CN1693384A - Multi-density ink-jet ink set for ink-jet printing - Google Patents

Abstract

A multi-density ink-jet ink set comprising two black ink compositions and at least three colour inks, wherein the first black ink composition has a lightness L* in the range of 35 to 65 as calculated from the spectral transmittance of a 1000-fold dilution of the first black ink composition, and the second black ink composition has an lightness L* value in the range of 70 to 100 as calculated from the spectral transmittance of a 1000-fold dilution of the second black ink composition. A method for ink-jet printing is also disclosed.

Description

The multi-density ink-jet ink sets that is used for ink jet printing

Technical field

[0001] the present invention relates to the composition for ink of ink jet printing, more specifically, the present invention relates to the multi-density ink-jet ink sets.

Background technology

[0002] when ink jet printing, small ink fluid dripped to be directly injected to be subjected on the black surface, printing equipment be subjected to do not have physics to contact between the black body.This printing equipment has stored printed data in the electronics mode, and controls a mechanism and ink droplet is ejected into image mode is subjected to Mo Tishang.Allow print head move to cross be subjected to black body can realize printing, or vice versa.About the early stage patent of ink-jet printer comprises US 3 739 393 (MEAD CORP), US 3 805273 (MEAD CORP) and US 3 891 121 (MEAD CORP).

[0003] there are several different approach can realize spraying ink droplet.In being referred to as the first kind method of continuous ink jet printing, the hole of print head is applied a pressure wave pattern, the ink stream that sprays from its hole is broken into even size and ink droplet at interval, if wish that these ink droplets can be with or without static charge.In a specific embodiments, make charged ink droplet deflect into accumulator tank by electric field, the not deflection of uncharged ink droplet falls being subjected to Mo Tishang simultaneously, forms image.In another embodiment, charged just ink droplet is fallen and is subjected to Mo Tishang, form image, and uncharged ink droplet is recovered.

[0004], can produce ink droplet according to " drop on demand ink jet " method (DOD) according to second class methods.Drop on demand ink jet equipment is that they need be on being subjected to black body just spray ink droplet during imaging, thereby has avoided ink droplet electrically charged, the complicacy of reflection hardware and ink collection.In the ink jet printing of drop on demand ink jet, mechanical movement (so-called " piezoelectricity " method) by piezoelectric transducer, or, can form ink droplet by the discontinuous pressure surge that picks moving (so-called " bubble type ink-jet " method, or " heat-sensitive type ink-jet " method) generation.

Should understand easily that [0005] the best of ink is formed the ink ejecting method that depends on employing, also depends on the character that is subjected to black body to be printed.

[0006] this ink is formed and roughly can be divided into following a few class:

Water base, its dry mechanism relates to absorption, infiltration and evaporation;

Oil base, its drying relate to absorption and infiltration;

The solvent base, its dry mechanism relates generally to evaporation;

Hot melt or phase transformation, its ink inside are liquid under injection temperature, and at room temperature are solids, and wherein replace dry by solidification;

UV-solidifies, and wherein replaces dry by polymerization.

[0007] in most of ink jet printings are used, printed images is the finished product of terminal user when handling.Be this situation in so-called proof is used for example, wherein the human consumer wishes this image of preview before using the extensive printing of printing press.Several proof technology are adoptable, but because the advantage of speed, cost and image true reappearance when adopting press printing, so ink-jet is just becoming most preferred process choice.Adopt the multi-density ink-jet ink sets can realize this image true reappearance.The multi-density ink-jet ink sets has adopted has roughly same form and aspect and the combination of the ink for ink-jet print of different colourity and brightness.Use the same tinting material or the use of different concns to have the roughly different colorant of same form and aspect, can prepare these ink for ink-jet prints.

[0008] US 6 670 409 (SEIKO EPSON) has provided a kind of like this multi-density ink-jet ink sets embodiment, this patent disclosure the inkjet recording ink group, comprising the light color inks of many colors, every kind of light color inks has at least a pigment, water and thin polymer particles; The dark color inks of many colors, every kind of dark color inks has at least a pigment and water, and wherein every kind of dark color inks or do not contain thin polymer particles perhaps contains thin polymer particles, and its amount is lower than any described light color inks.In US 6 670 409 (SEIKO EPSON), this inkjet recording ink group can be used for not needing to make the replacing operated system of this ink and recording medium to be used coupling.When this ink group is used to print common paper, can use four kinds of colors of these dark color inks, and for dedicated paper, can use three kinds of colors of these light color inks, wherein black colored three kinds of composite blacks that color constitutes that use by these light color inks.

[0009] EP 1 176 177A (SEIKO EPSON) disclose a kind of ink group, and it comprises first black ink composition and second black ink composition, wherein brightness (the L of first black ink composition ^*) be the 1-30 that calculates by the spectral-transmission favtor of 1000 times of described first black ink composition dilutions, and the L of second black ink composition ^*Value is, the 35-80 by the spectral-transmission favtor of 1000 times of described second black ink composition dilutions calculates also contains special tinting material.Adopt this two kinds of black ink compositions, can print the pattern of the different levels from black to white, have the light resistance of improvement and the graininess of reduction simultaneously.

[0010] EP 1 132 441A (SEIKO EPSON) disclose a kind of ink group, it comprises the dye ink and the paint ink of combination, wherein contain the multiple identical form and aspect that have, but at least a form and aspect have the ink of different densities, and at least a low density inks contains adding pigment wherein as tinting material.EP 1 132 441A (SEIKO EPSON) point out the combination of sole pigment ink (at least a light colour ink contains a kind of pigment as tinting material) and dye ink, and making might provide high image quality, high degree of anti-wiping the and high light resistance simultaneously.

[0011] US 20030008938 (SEIKO EPSON) discloses a kind of ink, it comprises dark colored inks water composition and light color composition for ink, their color is mutually the same, and colour density is not simultaneously, this ink is characterised in that dark colored inks water composition and every kind of pigment that all contains as tinting material of light color composition for ink, with the resin as dispersion agent, its feature also is in the dark colored inks water composition, this weight resin ratio B ₁With this pigment weight ratio P ₁Ratio (be B ₁/ P ₁) be lower than this weight resin ratio B in the light color composition for ink ₂With this pigment weight ratio P ₂Ratio (be B ₂/ P ₂), its feature also is B ₁With B ₂Be differing from each other.In addition, use pigment as tinting material, the image that obtains has outstanding photostabilization.

[0012] US 20030226473 (SEIKO EPSON) discloses a kind of ink group, it comprises at least a black ink composition that contains black pigment, with the light black composition for ink that contains black pigment, the black pigment concentration of this composition is lower than the pigment concentration of described black ink composition, and the ratio of the pigment concentration in the pigment concentration in the wherein this black ink composition and this light black composition for ink is 2-4.5.Because of light source different cause that the aberration of document image has reduced, the color reproduction scope broadening of image dark-part keeps high picture quality simultaneously, worsens situation at these dark-parts without any graininess.

[0013] use the multi-density ink to obtain and improved some performances, for example generation of color and light resistance, but simultaneously owing to increase the ink usage quantity during printing, consumption of ink improves, and produces some new problems like this.Higher quantity of ink can cause that ink is coalescent, bleeding and feathering problem.

[0014] therefore, people wished very once that a kind of ink jet printing method that uses the multi-density ink-jet ink sets was arranged, and the consumption of ink of this method is low, so obtain not having the image of picture quality defective, described picture quality defective for example is coalescent, bleeding and feathering.

