CN1692144A - Modified carbon black carbon black dispersion liquid and water base ink - Google Patents
Modified carbon black carbon black dispersion liquid and water base ink Download PDFInfo
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- CN1692144A CN1692144A CN 200380100284 CN200380100284A CN1692144A CN 1692144 A CN1692144 A CN 1692144A CN 200380100284 CN200380100284 CN 200380100284 CN 200380100284 A CN200380100284 A CN 200380100284A CN 1692144 A CN1692144 A CN 1692144A
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Abstract
There are provided a carbon black according to which long-term stable storage is possible, clogging is not prone to occurring, and the OD value is high and hence printing with a deep black color is possible, or a carbon black that can be used in a water-based ink that is used in ink jet printer printing, that has low settleability and can thus be stored stably for a long period, for which clogging is not prone to occurring, and for which the reflection density is high and hence printing with a high printing density and a deep black color is possible, a carbon black dispersion having the carbon black dispersed therein, and a water-based ink containing the carbon black. An embodiment of a modified carbon black of the present invention is a modified carbon black obtained by carrying out oxidation treatment on a carbon black having a primary particle diameter of 11 to 18 nm, a BET specific surface area of at least 180 m<SUP>2</SUP>/g, a DBP oil absorption of at least 180 mL/100 g, and a value of the BET specific surface area (m<SUP>2</SUP>/g) divided by the DBP oil absorption (mL/100 g) of 0.75 to 1.3, and is characterized in that at least lactone groups and carboxyl groups are introduced onto the surface thereof, and the ratio of the mean particle diameter to the primary particle diameter is at least 8.5. Moreover, a carbon black dispersion and a water-based ink of the present invention contain this modified carbon black.
Description
Technical field
The present invention relates to modified carbon black, say in detail, thereby relate to the carbon black that uses in printing ink, seal at ink-jet printer recording ink, a tool, disperse carbon black dispersion liquid that this carbon black forms and the water color ink that contains it with black inks such as printing ink.
Background technology
As the tinting material of the water color ink of using the ink-jet printer process black, be extensive use of carbon black.
Usually, the sooty raw material powder is the secondary cohesion piece that is called as aggregate, this secondary cohesion piece is to form by Van der Waals force or gathering only, adhere to, get together etc. each other as the coacervate that globular primary particle is roughly assembled the elementary aggregate that forms.Such carbon black feed stock powder can be to water-dispersion and sedimentation immediately under untreated state.
Contain such raw material powder and disperse the water color ink of its dispersion agent, viscosity height, difficult printing.So,, use the surface of oxygenated black raw material powder and introduced the hydrophilic functional group's of carboxyl and so on modified carbon black even in order not use dispersion agent also easily to be dispersed in the water.
As such modified carbon black, the inventor discloses the modified carbon black of its specific surface area of concrete regulation and DBP oil number (having used the oil number of phthalic acid dibutyl ester: be recited as the DBP oil number in this specification sheets) in patent documentation 1.Therefore contain the water color ink of this modified carbon black, viscosity is low, and reflection density value (being recited as the OD value in this specification sheets) height, can carry out dense printing with pitch black.Water color ink need to have sufficient ageing stability in practicality, but the ageing stability of these water color inks may not be sufficient in using with recording ink as ink-jet.
In addition, as modified carbon black, the carbon black of the thin carbon black feed stock powder of oxidized median size is arranged also.The water color ink that contains this modified carbon black is because good dispersity and difficult sedimentation, so the package stability excellence, is difficult for stopping up., when with this ink printing, the reflection density value is low, does not demonstrate practicality and sufficient printing density.The tone of printing ink has the tendency that becomes reddish black in addition.
Again, in patent documentation 2, disclose the used for water color ink charcoal blacks, this pigment specifically defines N
2SA, IA, N
2SA/IA, CTAB, DBP, 24M4DBP, Tint and all Sauerstoffatom with respect to the ratio of whole carbon atoms etc., this used for water color ink carbon black particularly in the occasion of using as ink for inking, has insufficient this problem of OD value.
Patent documentation 1: the spy opens the 2000-319573 communique
Patent documentation 2: the spy opens the 2001-81355 communique
The present invention finishes for solving above-mentioned problem, purpose is, is provided for the ink-jet printer printing, rate of descent is lower and can store steadily in the long term and be difficult for stopping up and reflection density value (OD value) Gao Erneng carries out the carbon black that uses in the water color ink of dense printing and disperses this sooty water color ink with pitch black.
Summary of the invention
The modified carbon black of the present invention by providing each shown in following (1)-(26) to constitute, water color ink etc., thus achieve the above object.
(1) a kind of modified carbon black is characterized in that, is to be at least 180m by oxide treatment primary particle particle diameter 11-18nm, BET specific surface area
2/ g, DBP oil number are at least this BET specific surface area (m of 180mL/100g, the DBP of unit oil number (mL/100g)
2/ g) be the carbon black of 0.75-1.3, thereby the modified carbon black that obtains is introduced lactone group and carboxyl at least on its surface, the averaged particles particle diameter with respect to the ratio of primary particle particle diameter be 8.5 or more than.
(2) according to (1) described modified carbon black, it is characterized in that the BET specific surface area (m of the above-mentioned DBP oil number of unit (mL/100g)
2/ g) be 0.9-1.1.
(3) according to (1) or (2) described modified carbon black, it is characterized in that the averaged particles particle diameter of above-mentioned modified carbon black is 150-250nm.
(4) according to wantonly 1 described modified carbon black of (1)-(3), it is characterized in that, with respect to the above-mentioned lactone group of carbon black weight in the above-mentioned modified carbon black be 500 μ mol/g or more than, same above-mentioned carboxyl be 700 μ mol/g or more than.
(5) according to wantonly 1 described modified carbon black of (1)-(4), it is characterized in that, the rate of descent demonstration 30% of above-mentioned modified carbon black or below.
According to wantonly 1 described modified carbon black of (1)-(5), it is characterized in that (6) above-mentioned lactone group and above-mentioned carboxyl adopt hypohalous acid or/and hypohalite carries out oxidation and is introduced into.
(7) according to wantonly 1 described modified carbon black of (1)-(6), it is characterized in that the absorbancy of mensuration liquid under the 500nm wavelength that is diluted to modified carbon black concentration 0.001 weight % is at least 0.47.
The result of the diligent investigation of the inventor obtains following knowledge opinion: by having adjusted rate of descent and average particle diameter from the dispersion of disperse black carbon, be adjusted into certain specific scope with specific solvent constituent ratio, can solve above-mentioned problem.Following invention (8)-(13) are based on such knowledge opinion and finish.Being constructed as follows of i.e. this invention.
(8) a kind of modified carbon black is characterized in that, is the modified carbon black that no dispersion agent just can disperse and/or be dissolved in water, is designated as S in the rate of descent (%) of the dispersion A that will be adjusted to this carbon black 13 weight %, water 87 weight %
A, the rate of descent (%) that will be adjusted to the dispersion B of this carbon black 5 weight %, glycerol 10 weight %, diglycol monotertiary n-butyl ether 10 weight %, water 75 weight % is designated as S
BThe time, 10≤S
A-S
B≤ 50, S
B≤ 40 relation is set up, and, accumulate the scope of diameter with 50% of the dispersion mensuration that is adjusted into this carbon black 0.3g/L at 150-350nm.
(9) according to (8) described modified carbon black, it is characterized in that 20≤S
A-S
B≤ 50, S
B≤ 30 relation is set up.
(10) according to (8) or (9) described modified carbon black, it is characterized in that, accumulate the scope of diameter at 150-250nm with 50% of the dispersion mensuration that is adjusted into above-mentioned sooty 0.3g/L.
(11) according to wantonly 1 described modified carbon black of (8)-(10), it is characterized in that above-mentioned carbon black is by primary particle particle diameter 11-18nm, BET specific surface area are at least 180m
2/ g, DBP oil number are at least this BET specific surface area (m of 180mL/100g, the DBP of unit oil number (mL/100g)
2/ g) carbon black for 0.75-1.3 carries out the modified carbon black that surface modification obtains.
(12) according to (11) described modified carbon black, it is characterized in that the BET specific surface area (m of the above-mentioned DBP of unit oil number (mL/100g)
2/ g) be 0.9-1.1.
(13) according to wantonly 1 described modified carbon black of (8)-(12), it is characterized in that, above-mentioned carbon black by utilizing hypohalous acid or/and hypohalite oxide treatment carbon black feed stock powder obtain.
(14) a kind of method of making modified carbon black, it is characterized in that, it is the method for making wantonly 1 described modified carbon black of (1)-(13), at least has following operation: add hypohalous acid or/and the aqueous solution of hypohalite in the liquid of the carbon black feed stock powder of the employing oven process preparation that suspended among the Xiang Zaishui, grinding medium with diameter 0.6-3mm uses dispersion machine, carry out oxide treatment, with 100-500 purpose metal mesh filter, with the liquid desalination that obtains.
(15) a kind of carbon black dispersion liquid is characterized in that, wantonly 1 described modified carbon black of (1)-(14) is scattered in the water and forms.
(16) a kind of water color ink is characterized in that, contains (1)-wantonly 1 described modified carbon black of (14).
(17) a kind of water color ink is characterized in that, contains wantonly 1 described modified carbon black of glycerol, glycol ethers compound and (8)-(13) at least.
(18) according to (17) described water color ink, it is characterized in that above-mentioned glycol ethers compound is selected from glycol butyl ether compound.
(19) according to wantonly 1 described water color ink of (16)-(18), it is characterized in that having the glue spread of printing ink on recording medium is 1mg/cm
2The time penetration period less than 1 second impregnability.
(20) according to wantonly 1 described water color ink of (16)-(19), it is characterized in that the surface tension under 20 ℃ is 45mN/m or following.
(21) according to (16), (19) or (20) described water color ink, it is characterized in that, contain the aqueous organic solvent of glycol butyl ether system.
