink-receptive material can be applied to the film backing by any conventional coating technique, e.g., deposition from a solution or dispersion of the resins in a solvent or aqueous medium, or blend thereof, by means of such processes as Meyer bar coating, curtain coating, slide hopper coating, knife coating, reverse roll coating, rotogravure coating, and the like, or combinations thereof.
  • Drying of the microporous ink-receptive layer(s) can be effected by conventional drying techniques, e.g., by heating in a hot air oven at a temperature appropriate for the specific film backing chosen. For example, a drying temperature of about 120°C is suitable for a polyester film backing.
  • Film substrates may be formed from any polymer capable of forming a self- supporting sheet, e.g., films of cellulose esters such as cellulose triacetate or diacetate, polystyrene, polyamides, vinyl chloride polymers and copolymers, polyolefin and polyallomer polymers and copolymers, polysulphones, polycarbonates, polyesters, and blends thereof.
  • cellulose esters such as cellulose triacetate or diacetate, polystyrene, polyamides, vinyl chloride polymers and copolymers, polyolefin and polyallomer polymers and copolymers, polysulphones, polycarbonates, polyesters, and blends thereof.
  • Suitable films may be produced from polyesters obtained by condensing one or more dicarboxylic acids or their lower alkyl diesters in which the alkyl group contains up to 6 carbon atoms, e.g., terephthalic acid, isophthalic, phthalic, 2.5-, 2,6-, and 2,7-naphthalene dicarboxylic acid, succinic acid, sebacic acid, adipic acid, azelaic acid, with one or more glycols such as ethylene glycol, 1,3- propanediol, 1 ,4-butanediol, and the like.
  • dicarboxylic acids or their lower alkyl diesters in which the alkyl group contains up to 6 carbon atoms, e.g., terephthalic acid, isophthalic, phthalic, 2.5-, 2,6-, and 2,7-naphthalene dicarboxylic acid, succinic acid, sebacic acid, adipic acid, azel
  • Preferred film substrates or backings are cellulose triacetate or cellulose diacetate, poly(ethylene naphthalate), polyesters, especially poly(ethylene terephthalate), and polystyrene films. Poly(ethylene terephthalate) is most preferred. It is preferred that film backings have a caliper ranging from 50 ⁇ m to 200 ⁇ m. Film backings having a caliper of less than 50 ⁇ m are difficult to handle using conventional methods for graphic materials. Film backings having calipers over 200 ⁇ m are stiffer, and present feeding difficulties in certain commercially available ink jet printers and pen plotters.
  • polyester film substrates When polyester film substrates are used, they can be biaxially oriented to impart molecular orientation, and may also be heat set for dimensional stability during fusion of the image to the support. These films may be produced by any conventional extrusion method.
  • primers include those known to have a swelling effect on the film backing polymer. Examples include halogenated phenols dissolved in organic solvents.
  • the surface of the film backing may be modified by treatment such as corona treatment or plasma treatment.
  • Microporous image-receptive sheets of the invention are particularly suitable for the production of imaged transparencies for viewing in a transmission mode or a reflective mode, i.e., in association with an overhead projector.
  • the environmental conditions for this test are 70°C and 50% relative humidity (RH).
  • the print pattern consists of solid fill columns of adjacent colors. The columns are " to Vi" wide, and 6-9 inches long.
  • After printing the material is placed on a flat surface, then placed in contact with bond paper. A 2 kg rubber roller 2.5" wide is then twice rolled over the paper.
  • the paper is then removed, and the dry time, D ⁇ is calculated by using the following formula: where T D is the length of time between the end of the printing and placing the image in contact with the bond paper.
  • L ⁇ is the length of image transfer to paper;
  • L P is the length of the printed columns, and T P is the time of printing.
  • a stock solution comprising the following materials:
  • the water and isopropanol examples show that without a high boiling liquid present the coating flakes off the web and an extreme amount of cracking occurs.
  • Example 2 This example demonstrates how the amount of high boiling organic liquid can be used to control the dry time.
