CN100349996C - Inkjet recording ink, recording process and recording apparatus - Google Patents

Inkjet recording ink, recording process and recording apparatus Download PDF

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CN100349996C
CN100349996C CNB2004800007344A CN200480000734A CN100349996C CN 100349996 C CN100349996 C CN 100349996C CN B2004800007344 A CNB2004800007344 A CN B2004800007344A CN 200480000734 A CN200480000734 A CN 200480000734A CN 100349996 C CN100349996 C CN 100349996C
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ink
recording ink
wetting agent
recording
printing ink
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CN1701103A (en
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坂内昭子
永井希世文
后藤明彦
小岛真理子
南场通彦
井上智博
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Ricoh Co Ltd
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Ricoh Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide ink for ink jet capable of forming high image quality even in plain paper and ensuring short-term and long-term reliability.

Description

Ink-jet recording ink, recording method and recording unit
Technical field
The present invention relates to ink-jet recording ink (inkjet recording ink) and print cartridge (ink cartridge) and use the recording method and the recording unit of this printing ink respectively.Specifically, the present invention relates to provide the excellent image quality and with blank sheet of paper bonded flying print ability, and stability in storage and the stable printing ink of injection (discharging) and use print cartridge, recording method and the recording unit of this printing ink respectively.
Background technology
Ink-jet printer is because their attractive features, and it is relatively low to print, carry out easily colour print, compact in size, low price and running cost on blank sheet of paper, and its market enlarges at present.
The desired typical performance of ink-jet recording ink is to realize high image quality such as tone, image density and spread and sink in oozing those performances of (bleeding); Obtain the dissolving in printing ink of reliability such as tinting material or those performances of the jetting stability of the stability in storage of dispersion stabilization, printing ink and printing ink; Guarantee the ability that document image keeps, as water-fast and fast to light those performances; With those performances that realize flying print such as rapid ink drying.Up to now, in order to realize these performances, various improvement have been proposed.
At first, the tinting material in the ink-jet recording ink is mainly based on dyestuff, and this is because due to the excellent tinctorial property of dyestuff and the high reliability; Recently, have fast light and water-proof purpose, contain pigment such as the sooty ink component has caused people's interest in order to make document image.
In addition, the size of ink droplet becomes littler at present, and therefore, in order to realize high-quality print image and flying print, it is littler that jet size also becomes.
Yet,, quite be difficult to guarantee jetting stability when pigment is used for tinting material and uses when having the printer of less jet size.Therefore, still untappedly go out to satisfy the ink-jet recording ink that these require and other must performance.
In the past, for the purpose of the stability that improves printer, a kind of method that addresses this problem was to provide a kind of along with as far as possible suppress low ink composite with the viscosity increase time lapse.For example, Japanese Patent Application Publication (JP-A) N2002-337449 disclose when with begin to compare, when the concentration of printing ink is concentrated to 2 times, the viscosity that suppresses printing ink changes to less than 10 times and arrives less than 3 times with change of granularity, can cause the following fact: condensing of pigment can prevent the expansion of printing ink, and can prevent that also printing ink from not having to print the appearance of pore region thereon.Yet, in the printing ink that is proposed, find to be difficult on blank sheet of paper, to form high-quality image.
In addition, JP-A No.2000-95983 discloses a kind of printing ink, wherein can evaporate composition evaporation residuum afterwards in the printing ink and still be liquid, and the viscosity of residuum is less than 10 times of initial viscosity.Yet this printing ink is based on dyestuff, even reliability is higher, but the relative mistake still of the picture quality on blank sheet of paper.
In addition, JP-A No.09-111166 discloses a kind of printing ink, and wherein the viscosity of the residuum of the moisture in the printing ink after 60 ℃ evaporate down is less than 10 times of viscosity before evaporating.Yet this printing ink is also based on dyestuff, even the weather resistance of the reliability of printing ink and picture quality is able to balance by adding water-soluble polymers, but water tolerance is still not enough.
In addition, to have proposed the printing ink of viscosity higher (5-15mPa.s) be to guarantee that high-quality image is necessary to JP-A No.2001-262025.According to this proposal, should regulate velocity of evaporation at initial period, guaranteeing reliability, and should add specific compound as viscosity control agent, regulate viscosity.Yet,, without any explanation, and when in the shower nozzle (head) of a fixed structure and size and nozzle, leaving standstill for a long time, think poor reliability, although it discloses the reliability of guaranteeing after 24 hours about the stability of the granularity of the pigment that will use.
As mentioned above, have full-bodied printing ink in order to guarantee high-quality print image under the print speed relatively fast, successfully to handle, yet, this have full-bodied printing ink and can not be handled well, and this is because this printing ink is difficult to guarantee its reliability at present.
Disclosure of the Invention
The present invention relates to a kind of recording ink, it comprises tinting material, wetting Agent for Printing Inks, tensio-active agent and the wetting agent that can be dispersed in the water, wherein when gross weight based on recording ink, moisture evaporated content is during less than 30wt%, and the viscosity increment rate relevant with moisture evaporation in the recording ink is 5.0mPa.s/% or lower; When moisture evaporated content was 30-45wt%, the viscosity increment rate relevant with moisture evaporation surpassed 50mPa.s/% or higher; And at the recording ink when the viscosity increment rate reaches 50mPa.s/% in the stage, the mean particle size of the tinting material in the recording ink is less than 5 times of the mean particle size of the tinting material in the home record printing ink, and be 0.8 micron or lower, wherein relevant with moisture evaporation viscosity increment rate (mPa.s/%) is defined as the ratio of the increase (mPa.s) of viscosity to the increase (%) of moisture evaporated content.
The feature of printing ink of the present invention is, the viscosity of printing ink is up to the gross weight based on recording ink, moisture evaporated content is that 30wt% is just actual to be increased, be that the viscosity increment rate is 5.0mPa.s/% or lower, and when moisture evaporated content is 30-45wt%, the viscosity of printing ink increases really fast, and promptly the viscosity increment rate surpasses 50mPa.s/%.
Because this feature promptly, is prepared printing ink of the present invention as mentioned above, because after ejection from nozzle and arrive time period before the paper during in, and in the moment that arrives on the paper, moisture evaporation, printing ink can increase its viscosity, thereby even can form high-quality image on blank sheet of paper.
When moisture evaporated content during less than 30wt%, the printing ink that viscosity significantly increases usually shows the jetting stability of going on business, and when moisture evaporated content during greater than 45wt%, the printing ink of viscosity increase tends to cause spread and sink in and oozes, this is because when printing ink is applied on the paper, due to viscosity is low.In addition, by design printing ink, make even in the stage when viscosity occurring and increase fast, the variation of mean particle size descends, thereby can guarantee in short-term and the reliability for a long time.
In the present invention, term " viscosity increment rate " is meant the numerical value of calculating as described below, and its unit is mPa.s/%.
The viscosity increment rate=[(viscosity (mPa.s) after the moisture evaporation-(viscosity (mPa.s) before the moisture evaporation)] ÷ (relevant moisture evaporation (%)).
In addition, term " moisture evaporated content " is meant the numerical value of calculating as described below, and its unit is %.
(because of the weight of moisture evaporation loss) ÷ (gross weight before the moisture evaporation) * 100
In addition, term " mean particle size " expression volume average particle sizes, the granularity when promptly particulate cumulative volume (cumulativevolume) is 50% volume.Measuring method as for volume average particle sizes, can adopt dynamic light scattering (Doppler light-scattering analysis), wherein laser beam is irradiated onto on the particle of doing pedesis in the printing ink, and analyzes the radiating frequency jitter of returning from particle (backscattering), to measure granularity.
Each component that the printing ink of feature of the present invention is satisfied in preparation consists essentially of tinting material, wetting Agent for Printing Inks, tensio-active agent and wetting agent, and wherein the combination of these components and blend ratio are important.In addition, add specific pH control agent and can provide printing ink with higher image quality and higher reliability as the pigment coagulation inhibitor is feasible.
About preparing the standard that exemplifies of above-mentioned " ink viscosity increases really fast when moisture evaporated content is 30-45wt% ", it is higher a bit and any wetting Agent for Printing Inks of viscosity ratio water height than water to have prepared boiling point is more much higher than water and viscosity ratio water is much higher wetting Agent for Printing Inks and boiling point, successfully blend water and these wetting Agent for Printing Inkss then, but be not limited to this.In addition, based in the intravital orientation of liquid or hydrogen-bonded application and higher equivalent moisture content, can be effective; In addition, can check the influence of content, avidity, the tensio-active agent that is added and the wetting agent of the tinting material that is added ideally to all kinds of SOLVENTS.For example, in some cases, it is not preferred mixing and accounting for whole wetting Agent for Printing Inks weight 80% or the higher rudimentary dibasic alcohol that is used for wetting Agent for Printing Inks routinely such as ethylene glycol or lower alcohol, unless combine with other wetting Agent for Printing Inks with higher and viscosity higher.
Description of drawings
Fig. 1 has shown the relation that exemplifies between moisture evaporated content and the ink viscosity (under 25 ℃).
Fig. 2 has shown the relation that exemplifies between the mean particle size of moisture evaporated content and printing ink.
Fig. 3 has shown the decline of dynamic surface tension exemplaryly.
Fig. 4 has shown that between moisture evaporated content and the ink viscosity another exemplifies relation.
Fig. 5 has shown that between the mean particle size of moisture evaporated content and printing ink another exemplifies relation.
Fig. 6 illustrates to have shown the print cartridge that exemplifies of the present invention.
Fig. 7 has illustrated to show the ink-jet recording device that exemplifies of the present invention.
