CN101298526A - Ink jet ink, ink jet recording method, ink cartridge, recording unit and ink jet recording apparatus - Google Patents
Ink jet ink, ink jet recording method, ink cartridge, recording unit and ink jet recording apparatus Download PDFInfo
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- CN101298526A CN101298526A CNA2008100946766A CN200810094676A CN101298526A CN 101298526 A CN101298526 A CN 101298526A CN A2008100946766 A CNA2008100946766 A CN A2008100946766A CN 200810094676 A CN200810094676 A CN 200810094676A CN 101298526 A CN101298526 A CN 101298526A
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Abstract
The present invention provides an ink jet ink having a magenta color which gives an image excellent in magenta color tone and also excellent in image fastness (lightfastness and gas resistance). The ink jet ink includes a first coloring material that is an anthrapyridone compound having a structure represented by general formula (I) and/or general formula (II) and a second coloring material that is an azo compound having a structure represented by general formula (III), wherein the mass ratio of the content of the first coloring material to the content of the second coloring material is from 2.5 or more to 10.0 or less.
Description
Technical field
The present invention relates to ink-jet China ink, ink jet recording method, print cartridge, record cell and ink jet recording device.
Background technology
Ink jet recording method is the method that forms image on recording medium such as common paper and the glossy media (glossy media) by ink droplet is applied to.This method drops into rapidly widely by the writing speed that reduces cost and improve ink jet recording device and uses.In addition, except being obtained by ink jet recording method the progress of high quality graphic aspect, along with popularizing rapidly of digital camera, ink jet recording method is used as the image output method that compares favourably with photographic silver halide (photograph) usually.
In recent years, the further raising (progress) of acquisition high quality graphic minimizes and follows colour gamut (color gamut) improvement of the introducing of polychrome China ink to reach by ink droplet.On the other hand, the demand of coloured material and China ink is uprised, wherein aspect the reliability of the improvement of coupling development and obstruction and jetting stability, require stricter character.
On the other hand, as the problem of ink jet recording method, mention that ink jet recording method is relatively poor aspect the image package stability of the recorded matter that obtains.Usually, compare with photographic silver halide, the image package stability of the recorded matter that obtains by ink jet recording method is low.When recorded matter is exposed to light, wet, heat especially for a long time, when being present in airborne environmental gas etc., having the coloured material deterioration on the recorded matter and be easy to produce the problem that picture tone changes and fades.
Especially, contain the fastness of the image that dyestuff forms as the dye ink of coloured material from use, particularly sunproof viewpoint has become a problem for the distinctive photostabilization of following chemical reaction of coloured material is low.Propose a lot of suggestions and solved this sunproof problem, thereby improved the photostabilization of image.Particularly proposed much the suggestion about the dyestuff that is used for magenta ink, it has low image package stability in various cyans, magenta and yellow ink.
For example, exist about the suggestion (Japanese Patent Application Laid-Open H08-073791 and Japanese Patent Application Laid-Open No.H09-255882) of xanthene dye with azoic dyestuff conduct can formation coloured material of image package stability such as water tolerance and excellent color tone that uses H acid.Yet the tone of xanthene dye is very good, but the non-constant of its photostabilization.On the other hand, use the azoic dyestuff of H acid may have good color tone, but its photostabilization and anti-gaseousness are poor.Although the research of the magenta dye that exploitation color harmony photostabilization is good is carried out on the dyestuff of these kinds widely, still not talkative photostabilization level and the dyestuff with other form and aspect are enough as being that the cyan dye of example compares with yellow dyes with the copper phthalocyaine dye.
In addition, exist about the suggestion (Japanese Patent Application Laid-Open No.2005-008868) of Anthrapyridone dyes as the good magenta dye of color harmony photostabilization.Yet, also do not have to obtain to satisfy to be equal to the sharpness (clarity) of dyestuff, anti-gaseousness and sunproof magenta dye with other form and aspect.
Existence is about can be by containing the suggestion (Japanese Patent Application Laid-Open 2005-105136 and Japanese Patent Application Laid-Open 2005-307068) that Anthrapyridone dyes and azoic dyestuff form the magenta ink of tone, ozone resistance and photostabilization excellent images.These are suggested and understand that thereby the magenta ink that can form anti-gaseousness and photostabilization excellent images can obtain with the characteristic that the azoic dyestuff with low anti-gaseousness and high-light-fastness uses benefit to taste each other by making to have high anti-gaseousness and hang down sunproof Anthrapyridone dyes.Yet, although by with only contain the image that Anthrapyridone dyes and one of azoic dyestuff China ink as coloured material forms and compare, the image that forms by the China ink that contains Anthrapyridone dyes and azoic dyestuff improves anti-gaseousness and photostabilization to a certain extent, but does not reach the fastness level that requires in recent years.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of ink-jet China ink with magenta tone, it provides tone, photostabilization and anti-gaseousness excellent images.In addition, the purpose of this invention is to provide a kind of ink-jet China ink with magenta tone, it provides tone, photostabilization, anti-gaseousness and optical density(OD) excellent images.Another object of the present invention provides ink jet recording method, print cartridge, record cell and the ink jet recording device of the above-mentioned ink-jet China ink of whole uses.
Achieve the above object by the present invention.Particularly, ink-jet China ink according to embodiment of the present invention comprises first coloured material and at least two kinds of coloured materials of second coloured material, and this first coloured material is by the compound of following general formula (I) expression and at least a by the compound of following general formula (II) expression; Second coloured material is the compound by following general formula (III) expression, wherein the mass ratio of the content of first coloured material (quality %) and the content (quality %) of second coloured material be from more than 2.5 to below 10.0.
General formula (I)
(wherein R represents hydrogen atom, alkyl, hydroxyalkyl, cyclohexyl, alkyl monosubstituted amino alkyl or dialkyl aminoalkyl independently; M represents hydrogen atom, basic metal, ammonium or organic ammonium independently; X represents linking group)
General formula (II)
(R wherein
1Expression hydrogen atom or alkyl; M represents 1 to 3 integer; M represents hydrogen atom, basic metal, ammonium or organic ammonium independently);
General formula (III)
(R wherein
2, R
3, R
4And R
5Represent alkyl independently of one another; M represents hydrogen atom, basic metal, ammonium or organic ammonium independently).
In addition, ink jet recording method according to another embodiment of the invention is wherein by the ink jet recording method of ink-jet systems eject China ink to write down by ink-jet systems eject China ink on recording medium, and wherein this China ink is the ink-jet China ink of above-mentioned formation.
In addition, Inkjet Cartridge according to another embodiment of the invention is to be provided with the print cartridge that is used to store black black reservoir, and wherein this China ink is the ink-jet China ink of above-mentioned formation.
In addition, be to be provided with to be used to the record cell storing the black reservoir of China ink and be used to spray the record-header of China ink according to the record cell of another embodiment of the present invention, wherein this China ink is the ink-jet China ink of above-mentioned formation.
In addition, be to be provided with to be used to the ink jet recording device storing the black reservoir of China ink and be used to spray the record-header of China ink according to the ink jet recording device of another embodiment of the present invention, wherein this China ink is the ink-jet China ink of above-mentioned formation.
Embodiment of the present invention can offer out the ink-jet China ink of tone, photostabilization and anti-gaseousness excellent images.In addition, embodiment of the present invention can provide the China ink of the ink-jet with magenta tone, and it provides tone, photostabilization, anti-gaseousness and optical density(OD) excellent images.Another embodiment of the present invention can provide ink jet recording method, print cartridge, record cell and the ink jet recording device of the above-mentioned ink-jet China ink of whole uses.
Description of drawings
Fig. 1 is the skeleton view of ink jet recording device.
Fig. 2 is the skeleton view of portion of ink jet recording device mechanism.
Fig. 3 is the sectional view of ink jet recording device.
Fig. 4 is the skeleton view that explanation is installed in print cartridge the state on the head cartridge (head cartridge).