  • a stock solution is prepared consisting of: Material Trade Name Percent
  • Dowanol TPM Dowanol TPM
  • 97 ⁇ m PVDC primed PET 100 grams
  • the resulting coatings are microporous, and approximately 35 microns thick.
  • These films are imaged on a Hewlett Packard 855C ink jet printer and the dry time is measured using the 100% solid fill pigmented black image area. Dry time is defined as the amount of time after imaging before no dye transfer occurs to a xerographic bond paper when placed in contact with the image.
  • Dry time is defined as the amount of time after imaging before no dye transfer occurs to a xerographic bond paper when placed in contact with the image.
  • the table below shows that as the amounts of Dowanol TPM increases the corresponding dry times decrease.
  • a stock solution is prepared consisting of:

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  • Inorganic Chemistry (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

The invention provides a coating solution capable of forming a microporous coating onto a substrate, such solution containing a substantial amount of at least one water miscible organic liquid having a boiling point greater than about 150°C, a colloidal silica comprising particles having a median particle size of up to about 200 nm, and at least one polymeric binder, wherein said microporous coating has a median pore diameter up to about 40 nm. The invention further provides a microporous coating formed from the coating solution and an ink-receptive sheet having such a microporous coating formed on at least one surface.

Description

MICROPOROUS INK-RECEPTIVE SHEET
Background of the Invention The invention provides a microporous ink-receptive film useful for imaging with ink jet printers, such films having coated on a substrate a porous ink-receptive coating having a median pore diameter up to about 40 nanometers, wherein the coating has been formed out of a solution containing a substantial amount of at least one water miscible organic liquid having a boiling point greater than about 150°C.
Description of Related Art Imaging devices such as ink jet printers are well known methods for printing various information including labels and multi-colored graphics. Presentation of such information has created a demand for transparent ink-receptive imageable receptors that are used as overlays in technical drawings and as transparencies for overhead projection. Imaging with either the ink jet printer or the pen plotter involves depositing ink on the surface of these transparent receptors. These imaging devices conventionally utilize inks that can remain exposed to air for long periods of time without drying.
Since it is desirable that the surface of these receptors be dry and non-tacky to the touch, even after absorption of significant amounts of liquid soon after imaging, transparent materials that are capable of absorbing significant amounts of liquid while maintaining some degree of durability and transparency, are useful as imageable receptors for imaging. The receptors must have a rapid sorption rate to give uniform appearing images free from coalescence and banding.
Liquid-absorbent materials disclosed in U.S. Patent Nos. 5,134,198, 5,192,617, 5,219,928 and 5,241,006 attempt to improve drying and decrease tack time. These materials comprise crosslinked polymeric compositions capable of forming continuous matrices for liquid absorbent semi-interpenetrating polymer networks. These networks are blends of polymers wherein at least one of the polymeric components is crosslinked after blending to form a continuous network throughout the bulk of the material, and through which the uncrosslinked polymeric components are intertwined in such a way as to form a macroscopically homogeneous composition.
WO 8806532 discloses a recording transparency and an aqueous method of preparation. The transparency is coated with one or more hydroxyethylcellulose polymer(s). The coating solution may also contain a surfactant to promote leveling and adhesion to the surface, and hydrated alumina for surface properties.
U.S. Patent No. 5,120,601 discloses a recording sheet comprising an ink receiving layer containing highly water absorptive resin particles and a binder. The resin particles include sodium, lithium and potassium polyacrylates: vinyl alcohol/acrylamide copolymers; sodium acrylate/acrylamide copolymer; cellulose polymers; starch polymers, and the like. Useful binders include any hydrophilic resin. US Patent No. 4,636,805 (Canon) discloses a recording medium comprising an ink receiving layer capable of fixing an ink within 3 minutes at 20°C and 65% R-H to the extent of 0.7ml/cm2. Embodiments include various gelatins; polyvinyl alcohols; starches; cellulose derivatives; polyvinylpyrrolidone, polyethyleneimine; polyvinylpyridinium halide, sodium polyacrylate, SBR and NBR latexes; polyvinylformal; PMMA; polyvinylbutyral; polyacrylonitrile; polyvinylchloride; polyvinylacetate; phenolic resins and so on.