(22) according to wantonly 1 described water color ink of (16)-(21), it is characterized in that, contain nonionic surfactant.
(23) according to (22) described water color ink, it is characterized in that above-mentioned nonionic surfactant is that acetylenic glycol is a tensio-active agent.
(24) a kind of recording method is to make printing ink adhere to the recording method that recording medium is printed, and it is characterized in that, uses wantonly 1 described water color ink of (16)-(23) as printing ink.
(25) a kind of ink jet recording method, be ejection printing ink drop, make this drop attached to the ink jet recording method that prints on the recording medium, it is characterized in that, use wantonly 1 described water color ink of (16)-(23) as printing ink.
(26) a kind of record is characterized in that, adopts (24) or (25) described recording method to carry out record.
The embodiment of invention
Below based on embodiment preferred explanation the present invention.
(embodiment A)
The modified carbon black of the present embodiment A is to introduce lactone group and carboxyl on the surface, and the averaged particles particle diameter is 8.5 or above modified carbon black with respect to the ratio of primary particle particle diameter, although the averaged particles particle diameter greatly to 150-250nm, rate of descent also be 30% or below.
This modified carbon black, the such carbon black of oxide treatment obtains: primary particle particle diameter (scope of the mean value of primary particle particle diameter) is 11-18nm, and the BET specific surface area is at least 180m
2/ g, be preferably 180-260m
2/ g, the DBP oil number is at least 180mL/100g, is preferably 180-300mL/100g, this specific surface area (m of 190-250mL/100g more preferably, and unit DBP oil number (mL/100g)
2/ g) in the scope of 0.75-1.3.
Adopt the above-mentioned DBP of sooty unit oil number specific surface area (specific surface area/DBP oil number) and, the averaged particles particle diameter is with respect to the water color ink of each value of the ratio (averaged particles particle diameter/primary particle particle diameter) of primary particle particle diameter modified carbon black preparation in above-mentioned scope, can be with the dense printing density printing of aterrimus.On the other hand, be used in the printing ink of this scope modified carbon black preparation in addition, be shallow black, can not print becomes aterrimus.
BET specific surface area (the m of the above-mentioned DBP of unit oil number (mL/100g)
2/ g) be 0.75-1.3,0.9-1.1 more preferably.
Above-mentioned sooty averaged particles particle diameter is with respect to the ratio of primary particle particle diameter, is that the mean number of the primary particle of contained, the cohesion of unit cohesion piece in the carbon black cohesion piece that is called as aggregate that forms with the primary particle cohesion is suitable.In order to satisfy desired rate of descent and OD value simultaneously, be prepared into the averaged particles particle diameter with respect to the ratio of primary particle particle diameter be 8.5 or above modified carbon black be important.More preferably the averaged particles particle diameter is 8.5-15.0 with respect to the ratio of primary particle particle diameter, further 9.0-12.0 preferably.
Adopting the primary particle particle diameter is the printing ink of the modified carbon black preparation of this scope, even the averaged particles particle diameter is 150-250nm, also rate of descent ink nozzle low, that be difficult for causing ink-jet printer stops up, and also difficult sedimentation, rotten etc. takes place, and has the long term storage stability of several years in practicality.
The scope of primary particle particle diameter is 11-18nm, more preferably 15-18nm.When using the primary particle particle diameter greater than the carbon black of this scope, with the carbon black ratio of primary particle particle diameter in this scope, the rate of descent of prepared printing ink rises several times-tens times sharp, cause easily stop up and because of long storage cause rotten.On the other hand, when using the primary particle particle diameter less than the carbon black of this scope, the rate of descent of printing ink is no problem, but viscosity uprises, the manufacturing of modified carbon black and the printing of the printing ink difficulty that becomes.
The modified carbon black that can prepare the good water color ink of long term storage stability, be to obtain by the oxide treatment of the raw material carbon black being implemented appropriateness, with respect to carbon black weight, preferred above-mentioned lactone group be 500 μ mol/g or more than, same above-mentioned carboxyl be 700 μ mol/g or more than.Because lactone group and carboxyl are the hydrophilic functional groups, so the interaction of this modified carbon black and water enhancing, modified carbon black electrostatic repulsion each other works.This hydrophilic functional group is many more, and repulsion is big more, is distributed to easily in the water, and the result is free settling not.
The modified carbon black of the present embodiment A, show rate of descent 30% or below.Rate of descent is by following mensuration.
Will be modulated into the liquid 30g of modified carbon black concentration 5 weight %, glycerol 10 weight %, diglycol monotertiary n-butyl ether 10 weight % enclose sedimentation pipe, carry out centrifugation with the universal gravity constant of 11000G and handled 10 minutes.Accurately its supernatant liquid of weighing 4g dilutes in the 1L volumetric flask.This diluent is measured 5mL hold entirely in the suction transfer pipet, in the 100mL volumetric flask, dilute.Measure the absorbancy W1 of this liquid under the 500nm wavelength.Absorbancy W0 when measuring the modulating liquid similarly dilute before the centrifugal treating calculates rate of descent by following calculating formula.
Rate of descent (%)=[1-(absorbancy W1)/(absorbancy W0)] * 100
Use the modified carbon black of the present embodiment A, the rate of descent that obtains under these conditions demonstration 30% or following low value.Thus, contain the carbon black dispersion liquid and the water color ink of the modified carbon black of such rate of descent, even for example the averaged particles particle diameter of modified carbon black is bigger as above-mentioned scope, also not sedimentation after the long storage of several years, not perishable, be stable.In addition, use the occasion of this water color ink on ink-jet printer, the ink nozzle that can not cause ink-jet printer stops up, and can print smooth-goingly.And therefore this dispersion liquid and printing ink can carry out dense printing etc. with aterrimus because the OD value is high.Preferred rate of descent be 25% or below.On the other hand, use the sooty printing ink that shows the rate of descent that surpasses above-mentioned scope, caused the sedimentation of stopping up and causing because of long storage.
Be 0.001 weight % and synthetic liquid in the absorbancy of 500nm with modified carbon black concentration be 0.47 or above for well.When water color ink uses the modified carbon black of absorbancy in this scope, with the aterrimus printing.When using absorbancy, to be with tawny black printing at this extraneous carbon black.
Manufacture method as modified carbon black, for example, at least has such operation: add hypohalous acid or/and the aqueous solution of hypohalite in the liquid of the carbon black feed stock powder of the employing oven process preparation that suspended among the Xiang Zaishui, carry out oxide treatment, reinstating dispersion machine with the grinding medium one of diameter 0.6-3mm stirs, with 100-500 purpose metal mesh filter, filtrate is adopted the ultra-filtration membrane desalination.
The carbon black feed stock powder is made with known carbon black manufacture method, lists the carbon black that obtains with oven process, carbon black that obtains with channel process etc.Oven process is such raw material powder preparation method: introduce fuel (coal gas or oil) and air in the special roasting kiln that can tolerate the pyritous brick lining that reaches about 2000 ℃, make it perfect combustion, after having formed 1400 ℃ or above high-temperature atmosphere, aqueous stock oil is sprayed continuously, make it thermolysis, water after containing the sooty high-temperature gas spraying that latter stage generates in stove, reaction is stopped, being separated into carbon black and exhaust with bag filter.
For oxygenated black, following method is for example arranged: the liquid phase oxidation of oxygenants such as the oxidation style of ingress of air, vapour phase oxidation process, use nitric acid, potassium permanganate, potassium bichromate, chlorous acid, perchloric acid, hypohalite, hydrogen peroxide, bromine aqueous solution, ozone water solution etc. with oxynitride, ozone reaction.Also can the using plasma processing etc. with surface modification.
Particularly preferred method is to use hypohalite wet oxidation sooty method.The concrete example of hypohalite lists clorox and potassium hypochlorite, considers from reactive point, preferred especially clorox.
By using hypohalous acid or its salt as oxygenant, carbon black feed stock powder surperficial oxidized introduced lactone group, carboxyl etc.Consider from reactive point, more preferably the aqueous solution of clorox.The usage quantity of hypohalous acid or its salt is adjusted according to the size of the BET specific surface area of carbon black feed stock powder.The BET specific surface area is more little, reduces the amount of hypohalous acid or its salt more, and the BET specific surface area is big more, increases the amount of hypohalous acid or its salt more.Reason is that specific surface area is more little, and few more with hypohalous acid reactive activity point, specific surface area is big more, and is many more with hypohalous acid reactive activity point.Even the hypohalous acid that the adding active site is above does not hinder reaction yet, but uses hypohalous acid lavishly, need more extra desalination operation.When reacting under the hypohalous acid amount below active site, do not reach lactone base unit weight, the carboxyl amount of target, the rate of descent variation.Be conceived to the result that effective chlorine density in above-mentioned hypohalous acid or its salt and carbon black surface area discuss and know, by adopting per unit carbon black surface area (m
2) be 0.6 * 10
-4-2.5 * 10
-4Mole, preferred 0.6 * 10
4-1.5 * 10
-4Hypohalous acid or its salt of the chlorine dose of mole come oxidation, can carry out good oxide treatment.
The carbon black feed stock powder is suspended in the operation of water, in order suitably to carry out oxidation operation, carbon black is mixed in the water fully and fused for one be important.But dispersion machine that usage load is high or homogenizer etc.In addition, can use water-soluble solvent in advance, make the solvent-saturated carbon black or in the mixed stocker of water-water-soluble solvent, carry out dispersion treatment.
In the manufacturing process of dispersion of sooty oxide treatment or pulverizing, as dispersion machine or pulverizer, can use ball mill, attritor, fluid jet mixing machine, vane type grinding machine, colloidal mill, sand mill (for example commercially available commodity " Super Mill ", " Agitator Mill ", " Dyno-mill ", " Beads Mill ") etc.Also can not necessarily use grinding medium, but use, can list the grinding medium of diameter 0.6-3mm to well.As above-mentioned grinding medium, can use granulated glass sphere, zirconium oxide bead, magnetic beads, stainless steel pearl etc., while as the treatment condition of carrying out in this oxidation dispersive operation, with rotating speed=500rpm or abovely carry out 3-10 hour for well at 10-70 ℃.Reaction was carried out easily when temperature of reaction was high, but temperature is when uprising, and hypohalite decomposes, and therefore reaction is preferably 40-60 ℃.
