CN101298526B - Ink jet ink, ink jet recording method, ink cartridge, recording unit and ink jet recording apparatus - Google Patents

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

Ink jet ink, ink jet recording method, print cartridge, record cell and ink jet recording device

Technical field

The present invention relates to ink jet ink, ink jet recording method, print cartridge, record cell and ink jet recording device.

Background technology

Ink jet recording method is by ink droplet being applied to recording medium as formed the method for image on common paper and glossy media (glossy media).The method drops into rapidly application widely by the writing speed reducing costs and improve ink jet recording device.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 has been typically used as the image output method comparing favourably with photographic silver halide (photograph).

In recent years, the further raising (progress) of acquisition high quality graphic is minimized and is followed colour gamut (color gamut) improvement of the introducing of polychrome China ink to reach by ink droplet.On the other hand, coloured material and black demand are uprised, wherein aspect the improvement of coupling development and the reliability of 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 poor aspect the image package stability of the recorded matter obtaining.Conventionally,, compared with photographic silver halide, the image package stability of the recorded matter obtaining by ink jet recording method is low.When recorded matter is exposed to especially for a long time light, wet, heat, while being present in airborne environmental gas etc., exists coloured material on recorded matter deteriorated and be easy to produce the problem that picture tone changes and fades.

Especially, from using the fastness, particularly sunproof viewpoint of the image forming as the dye ink of coloured material containing dyestuff, 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 suggestions about the dyestuff for magenta ink, it has low image package stability in various cyans, magenta and yellow ink.

For example, exist about xanthene dye and use the azoic dyestuff of H acid as forming image package stability as the suggestion of the coloured material of water tolerance and excellent color tone (Japanese Patent Application Laid-Open H08-073791 and Japanese Patent Application Laid-Open No.H09-255882).But 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 there is good tone, but its photostabilization and resistance to gaseousness are poor.Although the research of the good magenta dye of exploitation color harmony photostabilization is carried out widely on the dyestuff of these kinds, still to compare with yellow dyes as the cyan dye as an example of copper phthalocyaine dye example with the dyestuff with other form and aspect be enough to not talkative photostabilization level.

In addition, there is the suggestion (Japanese Patent Application Laid-Open No.2005-008868) as the good magenta dye of color harmony photostabilization about Anthrapyridone dyes.But, also do not obtain satisfied the be equal to sharpness (clarity) of the dyestuff with other form and aspect, resistance to gaseousness and sunproof magenta dye.

Exist about the suggestion (Japanese Patent Application Laid-Open 2005-105136 and Japanese Patent Application Laid-Open 2005-307068) that can form by containing Anthrapyridone dyes and azoic dyestuff the magenta ink of the image that tone, ozone resistance and photostabilization are good.These are suggested and understand that thereby the magenta ink that can form the resistance to gaseousness image good with photostabilization can obtain with mending the characteristic of tasting each other together with having the azoic dyestuff of low resistance to gaseousness and high-light-fastness with low sunproof Anthrapyridone dyes by making to have high resistance to gaseousness.But, although by comparing with the image only forming as the China ink of coloured material containing Anthrapyridone dyes and one of azoic dyestuff, the image forming by the China ink containing Anthrapyridone dyes and azoic dyestuff improves resistance to gaseousness and photostabilization to a certain extent, but does not reach the fastness level requiring in recent years.

Summary of the invention

Therefore, the object of this invention is to provide a kind of ink jet ink with magenta tone, it provides tone, photostabilization and the good image of resistance to gaseousness.In addition, the object of this invention is to provide a kind of ink jet ink with magenta tone, it provides tone, photostabilization, resistance to gaseousness and the good image of optical density(OD).Another object of the present invention is to provide ink jet recording method, print cartridge, record cell and the ink jet recording device of the above-mentioned ink jet ink of whole uses.

Achieved the above object by the present invention.Particularly, comprise the first coloured material and at least two kinds of coloured materials of the second coloured material according to the ink jet ink of embodiment of the present invention, this first coloured material is at least one of the compound being represented by following general formula (I) and the compound being represented by following general formula (II); The second coloured material is the compound being represented by following general formula (III), wherein the mass ratio of the content (quality %) of the content of the first coloured material (quality %) and the 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)

(wherein R ₁represent hydrogen atom or alkyl; M represents 1 to 3 integer; M represents hydrogen atom, basic metal, ammonium or organic ammonium independently);

General formula (III)

(wherein R ₂, R ₃, R ₄and R ₅represent independently of one another alkyl; M represents hydrogen atom, basic metal, ammonium or organic ammonium independently).

In addition, ink jet recording method is according to another embodiment of the invention the ink jet recording method to record by ink-jet systems eject China ink on recording medium by ink-jet systems eject China ink wherein, and wherein this China ink is the ink jet ink of above-mentioned formation.

In addition, Inkjet Cartridge is according to another embodiment of the invention the print cartridge being provided with for storing black black reservoir, and wherein this China ink is the ink jet ink of above-mentioned formation.

In addition, be to be provided with for storing black black reservoir and for spraying the record cell of black record-header, wherein this China ink is the ink jet ink of above-mentioned formation according to the record cell of another embodiment of the present invention.

In addition, be to be provided with for storing black black reservoir and for spraying the ink jet recording device of black record-header, wherein this China ink is the ink jet ink of above-mentioned formation according to the ink jet recording device of another embodiment of the present invention.

Embodiment of the present invention can offer out the ink jet ink of the good image of tone, photostabilization and resistance to gaseousness.In addition, embodiment of the present invention can provide the ink jet ink with magenta tone, and it provides tone, photostabilization, resistance to gaseousness and the good image of optical density(OD).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 ink of whole uses.

Brief description of the drawings

Fig. 1 is the skeleton view of ink jet recording device.

The skeleton view of portion of Tu2Shi 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 arranged on print cartridge the state on head cartridge (head cartridge).

Fig. 5 is the decomposition diagram of a box.

Fig. 6 is the front view of recording element substrate in an explanation box.