Fig. 5 is the decomposition diagram of a box.
Fig. 6 is the front view of recording element substrate in the explanation box.
Embodiment
Enumerate and describe in detail the preferred exemplary of the present invention below.
Notice that when compound was salt, this salt dissociated and is present in the China ink as ion, but for simplicity, with this state description is in the present invention " black saliferous ".
＜China ink 〉
Below detailed description is comprised the ink-jet China ink of the present invention component of (hereinafter, can only be called China ink).Attention: by the compound of general formula (I) expression, can abbreviate " compound of general formula (I) ", " compound of general formula (II) " and " compound of general formula (III) " respectively as by the compound of general formula (II) expression with by the compound of general formula (III) expression.
As the inventor's result of study, find to have good photostabilization and as the ideal tone of magenta ink image can every kind of dyestuff has the Anthrapyridone dyes of ad hoc structure and the ink composition of azoic dyestuff obtains by containing with specific ratio.
One of feature of China ink of the present invention is to be used in combination the compound of the compound of the following general formula (I) of representing Anthrapyridone dyes separately and/or following general formula (II) as first coloured material, and the compound of general formula (III) that will represent azoic dyestuff is as second coloured material.
＜the first coloured material: by the compound of general formula (I) expression and/or the compound of representing by general formula (II) 〉
China ink of the present invention must contain the compound of the compound of the following general formula (I) that has the good feature of color harmony photostabilization separately and/or following general formula (II) as first coloured material.In the present invention, especially preferably use the compound of general formula (I) as first coloured material.Hereinafter, these general formulas will be described.
General formula (I)
In general formula (I), R represents hydrogen atom, alkyl, hydroxyalkyl, cyclohexyl, alkyl monosubstituted amino alkyl or dialkyl aminoalkyl independently; M represents hydrogen atom, basic metal, ammonium or organic ammonium independently; X represents linking group.
General formula (II)
In general formula (II), R
1Expression hydrogen atom or alkyl; M represents 1 to 3 integer; M represents hydrogen atom, basic metal, ammonium or organic ammonium independently.
R in the general formula (I) represents hydrogen atom, alkyl, hydroxyalkyl, cyclohexyl, alkyl monosubstituted amino alkyl or dialkyl aminoalkyl independently.
As alkyl, can mention alkyl with 1 to 8 carbon atom.Specific examples comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, isobutyl-, n-pentyl, n-hexyl, n-heptyl and n-octyl.
As hydroxyalkyl, can mention hydroxyalkyl with 1 to 4 carbon atom.Specific examples comprises methylol, hydroxyethyl, hydroxypropyl and hydroxyl butyl.Alkyl in the hydroxyalkyl comprises straight chain, side chain and cyclic alkyl, preferred especially straight chained alkyl.The position of substitution of hydroxyl can be selected arbitrarily in the abovementioned alkyl, but the hydroxyl that replaces particularly preferably in end, for example, 2-hydroxyethyl, 3-hydroxypropyl and 4-hydroxyl butyl.
As the alkyl monosubstituted amino alkyl, can mention list (C
1-4) alkylamino (C
1-4) alkyl.Specific examples comprises monomethyl aminopropyl and single ethylamino propyl group.
As dialkyl aminoalkyl, can mention two (C
1-4) alkylamino (C
1-4) alkyl.Specific examples comprises dimethylaminopropyl and diethylamino ethyl.
In the present invention, one of the preferred hydrogen atom of R, alkyl and cyclohexyl in the general formula (I), more preferably one of hydrogen atom and alkyl, most preferable.
X in the general formula (I) represents linking group.The example of linking group comprises following linking group 1 to 7.In linking group 1 to 7, by symbol "
*" bonding part (bonding hand) of expression is the bonding part of each nitrogen-atoms, and one of two different triazine rings Direct Bonding is to each nitrogen-atoms.The preferred especially linking group 1 that uses in the following linking group.
Linking group 1:
In linking group 1, n represents 2 to 8, and is preferred 2 to 6, more preferably 2; Symbol "
*" represent the bonding position of one of two different triazine rings separately.
Linking group 2:
In linking group 2, R
aRepresent hydrogen atom or methyl independently; Symbol "
*" represent the bonding position of one of two different triazine rings separately.
Linking group 3:
In linking group 3, symbol "
*" represent the bonding position of one of two different triazine rings separately.
Linking group 4:
In linking group 4, symbol "
*" represent the bonding position of one of two different triazine rings separately.
Linking group 5:
In linking group 5, symbol "
*" represent the bonding position of one of two different triazine rings separately.
Linking group 6:
At linking group 6, m represents 2 to 4; Symbol "
*" represent the bonding position of one of two different triazine rings separately.
Linking group 7:
In linking group 7, symbol "
*" represent the bonding position of one of two different triazine rings separately.
At general formula (I) with (II), M represents one of hydrogen atom, basic metal, ammonium and organic ammonium independently.Alkali-metal example comprises lithium, sodium and potassium.The example of organic ammonium comprises ethanamide, benzamide, trimethylammonium amino, butyl amino, diethylamino, phenyl amino and trolamine.
According to the solvability in the aqueous medium that comprises China ink, the alkyl in the general formula (II) preferably has 1 to 3 carbon atom, and specific examples comprises methyl, ethyl, uncle's propyl group and Zhong Bingji.Notice that when this alkyl had carbon atom more than 4, the hydrophobicity of coloured material was may be for this coloured material too high so that be insoluble in the aqueous medium that comprises China ink.
The preferred embodiment of the compound of the compound of general formula (I) and general formula (II) comprises following exemplary compounds 1 to 4.Note of the formal description of following exemplary compounds with free acid.Certainly, the invention is not restricted to following exemplary compounds, as long as compound is included in the structure and definition thereof of one of general formula (I) and general formula (II).In the present invention, one of the exemplary compounds 1 in the following exemplary compounds of especially preferred use and exemplary compounds 3.Wherein, usage example compound 1 most preferably.
Exemplary compounds 1
[the A:SO in the formula
3 -HN
+(CH
2CH
2OH)
3]
Exemplary compounds 3
Exemplary compounds 4
[SO
3HNMe
3:SO
3 -·HN
+(CH
3)
3，COOHNMe
3:COO
-·HN
+(CH
3)
3]
[second coloured material :] by the compound of general formula (III) expression
China ink of the present invention must contain the compound of the good especially following general formula (III) of tone as second coloured material.
General formula (III)
In general formula (III), R
2, R
3, R
4And R
5Represent alkyl independently of one another; M represents hydrogen atom, basic metal, ammonium or organic ammonium independently.
According to the solvability in the aqueous medium that comprises China ink, the alkyl in the general formula (III) preferably has 1 to 3 carbon atom, and specific examples comprises methyl, ethyl, n-propyl and sec.-propyl.Notice that when this alkyl had carbon atom more than 4, the hydrophobicity of coloured material was may be for this coloured material too high so that be insoluble in the aqueous medium that comprises China ink.
In general formula (III), M represents one of hydrogen atom, basic metal, ammonium and organic ammonium independently.Alkali-metal example comprises lithium, sodium and potassium.The example of organic ammonium comprises ethanamide, benzamide, methylamino, butyl amino, diethylamino, triethyl amino and phenyl amino.
The preferred embodiment of the compound of general formula (III) comprises following exemplary compounds 5 to 7.Note of the formal description of following exemplary compounds with free acid.Certainly, the invention is not restricted to following exemplary compounds, as long as compound is included in the structure and definition thereof of general formula (III).In the present invention, the especially preferred exemplary compounds of using in the following exemplary compounds 6.
Exemplary compounds 5
Exemplary compounds 6
Exemplary compounds 7
[SO
3HNEt
3:SO
3 -·HN
+(C
2H
5)
3]
Note, limited as the structure of the azoic dyestuff of second coloured material in the present invention, promptly be monoazo-dyes.Can not obtain to have good sunproof image by containing it for one of the compound of the general formula of Anthrapyridone dyes (I) and compound of general formula (II) and its China ink for the compound combination of the following general formula (IV) of azoic dyestuff.
