CN100349995C - Alkali ink composite - Google Patents
Alkali ink composite Download PDFInfo
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- CN100349995C CN100349995C CNB981169538A CN98116953A CN100349995C CN 100349995 C CN100349995 C CN 100349995C CN B981169538 A CNB981169538 A CN B981169538A CN 98116953 A CN98116953 A CN 98116953A CN 100349995 C CN100349995 C CN 100349995C
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Abstract
The present invention discloses an ink composition which comprises a composition of one kind or multiple kinds of carboxylic acid ammonium salt and one kind of or multiple kinds of surface active agents, wherein the preferable surface active agents are nonionic ethoxylation surface active agents or hydroxylated or alkoxylated acetylene series polyoxyethylene surface active agents or anionic phosphate. The ink composition basically prevents phase separation caused by heating until a temperature of the ink composition is approximately 60 DEG C, and the preferable temperature is 70 DEG C.
Description
The present invention relates to tolerate the nontoxic alkali ink composite that thermic is separated.
Ink-jet printer has become reliable and has effectively installed.Usually, ink-jet printer uses a pen that is contained on the balladeur train, and balladeur train moves with respect to print surface.Little droplets of ink forms in pen and sprays towards printed medium.This pen is comprising the printhead that has orifice plate, and very tiny nozzle is arranged in the orifice plate, by the printing ink rapid heating with certain volume in the ink cartridge of adjacent nozzles, droplets of ink is gone out through nozzle ejection.Printing ink in the box can be used for example resistor heats.This process makes the overheated and formation steam bubble of the printing ink in the box.The ink vapors of rapid expansion forces droplets of ink to pass aperture.
Recently, relate to the ink composite that can use Huang, magenta and cyan ink composition to carry out the high-quality colour printing in the improvement aspect the hot ink jet printing.These three kinds of primary colors form FR colour when mixing with various array modes.Black printing can be realized by black ink being provided in addition or producing compound black with three kinds of former color inks.
Regrettably, the ink composite that has improved text print quality may increase the quantity of dye diffusion.More particularly, when the printing ink of two kinds of different colours got close to printing each other, they may spread mutually, form a uneven border each other.Dye diffusion just takes place when mixing mutually on the surface of color at printed medium or in printed medium inside.
The method of previous minimizing dye diffusion quantity comprises the use thermal source, for example heating type pressure paper bobbin, and/or special paper prescription.Thermal source can increase cost and make printer complicated, and needs the printing ink of special paper to limit the scope of application of printer.The method of previous minimizing colour-colored phase mutual diffusion also comprises add tensio-active agent in ink composite.Tensio-active agent reduces diffusion between the color by improving speed that printing ink penetrates printed medium usually.But the speed of penetrating that improves ink composite can reduce edge sharpness.
In addition, it is difficult finding suitable tensio-active agent.Suitable tensio-active agent changes the surface energy of printed medium, and the result improves the vertical seepage velocity (that is, printing ink enters the speed of printed medium) of ink composite and reduces the degree of side direction diffusion on the printed medium surface, thereby reduces dye diffusion.But tensio-active agent must have suitable hydrophilic-lipophilic balance (HLB balance).It is water miscible relatively that the agent of HLB value higher surface activity is tended to, and does not therefore have a lot of shortcomings of exemplary surfactants.It is heat-staple relatively that this class tensio-active agent also tends to.But this class tensio-active agent also can cause the lateral diffusion of more printing ink along the printed medium surface, thereby produces more unfavorable dye diffusion.The tensio-active agent that the HLB value is lower is generally poorly soluble in water, thereby makes printing ink less along the lateral diffusion on printed medium surface.Therefore, the relatively poor tensio-active agent of solvability causes dye diffusion less.Regrettably, the thermostability of the relatively poor tensio-active agent of solvability is also relatively poor.
More particularly, add tensio-active agent, the tensio-active agent of especially low HLB value can make ink composite be easier to be heated usually and be separated, and it has reduced the cloud point of ink composite." cloud point " speech is meant the temperature that ink composite is separated (that is, tensio-active agent in ink composite no longer dissolved temperature).The cloud point of most of surfactant compositions is generally about 45 ℃ or lower.
When reaching cloud point, ink composite has outward appearance and a plurality of phase of " muddiness ".Use is in or can reduces printing quality greatly near the ink composite of cloud point (or thermic is separated a little).In other words, if trigger or the droplets of ink of spraying in the ink composite that contains be in or, can cause Protean droplet of ink speed near its cloud point, and owing to droplet of ink is missed target its intended target and made deterioration in print quality.Therefore, in the past, the ink composite that contains low HLB value tensio-active agent is an ideal for the restriction dye diffusion, is unfavorable but this composition lacks thermostability.The ink composite that is separated that is heated has easily limited the temperature range that said composition can be used and store.When ink composite must store under warm environment or weather and/or use, ink composite preferably had high cloud point (that is, at least about 60 ℃, preferably about 70 ℃).
The method of previous minimizing black-colour dye diffusion quantity comprises for example one or more salt of adding in ink composite.This class salt generally includes the transition metal that belongs to IIA family, IIIA family, IIIB family and the positively charged ion gegenion of lanthanon, therefore poison relatively.In addition, these salts can cause ink composite drop " deceleration ", and this is meant a kind of phenomenon in the nozzle that occurs in ink-jet pen.Under drop ejection frequency fast, the evaporation of specific ink composite drop and injection meeting are slack-off suddenly or stop fully, that is, slow down.Obviously, the reduction of the drop ejection frequency cause owing to slowing down is the result that salt and nozzle surface in the ink composite react.
Another important characteristic of ink composite is to be printed on for example substrate, the substrate of silica-coating, the substrate of clay coated and the printing quality and the stability of the image on the polymeric media " special mediums " such as (as transparent films) of starch coated.The photostabilization of the printed image of ink composite on this class medium particularly importantly." photostabilization " speech is meant the image that printed because light that exists in the environment and oxygenant and rotten degree.Existing a lot of commercially available ink composite can not be in the suitable printing of the enterprising row image quality of this class medium.
