CA2209470A1 - Fusible printable coating for durable images - Google Patents
Fusible printable coating for durable imagesInfo
- Publication number
- CA2209470A1 CA2209470A1 CA002209470A CA2209470A CA2209470A1 CA 2209470 A1 CA2209470 A1 CA 2209470A1 CA 002209470 A CA002209470 A CA 002209470A CA 2209470 A CA2209470 A CA 2209470A CA 2209470 A1 CA2209470 A1 CA 2209470A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- ink jet
- coating composition
- coating
- substrate
- 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.)
- Abandoned
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/0054—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or film forming compositions cured by thermal means, e.g. infrared radiation, heat
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
- D06P5/2066—Thermic treatments of textile materials
- D06P5/2072—Thermic treatments of textile materials before dyeing
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
- D06P5/2066—Thermic treatments of textile materials
- D06P5/2077—Thermic treatments of textile materials after dyeing
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/30—Ink jet printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
- B41M5/508—Supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—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
- B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—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
- B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B41M5/5272—Polyesters; Polycarbonates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
- D06P1/5235—Polyalkenyl halides, e.g. PVC
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
- D06P1/5257—(Meth)acrylic acid
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5278—Polyamides; Polyimides; Polylactames; Polyalkyleneimines
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/56—Condensation products or precondensation products prepared with aldehydes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31591—Next to cellulosic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/3175—Next to addition polymer from unsaturated monomer[s]
- Y10T428/31757—Polymer of monoethylenically unsaturated hydrocarbon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31779—Next to cellulosic
- Y10T428/31783—Paper or wood
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
- Y10T428/31899—Addition polymer of hydrocarbon[s] only
- Y10T428/31902—Monoethylenically unsaturated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2762—Coated or impregnated natural fiber fabric [e.g., cotton, wool, silk, linen, etc.]
- Y10T442/277—Coated or impregnated cellulosic fiber fabric
- Y10T442/2787—Coating or impregnation contains a vinyl polymer or copolymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2762—Coated or impregnated natural fiber fabric [e.g., cotton, wool, silk, linen, etc.]
- Y10T442/277—Coated or impregnated cellulosic fiber fabric
- Y10T442/2811—Coating or impregnation contains polyimide or polyamide
Abstract
A coating composition which encompasses an aqueous dispersion of from about 2 to about 40 percent by dry weight, based on the dry weight of the coating composition, of a cationic polymer; and from about 60 to about 98 percent by dryweight, based on the dry weight of the coating composition, of a nonionic or cationic binder. The coating composition is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused. Alternatively, the coating composition may encompass an aqueous dispersion of a powdered thermoplastic polymer and from about 10 to about 150 dry parts by weight of a binder, based on 100 dry parts by weight of the powdered thermoplastic polymer.
Desirably, the coating composition will encompass an aqueous dispersion of a powdered thermoplastic polymer; from about 2 to about 50 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a cationic polymer; and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a nonionic or cationic binder.
The coating composition also may contain from about 1 to about 5 parts by weight, based on the weight of the coating composition, of a surfactant. When applied to a substrate, the coating composition permits printing on the substrate with ink jet inks to give a printed image which is durable, especially in the presence of water.
Desirably, the coating composition will encompass an aqueous dispersion of a powdered thermoplastic polymer; from about 2 to about 50 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a cationic polymer; and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a nonionic or cationic binder.
The coating composition also may contain from about 1 to about 5 parts by weight, based on the weight of the coating composition, of a surfactant. When applied to a substrate, the coating composition permits printing on the substrate with ink jet inks to give a printed image which is durable, especially in the presence of water.
Description
' CA 02209470 1997-07-08 FUSIBLE PRINTABLE COATING
FOR DURABLE IMAGES
Pa~l~gf~und of the Inveot;G,.
The present invention relates to printable materials. More particularly, the present invention relates to ink jet printable materials.
The popularity in recent years of personal computers in homes and businesses has stimulated the developi.,ent of several types of piinlera. The earlier, 10 relatively low cost printers were impact or dot-matrix pfinlers which utilized a ribbon and a plurality of pins to place a desired image on a substrate which typically was paper. While the better dot-matrix printers are capable of near letter-quality printing, they typically are both slow and noisy. Laser printers are quiet, produce high-quality images, and can print an excess of four pages per minute. Such printers, however, 15 tend to be too expensive for con"non use in homes and even in some smaller businesses. Ink jet printers fill the gap between dot-matrix printers and laser printera, both with respect to cost and image quality.
Ink jet inks, however, are ~queous-based systems. That is, the dyes employed in such inks are soluble in water. Thus, suLal~ales printed with ink jet inks have a 20 pronounced proclivity to run or even lose an image in the prese,)ce of moisture or water. Accordingly, there is a need for a means of pennitting printing on a substrate with ink jet inks, whereby the printed image is durable, especially in the pr~sence of water.
Summary of the In.~ tio The pr~se, It invention addresses some of the difficulties and problems ~iscussed above by providing a coating cGi"posiLion which en~mpasses an a~ueous dispersion of from about 2 to about 40 percent by dry weight, based on the dry weight 30 of the coating composition, of a cation c polymer; and from about 60 to about 98 percent by dry weight, based on the dry weight of the coating comrosilion, of a non.~n;c or calion.c binder. The coating co",,l~osition is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
The coating ~mpociliol1 also may contain from about 1 to about 5 parts by weight, ' CA 02209470 1997-07-08 based on the weight of the coating composition, of a non;on.c or calion;c sulra~ldnl.
For example, the su, ractant may be a non-onic s~" ra~lant.
The present invention also provides a coating coml~osilion which encom~Asses an aqueous dispersion of a powdered ll,ei"~Gplastic polymer and from5 about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered ll,ei",oplaslic polymer, of a binder. The coating composition is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused. If desired, the coating coillposiliGn may contain from about 1 to about 5 parts by weight, based on the weight of the coating cornrosition, of a 10 su,ractant. By way of example, the s--,ractanl may be a non-~n;c su,raclant.
The present invention further provides a coaUng co" ,position which encompasses an aqueous dispersion of a powdered lher",opl~slic polymer; from about 2 to about 50 dry parts by weight, based on 100 dry parts by weight of thepowdered ll,e,mopl~,Lic polymer, of a cation c polymer; and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered ll,e"nopl~-tic polymer, of a non;lon:c or cation-.c binder. Again, the coating ~"~position is thermally fusible and adapled to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused. The coating ~i"rosition optionally may contain from about 1 to about 10 parts of a nonionic or calionic su,ractant. For example, the SU, raclant may be a nonion.c s~" ra~,lant.
