CN1223276A - Block copolymers of oxazolines and oxazines as pigment dispersants and their use in ink jet inks - Google Patents
Block copolymers of oxazolines and oxazines as pigment dispersants and their use in ink jet inks Download PDFInfo
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- CN1223276A CN1223276A CN 98122643 CN98122643A CN1223276A CN 1223276 A CN1223276 A CN 1223276A CN 98122643 CN98122643 CN 98122643 CN 98122643 A CN98122643 A CN 98122643A CN 1223276 A CN1223276 A CN 1223276A
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Abstract
Aqueous dispersions having improved stability and which are particularly well suited for use as aqueous ink jet ink compositions comprise an aqueous vehicle which comprises water or a mixture of water and an organic solvent; a particulate solid, preferably a pigment; and a polyoxazoline or polyoxazine dispersant selected from the group of AB, ABA, and BAB block copolymers wherein the A block is hydrophobic, and the B block is hydrophilic, and wherein the polymer as a whole has a solubility in the aqueous vehicle of at least 0.1 wt % at 25 DEG C.
Description
The present invention relates to have the water dispersion of excellent stability, particularly the application of this dispersion on ink-jet printer in water-base pigment printing ink.
Water-based pigment dispersions is known in the art, its widely with various films such as application of paints on various matrix.Usually use nonionic or ion technology to stablize this pigment dispersion.When using the nonionic technology, stablizing of this pigment particles undertaken by a kind of polymkeric substance, and this polymkeric substance has water miscible hydrophilic segment, and this hydrophilic segment extends in the water and provides entropy or spatial stability.The typical polymers that is used for this purpose comprises polyvinyl alcohol, Mierocrystalline cellulose, the phenols of oxyethane modification, ethylene oxide/propylene oxide polymkeric substance.When the nonionic technology changes pH or particle pollution when insensitive, concerning many application, its topmost defective is that final product is responsive to water.Like this, if be used for application such as printing ink, this printing ink will be tending towards being coated in exposure place of moisture.In the particle technology, the stable of this pigment particles is that the ionic polymer of toxilic acid or vinyl sulfonic acid carries out by a kind of monomer neutral vinylformic acid that contains.This polymkeric substance provides stable by charged double-deck mechanism, and this mechanism is to repel by ionic to hinder the particle flocculation.Because in and component after application, be tending towards the evaporation, the water-soluble reduction of this polymkeric substance, final product is insensitive to water.It is desirable to,, can provide the polymeric dispersant of space and charged double-deck stabilizing power can prepare the pigment dispersion of powerful vitality by the structure of setting.
It is known having random and polymeric dispersant block structure.The unregulated polymer dispersion agent can prepare easily and at an easy rate by the polymerization technique of routine, and it can be by obtaining on many markets.Compare with unregulated polymer, the structural polymer dispersion agent provides improved dispersion stability usually, but under cationoid polymerisation and groups converted polymeric situation, needs more processing synthetic schemes usually or need more reaction conditions and highly purified raw material.A kind ofly for improving characteristic certain structure being established to easier and cheap polymerization process in this polymkeric substance, for more advanced high quality coating application with satisfy the needs of many novel fields such as ink-jet printer, is desired.
Spray ink Printing is a kind of non-impact Method of printing, and wherein numerary signal produces the printing ink dropping liquid on medium such as paper or transparent film.In thermal inkjet-printing, thermal resistance is used with evaporation printing ink, discharges its hole on from the spray ink Printing head to this matrix.Ignition process known to Here it is, wherein water is by heat of vaporization, makes residing component and temperature rapidly and degree of depth ground changes and raises.At the life period of printhead, repeat to this situation high frequency.In the zone in hole, this printing ink component can carry out the variation of the degree of depth from the rich solvent that Fu Shuizhi forms based on evaporation of water.This can make the pigment particles flocculation around printhead orifices, finally causes the hole plug of drop from the printer organization of wherein discharging of printing ink.This will cause the printing ink drippage or prevent the mistake that drop is discharged.
In the application of routine,, use the additive of many organic traits to give desired physical properties for final application.Its example comprises polymer binder, thickening material, and thixotropic agent applies auxiliary agent etc.In drying process, carry these components dense.For final coating, for keeping the quality of homogeneity and color, this pigment dispersion need adapt to variation like this.
