CN104073025A - Coloring dispersion agent, ink composition, inkjet recording method and colored member - Google Patents
Coloring dispersion agent, ink composition, inkjet recording method and colored member Download PDFInfo
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- CN104073025A CN104073025A CN201410120694.2A CN201410120694A CN104073025A CN 104073025 A CN104073025 A CN 104073025A CN 201410120694 A CN201410120694 A CN 201410120694A CN 104073025 A CN104073025 A CN 104073025A
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Abstract
The invention relates to a coloring dispersion agent, an ink composition, an inkjet recording method and a colored member. The invention provides the coloring dispersion agent for a red ink, a red ink composition which has excellent hue and excellent chroma and has extraordinarily excellent color emissivity for recording an image, and an inkjet recording method using the ink composition. The coloring dispersion agent of the invention comprises a coloring agent which is represented by a formula (1). Furthermore the ink composition contains the coloring dispersion agent and an organic solvent. In the formula (1), R1 and R2 respectively and independently represent a hydrogen atom, a chlorine atom or a methyl; and M represents an atom selected from Ba, Ca, Sr and Mn.
Description
Technical field
The ink composite that the present invention relates to painted dispersion liquid, contain this painted dispersion liquid, the colouring agent that uses the ink jet recording method of this ink composite and obtained by these.
Background technology
In shades of colour recording method, be exactly the droplet that produces ink as recording method one of representational method, that undertaken by ink-jet printer, make it be attached to the various materials (paper, film, cloth etc.) that are recorded and carry out record.The method is because record-header does not directly contact with being recorded material, thereby the sound producing is little, peace and quiet.And, there is the feature of easy miniaturization, high speed, thereby in recent years, in popularizing rapidly, also can expect to have from now on large lifting.
As one of the means of the higher image quality in ink jet recording method, except blue or green, pinkish red, yellow, black primitive colour, the so-called characteristic ink such as use red, green, blue are also proposed.In recent years, for this characteristic ink, also same with primitive colour ink, requirement improves color emissivity and the distinctiveness etc. of current obtained image.
As the tinting material for ink, dyestuff and water-fast in fact 2 kinds of pigment of general known water soluble.
As for example patent documentation 1, the dyestuff of using as red ink, has proposed the dyestuff that color emissivity is good, but the water tolerance, the photostabilization etc. that require for print, compared with pigment, be it is generally acknowledged poor.
In addition, as for example patent documentation 2, propose colo(u)rant dispersion good water tolerance, in ink, to use as jetted ink, but the ink of the requirement to form and aspect and color emissivity that not yet attains full and complete satisfaction.
On the other hand, as patent documentation 3, also propose to use Yellow ink and magenta ink, utilized ink jet recording method to form the method for red image.But, even this method also can produce the problem of the color emissivity decline of document image.
Prior art document
Patent documentation
Patent documentation 1 open patent 2012-193310 communique
Patent documentation 2 open patent 2010-43149 communiques
Patent documentation 3 open patent 2006-298978 communiques
Patent documentation 4 open patent 2006-176605 communiques
Summary of the invention
The problem that invention quasi-solution is determined
The object of the invention is to, be provided for red ink painted dispersion liquid, give the document image that form and aspect and colourity excellence and color emissivity are extremely excellent red ink composition, use the ink jet recording method of this ink composite.
For solving the means of problem
The present inventors have carried out continuous further investigation in order to solve above-mentioned problem, found that: by the painted dispersion liquid that contains the tinting material being represented by specific formula (1) and the ink composite that contains this painted dispersion liquid, can solve above-mentioned problem, and then complete the present invention.
, the present invention relates to following [1]～[14]:
[1] the painted dispersion liquid that one contains the tinting material being represented by following formula (1).
Change 1
(in formula (1), R
1and R
2represent independently respectively hydrogen atom, chlorine atom or methyl, M represents to be selected from the atom in Ba, Ca, Sr and Mn.）
[2] the painted dispersion liquid described in above-mentioned [1], wherein, in above-mentioned formula (1), R
1for methyl, R
2for chlorine atom.
[3] the painted dispersion liquid described in above-mentioned [1], wherein, in above-mentioned formula (1), M is Ba.
