JP2003514699A - Metal ion functionalized silica surface for ink receiver - Google Patents

Abstract

(57) SUMMARY The present invention provides an ink receiving medium comprising an organometallic polyvalent metal salt on a silica surface of a silica-filled microporous substrate. The silica surface may further include a surfactant and / or a binder.

Description

Detailed Description of the Invention

The present invention relates to ink receiving media, and more particularly to improving ink drying time, improving abrasion resistance of images after drying, improving water resistance of printed images, bleeding and feathering. A silica-filled microporous substrate having a coating layer that provides a high quality image that is resistant to.

The fixation of pigments in porous substrates is different than in non-porous substrates. Polypropylene membranes (ie, TIPS films) made using the thermally induced layer separation method according to the disclosures of US Pat. Nos. 4,539,256 and 5,120,594, as well as Minnesota Mining and Manufacturin.
In porous substrates such as EVAL (ethylene vinyl alcohol) film available from g Company (St. Paul, Minn.), the pigments settle beneath the surface and in some cases also within the capillary wall of the entire substrate. . This fixing is usually done by agglomeration of the metal ions of the pigmented ink at certain sequestered locations defined by the flow and location of the surfactant or combination of surfactant, anti-migration agent and ink desiccant. This is also controlled by the type and nature of the surfactant and other additives, and the pore size and pore size distribution of the relevant porous substrate.

In the case of TIPS films, for example, pigment agglomeration is due to the placement of pigment ions that have aggregated metal ions and agglomerates in isolated locations throughout the film where surfactants and other additives are placed by their flow. Occur. The chemical entanglement of the pigments is caused by the metal ions and the pigment dispersant, while sufficient mechanical entanglement is formed by the pores due to the pore size. At least part of the overall process of pigment immobilization in porous films such as TIPS films is a chemical process. However, there are other physical phenomena such as physical adsorption (physical adsorption) along the holes inside the film portions interconnected by holes. The imaged film typically has some lower optical density than if all of the pigmented ink could be placed on the surface.

Substrates with very limited pore size allow only water to penetrate and leave the pigment on the surface. In this situation, PPG Industries (Pittsb
urgh, Pennsylvania). The TESLIN film has a very small pore size (usually 0.02 to 0).
． 5 μm) Silica filled high density polyethylene substrate. T using pigment ink
When an image is formed on the ESLIN film, the pigment remains on the surface, penetrates the pores from the inside from the surface, and is not protected below the surface. Although such substrates provide very high optical density and high quality images, these images are not water resistant.

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

When imaged using an inkjet printer, the new ink-receptive media provide durable, high color strength, high quality images and, in addition, these images are non-tacky and fast to the touch. It becomes dry.

In another embodiment, the invention provides a silica-filled microporous substrate having a silica surface,
Imaged ink receiving medium comprising an organometallic polyvalent metal salt on the silica surface of a silica-filled microporous substrate and an ink on the surface of the silica-filled microporous substrate in contact with the organometallic polyvalent metal salt I will provide a. In a preferred embodiment, the ink colorant is
A pigment dispersion having a dispersant associated with a pigment that destabilizes, coagulates, aggregates, or solidifies upon contact with an ink receiving medium. The image is preferably formed using an inkjet printer head.

In another embodiment, the present invention provides an ink receptive media intermediate that includes an aqueous composition that includes an organometallic salt on the silica surface of a silica-filled microporous substrate.

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

In the ink receiving medium of the present invention, the silica surface of the silica-filled substrate is chemically modified to provide a silica-filled microporous substrate that is resistant to water and abrasion (ie, substantially water resistant). To be In addition, the ink-receiving medium of the present invention provides higher color density and clearer images than non-porous silica-filled substrates.

One of the advantages of the ink receiving medium of the present invention is that a laminated protective cover layer is not needed to obtain a water resistant image.

Other features of the ink receiving medium of the present invention include the use of pigmented inks,
High resolution, high density, wide color gamut, water resistance,
Examples include bleed resistance and quick-drying properties.