Still need such ink composite, their abilities are separated by thermic, dye diffusion does not take place and have other desired character, for example hypotoxicity, long shelf life, the anti-deceleration and the superior photostabilization on special medium.Known ink composite has one or more above-mentioned character.But the ink composite with all above-mentioned character does not almost have, because a kind of improvement of character usually causes another character or other character variation of composition.
The invention provides ink composite, wherein contain ammonium carboxylate salt and one or more tensio-active agents, preferred ethoxylated surfactant, perhaps hydroxylation or alkylating acetylene series polyoxyethylene surfactant.These ink composites below 60 ℃, more preferably are about below 70 ℃ about, have prevented to be subjected to pyrogenetic being separated basically.Ink composite of the present invention is still nontoxic relatively, can tolerate the deceleration phenomenon under the high frequency print speed, and is particularly suitable for the color jet-ink printing on the printed medium of wide range.In addition, when ink composite of the present invention prints, provide superior photostabilization edge sharpness and water tolerance on routine or special medium.
A kind of embodiment preferred of ink composite of the present invention contains the dyestuff of the 1-7% that has an appointment by weight, the non-ionic type ethoxylated surfactant of about 0.25-5%, about 0-40% with the miscible organic solvent of water, the ammonium carboxylate salt of about 2-12%, all the other mainly are water.Normally used other adjuvant in inkjet ink composition, for example pH buffer reagent and biocides or mycocide also can be added in the ink composite of the present invention.
The invention provides a kind of ink composite, wherein contain the carboxylic acid ammonium of 2-15 weight %, the tensio-active agent of 0.25-10 weight %, the organic solvent of 0-40 weight %, the dyestuff of 0.5-15 weight %, what the content of described carboxylic acid ammonium and tensio-active agent was enough to prevent to be heated and bring out is separated until about 70 ℃, and carboxylic acid ammonium wherein meets following chemical formula:
Wherein R is hydrogen or is selected from the following carbon structure that contains with 1-40 carbon atom: alkyl group, alkenyl, alkynyl, alkoxyl group, carboxyl, carboxylic acid ammonium and their mixture, alkyl group wherein, alkenyl, alkynyl, alkoxyl group, carboxyl, carboxylic acid ammonium comprise linear chain structure, branched structure, steric isomer, and comprise hydroxyl, sulfydryl, amido, carbonyl, carboxyl, halogen or their mixture;
Tensio-active agent is selected from the non-ionic type ethoxylate, hydroxylated acetylene series polyoxyethylene, oxyalkylated acetylene series polyoxyethylene, anionic phosphate and their mixture.
Above-mentioned carboxylic acid ammonium is ammonium hydrogen citrate, DL-Lactic acid ammonium salt, ammonium formiate, ammonium gluconate, ammonium tartrate, Succinic acid ammonium salt, propanedioic acid ammonium, ammonium fumarate, oxysuccinic acid ammonium, ammonium sebacate, ammonium laurate, pentanedioic acid ammonium, ammonium acetate, ammonium oxalate, ammonium adipate, pimelic acid ammonium, ammonium octanedioic acid, ammonium azelate or their mixture preferably.
Tensio-active agent is a kind of tensio-active agent of ethoxylation preferably.
Ethoxylated surfactant is secondary alcohol ethoxyl compound preferably, and it has aliphatic chain and 5 oxyethyl groups of 15 carbon atoms.
In addition, tensio-active agent can be selected from hydroxylated acetylene series polyoxyethylene, oxyalkylated acetylene series polyoxyethylene and their mixture.
Tensio-active agent also can be selected from the compound that (a) meets following formula
RO(CH
2CH
2O)
nH
R=C wherein
12-C
16, n=1-11.5 (b) meets the compound of following formula
Wherein n+m=0-50 and its mixture.
In a kind of preferred embodiment of above-mentioned ink composite, the carboxylic acid ammonium is that content is the composition of organizing under being selected from of 4-10% weight: ammonium hydrogen citrate, DL-Lactic acid ammonium salt, ammonium formiate, ammonium gluconate, ammonium tartrate, Succinic acid ammonium salt, propanedioic acid ammonium, ammonium fumarate, oxysuccinic acid ammonium, ammonium sebacate, ammonium laurate, pentanedioic acid ammonium, ammonium acetate, ammonium oxalate, ammonium adipate, pimelic acid ammonium, ammonium octanedioic acid, ammonium azelate and their mixture.
The present invention relates to the ink composite that preferred (but and nonessential) is used for thermal ink jet printers.The ink composite of this formulated has prevented composition component being separated when heating up basically, has reduced dye diffusion, has improved photostabilization, and has limited the toxic degree of ink composite.
Ink composite of the present invention is used in printed image on the very big class material.These materials are called " medium " or " printed medium " in this article, include but not limited to common cellulosic materials paper and " special medium ", the medium of starch coated and with the medium of silicon-dioxide and/or clay coated, mould material, atresia transparent polyester film and analogous material for example.These media can also comprise for example mordant of special additive, include but not limited to poly-hydroxyl quaternary ammonium salt.Ink composite of the present invention is particularly suitable for storing in warmer environment or weather and/or printing.
The work embodiment of ink composite contains the dyestuff of (except as otherwise noted, described percentage number average refers to weight) about 0.5-15%, the tensio-active agent of about 0.25-10%, the ammonium carboxylate salt of about 2-15% by weight.At present preferred salt is ammonium hydrogen citrate, DL-Lactic acid ammonium salt, ammonium dihydrogen citrate and their mixture, preferred surfactants is the secondary alcohol ethoxyl compound of non-ionic type at present, its the have an appointment aliphatic chain of 12-18 carbon atom and about 4-8 oxyethyl group, according to the Imperial Chemical Industries known to those skilled in the art (ICI) standard, its HLB value is about 10 to 13.The numerical range that is used for the ICI standard of tensio-active agent evaluation is from 1 to 20.It mainly is oleophilic characteristics that Schwellenwert 1 presentation surface promoting agent has, and it mainly is hydrophilic characteristic that 20 presentation surface promoting agents of high value have.Surplus materials in the ink composite mainly is a water; But, be generally used for other component in the ink composite, biological example kill agent, organic solvent, pH buffer reagent and known now or find from now on can be used for any other component in the similar ink composite, also can be used for forming ink composite of the present invention.