For with grinding medium, the dispersion liquid that obtains is removed oversize particle, with 100-500 purpose metal mesh filter.
With the desalination of the filtrate of metal mesh filter, for example adopt ultra-filtration membrane to proceed to specific conductivity less than 1.5mS/cm.When finishing desalination more than 1.5mS/cm, impurity such as NaCl are included in the printing ink, the package stability variation.
And, after the desalination, use separating centrifuge or strainer, remove 1 μ m or above oversize particle.Oversize particle is owing to sedimentation easily, and rate of descent increases, and causes that the ink nozzle of ink-jet printer stops up, and it is important therefore removing.
The pH regulator of the dispersion liquid that can obtain and the water-soluble acid basic neutralization that obtains by oxidation.As its used alkaline matter, can list alkali-metal oxyhydroxide (for example sodium hydroxide, potassium hydroxide and lithium hydroxide etc.), ammonia (water), various amine compound.
Preferred amine compound can list water miscible volatilization amine, alkanolamine etc.List volatile amine (for example methylamine, Trimethylamine, diethylamide, propyl group amine) particularly with the alkyl replacement of carbon number 1-3; The alkanolamine (for example thanomin, diethanolamine, trolamine, tri-isopropanolamine etc.) that replaces with the chain triacontanol base of carbon number 1-3; The alkyl alkanolamine that replaces with the chain triacontanol base of the alkyl of carbon number 1-3 and carbon number 1-3 etc.
The carbon black dispersion liquid of the present embodiment A is characterised in that, above-mentioned modified carbon black is scattered in the water and forms.Above-mentioned modified carbon black is that no dispersion agent just can disperse and/or the dissolved carbon black, and therefore above-mentioned carbon black dispersion liquid can be by adding water to above-mentioned carbon black and/or concentrating, and adjustment becomes desired carbon black concentration and obtains.In addition, also can add the additive of narrating later of water-miscible organic solvent and sanitas etc. arbitrarily as required.
The water color ink of the present embodiment A is characterized in that, contains above-mentioned modified carbon black at least.By containing above-mentioned modified carbon black, the dense and printing realistically of the black that water color ink can be distinct and dark.And excellent storage stability is even long storage also is difficult for taking place sedimentation.Above-mentioned carbon black generally contains 0.1-20 weight %, preferably contains the scope of 1-15 weight % with respect to the water color ink total amount.When content of carbon black less than 0.1 weight %, often print or the concentration of writing insufficient, in addition, when surpassing 20 weight %, the viscosity of water color ink sharply uprises, the stability in the time of might the printing ink ejection reduces.
In addition, the water color ink of the present embodiment A is characterized in that, also further having the glue spread of printing ink on recording medium is 1mg/cm
2The time penetration period less than 1 second impregnability.Glue spread is 1mg/cm
2The time penetration period less than 1 second printing ink, specifically refer to: for example on the area of 360dpi (point/inch) * 360dpi, be coated with the occasion of the water color ink of 50ng, even also do not made dirty the required time less than 1 second water color ink by printing ink up to contact print face.
These printing ink are the water-miscible organic solvent that diminishes by the surface tension of adding the aqueous solution and the short penetrant of tensio-active agent, improve the wettability to recording medium, thereby strengthen impregnability.As water-miscible organic solvent, list Trivalin SF classes, 1 such as cellosolve classes such as lower alcohols such as ethanol, propyl alcohol, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, diglycol monotertiary methyl ether, carbiphene, 2-hexylene glycol, 1,2-ethohexadiol etc. 1,2-alkyl diol class.Wherein, on the meaning that provides excellent impregnability, the aqueous organic solvent of glycol butyl ether systems such as preferred especially diglycol monotertiary butyl ether, triglycol single-butyl ether.
In addition, as tensio-active agent, can use nonionic surfactant, cationic surfactant, amphotericses etc. such as anionic surfactants such as fatty acid salt, alkyl sulfuric ester salt, Voranol EP 2001, polyoxyethylene phenyl ether.Wherein, nonionic surfactant is low whipability, thus preferred especially, and also on the meaning that provides excellent impregnability, preferred especially acetylenic glycol is a nonionic surfactant.
Wish to add these short penetrants, individually or be used in combination water-miscible organic solvent or tensio-active agent, be adjusted to ink surface tension under 20 ℃ be 45mN/m or following, preferably be adjusted into 40mN/m or following.
The water color ink of the present embodiment A, for example when being used for ink jet recording method, the ink setting for the nozzle tip that prevents to spray printing ink can add wetting Agent for Printing Inks.As wetting Agent for Printing Inks, from water-soluble and bibulous material, select, can use glycerol, ethylene glycol, glycol ether, triglycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1, ammediol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1,2, the 6-hexanetriol, polyalcohols such as tetramethylolmethane, 2-Pyrrolidone, the N-N-methyl-2-2-pyrrolidone N-, lactams such as ε-Ji Neixianan, urea, thiocarbamide, ethylidene-urea, 1, ureas such as 3-methylimidazole alkane ketone, maltose alcohol, Sorbitol Powder, gluconolactone, carbohydrates such as maltose.The usage quantity of these wetting Agent for Printing Inkss does not limit especially, general scope at 0.5-50 weight %.
Water color ink also can contain the additive of general fixing agent, pH regulator agent, antioxidant, UV light absorber, sanitas, mould inhibitor and so on beyond above-mentioned as required.
The water color ink that contains above-mentioned modified carbon black can be with aterrimus printing vivo deeply.For example, coating is adjusted to the water color ink 1mg/cm of modified carbon black concentration 5 weight %, glycerol 10 weight %, diglycol monotertiary n-butyl ether 10 weight %
2The time, the reflection density value (OD value) of measuring its ink lay with the Macbeth densometer is at least 1.4.
In addition, with by the printing of the synthetic water color ink of above-mentioned proportioning the time, L* value in the colored system of L*a*b* be 47 or below, the b* value is 0.7-0, if the L*a*b* color solid ties up to this scope, then when printing, be not with blueness or redness, under the degree that detects by an unaided eye, be equal to unresolvable degree, be aterrimus.In addition, the absorbancy of water color ink and reflection density value are in the above-mentioned scope, and it is big more, L* value and b* value are more little, good more.
The water color ink of the present embodiment A, also the various printing ink of using etc. and so on, seal as tool uses.The occasion that notes are used with ink composite as aqueous ballpoint pen etc. particularly, the record lettering feature is good, can not have that person's handwriting is inhomogenous to be write, and in addition, in the occasion of shorthand, can not write out the style of calligraphy characterized by hollow strokes by literal.The water color ink of the present embodiment A, as the ejection printing ink drop, make the ink for ink-jet recording of above-mentioned drop attached to the enterprising line item of recording medium, more can use aptly.
The ink jet recording method of the present embodiment A also can use from fine nozzle to spray printing ink, make this drop attached to any way on the recording medium with the drop form.
Several modes are described.The electrostatic attraction mode is at first arranged.This mode has: at nozzle with place between the accelerating electrode in the place ahead of nozzle and add highfield, with droplet-like continuously from nozzle ejection printing ink, droplets of ink is during circling in the air between deflection electrode, give deflection electrode printing information signal, thus the mode of record or do not make droplets of ink deflection and the mode that makes it to spray corresponding to the printing information signal.
The second way is, with pony pump printing ink liquid exerted pressure, and with mechanical vibration nozzles such as quartz (controlled) oscillators, the mode that droplets of ink is sprayed.The droplets of ink of spraying is charged when spraying, and droplets of ink gives deflection electrode printing information signal during circling in the air between deflection electrode, thereby carries out record.
The third mode is to use the mode of piezoelectric element, is to adopt piezoelectric element that printing ink is exerted pressure and the printing information signal simultaneously, makes the mode of droplets of ink injection record.
The 4th kind of mode is to utilize the effect of heat energy, makes the mode of printing ink volumetric expansion sharp, with microelectrode the printing ink heating bubbled according to the printing information signal, makes the mode of droplets of ink injection record.
Above any way can both be used in the ink jet recording method of the water color ink that has used the present embodiment A.
The record of the present embodiment A uses above-mentioned water color ink to write down at least and obtains.This record shows high printing density by using the water color ink of the present embodiment A.
As described above in detail, the modified carbon black of the present embodiment A can be easy, make in large quantities, even do not use dispersion agent and tensio-active agent, also can make it to be scattered in the water.Disperseed this sooty dispersion liquid not need dispersion agent, so viscosity is low, is suitable for low viscous water color ink.
Particularly this water color ink is suitable for ink-jet printer.The excellent storage stability of this printing ink, even long storage also is difficult for taking place sedimentation, quality keeps the time limit long.In addition, difficulty causes that the ink nozzle of ink-jet printer stops up.And, when using this printing ink, with the printing vivo deeply of distinct and dark black.
(embodiment B)
The modified carbon black of the present embodiment B is the modified carbon black that no dispersion agent just can disperse and/or be dissolved in water.The carbon black that no dispersion agent in embodiment B just can disperse and/or be dissolved in water is: make surface of pigments directly or by alkyl, alkylether radicals, aryl etc. indirectly in conjunction with many hydrophilic functional groups and/or its salt (be called dispersiveness later on and give base), so be that no dispersion agent just can disperse and/or be dissolved in the carbon black in the aqueous medium.At this, " no dispersion agent just disperses and/or is dissolved in the aqueous medium " do not use dispersion agent, the state that carbon black also stably exists with dispersible smallest particles particle diameter even mean in aqueous medium.At this, " dispersible smallest particles particle diameter " increases the sooty particle diameter that jitter time can not become littler than this value even mean.As giving base, can list carboxyl, lactone group, carbonyl, hydroxyl, sulfo group, phosphate and quaternary ammonium and their salt etc. with above-mentioned carbon blacksurface bonded dispersiveness.In this manual, the modified carbon black that sometimes so no dispersion agent just can be disperseed and/or be dissolved in the water is called from disperse black carbon.