General formula (IV)
In general formula (IV), R
1, R
2And R
3Independently expression have the replacement of 1 to 9 carbon atom or non-replacement alkyl, have 1 to 9 carbon atom alkoxyl group, halogen atom, hydrogen atom, hydroxyl, replacement or non-replacement formamyl, replacement or non-replacement sulfamyl, replacement or non-replacement amino, nitro, sulfonate group (sulfonategroup), have 1 to 9 carbon atom alkyl sulphonyl, have aryl sulfonyl, carboxyl or the carboxylic acid ester groups of 6 to 15 carbon atoms; I represents 0,1 or 2; R
4, R
5And R
6Represent hydrogen atom independently, have 1 to 18 carbon atom alkyl, have alkenyl, aryl, aralkyl, alicyclic radical or the heterocyclic radical of 2 to 18 carbon atoms, wherein the above-mentioned group except that hydrogen atom can have substituting group.
[content of coloured material]
The compound of the compound of general formula (I) and general formula (II) has the magenta tone that turns blue, and has the low characteristic of optical density(OD) of recorded matter.On the other hand, the compound of general formula (III) has the magenta tone of jaundice, and has the high characteristic of optical density(OD) of recorded matter.In the present invention, the image with ideal magenta tone (further details referring to following) can obtain by the compound combination that use has one of the compound of general formula (I) of above-mentioned characteristic and compound of general formula (II) and a general formula (III).
When further studying these coloured materials, the inventor obtains following content.That is, be used in combination these coloured materials, provide to have the sunproof photostabilization that makes up institute's estimated performance that compound had separately that surpasses by one of general formula (I) and general formula (II) and general formula (III) far away with specific mass ratio.Bring into play synergy and provide reason also unclear than being used in combination these coloured materials with extra fine quality, but the inventor is presumed as follows with the sunproof image that surpasses expection.Notice that in the following description, degree of fixation (fixability) is meant the amount of the dyestuff that is absorbed in the China ink on the porous insert with cationic charge (as aluminum oxide) that comprises recording medium China ink receiving layer.Low degree of fixation represents that the absorbed dose of dyestuff is little, and high degree of fixation represents that the absorbed dose of dyestuff is big.
The inventor's result of study has shown Anthrapyridone dyes, for example, is tending towards that by the compound of general formula (I) and general formula (II) the black receiving layer of recording medium is had lower degree of fixation.When the China ink that this is contained this Anthrapyridone dyes put on recording medium, because this dyestuff has the characteristic of low anchorage, so the absorbed dose on the porous insert was little.As a result, dyestuff may infiltrate black receiving layer along the black receiving layer thickness direction degree of depth.On the other hand, the inventor's result of study has shown azoic dyestuff, and for example the compound by general formula (III) is tending towards having higher degree of fixation on the black receiving layer of recording medium.When the China ink that this is contained this azoic dyestuff put on recording medium, because this dyestuff has the characteristic of high anchorage, so the absorbed dose on the porous insert was big.As a result, dyestuff may infiltrate black receiving layer along the only shallow degree of black receiving layer thickness direction ground.
When will contain all have above-mentioned characteristic its for one of the compound of the general formula of Anthrapyridone dyes (I) and compound of general formula (II) with and be the China ink of the present invention of compound of the general formula (III) of azoic dyestuff when putting on recording medium respectively, state is presumed as follows.That is, infer that the compound of general formula (I) and the compound of general formula (II) infiltrate black receiving layer along the black receiving layer thickness direction degree of depth, on the other hand, the compound of general formula (III) infiltrates black receiving layer along the only shallow degree of black receiving layer thickness direction ground.That is, the compound of the compound of general formula (I) and general formula (II) is different with the compound of general formula (III) along the distributing position of black receiving layer thickness direction.Owing to this reason, infer that the compound that is distributed in the general formula (III) of shallow position along black receiving layer thickness direction plays a part inhibition and is distributed in the compound of the compound of the general formula (I) that deep-seated puts and general formula (II) by photolysis along black receiving layer thickness direction.As a result, infer that being used in combination these coloured materials with the extra fine quality ratio can make us obtain the sunproof photostabilization that makes up institute's estimated performance that far has separately above the compound by one of the compound of general formula (I) and compound of general formula (II) and general formula (III).
Particularly, in order to obtain effect of the present invention, based on the mass ratio (first coloured material/second coloured material) of the content (quality %) of first coloured material of total black quality and the content (quality %) of second coloured material must be from more than 2.5 to below 10.0.That is, { (content of one of compound of the compound of general formula (I) and general formula (II))/(content of the compound of general formula (III)) } must be from more than 2.5 to below 10.0.By with the combination of first coloured material and second coloured material so that separately the mass ratio of content prepare following two kinds of synergistic effects that China ink obtains to surpass expection in above-mentioned scope.At first, first synergistic effect is the improvement that the photostabilization of the image that formed by China ink surpasses expection.Promptly, this synergistic effect provides the image photostabilization, and this image photostabilization far surpasses from image photostabilization that is obtained by one of the compound of general formula (I) and compound of general formula (II) and the desired photostabilization of sunproof combination that obtained by the compound of general formula (III).Then, second synergistic effect is the improvement of the tone of the image that formed by China ink.That is, have as the image of the desired tone of magenta ink can by be used in combination first coloured material and second coloured material so that separately the mass ratio of content in above-mentioned scope, obtain.Note, therein the mass ratio of the content of first coloured material and second coloured material less than 2.5 or situation greater than 10.0 China ink under, do not show these synergies.That is, the image photostabilization that obtains during with one of second coloured material with independent use first coloured material is compared, and does not observe sunproof significantly improving, and can not obtain to have the image as the desired tone of magenta ink.
The result of inventor's research has shown that the compound of general formula (I) provides has good sunproof image when the compound of compound that compares general formula (I) and general formula (II).Therefore, in the present invention, the compound of general formula (I) more preferably is used as the Anthrapyridone dyes of first coloured material.That is, this China ink preferably contains the compound formation of general formula (I) at least with first coloured material.The compound of general formula (I) is compared with the compound of general formula (II), provides that to have good sunproof reason hypothesis as follows.The compound of general formula (II) does not have linking group at intramolecularly, thus, under the situation of the compound by light deterioration general formula (II), deterioration anthrapyridone skeleton at first.On the other hand, the compound of general formula (I) has linking group at intramolecularly, thus, under the situation of the compound by light deterioration general formula (I), deterioration linking group deterioration anthrapyridone skeleton then at first.By this mechanism, the time of the compound of complete deterioration general formula (I) needs becomes longer relatively than the time of the compound needs of complete deterioration general formula (II).As a result, compare with the compound of general formula (II), the compound of general formula (I) can provide has good sunproof image.
In addition, in the present invention, preferably satisfy following condition, to obtain to provide image and to have as the magenta ink especially China ink of the image of ideal tone with especially good photostabilization and anti-gaseousness.That is, in China ink of the present invention, especially preferred first coloured material is the compound of above-mentioned general formula (I); With second coloured material be the compound of above-mentioned general formula (III); (first coloured material/second coloured material) is to below 10.0 more than 3.0.In addition, especially preferred (first coloured material/second coloured material) is to below 10.0 more than 9.0.
Particularly, mean following as the desirable tone of magenta ink in the present invention.Measure by writing down the L that load (duty) is set at 100% use image that magenta ink forms by CIE (International Commission on Illumination) regulation
*a
*b
*Than a in the color system
*And b
*, hue angle (H °) is by a
*And b
*Income value calculate based on following formula (A).To have hue angle (H °) from more than 0 to below 5 or from being defined as magenta ink to the China ink that is lower than 360 more than 350 with the desirable tone the present invention.In addition, especially being preferably based on the hue angle (H °) that following formula (A) calculates is to below 5 more than 0.Note above-mentioned a
*And b
*Value can for example use spectrophotometer (trade(brand)name: Spectrolino; Make by Gretag Macbeth) measure.Certainly, the invention is not restricted to above-mentioned measurement.
