CN1399595A

CN1399595A - Metal ion functionalized silica surface for ink receptors

Info

Publication number: CN1399595A
Application number: CN00816134A
Authority: CN
Inventors: O·法鲁克
Original assignee: 3M Innovative Properties Co
Current assignee: 3M Innovative Properties Co
Priority date: 1999-11-24
Filing date: 2000-03-28
Publication date: 2003-02-26
Also published as: WO2001038102A1; KR20020056948A; CA2389273A1; BR0015752A; JP2003514699A; EP1242248A1; DE60004397D1; AU4035900A; EP1242248B1

Abstract

The invention provides ink receptor mediums that included organometallic multivalent metal salt on the silica surface of a silica-filled microporous substrate. The silica surface also may further include a surfactant and/or a binder.

Description

The metal ion functionalized silica surface that is used for ink receptors

The present invention relates to printing ink and accept medium, particularly, the present invention relates to fill the microporous substrate of silica, this base material has the resistance to water of the afterwards visual wearability of the ink setting time of improving, drying, printed image and provides resistant and the coating of the high quality image of anti-line edge scared (feathering).

Pigment fixedly is different from fixing in non-porous base material in porous substrate.Such as adopting according to United States Patent (USP) 4,539,256 and 5,120, the polypropylene screen (being the TIPS film) of the 594 thermally induced phase separations preparations that disclose and from Minnesota Mining and Manufactureing Company, in the porous substrate of the EVAL that St.Paul, MN buy (ethylene-vinyl alcohol) film, pigment is fixed on surface (sub-surface) down, is fixed on sometimes in the capillary wall of base material integral body.Generally by by surfactant or surfactant, migration inhibitor and ink setting agent composition flow and the position determines that the metal ion of pigment based ink fixes in the flocculation of certain protective position.And thisly fixedly be subjected to the type of surfactant and other additive and the aperture of character and described porous substrate, the control of pore-size distribution.

For example in TIPS film situation, cause pigment flocculation by metal ion, flocculation or the pigment based ink of reuniting are located in such protective position, promptly in the thin-film body that surfactant and other additive are arranged, are subjected to their mobile control.The chemistry that is caused pigment by metal ion and pigment dispersing agent tangles, but also exists because aperture and the sufficient mechanical interlocking that provided by the hole.The whole procedure division that pigment is fixed on perforated membrane such as the TIPS film is that chemistry tangles.Yet, the phenomenon that also has physics as in the connected component in the hole of film along the physical absorption (physisorption) in hole.The optical density (OD) of imaging film generally all spreads over the situation at surperficial top a little less than all pigment based ink.

The base material that has utmost point finite aperture only allows the water diafiltration, and pigment is retained on the surface level.Available from PPGIndustries, Pittsburgh, the surface of the TESLIN board film of PA is exactly this situation.The TESILN film is that the very high density polyethylene (HDPE) base material of the filling silica of small-bore (being generally the 0.02-0.5 micron) is arranged.When the TESLIN film was used the pigment based ink imaging, pigment was stayed on the surface, can not be penetrated under the surface to enter in the hole, was protected under the surface.Such base material provides very high optical density (OD) and high-quality image, but such image is not water-fast.

In the embodiment, the invention provides a kind of printing ink of the microporous substrate of filling silica that comprises and accept medium, microporous substrate has silica surface and the organometallic multivalent metal salt on silica surface.Printing ink of the present invention is accepted medium also can be included in surfactant, adhesive or surfactant on the micropore surface of filling silica and the mixture of adhesive.Surfactant is preferably hydrophilic.The microporous substrate of filling silica can partly or cover the multivalence organic metal salt basically fully.

This novel printing ink is accepted medium when forming image with ink-jet printer, obtains durable, high colouring intensity and high-quality image, the inviscid and dry to touch promptly of this image.

In second embodiment, the invention provides and a kind ofly comprise the microporous substrate of filling silica and filling on the silica microporous substrate surface and the printing ink of the printing ink that contacts with the organic metal multivalent metal salt is accepted medium that microporous substrate has silica surface and the organometallic multivalent metal salt on silica surface.Ink colorant is the pigment dispersion that contains the dispersant that combines with pigment preferably in the embodiment at one, stabilization removal, flocculation can take place, reunite or condense at this pigment dispersion when printing ink is accepted medium and contacted.Use ink jetting head to form image preferably.

In the 3rd embodiment, the invention provides a kind of printing ink and accept the medium intermediate, this intermediate comprises the Aquo-composition that is included in the organic metal salt on the silica surface of filling the silica microporous substrate.

The present invention also provides a kind of printing ink that comprises the microporous substrate of filling silica and comprise the printing ink of pigment colorant to accept medium/printing ink cover group, this microporous substrate have silica surface and this surface and the organic metal multivalent metal salt.

Printing ink of the present invention is accepted medium provides a kind of silica surface of filling the silica base material by chemical modification to make it microporous substrate into water-fast and wear-resisting (substantially water-resistant) filling silica.In addition, printing ink of the present invention is accepted medium provides than higher color density of the base material of non-porous filling silica and beautiful image.

