CN100564460C - The water-based ink that is used for ink-jet printer - Google Patents

The water-based ink that is used for ink-jet printer Download PDF

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CN100564460C
CN100564460C CNB2004800030891A CN200480003089A CN100564460C CN 100564460 C CN100564460 C CN 100564460C CN B2004800030891 A CNB2004800030891 A CN B2004800030891A CN 200480003089 A CN200480003089 A CN 200480003089A CN 100564460 C CN100564460 C CN 100564460C
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water
ink
segmented copolymer
alkali
ratio
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CN1871313A (en
Inventor
井上均
山本智也
橘由纪子
大川隆行
森冈淳子
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Canon Precision Inc
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Canon Precision Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

A kind of water-based ink that is used for ink-jet printer comprises at least a water-insoluble tinting material, comprises segmented copolymer, water and the alkali of the polyvinyl ether structure of at least a hydrophilic segment and at least a hydrophobic segment.Each hydrophilic segment comprises acidic group.The content of described alkali is as follows: when the ratio of infrared absorption intensity of the ionic group that forms when hypothesis adds excess base in segmented copolymer is 100%, the ratio of infrared absorption intensity of the ionic group that the disassociation of the acidic group that is comprised in the segmented copolymer forms is at least 80%, and restricted condition is that the ratio of infrared absorption intensity that described content is no more than the ionic group that segmented copolymer forms is the twice of the minimum of 100% o'clock alkali.

Description

The water-based ink that is used for ink-jet printer
Technical field
The present invention relates to be used for the water-based ink (water based inks) of ink-jet printer.
Background technology
Along with popularizing of computer, ink-jet printer has obtained using widely.As the ink that is used for these ink-jet printers, water-based ink is because its security etc. is former thereby occupied position of mainstream.In these water-based inks, the water-based ink that utilizes water-soluble dye is owing to the colour developing ability of its excellence obtains the most general use.But, utilize the water-based ink of water-soluble dye to have following problem: because dye soluble makes formed image water-repellancy poor in water, and because dyestuff is in that molecular conformation makes image light or the gas such as ozone and degrade fast.
In order to overcome these problems, just present the polymolecular form that combines but not the ink of the insoluble tinting material (as pigment) of molecular conformation at research and utilization.In so-called image fastness, be better than the formed image of the ink that utilizes water-soluble colorant with these images that disperse ink formation as water-repellancy, photostabilization and gasproof aspect.But, disperse the shortcoming of ink to be stability in storage, and form than macroparticle, be easy to produce problem such as the vividness reduction of tinting material precipitation, ink port obstruction and color owing to tinting material passes through flocculation.
For the fine particle with soluble tinting material stably is distributed in the water medium, proposed to utilize and included the segment that is easy to adhere to these insoluble tinting materials and with the ink (referring to JP-A-5-179183) of the segmental segmented copolymer of water medium highly compatible with utilize the ink (referring to JP-A-9-188732) of graft copolymer.A kind of method has also been proposed, comprise: water-insoluble, oil-soluble colourant are dissolved in the organic solvent, the solution that is produced is mixed with segmented copolymer, next in the mixture that is obtained, add entry, produce water-bearing media, thereby make oil-soluble colourant deposit (JP-A-2002-97395) as fine particle.
In many cases, these segmented copolymers comprise the acidic group such as carboxyl, to strengthen the wetting ability of its hydrophilic radical.In water medium, these acidic groups are dissociated into radical ion, thereby present wetting ability.But,, must suitably add base, acidic group is neutralized for this purpose.If this neutralization is abundant inadequately, then acidic group can not dissociate fully, thereby can not show wetting ability.The segmented copolymer that wherein includes tinting material can not stably be distributed in the water medium.If opposite, alkali surpasses neutral point, and then excessive ion melts in ink.These excess amount of ions weaken the electrostatic repulsion forces of the block polymer particle that wherein includes tinting material, thereby make the dispersed particle flocculation.
Thereby, in aforesaid dispersion ink, very importantly control the degree of neutralization of acidic group in the segmented copolymer.But, under current situation, actual degree of neutralization can not determine, and currently is confined to add the quantity alkali so a kind of method suitable with acidic group that is calculated.But, the character more complicated of acidic group in polymkeric substance, and be not inevitable occurrence degree and the suitable neutralization of alkali number that is added.Thereby, be difficult to neutralization is controlled to any required degree.As a result, the potential problem is that the degree of neutralization of polymkeric substance may be in outside the optimum range.When disperseing the thing prolonged preservation or be kept at following time of high temperature such as 50 ℃ or 60 ℃, it is unstable that the dispersion of dispersed particle is tending towards becoming.When even if it is used in the common ink-jet printer,, also can produce problem such as tone variation or nozzle blockage because the size of particles of dispersed particle increases.
In view of said circumstances, the object of the present invention is to provide a kind of water-based ink that is used for ink-jet printer, it is the colorant particle decentralized, the storage stability excellence, and provide the hi-vision fastness such as water-repellancy, photostabilization and gasproof to print.
Summary of the invention
Can realize above-mentioned purpose by the present invention described below.Particularly, the invention provides a kind of water-based ink that is used for ink-jet printer, described water-based ink comprises at least a water-insoluble tinting material, the segmented copolymer that comprises the polyvinyl ether structure of at least a hydrophilic segment and at least a hydrophobic segment, wherein each hydrophilic segment comprises acidic group, this water-based ink also comprises water and alkali, it is characterized in that, the content of alkali is as follows: when hypothesis because the ratio of infrared absorption intensity (below be referred to as " ratio of infrared absorption intensity ") that in segmented copolymer, adds the ionic group that excess base forms when being 100%, then the ratio of infrared absorption intensity of the ionic group that forms of the disassociation of the acidic group that is comprised in the segmented copolymer is at least 80%, and restricted condition is that the ratio of infrared absorption intensity that described content is no more than the ionic group that is formed by segmented copolymer is the twice of the minimum of 100% o'clock alkali.
