CN1727413A - Liquid composition for ink jet, ink set for ink jet, ink jet recording method and ink jet recording apparatus - Google Patents

Abstract

The present invention provide an ink set for inkjet a drying time and long-term storage stability, an inkjet recording method, inkjet recording equipment and a liquid composition for inkjet used for these. It is an object to provide a liquid composition for ink jet which contains at least an organic acid having an acid dissociation constant pKa of 4.5 or less, a water-soluble solvent, and water, further comprising at least one of compounds selected from the following group, and this is utilized for an ink set for ink jet, an ink jet recording method and an ink jet recording apparatus, (a): a polyvalent metallic salt having an amount of addition to the organic acid which is equal to or more than 0.01 and is less than 1 in a mole ratio (the polyvalent metallic salt/organic acid); and (b): an organic amine compound having an amount of addition to the organic acid which is equal to or more than 0.1 and is equal to or less than 0.9 in a mole ratio (an organic amine compound/organic acid).

Description

The liquid composition that ink-jet is used, printing ink group, recording method and recording unit

Technical field

The present invention relates to spray ink Printing with liquid composition, spray ink Printing with printing ink group, ink jet recording method and ink-jet recording device.

Background technology

Be used for ink-jet system that printing ink is sprayed from the inkjet mouth of being made up of nozzle, slit or porous-film, little because of its volume, price is low, be applied in the multiple printer.In these ink-jet systems, come the piezoelectric ink jet system of ink-jet by the distortion that utilizes piezoelectric element, and the excellent properties that comes the hot ink-jet system of ink-jet all to have high resolving power and flying print aspect of the boiling phenomenon by heat energy utilization printing ink.

At present, the print speed that improves on common paper is regarded as one of important goal of ink-jet printer with the enhancing image quality.For this reason, someone has proposed a kind of method, its step is as follows: will contain have cationic compound liquid attached on the recording medium, allow this liquid infilter recording medium, infiltered recording medium and after its surface disappears at this liquid, rapidly a kind of printing ink that contains anionic dyestuff is attached on the surface of recording medium, thereby forms image (referring to No. 2667401 communique of Japanese Patent).But if shorten the time of drying of printing ink, image color may be not enough in this method; And if use the small amount of drop print image, then long-term jet power is not enough.

In addition, in order to obtain high speed drying property, high optical concentration and enhancing image quality, the someone has proposed a kind of colored ink group, it is characterized in that: black ink comprises water and water-soluble solvent; Be equal to or less than the time of drying on common paper 5 seconds; Colored ink comprises the flocculation agent that tinting material, water, water-soluble solvent and flocculation black ink component are used; The required time of infiltration on common paper is equal to or less than 5 seconds (for example, referring to TOHKEMY 2001-294788 communique).Use this system and pigment is used for the situation of the tinting material of colored ink at some, obtained good optical concentration, the paper of spreading and sinking between paper and look of spreading and sinking in.But because the existence of flocculation agent causes long term storage stability not enough.Ionogen and polyvalent metal salt are often used as flocculation agent, and time effect is excessive but its problem is them as flocculation agent.

In addition, for improving jet performance, the someone has proposed a kind of like this printing ink, and it comprises nitrogenous five-ring ketone acid, as pyrrolidone carboxylic acid or its salt (for example, referring to Japanese kokai publication sho 63-265681 communique, No. 2711888 communique of Japanese Patent and Te Kai 2000-109735 communique).This method is utilized the performance of keeping humidity of nitrogenous five-ring ketone acid salt, has the purpose that improves jet performance.Yet, to unite under the certain situation of use at liquid that comprises nitrogenous five-ring ketone acid and the liquid that contains as the coloured material mentioned in this invention, the stability of image quality and long storage can not have both at the same time.

As mentioned above, in traditional method, the stability of paper, time of drying and the long storage of spreading and sinking between optical concentration, the paper of spreading and sinking in, look etc. can not be met simultaneously.

Summary of the invention

Therefore, the purpose of this invention is to provide printing ink group, ink jet recording method and the ink-jet recording device that the excellent spray ink Printing of performance is used aspect the paper of spreading and sinking in, time of drying, long storage stable between optical concentration, the paper of spreading and sinking in, look.

In addition, the present invention also provides a kind of spray ink Printing liquid composition that is used for printing ink group, ink jet recording method and ink-jet recording device that described spray ink Printing uses.

A first aspect of the present invention relates to a kind of ink-jet liquid composition, and said composition comprises acid dissociation constant pKa value at least and is equal to or less than 4.5 organic acid, water-soluble solvent and water, also comprises at least a compound that is selected from following group:

(a): polyvalent metal salt, this polyvalent metal salt are counted with mol ratio (polyvalent metal salt/organic acid) with respect to described organic acid addition and are equal to or greater than 0.01 and less than 1; With

(b): organic amine compound, this organic amine compound are counted with mol ratio (organic amine compound/organic acid) with respect to described organic acid addition and are equal to or greater than 0.1 and less than 0.9.

Description of drawings

Fig. 1 is the stereographic map of surface structure of a preferred embodiment of expression ink-jet recording device of the present invention,

Fig. 2 is the stereographic map of the basic structure of the internal part in the expression ink-jet recording device shown in Figure 1,

Fig. 3 is the stereographic map of surface structure of another preferred embodiment of expression ink-jet recording device of the present invention,

Fig. 4 is the stereographic map of basic structure of the internal part of expression ink-jet recording device shown in Figure 3,

Fig. 5 is the figure of expression a kind of print pattern (print pattern A) of being used to assess among the embodiment, what this pattern was represented is the printing portion of liquid 1/ liquid composition among embodiment 1-1～1-3,2-1～2-3 and 3-1 and Comparative Examples 1-1～1-4 and the 2-1～2-4, and the liquid 1 of each embodiment and Comparative Examples and liquid composition are shown in table 1, table 5 and table 9;

Fig. 6 is the figure of expression a kind of print pattern (print pattern B) of being used to assess among the embodiment, what this pattern was represented is the print pattern of embodiment 1-4 and 2-4 and Comparative Examples 1-5 and 2-5, what wherein, the B1 in this pattern represented is the printing portion of liquid 3/ liquid composition; What B2 represented is the printing portion of liquid 1/ liquid composition; What B3 represented is the printing portion of liquid 2/ liquid composition; What B4 represented is the printing portion of liquid 4/ liquid composition, and the liquid 1～4 of described embodiment and Comparative Examples and liquid composition are shown in table 2 and table 6;

Fig. 7 is the figure of expression a kind of print pattern (print pattern C) of being used to assess among the embodiment, and what this pattern was represented is the print pattern of embodiment 1-5 and 2-5, and wherein, what the C1 in this pattern represented is the printing portion of liquid 3; What C2 represented is the printing portion of liquid 1/ liquid composition; What C3 represented is the printing portion of liquid 2; What C4 represented is the printing portion of liquid composition, and the liquid 1～3 of embodiment 1-5 and 2-5 and liquid composition are respectively shown in table 2 and table 6.

Embodiment

In order to solve problem of the present invention, the contriver has carried out positive research.The result has finished the present invention, and satisfied optical concentration simultaneously, the requirement of spread and sink between the paper of spreading and sinking in, look paper, time of drying and prolonged preservation stability aspect.

More specifically, ink-jet of the present invention contains acid dissociation constant pKa value at least with liquid composition and is equal to or less than 4.5 organic acid, water-soluble solvent and water, and the ink solutions that ink-jet is used can flocculate.

With in the liquid composition, preferred said composition also comprises at least a compound that is selected from following group in ink-jet of the present invention:

(a): polyvalent metal salt, this polyvalent metal salt are counted with mol ratio (polyvalent metal salt/organic acid) with respect to described organic acid addition and are equal to or greater than 0.01 and less than 1; With

(b): organic amine compound, this organic amine compound are counted with mol ratio (organic amine compound/organic acid) with respect to described organic acid addition and are equal to or greater than 0.1 and be equal to or less than 0.9.

With in the liquid composition, preferred described organic acid is a represented compound in the general formula (1) in ink-jet of the present invention.

General formula (1):

(in the formula, X represents O, CO, NH, NR, S or SO ₂, R represents alkyl; M represents hydrogen atom, basic metal or amine; 1 represents 1～5 integer; M represents 1 or 2; N represents 3～7 integer).

With in the liquid composition, the represented compound of preferred formula (1) is at least a compound that is selected from the group of being made up of the derivative and their salt of pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrroles's carboxylic acid, furancarboxylic acid, pyridine carboxylic acid, coumalic acid, thiophene carboxylic acid, nicotinic acid, above-claimed cpd in ink-jet of the present invention.

With in the liquid composition, preferably its pH value is for being equal to or greater than 2.5, and is equal to or less than 7.0 in ink-jet of the present invention.

With in the liquid composition, the weight-average molecular weight of preferred organic amine compound is for being equal to or less than 1000 in ink-jet of the present invention.

With in the liquid composition, with respect to the liquid composition total amount, the addition of organic amine compound in liquid composition is preferably and is equal to or greater than 0.01 quality %, and is equal to or less than 30 quality % in ink-jet of the present invention.

With in the liquid composition, with respect to the total amount of liquid composition, the addition of organic acid in liquid composition is preferably and is equal to or greater than 0.01 quality %, and is equal to or less than 30 quality % in ink-jet of the present invention.

The invention provides a kind of ink for inking group that comprises first liquid (ink solutions that ink-jet is used) and second liquid (liquid composition that ink-jet is used) at least.

First liquid comprises coloured material, water-soluble solvent and water at least; With

Second liquid is ink-jet liquid composition of the present invention.

In ink for inking group of the present invention, coloured material in first liquid is preferably pigment, and this pigment is at least a pigment that is selected from the group of being made up of following pigment: by polymeric dispersant dispersive pigment, from pigment dispersion and the pigment that is coated with resin.

In ink for inking group of the present invention, coloured material particulate volume average particle size is preferably and is equal to or greater than 30nm in first liquid, and is equal to or less than 250nm.

In ink for inking group of the present invention, the surface tension of first liquid is preferably and is equal to or greater than 20mN/m, and is equal to or less than 60mN/m.

In ink for inking group of the present invention, first liquid preferably comprises the resin that has hydroxy-acid group.

In ink for inking group of the present invention, second liquid preferably comprises and is selected from by dyestuff, surface by the pigment of sulfonic acid or sulfonate and at least a coloured material in the group that pigment dispersion is formed.

In ink for inking group of the present invention, the surface tension of second liquid is preferably and is equal to or greater than 20mN/m, and is equal to or less than 45mN/m.

In ink for inking group of the present invention, the viscosity of first liquid and second liquid is preferably and is equal to or greater than 1.2mpas, and is equal to or less than 25.0mPas.

In ink for inking group of the present invention, particle diameter is 5 μ m or is preferably greater than the particulate quantity of 5 μ m and is equal to or greater than 1,000/ μ L in the mixing solutions of first liquid and second liquid.

The invention provides a kind of ink jet recording method that uses the ink for inking group,

Wherein, described ink for inking group is the ink for inking group among the present invention, and

With first liquid and second liquid application on recording medium so that both be in contact with one another, thereby form image.

In ink jet recording method of the present invention, first liquid and second liquid are preferably with every 25ng (ng:10 ^-9Gram) or the amount that is less than 25ng be applied on the recording medium.

In ink jet recording method of the present invention, be used to form a pixel and described first liquid used and second liquid amount separately be preferably 1: 20 to 20: 1 than by quality ratio.

The invention provides and comprise jet recording device, this record-header is used for spraying to recording medium the various liquid of described ink for inking group,

Wherein, described ink for inking group is the ink for inking group among the present invention.

In ink-jet recording device of the present invention, first liquid and second liquid preferably are applied on the recording medium with every 25ng or the amount that is less than 25ng.

In ink-jet recording device of the present invention, be used to form a pixel and first liquid used and second liquid amount separately be preferably 1: 20～20: 1 than by quality ratio.

As mentioned above, ink-jet of the present invention is with liquid composition, ink for inking group, ink jet recording method and ink-jet recording device, performance excellence aspect paper, time of drying and the long term storage stability of spreading and sinking between optical concentration, the paper of spreading and sinking in, look.

Below will describe the present invention.

(ink for inking group and ink-jet liquid composition)

Comprise in the formation of ink for inking group of the present invention that first liquid reaches second liquid that first liquid is had throwing out.As second liquid, use be to contain acid dissociation constant pKa value to be equal to or less than 4.5 organic acid ink-jet with liquid composition (ink-jet liquid composition of the present invention); It is preferred that what use is also to comprise to become the organic amine compound of specific ratios or the ink-jet liquid composition of polyvalent metal salt with described organic acid.

Carry out printing by the mode that first liquid and second liquid are in contact with one another, can improve optical concentration, the paper of spreading and sinking between paper and look of spreading and sinking in.Although mechanism it be unclear that, but infer and to think: acid dissociation constant pKa value is equal to or less than the effect that 4.5 organic acid has first liquid that flocculates, and carry out printing and cause two kinds of liquid on recording medium, to be in contact with one another, like this, can make coloured material be retained in the surface of recording medium to high-density.