By way of example, the powdered II,e"~loplsstic polymer may be a polyethylene. Further by way of example, the powdered the""oplaslic polymer may be a polyamide. For example, the powdered U,e",lopl~slic polymer may be a copolymer of ~-cap~la.,ld"~ and lau,ola.:ta",. As an addilional example, the ~lion c polymer may be an a".:~e 0piuh'0r~hydrin copolymer. As yet a further example, the binder may bo an ethylene-vinyl acetate copolymer.
The present invention additionally provides an ink jet pri"t~ ~'e ",atelial which includes a substrate and a coating on the surfaces of the substrate. The coating is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused. The coating may be formed from any of the coating comrosilions described above. The substrate may be, by way of example only, a cellulosic sheet-like material. For example, the substrate may be a paper, such as a latex-i",pr~g"ated paper. As anotl,er example, the substrate may be a fiber or aplurality of fibers. For example, the substrate may be a yam. As a further example, the substrate may be a knitted or woven fabric. As still another example, the .' CA 02209470 1997-07-08 substrate may be a nonwoven web, such as a meltblown or spunbond nonwoven web.
The pr~senl invention still further provides a ~ tllod for producing a durable image on a substrate with water-soluble inks. The ",ell,od encomrAsses providing a 5 substrate and coating the substrate with a coating coi "posilion. The coating co",posilion encomrasses an aqueous clispersion of a powdered thermoplastic polymer, from about 2 to about 50 dry parts by weight, based on 100 dry parts byweight of the powdered the""oplaslic polymer, of a calionic polymer; and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the 10 powdered the- " ,opl ~slic polymer, of a nonionic or calion;c binder. The coating con,posilion is ll,e,."ally fusible and adapted to be receptive to water-soluble inks and to retain the water-soluble inks after being thermally fused. The coated substrate then is dried and an image is printed with water-soluble inks on the coating on the substrate. The resulting image-bearing coating on the substrate then is thermally 15 fused. By way of example, the water soluble inks may be ink jet inks.
Detailed D~sc- i~ tiGn of the Inventic- .
The term "yam" is used gene,ically herein to mean a continuous strand of 20 textile fibers, filaments, or ",alerial in a form suitable for knitting, weaving, or otherwise interlwining to form a textile fabric. Thus, the term in~4ldes, but is not limited to, the f~llow;ng forms: (1) a number of fibers twisted logell,er, i.e., spun yarn;
(2) a number of rila,nenls laid together without twist; (3) a number of r~la",ents laid togell,er with a degree of twist, including false twist; (4) a single rila",enl with or 25 without twist (i.e., a ",onofila..,ent); and (5) a narrow strip of ",alerial, such as paper, plastic film, or metal foil, with or without twist, intended for use in a textile construction.
As used herein, the term "fiber is meant to include both a continuous and a nonconlin.lous fiber. A continuous fiber may be a ",onGrila".ent or a fiber produced 30 by, for example, a spunbonding pr~cess. More generally, a continuous fiber isdeemed to be any fiber wherein the length of the fiber may be considered infinite in coi"parison with its ~lia",eter. A noncontinuous fiber is any fiber which is notcontinuous, such as a staple fiber. The term also is meant to include both the singular and the plural. That is, the temm "fiber is inlended to enco",pass a single fiber or a 35 plurality of fibers.
FOR DURABLE IMAGES
Pa~l~gf~und of the Inveot;G,.
The present invention relates to printable materials. More particularly, the present invention relates to ink jet printable materials.
The popularity in recent years of personal computers in homes and businesses has stimulated the developi.,ent of several types of piinlera. The earlier, 10 relatively low cost printers were impact or dot-matrix pfinlers which utilized a ribbon and a plurality of pins to place a desired image on a substrate which typically was paper. While the better dot-matrix printers are capable of near letter-quality printing, they typically are both slow and noisy. Laser printers are quiet, produce high-quality images, and can print an excess of four pages per minute. Such printers, however, 15 tend to be too expensive for con"non use in homes and even in some smaller businesses. Ink jet printers fill the gap between dot-matrix printers and laser printera, both with respect to cost and image quality.
Ink jet inks, however, are ~queous-based systems. That is, the dyes employed in such inks are soluble in water. Thus, suLal~ales printed with ink jet inks have a 20 pronounced proclivity to run or even lose an image in the prese,)ce of moisture or water. Accordingly, there is a need for a means of pennitting printing on a substrate with ink jet inks, whereby the printed image is durable, especially in the pr~sence of water.
Summary of the In.~ tio The pr~se, It invention addresses some of the difficulties and problems ~iscussed above by providing a coating cGi"posiLion which en~mpasses an a~ueous dispersion of from about 2 to about 40 percent by dry weight, based on the dry weight 30 of the coating composition, of a cation c polymer; and from about 60 to about 98 percent by dry weight, based on the dry weight of the coating comrosilion, of a non.~n;c or calion.c binder. The coating co",,l~osition is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
The coating ~mpociliol1 also may contain from about 1 to about 5 parts by weight, ' CA 02209470 1997-07-08 based on the weight of the coating composition, of a non;on.c or calion;c sulra~ldnl.
For example, the su, ractant may be a non-onic s~" ra~lant.
The present invention also provides a coating coml~osilion which encom~Asses an aqueous dispersion of a powdered ll,ei"~Gplastic polymer and from5 about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered ll,ei",oplaslic polymer, of a binder. The coating composition is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused. If desired, the coating coillposiliGn may contain from about 1 to about 5 parts by weight, based on the weight of the coating cornrosition, of a 10 su,ractant. By way of example, the s--,ractanl may be a non-~n;c su,raclant.
The present invention further provides a coaUng co" ,position which encompasses an aqueous dispersion of a powdered lher",opl~slic polymer; from about 2 to about 50 dry parts by weight, based on 100 dry parts by weight of thepowdered ll,e,mopl~,Lic polymer, of a cation c polymer; and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered ll,e"nopl~-tic polymer, of a non;lon:c or cation-.c binder. Again, the coating ~"~position is thermally fusible and adapled to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused. The coating ~i"rosition optionally may contain from about 1 to about 10 parts of a nonionic or calionic su,ractant. For example, the SU, raclant may be a nonion.c s~" ra~,lant.