In the present invention, the acidic group that comprises in the preferred block copolymer is a carboxyl, and tinting material is pigment or water-insoluble dyestuff.
In the present invention, the ratio of infrared absorption intensity of the formed ionic group of disassociation of the acidic group that comprises in the segmented copolymer reflects the amount of existing ionic group, and as the level of signification of indication degree of neutralization.More specifically, when adding excess base, the acidic group in the segmented copolymer is neutralized fully, and is dissociated by 100% ground basically.Under the situation of this alkali content, when acidic group in the hypothesis segmented copolymer fully in and the time formed ionic group ratio of infrared absorption intensity when being 100%, the ratio of infrared absorption intensity that ionic group produced on the other hand, also exists not by the dissociative acidic group less than 80%.Thereby segmented copolymer has lower wetting ability, thereby the dispersion of the fine particle of tinting material in water medium is unsettled.
On the other hand, if alkali content greater than the twice that realizes the minimum alkali number that neutralization fully (100% neutralization) is required, then the alkali of Cun Zaiing is above the amount suitable with acidic group.In this case, effects of ion intensity increases, make segmented copolymer with the particle of the tinting material formation that is wherein comprised between quiet repulsive force become more weak, be convenient to dispersed particle and flocculate mutually.
When the content of alkali makes the ratio of infrared absorption intensity that is neutralized into the group with ionic nature be at least neutralization fully (100% neutralization) 80% of ratio of infrared absorption intensity, and when the content of alkali is no more than the twice of minimum of the required alkali that neutralizes fully, acidic group is fully disassociation in segmented copolymer, and the additional ions that is formed by alkali is very not many, thereby can obtain the water-based ink of dispersion stabilization excellence.
Description of drawings
Fig. 1 represents that the percentage of size of particles when ink is preserved at high temperature increases.
Embodiment
To illustrate in greater detail the present invention based on preferred embodiment below.
The segmented copolymer that uses among the present invention has following character: it stably is distributed to the fine particle of tinting material in the ink as dispersion agent, and subsequently ink is applied on the recording medium such as paper, is used for tinting material is fixed to recording medium.The segmented copolymer that uses among the present invention comprises at least a hydrophilic block (A, A ') and at least a hydrophobic block (B, B '), and each hydrophilic block all comprises acidic group.
Arrangement for each block in the segmented copolymer does not have special restriction.But, from the viewpoint of dispersed enhanced tinting material is provided, the place, end of preferred polymers chain comprises hydrophilic block.The example of block arrangement comprises AB, ABA ' (wherein A can be identical or different with A '), AA ' B and BB ' A (wherein B and B ' can be identical or different).Note, A, A ', B, B ' they are homopolymer or copolymer block.
The preferred segmented copolymer that uses is such segmented copolymer among the present invention, wherein each segmented copolymer comprises the hydrophilic block that homopolymer or multipolymer by vinyl ether monomers form, the hydrophobic block that forms with homopolymer or multipolymer by vinyl ether monomers, and at least a monomer of forming hydrophilic block comprises one or more acidic groups.
The basic framework of these polymkeric substance for example preferably comprises, with the repeat unit structure of described formula (1) expression subsequently.But, at least a portion repeating unit described below must comprise acidic group, maybe can be by the group of the acidic group of formation such as hydrolysis such as carboxyl as carboxyl.
-(CH 2-CH(OR 1))- (1)
In the described in the above formula (1), R 1Represent aliphatic hydrocarbon groups, as alkyl, alkenyl, cycloalkyl or cycloalkenyl group; Perhaps one or more carbon atom can be by the aryl of nitrogen-atoms replacement, as phenyl, pyridyl, phenmethyl, toluyl, xylyl, alkylphenyl group, phenylalkyl, biphenyl or phenylpyridyl.One or more hydrogen atoms on the aromatic ring can be replaced by alkyl.R 1Carbonatoms be preferably 1 to 18.
R 1Also can serve as reasons-(CH (R 2)-CH (R 3)-O) p-R 4Or-(CH 2) m-(O) n-R 4The group of expression.In this case, R 2And R 3Can represent hydrogen atom or methyl group, R respectively 4Represent fat (fat) family hydrocarbyl group, as alkyl, alkenyl, cycloalkyl or cycloalkenyl group; Virtue (family) hydrocarbyl group that one or more carbon atom can be replaced by nitrogen-atoms, as phenyl, pyridyl, phenmethyl, toluyl, xylyl, alkylphenyl group, phenylalkyl, biphenyl or phenylpyridyl, the one or more hydrogen atoms on the aromatic ring can be replaced by alkyl arbitrarily;-CHO ,-CH 2CHO-,-CO-CH=CH 2,-CO-C (CH 3)=CH 2,-CH 2-CH=CH 2,-CH 2-C (CH 3)=CH 2Or-CH 2COOR 5In each of these groups, one or more hydrogen atoms can be substituted onto chemically feasible degree by the halogen atom such as fluorine, chlorine, bromine atoms.R 4Carbonatoms be preferably 1 to 18.R 5Represent hydrogen atom or alkyl.Preferably p is 1 to 18, and m is 1 to 36, and n is 0 or 1.