Why acid dissociation constant pKa value is the material that is applicable to flocculation first liquid if being equal to or less than 4.5 organic acid, following three reasons are arranged by inference:

＜1〉acid dissociation constant pKa value is equal to or less than 4.5 organic acid, and big and this organic acid of the dissociation degree of its acidic-group is acid.Therefore, be used at the coloured material that will have the anionic property surface functional group under the situation of first liquid, when two kinds of liquid contacted with each other, organic acid produced restraining effect to the disassociation of the surface functional group of coloured material in first liquid, and therefore coloured material flocculates.

＜2〉can think that acid dissociation constant pKa value is equal to or less than the effect that 4.5 organic acid has the pH buffer reagent.Therefore there is such specific character, promptly in specific acid pH scope, very little by the pH value fluctuation that hydrionic concentration causes.As a result, can think that the pH value remains on an acid side when first liquid and the second liquid intermingling, therefore the coloured material in first liquid can effectively be flocculated.

＜3〉acid dissociation constant pKa value is equal to or less than 4.5 organic acid, and it also has electrolytical effect.Therefore, under the situation of the coloured material that pigment is used for first liquid, can think that the electrostatic repulsion between the pigment is weakened, thereby promote flocculation.

In addition, why polyvalent metal salt is the material that is applicable to flocculation first liquid, mainly contains following two reasons by inference:

＜1〉in using the system of pigment, can think that polyvalent metal salt has weakened the electrostatic repulsion between the pigment, thereby produce the favourable condition that promotes pigment flocculation as coloured material.

＜2〉have the pigment of hydroxy-acid group or sneak under the situation of the liquid that comprises organic compound sneaking into the surface, can think that polyvalent metal and carboxylic acid have formed ionomer structure with hydroxy-acid group.Correspondingly, the molecular structure size increases, simultaneously, the hydrophilic group of surface of pigments because of quantity or the hydrophilic group of organic compound because of quantity reduce.Therefore, think that pigment or organic compound can flocculate.In addition, can think that organic compound also can flocculate when having carried another kind of coloured material.Therefore, except the situation of using pigment, using under the situation of dyestuff as coloured material, the flocculation of this coloured material is accelerated equally.

On the other hand, find that also organic acid and polyvalent metal salt cause following deficiency respectively:

Ideal situation is, acid dissociation constant pKa value is equal to or less than 4.5 organic acid and should uses with the part neutral condition, so that improve flocculation efficiency and improve image quality.But this moment, be difficult to satisfy simultaneously the requirement of image quality and long term storage stability.Although mechanism it be unclear that, can think, when organic acid adds fashionablely with high density, because its water-soluble deficiency, will produce deposition.

With regard to polyvalent metal salt, ideal situation is that the consumption that increases polyvalent metal salt is to improve flocculation efficiency and to improve image quality.But, under some situation that increases the polyvalent metal salt consumption, find to produce the directional property defective.Although mechanism it be unclear that, can think that the polyvalent metal salt sedimentation also sticks to the tip of nozzle, causes that the hydrophobicity of nozzle changes.

Based on these results, thereby carried out positive research work.Found that, organic acid and polyvalent metal salt are used by adequate rate, can make the performance of image quality, long term storage stability and long-term injection reliability aspect compatible.Although mechanism it be unclear that, can infer and think, produced intermolecular reactive force between polyvalent metal and the organic acid, as sequestering action, but make both all stable existences.And, know that polyvalent metal salt produces micro-water miscible hydroxide ion under alkaline condition.Can think that favourable part is, by polyvalent metal salt is added with organic acid, can suppress the generation of the hydroxide salt of polyvalent metal, thus the stabilization of obtaining.

Be used in combination by being equal to or less than 4.5 organic acid as the organic amine compound of dissolving organic acid alkaline reagents and acid dissociation constant pKa value, even under low neutral condition, the solvability of organic acid in water increased, thereby make the reliability of liquid composition and image quality compatible with each other.Although mechanism it be unclear that, infer and think that organic acid and organic amine compound all have hydrocarbon type skeleton, have increased affinity by hydrophobic interaction.

At first, first liquid is described.First liquid comprises coloured material, water-soluble solvent and water at least.

The coloured material that is used for first liquid can be dyestuff or pigment, and especially preferably uses pigment.The reasons are as follows.Deduction is thought: with second mixtures of liquids in, the easier flocculation of pigment ratio dyestuff.Especially, it is preferred being carried out dispersive pigment, from pigment dispersion and surface coverage the pigment of resin is arranged by polymeric dispersant.

Pigment dyestuff and mineral dye all can be used for pigment used among the present invention, and the example of black pigment comprises charcoal blacks, as furnace treated black, dim, acetylene black or thermally oxidized black.Can use also that to have black and three primary colors be cyan, pinkish red and xanchromatic pigment, can use in addition to have particular color such as red, green, blue, palm fibre or white pigment, have the metalluster pigment of golden yellow or silver color, colourless or light extender or plastic pigments.In addition, its surface adhesion has insoluble pigementation material in the particle, dyestuff of dyestuff or pigment, and silicon-dioxide, aluminum oxide or polymeric beads are made as coloured emulsion or coloured latex of nuclear, also can be used as pigment.For the present invention, can also use new synthetic pigment.

The specific examples of the pigment that uses among the present invention comprises Raven 7000, Raven 5750, Raven5250, Raven 5000 Ultra II, Raven 3500, Raver 2000, Raven 1500, Raven1250, Raven 1200, Raven 1190 ULTRA II, Raven 1170, Raven 1255, Raven1080, Raven 1060 (being made by the Columbian chemical company); Regal 400R, Regal330R, Regal 660R, Mogul L, Black Pearls L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300 and Monarch 1400 (making) by Cabot company; Color Black FW1, Color Black FW2, Color Black FW2V, Color Black 18, Color Black FW200, Color BlackS150, Color Black S160, Color Black S170, Printex35, PrintexU, PrintexV, Printex 140U, Printex 140V, Special Black 6, Special Black 5, Special Black4A, Special Black 4 (making) by Degussa company; No.25, No.33, No.40, No.47, No.52, No.900, No.2300, MCF-88, MA600, MA7, MA8 and MA100 (making) by Mitsubishi Chemical.But the used pigment of the present invention is not limited thereto.

The example of cyan comprise C.I. (Colour Index) Pigment blue-1 ,-2 ,-3 ,-15 ,-15:1 ,-15:2 ,-15:3 ,-15:4 ,-16 ,-22 and-60, but the used pigment of the present invention is not limited thereto.

The example of magenta comprise C.I. Pigment red-5 ,-7 ,-12 ,-48 ,-48:1 ,-57 ,-112 ,-122 ,-123 ,-146 ,-168 ,-184 and-202, but the used pigment of the present invention is not limited thereto.

The xanchromatic example comprises Pigment Yellow 73-1 ,-2 ,-3 ,-12 ,-13 ,-14 ,-16 ,-17 ,-73 ,-74 ,-75 ,-83,93 ,-95 ,-97 ,-98 ,-114,128 ,-129 ,-138 ,-151 ,-154 and-180, but the used pigment of the present invention is not limited thereto.

Be used for the pigment that is scattered in water certainly of the present invention and refer to the pigment that many water soluble groups are arranged on its surface, this pigment can stably be dispersed in the water under the condition of not adding any polymeric dispersant.In fact, can obtain by carrying out surface modification treatment, handle as so-called common pigments being carried out acid or alkaline purification, coupling agent treatment, polymer graft processing, Cement Composite Treated by Plasma or redox from the pigment that is scattered in water.

Except that the pigment of above-mentioned process surface modification, commercially available pigment such as Cab-o-jet-200, Cab-o-jet-300, IJX-253, IJX-266, IJX-273, IJX-444 and IJX-55 (making) by Cabot company, and Microjet Black CW-1 and CW-2 (making by Orient chemical industry company limited), also can be used as described from the pigment that is scattered in water.

For for pigment dispersion, the coloured material that the carboxylic acid group is arranged in its surperficial functional group is preferred for the coloured material that is used for first liquid.Supposition thinks, because acid dissociation constant pKa value is equal to or less than the disassociation that 4.5 organic acid can suppress carboxylic acid, the dissociation degree of carboxylic acid is reduced, thereby can promote to flocculate.

When coloured material surface used in first liquid has sulfonic group, preferably except that using coloured material, also add the polymkeric substance (resin that has hydroxy-acid group) that has hydroxy-acid group.The surface has sulfonic coloured material and is difficult to flocculation.Therefore, optical concentration, the paper of spreading and sinking between paper and look of spreading and sinking in often can not get improving.On the other hand, have in adding under the situation of polymkeric substance of hydroxy-acid group, polymkeric substance does not dissolve when two kinds of liquid phases mix.In this case, thus pigment is carried to and is flocculated in the polymkeric substance.Therefore can expect that optical concentration, the paper of spreading and sinking between paper and look of spreading and sinking in can improve.

Surface coverage has the pigment of resin to can be used as tinting material.This pigment is known as microcapsule pigment, and it comprises commercially available by Dainippon You Mo ﹠amp; The microcapsule pigment that chemical company and Toko Ink MFG Co., Ltd. make also is included as application of the present invention and the microcapsule pigment for preparing.

Water-soluble dye or dispersed dye all can be used for the present invention.The specific examples of water-soluble dye comprises: C.I. directly deceives-2 ,-4 ,-9 ,-11 ,-17 ,-19 ,-22 ,-32 ,-80 ,-151 ,-154 ,-168 ,-171 ,-194 and-195; C.I. sun blue-1 ,-2 ,-6 ,-8 ,-22 ,-34 ,-70 ,-71 ,-76 ,-78 ,-86 ,-112 ,-142 ,-165 ,-199 ,-200 ,-201 ,-202 ,-203 ,-207 ,-218 ,-236 ,-287 and-307; C.I. directly red-1 ,-2 ,-4 ,-8 ,-9 ,-11 ,-13 ,-15 ,-20 ,-28 ,-31 ,-33 ,-37 ,-39 ,-51 ,-59 ,-62 ,-63 ,-73 ,-75 ,-80 ,-81 ,-83 ,-87 ,-90 ,-94 ,-95 ,-99 ,-101 ,-110 ,-189 and 227; C.I. direct yellow-1 ,-2 ,-4 ,-8 ,-11 ,-12 ,-26 ,-27 ,-28 ,-33 ,-34 ,-41 ,-44 ,-48 ,-58 ,-86 ,-87 ,-88 ,-132 ,-135 ,-142 ,-144 and-173; C.I. food black-1 and-2; C.I. erie black-1 ,-2 ,-7 ,-16 ,-24 ,-26 ,-28 ,-31 ,-48 ,-52 ,-63 ,-107 ,-112 ,-118 ,-119 ,-121 ,-156 ,-172 ,-194 and-208; C.I. acid blue-1 ,-7 ,-9 ,-15 ,-22 ,-23 ,-27 ,-29 ,-40 ,-43 ,-55 ,-59 ,-62 ,-78 ,-80 ,-81 ,-83 ,-90 ,-102 ,-104 ,-111 ,-185 ,-249 and-254; C.I. Xylene Red-1 ,-4 ,-8 ,-13 ,-14 ,-15 ,-18 ,-21 ,-26 ,-35 ,-37 ,-52 ,-110 ,-144 ,-180 ,-249 ,-257 and-289; C.I. turmeric yellow-1 ,-3 ,-4 ,-7 ,-11 ,-12 ,-13 ,-14 ,-18 ,-19 ,-23 ,-25 ,-34 ,-38 ,-41 ,-42 ,-44 ,-53 ,-55 ,-61 ,-71 ,-76 ,-78 ,-79 and-122.

The specific examples of dispersed dye comprises: C.I. DISPERSE YELLOW-3 ,-5 ,-7 ,-8 ,-42 ,-54 ,-64 ,-79 ,-82 ,-83 ,-93 ,-100 ,-119 ,-122 ,-126 ,-160 ,-184:1 ,-186 ,-198 ,-204 and 224; C.I. DISPERSE ORANGE 30 200-13 ,-29 ,-31:1 ,-33 ,-49 ,-54 ,-66 ,-73 ,-119 and-163; C.I. Disperse Red-1 ,-4 ,-11 ,-17 ,-19 ,-54 ,-60 ,-72 ,-73 ,-86 ,-92 ,-93 ,-126 ,-127 ,-135 ,-145 ,-154 ,-164 ,-167:1 ,-177 ,-181 ,-207 ,-239 ,-240 ,-258 ,-278 ,-283 ,-311 ,-343 ,-348 ,-356 and-362; C.I. 63 DISPERSE Violet 63-33; C.I. EX-SF DISPERSE BLUE EX-SF 300-14 ,-26 ,-56 ,-60 ,-73 ,-87 ,-128 ,-143 ,-154 ,-165 ,-165:1 ,-176 ,-183 ,-185 ,-201 ,-214 ,-224 ,-257 ,-287 ,-354 ,-365 and-368; C.I. Disperse Green-6:1 and-9.