Embodiment

Enumerate and describe in detail the preferred exemplary of the present invention below.

Note, in the time that compound is salt, this salt dissociation is also present in China ink as ion, but for simplicity, is in the present invention " black saliferous " by this state description.

< China ink >

Below detailed description is comprised to the ink jet ink of the present invention component of (hereinafter, can only be called China ink).Attention: the compound being represented by general formula (I), the compound being represented by general formula (II) and the compound being represented by general formula (III) can be respectively referred to as " compound of general formula (I) ", " compounds of general formula (II) " and " compound of general formula (III) ".

As the inventor's result of study, find to have good photostabilization and as the desirable tone of magenta ink image can by containing with specific ratio, every kind of dyestuff has the Anthrapyridone dyes of ad hoc structure and the ink composition of azoic dyestuff obtains.

One of feature of China ink of the present invention is to be used in combination the compound of the following general formula (I) that represents separately Anthrapyridone dyes and/or the compound of following general formula (II) as the first coloured material, and using the compound of general formula (III) that represents azoic dyestuff as the second coloured material.

< the first coloured material: the compound being represented by general formula (I) and/or the compound > being represented by general formula (II)

China ink of the present invention must contain the compound of the following general formula (I) separately with the feature that color harmony photostabilization is good and/or the compound of following general formula (II) as the first coloured material.In the present invention, especially preferably use the compound of general formula (I) as the 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 ₁represent hydrogen atom or alkyl; M represents 1 to 3 integer; M represents hydrogen atom, basic metal, ammonium or organic ammonium independently.

R in general formula (I) represents hydrogen atom, alkyl, hydroxyalkyl, cyclohexyl, alkyl monosubstituted amino alkyl or dialkyl aminoalkyl independently.

As alkyl, can mention the 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 the hydroxyalkyl with 1 to 4 carbon atom.Specific examples comprises methylol, hydroxyethyl, hydroxypropyl and hydroxyl butyl.Alkyl in hydroxyalkyl comprises straight chain, side chain and cyclic alkyl, particularly preferably straight chained alkyl.In abovementioned alkyl, the position of substitution of hydroxyl can be selected arbitrarily, but the hydroxyl particularly preferably replacing endways, for example, 2-hydroxyethyl, 3-hydroxypropyl and 4-hydroxyl butyl.

As 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 general formula (I), more preferably one of hydrogen atom and alkyl, most preferable.

X in general formula (I) represents linking group.The example of linking group comprises following linking group 1 to 7.In linking group 1 to 7, the bonding part (bonding hand) being represented by symbol " * " is the bonding part of each nitrogen-atoms, and one of two different triazine rings Direct Bonding is to each nitrogen-atoms.Particularly preferably use the linking group 1 in following linking group.

Linking group 1:

In linking group 1, n represents 2 to 8, preferably 2 to 6, more preferably 2; Symbol " * " represents the bonding position of one of two different triazine rings separately.

Linking group 2:

In linking group 2, R _arepresent independently hydrogen atom or methyl; Symbol " * " represents the bonding position of one of two different triazine rings separately.

Linking group 3:

In linking group 3, symbol " * " represents the bonding position of one of two different triazine rings separately.

Linking group 4:

In linking group 4, symbol " * " represents the bonding position of one of two different triazine rings separately.

Linking group 5:

In linking group 5, symbol " * " represents the bonding position of one of two different triazine rings separately.

Linking group 6:

At linking group 6, m represents 2 to 4; Symbol " * " represents the bonding position of one of two different triazine rings separately.

Linking group 7:

In linking group 7, symbol " * " represents 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 in the solvability comprising in black aqueous medium, the alkyl in general formula (II) preferably has 1 to 3 carbon atom, and specific examples comprises methyl, ethyl, uncle's propyl group and Zhong Bingji.Note, in the time that this alkyl has more than 4 carbon atoms, the hydrophobicity of coloured material is may be for this coloured material too high so that be insoluble to and comprise in black aqueous medium.

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 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, especially preferably use one of exemplary compounds 1 in following exemplary compounds and exemplary compounds 3.Wherein, usage example compound 1 most preferably.

Exemplary compounds 1

Exemplary compounds 2

[the A:SO in 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]

[the second coloured material: the compound being represented by general formula (III)]

China ink of the present invention must contain the compound of the good especially following general formula (III) of tone as the second coloured material.

General formula (III)

In general formula (III), R ₂, R ₃, R ₄and R ₅represent independently of one another alkyl; M represents hydrogen atom, basic metal, ammonium or organic ammonium independently.

According in the solvability comprising in black aqueous medium, the alkyl in general formula (III) preferably has 1 to 3 carbon atom, and specific examples comprises methyl, ethyl, n-propyl and sec.-propyl.Note, in the time that this alkyl has more than 4 carbon atoms, the hydrophobicity of coloured material is may be for this coloured material too high so that be insoluble to and comprise in black aqueous medium.

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 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, especially preferably use the exemplary compounds 6 in following exemplary compounds.

Exemplary compounds 5

Exemplary compounds 6

Exemplary compounds 7

[SO ₃HNEt ₃:SO ₃ ^-·HN ⁺(C ₂H ₅) ₃]

Note, in the present invention, limited as the structure of the azoic dyestuff of the second coloured material, be monoazo-dyes.Can not obtain and there is good sunproof image with its China ink for the compound combination of the following general formula (IV) of azoic dyestuff by containing one of its compound of general formula (I) that is Anthrapyridone dyes and compound of general formula (II).

General formula (IV)

In general formula (IV), R ₁, R ₂and R ₃represent independently to there is the substituted or non-substituted alkyl of 1 to 9 carbon atom, the alkoxyl group with 1 to 9 carbon atom, halogen atom, hydrogen atom, hydroxyl, substituted or non-substituted formamyl, substituted or non-substituted sulfamyl, substituted or non-substituted amino, nitro, sulfonate group (sulfonategroup), have 1 to 9 carbon atom alkyl sulphonyl, there is 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 independently hydrogen atom, have 1 to 18 carbon atom alkyl, there is alkenyl, aryl, aralkyl, alicyclic radical or the heterocyclic radical of 2 to 18 carbon atoms, wherein the above-mentioned group except 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 turning 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 that has a desirable magenta tone (further details referring to below) can have one of the compound of general formula (I) of above-mentioned characteristic and compound of general formula (II) by use and obtain with the compound combination of general formula (III).