The above-mentioned occasion of using with the form of dispersion liquid or water color ink from disperse black carbon, owing to not needing to be included as the dispersion agent that disperses common pigment to contain, therefore the defoaming of dispersion agent of almost not resulting from reduces and bubbles, processing ease, and when in press using, the water color ink of the excellent in stability of printing is adjusted easily.In addition, therefore the degree of blackness height of carbon black self not only, and result from the significantly viscosity of dispersion agent and rise and be suppressed contains the pigment possibility that becomes more, can further improve the OD value.
The carbon black of the present embodiment B is characterized in that, is designated as S in the rate of descent (%) of the dispersion A that will be adjusted to this carbon black 13 weight %, water 87 weight %
A, the rate of descent (%) that will be adjusted to the dispersion B of this carbon black 5 weight %, glycerol 10 weight %, diglycol monotertiary n-butyl ether 10 weight %, water 75 weight % is designated as S
BThe time, 10≤S
A-S
B≤ 50, S
B≤ 40 relation is set up.In addition, more preferably 20≤S
A-S
B≤ 50, S
B≤ 30 relation is set up.
In this manual, rate of descent means the value of obtaining as described below.
To mix with the ratio of components of regulation and adjust sooty dispersion liquid 30g and enclose sedimentation pipe, and carry out centrifugation with the universal gravity constant of 11000G and handled 10 minutes.Accurately its supernatant liquid of weighing 4g dilutes in the 1L volumetric flask.This diluent is measured in the 5mL whole pipet, in the 100mL volumetric flask, dilute.Measure the absorbancy W1 of this liquid under the 500nm wavelength.Absorbancy W0 when measuring the modulating liquid similarly dilute before the centrifugal treating calculates rate of descent by following calculating formula.
Rate of descent S (%)=[1-(absorbancy W1)/(absorbancy W0)] * 100
The modified carbon black of the present embodiment B is characterized in that, the rate of descent S of the dispersion of adjusting with different composition
A, S
BDifference in the scope of 10-50, more preferably in the scope of 20-50, and, the rate of descent S of dispersion B
BBe 40 or following, be more preferably 30 or below.In order to obtain S
A-S
BValue less than 10, OD value high, need to select the high carbon black of the big rate of descent of particle diameter, but in the sort of occasion because this high rate of descent, therefore worry to take place the long-term great problems such as cause rotten, ink nozzle obstruction of placing.In addition, if select S
A-S
BThe low carbon black of value less than 10, rate of descent, though long-term place cause rotten, ink nozzle obstruction etc. then be difficult for to take place, the OD value of printed matter is low, for the red black of Huang.In contrast to this, satisfying the modified carbon black of the present embodiment B of above-mentioned important document, with the occasion that the form of dispersion or water color ink is printed, is aterrimus, can realize high OD value.In addition, the modified carbon black in the above-mentioned scope is difficult for taking place sedimentation on reality is used, and in the occasion of using with the form of dispersion or water color ink, even the several years long storage is not perishable yet, is stable therefore.In addition, the occasion of using on ink-jet printer is difficult for causing the obstruction of the ink nozzle of ink-jet printer, can print smooth-goingly.
The carbon black of the present embodiment B is characterized in that, accumulates the scope of diameter at 150-350nm with 50% of the dispersion mensuration that is adjusted into this carbon black 0.3g/L.In addition, more preferably above-mentioned 50% accumulation diameter is in the scope of 150-250nm.
In this manual, 50% accumulation diameter means the value of obtaining as described below.
Accurately weighing is adjusted to the dispersion A 2.3g of carbon black 13 weight %, water 87 weight %, dilutes in the 1L volumetric flask.This dilute dispersion is for example used sreen analysis meter MICROTRAC9340-UPA (trade(brand)name; The Microtrac corporate system) etc. device carries out particle size distribution, obtains the accumulation frequency and be 50% o'clock particle diameter.
The modified carbon black of 50% accumulation diameter in above-mentioned scope with the occasion that the form of dispersion or water color ink is printed, is aterrimus, can realize high OD value.On the other hand, 50% accumulation diameter is light/dark balance at above-mentioned extraneous carbon black, often can not be printed as pitch black.
The modified carbon black of the present embodiment B is preferably by being at least 180m to primary particle particle diameter 11-18nm, BET specific surface area
2/ g, DBP oil number are at least this BET specific surface area (m of 180mL/100g, the DBP of unit oil number (mL/100g)
2/ g) carbon black for 0.75-1.3 carries out the modified carbon black that surface modification obtains.In addition, the BET specific surface area (m of the more preferably above-mentioned DBP of unit oil number (mL/100g)
2/ g) be 0.9-1.1.
Sooty occasion in the above-mentioned scope of surface modification is adjusted rate of descent S
A, S
BThe pass tie up in the above-mentioned preferred range and 50% accumulation diameter is easy from disperse black carbon in above-mentioned preferable range.
The present embodiment B from disperse black carbon, for example by carbon black being implemented physical treatment or chemical treatment, make above-mentioned dispersiveness give base or have above-mentioned dispersiveness and give the spike of base and combine (grafting) with surface of pigments, thereby produce.
As above-mentioned physical treatment, for example can list vacuum plasma treatment etc.As above-mentioned chemical treatment, for example can list the oxidation style of ingress of air, with the vapour phase oxidation process of oxynitride, ozone reaction with in water, utilize the wet oxidation process of oxygenant oxidation surface of pigments such as nitric acid, potassium permanganate, potassium bichromate, chlorous acid, perchloric acid, hypohalite, hydrogen peroxide, bromine aqueous solution, ozone water solution and by para-amino benzoic acid etc. is combined with surface of pigments, thereby by the dispersed method of giving base of combinations such as phenyl etc.
In the present embodiment B, particularly preferred method is to use hypohalite wet oxidation sooty method.About the detailed content of this method, the suitable content that illustrates among the embodiment A that is suitable for.
Preferable production process as the modified carbon black of the present embodiment B, for example, at least has such operation: add hypohalous acid or/and the aqueous solution of hypohalite in the liquid of the carbon black feed stock powder of the employing oven process preparation that suspended among the Xiang Zaishui, carry out oxide treatment, grinding medium with diameter 0.6-3mm, stir with dispersion machine,, filtrate is adopted the ultra-filtration membrane desalination with 100-500 purpose metal mesh filter.
About each operation in this manufacture method (operation of suspension carbon black feed stock powder, sooty oxide treatment are disperseed or the manufacturing process that pulverizes etc. in water), with in embodiment A, illustrate identical, its content is suitable for by suitable.
The carbon black dispersion liquid of the present embodiment B is characterized in that, is scattered in the water from disperse black carbon and forms above-mentioned.Because above-mentioned carbon black is that no dispersion agent just can disperse and/or the dissolved carbon black, therefore above-mentioned carbon black dispersion liquid can be by adding water to above-mentioned carbon black and/or concentrating, and adjustment becomes desired carbon black concentration and obtains.In addition, also can add the additive of narrating later of water-miscible organic solvent and sanitas etc. arbitrarily as required.
The water color ink of the present embodiment B is characterized in that, contains above-mentioned modified carbon black at least.By containing above-mentioned carbon black, water color ink is distinct and pitch black, can vivo print deeply.And excellent storage stability is even long storage also is difficult for taking place sedimentation.Above-mentioned carbon black is generally with respect to the water color ink total amount, contains 0.1-20 weight %, preferably contains the scope of 1-15 weight %.When content of carbon black less than 0.1 weight %, often print or the concentration of writing insufficient, in addition, when surpassing 20 weight %, the viscosity of water color ink sharply uprises, the stability when worrying the printing ink ejection reduces.
The water color ink of the present embodiment B further contains glycerol, glycol ethers compound for better.In the above-mentioned glycol ethers compound, from giving viewpoint consideration easily effectively, more preferably be selected from glycol butyl ether compounds such as diglycol monotertiary n-butyl ether, triglycol list n-butyl ether, triglycol list tertbutyl ether, hexylene glycol list n-butyl ether to the impregnability of printing ink.As described above, the modified carbon black of the present embodiment B, because the rate of descent as the dispersion that contains glycerol, diglycol monotertiary n-butyl ether is that certain is below certain scope, therefore the water color ink that contains above-mentioned glycerol, glycol ethers compound and form, guarantee quite little rate of descent on one side, can realize suitable impregnability, reliability and high OD value on one side.
In addition, the water color ink of the present embodiment B, A is same with embodiment, it is characterized in that, and also further having the glue spread of printing ink on recording medium is 1mg/cm
2The time penetration period less than 1 second impregnability.
These printing ink are the water-miscible organic solvent that diminishes by the surface tension of adding the aqueous solution and the short penetrant of tensio-active agent, improve the wettability to recording medium, thereby strengthen impregnability.As water-miscible organic solvent and tensio-active agent, the compound that is fit to the present embodiment B is identical with the compound of enumerating that is suitable for above-mentioned embodiment A.
Wish to add these short penetrants, be used alone or in combination water-miscible organic solvent or tensio-active agent, be adjusted to ink surface tension under 20 ℃ be 45mN/m or following, preferably be adjusted into 40mN/m or following.
The water color ink of the present embodiment B, since identical with the situation of above-mentioned embodiment A, wetting Agent for Printing Inks etc. can be added.About the example and the usage quantity of this wetting Agent for Printing Inks, with in embodiment A, illustrate identical, its content is suitable for by suitable.
The water color ink of the present embodiment B beyond above-mentioned, also can similarly contain the additive of general fixing agent, pH regulator agent, antioxidant, UV light absorber, sanitas, mould inhibitor and so on as required with above-mentioned embodiment A.
