Classifications

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

• This invention relates to an ink jet recording sheet which is intended to be printed by an ink jet printer.
• Inkjet printers that is to say printers which form an image by firing a plurality of discrete drops of ink from one or more nozzles on to the surface of a recording sheet placed adjacent the nozzles, have recently enjoyed a large increase in sales.
• Such ink jet printers have the advantage that they can reproduce good quality text and images, in both monochrome and full color, can produce both reflection prints and transparencies, and are relatively inexpensive to manufacture and to operate, as compared with, for example, color laser printers, thermal wax transfer printers and dye sublimation printers. Accordingly, ink jet printers now dominate the home/small office market, and are often also used to provide color capability not available from the monochrome laser printers typically employed in larger offices.
• the medium also should not promote "wicking", that is to say spreading of ink by capillary action through fibrous media, such as paper.
• the medium must be capable of absorbing the ink without substantial distortion of the medium, since otherwise unsightly "cockling” (formation of ripples and similar folds) may occur, and most observers find such distortions unacceptable.
• the medium should be such that contact of the image with moist surfaces (such as sweaty fingers) does not result in bleeding of ink from the image.
• the surface characteristics, such as smoothness, glossiness and feel, of the image are largely determined by the same characteristics of the medium, the medium should possess characteristics appropriate to the type of image being printed.
• an ink jet printer is used to print a digital image produced by a camera or a scanner, the medium should be smooth and possess the high gloss and smooth feel of conventional silver-halide based photographic printing paper.
• US-A-4 592 951 describes an ink jet recording sheet comprising a transparent support carrying a layer of cross-linked poly(vinyl alcohol).
• US-A-4 575 465 describes an ink jet recording sheet comprising a transparent support carrying a layer formed from a mixture of vinylpyridine/ vinylbenzyl quaternary ammonium salt copolymer and a hydrophilic polymer selected from the group consisting of gelatin, poly(vinyl alcohol), and hydroxypropyl cellulose, and mixtures thereof.
• US-A-4 547 405 describes an ink jet recording sheet comprising a transparent support carrying a layer comprising a mixture of a coalesced block copolymer latex of poly(vinyl alcohol) with polyvinyl(benzyl ammonium chloride) and a water-soluble polymer selected from the group consisting of poly( vinyl alcohol), poly(vinylpyrrolidone) and copolymers thereof.
• US-A-4 904 519 describes an ink jet recording sheet comprising a transparent polymeric backing having on at least one major surface thereof a transparent, ink-receptive layer comprising a cross-linked, hydrolyzed copolymer of a vinyl ester comonomer selected from the group consisting of vinyl acetate, vinyl propionate and vinyl stearate, and a vinyl amide comonomer selected from the group consisting of N-vinyl pyrrolidone and vinyl acetamide, the degree of hydrolysis being from about 80 to 95%, and the cross-linking being effected by an agent selected from the group consisting of borates, titanates, dichromates and aldehydes.
• US-A-4 900 620 describes an ink jet recording sheet including a sheet-like substrate composed mainly of 70 to 100 wt % of wood pulp and 0 to 30 wt % of precipitated calcium carbonate and having a Stockigt sizing degree of not less than 2 seconds and not more than 25 seconds when formed into a sheet having a basis weight of 64 g/m 2 , and a coating layer composed mainly of white pigment, with the coating layer being formed on at least one side of the substrate at a weight of 1 to 10 g/m 2 .
• this sheet has a high ink absorption rate and is able to develop bright colors and sharp images.
• US-A-5 139 867 describes transparent image-recording elements that contain ink-receptive layers that can be imaged by the application of liquid ink dots.
• the ink-receptive layers contain a combination of:
• particles of a polyester namely a poly(cyclohexylenedimethylene- co-oxydiethylene isophthalate-co-sodio-sulfobenzenedicarboxylate); (iii) a homopolymer or a copolymer of an alkylene oxide containing from 2 to 6 carbon atoms;
• US-A-4 592 954 describes a transparency for ink jet printing comprised of a supporting substrate and thereover a coating consisting essentially of a blend of carboxymethyl cellulose, and polyethylene oxides. Also disclosed are papers for use in ink jet printing comprised of a plain paper substrate and a coating thereover consisting essentially of polyethylene oxides.