Among the present invention, with respect to the total mass of first liquid, the proportional range of used tinting material is for being not less than 0.1 quality % and being not more than 20 quality %, and the preferred proportion scope is for being not less than 1 quality % and being not more than 10 quality %.When tinting material when proportion is less than 0.1 quality % in this liquid, may can not get enough optical concentrations; And when the ratio of tinting material during, jet performance potentially unstable greater than 20 quality %.

In the present invention, polymeric dispersant also can be used in first liquid so that pigment is dispersed.On the other hand, using under the situation of the pigment that is scattered in water, also can use polymeric dispersant simultaneously.For polymeric dispersant, also can use non-ionic compound, anionic compound, cation compound and amphoteric substance.

With the monomeric multipolymer with α, β-ethylenically unsaturated group is example.Has α, the monomeric example of β-ethylenically unsaturated group comprises: vinylformic acid, methacrylic acid, Ba Dousuan, methylene-succinic acid, the methylene-succinic acid monoesters, toxilic acid, the toxilic acid monoesters, fumaric acid, fumaric monoalkylester, vinyl sulfonic acid, styrene sulfonic acid, the vinylnaphthalene sulphonate, vinyl alcohol, acrylamide, methacryloxy ethyl phosphate, di(2-ethylhexyl)phosphate (methylacryoyloxyethyl) ester, acid phosphoric acid methylacryoyloxyethyl phenylester, ethylene glycol bisthioglycolate (methacrylic acid) ester, Diethylene Glycol two (methacrylic acid) ester, styrene derivatives such as vinylbenzene, alpha-methyl styrene, vinyl toluene, vinyl cyclohexane, vinylnaphthalene, the vinylnaphthalene derivative, alkyl acrylate, phenyl acrylate, alkyl methacrylate, phenyl methacrylate, the methacrylic acid cycloalkyl ester, the Ba Dousuan alkyl ester, methylene-succinic acid dialkyl and dialkyl maleate.

By the polymkeric substance of the monomer that has olefinic α, β-unsaturated group, or, all can be used as polymeric dispersant by the multiple multipolymer that has the monomer of olefinic α, β-unsaturated group by the copolymerization acquisition by the homopolymerization acquisition.Wherein, concrete example comprises: vinylbenzene-styrene sulfonic acid ester copolymer, styrene-maleic acid copolymer, vinylbenzene-Sipacril 2739OF, the styrene-propene acid copolymer, vinylnaphthalene-maleic acid, vinylnaphthalene-Sipacril 2739OF, vinylnaphthalene-acrylic copolymer, alkyl acrylate-acrylic copolymer, alkyl methacrylate-Sipacril 2739OF, vinylbenzene-alkyl methacrylate-Sipacril 2739OF, styrene-propene acid alkyl ester-acrylic copolymer, vinylbenzene-methacrylic acid phenylester-Sipacril 2739OF and vinylbenzene-methacrylic acid cyclohexyl ester-Sipacril 2739OF.

The polymeric dispersant that is used for first liquid, preferred weight-average molecular weight is 2000～50000.Be lower than under 2000 the certain situation dispersing of pigments instability at the molecular weight of polymeric dispersant.On the other hand, be higher than at the molecular weight of polymeric dispersant under 50000 the certain situation, the liquid viscosity increase causes the discharging performance variation.Preferred weight-average molecular weight is 3500～20000.

The polymeric dispersant that adds in first liquid uses in the scope of 0.01 quality %～3 quality %.Under the certain situation of addition greater than 3 quality %, the viscosity of liquid increases, thereby makes the spray characteristic of liquid become unstable.On the other hand, under the certain situation of addition less than 0.01 quality %, the dispersing of pigments bad stability.The addition of polymeric dispersant more preferably is equal to or greater than 0.05 quality % and is equal to or less than 2.5 quality %; More preferably be equal to or greater than 0.1 quality % and be equal to or less than 2 quality %.

The volume average particle size of coloured material preferably is equal to or greater than 30nm in first liquid, and is equal to or less than 250nm.Volume average particle size refers to the particle diameter of coloured material particle itself or is stained with the coloured material particle grain size of the additive (if any) of dispersion agent and so on.In the present invention, use microtrack UPA particle-size analyzer 9340 (by Leeds ﹠amp; Northrup Co., Ltd. makes) as the instrument of measurement volumes median size.4ml printing ink is put into measuring cell, measure according to predetermined measuring method.For the parameter that in measurement, will import, with the viscosity of printing ink as viscosity, with the density of pigment density as discrete particles.This volume average particle size more preferably is equal to or greater than 50nm and is equal to or less than 200nm, and further preferably is equal to or greater than 75nm and is equal to or less than 175nm.Under the certain situation of particulate volume average particle size less than 30nm, optical concentration reduces in liquid.On the other hand, under the certain situation of above-mentioned volume average particle size greater than 250nm, package stability can not be maintained.

For water-miscible organic solvent used in first liquid, can use polyvalent alcohol, polyol derivative, nitrogen-containing solvent, alcohol and sulfur-bearing solvent.The specific examples of polyvalent alcohol comprises: ethylene glycol, Diethylene Glycol, propylene glycol, butyleneglycol, triethylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol and glycerol.The specific examples of polyol derivative comprises: the ethylene oxide adduct of glycol monomethyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, TC, Diethylene Glycol single-butyl ether, propylene glycol single-butyl ether, dipropylene glycol single-butyl ether and Glycerol dimer.The specific examples of nitrogen-containing solvent comprises: pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, hexanaphthene pyrrolidone and trolamine.The specific examples of alcohols comprises: ethanol, Virahol, butanols and benzylated polyol.The specific examples of sulfur-bearing solvent comprises: thiodiethanol, sulfo-two glycerine, tetramethylene sulfone and dimethyl sulfoxide (DMSO).In addition, also can use propylene carbonate and ethylene carbonate.

In first liquid, can use single water-miscible organic solvent, also the water-miscible organic solvent of same class or at least two classes can be mixed.The content of used water-miscible organic solvent is equal to or greater than 1 quality %, and is equal to or less than 60 quality %; And be preferably and be equal to or greater than 5 quality %, and be equal to or less than 40 quality %.In this liquid, under the certain situation of the content of water-miscible organic solvent less than 1 quality %, can not obtain enough optical concentrations.On the contrary, under the certain situation of the content of water-miscible organic solvent greater than 60 quality %, the viscosity of this liquid increases in this liquid, thereby makes the jet performance of this liquid become unstable.

Comprise water soluble resin or non-water-soluble resin in preferred first liquid.Its reason is can produce favourable part like this: acid dissociation constant pKa value is equal to or less than 4.5 organic acid and makes water soluble resin or non-water-soluble resin flocculation.Deduction is thought: when resin flocculates, can simultaneously coloured material be brought into.Correspondingly, the trend of generation is that the flocculating effect of coloured material is enhanced, thereby makes optical concentration, the paper of spreading and sinking between the paper of spreading and sinking in, look improves.

The compound that preferably contains hydroxy-acid group is as water soluble resin or non-water-soluble resin.The reasons are as follows.Deduction is thought: because exist acid dissociation constant pKa value to be equal to or less than 4.5 organic acid, the dissociation degree of hydroxy-acid group is lower, thereby promotes flocculation.Particularly will contain sulfonic compound, preferred water soluble resin or the non-water-soluble resin that contains hydroxy-acid group that add as under the situation of coloured material.Under the preferred situation, this examples for compounds comprises: styrene-propene acid copolymer, vinylbenzene-Sipacril 2739OF, styrene-maleic acid copolymer and AE.

With respect to the total amount of first liquid, the addition of water soluble resin or non-water-soluble resin is preferably and is equal to or greater than 0.01 quality %, and is equal to or less than 10 quality %; More preferably be equal to or greater than 0.1 quality %, and be equal to or less than 3 quality %.

The surface tension of first liquid is preferably and is equal to or greater than 20mN/m, and is equal to or less than 60mN/m.

This surface tension more preferably is equal to or greater than 20mN/m, and is equal to or less than 45mN/m; More preferably be equal to or greater than 20mN/m, and be equal to or less than 35mN/m.Under the certain situation of surface tension less than 20mN/m, liquid is spilled over to nozzle surface, thereby printing can not normally be carried out.On the other hand, under the certain situation of surface tension greater than 60mN/m, infiltration becomes slowly, thereby prolonged time of drying.

The viscosity of first liquid is preferably and is equal to or greater than 1.2mPas, and is equal to or less than 25.0mPas; More preferably be equal to or greater than 1.5mPas, and less than 10.0mpas; More preferably be equal to or greater than 1.8mPas, and less than 5.0mPas.Under the certain situation of viscosity greater than 25.0mPas of first liquid, the discharging performance variation.On the other hand, under the certain situation of viscosity less than 1.2mPas of first liquid, the jet performance variation.

In the scope that can obtain aforesaid surface tension and viscosity, add water.The addition of water is also without particular limitation, but the total amount of relative first liquid, the addition of water is preferably and is equal to or greater than 10 quality %, and is equal to or less than 99 quality %; More preferably be equal to or greater than 30 quality %, and be equal to or less than 80 quality %.

Next, second liquid (ink-jet liquid composition) is described.Preferred second liquid comprises acid dissociation constant pKa value and is equal to or less than 4.5 organic acid, water-soluble solvent and water, also should comprise polyvalent metal salt or organic amine compound.

Be equal to or less than 4.5 organic acid for described acid dissociation constant pKa, can use the compound of expression in the following general formula (1).

General formula (1)

In the formula, X represents O, CO, NH, NR, S or SO ₂, R represents alkyl.R is preferably CH ₃, C ₂H ₅, C ₂H ₄OH.X is preferably CO, NH, NR and O, more preferably CO, NH and O.M represents hydrogen atom, basic metal or amine; M is preferably H, Li, Na, K, monoethanolamine, diethanolamine and trolamine, more preferably H, Na and K, more preferably hydrogen atom.N represents 3～7 integer, is preferably to have six-ring or pentacyclic heterocycle, more preferably has pentacyclic heterocycle.M represents 1 or 2.If the compound of expression is saturated rings or unsaturated ring in the heterocycle, general formula (1).1 represents 1～5 integer.

Acid dissociation constant pKa is equal to or less than 4.5 organic acid example and comprises: the compound of expression and the derivative of above-claimed cpd in arginine, citric acid, glycine, L-glutamic acid, succsinic acid, tartrate, halfcystine, oxalic acid, fumaric acid, phthalic acid, toxilic acid, propanedioic acid, trimethyl-glycine, oxysuccinic acid, the general formula (1).

Under the preferred situation, acid dissociation constant pKa is equal to or less than 4.5 organic acid and comprises: the derivative or the salt of citric acid, glycine, L-glutamic acid, succsinic acid, tartrate, phthalic acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrroles's carboxylic acid, furancarboxylic acid, pyridine carboxylic acid, coumalic acid, thiophene carboxylic acid, nicotinic acid, these compounds.Under the preferred situation, described organic acid comprises: the derivative or the salt of pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrroles's carboxylic acid, furancarboxylic acid, pyridine carboxylic acid, coumalic acid, thiophene carboxylic acid, nicotinic acid, these compounds.Further preferred organic acid comprises: the derivative of pyrrolidone carboxylic acid, pyrone carboxylic acid, furancarboxylic acid, coumalic acid, these compounds or salt.

In the general formula (1) specific examples of the compound of expression comprise have furan structure, the compound of pyrrole structure, pyrroline structure, pyrrolidone structure, pyrone structure, pyrrole structure, thiophene structure, indole structure, pyridine structure and quinoline structure, also comprise having the compound of carboxyl in addition as functional group.The specific examples of this compound comprises: 2-Pyrrolidone-5-carboxylic acid, 4-methyl-4-valerolactone-3-carboxylic acid, furancarboxylic acid, the 2-benzofurancarboxylic acid, 5-methyl-pyromucic acid, 2, the 5-pyrotritaric acid, 2,5-furans dicarboxylic acid, 4-butyrolactone-3-carboxylic acid, 3-hydroxyl-pyrokomane-2, the 6-dicarboxylic acid, 2-pyrone-6-carboxylic acid, pyrokomane-2-carboxylic acid, 5-hydroxyl-pyrokomane-5-carboxylic acid, pyrokomane-2, the 6-dicarboxylic acid, 3-hydroxyl-pyrokomane-2, the 6-dicarboxylic acid, the thiophene carboxylic acid, 2-pyrroles's carboxylic acid, 2,3-dimethyl pyrrole-4-carboxylic acid, 2,4,5-trimethylammonium pyrroles-3-propionic acid, 3-hydroxy-2-indole carboxylic acid, 2,5-dioxo-4-methyl-3-pyrroline-3-propionic acid, pyrrolidine 2 carboxylic acid, the 4-oxyproline, 1-methylpyrrolidin-2-carboxylic acid, 5-carboxyl-1-methylpyrrolidin-2-acetate, 2-Pyridinecarboxylic Acid, the 3-pyridine carboxylic acid, the 4-pyridine carboxylic acid, pyridine dicarboxylic acid, pyridinetricarboxylic acid, pyridine-pentacarboxylic acid, 1,2,5,6-tetrahydrochysene-1-methylnicotinic acid, quinaldinic acid, the 4-quinoline carboxylic acid, 2-phenyl-4-quinoline carboxylic acid, 4-hydroxyl-quinaldinic acid and 6-methoxyl group-4-quinoline carboxylic acid.