Fig. 8 illustrated to show Fig. 7 ink-jet recording device exemplify internal structure.
Fig. 9 is the floor map that exemplifies internal structure that shows the ink-jet recording device of Fig. 7.
Figure 10 has shown the view of the part amplification that relates to ink gun of the present invention.
Figure 11 relates to ink gun of the present invention along the local cross sectional view of amplifying of channel direction.
Embodiment
About tinting material, usually because weather resistance is mainly used pigment, yet, optionally,, dyestuff can be combined with pigment in order in keeping the desired scope of weather resistance, to regulate color.
Pigment can be inorganic or pigment dyestuff, and can be with self-dispersion type pigment, by tensio-active agent and/or polymeric dispersant dispersive dispersion liquid, and emulsion-type pigment and use this pigment with resin-coated self-dispersion type pigment form.
The example of mineral dye comprises titanium oxide, ferric oxide, lime carbonate, barium sulfate, aluminium hydroxide, baryta yellow, cadmium red and chrome yellow, and the carbon black by methods known in the art such as contact process, oven process and hot manufactured.
The example of pigment dyestuff comprises azo pigment, as the azo pigment of azo lake, insoluble azo pigment, condensation and the azo pigment of chelating; Many ring pigment are as phthalocyanine pigment, perylene (perylene) pigment, perylene ketone (perynone) pigment, anthraquinone pigment, quinacridone pigment, dioxazine (dioxadine) pigment, indigo pigment, thioindigo color, isoindolinone (isoindolinone) pigment and quinophthalone (quinophthalone) pigment; The dyestuff sequestrant is as basic dyestuff sequestrant and matching stain sequestrant; Nitropigments; Nitroso pigments and aniline pigment etc.In the middle of these pigment, especially preferably glassware for drinking water there are those dyestuffs of high-affinity.
The specific examples of black pigment comprises carbon black (C.I. Pigment black 7), as furnace black, acetylene black and thermally oxidized black; Metal and metallic compound such as copper, iron (C.I Pigment black 11), and titanium oxide; With pigment dyestuff such as nigrosine.
The specific examples of coloured pigment comprises C.I. Pigment Yellow 73 1,3,12,13,14,17,24,34,35,37,42 (being Zh 1), 53,55,81,83,95,97,98,100,101,104,408,109,110,117,120,128,138,150,151,153 and 183; C.I. pigment orange 5,13,16,17,36,43 and 51; C.I. Pigment red 1,2,3,5,17,22,23,31,38,48:1,48:2 (permanent bordeaux 2B (Ca)), 48:3,48:4,49:1,52:2,53:1,57:1 (brilliant carmine 6B), 60:1,63:1,63:2,64:1,81,83,88,101 (red iron oxides), 104,105,106,108 (cadmium reds), 112,114,122 (quinacridone fuchsins), 123,146,149,166,168,170,172,177,178,179,185,190,193,209 and 219; C.I. pigment violet 1 (rhodamine color lake), 3,5:1,16,19,23 and 38; C.I. pigment blue 1,2,15,15:1,15:2,15:3 (phthalocyanine blue), 16,17:1,56,60 and 63; C.I. Pigment green 1,4,7,8,10,17,18 and 36; Deng.
Preferably, the surface of modified pigment so that at least a hydrophilic radical is directly connected on the surface of pigment, perhaps utilizes the atomic radical (intervening atomic groups) of other insertion to be connected on the surface of pigment.Specifically, can be chemically bonded on the surface of pigments,, adopt hypohalous acid and/or its salt, cause the oxidation of pigment, thereby produce this pigment perhaps by under the condition of humidity by making some functional groups such as sulfuryl or carboxyl.Especially advantageous conditions is, the surface of pigment is connected with carboxyl, and pigment can be dispersed in the water.This pigment with surface modification of carboxyl can provide dispersion stabilization and high-quality printing and the higher water tolerance of recording medium of printing also can be provided.
In addition, this printing ink condition even the redispersibility of printing ink also can be provided after ink setting, therefore in addition long-term stop printing after or even when the moisture of printing ink because of locating on every side to evaporate when descending at the nozzle location of ink head, can be under the situation of not stopping up ink flow, optionally, with simple cleaning, carry out suitable printing.In addition, when this self-dispersion type pigment typically when described tensio-active agent and wetting agent combine subsequently, it can provide high quality graphic and the high reliability with synergy.
Except aforementioned pigment, can be with water-insoluble or be that the structure formation that water miscible pigment is incorporated into the micro polymer intragranular is used polymer emulsion hardly.About containing the polymer emulsion of pigment, this structure can exemplify the polymer particles of encapsulated pigment and/or the polymer particles of adsorption pigment in its surface.In this structure, not necessarily require whole pigment by encapsulate or be adsorbed, but in the scope of deterioration effect of the present invention not, an amount of pigment can be dispersed in the emulsion.
The example that constitutes the polymkeric substance of polymer emulsion comprises vinyl polymer, polyester polymers and polyether polyols with reduced unsaturation; Especially optimal ethylene based polyalcohol and polyester polymers.
In addition, in the present invention, can be combined in the auxiliary pigment that is dispersed in down in the water-bearing media of dispersion agent.Preferred pigment is the employed pigment as known in the art of preparation known pigment dispersion liquid.
The example of this pigment comprises polyacrylic acid, polymethyl acrylic acid, vinylformic acid-acrylonitrile copolymer, vinyl-acetic ester-acrylate copolymer, vinylformic acid-alkyl acrylate copolymer, the styrene-propene acid copolymer, vinylbenzene-Sipacril 2739OF, styrene-propene acid-alkyl acrylate copolymer, vinylbenzene-methacrylic acid-alkyl acrylate copolymer, styrene--acrylic copolymer, styrene--vinylformic acid-alkyl acrylate copolymer, styrene-maleic acid copolymer, vinyl naphthalene-maleic acid, vinyl-acetic ester-ethylene copolymer, vinyl-acetic ester-vinyl fatty ester-ethylene copolymer, vinyl-acetic ester-maleate copolymer, vinyl-acetic ester-Ba Dousuan multipolymer, vinyl-acetic ester-acrylic copolymer etc.
The weight-average molecular weight of these multipolymers (Mw) is preferably 3000-50000, and more preferably 5000-30000 most preferably is 7000-15000.
At dispersed color stably and do not reduce in the scope of effect of the present invention, can select the content of dispersion agent suitably.Pigment (P) is preferably 1/0.06 to 1/3 to the ratio (P/D) of dispersion agent (D), and more preferably 1/0.125 to 1/3.
As mentioned above, carboxyl preferably is connected on the dispersion agent of printing ink, and then dispersion stabilization, print quality and water-proof effect can be provided.
Except these effects, carboxyl can provide to prevent to spread and sink in and be seeped into the bonus effect of back side of paper.Especially, under the auxiliary dispersive pigment down and wetting agent bonded situation of the dispersion agent that carboxyl is connected thereto, even when on wide relatively blank sheet of paper recording medium, printing, also can obtain such as sufficient rate of drying and seldom spread and sink in to be seeped into effect the back side.Think that reason is: because the reduction of printing ink pH, and after pigment is adhered on the recording medium, with be present near the recording medium surface the polyvalent metal ion such as the interaction of calcium ion, cause reducing the solubleness of dispersion agent itself and caused condensing of dispersion agent itself and pigment, this is that the dissociation constant of carboxyl is relatively low because compare with other acidic-group.
In the present invention, except pigment, can use following dyestuff.
The specific examples of matching stain and food dye comprises C.I. turmeric yellow 17,23,42,44,79 and 142; C.I. azogeramine, 8,13,14,18,26,27,35,37,42,52,82,87,89,92,97,106,111,114,115,134,186,249,254 and 289; C.I. acid blue 9,29,45,92 and 249; C.I. Acid Black 1,2,7,24,26 and 94; C.I. food yellow 3 and 4; C.I. Food Red 7,9 and 14; And C.I. food black 1 and 2.
The specific examples of substantive dyestuff comprises directly Huang 1,12,24,26,33,44,50,86,120,132,142 and 144 of C.I.; C.I. directly red 1,4,9,13,17,20,28,31,39,80,81,83,89,225 and 227; C.I. direct orange 26,29,62 and 102; C.I. sun blue 1,2,6,15,22,25,71,76,79,86,87,90,98,163,165,199 and 202; And C.I. directly deceives 19,22,32,38,51,56,71,74,75,77,154,168 and 171.
The specific examples of basic dyestuff comprises C.I. basic yellow 1,2,11,13,14,15,19,21,23,24,25,28,29,32,36,40,41,45,49,51,53,63,64,65,67,70,73,77,87 and 91; C.I. alkaline red 2,12,13,14,15,18,22,23,24,27,29,35,36,38,39,46,49,51,52,54,59,68,69,70,73,78,82,102,104,109 and 112; C.I. alkali blue 1,3,5,7,9,21,22,26,35,41,45,47,54,62,65,66,67,69,75,77,78,89,92,93,105,117,120,122,124,129,137,141,147 and 155; And C.I. basic black 2 and 8.
The specific examples of reactive dyestuffs comprises C.I. reactive black 3,4,7,11,12 and 17; Reactive yellow 1,5,11,13,14,20,21,22,25,40,47,51,55,65 and 67; C.I. reactive red 1,14,17,25,26,32,37,44,46,55,60,66,74,79,96 and 97; C.I. Reactive blue 1,2,7,14,15,23,32,35,38,41,63,80 and 95.
In the middle of these dyestuffs, be preferably matching stain and substantive dyestuff especially.