US Patent No. 4,701,837 (Canon) discloses a light transmissive recording medium having an ink receiving layer formed mainly of a water soluble polymer and a crosslinking agent. The crosslinked polymer has a crosslinking degree satisfying the water resistance of the receiving layer while giving the layer the ink receiving capacity of 0.2 microliters/square centimeter. A large variety of water soluble polymers are disclosed, including gelatin, casein, starch, gum arabic, sodium alginate, hydroxyethyl cellulose, carboxyethyl cellulose and the like; polyvinyl alcohols; saponified products of vinylacetate and other monomers; homopolymers or copolymers with other monomers of unsaturated carboxylic acids; copolymers or homopolymers with other vinyl monomers of sulfonated vinyl monomers; copolymers or homopolymers with other vinyl monomers of (meth)acrylamide; copolymers or homopolymers with other vinyl monomers of ethylene oxide, and so on. US Patent No. 5.277.965 (Xerox) discloses a recording medium comprising a base sheet with an ink receiving layer on one surface, and a heat absorbing layer on the other, and an anti-curl layer coated on the surface of the heat absorbing layer. The materials suitable for the ink-receptive layer can include hydrophilic materials such as binary blends of polyethylene oxide with one of the following group: hydroxypropyl methyl cellulose (Methocel®), hydroxyethyl cellulose; water-soluble ethylhydroxyethyl cellulose, hydroxybutylmethyl cellulose, hydroxypropyl cellulose, methyl cellulose, hydroxyethylmethyl cellulose; vinylmethyl ether/maleic acid copolymers; acrylamide/acrylic acid copolymers; salts of carboxymethylhydroxyethyl cellulose; cellulose acetate; cellulose acetate hydrogen phthalate, hydroxypropyl methyl cellulose phthalate: cellulose sulfate; PVA; PVP; vinyl alcohol/vinylacetate copolymer and so on.
US Patent No. 5,118.570 (Xerox) discloses a transparency comprising a hydrophilic coating and a plasticizer. In one specific embodiment directed to a humidity resistant ink jet transparency, the coating is comprised of a ternary mixture of hydroxypropyl cellulose, carboxymethyl cellulose, polyethylene oxide and a plasticizer. This coating can also have dispersed therein additives such as colloidal silica.
U.S. Patent No. 5,068,140 (Xerox) discloses a transparency comprised of a supporting substrate and an anticurl coating or coatings thereunder. In one specific embodiment, the transparency is comprised of an anticurl coating comprising two layers. The ink receiving layer in one embodiment is comprised of blends of poly(ethylene oxide), mixtures of poly(ethylene oxide) with a cellulose derivative such as sodium carboxymethyl cellulose, hydroxymethyl cellulose, and another component selected from a large variety of polymers and copolymers.
U.S. Patent 5,567,507 discloses an ink-jet receptive sheet comprising a multilayered ink-receptive coating having a thin upper layer comprising a high viscosity binder selected from the group consisting of methylcellulose, hydroxypropyl methylcellulose, and blends thereof, and further comprises an organic salt of polyethyleneimine. With the advent of pigmented inks, other problems are encountered when these same prior art materials are used as ink-receptive coatings. One of the problems can be characterized as "mud-cracking". Without wishing to be bound by theory, it is believed that the pigment, along with other ink components, e.g., polymeric dispersants. and possibly certain dissolved components of the receptor layer, form a separate layer on the surface of the ink-receptive coating. Upon drying, this layer can literally fracture, and result in cracks which are visible to the eye, and accompanying poor image quality and low optical densities. Therefore, other materials need to be incorporated into the coatings to improve image quality. Porous materials have been tried to improve ink absorption. U.S. Patent
4,460,637 discloses an ink-jet recording sheet comprising one or more layers, having a uppermost layer with a pore radius distribution showing a peak between 0.2 and 10 μm, and that the pore distribution radius of all ink receptive layers shows a peak in the same range and at least one other peak at 0.05 μm. The patent teaches that colloidal particles of silica, aluminum hydroxide, alumina, etc., are useful if agglomerated into particles having an average size of 1 to 5 μm.
