KR20020056948A - Metal ion functionalized silica surfaces for ink receptors - Google Patents

Abstract

The present invention seeks to provide an ink receptor medium comprising an organometallic polyvalent metal salt on a silica filled microporous substrate surface. In addition, such silica surfaces may further comprise surfactants and / or binders.

Description

Metal ion functionalized silica surface for ink receptors {METAL ION FUNCTIONALIZED SILICA SURFACES FOR INK RECEPTORS}

Pigment fixation in porous substrates is different from that in non-porous substrates. Polypropylene membranes (ie, TIPS films) made using thermally induced phase separation techniques according to the disclosures of U.S. Patent Nos. 4,539,256 and 5,120,594, and EVAL, commercially available from 3M Company, St. Paul, Minn. In microporous substrates, such as (ethylene vinyl alcohol) films, pigments settle below the surface, sometimes in capillary walls, which occupy most of the substrate. Fixation is typically performed by metal ion condensation of the pigmented ink at a specific forming site, indicated by the flow and location of the surfactant or combination of surfactant, anti-transferant and ink desiccant (s). That is, it is controlled by the pore size, size distribution of the porous substrate (s) as well as the type and nature of the surfactant (s) and other additives.

In the case of TIPS films, for example, pigment condensation is caused by metal ions, and the condensed or aggregated pigmented inks are in such provided positions, i.e. in most of the film in which surfactants and other additives specified by flow are located. Is placed. Chemical entanglement of the pigment is caused by the pigment dispersant and the metal ions, but there is sufficient mechanical entanglement provided by the pores due to the pore size. The whole process of pigments fixed in porous films, such as TIPS films, is partly a chemical process. However, there are also additional physical phenomena such as physical adsorption along the pores inside the void-interconnected bulk of the film. Typically the optical density of the imaged film is somewhat lower than in the case where all pigmented inks can be placed on top of the surface.

Substrates with largely limited pore sizes allow only moisture penetration with pigments at the surface level. This occurs on the surface of a film under the trade name TESLIN, available from Fiji Industries, Pittsburgh, Pennsylvania, USA. The trade name TESLIN film is a silica filled high density polyethylene substrate with a very small pore size (typically 0.02 to 0.5 μm). When the trade name TESLIN film is formed with pigmented inks, the pigment is retained on the surface and is not transmitted into the pores of the place located below the surface at a level below that surface. Such substrates provide images of high optical density and high quality, but the images do not have water fastness.

In one embodiment of the invention, the present invention provides an ink receptor medium comprising a silica filled microporous substrate having a silica surface and an organometallic polyvalent metal salt on the silica surface of the silica filled microporous substrate. In addition, the ink receptor medium of the present invention may further comprise a surfactant, a binder or a combination of a surfactant and a binder on the surface of the silica filled microporous substrate. The surfactant is preferably hydrophilic. The surface of the silica filled microporous substrate can be partially or substantially completely applied with the organometallic polyvalent salt.

When an image is formed using an inkjet printer, the novel ink receiving medium is non-tacky and provides an image having durability, high color intensity and high image quality with a quick-drying touch.

In another embodiment, the invention relates to an ink on the surface of a silica filled microporous substrate in contact with an organometallic polyvalent metal salt, and to a silica filled microporous substrate having a silica surface, and on a silica surface of a silica filled microporous substrate. An image formed ink receptor medium comprising an organometallic polyvalent metal salt is provided. In a preferred embodiment, the ink colorant is a pigment dispersion comprising a dispersant bound to a pigment that destabilizes, coagulates, solidifies or aggregates upon contact with the ink receiving medium. The image is preferably generated using an inkjet printer head.

In another embodiment, the present invention provides an ink receptor medium intermediate comprising an aqueous composition containing an organometallic salt on a silica filled microporous substrate silica surface.

The present invention also provides an ink receiving medium / ink set comprising a silica filled microporous substrate having a silica surface and an ink containing an organometallic polyvalent metal salt and a pigment colorant on the silica surface of the silica filled microporous substrate. .

The ink receptor medium of the present invention provides a silica filled microporous substrate having water resistance and abrasion resistance (ie, substantially water fastness) by chemically modifying the silica surface of the silica filled substrate. In addition, the ink receptor media of the present invention provide images with higher color density and higher resolution than non-porous silica filled substrates.

An advantage of the ink receiving medium of the present invention is that the laminated protective cover layer is not essential for obtaining a water resistant image.

Another feature of the ink receptive media of the present invention is that they can be used with pigmented inks, have a high resolution, high color density, provide a wide color gamut, have water fastness, are stain resistant, and provide fast drying. Is to provide.