The content of these tinting materials is preferably 3-15wt% in the printing ink, more preferably 5-12wt%.
As for wetting Agent for Printing Inks, for the present invention, be preferably and tend to form hydrogen bond, only represent viscosity higher, demonstrate higher equivalent moisture (equivalent moisture) and in the presence of water, demonstrate more low viscous those wetting Agent for Printing Inkss.
This examples of humectants that is selected from multivalence alcohol comprises glycerine, ethylene glycol, glycol ether, triglycol, propylene glycol, dipropyl glycol, 3 third glycol, 3-methyl isophthalic acid, 3-butyleneglycol, 1,3 butylene glycol, 2,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, Tetraglycol 99,1,6-hexylene glycol, 2-methyl-2,4-pentanediol, polyoxyethylene glycol, 1,2,4-trihydroxybutane, 1,2,6-hexanetriol etc.Along with the evaporation of moisture, glycerine provides the quick increase of viscosity, and on the other hand, it suppresses condensing of tinting material, thereby the excellent effect that prevents particle size growth is provided.Therefore, based on whole wetting Agent for Printing Inkss, comprise that the content of glycerine is preferably 20wt% or higher.In addition, the equivalent moisture content for higher is preferably glycerine.
Preferably, wetting Agent for Printing Inks comprises two or more multivalence alcohol, and described multivalence alcohol demonstrates 25wt% or higher equivalent moisture respectively under the condition of the relative humidity of 20 ℃ temperature and 60%.
In addition, aspect preferred in, one of multivalence alcohol is glycerine, and based on whole wetting Agent for Printing Inkss, the content of glycerine is 20wt%-80wt%.
As for glycerine bonded wetting Agent for Printing Inks, be preferably 1,3 butylene glycol and 3-methyl isophthalic acid, the 3-butyleneglycol.1,3 butylene glycol and 3-methyl isophthalic acid, 3-butyleneglycol can provide the more high equivalent weight moisture content that is similar to glycerine and high reliability more; And can provide such as the effect and the effect such as on paper surface, fully keeping the printing ink material of applying ink droplet (pictorial element) evenly launch on the paper.3-methyl isophthalic acid, 3-butyleneglycol especially can provide the effect of even expansion ink droplet, thereby can form high-quality image.
Aspect the raising reliability, glycerine can provide excellent effect, but but deterioration picture quality can provide too high viscosity after moisture evaporation, and when a large amount of glycerine of compounding, but the deterioration jet performance.The blend ratio of these butyleneglycols and glycerine is preferably 1: 4 to 4: 1, more preferably 1: 3 to 3: 1, most preferably is 1: 1 to 3: 1.
As for content, in the 10-40wt% scope, most preferably in the wetting Agent for Printing Inks content of 25-35wt%, can derive effect of the present invention based on the wetting Agent for Printing Inks of whole printing ink.Cross when low when the content of wetting Agent for Printing Inks, stability in storage and jetting stability may be not enough, and nozzle may be blocked.On the other hand, when the too high levels of wetting Agent for Printing Inks, may be difficult to dry printing ink, and tend to occur spreading and sinking in of letter and blend spreading and sinking in of color boundary and ooze, thereby cause lower picture quality.
In order to provide following difference described desired properties, tensio-active agent and wetting agent are incorporated in the printing ink of the present invention.The tensio-active agent that uses among the present invention is the tensio-active agent that especially can reduce static surface tension in about 100 milliseconds (hereinafter referred " msec "), thereby when ink droplet is applied on the paper, promotes ink penetration in paper.On the other hand, the wetting agent that uses among the present invention is especially to reduce the capillary wetting agent of relative dynamic in about 10-100msec, thereby when ink droplet is applied on the paper, promotes that printing ink launches on paper surface.
The combination of these tensio-active agents and wetting agent can provide a kind of printing ink, wherein pictorial element more suitably launches on paper and is penetrated in the paper at a relatively high speed, be quick-drying energy (rapid dryingproperty), thereby produce the production rate of higher-quality image and Geng Gao with higher production rate.
Tensio-active agent can be selected from amphoterics, nonionogenic tenside and anion surfactant suitably.Consider the dispersion stabilization of material and the relation between the picture quality, preferably use the ethylene oxide adduct (additive) of nonionogenic tenside such as polyoxyethylene alkyl phenyl ether, polyoxypropylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkylamide, polyoxyethylene block copolymer, fatty acid esters of sorbitan, Vykamol Sorbitol 8B, acetylene alcohol (acetylenealcohol).
In addition, can allow separately or be used in combination fluorine-containing tensio-active agent or silicone surfactant according to prescription.
In the middle of these, especially be preferably the nonionogenic tenside of formula (1) expression.
R-O-(C 2H 4O) m-H formula (1)
Wherein " R " expression has the alkyl of the straight or branched of 6-14 carbon atom, and " m " represents positive integer.
Consider picture quality, " R " preferably has 10 or the alkyl of more a plurality of carbon atoms, " m " preferred 7-9.
The content of ink composite internal surfactants is preferably 0.01-5.0wt%, more preferably 0.5-3.0wt%.When content during less than 0.01wt%, effect is not remarkable; When greater than 5.0wt%, the infiltration that arrives in the recording medium is too remarkable again, and can cause image deterioration and/or spread and sink in and be seeped into the back side.
The specific examples of the compound of above-mentioned molecular formula (1) expression includes, but are not limited to:
Table 1
C 8H 17O(C 2H 4O) 2H (1-1) C 10H 21O(C 2H 4O) 4H (1-2)
C 12H 25O(C 2H 4O) 3H (1-3) C 12H 25O(C 2H 4O) 7H (1-4)
C 12H 25O(C 2H 4O) 12H (1-5) C 13H 27O(C 2H 4O) 3H (1-6)
C 13H 27O(C 2H 4O) 5H (1-7) C 13H 27O(C 2H 4O) 7H (1-8)
C 13H 27O(C 2H 4O) 9H (1-9) C 13H 27O(C 2H 4O) 12H (1-10)
C 13H 27O(C 2H 4O) 20H (1-11) C 13H 27O(C 2H 4O) 30H (1-12)
C 13H 29O(C 2H 4O) 30H (1-13)
These tensio-active agents can separately or be used in combination.Even when tensio-active agent can not be dissolved in the recording liquid easily, in some cases, by combining with other tensio-active agent, this tensio-active agent is solubilized and long life-span of realization also.As for comprising the commercial surfactant of above-claimed cpd as its main ingredient, can exemplify BT series available from Nikko Chemicals Co., available from the Softanol series of Nippon ShokubaiCo. with available from the Dispernol of Nippon Yuski Co..
The wetting agent that uses among the present invention preferably contains and at least aly under 20 ℃ the solubleness of water is 0.2wt% or higher and less than the polyvalent alcohol of 5.0wt%.
The example of aliphatic dialcohol comprises 2-ethyl-2-methyl isophthalic acid, ammediol, 3,3-dimethyl-1 in the polyvalent alcohol, 2-butyleneglycol, 2,2-diethyl-1, ammediol, 2-methyl-2-propyl group-1, ammediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexylene glycol, 5-hexene-1,2-glycol, 2-ethyl-1,3-hexylene glycol etc.
In the middle of these, most preferably be 2-ethyl-1,3-hexylene glycol and/or 2,2,4-trimethylammonium-1,3-pentanediol.
The example of combinative other wetting agent comprises the alkyl and the aryl ethers of multivalence alcohol, as diglycol monotertiary phenyl ether, glycol monomethyl phenyl ether, ethylene glycol monoallyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether and Tetraglycol 99 chloro-phenyl-ether; With lower alcohol such as ethanol.Wetting agent is not limited to these compounds, and condition is that they may be dissolved in the printing ink and the adjusting desired properties.
The content of wetting agent is preferably 0.1-4.0wt%.When content during, can't obtain the quick-drying energy, thereby cause the unfolded image less than 0.1wt%.On the other hand, when content during, run into following problem greater than 4.0wt%: the dispersion stabilization deficiency of tinting material, nozzle tends to blocked, the infiltration that arrives in the recording medium surpasses required degree, and also tends to image density occur reducing and spread and sink in be seeped into the back side.
The pH control agent can be any material, and condition is can regulate the pH of recording liquid to required scope, and does not cause the negative influence of prepared recording liquid.
The example of pH control agent comprises amine such as diethanolamine, trolamine etc.; The oxyhydroxide of alkali metal such as lithium hydroxide, sodium hydroxide, potassium hydroxide etc.; Ammonium hydroxide; The oxyhydroxide of the oxyhydroxide, quaternary phosphine of quaternary ammonium, Quilonum Retard, salt of wormwood and alkali-metal other carbonate.
When an amount of multivalence alcohol that contains amino is used as the pigment coagulation inhibitor,, can improves dispersing of pigments stability more significantly, and can guarantee the reliability of jetting stability owing to the agglomerative reason that suppresses pigment.Its content depends on prescription and required pH value; Usually, be preferably 0.01-2.0wt%, more preferably 0.1-1.0wt%.In addition, in the embodiment of this invention, especially preferred 2-amino-2-ethyl-1, ammediol is the pigment coagulation inhibitor, and adds 2-amino-2-ethyl-1, ammediol can improve the possibility that the element that uses contacts with recording liquid on the ink flow path.
As for other additive component, water-miscible organic solvent such as 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, ε-Ji Neixianan, monoethanolamine and diethanolamine successfully can be incorporated in the printing ink of the present invention, dry too early to prevent printing ink.