Microporous substrates useful in the present invention are those referred to as "silica filled" microporous substrates. A "silica-filled" substrate is a substrate loaded with silica particles. These substrates are typically made by impregnating silica particles in a polymer matrix. This step involves axially stretching while coextruding both polymer and silica at appropriate processing temperatures and pressures to form pores in the resulting film. Usually, these substrates have very small pore sizes on the order of 0.02-0.5 μm and are 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. Usually, amorphous silica is composed of silicon dioxide in which oxygen atoms bridging between silicon atoms and silicon atoms are tetrahedrally bonded. In an aqueous environment, a proportion of silanol groups is present on the silica surface. Under acidic conditions this ratio increases. For example, in the present invention, A
It is considered that the l ⁺³ ion and the —COOH functional group react with the Si—OH group to form a —Al—O—Si— bond and a —C (═O) —O—Si— bond, which are bonded on the surface. To be Evidence of surface interactions has been demonstrated by infrared spectroscopy. 68 by infrared spectroscopy of aluminosilicates (eg kaolinite, kaolin, feldspar, etc.)
A characteristic absorption band can be seen at ⁰ to 1100 cm ^-1 (Sadtler Research
h Lab, Division of Bio-Rad Lab, spectrum numbers 354, 355). The IR spectrum of silica particles modified with a polyfunctional organic acid (such as sulfocarboxylic acid) according to the present invention is 1 as shown in FIG.
It has a similar absorption band with a carbonyl absorption band near 715 cm ^-1 .

Although not wishing to be bound theoretically, it is believed that the pigment ink aggregates, ie, the pigment is no longer in a dispersed state, by binding with M ^{+ (3-n)} ions bound to the surface.

Generally, the pigment is present in the dispersion used in the preparation of the pigment-based ink and its composition. In the case of anionic dispersants, anions such as carboxylate anions react instantaneously with the surface bound aluminum cations causing coagulation / aggregation of the ink. Thus the ink also binds to the surface, but is not prone to hydrolysis (it does not run off). The product materials on the silica surface, aluminum carboxylates and aluminum silicates, are usually insoluble end products.

A preferred silica-filled substrate is PPG Industries (Pittsbu).
RGH, Pennsylvania) under the trade names TESLIN and Texw
It is a trade name TEXWRITE (for example, TEXWRITE MP10) commercially available from ipe (Saddle River, NJ).

Useful organometallic salts are those having a polyvalent metal ion and a polyfunctional organic acid anion or counterion. Examples of polyvalent metal ions include, but are not limited to, Al, Ga, Ti, Zr, Hf, Zn, Mg, Ca, Nb, Ta, F.
e, Cu, Sn, Co, and the like. Examples of organic acids include, but are not limited to, aromatic dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and pentacarboxylic acids, sulfocarboxylic acids, disulfocarboxylic acids, trisulfocarboxylic acids, tetrasulfocarboxylic acids, And any combination thereof, hydroxycarboxylic acids, hydroxysulfonic acids, hydroxysulfocarboxylic acids, and combinations of any of these in any aromatic system.

[0019]   Specific examples of useful organometallic salts have the formula:

[Chemical 7] A metal sulfocarbonate (in the formula, where M is Cu, Mg, Zn, Ca, or Co, the ratio of x: y is 1: 2, and when M is Al, Ga, B, x: y). The ratio of y is 1: 3 or 2: 3), the formula:

[Chemical 8] A metal hydroquinone sulfonate of the formula: wherein M is Cu, Mg, Zn, Ca, or Co, the ratio of x: y is 1: 2 or 2: 2, and M is Al, Ga, B.
, Ti, Zr, or Hf, the x: y ratio is 1: 3, 2: 3, or 2
: 2), the formula:

[Chemical 9] Metal dihydroxybenzene disulfonate (in the formula, M is Cu, Mg, Zn, C
When a or Co, the ratio of x: y is 1: 2 or 2: 2 and M is Al.
, Ga, B, Ti, Zr, or Hf, the x: y ratio is 1: 1, 1: 3.
, 2: 2, or 4: 3) Formula:

[Chemical 10] A metal sulfosalicylate of the formula: wherein M is Cu, Mg, Zn, Ca, or Co, the ratio of x: y is 1: 2 or 1: 1 and M is Al, Ga, B, Ti.
, Zr, or Hf, the ratio of x: y is 1: 3, 2: 3, or 3: 3 and R is —COOH (Li, Na, or K)), formula:

[Chemical 11] A metal sulfophthalate of the formula where 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,
When B, Ti, Zr, or Hf, the x: y ratio is 1: 3, 2: 2, or 2: 3, R1 is H or -COOH (Li, Na, or K), R
2 is -COOH (Li, Na, or K)), and the formula:

[Chemical 12] A metal carboxylate salt of the formula (wherein M is Cu, Mg, Zn, Ca, or Co, the ratio of x: y is 1: 1, 2: 2, or 3: 2, M is Al, Ga, B,
When Ti, Zr, or Hf, the x: y ratio is 1: 3, 2: 2, or 2 :.
3, R1 is H or COOH (Li, Na, or K) and R2 is C
OOH (which is Li, Na, or K)).