• US-A-5 342 688 describes an ink-receptive sheet comprising a transparent substrate bearing on at least major surface thereof an ink-receptive layer which comprises at least one imaging polymer and an effective amount of polymeric mordant, which comprises a polymethylene backbone carrying pendant aminoguanidino groups.
• US-A-4 547 405 describes an ink jet recording sheet comprising a transparent support carrying a layer comprising a mixture of a coalesced block copolymer latex of poly(vinyl alcohol) with polyvinyl(benzyl ammonium chloride) and a water-soluble polymer selected from the group consisting of poly(vinyl alcohol), poly(vinylpyrrolidone) and copolymers thereof.
• US-A-4 575 465 describes an ink jet recording sheet comprising a transparent support carrying a layer formed from a mixture of vinylpyridine/ vinylbenzyl quaternary ammonium salt copolymer and a hydrophilic polymer selected from the group consisting of gelatin, poly( vinyl alcohol), and hydroxypropyl cellulose, and mixtures thereof.
• ink jet recording sheets having ink-receiving layers which contain poly(vinyl alcohol) can be improved by using as the poly(vinyl alcohol) a mixture of derivatized and non-derivatized poly(vinyl alcohol). It has also been found that the properties of ink jet recording sheets having ink-receiving layers containing hydrophilic polymers can be improved by using, in the ink-receiving layer, a specific sub-group of vinylbenzyl quaternary ammonium salt copolymers and/or a poly(vinylpyridine).
• the ink jet recording sheets containing a poly( vinylpyridine) display improved imaging properties; in particular, the water fastness of the images produced on these sheets is substantially improved.
• this invention provides an ink jet recording sheet comprising a support carrying an ink-receiving layer, this ink- receiving layer comprising a non-derivatized poly(vinyl alcohol) and a derivatized poly(vinyl alcohol).
• This form of the invention may hereinafter be called the "derivatized/non-derivatized sheet" of the invention.
• this invention provides an ink jet recording sheet comprising a support carrying an ink-receiving layer, this ink-receiving layer comprising a hydrophilic polymer, and at least one of (a) a poly(vinylbenzyl quaternary ammonium salt) of the formula:
• R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is independently alkyl of from 1 to 4
• each of R , R and R is independently alkyl of from 1 to 18 carbon atoms and the total number of carbon atoms in R 7 , R 8 and R 9 is from 13 to 20;
• M " is an anion; and each of a, b and c is the molar proportion of the respective repeating units) and (b) a poly( vinylpyridine).
• This form of the invention may hereinafter be called the "hydrophilic polymer sheet" of the invention.
• the derivatized/non-derivatized sheet and the hydrophilic polymer sheet of the present invention are not mutually exclusive; as described in more detail below, useful sheets can be prepared using, for example, a mixture of derivatized and non-derivatized poly(vinyl alcohol) as the hydrophilic polymer, together with a poly( vinylbenzyl quaternary ammonium salt) and/or a poly( vinylpyridine).
• This invention also provides a method of ink jet printing which comprises applying to an ink jet recording sheet a plurality of ink droplets generated from an ink jet printer, wherein the ink jet recording sheet is a sheet of the present invention.
• the derivatized poly(vinyl alcohol) used in the derivatized/non- derivatized sheet of the present invention differs from conventional (also, for convenience referred to herein as "underivatized") poly(vinyl alcohol) in that at least some of the hydroxyl groups present in the underivatized poly( vinyl alcohol) are replaced by ether or ester groupings, preferably the latter.
• a preferred type of derivatized poly(vinyl alcohol) for use in the present invention is an acetoacetylated poly(vinyl alcohol), in which the hydroxyl groups are esterified with acetoacetic acid.