At R 1And R 4In, the example of alkyl and alkenyl comprises: methyl, ethyl, propyl group, sec.-propyl, n-butyl, sec-butyl, t-butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and oil base, the example of cycloalkyl and cycloalkenyl group comprises: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and ring octyl group.
To exemplify the monomer (I-a is to I-o) of the repeating unit that comprises above-mentioned formula (1) expression and the structure of polymkeric substance (II-a is to II-c) below, but spendable polyvinyl ether structure is not limited to these among the present invention.
Figure C20048000308900081
Figure C20048000308900091
The preferred amount of each repeating unit in the polyvinyl ether (that is m, n and 1 in the polymkeric substance that, exemplifies in the above (II-a) to (II-c)) is respectively 1 to 10000.More specifically, its sum (that is the m+n+1 in the polymkeric substance that, exemplifies in the above (II-a) to (II-c)) is 10 to 20000.Number-average molecular weight is preferably 500 to 20000000, and more preferably 1000 to 5000000, most preferably 2000 to 2000000.In addition, can also be according to being grafted to the form on other polymkeric substance or using these polyvinyl ethers with the form of other repeat unit structure copolymerizations.In addition, each block also can be the form of vinyl ether monomers and another monomeric multipolymer.
Synthesis technique for the multipolymer with Vinyl Ether polymer blocks has no particular limits.But, can suitably use cation activity polymerization method or other suitable methods such as (JP-A-11-322942 and JP-A-11-322866) of people's propositions such as Aoshima.Use the cation activity polymerization can synthesize multiple polymers, as homopolymer, by multipolymer, block polymer, graftomer and gradient polymer (graduationpolymer) that two or more monomers constitute, its length (molecular weight) is accurately controlled.In addition, on the side chain of these polyvinyl ethers, can also introduce multiple functional group.
In the present invention, use these segmented copolymers according to the mode of the acidic group that is wherein comprised with the alkali neutralization respectively.The content of alkali is such in the feasible final water-based ink that produces of the amount of the alkali that adjusting is added, when hypothesis with excessive alkali with segmented copolymer fully in the time formed ionic group ratio of infrared absorption intensity when being 100%, dissociate in the segmented copolymer ratio of infrared absorption intensity of formed ionic group of acidic group is at least 80%, and this content is no more than the twice of minimum that the ratio of infrared absorption intensity that makes ionic group is the alkali of required adding in 100% o'clock.The example of spendable alkali comprises sodium hydroxide, potassium hydroxide, lithium hydroxide and tetraalkylphosphoniuhydroxide hydroxide quaternary ammonium, preferred sodium hydroxide, potassium hydroxide and lithium hydroxide.
In the present invention, segmented copolymer preferably accounts for 0.001 to 40wt.% of ink gross weight, more preferably accounts for 0.01 to 20wt.%.The ratio of segmented copolymer produces the image that wear resistance etc. reduces during less than 0.001wt.%, and the ratio of segmented copolymer causes ink to have too high viscosity when being higher than 40wt.%, and jetting stability is reduced, and blocks as the nozzle place.
The example of the water-insoluble tinting material that uses among the present invention comprises known traditionally water-insoluble tinting material, for example: pigment, oil-soluble colourant, dispersed dye and vat pigment; And water-soluble dye, as substantive dyestuff, matching stain, basic dyestuff and reactive dyestuffs, make it pass through some processing and water insoluble.
(black pigment)
" Raven760Ultra ", " Raven1060Ultra ", " Raven1080Ultra ", " Raven1100Ultra ", " Raven1170 ", " Raven1200 ", " Raven1250 ", " Raven1255 ", " Raven1500 ", " Raven2000 ", " Raven2500Ultra ", " Raven3500 ", " Raven5250 ", " Raven5750 ", " Raven7000 ", " Raven5000Ultra II ", " Raven1190UltraII " (trade name, product of ColumbianCarbon company);
" Black Pearls L ", " MOGUL-L ", " Rega1400R ", " Rega1660R ", " Rega1330R ", " Monarch800 ", " Monarch880 ", " Monarch900 ", " Monarch1000 " " Monarch1300 ", " Monarch1400 " (trade name, product of Cabot company);
" Color Black FW1 ", " Color Black FW2 ", " Color BlackFW200 ", " Color Black 18 ", " Color Black S160 ", " ColorBlack S170 ", " Special Black 4 ", " Special Black 4A ", " SpecialBlack 6 ", " Special Black 550 ", " Printex 35 ", " Printex45 ", " Printex 55 ", " Printex 85 ", " Printex 95 ", " PrintexU ", " Printex 1400U ", " Printex V ", " Printex 140V " (trade name, product of Degussa AG);
" No.25 ", " No.33 ", " No.40 ", " No.45 ", " No.47 ", " No.52 ", " No.900 ", " No.970 ", " No.2200B ", " No.2300 ", " No.2400B ", " MCF-88 ", " MA600 ", " MA77 ", " MA8 ", " MA100 ", " MA220 ", " MA230 " (trade name, the product of Mitsubishi chemical company).
(blue pigments)
C.I.Pigment Blue (below be referred to as " PB ") 1, C.I.PB-2, C.I.PB-3, C.I.PB-15, C.I.PB-15:2, C.I.PB-15:3, C.I.PB-15:4, C.I.PB-16, C.I.PB-22, C.I.PB-60 etc.