The dyestuff that in ink composite, contains the 1-5% that has an appointment, about 0.5-5% tensio-active agent, and the ammonium carboxylate salt content in the ink composite can obtain good effect during for about 4-10%.It seems that best result be that the situation that contains have an appointment 1.5% tensio-active agent and about 8% ammonium carboxylate salt in composition is issued at present.
In decision during dye strength, make the quantity of dyestuff can produce the interior absorption of the scope of wanting can obtain good result.For example, when following dyestuff produces in the table 1 listedly as a result the time, can obtain good effect in ink composite.
Table 1
Dyestuff NMax
*Absorbancy (± 0.005)
Acid yellow 23 tetramethylammonium 428 0.13
Direct yellow 132 402 0.12
Acid blue 9 sodium salt 628 0.16
Sun blue 199 tetramethylammoniums 618 0.09
Reactive red 180 514 0.09
Xylene Red 52 lithium salts 562 0.14
Direct yellow 132 and 410 0.09
Acid yellow 23 mixture 426 0.09
Pinkish red M377 and 518 0.09
Xylene Red 52 (Li) mixture 562 0.138
*With the absorbance unit that Hewlett-Packard's ultraviolet/visible II8452A photometer records when diluting at 1: 10000.
The purity of all components all is to be to form the purity that adopts in ink composite, the especially normal industrial practice of those ink composites of developing for thermal ink jet printers in the ink composite of the present invention.
For making ink composite of the present invention, at first to select one or more dyestuffs.There is suitable dyestuff of all kinds can supply to utilize; These dyestuffs can be water miscible, water-insoluble, black or chromatic.Here used " water miscible " speech is meant that the solubility limit of dyestuff in water is enough high, so that can produce the color saturation of desired printed image.In general, the solubility limit in water can satisfy most of desired color saturation targets above 2% weight.Here used " water-insoluble " speech is meant that at room temperature dyestuff is not seen dissolving in water.
Water-soluble dye is the preferred dye that forms ink composite of the present invention.Suitable water-soluble dye includes but not limited to following dyestuff: Xylene Red 52, Xylene Red 289, Xylene Red 27, reactive red 18, directly red 227, alkaline red 3, acid yellow 23, directly yellow 86, direct yellow 132, basic yellow 9, basic yellow 11, acid blue 9, alkali blue 9, sun blue 199, technology reactive black 31 (Process Reactive Black 31) eats and deceives 2, directly deceives 19, pinkish red M 377 (a kind of azoic dyestuff that has a triazine ring, can be from Ilford AG, RueDel ' Industrie, CH-1700 Fribourg, Switzerland obtains), and their mixture.
The water-insoluble dyestuff can be suitable for ink composite of the present invention.This class dyestuff includes but not limited to: solvent dye, vat pigment and some mordant dye.These dyestuffs have black miscellaneous and colored available.The example of water-insoluble solvent dye includes but not limited to: solvent black SB 3, SB 5, SB 46, SB 48, solvent blue 36, solvent blue 59, solvent red 1, solvent red 24, solvent red 68, solvent yellow SY 13, SY 14, SY 33 and SY 93.The example of suitable vat pigment includes but not limited to that urn is black 9, and urn is black 25, vat blue 1, and vat blue 6, urn is red 10, vat yellow 4 and their mixture.
The example of water-insoluble mordant dye includes but not limited to: mordant dyeing indigo plant 1, mordant rouge 7, mordant rouge 9, mordant yellow 26 and composition thereof.
Above-mentioned dyestuff usually comprises the gegenion that is used for charge balance.The anionic water-soluble dye, for example Xylene Red 27, have the sodium gegenion usually.But gegenion also can be K
+, Li
+And NH
4 +For acid yellow 23 and sun blue 199, gegenion is preferably tetramethyl-ammonium [(CH
3)
4N
+, TMA] because this gegenion further reduces the nozzle skinning significantly.The cation type water-soluble dyestuff, for example basic yellow 11, comprise such as Cl usually
-, Br
-, ZnCl
4 2-And NO
3 -Deng gegenion.
These concrete dyestuffs of being discussed are just as the example explanation.Should be appreciated that any dyestuff known now or that develop from now on, all can be used for implementing the present invention, as long as they have suitable characteristic.Suitable characteristic comprises good color tone, high chroma, qualified photobleaching characteristic, sufficiently high optical density(OD), as the sufficiently high solubleness in the fluid (being preferably water among the present invention) of ink vehicle, good saturation ratio and skinning performance, and with ink composite in the consistency of other component.In addition, suitable dyestuff does not damage the application of ink composite aspect the hot ink jet printing image of generation.
In ink composite of the present invention, to add at least a tensio-active agent so that the control that colour-coloured dye is spread is provided, promote printing ink evenly to cover and printing ink levelling on printed medium, form high-quality image and slow down printing ink and evaporate.Tensio-active agent is also by making ink penetration shorten the time of drying of printing ink image in the printed medium.
The tensio-active agent that is preferred in the ink composite of the present invention (for example comprises the non-ionic type alcohol ethoxylate surfactant, secondary alcohol ethoxyl compound tensio-active agent and alkyl phenyl ester surfactant), hydroxylation or oxyalkylated acetylene series polyoxyethylene surfactant, and aniorfic surfactant, for example phosphoric acid ester.