FIELD OF THE INVENTION The present invention relates to ink receptor media, and more particularly to improving the drying time of the ink, improving the abrasion resistance of the image after drying, improving the water fastness of the printed image, and preventing staining and feathering. A silica filled microporous substrate comprising a coating that provides a high quality with.

1 shows the IR spectrum of silica particles modified with a polyvalent organic acid.

Microporous substrates useful in the present invention are referred to as so-called 'silica filled' microporous substrates. "Silica filled" substrate means a substrate filled with silica particles. Such substrates are typically formed by impregnation of silica particles in a polymer matrix. Such processes include coextrusion of both polymer and silica at appropriate processing temperatures and pressures, as well as axial orientation that leads to voids in the resulting film. Typically, such substrates have very small pore sizes of 0.02 to 0.5 μm and can be prepared by the methods described in US Pat. Nos. 4,833,172, 4,861,644, 4,877,679 and 4,892,779.

The silica present on the surface of the microporous substrate is amorphous silica. Amorphous silica typically consists of silicon dioxide in which the silicon atoms are bonded to oxygen atoms bridged between the silicon atoms in a tetrahedral structure. In an aqueous environment, a certain proportion of silanol groups are present on the silica surface. Under acidic conditions, this ratio is increased. In the present invention, for example, Al ⁺³ ions and -COOH functional groups react with Si-OH groups to form -Al-O-Si- and -C (= 0) -O-Si-bonds which are surface bonded. Became known. Evidence of this surface interaction can be seen by the IR spectrum. IR spectra for aluminosilicates (eg kaolinite, kaolin, feldspar, etc.) have characteristic absorption bands at 680-1,100 cm ⁻¹ . References: Sadtler Research Lab, Division of Bio-Rad Lab, Spectrum Nos. 354, 355]. The IR spectrum of the silica particles modified by the polyvalent organic acid (eg sulfocarboxylic acid) according to the present invention has a similar absorption band accompanied by carbonyl absorption band at ˜1,715 cm ⁻¹ as shown in FIG. 1.

Without wishing to be bound by any particular theory, it is known that pigmented inks are condensed, i.e., pigments are removed from the dispersion by being bound to surface bound M ^{+ (3-n)} ions.

Generally, the pigments are based on the composition of the pigmented ink (s) and the dispersion (s) used in the preparation thereof. In the case of anionic dispersant (s), anions, for example carboxylate anions, will react instantaneously with the surface bound aluminum cations that will cause the ink to solidify / congeal. Thus, the ink is surface bound and does not cause a hydrolysis reaction (not erased by washing). The product materials aluminum carboxylate and aluminum silicate on the silica surface are usually insoluble final products.

Preferred silica filled substrates include the trade name TESLIN available from Fiji Industries, Pittsburgh, Pennsylvania, and the trade name TEXWRITE (eg, TEXWRITE MP10) available from Texwipe, Saddle River, NJ.

Useful examples of organometallic salts include those of polyvalent metal ions and polyvalent organic acid anions or counterions. Examples of such polyvalent metal ions include, but are not limited to, Al, Ga, Ti, Zr, Hf, Zn, Mg, Ca, Nb, Ta, Fe, Cu, Sn, Co, and the like. Examples of organic acids include any number of aromatic dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, pentacarboxylic acids, sulfocarboxylic acids, disulfocarboxylic acids and trisulfocarboxylic acids in any aromatic system. , Tetrasulfocarboxylic acid, and any combination thereof, hydroxycarboxylic acid, hydroxylsulfonic acid, hydroxylsulfocarboxylic acid, and any combination thereof, and the like, but is not limited thereto.

Specific examples of useful organometallic salts include [Wherein M is Cu, Mg, Zn, Ca or Co, the ratio of x: y is 1: 2, and when M is Al, Ga, B the ratio of x: y is 1: 3 or 2: 3 Metal sulfocarbolate;

Chemical formula [Wherein, when M is Cu, Mg, Zn, Ca or Co, the ratio of x: y is 1: 2 or 2: 2 and x: y when M is Al, Ga, B, Ti, Zr or Hf The ratio of 1: 3, 2: 3 or 2: 2;

Chemical formula [Wherein, when M is Cu, Mg, Zn, Ca or Co, the ratio of x: y is 1: 2 or 2: 2 and x: y when M is Al, Ga, B, Ti, Zr or Hf The ratio of 1: 1, 1: 3, 2: 2 or 4: 3] metal dihydroxybenzenedisulfonate;

Chemical formula [Herein, when M is Cu, Mg, Zn, Ca or Co, the ratio of x: y is 1: 2 or 1: 1, and when M is Al, Ga, B, Ti, Zr or Hf, x: y Is 1: 3, 2: 3 or 3: 3, and R is -COOH (Li, Na or K)] metal sulfosalicylate;