As for another additive component, preservative antifungal agent such as Sodium dehydroacetate, sodium sorbate, 2-pyridine mercaptan-1-sodium oxide, Sodium Benzoate and sodium pentachlorophenol can be incorporated in the printing ink of the present invention.
As for sequestrant as another additive, but exemplified by ethyl enediamine tetraacethyl sodium, nitrilotriacetic acid(NTA) sodium (sodium nitrilotriacetate), hydroxyethylethylene diamine tri-acetic acid sodium, diethylene triaminepentaacetic acid(DTPA) sodium and uramildiacetic acid sodium.
Rust-preventive agent as for as another additive can exemplify acid accumulator sulfite, Sulfothiorine, subunit diglycollic acid ammonium (ammonium thiodiglycolate), nitrous acid di-isopropyl ammonium, trinitrol, nitrous acid dicyclohexyl ammonium and benzotriazole etc.
Around nozzle location, before moisture evaporated content surpassed 30wt%, by printing ink being sprayed to printable area or nonprinting region, printing ink of the present invention can as one man form the image with better quality.In addition, following record condition makes full use of the feature of printing ink of the present invention: the volume of the ink droplet that sprays from nozzle is 3-40 skin liter (pico-liter) (hereinafter referred to as " pl "), the speed of ejection ink droplet is 6-20m/s, frequency is 1kHz or higher, and resolving power is 300 point/inches (hereinafter referred to as " dpi ") or higher.
Because when weight based on whole printing ink, when moisture evaporated content surpasses 30wt%, the quick retrogradation of printing ink of the present invention, therefore printing ink of the present invention should be used for following method and/or device, described method and/or device are included in moisture evaporated content and surpass before the 30wt%, the program of ejection printing ink on printable area or the nonprinting region.As for a kind of method that ink jet is arrived nonprinting region, calculate the scanning times of shower nozzle erecting frame (head-installed carriage), drive shower nozzle, when surpassing preset value with convenient scanning times, with ink jet to nonprinting region, thereby can spray a certain amount of printing ink.Preferably, setting is ejected into the quantity of ink on the nonprinting region, so that be maintained and do not reduce in the scope of print speed in reliability, and the printing ink of filling minimum, wherein can randomly set the quantity of ink that is ejected on the nonprinting region by changing the driving number of times of shower nozzle.
As for the method that receives ejection printing ink, consider the structure of recording unit, for example the printing ink susceptor can be arranged in the outside of the band of transmission log medium.Therefore, when scanning times surpasses pre-determined number,, can provide the recording unit of guaranteeing more stable jet performance by using with the method for ink jet in the printing ink susceptor that places on the nonprinting region.
In addition, because the recording unit of being furnished with record-header is provided, described record-header is by a plurality of pressurization liquid chambers (pressuring liquid room), has the nozzle that is not more than 35 microns hole with the intercommunication of pressurization liquid chamber, the printing ink feed path, oscillating plate, constitute with the electromechanical converting unit that oscillating plate is moved, and owing to provide the ink droplet of a plurality of continuous ejections before arriving recording medium to be merged into the parts of big drop, even therefore printing ink has higher viscosity, also can guarantee the jetting stability of printing ink.
The embodiment that provides below the reference set forth the present invention in more detail, but these should not be construed as limiting the invention.All percentage ratios and umber by weight, except as otherwise noted.
Embodiment
Embodiment 1-is about printing ink
Black ink
KM-9036 (Toyo Ink Co. self-dispersion type pigment) 50%
Glycerine (wetting Agent for Printing Inks) 10%
1,3 butylene glycol (wetting Agent for Printing Inks) 15%
2-ethyl-1,3-hexylene glycol (wetting agent) 2%
2-Pyrrolidone 2%
Tensio-active agent (1-9) 1%
Silicone antifoam agent KS508 (Shin-Etsu Che.) 0.1%
The deionized water balance amount
The ink composition in the above-mentioned prescription of blend fully at room temperature, the manufacture of ink composition, making the gained ink composite then is that 1.2 microns membrane filter experience is filtered by mean pore size, thus the printing ink of preparation embodiment 1.
Embodiment 2-is about printing ink
The preparation of polymers soln A
After the internal atmosphere of 1 liter of flask being furnished with agitator, thermometer, nitrogen inlet tube, reflux exchanger and dropping funnel fully with the nitrogen backfill, blend 11.2g vinylbenzene, 2.8g vinylformic acid, 12.0g lauryl methacrylate(LMA), 4.0g polyethylene glycol methacrylate-styrene polymer, 4.0g vinylbenzene macromonomer and 0.4g mercaptoethanol also are heated to 65 ℃.
Then, will dropwise be loaded in the flask through 2.5 hours by the mixing solutions that 100.8g vinylbenzene, 25.2g vinylformic acid, 108.0g lauryl methacrylate(LMA), 36.0g polyethylene glycol methacrylate-styrene polymer, 60.0g hydroxyethyl methylacrylate, 36.0g vinylbenzene macromonomer, 3.6g mercaptoethanol, the two methyl valeronitriles of 2.4g azo and 18g methylethylketone are formed.After being added dropwise to complete of solution, will dropwise be loaded in the flask through half an hour by the mixing solutions of two methyl valeronitriles of 0.8g azo and 18g methylethylketone.Keep 1 hour down with after allowing reaction at 65 ℃, in flask, add the two methyl valeronitriles of 0.8g azo, and further allow reaction 1 hour.After reaction is finished, the 364g methylethylketone is poured in the flask, collect the 800g polymers soln of 50% concentration then.
-contain polymer particles pigment aqueous dispersion preparation-
Fully stir potassium hydroxide aqueous solution, 20g methylethylketone and the 13.6g deionized water of 28.0g polymers soln A, 26.0g C.I. Pigment Yellow 73 97,13.6g 1mol/L, mediate with roller mill then.The gained paste is poured in the 200g deionized water, fully stirs then, then with vaporizer, evaporation methylethylketone and water, preparation yellow polymer particulate aqueous dispersion.
Yellow ink
The dispersion liquid 40% of yellow polymer particulate
Glycerine (wetting Agent for Printing Inks) 8%
1,3 butylene glycol (wetting Agent for Printing Inks) 20%
2,2,4-trimethylammonium-1,3-pentanediol (wetting agent) 2%
Tensio-active agent (1-8) 1.5%
Silicone antifoam agent KS508 (Shin-Etsu Che.) 0.1%
The deionized water balance amount
The ink composition in the above-mentioned prescription of blend fully at room temperature, the manufacture of ink composition, making the gained ink composite then is that 1.2 microns membrane filter experience is filtered by mean pore size, thus the printing ink of preparation embodiment 2.
Embodiment 3-is about printing ink
Contain the preparation of aqueous dispersion of the pigment of polymer particles
Prepare the aqueous dispersion of carmetta polymer particles according to the mode identical with embodiment 2, different is that pigment is replaced by the C.I pigment red 122.
Carmetta printing ink
The dispersion liquid 50% of carmetta polymer particles
Glycerine (wetting Agent for Printing Inks) 10%
1,3 butylene glycol (wetting Agent for Printing Inks) 18%
2,2,4-trimethylammonium-1,3-pentanediol (wetting agent) 2%
Tensio-active agent (1-8) 1.5%
Silicone antifoam agent KS508 (Shin-Etsu Che.) 0.1%
The deionized water balance amount
The ink composition in the above-mentioned prescription of blend fully at room temperature, the manufacture of ink composition, making the gained ink composite then is that 1.2 microns membrane filter experience is filtered by mean pore size, thus the printing ink of preparation embodiment 3.
Embodiment 4-is about printing ink
Contain the preparation of aqueous dispersion of the pigment of polymer particles
Prepare the aqueous dispersion of mazarine polymer particles according to the mode identical with embodiment 2, different is that pigment is replaced by the C.I pigment Blue 15: 3.
Mazarine printing ink
The dispersion liquid 40% of mazarine polymer particles
Glycerine (wetting Agent for Printing Inks) 10%
1,3 butylene glycol (wetting Agent for Printing Inks) 20%
2,2,4-trimethylammonium-1,3-pentanediol (wetting agent) 2%
Tensio-active agent (1-8) 1.5%
Silicone antifoam agent KS508 (Shin-Etsu Che.) 0.1%
The deionized water balance amount
The ink composition in the above-mentioned prescription of blend fully at room temperature, the manufacture of ink composition, making the gained ink composite then is that 1.2 microns membrane filter experience is filtered by mean pore size, thus the printing ink of preparation embodiment 4.
Comparative example 1-is about printing ink
From the yellow print cartridge of A company commercial distribution, draw an amount of printing ink, and 1 ink form evaluation as a comparative example.
Comparative example 2 is about printing ink
From the carmetta print cartridge of A company commercial distribution, draw an amount of printing ink, and 2 ink form evaluation as a comparative example.
Comparative example 3-is about printing ink
From the mazarine print cartridge of A company commercial distribution, draw an amount of printing ink, and 3 ink form evaluation as a comparative example.
Comparative example 4-is about printing ink
From the black print cartridge of A company commercial distribution, draw an amount of printing ink, and 4 ink form evaluation as a comparative example.
For the printing ink of embodiment 1-4 and comparative example 1-4, carry out following evaluation (1).
Estimate (1) and measure viscosity increment rate and the change of granularity relevant with moisture evaporation
Under the condition of 50 ℃ temperature and 10% humidity, each printing ink of a certain amount of embodiment 1-4 and comparative example 1-4 is left standstill; Measure the variation of ink by weight then; And also measure viscosity (25 ℃) and granularity after allowing to leave standstill for some time under the same conditions.Measure viscosity and, dilute 500 times of mensuration granularities with viscometer RL-500 (Toki SangyoCo.) with particle-size analyzer UPA 150 (Micro Track Co.).