As fixing agent, can use water miscible resene and water-based emulsion, waterborne polymeric micropartical etc.As water miscible resene, list water-soluble rosin class, alginate, polyvinyl alcohol, hydroxypropylcellulose, carboxymethyl cellulose, Natvosol, methylcellulose gum, styrene-propene acid resin, styrene-propene acid-acrylate resin, styrene-maleic acid resin, styrene-maleic acid half ester resin, vinylformic acid-acrylate resin, iso-butylene-maleic acid resin, Abietyl modified maleic acid resin, polyvinylpyrrolidone, gum arabic starch, PAH, polyvinylamine, polymine etc.As water-based emulsion and waterborne polymeric micropartical, list styrene-propene yogurt liquid, ACRYLIC EMULSION etc.
As the pH regulator agent,, can utilize over the pH regulator agent of in aqueous ink composition, using for the purpose that pH is set in the specific scope.Specifically can use amines such as alkali-metal oxyhydroxide such as lithium hydroxide, potassium hydroxide, sodium hydroxide, ammonia, trolamine, tri-isopropanolamine, diethanolamine etc.As the pH buffer reagent,, can utilize over the pH buffer reagent that in aqueous ink composition, uses for the purpose that pH is maintained in the specific scope.Specifically can use collidine, imidazoles, phosphoric acid, 3-(N-morpholino) propanesulfonic acid, three (methylol) aminomethane, boric acid etc.
As the antioxidant UV light absorber, the oxide compound of Tinuvin328,900,1130,384,292,123,144,622,770, Irgacor252,153, Irganox1010,1076,1035, MD1024 etc. or the lanthanon of biuret classes such as allophanate class, biuret, dimethyl biuret, tetramethyl-biuret such as use allophanate, methyl allophanate etc., L-xitix and salt thereof etc., Ciba-Geigy corporate system etc.
As the sanitas mould inhibitor, for example can be from Sodium Benzoate, sodium pentachlorophenol, 2-pyridine mercaptan-1-sodium oxide, sodium sorbate, Sodium dehydroacetate, 1, select among the 2-dibenzo isothiazoline-3-ketone (the Proxel CRL of Avecia company, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel TN) etc.
The water color ink of the present embodiment B is also same with above-mentioned embodiment A, and also the various printing ink as a tool usefulness, seal usefulness, ink for ink-jet recording etc. and so on use.Particularly this preferred version is identical with the water color ink of embodiment A with effect.
The ink jet recording method of the present embodiment B also can use from fine nozzle to spray printing ink, make this drop attached to any way on the recording medium with the drop form.The example of its several modes is identical with above-mentioned embodiment A, and the explanation in embodiment A also is suitable in the present embodiment B.
Above any way can both be used in the ink jet recording method of the water color ink that has used the present embodiment B.
The record of the present embodiment B uses above-mentioned water color ink to write down at least and obtains.This record shows high printing density by using the water color ink of the present embodiment B.
Above as embodiment preferred, enumerating embodiment A and embodiment B is that example has been described in detail, and as described, modified carbon black of the present invention can be easy, make in large quantities, even do not use dispersion agent and tensio-active agent, also can make it to be scattered in the water.Disperseed this sooty dispersion liquid not need dispersion agent, so viscosity is low, is suitable for low viscous water color ink.
Particularly this water color ink is suitable for ink-jet printer.The excellent storage stability of this printing ink, even long storage also is difficult for taking place sedimentation, quality keeps the time limit long.In addition, difficulty causes that the ink nozzle of ink-jet printer stops up.And, when using this printing ink, with the printing vivo deeply of distinct and dark black.
[embodiment]
Below describe relevant modified carbon black of the present invention in detail, contain its carbon black dispersion liquid and the embodiment of water color ink.The present invention is not limited by such embodiment.
(embodiment A)
The preparation of carbon black dispersion liquid a (being suitable for the carbon black of embodiment A)
Will be with the primary particle particle diameter=18nm of oven process preparation, BET specific surface area=185m
2The carbon black feed stock powder 200g of/g, DBP oil number=200mL/100g, BET specific surface area/DBP oil number=0.93 joins among the ion exchanged water 1500g, with dissolver stir on one side, be warmed up to 50 ℃ on one side.Thereafter, 50-60 ℃ with the aqueous solution that dripped clorox 2220g (effective chlorine density 12%) in 3.5 hours, just drip finish after, add the granulated glass sphere of diameter 3mm, stirred 30 minutes at 50 ℃, obtain containing the reaction solution of modified carbon black.With 400 this reaction solution of order metal mesh filter, separate glass pearl and unreacted carbon black and reaction solutions.The reaction solution that obtains to separation adds sodium hydroxide 5% aqueous solution, be adjusted to pH=7.5 after, with ultra-filtration membrane desalination and refining, reach 1.5mS/cm up to specific conductivity, further be concentrated to modified carbon black concentration and reach 17 weight %.This concentrated solution is added in the separating centrifuge, removes oversize particle, filter with 0.6 μ m strainer.In the filtrate that obtains, add ion exchanged water, with modified carbon black dilution, be distributed to and reach concentration 15 weight %.
The preparation of carbon black dispersion liquid b (being suitable for the carbon black of embodiment A)
Will be with the primary particle particle diameter=16nm of oven process preparation, BET specific surface area=220m
2The carbon black feed stock powder 500g of/g, DBP oil number=230mL/100g, BET specific surface area/DBP oil number=0.92 joins among the ion exchanged water 3750g, with dissolver stir on one side, be warmed up to 50 ℃ on one side.Thereafter, utilization has used the sand mill of zirconium oxide bead of diameter 0.8mm while pulverizing at 50-60 ℃ with the aqueous solution that dripped clorox 6600g (effective chlorine density 12%) in 3.5 hours, then utilize sand mill to continue to pulverize 30 minutes, obtain containing the reaction solution of modified carbon black.With 400 this reaction solution of order metal mesh filter, separate oxidation zirconium pearl and unreacted carbon black and reaction solutions.The reaction solution that obtains to separation adds potassium hydroxide 5% aqueous solution, be adjusted to pH=7.5 after, with ultra-filtration membrane desalination and refining, reach 1.5mS/cm up to specific conductivity, further be concentrated to modified carbon black concentration and reach 17 weight %.This concentrated solution is added in the separating centrifuge, removes oversize particle, filter with 0.6 μ m strainer.In the filtrate that obtains, add ion exchanged water, with modified carbon black dilution, be distributed to and reach concentration 15 weight %.
The preparation of carbon black dispersion liquid c (being suitable for the carbon black of embodiment A)
Will be with the primary particle particle diameter=17nm of oven process preparation, BET specific surface area=200m
2The carbon black feed stock powder 500g of/g, DBP oil number=220mL/100g, BET specific surface area/DBP oil number=0.91 joins among the ion exchanged water 3750g, with dissolver stir on one side, be warmed up to 50 ℃ on one side.Thereafter, utilization has used the sand mill of zirconium oxide bead of diameter 0.8mm while pulverizing at 50-60 ℃ with the aqueous solution that dripped clorox 6000g (effective chlorine density 12%) in 3.5 hours, then utilize sand mill to continue to pulverize 30 minutes, obtain containing the reaction solution of modified carbon black.With 400 this reaction solution of order metal mesh filter, separate oxidation zirconium pearl and unreacted carbon black and reaction solutions.The reaction solution that obtains to separation adds sodium hydroxide 5% aqueous solution, be adjusted to pH=7.5 after, with ultra-filtration membrane desalination and refining, reach 1.5mS/cm up to specific conductivity, further be concentrated to modified carbon black concentration and reach 17 weight %.This concentrated solution is added in the separating centrifuge, removes oversize particle, filter with 0.6 μ m strainer.In the filtrate that obtains, add ion exchanged water, with modified carbon black dilution, be distributed to and reach concentration 15 weight %.
The water color ink of (embodiment A 1)
In 23.3g carbon black dispersion liquid a, add ion exchanged water 32.7g, glycerol 7g, diglycol monotertiary n-butyl ether 7g, stir, the membrane filter (Millipore corporate system, trade(brand)name) of the tetrafluoroethylene system of employing, aperture 5 μ m filters, and has prepared the water color ink of embodiment A 1.
The water color ink of (embodiment A 2)
In 32.7g carbon black dispersion liquid a, add ion exchanged water 26.8g, glycerol 7g, triglycol list n-butyl ether 2.1g, Olfine E1010 (trade(brand)name, day, letter chemical industrial company made) 0.7g, trolamine 0.7g, stir, the membrane filter (Millipore corporate system, trade(brand)name) of the tetrafluoroethylene system of employing, aperture 5 μ m filters, and has prepared the water color ink of embodiment A 2.
The water color ink of (embodiment A 3)
In 23.3g carbon black dispersion liquid b, add ion exchanged water 32.7g, glycerol 7g, diglycol monotertiary n-butyl ether 7g, stir, the membrane filter (Millipore corporate system, trade(brand)name) of the tetrafluoroethylene system of employing, aperture 5 μ m filters, and has prepared the water color ink of embodiment A 3.
The water color ink of (embodiment A 4)
In 32.7g carbon black dispersion liquid b, add ion exchanged water 27.4g, glycerol 7g, triglycol list n-butyl ether 2.1g, Olfine STG (trade(brand)name, day, letter chemical industrial company made) 0.1g, trolamine 0.7g, stir, the membrane filter (Millipore corporate system, trade(brand)name) of the tetrafluoroethylene system of employing, aperture 5 μ m filters, and has prepared the water color ink of embodiment A 4.
The water color ink of (embodiment A 5)
In 23.3g carbon black dispersion liquid c, add ion exchanged water 32.7g, glycerol 7g, diglycol monotertiary n-butyl ether 7g, stir, the membrane filter (Millipore corporate system, trade(brand)name) of the tetrafluoroethylene system of employing, aperture 5 μ m filters, and has prepared the water color ink of embodiment A 5.