Chemical formula [Wherein when M is Cu, Mg, Zn, Ca or Co, the ratio of x: y is 3: 2, 2: 2 or 1: 1 and M is Al, Ga, B, Ti, Zr or Hf And the ratio x: y is 1: 3, 2: 2 or 2: 3, R ¹ is H or -COOH (Li, Na or K), R ² is -COOH (Li, Na or K)] Sulfophthalate;

Chemical formula [Wherein when M is Cu, Mg, Zn, Ca or Co, the ratio of x: y is 1: 1, 2: 2 or 3: 2, and M is Al, Ga, B, Ti, Zr or Hf And the ratio x: y is 1: 3, 2: 2 or 2: 3, R ¹ is H or -COOH (Li, Na or K), R ² is -COOH (Li, Na or K)] Carboxylates and the like.

Specific examples of preferred organometallic polyvalent metal salts include magnesium sulfophthalate, copper sulfophthalate, zirconium sulfophthalate, zirconium phthalate, aluminum sulfophthalate, aluminum sulfoisophthalate and combinations thereof.

In addition, the surface of the silica filled microporous substrate of the present invention may optionally further comprise a surfactant, a binder or a combination thereof. Occasionally, the chemical and physical properties of the microporous surface (eg surface energy) require the assistance of a surfactant to assist in the management of the ink fluid. Therefore, it may be advantageous to be able to impregnate at least one surfactant in the pore volume of the microporous substrate. Application of the surfactant may be carried out separately in a separate step, or in a single step, after mixing with the organometallic salt and coating it on the substrate, any water and / or organic solvent or solvents may be removed to remove the pigmented inkjet ink. Provide a surface suitable for a particular fluid component.

Surfactants can be cationic, anionic, nonionic or zwitterionic. Many of each type of surfactant are widely available to those skilled in the art. Thus, any surfactant, or combination of surfactant (s) or polymer (s), less preferably, makes the substrate hydrophilic, can be used.

Examples thereof include fluorochemical, silicone and hydrocarbon-based surfactants, and the like, where the surfactant may be anionic or nonionic, but is not limited thereto. In addition, non-ionic surfactants can be used by themselves or in combination with water and / or organic solvents or other anionic surfactants in solvents, such organic solvents being alcohols, ethers, amides, ketones. It is selected from the group consisting of.

Examples of various types of nonionic surfactants include E.I., Wilmington, Delaware, USA. ZONYL fluurocarbons such as ZONYL FSO available from DuPont de Nemua &Company; FLUORAD FC-170 or 171 available from 3M Company; BASF Corporation, Mount Olive, NJ, PLURONIC block copolymers of ethylene and propylene oxide to ethylene glycol bases commercially available from Chemicals Division; TWEEN polyoxyethylene sorbitan fatty acid esters available from IC Americas, Inc., Wilmington, Delaware, Inc .; TRITON X series octylphenoxy polyethoxy ethanol, available from Rohm and Haas Company, Philadelphia, Pennsylvania; SURFYNOL tetramethyl descindiol, commercially available from Air Products and Chemicals, Inc., Allentown, Pennsylvania; SILWET L-7614 and L-7607 silicone surfactants available from Union carbide Corporation, Danbury, Conn., And those known to those skilled in the art, and the like, but are not limited thereto.

Useful examples of anionic surfactants include 1) alkyl sulfates and sulfonates such as sodium dodecyl sulfate and potassium dodecanesulfonate; 2) sulfates of linear or branched aliphatic alcohols and polyethoxylated derivatives of carboxylic acids; 3) alkylbenzenes or alkylnaphthalene sulfonates and sulfates such as sodium laurylbenzene-sulfonate; 4) ethoxylated and polyethoxylated alkyl and aralkyl alcohol carboxylates; 5) glycinates such as alkyl sarcosinates and alkyl glycinates; 6) sulfosuccinates, including dialkyl sulfosuccinates; 7) isethionate derivatives; 8) N-acyltaurine derivatives such as sodium N-methyl-N-oleyltaurate; 9) amphoteric alkyl carboxylates optionally substituted with oxygen, nitrogen and / or sulfur atoms such as amphoteric propionate and alkyl and aryl betaines; And 10) alkyl phosphates, monoesters or diesters such as ethoxylated dodecyl alcohol phosphate esters, sodium salts; alkali metals and (alkyl) ammonium salts, and the like.

