CN100545223C - Ink-jet black ink, ink set, ink jet recording method, print cartridge, record cell and ink-jet recording device - Google Patents
Ink-jet black ink, ink set, ink jet recording method, print cartridge, record cell and ink-jet recording device Download PDFInfo
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- CN100545223C CN100545223C CN 200580021934 CN200580021934A CN100545223C CN 100545223 C CN100545223 C CN 100545223C CN 200580021934 CN200580021934 CN 200580021934 CN 200580021934 A CN200580021934 A CN 200580021934A CN 100545223 C CN100545223 C CN 100545223C
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Abstract
The object of the present invention is to provide a kind of ink-jet black ink, it can improve the anti-tackiness of nozzle of weathering resistance, optical concentration and record-header.The invention provides a kind of ink-jet black ink, it contains colorant and water-miscible organic solvent at least, it is characterized in that, described colorant is the compound or its salt shown in the following general formula (I), relative permittivity under 20 ℃ be more than 30.0 and less than 70.0 and more than 25 ℃ of following solubilized 1.0 quality % the content of the water-miscible organic solvent of compound or its salt shown in the following general formula (I), be more than the 50.0 quality % with respect to ink-jet with the total content of the whole water-miscible organic solvents that contain in the black ink.
Description
Technical field
The present invention relates to ink-jet black ink, ink set, ink jet recording method, print cartridge, record cell and ink-jet recording device.
Background technology
Ink-jet recording is by the fine droplet of various principle of work ejection inks, makes it attached on the recording mediums such as paper, thereby carries out the record of image, literal etc.In addition, ink-jet recording since have high-speed and low-noise, multicolor easily, the versatility of recording figure forming is big and do not need to develop, feature that photographic fixing is such, in recent years, as forming various record images devices, in the various uses headed by the massaging device, popularize just rapidly.Further, even can obtain with the polychrome printing that utilizes the plate-making mode, utilize the print of color photography mode to compare also not inferior record by the formed image of polychrome ink-jetting style, under the few situation of preparing department's number, more cheap than common polychrome printing and print, therefore, just be widely applied to full-colour image record field.
In addition, in recent years, the recording medium of using as ink-jet in order to obtain comparing favourably with the silver salt photo or to place oneself above thereon image quality, is using the recording medium that receives material with alumina or the such porous material of silica as ink.Particularly use the recording medium of alumina hydrate, because the alumina hydrate has positive charge, therefore the set of colorant that has negative charge in the ink is good, can obtain the color development preferable image, special aspect the image quality and gloss of full-colour image, have the strong point of comparing preferred grade with present recording medium.
Employed ink in the ink jet recording method, except reliabilities such as ink-jet adaptability, also require following characteristic: provide sufficient optical concentration to the record thing, drying property is good, document image does not have ink bleed, even contact water, ethanol etc. do not have the outflow of document image yet, the weathering resistance of document image is good etc.Wherein, require the weathering resistance of document image good very consumingly.So-called weathering resistance is meant the image fastness, that is, do not produce the variable color that causes by sunlight and various illumination light etc. fade (photostabilization), for the trace oxidizing gas (ozone, the NO that contain in the atmosphere
x, SO
xDeng) do not produce variable color fade (anti-gaseousness).
In the image fastness, at present the subject matter of finding is fade (photostabilization) of the image that caused by sunlight and various illumination light, and described problem of fading can seek to solve by the dyestuff that uses the photostabilization excellence.But, in recent years, the high image qualityization of accompanying image, the chance of indoor exploded view picture has increased, therefore the variable color that causes by the oxidizing gas in the atmosphere fade (anti-gaseousness) become important problem with photostabilization.
In addition, in recent years,,, used the recording medium that on base material, forms the ink receiving layer that comprises pigment and tackiness agent for distinctiveness, tone rendering and the optical concentration that improves ink as ink-jet recording medium.But from anti-gaseousness aspect, there is the situation that variable color is faded that obviously demonstrates in the image that is formed on the described recording medium, and expectation obtains improvement.
In the special fair 8-26263 communique of No. 02919615 communique of Japan's special permission and Japan, proposed in order to improve anti-gaseousness, the scheme that the improvement color harmony fades to the variable color of ozone gas.But in the ink-jet recording in recent years of the high image quality document image that can obtain comparing favourably with the silver salt photo, further improving of anti-gaseousness is necessary.
In addition, except improving the image fastness, when on the recording medium that porous materials such as alumina, silica is received material as ink, forming image,, require to improve image color (optical concentration) in order to obtain the degree of depth of sufficient gradation, shadow part.
In TOHKEMY 2000-290552 communique, proposed to use the scheme of the ink that contains two kinds of specific dyestuffs in order to improve image color.In addition, in TOHKEMY 2000-318300 communique, proposed recording medium is applied after the treatment agent that contains polymer substance, on recording medium, adhered to the ink that contains colorant and colorant is assembled, improved the scheme of image color.Further, in TOHKEMY 2002-275380 communique and the TOHKEMY 2003-292808 public affairs, propose to use new disazo dyes, trisazo dye, improved the scheme of image color.
Summary of the invention
In recent years, be accompanied by the requirement of high durableization, high image qualityization, studying and have image fastness and the higher ink of optical concentration more fully.
So people of the present invention carry out active research, found that the compound of following general formula (I) has sufficient image fastness, optical concentration is also than more excellent.
But the compound of following general formula (I) is sometimes according to its using method, and anti-tackiness is insufficient in the nozzle of record-header.In addition, although the compound optical concentration of following general formula (I) also than more excellent, wishes to become higher.
General formula (I)
(in the general formula (I), R
1, R
2Represent that independently of one another hydrogen atom, hydroxyl, amino, carboxyl, sulfonic group, carbonatoms are that 1～4 alkyl, carbonatoms are 1～4 alkoxyl group; R
3, R
4For hydrogen atom, carbonatoms be 1～4 alkyl, carbonatoms be 1～4 alkoxyl group, hydroxyl, can by hydroxyl or carbonatoms be carbonatoms that 1～4 alkoxyl group replaces be 1～4 alkyl, can by hydroxyl, carbonatoms be the carbonatoms of 1～4 alkoxyl group, sulfonic group or carboxyl substituted be 1～4 alkoxyl group, by the amino of alkyl or acyl substituted; N is 0 or 1.)
Therefore, the object of the present invention is to provide a kind of ink-jet black ink, it can improve the anti-tackiness of nozzle of weathering resistance, optical concentration and record-header.
In addition, another object of the present invention is to provide ink set, ink jet recording method, print cartridge, record cell and the ink-jet recording device that uses above-mentioned ink-jet to use black ink.
Above-mentioned purpose is finished by following the present invention.That is, ink-jet black ink of the present invention, it is the ink-jet black ink that contains colorant and water-miscible organic solvent at least, it is characterized in that,
Described colorant is the compound or its salt shown in the following general formula (I),
The relative permittivity under 20 ℃ be more than 30.0 and less than 70.0 and more than 25 ℃ of following solubilized 1.0 quality % the content of the water-miscible organic solvent of compound or its salt shown in the following general formula (I), be more than the 50.0 quality % with respect to ink-jet with the total content of the whole water-miscible organic solvents that contain in the black ink.