Non-ionic type secondary alcohol ethoxyl compound tensio-active agent can (Houston Texas) obtains as TERGITOL series, as TERGITOL 15-S-5 and TERGITOL 15-S-7 by for example Union Carbide Corporation.This secondary alcohol ethoxyl compound contains: (a) contain the aliphatic chain of regulation carbonatoms and (b) oxyethyl group of defined amount in chain.These tensio-active agents can provide with the form of mixtures of ethoxylate, therefore represent with the main compound in the mixture.Be fit to be used for implementing this class secondary alcohol ethoxyl compound of the present invention 12-18 carbon atom of in aliphatic chain, mainly having an appointment.The number of oxyethyl group mainly is between 4-8, is preferably 5-7.For example, " TERGITOL 15-S-5 " represents a kind of secondary alcohol ethoxyl compound tensio-active agent, mainly contains 15 carbon atoms and 5 oxyethyl groups in its aliphatic chain.It seems that at present dominant oxyethyl group number is less than 4 and can not fully dissolves in the secondary alcohol ethoxyl compound mixture in printing ink, and if dominant oxyethyl group outnumbers 8, then tensio-active agent has lost the effectiveness that prevents the coloured dye diffusion.
The nonionogenic tenside of another kind of typical ethoxylation is can be by Aldrich chemical company-Fluka Chemical (Milwaukee, the GENAPOL series that Wisconsin) obtains.This class material is by C
12-C
16Alcohol ethoxylate is formed, and is expressed as with formula 1
RO(CH
2CH
2O)
nH (1)
R=C wherein
12To C
16, typical chain length is 13 carbon atoms; N=1 to 11.5.
Another kind of representational ethoxylated non-ionic surface active agent is the IGEPAL CO that can obtain from Rhone-Poulenc company (Cranbury, New Jersey).These materials are by nonyl phenol (C entirely
9H
19C
5H
4OH) with oxyethane (C
2H
4O) reaction makes.For example, below each alkyl phenyl ethoxylated non-ionic surface active agent sell (being oxyethane percentage composition wherein): CO-210 (23%) with the trade mark of IGEPAL CO after production number, CO-430 (44%), CO-520 (50%),
CO-530(54％)，CO-610(60％)，CO-620(63％)，CO-630(65％)，CO-660(66％)
CO-710(68％)，CO-720(71％)，CO-730(75％)，CO-850(80％)
CO-880(86％)，CO-887(86％)，CO-890(89％)，CO-897(89％)
CO-970(91％)，CO-977(91％)，CO-987(93％)，CO-997(95％)。These tensio-active agents are listed under the CAS#9016-45-9.
Similar representational ethoxylated non-ionic type tensio-active agent is can be from shell chemical company (Houston, the NEODOL that Texas) obtains.Other non-ionic type alcohol ethoxylate tensio-active agent also can be used for the present invention, the EOT that can obtain for example from Rhone Poulenc company, and its trade name is ALCODET-260 or MIRAPON-E825.
Hydroxylation or oxyalkylated acetylene series polyoxyethylene surfactant can be from for example AirProducts and Chemicals (Lehigh Valley, Pennsyl-vania) obtain as SURFYNOL series, for example SURFYNOL 104, SURFYNOL CT-111, SURFYNOLCT-121 and SURFYNOL 465.This SURFYNOL series can be represented with formula 2:
N+m=0 to 50 wherein.
Can be used for aniorfic surfactant of the present invention, for example phosphoric acid lipid can be buied from Rhone-Poulenc company, and trade name is RHODAFAC RS-610.
In an embodiment preferred, contain in the ink composite amount to about 10% weight tensio-active agent (for example, one of last surfactant, above-mentioned surfactant mixtures, hydroxylation or oxyalkylated polyoxyethylene surfactant, or anion surfactant, as phosphoric acid ester, they can be used singly or in combination).When the total concn of the tensio-active agent in the ink composite can obtain good effect during for about 0.5-5% weight.Optimal results reaches under the following conditions so far: tensio-active agent is a secondary alcohol ethoxyl compound, aliphatic chain 12-18 the carbon atom of having an appointment, preferred about 15 carbon atoms, and 4-8 the oxyethyl group of having an appointment, preferred about 5-7 oxyethyl group, the HLB value is preferably about 10-13, and surfactant concentration is about 1.5% weight in the ink composite.
In ink composite of the present invention, add one or more ammonium carboxylate salt.These salt provide the control action kou to the black-colour dye diffusion, and have reduced ink composite and issue looks in higher temperatures and separate (that is, the cloud point of ink composite being brought up at least about 60 ℃, generally is about 70 ℃).Be not subjected to the constraint of particular theory, having proposed the minimizing that ink composite is separated when heating up is that the carboxylic acid ammonium influences tensio-active agent equilibrated result.Therefore, ink composite is very responsive to temperature, thereby has avoided being separated during triggering and improved stability under warm climate.
Preferred ammonium carboxylate salt of the present invention comprises the compound of formula 3 representatives at present:
Wherein R can be hydrogen (as an ammonium formiate), perhaps R can contain 1 carbon atom (as ammonium acetate) of having an appointment to about 40 carbon atoms the ammonium stearate of 36 carbon atoms (as have), can select as follows: hydrogen, alkyl group, alkenyl, alkynyl, alkoxyl group, carboxyl, carboxylic acid ammonium and their mixture, comprise straight chain and branched structure, and comprise all steric isomers.Alkyl group, alkenyl, alkynyl, alkoxyl group, carboxyl, carboxylic acid ammonium can also comprise hydroxyl, sulfydryl, amido, carbonyl, carboxyl, halogen or their mixture;
When using the carboxylic acid ammonium who is partially soluble in water at least, obtained good result, for example: ammonium hydrogen citrate, DL-Lactic acid ammonium salt, ammonium formiate, ammonium gluconate, ammonium tartrate, Succinic acid ammonium salt, the propanedioic acid ammonium, ammonium fumarate, oxysuccinic acid ammonium, ammonium sebacate, ammonium laurate, pentanedioic acid ammonium, ammonium acetate, ammonium oxalate, ammonium adipate, pimaric acid ammonium, ammonium octanedioic acid, ammonium azelate and their mixture.Optimum is to reach when selecting the carboxylic acid ammonium for ammonium hydrogen citrate, DL-Lactic acid ammonium salt and their mixture at present.