Moisture evaporated content of the present invention (%) is to allow to leave standstill in the humidity of 50 ℃ temperature and 10%, measures this measuring result that obtains after the moisture evaporated content then.
Fig. 1 has shown the relation between the viscosity (25 ℃) of moisture evaporated content (%) and printing ink; Fig. 2 has shown the relation between the mean particle size of moisture evaporated content (%) and printing ink.In Fig. 1 and 2, filled symbols is represented embodiment, hollow symbolic representation comparative example, and diamond symbols is corresponding to black ink, and square symbol is corresponding to Yellow ink, and triangle symbol is corresponding to carmetta printing ink, and circle symbol is corresponding to mazarine printing ink.
As illustrated in fig. 1 and 2, when the gross weight based on printing ink, when moisture evaporated content was 30-45%, the viscosity of printing ink of the present invention increased fast; And when moisture evaporated content be 50% or when higher, the viscosity of printing ink relatively increases.
In the stage that viscosity increases, the maintenance of the mean particle size of printing ink of the present invention is not more than 5 times of initial mean particle size, and this is similar to the behavior of the printing ink of comparison.
To one group of printing ink (being called " the printing ink group of embodiment 1 (ink set) ") of embodiment 1-4 and another group printing ink (being called " the printing ink group of comparative example 1 ") of comparative example 1-4, estimate (2).
Estimate the evaluation of (2)-print quality
With the pattern printing color image of constant print speed, wherein handle printing ink of the present invention with recording unit described below, and with the printer processes that adopts commerical prod A printing ink relatively.Naked eyes evaluation print image blends spreading and sinking in of color border about spreading and sinking in of letter and oozes.Estimate with paper be blank sheet of paper,
Express evaluation result with following grade:
Grade A: do not spread and sink in and ooze
Grade B: seldom spread and sink in and ooze
Grade C: some is spread and sunk in and oozes
Grade D: obviously spread and sink in and ooze
Table 2: estimate (2)
The printing ink group Letter is spread and sunk in and is oozed Spread and sink in and ooze in the color border
Embodiment 1 A A
Comparative example 1 C B
Before ink droplet is applied on the paper or meanwhile, therefore the printing ink in the printing ink group of embodiment 1 provide clearer image because moisture evaporation demonstrates higher viscosity than the printing ink in the printing ink group of comparative example 1, and especially do not have spreading and sinking in of letter to ooze.
Comparative example 5-is about the printing ink group
Prepare the printing ink group of comparative example 5 in the mode identical with the printing ink group of embodiment 1, different is tensio-active agent and the wetting agent that does not have compounding embodiment 1.
Comparative example 6-is about the printing ink group
Prepare the printing ink group of comparative example 6 in the mode identical with the printing ink group of embodiment 1, different is the wetting agent that does not have compounding embodiment 1.
Comparative example 7-is about the printing ink group
Prepare the printing ink group of comparative example 7 in the mode identical with the printing ink group of embodiment 1, different is the tensio-active agent that does not have compounding embodiment 1.
Relatively comparative example 6 and 7 and the printing ink group of embodiment 1 in the dynamic surface tension aspect of black ink, the result of acquisition is as shown in Figure 3.With dynamic surface tension survey meter BP-2 (KRUSS Co.), measure dynamic surface tension down at 25 ℃.Proof is in the printing ink that does not contain wetting agent, and dynamic surface tension does not descend during the 10-100 millisecond, also proves in the printing ink that does not contain tensio-active agent, and static surface tension does not descend in about 1000 milliseconds.
About the result with respect to the evaluation (1) of the printing ink group of comparative example 5-7, each printing ink of the printing ink group of comparative example 5 is 50% or when higher, demonstrating fast, viscosity increases at moisture evaporated content.Each printing ink of comparative example 6 and 7 printing ink group demonstrates fast at moisture evaporated content during for 38-42%, and viscosity increases.In addition, the result of evaluation (2) is as described below.
Table 3 is estimated (2)
The printing ink group Letter is spread and sunk in and is oozed Spread and sink in and ooze in the color border
Comparative example 5 D D
Comparative example 6 C C
Comparative example 7 C C
The result proves, the printing ink that does not contain tensio-active agent and wetting agent demonstrates significant letter and spreads and sinks in and blend the color border and spread and sink in and ooze.
Reference example 1-is about printing ink
Prepare the printing ink of reference example 1 in the mode identical with the printing ink of embodiment 4, the consumption that the consumption of different is glycerine is changed to 5wt% and 1,3 butylene glycol is changed to 23wt%.
Reference example 2-is about printing ink
Prepare the printing ink of reference example 2 in the mode identical with the printing ink of embodiment 4, the consumption that the consumption of different is glycerine changes to 23wt% and 1,3 butylene glycol changes to 5wt%.
About the result with respect to the evaluation (1) of the printing ink of embodiment 4 and reference example 1-2, the printing ink of reference example 1 is in the weight based on whole printing ink, and when moisture evaporated content was 35-38wt%, demonstrating viscosity increased; And the printing ink of reference example 2 demonstrates the viscosity increase when moisture evaporated content is 43-45wt%.In addition, the mean particle size of the printing ink of reference example 1 is changed to 4.8 times of initial state, and the printing ink of reference example 2 demonstrates variation seldom aspect size.Following result has shown that these printing ink relate to the evaluation (2) that letter is spread and sunk in and oozed.
Table 4 is estimated (2)
Printing ink Letter is spread and sunk in and is oozed
Embodiment 4 A
Reference example 1 A
Reference example 2 B
Embodiment 5-is about printing ink
Prepare the printing ink of embodiment 5 in the mode identical with the printing ink of embodiment 2, different is to comprise 0.5wt%2-amino-2-ethyl-1 in addition, and ammediol is in ink composite.
Embodiment 6-is about printing ink
Prepare the printing ink of embodiment 6 in the mode identical with the printing ink of embodiment 4, different is to comprise 0.5wt%2-amino-2-ethyl-1 in addition, and ammediol is in ink composite.
About result with respect to the evaluation (1) of the printing ink of embodiment 5 and embodiment 6, with do not contain 2-amino-2-ethyl-1, the printing ink of ammediol is compared, and embodiment 5 and each printing ink of 6 demonstrate less variation (referring to Figure 4 and 5) aspect granularity in the moisture evaporation process.In addition, relating to the spread and sink in evaluation (2) of oozing of letter shows that the printing ink of embodiment 5 and 6 is similar to and does not contain 2-amino-2-ethyl-1, the printing ink of ammediol.
Embodiment 2,4,5 and 6 and the printing ink of reference example 1,2 on carry out following evaluation (3).
Estimate (3): intermittent printing detects
Use IJ Printer IPSiD Jet 300 (31 microns of jet sizes, by Ricoh Co., Ltd. make) as evaluation appts, repeat this operation 10 times, when do not have to spray under the situation of (freely scanning) through predetermined amount of time, scanning bracket 30 seconds is printed 20 oil dripping China inks of each respective nozzle on glossy film in ink-jet, recovers mobile (50 are used for purging (purge)) then.
Estimate by naked eyes judgement enlarged photograph, wherein in the process of 20 of printings, particularly with respect to the ink dot of first ink droplet on inkjet direction, take pictures, judgment standard is as described below:
Grade A: on inkjet direction, can not have turbulent flow.Normal and the alignment of spot sizes.
Grade B: on inkjet direction, can not have turbulent flow.Ink dot is alinement almost, but size is somewhat little.
Grade C: on inkjet direction, have certain turbulent flow, but turbulent flow does not extend to the second line.
Grade D: first ink dot extends outside second ink dot.
Grade E: do not spray ink droplet.
Table 5 is estimated (3)
Printing ink Intermittent printing detects
Embodiment 2 B
Embodiment 4 B
Reference example 1 C
Reference example 2 B
Embodiment 5 A
Embodiment 6 A
The result shows, when the glycerol content in wetting Agent for Printing Inks during less than 20wt%, reliability is tended to deficiency, on the other hand, when glycerol content surpasses 80wt%, the probability that letter is spread and sunk in and oozed occurs.In addition, add 2-amino-2-ethyl-1, ammediol improves the reliability of spraying.
Embodiment 7-is about printing ink
Prepare dispersible pigment dispersion with following operation at first.
The yellow ultramarine dispersion liquid
CI. Pigment Yellow 73 20%
Polyoxyethylene oleyl ether ammonium sulfate 15%
Ethylene glycol 30%
The pure water equal amount
With sand mill each above-mentioned composition is disperseed, after blend, handle with rotary process then, in order that remove coarse relatively particle, thus preparation yellow ultramarine dispersion liquid.
Yellow ink
Yellow ultramarine dispersion liquid 20%
Glycerine 5%
Glycol ether 15%
2-ethyl-1-, 3-hexylene glycol 2%
Tensio-active agent (1-7) 2%
Silicone antifoam agent KS531 (Shin-Etsu Che.) 0.1%
The deionized water balance amount
The ink composition in the above-mentioned prescription of blend fully at room temperature, the manufacture of ink composition, making the gained ink composite then is that 1.2 microns membrane filter experience is filtered by mean pore size, thus the printing ink of preparation embodiment 7.
Embodiment 8-is about printing ink
Prepare dispersible pigment dispersion with following operation at first.
The magenta pigments dispersion liquid
CI. pigment red 122 30%
Polyoxyethylene oleyl ether ammonium sulfate 15%
Ethylene glycol 30%
The pure water equal amount
With three-roll mill each above-mentioned composition is disperseed, after the blend operation, handle with rotary process then, in order that remove coarse relatively particle, thus preparation magenta pigments dispersion liquid.