Acid dissociation constant pKa is equal to or less than 4.5 organic acid and can uses separately, also can with wherein at least two kinds be used in combination.

Acid-base titration curve when acid dissociation constant can be by 20 ℃ obtains.More particularly, preparation has the organic acid soln and the sodium hydroxide solution of known addition, and sodium hydroxide solution is joined organic acid soln.At this moment, measure the pH value of the amount of the sodium hydroxide solution that is added and organic acid soln in this case.Based on thus obtained data, theoretical curve is optimized to obtain acid dissociation constant.

For example, below will show the theoretical curve that uses trihydric acid:

[equation 1]

$V_B=\{\frac{\frac{K_1}{\left[H^{+}\right]}+2\frac{K_1{K}_2}{{\left[H^{+}\right]}^2}+3\frac{K_1{K}_2{K}_3}{{\left[H^{+}\right]}^3}}{1+\frac{K_1}{\left[H^{+}\right]}+\frac{K_1{K}_2}{{\left[H^{+}\right]}^2}+\frac{K_1{K}_2{K}_3}{{\left[H^{+}\right]}^3}}{C}_4-\left(\right[H^{+}]-[{\mathrm{OH}}^{-}\left]\right)\}\frac{V_A}{C_B+\left(\right[H^{+}]-[{\mathrm{OH}}^{-}\left]\right)}$

V _ARepresent the amount of this aqueous peracid solution, V _BRepresent the titer of this aqueous alkali solution, C _ARepresent the concentration of this aqueous peracid solution, C _BRepresent the concentration of this aqueous alkali solution, K ₁, K ₂And K ₃Represent one-level, secondary and three grades of dissociation constants of acid, [H ⁺] represent the hydrogen ion concentration in the aqueous solution, [OH ^-] represent the concentration of the hydroxide ion in the aqueous solution.

According to the present invention, the minimum value of pKa is used to have the compound of a plurality of acidic-groups.

With respect to the total amount of liquid, acid dissociation constant pKa is equal to or less than 4.5 organic acid addition and is preferably and is equal to or greater than 0.01 quality %, and is equal to or less than 30 quality %.This addition more preferably is equal to or greater than 0.1 quality %, and is equal to or less than 15 quality %; More preferably be equal to or greater than 0.25 quality %, and be equal to or less than 10 quality %.Be equal to or less than 4.5 organic acid for the acid dissociation constant pKa in second liquid, under the situation of this organic acid addition less than 0.01 quality %, the gathering of coloured material became insufficient when it contacted with first liquid, thereby made optical concentration, the paper of spreading and sinking between the paper of spreading and sinking in, look worsens.On the other hand, under the certain situation of addition greater than 30 quality %, jet performance variation and make this spouting of liquid undesired.

Be equal to or less than 4.5 organic acid second liquid for containing acid dissociation constant pKa, its pH value is preferably and is equal to or greater than 2.5, and is equal to or less than 7.0.This pH value more preferably is equal to or greater than 2.75, and is equal to or less than 6.0, and more preferably is equal to or greater than 3.0, and is equal to or less than 4.5.The pH of second liquid value less than 2.5 certain situation under, be damaged to such an extent as to the dissolving printhead takes place the oil ink passage parts of printhead.On the other hand, the pH of second liquid value greater than 7.0 situation under, the flocculation of coloured material became insufficient when it contacted with first liquid, thereby made optical concentration, the paper of spreading and sinking between the paper of spreading and sinking in, look worsens.

The polyvalent metal salt that is used for the present invention comprises: the salt of polyvalent metal ion, as the salt of aluminum ion, barium ion, calcium ion, cupric ion, iron ion, magnesium ion, mn ion, nickel ion, tin ion, titanium ion and zine ion; Hydrochloride, hydrobromate, hydriodate, vitriol, nitrate, phosphoric acid salt, thiocyanate-; Organic carboxylate is as acetate, oxalate, lactic acid salt, fumarate, Citrate trianion, salicylate and benzoate; And organic sulfonate.

Specific examples comprises these compounds: aluminum chloride, aluminum bromide, Tai-Ace S 150, aluminum nitrate, aluminium sodium sulfate, potassium aluminium sulfate, aluminum acetate, bariumchloride, barium bromide, barium iodide, barium oxide, nitrate of baryta, barium thiocyanide, calcium chloride, Calcium Bromide, calcium iodide, calcium nitrite, nitrocalcite, monocalcium phosphate, calcium thiocyanide, calcium benzoate, lime acetate, calcium salicylate, calcium tartrate, calcium lactate, Fumaric acid, calcium salt, citrate of lime, cupric chloride, cupric bromide, copper sulfate, cupric nitrate, venus crystals, iron(ic) chloride, iron bromide, ferric iodide, ferric sulfate, iron nitrate, ironic oxalate, ironic lactate, ferrous fumarate, ironic citrate, magnesium chloride, magnesium bromide, magnesium iodide, sal epsom, magnesium nitrate, magnesium acetate, magnesium lactate, Manganous chloride tetrahydrate, manganous sulfate, manganous nitrate, phosphate dihydrogen manganese, manganous acetate, manganese salicylate, manganese benzoate, manganous lactate, nickelous chloride, nickelous bromide, single nickel salt, nickelous nitrate, nickelous acetate, tin sulphate, titanium chloride, zinc chloride, zinc bromide, zinc sulfate, zinc nitrate, zinc thiocyanide and zinc acetate.

Polyvalent metal salt has produced the unusual effect of the component flocculation that makes in first liquid, and improve optical concentration, the unusual effect of the paper of spreading and sinking between the paper of spreading and sinking in, look.

Polyvalent metal salt can use separately, also can be with wherein at least two class polyvalent metal salts mixing use.And with respect to the total amount of second liquid, the content of used polyvalent metal salt in second liquid is 0.01 quality %～15 quality %, is preferably 0.1 quality %～10 quality %.

In second liquid, described polyvalent metal salt is counted with mol ratio (polyvalent metal salt/organic acid) with respect to described organic acid addition and is equal to or greater than 0.01 and less than 1.The addition of described polyvalent metal salt more preferably is equal to or greater than 0.05 with respect to the mol ratio of described organic acid addition, and is equal to or less than 0.9, and more preferably is equal to or greater than 0.05, and is equal to or less than 0.75.Be equal to or higher than with respect to the mol ratio of organic acid addition at the addition of polyvalent metal salt under 1 the situation, the stability of long-term jet performance and long storage inadequately.In addition, be lower than with respect to the mol ratio of organic acid addition at the addition of polyvalent metal salt under 0.01 the situation, the stability of long storage is not enough.

The organic amine compound that is used for second liquid can be any in primary amine, secondary amine, tertiary amine and quaternary ammonium compound and their salt.Specific examples comprises: tetra-allkylammonium, alkylamine, benzalkonium, alkyl pyridine, imidazoles, polyamine and their derivative or salt.Specific examples comprises: amylamine, butylamine, Propanolamine, propylamine, thanomin, ehtylethanolamine, 2 ethyl hexylamine, ethylmethylamine, Ethylbenzyl amine, quadrol, octylame, oleyl amine, cyclooctylamine, the ring butylamine, cyclopropylamine, hexahydroaniline, diisopropanolamine (DIPA), diethanolamine, diethylamide, two-2 ethyl hexylamine, diethylenetriamine, diphenylamine, dibutylamine, dipropylamine, dihexyl amine, diamyl amine, 3-(dimethylamino) propylamine, dimethyl amine, the dimethyl ethylene diamine, the dimethyl octylame, 1, the 3-dimethyl butylamine, dimethyl-1, the 3-propylene diamine, dimethylhexylamine, the ammonia butanols, aminopropanol, the ammonia propylene glycol, N-kharophen ethanol, 2-(the amino ethylamino of 2-)-ethanol, 2-amino-2-ethyl-1, ammediol, 2-(2-amino ethoxy)-ethanol, 2-(3, the 4-Dimethoxyphenyl)-ethamine, hexadecylamine, triisopropylamine, tri-isoamylamine, trolamine, trioctylphosphine amine, trityl amine, two (2-amino-ethyls) 1, the 3-propylene diamine, two (3-aminopropyl) ethylene diamine, two (3-aminopropyls) 1, the 3-propylene diamine, two (3-aminopropyl) methylamine, two (2-ethylhexyl) amine, two (trimethyl silyl (cylyl)) amine, butylamine, the butyl Isopropylamine, propanediamine, propyl diamine, hexylamine, amylamine, the 2-methyl cyclohexylamine, methyl-propylamine, methyl-benzyl amine, monoethanolamine, lauryl amine, nonyl amine, Trimethylamine, triethylamine, dimethyl propylamine, trimethylene diamine, hexamethylene-diamine, tetren, diethylethanolamine, tetramethyl ammonium chloride, tetraethylammonium bromide, the dihydroxy ethyl stearylamine, 2-heptadecyl-hydroxyethyl imidazole quinoline, lauryl dimethyl benzyl ammonium chloride, hexadecylpyridinium chloride, the stearylamide methyl chloropyridine, diaryl alkyl dimethyl ammonium chloride polymkeric substance, diarylamine polymkeric substance and monoarylamine polymkeric substance.

More preferably the compound of Shi Yonging has: trolamine, tri-isopropanolamine, 2-amino-2-ethyl-1, ammediol, thanomin, propanediamine and propylamine.

The weight-average molecular weight of organic amine compound is preferably 1000 or littler, more preferably is equal to or less than 500, more preferably is equal to or less than 250.The molecular weight of organic amine compound greater than 1000 certain situation under, its water-soluble reduction, causing acid dissociation constant pKa to be equal to or less than 4.5 organic acid dissolving can not fully be maintained.

With respect to the total amount of this liquid, the addition of organic amine compound is preferably and is equal to or greater than 0.01 quality %, and is equal to or less than 30 quality %.This addition more preferably is equal to or greater than 0.1 quality %, and is equal to or less than 15 quality %; More preferably be equal to or greater than 0.25 quality %, and be equal to or less than 10 quality %.Under the certain situation of organic amine compound in second liquid less than 0.01 quality %, the organic acid dissolving becomes insufficient, thereby causes the bad stability of long storage.On the other hand, under the situation of this addition greater than 30 quality %, the flocculating property variation in the mixture that constitutes with printing ink, thus cause image quality not enough.

In second liquid, organic amine compound is set at 1: 0.1 to 1: 0.9th with respect to the mol ratio (organic acid/organic amine compound) of organic acid addition, necessary.This mol ratio more preferably 1: 0.15 to 1: 0.75, more preferably 1: 0.2 to 1: 0.5.Under mol ratio the situation less than 1: 0.1 (consumption that be organic amine too little) of organic amine compound with respect to the organic acid addition, organic acid does not dissolve.On the other hand, under mol ratio the situation greater than 1: 0.9 (consumption that be organic amine too big) of organic amine compound with respect to the organic acid addition, the flocculation of coloured material becomes insufficient in the mixture that forms with first liquid, thereby makes image quality can not get strengthening.

Also can make second liquid comprise coloured material.For the coloured material that comprises in second liquid, be preferably dyestuff, surface have the pigment of sulfonic acid or sulphonate with from pigment dispersion.The reasons are as follows.By inference, these coloured materials are difficult for flocculation in acidic region, and acid dissociation constant pKa is equal to or less than 4.5 organic acid and the flocculation of polyvalent metal is also stoped.By using this coloured material, can improve the package stability of second liquid.Can use dyestuff, the surface identical with coloured material in aforementioned first liquid have the pigment of sulfonic acid or sulphonate with from pigment dispersion.

Pigment is being used under the situation of second liquid, the volume average particle size of granules of pigments is preferably and is equal to or greater than 30nm, and is equal to or less than 250nm.This volume average particle size more preferably is equal to or greater than 50nm, and is equal to or less than 200nm; More preferably be equal to or greater than 75nm, and be equal to or less than 175nm.Under the certain situation of particulate volume average particle size less than 30nm, optical concentration reduces in this liquid.On the other hand, under the certain situation of described volume average particle size greater than 250nm, package stability can not be kept.