General formula (I)
(in the general formula (I), R
1, R
2Represent that independently of one another hydrogen atom, hydroxyl, amino, carboxyl, sulfonic group, carbonatoms are that 1～4 alkyl, carbonatoms are 1～4 alkoxyl group; R
3, R
4For hydrogen atom, carbonatoms be 1～4 alkyl, carbonatoms be 1～4 alkoxyl group, hydroxyl, can by hydroxyl or carbonatoms be carbonatoms that 1～4 alkoxyl group replaces be 1～4 alkyl, can by hydroxyl, carbonatoms be the carbonatoms of 1～4 alkoxyl group, sulfonic group or carboxyl substituted be 1～4 alkoxyl group, by the amino of alkyl or acyl substituted; N is 0 or 1.)
In addition, the ink set of another embodiment of the present invention, it is the ink set that is made of a plurality of inks, it is characterized in that, as black ink, comprises the ink-jet black ink of above-mentioned composition.
In addition, the ink jet recording method of another embodiment of the present invention, it is the ink jet recording method that has with the step of ink ejecting method ejection ink, it is characterized in that described ink is the ink-jet black ink of above-mentioned composition.
In addition, the print cartridge of another embodiment of the present invention, it is the print cartridge that possesses the ink accommodation section that holds ink, it is characterized in that, described ink is the ink-jet black ink of above-mentioned composition.
In addition, the record cell of another embodiment of the present invention, it is the record cell that possesses the ink accommodation section that holds ink and be used to spray the record-header of ink, it is characterized in that described ink is the ink-jet black ink of above-mentioned composition.
In addition, the ink-jet recording device of another embodiment of the present invention, it is the jet recording device that possesses the ink accommodation section that holds ink and be used to spray ink, it is characterized in that described ink is the ink-jet black ink of above-mentioned composition.
According to the present invention, can provide the ink that has sufficient weathering resistance and can form high image of optical concentration or point, more preferably the also excellent ink-jet black ink of the anti-tackiness of the nozzle of record-header.Further, the record that has excellent weather resistance thing can be provided, and can provide gradation of drop-out colour high record thing by using this ink.
Description of drawings
Fig. 1 is the stereographic map of recording unit.
Fig. 2 is the stereographic map of the portion of mechanism of recording unit.
Fig. 3 is the sectional view of recording unit.
Fig. 4 is the stereographic map that is illustrated in the state that the China ink jar is installed in the head cartridge.
Fig. 5 is the exploded perspective view of head cartridge.
Fig. 6 is the front view of the recording element substrate in the expression head cartridge.
Embodiment
Below, enumerate that preferred embodiment the present invention will be described in more detail.
In addition, in the present invention, be under the situation of salt at compound, salt is dissociated into ion and exists in ink, but for the purpose of convenient, is expressed as " containing salt ".
The ink-jet that people of the present invention are contained compound or its salt shown in the general formula (I) and then contained specific water-miscible organic solvent with specific composition for use obtains the reason of effect of the present invention with black ink (below, abbreviate " ink " as), is presumed as follows.
The colorant that is contained from the ink of record-header ejection is adsorbed in recording medium after ink is fallen on the recording medium.Particularly receive as ink on the recording medium of material, use the ink of the colorant that contains band anionic property electric charge and when forming image, infer phenomenon as described below takes place at the porous material that is possessing band cationic electric charge.The colorant of the band anionic property electric charge that is contained from the ink of record-header ejection is after ink is fallen on the recording medium, to the porous material generation intensive absorption of band cationic electric charge.Its result, a kind of solid-liquid separation takes place in colorant that is contained in the ink and aqueous medium.That is, colorant is fixed near the receiving layer skin section of recording medium, and on the contrary, charged hardly aqueous medium is penetrated into the depth direction of recording medium.
And in order to obtain having the image of high optical concentration, following 3 is important.
(1) the molar absorptivity height of colorant,
(2) in order to improve optical transmission, the material that forms the receiving layer of recording medium is transparent to visible light as far as possible,
(3) the colorant density in the receiving layer of raising recording medium.
Just, after ink is fallen on the recording medium, if near the fixing colorant skin section of recording medium as far as possible just can avoid forming the influence that the muddiness of the material of receiving layer is brought, and raising colorant density, thereby can show high optical concentration.
So, people of the present invention are at normally used various water-miscible organic solvents in the ink for inkjet, and the colorant that is contained in each water-miscible organic solvent that contained in the ink and the ink is studied to the relation of the degree (depth of penetration) of the depth direction infiltration of recording medium.Its result as can be known, the ink that contains the ink of the high water-miscible organic solvent of the relative permittivity water-miscible organic solvent low with containing relative permittivity is compared, the colorant that is contained in the ink shoals to the degree (depth of penetration) of the depth direction infiltration of recording medium, and optical concentration improves.
People of the present invention are presumed as follows the reason that produces above-mentioned phenomenon.The water-soluble solvent polarizability height that relative permittivity is high, so water-miscible organic solvent can't cover the cationic electric charge of porous material surface when the receiving layer of recording medium permeates.So the cationic of described porous material does not reduce very much.Its result falls the colorant and the aqueous medium that are contained in the ink on the recording medium solid-liquid separation takes place fast, colorant can be anchored near the recording medium surface effectively.
And then, people of the present invention have carried out detailed research to the relative permittivity of the water-miscible organic solvent that the colorant that contained in the ink is contained in the degree (depth of penetration) of the depth direction infiltration of recording medium and ink, found that, by containing relative permittivity is more than 30.0 and the water-miscible organic solvent of less than 70.0, colorant can be anchored near the recording medium surface effectively.
As can be known, when particularly the colorant that is contained in the ink is a compound or its salt shown in the general formula (I), significantly embody above-mentioned effect.Its reason is speculated as: the compound or its salt shown in the general formula (I) is compared with employed colorant in the present ink for inkjet, and high molar absorptivity is not only arranged, and because its molecular weight is big, therefore the speed that moves between porous material diminishes.
Just, by using relative permittivity is more than 30.0 and the water-miscible organic solvent of less than 70.0, keep porous material cationic effect and since big little these 2 effects of effect of speed that therefore between porous material, move of the molecular weight of compound or its salt shown in the general formula (I) act on with multiplying each other, colorant can be anchored near the recording medium surface thus, can realize high optical concentration.
And then the compound or its salt weathering resistance shown in the general formula (I) is also very excellent, therefore, according to the present invention, can have high optical concentration and high fastness concurrently.
(colorant)
Employed colorant is the compound or its salt shown in the following general formula (I) in the ink of the present invention.Described colorant has excellent weather resistance.Particularly, can reach the high-weatherability and the high optical concentration of the object of the invention by using described colorant in the ink of forming in the present invention.
General formula (I)
(in the general formula (I), R
1, R
2Represent that independently of one another hydrogen atom, hydroxyl, amino, carboxyl, sulfonic group, carbonatoms are that 1～4 alkyl, carbonatoms are 1～4 alkoxyl group; R
3, R
4For hydrogen atom, carbonatoms be 1～4 alkyl, carbonatoms be 1～4 alkoxyl group, hydroxyl, can by hydroxyl or carbonatoms be carbonatoms that 1～4 alkoxyl group replaces be 1～4 alkyl, can by hydroxyl, carbonatoms be the carbonatoms of 1～4 alkoxyl group, sulfonic group or carboxyl substituted be 1～4 alkoxyl group, by the amino of alkyl or acyl substituted; N is 0 or 1.)