Examples of cationic surfactants include the formula C _n H _{2n + 1} N (CH ₃ ) ₃ X where X is OH, Cl, Br, HSO ₄ or a combination of OH and Cl, where n is an integer from 8 to 22 And alkylammonium salts of the formula C _n H _{2n + 1} N (C ₂ H ₅ ) ₃ X, wherein n is an integer from 12 to 18; Divalent surfactants such as those of the formula [C ₁₆ H ₃₃ N (CH ₃ ) ₂ C _m H _{2m + 1} ] X, wherein m is an integer from 2 to 12 and X is as described above; Aralkylammonium salts such as benzalkonium salts; Cetylethylpiperidinium salts such as those of the formula C ₁₆ H ₃₃ N (C ₂ H ₅ ) (C ₅ H ₁₀ ) X, wherein X is as described above.

The content of the organometallic polyvalent salt that can be used in the intermediate for absorbing the microporous substrate of the present invention may be 0.1 to 50% by weight, preferably 0.5 to 20% by weight.

The content of the surfactant that can be used in the intermediate for absorbing the microporous substrate of the present invention may be 0.01 to 10% by weight, preferably 0.1 to 5% by weight.

Optionally, organic binders can be used in the ink receiving media of the present invention. The organic binder is preferably water soluble or dispersible so that it can be easily incorporated into the intermediate composition used to coat the microporous substrate in forming the ink receiving medium of the present invention. Non-limiting examples of such organic binders include acrylic emulsions, styrene-acrylic emulsions, polyvinyl alcohols, polyvinyl alcohol / acrylic acid combinations, and combinations thereof. Such organic binders may be present at 0.1-50% by weight, preferably 1-30% by weight, based on the total weight of the coating or intermediate solution, including surfactants and metal salts, with the remainder being water and / or organic solvents.

Optionally, whitening pigments can be used in the ink receptive media of the present invention. Non-limiting examples of such milky pigments include titanium dioxide pigments, barium sulfate pigments and the like. Such whitening pigments may be present in the coating solution and may be from 0.01 to 50% by weight.

Optionally heat or ultraviolet light stabilizers can be used in the ink receptor of the present invention. Non-limiting examples of such additives include TINUVIN 123 or 622LD or CHIMASSORB 944 (hindered amine light stabilizer) available from Ciba Specialty Chemicals Corporation, Tarrytown, NY; UVINUL 3008 available from BASF Corporation Chemicals Division. Such stabilizers may be present in an amount of 0.2 to 20% by weight in the coating or intermediate solution to be impregnated in the microporous substrate. The content of the stabilizer is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight.

Optionally, ultraviolet absorbers can be used in the ink receiving media of the present invention. Non-limiting examples of such light absorbers include TINUVIN II 30 or 326 available from Ciba Specialty Chemicals Corporation; UVINUL 40501 1 available from BASF Corporation and SANDUVOR VSU or 3035 available from Sandoz Chemicals, Charlotte, NC. Such light absorbers may be present in the coating or intermediate solution, the content of which is from 0.01 to 20% by weight. The light absorber is preferably present in an amount of 1 to 10% by weight.

Optionally, antioxidants can be used in the ink receiving media of the present invention. Non-limiting examples of such antioxidants include IRGANOX 1010 or 1076 available from Ciba Specialty Chemicals Corporation; UVINUL 2003 AD available from BASF Corporation Chemicals Division.

Such antioxidants may be present in the coating or intermediate solution, which may be from 0.2 to 20% by weight. The antioxidant is preferably 0.4 to 10% by weight, more preferably 0.5 to 5% by weight.

The ink receiving medium of the present invention comprises two main opposing surfaces, which can be used for printing on both sides (eg inkjet technique). Optionally, one of these major faces may be placed on the supporting image, such as a wall, floor or ceiling of a building, the side of a truck, a bulletin board, or any other part that displays high quality visual graphics for education, entertainment or promotion. Used to bond.

3M offers a variety of imaging graphic receptor media and has developed a series of pressure sensitive adhesive formulations that can be used on major surfaces opposite to the surface to be imaged. Among these adhesives are described in US Pat. No. 5,141,790 to Calhoun et al .; 5,229,207 (Paquette et al.), 5,800,919 (Peacock et al.), 5,296,277 (Wilson et al.), 5,362,516 (Wilson et al.), EPO Patent Publication No. EP0,570,515B1 (Steelman et al.) And PCT patent applications WO97 / 31076 (Peloquin et al.) And WO98 / 29516 (Sher et al.).

None of these adhesive surfaces must be protected by a peeling or storage liner, such as those available from Rexam Release, Bedford Park, Illinois. Instead of adhesives, mechanical fasteners may be used when laminating on the opposite major face of the receptor of the present invention by any known method. Non-limiting examples of mechanical fasteners include hooks and loops, trade name Velcro, trade name Scotchmate and trade name Dual Lock fastening systems, as disclosed in PCT patent application specification WO98 / 39759 (Loncar).