Purpose of the present invention

[0015] the purpose of this invention is to provide a kind of multi-density ink-jet ink sets, it has low consumption of ink and dyeing time faster.

[0016] another object of the present invention provides a kind of method of ink jet printing, and this method obtains the image of high image quality, and this image has low coalescent, the good colorrendering quality and the light resistance of improvement.

[0017] other purpose of the present invention will become apparent from following explanation.

Brief description of the present invention

[0018] once was surprisingly found out that, and use the resulting color of black ink as much as possible that consumption of ink is reduced, and image fade died down.People expected once also that these black pigments had higher brightness because of the pigment and/or the dyestuff of low concentration.

[0019] use the multi-density ink-jet ink sets can realize purpose of the present invention, described multi-density ink-jet ink sets contains two kinds of black ink compositions and at least three kinds of color inks, wherein the brightness L of first kind of black ink composition ^*Value is, the 35-65 that is calculated by the spectral-transmission favtor of 1000 times of described first kind of black ink composition dilutions, and the brightness L of second kind of black ink composition ^*Value is, the 70-100 that is calculated by the spectral-transmission favtor of 1000 times of described second kind of black ink composition dilutions.

[0020] adopt a kind of ink jet printing method also can realize purpose of the present invention, this method comprises the steps:

(a) provide as previously defined multi-density ink-jet ink sets;

(b) ink for ink-jet print of described multi-density ink-jet ink sets is ejected into is subjected to Mo Tishang.

[0021] other advantage of the present invention and embodiment will become apparent by following explanation and see.

Disclosure of the present invention

Definition

[0022] the open term " ink-jet ink sets " that uses when of the present invention means the combination of two kinds of black inks and at least three kinds of color inks, for example magenta ink (M), cyan (C) and yellow ink (Y).

[0023] the open term " multi-density ink-jet ink sets " that uses when of the present invention means that as previously defined ink-jet ink sets it comprises that at least a form and aspect are roughly the same, and the combination of the colourity ink for ink-jet print different with brightness.

[0024] the open term " dyestuff " that uses when of the present invention means a kind of tinting material, is 10mg/L or more than the 10mg/L with its solubleness under relevant envrionment conditions in the medium of coating.

[0025] in DIN 55943 (this paper is referenced by reference it), term " pigment " is defined as inorganic or organic, coloured or non-coloured tinting material, under relevant envrionment conditions, in fact it be insoluble in the coated media, and therefore solubleness therein is less than 10mg/L.

[0026] the open term " filler " that uses when of the present invention means the inorganic or organic materials that exists in ink jet recording materials, this material is in order to change its performance, the adhesivity of supplementary layer and polyester film for example, ink jet recording materials opacity and antistatic property.

[0027] the open term " graininess " that uses when of the present invention means in document image the discharge inkblot that can identify by visual means.

[0028] the open term " UV " that uses when of the present invention is the abbreviation of uv-radiation.

[0029] the open term " uv-radiation " that uses when of the present invention means the electromagnetic radiation of wavelength 4-400nm.

[0030] the open term " actinic radiation " that uses when of the present invention means and can cause photochemically reactive electromagnetic radiation.

[0031] term " non-absorbent substantially ink-jet is subjected to black body " means that any ink-jet is subjected to black body, and it satisfies at least one standard in following two standards:

1) ink bleed is subjected to the black body degree of depth to be no more than 2 μ m to ink-jet;

2) being ejected in the 100pL ink droplet that ink-jet is subjected to Mo Tishang no more than 20% ink droplet disappeared in ink-jet and is subjected to Mo Tizhong in 5 seconds.If one or more coating layers are arranged, its dried thickness should be less than 5 μ m.Those skilled in the art can adopt standard method of analysis to determine to be subjected to black body whether to fall into above-mentioned two and non-absorbently substantially be subjected to black body standard.For example, can get a slice and be subjected to black body, adopt transmission electron microscope research whether to measure the ink bleed degree of depth greater than 2 μ m with after ink jet is on being subjected to black surface.Can obtain the more information of relevant suitable analysis method: DESIE in following article, G waits the people, substrate performance is to the influence of drop on demand ink jet printing, " the 18th nonimpact printing imaging science and technology international conference procceedings ", 2002, the 360-365 page or leaf.

[0032] term " alkyl " means any possibility variant of each carbonatoms in this alkyl group, promptly for three carbon atoms: n-propyl and sec.-propyl; For four carbon atom: normal-butyl, isobutyl-and the tertiary butyl; For five carbon atoms: n-pentyl, 1,1-dimethyl-propyl group, 2,2-dimethyl-propyl group and 2-methyl butyl etc.

[0033] term " carboxyl groups " mean-(C=O)-aryl and-(C=O)-alkyl group.

[0034] term " aliphatic group " means saturated straight chain, side chain and clicyclic hydrocarbon group.

[0035] term " unsaturated aliphatic group " means and contains at least one two keys or triple-linked straight chain, side chain and clicyclic hydrocarbon group.

[0036] the open term " aromatic group " that uses when of the present invention means the set of cyclic conjugated carbon atom, and they are characterised in that big resonance energy, for example benzene, naphthalene and anthracene.

[0037] term " clicyclic hydrocarbon group " means the set of cyclic conjugated carbon atom, and they do not constitute aromatic group, for example hexanaphthene.

[0038] the open term " replacement " that uses when of the present invention means that the hydrogen atom of in aliphatic group, aromatic group or clicyclic hydrocarbon group one or more carbon atoms and/or one or more carbon atoms is replaced by Sauerstoffatom, nitrogen-atoms, Siliciumatom, sulphur atom, phosphorus atom, selenium atom or tellurium atom.Some substituting groups comprise hydroxyl, ether group, hydroxy-acid group, ester group, amide group and amine groups like this.

[0039] term " heteroaromatic group " means aromatic group, and wherein at least one cyclic conjugated carbon atom is replaced by nitrogen-atoms or phosphorus atom.

[0040] term " heterocyclic group " means the clicyclic hydrocarbon group, and wherein at least one cyclic conjugated carbon atom is replaced by Sauerstoffatom, nitrogen-atoms, phosphorus atom, Siliciumatom, sulphur atom, selenium atom or tellurium atom.

The multi-density ink-jet ink sets

[0041] ink-jet printer can use multi-density ink-jet ink sets reproduced image.With the color of ink control chart picture, these inks are counted as independent variable.Every kind of ink has the tinctorial value of certain limit.This ink value is represented with n.All painted combination ranges, promptly the possible tinctorial value combination range of the institute of these inks in this multi-density ink-jet ink sets (it can deliver to this printing press) is super dimetric in n-dimensional space, is referred to as the color space.But in fact these combinations may be subjected to the restriction of print system itself.A representative instance is the quantity of ink that in fact can be ejected into this Mo Tishang of being subjected to.

[0042] on the other hand, represent color with tristimulus values usually.Typically, the color space, for example XYXZ or CieL ^*a ^*b ^*Be used to represent color, see as adopting Human VisibleSystem (HVS).

[0043] with the relation of this printing press modal representation between tinctorial value and colour.This printing press pattern is a kind of transformation from the colorant space to the color space.This printing press pattern is a kind of painted cube, may have many ink restrictions, and be referred to as Color Range.Characterize this ink-jet printer and be based on this printing press pattern.Because this is that a complicated operations is arranged, in most of the cases, change (one usually is referred to as gauged step) by these tinctorial values that will deliver to this printing press in very easy mode, it is stable that this printing press just can keep.