By way of example, the powdered II,e"~loplsstic polymer may be a polyethylene. Further by way of example, the powdered the""oplaslic polymer may be a polyamide. For example, the powdered U,e",lopl~slic polymer may be a copolymer of ~-cap~la.,ld"~ and lau,ola.:ta",. As an addilional example, the ~lion c polymer may be an a".:~e 0piuh'0r~hydrin copolymer. As yet a further example, the binder may bo an ethylene-vinyl acetate copolymer.
The present invention additionally provides an ink jet pri"t~ ~'e ",atelial which includes a substrate and a coating on the surfaces of the substrate. The coating is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused. The coating may be formed from any of the coating comrosilions described above. The substrate may be, by way of example only, a cellulosic sheet-like material. For example, the substrate may be a paper, such as a latex-i",pr~g"ated paper. As anotl,er example, the substrate may be a fiber or aplurality of fibers. For example, the substrate may be a yam. As a further example, the substrate may be a knitted or woven fabric. As still another example, the .' CA 02209470 1997-07-08 substrate may be a nonwoven web, such as a meltblown or spunbond nonwoven web.
The pr~senl invention still further provides a ~ tllod for producing a durable image on a substrate with water-soluble inks. The ",ell,od encomrAsses providing a 5 substrate and coating the substrate with a coating coi "posilion. The coating co",posilion encomrasses an aqueous clispersion of a powdered thermoplastic polymer, from about 2 to about 50 dry parts by weight, based on 100 dry parts byweight of the powdered the""oplaslic polymer, of a calionic polymer; and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the 10 powdered the- " ,opl ~slic polymer, of a nonionic or calion;c binder. The coating con,posilion is ll,e,."ally fusible and adapted to be receptive to water-soluble inks and to retain the water-soluble inks after being thermally fused. The coated substrate then is dried and an image is printed with water-soluble inks on the coating on the substrate. The resulting image-bearing coating on the substrate then is thermally 15 fused. By way of example, the water soluble inks may be ink jet inks.
Detailed D~sc- i~ tiGn of the Inventic- .
The term "yam" is used gene,ically herein to mean a continuous strand of 20 textile fibers, filaments, or ",alerial in a form suitable for knitting, weaving, or otherwise interlwining to form a textile fabric. Thus, the term in~4ldes, but is not limited to, the f~llow;ng forms: (1) a number of fibers twisted logell,er, i.e., spun yarn;
(2) a number of rila,nenls laid together without twist; (3) a number of r~la",ents laid togell,er with a degree of twist, including false twist; (4) a single rila",enl with or 25 without twist (i.e., a ",onofila..,ent); and (5) a narrow strip of ",alerial, such as paper, plastic film, or metal foil, with or without twist, intended for use in a textile construction.
As used herein, the term "fiber is meant to include both a continuous and a nonconlin.lous fiber. A continuous fiber may be a ",onGrila".ent or a fiber produced 30 by, for example, a spunbonding pr~cess. More generally, a continuous fiber isdeemed to be any fiber wherein the length of the fiber may be considered infinite in coi"parison with its ~lia",eter. A noncontinuous fiber is any fiber which is notcontinuous, such as a staple fiber. The term also is meant to include both the singular and the plural. That is, the temm "fiber is inlended to enco",pass a single fiber or a 35 plurality of fibers.
~ CA 02209470 1997-07-08 As used herein, the term "nonwoven web" is meant to include any nonwoven web, induding those prepa,~d by such meit-extrusion processes as meltblowing, coforming, and spunbonding. The term also includes nonwoven webs pl~pal~:d by air laying or wet laying relatively short fibers to form a web or sheet. Thus, the term includes nonwoven webs prepared from a papei",ahi"g fumish. Such fumish may include only cellulose fibers, a mixture of cellulose fibers and synthetic fibers, or only synthetic fibers. When the fumish contains only cellulose fibers or a mixture ofcellulose fibers and synthetic fibers, the resulting web is refe"ed to herein as a "cellulosic nonwoven web." Of course, such web also may contain additives and other materials, such as fillers, e.g., clay and titanium dioxide, as is well known in the pape""a'~ing art.
As already indicated, a nonwoven web de~ildbly will be fommed by such wel~
known prucesses as meltblowing, cofomming, spunbonding, and the like. By way of illual,a~on only, sudl p,~esses are exemplified by the f~ .ing r~ferences, each of which is inco,~uo,al~d herein by ,efer~nce:
(a) meltblowing ,efe~nces indude, by way of example, U.S. Patent Nos.
3,016,599 to R. W. Perry, Jr., 3,704,198 to J. S. Prentice, 3,755,527 to J. P. Keller et al., 3,849,241 to R. R. Butin et al., 3,978,185 to R. R. Butin et al., and 4,663,220 to T. J.
W;sneski et al. See, also, V. A. Wente, "Superfine Thel~l~op!~c Fibers", Industrial and Enaineerina ChemistrY. Vol. 48, No. 8, pp. 1342-1346 (1956); V. A. Wente et al.,"Manufacture of Superfine Organic Fibers", Navy Resea~h Laboratory, Washington, D.C., NRL Report 4364 (111437), dated May 25, 1954, United States Depa,b~ent of CGr"",e,oe, Office of Te-;hn ~-' Services; and Robert R. Butin and Dwight T. Loh:;&."p, "Melt Blowing - A One-Step Web Plucess for New Nonwoven Products", Joumal of theTechnical Assoo.~t;on of the PUID and Par er Industry, Vol. 56, No.4, pp. 74-77 (1973);
(b) coforming ,~er~nces (i.e."~ nces di3;,10sing a meltblowing process in which fibers or pa~ti~,les are commingled with the meltblown fibers as they are fommed) indude U.S. Patent Nos. 4,100,324 to R. A. Ande,son et al. and 4,118,531 to E. R.
Hauser; and (c) spunbonding ,~re,~,1ces indude, among others, U.S. Patent Nos.
3,341,394 to Kinney, 3,655,862 to Dora~;l"~er et al., 3,692,618 to Dolachner et al., 3,705,068 to Dobo et al., 3,802,817 to Matsuki et al., 3,853,651 to Porte, 4,064,605 to Akiyama et al., 4,091,140 to l l~""on, 4,100,319 to Schwark, 4,340,563 to Appel and Momlan, 4,405,297 to Appel and l~lo""an, 4,434,204 to l la,~"an et al., 4,627,811 to Greiser and Wagner, and 4,644,045 to Fowells.