4. organic solvent
Can use one or more organic solvents to prepare ink composite of the present invention.Usually use a kind of suitable solvent to form the mixture that contains selected dye substance.In an embodiment preferred, contain the water-miscible organic solvent of the 0-40% weight of having an appointment in the ink composite.The example that is fit to the water-miscible organic solvent of this usefulness includes but not limited to: C
1-C
4Fatty alcohol (as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol or isopropylcarbinol), amides (as methane amide or N,N-DIMETHYLACETAMIDE), ketone, polyketone class or ketols (as acetone or Pyranton), ethers (as tetrahydrofuran (THF) or two alkane), nitrogen heterocyclic ring ketone (2-Pyrrolidone, N-methylpyrrolidin-2-ketone, or 1,3-methylimidazole-2-ketone), polyalkylene glycol (as polyoxyethylene glycol or polypropylene glycol) contains C
2-C
6The aklylene glycol of alkylidene group and sulfo-glycol (ethylene glycol, propylene glycol, butyleneglycol, triethylene glycol, thiodiglycol, hexylene glycol and Diethylene Glycol), glycerine, polyvalent alcohol (for example 1,2, the 6-hexanetriol), and the lower alkyl ether of polyhydroxy-alcohol, 2-methyl cellosolve for example, 2-(2-methoxyethoxy) ethanol, 2-(2-ethoxy oxyethyl group) ethanol, 2-methoxyl group-2-oxyethyl group-cellosolvo, 2-[2-(2-methoxyethoxy) oxyethyl group] ethanol, and 2-[2-(2-ethoxy oxyethyl group) oxyethyl group] ethanol.
In above-mentioned solvent, preferred solvent comprises two pure and mild glycol ethers (ethylene glycol for example, Diethylene Glycol, triethylene glycol, or 2-methoxyl group-2-oxyethyl group-cellosolvo), molecular weight is at the polyoxyethylene glycol below 500, and heterocyclic ketones (2-Pyrrolidone for example, N-methylpyrrolidin-2-ketone or 1,3-methylimidazole-2-ketone).At present, optimum is by using about 1-20%1,5-pentanediol (1,5-pentamethylene glycol), the 2-Pyrrolidone of about 1-20% and/or the ethyl hydroxyl propylene glycol (EHPD) of about 1-20%.
The preferred pH value of ink composite of the present invention is about 3.5-7.5, and more preferably the pH value is about 4.5.
The pH of ink composite can regulate by adding any mineral acid, organic acid and composition thereof.For example, suitable mineral acid can be rare nitric acid, phosphoric acid, hydrochloric acid, sulfuric acid and their mixture.PH for from about 7 to about 9.5, at least a concentration is that the about 0.1% pH buffer reagent to about 7% weight is suitable.The pKa value of buffer reagent is preferably about 6.5-10.Such as TES (N-three (methylol) methyl-2-aminoethyl sulfonic acid), BICINE (N, N-two (2-hydroxyethyl) glycine), TEA (trolamine), TRIS (three (methylol) ethylamine) and BORAX buffer reagents such as (Sodium Tetraborate+hydrates) can use separately, combination with one another is used, or uses with other combinations of buffers.(we need not to narrate these.Our pH scope is 4.5-7).
When preparation ink composite of the present invention, can also usage quantity be the biocides of about 0.1-0.5% weight.The example of suitable biocides includes but not limited to the PROXEL CRL and the PROXEL GXL that can obtain from ICI (Britain), and the NUOSEPT C and the NUOSEPT 95 that can obtain from Nuodex company (Piscataway, New Jersey).
In order to further specify the present invention, state some embodiment below.These embodiment only for example explanation usefulness, never mean it is that the present invention is constrained to described concrete feature.
Desired organic solvent with suitable weight percentage when generally, preparing alkali ink composite of the present invention is placed in the ink composite hybrid bottle.In organic solvent, add suitable weight percentage desired surface promoting agent or surfactant composition subsequently.One or more ammonium salts that then in organic solvent/surfactant mixture, add suitable weight percentage.In this solution, add the water of about 10-20% weight then, the ink composite hybrid bottle is temporarily sealed.Make solution in the ink composite hybrid bottle at room temperature on the parallel rollers mixing tank, mix about 5-6 hour (or mix time enough, dissolve basically) with all components in the assurance solution.
After the mixing, add desired dyestuff in solution, its quantity should be enough to reflect desired absorbance.The pH of regulator solution mixes about 1 hour (or being enough to guarantee basic for some time uniformly of formed ink composite) on the parallel rollers mixing tank then.
Embodiment 1
On several different cellulose media and special medium, comprise the medium, clay coated of starch coated and/or the medium that silica gel applies, the VIPER PLUS of Hewlett-Packard for example, WEASAL prints with the hot ink-jet pen of Hewlett-Packard.Used ink composite has the aqueous composition of listing in the Table II:
Table II
Compound weight %
1,5-pentanediol 8
2-Pyrrolidone 7.5
EHPD 7.5
Tergitol?15-S-5 1
Ammonium hydrogen citrate 8
Rare nitric acid, phosphoric acid, hydrochloric acid are as required with pH
And/or sulfuric acid is adjusted to about 4.5
Acid yellow 23 (TMA) 0.16
*
*The absorbance unit that recorded under the extent of dilution at 1: 10000 with Hewlett-Packard's UV/VIS II 8452A photometer.