For second liquid, can use with first liquid in the identical water-soluble solvent of water-soluble solvent.The content of used water-miscible organic solvent is equal to or greater than 1 quality %, and is equal to or less than 60 quality %, and is preferably and is equal to or greater than 5 quality %, and is equal to or less than 40 quality %.In this liquid, under the certain situation of the content of water-miscible organic solvent less than 1 quality %, can not obtain enough optical concentrations.On the contrary, under the certain situation of the content of water-miscible organic solvent greater than 60 quality %, the viscosity of this liquid increases in this liquid, thereby makes the jet performance of this liquid become unstable.

In addition, also can in second liquid, add used polymeric dispersant in first liquid.

The surface tension of second liquid is preferably and is equal to or greater than 20mN/m, and is equal to or less than 45mN/m.This surface tension more preferably is equal to or greater than 20mN/m, and is equal to or less than 39mN/m; More preferably be equal to or greater than 20mN/m, and be equal to or less than 35mN/m.Under the certain situation of surface tension less than 20mN/m, this liquid is spilled over to nozzle surface, thereby printing can not normally be carried out.On the other hand, under the certain situation of surface tension greater than 45mN/m, infiltration becomes slowly, thereby prolonged time of drying.

The viscosity of second liquid is preferably and is equal to or greater than 1.2mPas, and is equal to or less than 25.0mPas; More preferably be equal to or greater than 1.5mPas, and be equal to or less than 10.0mPas; More preferably be equal to or greater than 1.8mPas, and be equal to or less than 5.0mpas.Under the certain situation of viscosity greater than 25.0mpas of first liquid and second liquid, the jet performance variation.On the other hand, under the certain situation of viscosity less than 1.2mPas, the bad stability of long storage.

In the scope that can obtain aforesaid surface tension and viscosity, add water.The addition of water is also without particular limitation, but with respect to the total amount of ink-jet with the liquid composition or second liquid, the addition of water is preferably and is equal to or greater than 10 quality %, and is equal to or less than 99 quality %; More preferably be equal to or greater than 30 quality %, and be equal to or less than 80 quality %.

In second liquid, also can add the flocculation agent of the component in first liquid that is used for flocculating.

For example, the example of flocculation agent comprises: alkalimetal ion, and as lithium ion, sodium ion and potassium ion.

Concrete example comprises an alkali metal salt, as lithium chloride, sodium-chlor, Repone K, Sodium Bromide, Potassium Bromide, sodium iodide, potassiumiodide, sodium sulfate, saltpetre, sodium acetate, potassium oxalate, Trisodium Citrate and potassium benzoate.

Compound can use separately, also at least two types compound can be used.And in this liquid of the present invention, the content of flocculation agent is 0.01 quality %～15 quality %, is preferably 0.1 quality %～10 quality %.

In the mixing solutions of first liquid and second liquid, particle diameter is that 5 μ m or bigger coarse grained quantity are preferably and are equal to or greater than 1,000/ μ L.Above-mentioned quantity more preferably is equal to or greater than 2,500/ μ L, more preferably is equal to or greater than 5,000/ μ L.In the mixing solutions of first liquid and second liquid, be under 5 μ m or the bigger certain situation of coarse grained quantity at particle diameter less than 1,000/ μ L, optical concentration reduces.

Particle diameter is that 5 μ m or bigger coarse grained quantity are to record by the following method in the mixing solutions of first liquid and second liquid: two kinds of liquid are mutually mixed with mass ratio at 1: 1, when stirring them, take out 2 μ L, measure with Accusizer TM770 optics particle size analyzer (by Particle SizingSystems Co., Ltd. makes).As the parameter in measuring, the density of input pigment is as the density of discrete particles.Through heating and the resulting pigment powder of dried pigment dispersion soln, can obtain the density of pigment with specific gravity hydrometer or pycnometric determination.

Below will the additive that can suitably be used for first liquid and second liquid (the present invention's ink-jet liquid composition) be described.

Tensio-active agent can be used for first liquid and second liquid.In the present invention, the compound that contains hydrophilic segment and hydrophobic part in the molecule simultaneously can be used as tensio-active agent effectively.In anion surfactant, cats product, amphoterics and the nonionogenic tenside any all can use.Also can use polymeric dispersant.

Available examples of anionic surfactants comprises: the phosphate ester salt of the sulfuric acid of the sulfuric acid of alkylbenzene sulfonate, alkyl benzene sulfonate, sulfonated alkyl naphathalene, higher fatty acid salt, high-grade aliphatic ester, the sulfonate of high-grade aliphatic ester, senior alcohol ether or sulfonate, senior alkyl sulfosuccinate, senior alkyl phosphate ester salt and higher alcobol ethylene oxide adduct.The example of the anion surfactant that is effectively used also comprises: dodecylbenzene sulfonate, alkylbenzene sulfonate, isopropyl naphthalene sulfonate, monobutyl phenylphenol monosulfonate, monobutyl phenylbenzene sulfonate and dibutyl phenylphenol stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate.

The example of nonionogenic tenside comprises: polypropylene glycol-ethylene oxide adduct, polyoxyethylene nonylplenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenylate, Voranol EP 2001, polyoxyethylene fatty acid ester, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkyl alcohol amide, acetylenediol, acetylenediol-oxygen ethene affixture, aliphatic alkane alcohol amide, glyceryl ester and sorbitol ester.

The example of cats product comprises: tetraalkylammonium salt, alkylamine salt, phenylmethane ammonium salt, Fixanol and imidazole salts, for example, dihydroxy ethyl octadecane amine, 2-heptadecene base-hydroxyethyl imidazole quinoline, dodecyl benzyl dimethyl ammonium chloride, hexadecylpyridinium chloride, kemanide S methyl chloropyridine.

Also can use bio-surfactant, as spiculisporic acid, rhamnolipid and lysolecithin.

During use, the amount that adds the tensio-active agent of first liquid and second liquid is preferably less than 10 quality %, more preferably 0.01 quality %～5 quality %, more preferably 0.01 quality %～3 quality %.Be equal to or greater than under the certain situation of 10 quality % the optical concentration of pigment ink and package stability variation at this addition.

Can use other following additive to come control performance, but as improving ejection: for example polymine, polyamine, polyvinylpyrrolidone, polyoxyethylene glycol; Derivatived cellulose, it comprises ethyl cellulose and carboxymethyl cellulose; Polysaccharide and their derivative; And water-soluble polymers; Polymer emulsion, it comprises acrylate polymer emulsion, polyether polyols with reduced unsaturation emulsion and wetting ability latex; Hydrophilic polymer gel, cyclodextrin, big cyclammonium, branch-shape polymer, crown ether, urea and their derivative; Ethanamide, contain the tensio-active agent of silicone and fluorine-containing tensio-active agent.Can use following additive to control pH value and electroconductibility: alkali metal compound, as potassium hydroxide, sodium hydroxide, lithium hydroxide; Nitrogenous compound is as ammonium hydroxide, trolamine, diethanolamine, thanomin and 2-amino-2-methyl-1-propanol; Alkaline earth metal compound is as calcium hydroxide; Acid is as sulfuric acid, hydrochloric acid and nitric acid; And strong acid weak base salt, as ammonium sulfate.

If necessary, also can add pH buffer reagent, antioxidant, mycocide, viscosity control agent, conductive agent and UV (ultraviolet ray) absorption agent.

(ink jet recording method and ink-jet recording device)

Ink jet recording method of the present invention is by utilizing ink for inking group of the present invention to implement to print, so that first liquid and second liquid contact with each other.And ink-jet recording device of the present invention comprises record-header, and this record-header is used for spraying to recording medium the liquid of ink for inking group of the present invention.Except being applicable to common ink-jet recording device, these also are applicable to the recording unit that is provided with the well heater used of control ink setting, or be applicable to following recording unit: this recording unit is provided with the intermediate transfer mechanism, and be used for recording materials are imprinted on the intermediate member, implement the transfer printing on recording medium such as paper then.

In ink jet recording method of the present invention (device), every quality of first liquid and second liquid all is preferably and is equal to or less than 25ng.This quality more preferably is equal to or greater than 0.5ng, and is equal to or less than 20ng; More preferably be equal to or greater than 2ng, and be equal to or less than 8ng.Under the certain situation of every quality greater than 25ng, the more serious paper of spreading and sinking in appears.It is the reasons are as follows.By inference, the contact angle of first liquid and second liquid and recording medium changes with the amount of drop, and therefore when increasing the amount of drop, drop spreads along the direction on paper surface easily.

In the ink discharge device of the drop that can eject different volumes from same nozzle, the amount of drop is meant the amount of the minimum drop that can implement printing.

In addition, with first liquid and second liquid application on recording medium, so that both are in contact with one another.When first liquid and second liquid were in contact with one another, the effect by flocculation agent made printing ink produce flocculation.The recording method of excellent performance aspect paper and time of drying like this can obtain spreading and sinking between optical concentration, the paper of spreading and sinking in, look.If both are in contact with one another, they can be adjacent to use, and also can cover mutually.

In addition,, use second liquid earlier, use first liquid then for the order of administration on recording medium.By using second liquid earlier, the component in first liquid that can flocculate effectively.Whenever first liquid can using after using second liquid.Be preferably 0.1 second of using behind second liquid or 0.1 second with interior first liquid of using.

In ink jet recording method of the present invention (device), for the mass ratio of the amount of application of the amount of application that forms needed first liquid of pixel and second liquid is preferably 1: 20 to 20: 1.This mass ratio more preferably 1: 10 to 10: 1; More preferably 1: 5 to 5: 1.The amount of application of first liquid much smaller than or under the certain situation of the amount of application of second liquid, flocculation becomes insufficient, thereby optical concentration is reduced, the paper of spreading and sinking in is more serious, and the paper of spreading and sinking between look worsens.When the minimum spacing that required image can be used in main scanning direction and time scanning direction with printing ink was divided, pixel was represented the lattice point of composition diagram picture.By giving each pixel, can adjust color and image color, thereby form image suitable printing ink group.

The effect of improving of paper of spreading and sinking between paper and look from spreading and sinking in is considered hot ink-jet recording system of ink jet recording method of the present invention (device) advantageous applications or piezoelectric ink jet register system.Its reason it be unclear that.Using under the situation of hot ink-jet recording system, though thereby printing ink is heated in course of injection viscosity is reduced, and ink temperature sharply reduces on recording medium, and viscosity increases suddenly.Therefore, can infer spread and sink between paper and the look effect of paper that it has that improving spreads and sinks in.On the other hand, under the situation of using the piezoelectric ink jet register system, can spray high viscosity liquid.May be to have suppressed the high viscosity liquid on the recording medium, therefore, can expect, spread and sink between paper and the look effect of paper that it has that improving spreads and sinks in along paper surface direction diffusion.

Below, will be described in detail with reference to the attached drawings the preferred embodiment of ink-jet recording device of the present invention.In the accompanying drawings, the parts with substantially the same function use same note numeral, and omit multiple and describe.

Fig. 1 is the stereographic map of surface structure of a preferred embodiment of expression ink-jet recording device of the present invention.Fig. 2 is the stereographic map of an internal part basic structure of expression ink-jet recording device (hereinafter will be referred to as image processing system) shown in Figure 1.Image processing system 100 in this embodiment has and can operate to form the structure of image by ink jet recording method according to the present invention.More specifically say, as Fig. 1 and shown in Figure 2, image processing system 100 is mainly by forming with the lower section: outer cover 6, can place the recording medium 1 of predetermined amount as the pallet 7 of common paper, be used for recording medium 1 by opening the image forming portion 8 (image formation unit) that is sent to the transfer roller (delivery unit) 2 in the image processing system 100 and is used for the surface that printing ink and liquid composition are ejected into recording medium 1 is also formed thus image.

Transfer roller 2 is by being arranged on the paper feeding mechanism that rotatable pair of rolls constitute in the image processing system 100, it play insert the recording medium 1 that is placed on pallet 7 and with the recording medium 1 of predetermined amount by opening the effect of periodically sending into image processing system 100.

Image forming portion 8 forms image with printing ink on recording medium 1 surface.Image forming portion 8 mainly by record-header 3, ink tank 5, signal transmission cable 9, carriage 10, guide rod 11, synchronous belt 12, driving pulley 13 with keep unit 14 and constitute.

Ink tank 5 has ink tank 51,52,53,54 and 55, and having stored in these ink tank has mutually different printing ink of color to be sprayed or liquid composition.For example, they have held as the black ink of first liquid (K), Yellow ink (Y), magenta ink (M) and cyan ink (C), and as the treatment soln of second liquid.Certainly, if comprise coloured material in second liquid, then there is no need to be provided for separately holding the ink tank of treatment soln.

In addition, as shown in Figure 2, signal transmission cable 9 all is connected on the record-header 3 with ink tank 5.When the external image recorded information when signal-transmitting cable 9 is input to record-header 3, record-header 3 sucks printing ink quantitatively from each ink tank, and according to this image recording information, with described ink jet on the recording medium surface.Except the transport picture recorded information, signal transmission cable 9 also works to the record-header 3 supply activation record heads 3 necessary energy time.