Correspondingly, need such dispersion agent: it can obtain by easy and cheap polymerization process, and for the improvement coating quality with for a kind of new purposes such as ink-jet printer, it will provide improved dispersion stability.
One aspect of the present invention provides a kind of water dispersion that improves characteristic that has, and comprising:
(a) aqueous carrier,
(b) granular solids,
(c) the polymeric dispersion agent is selected from AB, ABA and BAB segmented copolymer, and wherein the A block is hydrophobic, and the B block is hydrophilic, and the solubleness of wherein whole polymkeric substance in aqueous carrier is 0.1wt% at least in the time of 25 ℃;
(d) this polymeric dispersant is made up of monomer, and this monomer selects from the oxazoline monomer, oxazine monomer and composition thereof.
Water dispersion of the present invention is stable, containing the mixable organic cosolvent of water, aqueous additive such as thickening material, has wide matching in the latex emulsion, very pliable and tough, can be to the drying of system variation as coating, the ignition condition of thermal ink jet printers is regulated, show good resistance flocculence, obtained high colour intensity and gloss.
The main component of water dispersion of the present invention is (1) aqueous carrier; (2) granular solids; (3) Ju oxazoline Huo Ju oxazine dispersion agents.Depend on the concrete application of dispersion purposes, can have various other additives, as wetting agent, viscosity modifier, membrane-forming agent, cosolvent, thixotropic agent, tackiness agent applies auxiliary agent etc.Aqueous carrier
The variation of the composition of aqueous carrier will be depended on the final use of this dispersion.Certainly, aqueous carrier always contains water, is typically deionized water.Use for great majority, aqueous carrier comprises at least a water-soluble or mixable organic solvent of water simultaneously.Suitable choice of Solvent is depended on the needs of concrete application, surface tension and viscosity as expected, selected granular solids etc.
Use for jetted ink, aqueous carrier comprises the mixture of a kind of water and organic solvent.The exemplary of suitable solvent is disclosed in US 5,085, in 698, its disclosed content is incorporated in this is for reference.For hot jetted ink, most preferably a kind of have the organic solvent of at least 2 hydroxyls such as Diethylene Glycol and a mixture of deionized water, and wherein, based on all wts of printing ink, the content of water is 30～95wt%, preferred 60～95wt%.Granular solids
Be used for granular solids of the present invention and can be pigment, colloid silver halide, sheet metal, weedicide, sterilant, or biomaterial such as medicine etc.Selected concrete granular solids must can with the hydrophobic block bonding in the segmented copolymer.Preferably, granular solids can have can with " the bonding position " of this polymer-bound.Most above-mentioned granular solids all have very special functional group in its surface, and these functional groups can be used as the bonding position.
For the application on jetted ink or coating, granular solids is the mixture of a kind of pigment or two or more pigment.This term " pigment " refers to the tinting material that keeps with particle or crystal form in print procedure.All carbon blacks on its surface chemisorption oxygen complex, mainly be tart in nature, as carboxylic acid, quinone, lactonic acid or phenolic group group, the degree of its absorption depends on working condition.These acidic-groups on surface of pigments provide the bonding position for the dispersion agent that has basic functionality such as amine.Other has the pigment of acidic surface or basic surface, and the pigment or its surface that itself contain functional group have been contained functional group such as sulfonic acid, and phosphoric acid and hydroxy-acid group or basic group are that the compound modified pigment of amine type all can be used for the present invention.
And nearly all organic coloured pigment and many surface treatment compounds have aromatic character on its structure, provide additional aromatics and dispersion agent interactional position.The example that can be used to form the pigment of said composition comprises azo, anthraquinone, thioindigo oxazine, quinacridone (quinacridone), the color lake and the toner of matching stain material or basic dyestuff material, copper phthalocyanine and derivative thereof, and various mixture and improvement thing thereof.
The stability of the size impact dispersion of granular solids.The pedesis of fine particle will help to prevent particle flocculation and sedimentation.Like this, select special size of particles so that dispersion obtains optimum stabilization, and satisfy the special requirement in use of this dispersion.