In the time that further studying these coloured materials, the inventor obtains following content.; be used in combination these coloured materials with specific mass ratio, provide and there is the photostabilization that far exceedes the sunproof combination institute estimated performance being had separately by the compound of one of general formula (I) and general formula (II) and general formula (III).Act synergistically and provide that to have the reason of the sunproof image that exceedes expection also unclear than being used in combination the performance of these coloured materials with extra fine quality, but the inventor is presumed as follows.Note, in the following description, degree of fixation (fixability) refers to the amount of the dyestuff being 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 large.

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 to lower degree of fixation.In the time that this is put on to recording medium containing China ink of this Anthrapyridone dyes, because this dyestuff has the characteristic of low anchorage, therefore the absorbed dose on porous insert is 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, for example, on the black receiving layer of recording medium, be tending towards having higher degree of fixation by the compound of general formula (III).In the time that this is put on to recording medium containing China ink of this azoic dyestuff, because this dyestuff has the characteristic of high anchorage, therefore the absorbed dose on porous insert is large.As a result, dyestuff may only infiltrate black receiving layer along black receiving layer thickness direction shallow degree.

When by contain one of its compound of general formula (I) that is Anthrapyridone dyes all with above-mentioned characteristic and compound of general formula (II) taking and when the China ink of the present invention of the compound of the general formula (III) of azoic dyestuff puts on recording medium respectively, state is presumed as follows.; 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) only infiltrates black receiving layer along black receiving layer thickness direction shallow degree., the compound of the compound of general formula (I) and general formula (II) is different from the compound of general formula (III) along the distributing position of black receiving layer thickness direction.Due 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 to suppress to be distributed in the compound of general formula (I) that deep-seated puts and the compound of general formula (II) by photolysis along black receiving layer thickness direction.As a result, infer that being used in combination these coloured materials with extra fine quality ratio can make us far be exceeded the photostabilization of the sunproof combination institute estimated performance being had separately by the compound of 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, the mass ratio (the first coloured material/the second coloured material) of the content (quality %) of the first coloured material based on total black quality and the content (quality %) of the second coloured material must be from more than 2.5 to below 10.0., { (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 by the combination of the first coloured material and the second coloured material so that separately the mass ratio of content prepare China ink in above-mentioned scope and obtain the following two kinds of synergistic effects that exceed expection.First, first synergistic effect is the improvement that the photostabilization of the image that formed by China ink exceedes expection.; this synergistic effect provides image photostabilization, and this image photostabilization far exceedes the image photostabilization obtaining from one of compound of the compound by general formula (I) and general formula (II) and the desired photostabilization of sunproof combination being 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., have the tone desired as magenta ink image can by be used in combination the first coloured material and the second coloured material so that separately the mass ratio of content in above-mentioned scope, obtain.Note, the mass ratio of the content of the first coloured material and the second coloured material is less than 2.5 or be greater than in 10.0 black situation therein, does not show these synergies., the image photostabilization obtaining during with one of second coloured material with independent use the first coloured material is compared, and does not observe sunproof significantly improving, and can not obtain the image with the tone desired as magenta ink.

The result of inventor's research has shown that the compound of general formula (I) provides has good sunproof image in the time comparing the compound of general formula (I) and the compound of general formula (II).Therefore, in the present invention, the compound of general formula (I) is more preferably used as the Anthrapyridone dyes of the first coloured material., this China ink preferably contains at least compound formation of general formula (I) with the first coloured material.The Compound Phase ratio of the compound of general formula (I) and general formula (II), provides that to have good sunproof reason hypothesis as follows.The compound of general formula (II) does not have linking group in molecule, thus, in the case of by the compound of the deteriorated general formula of light (II), first deteriorated anthrapyridone skeleton.On the other hand, the compound of general formula (I) has linking group in molecule, and thus, in the case of by the compound of the deteriorated general formula of light (I), first deteriorated linking group is deteriorated anthrapyridone skeleton then.By this mechanism, it is relatively longer that the time that the compound of complete deteriorated general formula (I) needs becomes the time needing than the compound of complete deteriorated general formula (II).As a result, with the Compound Phase ratio of general formula (II), the compound of general formula (I) can provide has good sunproof image.

In addition, in the present invention, preferably meet following condition, provide to obtain the China ink that there is the image of especially good photostabilization and resistance to gaseousness and there is the image of the tone especially desirable as magenta ink.,, in China ink of the present invention, especially preferably the first coloured material is the compound of above-mentioned general formula (I); With the second coloured material be the compound of above-mentioned general formula (III); (the first coloured material/the second coloured material) is more than 3.0 to below 10.0.In addition, especially preferably (the first coloured material/the second coloured material) is more than 9.0 to below 10.0.