[4] the painted dispersion liquid described in above-mentioned [1], wherein, in above-mentioned formula (1), R
1for methyl, R
2for chlorine atom, M is Ba.
[5] the painted dispersion liquid described in any one in above-mentioned [1]～[4], wherein, as tinting material, also contains carbon black.
[6] the painted dispersion liquid described in any one in above-mentioned [1]～[5], wherein, as tinting material, also contains C.I. pigment orange.
[7] the painted dispersion liquid described in above-mentioned [6], wherein, C.I. pigment orange is selected at least one pigment the group from being made up of C.I. pigment orange 16,36,43 and 64.
[8] ink composite, it contains painted dispersion liquid and organic solvent described in any one in above-mentioned [1]～[7].
[9] above-mentioned [8] described ink composite, wherein, above-mentioned organic solvent is at least one polyvalent alcohol.
[10] the described ink composite in above-mentioned [8] or [9], wherein, the median size of the tinting material in above-mentioned ink composite is below the above 200nm of 50nm.
[11] ink jet recording method, it is by making the drop ejection of the ink composite described in any one in above-mentioned [8]～[10] according to recording signal, it is attached to and is recorded on material and carries out record.
[12] above-mentioned [11] described ink jet recording method, wherein, the above-mentioned material that is recorded is information transmission thin slice.
[13] colouring agent, it is painted by the ink composite described in any one in above-mentioned [8]～[10].
[14] ink-jet printer, the container that its filling contains the ink composite described in any one in above-mentioned [8]～[10].
The effect of invention
According to the present invention, can be provided for red ink painted dispersion liquid, give the document image that form and aspect and colourity excellence and color emissivity are extremely excellent red ink composition, use the ink jet recording method of this ink composite.
Embodiment
Below, explain the present invention.
And, in this manual, including embodiment waits, for " % " and " umber ", if not special explanation is all to record with quality criteria.In addition, in this manual, so-called " C.I. ", just refers to " color index ".
Above-mentioned painted dispersion liquid is the painted dispersion liquid of water system that contains water, contains the tinting material being represented by above-mentioned formula (1).
In formula (1), R1 represents hydrogen atom, chlorine atom or methyl, preferably chlorine atom or methyl, more preferably methyl.
In formula (1), R2 represents hydrogen atom, chlorine atom or methyl, preferably hydrogen atom or chlorine atom, more preferably chlorine atom.
In formula (1), M represents to be selected from the atom in Ba, Ca, Sr and Mn.Be preferably Ba or Ca, more preferably Ba.
In above-mentioned, preferred combination is each other preferred, and preferred combination is each other further preferred.Also be same for the combination between preferred and preferred.
The concrete example of the compound being represented by above-mentioned formula (1) is recited in to following table 1, but the present invention is not limited to these concrete examples.
Table 1
| Tinting material numbering | R 1 | R 2 | M | C.I. title |
| 1 | CH 3 | H | Ca | C.I. Pigment red 57:1 |
| 2 | CH 3 | Cl | B a | C.I. pigment red 4 8:1 |
| 3 | CH 3 | Cl | Ca | C.I. pigment red 4 8:2 |
| 4 | CH 3 | Cl | Sr | C.I. pigment red 4 8:3 |
| 5 | CH 3 | Cl | Mn | C.I. pigment red 4 8:4 |
| 6 | Cl | CH 3 | Ca | C.I. Pigment red 52:1 |
The tinting material being represented by above-mentioned formula (1), especially at the tinting material shown in upper table 1, is generally also referred to as solubility azo pigment or azo lake pigment, is the pigment dyestuff in molecule with azo-group.
Normally by the compound being obtained from the diazo coupling reaction of aromatic amines and naphthol compound is become to the tinting material that various metal-salts obtain.
As the tinting material being represented by above-mentioned formula (1), can obtain the tinting material of the trade(brand)names such as such as bright fuchsin 6B (Block リ リ ア Application ト カ mono-ミ Application 6B), permanent bordeaux 2B as commercially available product, ウ オ Star チ Application グ レ ッ De (Watching Red), Bonn red (ボ Application レ Star De).
Above-mentioned painted dispersion liquid can also contain carbon black as tinting material.By containing carbon black, in the time of modulation ink composite, can obtain having more the thing that records of concentration sense.