-' CA 02209470 1997-07-08 Other ,.,eU,Gds for pr~pa~i~,g nonwoven webs are, of course, known and may be employed. Such n~eUIods include air laying, wet laying, carding, and the like. In some cases, it may be either desirable or necessA~ to stabilize the nonwoven web by known means, such as themlal pattem bonding, through-air bonding, and hydr~e"tangling.The terms Udurable~ and "retain the ink jet inks" are synonymous and mean that the ink jet inks placed on a substrate in accorr ance with the present invention are stable or durable in the presence of moisture or water. That is, after fusing the coating, the ink jet inks, for all prd~ical purposes, are not removed by water. Thus, the image formed on the substrate by the ink jet inks essenlially retains its original shape and brigl,lness in the presence of water.
In gener~l terrns, the coating of the prese"l invention is suitable for ceilulosic nonwoven webs, such as paper; film; yams; fabric; and any other substrate which is capable of being printed on by an ink jet printer. The coating is absorbent and accepls ink jet printing with minimal feathering or bleeding. After printing, the coating is fused by heating to around 350~F (about 177~C). Fusing consolidatss the~ coating into a durable film which retains the ink jet inks when the substrate is soaked in water, even though the inks are water soluble.
In one embodiment, the coating co"~posilion of the present invention is an ~queous dispe-~ion of from about 2 to about 40 pe,~ent by dry weight, based on the dry weight of the coating co"~position, of a calion o polymer, and from about 60 to about 98 per~nt by dry weight, based on the dry weight of the coating co",position, of a non;an-c or calion.c binder. The~ coating co,.,posilion is thermally fusible and ad~l~te~d to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
Examples of cation,c polymers include, by way of illusl-dlion only, polya",;des,an~:ie epichlor~hydrin resins, polyethyl~ne;n~ines, polyacrylarn:ies, and urea-formaldehyde resins. Examples of non.onic and cation o binders include, also by way of illua~ dtion only, acrylic latices, ethylene-vinyl acetate copolymer latices, and polyethylene disper~ions.
The solids contenl of the coating con~positiGn may be varied widely, depending upon the substrate to be coated and the ,.,etl,od of coating. For exa,-,pl~, the solids content of the coating composition may be in a range of from about 5 to about 60 percent by weight, athough lower or higher solids levels may be appr~priate in some cases. As another example, the solids content of the coating compositionmay be in a range of from about 15 to about 45 percent by weight.
-' CA 02209470 1997-07-08 In anGIl ,er embodiment, the coating cG" ,positiGn includes a powder~d hellllGpl~stic polymer and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered ll,ei",opl~slic polymer, of a binder. The coating composition is thermally fusible and adapted to be receptive to ink jet inks 5 and to retain the ink jet inks after being thermally fused.
Examplcs of powdered the""Gplaslic polymers include polyethylenes, such as Mic~po~dera MPP 635G, and polyalr,:des, such as Orgasol~ 3501 EXD NAT1.
Examples of binders include, in add;tion to those listed above, poly(vinyl acetate) latices, styrene-acrylate copolymer latices, and poly(vinyl cl,'oride) latices.
In a further embodiment, the coating composition is an aqueous dispersion of a powdered the""opl~slic polymer; from about 2 to about 50 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a calion c polymer; and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered ll,ei",Gplaslic polymer, of a non;cn.c or cation.c 15 binder. As with the preceding embodiments, the coating cGillpositiGn is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
By way of illusl,dlion, a coating composition which contains polyamide polymer parlicles, a c~lion-.c polymer, and an ethylene-vinyl acetate latex binder 20 results in a coating which gives little to no ink bleed or feathering, fast ink drying, and le: c~"Pnt ,~s~'ution. Furthermore, no pressure is needed after printing to obtain a durable, water-fast image.
The coating cG",posilion of the present invention also may include a su,raclan~, typically at a level of from about 1 to about 5 parts by weight, based on 25 the weight of the coating cGIllrositiGn. In general, the su,ractant may be an on c calion:r, or nonionic, unless a calion,c polymer is present in the coating eGr"positiGn.
When a c~lion-c polymer is present, the su,raclant may be a calion c or nonionic- su. ractant. For example, the su, ra-,lanl may be a noni~n-~ su, raclant.
If desired, the coating cGi"position also may contain minor amounts of other 30 ",dl~,;als, examples of which are fillers, such as silica; a"tifoar,ling agents; and the like.
As noted earlier, the present invention also provides a ",ell,Gd for producing adurable image on a substrate with water-soluble inks. The method encomp~sses providing a substrate as already deri"ed and coating the substrate with a coating 35 co",position. The coating cG",posilion encGmpasses an aqueous disperaion of a powdered lhe,-nopl~slic polymer; from about 2 to about 50 dry parts by weight, based on 100 dry parts by weight of the powdered the-",Gpl~slic polymer of a ca~ion.c polymer and from about 10 to about 150 dry parts by weight based on 100 dry parts by weight of the powdered thermoplastic polymer, of a nonion-.c or calion c binder.
5 The coating ~",po~ition is thermally fusible and adapted to be receptive to water-soluble inks and to retain the water-soluble inks after being thermally fused. The coated substrate then is dried and an image is printed with water-soluble inks on the coating on the substrate. The resulting image-bearing coating on the substrate then is thermally fused. By way of example, the water soluble inks may be ink jet inks.
In gene.dl, the substrate may be coated by any means known to those having ordinary skill in the art. For example, the substrate may be coated by spraying dipping and nipping doctor blade, silk-screening direct and offset gravure printing and the like. Drying and fusing of the coating also may be carried out by known means. Drying typically will be acco..,r !,shed at ten,perdtures below about 100~C.
15 The fusing tempe,dture typically will depend on the coating cGn~positiol1 but generally may be in a range of from about 150~C to about 200~C. However, lower or higher fusing tel.,perat.lres may be appr~pndle in some in~lances.
The pr~sent invention is further des., ibed by the examples which follow. Such examples however are not to be construed as limiting in any way either the spirit or 20 the scope of the presenl invention. In the exs",F'es all parts are dry parts by weight per 100 parts by weight of powdered thel"~Gpl~slic polymer unless stated otherwise.