• Acetoacetylated poly(vinyl alcohol) is available commercially, for example as Gohsefimer Z-200, sold by Nippon Gohsei, No. 9-6, Nozaki-cho, Kita-ku, Osaka, Japan. This material is stated by the manufacturer to be a super hydrolyzed poly( vinyl alcohol) having a degree of hydrolysis of 99-100%, a viscosity in 4% aqueous solution at 20°C of 13.3-14.3 cps and a pH in the same solution of 3.5-5.
• a preferred underivatized poly(vinyl alcohol) for use in the derivatized/non-derivatized sheet is Airvol-205, sold by Air Products, Allentown, Pennsylvania, United States of America. This material is stated by the manufacturer to be a partially hydrolyzed poly(vinyl alcohol) having a degree of hydrolysis of 87- 89%, a viscosity in 4% aqueous solution at 20°C of 5.2-6.2 cps and a pH in the same solution of 4.5-6.5.
• the ink-receiving layer of the derivatized/non-derivatized sheet also desirably comprises a mordant to improve the ink binding ability of the layer.
• a mordant for this purpose are poly(vinylbenzyl quaternary ammonium salts), especially those of the formula given above.
• the poly(vinylbenzyl quaternary ammonium salt) is one in which R is an alkyl group containing at least 11 carbon atoms, and R 8 and R 9 are each a methyl group.
• R is an alkyl group containing at least 11 carbon atoms
• R 8 and R 9 are each a methyl group.
• a specific preferred mordant of this type is that in which each of R 1 , R 2 , R 3 , R 8 and R 9 is a methyl group; each of R 4 , R 5 and R 6 is an ethyl group; and R 7 is an n-C 1 H 25 group; for convenience, this material is referred to in the Examples below simply as "Terpolymer".
• the molar proportions a, b and c are desirably in the ratios 5-10:5-10: 1.
• hydrophilic polymer sheets of the present invention contain a poly(vinylbenzyl quaternary ammonium salt), the preferred salts are the same as those preferred for use in the derivatized/non-derivatized sheets, as discussed in the preceding paragraph.
• hydrophilic polymer sheets of the present invention contain a poly(vinylpyridine), this polymer is very desirably a poly(4-vinylpyridine).
• the hydrophilic polymer used with poly(4-vinylpyridine) is poly( vinyl alcohol) and the poly(4-vinylpyridine) is prepared by polymerizing 4-vinylpyridine in the presence of at least part of the poly( vinyl alcohol).
• Such a polymerization may be conducted by the processes described in US-A-3 208 964 and US-A-3 507 846, but poly(4-vinylpyridine) produced by these two processes tends to produce some non- uniformity in black areas of images produced from the recording sheet. It is believed (although the invention is in no way limited by this belief) that this non-uniformity is due to the suspension polymerization mechanism of the processes described in these two patents, which may tend to cause certain heterogeneities in the product.
• the uniformity of black areas of images produced on the present recording sheet is improved by effecting the polymerization of the 4-vinylpyridine using a precipitation polymerization procedure in which substantially all of the initiator, and most if not all of the 4-vinylpyridine, are present in solution.
• the poly(4-vinylpyridine) used in the present recording sheet is prepared by preparing an aqueous dispersion of poly( vinyl alcohol) and contacting this aqueous solution with less than about 10 percent by weight (based upon the weight of the aqueous solution of 4-vinylpyridine monomer and a water-soluble free radical initiator.
• a preferred free radical initiator for use in this reaction is 2,2'-azobis(2-amidinopropane) hydrochloride, solid commercially by Wako Chemical, USA Inc., 1600 Bellwood Rd., Richmond,
• the poly( vinyl alcohol) is present, and functions as an emulsifier and viscosity enhancer. It should be noted that in many cases it is not necessary to include in the polymerization reaction all of the poly(vinyl alcohol) which will eventually be admixed with the poly(4-vinylpyridine) in the ink-receiving layer.