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

The surface of the silica-filled microporous substrate of the present invention can optionally further comprise a surfactant, a binder, or a combination thereof. In some cases, depending on the chemical and physical properties of the microporous surface (eg, surface energy), surfactants are needed to help control the ink fluid. Therefore, it may be advantageous to impregnate at least one surfactant into the pores of the microporous substrate. The use of the surfactant can be carried out as a separate and separate step, or it can be mixed with the organometallic salt and coated on the substrate in one step, followed by removal of water and / or organic solvent. , A surface particularly suitable for the particular fluid component of the pigmented inkjet ink can be obtained.

The surfactant may be a cationic, anionic, nonionic or zwitterionic one. Many of each type of surfactant are widely available to those skilled in the art. Thus, any surfactant or combination of surfactants, or less preferred polymers that render the substrate hydrophilic can be used.

Examples of such agents include, but are not limited to, fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants, and these surfactants are anionic. It may be ionic or nonionic. Further, the nonionic surfactant can be used as it is, or can be used in water and / or an organic solvent in combination with another anionic surfactant, and as these organic solvents, It is selected from the group consisting of alcohols, ethers, amides, ketones and the like.

A variety of nonionic surfactants can be used, including but not limited to E.I. I. du Pont de Nemours and Co. (W
ZONYL Fluorocarbons, such as ZONYL FSO; Minnesota Mining and M
FLUORAD F available from the anufacturing Company
C-170 or 171 surfactant; BASF Corp. Chemicals
PLs based on ethylene oxide and propylene oxide and ethylene glycol available from Division (Mount Olive, NJ)
URONIC block copolymers; ICI Americas, Inc. (Wi
Tween EN polyoxyethylene sorbitan fatty acid ester available from Rimington, Delaware); Rohm and Haas Co. (Phila
TRITON X-series octylphenoxypolyethoxyethanol available from Delphia, PA; Air Products an
d Chemicals, Inc. SURFYNOL tetramethyldecyne diol available from (Allentown, PA); and Unio
n Carbide Corp. SILWET L-7614 and L-7607 silicone surfactants, available from (Danbury, Connecticut), and the like, as known to those of skill in the art.

Useful anionic surfactants include, but are not limited to: 1) alkali metal and (alkyl) ammonium salts of alkyl sulphates and alkyl sulphonates, eg sodium dodecyl sulphate and potassium dodecane sulphonate, 2) Alkali metal salts and (alkyl) ammonium salts of polyethoxylated derivatives of straight or branched chain aliphatic alcohols and carboxylic acids; 3
) Alkylbenzene sulphonates or alkylnaphthalene sulphonic acids and alkali metal salts and (alkyl) ammonium salts of alkylbenzene sulphates or alkylnaphthalene sulphates, eg sodium laurylbenzene sulphonate, 4) ethoxylated and polyethoxylated alkyl alcohols and aralkyl alcohol carboxylates 5) Alkali metal salts and (alkyl) ammonium salts of 5) Alkali metal salts and (alkyl) ammonium salts of glycinates such as alkyl sarcosinates and alkyl glycinates, 6
) Alkali metal salts and (alkyl) ammonium salts of sulfosuccinates such as diallyl sulfosuccinate, 7) Alkali metal salts and (alkyl) ammonium salts of isethionate derivatives, 8) Alkali metal salts of N-acyltaurine derivatives and (Alkyl) ammonium salts such as sodium N-methyl-N-oleyltaurine, 9) Alkali of amphoteric alkylcarboxylates such as alkyl and aryl betaines and amphoteric propionates optionally substituted with oxygen, nitrogen and / or sulfur atoms. Metal salts and (alkyl) ammonium salts, and 10) Alkali metal salts of alkylphosphate monoesters or diesters and (alkyl) ammonium salts, such as ethoxylated dodecyl alcohol phosphates. Include sodium salt.

Useful cationic surfactants include those of the formula C _n H _{2n + 1} N (CH ₃ ) ₃ X (wherein
X is OH, Cl, Br, HSO ₄ , or a combination of OH and Cl, and n
It is an 8 to 22 integer) and formula _{C n H 2n + 1 N (} C 2 H 5) 3 X ( wherein, n 12
An alkylammonium salt having an integer of -18); a Gemini surfactant,
For example, having the formula [C ₁₆ H ₃₃ N (CH ₃ ) ₂ C _m H _{2m + 1} ] X, where m is an integer from 2 to 12 and X is as defined above; aralkyl Ammonium salts, such as benzalkonium salts; and cetylethylpiperidinium salts, such as C ₁₆ H ₃₃ N (C ₂ H ₅ ) (C ₅ H ₁₀ ) X, where X is as defined above. Can be mentioned.