U.S. Patent 5,372,884 discloses an ink jet recording sheet comprising an ink receiving layer containing a cation-modified non-spherical colloidal silica. The cation modifier is preferably hydrous aluminum oxide, hydrous zirconium oxide or hydrous tin oxide. The sheet is disclosed to be quick drying and superior in water resistance. U.S. Patent 4,816,333 discloses a continuous gelled network of silica particles useful as a coating for film. A polymeric binder may also be present.
U.S. Patent 5.002,825 discloses a surface porous film useful for offset printing and ink-jet recording. The porous layer is prepared by mixing a water-dispersible polymer and specific colloidal silica containing a plurality of linearly connected primary particles to generate undulation in the layer.
U.S. Patent 5,612,281 discloses a recording sheet for ink-jet recording, electrographic recording or thermal transfer recording comprises a transparent colorant receptive layer having a void volume of 50% to 80% in which the network is formed from silica fine particles having a mean primary particle diameter of 10 nm or less and a water soluble resin wherein the weight of the silica particles to the resin is
1.5/1 to about 10/1. Pores between 5 and 30 nm are disclosed.
U.S. Patent 5.679,451 discloses a recording medium providing an ink receptive layer containing a pigment having an aggregated particle diameter of from 0.5 to 50 μm and a binder.
U.S. Patent 5.639,546 discloses a coated product comprising a thermoplastic sheet support bearing on at least one surface an adhesion promoting cured layer comprising 30-80% individually dispersed colloidal metal oxide particles having average particle size 10-100 nm, and 20-70% crosslinked polymer matrix derived from one or more ethyleneically unsaturated monomers and a photoinitiator. Silica particles are disclosed as one of the preferred embodiments.
U.S. Patent 5,397,827 discloses thermoplastic polyester compositions containing special colloidal silica particles having a straight chain or a branched shape for use in films, particularly for magnetic tape. Preferred embodiments of this invention also have reduced image bleeding, improved shelf life, even when it is exposed to elevated temperature and high humidity, or in cases where solvent is prevented from leaving the coating, e.g., when stored in a transparency protector, and also display excellent drytimes.
The present invention discloses a coating which has been formed from a coating solution containing a high boiling point organic liquid. The coating contains a colloidal silica and has a small median pore size. The coating provides a superior ink- receptor for use with ink-jet imaging devices exhibiting both quick drying and low haze properties.
Summary of the Invention The invention provides a coating solution capable of forming a microporous coating onto a substrate, such solution containing a) a substantial amount of at least one water miscible organic liquid having a boiling point greater than 150°C, b) a colloidal silica comprising particles having a median particle size of up to 200 nm, and c) at least one polymeric binder. wherein said microporous coating has a median pore diameter up to 40 nm.
The invention further provides a microporous coating, such coating containing a colloidal silica comprising particles having a median particle size of up to 200 nm. at least one polymeric binder, wherein the microporous coating has a median pore diameter up to 40 nm, and was formed from a solution further comprising at least 3 % of at least one water miscible organic liquid having a boiling point of at least about 150°C.
Preferred microporous coatings of the invention comprise an elongated colloidal silica, although spherical colloidal silica of small particle size is also useful.
The invention further provides a coated ink-receptive sheet comprising a substrate having two surfaces, at least one surface having a microporous coating comprising a colloidal silica sol comprising particles having a median particles size of up to 200 nm, at least one polymeric binder, wherein said microporous coating has a median pore diameter up to 40 nm, said microporous coating having been formed from a solution further comprising at least 3% of at least one water miscible organic liquid having a boiling point of at least 150°C.
As used herein, these terms have the following meanings.
1. The term "high boiling organic liquid" means an organic solvent having a boiling point of at least about 150°C.
2. The term "miscible" means capable of mixing in any ratio without separation into two phases.
3. The term "microporous" means a porous material whose majority of pore diameters are less than 100 nm. All parts, percents, and ratios herein are by weight unless otherwise specifically stated.