In jetted ink, pigment particles needs enough little, so that through inkjet-printing device, especially can unrestricted flow at the printing ink of the discharge nozzle that has 10～50 microns of diameters usually.In addition, also wish to use small-particle to improve colour intensity and gloss to greatest extent.Size of particles is generally about 0.005～15 micron.Preferably, pigment particle size is 0.005～1 micron.Also can use the fine particle of metal or metal oxide (as copper, iron, steel, aluminium, silicon-dioxide, aluminum oxide, titanium dioxide etc.) to implement the present invention, and can find in magnetic jetted ink preparation application and in electronic industry other is coated with the application that is covered with.The Ju oxazoline is with the Ju oxazine
Being used for Ju oxazoline Huo Ju oxazine dispersion agent of the present invention is AB, ABA, or BAB segmented copolymer, wherein the A block is hydrophobic, the B block is hydrophilic, and the solubleness of wherein whole polymkeric substance in aqueous carrier is 0.1wt% at least in the time of 25 ℃, preferably is 0.5wt% at least in the time of 25 ℃.
In general, when substituting group is a kind of low alkyl group (as methyl, ethyl) or when containing hydrophilic radical (as ether, hydroxyl), 2-replaces De oxazoline and 2-, and to replace the De oxazine be hydrophilic.Similarly, when substituting group is a kind of chain alkyl, aryl or similarly during hydrophobic grouping, these compounds are hydrophobic.Be somebody's turn to do poly-oxazoline and poly-oxazine polymkeric substance and have following general formula (its Chinese style A represents the A block, and formula B represents the B block):
Wherein
X is 1～100, preferred 1～10;
Y is 5～500, preferred 5～100;
Y/x is 5～100, preferred 5～50;
Z is by formula R
3(L)
rThe divalent linker of expression, wherein R
3Be alkylidene group or the arylidene that contains 2～10 carbon atoms, L is O, S, C (O), OC (O), (O) CO, SC (O), or SO
2Group, r=0 or 1; M and p are integer 2 (oxazolines independently) or 3 (oxazines);
N=0 or 1;
R
1For containing the alkyl of 4～20 carbon atoms, aryl, aralkyl, or alkaryl;
R
2For containing the alkyl that 1～3 carbon atom also can randomly contain one or more hydroxyls or ether group.
Be noted that it (is R that this hydrophobic A block can contain hydrophilic monomer
1Can be to contain 1～3 carbon atom alkyl), (be R and hydrophilic B block can contain hydrophobic monomer
2Can be the alkyl that contains 3～30 carbon atoms, aralkyl, aryl or alkaryl).Yet, it should be noted that whole A block keeps hydrophobic, it is hydrophilic that whole B block keeps, and the solubleness of whole dispersion agent is 0.1wt% at least in the time of 25 ℃.
The Ju oxazine is used for Qian Duan Ju oxazoline of the present invention with can be prepared easily by well known to a person skilled in the art the whole bag of tricks.For example, can be described in Prog.Polvm.Sci:Vol.15 by use, 751-823, the method in 1990, following monomer is carried out cationoid polymerisation and gets:
Z wherein, R
1, R
2, the definition of m and p as above, n=0 or 1.Effectively initiator comprises (ⅰ) Lewis acid and stable salt such as BF thereof
3OEt, AlCl
3, SbF
5And Et
3O
+BF
4 -(ⅱ) protonic acid such as CF
3SO
3H, HClO
4And HBr; (ⅲ) sulphonate and sulphonic acid anhydride such as CF
3SO
3CH
3(CH
3SO
2)
2O; (ⅳ) alkyl halide such as CH
3I and C
6H
5CH
2Br; (ⅴ) electron acceptor such as tetracyanoethylene and 7,7,8,8 ,-tetracyano-p-quinodimethane (tetracyanoquinodimethane).
The AB segmented copolymer can wherein, because cationoid polymerisation is a kind of living polymerization process, after the first block monomer really changes into polymkeric substance, join the second block monomer in the same reactor by " still two step copolymerization " preparation.The AB segmented copolymer also can be by " still one step copolymerization " preparation, and wherein all monomers join in the reactor at one time, and condition is that monomeric activity is obviously different in two blocks.The preparation of ABA and BAB triblock copolymer can be under two functional initiator, by being undertaken by the initial two-stage polymerization process of mid-block, or are undertaken by multistep technology, and wherein this block is to form in proper order from an end.This polymerization can body or the solution form carry out.