Below, the object lesson as the compound or its salt shown in the general formula (I) illustrates exemplary compounds 1～3.Certainly, the colorant that uses among the present invention is not limited to these.In addition, also can use colorant more than 2 kinds simultaneously.In addition, in general formula (I), n=0 is expressed as follows and states exemplary compounds 2 such SO
3The position of H is H.
The lower limit of the content of compound or its salt shown in the general formula in the ink of the present invention (I) is preferably more than the 0.1 quality % with respect to the ink total mass, more preferably more than the 1.0 quality %.This is because during the lower limit less than 0.1 quality % of content, can't fully obtain the high optical concentration of effect of the present invention and high weathering resistance.In addition, the upper limit of the content of compound or its salt shown in the general formula (I) is preferably below the 15.0 quality % with respect to the ink total mass, more preferably below the 7.0 quality %.This is because when the upper limit of content surpassed 15.0 quality %, compound or its salt was assembled on recording medium shown in the general formula (I), produced the phenomenon (general bronzing) of sending metalluster.
(verification method of dyestuff)
In the checking of employed colorant, can be suitable for the verification method of following (1)～(3) of using high performance liquid chromatography (HPLC) in the present invention.
(1) retention time at peak
(2) maximum absorption wavelength at the peak of (1)
(3) the mass spectral M/Z at the peak of (1) (posi, nega)
The analysis condition of high performance liquid chromatography is as follows.To with the ink solution of pure water dilution into about 1000 times, carry out efficient liquid phase chromatographic analysis with following condition, measure the retention time (retention time) at peak and the maximum absorption wavelength at peak.
Post: Symmetry C18 2.1mm * 150mm
Column temperature: 40 ℃
Flow velocity: 0.2ml/min
·PDA：210nm～700nm
Moving phase and gradient condition: table 1
Table 1
| 0-5min | 5-40min | 40-45min | |
| A water | 85％ | 85％→0％ | 0％ |
| B methyl alcohol | 10％ | 10％→95％ | 95％ |
| The C0.2mol/l ammonium acetate solution | 5％ | 5％ | 5％ |
In addition, mass spectroscopy condition is as follows.To resulting peak, measure mass spectrum with following condition, measure posi, the nega of the strongest M/Z that is detected respectively.
The ionization method
ESI capillary voltage 3.5kV
300 ℃ of gases desolvate
120 ℃ of ion source temperatures
Detector posi 40V 200-1500amu/0.9sec
nega 40V 200-1500amu/0.9sec
The value of the retention time of exemplary compounds 1, maximum absorption wavelength, M/Z (posi), M/Z (nega) is as shown in table 2.Under the situation that meets the value shown in the table 2, can be judged as and meet compound used in the present invention.
Table 2
(other colorant)
In the present invention, except above-claimed cpd, can also use above-mentioned other colorant in addition as the toning colorant.
In addition, in order to form full-colour image etc., ink of the present invention can use with the combination of inks with other tone.For example, cyan, magenta ink, yellow ink etc.In addition, also these inks and the thin ink with same tone can be used in combination.These have the ink of other tone or the colorant of thin ink, can use known colorant, also can use new synthetic colorant.
Below, with toning with colorant, the object lesson that reaches the used colorant of other ink of using with black ink of the present invention illustrates by tone.Certainly, the present invention is not limited to these.
[magenta colorant]
C.I. directly red: 2,4,9,11,20,23,24,31,39,46,62,75,79,80,83,89,95,197,201,218,220,224,225,226,227,228,229,230 etc.
C.I. Xylene Red: 6,8,9,13,14,18,26,27,32,35,42,51,52,80,83,87,89,92,106,114,115,133,134,145,158,198,249,265,289 etc.
C.I. Food Red: 87,92,94 etc.
C.I. directly purple: 107 etc.
[cyan colorant]
1,15,22,25,41,76,77,80,86,90,98,106,108,120,158,163,168,199,226,307 C.I. sun blue:, etc.
C.I. acid blue: 1,7,9,15,22,23,25,29,40,43,59,62,74,78,80,90,100,102,104,112,117,127,138,158,161,203,204,221,244 etc.
[yellow colorant]
C.I. directly yellow: 8,11,12,27,28,33,39,44,50,58,85,86,87,88,89,98,100,110,132,173 etc.
C.I. turmeric yellow: 1,3,7,11,17,23,25,29,36,38,40,42,44,76,98,99 etc.
[black pigment]
C.I. directly black: 17,19,22,31,32,51,62,71,74,112,113,154,168,195 etc.
C.I. erie black: 2,48,51,52,110,115,156 etc.
C.I. food is black: 1,2 etc.
Dyestuff shown in the following general formula (II) or its salt
General formula (II)
(in the general formula (II), R
1, R
2, R
3, R
4Represent independently of one another hydrogen atom, hydroxyl, amino, carboxyl, sulfonic group, carbonatoms be 1～4 alkyl, carbonatoms be 1～4 alkoxyl group, by hydroxyl, carbonatoms be the alkoxyl group of 1～4 alkoxyl group, sulfonic group or carboxyl substituted, the carbonatoms that can further be replaced by carboxyl or sulfonic group be 1～4 alkoxyl group, by the amino of phenyl, alkyl or acyl substituted, n is 0 or 1.In addition, in general formula (II), n=0 represents to be all SO mutually with the compound or its salt shown in the general formula (I)
3The position of H is H.)
The condensation dye of the compound shown in compound shown in the following general formula (III) and the following general formula (IV)
General formula (III)
(in the general formula (III), M is hydrogen atom or alkali metal atom.)
General formula (IV)
(in the general formula (IV), R
1, R
2, R
3, R
4, R
5Represent that independently of one another hydrogen atom, halogen atom, hydroxyl, sulfonic group, carboxyl, carbonatoms are that 1～4 alkyl, carbonatoms are 1～4 alkoxyl group.)
(aqueous medium)
(relative permittivity under 20 ℃ is more than 30.0 and less than 70.0, and, at 25 ℃ of water-miscible organic solvents that can dissolve compound or its salt shown in the above general formulas of 1.0 quality % (I) down)
Relative permittivity under 20 ℃ used in the present invention is more than 30.0 and less than 70.0, and at 25 ℃ of water-miscible organic solvents that can dissolve compound or its salt shown in the above general formulas of 1.0 quality % (I) down, so long as show the relative permittivity of above-mentioned scope and the deliquescent water-miscible organic solvent of described compound or its salt, just be not particularly limited.Relative permittivity under 20 ℃ is more than 30.0 and less than 70.0, and, at 25 ℃ of object lessons that can dissolve the water-miscible organic solvent of compound or its salt shown in the above general formulas of 1.0 quality % (I) down, can list glycerine, ethylene glycol, Diethylene Glycol, 1,2-propylene glycol, 1, ammediol, 1, the 4-butyleneglycol.Wherein special preferably glycerine, ethylene glycol.When the compound or its salt combination shown in these water-miscible organic solvents and the general formula (I) is used as ink for inkjet, the ejection excellence of ink.