As above-mentioned carbon black, preferably furnace treated black, dim, acetylene black, thermally oxidized black etc.As the concrete example of carbon black, can list: for example Raven760ULTRA, Raven780ULTRA, Raven790ULTRA, Raven1060ULTRA, Raven1080ULTRA, Raven1170, Raven1190ULTRAII, Raven1200, Raven1250, Raven1255, Raven1500, Raven2000, Raven2500ULTRA, Raven3500, Raven5000ULTRA II, Raven5250, Raven5750, Raven7000 (being to be produced by Colombia's carbon (コ ロ Application PVC ア カ ー ボ Application) company above); Monarch700, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Regal1330R, Regal1400R, Rega1660R, Mogu L(are produced by Cabot (キ ャ ボ ッ ト) company); Color Black FW1, Color Black FW2, Color BlackFW2V, Color Black FW200, Color Black S150, Color Black S160, ColorBlack S170, Printex35, Printex U, Printex V, Printex140U, Printex140V, SpecIal Black4, SpecIal Black4A, SpecIal Black5, Special Black6(are produced by Degussa (デ グ サ) company); MA7, MA8, MA100, MA600, MCF-88, No.25, No.33, No.40, No.47, No.52, No.900, No.2300(are produced by Mitsubishi Chemical Ind) etc.
Above-mentioned painted dispersion liquid can also contain C.I. pigment orange., above-mentioned painted dispersion liquid, except the tinting material being represented by above-mentioned formula (1), can also contain from the tinting material of carbon black and the selection of C.I. pigment orange.
As C.I. pigment orange, have no particular limits, preferably selected at least one pigment from the group being formed by C.I. pigment orange 16,36,43 and 64.By containing C.I. pigment orange, can obtain distinctiveness high record thing.
The total mass of the tinting material containing with respect to above-mentioned painted dispersion liquid, the content of tinting material being represented by above-mentioned formula (1) is generally 100～80%, is preferably 100～90%, and more preferably 100～95.
In addition, in the time that above-mentioned painted dispersion liquid contains carbon black and/or C.I. pigment orange, carbon black and C.I. pigment orange be generally 100/0～0/100 with quality criteria containing proportional, be preferably 90/10～10/90, more preferably 80/20～15/85.
In the time modulating above-mentioned painted dispersion liquid, preferably use dispersion agent.Kind by suitable selection dispersion agent, acid number, molecular weight etc., also can be formed as the median size of tinting material below 300nm, preferably 50nm～200nm, more preferably 60nm～120nm.Thus, when the ink composite that contains above-mentioned painted dispersion liquid in modulation, the dispersion stabilization of tinting material and the ejection excellent in stability during for ink-vapor recording, can improve the lettering concentration of document image simultaneously.The median size of look material can adopt laser scattering method.
As making tinting material be scattered in the method in water, can for example use the known methods such as sand mill (being also ball mill), roller mill, ball mill, paint shaker, ultrasonic wave separating apparatus, microfluidizer.In these, preferred sand mill.Use sand mill to carry out dispersion liquid modulation preferably by using the little pearl (0.01mm～1mm diameter) of diameter, increase the filling ratio of pearl etc., improving the condition modulated dispersion liquid of dispersion efficiency.
In addition, after dispersion liquid modulation, also preferably carry out, by filtration and/or centrifugation etc., removing pearl etc., remove the larger tinting material of the median size back of the body that departs from objectives simultaneously.
In addition, in the time of modulation dispersion liquid, in the time producing foaming etc., in order to suppress this phenomenon, also can add the defoamers such as known silicone, acetylenic glycols class in denier ground.But, in defoamer, also there is the dispersion or the micronized composition that hamper toner, preferably suitably do not use the stability after disperseing or disperseing is brought to the defoamer of impact.
As above-mentioned dispersion agent, can list: for example, the natural polymers such as lignosulfonic acid, shellac; Polyacrylic acid, styrene-propene acid copolymer, Styrene And Chloroalkyl Acrylates-alkyl acrylate copolymer, styrene-maleic acid copolymer, styrene-maleic acid-alkyl acrylate copolymer, Styrene-methyl Acrylic Acid Copolymer, vinylbenzene-methacrylic acid-alkyl acrylate copolymer, styrene-maleic acid half ester copolymer, vinylnaphthalene-acrylic copolymer, vinylnaphthalene-maleic acid etc.