(red pigment)
C.I.Pigment Red (below be referred to as " PR ")-5, C.I.PR-7, C.I.PR-12, C.I.PR-48, C.I.PR-48:1, C.I.PR-57, C.I.PR-112, C.I.PR-122, C.I.PR-123, C.I.PR-146, C.I.PR-168, C.I.PR-184, C.I.PR-202, C.I.PR-207 etc.;
(yellow ultramarine)
C.I.Pigment Yellow (below be referred to as " PY ")-12, C.I.PY-13, C.I.PY-14, C.I.PY-16, C.I.PY-17, C.I.PY-74, C.I.PY-83, C.I.PY-93, C.I.PY-95, C.I.PY-97, C.I.PY-98, C.I.PY-114, C.I.PY-128, C.I.PY-129, C.I.PY-151, C.I.PY-154 etc.;
(oil soluble yellow ultramarine)
C.I.Solvent Yellow (below be referred to as " SY ")-1, C.I.SY-2, C.I.SY-3, C.I.SY-13, C.I.SY-19, C.I.SY-21, C.I.SY-22, C.I.SY-29, C.I.SY-36, C.I.SY-37, C.I.SY-38, C.I.SY-39, C.I.SY-40, C.I.SY-43, C.I.SY-44, C.I.SY-45, C.I.SY-47, C.I.SY-62, C.I.SY-63, C.I.SY-71, C.I.SY-76, C.I.SY-81, C.I.SY-85, C.I.SY-86 etc.;
(oil soluble orchil)
C.I.Solvent Red (below be referred to as " SR ")-35, C.I.SR-36, C.I.SR-37, C.I.SR-38, C.I.SR-39, C.I.SR-40, C.I.SR-58, C.I.SR-60, C.I.SR-65, C.I.SR-69, C.I.SR-81, C.I.SR-86, C.I.SR-89, C.I.SR-92, C.I.SR-97, C.I.SR-99, C.I.SR-100, C.I.SR-109, C.I.SR-118, C.I.SR-119, C.I.SR-122 etc.;
(oil soluble blue dyes)
C.I.Solvent Blue (below be referred to as " SB ")-14, C.I.SB-24, C.I.SB-26, C.I.SB-34, C.I.SB-37, C.I.SB-39, C.I.SB-42, C.I.SB-43, C.I.SB-44, C.I.SB-45, C.I.SB-48, C.I.SB-52, C.I.SB-53, C.I.SB-55, C.I.SB-59, C.I.SB-67 etc.;
(oil soluble black dyes)
C.I.Solvent Black (below be referred to as " SBk ")-5, C.I.SBk-8, C.I.SBk-14, C.I.SBk-17, C.I.SBk-19, C.I.SBk-20, C.I.SBk-22, C.I.SBk-24, C.I.SBk-26, C.I.SBk-28, C.I.SBk-43 etc.;
(dispersed dye)
C.I.Disperse Yellow-88, C.I.Disperse Red-349, C.I.Disperse Blue-160, C.I.Disperse Black-1 etc.;
(vat yellow dyestuff)
C.I.Vat Yellow (below be referred to as " VY ")-2, C.I.VY-4, C.I.VY-10, C.I.VY-20, C.I.VY-33 etc.;
(urn orange dyestuff)
C.I.Vat Orange (below be referred to as " VO ")-1, C.I.VO-2, C.I.VO-3, C.I. solubilising VO-3, C.I.VO-5, C.I.VO-7, C.I.VO-9, C.I.VO-13, C.I.VO-15 etc.;
(urn red)
C.I.Vat Red (below be referred to as " VR ")-1, C.I.VR-2, C.I.VR-10, C.I.VR-13, C.I.VR-15, C.I.VR-16, C.I.VR-61 etc.;
(urn violet dyestuff)
C.I.Vat Violet (below be referred to as " VV ")-1, C.I.VV-2, C.I.VV-9, C.I.VV-13, C.I.VV-21 etc.;
(the blue dyestuff of father-in-law)
C.I.Vat Blue (below be referred to as " VB ")-1, C.I. solubilising VB-1, C.I.VB-3, C.I.VB-4, C.I.VB-5, C.I. solubilising VB-5, C.I.VB-6, C.I.VB-8, C.I.VB-12, C.I.VB-14, C.I.VB-18, C.I.VB-19, C.I.VB-20, C.I.VB-29, C.I.VB-35, C.I.VB-41 etc.;
(father-in-law's green dye)
C.I.Vat Green (below be referred to as " VG ")-1, C.I.VG-2, C.I.VG-3, C.I.VG-4, C.I.VG-8, C.I.VG-9 etc.;
(father-in-law's brown dye)
C.I.Vat Brown (below be referred to as " VBr ")-1, C.I.VBr-3, C.I.VBr-25, C.I.VBr-44, C.I.VBr-46 etc.;
(father-in-law deceives dyestuff)
C.I.Vat Black (below be referred to as " VBk ")-1, C.I.VBk-8, C.I.VBk-9, C.I.VBk-13, C.I.VBk-14, C.I.VBk-20, C.I.VBk-25, C.I.VBk-27, C.I.VBk-29, C.I.VBk-36, C.I.VBk-56, C.I.VBk-57, C.I.VBk-59, C.I.VBk-60 etc.;
(direct black dyes)
C.I.Direct Black (below be referred to as " DBk ")-17, C.I.DBk-19, C.I.DBk-22, C.I.DBk-32, C.I.DBk-38, C.I.DBk-51, C.I.DBk-62, C.I.DBk-71, C.I.DBk-108, C.I.DBk-146, C.I.DBk-154 etc.;
(directly yellow dye)
C.I.Direct Yellow (below be referred to as " DY ")-12, C.I.DY-24, C.I.DY-26, C.I.DY-44, C.I.DY-86, C.I.DY-87, C.I.DY-98, C.I.DY-100, C.I.DY-130, C.I.DY-142 etc.;
(directly red)
C.I.Direct Red (below be referred to as " DR ")-1, C.I.DR-4, C.I.DR-13, C.I.DR-17, C.I.DR-23, C.I.DR-28, C.I.DR-31, C.I.DR-62, C.I.DR-79, C.I.DR-81, C.I.DR-83, C.I.DR-89, C.I.DR-227, C.I.DR-240, C.I.DR-242, C.I.DR-243 etc.;