Particularly, mean following as the desirable tone of magenta ink in the present invention.Measure the L by CIE (International Commission on Illumination) regulation that is set as 100% use image that magenta ink forms by recording load (duty) ^*a ^*b ^*than a in color system ^*and b ^*, hue angle (H °) is by a ^*and b ^*income value calculate based on following formula (A).By have hue angle (H °) from more than 0 to below 5 or from more than 350 to being defined as the magenta ink with the desirable tone the present invention lower than 360 China ink.In addition, be especially preferably based on following formula (A) calculate hue angle (H °) be more than 0 to below 5.Note above-mentioned a ^*and b ^*value can for example use spectrophotometer (trade(brand)name: Spectrolino; Manufactured 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 (the 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 (fourth quadrant): H °=360+tan ^-1(b ^*/ a ^*)

As mentioned above, China ink of the present invention requires the content (quality %) of compound (hereinafter referred to the first coloured material) of one of general formula (I) and general formula (II) and the content (quality %) of the compound (hereinafter referred to the second coloured material) of general formula (III) 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 (the first coloured material/the second coloured material)=from 2.5 to 10.0.In addition the content that, especially preferred China ink of the present invention is each coloured material meets the following form forming.First, in China ink the content of the first coloured material (quality %) preferably from more than 2.5 quality % to 10.0 quality %, based on total black quality.In addition, in China ink the content of the second coloured material (quality %) preferably from more than 0.5 quality % to 2.0 quality %, based on total black quality.And, in China ink content (quality %) summation of the first coloured material and the second coloured material be preferably from more than 4.0 quality % to 10.0 quality %, based on total black quality.In China ink, the content of coloured material (quality %) summation is not preferred lower than 4.0 quality %, 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 exceedes 10.0 quality %, and this is because can not obtain characteristics of inkjet as resistance to bond.

[method of inspection of coloured material]

Use the following method of inspection (1) to (3) of high performance liquid chromatography (HPLC) to can be used for checking whether be contained in China ink for coloured material of the present invention.

(1) peak retention time

(2) maximum absorption wavelength at the peak of (1)

(3) the mass spectrographic 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 the liquid (China ink) of approximately 1,000 times as measure sample with pure water.Then, carry out under the following conditions the analysis by high performance liquid chromatography, thereby measure the maximum absorption wavelength at peak retention time and peak.

One post: SunFire C ₁₈(by Japan Waters Co., Ltd. manufactures), 2.1mm × 150mm, column temperature: 40 DEG C

-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％
					C:0.2mol/L ammonium acetate solution	5％	5％	5％	5％

In addition, as follows for mass spectrographic analysis condition.Measure under the following conditions the mass spectrum at gained peak, measure each just (positive) and negative (negative) of the M/Z detecting the most by force.

-ionization method

-ESI

Capillary voltage: 3.5kV

Desolventizing gas: 300 DEG C

Ion source temperature: 120 DEG C

-detector

Posi:40V 200 is to 1,500amu/0.9sec

Nega:40V 200 is to 1,500amu/0.9sec

Under aforesaid method and condition, the first coloured material specific examples exemplary compounds 1 as each self-colored material representative example and exemplary compounds 3 and the second coloured material specific examples exemplary compounds 6 are measured.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, unknown China ink is measured and the observed value of gained in the scope of the value shown in table 2 time, can determine that China ink comprises corresponding to the compound for compound of the present invention.

Table 2

(aqueous medium)

One of water and its aqueous medium for the mixed solvent of water and water-miscible organic solvent can be used for China ink of the present invention.Deionized water (ion exchanged water) is preferably used as this water.The content (quality %) of Mo Zhongshui preferably from more than 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 5.0 quality % to 90.0 quality %, more preferably from more than 10.0 quality % to 50.0 quality %, based on total black quality.When the content of water-miscible organic solvent is during lower than above-mentioned scope, this China ink for ink jet recording device in the situation that, may not obtained to stability as jetting stability.On the other hand, when the content of water-miscible organic solvent is during 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: have the alkanol of 1 to 4 carbon atom as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol and the trimethyl carbinol; Acid amides is as dimethyl formamide and N,N-DIMETHYLACETAMIDE; One of ketone and keto-alcohol are as acetone and diacetone alcohol; Ether as tetrahydrofuran (THF) with diox; Polyalkylene glycol is as polyoxyethylene glycol and polypropylene glycol; Glycol is as ethylene glycol, propylene glycol, butyleneglycol, glycol ether, triglycol, hexylene glycol and thiodiglycol; The aklylene glycol that wherein alkylidene group has 2 to 6 carbon atoms is as 1,5-PD, 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 is as MPEG-550 acetic ester; Polyol alkyl ether is as ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, glycol ether methyl ether, diethylene glycol monoethyl ether, triglycol monomethyl ether and triglycol list ethyl ether; METHYLPYRROLIDONE, 2-Pyrrolidone and DMI.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 said components, if needed, China ink of the present invention can comprise the water-soluble organic compounds for solid under normal temperature, as comprises the polyvalent alcohol of TriMethylolPropane(TMP) and trimethylolethane, and comprises the urea derivatives of urea and ethylidene-urea.In addition,, while needs, China ink of the present invention can comprise various additives as tensio-active agent, pH adjusting agent, rust-preventive agent, antiseptic-germicide, mould inhibitor, antioxidant, anti-reductive agent, evaporation accelerators, sequestrant and water-soluble polymers.

Other black > of <

In addition,, in order to form full-colour image, China ink of the present invention can be used in combination from the China ink having with the different tones of tone of China ink of the present invention.China ink of the present invention is preferably used in combination with for example selecting at least any China ink in the free following group 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 having with the basic identical tone of tone of every kind of these China inks.Can be known coloured material or new synthetic coloured material for the coloured material of these China inks or light color China ink.

< recording medium >

Can be any recording medium for the recording medium that uses China ink of the present invention to form image, as long as this recording medium is by China ink being applied thereto to the recording medium recording.In the present invention, preferably use the recording medium for ink-jet, wherein make coloured material if dyestuff and pigment adsorption are in the particulate of vesicular structure that forms black receiving layer.Especially preferably use the recording medium with so-called space absorption-type China ink receiving layer, this China ink receiving layer absorbs China ink by the space forming in the black receiving layer on supporting mass.Space absorption-type China ink receiving layer mainly comprises particulate and can further comprise as required tackiness agent and other additives.

Particularly, can be by following for particulate: mineral dye is if silicon-dioxide, clay, talcum, calcium carbonate, kaolin, aluminum oxide are as alumina and hydrated aluminum oxide, diatomite, titanium oxide, hydrotalcite and zinc oxide; And pigment dyestuff is 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 is as carboxymethyl cellulose, Natvosol and Vltra tears; Ethylenic copolymer latex is 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 as required additive.The example of additive comprises dispersion agent, thickening material, pH adjusting agent, lubricant, flow ability modifying agent, tensio-active agent, defoamer, releasing agent, white dyes, UV light absorber, antioxidant and dyestuff fixing salt.