Example 1 A coating co."posiliGn was pr~pared which consisled of a 30% total solids mixture of 100 dry parts of a polyamide (Orgasol~ 3501 EXD NAT1 a 10-micrometer average particle size copolymer of ~-caprula~;ta--, and la~,ula-1a,,,, having a melting point of 160~C and available from Elf Atochem France) 50 dry parts of a poly(vinyl alcohol)-stabilized ethylene-vinyl acetate copolymer (Airflex~ 140 available from Air Products and Chem~ s Inc., Allentown, Pennsylvania), 13.5 dry par~s of an amide-epiul,lor~hydrin cation;c copolymer (Reten~ 204LS, sur plied by Hercules Inc., Wilmington, Delaware), and 5 dry parts of a polyethoxylated octylphenol non on csu.raclant (Triton~ X100, Rohm & Haas Co., St. Louis, Missouri). The coating composition was applied to both a com",e~ially available uncoated durable label stock and a co.n",er~ially available banner ",alerial. A #24 Meyer rod was used to apply the coating cG~Iposilion in each case, resulting in a coating basis weight of about 22 grams per square meter (gsm) of dry coating. The coating was dried at 85~C. A test pattem with a Canon BJC 600 ink jet printer gave a very well-resolved image on both subs~r~tes with little or no feathering. After fusing at 350~F (about 177 5 ~C) either for 30 seconds in an oven or for 15 seconds in a heat press against a release paper, the coating consol.daled, or fused, and the inks bled only a trace of color into water after soaking for two days.
Example 2 The coating co",posiliGn described in Example 1 was used to treat a rayon yam (type 1 52/SS from Robison-Anton) by dipping the yam into the coating cG"~posilion and removing excess cG",posilion with a rubber-over-steel nip wringer.
Wet pickup was 7.5 parts per 100 parts yam. After drying at 95~C, the yam was 15 tested by dipping yam san,~'es separdtely into each of four ink jet inks fromIndependent Ink Co., i.e., cyan""agenla, yellow, and black. The yam samples wereblotted with absorbent paper to remove excess ink, then heat treated with no pressure for 30 seconds at 175~C. When placed between wet blotters and pressed, there was a little ink bleed into the blotters from each yam sample.
Example 3 The procedure of Example 2 was repeated, except that the amount of calion c polymer in the coating cGI"positiGn was increased from 50 parts to 100 parts. Yam 25 treated as described in Example 2 gave only faint traces of dye on the wet blotters for the cyan""agen~a and yellow inks, and slightly greater black staining. The yarn colors were dark and rich, indicating good abs~, bency of the yam before fusing. If the yam was heat treated for 30 seconds at 175~C before dipping, it accepted the inkpoorly and s~ ~hsequent heat ~ ealing was not effective for retaining the dyes. The yam 30 app3rently required a higher propo~tiGn of calion ~ polymer because the total amount of coating was only about 7.5 parts per hundred parts of fiber. Treating the yam with the cationic polymer alone did not provide any dye ~etenliGn to the yam, nor didtreating it with binder alone. Fairly good dye retention could be obtained with a combination of calion-~ polymer and binder, but dye pickup was lower.
While the spe~ificdtion has been described in detail with r~spe-,l to specific embodiments thereof, it will be appreciated by those skilled in the art, upon attaining an under~landing of the foregoing, may readily conceive of allerdlions to, varia~ions of, and equivalents to these embodiments. Accor~lingly, the scope of the prt:sent 5 invention should be assessed as that of the appended claims and any equivalents thereto. For example, the coating CGIllpOSition of the present invention should be effective with any water-soluble ink system, not just ink jet printer inks. Other varialions and ,nGdifications will be readily apparenl to those having ordinary skill in the art.
As already indicated, a nonwoven web de~ildbly will be fommed by such wel~
known prucesses as meltblowing, cofomming, spunbonding, and the like. By way of illual,a~on only, sudl p,~esses are exemplified by the f~ .ing r~ferences, each of which is inco,~uo,al~d herein by ,efer~nce:
(a) meltblowing ,efe~nces indude, by way of example, U.S. Patent Nos.
3,016,599 to R. W. Perry, Jr., 3,704,198 to J. S. Prentice, 3,755,527 to J. P. Keller et al., 3,849,241 to R. R. Butin et al., 3,978,185 to R. R. Butin et al., and 4,663,220 to T. J.
W;sneski et al. See, also, V. A. Wente, "Superfine Thel~l~op!~c Fibers", Industrial and Enaineerina ChemistrY. Vol. 48, No. 8, pp. 1342-1346 (1956); V. A. Wente et al.,"Manufacture of Superfine Organic Fibers", Navy Resea~h Laboratory, Washington, D.C., NRL Report 4364 (111437), dated May 25, 1954, United States Depa,b~ent of CGr"",e,oe, Office of Te-;hn ~-' Services; and Robert R. Butin and Dwight T. Loh:;&."p, "Melt Blowing - A One-Step Web Plucess for New Nonwoven Products", Joumal of theTechnical Assoo.~t;on of the PUID and Par er Industry, Vol. 56, No.4, pp. 74-77 (1973);
(b) coforming ,~er~nces (i.e."~ nces di3;,10sing a meltblowing process in which fibers or pa~ti~,les are commingled with the meltblown fibers as they are fommed) indude U.S. Patent Nos. 4,100,324 to R. A. Ande,son et al. and 4,118,531 to E. R.
Hauser; and (c) spunbonding ,~re,~,1ces indude, among others, U.S. Patent Nos.
3,341,394 to Kinney, 3,655,862 to Dora~;l"~er et al., 3,692,618 to Dolachner et al., 3,705,068 to Dobo et al., 3,802,817 to Matsuki et al., 3,853,651 to Porte, 4,064,605 to Akiyama et al., 4,091,140 to l l~""on, 4,100,319 to Schwark, 4,340,563 to Appel and Momlan, 4,405,297 to Appel and l~lo""an, 4,434,204 to l la,~"an et al., 4,627,811 to Greiser and Wagner, and 4,644,045 to Fowells.