There is no particular limitation for the scope of the quality molecular-weight average (MW) of above-mentioned dispersion agent, but be preferably 3000～50000 scope, more preferably 7000～25000 scope.
In addition, also can use commercially available water soluble resin as dispersion agent.As its concrete example, can list: the ジ ョ Application Network リ Le that for example U.S. village minister (ジ ョ Application ソ Application Port リ マ ー) company produces
tM(JONCRYL
tM) the styrene-propene acid resins such as 62,67,68,678,687; ジ ュ リ マ ー
tM(Mowinyl
tM) S-100A(ヘ キ ス ト (Hoechst) Synesis Company produce modification vinyl acetate resin); ジ ュ リ マ ー
tM(Gelymer
tM) acrylate copolymer produced of the pure medicine of AT-210(Japan (Co., Ltd.)); Etc..In these, preferably contain the resin of carboxyl at its molecule.In this manual, subscript " TM " refers to trade mark.
Above-mentioned ink composite contains above-mentioned painted dispersion liquid and organic solvent.
The painted dispersion liquid containing as above-mentioned ink composite, can list: the painted dispersion liquid that contains the tinting material being represented by above-mentioned formula (1); The painted dispersion liquid that contains the tinting material, carbon black and/or the C.I. pigment orange that are represented by above-mentioned formula (1).In addition, also can modulate respectively the painted dispersion liquid that contains separately the tinting material, carbon black or the C.I. pigment orange that are represented by above-mentioned formula (1), suitably contain this 3 kinds of dispersion liquids.
The total amount of the tinting material that above-mentioned ink composite contains is generally 1～30% with respect to the total mass of ink composite, is preferably 1～10%, and more preferably 2～7%.
The organic solvent containing as above-mentioned ink composite, can list water-miscible organic solvent.
As its concrete example, can list: C1～C3 alcohol such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol; The ether compounds such as 1,2-glycol dimethyl ether, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane; The ketones such as acetone; Polyvalent alcohol; Acetic acid etc.These water-miscible organic solvents both can use a kind, also can combine multiple.
As above-mentioned polyvalent alcohol, can list: 1,2-hexylene glycol, 1,6-hexylene glycol, three methanol-based propane, 1,2,6-hexanetriol etc. has aliphatics C1～C6 alkanol of 2 or 3 hydroxyls; Ethylene glycol, glycol ether, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,4-butyleneglycol, 1,6-hexylene glycol, glycol ether, triethylene glycol, TEG, dipropylene glycol, polyoxyethylene glycol, polypropylene glycol, thiodiglycol, dithiodiglycol etc. have single aklylene glycol or sulfo-glycol, oligo alkylene glycols or sulfo-glycol or polyalkylene glycol or the sulfo-glycol of C2～C6 alkylidene group unit; The glycerols such as glycerine, Glycerol dimer etc.Both can use separately these organic solvents, also can use two or more simultaneously.
In these, preferably glycerine class (preferably glycerine), there is single aklylene glycol, oligo alkylene glycols or the polyalkylene glycol (preferably glycol ether, triethylene glycol and 1,2-PD) of C2～C6 alkylidene group unit.
Above-mentioned ink composite preferably at least contains a kind of polyvalent alcohol as water-miscible organic solvent.By containing polyvalent alcohol, can adjust the viscosity of ink composite, and also can expect the dry effect preventing.
The content of above-mentioned water-miscible organic solvent is generally 10～60% in the total mass of ink composite, is preferably 10～40%.
As the pH of above-mentioned ink composite, for storage stability is improved, preferably pH5～11, more preferably pH7～10.
As the surface tension of ink composite, with regard to static surface tension, be preferably 10～36mN/m, more preferably 20～36mN/m.
As the viscosity of ink composite, be generally 3～20m Pas, be preferably 3～10m Pas.
These are all the measured values at 25 DEG C, and the pH of ink composite and surface tension can suitably be adjusted by pH adjusting agent described later, tensio-active agent etc.