Particularly, in the time using China ink of the present invention to form image, preferably using its China and Mexico's receiving layer is the recording medium that is had median size and be no more than the particulate formation of 1 μ m by uses.The specific examples of particulate comprises silicon dioxide microparticle and alumina particulate.Preferred silicon dioxide microparticle comprises those taking colloid silica as representative.Can use industrial available colloid silica, but especially preferably for example use, be 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 suitable a kind of hydrated aluminum oxide as the pseudobochmite being expressed from the next:

AlO _3-n(OH) _2n·mH ₂O

Wherein n is integer 1 to 3; M is 0 to 10, preferably 0 to 5, condition is that m is 0 when different with n).

Under many circumstances, mH ₂o also represents not participate in mH ₂the eliminable water that O lattice forms.For this reason, m can be one of integer and non integer value.In addition,, in the time of the such hydrated aluminum oxide of heating, m can reach 0.

Hydrated aluminum oxide can be produced by following currently known methods.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 with the method neutralizing by being disclosed in the aqueous solution that wherein aqueous solution of one of sodium sulfate and aluminum chloride is joined to sodium aluminate in Japanese Patent Application Laid-Open S57-044605.

Recording medium preferably has the supporting mass for supporting above-mentioned black receiving layer.This material can use any material without any restrictions for supporting, as long as can be formed black receiving layer and be formed the supporting mass that is enough to the rigidity being transferred by the transfer mechanism of ink jet recording device 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 plastic supporting body, it comprises following material: for example, as polyester (, polyethylene terephthalate), cellulose triacetate, polycarbonate, polyvinyl chloride, polypropylene and polyimide.Also can use the resin-coated paper with polyolefin resin coating layer (for example: RC paper) that adds white pigment at least one side of base paper 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 be especially preferred for its China and Mexico by ink-jet systems eject with the ink-jet recording method at the enterprising line item of recording medium.This ink-jet recording method comprises that its China and Mexico are by mechanical energy being put on to the recording method that this China ink sprays, and its China and Mexico are by putting on heat energy 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 >

The suitable print cartridge recording for the China ink of the application of the invention comprises the print cartridge being provided with for storing black black reservoir.

< record cell >

Comprise and being provided with for storing black black reservoir and for discharging the record cell of black record-header for the suitable record cell that records with China ink of the present invention.Particularly, can be preferably with above-mentioned record-header wherein by applying corresponding to the heat energy of recording signal and spray black record cell to China ink.Particularly, preferably will there is the record-header that comprises metal and the metal oxide surface, heating part contacting with liquid one of at least for the present invention.The specific examples one of at least of the metal that the surface, above-mentioned heating part contacting with liquid comprises and metal oxide comprises that metal is 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 for storing black black reservoir and for spraying the ink jet recording device of black record-header.Particularly, can mention wherein the China ink with the record-header for storing black black reservoir by apply the ink jet recording device spraying corresponding to the heat energy of recording signal to China ink.

Below by the schematic configuration of mechanism's part of description ink jet recording device.Ink jet recording device has paper feed portion, paper transport unit, seat part, paper discharge portion, cleaning section and for the protection of above-mentioned part and the outer packaging portion of pattern is provided to them, 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 describing the view of ink jet recording device internal mechanism, and wherein Fig. 2 illustrates the skeleton view of observing from upper right side, and Fig. 3 illustrates the partial elevation view of ink jet recording device.

In the time that paper feed arrives recording unit, only have the recording medium of specified quantity to be sent to roll gap portion, this roll gap portion comprises the intake roller M2080 and the separate roller M2041 that contain into the paper feed portion of bracket M2060.The recording medium transmitting is separated in roll gap portion, only transmits uppermost recording medium.The recording medium that sends 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.Drive and rotate the roller group that comprises transfer roller M3060 and pinch roll M3070 by LF electric motor E0002, thereby transmitting recording medium by platen M3040.

In seat part, when form image on recording medium time, record-header H1001 (Fig. 4: the details of this structure will describe in detail in the back) is arranged in target image and forms position, and according to from the signal of electric substrate E0014, China ink being ejected on recording medium.In the time recording by record-header H1001, wherein bearing M4000 is in the main-scanning of longitudinally carrying out with wherein alternately repeat in the subscan of cross drive recorded matter by transfer roller M3060, thereby on recording medium, forms image.Finally, the recording medium that has formed image on it is sandwiched in the roll gap portion between the first paper distributing roller M3110 and the ratchet M3120 in paper discharge portion, and is transmitted and is expelled to paper discharge dish M3160.

Cleaning section cleans record-header H1001 before and after forming image.Operating pumps M5000 in using the jet orifice that covers M5010 lid record-header H1001, to draw unnecessary China ink from the jet orifice of record-header H1001.In addition, draw while opening and remain in the China ink that cover M5010 inside adhesion and other deleterious effects to prevent from being caused by residual China ink at lid M5010.

(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 arranged on to the view on head cartridge H1000.Head cartridge H1000 has record-header H1001, the unit of print cartridge H1900 is installed and from print cartridge H1900, China ink is offered to record-header and is the unit being removably mounted on bearing M4000.

For ink jet recording device, yellow, magenta, cyan, black, shallow magenta, light cyan and green ink form image.Therefore, for print cartridge H1900 prepares seven kinds of colors independently.Note, China ink of the present invention is used at least one with inking.In addition, as shown in Figure 4, each print cartridge H1900 is dismountable with respect to head cartridge H1000.Print cartridge H1900 can also be arranged on the state installation and removal on bearing M4000 with head cartridge H1000.

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 Si substrate, forms multiple for spraying black recording element (nozzle) in one side by photolithography.By film technique form made by aluminium etc. provide the electric distribution of electric energy to each recording element, form corresponding to the multiple black stream of recording element separately by photolithography.In addition the ink supply port that, is formed for the China ink to offer multiple black streams makes open in rear surface.