• the poly(4-vinylpyridine) in the ink-receiving layer is to comprise a mixture of a derivatized and an underivatized poly( vinyl alcohol) (i.e., when the sheet is to be both a derivatized/non-derivatized sheet and a hydrophilic polymer sheet of the present invention), it is often advantageous to include only the underivatized poly(vinyl alcohol) in the polymerization reaction and to add the derivatized poly( vinyl alcohol) later.
• the optimum weight ratio of poly(vinyl alcohol) to total weight of poly( vinylbenzyl quaternary ammonium salt) and poly( vinylpyridine) for any particular ink may be determined by skilled persons using routine empirical tests; however, for general guidance it may be stated that typically from 3 to 15 parts, desirably from 5 to 8 parts, by weight of the poly(vinyl alcohol) per total part by weight of the poly(vinylbenzyl quaternary ammonium salt) and the poly(vinylpyridine) produces optimum results.
• this poly(vinyl alcohol) is desirably a mixture of derivatized and non-derivatized poly(vinyl alcohol), and desirably the weight ratio of the non-derivatized poly(vinyl alcohol) to the derivatized poly( vinyl alcohol) is in the range of 2:1 to 1:2, with the derivatized poly(vinyl alcohol) desirably being an acetoacetylated poly(vinyl alcohol).
• ink jet receiving sheets of the present invention containing poly(vinyl alcohol), to produce an ink-receiving layer of optimum toughness and control of ink spreading, it is desirable that the poly( vinyl alcohol) be cross-linked.
• cross-linking may be effected with any of the known cross-linking agents for poly(vinyl alcohol), for example the boron compounds and chromium chloride described in the aforementioned US-A-4 592 951.
• the cross-linking agent be an aldehyde.
• the preferred type of cross-linking agent is a diepoxy cross-linking agent; one preferred cross-linking agent of this type is 1,4-butanediol diglycidyl ether.
• diepoxy cross- linking agents actually perform better under basic conditions, in practice in the present invention it may be desirable to include an acid, for example acetic acid or lactic acid, to solubilize the poly(4-vinylpyridine) in the composition used to form the ink-receiving layer, and diepoxy cross-linking agents can still provide a satisfactory degree of cross-linking in the presence of such an acid.
• an acid for example acetic acid or lactic acid
• diepoxy cross-linking agents can still provide a satisfactory degree of cross-linking in the presence of such an acid.
• Whichever type of cross-linking agent is employed, it will typically be present in an amount of less than about 3 percent by weight of the ink-receiving layer.
• the ink- receiving layer of all the present sheets also advantageously comprises poly(vinyl pyrrolidone); this polymer acts to control ink reception by the ink-receiving layer and to control dot spread, i.e., the tendency for the ink droplets to spread laterally across the sheet.
• This polymer also improves the gloss of the sheet, producing a sheet with an appearance closely resembling that of conventional silver-halide based photographic printing paper.
• starch granules typically in an amount of from 2 to 8 percent by weight of the ink-receiving layer in the ink-receiving layer in order that the feel of the sheet will closely resemble that of photographic printing paper.
• a surfactant in the ink-receiving layer further improves the ability of the layer to control dot spread; linear alkoxylated fatty alcohol surfactants, such as that sold commercially by BASF, Parsippany, New Jersey, United States of America, under the trade name Plurafac C17, are preferred for this purpose.
• a surfactant such as that sold commercially by BASF, Parsippany, New Jersey, United States of America, under the trade name Plurafac C17
• silica gel in the ink-receiving layer; such silica gel will typically be present in an amount of from 1 to 4 percent by weight of the ink-receiving layer.
• silica gel has been found to increase the smudge resistance of the image and also facilitates sheet handling during printing.
• Most ink jet printers intended for home or small office use have an input tray for recording sheets at the front of the printer. Sheets withdrawn from this tray are carried 180° around a roller or roller assembly and thence across a platen, above which one or more ink jet heads reciprocate to effect printing.
• the sheets are carried from the platen to an output tray positioned vertically above the input tray; typically, movable support members are provided on the output tray to hold a sheet emerging from the platen above the output tray for a few seconds, in order to prevent the sheet still "wet” from printing coming into contact with the preceding sheet and thus avoid smearing of the image on either sheet.