(sun blue dyestuff)
C.I.Direct Blue (below be referred to as " DB ")-6, C.I.DB-22, C.I.DB-25, C.I.DB-71, C.I.DB-78, C.I.DB-86, C.I.DB-90, C.I.DB-106, C.I.DB-199 etc.;
(direct orange dyestuff)
C.I.Direct Orange (below be referred to as " DO ")-34, C.I.DO-39, C.I.DO-44, C.I.DO-46, C.I.DO-60 etc.;
(substantive dyestuff) with color outside the above-mentioned color
C.I.Direct Violet-47, C.I.Direct Violet-48 etc.; C.I.Direct Brown-109, C.I.Direct Green-59 etc.;
(acid black dye)
C.I.Acid Black (below be referred to as " ABk ")-2, C.I.ABk-7, C.I.ABk-24, C.I.ABk-26, C.I.ABk-31, C.I.ABk-52, C.I.ABk-63, C.I.ABk-112, C.I.ABk-118, C.I.ABk-168, C.I.ABk-172, C.I.ABk-208 etc.;
(acid yellow dye)
C.I.Acid Yellow (below be referred to as " AY ")-11, C.I.AY-17, C.I.AY-23, C.I.AY-25, C.I.AY-29, C.I.AY-42, C.I.AY-49, C.I.AY-61, C.I.AY-71 etc.;
(acid red dye)
C.I.Acid Red (below be referred to as " AR ")-1, C.I.AR-6, C.I.AR-8, C.I.AR-32, C.I.AR-37, C.I.AR-51, C.I.AR-52, C.I.AR-80, C.I.AR-85, C.I.AR-87, C.I.AR-92, C.I.AR-94, C.I.AR-115, C.I.AR-180, C.I.AR-254, C.I.AR-256, C.I.AR-289, C.I.AR-315, C.I.AR-317 etc.;
(acid blue dye)
C.I.Acid Blue (below be referred to as " AB ")-9, C.I.AB-22, C.I.AB-40, C.I.AB-59, C.I.AB-93, C.I.AB-102, C.I.AB-104, C.I.AB-113, C.I.AB-117, C.I.AB-120, C.I.AB-167, C.I.AB-229, C.I.AB-234, C.I.AB-254 etc.;
(matching stain) with color except that above-mentioned color
C.I.Acid Orange-7, C.I.Acid Orange-19, C.I.AcidViolet-49 etc.;
(basic black or red)
C.I.Acid Black-2 etc.; C.I.Basic Red (below be referred to as " BR ")-1, C.I.BR-2, C.I.BR-9, C.I.BR-12, C.I.BR-13, C.I.BR-14, C.I.BR-27 etc.;
(alkali blue dyestuff)
C.I.Basic Blue (below be referred to as " BB ")-1, C.I.BB-3, C.I.BB-5, C.I.BB-7, C.I.BB-9, C.I.BB-24, C.I.BB-25, C.I.BB-26, C.I.BB-28, C.I.BB-29 etc.;
(basic dyestuff) with the color except that above-mentioned color
C.I.Basic Violet-7, C.I.Basic Violet-14, C.I.BasicViolet-27 etc.; C.I.FoodBlack-1, C.I.FoodBlack-2 etc.;
(reactive black dye)
C.I.Reactive Black (below be referred to as " RBk ")-1, C.I.RBk-5, C.I.RBk-8, C.I.RBk-13, C.I.RBk-14, C.I.RBk-23, C.I.RBk-31, C.I.RBk-34, C.I.RBk-39 etc.;
(Yellow reactive dyes)
C.I.Reactive Yellow (below be referred to as " RY ")-2, C.I.RY-3, C.I.RY-13, C.I.RY-15, C.I.RY-17, C.I.RY-18, C.I.RY-23, C.I.RY-24, C.I.RY-37, C.I.RY-42, C.I.RY-57, C.I.RY-58, C.I.RY-64, C.I.RY-75, C.I.RY-76, C.I.RY-77, C.I.RY-79, C.I.RY-81, C.I.RY-84, C.I.RY-85, C.I.RY-87, C.I.RY-88, C.I.RY-91, C.I.RY-92, C.I.RY-93, C.I.RY-95, C.I.RY-102, C.I.RY-111, C.I.RY-115, C.I.RY-116, C.I.RY-130, C.I.RY-131, C.I.RY-132, C.I.RY-133, C.I.RY-135, C.I.RY-137, C.I.RY-139, C.I.RY-140, C.I.RY-142, C.I.RY-143, C.I.RY-144, C.I.RY-145, C.I.RY-146, C.I.RY-147, C.I.RY-148, C.I.RY-151, C.I.RY-162, C.I.RY-163 etc.;
(active red dye)
C.I.Reactive Red (below be referred to as " RR ")-3, C.I.RR-13, C.I.RR-16, C.I.RR-21, C.I.RR-22, C.I.RR-23, C.I.RR-24, C.I.RR-29, C.I.RR-31, C.I.RR-33, C.I.RR-35, C.I.RR-45, C.I.RR-49, C.I.RR-55, C.I.RR-63, C.I.RR-85, C.I.RR-106, C.I.RR-109, C.I.RR-111, C.I.RR-112, C.I.RR-113, C.I.RR-114, C.I.RR-118, C.I.RR-126, C.I.RR-128, C.I.RR-130, C.I.RR-131, C.I.RR-141, C.I.RR-151, C.I.RR-170, C.I.RR-171, C.I.RR-174, C.I.RR-176, C.I.RR-177, C.I.RR-183, C.I.RR-184, C.I.RR-186, C.I.RR-187, C.I.RR-188, C.I.RR-190, C.I.RR-193, C.I.RR-194, C.I.RR-195, C.I.RR-196, C.I.RR-200, C.I.RR-201, C.I.RR-202, C.I.RR-204, C.I.RR-206, C.I.RR-218, C.I.RR-221 etc.;
(reactive blue dye)