The measuring method of the cloud point of the ink composite of this embodiment is earlier ink composite to be heated about 6-7 hour in following temperature range: about 45 ℃-55 ℃; 55 ℃-60 ℃; 65 ℃-70 ℃; With at about 75 ℃.Visualize ink composite termly in heat-processed is checked being separated or the appearance of composition muddiness of ink composite component.The ink composite of this embodiment does not all have the sign that is separated under above-mentioned any test temperature.In addition, the ink composite of this embodiment demonstrates excellent black-colour and colour-coloured dye diffusion characteristics and good edge sharpness printing characteristic on cellulose paper and special medium.The ink composite of this embodiment is difficult for slowing down under high injection frequency.
For measuring the photostabilization of this embodiment ink composite, the illumination condition of simulation office also exposes printed image being equivalent under the typical office illumination condition in 1 year.Subsequently with the color comparison of color and the unexposed print image of primary of the print image of exposure.The ink composite of finding present embodiment all has good photostabilization on cellulose paper and special medium.
The total amount of organic of the ink composite of listing in the Table II is estimated as about 15-40%, and the surface tension of ink composite is about 25-35dynes/cm after measured, and the viscosity of ink composite is about 2.5-5 centipoise.
Embodiment 2
On several different cellulose media and special medium, comprise the medium of medium, clay coated and/or the silica-coating of starch coated, for example VIPER PLUS, the WEASAL of Hewlett-Packard print with the hot ink-jet pen of Hewlett-Packard.The ink composite that uses has the water base composition of listing in the Table III
Table III
Compound weight %
1,5-pentanediol 8
2-Pyrrolidone 7.5
EHPD 7.5
Tergitol?15-S-5 1
Ammonium hydrogen citrate 8
Rare nitric acid, phosphoric acid, hydrochloric acid are transferred pH as required
And/or sulfuric acid saves about about 4.5
Reactive red 180 (TMA) 0.12
*
Xylene Red 52 (Li) 0.18
*
*The absorbance unit that recorded under the thinning ratio at 1: 10000 with Hewlett-Packard's UV/VIS II 8452A photometer.
The cloud point of this embodiment ink composite is pressed described in the embodiment 1 and is measured.The ink composite of this embodiment is separated or muddy sign all not having under any test temperature of 70 ℃.In addition, this embodiment ink composite demonstrates excellent black-colour and colour-coloured dye diffusion property and good edge sharpness printing characteristics on cellulose paper and special medium.This embodiment ink composite is difficult for slowing down under high injection frequency.
The photostabilization of the ink composite of this embodiment is pressed described in the embodiment 1 and is measured.Find that this embodiment ink composite all has good photostabilization on cellulose paper and special medium.
The total amount of organic of the ink composite of listing in the Table III is estimated as 15-40%, and the surface tension of ink composite is about 25-35 dynes/cm after measured, and the viscosity of ink composite is about 2.5-5 centipoise.
Embodiment 3
On several different cellulose media and special medium, comprise the medium of medium, clay coated and/or the silica-coating of starch coated, the VIPER PLUS of Hewlett-Packard for example, WEASAL prints with the hot ink-jet pen of Hewlett-Packard.Used ink composite has the water base composition that Table IV is listed:
Table IV
Compound weight %
1,5-pentanediol 8
2-Pyrrolidone 7.5
EHPD 7.5
Tergitol?15-S-5 1
Ammonium hydrogen citrate 8
Rare nitric acid, phosphoric acid, hydrochloric acid are regulated as required
And/or about sulfuric acid pH to 4.5
Sun blue 199 0.12
*
Acid blue 9 0.16
*
*The absorbance unit that recorded under the extent of dilution at 1: 10000 with Hewlett-Packard's UV/VIS II 8452A photometer.
The cloud point of this embodiment ink composite is pressed described in the embodiment 1 and is measured.This embodiment ink composite is separated or muddy sign showing under any test temperature of 70 ℃.In addition, this embodiment ink composite demonstrates excellent black-colour and colour-coloured dye diffusion characteristics and good edge sharpness printing characteristic on cellulose paper and special medium.This embodiment ink composite is difficult for slowing down under high injection frequency.
The photostabilization of this embodiment ink composite is by measuring described in the above embodiment 1.Find that this embodiment ink composite all has good photostabilization on cellulose paper and special medium.
The total amount of organic of the ink composite of listing in the Table IV is estimated as 15-40%, and the surface tension of ink composite is about 25-35 dynes/cm after measured, and the viscosity of ink composite is about 2.5-5 centipoise.
Embodiment 4
On several different cellulose media and special medium, comprise the medium of medium, clay coated and/or the silica-coating of starch coated, the VIPER PLUS of Hewlett-Packard for example, WEASAL prints with the hot ink-jet pen of Hewlett-Packard.Used ink composite has the water base composition that Table V is listed:
Table V
Compound weight %
1,5-pentanediol 8
2-Pyrrolidone 7.5
EHPD 7.5
IGEPAL?CO-620 1.5
Ammonium hydrogen citrate 8
Rare nitric acid, phosphoric acid, hydrochloric acid are regulated as required
And/or sulfuric acid is to pH about 4.5
Sun blue 199 0.12
*
Acid blue 9 0.16
*
*The absorbance unit that recorded under the thinning ratio at 1: 10000 with Hewlett-Packard's US/VIS II 8452A photometer.
The cloud point of this embodiment ink composite is pressed described in the embodiment 1 and is measured.This embodiment ink composite is separated or muddy sign all not having under any test temperature of 70 ℃.In addition, this embodiment ink composite demonstrates excellent black-colour and colour-coloured dye diffusion property and good edge sharpness printing characteristics on cellulose paper and special medium.The present embodiment ink composite is difficult for slowing down under high injection frequency.
The photostabilization of this embodiment ink composite is by measuring described in the above embodiment 1.Find that this embodiment ink composite all has good photostabilization on cellulose paper and special medium.