The advantage that printing ink of the present invention is accepted medium is the protection jacket layer that does not need lamination, just can obtain water-fast image.

The further feature that printing ink of the present invention is accepted medium comprises: with the pigment based ink operation, have high-resolution, high color density, wide colour gamut is provided, and is water-fast, anti-soil, rapid drying is provided.

Fig. 1 is the infrared spectrum by the silica dioxide granule of multifunctional modified with organic acids.

The microporous substrate of so-called " filling silica " to the useful microporous substrate of the present invention. The base material of " filling silica " is the base material that is filled with silica dioxide granule. The common employing of these base materials is impregnated into silica dioxide granule in the polymeric matrix and prepares. This method relates to the coextrusion under suitable processing temperature and pressure and axle orientation with polymer and silica, produces the hole in the film that makes. These base materials generally have the very little aperture in the 0.02-0.5 micron dimension, can be according to United States Patent (USP)s 4,833, and 172,4,861,644,4,877,679 and 4,892, the method preparation described in 779.

The silica that exists on the microporous substrate surface is amorphous silica. Amorphous silica generally is comprised of the silica that silicon atom is attached to the oxygen atom of bridge joint between silicon atom on four sides. In water environment, there is the silanol group of certain percentage at silica surface. Under acid condition, this percentage increases. Among the present invention, for example, think Al⁺³Ion and-COOH functional group and Si-OH radical reaction, obtain-Al-O-Si-be connected C (=O)-O-Si-connection, they are surface conjunctions. Infrared spectrum has shown the evidence of this surface interaction. The infrared spectrum of alumino-silicate (such as kaolinite, kaolin, feldspar etc.) is presented at the characteristic absorption band of 680-1100cm-1. (referring to Sadtler Research Lab, Division of Bio-Rad Lab, Spectrum Nos.354,355). As shown in Figure 1, the present invention has similar absorption band by the IR spectrum of the silica dioxide granule of multifunctional organic acid (such as the sulfo group carboxylic acid) modification, at 1715cm^-1With the carbonyl absorption band.

Although not bound by theory, think that pigment based ink flocculates, namely by with the M that is combined in the surface^+(3-n)Ions binding, pigment shifts out from dispersion. Pigment generally remain on for the preparation of with the combination pigment based ink dispersant in. To anionic dispersing agents, anion for example Carboxylic Acid Ions can spontaneously react with the aluminium cations that is combined in the surface, causes condensing/flocculating of printing ink. Therefore, this printing ink also is surface conjunction and (can not flush away) of facile hydrolysis not. Product on silica surface, aluminum carboxylate and alumina silicate generally are insoluble end products.

The base material of filling preferably silica has the Industries from PPG, and the commodity that Pittsburgh, PA buy are called TESLIN, and from Texwipe, Saddle River, NJ, the commodity of buying are called TEXWRITE (for example TEXWRITE MP10).

Useful organic metal salt is to have those of polyvalent metal ion and multifunctional organic anion or counter ion counterionsl gegenions. Polyvalent metal ion includes but not limited to Al, Ga, Ti, Zr, Hf, Zn, Mg, Ca, Nb, Ta, Fe, Cu, Sn, Co etc. The organic acid example includes but not limited to aromatic dicarboxylic acid, tricarboxylic acids, tetrabasic carboxylic acid and pentacarboxylic acid, sulfo group carboxylic acid, disulfo carboxylic acid, three sulfo group carboxylic acids, four sulfo group carboxylic acids and their any combination, hydroxycarboxylic acid, hydroxyl sulfoacid, hydroxyl sulfo group carboxylic acid and their any combination.

The object lesson of useful organic metal salt comprises the sulfo group phenol slaine with following formula:Wherein, when M was Cu, Mg, Zn, Ca or Co, the ratio of x: y was 1: 2, and when M was Al, Ga, B, the ratio of x: y was 1: 3 or 2: 3;

Hydroquinone sulfonic acid slaine with following formula:Wherein, when M was Cu, Mg, Zn, Ca or Co, the ratio of x: y was 1: 2 or 2: 2, and when M was Al, Ga, B, Ti, Zr or Hf, the ratio of x: y was 1: 3,2: 3 or 2: 2;

Metallic dixhydroxybenzenedisulfonates with following formula:

Wherein, when M was Cu, Mg, Zn, Ca or Co, the ratio of x: y was 1: 2 or 2: 2, and when M was Al, Ga, B, Ti, Zr or Hf, the ratio of x: y was 1: 1,1: 3,2: 2 or 4: 3;

Sulfosalicylic acid slaine with following formula: Wherein, when M was Cu, Mg, Zn, Ca or Co, the ratio of x: y was 1: 2 or 1: 1; When M was Al, Ga, B, Ti, Zr or Hf, the ratio of x: y was 1: 3,2: 3 or 3: 3; R is-COOH (Li, Na or K Yi);

Sulfo group phthalic acid slaine with following formula:

Wherein, when M was Cu, Mg, Zn, Ca or Co, the ratio of x: y was 3: 2,2: 2 or 1: 1, and when M was Al, Ga, B, Ti, Zr or Hf, the ratio of x: y was 1: 3,2: 2 or 2: 3; R1 be H or-COOH (Li, Na or K); R2 is-COOH (Li, Na or K); With

Metal carboxylate with following formula: Wherein, when M was Cu, Mg, Zn, Ca or Co, the ratio of x: y was 1: 1,2: 2 or 3: 2, and when M was Al, Ga, B, Ti, Zr or Hf, the ratio of x: y was 1: 3,2: 2 or 2: 3; R1 is H or COOH (Li, Na or K); R2 is COOH (Li, Na or K).