Fig. 6 is the frontview amplifying, 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 also referred to as nozzle rows) corresponding to the black color of difference.The first recording element substrate H1100 has the nozzle rows for three kinds of colors: for the nozzle rows H2000 of yellow ink, for the nozzle rows H2100 of magenta ink with for the nozzle rows H2200 of cyan ink.The second recording element substrate H1101 has the nozzle rows for four kinds of colors: for the nozzle rows H2300 of light cyan China ink, for the nozzle rows H2400 of black ink, for the nozzle rows H2500 of green ink with for the nozzle rows H2600 of shallow magenta ink.

Each nozzle rows comprises (point/inch with 1,200dpi; Reference value) 768 nozzles arranging on recording medium delivery direction for interval, each nozzle ejection approximately 2 skins rise China ink.The port area of each nozzle spray-orifice is made as approximately 100 μ m ².

Hereinafter, with reference to Figure 4 and 5, the present invention is described.The first recording element substrate H1100 and the second recording element substrate H1101 combination are also fixed on the first pole plate H1200, are formed for China ink to offer 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 on the first pole plate H1200.The second pole plate H1400 is so that the mode of electric wiring substrate H1300, the first recording element substrate H1100 and the second recording element substrate H1101 electrical connection supports electric wiring substrate H1300.

Electricity wiring substrate H1300 applies the electrical signal that is formed on the each nozzle ejection China ink on the first recording element substrate H1100 and the second recording element substrate H1101 for causing.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; Be positioned at the end of electric distribution 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 H1600 and is fixed on the cartridge carrier H1500 that supports print cartridge H1900 for the means by for example ultrasonic welding.Thus, form the black stream H1501 by way 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 engaging with print cartridge H1900, so that strainer H1700 prevents that dust from entering from outside.Caulking gum H1800 is arranged on the part that black stream H1501 engages with print cartridge H1900, to prevent from then on part evaporation of China ink.

In addition, as mentioned above, by using binding agent by connecting cartridge carrier portion and recording head H1001 and make head cartridge H1000.Cartridge carrier portion comprises that cartridge carrier H1500, stream form assembly H1600, strainer H1700 and caulking gum H1800, record head H1001 and comprise 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.

At this by being described as the embodiment of record-header according to the record-header of hot ink ejecting method, in this record-header by for generation of for causing that the means of electrothermal transducer (recording element) that China ink produces the heat energy of film boiling according to electrical signal carry out record.As representative configurations 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.The method can be used for any of so-called type as required and so-called successive type.

Particularly, because underlying cause, the method is for type is effective as required.The actuate signal that at least one is also caused to the unexpected intensification that exceedes nucleate boiling corresponding to recorded information imposes on the electrothermal transducer configuring corresponding to holding black liquid flow path, thereby causes that electrothermal transducer produces heat energy and makes China ink produce film boiling.As a result, corresponding to actuate signal formation bubble one to one 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 suitably for the following ink jet recording device that utilizes mechanical energy.The ink jet recording device of this form comprises that the nozzle with multiple nozzles forms substrate, is oppositely arranged and comprises the components of stres of piezoelectric and electro-conductive material with nozzle, and fill this components of stres China ink around, wherein this components of stres moves by impressed voltage, with from nozzle ejection China ink.

It is this equipment separately that ink jet recording device is not limited to as mentioned above wherein record-header and print cartridge, and can be wherein record-header and print cartridge is integrated thereby their inseparable equipment.Print cartridge also can with to be arranged on that record-header on bearing can divide or integrated inseparably, the fixed part that maybe can be arranged on ink jet recording device is to provide China ink to record-header by ink supply assembly as pipe.In addition,, when print cartridge is provided with when structure to record-header of suitable negative pressure is provided, 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 execute biased spring portion for the internal volume direction at balloon dilator.In addition, recording unit can adopt continuous recording method as above, or can be the form by recording element being arranged in to the line-at-a-time printer obtaining corresponding to the whole width range of recording medium.

(embodiment)

Below, with reference to embodiment and the present invention of comparative example more detailed description.But 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 ".

< prepares coloured material >

(synthetic exemplary compounds 1)

(A) under agitation to adding in succession the compound of 94.8 parts of following formulas (1), 3.0 parts of sodium carbonate and 144.0 parts of ethyl benzoylacetates (ethylbenzoylacetate) in 360 parts of dimethylbenzene, gained mixture is heated to 140 to 150 DEG C of temperature, and makes its reaction 8 hours.During reaction, the second alcohol and water component distillation that produces in reaction is gone out to system with dimethylbenzene, thereby complete reaction.Reaction mixture is cooled to 30 DEG C of temperature, adds wherein 240 parts of methyl alcohol.Gained mixture is stirred 30 minutes.Then, the solid by filtration of separating out is separated.By 360 parts of methanol wash for gained solid, then dry, thus the faint yellow needle-like crystal of the compound of 124.8 parts of following formulas of acquisition (2).

Formula 1

Formula 2

(B) under agitation to 300.0 parts of N, in dinethylformamide, add in succession compound, 75.0 parts of 3-acetylaminoanilines (meta-aminoacetanilide), 24.0 parts of copper acetate dihydrates and 12.8 parts of sodium carbonate of 88.8 parts of formulas (2) that obtain above, gained mixture is heated to 120 to 130 DEG C of temperature and makes its reaction 3 hours.Reaction mixture is cooled to approximately 50 DEG C of temperature, adds wherein 120 parts of methyl alcohol.Gained mixture is stirred 30 minutes.Then, the solid by filtration of separating out is separated.Hot wash by gained solid with 500 parts of methyl alcohol and 80 DEG C, then dry, 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 to the oleum that adds 170.0 part 28.0% in 130 part of 98.0% sulfuric acid, to prepare the oleum of 300 part 12%.The compound that adds wherein the formula (3) more than 51.3 parts obtaining under water cooling below temperature 50 C, is heated to 85 to 90 DEG C of temperature by gained mixture, and makes its reaction 4 hours.Gained reaction mixture is poured in 600 portions of frozen water, simultaneously by adding ice to prevent the intensification causing due to heat release, thereby kept the temperature of mixture below 40 DEG C.Reaction mixture is mixed to the amount of acquisition with other water and be the mixture of 1000 parts, then filter to remove insoluble substance.In gained filtrate, add hot water taking acquisition amount as 1500 parts of mixtures.Add wherein 300 parts of sodium-chlor, keep the temperature of mixture at 60 to 65 DEG C simultaneously, then stir 2 hours.Then, the crystal of separating out is separated by filtering.By 300 part of 20% sodium chloride aqueous solution washing fully extruding for gained crystal, thereby obtain 100.3 portions of wet cakes, this wet cake is containing the red crystals of the compound of 59.2 parts of following formulas (4).