For the polymkeric substance of x=1 wherein, initiator such as benzyl bromide with hydrophobic grouping can be used for polymerization 2-alkyl-2-oxazoline to obtain desired AB segmented copolymer.Hydrophilic B block also can at first synthesize, and hydrophobic then nucleophilic compound such as benzyl amine stop active end, and obtain hydrophobic A block.
For the application on jetted ink, the number-average molecular weight that is preferred for Ju oxazoline Huo Ju oxazine of the present invention is lower than 20,000, preferably is lower than 15,000, usually 1,000～6, and 000.Content based on whole ink composite ， Ju oxazoline Huo Ju oxazines is about 0.1～10wt%, preferred about 0.1～5wt%.If the amount of this polymkeric substance is too high, ink colors intensity can not be accepted, and will to keep desirable ink viscosity will be difficult.
For the application of others, the technician by this Application Areas determines to molecule quantitative limitation (if having) and dispersion agent available concentration.Other composition
The needs that depend on concrete application can use various types of additives to improve the character of this dispersion.Example comprises organic cosolvent, and coalescing agent comprises that water-soluble polymers and water can disperse the polymeric binder of latex emulsion, thickening material, and thixotropic agent, tensio-active agent applies auxiliary agent, biocides, sequestrant etc.
For the application of this dispersion on jetted ink, negatively charged ion, positively charged ion, nonionic or amphoterics, based on the weight of whole printing ink, its consumption is 0.01～5, preferred 0.2～2%.Biocides such as Dowicides (Dow Chemical, Midland, MI), Nuosept (Huls America, Inc; Piscataway, NJ), Omidines (Olin Corp; Cheshire, CT), Nopcocides (Henkel Corp; Ambler, PA), Troysans (Troy Chemical Corp; Newark, NJ) and Sodium Benzoate; Sequestrant such as EDTA; Other known additive such as wetting agent, viscosity modifier and other polymkeric substance also can add to improve the various performances of ink composite.
In preferred embodiments, this dispersion is as the pigment dispersion of aqueous ink jet ink composition, and it can be prepared by well known to a person skilled in the art any ordinary method.The representative formula of inkjet ink composition is:
Aqueous carrier: when selecting pigment dyestuff,, be 70～99.8% based on all wts of printing ink, preferred about 94～99.8%; When selecting mineral dye, about 25～99.8%, preferred 70～99.8%;
Pigment: for pigment dyestuff, be 0.1～30wt% pigment, but, be generally about 0.1～15%, preferred about 0.1～8% based on the weight of whole ink composites; For mineral dye (having high specific weight), be generally higher weight percentage.
Polymer dispersant: based on the weight of whole ink composites, be about 0.1～10wt%, preferred about 0.1～5wt%.
The surface tension that the pigment inkjet ink that is fit to use with ink-jet print system has is about 20dyne/cm～about 70dyne/cm, more preferably 30dyne/cm～70dyne/cm in the time of 20 ℃.Acceptable viscosity in the time of 20 ℃ for being not more than 20cP, preferred about 1.0～10.0cP.
Embodiment polymkeric substance I: poly-(2-ethyl-2-oxazoline)-b-poly-(2-phenyl-2-oxazoline)
The orthodichlorobenzene of 100ml and the N-methyl of 1.25gm (5mmol)-2-methyl-2-oxazoline triflate under argon gas atmosphere, are placed dry round-bottomed flask, and this flask is furnished with the air operated glassed agitator, reflux exchanger and dropping funnel.This flask places 100 ℃ oil bath, adds the 2-ethyl-2-oxazoline of 30mL (295mmol) then.Under this temperature, reaction mixture was stirred 4 hours.Then, add 2-phenyl-2-oxazoline of 4mL (30mmol), this mixture stirs under same temperature and spends the night.Temperature risen to 130 ℃ in second day, continue reaction again and finished this polymerization in 8 hours.After cool to room temperature, this reaction mixture dilutes with methylene dichloride, is deposited in the ether then.The polymkeric substance that elimination obtains, with the ether washing, then in vacuum chamber in 50 ℃ of following dried overnight.Its output is the 40.3gm polymkeric substance.