In a preferred embodiment of the present invention, the microporous substrate is impregnated with an organometallic salt and, if necessary, a suitable surfactant, followed by drying at 100 ° C to 120 ° C. After the receptors are dried, images can be formed using conventional inkjet image forming techniques, which are shaped into commercially available printers.

Impregnation of the organometallic polyvalent salt can be accomplished by dissolving or mixing the salt or salt with a surfactant in deionized water or a mixture of alcohol and deionized water. Impregnation of the solution can be carried out using conventional apparatus and techniques such as, for example, slot feeding knives, rotogravure devices, padding operations, dipping, spraying and the like. The organometallic polyvalent metal salt preferably fills the pores of the substrate without leaving a substantial amount on the surface. Excess solids may occlude voids, which in turn cause oozing and slow drying time during image formation. The coating weight depends on the porosity, thickness and chemical nature of the substrate, but this can be readily determined by routine optimization. Typical wet coating weights are from 1 to 500 g / m 2, preferably from 10 to 50 g / m 2, more preferably from 15 to 30 g / m 2. Optional additives may be added before or during the impregnation of the ink receptor intermediate.

Pigment-based inks have become more common in the printing industry, but dye-based inks have been used before. The use of pigment colorants is preferred over dye colorants due to the durability and ultraviolet light stability in outdoor applications.

Further, with respect to the ink according to the present invention, the present invention relates to a water-based ink rather than a solvent-based ink. Water-based inks are preferred in the printing industry for any other reason, due to current environmental and sanitary reasons.

3M produces a number of excellent pigmented inkjet inks for thermal inkjet printers. Among these products are Series 8551, 8552, 8553 and 8554 pigmented inkjet inks. The four primary colors of cyan, magenta, yellow and black can form a plurality of colors of about 256 colors in a digital image. In addition, pigmented inkjet inks and components for these are also described in Hewlett-Packard Corporation and E.I., Palo Alto, CA. It is produced by producers including Du Pont de Nemua & Company and many other companies that can participate in many commercial trade shows in the image forming and signaling industry.

The metal ion functionalized silica surface of the present invention can trap and aggregate or coagulate pigmented inks or colorants, which can fix the colorants on the silica surface. This property is particularly suitable for the metal ion functionalized silica surface of the present invention to be used as ink receptor.

In the following examples, "parts" are based on weight, unless otherwise specified.

The HP Designjet 2500cp Thermal Inkjet Printer, available from Hewlett-Packard Corporation, is used in conjunction with the manufacturer's recommended inks (part numbers C1806A, C1807A, C1808A, and C1809A). The aforementioned black, yellow, magenta and cyan inks are known to be pigment based.

In the following examples the exact nature of the printed image is not so important in order to be able to reproduce the results obtained here. The picture used is a standard test pattern (eg, CCL, circle test, photographic picture, etc.).

Wash fastness test

A printed film was placed under a utility sink faucet (25 ° C.-30 ° C.) in a fully open run to evaluate wash fastness. The wet film formed was wiped with paper towels until dry. If no perturbation or reduction occurs that makes it impossible to discern the color density, the wash fastness test is considered to have passed. Color density loss (%) was measured using a GRETAG M50 reflectance spectrophotometer commercially available from Gretack-Macbeth, Gastonia, North Carolina, USA, unless otherwise noted.

Example 1

The surface of the CHANGEABLE OPAQUE IMAGING MEDIA 8522CP, commercially available at 3M, was produced using # 4 Meyer Rod, commercially available from Aldi Specialties, Webster, NY, to produce a nominal wet coating thickness of 0.0091 mm. Composition I was flood coated. The coated substrate was dried at 120 ° C. to 130 ° C. for 1 to 2 minutes to provide an ink receptor medium. When an image was formed using an HP Designjet 2500cp thermal inkjet printer, a very high density, high quality instantaneous drying image was obtained. This image is anti-fingerprint, has excellent edge resolution (no special feathering occurs), and has passed the wash fastness test visually.

Composition I ingredient part Aluminum sulfophthalate (III) (organic metal salt) 10 Dihexylsulfosuccinate-Na salt (surfactant) 6 Polyvinylpyrrolidone / acrylic acid (PVP / AA) (75:25) (binder) 2 Isopropyl Alcohol 25 Deionized water 57

Example 2

A 24 ″ × 16 ″ (61 × 41 cm) TESLIN film substrate was flood coated with Composition I on half of its surface (described in Example 1) and the other half was uncoated. The coated substrate was dried as described above to form an ink receptor medium. The dry substrate was imaged using an HP Designjet-2500cp thermal inkjet printer to obtain an image with a very high color density as described above. The burn of the coated portion of the burn gives a denser image than the uncoated surface. The substrate on which the image was formed was laminated on an aluminum plate / backing (poster plate) and subjected to a wash fastness test. Images on uncoated TESLIN film substrates were erased by washing. The clearing of the image was very pronounced and easily observed with the naked eye. Images on the coated TESLIN film surface (invention) passed the wash fastness test with minor color loss (about 1%).