[0044], in this aligning step, usually these inks is merged for the multi-density ink.This means that the tinctorial value corresponding to the multi-density ink-jet ink sets is divided into 2 or 2 above multi-density ink values by this aligning step.For these tinctorial values before and after the aligning step are made a distinction, these values before the aligning step are called total ink value or total tinctorial value, and these values behind the aligning step simply are called ink value or tinctorial value.Generally speaking, total tinctorial value is Cyan (C), Magenta (M), Yellow (Y) and Black (K).The total value of cyan and magenta in most of the cases changes into two multi-density inks; Be light and darkcyan and magenta type.In many cases, also once specified the multi-density ink-jet ink sets to comprise light black and aterrimus ink for ink-jet print.

[0045] by providing a kind of multi-density ink-jet ink sets can realize purpose of the present invention, this multi-density ink-jet ink sets comprises two black ink compositions and at least three kinds of color inks, wherein the brightness L of first black ink composition ^*Value is, the 35-65 that is calculated by the spectral-transmission favtor of 1000 times of described first kind of black ink composition dilutions, and the brightness L of second black ink composition ^*Value is, the 70-100 that is calculated by the spectral-transmission favtor of 1000 times of described first kind of black ink composition dilutions.First kind of black ink composition can be regarded " light black " ink as, and second kind of black ink can be regarded " very light black " ink as.

[0046] in a preferred embodiment, multi-density ink-jet ink sets of the present invention comprises seven kinds of inks, i.e. two kinds of multi-density cyan, two kinds of multi-density magenta inks, a kind of yellow ink and two kinds of multi-density black inks.

Ink for ink-jet print

[0047] ink for ink-jet print of multi-density ink-jet ink sets of the present invention contains at least a pigment, at least a dyestuff, or its combination, makes this ink have desirable color.This pigment and/or dyestuff are any significant quantity in this composition for ink, generally speaking are in the about 0.5-20% of ink weight.

[0048] ink for ink-jet print of multi-density ink-jet ink sets of the present invention can contain at least a wetting agent, because it can slow down evaporation of ink speed and can prevent spray nozzle clogging.

[0049] ink for ink-jet print of multi-density ink-jet ink sets of the present invention can also contain at least a tensio-active agent.This tensio-active agent can be negatively charged ion, positively charged ion, nonionic or zwitterionic tensio-active agent, and adding total amount is to be lower than 20 weight % in total ink weight.

[0050] can add biocides in the ink for ink-jet print of multi-density ink-jet ink sets of the present invention in the past, to prevent from ink for ink-jet print, to grow harmful microorganism along with time lapse.Can use biocides single or combination.

[0051] ink for ink-jet print of multi-density ink-jet ink sets of the present invention can also contain the thickening material of at least a adjustment ink viscosity.

[0052] ink for ink-jet print of multi-density ink-jet ink sets of the present invention can also contain at least a antioxidant that improves image storage stability.

[0053] ink for ink-jet print of multi-density ink-jet ink sets of the present invention can contain water and/or organic solvent, for example alcohol, fluorated solvent and dipole aprotic solvent.Preferred solvent is methyl alcohol, ethanol, propyl alcohol, 1-butanols, 1-amylalcohol, 2-butanols, uncle-butanols, ethylene glycol, glycol ether, N-Methyl pyrrolidone, N,N-dimethylacetamide, N, dinethylformamide, 2,4-diacetylmethane and Perfluoroacetone.

[0054] in a specific embodiments, the ink for ink-jet print of multi-density ink-jet ink sets of the present invention is the ink for ink-jet print of radiation-hardenable, wherein contains the compound of radiation-hardenable.The compound of this radiation-hardenable can be selected from and can adopt the ink-jet printer curing to carry out polymeric monomer and/or oligopolymer.

[0055] the radiation-hardenable ink for ink-jet print of multi-density ink-jet ink sets of the present invention preferably also contains at least a light trigger.

[0056] the radiation-hardenable ink for ink-jet print of multi-density ink-jet ink sets of the present invention preferably also contains at least a initiator.

[0057] ink for ink-jet print of multi-density ink-jet ink sets of the present invention can contain additive, for example buffer reagent, mould inhibitor, pH regulator agent, conductivity adjustment agent, sequestrant, rust-preventive agent, photostabilizer, monomer, dendrimers, polymkeric substance etc.If wish that the ink for ink-jet print of multi-density ink-jet ink sets of the present invention can contain the additive of any significant quantity.The pH regulator agent example that is suitable for ink of the present invention includes, without being limited to bronsted lowry acids and bases bronsted lowry, comprising alkali metal hydroxide, as lithium hydroxide, sodium hydroxide and potassium hydroxide.Therefore the amount that contains also should depend on the particular combinations that wherein contains.

[0058] ink for ink-jet print of multi-density ink-jet ink sets of the present invention can also contain conduction or semiconductive polymer, for example polyaniline, polypyrrole, Polythiophene, picture poly-(ethylidene dioxy thiophene) (PEDOT), replacement or unsubstituted poly-(phenylene vinylidene) (PPV ' s), picture PPV and MEH-PPV, poly-fluorenes is as PF6 etc.

Pigment

[0059] pigment particle should be enough little, can make the ink free-flow cross ink-jet printing apparatus, and by nozzle, its diameter is 10-50 μ m normally especially.Granularity also influences the stability of colo(u)rant dispersion.For the tinctorial strength of maximum, also wish to use little particulate.

[0060] average particle diameter of this pigment should be 0.005-15 μ m.Preferably, the mean particle size of this pigment is 0.005-5 μ m, most preferably 0.005-1 μ m, particularly preferably 0.005-0.3 μ m.As long as can reach purpose of the present invention, can use bigger pigment granularity.

[0061] for example among EP 776952A, US 5 538 548, US 5 443 628, EP 259130A, US 5 285 064, EP 429 828A and EP 526 198A very thin pigment dispersion and preparation method thereof is disclosed.

[0062] this pigment can be black, cyan, magenta, yellow, redness, blueness, green, brown and mixture colors thereof etc.For example, suitable paint material comprises carbon black, Regal 400R, Mogul L, the Elftex 320 of picture CabotCo., or the CarbonBlack FW18 of DEGUSSA Co., Special Black 250, Special Black 350, Special Black 550, Printex 25, Printex 35, Printex 55, Printex150T, and Pigment Black7.US 5 389 133 discloses the additional example (XEROX) of suitable pigments.