Embodiment 5
On several different cellulose media and special medium, comprise the medium of medium, clay coated and/or the silica-coating of starch coated, the VIPER PLUS of Hewlett-Packard for example, WEASAL prints with the hot ink-jet pen of Hewlett-Packard.The ink composite that uses has the water base composition that Table VI is listed:
Table VI
Compound weight %
1,5-pentanediol 8
2-Pyrrolidone 7.5
EHPD 7.5
IGEPAL?CO?630 1.5
Ammonium hydrogen citrate 8
Rare nitric acid, phosphoric acid, hydrochloric acid are regulated as required
And/or sulfuric acid is to about pH 4.5
Sun blue 199 0.12
*
Acid blue 9 0.16
*
*The absorbance unit that recorded under the thinning ratio at 1: 10000 with Hewlett-Packard's UV/VIS II 8452A photometer.
The cloud point of this embodiment ink composite is according to measuring described in the top embodiment 1.This embodiment ink composite is separated or muddy sign all not having under any test temperature of 70 ℃.In addition, this embodiment ink composite demonstrates excellent black-colour and colour-coloured dye diffusion characteristics and good edge sharpness printing characteristic on cellulose paper and special medium.This embodiment ink composite is difficult for slowing down under the high frequency jet frequency.
The photostabilization of this embodiment ink composite is according to measuring described in the embodiment 1.Find that this embodiment ink composite all has good photostabilization on cellulose paper and special medium.
Embodiment 6
On several different cellulose media and special medium, comprise the medium of medium, clay coated and/or the silica-coating of starch coated, the VIPER PLUS of Hewlett-Packard for example, WEASAL prints with the hot ink-jet pen of Hewlett-Packard.Used ink composite has the water base composition in the Table VII of being listed in:
Table VII
Compound weight %
1,5-pentanediol 8
2-Pyrrolidone 7.5
EHPD 7.5
ALCODET-260 1.5
Ammonium hydrogen citrate 8
Rare nitric acid, phosphoric acid, hydrochloric acid are regulated as required
And/or sulfuric acid is to pH about 4.5
Sun blue 199 0.12
*
Acid blue 9 0.16
*
*The absorbance unit that recorded under the thinning ratio at 1: 10000 with Hewlett-Packard's UV/VIS II 8452A photometer.
The cloud point of this embodiment ink composite is according to measuring described in the top embodiment 1.This embodiment ink composite is separated or muddy sign all not having under any test temperature of 70 ℃.In addition, this embodiment ink composite demonstrates excellent black-colour and colour-coloured dye diffusion characteristics and good edge sharpness printing characteristic on cellulose paper and special medium.This embodiment ink composite is difficult for slowing down under high injection frequency.
The photostabilization of this embodiment ink composite is according to measuring described in the embodiment 1.Find that this embodiment ink composite all has good photostabilization on cellulose paper and special medium.
Embodiment 7
On several different cellulose media and special medium, comprise the medium of medium, clay coated and/or the silica-coating of starch coated, the VIPER PLUS of Hewlett-Packard for example, WEASAL prints with the hot ink-jet pen of Hewlett-Packard.Used ink composite has the water base composition of listing in the Table VIII:
Table VIII
Compound weight %
1,5-pentanediol 8
2-Pyrrolidone 7.5
EHPD 7.5
MYRAPON-E825 1.5
Ammonium hydrogen citrate 8
Rare nitric acid, phosphoric acid, hydrochloric acid are regulated as required
And/or sulfuric acid is to about pH 4.5
Sun blue 199 0.12
*
Acid blue 9 0.16
*
*The absorbance unit that recorded under the thinning ratio at 1: 10000 with Hewlett-Packard's UV/VIS II 8452A photometer.
The cloud point of this embodiment ink composite is according to measuring described in the above embodiment 1.This embodiment ink composite is separated or muddy sign all not having under any test temperature of 70 ℃.In addition, this embodiment ink composite demonstrates excellent black-colour and colour-coloured dye diffusion characteristics and good edge sharpness printing characteristic on cellulose paper and special medium.This embodiment ink composite is difficult for slowing down under the high frequency jet frequency.
The photostabilization of this embodiment ink composite is pressed described in the embodiment 1 and is measured.Find that this embodiment ink composite all has good photostabilization on cellulose paper and special medium.
Embodiment 8
On several different cellulose media and special medium, comprise the medium of medium, clay coated and/or the silica-coating of starch coated, the VIPER PLUS of Hewlett-Packard for example, WEASAL prints with the hot ink-jet pen of Hewlett-Packard.Used ink composite has the water base composition that is listed among the Table I X:
Table I X
Compound weight %
1,5-pentanediol 8
2-Pyrrolidone 7.5
EHPD 7.5
MYRAPON-E825 1.5
Ammonium hydrogen citrate 8
Rare nitric acid, phosphoric acid, hydrochloric acid are regulated as required
And/or sulfuric acid pH is to about 4.5
Direct yellow 132 and 0.16
Acid yellow 23 0.16
*The absorbance unit that recorded under the thinning ratio at 1: 10000 with Hewlett-Packard's US/VIS II 8452A photometer.
The cloud point of this embodiment ink composite is according to measuring described in the top embodiment 1.This embodiment ink composite is not all having the sign that is separated with muddy under any test temperature of 70 ℃.In addition, this embodiment ink composite all shows excellent black-colour and colour-coloured dye diffusion characteristics and good edge sharpness printing characteristic on cellulose paper and special medium.This embodiment ink composite is difficult for slowing down under high injection frequency.
The photostabilization of this embodiment ink composite is according to measuring described in the top embodiment 1.Find that this embodiment ink composite all has good photostabilization on cellulose paper and special medium.
Embodiment 9
On several different cellulose media and special medium, comprise the medium of medium, clay coated and/or the silica-coating of starch coated, for example the VIPER PLUS and the WEASAL of Hewlett-Packard print with the hot ink-jet pen of Hewlett-Packard.Used ink composite has the water base composition of listing in the Table X:
Table X
Compound weight %
1,5-pentanediol 8
2-Pyrrolidone 7.5
EHPD 7.5
MYRAPON-E825 1.5
Ammonium hydrogen citrate 8
Rare nitric acid, phosphoric acid, hydrochloric acid are regulated as required
And/or sulfuric acid pH is to about 4.5
Pinkish red M377 and 0.18
Xylene Red 52 (Li) 0.18
*The absorbance unit that recorded under the thinning ratio at 1: 10000 with Hewlett-Packard's UV/VIS II 8452A photometer.