Formula 4

(D) in 60 parts of water, add 67.7 portions of wet cakes of the compound of the formulas (4) of acquisition above.Then, add wherein 24 part of 25% sodium chloride aqueous solution, stir subsequently.In addition, add wherein 25% aqueous sodium hydroxide solution to dissolve this compound, simultaneously by 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, the anion surfactant of being manufactured by Lion KK), add wherein 8.9 parts of cyanuryl chlorides, stir subsequently 30 minutes, thereby obtain suspension.Gained suspension is added in the solution containing above formula (4) compound obtaining.Then, gained mixture is reacted 4 hours at 25 to 30 DEG C of temperature, use 10% aqueous sodium hydroxide solution that the pH of mixture is remained in 2.7 to 3.0 scope simultaneously, thereby obtain the reaction mixture containing following formula (5) compound.

Formula 5

(E) in the reaction mixture containing above formula (5) compound obtaining, 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 DEG C, simultaneously by adding 25% aqueous sodium hydroxide solution the pH of mixture to be remained in 6.5 ± 0.3 scope.Make mixture this temperature range reaction 1 hour, thereby obtain the reaction mixture containing following formula (6) compound.

Formula 6

(F) add 1.2 parts of quadrols to the reaction mixture containing formula (6) compound of above acquisition.Then, the temperature of mixture is increased to 78 to 82 DEG C, simultaneously by adding 25% aqueous sodium hydroxide solution the pH of mixture to be remained in 7.8 to 8.2 scope.Make mixture this temperature range reaction 1 hour.Subsequently, add wherein water, thereby acquisition amount is the mixture of approximately 350 parts, is then filtered to remove insoluble substance.In gained filtrate, add the mixture of water taking acquisition amount as 400 parts.Add wherein concentrated hydrochloric acid, the temperature of mixture is remained on to 55 ± 2 DEG C simultaneously, with by the pH regulator to 3 of mixture.Then, in 15 minutes, in mixture, add 40 parts of sodium-chlor, stir subsequently 30 minutes, and further add concentrated hydrochloric acid with by the pH regulator to 2 of mixture.The acidic aqueous solution of gained is stirred 1 hour, the crystal of separating out is separated by filtering.Gained crystal is washed with 100 part of 20% sodium chloride aqueous solution, thereby obtain the wet cake of the redness containing exemplary compounds 1 as above.

(G) the wet cake obtaining is above added in 500 parts of methyl alcohol.The temperature of gained mixture is risen to 60 to 65 DEG C, mixture is stirred 1 hour.The crystal of separating out is separated by filtering, by methanol wash dry, thus the exemplary compounds 1 of acquisition free acid form.

(synthetic exemplary compounds 3)

Exemplary compounds 3 is synthetic by being described in method in the embodiment 4 of WO 2004/104108.

(synthetic exemplary compounds 5 and 6)

Description is used as to exemplary compounds 5 with the dyestuff f-1 in Japanese Patent Application Laid-Open 2002-371213, will be described in compound d-5 in Japanese Patent Application Laid-Open 2006-143989 and be used as exemplary compounds 6.

(synthetic other coloured materials)

For the following comparative compound 1 of Anthrapyridone dyes, synthesized by the method being described in Japanese Patent Application Laid-Open 2003-192930.For the following comparative compound 2 and 3 of azoic dyestuff, synthesized by the method being described in Japanese Patent Application Laid-Open H08-073791.Following comparative compound 4 is directly Huang 132 of C.I., and it is azoic dyestuff.

Comparative compound 1

Comparative compound 2

Comparative compound 3

Comparative compound 4

< prepares black >

Component shown in following table 3 and 4 is mixed and fully stir.Then, be that the strainer of 0.2 μ m filters gained mixture under pressure by aperture, thus the China ink of Preparation Example 1 to 11 and comparative example 1 to 21.

< prepares recording medium >

To be applied to and there is basic weight 155g/m containing the resin combination of 70 parts of Low Density Polyethylenes, 20 parts of high density polyethylene(HDPE)s and 10 parts of titanium dioxide ²body paper two sides so that composition is with 25g/m ²amount apply, thereby produce for resin cover supporting mass assembly.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 record of production medium, it comprise air gap type (void type) black receiving layer and have according to JAPAN TAPPI paper pulp test method(s) No.49-1 measure be 5.0 at 3 minutes rear surface pH.

< evaluates >

The embodiment obtaining above and the various China inks of comparative example are packed in the ink jet recording device (trade(brand)name: PIXUS iP8600) that utilizes heat energy.Be 23 DEG C of temperature, relative humidity 55%, recording density 2 by printing condition setting, 400dpi × 1,200dpi and injection 2.5pL.Then, on the above recording medium obtaining, form wherein and to make to record load with 10% increment and change to 100% image from 0%, this image is air-dry 24 hours 23 DEG C of temperature and relative humidity 55% time.Then tone (hue angle and optical density(OD)) and image fastness (photostabilization and ozone resistance) are evaluated by method as described below.