The amount of organometallic polyvalent salt that can be used in the intermediate for imbibing on the microporous substrate of the present invention is in the range of 0.1% to 50% by weight, preferably 0.5% by weight. ~
It can be in the range of 20% by weight.

The amount of surfactant that can be used in the intermediate for imbibing on the microporous substrate of the present invention is 0.01% to 10% by weight, preferably 0.1% to 5% by weight.
Can range from.

Optionally, an organic binder can be used in the ink receiving medium of the present invention. The organic binder is soluble in water so that it can be easily incorporated into the intermediate composition used to coat the microporous substrate when making the ink-receiving medium of the present invention. Or dispersible. Non-limiting examples of such organic binders include acrylic emulsions, styrene-acrylic emulsions, polyvinyl alcohols, polyvinyl alcohol / acrylic acid combinations, and combinations thereof. Such an organic binder may include 0.1% of a coating solution or an intermediate solution based on the total weight of the coating solution or the intermediate solution containing a surfactant and a metal salt and the balance being water and / or an organic solvent. ~ 50% by weight, preferably 1
Can be present at -30% by weight.

Optionally, opacifying pigments can be used in the ink receiving medium of the present invention. Non-limiting examples of such opaque pigments include titanium dioxide pigments, barium sulfate pigments and the like. Such opacifying pigments can be present in the coating solution and can range from 0.01% to 50% by weight. Preferably, the opacifying pigment is present in an amount of 1-30% by weight.

Optionally, heat stabilizers or UV light stabilizers can be used in the ink receiving medium of the present invention. Non-limiting examples of such additives include Ciba Spec.
ialty Chemicals Corp. (Tarrytown, NY) TINUVIN 123 or 622LD, or CH
IMASSORB 944 (hindered amine light stabilizer), as well as BASF
UVINUL 3008 available from Corporation Chemicals Division. Such stabilizers can be present in the coating or intermediate solutions impregnated into the microporous substrate in the range of 0.2% to 20% by weight. Preferably, the stabilizer is present in an amount of 0.1-10% by weight, more preferably 0.5-5% by weight.

A UV absorber can optionally be used in the ink receiving medium of the present invention.
Non-limiting examples of such absorbents include Ciba Specialty C
chemicals Corp. More available TINUVIN II 30 or 326; UVINUL 4 available from BASF Corporation
0501 1; and Sandoz Chemicals (Charlott
e., North Carolina) SANDUVOR VSU or 303
5 is mentioned. Such absorbents can be present in the coating or intermediate solutions and can range from 0.01% to 20% by weight. Preferably, the absorbent is present in an amount of 1-10% by weight.

Antioxidants may optionally be used in the ink receiving medium of the present invention. Non-limiting examples of such antioxidants include Ciba Specialty.
Chemicals Corp. More available IRGANOX 1010 or 1076; and BASF Corporation Chemicals
UVINUL 2003 AD available from Division.

Such antioxidants can be present in the coating solution or the intermediate solution and can range from 0.2% to 20% by weight. Preferably, the antioxidant is present in an amount of 0.4-10% by weight, more preferably 0.5-5% by weight.
Present in an amount of.

The ink receiving medium of the present invention has two main surfaces facing each other, and both surfaces can be used for printing (for example, an inkjet method). Finished images, optionally on a supporting surface such as a building wall, floor or ceiling, side of a truck, billboard, or any other place where high quality images can be displayed for education, entertainment, or information One major surface can be used for the purpose of adhering the.

Minnesota Mining and Manufacturing
Company offers a variety of image receiving media and has developed many types of pressure sensitive adhesive formulations that can be used on the major surface opposite the surface intended for imaging. Among these adhesives, among others, US Pat. No. 5,141,790 (C
alhoun et al.), 5,229,207 (Paquette et al.), 5,8.
00,919 (Peacock et al.), 5,296,277 (Wilson).
Et al., 5,362,516 (Wilson et al.), EPO Patent Publication EP 0.
570 515 B1 (Steelman et al.), And those disclosed in PCT patent application numbers WO 97/31076 (Peloquin et al.) And WO 98/29516 (Sher et al.).