Above-mentioned ink composite at least contains above-mentioned painted dispersion liquid, water-miscible organic solvent and water, as required, also can add ink modulator.In the time of the ink that this ink composite is used as ink-vapor recording, the content of the inorganic impurity such as muriate (such as sodium-chlor), vitriol (such as sodium sulfate) of the metallic cation in the painted dispersion liquid preferably containing at ink composite of the present invention is few.The target of this inorganic impurity content is to be approximately below 1% with respect to the total mass of tinting material, and lower limit can be below the limit of detection of Analytical equipment, 0%.As the method for manufacturing the tinting material that inorganic impurity is few, can be by for example the method for inorganic impurity exchange adsorption etc. being carried out to desalting treatment by ion exchange resin.
As above-mentioned ink modulator, can list such as Antisepticize and mildew preventive, pH adjusting agent, chelating reagent, rust-preventive agent, Water-soluble UV-absorbents, water-soluble high-molecular compound, oxidation inhibitor, tensio-active agent etc.Below, relevant these ink modulators are described.
As the concrete example of mould inhibitor, can list: Sodium dehydroacetate, sodium benzoate, mercaptopyridine-1-oxidation sodium salt, ethyl p-hydroxybenzoate, 1,2-benzisothiazole-3-ketone and salt thereof etc.
As the concrete example of sanitas, can list: the compounds such as such as organosulfur class, organonitrogen sulphur class, organic halogen class, halogenated aryl sulfone class, iodine propine class, halogenated alkylthio class, nitrile, pyridines, oxine class, benzothiazoles, isothiazoline class, dithiols, pyridine-N-oxide class, nitropropane class, organic tin, phenol, quaternary ammonium salt, triazines, thiazides, phenyl amines, adamantane, dithiocarbamate(s), bromination indane ketone, benzyl acetate bromide class, inorganic salts.
As the concrete example of organic halogen compounds, can list for example sodium pentachlorophenol.
As the concrete example of pyridine-N-oxide based compound, can list for example 2-pyridine mercaptan-1-and be oxidized sodium salt.
As the concrete example of isothiazoline based compound, can list such as BIT, Kathon, CMIT, CMIT magnesium chloride, CMIT calcium chloride, MIT calcium chloride etc.
As the concrete example of other Antisepticize and mildew preventive, can list: sodium acetate, anhydrous, sodium sorbate, sodium benzoate, ア ー チ ケ ミ カ Le (Arch Chemical) manufacturer of company name of an article プ ロ Network セ Le
tM(Prokcel
tM) GXL(S) or Prokcel
tMxL-2(S) etc.
As pH adjusting agent, only otherwise can modulated ink composite be brought detrimentally affect and its pH can be controlled in above-mentioned scope, just can use material arbitrarily.As its concrete example, can list: for example, the alkanolamines such as diethanolamine, trolamine, N methyldiethanol amine; The alkali-metal oxyhydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide; Ammonium hydroxide (ammoniacal liquor); The alkali-metal carbonate such as Quilonum Retard, sodium carbonate, sodium bicarbonate, salt of wormwood; The organic acid such as water glass, Potassium ethanoate an alkali metal salt; The mineral alkalis such as Sodium phosphate dibasic; Etc..
As the concrete example of chelating reagent, can list: for example, disodium ethylene diamine tetraacetate, sodium nitrilo triacetate, hydroxyethylethylene diamine tri-acetic acid sodium (ヒ De ロ キ シ エ チ Le エ チ レ Application ジ ア ミ Application three jealous woman acid Na ト リ ウ system), diethylene triamine pentacetic acid (DTPA) sodium (ジ エ チ レ Application ト リ ア ミ Application five jealous woman acid Na ト リ ウ system), uridylic sodium diacelate etc.
As the concrete example of rust-preventive agent, can list: for example, acid accumulator sulfite, Sulfothiorine, ammonium mercaptoacetate, di-isopropyl ammonium nitrate, trinitrol (four nitric acid ペ Application タ エ リ ス リ ト ー Le), dicyclohexyl amine nitrite (ジ シ Network ロ ヘ キ シ Le ア Application モ ニ ウ system Na イ ト ラ イ ト) etc.
As the concrete example of Water-soluble UV-absorbents, can list: for example, the Benzophenones compound of sulfonation, benzotriazole compound, salicylic acid compounds, cinnamic acid compound, compound in triazine class.
As the concrete example of water-soluble high-molecular compound, can list: polyoxyethylene glycol, polyvinyl alcohol, derivatived cellulose, polyamine, poly-imines etc.