Formula (A)
a
*〉=0, b
*In 〉=0 (first quartile): H °=tan
-1(b
*/ a
*)
a
*≤ 0, b
*In 〉=0 (second quadrant): H °=180+tan
-1(b
*/ a
*)
a
*≤ 0, b
*In≤0 (third quadrant): H °=180+tan
-1(b
*/ a
*)
a
*〉=0, b
*In≤0 (four-quadrant): H °=360+tan
-1(b
*/ a
*)
As mentioned above, China ink of the present invention requires the content (quality %) of compound (hereinafter being called second coloured material) of content (quality %) and general formula (III) of the compound (hereinafter being called first coloured material) of one of general formula (I) and general formula (II) to be in specific ratio.That is, the mass ratio of the content of these coloured materials in China ink be necessary for from more than 2.5 to below 10.0, that is, and (first coloured material/second coloured material)=from 2.5 to 10.0.In addition, the especially preferred China ink of the present invention content that is each coloured material satisfies the form of following formation.At first, in the China ink content of first coloured material (quality %) preferably from more than the 2.5 quality % to 10.0 quality %, based on total black quality.In addition, in the China ink content of second coloured material (quality %) preferably from more than the 0.5 quality % to 2.0 quality %, based on total black quality.And, in the China ink content (quality %) summation of first coloured material and second coloured material be preferably from more than the 4.0 quality % to 10.0 quality %, based on total black quality.To be lower than 4.0 quality % be not preferred to the content of coloured material (quality %) summation in the China ink, and this is because can not fully obtain the image density of recorded matter.On the other hand, it is not preferred that content (quality %) summation surpasses 10.0 quality %, and this is because can not obtain characteristics of inkjet such as resistance to bond.
[method of inspection of coloured material]
Using the following method of inspection (1) to (3) of high performance liquid chromatography (HPLC) to can be used for check is used for coloured material of the present invention and whether is contained in China ink.
(1) peak retention time
(2) maximum absorption wavelength at the peak of (1)
(3) the mass spectral M/Z (just) at the peak of (1) and M/Z (bearing)
The analysis condition of high performance liquid chromatography is as follows.To dilute about 1,000 times liquid (China ink) as measure sample with pure water.Then, carry out analysis under the following conditions, thereby measure the maximum absorption wavelength at peak retention time and peak by high performance liquid chromatography.
-post: SunFire C
18(by Japan Waters Co., Ltd. makes), 2.1mm * 150mm, column temperature: 40 ℃
-flow velocity: 0.2mL/min
-PDA:200nm to 700nm
-moving phase and gradient condition: following table 1
Table 1
| 0 to 5 minute | 5 to 24 minutes | 24 to 31 minutes | 31 to 45 minutes | |
| A: water | 85％ | 85％→45％ | 45％→0％ | 0％ |
| B: methyl alcohol | 10％ | 10％→50％ | 50％→95％ | 95％ |
| The C:0.2mol/L ammonium acetate solution | 5％ | 5％ | 5％ | 5％ |
In addition, it is as follows to be used for mass spectral analysis condition.Measure the mass spectrum at gained peak under the following conditions, each that measure the strongest detected M/Z be (positive) and bear (negative) just.
-ionization method
-ESI
Capillary voltage: 3.5kV
Desolventizing gas: 300 ℃
Ion source temperature: 120 ℃
-detector
Posi:40V 200 to 1,500amu/0.9sec
Nega:40V 200 to 1,500amu/0.9sec
Under aforesaid method and condition, to measuring as the first coloured material specific examples exemplary compounds 1 of each self-colored material representative example and exemplary compounds 3 and the second coloured material specific examples exemplary compounds 6.Table 2 illustrates the income value of retention time, maximum absorption wavelength, M/Z (just) and M/Z (bearing).When under above-mentioned same procedure and condition, the China ink of the unknown is measured and the observed value of gained in the scope of the value shown in the table 2 time, can determine that China ink comprises corresponding to the compound that is used for compound of the present invention.
Table 2
(aqueous medium)
Water and its can be used for China ink of the present invention for one of aqueous medium of the mixed solvent of water and water-miscible organic solvent.Deionized water (ion exchanged water) is preferably used as this water.The content of Mo Zhongshui (quality %) preferably from more than the 10.0 quality % to 90.0 quality %, based on total black quality.
To not restriction especially of water-miscible organic solvent, as long as it is water-soluble, the example comprises alcohol, polyvalent alcohol, polyglycol, glycol ethers, nitrogenous polar solvent and sulfur-bearing polar solvent.The content (quality %) of water-miscible organic solvent in China ink preferably from more than the 5.0 quality % to 90.0 quality %, more preferably from more than the 10.0 quality % to 50.0 quality %, based on total black quality.When the content of water-miscible organic solvent is lower than above-mentioned scope, this China ink is being used under the situation of ink jet recording device, may not obtain stability as jetting stability.On the other hand, when the content of water-miscible organic solvent was higher than above-mentioned scope, the viscosity of China ink may increase to cause poor China ink supply.
The specific examples of water-miscible organic solvent comprises: alkanol such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol and the trimethyl carbinol with 1 to 4 carbon atom; Acid amides such as dimethyl formamide and N,N-DIMETHYLACETAMIDE; One of ketone and keto-alcohol are as acetone and diacetone alcohol; Ether such as tetrahydrofuran (THF) are with diox; Polyalkylene glycol such as polyoxyethylene glycol and polypropylene glycol; Glycol such as ethylene glycol, propylene glycol, butyleneglycol, glycol ether, triglycol, hexylene glycol and thiodiglycol; Wherein alkylidene group have 2 to 6 carbon atoms aklylene glycol as 1,5-pentanediol, 1,6-hexylene glycol, 2-methyl isophthalic acid, ammediol, 3-methyl isophthalic acid, 5-pentanediol and 1,2,6-hexanetriol; Two (2-hydroxyethyl) sulfone; Lower alkyl ether acetic ester such as polyoxyethylene glycol monomethyl ether acetic ester; Polyol alkyl ether such as glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol ether methyl ether, diethylene glycol monoethyl ether, triglycol monomethyl ether and triglycol list ethyl ether; N-N-methyl-2-2-pyrrolidone N-, 2-Pyrrolidone and 1,3-dimethyl-2-imidazolone.Certainly, the invention is not restricted to these.These water-miscible organic solvents can be used alone or in combination as required.
(other additives)
Except that said components, if desired, it is the solid water-soluble organic compounds that China ink of the present invention can comprise under the normal temperature, as comprises the polyvalent alcohol of TriMethylolPropane(TMP) and trimethylolethane, and the urea derivatives that comprises urea and ethylidene-urea.In addition, when needing, China ink of the present invention can comprise various additives such as tensio-active agent, pH regulator agent, rust-preventive agent, antiseptic-germicide, mould inhibitor, antioxidant, anti-reductive agent, evaporation accelerators, sequestrant and water-soluble polymers.
＜other China inks 〉
In addition, in order to form full-colour image, China ink of the present invention can be used in combination with the China ink that has with the different tones of tone of China ink of the present invention.China ink of the present invention preferably is used in combination with any China ink at least that for example is selected from by in the following group of forming: black ink, cyan ink, magenta ink, yellow ink, red ink, green ink and blue ink.In addition, also can be used in combination with the so-called light China ink that has with every kind the basic identical tone of tone of these China inks.The coloured material that is used for these China inks or light color China ink can be known coloured material or new synthetic coloured material.