In the present invention, relative permittivity under 20 ℃ is more than 30.0 and less than 70.0, and, at 25 ℃ of content that can dissolve the water-miscible organic solvent of compound or its salt shown in the above general formulas of 1.0 quality % (I) down, with respect to the total content of the whole water-miscible organic solvents that contained in the ink, must be more than 50.0%.The situation of the ratio less than 50.0% of content and the ratio of content are that the situation more than 50.0% is compared, and the optical concentration of record thing reduces, and can't fully obtain effect of the present invention.In addition, the water-miscible organic solvent that is contained in the ink, can be that relative permittivity under 20 ℃ is more than 30.0 and less than 70.0 all, and, at 25 ℃ of water-miscible organic solvents that can dissolve compound or its salt shown in the above general formulas of 1.0 quality % (I) down.
In addition, relative permittivity under 20 ℃ used in the present invention is more than 30.0 and the water-miscible organic solvent of less than 70.0, must 25 ℃ down the reasons of compound or its salt shown in the dissolving above general formulas of 1.0 quality % (I) be for the adhesion that improves the record-header nozzle restorative.Just, if at 25 ℃ of content that can dissolve the water-miscible organic solvent of compound or its salt shown in the above general formulas of 1.0 quality % (I) down, total content with respect to whole water-miscible organic solvents that ink contained is lower than 50.0%, then the restorative reduction of adhesion under high temperature or low wet environment.
In addition, the mensuration of colorant solvability (solubleness) is carried out in the following order.In 100ml beaker (JIS R3503), add the aqueous solution that 50 grams have dissolved described colorant, be positioned over temperature and be 60 ℃, humidity and be in 20% the thermostatic bath, evaporation drying to per 3 hours quality change is below 0.01 gram.Then, the material with mortar grinding gained obtains powder.Under 25 ℃, make this powder dissolving until becoming state of saturation with respect to the target water-miscible organic solvent.Be used to value that the quality of the needed colorant of the state of reaching capacity tries to achieve divided by the total mass of water-miscible organic solvent and colorant as dissolution rate (solubleness).In addition, originally be under the situation of colorant of powder state, under 25 ℃, make its dissolving until becoming state of saturation, be used to value that the quality of the needed colorant of the state of reaching capacity tries to achieve divided by the total mass of water-miscible organic solvent and colorant as dissolution rate (solubleness) with respect to the target water-miscible organic solvent.
(other water-miscible organic solvent and water)
In ink of the present invention, except the relative permittivity under above-mentioned 20 ℃ is more than 30.0 and less than 70.0, and, 25 ℃ can dissolve down the water-miscible organic solvent of compound or its salt shown in the above general formulas of 1.0 quality % (I) beyond, obtaining the interpolation effect that these brought and not damaging in the scope of target effect of the present invention, can make the mixed solvent of water or water and various water-miscible organic solvents.
Water-miscible organic solvent, so long as water-solublely just be not particularly limited, can use carbonatomss such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, isopropylcarbinol, Pentyl alcohol is 1～5 alkyl alcohols; Amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE; Ketone such as acetone, diacetone alcohol or ketols; Ethers such as tetrahydrofuran (THF), dioxane; Oxyethane or epoxy propane copolymers such as triethylene glycol, TEG, dipropylene glycol, tripropylene glycol, polyoxyethylene glycol, polypropylene glycol; Propylene glycol, triglycol, 1,2, aklylene glycol classes such as 6-hexanetriol; Low alkyl group ethers such as glycol monomethyl methyl (or ethyl) ether, Diethylene Glycol monomethyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether; The lower dialkyl ethers of polyvalent alcohols such as triethylene glycol dimethyl (or ethyl) ether, TEG dimethyl (or ethyl) ether; Alkanolamine such as monoethanolamine, diethanolamine, trolamine; Tetramethylene sulfone, N-N-methyl-2-2-pyrrolidone N-, 2-Pyrrolidone etc.Above-mentioned water-miscible organic solvent can use separately, perhaps also can be used as mixture and uses.
Relative permittivity under these water-miscible organic solvents and above-mentioned 20 ℃ is more than 30.0 and less than 70.0, and, at 25 ℃ of total contents that can dissolve the water-miscible organic solvent of compound or its salt shown in the above general formulas of 1.0 quality % (I) down, be preferably 10 quality %～95 quality % with respect to the ink total mass, more preferably 10 quality %～80 quality %.Under the situation that content lacks than this scope, the adhesion of record-header is restorative to go wrong, and under the situation that content is Duoed than this scope, it is big that the viscosity of ink becomes, and the continuous ejection of ink goes wrong.
In addition, water preferably uses deionized water (ion exchanged water).The content of water is 10 quality %～90 quality % with respect to the ink total mass preferably.
(other additive)
In addition, in the present invention, can also contain various additives such as tensio-active agent, pH regulator agent, rust-preventive agent, sanitas, mould inhibitor, antioxidant, anti-reductive agent, evaporation accelerators, sequestrant, water-soluble polymers as required.
For example, the object lesson of tensio-active agent has nonionic surfactants such as anion surfactant, Voranol EP 2001 class, polyxyethylated ester class, polyoxyethylene sorbitol acid anhydride alkyl esters, acetylene alcohol, acetylenediol such as fatty acid salt, higher alcohol sulfate salt, liquid aliphatic oil sulfuric ester salt, alkylallyl sulfonate class, can suitably select to use these tensio-active agents more than a kind or 2 kinds.Wherein particularly acetylene alcohols, acetylenediol class have been given play to the effect of perviousness excellence to common paper, and be therefore preferred.The content of tensio-active agent in ink is 0.01 quality %～5 quality % with respect to the ink total mass preferably.
For the generation of the wetting printing distortion (departing from of the landing point of ink droplet) that causes of the spray nozzle front end that effectively suppresses record-header etc. and give the ejection characteristic, preferred ink is more than the 10mN/m (dyn/cm) in the surface tension under 25 ℃, more preferably more than the 20mN/m, and, surface tension be below the 60mN/m in this wise the content of decision table surface-active agent be preferred.In addition, when ink of the present invention is applicable to ink-jet recording device, have desired viscosity and the ink of pH in order to obtain good ejection characteristic, preferably to be adjusted into.
＜recording medium 〉
Employed recording medium when using ink of the present invention to form image is so long as just can use any recording medium by applying the recording medium that ink writes down.Wherein, the recording medium that forms by the porous matter particulate of band cationic electric charge of ink receiving layer preferably.Be that particulate below the 1 μ m is the recording medium that main body forms the ink receiving layer further preferably with median size.
The object lesson of described particulate can list aluminum oxide, alumina hydrate, with aluminium the surface carried out the cation-modified silica of surface-treated, has been to make on the silica granule surface of anionic property to have the cationic group and can react resulting silica granule etc. with the compound of the group (trimethoxy silylation etc.) of silica granule reaction on the surface.Wherein, the alumina hydrate that preferably is expressed from the next.
Al
2O
3-n(OH)
2n·
mH
2O
(in following formula, n represents any in 1,2 or 3 the integer, and m represents 0～10, preferably represents 0～5 value.Wherein, m and n are not 0 simultaneously.MH
2O also represents and mH as a rule
2The departing water that the formation of O lattice is irrelevant, therefore, m can round numbers or non-integral value.In addition, if heat this kind material, then m can reach 0 value.)