Example 3

The procedure of Example 2 was repeated except that no dihexylsulfosuccinate Na salt in composition I was used and deionized water in equimolar content was used. The image on the coated substrate was very high in image density, without staining and no feathering, except that about 5-10% of black and green color was lost during the wash fastness test.

Example 4

The procedure of Example 2 was repeated except that no equimolar content of deionized water was used without using the PVP / AA binder in composition I. Images on the coated substrate have a very high image density, which is free of stains and feathers, except that black color appears more at the top of the surface, and about 5-10% of the black and green color are lost during the wash fastness test. No ring occurred.

Example 5

The procedure of Example 2 was repeated except that no PVP / AA binder and dihexylsulfosuccinate-Na salt were used in composition I, except that equimolar amounts of deionized water were used. The image on the coated substrate has a very high image density, which is free from staining and no feathering, except that black appears more on top of the surface, some bands are formed, and some pigment bidding and coalescence has occurred. No. In wash fastness tests, about 5-10% of black and green colors were lost.

Example 6

The procedure of Example 2 was repeated except that bis aluminum (III) sulfophthalate was used in place of aluminum (III) sulfophthalate. The effect is that the content of aluminum ions in the composition is increased. The image on the coated substrate was very high in image density, free of stains, and no feathering occurred. However, the image was somewhat less dry than the image of Example 2 after printing and lost about 5-10% of red and green color in the wash fastness test.

Example 7

The procedure of Example 2 was repeated except that tris aluminum (III) sulfophthalate was used in place of aluminum (III) sulfophthalate. Its effect is an increase in the content of aluminum ions in the composition. Images on the coated substrate showed ink bidding, coalescence, feathering and staining, and the images did not dry after printing. About 30-40% of the red and green colors were lost in the wash fastness test.

Example 8

The following composition II was flood coated onto the surface of the silica filled substrate, as described in Example 1, to produce a nominal wet coating thickness of about 0.0091 mm. The coated film was dried as in Example 1 to form an ink receptor medium. When the image was formed using an HP Designjet 2500cp thermal inkjet printer, the ink receptor medium obtained a very high density, high quality instantaneous drying image. This image was free of finger stains, no feathering, and substantially passed the wash fastness test.

In Examples 1-8, burns on uncoated portions of the substrate were erased (failed) by washing in the wash fastness test.

Composition II ingredient part Zirconium Tetrakis (Sulfophthalate) (Organic Metal Salt) 9 Dihexylsulfosuccinate-Na salt (surfactant) 6 Isopropyl Alcohol 25 Deionized water 58

Example 9

A piece of 24 ″ × 16 ″ (61 × 41 cm) of TESLIN film was flood coated with Composition II on one half of its surface (described in Example 1) and the other half was uncoated. The coated substrate was dried as described above to form an ink receptor medium. The dry substrate was imaged using an HP Designjet thermal inkjet printer to obtain an image with a very high density as described above. The burn of the coated portion of the burn gives a denser image than the uncoated surface. The substrate on which the image was formed was laminated on an aluminum plate / backing (poster plate). Burns were subjected to a wash fastness test. 90% of the burn on the uncoated surface was erased by washing. The image in the coated image in the image (invention) remained with a slight color loss (about 3-5%).

Example 10

The procedure of Example 9 was repeated except that titanium tetrakis (sulfophthalate) was used instead of zirconium tetrakis (sulfophthalate). The printed image is similar in image quality to the image of Example 9. Burns on portions of the uncoated substrate were erased by washing, and about 10-20% of the portions of the coated substrate were erased by washing after the wash fastness test.

Example 11

The procedure of Example 9 was repeated except that copper (II) sulfosalicylate was used instead of zirconium tetrakis (sulfophthalate). The printed image is similar in image quality to the image of Example 9. Burns on portions of the uncoated substrate were erased by washing, and about 5-10% of images of portions of the coated substrate were erased by washing after the wash fastness test.

Example 12

The following composition III was flood coated onto a CHANGEABLE OPAQUE IMAGING MEDIA 8522cp film so that a nominal wet coating thickness of 0.0091 mm was produced and then dried as described in Example 1 to form an ink receptor medium. When an image was formed on an ink receptor medium using an HP Designjet 2500cp thermal inkjet printer, the ink receptor medium obtained an instantaneous drying image of very high density and high quality. This image was stainless, no feathering occurred, and substantially passed the wash fastness test.