C.I.Reactive Blue (below be referred to as " RB ")-2, C.I.RB-3, C.I.RB-5, C.I.RB-8, C.I.RB-10, C.I.RB-13, C.I.RB-14, C.I.RB-15, C.I.RB-18, C.I.RB-19, C.I.RB-21, C.I.RB-25, C.I.RB-27, C.I.RB-28, C.I.RB-38, C.I.RB-39, C.I.RB-40, C.I.RB-41, C.I.RB-49, C.I.RB-52, C.I.RB-63, C.I.RB-71, C.I.RB-72, C.I.RB-74, C.I.RB-75, C.I.RB-77, C.I.RB-78, C.I.RB-79, C.I.RB-89, C.I.RB-100, C.I.RB-101, C.I.RB-104, C.I.RB-105, C.I.RB-119, C.I.RB-122, C.I.RB-147, C.I.RB-158, C.I.RB-160, C.I.RB-162, C.I.RB-166, C.I.RB-169, C.I.RB-170, C.I.RB-171, C.I.RB-172, C.I.RB-173, C.I.RB-174, C.I.RB-176, C.I.RB-179, C.I.RB-184, C.I.RB-190, C.I.RB-191, C.I.RB-194, C.I.RB-195, C.I.RB-198, C.I.RB-204, C.I.RB-211, C.I.RB-216, C.I.RB-217 etc.;
(active orange dye)
C.I.Reactive Orange (below be referred to as " RO ")-5, C.I.RO-7, C.I.RO-11, C.I.RO-12, C.I.RO-13, C.I.RO-15, C.I.RO-16, C.I.RO-35, C.I.RO-45, C.I.RO-46, C.I.RO-56, C.I.RO-62, C.I.RO-70, C.I.RO-72, C.I.RO-74, C.I.RO-82, C.I.RO-84, C.I.RO-87, C.I.RO-91, C.I.RO-92, C.I.RO-93, C.I.RO-95, C.I.RO-97, C.I.RO-99 etc.;
(reactive violet rowland dyestuff)
C.I.Reactive Violet (below be referred to as " RV ")-1, C.I.RV-4, C.I.RV-5, C.I.RV-6, C.I.RV-22, C.I.RV-24, C.I.RV-33, C.I.RV-36, C.I.RV-38 etc.;
(active green dye)
C.I.Reactive Green (below be referred to as " RG ")-5, C.I.RG-8, C.I.RG-12, C.I.RG-15, C.I.RG-19, C.I.RG-23 etc.;
(active palm dye)
C.I.Reactive Brown (below be referred to as " RBr ")-2, C.I.RBr-7, C.I.RBr-8, C.I.RBr-9, C.I.RBr-11, C.I.RBr-16, C.I.RBr-17, C.I.RBr-18, C.I.RBr-21, C.I.RBr-24, C.I.RBr-26, C.I.RBr-31, C.I.RBr-32, C.I.RBr-33 etc.
Tinting material preferably accounts for 0.1 to 20wt.% of ink gross weight, more preferably accounts for 1 to 10wt.%.The ratio of tinting material can not form the print image with any enough colour densities during less than 0.1wt.%, and the ratio of tinting material can cause that jetting stability reduces during greater than 20wt.%, as: the nozzle place blocks, but colour density does not increase basically.
Water-based ink according to the present invention comprises water as main liquid medium, but it can comprise one or more water-soluble organic mediums in addition.When ink according to the present invention was used in the ink-jet printer, these organic mediums were used for preventing solidifying at nozzle segment owing to ink dried causes ink.The object lesson of these organic mediums comprises such as alcohol Virahol and the butanols; Such as: ethylene glycol, glycol ether, triglycol, Tetraglycol 99, propylene glycol, dipropylene glycol, trimerization propyl alcohol, 1,2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, thiodiglycol, neopentyl glycol, 1, the glycol of 4-cyclohexanediol and polyoxyethylene glycol; The alkylene glycol monoalky lether, as: glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl isopropyl ether, ethylene glycol monoalkyl ether, diglycol monotertiary methyl ether, carbiphene, diglycol monotertiary butyl ether, triglycol monomethyl ether, triglycol list ethyl ether, propylene glycol monomethyl ether dipropyl (support) glycol monomethyl ether; Such as: glycerol, 1,2,4-trihydroxybutane, 1,2,5-pentan-thiol, 1,2, the polyvalent alcohol of 6-hexylmercaptan, trimethylolethane, TriMethylolPropane(TMP) and tetramethylolmethane; Such as: tetrahydrofuran (THF) is with the cyclic ethers of diox; And methyl-sulphoxide, Pyranton, glycerol monoalkyl ether, N-N-methyl-2-2-pyrrolidone N-, 2-Pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidone, tetramethylene sulfone, urea, β-dihydroxy ethyl urea, hexanedione, DIMETHYL FORMAMIDE, dimethyl acetamide and phenoxyethyl alcohol.