Any of these adhesive surfaces may have a Rexam Release (Bedford P
It should be protected by a release or storage liner such as that marketed by ark, Illinois). Instead of an adhesive, mechanical fasteners may be used when laminated in known manner to the opposing major surfaces of the receiver of the present invention. Non-limiting examples of mechanical fasteners include hooks and loops, Velcro ^™ , Scotchmat
e ^™ , and Dual Lock ^™ fasteners, such as published PCT
Patent application number WO98 / 39759 (Loncar).

A preferred embodiment of the present invention is prepared by impregnating a microporous substrate with an organic metal salt, optionally with a suitable surfactant, and then drying at a temperature of 100 to 120 ° C. . After the receiver is dried, the receiver can be imaged by conventional inkjet imaging methods implemented on commercially available printers.

Impregnation with the organometallic polyvalent salt can be carried out by dissolving or mixing the salt or the salt and the surfactant in deionized water or a mixture of alcohol and deionized water. Impregnation of this solution can be carried out using conventional equipment and techniques such as slot knives, rotogravure equipment, padding operations, dipping, spraying and the like.
The organometallic polyvalent metal salt preferably fills the pores of the substrate without a substantial amount of the metal salt remaining on the surface. Excess solids can fill the pores, which can cause contamination and slow dry times during imaging. The coating weight will vary with the substrate porosity, thickness, and chemistry, but can be readily determined by routine optimization. Usually, the weight of the undried coating agent is 1 to 500 g /
m ² , preferably 10 to 50 g / m ² , and more preferably 15 to 30 g.
/ M ² . Optional additives can be added before, during, or after impregnation of the ink receiver intermediate.

The printing industry has traditionally employed dosimeter inks, but pigment-based inks are becoming more prevalent. The use of pigment colorants is preferred over dye colorants because they are durable and ultraviolet light stable in outdoor applications.

Further, a water-based ink is considered as a reference ink for the present invention, and not a solvent-based ink. Currently, aqueous inks are preferred in the printing industry, especially for environmental and health reasons.

Minnesota Mining and Manufacturing
Company manufactures many types of superior pigmented inkjet inks for thermal inkjet printers. Among these products are among others the series 8551, 8552, 8553, and 8554 pigmented inkjet inks. By using the four main colors of cyan, magenta, yellow, and black, it is possible to form digital images of 256 colors or more. In addition, pigmented inkjet inks and their components are also manufactured by other sources, eg, Hewlett-Packard Corp. (Palo
Alto, California) and E.I. I. du Pont de Nemuu
rs and Co. , And many other companies whose commercial transactions can be linked to the imaging and visual signage industries.

The metal ion functionalized silica surface of the present invention is capable of entrapping and aggregating or coagulating pigment inks or colorants, which allows the colorants to be fixed onto the silica surface. Due to these properties, the metal ion functionalized silica surface of the present invention is particularly suitable as an ink receiver.

EXAMPLES In the following examples, unless otherwise stated, the term “parts” means parts by weight.

HP Design available from Hewlett-Packard Corp.
An njet 2500cp thermal inkjet printer was used with the manufacturer's recommended inks (Part Nos. C1806A, C1807A, C1808A, C1809A). The above black, yellow, magenta, and cyan inks appeared to be pigmentary.

The exact nature of the images printed in the following examples is not critical to the reproducibility of the results obtained. The images used were standard test patterns (eg CCL, circle test photographic images, etc.).

Washing fastness test The washing fastness of the printing film was evaluated by placing it under a sink water faucet (25 to 30 ° C) in a completely opened state. The wet imaging film was wiped dry with a paper towel. The wash fastness test was deemed to have passed if no discernible bleeding or reduction in color density occurred. Unless specified otherwise, Gretag-Macbeth (Ga
GRETAG M50 RE available from Stonia, NC)
The color density reduction rate was measured using FLECTANCE SPECTROPHOTOMETER.

Example 1 Minnesota Mining using No. 4 Meyer Rod available from RD Specialties (Webster, NY)
and silica-filled film available from And Manufacturing Company (CHANAGEABLE OPAGUE IMAGING MEDI
A 8522 CP) is flow coated with Composition I to give a nominal wet thickness of 0.
． 0091 mm was obtained. The coated substrate was dried at 120-130 ° C for 1-2 minutes to make an ink receiving medium. HP Designjet 2500
When imaged using a cp thermal inkjet printer, very dry and high quality images were obtained that dried instantly. The image was not rubbed with a finger, had good edge resolution (no noticeable feathering), and passed the visual washfastness test.