And record-header 3 is provided with and is fixed on the carriage 10, and guide rod 11 and the synchronous belt 12 that links to each other with driving pulley 13 also are connected with carriage 10.By this structure, record-header 3 also can be gone up slip in Y direction (main scanning direction) along guide rod 11, and this direction is parallel and vertical with the delivery direction X (inferior scanning direction) of recording medium 1 with recording medium 1 surface.

Image processing system 100 comprises the control unit (not shown), and this unit is used for according to image recording information, regulates the driving sequential (driving timing) of record-header 3 and the driving sequential of carriage 10.Therefore, according to image recording information, can in the recording medium 1 lip-deep prospective region that transmits with predetermined speed along delivery direction X, form image continuously.

Keeping unit 14 is connected with the reliever (not shown) by conduit.In addition, keep unit 14 and link to each other with the nozzle segment of record-header 3, it has the function that nozzle interior with record-header 3 is set as decompression state and from the nozzle of record-header 3 printing ink is sucked thus.Keep unit 14 by setting, necessary in the operational process of image processing system 100, can remove the excess of ink that sticks on the nozzle; Or in operation stop condition, can suppress printing ink and evaporate from nozzle.

Fig. 3 is the stereographic map of surface structure of another preferred embodiment of expression ink-jet recording device of the present invention, and Fig. 4 is the stereographic map of basic structure of the internal part of expression ink-jet recording device (hereinafter will be referred to as image processing system) shown in Figure 3.Image processing system 100 in this embodiment has and can operate to form the structure of image by ink jet recording method according to the present invention.

Fig. 3 and image processing system 100 shown in Figure 4 comprise record-header 3, and the width of this record-header is equal to or greater than the width of recording medium 1.This image processing system 100 does not comprise carriage physical construction, but comprise along time scanning direction (delivery direction of recording medium 1: the paper feeding mechanism direction of arrow X) (be transfer roller 2 in this embodiment, but can be the paper feeding mechanism of for example belt).(delivery direction of recording medium 1: the direction of arrow X) dispose ink tank 51～55 successively, and dispose the nozzle group who is used to spray shades of colour (comprising treatment soln) along time scanning direction equally, this part is not shown in the diagram for time scanning direction, record-header 3 edge.Because other structure is identical with the structure of image processing system 100 shown in Figure 1, so associated description is omitted.

By utilizing record-header 3, Fig. 3 and image processing system 100 shown in Figure 4 can be concentrated along horizontal (main scanning direction) of recording medium 1 and print.Therefore, compare with that class device with carriage mechanism, the structure of this type of device is more simplified, and print speed improves manyly.

Embodiment

Below incite somebody to action embodiment by reference, the present invention is more specifically described.The invention is not restricted to any one embodiment.

＜pigment treatment process 1 〉

Operation ultrasonic wave homogenizer is handled commercially available colo(u)rant dispersion solution.Then, dispersion soln is carried out centrifugation handles (8000rpm (rev/min) * 30 minutes), removing residue part (account for initial charging capacity 20%), thereby obtain colo(u)rant dispersion solution.

＜pigment treatment process 2 〉

The dispersion agent of the pigment of 10 quality % and 1.5 quality % is added in the ion exchanged water of specified amount and stirred.Operation ultrasonic wave homogenizer is handled so that colo(u)rant dispersion above-mentioned mixing liquid.And, dispersion soln is carried out centrifugation handle (8000 rev/mins * 30 minutes), remove residue part (account for initial charging capacity 20%), thereby obtain colo(u)rant dispersion solution.

＜pigment treatment process 3 〉

Heating Sulphanilic Acid solution adds 100g pigment while stirring.Stir the mixture, be cooled to room temperature simultaneously, and splash into the 14g concentrated nitric acid.The 10g sodium nitrite solution is added in the above-mentioned solution, and be stirred to the reaction end.Pigment is carried out desalting treatment.Add ion exchanged water, the concentration that makes the surface finish pigment that is obtained is 12 weight %, regulates pH to 7.5, carries out dispersion treatment with the ultrasonic wave homogenizer then.With centrifuge separator dispersion soln is carried out centrifugation and handle (8000 rev/mins * 30 minutes), remove residue part (account for total amount 20%), thereby obtain colo(u)rant dispersion solution.

＜liquid preparation method 〉

Coloured material solution, water-miscible organic solvent, tensio-active agent and ion exchanged water are added with suitable amount, with the composition that obtains being scheduled to, and with mixing solutions mixing and stirring.Make the liquid that obtains thus by 5 μ m strainers then, promptly obtain required liquid.

(liquid 1-A)

Utilization is handled the pigment that obtains according to pigment treatment process 1, and method according to the rules is prepared.

-form-

● Cabojet-300 (producing) (from pigment dispersion/hydroxy-acid group): 4 quality % by Cabot company

● styrene-propene acid-sodium acrylate copolymer: 1 quality %

● Diethylene Glycol: 20 quality %

● glycerol: 5 quality %

● acetylenediol ethylene oxide adduct: 0.5 quality %

● ion exchanged water: surplus

The pH value of this liquid is 8.5, and volume average particle size is 93nm, and surface tension is 31mN/m, and viscosity is 3.3mPas.Each physicals value all is to record in the time of 20 ℃.

(liquid 1-B)

Utilization is handled the pigment that obtains according to pigment treatment process 1, and method according to the rules is prepared.

-form-

● Cabojet-200 (producing) (from pigment dispersion/sulfonic group): 4 quality % by Cabot company

● styrene-propene acid-sodium acrylate copolymer: 1 quality %

● Diethylene Glycol: 20 quality %

● glycerol: 5 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

The pH value of this liquid is 8.6, and volume average particle size is 102nm, and surface tension is 31mN/m, and viscosity is 3.2mPas.Each physical property values all is to record in the time of 20 ℃.

(liquid 1-C)

Utilization is handled the pigment that obtains according to pigment treatment process 2, and method according to the rules is prepared.

-form-

● Mogul L (producing) (pigment/no surface functional group): 4 quality % by Cabot company

● styrene-propene acid-sodium acrylate copolymer: 0.6 quality %

● Diethylene Glycol: 15 quality %

● Glycerol dimer ethylene oxide adduct: 5 quality %

● polyoxyethylene-2-ethylhexyl ether: 0.75 quality %

● ion exchanged water: surplus

The pH value of this liquid is 8.2, and volume average particle size is 120nm, and surface tension is 32mN/m, and viscosity is 3.3mPas.Each physicals value all is to record in the time of 20 ℃.

(liquid 1-D)

Utilization is handled the pigment that obtains according to pigment treatment process 1, and method according to the rules is prepared.

-form-

● Cabojet-200 (producing) (from pigment dispersion/sulfonic group): 4 quality % by Cabot company

● Diethylene Glycol: 20 quality %

● glycerol: 5 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

The pH value of this liquid is 8.9, and volume average particle size is 96nm, and surface tension is 31mN/m, and viscosity is 3.1mPas.Each physicals value all is to record in the time of 20 ℃.

(liquid 1-E)

-form-

● Diethylene Glycol: 30 quality %

● tartrate (pKa=3.0): 4.5 quality %

● magnesium nitrate hexahydrate: 3 quality %

● sodium hydroxide: 0.6 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

The pH value of this liquid is 3.8, and surface tension is 30mN/m, and viscosity is 2.8mPa.s.Each physicals value all is to record in the time of 20 ℃.

(liquid 1-F)

-component-

● Diethylene Glycol: 30 quality %

● pyromucic acid (pKa=2.4): 4 quality %

● magnesium nitrate hexahydrate: 0.11 quality %

● sodium hydroxide: 0.75 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

The pH value of this liquid is 4.3, and surface tension is 31mN/r, and viscosity is 2.5mPas.Each physicals value all is to record in the time of 20 ℃.

(liquid 1-G)

-form-

● Diethylene Glycol: 30 quality %

● Succinic Acid (pKa=4.0): 2 quality %

● magnesium nitrate hexahydrate: 4 quality %

● sodium hydroxide: 1 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

The pH value of this liquid is 4.3, and surface tension is 32mN/m, and viscosity is 2.7mPas.Each physicals value all is to record in the time of 20 ℃.

(liquid 1-H)

-form-

● Diethylene Glycol: 30 quality %

● acetate (pKa=4.56): 6 quality %

● magnesium nitrate hexahydrate: 0.03 quality %

● sodium hydroxide: 3.5 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

The pH value of this liquid is 7.2, and surface tension is 31mN/m, and viscosity is 2.6mPas.Each physicals value all is to record in the time of 20 ℃.

(liquid 1-I)

Utilization is handled the pigment that obtains according to pigment treatment process 1, and method according to the rules is prepared.

-form-

● Cabojet-250 (producing) (from pigment dispersion/sulfonic group): 4 quality % by Cabot company

● styrene-propene acid-potassium acrylate multipolymer: 1 quality %

● Diethylene Glycol: 20 quality %

● propylene glycol: 5 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

The pH value of this liquid is 7.8, and volume average particle size is 86nm, and surface tension is 30mN/m, and viscosity is 3.3mPas.Each physicals value all is to record in the time of 20 ℃.

(liquid 1-J)

Utilization is handled the pigment that obtains according to pigment treatment process 3, and method according to the rules is prepared.

-form-

● C.I. pigment red 122 (from pigment dispersion/sulfonic group): 4 quality %

● vinylbenzene-methacrylic acid-methacrylic acid potassium multipolymer: 1 quality %

● Diethylene Glycol: 15 quality %

● N-N-methyl-2-2-pyrrolidone N-: 5 quality %

● tetramethylene sulfone: 5 quality %

● acetylenediol ethylene oxide adduct: 1 quality %.

● ion exchanged water: surplus

The pH value of this liquid is 8.0, and volume average particle size is 103nm, and surface tension is 30mN/m, and viscosity is 3.1mPas.Each physicals value all is to record in the time of 20 ℃.

(liquid 1-K)

Utilization is handled the pigment that obtains according to pigment treatment process 3, and method according to the rules is prepared.

-form-

● C.I. pigment Yellow 12 8 (from pigment dispersion/sulfonic group): 4 quality %

● styrene-propene acid-potassium acrylate multipolymer: 1 quality %

● Diethylene Glycol: 20 quality %

● Diethylene Glycol single-butyl ether: 5 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

The pH value of this liquid is 7.9, and volume average particle size is 130nm, and surface tension is 30mN/m, and viscosity is 3.1mPas.Each physical property values all is to record in the time of 20 ℃.

(liquid 1-L)

Utilization is handled the pigment that obtains according to pigment treatment process 1, and method according to the rules is prepared.

-form-

● Cabojet-250 (producing) (from pigment dispersion/sulfonic group): 4 quality % by Cabot company

● glycerol: 15 quality %

● ethylene glycol: 5 quality %

● propylene glycol: 5 quality %

● pyromucic acid (pKa=2.4): 4 quality %

● calcium nitrate tetrahydrate: 2 quality %

● sodium hydroxide: 0.8 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

The pH value of this liquid is 4.4, and volume average particle size is 104nm, and surface tension is 30mN/m, and viscosity is 3.0mPas.Each physical property values all is to record in the time of 20 ℃.

(liquid 1-M)

-form-

● Diethylene Glycol: 30 quality %

● tartrate (pKa=3.0): 4.5 quality %

● magnesium nitrate hexahydrate: 8.5 quality %

● sodium hydroxide: 0.6 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

The pH value of this liquid is 3.3, and surface tension is 30mN/m, and viscosity is 3.1mPas.Each physicals value all is to record in the time of 20 ℃.

(liquid 1-N)

-form-

● Diethylene Glycol: 30 quality %

● tartrate (pKa=3.0): 4.5 quality %

● magnesium nitrate hexahydrate: 0.05 quality %

● sodium hydroxide: 1.3 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

The pH value of this liquid is 7.5, and surface tension is 30mN/m, and viscosity is 3.1mPas.Each physicals value all is to record in the time of 20 ℃.

(liquid 1-O)

-form-

● Diethylene Glycol: 30 quality %

● hydrochloric acid (mineral acid): 0.36 quality %

● magnesium nitrate hexahydrate: 4 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

The pH value of this liquid is less than 0 (can't measure), and surface tension is 30mN/m, and viscosity is 2.5mPas.Each physicals value all is to record in the time of 20 ℃.

(embodiment 1-1～1-5 and Comparative Examples 1-1～1-5)

The printing ink group of use shown in table 1 and 2 prints.The method that prints is, by using the test printhead (every amount is 14ng) of 800dpi (point/inch) and 256 nozzles, second liquid (ink-jet liquid composition) is ejected on the FX-P paper (being produced by Fuji Xerox Co., Ltd), and sprays first liquid (liquid 1 to 4 in the table) in the above.This is printed in the common environment (temperature is 23 ± 0.5 ℃, and humidity is 55 ± 5%R.H (relative humidity)) and carries out, and forms the first used liquid of pixel and the mass ratio of second liquid and is set at 1: 0.2.According to the print pattern A～C shown in Fig. 5～7, assess (not comprising time of drying and long term storage stability) to printing the sample of in common environment, placing 24 hours the back.