These organic mediums can be solid or liquid, as long as its water soluble.Even, wish that its boiling point is higher than the boiling point of water, promptly for example: 120 ℃ or higher owing under the condition of water evaporation, also require these organic mediums to be retained in the ink.But, these organic mediums need not be confined to high boiling medium, because they and segmented copolymer interact, and more are not easy to volatilize during than its independent heating.
These organic mediums can separately or be used in combination.These organic mediums can account for 5 to 50wt.% of ink gross weight, preferably account for 10 to 30wt.%.In addition, except mentioned component, can in ink of the present invention, add multiple additives, as: tensio-active agent, pH regulator agent, antioxidant and mould inhibitor.
Can be by in predetermined liquid medium, adding tinting material and segmented copolymer, and applying under hyperacoustic condition or in dispersion agent, it is being carried out so making ink of the present invention such as the dispersion treatment pearl mill or the ball milling.
Ink of the present invention can suitably be used in by applying energy to ink, ink is dispersed, thereby implements in the ink jet recording method of record.Can use heat energy or mechanical energy as energy.But, the particularly preferred heat energy that is to use.
The ink-vapor recording printer of described use ink of the present invention comprises the average family printer of main use A4 size paper, specially for printing printer and the commercial large-scale printer that business card and other cards design.The large-scale printer that ink of the present invention is specially adapted to need assurance hi-vision fastness and uses a large amount of inks.
The example of the recording medium that available ink according to the present invention writes down does not in the above apply ink jetting paper, postcard or the namecard, label paper, corrugated cardboard and the ink-jet film that scribble the ink receiving layer on the so-called common paper of specific coatings, at least one side above comprising.
Embodiment
The various details specific embodiment.But, notice that the present invention is subjected to the restriction of following example absolutely not.In example, unless otherwise indicated, otherwise all implications of " part " and " % " are all based on weight.
(1) ABC triblock copolymer (polymkeric substance 1) is synthetic
Have the Glass Containers of threeway neck with nitrogen purge, then under nitrogen atmosphere 250 ℃ of heating, to remove any planar water.With system cools after room temperature, the 1-IVE of packing into (12mmol), ethyl acetate (16mmol), 1-isobutoxy ethyl acetate (0.1mmol) and toluene (11mL).When the internal temperature of system is cooled to 0 ℃, add tri-chlorination two aluminium (aluminum sesquichloride, 0.2mmol) so that initiated polymerization, and the A segment of synthetic triblock copolymer.
Use gel infiltration column chromatography (GPC, " HLC-8220 ", trade name; Make by TOSOH company), according to time-sharing format monitoring molecular weight.After the A segment is finished polymerization, add 2-acetyl Vinyl Ether (12mmol), cause that the B segmental is synthetic.Use GPC according to mode same as described above, add ethyl 4 (2-ethylene oxy oxyethyl group) benzene (first) acid esters (10mmol), synthetic C segment by after monitoring polymerization, confirming the complete polymerization of B segment.By with in the 0.3% ammonia soln adding system in the methyl alcohol, finish polyreaction.
Use nuclear magnetic resonance spectrometer (NMR, " DPX 400 ", trade name; Make by Bruker BioSpin company) and the triblock copolymer that generated of GPC evaluation.These two kinds of analytical procedures all demonstrate has synthesized target substance satisfactorily.Proofread and correct the estimation of being done based on polystyrene standard, the number-average molecular weight of the triblock copolymer that is obtained (Mn) is 30000, and the ratio (Mw/Mn) of weight-average molecular weight (the Mw)/number-average molecular weight (Mn) of expression molecular distribution is 1.3.
In the mixed solvent of sodium hydroxide (5-times of equivalent) and methyl alcohol, the ether moiety hydrolysis in the triblock copolymer in the C segment distills solvent afterwards, obtains carboxylic acid polyalcohol.
(2) synthetic (polymkeric substance 2) of AB Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock
Have the Glass Containers of threeway neck with nitrogen purge, then under nitrogen atmosphere 250 ℃ of heating, to remove any planar water.With system cools after room temperature, the 1-isobutyl vinyl ether (12mmol) of packing into, ethyl acetate (16mmol), 1-isobutoxy ethyl acetate (0.1mmol) and toluene (11mL).When the internal temperature of system is cooled to 0 ℃, add tri-chlorination two aluminium (0.2mmol) so that initiated polymerization, and the A segment of synthetic Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock.
Use gel infiltration column chromatography (GPC, " HLC-8220 ", trade name; Make by TOSOH company), according to time-sharing format monitoring A segmental molecular weight.After the A segment is finished polymerization, add 2-(ethoxycarbonyl) ethyl vinyl ether (10mmol), cause that the B segmental is synthetic.By with in the 0.3% ammonia soln adding system in the methyl alcohol, finish polyreaction.Use nuclear magnetic resonance spectrometer (NMR, " DPX 400 ", trade name; Make by Bruker BioSpin company) and the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock that generated of GPC evaluation.These two kinds of analytical procedures all demonstrate has synthesized target substance satisfactorily.Proofread and correct the estimation of being done based on polystyrene standard, the number-average molecular weight of the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock that is obtained (Mn) is 25000, and the ratio (Mw/Mn) of weight-average molecular weight (the Mw)/number-average molecular weight (Mn) of expression molecular distribution is 1.3.
