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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
  • C09D101/08—Cellulose derivatives
  • C09D101/26—Cellulose ethers
  • C09D101/28—Alkyl ethers
  • C09D101/284—Alkyl ethers with hydroxylated hydrocarbon radicals
• • 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
  • B41M5/506—Intermediate layers
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
• • 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
  • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

• the present invention is in respect of printing media which may be ink jet printed and to coating compositions which may be used to form the printing media.
• the invention comprises several principal embodiments, or Parts, and various embodiments within each Part. Except a ⁇ noted below, the descriptions of the various Parts are substantially autonomous.
• Ink-jet printing produces little noise and can be used to print single color images or multicolor images on various substrates.
• Plain paper or paper having a low degree of sizing can be used as the printing substrate, but these suffer from the disadvantage that a clear image cannot be obtained because of the diffusion of the ink into the paper. More particularly, the image lacks sharp resolution, and in the case of color printing, the image lacks good optical density.
• ink-jet printed images of improved quality In order to achieve ink-jet printed images of improved quality, coated papers have been employed as the printing substrates.
• the image quality varies depending upon the type of coating employed. In most instances image quality is better than that obtained using uncoated paper, but it is still less than desired.
• ink-jet printing has been used to print single color images or multicolor images on organic polymer media, but spreading of the ink on organic polymer surfaces presents many problems, including lack of sharp image resolution, and in the case of color printing, the image lacks good optical density. Coatings have provided some improvement, but image quality is still far less than desired. Ink jet printing inks contain large amounts of solvents.
• One coating used m the past is a porous coating comprising substantially transparent, colorless alumina monohydroxide, e.g., pseudo-boehmite, and organic polymer. Such coatings were porous because it was believed that coating porosity was necessary to accomplish rapid solvent removal. Images of somewhat improved quality were obtained using these coatings, but image quality was still less than desired.
• Part I of the invention is a printing medium comprising: (a) a substrate having at least one surface; and (b) a substantially nonporous coating on the surface wherein the coating comprises transparent, colorless alumina monohydroxide and water-soluble organic polymer, and wherein the water-soluble organic polymer comprises water-soluble cellulosic organic polymer and water-soluble noncellulosic organic polymer.
• a coating is substantially nonporous when the pore volume of the coating is less than 0.01 cubic centimeters per gram (cm 3 /g) . Often the pore volume of the coating is less than 0.005 cm /g.
• the pore volume i ⁇ less than 0.001 cm /g.
• the pore volume of the coating is determined using a Micromeritics Model ASAP 2400 Accelerated Surface Area and Porosimetry Instrument (Micromeritics Instrument Corporation) and nitrogen as the adsorbate in accordance with the accompanying operating manual in which the following choices and modifications are followed:
• AlO(OH) is known. Its preparation and properties are described by B. E. Yoldas in The American Ceramic Society Bulletin. Vol. 54, No. 3, (March 1975), pages 289-290, in Journal of Applied Chemical Biotechnology, Vol. 23 (1973), pages 803-809, and in Journal of Materials Science. Vol. 10 (1975) , pages 1856-1860. Briefly, aluminum isopropoxide or aluminum secondary-butoxide are hydrolyzed in an excess of water with vigorous agitation at from 75 C to 80°C to form a slurry of aluminum monohydroxide.
• the aluminum monohydroxide is then peptized at temperatures of at least 80°C with an acid to form a clear alumina monohydroxide sol which exhibits the Tyndall effect when illuminated with a narrow beam of light. Since the alumina monohydroxide of the sol is neither white nor colored, it i ⁇ not a pigment and does not function as a pigment in the present invention.
• the acid employed is noncomplexing with aluminum, and it has sufficient strength to produce the required charge effect at low concentration.
• Nitric acid, hydrochloric acid, perchloric acid, acetic acid, chloroacetic acid, and formic acid meet these requirements.
• the acid concentration is usually in the range of from 0.03 to 0.1 mole of acid per mole of aluminum alkoxide.
• Pseudo-boehmite is indeed the preferred transparent, colorless alumina monohydroxide for use in the present invention.
• the amount of transparent, colorless alumina monohydroxide in the coating may vary widely. Often the transparent, colorless alumina monohydroxide constitutes from 10 to 87 percent by weight of the coating. In many cases the transparent, colorless alumina monohydroxide constitutes from 50 to 85 percent by weight of the coating. From 70 to 85 percent by weight is preferred.
• the water-soluble organic polymer comprises water-soluble cellulosic organic polymer and water-soluble noncellulosic organic polymer.
• Organic polymer of either or both classes may or may not be insolubilized as desired.
• insolubilized water-soluble organic polymer is organic polymer which is water-soluble when applied to the substrate and which i ⁇ completely or partially insolubilized after such application.
• the insolubilizer reacts with water-soluble noncellulosic organic polymer to provide the desired degree of insolubilization to the total organic polymer of the coating.
• water-soluble cellulosic organic polymers there are many widely varying types of water-soluble cellulosic organic polymers which may be employed in the present invention. Of these, the water-soluble cellulose ethers are preferred water-soluble cellulosic organic polymers. Many of the water-soluble cellulose ethers are also excellent water retention agents.
• water-soluble cellulose ethers examples include water-soluble methylcellulose [CAS 9004-67-5] , water-soluble carboxymethylcellulose, water-soluble sodium carboxymethylcellulose [CAS 9004-32-4] , water- ⁇ oluble ethylmethylcellulo ⁇ e, water-soluble hydroxyethylmethylcellulose [CAS 9032-42-2] , water-soluble hydroxypropylmethylcellulose [CAS 9004-65-3] , water-soluble hydroxyethylcellulose [CAS 9004-62-0] , water-soluble ethylhydroxyethylcellulose, water-soluble sodium carboxymethylhydroxyethylcellulose, water-soluble hydroxypropylcellulose [CAS 9004-64-2] , water-soluble hydroxybutylcellulose [CAS 37208-08-5] , water-soluble hydroxybutylmethylcellulose [CAS 9041-56-9] and water-soluble cellulose sulfate sodium salt [CAS 9005-22-5] . Water-soluble hydroxypropylcellulose is preferred.
• Water-soluble hydroxypropylcellulose is a known material and is available commercially in ⁇ everal different average molecular weights .
• the weight average molecular weight of the water-soluble hydroxypropylcellulose used in the present invention can vary widely, but usually it is in the range of from 100,000 to 1,000,000. Often the weight average molecular weight is in the range of from 100,000 to 500,000. From 200,000 to 400,000 is preferred. Two or more water-soluble hydroxypropylcelluloses having different average molecular weights may be admixed to obtain a water-soluble hydroxypropyl cellulose having a differing average molecular weigh .
• water-soluble noncellulosic organic polymers which may be employed in the present invention.
• the water-soluble noncellulosic organic polymers include water-soluble poly(vinyl alcohol), water-soluble poly(vinylpyrrolidone) , water-soluble poly(vinylpyridine) , water-soluble poly(ethylene oxide), water-soluble poly(ethylenimine) , water-soluble ethoxylated poly(ethyleni ine) , water-soluble poly(ethylenimine) - epichlorohydrin, water-soluble polyacrylate, water-soluble sodium polyacrylate, water-soluble poly(acrylamide) , water-soluble carboxy modified poly(vinyl alcohol) , water- ⁇ oluble poly(2-acrylamido-2-methylpropane sulfonic acid) , water-soluble poly(styrene sulfonate) , water-soluble vinylmethyl ether/maleic acid copolymer, water-soluble water-soluble noncellulosic organic poly
• Water-soluble poly(vinyl alcohol) is preferred.
• Water-soluble poly(vinyl alcohol) may be broadly classified as one of two type ⁇ .