" optical concentration "

Use X-Rite 404 (making) to measure the optical concentration of the printing portion of each print pattern by X-Rite company limited.The printing portion of a printed drawings case in office does not satisfy under the situation of standard, to be set at the assessment result (for example: if any printing portion is " a " for " b " remaining printing portion, then the assessment result with this sample is set at " b ") of " more rudimentary ".In following all appraisal procedures, all adopt same evaluation criteria.

-evaluation criteria (black ink)-

A... optical concentration is equal to or greater than 1.4

B... optical concentration is equal to or greater than 1.3 and less than 1.4

C... optical concentration is less than 1.3

-evaluation criteria (colored ink)-

A... optical concentration is for being equal to or greater than 1.1

B... optical concentration is equal to or greater than 1.0 and less than 1.1

C... optical concentration is less than 1.0

" paper of spreading and sinking between look "

Between checking colors, spread and sink in the assessment of paper, print pattern, it is compared with the border sample of the predetermined paper degree of spreading and sinking in is arranged at boundary member, thereby can carry out the sensory evaluation with adjacent different colours.

-evaluation criteria-

A... the paper of spreading and sinking on a small quantity

What b... produced spreads and sinks in paper in admissible scope

C... the paper of spreading and sinking in that is produced significantly exceeds the scope of permission

" paper of spreading and sinking in "

Print pattern, the printing portion of spread and sink in the paper degree and the border sample of printing portion is compared, thereby can carry out the sensory evaluation with meticulous lines.

-evaluation criteria-

A... the paper of spreading and sinking on a small quantity

What b... produced spreads and sinks in paper in admissible scope

C... the paper of spreading and sinking in that is produced significantly exceeds the scope of permission

" time of drying "

From printing 100% pattern that covers, through behind the preset time, with another FX-C2 paper with 1.9 * 10 ⁴N/m ²Load be pressed on the print pattern.The required time is counted time of drying when no longer shifting on FX-C2 paper one side of being pressed with liquid at this moment.

-evaluation criteria-

A... time of drying was less than 3 seconds

B... be equal to or greater than 3 seconds time of drying and less than 10 seconds

C... be equal to or greater than 10 seconds time of drying

" long term storage stability "

For long term storage stability, first liquid and liquid composition were placed in Evaluation Environment 3 years, and the viscosity and the surface tension that compare the initial period and place later printing ink.

-evaluation criteria-

A... the eigenwert after placing is compared with initial eigenwert, and its velocity of variation is less than 5%

B... the eigenwert after placing is compared with initial eigenwert, and its velocity of variation is equal to or greater than 5% and less than 15%

C... the eigenwert after placing is compared with initial eigenwert, and its velocity of variation is equal to or greater than 15%

" long-term jet performance "

Long-term jet performance is to judge according to the decay of the jet velocity on first liquid and each comfortable record-header of second liquid.More particularly, record jet velocity in original state.Then, carry out 5 * 10 ⁸The printing of individual pulse.Subsequently, measure jet velocity.Calculate 5 * 10 ⁸The ratio of the jet velocity when jet velocity after individual pulse is printed and initial conditions, and press commentary and estimate standard and assessed.

-evaluation criteria-

A... carry out 5 * 10 ⁸Jet velocity after individual pulse is printed is equal to or greater than 85% of initial jet velocity

B... carry out 5 * 10 ⁸Jet velocity after individual pulse is printed be equal to or greater than initial jet velocity 60% and less than 85% of this jet velocity

C... carry out 5 * 10 ⁸Jet velocity after individual pulse is printed is less than 60% of initial jet velocity.

The conclusion of＜assessment result 〉

Assessment result is summarized in table 3 and the table 4.Shown in table 3 and table 4, swim between optical concentration, the paper of spreading and sinking in, look paper, time of drying, long term storage stability and long-term jet performance show excellence in embodiment 1-1～1-5, in these embodiments, comprise acid dissociation constant pKa and be equal to or less than 4.5 organic acid and polyvalent metal salt, and first liquid and liquid composition all are applied on the recording medium, thereby both are contacted with each other.

[table 1]

		Printing ink	Print pattern	pKa	Polyvalent metal salt and organic acid mol ratio	pH	Viscosity	Surface tension (mN/m)	Volume average particle size (nm)	Be equal to or greater than the number of particles (individual/μ L) of 5 μ m in the mixture at 1: 1
											Embodiment 1-1	Liquid 1	1-A	A	-	-	8.5	3.3	31	93	9810
Liquid composition (second liquid)	1-E	2.99	0.39	3.8	2.8	30	-
								Embodiment 1-2	Liquid 1	1-B		A	-		-	8.6	3.2	31	102	8960
Liquid composition (second liquid)	1-F	2.41	0.012	4.3	2.5	31	-
									Embodiment 1-3	Liquid 1	1-C		A	-	-	8.2	3.3	32	120		6150
Liquid composition (second liquid)	1-G	4.00	0.92	4.3	2.7	32	-
								Comparative Examples 1-1		Liquid 1	1-D	A		-	-	8.9	3.1	31	96	23
Liquid composition (second liquid)	1-H	4.56	0.0017	7.2	2.6	31	-
									Comparative Examples 1-2	Liquid 1	1-A		A	-	-	8.5	3.3	31	93		12400
Liquid composition (second liquid)	1-M	3.0	1.1	3.3	3.1	30	-
								Comparative Examples 1-3		Liquid 1	1-A	A		-		8.5	3.3	31	93	310
Liquid composition (second liquid)	1-N	3.0	0.007	7.3	3.1	30	-
									Comparative Examples 1-4	Liquid 1	1-A		A	-	-	8.5	3.3	31	93		7060
Liquid composition (second liquid)	1-O	-(mineral acid)	-	＜0	2.5	30	-

[table 2]

		Printing ink	Print pattern	pKa	Polyvalent metal salt and organic acid mol ratio	pH	Viscosity	Surface tension (mN/m)	Volume average particle size (nm)	Be equal to or greater than the number of particles (individual/μ L) of 5 μ m in the mixture at 1: 1
											Embodiment 1-4	Liquid 1	1-A	B	-	-	8.5	3.3	31	93	7650 (A/E)
Liquid 2	1-I	-	-	7.8	3.3	30	86
								Liquid 3	1-J	-		-	8.0		3.1	30	103
Liquid 4	1-K	-	-	7.9	3.1	30	130
								Liquid composition	1-E	2.99		0.39	3.8		2.8	30	-
Embodiment 1-5	Liquid 1	1-B	C	-	-	8.6	3.2											31	102	7030 (B/L)
								Liquid 2	1-J	-	-	8.0	3.1	30	103
	Liquid 3	1-K		-	-	7.9	3.1									30	130
								Liquid composition	1-L	2.41	0.24	4.4	3.0	30	104
	Comparative Examples 1-5	Liquid 1		1-A	D	-	-									8.5	3.3	31	93		50 (A/H)
Liquid 2			1-I					-	-	7.8	3.3	30	86
		Liquid 3		1-J		-								8.0	3.1	30	103
Liquid 4			1-K					-	-	7.9	3.1	30	130
		Liquid composition		1-H		4.56	0.0017							7.2	2.6	31	-

[table 3]

	Optical concentration	The paper of spreading and sinking in	Time of drying	Long term storage stability	Long-term jet performance
						Embodiment 1-1	a	a	a	a	a
Embodiment 1-2	a	a	a	a	a
						Embodiment 1-3	a	a	a	a	a
Comparative Examples 1-1	c	c	a	a	a
						Comparative Examples 1-2	a	a	a	c	c
Comparative Examples 1-3	c	c	a	a	a
						Comparative Examples 1-4	a	a	a	c	c

[table 4]

	Optical concentration	The paper of spreading and sinking in	The paper of spreading and sinking between look	Time of drying	Long term storage stability	Long-term jet performance
							Embodiment 1-4	a	a	a	a	a	a
Embodiment 1-5	a	a	a	a	a	a
							Comparative Examples 1-5	c	c	a	a	a	a

(liquid 2-A)

Utilization is handled the pigment that obtains according to pigment treatment process 1, and method according to the rules is prepared.

-form-

● Cabojet-300 (producing) (from pigment dispersion/hydroxy-acid group): 4 quality % by Cabot company

● styrene-propene acid-sodium acrylate copolymer: 1 quality %

● Diethylene Glycol: 20 quality %

● glycerol: 5 quality %

● acetylenediol ethylene oxide adduct: 0.5 quality %

● ion exchanged water: surplus

In the time of 20 ℃, the pH value that records this liquid is 8.5, and volume average particle size is 93nm, and surface tension is 31mN/m, and viscosity is 3.3mPas.

(liquid 2-B)

Utilization is handled the pigment that obtains according to pigment treatment process 1, and method according to the rules is prepared.

-form-

● Cabojet-200 (producing) (from pigment dispersion/sulfonic group): 4 quality % by Cabot company

● styrene-propene acid-sodium acrylate copolymer: 1 quality %

● Diethylene Glycol: 20 quality %

● glycerol: 5 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

In the time of 20 ℃, the pH value that records this liquid is 8.6, and volume average particle size is 102nm, and surface tension is 31mN/m, and viscosity is 3.2mPas.

(liquid 2-C)

Utilization is handled the pigment that obtains according to pigment treatment process 2, and method according to the rules is prepared.

-form-

● Mogul L (producing) (pigment/no surface functional group): 4 quality % by Cabot company

● styrene-propene acid-sodium acrylate copolymer: 0.6 quality %

● Diethylene Glycol: 15 quality %

● two glycerol ethylene oxide adducts: 5 quality %

● polyoxyethylene-2-ethylhexyl ether: 0.75 quality %

● ion exchanged water: surplus

In the time of 20 ℃, the pH value that records this liquid is 8.2, and volume average particle size is 120nm, and surface tension is 32mN/m, and viscosity is 3.3mPas.

(liquid 2-D)

Utilization is handled the pigment that obtains according to pigment treatment process 1, and method according to the rules is prepared.

-form-

● Cabojet-200 (producing) (from pigment dispersion/sulfonic group): 4 quality % by Cabot company

● Diethylene Glycol: 20 quality %

● glycerol: 5 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

In the time of 20 ℃, the pH value that records this liquid is 8.9, and volume average particle size is 96nm, and surface tension is 31mN/m, and viscosity is 3.1mPas.

(liquid 2-E)

-form-

● Diethylene Glycol: 30 quality %

● pyromucic acid (pKa=2.41): 7.5 quality %

● trolamine: 3 quality %

● acetylenediol ethylene oxide adduct: 1 quality %.

● ion exchanged water: surplus

In the time of 20 ℃, the pH value that records this liquid is 3.6, and surface tension is 31mN/m, and viscosity is 2.9mPas.

(liquid 2-F)

-form-

● Diethylene Glycol: 30 quality %

● nicotinic acid (pKa=2.05): 7.5 quality %

● tri-isopropanolamine: 4.5 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

In the time of 20 ℃, the pH value that records this liquid is 4.0, and surface tension is 31mN/m, and viscosity is 2.8mPas.

(liquid 2-G)

-form-

● Diethylene Glycol: 30 quality %

● acetate (pKa=4.56): 6 quality %

● sodium hydroxide: 2 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

In the time of 20 ℃, the pH value that records this liquid is 5.5, and surface tension is 31mN/m, and viscosity is 2.6mPas.

(liquid 2-H)

Utilization is handled the pigment that obtains according to pigment treatment process 1, and method according to the rules is prepared.

-form-

● Cabojet-250 (producing) (from pigment dispersion/sulfonic group): 4 quality % by Cabot company

● styrene-propene acid-potassium acrylate multipolymer: 1 quality %

● Diethylene Glycol: 20 quality %

● propylene glycol: 5 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

In the time of 20 ℃, the pH value that records this liquid is 7.8, and volume average particle size is 86nm, and surface tension is 30mN/m, and viscosity is 3.3mPas.

(liquid 2-I)

Utilization is handled the pigment that obtains according to pigment treatment process 3, and method according to the rules is prepared.

-form-

● C.I. pigment red 122 (from pigment dispersion/sulfonic group): 4 quality %

● vinylbenzene-methacrylic acid-methacrylic acid potassium multipolymer: 1 quality %

● Diethylene Glycol: 15 quality %

● N-N-methyl-2-2-pyrrolidone N-: 5 quality %

● tetramethylene sulfone: 5 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

In the time of 20 ℃, the pH value that records this liquid is 8.0, and volume average particle size is 103nm, and surface tension is 30mN/m, and viscosity is 3.1mPas.

(liquid 2-J)

Utilization is handled the pigment that obtains according to pigment treatment process 3, and method according to the rules is prepared.