The object lesson of organic metal multivalent metal salt comprises preferably: sulfosalicylic phthalate magnesium, sulfosalicylic phthalate copper, sulfosalicylic phthalate zirconium, phthalic acid zirconium, sulfosalicylic phthalate aluminium, sulfoisophthalic acid aluminium and their combination.

The surface that the present invention fills the microporous substrate of silica can also be chosen wantonly and comprise surfactant, adhesive or their mixture.Sometimes, the chemical property of micropore surface and physical property (for example surface energy) need surfactant to help to control the printing ink fluid.So it is favourable that at least a surfactant is impregnated in the hole of microporous substrate.The coating of surfactant can be used as separately and independent step is carried out, or is incorporated in the step with the organic metal salt knot and is coated on the base material, except that anhydrating and/or organic solvent, provides the surface of the particular fluid component that is particularly suitable for pigment-based ink jet subsequently.

Surfactant can be cation, anion, nonionic or zwitterionic surfactant.Many surfactants of every type all are available to those skilled in the art.Therefore, can use the combination of any surfactant or surfactant even the polymer of substrate hydrophilic can be provided, but this not preferred.

These surfactants comprise but are not limited to fluorine chemical, silicone and alkyl surfactant that described surfactant can be anionic or non-ionic.And non-ionic surface active agent can use separately or mix use with another kind of anion surfactant in water and/or organic solvent or solvent, and described organic solvent is selected from alcohols, ethers, amide-type, ketone etc.

Can use various types of non-ionic surface active agents, include but not limited to Co., Wilmington, the ZONYL fluorohydrocarbon of DE such as ZONYL FSO available from E.I.du Pont deNemours and; FLUORAD FC-170 or 171 surfactants available from MinnesotaMining Manufacturing Company; Available from BASFCorp.Chemicals Division, Mount Olive, the block copolymer PLURONIC of the ethene of NJ and propylene oxide and ethylene glycol; Available from ICI Americas, Inc., Wilmington, the polyoxyethylene sorbitan fatty acid esters TWEEN of DE; Available from Rohm and Haas Co., Philadelphia, the TRITON X series of the Octylphenoxy multi-ethoxyl alcohol of PA; Available from Air products and Chemicals, Inc., Allentown, the tetramethyl decynediol of PA (tetramethyl decynediol) SURFYNOL; With available from Union Carbide Corp., Danbury, the SILWET L-7614 of CT and L-7607 silicon surface active agent, these surfactants are all understood by those skilled in the art.

Useful anion surfactant includes but not limited to alkali metal salt and (alkyl) ammonium salt: 1) alkyl sulfate and sulfonate such as lauryl sodium sulfate and dodecyl sodium sulfonate potassium; 2) sulfate of the polyethoxylated derivative of straight or branched aliphatic series alcohol and carboxylic acid; 3) alkylbenzene or alkylnaphthalene sulfonate and sulfate such as sodium lauryl benzene sulfonate; 4) ethoxylation and alkyl polyethoxylated and aralkyl alcohol carboxylate; 5) Glycinates such as alkyl sarcosine salt and p dialkylaminobenzoic acid salt; 6) sulfosuccinate comprises dialkyl sulfosuccinates; 7) isethionic acid salt derivative; 8) N-acyl group taurine derivatives (N-acyltaurine derivatives) is as N-methyl-N-oil base sodium taurocholate; 9) both sexes alkyl carboxylate such as both sexes propionate and alkyl and aryl betaine, optional by oxygen, nitrogen and/or sulphur atom replacement; With 10) sodium salt of the dodecyl alcohol phosphate of alkyl phosphate monoester or diester such as ethoxylation.

Useful cationic surfactant comprises having formula C _nH _2n+1N (CH ₃) ₃The alkylammonium salt of X, wherein, X is OH, Cl, Br, HSO ₄Or the combination of OH and Cl, wherein n is the integer of 8-22; Formula C _nH _2n+1N (C ₂H ₅) ₃The alkylammonium salt of X, wherein, n is the integer of 12-18; The double structure surfactant for example has those of following formula: [C ₁₆H ₃₃N (CH ₃) ₂C _mH _2m+1] X, wherein m is the integer of 2-12, X is according to top definition; Aralkyl ammonium salt such as benzene are pricked ammonium salt; With cetyl ethyl piperidine salt, for example C ₁₆H ₃₃N (C ₂H ₅) (C ₅H ₁₀) X, wherein, X is according to top definition.