1HNMR shows to have the ethyl/phenyl of 10/1 ratio in this polymkeric substance.GPC (in THF, being standard): Mn=4850, Mw=7070 with the polystyrene.Polymkeric substance II: poly-(2-the ethyl-2-oxazoline)-b-of poly-(2-phenyl-2-oxazoline)-b-poly-(2-phenyl-2-oxazoline)
The xylene monosulfonic acid glycol ester of 100ml solvent orthodichlorobenzene and 1.90gm (5mmol) under argon gas atmosphere, is placed dry round-bottomed flask, and this flask is furnished with the air operated glassed agitator, reflux exchanger and rubber septum.This flask places 100 ℃ oil bath, adds the 2-ethyl-2-oxazoline of 30mL (295mmol) then.Under this temperature, reaction mixture was stirred 4 hours.Then, add 2-phenyl-2-oxazoline of 4mL (30mmol), temperature is risen to 130 ℃ then.After this reaction mixture of stirring 3 hours, this temperature is reduced to 100 ℃, this mixture under agitation spends the night.After cool to room temperature, this reaction mixture dilutes with methylene dichloride, is deposited in the ether then.The polymkeric substance that elimination obtains washs with ether, then in vacuum chamber in 50 ℃ of following dried overnight.Its output is the 32.7gm polymkeric substance.
1HNMR shows to have the ethyl/phenyl of 9/1 ratio in this polymkeric substance.GPC (in THF, being standard): Mn=7610, Mw=13900 with the polystyrene.Polymkeric substance III: poly-(2-ethyl-2-oxazoline) with dodecyl chain end
The dodecyl iodide of the 2-ethyl-2-oxazoline of 41mL (406mmol) and 10mL (41mmol) under argon gas atmosphere, are placed dry 100mL round-bottomed flask, and this flask is furnished with magnetic stirrer and reflux exchanger.This flask places 80 ℃ oil bath, this mixture of vigorous stirring.After 2 hours, reaction mixture colour-darkening and curing.Temperature is risen to 90 ℃, kept again 3.5 hours.After cool to room temperature, the solid that obtains is dissolved in the chloroform, be deposited in the ether then.With the supernatant liquid decant, then that this solid is dry down in 50 ℃ in a vacuum.Obtain the dark orange powder of 42.8gm.GPC (in THF, being standard): Mn=3130, Mw=3990 with the polystyrene.Polymkeric substance IV: poly-(2-phenyl-2-the oxazoline)-b-of poly-(2-ethyl-2-oxazoline)-b-poly-(2-ethyl-2-oxazoline)
With the 20mL orthodichlorobenzene, 1 of the 2-phenyl-2-oxazoline of 4mL (30mmol) and 2.6gm (5mmol), 4-two (4,5-dihydro-2-oxazolinyl) the triflate salt of benzene is under argon gas atmosphere, place dry round-bottomed flask, this flask is furnished with the air operated glassed agitator, reflux exchanger and rubber septum.This flask places 130 ℃ oil bath, and this reaction mixture stirred 6 hours under this temperature.And then add the 80mL orthodichlorobenzene, temperature of reaction is reduced to 100 ℃.Add the 30mL2-ethyl-2-oxazoline, this mixture stirred 3 hours under this temperature then.After cool to room temperature, this reaction mixture dilutes with methylene dichloride, is deposited in the ether then.By will further purifying in ether with redeposition in its dissolving methylene chloride/methanol mixture.The material that elimination obtains washs with ether, then in vacuum chamber in 50 ℃ of following dried overnight.Its output is the 23.4gm polymkeric substance.