[0049]

[Table 1]

EXAMPLE 2 Half of the surface of a 24 inch × 16 inch (61 × 41 cm) TESLIN film substrate is flow coated (as described in Example 1) with the other half coated. I left without doing it. The coated substrate was dried as described above to make an ink receiving medium. HP Design on the dried substrate
Imaging with a jet-2500 cp thermal inkjet printer resulted in very high color density images as described above. The image formed on the coated portion was higher in density than the uncoated surface. The imaged substrate was laminated onto an aluminum plate / backing (poster board) and a wash fastness test was performed. The image on the uncoated portion of the TESLIN film substrate washed out. The fading of the image was very obvious and could be easily confirmed with the naked eye. The image on the coated TESLIN film surface (invention) passed the washfastness test with little color loss (about 1%).

Example 3 The procedure of Example 2 was repeated except that the dihexyl sulfosuccinate Na salt of Composition I was not used, and instead the same amount of deionized water was used. Images on coated substrates show about 5-10% black and green during washfastness test.
Except for the loss of image, there was no blurring or feathering and the image was very dense.

Example 4 The procedure of Example 2 was repeated, except that the PVP / AA binder of Composition I was not used and instead the same amount of deionized water was used. The procedure of Example 2 was repeated. The image on the coated substrate was very devoid of bleeding and feathering except that more black appeared on top of the surface and the wash fastness test lost about 5-10% of the black and green. It was a high density image.

Example 5 of Example 2 except that neither the PVP / AA binder of Composition I nor the dihexyl sulfosuccinate Na salt was used, and instead the same amount of deionized water was used. The procedure was repeated. The image on the coated substrate shows that the washfastness test resulted in more black appearing on top of the surface, with some coalescence resulting in beading in some of the pigments and small banding in some. The image had very high density without bleeding or feathering. In the wash fastness test, about 5-10% of black and green were lost.

Example 6 The procedure of Example 2 was repeated except that Bisaluminum (III) sulfophthalate was used instead of Aluminum (III) sulfophthalate in Composition I. This increased the amount of aluminum ions in the composition. The image on the coated substrate was a very high density image with no bleeding or feathering.
However, it dried slightly slower after printing than the image of Example 2 and lost about 5-10% of red and green in the washfastness test.

Example 7 The procedure of Example 2 was repeated except that the aluminum (III) sulfophthalate of Composition I was replaced with tris aluminum (III) sulfophthalate. This increased the amount of aluminum ions in the composition. The image on the coated substrate showed ink beading, coalescence, feathering, bleeding and the image did not dry after printing. In the wash fastness test, about 30-40% of red and green were lost.

Example 8 Composition II was flow coated onto the surface of a silica-filled substrate as described in Example 1 to give a nominal wet thickness of about 0.0091 mm. The coated film was dried as in Example 1 to make an ink receiving medium. HP Design
When imaged using a jet 2500 cp thermal inkjet printer, very high density, high quality, instant dry images were obtained. There was no image bleeding or feathering and the wash fastness test was substantially passed.

In Examples 1-8, the image of the uncoated portion of the substrate ran off in the wash fastness test (fail).

[0058]

[Table 2]

Example 9 Half of the surface of a 24 inch x 16 inch (61 x 41 cm) TESLIN film substrate is flow coated (as described in Example 1) with the other half coated. I left without doing it. The coated substrate was dried as described above to make an ink receiving medium. HP Designj on the dried substrate
Imaging using et thermal inkjet resulted in very high color density images as described above. The image formed on the coated portion was higher in density than the uncoated surface. The image-formed substrate is an aluminum plate /
Laminated on backing (poster board). A washfastness test of this image was then performed. 90% of the image on the uncoated surface washed off. The image of the coated part (invention) remained with a slight (about 3-5%) loss of color.

Example 10 The procedure of Example 9 was repeated except that titanium tetrakis (sulfophthalate) was used instead of tetrakis (sulfophthalate) zirconium. The printed image was of similar quality to the image of Example 9. After the wash fastness test, the image of the uncoated portion of the substrate was washed off, about 10-20 of the image of the coated portion of the substrate.
% Flowed down.

Example 11 Copper sulfosalicylate (instead of tetrakis (sulfophthalate) zirconium (
The procedure of Example 9 was repeated except that II) was used. The printed image was of similar quality to the image of Example 9. After the washfastness test, the image on the uncoated portion of the substrate was washed off and about 5-10% of the image on the coated portion of the substrate was washed off.