• the fir ⁇ t type i ⁇ fully hydrolyzed water-soluble poly(vinyl alcohol) in which less than 1.5 mole percent acetate groups are left on the molecule.
• the second type is partially hydrolyzed water-soluble poly(vinyl alcohol) in which from 1.5 to as much as 20 mole percent acetate groups are left on the molecule.
• the water- ⁇ oluble organic polymer may comprise either type or a mixture of both.
• the fully hydrolyzed water-soluble poly(vinyl alcohol) is preferred.
• the amount of water-soluble organic polymer in the coating may vary widely. Often the water-soluble organic polymer constitutes from 13 to 90 percent by weight of the coating. In many cases the water-soluble organic polymer constitutes from 15 to 50 percent by weight of the coating. From 15 to 30 percent by weight is preferred.
• the water-soluble organic polymer of the coating comprises water-soluble cellulosic organic polymer and water-soluble noncellulosic organic polymer.
• the water-soluble cellulosic organic polymer constitutes from 5 to 95 percent by weight of the water-soluble organic polymer and the water-soluble noncellulosic organic polymer constitutes from 5 to 95 percent by weight of the water-soluble organic polymer.
• the water-soluble cellulosic organic polymer constitutes from 30 to 90 percent by weight of the water-soluble organic polymer and the water-soluble noncellulosic organic polymer constitutes from 10 to 70 percent by weight of the water-soluble organic polymer.
• the water-soluble cellulosic organic polymer constitutes from 60 to 80 percent by weight of the water-soluble organic polymer and the water-soluble noncellulosic organic polymer constitutes from 20 to 40 percent by weight of the water-soluble organic polymer.
• the coating comprising transparent, colorless alumina monohydroxide and organic polymer may itself be substantially transparent, substantially opaque, or of intermediate transparency. It may be sub ⁇ tantially colorless, it may be highly colored, or it may be of an intermediate degree of color.
• the coating comprising transparent alumina monohydroxide and organic polymer is itself substantially transparent and sub ⁇ tantially colorle ⁇ .
• the coating is substantially transparent if the luminous transmission in the visible region is at least 80 percent of the incident light. Often the luminous transmis ⁇ ion is at least 85 percent of the incident light. Preferably the luminous transmission i ⁇ at lea ⁇ t 90 percent. Also as used herein and in the claims, the coating is substantially colorless if the transmission is sub ⁇ tantially the same for all wavelengths in the visible region.
• the sub ⁇ trate may be any substrate at least one surface of which is capable of bearing the coating discussed above. In most instances the sub ⁇ trate i ⁇ in the form of an individual sheet or in the form of a roll, web, strip, film, or foil of material capable of being cut into sheets.
• the substrate may be porous throughout, but it is preferred that printing medium comprise: (a) a substrate having at least one substantially nonporous surface; and (b) a sub ⁇ tantially nonporous coating on the surface wherein the coating comprises transparent, colorless alumina monohydroxide and organic polymer, and wherein the water-soluble organic polymer comprises water-soluble cellulosic organic polymer and water-soluble noncellulosic organic polymer.
• porous substrate An example of a porous substrate is paper. Another example is cloth.
• the ⁇ ub ⁇ trate may be ⁇ ubstantially nonporous throughout or the surface may be sub ⁇ tantially nonporou ⁇ irrespective of how much of the remainder of the substrate is porous.
• substrate ⁇ which are ⁇ ubstantially nonporou ⁇ throughout and hence have at least one ⁇ ubstantially nonporous surface
• substrate ⁇ examples include sheet ⁇ or films of organic polymer such as poly(ethylene terephthalate) , polyethylene, polypropylene, cellulose acetate, and copolymers ⁇ uch a ⁇ saran.
• Additional examples include metal foil ⁇ ⁇ uch as aluminum foil.
• a porous or microporous foam comprising thermoplastic organic polymer which foam has been compressed to such an extent that the resulting deformed material is substantially nonporous.
• the sub ⁇ trate may or may not include one or more coating ⁇ or laminations between the base stock and the sub ⁇ tantially nonporou ⁇ coating which compri ⁇ e ⁇ alumina monohydroxide and organic polymer and which is de ⁇ cribed above.
• Ba ⁇ e ⁇ tocks which are normally porous such as for example paper, cloth, nonwoven fabric, felt, porous foam, or microporou ⁇ foam may be coated or laminated to render one or more surface ⁇ substantially nonporous and thereby provide substrates having at least one substantially nonporous surface.
• the substrate may be substantially tran ⁇ parent, it may be substantially opaque, or it may be of intermediate transparency.
• the substrate must be sufficiently transparent to be useful for the application.
• transparency of the substrate i ⁇ not so important.
• the printing media of Part I of the invention may be made by coating a substantially nonporous surface of the substrate with a coating composition comprising: (a) transparent, colorless alumina monohydroxide; (b) aqueous solvent; and (c) water-soluble organic polymer dis ⁇ olved in the aqueous solvent; wherein the water-soluble organic polymer comprises water-soluble cellulosic organic polymer and water-soluble noncellulosic organic polymer.
• a coating composition comprising: (a) transparent, colorless alumina monohydroxide; (b) aqueous solvent; and (c) water-soluble organic polymer dis ⁇ olved in the aqueous solvent; wherein the water-soluble organic polymer comprises water-soluble cellulosic organic polymer and water-soluble noncellulosic organic polymer.
• the weight ratio of the alumina monohydroxide to water-soluble organic polymer in the coating composition may vary considerably, but it is usually in the range of from 11:100 to 670:100. Often the weight ratio is in the range of from 100:100 to 567:100. Preferably it is in the range of from 233:100 to 567:100.
• the discussions above in respect of the proportions of water-soluble cellulosic organic polymer and water-soluble noncellulosic organic polymer water-soluble organic polymer in - li ⁇ the water-soluble organic polymer, are applicable to the coating composition as well as to the coating.
• the aqueous solvent is water.
• Organic cosolvents miscible with water may optionally be present when desired.
• the amount of aqueous solvent present in the coating composition may vary widely. The minimum amount is that which will produce a coating composition having a visco ⁇ ity low enough to apply as a coating. The maximum amount is not governed by any theory, but by practical considerations such as the co ⁇ t of the solvent, the minimum desired thickness of the coating to be deposited, and the cost and time required to remove the solvent from the applied wet coating. U ⁇ ually, however, the aqueous solvent constitutes from 80 to 98 percent by weight of the coating composition. Often the aqueous solvent constitutes from 85 to 95 percent by weight of the coating composition. Preferably aqueous solvent constitutes from 85 to 90 percent by weight of the composition.
• a material which may optionally be present in the coating composition is insolubilizer.
• Insolubilizers are materials which react with functional groups of water-soluble organic polymer ⁇ , especially those of water- ⁇ oluble noncellulosic organic polymers, and generally function as crosslinking agents. There are many available insolubilizers which may be used.
• insolubilizers include, but are not limited to, Curesan ® 199 insolubilizer (PPG Industries, Inc., Pittsburgh, PA), Curesan ® 200 insolubilizer (PPG Industries, Inc.), Sequarez ® 700C insolubilizer (Sequa Chemicals, Inc., Chester, SC) , Sequarez ® 700M insolubilizer (Sequa Chemicals, Inc.), Sequarez ® 755 insolubilizer (Sequa Chemicals, Inc.), Sequarez ® 770 insolubilizer (Sequa Chemicals, Inc.), Berset ® 39 insolubilizer (Bercen Inc., Cranston, RI), Berset ® 47 insolubilizer (Bercen Inc.), Berset ® 2185 insolubilizer (Bercen Inc.), and Berset ® 2586 insolubilizer (Bercen Inc.
• the amount of insolubilizer pre ⁇ ent in the coating composition may vary considerably.