The water color ink of (embodiment A 6)
In 32.7g carbon black dispersion liquid c, add ion exchanged water 26.8g, glycerol 7g, triglycol list n-butyl ether 2.1g, Olfine E1010 (trade(brand)name, day, letter chemical industrial company made) 0.7g, trolamine 0.7g, stir, the membrane filter (Millipore corporate system, trade(brand)name) of the tetrafluoroethylene system of employing, aperture 5 μ m filters, and has prepared the water color ink of embodiment A 6.
For the above-mentioned water color ink that contains the carbon black dispersion liquid a-c of modified carbon black and use the embodiment A 1-A6 of their preparations, carry out evaluation of physical property as described below.
(the averaged particles particle size determination of modified carbon black)
The aqueous solution that is adjusted to the modified carbon black concentration of 0.065 weight % is used sreen analysis meter MICROTRAC9340-UPA (trade(brand)name; The Microtrac corporate system) measures.
(mensuration of the lactone group of modified carbon black and carboxyl amount)
The modified carbon black that obtains 60 ℃ of dryings 15 hours, is used this carbon black, use thermolysis gas phase chromatographic device HP5890A (trade(brand)name, Hewlett-Packard corporate system), be determined at 358 ℃ of lactone group and decompose the CO that produces
2, decompose the CO that produces at 650 ℃ of carboxyls
2By measured value conversion sooty lactone group and carboxyl amount.
(viscosity measurement of carbon black dispersion liquid)
The dispersion liquid that is adjusted to 15 weight % modified carbon black concentration is used E type viscometer RE550L (trade(brand)name; East machine industry corporate system) measures.
(the absorbance measurement method of modified carbon black)
Use spectrophotometer UV-1600PC (trade(brand)name; Shimadzu Seisakusho Ltd.'s corporate system) measures the aqueous solution that modified carbon black concentration is adjusted to 0.001 weight %.
(measuring method of the rate of descent of modified carbon black)
Will be modulated into the liquid 30g of modified carbon black concentration 5 weight %, glycerol 10 weight %, diglycol monotertiary n-butyl ether 10 weight % enclose sedimentation pipe, carry out centrifugation with the universal gravity constant of 11000G and handled 10 minutes.Accurately its supernatant liquid of weighing 4g dilutes in the 1L volumetric flask.Then, this diluent is measured in the 5mL whole pipet, in the 100mL volumetric flask, dilute.Measure the absorbancy W1 of this liquid under the 500nm wavelength.Absorbancy W0 when measuring the modulating liquid similarly dilute before the centrifugal treating calculates rate of descent by following calculating formula.
Rate of descent (%)=[1-(absorbance W1)/(absorbance W0)] * 100
(the settled measuring method after water color ink is placed)
Place water color ink 50g after half a year in room temperature, have or not sedimentation through visual judgement.
(mensuration of the colored system of the reflection density value of the print that obtains by water color ink and L*a*b*)
The water color ink that obtains is filled into ink-jet recording device EM-900C (trade(brand)name; The Seiko Epson corporate system), be printed onto on the neutral common paper Xerox-P (trade(brand)name, Fuji Xerox corporate system).Wherein, when printing, being adjusted to glue spread is 1mg/cm
2Behind the dry print, utilize Macbeth densometer TR-927 (trade(brand)name, Kollmorgen corporate system) to measure reflection density value (OD value).In addition, utilize spectrocolorimeter JP7100F (trade(brand)name, JUKI corporate system) that the colored system of L*a*b* is measured.Visual observation should the time tone.
These the results are shown in table 1.
Table 1
| Embodiment | ||||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | |||
| The carbon black feed stock powder | Primary particle particle diameter (nm) | ????18 | ????16 | ????17 | ||||
| BET specific surface area (m 2/g) | ????185 | ????220 | ????200 | |||||
| DBP oil number (mL/100g) | ????200 | ????230 | ????220 | |||||
| BET specific surface area/DBP oil number | ????0.93 | ????0.92 | ????0.91 | |||||
| Modified carbon black | Averaged particles particle diameter (nm) | ????190 | ????180 | ????190 | ||||
| Averaged particles particle diameter/primary particle particle diameter | ????10.6 | ????11.3 | ????11.2 | |||||
| Lactone group amount (μ mol/g) | ????531 | ????580 | ????559 | |||||
| Carboxyl amount (μ mol/g) | ????715 | ????796 | ????776 | |||||
| Absorbancy (measuring wavelength 500nm) | ????0.477 | ????0.472 | ????0.476 | |||||
| Rate of descent (%) | ????18 | ????10 | ????15 | |||||
| Carbon black dispersion liquid | Carbon black dispersion liquid | ????A | ????B | ????℃ | ||||
| Viscosity (mPas) | ????8 | ????10 | ????9 | |||||
| Water color ink | Have or not sedimentation after the placement | Not sedimentation | Not sedimentation | Not sedimentation | Not sedimentation | Not sedimentation | Not sedimentation | |
| The OD value of print | ????1.49 | ????1.43 | ????1.47 | ????1.40 | ????1.48 | ????1.41 | ||
| The colored system of the L*a*b* of print | The L* value | ????45.86 | ????46.30 | ????46.00 | ????46.93 | ????46.00 | ????46.58 | |
| The a* value | ????0.53 | ????0.53 | ????0.51 | ????0.51 | ????0.50 | ????0.50 | ||
| The b* value | ????0.64 | ????0.64 | ????0.61 | ????0.61 | ????0.63 | ????0.63 | ||
| The tone of print | Pitch black | Pitch black | Pitch black | Pitch black | Pitch black | Pitch black | ||
Know clearly that by table 1 use the water color ink of the modified carbon black preparation of embodiment A, its carbon black not sedimentation for a long time when printing, becomes pitch black.
As a comparative example, the carbon black feed stock powder that replacement is used in embodiment A, the carbon black feed stock powder that Comparative examples A 1-A5 put down in writing shown in the use table 2 in addition, has similarly prepared modified carbon black and the carbon black dispersion liquid of Comparative examples A 1-A5 with the manufacture method of carbon black dispersion liquid a.Further use at this carbon black dispersion liquid that obtains, similarly prepared the water color ink of Comparative examples A 1-A5 with the preparation method of the water color ink of embodiment A 1.For the above-mentioned modified carbon black that obtains, carbon black dispersion liquid and water color ink, carried out the evaluating characteristics same with embodiment A 1-A6.It the results are shown in table 2.
Table 2
| Comparative example | |||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | |||
| The carbon black feed stock powder | Primary particle particle diameter (nm) | ????17 | ????24 | ????18 | ????18 | ????40 | |
| BET specific surface area (m 2/g) | ????200 | ????125 | ????163 | ????200 | ????58 | ||
| DBP oil number (mL/100g) | ????150 | ????110 | ????162 | ????165 | ????168 | ||
| BET specific surface area/DBP oil number | ????1.33 | ????1.14 | ????1.01 | ????1.21 | ????0.35 | ||
| Modified carbon black | Averaged particles particle diameter (nm) | ????110 | ????160 | ????180 | ????175 | ????305 | |
| Averaged particles particle diameter/primary particle particle diameter | ????6.5 | ????6.7 | ????10 | ????9.7 | ????7.6 | ||
| Lactone group amount (μ mol/g) | ????650 | ????315 | ????486 | ????517 | ????155 | ||
| Carboxyl amount (μ mol/g) | ????900 | ????500 | ????680 | ????715 | ????253 | ||
| Absorbancy (measuring wavelength 500nm) | ????0.415 | ????0.510 | ????0.446 | ????0.431 | ????0.455 | ||
| Rate of descent (%) | ????9 | ????68 | ????58 | ????19 | ????98 | ||
| Carbon black dispersion liquid | Viscosity (mPas) | ????4 | ????3.2 | ????3.8 | ????4.6 | ????2.0 | |
| Water color ink | Have or not sedimentation after the placement | Not sedimentation | Sedimentation is arranged | Sedimentation is arranged | Not sedimentation | Sedimentation is arranged | |
| The OD value of print | ????1.38 | ????1.47 | ????1.37 | ????1.36 | ????1.35 | ||
| The colored system of the L*a*b* of print | The L* value | ????47.56 | ????45.47 | ????47.59 | ????47.88 | ????47.02 | |
| The a* value | ????0.50 | ????0.53 | ????0.50 | ????0.50 | ????0.33 | ||
| The b* value | ????1.06 | ????0.38 | ????1.09 | ????1.11 | ????-1.0 | ||
| The tone of print | The yellow red black of band | Pitch black | The yellow red black of band | The yellow red black of band | What band was blue deceives | ||
Clearly know by table 2, use the water color ink of the inapplicable modified carbon black preparation of embodiment A, the carbon black sedimentation, or when printing, for having yellow red or blue black.
(Embodiment B)
[preparation of carbon black dispersion liquid 1 (being suitable for the carbon black of embodiment B)]
Will be with the primary particle particle diameter=17nm of oven process preparation, BET specific surface area=215m
2The carbon black feed stock powder 500g of/g, DBP oil number=210mL/100g, BET specific surface area/DBP oil number=1.02 joins among the ion exchanged water 3750g, with dissolver stir on one side, be warmed up to 50 ℃ on one side.Thereafter, utilization has used the sand mill of zirconium oxide bead of diameter 0.8mm while pulverizing at 50-60 ℃ with the aqueous solution that dripped clorox 6600g (effective chlorine density 12%) in 3.5 hours, then utilize sand mill to continue to pulverize 30 minutes, obtain containing the reaction solution of modified carbon black.With 400 this reaction solution of order metal mesh filter, separate oxidation zirconium pearl and unreacted carbon black and reaction solutions.The reaction solution that obtains to separation adds KOH 5% aqueous solution, be adjusted to pH=7.5 after, with ultra-filtration membrane desalination and refining, reach 1.5mS/cm up to specific conductivity, further be concentrated to modified carbon black concentration and reach 17 weight %.This concentrated solution is added in the separating centrifuge, removes oversize particle, filter with 0.6 μ m strainer.In the filtrate that obtains, add ion exchanged water, modified carbon black is diluted to reaches concentration 13 weight %, obtain carbon black dispersion liquid 1.Measuring the rate of descent of this carbon black dispersion liquid 1 with aforesaid method, is 54%.In addition, ratio with 38.5 weight % carbon black dispersion liquids 1 (being converted into carbon black concentration is 5 weight %), glycerol 10 weight %, diglycol monotertiary n-butyl ether 10 weight %, ion exchanged water 41.5 weight % stirs, mixes, make dispersion, measure with aforesaid method, the result is 26%.In addition, accurately weighing 2.31g carbon black dispersion liquid 1 makes the dispersion (being converted into carbon black concentration is 0.30g/L) of diluting in the 1000mL volumetric flask, uses sreen analysis meter MICROTRAC9340-UPA (trade(brand)name; The Microtrac corporate system) measure 50% accumulation diameter, the result is 200nm.