Example 12 CHANGEABLE OPAQUE IMAGING MEDIA 852
Composition III was flow coated onto a 2CP film as described in Example 1 to form a nominal wet thickness of 0.0091 mm and then dried to make an ink receiving medium. When imaged using a HP Designjet 2500 cp thermal ink jet printer, this ink receiver provides a very high density, high quality, instant dry image that is wash-fast and wash-fast. I also passed the degree test.

[0063]

[Table 3]

Example 13 Composition III is flow coated (as described in Example 1) on one half of the surface of a 24 ″ × 16 ″ (61 × 41 cm) TESLIN film substrate and the other half is coated. I left without doing it. The coated substrate was dried as described above to make an ink receiving medium. HP Design on the dried substrate
Imaging using a jet 2500 cp thermal inkjet yielded very high color density images as described above. The image formed on the coated portion was higher in density than the uncoated surface. The imaged substrate was laminated onto an aluminum plate / backing (poster board). A washfastness test of this image was then performed. 90% of the image on the uncoated surface washed off.
The image of the coated portion (invention) remained with a small amount (about 10-15%) of color loss and substantially passed the washfastness test.

Example 14 Composition IV was flow coated onto a TESLIN film as described in Example 1 to form a nominal wet thickness of 0.0091 mm and then dried to make an ink receiving medium. HP Designjet 2500c is applied to this ink receiving medium.
When imaged using a p-thermal inkjet printer, the ink receiver produced very high density, high quality, and instant dry images with significant amounts of ink beading and coalescence.

[0066]

[Table 4]

Example 15 (Comparative) Half of the surface of a 24 ″ × 16 ″ (61 × 41 cm) TESLIN film substrate was flow coated (as described in Example 1) with the other half. The surface of was left uncoated. The coated substrate was dried as described above to make an ink receiving medium. HP Designj on the dried substrate
Imaging using the et 2500 cp thermal ink jet resulted in very high color density images as described above. The image formed on the coated portion was higher in density than the uncoated surface. The imaged substrate was laminated onto an aluminum plate / backing (poster board). A washfastness test of this image was then performed. Both images flowed down by about 75-85%.

Example 16 Except that sulfophthalic acid (9.6 parts) was added to 93.4 parts of Composition IV.
The procedure of Example 15 was repeated. The printed image was of similar quality to the image of Example 15. However, the loss of image color due to the wash fastness test is only about 20-3.
It was 0%. This significant improvement shows the advantage 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: phthalic acid molar ratio of 1: 3) was added to 95.5 parts of Composition IV. . The printed image was of similar quality to the image of Example 15. However, the color loss of the image by the wash fastness test was only about 10-20%. This significant improvement shows the advantage of using the organometallic salts according to the invention.

Example 18 Performed, except that 1,2,4-benzenetricarboxylic acid (5.7%, aluminum sulphate: tricarboxylic acid molar ratio 1: 3) was added to 94.3 parts of composition IV. The procedure of Example 15 was repeated. When the wash fastness test was performed, the color loss of the image was only about 20-30% and some feathering occurred. This significant improvement shows the advantage of using the organometallic salts according to the invention.

Example 19 Composition I is flow coated and dried as described in Example 1 onto a TEXWRITE MP-10 silica filled substrate (silica filled HDPE film from Texwipe Co.) to form an ink receiving medium. It was made. When an image was formed on this substrate as described in Example 1, an image of the same quality as the image of Example 1 was obtained. A wash fastness test showed that about 5-7% of the image had run off.

Example 20 The procedure of Example 1 was repeated except that TESLIN film was used as the substrate. The image quality and washfastness of this sample were similar to Example 1.

Example 21 The procedure of Example 8 was repeated except that TESLIN film was used as the substrate. The image quality and washfastness of this sample were similar to Example 8.

[0074]   The present invention is not limited to the above embodiments.

[Brief description of drawings]

[Figure 1]   3 is an infrared spectrum of silica particles modified with a polyfunctional organic acid.