• the weight ratio of the insolubilizer to the water-soluble noncellulosic organic polymer is usually in the range of from 0.05:100 to 25:100. Often the weight ratio is in the range of from 2:100 to 10:100. From 4:100 to 6:100 is preferred. These ratios are on the basi ⁇ of in ⁇ olubilizer dry ⁇ olid ⁇ and water- ⁇ oluble noncellulo ⁇ ic organic polymer dry ⁇ olid .
• coating composition There are many other materials which may optionally be present in the coating composition. These include such material ⁇ a ⁇ lubricants, waxes, antioxidants, organic solvents, mordants, lakes, and pigments. The listing of such material ⁇ i ⁇ by no mean ⁇ exhaustive. These and other ingredients may be employed in their customary amounts for their customary purposes so long as they do not seriously interfere with good coating composition formulating practice.
• the coating compositions are usually prepared by simply admixing the various ingredients.
• the ingredients may be mixed in any order, but it is preferred to mix the dry ingredients together before mixing with liquid. Although the mixing of liquid and solids i ⁇ u ⁇ ually accomplished at room temperature, elevated temperatures are sometimes used. The maximum temperature which is usable depends upon the heat stability of the ingredients.
• the coating compositions are generally applied to the surface of the substrate using substantially any technique known to the art. These include spraying, curtain coating, dipping, rod coating, blade coating, roller application, ⁇ ize pre ⁇ , printing, brushing, drawing, die-slot coating, and extrusion. The coating is then formed by removing the solvent from the applied coating composition. This may be accomplished by any conventional drying technique. Coating composition may be applied once or a multiplicity of times.
• the applied coating is usually but not necessarily dried, either partially or totally, between coating applications.
• the solvent is ⁇ ubstantially removed, u ⁇ ually by drying.
• the substantially nonporous coating containing the transparent alumina monohydroxide and water-soluble organic polymer may be overlaid with an overcoating comprising ink-receptive organic polymer.
• the overcoating may be formed by applying an overcoating composition comprising solvent and ink-receptive organic polymer dissolved in the solvent and removing the solvent, as for example, by drying.
• the solvent is an aqueous solvent and the ink-receptive organic polymer i ⁇ water- ⁇ oluble cellulo ⁇ ic organic polymer, both of which have been described above in respect of the alumina monohydroxide-containing coating.
• Water is an especially preferred aqueous solvent and hydroxypropylcellulose is an especially preferred water-soluble cellulosic organic polymer.
• the relative proportions of aqueous solvent and organic polymer present in the overcoating composition may vary widely.
• the minimum proportion is that which will produce an overcoating composition having a visco ⁇ ity low enough to apply as an overcoating.
• the maximum proportion is not governed by any theory, but by practical con ⁇ iderations such as the cost of the solvent and the cost and time required to remove the solvent from the applied wet overcoating.
• the weight ratio of aqueous solvent to organic polymer is from 18:1 to 50:1. Often the weight ratio is from 19:1 to 40:1. Preferably weight ratio is from 19:1 to 24:1.
• the overcoating composition may be prepared by admixing the ingredients. It may be applied and dried using any of the coating and drying techniques discussed above. When an overcoating composition is to be applied, it may be applied once or a multiplicity of times.
• the coated substrate may optionally be calendered.
• calendering i ⁇ accomplished between two rolls.
• the roll contacting the coating of the coated substrate is a metal-surfaced roll.
• the other roll is preferably, but not necessarily, surfaced with a somewhat resilient material such as an elastomer of medium hardness.
• the roll temperature may be widely varied, but usually the roll temperature is in the range of from 20°C to 100°C. Often the roll temperature is in the range of from 30°C to 80°C. From 40°C to 60°C is preferred.
• the force per unit length of the nip may be widely varied.
• the force per unit length of the nip is in the range of from 85 to 350 kilonewton ⁇ per meter (kN/m) .
• the force per unit length of the nip is in the range of from 120 to 275 kN/m. Preferably it is in the range of from 155 to 200 kN/m.
• the gloss of the coated sub ⁇ trate may vary widely. Although lower glo ⁇ ses are acceptable for many purposes , it is preferred that the gloss be at least 20. As used herein gloss is determined according to TAPPI Standard T480 om-92.
• Part I of the invention is further described in conjunction with the following examples which are to be considered illustrative rather than limiting, and in which all parts are parts by weight and all percentages are percentages by weight unless otherwise specified.
• EXAMPLE 1 With stirring, 248 grams of aluminum tri - sec- butoxide [CAS 2269-22-9] was added to 2 liter ⁇ of water at 70°C in a gla ⁇ s container. To this mixture 6 grams of 60 percent concentrated nitric acid was added. The reaction mixture was stirred for 15 minutes on a hot plate. The glas ⁇ container containing the reaction mixture was then sealed with a lid and placed in an oven at 95°C for 2 days. During the two-day period in the oven the precipitate in the reaction mixture was peptized. The resulting colloidal dispersion was concentrated in an unsealed container to 600 grams by boiling to produce a colloidal dispersion (sol) containing 10 percent by weight colloidal alumina monohydroxide.
• sol colloidal dispersion
• F.XAMPLE 2 To 300 grams of alumina monohydroxide sol prepared as in Example 1 was added 6 grams of hydroxypropyl cellulose (HPC) having a weight average molecular weight of 370,000 (Aldrich Chemical Company, Inc.), and 3 grams of Airvol ® 205S poly(vinyl alcohol) (Air Products and Chemicals Inc.) . The mixture was stirred until the HPC and the poly(vinyl alcohol) (PVA) had completely dissolved giving a coating composition containing about 13 percent solids. The coating composition wa ⁇ applied to poly(ethylene terephthalate) (PET) transparencies with a Meyer Rod (13.7 g/m ) and allowed to dry at room temperature. The coating wa ⁇ about 20 ⁇ m thick and clear. The coated transparencies were then printed by an HP- 350 ink jet printer. The ink jet printed transparencie ⁇ exhibited excellent ability to maintain the edge acuity of ink pattern ⁇ , excellent color fidelity, and resistance against scratches .
• HPC hydroxypropyl
• Example 2 wa ⁇ repeated except that one gram of
• 3-methacryloxypropyltrimethoxysilane [CAS 2530-85-0] was added to each 100 grams of coating composition prepared as in Example 2.
• the dry coating and ink jet printed transparencies showed excellent water resistance after being soaked in water for one hour.
• EXAMPLE 4 One gram of tetramethyl orthosilicate [CAS 681-84-5] was added to each 100 grams of coating composition prepared as in Example 2. After several hours the resulting coating composition was applied to PET transparencie ⁇ in a manner similar to that of Example 2. After the coating had dried, the coated transparencies were ink jet printed. The ink jet printed transparencies exhibited water fastness when soaked in water for a period of hours.
• Example 2 PVA, and 70 grams of water. The mixture was stirred until the HPC and PVA had di ⁇ olved. The re ⁇ ulting coating compo ⁇ ition was applied to PET transparencies in a manner similar to that of Example 2. After the coating had dried, the coated transparencies were ink jet printed on an Epson ink jet printer. The quality of the ink jet printed transparencies was excellent.
• Example 6 To 100 grams of alumina monohydroxide sol prepared as in Example 1 wa ⁇ added 2 gram ⁇ of HPC having a weight average molecular weight of 370,000, 2 gram ⁇ of Airvol ® 205S PVA, 2 gram ⁇ of poly(vinyl pyrrolidone) [CAS 9003-39-8] (Aldrich Chemical Company, Inc.) (PVP) having a weight average molecular weight of 10,000, and 50 grams of water. The mixture was stirred until the HPC, PVA, and PVP had dis ⁇ olved. The resulting coating composition was applied to PET transparencie ⁇ in a manner similar to that of Example 2.