• the roller or roller assembly is usually only about 4 cm in diameter, and the recording sheet must be able to be wrapped around that small diameter without acquiring a permanent "set", so that the sheet will lie flat on the platen and in the output tray.
• the ink-receiving layer may comprise various conventional additives, for example ultraviolet absorbers, antioxidants, humectants, bactericides, fungicides and cross-linking agents.
• the support employed in the present invention is not critical, and will normally be chosen having regard to the type of image which is intended to be produced, the proposed use of the image and the specific ink employed.
• the support may be transparent or opaque, depending upon whether a transparency or reflection print is desired.
• Polymeric films of both synthetic and naturally occurring polymeric materials may be employed.
• suitable transparent polymeric materials include polymethacrylic acid; methyl and ethyl esters; polyamides, such as nylons; polyesters, such as the polymeric films derived from ethylene glycol terephthalate acid; polymeric cellulose derivatives; polycarbonates; polystyrene and the like.
• Non- transparent supports include paper and synthetic papers such as silica-based synthetic papers.
• subcoats or surface treatments of the support such as corona discharge, may be employed.
• the ink jet recording sheet of the present invention is primarily intended for use with aqueous and alcohol based inks, although we do not exclude the possibility that the sheet may be useful in conjunction with inks based upon hydrophobic organic solvents such as hydrocarbons.
• the ink jet recording sheet of the present invention can be prepared by conventional coating techniques. As illustrated in the Examples below, typically the various components of the ink-receiving layer will be prepared in the form of an aqueous solution or dispersion, coated on to the desired support and dried to produce the final recording sheet.
• the proportions of the various components in the ink receiving layer may vary over a considerable range, but persons skilled in the art of preparing ink jet recording media will be able to determine the optimum proportions for any specific formulation by routine empirical tests.
• the following examples of preferred ranges of compositions of the ink-receiving layers in the present sheets are provided:
• Derivatized/non-derivatized sheet from about 20 to about 40 parts by weight of a non-derivatized poly(vinyl alcohol); from about 20 to about 40 parts by weight of an acetoacetylated poly( vinyl alcohol); from about 5 to about 15 parts by weight of an a poly(vinylbenzyl quaternary ammonium salt); from about 15 to about 30 parts by weight of poly(vinylpyrrolidone); from 0 to about 5 (most desirably about 2) parts by weight of a poly(alkyl acrylate) or poly(alkyl methacrylate); and from 0 to about 1 (most desirably about 0.2) part by weight of a surfactant; 2.
• Hydrophilic polymer sheet containing a poly( vinylpyridine) from about 50 to about 80 parts by weight of poly( vinyl alcohol); from about 5 to about 15 parts by weight of poly(4- vinylpyridine); from about 15 to about 30 parts by weight of poly(vinylpyrrolidone); and from 0 to about 1 (most desirably about 0.2) part by weight of a surfactant.
• the optimum proportions of the various components in the ink-receiving layer of the present recording sheet may vary depending upon the chemical composition of the ink with which it is intended to be used, since such factors as ink spread, glossiness etc. are greatly affected by chemical interactions between the ink and the ink-receiving layer.
• the ink to be used for imaging contains a glycol ether cosolvent in addition to water, it is advantageous to increase significantly the proportion of poly( vinyl pyrrolidone) in the ink-receiving layer, up to as much as 80 percent of the layer, with consequent decreases in the proportion of the poly(vinyl alcohol) and the poly(vinyl pyridine).
• the ink-receiving layer may comprises: from about 10 to about 30 parts by weight of poly( vinyl alcohol) (which may be all derivatized poly(vinyl alcohol)); from about 5 to about 15 parts by weight of poly(4-vinylpyridine); from about 50 to about 80 parts by weight of poly( vinyl pyrrolidone); from 0 to about 5 parts by weight of silica gel; from 0 to about 5 parts by weight of a cross-linking agent capable of cross-linking poly( vinyl alcohol) and poly(4- vinylpyridine); and from 0 to about 1 part by weight of a surfactant.