The alumina hydrate can pass through United States Patent (USP) the 4th, 242, No. 271, United States Patent (USP) the 4th, 202, the hydrolysis of the aluminium alkoxide of being put down in writing for No. 870, the hydrolysis of sodium aluminate, perhaps the aqueous solution that adds sodium sulfate, aluminum chloride etc. in the aqueous solution of sodium aluminate etc. put down in writing of the special public clear 57-44605 communique of Japanese Patent carries out known method such as neutral method and makes.
Use the excellences such as anchorage of the recording medium of above-mentioned alumina hydrate, so preferred owing to the colorant of the gloss, the transparency and the ink that are used for realizing that photograph image quality as described above is required.
The object lesson of tackiness agent can list water-soluble polymer, latex etc.For example, can use ethene copolymer latex, polyvinylpyrrolidone, maleic anhydride or its multipolymer, acrylate copolymers etc. such as derivatived celluloses such as polyvinyl alcohol or its modifier, starch or its modifier, gelatin or its modifier, gum arabic, carboxymethyl cellulose, Natvosol, Vltra tears, SBR latex, NBR latex, methyl methacrylate butadi ene copolymer latex, functional group modification polymer latex, ethylene vinyl acetate copolymer.Can from these, select a kind or make up as required more than 2 kinds and to use.
The ratio of mixture of particulate and tackiness agent is 1: 1～100: 1 with mass ratio preferably.Be limited to more than the 50 quality % under alumina particulate or the silica microparticle preferred content in the ink receiving layer, more preferably more than the 70 quality %, more preferably more than the 80 quality %, it is only being limited to below the 99 quality % on the content.The glue spread of ink receiving layer is preferably 10g/m in the drying solid composition
2More than, most preferably be 10～60g/m
2
Recording medium preferably has the supporter that is used to support above-mentioned ink receiving layer.As long as supporter can form the ink receiving layer by above-mentioned porous matter particulate, and provide the rigidity that to carry by the transfer mechanism of ink-jet printer etc., then have no particular limits, can use any supporter.For example between supporter and ink receiving layer, have mineral dyes such as barium sulfate, titanium oxide, zinc oxide etc. and can use resin coated paper with porous layer or the supporter that tackiness agent is coated with formation.
Also can use other additive in the ink receiving layer, for example, can list dispersion agent, thickening material, pH regulator agent, lubricant, mobile properties-correcting agent, tensio-active agent, defoamer, releasing agent, white dyes, UV light absorber, antioxidant etc. as required.
＜ink set 〉
Ink of the present invention also can be fit to use when forming ink set with other combination of inks.Ink set of the present invention is the state that other inks such as ink of the present invention and cyan, magenta ink, yellow ink, black ink are used together.In addition, can make up other inks, be not particularly limited as ink set.And so-called ink set comprises that a plurality of China inks jar integrally formed China ink jar itself is natural among the present invention, also comprises the situation that a plurality of independent China ink jars are used in combination, and then also comprises described China ink jar and the integrated situation about forming of record-header.
＜ink jet recording method 〉
Ink of the present invention is particularly suitable for having the ink jet recording method with the step of ink ejecting method ejection ink.Ink jet recording method comprises following method: ink is applied mechanical energy and spray the recording method of ink, and spray recording method of ink etc. by ink being applied heat energy.Particularly in the present invention, the preferred ink jet recording method that utilizes heat energy that uses.
＜print cartridge 〉
Be suitable for the print cartridge that uses ink of the present invention to write down, can list print cartridge with the ink accommodation section that holds these inks.
＜record cell 〉
Be suitable for the record cell that uses ink of the present invention to write down, can list and have the ink accommodation section that holds these inks and the record cell of record-header.Especially, can list described record-header and ink be applied heat energy, produce the record cell of ink droplets by described heat energy corresponding to recording signal.
＜ink-jet recording device 〉
The recording unit that is suitable for using ink of the present invention to write down can list indoor ink to the record-header with the ink accommodation section that holds these inks and apply heat energy corresponding to recording signal, produces the device of ink droplets by described heat energy.
Below, the general configuration of the portion of mechanism of ink-jet recording device is described.According to the effect of each mechanism, the recording unit main body is by sheet feed section, with paper delivery section, carriage portion, row's paper portion, cleaning section and protect the housing department with appearance design of these parts to constitute.Below, these parts are carried out briefly bright.
Fig. 1 is the stereographic map of recording unit, and in addition, Fig. 2 and Fig. 3 are the figure that is used for the internal mechanism of declare record apparatus main body, and Fig. 2 is the stereographic map that expression is seen from upper right quarter, and Fig. 3 is the sectional view of recording unit main body.
When carrying out paper supply in recording unit, at first, at the sheet feed section that comprises sheet feed stacker M2060, only the recording medium with the regulation number is sent to the roll gap portion that is made of paper feed roller M2080 and separate roller M2041.The recording medium of being sent into is only carried the recording medium of the top after roll gap portion is separated.After being fed to recording medium with the paper delivery section and being directed into pressure roller retainer M3000 and paper guide baffle plate M3030, be fed to this roller centering of conveying roller M3060 and pressure roller M3070.The roller that is made of conveying roller M3060 and pressure roller M3070 is to being driven and be rotated by LF motor E0002, and recording medium is rotated on the paper-pressing part M3040 by this and carries.
In carriage portion, when on recording medium, forming image, make record-header H1001 (Fig. 4) be configured in target image and form on the position, according to signal, to recording medium ejection ink from electric base E0014.About the detailed structure of record-header H1001 as described later, but its structure is to form on recording medium the structure of image by hocket repeatedly record main-scanning and subscan, when above-mentioned record main-scanning is write down by record-header H1001, balladeur train M4000 is scanned along column direction, and above-mentioned subscan makes recording medium carry along line direction by conveying roller M3060.
Form the record images medium at last and be sandwiched in the roll gap of the 1st exit roller M3110 and ratchet M3120, be transferred and be discharged on the paper disc M3160 at row paper portion place.
In addition, in cleaning section, for the record-header H1001 before and after the image recording is cleaned, make pump M5000 generation do the time spent under the tight state of contact of ink jet exit of covering M5010 and record-header H1001 when making, H1001 aspirates unwanted ink etc. from record-header.In addition, by opening under the state that covers M5010, suction remains in the ink that covers among the M5010, can not cause adhesion that residual ink causes and disadvantage subsequently.
(structure of record-header)
Structure to head cartridge H1000 describes.Head cartridge H1000 has the parts of record-header H1001 and lift-launch China ink jar H1900 and is used for the parts to record-header supply ink from China ink jar H1900, and releasably is equipped on the balladeur train M4000.
Fig. 4 is the state of China ink jar H1900 is installed in expression to head cartridge H1000 figure.Recording unit forms image by yellow, magenta, cyan, black, light magenta, nattierblue and green ink, therefore, and part that China ink jar H1900 also independently prepares 7 kinds of colors.In above-mentioned ink, at least a ink uses ink of the present invention.And, as shown in the figure, can freely load and unload with respect to head cartridge H1000 respectively.In addition, the loading and unloading of China ink jar H1900 can be carried out under the state that head cartridge H1000 is equipped on the balladeur train M4000.