• the coated transparencie ⁇ were ink jet printed on an Epson ink jet printer. Not only wa ⁇ the quality of the ink jet printed transparencies excellent, but the inks dried much faster than on many commercially available transparencie ⁇ .
• KXAMPLE 7 To 100 grams of alumina monohydroxide sol prepared as in Example 1 was added 3.5 grams of Airvol ® 205S PVA, 1.5 grams of PVP having a weight average molecular weight of 10,000, and one gram of 3-methacryloxypropyltrimethoxysilane. The mixture wa ⁇ stirred until the PVA and PVP had dis ⁇ olved and then allowed to stand overnight. The resulting coating composition was applied to PET transparencie ⁇ in a manner ⁇ imilar to that of Example 2. After the coating had dried, the coated transparencies were ink jet printed by an HP-855 ink jet printer which is a heaterless printer. The ink dried within 30-60 seconds and the ink jet printed transparencies were of excellent quality.
• Example 2 To 150 grams of alumina monohydroxide sol prepared as in Example 1 was added one gram of HPC having a weight average molecular weight of 370,000, 2 grams of Airvol ® 205S PVA, one gram of PVP having a weight average molecular weight of 10,000, and 1.5 grams of
• a solution wa ⁇ prepared by dissolving 10 grams of HPC having a weight average molecular weight of 370,000 and 5 grams of Airvol ® 205S PVA in 285 gram ⁇ of water. Portion ⁇ of this solution were admixed with portions of alumina monohydroxide sol prepared as in Example 1 to form a series of coating compositions having varying organic polymer to alumina monohydroxide ratios. These coating compositions were applied to glass sub ⁇ trate ⁇ and to PET transparencie ⁇ . The wet coatings were then dried at room temperature. The dried coatings were peeled from the glas ⁇ substrates with a blade and the pore volumes were ascertained using the procedure earlier described. The weight percents of organic polymer in the dry coatings and the corresponding pore volumes are shown in Table 1.
• the first coating composition wa ⁇ applied to photographic resin coated basestock at a coating weight of 11.8 g/m using a hand drawn Meyer Rod applicator and air dried at room temperature to form a first coating.
• the second coating composition was applied to the first coating at a coating weight of 11.8 g/m using a hand drawn Meyer Rod applicator and air dried at room temperature to form a ⁇ econd coating.
• the resulting articles were high glos ⁇ printing sheets .
• the above high gloss sheets were printed on an Epson Color Stylist Ink Jet Printer and a Canon BJC 610 Ink Jet Printer.
• the print densitie ⁇ are ⁇ hown in Table 2.
• one embodiment of Part II of the invention i ⁇ a printing medium comprising: (a) a substrate having at least one surface; and (b) a coating on the surface wherein the coating comprises: (1) a binder comprising mainly organic polymer, wherein poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitutes at least 20 percent by weight of the organic polymer; and (2) discrete particles dispersed in the binder, which particles have a number average particle size in the range of from 1 to 500 nanometers.
• the coating may be substantially nonporous or it may be porous .
• the number average particle size of the particles is in the range of from 1 to 500 nanometers. Often the number average particle size is in the range of from 1 to 100 nanometers. Frequently the number average particle size is in the range of from 1 to 50 nanometers. Preferably the number average particle size i ⁇ in the range of from 1 to 20 nanometers.
• average particle size is determined by transmission electron microscopy.
• the amount of the di ⁇ crete particle ⁇ in the coating may vary widely. Often the particle ⁇ constitute from 20 to 70 percent by weight of the coating. In many case ⁇ the particle ⁇ constitute from 40 to 60 percent by weight of the coating. From 45 to 55 percent by weight is preferred.
• the discrete particles may be discrete inorganic particles, discrete crosslinked organic particles, or a mixture thereof .
• the discrete particles are often discrete particles of metal oxide.
• the metal oxide constituting the particles may be a simple metal oxide (i.e., the oxide of a single metal) or it may be a complex metal oxide (i.e., the oxide of two or more metals) .
• the particles of metal oxide may be particles of a single metal oxide or they may be a mixture of different particles of different metal oxide ⁇ .
• Example ⁇ of suitable metal oxides include alumina, silica, and titania. Other oxides may optionally be present in minor amount. Examples of such optional oxides include, but are not limited to, zirconia, hafnia, and yttria. Other metal oxides that may optionally be present are those which are ordinarily present as impurities such a ⁇ for example, iron oxide. For purposes of the present specification and claims, silicon is considered to be a metal.
• alumina monohydroxide When the particles are particles of alumina, most often the alumina i ⁇ alumina monohydroxide. Particles of alumina monohydroxide, AlO(OH) , and their preparation are known. The preparation and properties of alumina monohydroxide are de ⁇ cribed by B. E. Yolda ⁇ in The American Ceramic Society Bulletin, Vol. 54, No. 3, (March 1975), page ⁇ 289-290, in Journal of Applied Chemical Biotechnology. Vol. 23 (1973), page ⁇ 803-809, and in Journal of Material ⁇ Science, Vol. 10 (1975) , page ⁇ 1856-1860.
• aluminum isopropoxide or aluminum secondary-butoxide are hydrolyzed in an exces ⁇ of water with vigorou ⁇ agitation at from 75 C to 80°C to form a slurry of aluminum monohydroxide.
• the aluminum monohydroxide is then peptized at temperatures of at lea ⁇ t 80°C with an acid to form a clear alumina monohydroxide sol which exhibits the Tyndall effect when illuminated with a narrow beam of light. Since the alumina monohydroxide of the sol is neither white nor colored, it is not a pigment and does not function a ⁇ a pigment in the pre ⁇ ent invention.
• the acid employed is noncomplexing with aluminum, and it has sufficient strength to produce the required charge effect at low concentration.
• Nitric acid, hydrochloric acid, perchloric acid, acetic acid, chloroacetic acid, and formic acid meet these requirements.
• the acid concentration is usually in the range of from 0.03 to 0.1 mole of acid per mole of aluminum alkoxide.
• the alumina monohydroxide produced in thi ⁇ manner i ⁇ pseudo-boehmite.
• Pseudo-boehmite is indeed the preferred alumina monohydroxide for use in the present invention.
• the alumina monohydroxide is not a pigment and does not function a ⁇ a pigment in the present invention. In most instance ⁇ the alumina monohydroxide is transparent and colorless.
• Colloidal silica is also known. Its preparation and properties are described by R. K. Her in The Chemistry of Silica, John Wiley & Sons, Inc., New York (1979) ISBN 0-471-02404-X, pages 312-337, and in United States Patents No. 2,601,235; 2,614,993; 2,614,994; 2,617,995; 2,631,134; 2,885,366; and 2,951,044, the disclosure ⁇ of which are, in their entireties, incorporated herein by reference.
• Example ⁇ of commercially available colloidal ⁇ ilica include Ludox® HS, LS, SM, TM and CL-X colloidal silica (E. I.
• du Pont de Nemours & Company, Inc. in which the counter ion is the sodium ion
• Ludox® AS colloidal silica E. I. du Pont de Nemour ⁇ & Company, Inc.
• the counter ion is the ammonium ion
• Ludox® AM colloidal silica E. I. du Pont de Nemours & Company, Inc.
• some of the silicon atoms have been replaced by aluminum atoms and the counter ion is the sodium ion.
• Colloidal titania i ⁇ also known. Its preparation and properties are described in United States Patent No. 4,275,118. Colloidal titania may al ⁇ o be prepared by reacting titanium i ⁇ opropoxide [CAS 546-68-9] with water and tetramethyl ammonium hydroxide.
• the discrete particles are frequently discrete particles of crosslinked organic polymer.
• crosslinked organic polymer examples include crosslinked melamine- formaldehyde polymer, crosslinked resorcinol-formaldehyde polymer, crosslinked phenol-resorcinol-formaldehyde polymer, crosslinked (meth) acrylate polymer, and crosslinked styrene- divinylbenzene polymer.