(tone: hue angle)

Be that 100% image section is measured the L by CIE (International Commission on Illumination) regulation to wherein record load in the above recorded matter obtaining ^*a ^*b ^*than a in color system ^*and b ^*.Note at light source being that D50 and the visual field are to use spectrophotometer (trade(brand)name: Spectrolino under the condition of 2 °; Manufactured by GretagMacbeth) measurement a ^*and b ^*value.Each hue angle (H °) is by a of gained ^*and b ^*value based on following formula (A) calculate, thereby evaluate 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 (the 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 (fourth quadrant): H °=360+tan ^-1(b ^*/ a ^*)

A:H is more than 0 to below 5.

B:H for be greater than 5 to below 10 and more than 350 to being less than one of 360.

C:H is in being greater than 10 and be less than between 350.

(tone: optical density(OD))

Be that 100% image section uses spectrophotometer (trade(brand)name: Spectrolino to wherein record load in the above recorded matter obtaining; Manufactured by Gretag Macbeth) measure optical density(OD), to evaluate 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 the acceptable level of optical density(OD) as magenta, and C represents the unacceptable level of optical density(OD) as 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 more than 1.5 to being less than 2.0.

C: optical density(OD) is less than 1.5.

(image fastness: photostabilization)

Be that 50% image section is measured the L by CIE (International Commission on Illumination) regulation to wherein record load in the above recorded matter obtaining ^*a ^*b ^*than the L in color system ^*, a ^*and b ^*(being called " the Lab value before light fastness test ").Then this recorded matter is used to super xenon lamp trier (trade(brand)name: SX-75, by Suga Test Instruments Co., Ltd. manufactures) under the condition of 24 DEG C of exposure intensity 100 kiloluxs, relative humidity 60% and vessel temps, expose 168 hours.Then be, that 50% image section is measured L to wherein record load in recorded matter ^*, a ^*and b ^*(being called " the Lab value after light fastness test ").Note at light source being that D50 and the visual field are to use spectrophotometer (Spectrolino under the condition of 2 °; Manufactured by Gretag Macbeth) measurement L ^*, a ^*and b ^*.According to the Lab value of gained before and after light fastness test, calculate aberration (Δ E) based on following formula (B), thereby evaluate photostabilization.Sunproof standard is as described below, and the evaluation result being 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 large after light fastness test.

Formula (B)

$\mathrm{\&Delta;E}=\sqrt{{(L_1-L_2)}^2+{(a_1-a_2)}^2+{(b_1-b_2)}^2}$

L ₁, a ₁, b ₁: the Lab value before light fastness test

L ₂, a ₂, b ₂: the Lab value after light fastness test

A: Δ E is less than 17.

B: Δ E for from more than 17 to being less than 20.

C: Δ E is more than 20.

(image fastness: ozone resistance)

Be that 50% image section is measured the L by CIE (International Commission on Illumination) regulation to wherein record load in the above recorded matter obtaining ^*a ^*b ^*than the L in color system ^*, a ^*and b ^*(being called " the Lab value before ozone resistance test ").Then this recorded matter is used ozone testing installation (trade(brand)name: OMS-H, by Suga Test Instruments Co., Ltd. manufactures) to expose 4 hours under the condition of 24 DEG C of concentration of ozone gas 10ppm, relative humidity 60% and vessel temps.Then be, that 50% image section is measured L to wherein record load in recorded matter ^*, a ^*and b ^*(being called " the Lab value after ozone resistance test ").Note at light source being that D50 and the visual field are to use spectrophotometer (Spectrolino under the condition of 2 °; Manufactured 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 evaluate 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 image fade is large after ozone resistance test.

Formula (C)

$\mathrm{\&Delta;E}=\sqrt{{(L_1-L_2)}^2+{(a_1-a_2)}^2+{(b_1-b_2)}^2}$

L1, a1, b1: the Lab value before ozone resistance test

L2, a2, b2: the Lab value after ozone resistance test

A: Δ E is less than 2.

B: Δ E for from more than 2 to being 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 widest explanation, so that comprises all improvement and equivalent structure and function.

Claims (11)

1. an ink jet ink, it comprises the first coloured material and at least two kinds of coloured materials of the second coloured material,

Wherein, this first coloured material serve as reasons following general formula (I) represent compound

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

This second coloured material serve as reasons following general formula (III) represent compound:

Wherein R ₂, R ₃, R ₄and R ₅represent independently of one another alkyl; M represents hydrogen atom, basic metal, ammonium or organic ammonium independently,

Wherein the mass ratio of the content in quality % of this first coloured material and the content taking quality % of this second coloured material as more than 2.5 to below 10.0.

2. ink jet ink according to claim 1, the wherein R in general formula (III) ₂, R ₃, R ₄and R ₅represent ethyl.

3. ink jet ink according to claim 1, wherein the X in general formula (I) is linking group 1,

Described linking group 1 is

Wherein, n represents 2 to 8; Symbol " * " represents the bonding position of one of two different triazine rings separately.

4. ink jet ink according to claim 1, wherein said mass ratio is more than 9.0 to below 10.0.

5. ink jet ink according to claim 1, wherein the content taking quality % of the first coloured material described in China ink more than 2.5 quality % to 10.0 quality %, based on total black quality.

6. ink jet ink according to claim 1, wherein the content taking quality % of the second coloured material described in China ink more than 0.5 quality % to 2.0 quality %, based on total black quality.

7. ink jet ink according to claim 1, wherein the content summation taking quality % of the first coloured material described in China ink and the second coloured material more than 4.0 quality % to 10.0 quality %, based on total black quality.

8. an ink jet recording method, wherein by ink-jet systems eject China ink with at the enterprising line item of recording medium, wherein this China ink is ink jet ink according to claim 1.

9. a print cartridge, it is provided with for storing black black reservoir, and wherein this China ink is ink jet ink according to claim 1.

10. a record cell, it is provided with for storing black black reservoir and for spraying black record-header, wherein this China ink is ink jet ink according to claim 1.

11. 1 kinds of ink jet recording devices, it is provided with for storing black black reservoir and for spraying black record-header, wherein this China ink is ink jet ink according to claim 1.