-' CA 02209470 1997-07-08 Other ,.,eU,Gds for pr~pa~i~,g nonwoven webs are, of course, known and may be employed. Such n~eUIods include air laying, wet laying, carding, and the like. In some cases, it may be either desirable or necessA~ to stabilize the nonwoven web by known means, such as themlal pattem bonding, through-air bonding, and hydr~e"tangling.The terms Udurable~ and "retain the ink jet inks" are synonymous and mean that the ink jet inks placed on a substrate in accorr ance with the present invention are stable or durable in the presence of moisture or water. That is, after fusing the coating, the ink jet inks, for all prd~ical purposes, are not removed by water. Thus, the image formed on the substrate by the ink jet inks essenlially retains its original shape and brigl,lness in the presence of water.
In gener~l terrns, the coating of the prese"l invention is suitable for ceilulosic nonwoven webs, such as paper; film; yams; fabric; and any other substrate which is capable of being printed on by an ink jet printer. The coating is absorbent and accepls ink jet printing with minimal feathering or bleeding. After printing, the coating is fused by heating to around 350~F (about 177~C). Fusing consolidatss the~ coating into a durable film which retains the ink jet inks when the substrate is soaked in water, even though the inks are water soluble.
In one embodiment, the coating co"~posilion of the present invention is an ~queous dispe-~ion of from about 2 to about 40 pe,~ent by dry weight, based on the dry weight of the coating co"~position, of a calion o polymer, and from about 60 to about 98 per~nt by dry weight, based on the dry weight of the coating co",position, of a non;an-c or calion.c binder. The~ coating co,.,posilion is thermally fusible and ad~l~te~d to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
Examples of cation,c polymers include, by way of illusl-dlion only, polya",;des,an~:ie epichlor~hydrin resins, polyethyl~ne;n~ines, polyacrylarn:ies, and urea-formaldehyde resins. Examples of non.onic and cation o binders include, also by way of illua~ dtion only, acrylic latices, ethylene-vinyl acetate copolymer latices, and polyethylene disper~ions.
The solids contenl of the coating con~positiGn may be varied widely, depending upon the substrate to be coated and the ,.,etl,od of coating. For exa,-,pl~, the solids content of the coating composition may be in a range of from about 5 to about 60 percent by weight, athough lower or higher solids levels may be appr~priate in some cases. As another example, the solids content of the coating compositionmay be in a range of from about 15 to about 45 percent by weight.
-' CA 02209470 1997-07-08 In anGIl ,er embodiment, the coating cG" ,positiGn includes a powder~d hellllGpl~stic polymer and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered ll,ei",opl~slic polymer, of a binder. The coating composition is thermally fusible and adapted to be receptive to ink jet inks 5 and to retain the ink jet inks after being thermally fused.
Examplcs of powdered the""Gplaslic polymers include polyethylenes, such as Mic~po~dera MPP 635G, and polyalr,:des, such as Orgasol~ 3501 EXD NAT1.
Examples of binders include, in add;tion to those listed above, poly(vinyl acetate) latices, styrene-acrylate copolymer latices, and poly(vinyl cl,'oride) latices.
In a further embodiment, the coating composition is an aqueous dispersion of a powdered the""opl~slic polymer; from about 2 to about 50 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a calion c polymer; and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered ll,ei",Gplaslic polymer, of a non;cn.c or cation.c 15 binder. As with the preceding embodiments, the coating cGillpositiGn is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
By way of illusl,dlion, a coating composition which contains polyamide polymer parlicles, a c~lion-.c polymer, and an ethylene-vinyl acetate latex binder 20 results in a coating which gives little to no ink bleed or feathering, fast ink drying, and le: c~"Pnt ,~s~'ution. Furthermore, no pressure is needed after printing to obtain a durable, water-fast image.
The coating cG",posilion of the present invention also may include a su,raclan~, typically at a level of from about 1 to about 5 parts by weight, based on 25 the weight of the coating cGIllrositiGn. In general, the su,ractant may be an on c calion:r, or nonionic, unless a calion,c polymer is present in the coating eGr"positiGn.
When a c~lion-c polymer is present, the su,raclant may be a calion c or nonionic- su. ractant. For example, the su, ra-,lanl may be a noni~n-~ su, raclant.
If desired, the coating cGi"position also may contain minor amounts of other 30 ",dl~,;als, examples of which are fillers, such as silica; a"tifoar,ling agents; and the like.
As noted earlier, the present invention also provides a ",ell,Gd for producing adurable image on a substrate with water-soluble inks. The method encomp~sses providing a substrate as already deri"ed and coating the substrate with a coating 35 co",position. The coating cG",posilion encGmpasses an aqueous disperaion of a powdered lhe,-nopl~slic polymer; from about 2 to about 50 dry parts by weight, based on 100 dry parts by weight of the powdered the-",Gpl~slic polymer of a ca~ion.c polymer and from about 10 to about 150 dry parts by weight based on 100 dry parts by weight of the powdered thermoplastic polymer, of a nonion-.c or calion c binder.
5 The coating ~",po~ition is thermally fusible and adapted to be receptive to water-soluble inks and to retain the water-soluble inks after being thermally fused. The coated substrate then is dried and an image is printed with water-soluble inks on the coating on the substrate. The resulting image-bearing coating on the substrate then is thermally fused. By way of example, the water soluble inks may be ink jet inks.
In gene.dl, the substrate may be coated by any means known to those having ordinary skill in the art. For example, the substrate may be coated by spraying dipping and nipping doctor blade, silk-screening direct and offset gravure printing and the like. Drying and fusing of the coating also may be carried out by known means. Drying typically will be acco..,r !,shed at ten,perdtures below about 100~C.
15 The fusing tempe,dture typically will depend on the coating cGn~positiol1 but generally may be in a range of from about 150~C to about 200~C. However, lower or higher fusing tel.,perat.lres may be appr~pndle in some in~lances.
The pr~sent invention is further des., ibed by the examples which follow. Such examples however are not to be construed as limiting in any way either the spirit or 20 the scope of the presenl invention. In the exs",F'es all parts are dry parts by weight per 100 parts by weight of powdered thel"~Gpl~slic polymer unless stated otherwise.