• the binder functions as a matrix for the di ⁇ crete particles dispersed therein.
• the binder comprises mainly organic polymer but it may optionally contain minor amounts of conventional adjuvants as will be discussed more fully later in connection with the coating composition used to form the coating of the printing medium.
• the binder of the coating comprises film-forming organic polymer or insolubilized film-forming organic polymer.
• the film-forming polymer may be water-soluble or water-disper ⁇ ible organic polymer.
• Poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 is known. Such materials are ordinarily formed by polymerizing ethylene oxide [CAS 75-21-8] , usually in the presence of a small amount of an initiator such as low molecular weight glycol or triol .
• initiators examples include ethylene glycol [CAS 107-21-1] , diethylene glycol [CAS 111-46-6] , triethylene glycol [CAS 112-27-6] , tetraethylene glycol [CAS 112-60-7] , propylene glycol [CAS 57-55-6] , trimethylene glycol [CAS 504-63-2] , dipropylene glycol [CAS 110-98-5] , glycerol [CAS 56-81-5] , trimethylolpropane [CAS 77-99-6] , and ⁇ , ⁇ -diaminopoly(propylene glycol) [CAS 9046-10-0] .
• One or more other lower alkylene oxides such as propylene oxide [CAS 75-56-9] and trimethylene oxide [CAS 503-30-0] may al ⁇ o be employed a ⁇ comonomer with the ethylene oxide, whether to form random polymers or block polymers, but they should be used only in those small amounts a ⁇ will not render the resulting polymer both water-insoluble and nondisper ⁇ ible in water.
• propylene oxide [CAS 75-56-9] and trimethylene oxide [CAS 503-30-0] may al ⁇ o be employed a ⁇ comonomer with the ethylene oxide, whether to form random polymers or block polymers, but they should be used only in those small amounts a ⁇ will not render the resulting polymer both water-insoluble and nondisper ⁇ ible in water.
• poly(ethylene oxide) i ⁇ intended to include the foregoing copolymers of ethylene oxide with small amounts of lower alkylene oxide, as well a ⁇ homopolymers of ethylene oxide.
• the configuration of the poly(ethylene oxide) can be linear, branched, comb, or star-shaped.
• the preferred terminal groups of the poly(ethylene oxide) are hydroxyl groups, but terminal lower alkoxy groups such as methoxy groups may be present provided their types and numbers do not render the poly(ethylene oxide) polymer unsuitable for its purpose. In most cases the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 is water-insoluble.
• the preferred poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 is a water-soluble homopolymer of ethylene oxide produced using a small amount of ethylene glycol as an initiator.
• the weight average molecular weight of the poly(ethylene oxide) is in the range of from 100,000 to 3,000,000.
• the weight average molecular weight of the poly(ethylene oxide) is in the range of from 150,000 to 1,000,000.
• the weight average molecular weight of the poly(ethylene oxide) is in the range of from 200,000 to 1,000,000. From 300,000 to 700,000 is preferred.
• the amount of organic polymer of the binder in the coating may vary widely. Often the organic polymer of the binder constitutes from 30 to 80 percent by weight of the coating. In many cases the organic polymer of the binder constitutes from 40 to 60 percent by weight of the coating. From 45 to 55 percent by weight is preferred.
• the organic polymer of the binder may optionally also comprise additional organic polymer other than poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000.
• additional organic polymers are film-forming organic polymers or insolubilized film-forming organic polymers.
• additional film-forming organic polymers include, but are not limited to, water-soluble poly(ethylene oxide) having a weight average molecular weight below 100,000, water-soluble poly(ethylene oxide) having a weight average molecular weight above 3,000,000, water-soluble cellulosic organic polymers such as those heretofore described in respect of Part I, water-soluble noncellulosic organic polymers such a ⁇ tho ⁇ e heretofore de ⁇ cribed in re ⁇ pect of Part I, water dispersible polymers such as poly(ethylene-co-acrylic acid) , or a mixture of two or more thereof. Both of such Part I descriptions are, in their entireties, incorporated herein by reference.
• water- ⁇ oluble polyacrylates which can advantageously be used include the water-soluble anionic polyacrylates and the water-soluble cationic polyacrylates. Water-soluble anionic polyacrylates are themselves well known.
• water-soluble cationic polyacrylates are themselves well known. Usually, but not necessarily, they are copolymers of one or more (meth)acrylic esters and enough amino-functional ester of (meth) acrylic acid to provide sufficient ammonium cations to render the acrylic polymer water-soluble. Such ammonium cations may be primary, secondary, tertiary, or quaternary. Usually the water soluble cationic polyacrylate i ⁇ a primary, secondary, tertiary, or quaternary ammonium ⁇ alt, or it i ⁇ a quaternary ammonium hydroxide.
• the film-forming organic polymer may optionally be reacted with cros ⁇ linking agent (al ⁇ o known a ⁇ in ⁇ olubilizer) to form in ⁇ olubilized organic polymer.
• cros ⁇ linking agent al ⁇ o known a ⁇ in ⁇ olubilizer
• examples of cros ⁇ linking agent ⁇ and their amounts are disclo ⁇ ed in Part I and such disclosures are, in their entireties, incorporated herein by reference.
• the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitutes at least 20 percent by weight of the organic polymer of the binder.
• the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitute ⁇ at lea ⁇ t 51 percent by weight of the organic polymer of the binder.
• the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitute ⁇ at lea ⁇ t 60 percent by weight of the organic polymer of the binder.
• the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitutes at least 90 percent by weight of the organic polymer of the binder.
• the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitute ⁇ at least 95 percent by weight of the organic polymer of the binder. In many cases the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitutes at least 99 percent by weight of the organic polymer of the binder. In some cases the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitutes 100 percent by weight of the organic polymer of the binder. When optional additional organic polymer is pre ⁇ ent in the binder, it usually constitute ⁇ from 1 to 80 percent by weight of the organic polymer of the binder.
• the optional additional organic polymer con ⁇ titutes from 1 to 49 percent by weight of the organic polymer of the binder. In many case ⁇ the optional additional organic polymer constitutes from 1 to 40 percent by weight of the organic polymer of the binder. Often the optional additional organic polymer constitutes from 1 to 10 percent by weight of the organic polymer of the binder. Frequently the optional additional organic polymer constitutes from 1 to 5 percent by weight of the organic polymer of the binder.
• the coating may be sub ⁇ tantially transparent, substantially opaque, or of intermediate transparency. It may be sub ⁇ tantially colorless, it may be highly colored, or it may be of an intermediate degree of color. Preferably the coating i ⁇ substantially transparent and ⁇ ub ⁇ tantially colorless.
• a coating is substantially transparent if its luminous transmis ⁇ ion in the vi ⁇ ible region i ⁇ at least 80 percent of the incident light. Often the luminous transmission of the coating is at least 85 percent of the incident light. Preferably the luminous transmis ⁇ ion of the coating is at lea ⁇ t 90 percent.
• a coating is substantially colorless if the luminous transmission is substantially the same for all wavelengths in the visible region, viz., 400 to 800 nanometers.
• the thicknes ⁇ of the coating may vary widely, but in most instances the thicknes ⁇ of the coating i ⁇ in the range of from 1 to 40 ⁇ m. In many case ⁇ the thickne ⁇ s of the coating i ⁇ in the range of from 5 to 40 ⁇ m. Often the thickness is in the range of from 8 to 30 ⁇ m. From 12 to 18 ⁇ m i ⁇ preferred.
• the ⁇ ubstrate may be any sub ⁇ trate at lea ⁇ t one surface of which i ⁇ capable of bearing the coating discussed above.
• the ⁇ ubstrate is in the form of an individual sheet or in the form of a roll, web, ⁇ trip, film, or foil of material capable of being cut into ⁇ heets.