＜recording medium 〉
Be used to use China ink of the present invention to form the record images medium and can be any recording medium, as long as this recording medium is for by being applied thereto China ink the recording medium that writes down.In the present invention, preferably be used for the recording medium of ink-jet, wherein make coloured material such as dyestuff and pigment adsorption particulate in the vesicular structure that forms black receiving layer.Especially the preferred recording medium with so-called space absorption-type China ink receiving layer that uses, this China ink receiving layer absorbs China ink by the space that forms in the black receiving layer on supporting mass.Space absorption-type China ink receiving layer mainly comprises particulate and can further comprise tackiness agent as required and other additives.
Particularly, can be with the following particulate that is used for: mineral dye such as silicon-dioxide, clay, talcum, lime carbonate, kaolin, aluminum oxide such as alumina and hydrated aluminum oxide, diatomite, titanium oxide, hydrotalcite and zinc oxide; And pigment dyestuff such as urea-formaldehyde resin, ethenoid resin and styrene resin.These particulates can be used alone or in combination as required.
Tackiness agent comprises water-soluble polymers and latex, and its specific examples comprises following: polyvinyl alcohol, starch, gelatin and modification body thereof; Gum arabic; Derivatived cellulose such as carboxymethyl cellulose, Natvosol and Vltra tears; Ethylenic copolymer latex such as SBR latex, NBR latex, methyl methacrylate butadi ene copolymer latex, the polymer-modified latex of functional groups and vinyl-vinyl acetate copolymer; Polyvinylpyrrolidone; Maleic anhydride and multipolymer thereof and acrylic copolymer.These tackiness agents can be used alone or in combination as required.
In addition, can use additive as required.The example of additive comprises dispersion agent, thickening material, pH regulator agent, lubricant, flow ability modifying agent, tensio-active agent, defoamer, releasing agent, white dyes, UV light absorber, antioxidant and dyestuff fixing salt.
Particularly, when using China ink of the present invention to form image, preferably using its China and Mexico's receiving layer is to have the recording medium that median size is no more than the particulate formation of 1 μ m by use.The specific examples of particulate comprises silicon dioxide microparticle and alumina particulate.Preferred silicon dioxide microparticle comprises with the colloid silica being those of representative.Can use the industrial colloid silica that gets, but especially preferred for example the use is described in the colloid silica in Japanese Patent 2803134 and 2881847.Preferred alumina particulate comprises hydrated aluminum oxide particulate (aluminum oxide pigment).
In above-mentioned aluminum oxide pigment, can especially mention as the suitable pseudobochmite of a kind of hydrated aluminum oxide as being expressed from the next:
AlO
3-n(OH)
2n·mH
2O
Wherein n is an integer 1 to 3; M is 0 to 10, and is preferred 0 to 5, and condition is that m and n are not 0 simultaneously).
Under many circumstances, mH
2O also represents not participate in mH
2The eliminable water that the O lattice forms.For this reason, m can be one of integer and non integer value.In addition, when the such hydrated aluminum oxide of heating, m can reach 0.
Hydrated aluminum oxide can be by following currently known methods production.For example, it can be by as United States Patent (USP) 4,242,271 and United States Patent (USP) 4,202,870 in the hydrolysis production of disclosed aluminum alkoxide and sodium aluminate.In addition, it can be produced to carry out the neutral method by being disclosed in the aqueous solution that wherein aqueous solution of one of sodium sulfate and aluminum chloride is joined sodium aluminate among the Japanese Patent Application Laid-Open S 57-044605.
Recording medium preferably has the supporting mass that is used to support above-mentioned black receiving layer.Can use any material to be used for supporting and do not have any restriction, be enough to the inflexible supporting mass that the transfer mechanism by ink jet recording device is transferred as long as this material can be formed black receiving layer and be formed by above-mentioned small porous particle.For example, can use the paper supporting mass that comprises the pulpwood that mainly comprises native cellulose fibre.Also can use the plastic supporting body, it comprises following material: as polyester (for example, polyethylene terephthalate), cellulose triacetate, polycarbonate, polyvinyl chloride, polypropylene and polyimide.Also can use on the one side at least of basic paper paper, add white pigment the resin-coated paper with polyolefin resin coating layer (for example: RC paper).
Especially, in the present invention, the pH on recording medium surface preferably from more than 3.0 to below 8.0.In addition, in order fully to obtain effect of the present invention, the pH on recording medium surface especially preferably from more than 4.0 to below 6.0.
＜ink-jet recording method 〉
China ink of the present invention especially be preferred for its China and Mexico by ink-jet systems eject with ink-jet recording method at the enterprising line item of recording medium.This ink-jet recording method comprise its China and Mexico by the recording method that mechanical energy put on this China ink and spray and its China and Mexico by heat energy being put on the recording method that this China ink sprays.Particularly, in the present invention, can preferably use the ink-jet recording method that utilizes heat energy.
＜print cartridge 〉
Be used for suitable print cartridge that the China ink of the application of the invention writes down and comprise the print cartridge that is provided with the black reservoir that is used to store China ink.
＜record cell 〉
The suitable record cell that is used to use China ink of the present invention to write down comprises being provided with and is used to the record cell storing the black reservoir of China ink and be used to discharge the record-header of China ink.Particularly, can preferably use wherein above-mentioned record-header by apply the record cell that sprays China ink corresponding to the heat energy of recording signal to China ink.Particularly, preferably will have the record-header that comprises metal and the metal oxide surface, heating part that contacts with liquid one of at least and be used for the present invention.One of at least the specific examples of metal that the surface, above-mentioned heating part that contacts with liquid comprises and metal oxide comprises metal such as Ta, Zr, Ti, Ni and Al and metal oxide thereof.
＜ink jet recording device 〉
Use the suitable ink jet recording device of China ink of the present invention to comprise to be provided with and be used to the ink jet recording device storing the black reservoir of China ink and be used to spray the record-header of China ink.Particularly, the ink jet recording device that sprays by the heat energy that applies to China ink corresponding to recording signal of the China ink that can mention the record-header that wherein will have the black reservoir that is used for storing China ink.
The schematic configuration of mechanism's part of ink jet recording device below will be described.Ink jet recording device has paper feed portion, paper transport unit, seat part, paper discharge portion, cleaning section and is used to protect above-mentioned part and provides the outer packaging portion of pattern to them, and every part wherein plays the effect of each mechanism.
Fig. 1 is the skeleton view of ink jet recording device.Fig. 2 and 3 is for being used to describe the view of ink jet recording device internal mechanism, and wherein Fig. 2 illustrates the skeleton view of observing from the upper right side, and Fig. 3 illustrates the partial elevation view of ink jet recording device.
When paper feed when the recording unit, have only the recording medium of specified quantity to be sent to roll gap portion, this roll gap portion comprises and contains into the intake roller M2080 and the separate roller M2041 of the paper feed portion of carriage M2060.The recording medium that transmits is separated in roll gap portion, only transmits uppermost recording medium.The recording medium that sends the paper transport unit to leads to be sent in the roller group (roller pair) that comprises transfer roller M3060 and pinch roll M3070 by pinch roll stand (pinch roller holder) M3000 and dancing roll baffle plate (paper guideflapper) M3030.Comprise the roller group of transfer roller M3060 and pinch roll M3070 by LF electric motor E0002 driving and rotation, thereby transmit recording medium by platen M3040.
In seat part, when forming image on recording medium, record-header H1001 (Fig. 4: the details of this structure will describe in detail in the back) is arranged in target image and forms the position, and according to the signal from electric substrate E0014 China ink is ejected on the recording medium.When writing down by record-header H1001, wherein bearing M4000 is in the main-scanning of vertically carrying out with wherein alternately repeat in the subscan of cross drive recorded matter by transfer roller M3060, thereby forms image on recording medium.Finally, formed the record images medium on it and be sandwiched in the first paper distributing roller M3110 in the paper discharge portion and the roll gap portion between the ratchet M3120, and be transmitted and be expelled to paper discharge dish M3160.