• poly( vinyl alcohol) which may be all derivatized poly(vinyl alcohol)
• poly(4-vinylpyridine) from about 50 to about 80 parts by weight of poly( vinyl pyrrolidone)
• silica gel from 0 to about 5 parts by weight of silica gel
• Example 1 A dispersion was formed from the following components; all parts by weight are quoted on a dry solids basis: Parts by weight
• the surfactant (1.4 grams of a 10 weight percent aqueous solution), poly(methyl methacrylate) (35 grams of a 4 weight percent aqueous dispersion) and the poly(vinyl pyrrolidone) (192.5 grams of an 8 weight percent aqueous solution) were then added, and the resultant mixture mixed for a further 30 minutes to produce a dispersion suitable for coating.
• the dispersion thus produced was coated on to 7.6 mil polyclad photo paper using a No. 24 Mayer rod at a coating weight of 4.2 g/m 2 , and the coated sheets were dried at 80°C in an oven for 10 minutes.
• the dried ink jet recording sheets were tested using a Lexmark 2050 printer and were found to give excellent color images with minimal ink spread and smearing.
• the printed sheets had a gloss and feel closely resembling that of conventional silver-halide based photographic printing paper.
• To test waterfastness the printed images were placed into a beaker of deionized water for three minutes, taken out, shaken for 10 seconds and put back into water for another two minutes. The washed images showed very little dye fading. This is an indication of excellent waterfastness.
• Example 2 (Control) This Example illustrates that the excellent results achieved in Example 1 are not achieved using underivatized poly( vinyl alcohol) alone.
• a dispersion was formed from the following components; all parts by weight are quoted on a dry solids basis:
• the dispersion thus produced was coated, dried and the resultant sheet printed in the same way as in Example 1 above.
• the printed sheets were found to have a soft, tacky image in black areas.
• Example 3 (Control) This Example illustrates that the excellent results achieved in Example 1 are not achieved using derivatized poly(vinyl alcohol) alone.
• a dispersion was formed from the following components; all parts by weight are quoted on a dry solids basis:
• Example 2 illustrates that the excellent results achieved in Example 1 are not achieved using a copolymer of vinylpyridine and a vinylbenzyl quaternary ammonium salt.
• Copolymer A used in the dispersion below was a copolymer of
• a dispersion was formed from the following components; all parts by weight are quoted on a dry solids basis: Parts by weight
• Example 5 The dispersion thus produced was coated, dried and the resultant sheet printed in the same way as in Example 1 above.
• the printed sheets were found to have excellent color images with minimal ink spread and smearing. Also, the printed sheets had a gloss and feel closely resembling that of conventional silver- halide based photographic printing paper.
• To test waterfastness the printed images were placed into a beaker of deionized water for three minutes, taken out, shaken for 10 seconds and put back into water for another two minutes. The washed images showed approximately 30% dye fading, indicating poor waterfastness.
• Example 5 Control
• Example 2 illustrates that the excellent results achieved in Example 1 are not achieved using a copolymer of vinylpyridine and a vinylbenzyl quaternary ammonium salt.
• Copolymer B used in the dispersion below was a copolymer of 4- vinylpyridine and vinylbenzyltrimethylammonium chloride, at a monomer ratio of
• a dispersion was formed from the following components; all parts by weight are quoted on a dry solids basis:
• the dispersion thus produced was coated, dried and the resultant sheet printed in the same way as in Example 1 above.
• the printed sheets were found to have excellent color images with minimal ink spread and smearing. Also, the printed sheets had a gloss and feel closely resembling that of conventional silver- halide based photographic printing paper.
• To test waterfastness the printed images were placed into a beaker of deionized water for three minutes, taken out, shaken for 10 seconds and put back into water for another two minutes. The washed images showed approximately 40% dye fading, indicating poor waterfastness.
• Example 1 are not achieved using a terpolymer of vinylpyridine, a vinylbenzyl quaternary ammonium salt and hydroxyethylcellulose.