The amount ranges of the multivalence organic metal salt that is used for flooding microporous substrate of the present invention and uses at intermediate is 0.1-50% (weight), is preferably 0.5-20% (weight).

Be used for flooding microporous substrate of the present invention and be 0.01-10% (weight), be preferably 0.1-5% (weight) in the dosage of surfactant scope that intermediate uses.

Randomly, accept to use in the medium organic bond at printing ink of the present invention.Organic bond solubilized or be dispersed in the water makes them be easy to be added to the midbody composite that is used for applying porous base material preferably, forms printing ink of the present invention and accepts medium.The non-limitative example of such organic bond comprises acrylic emulsion, styrene-propene yogurt liquid, polyvinyl alcohol, polyvinyl alcohol/acrylic acid mixture and their combination etc.The amount of such organic bond in coating or intermediate solution is the 0.1-50% of coating or intermediate solution gross weight, is 1-30% preferably, and coating or intermediate solution comprise the water and/or the organic solvent of surfactant and slaine and surplus.

Randomly, accept to use opaque pigment in the medium at printing ink of the present invention.The unrestricted example of such opaque pigment comprises TiO 2 pigment, barium sulfate pigment etc.Opaque pigment amount in coating solution is 0.01-50% (weight), is 1-30% (weight) preferably.

Randomly, accept to use heat stabilizer or UV light stabilizing agent in the medium at printing ink of the present invention.The unrestricted example of such additive comprises the Corp. available from Ciba Specialty Chemicals, Tarrytown, the TINUVIN 123 of NY or 622LD or CHIMASSORB 944 (hindered amine light stabilizer); With UVINUL 3008 available from BASFCorporation Chemicals Division.The amount of such stabilizing agent in coating that is impregnated into microporous substrate or intermediate solution is 0.1-10% (weight) in 0.2-20% (weight) scope preferably, more preferably 0.5-5% (weight).

Randomly, accept to use in the medium UV absorbers at printing ink of the present invention.The unrestricted example of such UV absorbers comprises the TINUVIN II30 or 326 of Ciba Specialty Chemicals Corp.; UVINUL 405011 available from BASF Corporation; With available from Sandoz Chemicals, Charlotte, the SANDUVOR VSU or 3035 of NC.The amount of such absorbent in coating or intermediate solution is 1-10% (weight) in 0.01-20% (weight) scope preferably.

Randomly, accept to use in the medium antioxidant at printing ink of the present invention.The unrestricted example of good oxidant like this comprises the IRGANOX 1010 or 1076 available from Ciba Specialty Chemicals Corp.; With UVINUL 2003 AD available from BASF CorporationChemicals Division.

The amount of such antioxidant in coating or intermediate solution is 0.4-10% (weight) in 0.2-20% (weight) scope preferably, more preferably 0.5-5% (weight).

Printing ink of the present invention is accepted medium and is had two opposed major surfaces, is used in printing (for example, passing through ink-jet method) on these two surfaces.Randomly, first type surface image of being used for finishing be adhered to stayed surface such as building walls, floor or ceiling, truck sidewall, billboard or show be used to educate, the high quality image of amusement or information Anywhere.

3M company provides various image receptor mediums, and develops a series of pressure-sensitive adhesion agent prescriptions, can be used for the first type surface with the imaging surface opposite.These adhesives are disclosed in United States Patent (USP) 5,141,790 (people such as Calhoun), 5,229,207 (people such as Paquette), 5,800,919 (people such as Peacock), 5,296,277 (people such as Wilson), 5,362,516 (people such as Wilson); EPO patent disclosure EP 0 570 515 B1 (people such as Sreelamn) and PCT patent application WO 97/31076 (people such as Peloquin) and WO 98/29516 (people such as Sher).

These adhesive surfaces all will be with peeling off wadding or deposit wadding protection, as Rexam Release, and BedfordPark, those that IL sells.Replace adhesive can use mechanical fixed part, if accept the corresponding main surfaces of medium with the present invention that is added to of certain known way.The unrestricted example of mechanical fixed part comprises hook and ring, as the Velcro of disclosed PCT kind application WO 98/39759 (Loncar) announcement ^TM, Scotchmate ^TMAnd DualLock ^TMFixed system.

Of the present invention than in the good model, flood microporous substrate by using organic metal salt and suitable surfactant, and carry out 100-120 ℃ of drying subsequently on request.After the acceptor drying, use commercially available printer, adopt conventional ink-jet imaging technique to carry out imaging.

The dipping of multivalence organic metal salt can be finished by dissolving or salt-mixture or salt and surfactant in the mixture of deionized water or pure and mild deionized water.Available conventional equipment of the dipping of solution and technology are carried out, for example slit feed scraper, rotogravure device, padding, dipping, spraying etc.Preferably the multivalence organic metal salt is filled substrate pores and is not had significant quantity to stay on the surface.Excessive solid can stop up hole, can besmirch when causing forming image thus and drying time long.Coating weight depends on porosity, thickness and the chemical property of base material, but can easily determine by conventional optimization.Common wet coating weight is about 1-500 gram/rice ², better be to be about 10-50 gram/rice ², be more preferably and be about 15-30 gram/rice ²Can be before dipping printing ink be accepted intermediate, during or add optional additive afterwards.