Fig. 5 is the exploded perspective view of head cartridge H1000.In the drawings, head cartridge H1000 is formed parts H1600, strainer H1700, caulking gum H1800 etc. and is constituted by the 1st recording element substrate H1100 and the 2nd recording element substrate H1101, the 1st dull and stereotyped H1200, the 2nd dull and stereotyped H1400, electrical wiring substrate H1300, China ink jar retainer H1500, stream.
The 1st recording element substrate H1100 and the 2nd recording element substrate H1101 are the Si substrate, have formed a plurality of recording elements (nozzle) that are used to spray ink on one face by photoetching technique.Electrical wirings such as Al to the power supply of each recording element form by film technique, also can form by photoetching technique corresponding to a plurality of ink flow paths of each recording element.And the ink supply port that is used for supplying with inks to a plurality of ink flow paths is opening inside.
Fig. 6 is used to illustrate that the master of the structure of the 1st recording element substrate H1100 and the 2nd recording element substrate H1101 looks enlarged view.H2000～H2600 is the recording element row (hereinafter referred to as nozzle rows) corresponding to each different ink colors, constitutes the nozzle rows H2000 that is used to supply with yellow ink, 3 nozzle rows corresponding to these 3 kinds of colors that are used for the nozzle rows H2100 of supply red ink and are used to supply with the nozzle rows H2200 of cyan in the 1st recording element substrate H1100.In the 2nd recording element substrate H1101, constitute nozzle rows H2300, the nozzle rows H2400 that is used to supply with black ink that is used to supply with the nattierblue ink, 4 nozzle rows that are used to supply with the nozzle rows H2500 of orange ink and are used to supply with the nozzle rows H2600 of light magenta ink corresponding to these 4 kinds of colors.
Each nozzle rows by on the throughput direction of recording medium with 1200dpi (dot/inch; 768 nozzles of spacing parallel arranging reference value) constitute, and spray the ink droplet that about 2 skins rise.The port area of each nozzle ejiction opening is set at about 100 μ m
2In addition, the 1st recording element substrate H1100 and the 2nd recording element substrate H1101 are bonded and fixed on the 1st dull and stereotyped H1200, at this, are formed with the ink supply port H1201 that is used for to the 1st recording element substrate H1100 and the 2nd recording element substrate H1101 supply ink.
And, on the 1st dull and stereotyped H1200, be adhesively fixed with the 2nd dull and stereotyped H1400 with peristome, the 2nd dull and stereotyped H1400 maintains electrical wiring substrate H1300, so that electrical wiring substrate H1300 is electrically connected with the 1st recording element substrate H1100 and the 2nd recording element substrate H1101.
Electrical wiring substrate H1300 applies and is used for from being formed at the electrical signal of each nozzle ejection ink on the 1st recording element substrate H1100 and the 2nd recording element substrate H1101, and have electrical wiring corresponding to the 1st recording element substrate H1100 and the 2nd recording element substrate H1101, and be positioned at this electrical wiring end be used to receive external signal input terminal H1301 from the electrical signal of recording unit main body.External signal input terminal H1301 positioning and fixing is in the back side one side of China ink jar retainer H1500.
On the other hand, in the China ink that keeps China ink jar H1900 jar retainer H1500, for example be fixed with stream and form parts H1600, formed the ink flow path H1501 that leads to the 1st dull and stereotyped H1200 from China ink jar H1900 by ultrasonic welding.
China ink jar side end at the ink flow path H1501 that engages with China ink jar H1900 is provided with strainer H1700, so that can prevent the intrusion from the dust of outside.In addition, with engagement part that China ink jar H1900 engages on caulking gum H1800 is installed, can prevent that ink from evaporating from the engagement part.
And, to form the China ink jar retainer portion that parts H1600, strainer H1700 and caulking gum H1800 constitute by China ink jar retainer H1500, stream by bonding grade as described above, combine with the record head H1001 that constitutes by the 1st recording element substrate H1100, the 2nd recording element substrate H1101, the 1st dull and stereotyped H1200, electrical wiring substrate H1300 and the 2nd dull and stereotyped H1400, constituted head cartridge H1000 thus.
In addition, at this, a mode as record-header, the record-header that uses Bubble Jet (registered trademark) mode that electricity-heat converter (recording element) writes down given an example narrate, above-mentioned electricity-heat converter generates and is used for making ink produce the heat energy of filmwise boiling according to electrical signal.
About its representational structure and principle, for example preferably use in the 4th, 723, No. 129 specification sheetss of United States Patent (USP), the 4th, 740, No. 796 specification sheetss of United States Patent (USP) disclosed ultimate principle to carry out.This mode is asked any ways such as service type, successive type applicable to what is called, especially, under situation for the request service type, electricity-heat converter with thin slice that maintains liquid (ink) and the corresponding configuration of liquid flow path is applied at least one surpass the actuate signal that the temperature of nucleate boiling rises rapidly according to recorded information, thereby make electricity-heat converter produce heat energy, on the heat effect face of record-header, produce filmwise boiling, the result can form and this actuate signal bubble in the liquid (ink) one to one, is effective therefore.By growth, the contraction of this bubble, spray liquid (ink) through ejection with opening, form at least one drop.When this actuate signal adopts pulse mode, can immediately, suitably carry out growth, the contraction of bubble, therefore can realize the ejection of the good especially liquid of responsiveness (ink), be more preferred.
In addition, mode as the ink-jet recording device that has utilized second mechanical energy, can exemplify out such request service type ink jet print head, it comprises: the nozzle with a plurality of nozzles forms substrate, the relative components of stres that is made of piezoelectric and electro-conductive material that disposes with nozzle, the ink on every side that is full of this components of stres; This request service type ink jet print head makes the components of stres displacement by applying voltage, from the small droplets of nozzle ejection ink.
In addition, ink-jet recording device is not limited to the ink-jet recording device of as described above ink gun and China ink jar split, also can be ink gun and the ink-jet recording device of China ink jar inseparable one.In addition, China ink jar also can be arranged on the fixed position of device except separable or inseparable ground integrated and carry on the balladeur train with respect to ink gun, by the providing ink parts for example ink barrel supply with the form of ink to record-header.In addition, in China ink jar, be provided for record-header is applied under the situation of structure of suitable negative pressure, can adopt in the ink accommodation section of China ink jar the mode of cartridge to be set or to have flexible ink bag container and the direction of its internal volume is expanded in effect to the ink bag container the mode etc. of spring portion of reactive force.In addition, recording unit can also adopt the mode of the line-at-a-time printer that the proper alignment recording element forms in corresponding to the scope of recording medium overall with except adopting above-mentioned serial recording mode.
Embodiment
Below, the present invention will be described in more detail to use embodiment and comparative example, and still, as long as in the scope that does not exceed spirit of the present invention, the present invention is not subjected to any restriction of following examples.In addition, if do not specify, the ink composition of embodiment, comparative example means it is " mass parts ".