[preparation of carbon black dispersion liquid 2 (being suitable for the carbon black of embodiment B)]
Will be with the primary particle particle diameter=18nm of oven process preparation, BET specific surface area=185m
2The carbon black feed stock powder 200g of/g, DBP oil number=200mL/100g, BET specific surface area/DBP oil number=0.93 joins among the ion exchanged water 1500g, with dissolver stir on one side, be warmed up to 50 ℃ on one side.Thereafter, 50-60 ℃ with the aqueous solution that dripped clorox 2220g (effective chlorine density 12%) in 3.5 hours, just drip finish after, add the granulated glass sphere of diameter 3mm, stirred 30 minutes at 50 ℃, obtain containing the reaction solution of modified carbon black.With 400 this reaction solution of order metal mesh filter, separate glass pearl and unreacted carbon black and reaction solutions.The reaction solution that obtains to separation adds the NaOH5% aqueous solution, be adjusted to pH=7.5 after, with ultra-filtration membrane desalination and refining, reach 1.5mS/cm up to specific conductivity, further be concentrated to modified carbon black concentration and reach 17 weight %.This concentrated solution is added in the separating centrifuge, removes oversize particle, filter with 0.6 μ m strainer.In the filtrate that obtains, add ion exchanged water, modified carbon black is diluted to reaches concentration 13 weight %, obtain carbon black dispersion liquid 2.
Measuring the rate of descent of this carbon black dispersion liquid 2 with aforesaid method, is 45%.In addition, ratio with 38.5 weight % carbon black dispersion liquids 2 (being converted into carbon black concentration is 5 weight %), glycerol 10 weight %, diglycol monotertiary n-butyl ether 10 weight %, ion exchanged water 41.5 weight % stirs, mixes, make dispersion, measure with aforesaid method, the result is 18%.In addition, accurately weighing 2.31g carbon black dispersion liquid 2 makes the dispersion (being converted into carbon black concentration is 0.30g/L) of diluting in the 1000mL volumetric flask, uses sreen analysis meter MICROTRAC9340-UPA (trade(brand)name; The Microtrac corporate system) measure 50% accumulation diameter, the result is 190nm.
[preparation of carbon black dispersion liquid 3 (the inapplicable carbon black of embodiment B)]
Will be with the primary particle particle diameter=20nm of oven process preparation, BET specific surface area=125m
2The carbon black feed stock powder 500g of/g, DBP oil number=170mL/100g, BET specific surface area/DBP oil number=0.74 joins among the ion exchanged water 3750g, with dissolver stir on one side, be warmed up to 50 ℃ on one side.Thereafter, utilization has used the sand mill of zirconium oxide bead of diameter 0.8mm while pulverizing at 50-60 ℃ with the aqueous solution that dripped clorox 6600g (effective chlorine density 12%) in 3.5 hours, then utilize sand mill to continue to pulverize 30 minutes, obtain containing the reaction solution of modified carbon black.With 400 this reaction solution of order metal mesh filter, separate oxidation zirconium pearl and unreacted carbon black and reaction solutions.The reaction solution that obtains to separation adds KOH 5% aqueous solution, be adjusted to pH=7.5 after, with ultra-filtration membrane desalination and refining, reach 1.5mS/cm up to specific conductivity, further be concentrated to modified carbon black concentration and reach 17 weight %.This concentrated solution is added in the separating centrifuge, removes oversize particle, filter with 0.6 μ m strainer.In the filtrate that obtains, add ion exchanged water, modified carbon black is diluted to reaches concentration 13 weight %, obtain carbon black dispersion liquid 3.
Measuring the rate of descent of this carbon black dispersion liquid 3 with aforesaid method, is 72%.In addition, ratio with 38.5 weight % carbon black dispersion liquids 3 (being converted into carbon black concentration is 5 weight %), glycerol 10 weight %, diglycol monotertiary n-butyl ether 10 weight %, ion exchanged water 41.5 weight % stirs, mixes, make dispersion, measure with aforesaid method, the result is 65%.In addition, accurately weighing 2.31g carbon black dispersion liquid 3 makes the dispersion (being converted into carbon black concentration is 0.30g/L) of diluting in the 1000mL volumetric flask, uses sreen analysis meter MICROTRAC9340-UPA (trade(brand)name; The Microtrac corporate system) measure 50% accumulation diameter, the result is 224nm.
[preparation of carbon black dispersion liquid 4 (the inapplicable carbon black of embodiment B)]
Will be with the primary particle particle diameter=16nm of oven process preparation, BET specific surface area=250m
2The carbon black feed stock powder 200g of/g, DBP oil number=155mL/100g, BET specific surface area/DBP oil number=1.61 joins among the ion exchanged water 1500g, with dissolver stir on one side, be warmed up to 50 ℃ on one side.Thereafter, 50-60 ℃ with the aqueous solution that dripped clorox 2220g (effective chlorine density 12%) in 3.5 hours, just drip finish after, add the granulated glass sphere of diameter 3mm, stirred 30 minutes at 50 ℃, obtain containing the reaction solution of modified carbon black.With 400 this reaction solution of order metal mesh filter, separate glass pearl and unreacted carbon black and reaction solutions.The reaction solution that obtains to separation adds the NaOH5% aqueous solution, be adjusted to pH=7.5 after, with ultra-filtration membrane desalination and refining, reach 1.5mS/cm up to specific conductivity, further be concentrated to modified carbon black concentration and reach 17 weight %.This concentrated solution is added in the separating centrifuge, removes oversize particle, filter with 0.6 μ m strainer.In the filtrate that obtains, add ion exchanged water, modified carbon black is diluted to reaches concentration 13 weight %, obtain carbon black dispersion liquid 4.
Measuring the rate of descent of this carbon black dispersion liquid 4 with aforesaid method, is 7%.In addition, ratio with 38.5 weight % carbon black dispersion liquids 4 (being converted into carbon black concentration is 5 weight %), glycerol 10 weight %, diglycol monotertiary n-butyl ether 10 weight %, ion exchanged water 41.5 weight % stirs, mixes, make dispersion, measure with aforesaid method, the result is 6%.In addition, accurately weighing 2.31g carbon black dispersion liquid 4 makes the dispersion (being converted into carbon black concentration is 0.30g/L) of diluting in the 1000mL volumetric flask, uses sreen analysis meter MICROTRAC9340-UPA (trade(brand)name; The Microtrac corporate system) measure 50% accumulation diameter, the result is 120nm.
The water color ink of (Embodiment B 1)
Ratio with 38.5 weight % carbon black dispersion liquids 1 (being converted into carbon black concentration is 5 weight %), glycerol 10 weight %, diglycol monotertiary n-butyl ether 10 weight %, ion exchanged water 41.5 weight % stirs, membrane filter (the trade(brand)name of the tetrafluoroethylene system of employing, aperture 5 μ m, the Millipore corporate system) filters, prepared the water color ink of Embodiment B 1.
The water color ink of (Embodiment B 2)
With 53.8 weight % carbon black dispersion liquids 1 (being converted into carbon black concentration is 7 weight %), glycerol 10 weight %, triglycol list n-butyl ether 3 weight %, Olfine E1010 (trade(brand)name, day letter chemical industrial company manufacturing) ratio of 1 weight %, trolamine 0.9 weight %, ion exchanged water 31.3 weight % stirs, the membrane filter (Millipore corporate system, trade(brand)name) of the tetrafluoroethylene system of employing, aperture 5 μ m filters, and has prepared the water color ink of Embodiment B 2.
The water color ink of (Embodiment B 3)
Use carbon black dispersion liquid 2 as carbon black dispersion liquid, in addition, similarly modulated the water color ink of Embodiment B 3 with the water color ink of Embodiment B 1.
The water color ink of (Embodiment B 4)
Use carbon black dispersion liquid 2 as carbon black dispersion liquid, in addition, similarly modulated the water color ink of Embodiment B 4 with the water color ink of Embodiment B 2.
The water color ink of (comparative example B1)
Use carbon black dispersion liquid 3 as carbon black dispersion liquid, in addition, similarly modulated the water color ink of comparative example B1 with the water color ink of Embodiment B 2.
The water color ink of (comparative example B2)
Use carbon black dispersion liquid 4 as carbon black dispersion liquid, in addition, similarly modulated the water color ink of comparative example B2 with the water color ink of Embodiment B 2.
For the above-mentioned Embodiment B 1-B4 of modified carbon black, the water color ink of comparative example B1-B2 of containing, carry out following evaluation.
(the settled measuring method after water color ink is placed)
Place water color ink 50g after half a year in room temperature, have or not sedimentation through visual judgement.
(mensuration of the OD value of the print that obtains by water color ink)
The water color ink that obtains is filled into ink-jet recording device EM-900C (trade(brand)name; The Seiko Epson corporate system), be printed on the neutral common paper Xerox-P (trade(brand)name, Fuji Xerox corporate system).Wherein, when printing, being adjusted to glue spread is 1mg/cm
2Behind the dry print, utilize Macbeth densometer TR-927 (trade(brand)name, Kollmorgen corporate system) to measure reflection density value (OD value).In addition, the tone of visual observation print.