[0063] pigment that is suitable for the ink for ink-jet print of multi-density ink-jet ink sets of the present invention comprises C.I.Pigment Yellow 17, C.I.Pigment Blue 27, C.I.Pigment Red 49:2, C.I.Pigment Red 81:1, C.I.Pigment Red 81:3, C.I.Pigment Red81:x, C.I.Pigment Yellow 83, C.I.Pigment Red 57:1, C.I.Pigment Red49:1, C.I.Pigment Violet 23, C.I.Pigment Green 7, C.I.Pigment Blue61, C.I.Pigment Red 48:1, C.I.Pigment Red 52:1, C.I.Pigment Violet1, C.I.Pigment White 6, C.I.Pigment Blue 15, C.I.Pigment Yellow12, C.I.Pigment Blue 56, C.I.Pigment Orange 5, C.I.Pigment Black7, C.I.Pigment Yellow 14, C.I.Pigment Red 48:2, C.I.Pigment Blue15:3, C.I.Pigment Yellow 1, C.I.Pigment Yellow 3, C.I.Pigment Yellow13, C.I.Pigment Orange 16, C.I.Pigment Yellow 55, C.I.Pigment Red41, C.I.Pigment Orange 34, C.I.Pigment Blue 62, C.L.Pigment Red22, C.I.Pigment Red 170, C.I.Pigment Red 88, C.I.Pigment Yellow151, C.I.Pigment Red 184, C.I.Pigment Blue 1:2, C.I.Pigment Red3, C.I.Pigment Blue 15:1, C.I.Pigment Blue 15:3, C.I.Pigment Blue15:4, C.I.Pigment Red 23, C.I.Pigment Red 112, C.I.Pigment Yellow126, C.I.Pigment Red 169, C.I.Pigment Orange 13, C.I.Pigment Red1-10,12, C.I.Pigment Blue 1:X, C.I.Pigment Yellow 42, C.I.PigmentRed 101, C.I.Pigment Brown 6, C.I.Pigment Brown 7, C.I.PigmentBrown 7:X, C.I.Pigment Black 11, C.I.Pigment Metal 1, C.I.PigmentMetal 2, C.I.Pigment Yellow 128, C.I.Pigment Yellow 93, C.I.PigmentYellow 74, C.I.Pigment Yellow 138, C.I.Pigment Yellow 139, C.I.Pigment Yellow 154, C.I.Pigment Yellow 185, C.I.Pigment Yellow180, C.I.Pigment Red 122, C.I.Pigment Red 184, the aluminium phthalocyanine pigment of bridging are some pigment sosoloid.

[0064] other pigment can be selected from HERBST, and people such as W. are at " industrial pigment dyestuff, production, performance, application (Industrial Organic Pigments, Production, Properties, Applications) ", the 2nd edition, vch, those disclosed pigment in 1997.

[0065] pigment very preferably is Pigment Yellow 1,3,128,109,93,17,14,10,12,13,83,65,75,74,73,138,139,154,151,180,185; Pigment Red 122,22,23,17,210,170,188,185,146,144,176,57:1,184,202,206,207; Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1, Pigment Blue 15:4, Pigment Blue 15:6, PigmentBlue 16; Carbon black.

[0066] this pigment can the dispersion form add, and this dispersion contains dispersion agent, and it also is referred to as pigment stabiliser.This dispersion agent can for example be the urethane of polyester, polyacrylate(s), is the high molecular weight block copolymer form especially, and its typical add-on is in pigment weight 2.5-100%.Suitable example is the DISPERBYK that obtains from BYK CHEMIE ^TMDispersion agent, or the SOLSPERSE that obtains from ZENECA ^TMDispersion agent.HERBST, people such as W. are in " industrial pigment dyestuff, production, performance, application ", and the 2nd edition, vch discloses non--polymeric dispersant and some polymeric dispersant details in 1997.

[0067] in DE 19636382 (BAYER), US 5 720 802 (XEROX), US 5 713993 (DU PONT), US 5 085 689 (BASF) and US 2 303 376 (FUJITSUISOTEC) suitable pigment stabiliser is disclosed also.

Dyestuff

[0068] dyestuff that is suitable for ink for ink-jet print of the present invention comprises substantive dyestuff, matching stain, basic dyestuff and reactive dyestuffs.

[0069] substantive dyestuff that is suitable for ink for ink-jet print of the present invention comprises:

^*C.I.Direct Yellow 1,4,8,11,12,24,26,27,28,33,39,44,50,58,85,86,100,110,120,132,142 and 144;

^*C.I.Direct Red 1,2,4,9,11,134,17,20,23,24,28,31,33,37,39,44,47,48,51,62,63,75,79,80,81,83,89,90,94,95,99,220,224,227 and 343;

^*C.I.Direct Blue 1,2,6,8,15,22,25,71,76,78,80,86,87,90,98,106,108,120,123,163,165,192,193,194,195,196,199,200,201,202,203,207,236 and 237;

^*C.I.Direct Black 2,3,7,17,19,22,32,38,51,56,62,71,74,75,77,105,108,112,117,154 and 195;

[0070] matching stain that is suitable for ink for ink-jet print of the present invention comprises:

^*C.I.Acid?Yellow?2、3、7、17、19、23、25、20、38、42、49、59、61、72、99；

^*C.I.Acid Orange 56 and 64;

^*C.I.Acid Red 1,8,14,18,26,32,37,42,52,57,72,74,80,87,115,119,131,133,134,143,154,186,249,254 and 256;

^*C.I.Acid Violet 11,34 and 75;

^*C.I.Acid Blue 1,7,9,29,87,126,138,171,175,183,234,236 and 249;

^*C.I.Acid Green 9,12,19,27 and 41;

^*C.I.Acid Black 1,2,7,24,26,48,52,58,60,94,107,109,110,119,131 and 155;

[0071] reactive dyestuffs that are suitable for ink for ink-jet print of the present invention comprise:

^*C.I.Reactive Yellow 1,2,3,14,15,17,37,42,76,95,168 and 175;

^*C.I.Reactive Red 2,6,11,21,22,23,24,33,45,111,112,114,180,218,226,228 and 235;

^*C.I.Reactive Blue 7,14,15,18,19,21,25,38,49,72,77,176,203,220,230 and 235;

^*C.I.Reactive Orange 5,12,13,35 and 95;

^*C.I.Reactive Brown 7,11,33,37 and 46;

^*C.I.Reactive Green 8 and 19;

^*C.I.Reactive Violet 2,4,6,8,21,22 and 25;

^*C.I.Reactive Black 5,8,31 and 39;

[0072] basic dyestuff that is suitable for ink for ink-jet print of the present invention comprises:

^*C.I.Basic Yellow 11,14,21 and 32;

^*C.I.Basic Red 1,2,9,12 and 13;

^*C.I.Basic Violet 3,7 and 14;

^*C.I.Basic Blue 3,9,24 and 25;

[0073] dyestuff may just the ideal color occur in suitable pH scope.Therefore, ink for ink-jet print of the present invention preferably also comprises the pH damping fluid, for example potassium hydroxide (KOH).

Wetting agent

[0074] suitable wetting agent comprises triacetin, N-N-methyl-2-2-pyrrolidone N-, glycerol, urea, thiocarbamide, ethylidene-urea, alkyl urea, alkyl thiourea, dialkyl ureas and dialkyl thiourea, di-alcohols, comprising ethylene glycol, propylene glycol, glycerol, butyleneglycol, pentanediol and hexylene glycol; Glycols is comprising propylene glycol, polypropylene glycol, ethylene glycol, polyoxyethylene glycol, glycol ether, Tetraglycol 99 and composition thereof and derivative.Preferred wetting agent is a polyoxyethylene glycol, and the amount that is added to the wetting agent in this ink for ink-jet print prescription is the 0.1-20 weight % of this prescription, more preferably 0.1-10 weight %, most preferably 4.0-6.0 weight %.

Tensio-active agent

[0075] suitable tensio-active agent comprises that adducts, acetylenediol and its ethylene oxide adduct of adducts, oxyethane and polyhydric alcohol fatty acid ester of adducts, oxyethane and alkylphenol of soap, high alcohol ester salt, alkylbenzene sulfonate, sulfosuccinate salt and phosphoric acid high alcohol ester salt (for example Sodium dodecylbenzene sulfonate and dioctyl sulfosuccinate salt sodium), oxyethane and higher alcohols is (for example from AIR PRODUCTS﹠amp; Polyoxygenated ethylidene nonyl phenylate and SURFYNOL that CHEMICALS INC. obtains ^TM104,440,465 and TG).