Printing industry had been used dye-based ink in the past, although the use of pigment based ink is more and more general.When using out of doors, because its durability and UV stable use pigment colorant to be better than the dye coloring agent.

In addition, printing ink of the present invention is meant water-based inks but not solvent-based ink.Owing to environment and healthy reason and some other reason, be preferably water-based inks in the printing industry at present.

Minnesota Mining and Manufacturing Company has made a large amount of outstanding pigment-based ink jet inks that are used for thermal ink jet printers.8551,8552,8553 and 8554 serial pigment based ink jet inks are arranged in these products.The use of four kinds of main color cyans, magenta, yellow and black makes can form 256 kinds or more colors in digital image.In addition, pigment-based ink jet inks and component thereof are also made by other producer, comprise Hewlett-Packard and E.I.du Pont deNemous and Co., and many other companies that are distributed in many commerce and trade field also are devoted to image and sign industry.

Metal ion functionalized silica surface of the present invention can be caught and flocculate or condense pigment based ink or colouring agent, and therefore colouring agent is fixed on the silica surface.This performance makes the metal ion functionalized silica surface of the present invention be especially suitable for use as ink receptors.

Embodiment

In the following embodiments, unless otherwise noted, term " part " refers to weight portion.

Use derives from the HP Designjet 2500 CP thermal ink jet printers of Hewlett-Packard, with printing ink (print cartridge C1806A, C1807A, C1808A, the C1809A) use of this manufacturer recommendation.Believe that above-mentioned black, yellow, magenta and cyan ink are pigment based ink.

For reproducing the result who is obtained, below the definite performance of the image printed among the embodiment unimportant.The image that uses is code test image (for example, CCL, ring test, a light image etc.).

The washability test

Estimate the washability of printing rear film, film is placed the tap below (25-30 ℃) of the multipurpose tank of open fully running.With the imaging film of paper handkerchief wiping humidity up to doing.If what do not take place to pick out besmirches or color density reduction, then washability pass the test.Unless otherwise noted, use available from Gretag-Macbeth, Gastonia, the GRETAG M50 REFLECTANCE SPECTROPHOTOMETER of NC measures color density loss percentage.

Embodiment 1

Use derives from RD Specialties, Webster, the #4Meyer Rod of NY is with film (the CHANGEABLE OPAGUE IMAGING MEDIA 8522CP of composition-I flow coat at filling silica, available from MinnesotaMining and Manufacturing Company) on, make nominal thickness and be 0.0091 millimeter wet coating.Base material after the coating provided printing ink to accept medium at 120-130 ℃ of dry 1-2 minute.When using HP Designjet2500cp thermal ink jet printers to carry out imaging, obtain very high density, high-quality dry at once image.The anti-finger of this image besmirches, and have good edge and define (edge definition) (do not have can notice line edge scared), and perusal meets the washability test.

Composition-I

Component	Part
Component	Part	Sulfosalicylic phthalate aluminium (III) (organic metal salt)	10
Dihexyl sulfosuccinic acid-sodium salt (surfactant)	6		10
Dihexyl sulfosuccinic acid-sodium salt (surfactant)	6	PVP/acrylic acid (PVP/AA) (75: 25) (adhesive)	2
Isopropyl alcohol	25	PVP/acrylic acid (PVP/AA) (75: 25) (adhesive)	2
Isopropyl alcohol	25	Deionized water	57

Embodiment 2

At half surperficial upper reaches coating combination-I (as described in example 1 above) of 24 inches * 16 inches (61 * 41 centimetres) TESLIN film substrates, second half is not coated with.Base material after the coating is accepted medium according to the top described dry printing ink that forms.As mentioned above, on the base material of drying, carry out imaging, obtain the image of very high color density with HP Designjet 2500cp thermal ink jet printers.Be higher than image on the non-coated surface in the density of the image of coated portion.Substrate layer after the imaging is pressed on aluminium sheet/backing (notice board), and carries out the washability test.Image on uncoated TESLIN film substrate is washed off.Image fades very obvious, with the naked eye just can observe.Image (the present invention) at the TESLIN film surface that is coated with does not have tangible color and luster loss (about 1%), washability pass the test.

Embodiment 3

Repeat the step of embodiment 2, difference is, the dihexyl sulfosuccinic acid sodium salt of cancellation composition-I replaces the deionized water of equivalent.Image on coated substrate is the very high image of density, and this image does not besmirch with line edge scared, and just black and the green at the about 5-10% of washability duration of test loses.

Embodiment 4

Repeat the step of embodiment 2, difference is, the PVP/AA adhesive of cancellation composition-I replaces the deionized water of equivalent.Image on coated substrate is the very high image of density, and this image does not besmirch with line edge scared, just more black occur in surface top layer, and black and the green of the about 5-10% of washability duration of test loses.