The modulation of＜colorant 〉
(modulation of compound (α))
In the water that has added yellow soda ash, add the compound of following formula (A) and dissolve, add hydrochloric acid, Sodium Nitrite again, carry out diazotization.In the muddy liquid of this diazonium, add 6-phenyl amino-1-hydroxyl naphthalene-3-sulfonic acid aqueous solution, under sodium carbonates' presence, dissolve, obtain reaction solution (A).Then, dissolving 2-thionamic acid adds hydrochloric acid, Sodium Nitrite in the presence of sodium hydroxide, carries out diazotization.Then, dissolving 6-amino-1-hydroxyl naphthalene-3-sulfonic acid adds acetic anhydride in the presence of sodium hydroxide, carries out acetylize.Under sodium carbonates' presence, to wherein dripping the muddy liquid of above-mentioned diazotization, carry out linked reaction, obtain reaction solution (B).In this reaction solution (B), add sodium hydroxide, then add sodium-chlor and saltout, obtain compound.In the presence of sodium hydroxide, this compound of dissolving adds hydrochloric acid, Sodium Nitrite in water, carries out diazotization.Under sodium carbonates' presence, in the muddy liquid of this diazonium, drip solution (A), finish linked reaction, obtain reaction solution.This reaction solution is saltoutd with sodium-chlor, filters then, thereby obtains compound (C).At N, in the dinethylformamide, add 2-nitro-4-cresols, toluene, potassium hydroxide, by with the methylbenzene azeotropic dephlegmate, drip propane sultone, add sodium hydroxide then, after it is concentrated, in autoclave, add the palladium charcoal, charge into hydrogen and obtain solution.By interpolation hydrochloric acid, Sodium Nitrite it is carried out diazotization, drip above-mentioned reaction solution (A), in the presence of sodium hydroxide, finish linked reaction, obtain reaction solution.By interpolation hydrochloric acid, Sodium Nitrite this reaction solution is carried out diazotization, in the aqueous solution that has dissolved above-claimed cpd (C), add the muddy liquid of this diazonium, finish linked reaction.With sodium-chlor it is saltoutd, filters, washs, thereby obtain compound (α).
Formula (A)
Compound (α)
The modulation of＜ink 〉
Various compositions shown in following table 3 and the table 4 are mixed, after fully stirring, carry out pressure filtration, modulate the ink of embodiment 1～7 and comparative example 1～9 with the strainer of aperture 0.2 μ m.
Table 3
(
*1) acetylenediol ethylene oxide adduct
(tensio-active agent; The manufacturing of Off ア イ Application ケ ミ カ Le is ground in the river)
Table 4
(
*1) acetylenediol ethylene oxide adduct
(tensio-active agent; The manufacturing of Off ア イ Application ケ ミ カ Le is ground in the river)
The manufacturing of＜recording medium 〉
In the pulp that contains bleached hardwood kraft pulp (LBPK) that 80 mass parts freenesss are 450mlCSF (Canadian StandaradFreeness), softwood tree bleached kraft pulp (NBPK) that 20 mass parts freenesss are 480mlCSF, add 0.60 mass parts cationic starch, 10 mass parts water-ground limestones, 15 mass parts light calcium carbonates, 0.10 mass parts alkyl ketene dimer, 0.03 mass parts cationic polyacrylamide, 0.40 mass parts Tai-Ace S 150, the preparation paper stock., in fourdrinier machine copy system described paper stock, carry out 3 road wet pressings, with multi-cartridge moisture eliminator drying thereafter.With the size press device impregnation Sumstar 190 aqueous solution, make solids component be 1.0g/m thereafter,
2, after the drying, carry out the machine satinage, obtaining Substance is 155g/m
2, degree of sizing is that 100 seconds, Gas permeability are that 50 seconds, Buick smoothness are that 30 seconds, the sharp rigidity of lattice are the base material of 11.0mN.
Then, on the base material of above-mentioned gained, following formation undercoat.At first, preparation is used to form the coating fluid of undercoat.Containing 100 mass parts kaolin (UltraWhite90; Engelhard makes)/mass ratio of zinc oxide/aluminium hydroxide is that the solid component concentration of 65/10/25 filler and the commercially available polyacrylic dispersion agent of 0.1 mass parts is in 70% the slurry, add 7 mass parts commercial styrene-butadiene-based latex, adjusting to solids component is 60%, obtains composition.Then, use knife coater, the coating said composition makes that drying coated amount is 15g/m on the two sides of base material
2, drying.Thereafter, carry out the machine satinage with linear pressure 150kgf/cm, obtaining Substance is 185g/m
2, degree of sizing is that 300 seconds, Gas permeability are that 3000 seconds, Buick smoothness are that 200 seconds, the sharp rigidity of lattice are the base material of the band undercoat of 11.5mN.The whiteness of the base material of band undercoat is 5 samples to the A4 size after the cutting, measures and obtain its mean value respectively.Its result, whiteness is L:95, a
*: 0, b
*:-2 (form and aspect with JIS Z8729 are obtained).
Then, form the ink receiving layer.The formation of ink receiving layer is after the coating of above-mentioned second surface treatment step,, after the firm impregnation of coating fluid is in undercoat, forms the ink receiving layer on undercoat that is.
It is as follows to form employed coating fluid of ink receiving layer and coating process etc.In the 4 quality % aqueous solution of aluminum chloride, add sodium aluminate, the pH of solution is adjusted into 4., under agitation make solution be warmed up to 90 ℃, stir a little while thereafter., in described solution once more add sodium aluminate, the pH of solution is adjusted into 10, remaining on the slaking reaction that carried out under 90 ℃ the state 40 hours thereafter.Thereafter, solution is reduced to room temperature, adjusting pH is about 7～8, obtains dispersion liquid.This dispersion liquid is carried out desalting treatment, thereafter, carry out dispergation with acetic acid and handle, obtain the colloidal sol of alumina hydrate.Concentrate this colloidal sol, obtain the solution of 17 quality %.In addition, with polyvinyl alcohol (trade(brand)name: PVA117; Kuraray makes) be dissolved in the pure water, obtain the solution of 9 quality %.Above-mentioned sol solution and polyvinyl alcohol solution are mixed stirring, make that alumina hydrate solids composition and polyvinyl alcohol solids component are 10: 1 by quality ratio, obtain dispersion liquid.Use the mould coating machine, on base material, be coated with, make the drying coated amount of described dispersion liquid become 35g/m with per minute 30m
2170 ℃ dry substrate form ink receiving layer thereafter.Use the rewetting cast coater, the wet treatment again of hot water is used on the ink receiving layer surface of this recording medium, obtain recording medium.
The relative permittivity of＜water-miscible organic solvent 〉
Use LCR メ one 4284A (Japanese ヒ ユ one レ Star ト パ Star カ one De manufacturing), under the condition of 20 ℃ of room temperatures, mensuration frequency 1MHz, measure the relative permittivity of various water-miscible organic solvents.The result is shown in the table 5.
Table 5
| The solvent name | Relative permittivity (mensuration frequency: 1MHz) |
| Glycerine | 43.0 |
| Ethylene glycol | 38.1 |
| 1, the 2-propylene glycol | 32.2 |
| 1, ammediol | 34.8 |
| 1, the 4-butyleneglycol | 31.3 |
| Diethylene Glycol | 32.5 |
| 2-Pyrrolidone | 27.5 |
| 1,2, the 6-hexanetriol | 28.5 |
| Diethylene glycol monobutyl ether | 10.3 |
| Acetylenol E100( ＊1) | 8.2 |
(
*1) acetylenediol ethylene oxide adduct
(tensio-active agent; The manufacturing of Off ア イ Application ケ ミ カ Le is ground in the river)
The dissolution rate of＜compound (α) 〉
In 100ml beaker (JIS R3503), add the aqueous solution that 50 grams have dissolved colorant, be positioned over temperature and be 60 ℃, humidity and be in 20% the thermostatic bath, evaporation drying to per 3 hours quality change is below 0.01 gram.Then, the material with mortar grinding gained obtains powder.Under 25 ℃, make this powder dissolving, until becoming state of saturation with respect to various water-miscible organic solvents.The value of trying to achieve divided by the total mass of water-miscible organic solvent and colorant for the quality of the needed colorant of the state of reaching capacity is as dissolution rate (solubleness).The results are shown in the table 6.