Detailed Description of the Invention High boiling organic liquids or solvents useful in formulations and microporous coatings of the materials of the invention include those organic solvents which are liquids at room temperature and which have a boiling point of at least about 150°C, preferably at least about 200°C. Examples include di(ethylene glycol) methyl ether, di(propylene glycol) methyl ether, tri(propylene glycol) methyl ether, and N- methylpyrrolidone. and the like. Useful commercial embodiments include Dowanol TPM Glycol Ether, available from Dow Chemicals, and M-pyrol. available from I.S.P. Technologies Inc., Wayne. NJ. While not wishing to be bound by theory, it is believed that the slow evaporation of the high boiling liquid contributes to the even drying and the minimizing of cracking of the coating surface.
The amount of high boiling liquid in the solution is up to 30% of the coating solution, preferably from 5 to 15%. When the material is coated and the coating is allowed to dry, or is dried by introduction of heat or light, much of the liquid evaporates, and subsequent to such drying, less than 10% of the coating is high boiling organic liquids.
The coating solution and microporous coating contain a significant amount of a colloidal silica. The silica comprises from 5 to 35% of the coating solution, and at least 65% of the coating formed therefrom. Useful colloidal silicas have median particle sizes of up to 200 nanometers
(nm). The particles can be spherical or elongated, with elongated being preferred. Both spherical and elongated colloidal silicas are commercially available from companies such as Nalco Chemical Company, E.I. DuPont de Nemours Co, Inc., and as Snowtex. from Nissan Chemical Industries, Ltd. The microporous coatings also contain a polymeric binder. Most conventional polymeric binders are useful. The binder may be in the form of a water soluble resin or a non-water soluble dispersion.
Useful water soluble resins or nonwater soluble dispersions include various gelatins, including reaction products of gelatins with anhydrides of dibasic organic acids, starches such as oxidized or cation-modified starches, vinyl acetate polymer latexes such as polyvinyl acetate, vinyl acetate-maleate copolymer, vinyl acetate- acrylate copolymers, (meth)acrylate polymers, ethylene-acrylate copolymers, styrene- acrylate copolymers, salts of acrylic acid-methacrylic acid copolymers; glycols such as polyethylene glycol, polypropylene glycol, polyvinyl ethers, synthetic polymers such as polyvinylpyrrolidones, and modified polyvinylpyrrolidones such as
NVP/vinyl acetate copolymers, e.g., those available commercially from as "S-630" and "W735", NVP DMAEMA copolymers available as Gafquat® 755, NVP/acrylic acid copolymers. available as ACRYLIDONE®, and NVP/MEAHEMA/AA copolymers, such as "copolymer 958", all of which are available from I.S.P. Technologies Inc.. Wayne, NJ, modified polyvinylalcohols include polyvinylalcohols having various percentages of vinylacetate, methylcellulose polymers, and the like. Useful polymeric binders also include cellulose binders such as methylcellulose, hydroxypropylmethylcellulose and hydroxyethyl-methylcellulose hydroxyethyl cellulose, hydroxymethyl cellulose, and carboxymethyl cellulose, ethylcellulose, ethylhydroxyethyl cellulose and hydroxybutyl cellulose, and the like. Useful dispersions include polyester dispersions and polyurethane dispersions.
Examples include hydrophilic urethane resins having a polyester urethane backbone prepared by reaction of a monocarboxylic acid having two hydroxyl groups per molecule or a dicarboxylic acid with a diol. and subsequently reacting the terminal hydroxyl groups with an aromatic or aliphatic isocyanate. The polymeric binder can also contain or consist of a crosslinked semi- interpenetrating network, or "SIPN". The SIPN for this ink-receptive coating would be formed from polymer blends comprising (a) at least one crosslinkable polyethylene-acrylic acid copolymer, (b) at least one hydrophilic liquid absorbent polymer, and (c) a crosslinking agent. The SIPNs are continuous networks wherein the crosslinked polymer forms a continuous matrix, as disclosed in U.S. Patents 5,389,723, 5,241,006, 5,376,727, and 5.208,092.