1HNMR shows to have the ethyl/phenyl of 9/1 ratio in this polymkeric substance.GPC (in THF, being standard): Mn=3090, Mw=4580 with the polystyrene.Printing ink 1
10gm polymkeric substance I is dissolved in the polymers soln of preparation 10% in the deionized water of 90gm.Using potassium hydroxide solution (45%) to regulate its pH value is 8.0.The FW18 charcoal blacks (Degussa Corp.) and the 80gm deionized water that add 20gm.Above-mentioned component carries out pre-mixing by mechanical stirring in plastic beaker, till cannot see caking or dry pulp piece.This mixture is dispersed in the miniature fluidized-bed reactor (MicrofluidicsCorp.), is about 10 at liquid pressure, under the 000psi, with it through exposure chamber 8 times.The generation pigment dispersion has 10% pigment concentration, and median size wherein is 115nm, is measured by Brookhaven Bi-90 particle size analysis instrument.This pigment dispersion is discharged with Liponics EG-1 (Lipo Chemicals) and 2-Pyrrolidone, the printing ink for preparing a kind of black pigment, it comprises 3.5wt% pigment, 1.75wt% polymeric dispersant, the 2-Pyrrolidone of 5.0wt%Liponics EG-1 and 10wt%.Printing ink 2
Prepare printing ink 2 in printing ink 1 same mode, different is, with 10 gram polymkeric substance II replace polymeric I, this mixture is through exposure chamber 10 times.The generation pigment dispersion has 10% pigment concentration, and median size wherein is 138nm, is measured by Brookhaven Bi-90 particle size analysis person.Discharge this concentrate, obtain printing ink with printing ink 1 identical component.Printing ink 3
15gm polymkeric substance III is dissolved in the polymers soln of preparation 10% in the deionized water of 135.0gm.The FW18 charcoal blacks and the 120gm deionized water that add 30gm.After above-mentioned component mixes by mechanical stirring in plastic beaker, till cannot see caking or dry pulp piece, this mixture being dispersed in the miniature fluidized-bed reactor, is about 10 at liquid pressure, under the 000psi, with it through exposure chamber 10 times.The generation pigment dispersion has 10% pigment concentration, and median size wherein is 128nm, is measured by BrookhavenBI-90 particle size analysis instrument.PH value is 3.42.The dispersion of printing ink 1 is discharged, and prepares a kind of printing ink, and this printing ink comprises 3.0wt% pigment, 1.75wt% polymeric dispersant, the 2-Pyrrolidone of 5.0wt%Liponics EG-1 and 10wt%.Printing ink 4
Repeat the step of printing ink 2, different is to replace the polymkeric substance II with 10gm polymkeric substance IV.The generation pigment dispersion has 10% pigment concentration, and median size wherein is 180nm, is measured by BrookhavenBI-90 particle size analysis instrument.Discharge this concentrate as the preparation method of printing ink 2, it has same prescription.The preparation of printing ink and test
This printing ink is placed the storer of hot ink-jet contact, be loaded in Hewlett Packard DeskJet500C ink-jet printer (Hewlett Packard Co.).Black solid line zone, various font alphanumeric characters, and dot matrix is printed on Gilbert bond paper (25% cotton, Mead Co).Optical density(OD) (OD) is passed through X-Rite densometer, model 418 (X-Rite, Inc in solid area; ) measure.Judge print quality (PQ) by the homogeneity of edge acuity and density.Its result is presented in the table 1.
Table 1
Printing ink OD PQ
1 1.25 is outstanding
2 1.24 is outstanding
3 1.13 is outstanding
5 1.55 is outstanding
Printing ink of the present invention shows neutral black color and solid edge acuity.Based on taking off the cover destructive procedure, the printing ink of all experiments is friendly and reliable, can print smoothly for a long time.
Claims (10)
1, a kind of water dispersion comprises:
(a) aqueous carrier,
(b) granular solids,
(c) block polymer dispersant is selected from AB, ABA and BAB segmented copolymer, and wherein the A block is hydrophobic, and the B block is hydrophilic, and the solubleness of wherein whole polymkeric substance in aqueous carrier is 0.1wt% at least in the time of 25 ℃;
(d) this block polymerization dispersion agent is made up of monomer, and this monomer is selected from the oxazoline monomer that 2-replaces, oxazine monomer that 2-replaces and composition thereof.
2, the dispersion of claim 1, wherein this block polymer dispersant comprises the polymkeric substance (formula A represents the A block, and formula B represents the B block) with following general formula:
Wherein
X is 1～100;
Y is 5～500;
Y/x is 5～100;
Z is by formula R
3(L)
rThe divalent linker of expression,
Wherein
R
3For containing the alkylidene group of 2～10 carbon atoms, arylidene or arylmethylene alkyl,
L is O, S, C (O), OC (O), (O) CO, SC (O), or SO
2Group, r=0 or 1;
M=2 or 3;
P=2 or 3;
N=0 or 1;
R
1For containing the alkyl of 4～20 carbon atoms, aryl, aralkyl, or alkaryl;
R
2For containing the alkyl that 1～3 carbon atom also can randomly contain one or more hydroxyls or ether group.
3, the dispersion of claim 2, wherein x is 1～10, and y is 5～100, and y/x is 5～50.