• the sub ⁇ trate may be porou ⁇ throughout, it may be nonporou ⁇ throughout, or it may comprise both porous regions and nonporous regions.
• porous substrates examples include paper, paperboard, wood, cloth, nonwoven fabric, felt, unglazed ceramic material, polymer membranes, porous foam, and microporous foam.
• substrates which are sub ⁇ tantially nonporous throughout include sheets or films of organic polymer such as poly(ethylene terephthalate) , polyethylene, polypropylene, cellulose acetate, poly(vinyl chloride), and copolymers such as ⁇ aran.
• the ⁇ heet ⁇ or film ⁇ may be metallized or unmetallized a ⁇ de ⁇ ired.
• Additional examples include metal substrates including but not limited to metal foils such as aluminum foil and copper foil.
• a porous or microporous foam comprising thermoplastic organic polymer which foam has been compres ⁇ ed to ⁇ uch an extent that the resulting deformed material is substantially nonporous.
• Still another example is glass.
• Base stocks which are normally porous such as for example paper, paperboard, wood, cloth, nonwoven fabric, felt, unglazed ceramic material, polymer membranes, porous foam, or microporous foam may be coated or laminated to render one or more surfaces sub ⁇ tantially nonporous and thereby provide substrates having at least one substantially nonporous surface.
• the substrate may be sub ⁇ tantially tran ⁇ parent, it may be substantially opaque, or it may be of intermediate transparency. For some applications ⁇ uch a ⁇ ink jet printed overhead slides, the substrate must be sufficiently transparent to be useful for that application. For other applications such as ink jet printed paper, transparency of the substrate is not so important.
• the printing media of one embodiment Part II of the invention may be made by coating a surface of the sub ⁇ trate with a coating composition compri ⁇ ing: (a) di ⁇ crete particle ⁇ having a number average particle ⁇ ize in the range of from 1 to 500 nanometers; (b) an aqueous liquid medium; and (c) film-forming organic polymer dis ⁇ olved or di ⁇ persed in the aqueous liquid medium wherein poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitutes at least 20 percent by weight of the organic polymer; and thereafter ⁇ ubstantially removing the aqueous liquid medium.
• a coating composition compri ⁇ ing: (a) di ⁇ crete particle ⁇ having a number average particle ⁇ ize in the range of from 1 to 500 nanometers; (b) an aqueous liquid medium; and (c) film-forming organic polymer dis ⁇ olved or di ⁇ persed in the aqueous liquid medium wherein poly(ethylene oxide)
• the coating composition can be in the form of an aqueous solution in which case the aqueous liquid medium is an aqueous solvent, or the coating composition can be in the form of an aqueous dispersion in which instance the aqueous liquid medium is an aqueous dispersion liquid.
• the weight ratio of the particles to organic film-forming polymer in the coating composition may vary considerably, but it is usually in the range of from 54:100 to 233:100. Often the weight ratio is in the range of from 67:100 to 150:100. Preferably it is in the range of from 82:100 to 122:100.
• the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitutes at least 20 percent by weight of the film-forming organic polymer of the coating composition.
• the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitutes at lea ⁇ t 51 percent by weight of the film-forming organic polymer of the coating composition.
• the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitute ⁇ at least 60 percent by weight of the film-forming organic polymer of the coating composition.
• the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitutes at least 90 percent by weight of the film-forming organic polymer of the coating composition.
• the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitutes at least 95 percent by weight of the film-forming organic polymer of the coating composition.
• the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitutes at least 99 percent by weight of the film-forming organic polymer of the coating composition.
• the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 constitutes 100 percent by weight of the film-forming organic polymer of the coating composition.
• additional organic film-forming polymer When additional organic film-forming polymer is pre ⁇ ent, it usually constitutes from 1 to 80 percent by weight of the organic film-forming polymer of the coating composition. Generally the additional organic film-forming polymer constitute ⁇ from 1 to 49 percent by weight of the organic film-forming polymer of the coating composition. Often the additional organic film-forming polymer constitute ⁇ from 1 to 40 percent by weight of the organic film- orming polymer of the coating composition. In many cases the additional organic film-forming polymer constitutes from 1 to 10 percent by weight of the organic film-forming polymer of the coating composition. Frequently the additional organic film-forming polymer constitutes from 1 to 5 percent by weight of the organic film-forming polymer of the coating composition.
• the aqueous liquid medium is water.
• Organic cosolvent ⁇ mi ⁇ cible with water may optionally be present when desired.
• the amount of aqueous liquid medium present in the coating composition may vary widely. The minimum amount is that which will produce a coating composition having a viscosity low enough to apply as a coating. The maximum amount is not governed by any theory, but by practical considerations such as the cost of the liquid medium, the minimum desired thicknes ⁇ of the coating to be depo ⁇ ited, and the cost and time required to remove the aqueous liquid medium from the applied wet coating. Usually, however, the aqueous liquid medium constitutes from 75 to 98 percent by weight of the coating composition.
• the aqueous liquid medium con ⁇ titutes from 85 to 98 percent by weight of the coating composition. Often the aqueous liquid medium constitutes from 86 to 96 percent by weight of the coating composition. Preferably aqueous liquid medium con ⁇ titutes from 88 to 95 percent by weight of the composition.
• the particles having a number average particle size in the range of from 1 to 500 nanometers and the film-forming organic polymer together usually constitute from 2 to 25 percent by weight of the coating composition. Frequently such particles and the film-forming organic polymer together constitute from 2 to 15 percent by weight of the coating composition. Often such particles and the film-forming organic polymer together constitute from 4 to 14 percent by weight of the coating composition. Preferably such particles and the film-forming organic polymer together constitute from 5 to 12 percent by weight of the coating composition.
• mordant A material which may optionally be present in the coating composition is mordant.
• mordant for purpose ⁇ of the pre ⁇ ent specification and claims mordant i ⁇ considered not to be a part of the film-forming organic polymer of the binder.
• Mordants also known as ink-fixing agents, are materials which interact, usually by reaction or absorption, with binder, dye, and/or pigment of the ink applied to the coated substrate. There are many available mordants which may be used. Suitable mordants include, but are not limited to, the poly(ethylenimines) , the ethoxylated poly(ethylenimines) , and other derivative ⁇ of poly(ethylenimine) .
• Examples include LupasolTM SC-61B ink-fixing agent (BASF Aktiengesellschaft) , LupasolTM SC-62J mordant (BASF Aktiengesellschaft) , and LupasolTM SC-86X mordant (BASF Aktiengesellschaft) , LupasolTM PS mordant (BASF Aktiengesellschaft) , LupasolTM G-35 mordant (BASF Aktienge ⁇ ell ⁇ chaft) , and LupasolTM FG mordant (BASF Aktiengesellschaft) .
• the amount of mordant present in the coating composition may vary considerably.
• the weight ratio of the mordant to the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 is usually in the range of from 0.5:100 to 30:100.
• the weight ratio is in the range of from 0.5:100 to 20:100.
• the weight ratio is in the range of from 1:100 to 10:100. From 2:100 to 5:100 is preferred.
• ⁇ urfactant Another material which may optionally be present in the coating composition is ⁇ urfactant .
• surfactant is considered not to be a part of the organic film-forming polymer of the binder.
• suitable surfactants include, but are not limited to, Fluorad ® FC-170-C surfactant (3M Company) , and Triton ® X-405 surfactant (Union Carbide Corporation) .
• the amount of ⁇ urfactant present in the coating composition may vary considerably.
• the weight ratio of the surfactant to the poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000 is usually in the range of from 0.01:100 to 10:100. In many instance ⁇ the weight ratio i ⁇ in the range of from 0.1:100 to 10:100. Often the weight ratio i ⁇ in the range of from 0.2:100 to 5:100. From 0.5:100 to 2:100 is preferred. These ratios are on the basi ⁇ of surfactant dry solids and poly(ethylene oxide) dry solids.