The material may also comprise additives in addition to the binders that can improve dry times, color quality, tack, haze and the like, in such amounts as do not effect the overall properties of the coated material. Useful additives include such as catalysts, thickeners, adhesion promoters, glycols, defoamers, surfactants, thickeners, silane coupling agents and the like, so long as the addition does not negatively impact the drying time.
A preferred additive is a silane coupling agent; especially preferred are amino functional silane coupling agents. Some useful silane coupling agents are selected from (3 chloropropyl) trimethoxysilane, γ-methacryloxypropyltrimethoxy silane, γ-aminopropyltrimethoxy silane, N-β-(aminoethyl)- γ-aminopropyltrimethoxy silane, triamino functional silane, and N-β-(aminoethyl)- γ-aminopropylmethyldimethoxy silane. and the like. Preferred amounts of coupling agent comprise less than 1% of the solution and less than 10% of the final coating.
The solution capable of forming the microporous ink-receptive material can be applied to the film backing by any conventional coating technique, e.g., deposition from a solution or dispersion of the resins in a solvent or aqueous medium, or blend thereof, by means of such processes as Meyer bar coating, curtain coating, slide hopper coating, knife coating, reverse roll coating, rotogravure coating, and the like, or combinations thereof. Drying of the microporous ink-receptive layer(s) can be effected by conventional drying techniques, e.g., by heating in a hot air oven at a temperature appropriate for the specific film backing chosen. For example, a drying temperature of about 120°C is suitable for a polyester film backing.
Film substrates may be formed from any polymer capable of forming a self- supporting sheet, e.g., films of cellulose esters such as cellulose triacetate or diacetate, polystyrene, polyamides, vinyl chloride polymers and copolymers, polyolefin and polyallomer polymers and copolymers, polysulphones, polycarbonates, polyesters, and blends thereof. Suitable films may be produced from polyesters obtained by condensing one or more dicarboxylic acids or their lower alkyl diesters in which the alkyl group contains up to 6 carbon atoms, e.g., terephthalic acid, isophthalic, phthalic, 2.5-, 2,6-, and 2,7-naphthalene dicarboxylic acid, succinic acid, sebacic acid, adipic acid, azelaic acid, with one or more glycols such as ethylene glycol, 1,3- propanediol, 1 ,4-butanediol, and the like.
Preferred film substrates or backings are cellulose triacetate or cellulose diacetate, poly(ethylene naphthalate), polyesters, especially poly(ethylene terephthalate), and polystyrene films. Poly(ethylene terephthalate) is most preferred. It is preferred that film backings have a caliper ranging from 50 μm to 200 μm. Film backings having a caliper of less than 50 μm are difficult to handle using conventional methods for graphic materials. Film backings having calipers over 200 μm are stiffer, and present feeding difficulties in certain commercially available ink jet printers and pen plotters. When polyester film substrates are used, they can be biaxially oriented to impart molecular orientation, and may also be heat set for dimensional stability during fusion of the image to the support. These films may be produced by any conventional extrusion method. To promote adhesion of the microporous ink-receptive layer to the film backing, it may be desirable to treat the surface of the film backing with one or more primers, in single or multiple layers. Useful primers include those known to have a swelling effect on the film backing polymer. Examples include halogenated phenols dissolved in organic solvents. Alternatively, the surface of the film backing may be modified by treatment such as corona treatment or plasma treatment.
Microporous image-receptive sheets of the invention are particularly suitable for the production of imaged transparencies for viewing in a transmission mode or a reflective mode, i.e., in association with an overhead projector.
The following examples are for illustrative purposes, and do not limit the scope of the invention, which is that defined by the claims.
Test Methods Image Density The transmissive image density is measured using Macbeth TD 903 densitometer with the gold and status A filters.