Cleaning section cleans record-header H1001 before and after forming image.Operating pumps M5000 in the jet orifice that covers M5010 lid record-header H1001 draws unnecessary China ink with the jet orifice from record-header H1001.In addition, absorption remains in China ink adhesion and other deleterious effects to prevent to be caused by residual China ink that cover M5010 inside when lid M5010 opens.
(structure of record-header)
The structure of head cartridge H1000 is described.Fig. 4 is the formation of declare record head box H1000 and how print cartridge H1900 is installed in view on the head cartridge H1000.Head cartridge H1000 has record-header H1001, the unit of print cartridge H1900 is installed and China ink is offered record-header and for being removably mounted on the unit on the bearing M4000 from print cartridge H1900.
Ink jet recording device forms image with yellow, magenta, cyan, black, shallow magenta, light cyan and green ink.Therefore, prepare seven kinds of colors independently for print cartridge H1900.Notice that China ink of the present invention is used at least a of above China ink.In addition, as shown in Figure 4, each print cartridge H1900 is dismountable with respect to head cartridge H1000.Print cartridge H1900 can also mount and dismount with the state that head cartridge H1000 is installed on the bearing M4000.
Fig. 5 is the decomposition diagram of head cartridge H1000.Head cartridge H1000 comprises that recording element substrate, pole plate (plate), electric wiring substrate H1300, cartridge carrier H1500, stream form assembly H1600, strainer H1700 and caulking gum H1800.Recording element substrate comprises the first recording element substrate H1100 and the second recording element substrate H1101, and pole plate comprises the first pole plate H1200 and the second pole plate H1400.
Each of the first recording element substrate H1100 and the second recording element substrate H1101 is a S i substrate, forms a plurality of recording elements (nozzle) that are used to spray China ink in the one side by photolithography.Forming by what aluminium etc. was made by film technique provides the electric distribution of electric energy to each recording element, forms corresponding to a plurality of black stream of recording element separately by photolithography.In addition, be formed for the ink supply port that China ink offers a plurality of black streams is made open in the rear surface.
Fig. 6 is the frontview that amplifies, and in order to describe the structure of the first recording element substrate H1100 and the second recording element substrate H1101, this illustrates the recording element row H2000 to H2600 (hereinafter being also referred to as nozzle rows) corresponding to the black color of difference.The first recording element substrate H1100 has the nozzle rows that is used for three kinds of colors: be used for yellow ink nozzle rows H2000, be used for the nozzle rows H2100 of magenta ink and be used for the nozzle rows H2200 of cyan ink.The second recording element substrate H1101 has the nozzle rows that is used for four kinds of colors: be used for the light cyan China ink nozzle rows H2300, be used for black ink nozzle rows H2400, be used for the nozzle rows H2500 of green ink and be used for the nozzle rows H2600 of shallow magenta ink.
Each nozzle rows comprises with 1,200dpi (point/inch; Reference value) 768 nozzles for arranging on the recording medium delivery direction at interval, about 2 skins of each nozzle ejection rise China ink.The port area of each nozzle spray-orifice is made as about 100 μ m
2
Hereinafter, will the present invention be described with reference to Figure 4 and 5.The first recording element substrate H1100 and second recording element substrate H1101 combination also are fixed in the first pole plate H1200, are formed for China ink is offered the ink supply port H1201 of the first recording element substrate H1100 and the second recording element substrate H1101 on the first pole plate H1200.The second pole plate H1400 with opening also in conjunction with and be fixed in the first pole plate H1200.The second pole plate H1400 is so that the mode that electric wiring substrate H1300, the first recording element substrate H1100 and the second recording element substrate H1101 are electrically connected supports electric wiring substrate H1300.
Electricity wiring substrate H1300 applies and is used to cause the electrical signal that is formed on each the nozzle ejection China ink on the first recording element substrate H1100 and the second recording element substrate H1101.Electricity wiring substrate H1300 has: corresponding to each the electric distribution of the first recording element substrate H1100 and the second recording element substrate H1101; The end that is positioned at electric distribution is to receive the external signal input end station H1301 of electrical signal from ink jet recording device.This external signal input end station H1301 is positioned at and is fixed on the back side one side of cartridge carrier H1500.
Stream forms assembly H 1600 and is fixed in the cartridge carrier H1500 that is used for supporting by the means of for example ultrasonic welding print cartridge H1900.Thus, formation is by way of the black stream H1501 of print cartridge H1900 to the first pole plate H1200.Strainer H1700 is arranged on the terminal portions of the print cartridge side of the black stream H1501 that engages with print cartridge H1900, so that strainer H1700 prevents that dust from entering from the outside.Caulking gum H1800 is installed in black stream H1501 and print cartridge H1900 engaging portion, to prevent China ink part evaporation from then on.
In addition, as mentioned above, make head cartridge H1000 by connecting cartridge carrier portion with record head H1001 by using binding agent.Cartridge carrier portion comprises that cartridge carrier H1500, stream form assembly H1600, strainer H1700 and caulking gum H1800, and record head H1001 comprises the first recording element substrate H1100, the second recording element substrate H1101, the first pole plate H1200, electric wiring substrate H1300 and the second pole plate H1400.
By will being described, in this record-header, be used to cause that by being used to produce China ink produces the heat energy of film boiling according to electrical signal the means of electrothermal transducer (recording element) carry out record at this according to the record-header of hot ink ejecting method embodiment as record-header.As exemplary configuration and principle, preferably use the ultimate principle of discussing in for example United States Patent (USP) 4,723,129 and United States Patent (USP) 4,740,796.This method can be used for any of so-called type as required and so-called successive type.
Particularly, because underlying cause, this method is for type is effective as required.Impose on the electrothermal transducer that disposes corresponding to the liquid flow path that holds China ink with at least a corresponding to recorded information and the actuate signal that cause to surpass the unexpected intensification of nucleate boiling, thereby cause that electrothermal transducer produces heat energy and makes China ink produce film boiling.As a result, corresponding to one to one actuate signal formation bubble in China ink.The breathing of bubble is sprayed China ink by jet orifice, thereby forms at least one ink droplet.Actuate signal is pulse mode more preferably, because the breathing of bubble can be carried out at once and suitably, therefore can spray China ink with good responsive.
China ink of the present invention also can be used for the following ink jet recording device that utilizes mechanical energy suitably.The ink jet recording device of this form comprises that the nozzle with a plurality of nozzles forms substrate, is oppositely arranged and comprises the components of stres of piezoelectric and electro-conductive material with nozzle, and fill China ink around this components of stres, wherein this components of stres moves by impressed voltage, with from the nozzle ejection China ink.
Ink jet recording device is not limited to as mentioned above wherein that record-header and print cartridge are this equipment separately, and can be wherein record-header and print cartridge is integrated thereby their inseparable equipment.Print cartridge also can with to be installed in that record-header on the bearing can divide or integrated inseparably, the fixed part that maybe can be installed in ink jet recording device is to provide China ink by ink supply assembly such as pipe to record-header.In addition, when print cartridge is provided with the negative pressure that is used to provide suitable to the structure of record-header, can adopt following structure.That is, cartridge can be arranged on the black reservoir of print cartridge, or print cartridge can have flexible storage China ink bag and the spring portion that is used for applying in the internal volume direction of balloon dilator bias voltage.In addition, recording unit can adopt aforesaid continuous recording method, or can be the form of the line-at-a-time printer that obtains by the whole width range that recording element is arranged in corresponding to recording medium.
(embodiment)
Below, with reference example and the present invention of comparative example more detailed description.Yet unless embodiment departs from purport of the present invention, the present invention is not limited to these embodiment.Unless otherwise indicated, the term of the various black components in embodiment and comparative example " part " expression " mass parts ".