Biocides

[0076] suitable biocides that is used for ink for ink-jet print of the present invention comprises dehydration sodium acetate, 2-phenoxyethyl alcohol, Sodium Benzoate, pyridine thion-1-oxide compound (pyridine-1-oxide), ethyl p-hydroxybenzoate and 1,2-benzisothiazole-3-ketone and salt thereof.The preferred biocides that is used for ink for ink-jet print of the present invention is the Proxel that obtains from ZENECA COLOURS ^TMGXL.

[0077] the biocides add-on is preferably in ink for ink-jet print 0.001-3 weight %, more preferably 0.01-1.00 weight %.

Thickening material

[0078] the suitable thickening material that uses for the ink for ink-jet print of multi-density ink-jet ink sets of the present invention comprises urea or urea derivative, Natvosol, carboxymethyl cellulose, hydroxypropylcellulose, the chitin of deriving, derivatized starch, carrageenin and amylopectin; The polyvinyl acetate (PVA) of the polyacrylamide of DNA, protein, poly-(styrene sulfonic acid), styrene-maleic anhydride copolymer, alkyl vinyl ether-copolymer-maleic anhydride, polyacrylamide, partial hydrolysis, polyacrylic acid, polyvinyl alcohol, partial hydrolysis, polyacrylic acid hydroxy methacrylate, poly-ethylene methacrylic ether, Polyvinylpyrolidone (PVP), poly-(2-vinyl pyridine), poly-(4-vinylpridine) and poly-(diallyldimethylammonium chloride).

[0079] add-on of thickening material is preferably in ink for ink-jet print 0.01-20 weight %, more preferably 0.1-10 weight %.

[0080] preferably, at velocity of shear 100s ^-1Under temperature 20-110 ℃, the ink for ink-jet print viscosity of multi-density ink-jet ink sets of the present invention is lower than 100mPa.s, more preferably is lower than 50mPa.s, most preferably is lower than 30mPa.s.

Antioxidant

[0081], can use the preventive that fades of various organic and metal complexes classes among the present invention as improving the antioxidant of image storage stability.Organic preventive that fades comprises quinhydrones, alkoxyl group phenol, dialkoxy phenol, phenol, aniline, amine, indane, cumarone, alkoxyl aniline and heterocycle, and metal complexes comprises nickel complex and Zn complex.More particularly, as at " Research disclosure ", No.17643, VII, Section I or J, No.15162, the compound of describing among the No.18716, No.15162 enumerates the compound of describing in the patent, the compound and the examples of compounds that comprise with the typical compound formula described in JP62215272A (FUJI) the 127-137 page or leaf.

[0082] add-on of this stablizer is preferably in ink 0.1-30 weight %, more preferably 1-10 weight %.

Monomer and oligopolymer

[0083] adopt the curing of ink-jet printer to make monomer and/or oligopolymer polymerization.Monomer, oligopolymer or prepolymer can have different functionality, can use comprise single-, two-, three-and the mixture of high functionality monomer, oligopolymer or prepolymer combination more.These components are the UV solidified preferably.

[0084] ratio of regulating between these monomers and the oligopolymer also is a kind of method of regulating this ink viscosity.Higher functionality can obtain higher viscosity.

[0085] can utilize common Raolical polymerizable, make the photocuring system of using up acid or light alkali propellant, or any method in the photo-induced alternative copolymerization reaction.Generally speaking, Raolical polymerizable and cationic polymerization are preferred, but also can utilize the photo-induced alternative copolymerization reaction without any need for initiator.In addition, the mixing system of these system in combination also is effective.

[0086] Raolical polymerizable is the method for extensive employing.But cationic polymerization is being the highest aspect the efficient because of oxygen initiated polymerization of no use, but it is slow, and cost is also high.If the employing cationic polymerization preferably uses superoxide.

[0087] common known any polymerizable compound can use in this technical field.Be used for multi-density ink-jet ink sets of the present invention ink for ink-jet print particularly preferably be simple function and/or polyfunctional acrylate monomer, oligopolymer or prepolymer, vinylformic acid isopentyl ester for example, the stearyl acrylate ester, lauryl acrylate, Octyl acrylate, decyl acrylate, vinylformic acid isopentyl styl ester, the different stearyl ester of vinylformic acid, vinylformic acid 2-ethylhexyl-diethyl diester, vinylformic acid 2-hydroxyl butyl ester, 2-acryloxy ethyl hexahydrophthalic acid, vinylformic acid butoxy ethyl ester, vinylformic acid oxyethyl group two sweet esters, vinylformic acid methoxyl group two sweet esters, the vinylformic acid methoxyl group gathers the second diester, vinylformic acid methoxy propyl diester, the vinylformic acid phenoxy ethyl, tetrahydrofurfuryl acrylate, isobornyl acrylate, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, the Vinyl Ether acrylate, 2-acryloxy ethyl succsinic acid, 2-acryloxy ethyl phthalic acid, 2-propenyloxy group ethyl-2-hydroxyethyl-phthalic acid, interior ester modified soft propene acid esters, vinylformic acid tertiary butyl cyclohexyl, the diacrylate triglyceride, diacrylate four sweet esters, diacrylate is gathered the second diester, diacrylate two propylene diesters, diacrylate three propylene diesters, diacrylate is gathered propylene diester, diacrylate 1,4-fourth diester, diacrylate 1, the own diester of 6-, diacrylate 1, the 9-azelaoyl, new penta diester of diacrylate, diacrylate dihydroxymethyl tristane ester, dihydroxyphenyl propane EO (oxyethane) and diacrylate adducts, bisphenol-ap O (propylene oxide) and diacrylate adducts, the hydroxy new pentane acid ester neopentylglycol diacrylate, ethoxylated neopentylglycol diacrylate, alkoxylate dihydroxymethyl tristane diacrylate and diacrylate are gathered the fourth diester, Viscoat 295, the Viscoat 295 of EO modification, three vinylformic acid three (propylene glycol) esters, the Viscoat 295 of caprolactone modification, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, tetramethylolmethane oxyethyl group tetraacrylate, dipentaerythritol acrylate, the ditrimethylolpropane tetraacrylate, glycerol propoxy-triacrylate, dipentaerythritol acrylate with the hexanolactam modification, or the N-vinylamide, as N-caprolactam or N-vinyl formamide; Or the acrylamide of acrylamide or replacement, as acryloyl morpholine.

[0088] in addition, the methacrylic ester corresponding to the aforesaid propylene acid esters can use with these acrylate.In these methacrylic esters, it is preferred that methacrylic acid methoxy base gathers the poly-second diester of second diester, methacrylic acid methoxy base triglyceride, methacrylic acid hydroxyl ethyl ester, methacrylic acid phenoxy ethyl, cyclohexyl methacrylate, dimethacrylate four sweet esters, dimethacrylate because its high relatively susceptibility and with the adhesivity of improving that is subjected to black surface.

[0089] in addition, this ink for ink-jet print can also contain polymerizable oligomers.These polymerizable oligomers examples comprise epoxy acrylate, aliphatic urethane acrylate, aromatic urethanes acrylate, polyester acrylate and straight chain acrylic acid oligomer.

Light trigger

[0090] catalyzer that is referred to as light trigger causes this polyreaction usually.The intensity of activation that this light trigger needs is lower than monomer or oligopolymer generates the intensity of activation that polymkeric substance needs.