Dry Time
The environmental conditions for this test are 70°C and 50% relative humidity (RH). The print pattern consists of solid fill columns of adjacent colors. The columns are " to Vi" wide, and 6-9 inches long. After printing the material is placed on a flat surface, then placed in contact with bond paper. A 2 kg rubber roller 2.5" wide is then twice rolled over the paper. The paper is then removed, and the dry time, Dτ is calculated by using the following formula:
Figure imgf000011_0001
where TD is the length of time between the end of the printing and placing the image in contact with the bond paper. Lτ is the length of image transfer to paper; LP is the length of the printed columns, and TP is the time of printing. Example 1
A stock solution is prepared comprising the following materials:
Material Trade Name Percent
Chain colloidal silica Snowtex UP 67.73
Chain colloidal silica Snowtex OUP 14.73
Polyurethane dispersion Sancure 815 16.93
Hydroxyethyl cellulose Natrosol 250 HHR 0.29
Silane coupling agent Silquest A1120 0.25
Surfactant Zonyl FSO 0.07
To 40 grams of this stock solution is added 4.3 grams of each of the materials listed in the table below, most them being high boiling liquids. These solutions are knife coated on 97 μm PVDC primed PET at 150 μm wet and forced air dried at 140°C for 3 min. The resulting microporous coatings are approximately 25 microns thick. The films are then visually examined for cracking and flaking. The results are given in the table below.
Material Trade Name Flaking Cracking
Water - Yes Extreme - many large cracks
Isopropanol - Yes Extreme - many large cracks
Diethylene glycol - No Many very fine cracks
N-methylpyrrolidone M-pyrol No Few very fine cracks
Dipropylene glycol - No No
Di(propylene glycol) methyl ether Dowanol DPM No No
Di(ethylene glycol) butyl ether Dowanol DB No No
Di(propylene glycol) propyl ether Dowanol DPnP No No
Tri(propylene glycol) methyl ether Dowanol TP No No
The water and isopropanol examples show that without a high boiling liquid present the coating flakes off the web and an extreme amount of cracking occurs. The remaining examples, which are all high boiling liquids, exhibit no flaking and greatly reduced or no cracking.
Example 2 This example demonstrates how the amount of high boiling organic liquid can be used to control the dry time. A stock solution is prepared consisting of: Material Trade Name Percent
Chain colloidal silica Snowtex UP 36.70
Chain colloidal silica Snowtex OUP 48.94
Polyurethane dispersion Sancure 815 13.60
Hydroxyethyl cellulose Natrosol 250 HHR 0.36
Silane coupling agent Silquest A1 120 0.33
Surfactant Zonyl FSO 0.07
To 100 grams of stock solution is added varying amounts of Dowanol TPM. These solutions are machine coated on 97 μm PVDC primed PET and force air dried at 150°C for 1.5 min. The resulting coatings are microporous, and approximately 35 microns thick. These films are imaged on a Hewlett Packard 855C ink jet printer and the dry time is measured using the 100% solid fill pigmented black image area. Dry time is defined as the amount of time after imaging before no dye transfer occurs to a xerographic bond paper when placed in contact with the image. The table below shows that as the amounts of Dowanol TPM increases the corresponding dry times decrease.
Dowanol TPM(g) Dry time (sec)
9.51 120
11.70 80
12.80 40
Example 3
The following example shows that addition of a silane coupling agent can significantly improve the clarity or haze of the film. A stock solution is prepared consisting of:
Material Trade Name Percent
Chain colloidal silica sol Snowtex UP 33.24
Chain colloidal silica sol Snowtex OUP 44.32
Polyurethane dispersion Sancure 815 9.23
High boiling point organic liquid Dowanol TPM 12.83
Hydroxyethyl cellulose Natrosol 250 HHR 0.31
Surfactant Zonyl FSO 0.07
To 100 grams of stock solution is added 0.26 grams of various silane coupling agents. The solutions are knife coated 200 μm (8 mils) wet on 97 μm PVDC primed
PET and forced air dried at 140°C for 3 min. The table below shows the silane coupling agents investigated and the corresponding film haze. The percent haze of the samples is measured on the Gardener XL-21 1 Hazegard System. Chemical Name Trade Name Percent
Haze
None None Too great to measure
(3 chloropropyl) trimethoxysilane - 49.5 γ-methacryloxypropyltrimethoxy silane Silquest A- 174 44.5 γ-aminopropyltrimethoxy silane Silquest A-l 1 10 4.5 N-β-(aminoethyl)-γ-arninopropyltrimethoxy silane Silquest A-l 120 4.0 Triamino functional silane Silquest A-l 130 3.7 N-β-(arninoethyl)-γ-aminopropylmethyldirnethoxy silane Silquest A-2120 4.2

Claims

What is Claimed is:
1. A microporous ink-receptive coating comprising a colloidal silica comprising particles having a median particle size of up to 200 nm. and at least one polymeric binder, wherein said microporous coating has a median pore diameter up to 40 nm. said coating having been formed from a solution further comprising at least 3% of at least one water miscible organic liquid having a boiling point of at least 150°C.