＜preparation coloured material 〉
(synthetic exemplary compounds 1)
(A) under agitation in 360 parts of dimethylbenzene, add the compound of 94.8 parts of following formulas (1), 3.0 parts of yellow soda ash and 144.0 parts of ethyl benzoylacetates (ethylbenzoylacetate) in succession, with the gained mixture heating up to 140 to 150 ℃ of temperature, and make its reaction 8 hours.During reaction, the second alcohol and water component distillation that will produce in will reacting with dimethylbenzene goes out system, thereby finishes reaction.Reaction mixture is cooled to 30 ℃ of temperature, to wherein adding 240 parts of methyl alcohol.The gained mixture was stirred 30 minutes.Then, with the solid by filtration separated out and separate.The gained solid is with 360 parts of methanol wash, dry then, thus the faint yellow needle-like crystal of the compound of 124.8 parts of following formulas (2) obtained.
Formula 1
(B) under agitation to 300.0 parts of N, compound, 75.0 parts of 3-acetylaminoanilines (meta-aminoacetanilide), 24.0 part of one hydrated copper acetate and 12.8 parts of yellow soda ash of adding more than 88.8 parts the formula (2) that obtains in the dinethylformamide in succession, with the gained mixture heating up to 120 to 130 ℃ of temperature and make its reaction 3 hours.Reaction mixture is cooled to about 50 ℃ of temperature, to wherein adding 120 parts of methyl alcohol.The gained mixture was stirred 30 minutes.Then, with the solid by filtration separated out and separate.With of the hot wash of gained solid with 500 parts of methyl alcohol and 80 ℃, dry then, thus obtain the red crystals of turning blue of the compound of 79.2 parts of following formulas (3).
Formula 3
(C) under water cooling, under agitation in 130 part of 98.0% sulfuric acid, add 170.0 part 28.0% oleum, to prepare 300 part 12% oleum.Under water cooling temperature below 50 ℃ to the compound that wherein adds more than 51.3 parts the formula (3) that obtains, the gained mixture heating up to 85 to 90 ℃ of temperature, and is made its reaction 4 hours.The gained reaction mixture is poured in 600 portions of frozen water, simultaneously by adding that ice prevents because the intensification that heat release causes, thereby the temperature that keeps mixture is below 40 ℃.It is 1000 parts mixture that reaction mixture and other water are mixed with the acquisition amount, filters then to remove insoluble substance.Adding hot water in gained filtrate is 1500 parts of mixtures with the acquisition amount.To wherein adding 300 parts of sodium-chlor, the temperature that keeps mixture simultaneously then stirred 2 hours at 60 to 65 ℃.Then, the crystal of separating out is separated by filtration.The gained crystal is also fully pushed with 300 part of 20% sodium chloride aqueous solution washing, thereby obtain 100.3 portions of wet cakes, this wet cake contains the red crystals of the compound of 59.2 parts of following formulas (4).
Formula 4
(D) the wet cake of the compound of the formula (4) that adding obtains more than 67.7 parts in 60 parts of water.Then, to wherein adding 24 part of 25% sodium chloride aqueous solution, stir subsequently.In addition, to wherein adding 25% aqueous sodium hydroxide solution to dissolve this compound, simultaneously with the pH regulator to 3 of mixture to 4.On the other hand, in 60 portions of frozen water, add 0.4 part of Lipal OH (trade(brand)name is by the anion surfactant of Lion KK manufacturing), to wherein adding 8.9 parts of cyanuryl chlorides, stirred subsequently 30 minutes, thereby obtain suspension.Gained suspension is added in the solution of formula (4) compound that contains above acquisition.Then, make the gained mixture, use 10% aqueous sodium hydroxide solution that the pH of mixture is remained in 2.7 to 3.0 the scope simultaneously, thereby obtain to contain the reaction mixture of following formula (5) compound in the reaction 4 hours down of 25 to 30 ℃ of temperature.
Formula 5
(E) in the reaction mixture of the formula that contains above acquisition (5) compound, add 9.5 part of two hydration p-phenolsulfonic acid sodium (sodium p-phenolsulfonate dihydrate).Then, the temperature of mixture is increased to 50 to 55 ℃, the pH of mixture is remained in 6.5 ± 0.3 the scope by adding 25% aqueous sodium hydroxide solution simultaneously.Make mixture this temperature range reaction 1 hour, thereby obtain to contain the reaction mixture of following formula (6) compound.
Formula 6
(F) reaction mixture that contains formula (6) compound to above acquisition adds 1.2 parts of quadrols.Then, the temperature of mixture is increased to 78 to 82 ℃, the pH of mixture is remained in 7.8 to 8.2 the scope by adding 25% aqueous sodium hydroxide solution simultaneously.Make mixture this temperature range reaction 1 hour.Subsequently, to wherein adding entry, thereby the acquisition amount is about 350 parts mixture, then it is filtered to remove insoluble substance.In gained filtrate, add entry and be 400 parts mixture with the acquisition amount.To wherein adding concentrated hydrochloric acid, the temperature with mixture remains on 55 ± 2 ℃ simultaneously, with the pH regulator to 3 with mixture.Then, in 15 minutes, in mixture, add 40 parts of sodium-chlor, stir 30 minutes subsequently, and further add concentrated hydrochloric acid with pH regulator to 2 with mixture.The acidic aqueous solution of gained was stirred 1 hour, the crystal of separating out is separated by filtration.The gained crystal is washed with 100 part of 20% sodium chloride aqueous solution, thereby obtain the aforesaid wet cake of redness that contains exemplary compounds 1.
(G) the wet cake with above acquisition is added in 500 parts of methyl alcohol.The temperature of gained mixture is risen to 60 to 65 ℃, mixture was stirred 1 hour.The crystal of separating out is separated by filtration, with methanol wash and dry, thus the exemplary compounds 1 of acquisition free acid form.
(synthetic exemplary compounds 3)
Exemplary compounds 3 is synthetic by the method among the embodiment 4 that is described in WO 2004/104108.
(synthetic exemplary compounds 5 and 6)
Dyestuff f-1 among description and the Japanese Patent Application Laid-Open 2002-371213 as exemplary compounds 5, will be described in compound d among the Japanese Patent Application Laid-Open 2006-143989-5 as exemplary compounds 6.
(synthetic other coloured materials)
Be the following comparative compound 1 of Anthrapyridone dyes, synthetic by the method that is described among the Japanese Patent Application Laid-Open 2003-192930.Be the following comparative compound 2 and 3 of azoic dyestuff, synthetic by the method that is described among the Japanese Patent Application Laid-Open H08-073791.Following comparative compound 4 is a directly Huang 132 of C.I., and it is an azoic dyestuff.
Comparative compound 1
Comparative compound 3
Comparative compound 4
＜preparation China ink 〉
Component shown in following table 3 and 4 is mixed and fully stirring.Then, be that the strainer of 0.2 μ m filters the gained mixture by the aperture under pressure, thus the China ink of preparation embodiment 1 to 11 and comparative example 1 to 21.
＜preparation recording medium 〉
The resin combination that will contain 70 parts of new LDPE (film grade)s, 20 parts of high density polyethylene(HDPE)s and 10 parts of titanium dioxide is applied to has basic weight 155g/m
2The body paper two sides so that composition is with 25g/m
2Amount apply, thereby produce the supporting mass assembly that covers with resin.Then, will comprise that hydrated aluminum oxide and polyvinyl alcohol are formed on the supporting mass assembly of gained as the black receiving layer of main ingredient.Thereby the record of production medium, it comprises air gap type (void type) black receiving layer and has what measure according to JAPAN TAPPI paper pulp test method(s) No.49-1 is 5.0 at 3 minutes rear surface pH.
＜estimate
Ink jet recording device (the trade(brand)name: PIXUS iP8600) that the various China inks of the embodiment of above acquisition and comparative example are packed into and utilized heat energy.With printing condition setting is 23 ℃ of temperature, relative humidity 55%, recording density 2,400dpi * 1,200dpi and injection 2.5pL.Then, on the recording medium of above acquisition, form wherein with 10% increment and make the record load change to 100% image from 0%, this image is air-dry 24 hours 23 ℃ of temperature and relative humidity 55% time.Then tone (hue angle and optical density(OD)) and image fastness (photostabilization and ozone resistance) are estimated by method as described below.