• the pH of the coating composition may vary considerably. In most instance ⁇ the pH i ⁇ in the range of from 3 to 10. Often the pH is in the range of from 3 to 6. Frequently the pH is in the range of from 3 to 5.5. In many instance ⁇ the pH is in the range of from 3.5 to 4.5. In other instances the pH is in the range of from 7 to 9.
• the coating compositions are usually prepared by simply admixing the various ingredients.
• the ingredients may be mixed in any order. Although the mixing of liquid and solid ⁇ is usually accomplished at room temperature, elevated temperatures are sometimes used. The maximum temperature which is usable depends upon the heat stability of the ingredients.
• the coating compositions are generally applied to the surface of the substrate using any conventional technique known to the art. These include spraying, curtain coating, dipping, rod coating, blade coating, roller application, size press, printing, brushing, drawing, slot-die coating, and extrusion.
• the coating is then formed by removing the solvent from the applied coating composition. This may be accomplished by any conventional drying technique.
• Coating composition may be applied once or a multiplicity of times. When the coating composition is applied a multiplicity of times, the applied coating is usually but not necessarily dried, either partially or totally, between coating applications. Once the coating composition has been applied to the substrate, the solvent i ⁇ ⁇ ub ⁇ tantially removed, usually by drying.
• the above-described coatings may be overlaid with an overcoating comprising ink-receptive organic film-forming polymer.
• the overcoating may be formed by applying an overcoating composition comprising a liquid medium and ink-receptive organic film-forming polymer dissolved or dispersed in the liquid medium and removing the liquid medium, as for example, by drying.
• the liquid medium i ⁇ an aqueous ⁇ olvent and the ink-receptive organic film-forming polymer i ⁇ water- ⁇ oluble poly(ethylene oxide) having a weight average molecular weight in the range of from 100,000 to 3,000,000, both of which have been described above in respect of earlier described embodiments of the invention.
• Water is an especially preferred aqueous solvent.
• the relative proportions of liquid medium and organic film-forming polymer present in the overcoating composition may vary widely.
• the minimum proportion is that which will produce an overcoating composition having a viscosity low enough to apply as an overcoating.
• the maximum proportion is not governed by any theory, but by practical considerations such as the cost of the liquid medium and the cost and time required to remove the liquid medium from the applied wet overcoating.
• the weight ratio of liquid medium to film-forming organic polymer is from 18:1 to 50:1.
• the weight ratio i ⁇ from 19:1 to 40:1.
• weight ratio is from 19:1 to 24:1.
• Optional ingredients such as those discussed above may be present in the overcoating composition when desired.
• the overcoating composition may be prepared by admixing the ingredients. It may be applied and dried using any of the coating and drying techniques discus ⁇ ed above. When an overcoating compo ⁇ ition i ⁇ to be applied, it may be applied once or a multiplicity of time ⁇ .
• the gloss of the coated substrate may vary widely. Although lower glosse ⁇ are acceptable for many purpo ⁇ e ⁇ , it i ⁇ preferred that the gloss be at least 20. As used herein gloss is determined according to TAPPI Standard T653 pm-90.
• Part II of the invention is further described in conjunction with the following examples which are to be considered illustrative rather than limiting, and in which all parts are parts by weight and all percentages are percentage ⁇ by weight unless otherwise specified.
• XAMPT.F One liter of deionized water was heated to 80°C with vigorous stirring in a large open beaker. While continuing the stirring, 71 grams of titanium isopropoxide was slowly added. A white precipitate formed immediately. Stirring at 80°C was continued for 90 minutes during which period the volume boiled down to approximately 750 milliliters. The slurry was poured into a one-liter round bottom flask.
• a poly(ethylene oxide) (PEO) solution wa ⁇ formed by di ⁇ solving 150 grams poly(ethylene oxide) having a weight average molecular weight of about 400,000 in 2850 grams of deionized water. The mixture was stirred until all poly(ethylene oxide) was dissolved giving a composition containing 5.0 percent solids. To 55 grams of the above PEO solution was added
• the coating composition was applied to commercially available glo ⁇ y polyethylene-coated paper with a Meyer Rod
• the coated paper wa ⁇ then printed on the coated ⁇ ide by a Hewlett-Packard 1600C ink jet printer and a Hewlett-Packard 850C ink jet printer.
• EXAMPLE 12 To 120 gram ⁇ of a poly(ethylene oxide) solution prepared as described in Example 11 were added 20 grams of a colloidal ⁇ ilica sol (Ludox ® HS-40; E.I. Dupont de Nemours & Co.) containing 40 percent by weight of silica and 16 grams of a poly(ethylene-co-acrylic acid) di ⁇ per ⁇ ion (Adcote ® 50T4983; Morton Adhe ⁇ ive ⁇ ) containing 25 percent by weight of polymer. Into thi ⁇ mixture was added with stirring 78 milligrams
• FluoradTM FC-170-C surfactant ' to form a coating composition.
• the coating composition was applied to poly(ethylene terephthalate) transparencies with a Meyer Rod #150 and allowed to dry under an infrared heating lamp. The dry coating was about 20 micrometers thick and it was clear.
• the coated transparencies were then printed on the coated side by a Hewlett-Packard 1600C ink jet printer.
• the ink jet printed transparencies exhibited excellent ability to maintain the edge acuity of ink patterns, excellent color fidelity, and were dry to touch as they came out of the printer.
• a test with a roller ⁇ howed no color tran ⁇ fer to paper after 5 seconds.
• a water test ⁇ howed excellent water fa ⁇ tne ⁇ of the ink dyes in all colors. Pigmented black ink in the test patterns showed no cracking.
• Example 11 To 120 grams of a poly(ethylene oxide) solution prepared a ⁇ de ⁇ cribed in Example 11 were added 7.5 gram ⁇ of a colloidal ⁇ ilica sol (Ludox ® HS-40; E.I. Dupont de Nemours & Co.) containing 40 percent by weight of silica. Into thi ⁇ mixture was added with stirring 64 mg FluoradTM FC-170-C surfactant to form a coating composition.
• a colloidal ⁇ ilica sol Lidox ® HS-40; E.I. Dupont de Nemours & Co.
• the coating compo ⁇ ition wa ⁇ applied to poly(ethylene terephthalate) transparencies with a Meyer Rod #150 and allowed to dry under an infrared heating lamp.
• the dry coating was about 20 micrometers thick and it was clear.
• the coated transparencie ⁇ were then printed on the coated ⁇ ide by a Hewlett-Packard 1600C ink jet printer and a Hewlett-Packard 850C ink jet printer.
• the printed tran ⁇ parencie ⁇ showed excellent print quality.
• EXAMPLE 14 Sixty-five grams of a low molecular weight, partially methylated melamine-formaldehyde resin (Resimene ® AQ-7550; Monsanto Co.) containing 78% solids was added to 435 grams of deionized water. The mixture was stirred at room temperature until a homogeneous solution was formed. Next, concentrated hydrochloric acid was added while stirring to lower the pH to a value of 3.2.
• the acidified solution was then covered and placed in an oven at 85°C for 3 hours.
• the resultant melamine-formaldehyde sol had a light blue haze re ⁇ ulting from Rayleigh ⁇ cattering indicating a number average particle ⁇ ize less than 500 nanometers.
• the sol contained approximately 10 percent by weight of a partially cros ⁇ linked melamine-formaldehyde (MF) polymer.
• MF partially cros ⁇ linked melamine-formaldehyde
• the coating composition was applied to poly(ethylene terephthalate) transparencies with a Meyer Rod #150 and allowed to dry under an infrared heating lamp.
• the dry coating was about 20 micrometers thick and it was clear.