[0091] this light trigger absorb light is that generation free radical or positively charged ion are necessary.Free radical or positively charged ion are the high energy particles that brings out monomer, oligopolymer and polymer polymerizing, thereby and polyfunctional monomer and oligopolymer also bring out crosslinked.

[0092] the light trigger preferred amounts is in total ink weight 1-10 weight %, more preferably 1-6 weight %.

[0093] divides two steps, can realize carrying out irradiation with actinic radiation by changing wavelength or intensity.Under such certain situation, preferably two photoinitiators use together.

[0094] light trigger is that radically curing is necessary; can include, without being limited to following compound or its combination: the benzophenone of benzophenone and replacement; 1-hydroxy-cyclohexyl benzophenone; thioxanthone; the picture isopropyl thioxanthone; 2-hydroxy-2-methyl-1-phenyl third-1-ketone; 2-benzyl-2-dimethylamino-(4-morpholino phenyl) fourth-1-ketone; biphenyl acyl group dimethyl ketone acetal; two (2; the 6-dimethylbenzoyl)-2; 4; 4-tri-methyl-amyl phosphine oxide; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino third-1-ketone; 2; 2-dimethoxy-1; 2-phenylbenzene second-1-ketone or 5,7-two iodo-3-butoxy-6-fluorones; phenylbenzene fuorine iodine and phosphofluoric acid triphenyl sulphur.

[0095] the appropriate light initiator that uses for multi-density ink-jet ink sets radiation curable ink-jet ink of the present invention comprises the Irgacure that is obtained by CIBA SPECIALTY CHEMICALS ^TM184, Irgacure ^TM500, Irgacure ^TM907, Irgacure ^TM369, Irgacure ^TM1700, Irgacure ^TM651, Irgacure ^TM819, Irgacure ^TM1000, Irgacure ^TM1300, Irgacure ^TM1870, Darocur ^TM1173, Darocurr ^TM4265 and Darocur ^TMITX is by the Lucerin TPO of BASF AG acquisition, by the Esacure of LAMBERTI acquisition ^TMKT046, Esacure ^TMKIP150, Esacure ^TMKT37 and Esacure ^TMEDB is by the H-Nu of SPECTRA GROUP Ltd. acquisition ^TM470 and H-Nu ^TM470X, and isopropyl thioxanthone.

Inhibitor

[0096] suitable polymerization retarder comprises phenol antioxidant, hindered amine as light stabilizer, Phosphorus antioxidant, normally used Hydroquinone monomethylether in (methyl) acrylate monomer, also can use quinhydrones, tert-butyl catechol, pyrogallol.In these inhibitor, by the vinylformic acid deutero-phenolic compound of two keys is arranged in molecule, even in airtight oxygen-free environment, have inhibition because of it during heating but particularly preferred.Suitable inhibitor for example is by Sumitomo Chemical Co., the Sumilizer that Ltd. produces ^TMGA-80, Sumilizer ^TMGM and Sumilizer ^TMGS.

[0097] can reduce ink to the solidified susceptibility owing to add excessive polymerization inhibitor, so preferably before fusion, determine to prevent the amount of polyreaction.The amount of polymerization inhibitor is normally in total ink weight 200-20000ppm.

[0098] appropriate combination of reduction oxygen quenching polymeric compounds and Raolical polymerizable inhibitor is: 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1 and 1-hydroxy-cyclohexyl-phenyl-ketone; 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino third-1-ketone or 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino third-1-ketone and diethyl thioxanthone or isopropyl thioxanthone; Benzophenone and the acrylate derivative that uncle's amino group is arranged, and tertiary amine adducts.Usually use a kind of amine compound to reduce the polymerization retardation effect of oxygen, or improve susceptibility.But, when amine compound is used in combination with the high acid value compound, be easy to reduce stability in storage at high temperature.Therefore, in ink jet printing, should avoid using amine compound and high acid value compound especially.

[0099] can use the synergy additive to improve and solidify quality, reduce the influence of oxygen quenching effect.Some additives comprise and are not limited to from the ACTILANE of AKZO NOBEL acquisition like this ^TM800 and ACTILANE ^TM725, from the Ebecryl of UCB CHEMICALS acquisition ^TMP115 and Ebecryl ^TM350, from CD1012, Craynor CN 386 (acrylate of amine modification) and the Craynor CN 501 (ethoxylated trimethylolpropane triacrylate of amine modification) of CRAY VALLEY acquisition.

[0100] this synergy additive level scope is in radiation curable ink-jet ink gross weight 0-50 weight %, preferably 5-35 weight %.

Solvent

[0101] ink for ink-jet print of multi-density ink-jet ink sets of the present invention can contain water and/or organic solvent as solvent, for example alcohol, fluorated solvent and dipole aprotic solvent.Preferably, the solvent strength of this ink for ink-jet print is in ink for ink-jet print gross weight 10-80 weight %, particularly preferably 20-50 weight %.

[0102] the radiation curable ink-jet ink of multi-density ink-jet ink sets of the present invention preferably is made up of 100% solid.Sometimes, add the minute quantity organic solvent, improving and solidify the back at UV may be favourable with being subjected to the adhesive attraction of black surface.In this case, the solvent of adding can be any amount in the scope that can not cause solvent resistance and VOC problem, preferably in radiation curable ink-jet ink gross weight 0.1-5.0 weight %, preferably 0.1-3.0 weight %.

[0103] appropriate organic solvent comprises alcohol, aromatic hydrocarbon, ketone, ester, aliphatic hydrocrbon, higher fatty acid, Trivalin SF, cellosolve, high-grade aliphatic ester.Suitable alcohol comprises methyl alcohol, ethanol, propyl alcohol and 1-butanols, 1-amylalcohol, 2-butanols, uncle-butanols.Suitable aromatic hydrocarbon comprises toluene and dimethylbenzene.Suitable ketone comprises methylethylketone, methyl iso-butyl ketone (MIBK), 2,4-diacetylmethane and Perfluoroacetone.In addition, can make spent glycol, glycol ether, N-Methyl pyrrolidone, N, N-dimethylformamide, N, dinethylformamide.

Be subjected to black body material

[0104] ink-jet of using with the ink for ink-jet print of multi-density ink-jet ink sets of the present invention is subjected to black body material to comprise supporting layer and one or more layers ink receptive layer.Ink receptive layer contains at least a binding agent.Preferably, this ink receptive layer is a porous, contains binding agent and filler.

[0105] this binding agent can be selected from the compound of knowing in this technical field, comprising Natvosol, hydroxypropylcellulose, hydroxyethylmethyl-cellulose, Vltra tears, hydroxy butyl methyl cellulose, methylcellulose gum, Xylo-Mucine, carboxymethyl hydroxyethyl cellulose sodium, water miscible Type 3U, cellulose sulfate, polyvinyl alcohol, vinyl alcohol copolymer, polyvinyl acetate (PVA), the polyvinyl acetal, Polyvinylpyrolidone (PVP), polyacrylamide, acrylamide/acrylic acid copolymer, polystyrene, styrol copolymer, the acrylic or methacrylic acid polymer, styrene/acrylic acid co-polymer, ethylene-vinyl acetate copolymer, methoxy ethylene/maleic acid, poly-(2-acrylamido-2-methyl propane sulfonic acid), Diethylenetriamine-adipat copolymers, polyvinylpyridine, polyvinyl imidazol, modified polyethylene imines Epicholorohydrin, the ethoxylation polymine, polyethylene oxide, urethane, melamine resin, gelatinum, carrageenin, dextran, gum arabic, casein food grade, pectin, albumin, starch, the collagen derivative, collodion and agar.