(tone: hue angle)
To wherein in the recorded matter of above acquisition the record load be that 100% image section is measured the L by CIE (International Commission on Illumination) regulation
*a
*b
*Than a in the color system
*And b
*Attention is that the D50 and the visual field are to use spectrophotometer (trade(brand)name: Spectrolino under 2 ° the condition at light source; Make by GretagMacbeth) measurement a
*And b
*Value.Each hue angle (H °) is by a of gained
*And b
*Value calculate based on following formula (A), thereby estimate tone (hue angle).The standard of tone (hue angle) is as described below, is shown in table 5 by the evaluation result of this standard gained.In following judgement criteria, A and B represent to have the China ink of desirable magenta tone, and C represents as the unacceptable China ink of magenta tone.
Formula (A)
a
*〉=0, b
*In 〉=0 (first quartile): H °=tan
-1(b
*/ a
*)
a
*≤ 0, b
*In 〉=0 (second quadrant): H °=180+tan
-1(b
*/ a
*)
a
*≤ 0, b
*In≤0 (third quadrant): H °=180+tan
-1(b
*/ a
*)
a
*〉=0, b
*In≤0 (four-quadrant): H °=360+tan
-1(b
*/ a
*)
A:H is to below 5 more than 0.
B:H is to below 10 and 350 above extremely less than one of 360 greater than 5.
C:H is in greater than 10 with less than between 350.
(tone: optical density(OD))
To wherein in the recorded matter of above acquisition the record load be that 100% image section uses spectrophotometer (trade(brand)name: Spectrolino; Make by Gretag Macbeth) measuring light density, to estimate tone (optical density(OD)).The judgement criteria of tone (optical density(OD)) is as described below, and the evaluation result of gained is shown in table 5.In following judgement criteria, A and B represent that as the acceptable level of the optical density(OD) of magenta C represents as the unacceptable level of the optical density(OD) of magenta, because optical density(OD) is too low so that image is light.
A: optical density(OD) is more than 2.0.
B: optical density(OD) is extremely less than 2.0 more than 1.5.
C: optical density(OD) is less than 1.5.
(image fastness: photostabilization)
To wherein in the recorded matter of above acquisition the record load be that 50% image section is measured the L by CIE (International Commission on Illumination) regulation
*a
*b
*Than the L in the color system
*, a
*And b
*(being called " the Lab value before the light fastness test ").Then this recorded matter is used super xenon lamp trier (trade(brand)name: SX-75, by Suga Test Instruments Co., Ltd. makes) under the condition of 24 ℃ of exposure intensity 100 kiloluxs, relative humidity 60% and vessel temps, to expose 168 hours.Then, to wherein in recorded matter the record load be that 50% image section is measured L
*, a
*And b
*(being called " the Lab value behind the light fastness test ").Attention is that the D50 and the visual field are to use spectrophotometer (Spectrolino under 2 ° the condition at light source; Make by Gretag Macbeth) measurement L
*, a
*And b
*According to the Lab value of gained before and after the light fastness test, calculate aberration (Δ E) based on following formula (B), thereby estimate photostabilization.Sunproof standard is as described below, and the evaluation result that is obtained by this standard is shown in table 5.In following judgement criteria, A and B represent acceptable level, and C represents unacceptable level, because the degree of image fade is big behind the light fastness test.
Formula (B)
L
1, a
1, b
1: the Lab value before the light fastness test
L
2, a
2, b
2: the Lab value behind the light fastness test
A: Δ E is less than 17.
B: Δ E be from more than 17 to less than 20.
C: Δ E is more than 20.
(image fastness: ozone resistance)
To wherein in the recorded matter of above acquisition the record load be that 50% image section is measured the L by CIE (International Commission on Illumination) regulation
*a
*b
*Than the L in the color system
*, a
*And b
*(being called " the Lab value before the ozone resistance test ").Then this recorded matter is used ozone testing installation (trade(brand)name: OMS-H, by Suga Test Instruments Co., Ltd. makes) under the condition of 24 ℃ of concentration of ozone gas 10ppm, relative humidity 60% and vessel temps, to expose 4 hours.Then, to wherein in recorded matter the record load be that 50% image section is measured L
*, a
*And b
*(being called " the Lab value behind the ozone resistance test ").Attention is that the D50 and the visual field are to use spectrophotometer (Spectrolino under 2 ° the condition at light source; Make by Gretag Macbeth) measurement L
*, a
*And b
*From the Lab value of ozone resistance test front and back gained, calculate aberration (Δ E) based on following formula (C), thereby estimate ozone resistance.The standard of ozone resistance is as described below.
Evaluation result is shown in table 5.In following judgement criteria, A and B represent acceptable level, and C represents unacceptable level, because the degree of ozone resistance test back image fade is big.
Formula (C)
L1, a1, b1: the Lab value before the ozone resistance test
L2, a2, b2: the Lab value after the ozone resistance test
A: Δ E is less than 2.
B: Δ E be from more than 2 to less than 4.
C: Δ E is more than 4.
Table 5
Although reference example embodiment of the present invention is described, should understands and the invention is not restricted to disclosed exemplary.The scope of following claims meets the wideest explanation, so that comprises all improvement and equivalent structure and function.
Claims (6)
1. ink-jet China ink, it comprises first coloured material and at least two kinds of coloured materials of second coloured material,
Wherein, this first coloured material compound of following general formula (I) expression of serving as reasons
Wherein R represents hydrogen atom, alkyl, hydroxyalkyl, cyclohexyl, alkyl monosubstituted amino alkyl or dialkyl aminoalkyl independently; M represents hydrogen atom, basic metal, ammonium or organic ammonium independently; X represents linking group; And/or
Compound by following general formula (II) expression:
R wherein
1Expression hydrogen atom or alkyl; M represents 1 to 3 integer; M represents hydrogen atom, basic metal, ammonium or organic ammonium independently; And
The serve as reasons compound of following general formula (III) expression of this second coloured material:
R wherein
2, R
3, R
4And R
5Represent alkyl independently of one another; M represents hydrogen atom, basic metal, ammonium or organic ammonium independently,
Wherein the content of this first coloured material (quality %) is to below 10.0 more than 2.5 with the mass ratio of the content (quality %) of this second coloured material.
2. ink-jet China ink according to claim 1, wherein this first coloured material comprises the compound by general formula (I) expression at least.
3. an ink jet recording method wherein passes through the ink-jet systems eject China ink with at the enterprising line item of recording medium, should China ink be ink-jet China ink according to claim 1 wherein.
4. print cartridge, it is provided with the black reservoir that is used to store China ink, should China ink be ink-jet China ink according to claim 1 wherein.
5. record cell, it is provided with the record-header that is used to store the black reservoir of China ink and is used to spray China ink, should China ink be ink-jet China ink according to claim 1 wherein.
6. ink jet recording device, it is provided with the record-header that is used to store the black reservoir of China ink and is used to spray China ink, should China ink be ink-jet China ink according to claim 1 wherein.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007-120475 | 2007-05-01 | ||
| JP2007120475 | 2007-05-01 | ||
| JP2008-107005 | 2008-04-16 | ||
| JP2008107005A JP4873750B2 (en) | 2007-05-01 | 2008-04-16 | Ink jet ink, ink jet recording method, ink cartridge, recording unit, and ink jet recording apparatus |
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| Publication Number | Publication Date |
|---|---|
| CN101298526A true CN101298526A (en) | 2008-11-05 |
| CN101298526B CN101298526B (en) | 2014-08-20 |
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Country Status (2)
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101298526B (en) | 2014-08-20 |
| JP2008297542A (en) | 2008-12-11 |
| JP4873750B2 (en) | 2012-02-08 |
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