Carmetta printing ink
Magenta pigments dispersion liquid 25%
Glycerine 5%
Glycol ether 15%
2-ethyl-1-, 3-hexylene glycol 2%
Tensio-active agent (1-7) 2%
Silicone antifoam agent KS531 (Shin-Etsu Che.) 0.1%
The deionized water balance amount
The ink composition in the above-mentioned prescription of blend fully at room temperature, the manufacture of ink composition, making the gained ink composite then is that 1.2 microns membrane filter experience is filtered by mean pore size, thus the printing ink of preparation embodiment 8.
Embodiment 9-is about printing ink
Prepare dispersible pigment dispersion with following operation at first.
The blue lake dispersion liquid
CI. pigment Blue 15: 3 30%
Polyoxyethylene oleyl ether ammonium sulfate 15%
Ethylene glycol 30%
The pure water equal amount
With wet wheeling machine each above-mentioned composition is disperseed, after blend, handle with rotary process then, in order that remove coarse relatively particle, thus preparation blue lake dispersion liquid.
Mazarine printing ink
Blue lake dispersion liquid 15%
Glycerine 5%
Glycol ether 2%
Tensio-active agent (1-7) 1%
Silicone antifoam agent KS531 (Shin-Etsu Che.) 0.1%
The deionized water balance amount
The ink composition in the above-mentioned prescription of blend fully at room temperature, the manufacture of ink composition, making the gained ink composite then is that 1.2 microns membrane filter experience is filtered by mean pore size, thus the printing ink of preparation embodiment 9.
Embodiment 10-is about printing ink
Prepare dispersible pigment dispersion with following operation at first.
Self-dispersion type blue lake dispersion liquid
20 parts of C.I. pigment Blue 15s of blend: 3 and 70 parts of tetramethylene, form mixing material and in oil bath this compounding of heating expect 120 ℃, add 10 parts of thionamic acids then, allow sulfonation 5 hours.After cooling, handle the gained reaction product with rotary process, in order that remove coarse relatively particle, thus preparation self-dispersion type blue lake dispersion liquid.
Mazarine printing ink
Self-dispersion type blue lake dispersion liquid 50%
Glycerine 5%
Glycol ether 15%
2,2,4-trimethylammonium-1,3-pentanediol 2%
Tensio-active agent (1-7) 1%
Silicone antifoam agent KS531 (Shin-Etsu Che.) 0.1%
The deionized water balance amount
The ink composition in the above-mentioned prescription of blend fully at room temperature, the manufacture of ink composition, making the gained ink composite then is that 1.2 microns membrane filter experience is filtered by mean pore size, thus the printing ink of preparation embodiment 10.
About the result with respect to the evaluation (1) of the printing ink of embodiment 7 and 8, when moisture evaporated content was 30-45%, all occurring viscosity on these two kinds of printing ink increased, and the mean particle size separately in this scope is less than 5 times of initial state size separately.
Embodiment 2-is about the printing ink group
The printing ink of embodiment 1 and 7-9 is estimated as the printing ink group of embodiment 2.
Embodiment 3-is about the printing ink group
Embodiment 1,7,8 and 10 printing ink are estimated as the printing ink group of embodiment 3.
About the evaluation (2) with respect to the printing ink group of embodiment 2 and 3, the result is as described below:
Table 6 is estimated (2)
The printing ink group Letter is spread and sunk in and is oozed Spread and sink in and ooze in the color border
Embodiment 2 A A
Embodiment 3 A A
About the evaluation (3) with respect to the printing ink of embodiment 7-10, the result is as described below:
Table 7 is estimated (3)
Printing ink Intermittent printing detects
Embodiment 7 B
Embodiment 8 B
Embodiment 9 B
Embodiment 10 B
Embodiment 11-is about printing ink
Prepare the printing ink of embodiment 11 in the mode identical with the printing ink of embodiment 1, different is that 1,3 butylene glycol is replaced by the 3-methyl isophthalic acid, the 3-butyleneglycol.
Embodiment 12-is about printing ink
The printing ink for preparing embodiment 12 in the mode identical with the printing ink of embodiment 2, the aqueous dispersion that different is contains the polymer particles of C.I. Pigment Yellow 73 97 is replaced by the aqueous dispersion of the polymer particles that contains C.I. Pigment Yellow 73 74,1, the 3-butyleneglycol is replaced by the 3-methyl isophthalic acid, the 3-butyleneglycol.
Embodiment 13-is about printing ink
Prepare the printing ink of embodiment 13 in the mode identical with the printing ink of embodiment 3, different is that 1,3 butylene glycol is replaced by the 3-methyl isophthalic acid, the 3-butyleneglycol.
Embodiment 14-is about printing ink
Prepare the printing ink of embodiment 14 in the mode identical with the printing ink of embodiment 4, different is that 1,3 butylene glycol is replaced by the 3-methyl isophthalic acid, the 3-butyleneglycol.
About the result with respect to the evaluation (1) of the printing ink of embodiment 11-14, when moisture evaporated content was 30-45%, occurring viscosity on each printing ink increased, and the mean particle size separately in this scope is less than 5 times of initial state size separately.
Embodiment 4-is about the printing ink group
The printing ink of embodiment 11-14 is estimated as the printing ink group of embodiment 4.About the evaluation (2) with respect to the printing ink group of embodiment 4, the result is as described below:
Table 8 is estimated (2)
The printing ink group Letter is spread and sunk in and is oozed Spread and sink in and ooze in the color border
Embodiment 4 A A
About the evaluation (3) with respect to the printing ink of embodiment 1 1-14, the result is as described below:
Table 9 is estimated (3)
Printing ink Intermittent printing detects
Embodiment 11 A
Embodiment 12 A
Embodiment 13 A
Embodiment 14 A
-print cartridge-
Can be by aforementioned recording ink of the present invention be loaded in the container, thus provide print cartridge of the present invention and print cartridge of the present invention can comprise other assembly of suitable selection as requested.
Can be depending on application and select the shape of container, structure, size and material etc. suitably; For example, container can be made up of Printing ink bag, and described Printing ink bag is formed by the laminated film of aluminium, resin molding etc.
An aspect with reference to figure 6 explanations print cartridge of the present invention.Print cartridge 1 shown in Figure 6 comprises the Printing ink bag 2 of dress envelope recording ink and holds the shell (housing) 3 of Printing ink bag 2.Fill by the film formed Printing ink bag 2 of the lamination of aluminium (it for flexible and be essentially rectangle) and be contained in the shell 3 with recording ink of the present invention.Shell 3 is made up of first housing parts 11, second housing parts 12, the 3rd housing parts 13.In print cartridge 1, first housing parts 11 and second housing parts 12 are tightened and are fixed with helical element.In Fig. 6,25 expression printing ink infeed mouth, and the liner of box is inserted in 44 and 45 expressions, and 64 expressions will determine that color correctly is installed to the liner on the box.
Print cartridge of the present invention can be installed and be applied on the various ink-jet recording device in the mode that allows to install and take out, and preferably installs and is applied on the ink-jet recording device of the present invention in the mode that allows to install and take out.
-ink-jet recording device and ink jet recording method-
Ink-jet recording device of the present invention comprises at least one unit that sprays ink droplet and other unit of selecting suitably as requested, as pulsing unit, control unit etc.
Ink jet recording method of the present invention comprises other step that sprays ink droplet at least and select suitably as requested, as pulsing, control etc.
Can preferably carry out ink jet recording method of the present invention with ink-jet recording device of the present invention; With can preferably carry out other with other unit.
The unit of the method for-ejection ink droplet and ejection ink droplet-
In the method for ejection ink droplet, apply pulse to recording ink of the present invention, spray ink droplet then, form image.
In the unit of ejection ink droplet, pulse is applied on the recording ink of the present invention, spray ink droplet then, form image.Can have no specific limited ground and select the unit of ejection ink droplet, for example comprise the various nozzles that spray printing ink.
In implementing method of the present invention, at least a portion in the nozzle member of preferred liquid chamber part, choked flow part, oscillating plate and ink gun is formed by the material of siliceous or nickel.
Preferably, the inlet diameter of inkjet nozzle is 30 microns or low excessively, more preferably 1 micron to 20 microns.
Can generate above-mentioned pulse by for example above-mentioned pulsing unit.Can have no especially restrictedly suitable strobe pulse; For example, pulse can be heat (temperature), pressure, vibration, radiation etc.These can separately or be used in combination.In the middle of these, preferred heat and pressure.
Specifically, the unitary example of pulsing comprises heating unit, pressure assembly, piezoelectric element, vibration machine spare, ultra-sonic generator spare, light etc.; More particularly, can exemplify piezo-activator such as piezoelectric element, based on the thermal actuator of the phase transformation of film between liquid and steam, based on the shape memory alloy actuator of phase transition temperature, based on electrostatic actuator of electrostatic force etc. with electrical heating element such as heating resistor.
Can have no restrictedly to select suitably to spray the method for ink droplet according to aforementioned pulse.Belong under the situation of " heat " in pulse, on this method can exemplify and be applied to recording ink in record-header corresponding to the heat energy of recording signal with the heat head, in recording ink, produce bubble by heat energy then, thereby from the nozzle of record-header, penetrate recording ink because of the pressure of bubble with ink droplets.Perhaps belong under the situation of " pressure " in pulse, this method can exemplify, apply pressure on the piezoelectric element, described piezoelectric element arrangement also adheres in the so-called pressure chamber on the ink pathway that leads to record-header, piezoelectric element deflection as a result, thereby reduce the volume of pressure chamber, from the nozzle of record-header, penetrate recording ink then with ink droplets.