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Claims (24)

[Claims] 1. A silica-filled microporous substrate having a silica surface,   An organometallic polyvalent metal salt on the silica surface of the silica-filled microporous substrate, An ink receiving medium including. 2. The ink receptive medium of claim 1, further comprising a surfactant on the silica surface of the silica-filled microporous substrate. 3. The ink receptive medium of claim 2, further comprising a binder on the silica surface of the silica-filled microporous substrate. 4. The organometallic polyvalent salt has the formula: A metal sulfocarbonate (in the formula, where M is Cu, Mg, Zn, Ca, or Co, the ratio of x: y is 1: 2, and when M is Al, Ga, B, x: y). The ratio of y is 1: 3 or 2: 3), with the formula: A metal hydroquinone sulfonate of the formula: wherein M is Cu, Mg, Zn, Ca, or Co, the ratio of x: y is 1: 2 or 2: 2, and M is Al, Ga, B.
, Ti, Zr, or Hf, the x: y ratio is 1: 3, 2: 3, or 2
: 2), the formula: Metal dihydroxybenzene disulfonate (in the formula, M is Cu, Mg, Zn, C
When a or Co, the ratio of x: y is 1: 2 or 2: 2 and M is Al.
, Ga, B, Ti, Zr, or Hf, the x: y ratio is 1: 1, 1: 3.
, 2: 2, or 4: 3) Formula: A metal sulfosalicylate of the formula: wherein M is Cu, Mg, Zn, Ca, or Co, the ratio of x: y is 1: 2 or 1: 1 and M is Al, Ga, B, Ti.
, Zr, or Hf, the ratio of x: y is 1: 3, 2: 3, or 3: 3 and R is —COOH (Li, Na, or K)), 5] A metal sulfophthalate of the formula where 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,
When B, Ti, Zr, or Hf, the x: y ratio 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)), and the formula: A metal carboxylate salt of the formula (wherein M is Cu, Mg, Zn, Ca, or Co, the ratio of x: y is 1: 1, 2: 2, or 3: 2, M is Al, Ga, B,
When Ti, Zr, or Hf, the x: y ratio is 1: 3, 2: 2, or 2 :.
3, R ¹ is H or COOH (Li, Na, or K) and R ² is CO
The ink receiving medium of claim 1 selected from the group consisting of OH (which is (Li, Na, or K)), 5. The organometallic polyvalent metal salt is magnesium sulfophthalate,
The ink receiving medium according to claim 1, which is copper sulfophthalate, zirconium sulfophthalate, zirconium phthalate, aluminum sulfophthalate, aluminum sulfoisophthalate, or a combination thereof. 6. The surfactant is a nonionic surfactant, a cationic surfactant, an anionic surfactant, or a combination of an anionic surfactant and a nonionic surfactant. The ink-receiving medium of claim 2, wherein: 7. The ink receiving medium according to claim 2, wherein the surfactant is an anionic surfactant. 8. The ink receiver according to claim 6, wherein the anionic surfactant is dihexyl sulfosuccinate sodium salt. 9. The ink receptive 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. 10. The ink receiving medium according to claim 1, wherein the silica-filled microporous substrate has pores having a pore diameter of 0.02 to 0.5 μm. 11. An ink receiving medium comprising a silica-filled microporous substrate having a silica surface, an organometallic polyvalent salt on the silica surface of the silica-filled microporous substrate, and an ink containing a pigment colorant. Ink set. 12. The ink receptive medium / ink set of claim 11, further comprising a surfactant on the silica surface of the microporous substrate. 13. The organic metal polyvalent metal salt is magnesium sulfophthalate, copper sulfophthalate, zirconium sulfophthalate, zirconium phthalate, aluminum sulfophthalate, aluminum sulfoisophthalate, or a combination thereof. Ink receiving medium / ink set. 14. The surface active agent is an anionic surface active agent.
The ink receiving medium / ink set described in 1. 15. An ink receptive medium intermediate comprising an aqueous composition comprising an organometallic salt on the silica surface of a silica filled microporous substrate. 16. The ink receiver intermediate according to claim 15, further comprising a surfactant. 17. The ink receiver intermediate according to claim 16, further comprising an organic solvent. 18. The ink receiver intermediate according to claim 17, further comprising an organic binder. 19. The polyvalent metal salt according to claim 16, which is magnesium sulfophthalate, copper sulfophthalate, zirconium sulfophthalate, zirconium phthalate, aluminum sulfophthalate, aluminum sulfoisophthalate, or a combination thereof. Ink receptor intermediate. 20. The surface active agent is an anionic surface active agent.
The ink-receptor intermediate as described in 1. 21. The ink receptive medium of claim 1 having an image on the silica surface. 22. The imaged ink receptive medium of claim 21, wherein the image is an inkjet image. 23. The imaged ink receptive medium of claim 21, wherein the image is washfast. 24. Applying ink to an ink receptive medium surface using an inkjet printer head, wherein the ink receptive medium comprises a silica-filled microporous substrate having a silica surface, and the silica-filled microporous substrate. A method of imaging an ink receiver comprising an organometallic polyvalent metal salt on a silica surface.