Embodiment 5

Repeat the step of embodiment 2, difference is, PVP/AA adhesive and the dihexyl sulfosuccinic acid sodium salt of cancellation composition-I replace the deionized water of equivalent.Image on coated substrate is the very high image of density, and this image does not besmirch with line edge scared, just more black occur in surface top layer, and have some pigment Cheng Zhu and with some little be with coalescent.In the washability test, the black of about 5-10% and green loss.

Embodiment 6

Repeat the step of embodiment 2, difference is with the sulfosalicylic phthalate aluminium (III) among sulfosalicylic phthalate two aluminium (III) replacement composition-I.The result has increased the aluminium amount in the composition.Image on coated substrate is the very high image of density, and this image does not besmirch with line edge scared.Yet the image after the printing is dry slightly poor than embodiment 2, in the washability test, and the redness of about 5-10% and green loss.

Embodiment 7

Repeat the step of embodiment 2, difference is with the sulfo group phthalic acid aluminium (III) among sulfo group phthalic acid three aluminium (III) replacement composition-I.The result has increased the aluminium amount in the composition.Image on coated substrate show printing ink Cheng Zhu, coalescent, line edge is scared, besmirch, and print image is moist.In the washability test, the redness of about 30-40% and green loss.

Embodiment 8

Described according to embodiment 1, composition-II flow coat is being filled on the film of silica, make nominal thickness and be 0.0091 millimeter wet coating.Base material after the coating forms printing ink and accepts medium according to embodiment 1 described drying.When using HP Designjet 2500cp thermal ink jet printers to carry out imaging, this printing ink is accepted medium very high density, high-quality dry at once image is provided.This image does not besmirch, does not have line edge scared, tests by washability basically.In embodiment 1-8, the image on the uncoated part of base material is washed off (defective) in Water Resistance Test.Composition-II

Component	Part
Component	Part	Four (sulfosalicylic phthalate) zirconium (organic metal salt)	9
Dihexyl sulfosuccinic acid-sodium salt (surfactant)	6		9
Dihexyl sulfosuccinic acid-sodium salt (surfactant)	6	Isopropyl alcohol	25
Deionized water	58	Isopropyl alcohol	25

Embodiment 9

At half surperficial upper reaches coating combination-II (as described in example 1 above) of 24 inches * 16 inches (61 * 41 centimetres) TESLIN film substrates, second half is not coated with.Base material after the coating is accepted medium according to the top described dry printing ink that forms.As mentioned above, on the base material of drying, carry out imaging, obtain the image of very high color density with HP Designjet 2500cp thermal ink jet printers.Be higher than image on the non-coated surface in the density of the image of coated portion.Base material after the imaging is superimposed upon aluminium sheet/backing (notice board), and carries out the washability test.Image 90% on non-coated surface is washed off.Image (the present invention) in coated portion does not have tangible color and luster loss (about 3-5%), washability pass the test.

Embodiment 10

Repeat the step of embodiment 9, difference is to replace four (sulfosalicylic phthalate) zirconium with four (sulfosalicylic phthalate) titanium.The image class of image quality after the printing and embodiment 9 seemingly.After the washability test, the image on non-coated surface is washed off, and the visual 10-20% of base material coated portion is washed off.

Embodiment 11

Repeat the step of embodiment 9, difference is to replace four (sulfosalicylic phthalate) zirconium with sulfosalicylic acid copper (II).The image class of image quality after the printing and embodiment 9 seemingly.After the washability test, the image of the uncoated part of base material is washed off, and the about 5-10% of the image of base material coated portion is washed off.

Embodiment 12

Composition-III flow coat on CHANGEABLE OPAGUE IMAGING MEDIA 8522CP film, is formed the about 0.0091 millimeter wet coating of nominal thickness, accept medium according to embodiment 1 described formation printing ink then.Accept to carry out on the medium imaging with HP Designjet 2500cp thermal ink jet printers at printing ink, this printing ink is accepted medium very high density, high-quality dry at once image is provided, this image does not besmirch, does not have line edge scared, tests by washability.

Composition-III

Component	Part
Component	Part	Sulfosalicylic phthalate magnesium (organic metal salt)	10
Dihexyl sulfosuccinic acid-sodium salt (surfactant)	6	Sulfosalicylic phthalate magnesium (organic metal salt)	10
Dihexyl sulfosuccinic acid-sodium salt (surfactant)	6	PVP/AA (75: 25) (adhesive)	2
Isopropyl alcohol	25	PVP/AA (75: 25) (adhesive)	2
Isopropyl alcohol	25	Deionized water	57

Embodiment 13

At half surperficial upper reaches coating combination-III (as described in example 1 above) of 24 inches * 16 inches (61 * 41 centimetres) TESLIN film substrates, second half is not coated with.Base material after the coating is accepted medium according to the top described dry printing ink that forms.As mentioned above, on the base material of drying, carry out imaging, obtain very highdensity image with HP Designjet 2500cp thermal ink jet printers.Be higher than image on the non-coated surface in the density of the image of coated portion.Base material after the imaging is superimposed upon aluminium sheet/backing (notice board), and carries out the washability test.Image 90% on non-coated surface is washed off.Image (the present invention) in coated portion has a spot of color and luster loss (about 10-15%), and the washability test is qualified substantially.