Example 1 A coating co."posiliGn was pr~pared which consisled of a 30% total solids mixture of 100 dry parts of a polyamide (Orgasol~ 3501 EXD NAT1 a 10-micrometer average particle size copolymer of ~-caprula~;ta--, and la~,ula-1a,,,, having a melting point of 160~C and available from Elf Atochem France) 50 dry parts of a poly(vinyl alcohol)-stabilized ethylene-vinyl acetate copolymer (Airflex~ 140 available from Air Products and Chem~ s Inc., Allentown, Pennsylvania), 13.5 dry par~s of an amide-epiul,lor~hydrin cation;c copolymer (Reten~ 204LS, sur plied by Hercules Inc., Wilmington, Delaware), and 5 dry parts of a polyethoxylated octylphenol non on csu.raclant (Triton~ X100, Rohm & Haas Co., St. Louis, Missouri). The coating composition was applied to both a com",e~ially available uncoated durable label stock and a co.n",er~ially available banner ",alerial. A #24 Meyer rod was used to apply the coating cG~Iposilion in each case, resulting in a coating basis weight of about 22 grams per square meter (gsm) of dry coating. The coating was dried at 85~C. A test pattem with a Canon BJC 600 ink jet printer gave a very well-resolved image on both subs~r~tes with little or no feathering. After fusing at 350~F (about 177 5 ~C) either for 30 seconds in an oven or for 15 seconds in a heat press against a release paper, the coating consol.daled, or fused, and the inks bled only a trace of color into water after soaking for two days.
Example 2 The coating co",posiliGn described in Example 1 was used to treat a rayon yam (type 1 52/SS from Robison-Anton) by dipping the yam into the coating cG"~posilion and removing excess cG",posilion with a rubber-over-steel nip wringer.
Wet pickup was 7.5 parts per 100 parts yam. After drying at 95~C, the yam was 15 tested by dipping yam san,~'es separdtely into each of four ink jet inks fromIndependent Ink Co., i.e., cyan""agenla, yellow, and black. The yam samples wereblotted with absorbent paper to remove excess ink, then heat treated with no pressure for 30 seconds at 175~C. When placed between wet blotters and pressed, there was a little ink bleed into the blotters from each yam sample.
Example 3 The procedure of Example 2 was repeated, except that the amount of calion c polymer in the coating cGI"positiGn was increased from 50 parts to 100 parts. Yam 25 treated as described in Example 2 gave only faint traces of dye on the wet blotters for the cyan""agen~a and yellow inks, and slightly greater black staining. The yarn colors were dark and rich, indicating good abs~, bency of the yam before fusing. If the yam was heat treated for 30 seconds at 175~C before dipping, it accepted the inkpoorly and s~ ~hsequent heat ~ ealing was not effective for retaining the dyes. The yam 30 app3rently required a higher propo~tiGn of calion ~ polymer because the total amount of coating was only about 7.5 parts per hundred parts of fiber. Treating the yam with the cationic polymer alone did not provide any dye ~etenliGn to the yam, nor didtreating it with binder alone. Fairly good dye retention could be obtained with a combination of calion-~ polymer and binder, but dye pickup was lower.
While the spe~ificdtion has been described in detail with r~spe-,l to specific embodiments thereof, it will be appreciated by those skilled in the art, upon attaining an under~landing of the foregoing, may readily conceive of allerdlions to, varia~ions of, and equivalents to these embodiments. Accor~lingly, the scope of the prt:sent 5 invention should be assessed as that of the appended claims and any equivalents thereto. For example, the coating CGIllpOSition of the present invention should be effective with any water-soluble ink system, not just ink jet printer inks. Other varialions and ,nGdifications will be readily apparenl to those having ordinary skill in the art.
Claims (39)
1. A coating composition comprising an aqueous dispersion of:
from about 2 to about 40 percent by dry weight, based on the dry weight of the coating composition, of a cationic polymer; and from about 60 to about 98 percent by dry weight based on the dry weight of the coating composition of a nonionic or cationic binder;
wherein the coating composition is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
from about 2 to about 40 percent by dry weight, based on the dry weight of the coating composition, of a cationic polymer; and from about 60 to about 98 percent by dry weight based on the dry weight of the coating composition of a nonionic or cationic binder;
wherein the coating composition is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
2. The coating composition of Claim 1 which further comprises from about 1 to about 5 parts by weight based on the weight of the coating composition of a nonionic or cationic surfactant.
3. The coating composition of Claim 2, in which the surfactant is a nonionic surfactant.
4. A coating composition comprising an aqueous dispersion of:
a powdered thermoplastic polymer; and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a binder;
wherein the coating composition is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
a powdered thermoplastic polymer; and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a binder;
wherein the coating composition is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
5. The coating composition of Claim 4 which further comprises from about 1 to about 5 parts by weight, based on the weight of the coating composition of a surfactant.
6. The coating composition of Claim 5 in which the surfactant is a nonionic surfactant.
7. A coating composition comprising an aqueous dispersion of:
a powdered thermoplastic polymer;
from about 2 to about 50 dry parts by weight based on 100 dry parts by weight of the powdered thermoplastic polymer, of a cationic polymer; and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a nonionic or cationic binder;
wherein the coating composition is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
a powdered thermoplastic polymer;
from about 2 to about 50 dry parts by weight based on 100 dry parts by weight of the powdered thermoplastic polymer, of a cationic polymer; and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a nonionic or cationic binder;
wherein the coating composition is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
8. The coating composition of Claim 7 which further comprises from about 1 to about 10 parts of a nonionic or cationic surfactant.
9. The coating composition of Claim 8, in which the surfactant is a nonionic surfactant.
10. The coating composition of Claim 7, in which the powdered thermoplastic polymer is a polyethylene.
11. The coating composition of Claim 7, in which the powdered thermoplastic polymer is a polyamide.
12. The coating composition of Claim 11, in which the powdered thermo-plastic polymer is a copolymer of .epsilon.-caprolactam and laurolactam.
13. The coating composition of Claim 11, in which the cationic polymer is an amide-epichlorohydrin copolymer.
14. The coating composition of Claim 11, in which the binder is an ethylene-vinyl acetate copolymer.
15. An ink jet printable material which comprises;
a substrate; and a coating on the surfaces of the substrate, which coating comprises;
from about 10 to about 40 percent by weight, based on the weight of the coating, of a cationic polymer; and from about 60 to about 90 percent by weight, based on the weight of the coating, of a nonionic or cationic binder;
wherein the coating is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
a substrate; and a coating on the surfaces of the substrate, which coating comprises;
from about 10 to about 40 percent by weight, based on the weight of the coating, of a cationic polymer; and from about 60 to about 90 percent by weight, based on the weight of the coating, of a nonionic or cationic binder;
wherein the coating is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
16. The ink jet printable material of Claim 15, in which the coating further comprises from about 1 to about 5 parts by weight based on the weight of the coating composition of a nonionic or cationic surfactant.