Composition III ingredient part Magnesium sulfophthalate (organic metal salt) 10 Dihexylsulfosuccinate-Na salt (surfactant) 6 PVP / AA (75:25) (binder) 2 Isopropyl Alcohol 25 Deionized water 57

Example 13

A piece of 24 ″ × 16 ”(61 × 41 cm) of TESLIN film was flood coated with Composition III on half of its surface (described in Example 1) and the other half was uncoated. The coated substrate was dried as described above to form an ink receptor medium. The dry substrate was imaged using an HP Designjet 2500cp thermal inkjet printer to obtain an image with a very high density as described above. The burn of the coated portion of the burn gives a denser image than the uncoated surface. The substrate on which the image was formed was laminated on an aluminum plate / backing (poster plate). Burns were subjected to a wash fastness test. 90% of the burn on the uncoated surface was erased by washing. Images in the coated portion of the surface (invention) remained with minor color loss (about 10-15%) and substantially passed the wash fastness test.

Example 14

Flood coating with the following composition IV on a TESLIN film to produce a nominal wet coating thickness of 0.0091 mm, followed by drying as described in Example 1 to form an ink receptor medium. When an image was formed on an ink receptor medium using an HP Designjet 2500cp thermal inkjet printer, the ink receptor medium was instantaneously dried at a very high density, high quality, and an image with a considerable amount of ink bidding and coalescence was obtained.

Composition IV ingredient part Aluminum sulfate, 14H ₂ O (inorganic salt) 3 Dihexylsulfosuccinate-Na salt (surfactant) 6 PVP / AA (75:25) (binder) 2 Isopropyl Alcohol 25 Deionized water 64

Example 15 (Comparative)

A piece of 24 ″ × 16 ″ (61 × 41 cm) of TESLIN film was flood coated with Composition IV on half of its surface (described in Example 1) and the other half was uncoated. The coated substrate was dried as described above to form an ink receptor medium. The dry substrate was imaged using an HP Designjet 2500cp thermal inkjet printer to obtain an image with a very high density as described above. The burn of the coated portion of the burn gives a denser image than the uncoated surface. The substrate on which the image was formed was laminated on an aluminum plate / backing (poster plate). Burns were subjected to a wash fastness test. These two burns were erased by washing to about 75-85%.

Example 16

The procedure of Example 15 was repeated except that sulfophthalic acid (9.6 parts) was added to 93.4 parts of Composition IV. The printed image was similar in image quality to the image of Example 15. However, only about 20-30% of the image color was lost in the wash fastness test. Such a marked improvement is to illustrate the advantages of using the organometallic salts according to the invention.

Example 17

The procedure of Example 15 was repeated except that phthalic acid (4.5 parts, aluminum sulfate: molar acid molar ratio 1: 3) was added to 95.5 parts of Composition IV. The printed image was similar in image quality to the image of Example 15. However, only about 10-20% of the image color was lost in the wash fastness test. Such a marked improvement is to illustrate the advantages of using the organometallic salts according to the invention.

Example 18

The procedure of Example 15 was repeated except that 1,2,4-benzenetricarboxylic acid (5.7 parts, aluminum sulfate: tricarboxylic acid molar ratio 1: 3) was added to 94.3 parts of Composition IV. After the wash fastness test, only about 20-30% of the image color was lost, and some feathering occurred. Such improvement illustrates the advantages of using the organometallic salt according to the present invention.

Example 19

After flood coating with Composition I on a TEXWRITE MP-10 silica filled substrate (silica filled HDPE film available from Texwipe Company), it was dried as described in Example 1 to form an ink receptor medium. The substrate was image-formed as described in Example 1 to provide an image having image quality similar to that of Example 1. About 5-7% of the burns were erased by washing in the wash fastness test.

Example 20

The procedure of Example 1 was repeated except that a TESLIN film piece was used as the substrate. The image quality and wash fastness test of the sample were the same as in Example 1.

Example 21

The procedure of Example 8 was repeated except that a TESLIN film piece was used as the substrate. The image quality and wash fastness test of the sample were the same as in Example 1.

The present invention is not limited by the above embodiments.