2. A microporous coating according to claim 1 wherein the colloidal silica has elongated particles.
3. A microporous coating according to claim 1 wherein the colloidal silica comprises at least 50% percent of the coating.
4. A microporous coating according to claim 1 wherein the median pore diameter is from 4 nm to 20 nm.
5. A microporous coating according to claim 1 wherein the polymeric binder is selected from the group consisting of aqueous polyurethanes, aqueous polyesters, polyethylene-acrylic acid copolymers, hydroxyethyl cellulose, polyethylene oxide, and polyvinylpyrrolidone.
6. A microporous coating according to claim 1 wherein the polymeric binder comprises from 5% to 35% of the coating.
7. A microporous coating according to claim 1 wherein said coating further comprises a silane coupling agent.
8. A microporous coating according to claim 7 wherein said silane coupling agent is selected from the group consisting of (3 chloropropyl) trimethoxysilane, γ-methacryloxypropyltrimethoxy silane, γ-aminopropyltrimethoxy silane, N-β-(aminoethyl)- γ-aminopropyltrimethoxy silane, triamino functional silane, and N-β-(aminoethyl)- γ-aminopropylmethyldimethoxy silane.
9. An ink-receptive sheet comprising a substrate having two surfaces, at least one surface bearing thereon a microporous coating according to any of claims 1 - 8.
10. A coating solution capable of forming a microporous coating according to claim 1 onto a substrate, such solution comprising a) a substantial amount of at least one water miscible organic liquid having a boiling point greater than 150°C, b) a colloidal silica comprising particles having a median particles size of up to 200 nm. and c) at least one polymeric binder.
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WO2002078967A1 (en) * 2001-03-30 2002-10-10 Imperial Chemical Industries Plc Improvements in or relating to inkjet receiver media
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WO2020003188A3 (en) * 2018-06-29 2020-02-13 3M Innovative Properties Company Ink-receptive layers for durable labels
US11905429B2 (en) 2017-11-17 2024-02-20 3M Innovative Properties Company Ink-receptive layers for durable labels
US12331213B2 (en) 2019-06-27 2025-06-17 3M Innovative Properties Company Ink-receptive layers for durable labels

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US5518809A (en) * 1992-09-18 1996-05-21 Minnesota Mining And Manufacturing Company Water-based transparent image recording sheet for plain paper copiers
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6764725B2 (en) 2000-02-08 2004-07-20 3M Innovative Properties Company Ink fixing materials and methods of fixing ink
US6974609B2 (en) 2000-02-08 2005-12-13 Engle Lori P Media for cold image transfer
US7005162B2 (en) 2000-02-08 2006-02-28 3M Innovative Properties Company Methods of fixing ink
WO2002078967A1 (en) * 2001-03-30 2002-10-10 Imperial Chemical Industries Plc Improvements in or relating to inkjet receiver media
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EP2321375A4 (en) * 2008-08-07 2012-02-22 3M Innovative Properties Co Acicular silica coating for enhanced hydrophilicity/transmittivity
US11905429B2 (en) 2017-11-17 2024-02-20 3M Innovative Properties Company Ink-receptive layers for durable labels
WO2020003188A3 (en) * 2018-06-29 2020-02-13 3M Innovative Properties Company Ink-receptive layers for durable labels
CN112334552A (en) * 2018-06-29 2021-02-05 3M创新有限公司 Ink-receptive layer for durable labels
US12331213B2 (en) 2019-06-27 2025-06-17 3M Innovative Properties Company Ink-receptive layers for durable labels

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