As the concrete example of oxidation inhibitor, can use the preventing agent of fading of for example various organics and metal complex class.As the example of the preventing agent of fading of above-mentioned organic, can list: hydroquinone type, alkoxy benzene phenols, dialkoxy phenol, phenol, phenyl amines, amine, indane class, chroman class, alkoxy benzene amine, heterocyclic etc.
As the concrete example of tensio-active agent, can list the known tensio-active agents such as such as negatively charged ion, positively charged ion, zwitter-ion, nonionic.
As anion surfactant, can list: alkyl sulphonyl carboxylate salt, sulfonated α-olefin, polyethylene oxide alkyl ethers acetate, N-acylamino acid or its salt, N-acyl methyl taurine salt, alkyl-sulphate polyoxygenated sulfated alkyl ether, alkyl-sulphate polyethylene oxide alkyl ethers phosphoric acid salt, RA rosin acid, Viscotrol C sulfuric acid, lauryl alcohol sulfuric acid, alkylphenol type phosphoric acid ester, alkyl type phosphoric acid ester, alkylaryl sulphonate, diethyl sulfosuccinate, two (ethylhexyl) sulfosuccinate, dioctyl sulfosuccinate etc.
As cats product, can list: 2-vinylpyridine derivative, poly-4-vinylpyridine derivative etc.
As zwitterionics, can list: lauryl dimethyl oxyneurine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazole quinoline trimethyl-glycine, coco-nut oil fatty acid amido propyl dimethylamino acetic acid trimethyl-glycine, the poly-aminoethyl glycine of poly-octyl group, imidazolidine derivatives etc.
As nonionogenic tenside, can list: the ethers such as polyoxyethylene nonylphenol ether (Port リ オ キ シ エ チ レ Application ノ ニ Le Off ェ ニ Le エ ー テ Le), polyoxyethylene octylphenol ether, dodecyl phenol polyethenoxy ether, oleyl Soxylat A 25-7, laureth, alkyl polyoxyethylene ether; The ester classes such as polyoxyethylene oleic acid ester, distearyl acid polyoxyethylene ester, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquialter isostearate, Aceonon 300 MO, polyoxyethylene stearic acid ester; 2,4,7,9-tetramethyl--5-decine-4,7-glycol, 3,6-dimethyl-4-octyne-3,6-glycol, 3, alkyne diol (alcohol) classes such as 5-dimethyl-1-hexin-3-alcohol; The commodity サ ー Off ィ ノ ー Le by name that Xin chemical company produces
tM(Surfynol
tM) 104PG50,105PG50,82,420,440,465,485, オ Le Off ィ Application
tM(Olfine
tM) STG; Polyoxyethylene glycol ethers (the Tergitol that for example SIGMA-ALDRICH company produces
tM15-S-7 etc.); Deng.In these, each series of preferred Surfynol (preferably Surfynol
tM104PG50, Surfynol
tM440, Surfynol
tM465).
Above-mentioned ink modulator can be used alone or as a mixture respectively.
As above-mentioned ink jet recording method, can list such ink jet recording method: by make the drop ejection of above-mentioned ink composite according to recording signal, it is attached to and is recorded on material and carries out record.
As ink-jetting style, can list: for example, utilize electrostatic attraction and make the electric charge control mode of ink ejection; Utilize the black mode (pressure pulse mode) of dripping as required of the vibration pressure of piezoelectric element; Change electrical signal into acoustic beam, expose to ink, utilize its radiation pressure and make the sound ink-jetting style of ink ejection; Heat ink and form bubble, utilizing the thermal-induction type ink-jet of the pressure producing is bubble type ink-jet (registered trademark) mode; Deng.
Be not particularly limited as being recorded material, can list: for example, all do not there is the common paper of ink-receiver layer, medium for intaglio printing or offset printing etc.; There is the information transmission thin slices such as ink-jet dedicated paper, ink-jet film special, glossy paper or the glossy film of ink-receiver layer; Fiber or cloth (Mierocrystalline cellulose, nylon, wool etc.), leather, colour filter base material; Deng.
As utilizing above-mentioned ink jet recording method in the method that is recorded the enterprising line item of material, can list: for example, the container that contains above-mentioned ink composite is filled in to the position of the regulation of ink-jet printer, utilize above-mentioned ink jet recording method in the method that is recorded the enterprising line item of material.