4, the dispersion of claim 1 also comprises at least a organic component, is selected from organic solvent, polymer binder, water-soluble polymers,, water can disperse latex emulsion, thickening material, coalescing agent, tensio-active agent, biocides, thixotropic agent, sequestrant and coating auxiliary agent.
5, the dispersion of claim 1, wherein granular solids is selected from pigment, colloid silver halide, sheet metal, weedicide, sterilant and biomaterial.
6, the dispersion of claim 1, wherein this aqueous carrier is the mixture of water and water-miscible organic solvent.
7, a kind of inkjet ink composition that comprises claim 1 dispersion, wherein this aqueous carrier comprises the mixture of a kind of water and water-miscible organic solvent, granular solids wherein is a pigment.
8, the printing ink of claim 7, wherein the number-average molecular weight that has of this block polymer dispersant is 1,000～20,000.
9, the printing ink of claim 7, wherein this pigment has and is of a size of 0.01～5 micron.
10, the printing ink of claim 7 based on all wts of this printing ink, has following surface compositions:
(a) aqueous carrier of 70～99.8wt%;
(b) pigment of 0.1～30wt%;
(c) 0.1～10wt% polymer dispersant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98122643 CN1223276A (en) | 1997-11-04 | 1998-11-04 | Block copolymers of oxazolines and oxazines as pigment dispersants and their use in ink jet inks |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/963839 | 1997-11-04 | ||
| CN 98122643 CN1223276A (en) | 1997-11-04 | 1998-11-04 | Block copolymers of oxazolines and oxazines as pigment dispersants and their use in ink jet inks |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1223276A true CN1223276A (en) | 1999-07-21 |
Family
ID=5227840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98122643 Pending CN1223276A (en) | 1997-11-04 | 1998-11-04 | Block copolymers of oxazolines and oxazines as pigment dispersants and their use in ink jet inks |
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| US7029109B2 (en) | 2001-08-22 | 2006-04-18 | Canon Kabushiki Kaisha | Ink, ink set, ink jet recording method, ink jet recording apparatus, recording unit and ink cartridge |
| CN1304447C (en) * | 2001-08-07 | 2007-03-14 | 佳能株式会社 | Stimulus responsive composition, method and device for forming image using same |
| CN100339437C (en) * | 2002-03-06 | 2007-09-26 | 佳能株式会社 | Dispersion composition containing functional substance, method of forming image and image forming apparatus |
| CN100339427C (en) * | 2003-12-23 | 2007-09-26 | 三星电子株式会社 | Block copolymeric dispersant for pigment particle in aqueous system, and ink composition comprising the same |
| CN100376613C (en) * | 2002-07-03 | 2008-03-26 | 佳能株式会社 | Block polymer compound, polymer composition containing the same, image forming method and image forming apparatus utilizing the same |
| WO2010036867A1 (en) * | 2008-09-25 | 2010-04-01 | E. I. Du Pont De Nemours And Company | Block copolymer pigment dispersants |
-
1998
- 1998-11-04 CN CN 98122643 patent/CN1223276A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304447C (en) * | 2001-08-07 | 2007-03-14 | 佳能株式会社 | Stimulus responsive composition, method and device for forming image using same |
| US7029109B2 (en) | 2001-08-22 | 2006-04-18 | Canon Kabushiki Kaisha | Ink, ink set, ink jet recording method, ink jet recording apparatus, recording unit and ink cartridge |
| CN100339437C (en) * | 2002-03-06 | 2007-09-26 | 佳能株式会社 | Dispersion composition containing functional substance, method of forming image and image forming apparatus |
| US7479512B2 (en) | 2002-03-06 | 2009-01-20 | Canon Kabushiki Kaisha | Dispersion composition containing functional substance, method of forming image and image forming apparatus |
| CN100376613C (en) * | 2002-07-03 | 2008-03-26 | 佳能株式会社 | Block polymer compound, polymer composition containing the same, image forming method and image forming apparatus utilizing the same |
| CN100339427C (en) * | 2003-12-23 | 2007-09-26 | 三星电子株式会社 | Block copolymeric dispersant for pigment particle in aqueous system, and ink composition comprising the same |
| WO2010036867A1 (en) * | 2008-09-25 | 2010-04-01 | E. I. Du Pont De Nemours And Company | Block copolymer pigment dispersants |
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