[0106] implementing preferred binder of the present invention is polyvinyl alcohol (PVA), vinyl alcohol copolymer or modified polyethylene alcohol.

[0107] this filler can be selected from the mineral filler of knowing in this technical field, for example silicon-dioxide, talcum, clay, hydrotalcite, kaolin, wilkinite, lime carbonate, magnesiumcarbonate, alkaline magnesium carbonate, silico-aluminate, aluminium three oxyhydroxide, aluminum oxide (aluminum oxide), titanium dioxide, zinc oxide, barium sulfate, calcium sulfate, zinc sulphide, stain white, boehmite (hydrated alumina), zirconium white or mixed oxide.

[0108] in a preferred embodiment, this filler is selected from silicon-dioxide, silico-aluminate, aluminum oxide, lime carbonate, hydrated alumina and aluminium three oxyhydroxide.

[0109] also can use the mixture of different fillers.

[0110] in another embodiment, this filler can be selected from organic fine particles, for example polystyrene, polymethylmethacrylate, siloxanes, carbamide condensation polymer, urea-formaldehyde condensation polymkeric substance, polyester and polymeric amide.Can use inorganic and the organic filler mixture.But this filler most preferably is mineral filler.

[0111] this ink receptive layer can also contain the common component that people know, and for example works the cationic substance of doing the mordant effect, works tensio-active agent, stiffening agent, softening agent, stablizer, whitening agent and the matting agent of doing the coatings additive(s) effect.

[0112] adopt common coating technique, for example dipping, blade coating, squeezing and coating, spin coating, slide hopper coating and curtain coating are coated with different layers on upholder.

[0113] the radiation curable ink-jet ink of multi-density ink-jet ink sets of the present invention is to be applicable to the non-absorbent substantially black body that is subjected to, the paper of for example auxiliary or non-auxiliary polyethylene terephthalate carrier and coating resin, for example paper of the paper of painting polyethylene and painting polypropylene.It is this that to be subjected to black body can be transparent, translucent or opaque.

[0114] for the radiation curable ink-jet ink of multi-density ink-jet ink sets of the present invention use suitable to be subjected to black body be polymeric substrate, for example cellulose acetate propionic ester, cellulose acetate butyric ester, polyester, for example polyethylene terephthalate (PET) and Polyethylene Naphthalate (PEN); Oriented polystyrene (OPS); Oriented nylon (ONy); Polypropylene (PP); Oriented polypropylene (OPP); Polyvinyl chloride (PVC); And various polymeric amide, polycarbonate, polyimide, polyolefine, poly-(vinyl acetal), polyethers and polysulphonamide, the opaque and white polyester, polyethylene terephthalate and polypropylene are extruded adulterant.Acrylic resin, resol, glass and metal also can be as being subjected to black body.At HERBST, people such as W., " industrial pigment dyestuff, production, performance, application ", the 2nd edition, vch can see other suitable ink material that is subjected in 1997.The polyester film ground, special polyethylene terephthalate is preferred for the special type application that some has excellent dimensional stability.Use a kind of like this polyester as being subjected to Mo Tishi,, then can utilize supplementary layer to improve combining of ink for ink-jet print layer and ground if it is subjected to black body with non-auxiliary ground formation is non-absorbent substantially.Useful supplementary layer for this purpose is that people know in the camera technique field, and these supplementary layers comprise for example vinylidene chloride polymer, kine bias chloroethylene/acrylonitrile/vinylformic acid trimer or vinylidene chloride/methyl acrylate/methylene-succinic acid trimer.Stablizer, levelling additive, matting agent, physics film performance conditioning agent as wax, also can add in this supplementary layer as needs.

Embodiment

[0115] by following embodiment the present invention will be described in more detail now.The multi-density ink-jet ink sets of this embodiment a kind of to having only " black ink " with have the multi-density ink-jet ink sets of " light black ink " and " very light black ink " to compare.

Material

[0116] material that uses of these embodiment all obtains from general merchandise resources easily, ALDRICH CHEMICAL Co. (Belgium) for example, unless otherwise noted.Used following material:

[0117] black dyes is the Duasyn Schwarz KRL-SF that obtains from CLARINT.

[0118] yellow dyes is the Duasyn Yellow 3GF-SF that obtains from CLARINT.

[0119] magenta dye is the Duasyn Briljiant RedF3b-SF that obtains from CLARINT.

[0120] cyan dye is the Duasyn Direct TurquoiseBlue Koperftalocyanine that obtains from CLARINT.

[0121] glycerine obtains from OLEON.

[0122] 1,2-hexylene glycol obtains from DEGUSSA.

[0123] Proxel ^TMUltra5 obtains from AVECIA.

[0124] AgfaJet Grand Shrpa ink-jet inkset (CMYK+ nattierblue+light magenta) obtains from AGFA.

[0125] AgfaJet Digital Proofing Base is that the photographic-grade ink-jet of the coating resin (PE) that obtains from AGFA is subjected to black body.

Measuring method

1, brightness L ^*

[0126] ink of 1000 times of dilute with waters has been measured brightness L ^*The 1cm quartz cell of spectrophotometer Agilent8453 (AGILENT makes) is filled the ink of 1000 times of dilutions.

[0127] in R (45/0) geometry mode, determined L according to ASTM Norm E179-90 ^*, a ^*And b ^*The CIELAB-value is estimated according to ASTM Norm E308-90.

[0128] brightness L ^*Obtain for 2 ° according to light source D65 and visual angle.

2, consumption of ink

[0129] at printing 42m, each ink for ink-jet print box weight of weighing can be measured exhausted amount of ink like this before and after the image.

3, light resistance

[0130] can be used in printing sample that printing measured in back one hour with at hue shift Δ E mensuration light resistance between the same printing sample after under the office environment condition x days.Use spectrophotometer DTP41 (obtaining) to measure printing sample, to determine in CIE (International Commission on Illumination), to spell out the CieL of aberration finger-length measurement from X-RITE ^*a ^*b ^*The colour system coordinate.Under light source D50, no any light source spectral filter, absolute white condition, carried out this measurement as 2 ° at reference white and visual angle.

[0131] in following equation, for L ₁ ^*, a ₁ ^*And b ₁ ^*, substitution was measured the resulting brightness value L of new printing sample in back one hour in printing ₁ ^*With hue value a ₁ ^*And b ₁ ^*, for L ₂ ^*, a ₂ ^*And b ₂ ^*, substitution is the same resulting brightness value L of printing sample after under the office environment condition x days ₂ ^*With hue value a ₂ ^*And b ₂ ^*, can determine foxy Δ E:

$\mathrm{\ΔE}=\sqrt{{({L_1}^{*}-{L_2}^{*})}^2+{({a_1}^{*}-{a_2}^{*})}^2+{({b_1}^{*}-{b_2}^{*})}^2}$

Foxy Δ E value 1.0 has been the naked visible of looking.

4, dyeing time

[0132] carried out a kind of evaluation, wherein be subjected to have printed some high quantity of ink spots on the black body, and the sample in the printing of printing relief passes through laminating machine APL850 (obtaining from AGFA) facing to the black body sheet pressurization that is subjected to equally of not printing, to check the transfer case of ink.Measure not see and shift the needed time.Identify the grade of these samples according to the standard that describes below.