Embodiment 14

Described according to embodiment 1, composition-IV flow coat on the TESLIN film, is formed the about 0.0091 millimeter wet coating of nominal thickness, accept medium according to embodiment 1 described formation printing ink then.When printing ink was accepted to carry out imaging on the medium, this printing ink was accepted medium high density, high-quality is provided with HP Designjet2500cp thermal ink jet printers, and the image of Ganing at once has the printing ink Cheng Zhu of significant quantity and coalescent on this image.Composition-IV

Component	Part
Component	Part	Aluminum sulfate, 14H ₂O (inorganic salts)	3
Dihexyl sulfosuccinic acid-sodium salt (surfactant)	6	Aluminum sulfate, 14H ₂O (inorganic salts)	3
Dihexyl sulfosuccinic acid-sodium salt (surfactant)	6	PVP/AA (75: 25) (adhesive)	2
Isopropyl alcohol	25	PVP/AA (75: 25) (adhesive)	2
Isopropyl alcohol	25	Deionized water	64

Embodiment 15 (comparative example)

At half surperficial upper reaches coating combination-IV (as described in example 1 above) of 24 inches * 16 inches (61 * 41 centimetres) TESLIN film substrates, second half is not coated with.Base material after the coating is accepted medium according to the top described dry printing ink that forms.As mentioned above, on the base material of drying, carry out imaging, obtain very highdensity image with HP Designjet 2500cp thermal ink jet printers.Be higher than image on the non-coated surface in the density of the image of coated portion.Base material after the imaging is superimposed upon aluminium sheet/backing (notice board), and carries out the washability test.Image on two parts is all washed off 75-85%.

Embodiment 16

Repeat the step of embodiment 15, difference is to add sulfosalicylic phthalate (9.6 parts) in 93.4 parts of composition-IV.The image class of image quality after the printing and embodiment 15 seemingly.But, visual color and luster loss in the washability test of 20-30% is only arranged approximately.This significantly improves and shows the advantage of using organic metal salt of the present invention.

Embodiment 17

Repeat the step of embodiment 15, difference is to add phthalic acid (4.5 parts, aluminum sulfate-phthalic acid mol ratio is 1: 3) in 95.5 parts of composition-IV.The image class of image quality after the printing and embodiment 15 seemingly.But, visual color and luster loss in the washability test of 10-20% is only arranged approximately.This significantly improves and shows the advantage of using organic metal salt of the present invention.

Embodiment 18

Repeat the step of embodiment 15, difference is to add 1,2 in 94.3 parts of composition-IV, 4-benzene tricarbonic acid (5.7 parts, aluminum sulfate-tricarboxylic acids mol ratio is 1: 3).Carry out the washability test subsequently, the visual color and luster loss of 20-30% is only arranged approximately, some scared phenomenons also take place.This significantly improves and shows the advantage of using organic metal salt of the present invention.

Embodiment 19

Described according to embodiment 1, composition-I flow coat is filled on the base film (the HDPE film of the filling silica of being buied by Texwipe Co.) of silica at TEXWRITE MP-10, carry out drying as embodiment 1 then, form printing ink and accept medium.According to accepting to carry out on the medium imaging at printing ink described in the embodiment 1, the image class of image quality that provides and embodiment 1 seemingly.About 5-7% image is washed off in the washability test.

Embodiment 20

Repeat the step of embodiment 1, difference is to use the TESLIN film as base material.The image quality of sample is identical with embodiment 1 with washability.

Embodiment 21

Repeat the step of embodiment 8, difference is to use the TESLIN film as base material.The image quality of sample is identical with embodiment 1 with washability.

The present invention is not limited to the foregoing description.

Claims

1. a printing ink is accepted medium, comprises:

Microporous substrate with filling silica of silica surface;

Multivalence organic metal salt on the silica surface of the microporous substrate of filling silica.

2. printing ink as claimed in claim 1 is accepted medium, it is characterized in that described printing ink accepts the surfactant on the silica surface that medium also is included in the microporous substrate of filling silica.

3. printing ink as claimed in claim 2 is accepted medium, it is characterized in that described printing ink accepts the adhesive on the silica surface that medium also is included in the microporous substrate of filling silica.