The cloud point of this embodiment ink composite is according to measuring described in the embodiment 1.This embodiment ink composite is separated or muddy sign all not having under any test temperature of 70 ℃.In addition, this embodiment ink composite demonstrates excellent black-colour and colour-coloured dye diffusion characteristics and good edge sharpness printing characteristic on cellulose paper and special medium.This embodiment ink composite is difficult for slowing down under high injection frequency.
The photostabilization of this embodiment ink composite is according to measuring described in the above embodiment 1.Find that this embodiment ink composite all has good photostabilization on cellulose paper and special medium.
Though the invention has been described together with preferred and alternate embodiment, but those of ordinary skills will be understood that, under the situation of the scope and spirit of the present invention that do not depart from the qualification of claims and Equivalent thereof, can make various changes and modification to ink composite as herein described and method.
Claims (7)
1. ink composite, the carboxylic acid ammonium of 2-15 weight %, the tensio-active agent of 0.25-10 weight %, the organic solvent of 0-40 weight %, the dyestuff of 0.5-15 weight % are wherein arranged, what the content of described carboxylic acid ammonium and tensio-active agent was enough to prevent to be heated and bring out is separated until about 70 ℃, and carboxylic acid ammonium wherein meets following chemical formula:
Wherein R is hydrogen or is selected from the following carbon structure that contains with 1-40 carbon atom: alkyl group, alkenyl, alkynyl, alkoxyl group, carboxyl, carboxylic acid ammonium and their mixture, alkyl group wherein, alkenyl, alkynyl, alkoxyl group, carboxyl, carboxylic acid ammonium comprise linear chain structure, branched structure, steric isomer, and comprise hydroxyl, sulfydryl, amido, carbonyl, carboxyl, halogen or their mixture;
Tensio-active agent is selected from the non-ionic type ethoxylate, hydroxylated acetylene series polyoxyethylene, oxyalkylated acetylene series polyoxyethylene, anionic phosphate and their mixture.
2. the ink composite of claim 1, carboxylic acid ammonium wherein is selected from ammonium hydrogen citrate, DL-Lactic acid ammonium salt, ammonium formiate, ammonium gluconate, ammonium tartrate, Succinic acid ammonium salt, propanedioic acid ammonium, ammonium fumarate, oxysuccinic acid ammonium, ammonium sebacate, ammonium laurate, pentanedioic acid ammonium, ammonium acetate, ammonium oxalate, ammonium adipate, pimelic acid ammonium, ammonium octanedioic acid, ammonium azelate and their mixture.
3. the ink composite of claim 1, wherein tensio-active agent is a kind of tensio-active agent of ethoxylation.
4. the ink composite of claim 3, ethoxylated surfactant wherein is a secondary alcohol ethoxyl compound, it has aliphatic chain and 5 oxyethyl groups of 15 carbon atoms.
5. the ink composite of claim 1, tensio-active agent wherein is selected from hydroxylated acetylene series polyoxyethylene, oxyalkylated acetylene series polyoxyethylene and their mixture.
6. the ink composite of claim 1, wherein tensio-active agent is selected from the compound that (a) meets following formula
RO(CH
2CH
2O)
nH
R=C wherein
12-C
16, n=1-11.5 (b) meets the compound of following formula
Wherein n+m=0-50 and its mixture.
7. the ink composite of claim 6, carboxylic acid ammonium wherein is that content is the composition of group under being selected from of 4-10% weight: ammonium hydrogen citrate, DL-Lactic acid ammonium salt, ammonium formiate, ammonium gluconate, ammonium tartrate, Succinic acid ammonium salt, propanedioic acid ammonium, ammonium fumarate, oxysuccinic acid ammonium, ammonium sebacate, ammonium laurate, pentanedioic acid ammonium, ammonium acetate, ammonium oxalate, ammonium adipate, pimelic acid ammonium, ammonium octanedioic acid, ammonium azelate and their mixture.
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| CNB981169538A CN100349995C (en) | 1998-08-28 | 1998-08-28 | Alkali ink composite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB981169538A CN100349995C (en) | 1998-08-28 | 1998-08-28 | Alkali ink composite |
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| CN100349995C true CN100349995C (en) | 2007-11-21 |
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Cited By (1)
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| CN103097435A (en) * | 2010-08-19 | 2013-05-08 | 株式会社理光 | Liquid composition, recording method, and recorded matter |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100447209C (en) * | 2001-07-02 | 2008-12-31 | 研能科技股份有限公司 | Ink composition |
| CN102453353A (en) * | 2010-10-14 | 2012-05-16 | 研能科技股份有限公司 | Composition for reducing pigment interaction during dyeing |
| US8506694B2 (en) * | 2011-04-27 | 2013-08-13 | Xerox Corporation | Phase separation ink |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5626655A (en) * | 1995-07-11 | 1997-05-06 | Hewlett-Packard Company | Use of co-surfactants to adjust properties of ink-jet inks |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5626655A (en) * | 1995-07-11 | 1997-05-06 | Hewlett-Packard Company | Use of co-surfactants to adjust properties of ink-jet inks |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103097435A (en) * | 2010-08-19 | 2013-05-08 | 株式会社理光 | Liquid composition, recording method, and recorded matter |
| CN103097435B (en) * | 2010-08-19 | 2015-03-11 | 株式会社理光 | Liquid composition, recording method, and recorded matter |
| US8980408B2 (en) | 2010-08-19 | 2015-03-17 | Ricoh Company, Ltd. | Liquid composition, recording method, and recorded matter |
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