• FluoradTM FC-170-C surfactant to form a coating composition.
• the coating composition was applied to poly(ethylene terephthalate) transparencies with a Meyer Rod #150 and allowed to dry under an infrared heating lamp.
• the dry coating was about 20 micrometers thick and it was clear.
• the coated tran ⁇ parencie ⁇ were then printed on the coated ⁇ ide by a Hewlett-Packard 1600C ink jet printer and a Hewlett-Packard 850C ink jet printer.
• the printed tran ⁇ parencie ⁇ ⁇ howed excellent print quality.
• EXAMPLE 16 The following initial charge and feed ⁇ ⁇ hown in Table 3 were u ⁇ ed in the preparation of aqueous ⁇ econdary amine and hydroxyl functional acrylic polymer via ⁇ olution polymerization technique.
• the initial charge wa ⁇ heated in a reactor with agitation to reflux temperature (80°C) .
• Feed 1 wa ⁇ added in a continuous manner over a period of 3 hours.
• the reaction mixture was held at reflux for 3 hours.
• the resultant acrylic polymer solution had a total solids content of 61.7 percent (determined by weight difference of a sample before and after heating at 110°C for one hour) and number average molecular weight of 4792 as determined by gel permeation chromatography using polystyrene as the standard.
• Feed 2 was added over five minutes at room temperature with agitation.
• Feed 3 was added over 30 minutes while the reaction mixture was heated for azeotropic distillation of isopropanol. When the distillation temperature reached 99°C, the distillation was continued about one more hour and then the reaction mixture was cooled to room temperature. The total distillate collected was 550.6 grams.
• the product which was a cationic acrylic polymer aqueous solution, had a solids content of 32.6 percent (determined by weight difference of a sample before and after heating at 110°C for one hour) , and a pH of 5.25.
• Example 11 To 50 grams of a poly(ethylene oxide) solution prepared as described in Example 11 were added 12.5 grams of colloidal alumina sol prepared as described in Example 1 of Part I and 4.3 grams of the above cationic acrylic polymer aqueous solution. Into this mixture was added with stirring 50 milligram ⁇ FluoradTM FC-170-C ⁇ urfactant to form a coating composition.
• the coating composition was applied to poly(ethylene terephthalate) transparencie ⁇ with a Meyer Rod #150 and allowed to dry under an infrared heating lamp.
• the dry coating wa ⁇ about 20 micrometer ⁇ thick and it was clear.
• the coated transparencies were then printed on the coated side by a Hewlett-Packard 1600C ink jet printer and a Hewlett-Packard 850C ink jet printer. The printed transparencies showed excellent print quality.
• the coated transparencies were then printed on the coated side by a Hewlett-Packard 1600C ink jet printer.
• the ink jet printed transparencies exhibited excellent ability to maintain the edge acuity of ink patterns, excellent color fidelity, and were dry to touch as it came out of the printer.
• a test with a roller showed no color transfer to paper after 5 seconds.
• a water test showed excellent water fastne ⁇ s of the ink dyes in all colors. Pigmented black ink in the te ⁇ t pattern ⁇ ⁇ howed no cracking.
• EXAMPLE 18 The coating compo ⁇ ition prepared in Example 12 wa ⁇ applied ⁇ imilarly onto commercially available glossy polyethylene-coated paper and onto commercially available gelatine-coated paper and dried.
• the ⁇ e paper ⁇ were printed on the coated side using a Hewlett-Packard 850C ink jet printer, they ⁇ howed photographic quality prints with high gloss, about 90%, again with excellent color fidelity, edge acuity, and water and light fastness.
• Example ll The coating composition prepared in Example ll was applied similarly onto cloth, and aluminum foil. After the coating had dried, these coated sub ⁇ trate ⁇ were ink jet printed with excellent results.
• EXAMPLE 19 To 100 grams of colloidal alumina sol prepared in Example 12, 7 grams of poly(ethylene oxide) with a weight average molecular weight of about 200,000 wa ⁇ added. An additional 43 grams of water was al ⁇ o added to facilitate complete dissolution of the poly(ethylene oxide) . The mixture was stirred until complete dissolution of the poly(ethylene oxide) took place yielding 150 grams of solution containing 12 grams of solids (8 percent solids) . With stirring, one gram of LupasolTM SC ® -J 5 percent poly(ethylenimine) solution, was added to form a coating composition.
• Example 12 the coating composition was applied to transparencies and dried with a hot air blower for several minutes until the coatings were dry.
• the coated transparencie ⁇ were printed on the coated ⁇ ide by a Hewlett-Packard 1600C ink jet printer and a Hewlett-Packard 850C ink jet printer.
• the printed transparencie ⁇ showed excellent print quality.
• Two solutions were prepared as follows: Solution A: A poly(ethylene oxide) (PEO) solution was formed by dis ⁇ olving 150 grams poly(ethylene oxide) having a weight average molecular weight of about 400,000 in 2850 grams of water.
• PEO poly(ethylene oxide)
• Solution B 408 grams of aluminum isopropoxide was introduced to 4 liters of water at 70°C with stirring. To this mixture was added 11 grams of 60 percent concentrated nitric acid with stirring. The resulting mixture was ⁇ ealed with a lid and placed in an oven at 95°C to be peptized. After 3 days, the lid was opened and the colloidal ⁇ ol wa ⁇ allowed to evaporate to a final total weight of 800 gram ⁇ and an AlO(OH) concentration of 15% by weight. Variou ⁇ coating compositions were made by mixing these two solutions as shown in Table 4 :
• Coating Composition No. 2 gram ⁇ 100 100 100 100 100 100 100 100
• the ⁇ e solutions were each coated on a separate poly(ethylene terephthalate) transparency approximately 20-25 ⁇ m thick.
• the coated transparencie ⁇ were printed on the coated ⁇ ide by a Hewlett-Packard 1600C ink jet printer.
• EXAMPLE 22 With stirring 22.35 kg. of aluminum tri-secondary butoxide wa ⁇ charged with ⁇ tirring into a reactor containing 75 kg of water at about 78°C. Four hundred twenty grams of 70% nitric acid was diluted in 1110 grams of water and added into the same reactor immediately after the charging of aluminum tri-secondary butoxide. The system was closed when the reactor wa ⁇ heated to about 120°C gaining pressure to about 276 kilopascals, gauge. The reactor was held at this temperature for 5 hours then cooled to 70°C and opened. Then the reactor was heated to boil off the alcohol and water-alcohol azeotrope of the hydroly ⁇ i ⁇ reaction until the concentration of the sol reached about 10 weight percent AlO (OH) , about 54 kg. total, having a pH of 3.8-4.0 and a turbidity of 112.
• OH weight percent AlO
• this colloidal alumina sol 11 grams of poly(ethylene oxide) having a weight average molecular weight of about 400,000 and 150 grams of water were added and stirred until the poly(ethylene oxide) was completely dissolved.
• this ⁇ ufficient nitric acid wa ⁇ added to lower the pH to within a range of 3.5 to 4.0.
• 12.5 grams of 5% LupasolTM SC 61-B mordant was added followed by the addition of 0.075 gram of FluoradTM FC-170-C surfactant.
• the solution was coated on poly(ethylene terephthalate) transparencies using a Meyer Rod #150. The coating was heat dried. No haze wa ⁇ observed.
• the coated transparencies were printed on the coated side by a Hewlett-Packard 1600C ink jet printer to produce printed transparencies having excellent print quality, edge acuity, and color fidelity. Ink drying time wa ⁇ le ⁇ than 5 ⁇ econd ⁇ . The printed tran ⁇ parencie ⁇ were free from observed scratches and ink cracking.

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• 1996
  • 1996-12-06 WO PCT/US1996/019353 patent/WO1997022476A2/en not_active Application Discontinuation
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