The recording ink drop of ejection is preferably dimensioned to be 3-40pl, and the viscosity of the drop of ejaculation is preferably 5-20m/sec, and driving frequency is preferably 1kHz or higher, and resolving power is preferably 300dpi or higher.
Can have no restrictedly to select suitably aforementioned control unit according to application,, for example can utilize the instrument such as sequencer (sequencer), computer as long as can normally control each unit.
An aspect of the ink jet recording method of the present invention that utilizes ink-jet recording device of the present invention will be described with reference to the accompanying drawings.Ink-jet recording device shown in Figure 7 comprises main body 101, is installed on the main body 101 paper supply tray 102 in order to the filling paper, is installed on the main body 101 in order to store the paper delivery pallet 103 and the print cartridge mounting portion 104 of the paper of document image (formation).Upside in print cartridge mounting portion 104 is arranged the function part 105 of being furnished with operative pin (operating key) and indicating meter etc.Print cartridge mounting portion 104 comprises closure/open protecgulum 115, in order that install and take out print cartridge 1.The lid on top is represented with 111 and the front is represented with 112.
In main body 101, shown in Fig. 8 and 9, by guide rod 131 supporting brackets 133 in left side and the support of right side plate (not shown), with pull bar 132 as supporting element, so that support 133 can be free to slide on the main scanning direction and can scan by the main scan motor (not shown) on the direction shown in the arrow in Fig. 9.
Support 133 comprises the record-header 134 of being furnished with 4 ink jet print heads, the various recording ink drops of this 4 each record-header ejection yellow (Y), mazarine (C), carmetta (M) and black (BK), record-header 134 wherein is installed is made each ink export and main scanning direction intersect, and the printing ink of discharging moves down.
The ink jet print head of record-header 134 can comprise that the energy generating unit is in order to discharge recording ink, for example piezo-activator such as piezoelectric element, based on the thermal actuator of the phase transformation of film between liquid and steam, based on the shape memory alloy actuator of phase transition temperature with based on electrostatic actuator of electrostatic force etc. with electrical heating element such as heating resistor.
In addition, son jar (subtank) 135 in adjustment notch color on the support 133 is fed on the record-header 134 in order to the printing ink with marker color.The print cartridge 1 of recording ink of the present invention on being installed in print cartridge mounting portion 104 is through recording ink supply pipe (not shown) feed and be fed to the son jars 135.
On the other hand, the paper feed of the filling accumulation paper 142 on the paper accumulation part 141 of paper feed pallet 103 partly comprises lune roller (intake roller 143) and separating pad (separating pad) 144, in described separating pad, the lune roller loads the paper from paper accumulation part 141 one by one independently, separating pad 144 be arranged in intake roller 143 reverse side and by the material of relative higher coefficient of friction form and separating pad 144 to intake roller 143 pressurizations.
The transport portion of the paper 142 of the paper feed part in the space of conveying under the record-header 134 comprises conveying belt 151, and described conveying belt 151 attracts paper 142 and carries it by electrostatic effect; Count roll 152, described count roll 152 be by with the pinching of conveying belt 151, and transports paper 142 from the paper feed part through liner 145; Carry liner 153, described conveying liner 153 almost is supplied to conveying belt 151 with the paper 142 that vertical direction is carried with about 90 degree break-ins; With top pressure roller 155, described top pressure roller 155 pushes facing to conveying belt 151 by pressurizing member 154; Charged roller 156 with the surface charging that makes conveying belt 151.
Conveying belt 151 is endless belts, and it is connected across on conveying roller 157 and the bridle rolls 158 and can rotates along the belt throughput direction.At the back side of conveying belt 151, guiding parts 161 is arranged in the respective regions place with print area on record-header 134 sides.In addition, the paper 142 by record-header 134 records is partly discharged in paper delivery, and it comprises in order to separate disengaging pawl 171, exit roller 172 and the exit roller 173 from the paper 142 of conveying belt 151.Paper delivery pallet 103 is arranged in the below of exit roller 172.
At the back side of main body 101, two-sided paper feed unit 181 is installed in the mode that allows to install and take out.The paper 142 that is returned by the reverse rotation of conveying belt 151 is clamped in two-sided paper feed unit 181, and overturns it, and then it is loaded between count roll 152 and the conveying belt 151.By the way, on two-sided paper feed unit 181, provide manual paper feed part 182.
In ink-jet recording device, partly load paper from paper feed one by one independently, guide and conveying by liner 145 with the paper 142 of almost vertical direction filling, between conveying belt 151 and count roll 152, pinch simultaneously.Then, guide paper 142 by carrying liner 153, on conveying belt 151, pressurize, and throughput direction is overturn about 90 spend by terminal pressure roller 155 at leading end.
In this stage, make conveying belt 151 charged by charged roller 156, thereby be connected to conveyance of sheets 142 under the condition on the conveying belt 151 at static.Then,, can to immobilized paper 142, write down delegation's image by spraying ink droplet by according to picture signal and traversing carriage 133 activation record heads 134, mobile within a predetermined distance then paper 142, and note delegation.When the signal of the last record that arrives posting field or tail signal are received, end recording operation and paper 142 is moved on the paper delivery pallet 103.
In addition, when detecting recording ink residual in son jars 135 when exhausting, will be fed in the son jar 135 from the recording ink of the required amount of print cartridge 1.
In ink-jet recording device, when the recording ink in the print cartridge 1 of the present invention is consumed fully, change the only Printing ink bag in print cartridge 12 by the shell 3 that decomposes print cartridge 1.The structure of Gong the alternate structure of print cartridge such as vertical type or positive injection is to allow the stable material-supplying of recording ink.Therefore, even under the situation of the situation that occupied by some objects of the upper space that is placed in main body 101 at device of the present invention, for example, even in device of the present invention is enclosed in the space (in a lack) that does not have whatever or some objects when being arranged on the main body, also can easily replace print cartridge 1.
By the way, although embodiments of the invention are that the present invention similarly can use on the line ink-jet recording device of being furnished with line (line type) shower nozzle on string type (reciprocating type) ink-jet recording device that is applied to the front.
In addition, ink-jet recording device of the present invention and ink jet recording method may be used on the various records based on ink-vapor recording, for example use on the set composite of printer, facsimile recorder, duplicating machine printer/facsimile recorder/duplicating machine of ink-vapor recording.
Recording unit of the present invention below is described.
Figure 10 has shown the view that amplify the part of ink gun of the present invention, and Figure 11 is the cross sectional view of the local ink gun that amplifies on channel direction.
Ink gun comprises flange (flame) 10, and it is formed for providing the structure of the common liquid chamber 1b that is with the ink inlet (not shown); Access panels 20, it is formed for forming choked flow part 2a and pressurization liquid chamber 2b, and with the structure that is connected hole 2c of nozzle 3a intercommunication; Form the nozzle plate of nozzle 3a; The oscillating plate 60 of convex portion 6a, tympanum part 6b and ink inlet 6c in containing; Bond to laminated piezoelectric device 50 on the oscillating plate by bonding coat 70; With the fixing matrix 40 of laminated piezoelectric device 50.Matrix 40 is formed by barium titanate ceramics, and arranges and the laminated piezoelectric element 50 of bonding two rows.
The layer of the piezoelectric layer (not shown) by the alternatively laminated 10-50 micron thickness/layer of forming by lead zirconate titanate and the inner electrode layer (not shown) of number micron thickness/forms by silver/palladium (AgPb), formation piezoelectric element 50.Interior electrode (not shown) links to each other with the end of outer electrode (not shown) at them.
By hemisect formula cutting processing, with piezoelectric element 50 be divided into veteranellinae shape (ctenidium shape) as or drive part 5f and support part 5g.
By carrying out the length of the processing restriction outer electrode (not shown) outside such as blocking,, and make these become independently electrode so that separately by hemisect formula cutting processing.Other keep electric continuity, and not separately and make and become common electrode 5e by cutting type processing.
With soft solder flux EPC80 is bonded on the absolute electrode (not shown) of drive element.In addition, provide electrode layer, common electrode 5e is connected to around the Gnd electrode of FPC80 by a end at laminated piezoelectric element.The driver IC (not shown) is installed on the FPC80, thereby control is applied to application on the drive part 5f with driving voltage.
Oscillating plate 60 is formed by following parts: the tympanum part 6b of film; Convex portion 6a in the island (island part), described island convex portion 6a forms and is connected to the laminated piezoelectric device 50 that is used to become drive part 5f at the centre portions of tympanum part 6b; Contain the thick film part that is connected on the bearing beam of supporting the part (not shown); With the hole of ink inlet 6c, it is coated with by electrical forming processing with two-layer Ni plate.As for the tympanum part, thickness is 3 microns, and width is 35 microns (sides).
Composition bonding coat 70 by containing clearance material is realized bonding between the drive part 5f of convex portion 6a and piezoelectric element 50 in the island of oscillating plates 60.
Access panels 20 is formed by silicon single-crystal.In silicon single-crystal, come patterned trench and inserting hole (penetration) by etching and processing, wherein groove is used to form choked flow part 2a and pressurization liquid chamber 2b; And inserting hole is used for forming joint access 2c in the position corresponding to nozzle.
Rest part after etching has formed the dividing wall of pressurization liquid chamber 2b.In this structure of shower nozzle, the etched width that choked flow part 2a provides part to narrow down.