• Copolymer C used in the dispersion below was a terpolymer of 4-vinylpyridine, vinylbenzyltrimethylammonium chloride and hydroxyethyl- cellulose.
• a dispersion was formed from the following components; all parts by weight are quoted on a dry solids basis:
• the surfactant (1.4 grams of a 10 weight percent aqueous solution), poly(methyl methacrylate) (35 grams of a 4 weight percent aqueous dispersion) and the poly(vinyl pyrrolidone) (192.5 grams of an 8 weight percent aqueous solution) were then added, and the resultant mixture mixed for a further 30 minutes to produce a dispersion suitable for coating.
• the dispersion thus produced was coated, dried and the resultant sheet printed in the same way as in Example 1 above.
• the printed sheets were found to have excellent color images with minimal ink spread and smearing. Also, the printed sheets had a gloss and feel closely resembling that of conventional silver- halide based photographic printing paper. To test waterfastness, the printed images were placed into a beaker of deionized water for three minutes, taken out, shaken for
• Example 7 This Example illustrate a preferred process for the preparation of a mixed poly( vinyl alcohol)/poly(4-vinylpyridine) solution for use in a hydrophilic polymer sheet of the present invention.
• the weight average molecular weight of the poly(4-vinylpyridine) produced by the above polymerization process is about 250,000.
• the residual 4-vinylpyridine monomer concentration determined by gas chromatography (10% polyethylene glycol, 2% potassium hydroxide, glass column, l A inch by 12 foot), is 97 parts per million (ppm).
• the fluid was heated to about 90°C for thirty (30) minutes to destroy any remaining V50. After cooling the resultant fluid to about 60°C, 72.8 kg of 88% aqueous lactic acid and 1243 L of deionized water were added with stirring for thirty (30) minutes while maintaining the solution at about 60°C to solubilize the poly(4-vinylpyridine), and then, cooled to room temperature.
• Example 8 This Example illustrate a second preferred process for the preparation of a mixed poly(vinyl alcohol)/poly(4-vinylpyridine) solution for use in a hydrophilic polymer sheet of the present invention.
• 2.6 kg of poly(vinyl alcohol) Airvol 540, partially hydrolyzed
• 41 kg of deaerated, deionized water at about 95°C under nitrogen.
• the residual 4-vinylpyridine monomer concentration, determined by gas chromatography in the same way as in Example 7 above is 42 ppm.
• the fluid was heated to about 90°C for thirty (30) minutes to destroy any remaining V50.
• 565 g of 88% aqueous acetic acid and 1 kg of deionized water were added with stirring for thirty (30) minutes while maintaining the solution at about 60°C to solubilize the poly(4-vinylpyridine), and then, cooled to room temperature.
• Example 9 This Example illustrates the preparation and printing of a hydrophilic polymer sheet of the present invention using the mixed polymer solution prepared in Example 7 above.
• a dispersion was formed from the following components; all parts by weight are quoted on a dry solids basis: Parts by weight
• Acetoacetylated poly(vinyl alcohol) (Z200) 39.0 Poly(vinyl pyrrolidone) 27.5
• the dispersion thus produced was coated on to a 7.6 mil poly clad photo paper using a No. 24 Mayer rod at a coating weight of 4.2 g/m 2 , and the coated sheets were dried in a 80 °C oven for 10 minutes.
• the dried ink jet recording sheets were tested using a Hewlett Packard Deskjet (Registered Trade Mark) 693C printer and were found to give excellent color images with minimal ink spread and smearing. Also, the printed sheets had a gloss and feel closely resembling that of conventional silver-halide based photographic printing paper.
• cyan, magenta and yellow printed images were placed into a beaker of deionized water for three minutes, taken out, shaken for 10 seconds and put back into water for another two minutes. After the washed samples dried, color densities of cyan, magenta, and yellow were recorded using an X-Rite 310 photographic densitometer, supplied by X-Rite, Inc., Grandville, Michigan, United States of America, equipped with the appropriate filter. The optical densities of the dry images before and after the immersion were as follows:

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