These the results are shown in table 3.
Table 3
| Dispersion liquid 1 | Dispersion liquid 2 | Dispersion liquid 3 | Dispersion liquid 4 | ||||
| The carbon black feed stock powder | The primary particle particle diameter | ??17 | ??18 | ??20 | ??16 | ||
| The BET specific surface area | ??215 | ??185 | ??125 | ??250 | |||
| The DBP oil number | ??210 | ??200 | ??170 | ??155 | |||
| ?BET/DBP | ??1.02 | ??0.93 | ??0.74 | ??1.61 | |||
| Modified carbon black | Rate of descent S A?(*1) | ??54 | ??45 | ??72 | ??7 | ||
| Rate of descent S B?(*2) | ??26 | ??18 | ??65 | ??6 | |||
| ?S A-S B | ??28 | ??27 | ??7 | ??1 | |||
| 50% accumulation diameter | ??200 | ??190 | ??224 | ??120 | |||
| Water color ink | Title | Embodiment B 1 | Embodiment B 2 | Embodiment B 3 | Embodiment B 4 | Comparative example B1 | Comparative example B2 |
| Sedimentation after long-term the placement | Do not have | Do not have | Do not have | Do not have | Have | Do not have | |
| The OD value | ??1.52 | ??1.45 | ??1.49 | ??1.43 | ??1.38 | ??1.29 | |
| Tone | Pitch black | Pitch black | Pitch black | Pitch black | Pitch black | The yellow red black of band | |
(* 1) S
A: modulation becomes the rate of descent (%) of the dispersion A of carbon black 13 weight %, water 87 weight %
(* 2) S
B: modulation becomes the rate of descent (%) of the dispersion B of carbon black 5 weight %, glycerol 10 weight %, diglycol monotertiary n-butyl ether 10 weight %, water 75 weight %
Clearly know by table 3,, in addition, show high OD value even use long-term placement of the synthetic water color ink of modified carbon black in the scope of embodiment B also sedimentation can not take place, and, pitch black print provided.On the other hand, use contains rate of descent S
A-S
BValue is at the water color ink of the comparative example B1 of extraneous sooty dispersion liquid 3 of the present invention, though show high OD value, and, provide the print of dark slightly black, place generation sedimentation as a result through long-term.In addition, use contains rate of descent S
A-S
BValue and 50% accumulation diameter are at the water color ink of the comparative example B2 of the extraneous sooty dispersion liquid 4 of embodiment B, though after long-term the placement sedimentation does not take place, the OD value is low, provides the print of the black of band yellowish red color.
The rate of descent S of each water color ink of Embodiment B 1-B4 and comparative example B1, B2
CAs follows.This S
CThe mensuration of (rate of descent of water color ink), be that the dispersion liquid (liquid of hybrid modulation) that will be sealing into sedimentation pipe in the measuring method of the rate of descent (sooty dispersion liquid 1 and 2 rate of descent) at above-mentioned modified carbon black is altered to water color ink, carry out with same program in addition.
S
C(rate of descent of water color ink)
Embodiment B 1 ... 26
Embodiment B 2 ... 22
Embodiment B 3 ... 25
Embodiment B 4 ... 20
Comparative example B1 ... 62
Comparative example B2 ... 5
Distinguish the rate of descent S of water color ink by this result
CFor with the rate of descent S of dispersion liquid
BIdentical degree if use modified carbon black of stipulating by the rate of descent of relevant embodiment B regulation and the dispersion liquid that contains it, then can obtain desired water color ink.
Industrial applicibility
The invention provides in the ink-jet printer printing use, sedimentation rate is lower can store steadily in the long term and be difficult for stopping up and reflection density value (OD value) height, can with the pitch black water color ink that carries out the carbon black that uses in the water color ink of dense printing and disperse it, the utilizability on the industry be arranged.
Claims (26)
1. a modified carbon black is characterized in that, is to be at least 180m by oxide treatment primary particle particle diameter 11-18nm, BET specific surface area
2/ g, DBP oil number are at least this BET specific surface area (m of 180mL/100g, the DBP of unit oil number (mL/100g)
2/ the modified carbon black that g) obtains for the carbon black of 0.75-1.3 has been introduced lactone group and carboxyl at least on its surface, the averaged particles particle diameter with respect to the ratio of primary particle particle diameter be 8.5 or more than.
2. modified carbon black according to claim 1 is characterized in that, the BET specific surface area (m of the above-mentioned DBP of unit oil number (mL/100g)
2/ g) be 0.9-1.1.
3. modified carbon black according to claim 1 and 2 is characterized in that, the averaged particles particle diameter of above-mentioned modified carbon black is 150-250nm.
4. according to wantonly 1 described modified carbon black of claim 1-3, it is characterized in that, with respect to the above-mentioned lactone group of the carbon black weight in the above-mentioned modified carbon black be 500 μ mol/g or more than, same above-mentioned carboxyl be 700 μ mol/g or more than.
5. according to wantonly 1 described modified carbon black of claim 1-4, it is characterized in that, the rate of descent of above-mentioned modified carbon black show 30% or below.
6. according to wantonly 1 described modified carbon black of claim 1-5, it is characterized in that above-mentioned lactone group and above-mentioned carboxyl adopt hypohalous acid or/and hypohalite carries out oxidation and is introduced into.
7. according to wantonly 1 described modified carbon black of claim 1-6, it is characterized in that the absorbancy of mensuration liquid under the 500nm wavelength that is diluted to modified carbon black concentration 0.001 weight % is at least 0.47.
8. a modified carbon black is characterized in that, is the modified carbon black that no dispersion agent just can disperse and/or be dissolved in water, is designated as S in the rate of descent (%) of the dispersion A that will be adjusted to this carbon black 13 weight %, water 87 weight %
A, the rate of descent (%) that will be adjusted to the dispersion B of this carbon black 5 weight %, glycerol 10 weight %, diglycol monotertiary n-butyl ether 10 weight %, water 75 weight % is designated as S
BThe time, 10≤S
A-S
B≤ 50, S
B≤ 40 relation is set up, and, accumulate the scope of diameter with 50% of the dispersion mensuration that is adjusted into this carbon black 0.3g/L at 150-350nm.
9. modified carbon black according to claim 8 is characterized in that 20≤S
A-S
B≤ 50, S
B≤ 30 relation is set up.
10. according to Claim 8 or 9 described modified carbon blacks, it is characterized in that the 50% accumulation diameter of measuring with the dispersion that is adjusted into above-mentioned carbon black 0.3g/L is in the scope of 150-250nm.
11. wantonly 1 described modified carbon black according to Claim 8-10 is characterized in that, above-mentioned carbon black is by primary particle particle diameter 11-18nm, BET specific surface area are at least 180m
2/ g, DBP oil number are at least this BET specific surface area (m of 180mL/100g, the DBP of unit oil number (mL/100g)
2/ g) carbon black for 0.75-1.3 carries out the modified carbon black that surface modification obtains.
12. modified carbon black according to claim 11 is characterized in that, the BET specific surface area (m of the above-mentioned DBP of unit oil number (mL/100g)
2/ g) be 0.9-1.1.
13. wantonly 1 described modified carbon black according to Claim 8-12 is characterized in that, above-mentioned carbon black by utilizing hypohalous acid or/and hypohalite oxide treatment carbon black feed stock powder obtain.
14. method of making modified carbon black, it is characterized in that, it is the method for making wantonly 1 described modified carbon black of claim 1-13, at least has following operation: add hypohalous acid or/and the aqueous solution of hypohalite in the liquid of the carbon black feed stock powder of the employing oven process preparation that suspended among the Xiang Zaishui, with the grinding medium of diameter 0.6-3mm, use dispersion machine, carry out oxide treatment, with 100-500 purpose metal mesh filter, with the liquid desalination that obtains.
15. a carbon black dispersion liquid is characterized in that, wantonly 1 described modified carbon black of claim 1-14 is scattered in the water and forms.
16. a water color ink is characterized in that, contains wantonly 1 described modified carbon black of claim 1-14.
17. a water color ink is characterized in that, contains wantonly 1 described modified carbon black of glycerol, glycol ethers compound and claim 8-13 at least.
18. water color ink according to claim 17 is characterized in that, above-mentioned glycol ethers compound is selected from glycol butyl ether compound.
19. wantonly 1 the described water color ink according to claim 16-18 is characterized in that having the glue spread of printing ink on recording medium is 1mg/cm
2The time penetration period less than 1 second impregnability.
20. wantonly 1 the described water color ink according to claim 16-19 is characterized in that the surface tension under 20 ℃ is 45mN/m or following.
21. according to claim 16,19 or 20 described water color inks, it is characterized in that, contain the aqueous organic solvent of glycol butyl ether system.
22. wantonly 1 the described water color ink according to claim 16-21 is characterized in that, contains nonionic surfactant.
23. water color ink according to claim 22 is characterized in that, above-mentioned nonionic surfactant is that acetylenic glycol is a tensio-active agent.
24. a recording method, be make printing ink adhere to, to the recording method that recording medium prints, it is characterized in that, use wantonly 1 described water color ink of claim 16-23 as printing ink.
25. an ink jet recording method, be ejection printing ink drop, make this drop attached to the ink jet recording method that prints on the recording medium, it is characterized in that, use wantonly 1 described water color ink of claim 16-23 as printing ink.
26. a record is characterized in that, employing claim 24 or 25 described recording methods are write down and are obtained.
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|---|---|---|---|
| JP2002381301 | 2002-12-27 | ||
| JP381301/2002 | 2002-12-27 | ||
| JP91214/2003 | 2003-03-28 | ||
| JP100252/2003 | 2003-04-03 |
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| CN1692144A true CN1692144A (en) | 2005-11-02 |
| CN100340611C CN100340611C (en) | 2007-10-03 |
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| IL116377A (en) * | 1994-12-15 | 2003-05-29 | Cabot Corp | Reaction of carbon black with diazonium salts, resultant carbon black products and their uses |
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