Table 6
| The solvent name | Dissolution rate (25 ℃) |
| Glycerine | 14.9 |
| Ethylene glycol | 26.7 |
| 1, the 2-propylene glycol | 1.5 |
| 1, ammediol | 5.4 |
| 1, the 4-butyleneglycol | 1.1 |
| Diethylene Glycol | 28.2 |
| 2-Pyrrolidone | 22.3 |
| 1,2, the 6-hexanetriol | 1.8 |
| Diethylene glycol monobutyl ether | 0.011 |
| Acetylenol E100( ＊1) | 0.025 |
(
*1) acetylenediol ethylene oxide adduct
(tensio-active agent; The manufacturing of Off ア イ Application ケ ミ カ Le is ground in the river)
＜estimate
According to following metewand following project is estimated.
＜optical concentration 〉
Ink-jet printer (the trade(brand)name of making in Canon: the ink that loads above-mentioned embodiment that obtains 1～7 and comparative example 1～9 BJ F900) respectively, in temperature is that 25 ℃, humidity are in 60% the environment, to the above-mentioned recording medium that obtains, the marking ink applied amount is 100% full pattern spot.In temperature is that 25 ℃, humidity are 60% environment with dry 24 hours of the record thing of gained, then image is carried out the mensuration of optical concentration (image color).In addition, use spectrophotometer (Spectorolino in the mensuration; Gretag Macbeth makes).The benchmark of optical concentration is as follows.Evaluation result is shown in table 7.
AA: optical concentration is more than 2.50
A: optical concentration is 2.45 above less thaies 2.50
B: optical concentration is more than 2.40 and less than 2.45
C: optical concentration less than 2.40
＜adhesion is restorative 〉
Ink-jet printer that Canon makes (trade(brand)name: BJ F900) fill the ink of the embodiment 1～7 of above-mentioned gained and comparative example 1～9 with the record head after, unload the record head, ejiction opening is exposed under the environment gas, is that 35 ℃, humidity are to place for 2 weeks in 15% the environment in temperature., will write down head once more be installed to printer main body on, carry out ink suction recovery operation and printing, restorative evaluation of adhering thereafter.The restorative benchmark of adhering is as follows.Evaluation result is shown in the table 7.
A: install after the record-header, aspirate in 2 times, all nozzles return to and can spray no problemly
B: install after the record-header, in the suction more than 3 times, 4 times, all nozzles can return to no problemly and spray
C: install after the record-header, even if carry out suction more than 5 times, the also nozzle that exists part to spray
Table 7
(
*2) the quality % of the total content of the water-miscible organic solvent that contains in black ink with respect to ink-jet at the content of the water-miscible organic solvent of compound or its salt shown in 25 ℃ of following solubilized above general formulas of 1.0 quality % (I)
The application requires to enjoy in the right of priority of Japanese patent application 2005-192194 number of Japanese patent application 2004-196448 number that proposed on July 2nd, 2004 and proposition on June 30th, 2005, quotes the part of its content as the application.
Claims (5)
1. ink-jet black ink, it contains colorant and water-miscible organic solvent at least, it is characterized in that,
Described colorant is the compound or its salt shown in the following general formula I,
Relative permittivity under 20 ℃ is more than 30.0 and less than 70.0 and at the content of the water-miscible organic solvent of compound or its salt shown in 25 ℃ of above following general formula I of following solubilized 1.0 quality %, is more than the 50.0 quality % with respect to ink-jet with the total content of the whole water-miscible organic solvents that contain in the black ink
With respect to the ink total mass, the content of compound or its salt shown in the general formula I is below the above 15.0 quality % of 0.1 quality %,
General formula I
In the general formula I, R
1, R
2Represent that independently of one another hydrogen atom, hydroxyl, amino, carboxyl, sulfonic group, carbonatoms are that 1～4 alkyl, carbonatoms are 1～4 alkoxyl group; R
3, R
4For hydrogen atom, carbonatoms be 1～4 alkyl, carbonatoms be 1～4 alkoxyl group, hydroxyl, can by hydroxyl or carbonatoms be carbonatoms that 1～4 alkoxyl group replaces be 1～4 alkyl, can by hydroxyl, carbonatoms be the carbonatoms of 1～4 alkoxyl group, sulfonic group or carboxyl substituted be 1～4 alkoxyl group, by the amino of alkyl or acyl substituted; N is 0 or 1.
2. ink-jet black ink according to claim 1, wherein, described relative permittivity under 20 ℃ is more than 30.0 and less than 70.0, and, water-miscible organic solvent at the compound or its salt shown in 25 ℃ of above following general formula I of following solubilized 1.0 quality % is selected from glycerine, ethylene glycol, Diethylene Glycol, 1,2-propylene glycol, 1, ammediol, 1 is in the group that the 4-butyleneglycol is formed.
3. ink set, it is made of a plurality of inks, it is characterized in that, as black ink, comprises claim 1 or 2 described inks.
4. ink jet recording method, the step that it has with ink ejecting method ejection ink is characterized in that described ink is claim 1 or 2 described ink-jet black inks.
5. print cartridge, it possesses the ink accommodation section that holds ink, it is characterized in that, and described ink is claim 1 or 2 described ink-jet black inks.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP196448/2004 | 2004-07-02 | ||
| JP2004196448 | 2004-07-02 | ||
| JP192194/2005 | 2005-06-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1977007A CN1977007A (en) | 2007-06-06 |
| CN100545223C true CN100545223C (en) | 2009-09-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580021934 Expired - Fee Related CN100545223C (en) | 2004-07-02 | 2005-07-04 | Ink-jet black ink, ink set, ink jet recording method, print cartridge, record cell and ink-jet recording device |
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| CN (1) | CN100545223C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107020817A (en) * | 2016-01-08 | 2017-08-08 | 佳能株式会社 | Liquid discharge apparatus and liquid discharging head |
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| JP2002226750A (en) * | 2001-02-06 | 2002-08-14 | Sharp Corp | Water-based ink |
| CN1389527A (en) * | 2001-06-05 | 2003-01-08 | 户田工业株式会社 | Colourant for ink-jet printing ink, ink-jet printing ink, pigment-water dispersion liquid comprising said colourant, and organic and inorganic compound particles |
| CN1403512A (en) * | 2001-08-22 | 2003-03-19 | 佳能株式会社 | Printing ink, printing ink composition, ink-jet recording method, ink jet recording apparatus, recording unit and ink box |
| WO2003106572A1 (en) * | 2002-06-01 | 2003-12-24 | Avecia Limited | Printing process using specified azo compounds |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107020817A (en) * | 2016-01-08 | 2017-08-08 | 佳能株式会社 | Liquid discharge apparatus and liquid discharging head |
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| CN1977007A (en) | 2007-06-06 |
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