17. The ink jet printable material of Claim 16, in which the surfactant is a nonionic-surfactant.
18. An ink jet printable material which comprises:
a substrate; and a coating on the surfaces of the substrate which coating comprises:
a powdered thermoplastic polymer; and from about 10 to about 150 parts by weight, based on 100 parts by weight of the powdered thermoplastic polymer, of a binder;
wherein the coating is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
a substrate; and a coating on the surfaces of the substrate which coating comprises:
a powdered thermoplastic polymer; and from about 10 to about 150 parts by weight, based on 100 parts by weight of the powdered thermoplastic polymer, of a binder;
wherein the coating is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
19. The ink jet printable material of Claim 18, in which the coating further comprises from about 1 to about 5 parts by weight, based on the weight of the coating, of a surfactant.
20. The ink jet printable material of Claim 19 in which the surfactant is a nonionic surfactant.
21. An ink jet printable material which comprises;
a substrate; and a coating on the surfaces of the substrate, which coating comprises:
a powdered thermoplastic polymer;
from about 2 to about 50 parts by weight based on 100 parts by weight of the powdered thermoplastic polymer, of a cationic polymer; and from about 10 to about 150 parts by weight, based on 100 parts by weight of the powdered thermoplastic polymer, of a nonionic or cationic binder;
wherein the coating composition is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
a substrate; and a coating on the surfaces of the substrate, which coating comprises:
a powdered thermoplastic polymer;
from about 2 to about 50 parts by weight based on 100 parts by weight of the powdered thermoplastic polymer, of a cationic polymer; and from about 10 to about 150 parts by weight, based on 100 parts by weight of the powdered thermoplastic polymer, of a nonionic or cationic binder;
wherein the coating composition is thermally fusible and adapted to be receptive to ink jet inks and to retain the ink jet inks after being thermally fused.
22. The ink jet printable material of Claim 21 in which the coating further comprises from about 1 to about 10 parts of a nonionic or cationic surfactant.
23. The ink jet printable material of Claim 22, in which the surfactant is a nonionic surfactant.
24. The ink jet printable material of Claim 21, in which the powdered thermoplastic polymer is a polyethylene.
25. The ink jet printable material of Claim 21 in which the powdered thermoplastic polymer is a polyamide.
26. The ink jet printable material of Claim 25, in which the powdered thermoplastic polymer is a copolymer of .epsilon.-caprolactam and laurolactam.
27. The ink jet printable material of Claim 21 in which the cationic polymer is an amide-epichlorohydrin copolymer.
28. The ink jet printable material of Claim 21, in which the binder is an ethylene-vinyl acetate copolymer.
29. The ink jet printable material of Claim 21, in which the substrate is a cellulosic nonwoven web.
30. The ink jet printable material of Claim 29, in which the substrate is a paper.
31. The ink jet printable material of Claim 30 in which the substrate is a latex-impregnated paper.
32. The ink jet printable material of Claim 21, in which the substrate is a fiber.
33. The ink jet printable material of Claim 21 in which the substrate comprises a yarn.
34. The ink jet printable material of Claim 33 in which the substrate comprises a knitted or woven fabric.
35. The ink jet printable material of Claim 31, in which the substrate comprises a nonwoven web.
36. The ink jet printable material of Claim 35 in which the substrate comprises a meltblown or spunbond nonwoven web.
37. A coating composition comprising an aqueous dispersion of:
a powdered thermoplastic polymer;
from about 2 to about 50 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a cationic polymer, and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a nonionic or cationic binder;
wherein the coating composition is thermally fusible and adapted to be receptive to water-soluble inks and to retain the water-soluble inks after being thermally fused.
a powdered thermoplastic polymer;
from about 2 to about 50 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a cationic polymer, and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a nonionic or cationic binder;
wherein the coating composition is thermally fusible and adapted to be receptive to water-soluble inks and to retain the water-soluble inks after being thermally fused.
38. A method for producing a durable image on a substrate with water-soluble inks, the method comprising:
providing a substrate;
coating the substrate with a coating composition which comprises an aqueous dispersion of:
a powdered thermoplastic polymer;
from about 2 to about 50 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a cationic polymer, and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a nonionic or cationic binder;
wherein the coating composition is thermally fusible and adapted to be receptive to water-soluble inks and to retain the water-soluble inks after beingthermally fused;
drying the coated substrate;
printing an image with water-soluble inks on the coating on the substrate; and thermally fusing the coating on the substrate.
providing a substrate;
coating the substrate with a coating composition which comprises an aqueous dispersion of:
a powdered thermoplastic polymer;
from about 2 to about 50 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a cationic polymer, and from about 10 to about 150 dry parts by weight, based on 100 dry parts by weight of the powdered thermoplastic polymer, of a nonionic or cationic binder;
wherein the coating composition is thermally fusible and adapted to be receptive to water-soluble inks and to retain the water-soluble inks after beingthermally fused;
drying the coated substrate;
printing an image with water-soluble inks on the coating on the substrate; and thermally fusing the coating on the substrate.
39. The method of Claim 38, in which the water-soluble inks are ink jet inks.
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-
1997
- 1997-07-08 CA CA002209470A patent/CA2209470A1/en not_active Abandoned
- 1997-08-07 DE DE69708007T patent/DE69708007D1/en not_active Expired - Lifetime
- 1997-08-07 EP EP97113711A patent/EP0825031B1/en not_active Expired - Lifetime
- 1997-08-07 ES ES97113711T patent/ES2163073T3/en not_active Expired - Lifetime
- 1997-08-15 JP JP9220271A patent/JPH10203010A/en active Pending
- 1997-10-20 US US08/954,440 patent/US5925712A/en not_active Expired - Lifetime
- 1997-10-20 US US08/954,565 patent/US5962149A/en not_active Expired - Lifetime
-
1999
- 1999-04-05 US US09/285,958 patent/US6033739A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH10203010A (en) | 1998-08-04 |
DE69708007D1 (en) | 2001-12-13 |
EP0825031A1 (en) | 1998-02-25 |
US6033739A (en) | 2000-03-07 |
US5925712A (en) | 1999-07-20 |
EP0825031B1 (en) | 2001-11-07 |
ES2163073T3 (en) | 2002-01-16 |
US5962149A (en) | 1999-10-05 |
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Legal Events
Date | Code | Title | Description |
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FZDE | Discontinued |