Claims (24)

Silica filled microporous substrates having a silica surface; Organometallic Multivalent Metal Salt on Silica Surface of Silica Filled Microporous Substrate Ink receptor medium comprising a. The ink acceptor medium of claim 1, further comprising a surfactant on the silica surface of the silica filled microporous substrate. The ink receptor medium of claim 2 further comprising a binder on the silica surface of the silica filled microporous substrate. The method of claim 1 wherein the organometallic polyvalent salt is Chemical formula [Herein, when M is Cu, Mg, Zn, Ca or Co, the ratio of x: y is 1: 2, and when M is Al, Ga, B, the ratio of x: y is 1: 3 or 2: 3. Metal sulfocarbolate; Chemical formula [Wherein, when M is Cu, Mg, Zn, Ca or Co, the ratio of x: y is 1: 2 or 2: 2 and x: y when M is Al, Ga, B, Ti, Zr or Hf The ratio of 1: 3, 2: 3 or 2: 2; Chemical formula [Wherein, when M is Cu, Mg, Zn, Ca or Co, the ratio of x: y is 1: 2 or 2: 2 and x: y when M is Al, Ga, B, Ti, Zr or Hf The ratio of 1: 1, 1: 3, 2: 2 or 4: 3] metal dihydroxybenzenedisulfonate; Chemical formula [Herein, when M is Cu, Mg, Zn, Ca or Co, the ratio of x: y is 1: 2 or 1: 1, and when M is Al, Ga, B, Ti, Zr or Hf, x: y Is 1: 3, 2: 3 or 3: 3, and R is -COOH (Li, Na or K)] metal sulfosalicylate; Chemical formula [Wherein when M is Cu, Mg, Zn, Ca or Co, the ratio of x: y is 3: 2, 2: 2 or 1: 1 and M is Al, Ga, B, Ti, Zr or Hf And the ratio x: y is 1: 3, 2: 2 or 2: 3, R ¹ is H or -COOH (Li, Na or K), R ² is -COOH (Li, Na or K)] Sulfophthalate; Chemical formula [Wherein when M is Cu, Mg, Zn, Ca or Co, the ratio of x: y is 1: 1, 2: 2 or 3: 2, and M is Al, Ga, B, Ti, Zr or Hf And the ratio x: y is 1: 3, 2: 2 or 2: 3, R ¹ is H or -COOH (Li, Na or K), R ² is -COOH (Li, Na or K)] Carboxylate Ink receptor medium is selected from the group selected from the group consisting of. The ink receptor medium according to claim 1, wherein the organometallic polyvalent metal salt is magnesium sulfophthalate, copper sulfophthalate, zirconium sulfonate, zirconium phthalate, aluminum sulfophthalate, aluminum sulfoisophthalate, or a combination thereof. The ink receptor medium of claim 2 wherein the surfactant is a nonionic, cationic, anionic or a combination of anions and nonionic surfactants. The ink receptor medium of claim 2 wherein the surfactant is anionic. The ink receptor medium of claim 6 wherein the anionic surfactant is dihexylsulfosuccinate sodium salt. The ink receptor medium of claim 3 wherein the binder is selected from the group consisting of acrylic emulsions, styrene-acrylic emulsions, polyvinyl alcohols, polyvinyl alcohol / acrylic acid combinations, and combinations thereof. The ink receptor medium of claim 1 wherein the silica filled microporous substrate has pores having a pore size of 0.02 to 0.5 μm. Silica filled microporous substrates having silica surfaces, organometallic polyvalent salts on silica surfaces of such substrates; And an ink comprising a pigment colorant. The ink receiving medium / ink set of claim 11 wherein the silica surface of the microporous substrate further comprises a surfactant on its surface. The ink receiving medium / ink set according to claim 12, wherein the organometallic polyvalent metal salt is magnesium sulfophthalate, copper sulfophthalate, zirconium sulfophthalate, zirconium phthalate, aluminum sulfophthalate, aluminum sulfoisophthalate, or a combination thereof. The ink receiving medium / ink set of claim 13 wherein the surfactant is an anionic surfactant. An ink acceptor media intermediate comprising an aqueous composition comprising an organometallic salt on a silica filled microporous substrate silica surface. The ink acceptor media intermediate of claim 15, further comprising a surfactant. The ink acceptor media intermediate of claim 16, further comprising an organic solvent. 18. The ink acceptor media intermediate of claim 17, further comprising an organic binder. The ink acceptor medium intermediate of claim 16 wherein the organometallic polyvalent salt is magnesium sulfophthalate, copper sulfophthalate, zirconium sulfophthalate, zirconium phthalate, aluminum sulfophthalate, aluminum sulfoisophthalate, or combinations thereof. 20. The ink receptor medium intermediate of claim 19, wherein the surfactant is an anionic surfactant. The ink receptor medium of claim 1 having an image on a silica surface. The ink receptor medium of claim 21 wherein the image is an inkjet image. The ink receptor medium of claim 21 wherein the image has wash fastness. Applying ink to the surface of the ink receptor medium using an inkjet printer head, wherein the ink receptor medium comprises a silica filled microporous substrate having a silica surface; And organometallic polyvalent metal salts on the silica surface of the silica filled microporous substrate.