4. printing ink as claimed in claim 1 is accepted medium, it is characterized in that described multivalence organic metal salt is selected from the sulfo group phenol slaine with following formula: Wherein, when M was Cu, Mg, Zn, Ca or Co, the ratio of x: y was 1: 2, and when M was Al, Ga, B, the ratio of x: y was 1: 3 or 2: 3;

Hydroquinone sulfonic acid slaine with following formula:

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

Metallic dixhydroxybenzenedisulfonates with following formula: Wherein, when M was Cu, Mg, Zn, Ca or Co, the ratio of x: y was 1: 2 or 2: 2, and when M was Al, Ga, B, Ti, Zr or Hf, the ratio of x: y was 1: 1,1: 3,2: 2 or 4: 3;

Sulfosalicylic acid slaine with following formula: Wherein, when M was Cu, Mg, Zn, Ca or Co, the ratio of x: y was 1: 2 or 1: 1; When M was Al, Ga, B, Ti, Zr or Hf, the ratio of x: y was 1: 3,2: 3 or 3: 3; R is-COOH (Li, Na or K);

Sulfo group phthalic acid slaine with following formula: Wherein, when M was Cu, Mg, Zn, Ca or Co, the ratio of x: y was 3: 2,2: 2 or 1: 1, and when M was Al, Ga, B, Ti, Zr or Hf, the ratio of x: y was 1: 3,2: 2 or 2: 3; R ¹Be H or-COOH (Li, Na or K); R ²Be-COOH (Li, Na or K); With

Metal carboxylate with following formula: Wherein, when M was Cu, Mg, Zn, Ca or Co, the ratio of x: y was 1: 1,2: 2 or 3: 2, and when M was Al, Ga, B, Ti, Zr or Hf, the ratio of x: y was 1: 3,2: 2 or 2: 3; R ¹Be H or COOH (Li, Na or K); R ²Be COOH (Li, Na or K).

5. printing ink as claimed in claim 1 is accepted medium, it is characterized in that described multivalence organic metal salt is sulfosalicylic phthalate magnesium, sulfosalicylic phthalate copper, sulfosalicylic phthalate zirconium, phthalic acid zirconium, sulfosalicylic phthalate aluminium, sulfoisophthalic acid aluminium or their combination.

6. printing ink as claimed in claim 2 is accepted medium, it is characterized in that described surfactant is the mixture of nonionic, cationic, anionic or anionic and nonionic surface active agent.

7. printing ink as claimed in claim 2 accepts medium, it is characterized in that described surfactant is an anionic.

8. printing ink as claimed in claim 6 is accepted medium, it is characterized in that described anionic surfactant is dihexyl sulfosuccinic acid-sodium salt.

9. printing ink as claimed in claim 3 is accepted medium, it is characterized in that described adhesive is selected from acrylic emulsion, styrene-propene yogurt liquid, polyvinyl alcohol, polyvinyl alcohol/acrylic acid combination or their combination.

10. printing ink as claimed in claim 1 is accepted medium, it is characterized in that the microporous substrate of described filling silica has the hole that the aperture is the 0.02-0.5 micron.

11. a printing ink is accepted medium/printing ink tackling, comprises the filling silica microporous substrate with silica surface and the multivalence organic metal salt on the silica surface of described base material, and the printing ink that comprises pigment colorant.

12. printing ink as claimed in claim 11 is accepted medium/printing ink tackling, the silica surface that it is characterized in that described microporous substrate also comprises surfactant thereon.

13. printing ink as claimed in claim 12 is accepted medium/printing ink tackling, it is characterized in that described multivalence organic metal salt is sulfosalicylic phthalate magnesium, sulfosalicylic phthalate copper, sulfosalicylic phthalate zirconium, phthalic acid zirconium, sulfosalicylic phthalate aluminium, sulfoisophthalic acid aluminium or their combination.

14. printing ink as claimed in claim 13 is accepted medium/printing ink tackling, it is characterized in that described surfactant is an anionic surfactant.

15. a printing ink is accepted the medium intermediate, comprising:

The Aquo-composition that comprises organic metal salt at the silica surface of the microporous substrate of filling silica.

16. printing ink as claimed in claim 15 is accepted the medium intermediate, it is characterized in that described intermediate also comprises surfactant.

17. printing ink as claimed in claim 16 is accepted the medium intermediate, it is characterized in that described intermediate also comprises organic solvent.

18. printing ink as claimed in claim 17 is accepted the medium intermediate, it is characterized in that described intermediate also comprises organic bond.

19. printing ink as claimed in claim 16 is accepted the medium intermediate, it is characterized in that described multivalence organic metal salt is sulfosalicylic phthalate magnesium, sulfosalicylic phthalate copper, sulfosalicylic phthalate zirconium, phthalic acid zirconium, sulfosalicylic phthalate aluminium, sulfoisophthalic acid aluminium or their combination.

20. printing ink as claimed in claim 19 is accepted the medium intermediate, it is characterized in that described surfactant is an anionic surfactant.

21. printing ink as claimed in claim 1 is accepted medium, has image at described silica surface.

22. the printing ink of imaging as claimed in claim 21 is accepted medium, it is characterized in that described image is the printing ink ink jet image.

23. the printing ink of imaging as claimed in claim 21 is accepted medium, it is characterized in that described image is a washability.

24. a method that makes the ink receptors imaging comprises the following steps: to use ink jetting head to accept dielectric surface at printing ink and uses printing ink, described printing ink is accepted the microporous substrate that medium comprises the filling silica with silica surface; With the multivalence organic metal salt on the silica surface of the microporous substrate of filling silica.