Nozzle plate 30 is processed to form by electroforming by metallic substance such as Ni-plate, and has many nozzle 3a, and described nozzle serves as the effect of the fine outlet of drawing ink droplet.Internal structure or interior shape are horn shape (horn-like), and wherein column or taper also are admissible.The size of nozzle 3a is about 20-35 micron as the diameter in the ink droplet exit.The spacing of every row's nozzle is 150dpi.
On the surface of the ink-jet side of nozzle plate 30, provide the waterproof layer (not shown).Surface treatment on waterproof layer is, for example the PTFE-Ni co-precipitation is electroplated, the galvanic deposit coating of fluoride resin, and transpirable fluoride resin is as fluoridizing the coating of bituminous vapor deposition, the baking of silicone resin or with flow of solvent coating fluoride resin etc.Can select this surface treatment according to ink performance, so that stabilization droplet profile, jet performance, thereby realize high-quality image.
By resin moulded production flange 10, wherein on described flange 10, be formed for the groove of ink inlet (not shown) and shared liquid chamber 1b.
In the inkjet nozzle of the above structure, owing to depend on recording signal, on drive part 5f, apply drive waveforms (pulsed voltage 10-50V), be at drive part 5f and produce displacement on the laminating direction, thereby by 30 pairs of pressurizations of oscillating plate liquid chamber 2b pressurization, with pressure boost, and from nozzle 3a, spray ink droplet.
When stopping the injection of ink droplet, the ink pressure in pressurization liquid chamber 2b descends and pass through the inertia of ink flow and the discharge of driving pulse in pressurization liquid chamber 2b, produces negative pressure, thereby forwards the stage of filling printing ink to.That is to say that the ink flow that infeeds from the China ink jar flow to the choked flow part 2a through ink flow inlet 6c, fills pressurization liquid chamber 2b then in shared liquid chamber 1b and from shared liquid chamber 1b.
The effect that the residual pressure of decaying after choked flow part 2a is provided at and sprays vibrates, but because surface tension, its disturbs and recharges.Therefore, the decay of balance residual pressure and time of recharging well, and can assign to shorten section cycling time between ink jet operation (working time) by selecting resistive portion suitably.
The invention effect
Such as above concrete and detailed description, according to the present invention, the recording ink that comprises colouring agent, NMF, surfactant and the wetting agent that can be dispersed in water is provided, wherein prepare ink-jet recording ink, take the moisture of box lunch evaporation during as 30-45wt%, viscosity increases fast, and namely the viscosity increment rate surpasses 50mPa.s/%, thereby even can form high quality graphic at blank sheet of paper. In addition, by design printing ink so that even in the stage when viscosity fast occurring and increase, the variation of particle mean size descends, and can guarantee the reliability in short and long-time section. In addition, the recording method of the application of the invention and tape deck can form image in the situation of higher jetting stability and better quality.

Claims (14)

1. recording ink, it comprises tinting material, wetting Agent for Printing Inks, tensio-active agent and the wetting agent that can be dispersed in the water,
Wherein when based on the gross weight of recording ink, moisture evaporated content is during less than 30wt%, and the viscosity increment rate relevant with moisture evaporation in the recording ink is 5.0mPa.s/% or lower,
When moisture evaporated content is 30-45wt%, the viscosity increment rate relevant with moisture evaporation surpass 50mPa.s/% or higher and
At the recording ink when the viscosity increment rate reaches 50mPa.s/% in the stage, the mean particle size of the tinting material in the recording ink is less than 5 times of the mean particle size of the tinting material in the home record printing ink, and is 0.8 micron or lower,
Wherein relevant with moisture evaporation viscosity increment rate (mPa.s/%) is defined as the ratio of the increase (mPa.s) of viscosity to the increase (%) of moisture evaporated content, and
Wherein wetting Agent for Printing Inks comprises glycerine and butyleneglycol, and the content of glycerine is the gross weight 20-80wt% based on wetting Agent for Printing Inks.
2. the recording ink of claim 1, wherein recording ink comprises the tinting material of 3-50wt%, 10-40wt% wetting Agent for Printing Inks, the wetting agent of 0.01-5wt% tensio-active agent and 0.1-4.0wt%.
3. the recording ink of claim 1, wherein tinting material is following pigment: owing to being directly connected on the described surface of pigments or utilizing the atomic radical of other insertion to be connected to the reason of at least a hydrophilic radical on the described surface of pigments, do not having under the situation of dispersion agent, described pigment can be processed to be distributed in the water.
4. the recording ink of claim 1, wherein tinting material is by at least a tensio-active agent and polymeric dispersant dispersive pigment.
5. the recording ink of claim 1, wherein tinting material is by with water-insoluble or be that water miscible colorant is incorporated into the polymer emulsion that the micro polymer intragranular forms hardly.
6. the recording ink of claim 1, wherein wetting agent comprises at least a polyvalent alcohol, described polyvalent alcohol demonstrates 0.2wt% or higher and less than the solubleness of 5.0wt% to water under 20 ℃.
7. the recording ink of claim 6, wherein polyvalent alcohol is a 2-ethyl-1, the 3-hexylene glycol.
8. the recording ink of claim 6, wherein polyvalent alcohol is 2,2,4-trimethylammonium-1,3-pentanediol.
9. the recording ink of claim 1 wherein further is mixed with the pigment coagulation inhibitor.
10. print cartridge that contains recording ink, wherein said recording ink comprises tinting material, wetting Agent for Printing Inks, tensio-active agent and the wetting agent that can be dispersed in the water,
When the gross weight based on recording ink, moisture evaporated content is during less than 30wt%, and the viscosity increment rate relevant with moisture evaporation in the recording ink is 5.0mPa.s/% or lower,
When moisture evaporated content is 30-45wt%, the viscosity increment rate relevant with moisture evaporation surpass 50mPa.s/% or higher and
At the recording ink when the viscosity increment rate reaches 50mPa.s/% in the stage, the mean particle size of the tinting material in the recording ink is less than 5 times of the mean particle size of the tinting material in the home record printing ink, and is 0.8 micron or lower,
Wherein relevant with moisture evaporation viscosity increment rate (mPa.s/%) is defined as the ratio of the increase (mPa.s) of viscosity to the increase (%) of moisture evaporated content, and
Wherein wetting Agent for Printing Inks comprises glycerine and butyleneglycol, and the content of glycerine is the gross weight 20-80wt% based on wetting Agent for Printing Inks.
11. an ink jet recording method, wherein said ink jet recording method is included in around the nozzle location, and in the gross weight based on recording ink, the moisture evaporated content of recording ink surpasses before the 30wt%, and recording ink is sprayed to printable area or nonprinting region,
Wherein said recording ink comprises tinting material, wetting Agent for Printing Inks, tensio-active agent and the wetting agent that can be dispersed in the water,
When the gross weight based on recording ink, moisture evaporated content is during less than 30wt%, and the viscosity increment rate relevant with moisture evaporation in the recording ink is 5.0mPa.s/% or lower,
When moisture evaporated content is 30-45wt%, the viscosity increment rate relevant with moisture evaporation surpass 50mPa.s/% or higher and
At the recording ink when the viscosity increment rate reaches 50mPa.s/% in the stage, the mean particle size of the tinting material in the recording ink is less than 5 times of the mean particle size of the tinting material in the home record printing ink, and is 0.8 micron or lower,
Wherein relevant with moisture evaporation viscosity increment rate (mPa.s/%) is defined as the ratio of the increase (mPa.s) of viscosity to the increase (%) of moisture evaporated content, and
Wherein wetting Agent for Printing Inks comprises glycerine and butyleneglycol, and the content of glycerine is the gross weight 20-80wt% based on wetting Agent for Printing Inks.
12. the ink jet recording method of claim 11, wherein the volume from the ink droplet of nozzle ejection is a 3-40 skin liter, and the speed of ink droplet is 6-20m/s, and frequency is 1kHz or higher, and resolving power is 300 point/inches.
13. a recording unit, it comprises record-header, wherein said record-header by a plurality of pressurization liquid chambers, have and the nozzle that is not more than 35 microns hole of the liquid chamber intercommunication of pressurizeing, the printing ink feed path, oscillating plate and the electromechanical converting unit that oscillating plate is moved constitute,
Recording ink is incorporated in the recording unit, and wherein said recording ink comprises tinting material, wetting Agent for Printing Inks, tensio-active agent and the wetting agent that can be dispersed in the water,
When the gross weight based on recording ink, moisture evaporated content is during less than 30wt%, and the viscosity increment rate relevant with moisture evaporation in the recording ink is 5.0mPa.s/% or lower,
When moisture evaporated content is 30-45wt%, the viscosity increment rate relevant with moisture evaporation surpass 50mPa.s/% or higher and
At the recording ink when the viscosity increment rate reaches 50mPa.s/% in the stage, the mean particle size of the tinting material in the recording ink is less than 5 times of the mean particle size of the tinting material in the home record printing ink, and is 0.8 micron or lower,
Wherein relevant with moisture evaporation viscosity increment rate (mPa.s/%) is defined as the ratio of the increase (mPa.s) of viscosity to the increase (%) of moisture evaporated content, and
Wherein wetting Agent for Printing Inks comprises glycerine and butyleneglycol, and the content of glycerine is the gross weight 20-80wt% based on wetting Agent for Printing Inks.
14. the recording unit of claim 13, wherein around nozzle location, in the gross weight based on recording ink, the moisture evaporated content of recording ink surpasses before the 30wt%, recording ink is sprayed to printable area or nonprinting region, thereby form coloured image.
CNB2004800007344A 2003-06-30 2004-06-29 Inkjet recording ink, recording process and recording apparatus Expired - Lifetime CN100349996C (en)

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