[0133] standard:

1=is fast (no any transfer in 5 minutes) very

2=fast (no any transfer in 10 minutes)

3=slow (no any transfer in 15 minutes)

4=is slow (no any transfer in 20 minutes) very

The preparation of multi-density ink for ink-jet print

[0134] under agitation with glycerine, 1, the mixed composition for ink that gets of 2-hexylene glycol and portion water.Succeedingly adds these dyestuffs then.Add biocides Proxel again ^TMUltra 5.PH regulator is arrived pH8.0.Add water and supply 100%.Allow this ink by 1 μ Millipore ^TMStrainer.

[0135] composition for ink of ink-LB and ink-VLB is listed in table 1.The amount of each compound is to represent with weight % in the ink gross weight.

[0136]

Table 1

Weight %	Ink-LB	Ink-VLB
			Black dyes	????2.70	????0.68
Yellow dyes	????0.20	????0.05
			Magenta dye	????0.20	????0.05
Cyan dye	????0.24	????0.06
			Glycerine	????25.00	????25.00
1, the 2-hexylene glycol	????7.00	????7.00
			??Proxel TMUltra?5	????0.80	????0.80
Water	Reach 100%	Reach 100%

[0137] according to table 2, use the AgfaJet Grand Shrpa ink for ink-jet print of acquisition from the market and/or the ink-LB and the ink-VLB of preparation, prepared two multi-density ink-jet ink sets.

[0138]

Table 2

Ink type	????COMP-1	????INV-1
			Magenta ink	AgfaJet?Grand?Shrpa?M	?AgfaJet?Grand?Shrpa?M
Light magenta ink	AgfaJet?Grand?Shrpa?LM	?AgfaJet?Grand?Shrpa?LM
			Cyan	AgfaJet?Grand?Shrpa?C	?AgfaJet?Grand?Shrpa?C
The nattierblue ink	AgfaJet?Grand?Shrpa?LC	?AgfaJet?Grand?Shrpa?LC
			Yellow ink	AgfaJet?Grand?Shrpa?Y	?AgfaJet?Grand?Shrpa?Y
Black ink	AgfaJet?Grand?Shrpa?K	????????-
			The light black ink	?????????-	Ink-LB
Unusual light black ink	?????????-	Ink-VLB

[0139] table 3 is listed the measurement brightness L of black ink ^*Value.

[0140]

Table 3

Ink	????L *
		Ink-LB	????51.98
Ink-VLB	????84.55
		????AgfaJet?Grand?Shrpa?K	????17.47

Estimate

[0141] ink cartridge of multi-density ink-jet ink sets COMP-1 and INV-1 is put into the AgfaJet Grand Grand Shrpa (obtaining from AGFA).Each multi-density ink-jet ink sets all adopts the printing press pattern to pass through aligning step, it proofreaies and correct the image processing software Apogee PDF RIP (obtaining from AGFA) that adopts Proofers 2.2u1b8, and be set as follows: printed resolution: 720 * 720dpi, quality mode: unidirectional printing, 4 road spray patterns; Inkless water-dispersion; No ICC profile, error is scattered ON.

[0142] use multi-density ink-jet ink sets COMP-1 and INV-1 printing with the set of diagrams picture.Table 4 is listed exhausted amount of ink.

[0143]

Table 4

Ink	????????COMP-1		??????????INV-1
					????mL/m 2	????％	???mL/m 2	????％
	Cyan	????1.04	????7.7	????0.75					????6.0
Magenta					????1.76	????13.1	????1.08	????8.7
	Yellow	????2.74	????20.4	????1.83					????14.7
Black					????0.98	????7.3	????---	????---
	Light black	????---	????---	????2.75					????22.1
Unusual light black					????---	????---	????3.18	????25.6
	Nattierblue	????3.00	????22.3	????1.20					????9.7
Light magenta					????3.92	????29.2	????1.64	????13.2
	Total flow	????13.44	????100.0	????12.43					????100.0

[0144] can know by table 4 and find out that the exhausted amount of ink comparison of multi-density ink-jet ink sets INV-1 of the present invention is than multi-density ink-jet ink sets COMP-1 low 9%.In addition, the color ink water yield of printing these images uses significantly reduces, and is replaced by black ink.Multi-density ink-jet ink sets INV-1 of the present invention has used the black ink more than 47%, and contrast multi-density ink-jet ink sets COMP-1 is 7.3%.

[0145] use the sample of multi-density ink-jet ink sets INV-1 printing of the present invention to demonstrate, its time of drying (in 5 minutes without any shifting) is than the weak point of the sample that uses contrast multi-density ink-jet ink sets COMP-1 printing (in 20 minutes without any shifting).

[0146] to being exposed to the printing sample after environment light condition is assigned 4 days, measures photostabilization, adopted tonal range 10%, 20%, 40% and 80% gray tone.

[0147]

Table 5

Neutralc tint	The Δ E of COMP-1	The Δ E of INV-1
			????10％	????0.92	????0.54
????20％	????1.02	????0.52
			????40％	????0.95	????0.45
????60％	????0.99	????0.54
			????80％	????1.14	????0.75

[0148] moistureproof wrinkling (contract proofing) is a kind of very overcritical application for the stable printing product.People's eyes are responsive especially to grey neutrality.Wrinkling for this protection against the tide, do not accept toward a kind of color (for example yellowy grey) skew.Table 5 shows, under 4 days environment light conditions only after, use the sample of contrast multi-density ink-jet ink sets COMP-1 printing to demonstrate hue shift Δ E value greater than 1.0, this is clearly visible colour-change in neutralc tint.Use the sample of multi-density ink-jet ink sets INV-1 printing of the present invention, all Δ E values are all less than 1.0.

[0149],, will not show yet and see and do not exceed the scope of the invention that limits as claim so those skilled in the art can make many modifications to it owing to describe preferred specific embodiments of the present invention in detail.

Claims (8)

1, a kind of multi-density ink-jet ink sets, it comprises two kinds of black ink compositions and at least three kinds of color inks, wherein the brightness L of first kind of black ink composition ^*Value is, the 35-65 that is calculated by the spectral-transmission favtor of 1000 times of described first kind of black ink composition dilutions, and the brightness L of second kind of black ink composition ^*Value is, the 70-100 that is calculated by the spectral-transmission favtor of 1000 times of described second kind of black ink composition dilutions.

2, multi-density ink-jet ink sets according to claim 1, it comprises at least two kinds of multi-density cyan, two kinds of multi-density magenta inks and a kind of yellow ink.

3, multi-density ink-jet ink sets according to claim 1 and 2, at least a ink for ink-jet print is a radiation-hardenable in the wherein said multi-density ink-jet ink sets.

4, multi-density ink-jet ink sets according to claim 3, at least a ink for ink-jet print contains a kind of light trigger in the wherein said multi-density ink-jet ink sets.

5, a kind of ink jet printing method, this method comprises the steps:

(a) provide the multi-density ink-jet ink sets that limits as claim 1;

(b) ink for ink-jet print of described multi-density ink-jet ink sets is ejected into is subjected to Mo Tishang.

6, method according to claim 5, wherein said multi-density ink-jet comprises at least two kinds of multi-density cyan, two kinds of multi-density magenta inks and a kind of yellow ink.

7, according to claim 5 or 6 described methods, at least a ink for ink-jet print is a radiation-hardenable in the wherein said multi-density ink-jet ink sets.

8, a kind of multi-density ink-jet ink sets according to claim 7, at least a ink for ink-jet print contains light trigger in the wherein said multi-density ink-jet ink sets.