-form-

● C.I. pigment Yellow 12 8 (from pigment dispersion/sulfonic group): 4 quality %

● styrene-propene acid-potassium acrylate multipolymer: 1 quality %

● Diethylene Glycol: 20 quality %

● Diethylene Glycol single-butyl ether: 5 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

In the time of 20 ℃, the pH value that records this liquid is 7.9, and volume average particle size is 130nm, and surface tension is 30mN/m, and viscosity is 3.1mPas.

(liquid 2-K)

Utilization is handled the pigment that obtains according to pigment treatment process 1, and method according to the rules is prepared.

-form-

● Cabojet-250 (producing) (from pigment dispersion/sulfonic group): 4 quality % by Cabot company

● glycerol: 15 quality %

● ethylene glycol: 5 quality %

● propylene glycol: 5 quality %

● L-glutamic acid (pKa=2.18): 6 quality %

● tri-isopropanolamine: 3.5 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

In the time of 20 ℃, the pH value that records this liquid is 4.6, and volume average particle size is 95nm, and surface tension is 31mN/m, and viscosity is 3.2mPas.

(liquid 2-L)

-form-

● Diethylene Glycol: 30 quality %

● pyromucic acid (pKa=2.41): 7.5 quality %

● trolamine: 0.9 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

In the time of 20 ℃, the pH value that records this liquid is 3.2, and surface tension is 31mN/m, and viscosity is 2.6mPas.

(liquid 2-M)

-form-

● Diethylene Glycol: 30 quality %

● pyromucic acid (pKa=2.41): 7.5 quality %

● trolamine: 10.98 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

In the time of 20 ℃, the pH value that records this liquid is 7.3, and surface tension is 31mN/m, and viscosity is 3.3mPas.

(liquid 2-N)

-form-

● Diethylene Glycol: 30 quality %

● pyromucic acid (pKa=2.41): 7.5 quality %

● polyallylamine (PAA-01 (weight-average molecular weight is 1100) is by Nitto Boseki Co., and Ltd. produces): 6.5 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

In the time of 20 ℃, the pH value that records this liquid is 7.8, and surface tension is 32mN/m, and viscosity is 4.2mPas.

(embodiment 2-1～2-5 and Comparative Examples 2-1～2-5)

By using as table 1 to the printing ink group shown in 2, adopt with embodiment 1-1～1-5 and Comparative Examples 1-1～1-5 in same way as print and assess.

The conclusion of＜assessment result 〉

Assessment result is summarized in table 7 and the table 8.Shown in table 7 and table 8, paper, time of drying, the long term storage stability of spreading and sinking between optical concentration, the paper of spreading and sinking in, look shows excellent in embodiment 2-1～2-5, in these embodiments, comprise acid dissociation constant pKa and be equal to or less than 4.5 organic acid and organic amine compound, and first liquid and liquid composition all are applied on the recording medium, so that both contact with each other.

(embodiment 3-1)

By using liquid composition 3-A and the printing ink group in the table 9, print in the mode identical with embodiment 1 and 2.It the results are summarized in table 10.

(liquid 3-A)

-form-

● Diethylene Glycol: 30 quality %

● pyromucic acid (pKa=2.41): 5 quality %

● magnesium nitrate hexahydrate: 4 quality %

● sodium hydroxide: 1.1 quality %

● trolamine: 1 quality %

● acetylenediol ethylene oxide adduct: 1 quality %

● ion exchanged water: surplus

The pH value of this liquid is 3.8, and surface tension is 31mN/m, and viscosity is 3.2mPas.Each physicals value records in the time of 20 ℃.

[table 5]

		Printing ink	Print pattern	pKa	The molecular weight of organic amine	The mol ratio of organic acid and organic amine	pH	Viscosity	Surface tension (mN/m)	Volume average particle size (nm)	In 1: 1 mixture more than or equal to the number of particles (individual/μ L) of 5 μ m
												Embodiment 2-1	Liquid 1	2-A	A	-	-	-	8.5	3.3	31	93	7650
Liquid composition	2-E	2.41	149.2	1∶0.30	3.6	2.9	31	-
									Embodiment 2-2	Liquid 1	2-B		A	-		-	-	8.6	3.2	31	102	9130
Liquid composition	2-F	2.05	191.3	1∶0.38	4.0	2.8	31	-
										Embodiment 2-3	Liquid 1	2-C		A	-	-	-	8.2	3.3	32	120		8900
Liquid composition	2-F	2.05	191.3	1∶0.38	4.0	2.8	31	-
									Comparative Examples 2-1		Liquid 1	2-D	A		-	-	-	8.9	3.1	31	96	50
Liquid composition	2-G	4.56	Do not have	-	5.5	2.6	31	-
										Comparative Examples 2-2	Liquid 1	2-A		A	-	-	-	8.5	3.3	31	93		8100
Liquid composition	2-L	2.41	149.2	1∶0.09	3.2	2.6	31	-
									Comparative Examples 2-3		Liquid 1	2-A	A		-		-	8.5	3.3	31	93	82
Liquid composition	2-M	2.41	149.2	1∶1.1	7.3	3.3	31	-
										Comparative Examples 2-4	Liquid 1	2-A		A		-	-	8.5	3.3	31	93		120
Liquid composition	2-N	2.41	1100	1∶0.088	7.8	4.2	32	-

[table 6]

		Printing ink	Print pattern	pKa	In the molecule of organic amine	The mol ratio of organic acid and organic amine	pH	Viscosity	Surface tension (mN/m)	Volume average particle size (nm)	In 1: 1 mixture more than or equal to the number of particles (individual/μ L) of 5 μ m
												Embodiment 2-4	Liquid 1	2-A	B	-	-	-	8.5	3.3	31	93	7650 (A/E)
Liquid 2	2-H	-	-	-	7.8	3.3	30	86
									Liquid 3	2-I	-		-	-		8.0	3.1	30	103
Liquid 4	2-J	-	-	-	7.9	3.1	30	130
									Liquid composition	2-E	2.41		149.2	1∶0.30		3.6	2.9	31	-
Embodiment 2-5	Liquid 1	2-B	C	-	-	-	8.6	3.2												31	102	6340 (B/K)
									Liquid 2	2-I	-	-	-	8.0	3.1	30	103
	Liquid 3	2-J		-	-	-	7.9	3.1										30	130
									Liquid composition	2-K	2.18	191.3	1∶0.45	4.6	3.2	31	95
	Comparative Examples 2-5	Liquid 1		2-A	B	-	-	-										8.5	3.3	31	93		50 (A/G)
Liquid 2			2-H						-	-	-	7.8	3.3	30	86
		Liquid 3		2-I		-	-	-								8.0	3.1	30	103
Liquid 4			2-J						-	-	-	7.9	3.1	30	130
		Liquid composition		2-G		4.56	Do not have	-								5.5	2.6	31	-

[table 7]

	Optical concentration	The paper of spreading and sinking in	Time of drying	Long term storage stability
					Embodiment 2-1	a	a	a	a
Embodiment 2-2	a	a	a	a
					Embodiment 2-3	a	a	a	a
Comparative Examples 2-1	c	c	a	a
					Comparative Examples 2-2	a	a	a	b
Comparative Examples 2-3	c	c	a	a
					Comparative Examples 2-4	c	c	a	a

[table 8]

	Optical concentration	The paper of spreading and sinking in	The paper of spreading and sinking between look	Time of drying	Long term storage stability
						Embodiment 2-4	a	a	a	a	a
Embodiment 2-5	a	a	a	a	a
						Comparative Examples 2-5	c	c	a	a	a

[table 9]

		Printing ink	Print pattern	pKa	The mol ratio of organic acid and polyvalent metal salt	The mol ratio of organic acid and organic amine	pH	Viscosity	Surface tension (mN/m)	Volume average particle size (nm)	In 1: 1 mixture more than or equal to the number of particles (individual/μ L) of 5 μ m
												Embodiment 3-1	Liquid 1	1-A	A	-	-	-	8.5	3.3	31	93	8429
Liquid composition	3-A	2.41	1∶0.35	1∶0.15	3.8	3.2	31	-

[table 10]

	Optical concentration	The paper of spreading and sinking in	Time of drying	Long term storage stability
					Embodiment 3-1	a	a	a	a

Claims (22)

1. spray ink Printing liquid composition, said composition comprises acid dissociation constant pKa at least and is equal to or less than 4.5 organic acid, water-soluble solvent and water, also comprises to be selected from following group at least a compound:

(a): polyvalent metal salt, this polyvalent metal salt are counted with mol ratio (polyvalent metal salt/organic acid) with respect to described organic acid addition and are equal to or greater than 0.01 and less than 1; With

(b): organic amine compound, this organic amine compound are counted with mol ratio (organic amine compound/organic acid) with respect to described organic acid addition and are equal to or greater than 0.1 and be equal to or less than 0.9.

2. spray ink Printing liquid composition as claimed in claim 1, wherein, described organic acid is the compound by following general formula (1) expression:

General formula (1),

Wherein, X represents O, CO, NH, NR, S or SO ₂, R represents alkyl; M represents hydrogen atom, basic metal or amine; L represents 1～5 integer; M represents 1 or 2; N represents 3～7 integer.

3. spray ink Printing liquid composition as claimed in claim 2, wherein, the compound by described general formula (1) expression is at least a compound that is selected from the group of being made up of the derivative and their salt of pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrroles's carboxylic acid, furancarboxylic acid, pyridine carboxylic acid, coumalic acid, thiophene carboxylic acid, nicotinic acid, these compounds.

4. spray ink Printing liquid composition as claimed in claim 1, wherein, the pH value of said composition is equal to or greater than 2.5, and is equal to or less than 7.0.

5. spray ink Printing liquid composition as claimed in claim 1, wherein, the weight-average molecular weight of described organic amine compound is for being equal to or less than 1000.

6. spray ink Printing liquid composition as claimed in claim 1, wherein, with respect to the total amount of described liquid composition, the addition of organic amine and is equal to or less than 30 quality % for being equal to or greater than 0.01 quality % in the described liquid composition.

7. spray ink Printing liquid composition as claimed in claim 1, wherein, with respect to the total amount of described liquid composition, the organic acid addition and is equal to or less than 30 quality % for being equal to or greater than 0.01 quality % in the described liquid composition.

8. spray ink Printing printing ink group, this printing ink group has first liquid and second liquid at least;

Described first liquid comprises coloured material, water-soluble solvent and water at least, and described second liquid is the described spray ink Printing liquid composition of claim 1.

9. spray ink Printing printing ink group as claimed in claim 8, wherein, the coloured material in described first liquid is at least a pigment that is selected from the group of being made up of following pigment: by polymeric dispersant dispersive pigment, from pigment dispersion and the pigment that is coated with resin.

10. spray ink Printing printing ink group as claimed in claim 9, wherein, the coloured material particulate volume average particle size in described first liquid is equal to or greater than 30nm, and is equal to or less than 250nm.

11. spray ink Printing as claimed in claim 8 printing ink group, wherein, the surface tension of described first liquid is equal to or greater than 20mN/m, and is equal to or less than 60mN/m.

12. spray ink Printing as claimed in claim 8 printing ink group, wherein, described first liquid comprises the resin that has hydroxy-acid group.

13. spray ink Printing as claimed in claim 8 printing ink group, wherein, described second liquid comprises at least a coloured material that is selected from the group of being made up of following material: dyestuff, surface have the pigment of sulfonic acid or sulfonate with from pigment dispersion.

14. spray ink Printing as claimed in claim 8 printing ink group, wherein, the surface tension of described second liquid is equal to or greater than 20mN/m, and is equal to or less than 45mN/m.

15. spray ink Printing as claimed in claim 8 printing ink group, wherein, the viscosity of described first liquid and second liquid is equal to or greater than 1.2mPas, and is equal to or less than 25.0mPas.

16. spray ink Printing as claimed in claim 8 printing ink group, wherein, in the mixing solutions of described first liquid and second liquid, the particulate quantity that particle diameter is equal to or greater than 5 μ m is equal to or greater than 1,000/ μ L.

17. an ink jet recording method that uses the described spray ink Printing of claim 8 with the printing ink group, wherein, with described first liquid and second liquid application on recording medium so that both be in contact with one another, thereby form image.

18. ink jet recording method as claimed in claim 17, wherein, with every amount that is equal to or less than 25ng, with described first liquid and second liquid application on described recording medium.

19. ink jet recording method as claimed in claim 17, wherein, be used to form a pixel and described first liquid used and second liquid amount separately be 1: 20 to 20: 1 than by quality ratio.

20. an ink-jet recording device, this device comprises record-header, and this record-header is used for the described spray ink Printing of claim 8 with the various spouting of liquid of printing ink group to recording medium.

21. ink-jet recording device as claimed in claim 20, wherein, with every amount that is equal to or less than 25ng, with described first liquid and second liquid application on described recording medium.

22. ink-jet recording device as claimed in claim 20, wherein, be used to form a pixel and described first liquid used and second liquid amount separately be 1: 20 to 20: 1 than by quality ratio.

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