In the mixed solvent of sodium hydroxide (5-times of equivalent) and methyl alcohol, the ether moiety hydrolysis in the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock in the B segment distills solvent afterwards, obtains carboxylic acid polyalcohol.
(3) measurement of the degree of neutralization of segmented copolymer
These two kinds of segmented copolymers are dissolved into 2% concentration respectively in tetrahydrofuran (THF).Subsequently, add aqueous sodium hydroxide solution, a droplet of every kind of solution is placed on the calcium fluoride mono crystal sheet, dry afterwards, and by infrared absorption spectrometer (" FT/IR5300 ", trade name; Make by JASC0 company) measure its infrared absorption spectrum.On each of two kinds of segmented copolymers, through observing the 1547cm that is absorbed as that carboxylic ions caused -1
According to 1119cm so that ether group was produced -1Ratio of infrared absorption intensity be the relative intensity of two kinds of segmented copolymers determining of standard, the ratio of infrared absorption intensity that carboxylic ions caused between them relatively.In addition, suppose fully in the time carboxylic ions relative ratio of infrared absorption intensity be 100%, the relative ratio of infrared absorption intensity and the ratio of above-mentioned relative ratio of infrared absorption intensity that carboxylic ions produced in every kind of sample is defined as the degree of neutralization of this sample.
(4) preparation of ink
By using in the aqueous sodium hydroxide solution of 0.1N and corresponding triblock copolymer or Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock (1 part), institute's neutral multipolymer and corresponding tinting material (1 part) are added N, dinethylformamide (19 parts), in the mixture that is produced, add entry, it is 20 parts that water in described water and the aqueous sodium hydroxide solution is combined, and removes N by Rotary Evaporators, dinethylformamide, add glycol ether (2 parts) and glycerine (2 parts) then, the water-based ink shown in the preparation table 1.
Table 1
Polymkeric substance Tinting material The amount * of alkali Degree of neutralization (%)
Ink 1 1 C.I.Solvent Blue 44 0.5 80
Ink 2 1 C.I.Solvent Blue 44 1 100
Ink 3 1 C.I.Solvent Blue 44 1.25 100
Ink 4 1 C.I.Solvent Blue 44 1.5 100
Ink 5 1 C.I.Solvent Blue 44 2 100
Ink 6 1 C.I.Solvent Yellow 21 0.5 80
Ink 7 1 C.I.Solvent Yellow 21 1 100
Ink 8 1 C.I.Solvent Yellow 21 1.25 100
Ink 9 1 C.I.Solvent Yellow 21 2 100
Ink 10 1 Carbon Black MA8 0.5 80
Ink 11 1 Carbon Black MA8 1 100
Ink 12 1 Carbon Black MA8 1.25 100
Ink 13 1 Carbon Black MA8 2 100
Ink 14 2 C.I.Solvent Blue 44 0.5 80
Ink 15 1 C.I.Solvent Blue 44 0.25 65
Ink 16 1 C.I.Solvent Blue 44 2.25 100
Ink 17 1 C.I.Solvent Blue 44 2.5 100
Ink 18 1 C.I.Solvent Yellow 21 0.25 65
Ink 19 1 C.I.Solvent Yellow 21 2.5 100
Ink 20 1 Carbon Black MA8 0.25 65
Ink 21 1 Carbon Black MA8 0.125 30
Ink 22 1 Carbon Black MA8 2.25 100
Ink 23 1 Carbon Black MA8 2.5 100
Ink 24 2 C.I.Solvent Blue 44 0.33 70
Ink 25 2 C.I.Solvent Blue 44 2.5 100
* hypothesis realizes that the required minimum alkali number of 100% degree of neutralization is 1, expresses the amount of the alkali of actual adding.
(classification)
Water-based ink shown in the table 1 1～25 is placed at least 4 week under 60 ℃, and measures the size of particles of its tinting material by the dynamic light scattering method.The result, use the ink of vinyl ether segmented copolymer to have high dispersion stability as shown in fig. 1 as can be known, and particularly when the amount of the degree of neutralization of segmented copolymer and the alkali that added is among the present invention within the specified respective range, can realize more stable dispersion.
Utilizability on the industry
Can find out that from top description the present invention can be provided for the water-based ink of ink-jet printer, it is the colorant particle decentralized, and storage stability is excellent, and the printing of hi-vision fastness (such as water proofing property, light resistance and anti-gaseousness) is provided.

Claims (4)

1. water-based ink that is used for ink-jet printer, described water-based ink comprises at least a water-insoluble tinting material, the segmented copolymer that comprises the polyvinyl ether structure of at least a hydrophilic segment and at least a hydrophobic segment, each hydrophilic segment comprises acidic group, this water-based ink also comprises water and alkali, it is characterized in that, the content of described alkali is as follows: when the ratio of infrared absorption intensity of the ionic group that forms when hypothesis adds excess base in segmented copolymer is 100%, the ratio of infrared absorption intensity of the ionic group that the disassociation of the acidic group that is comprised in the segmented copolymer forms is at least 80%, and restricted condition is that the ratio of infrared absorption intensity that described content is no more than the ionic group that segmented copolymer forms is the twice of the minimum of 100% o'clock alkali.
2. water-based ink according to claim 1, the acidic group that is comprised in the wherein said segmented copolymer is a carboxyl.
3. water-based ink according to claim 1 and 2, wherein said tinting material are pigment.
4. water-based ink according to claim 1 and 2, wherein said tinting material are the water-insoluble dyestuff.
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