Above-mentioned ink jet recording method also can use above-mentioned red ink composition and such as known magenta, green grass or young crops, Huang and green, blue (or purple), the ink composite of all kinds such as orange as required simultaneously, carries out full color record.
Ink composite of all kinds is injected in container separately, this each container and the container that contains above-mentioned red ink composition are similarly filled in ink-jet printer regulation position and be used to ink-vapor recording.
The red ink composition of the application of the invention, can obtain the document image that lettering concentration and chroma are all high, and can obtain visually also having concentration sense, and what distinctness and colour gamut were wide records thing.In addition can obtain, the image of the various soundness excellences such as frictional property, water tolerance, photostabilization, thermotolerance, resistance to oxidation gas (such as ozone gas) property.
Embodiment
Below, although specifically describe the present invention by embodiment, the present invention is not subject to any restriction of following embodiment.In addition, if not special explanation such as the operation of each building-up reactions, crystallization etc. is all under agitation carried out.
In addition, the MS-70 that the content of the solid substance in dispersion soln uses the A & D of Co., Ltd. to produce, obtains by dry weight method.
[embodiment 1]: the modulation (1) of red painted dispersion liquid
By 9.38 parts of JONCRYL68(MW:13000) and 5 parts of trolamines be dissolved in 98.1 parts of ion exchanged waters, stir 1 hour.In obtained solution, add C.I.Pigment Red48:1(37.5 part), under the condition of 1500rpm, in sand mill, carry out the dispersion treatment of 20 hours.The red painted dispersion liquid that drip 150 parts of ion exchanged waters in obtained dispersion liquid after, then by filtering this liquid, obtained solid content and be 13.2%, the median size of tinting material is 131nm.Using obtained painted dispersion liquid as dispersion liquid 1.
[embodiment 2]: the modulation (2) of red painted dispersion liquid
By 9.38 parts of JONCRYL68(MW:13000) and 5 parts of trolamines be dissolved in 98.1 parts of ion exchanged waters, stir 1 hour.In obtained solution, add C.I.Pigment Red48:1(35.6 part) and C.I.Pigment Orange16(1.9 part), under the condition of 1500rpm, in sand mill, carry out the dispersion treatment of 20 hours.The red painted dispersion liquid that drip 150 parts of ion exchanged waters in obtained dispersion liquid after, then by filtering this liquid, obtained solid content and be 14.4%, the median size of tinting material is 110nm.Using obtained painted dispersion liquid as dispersion liquid 2.
[embodiment 3]: the modulation of the painted dispersion liquid of black
The C.I.Pigment Red48:1 using in embodiment 1 is replaced with to carbon black, in addition, the painted dispersion liquid of the black that the content that obtains similarly to Example 1 solid substance is 17.3%, the median size of tinting material is 98nm.Using obtained painted dispersion liquid as dispersion liquid 3.
[embodiment 4～8]: the modulation of ink
After the painted dispersion liquid obtaining at embodiment 1 is mixed with each composition of recording in following table 2, with the film filter filtration inclusion of 3 μ m, obtained the red ink composition of the present invention that evaluation test is used in 3.
In following table 2, the numerical value of each composition refers to umber.
[comparative example 1]: the modulation of red painted dispersion liquid
The C.I.Pigment Red48:1 using in embodiment 4 is replaced with to C.I.Pigment Red254, in addition, the red dispersion liquid of the relatively use that the content that has obtained similarly to Example 4 solid substance is 12.8%.By obtained painted dispersion liquid dispersion liquid 1 as a comparison.
[comparative example 2]: the modulation of yellow painted dispersion liquid
The C.I.Pigment Red48:1 using in embodiment 4 is replaced with to C.I.Pigment Yellow74, in addition, the yellow dispersion liquid that the comparative example that the content that obtains similarly to Example 4 solid substance is 18.9% is used.By obtained painted dispersion liquid dispersion liquid 2 as a comparison.
[comparative example 3]: the modulation of the painted dispersion liquid of magenta
The C.I.Pigment Red48:1 recording in embodiment 4 is replaced with to C.I.Pigment Magenat122, in addition, the magenta dispersion liquid that the comparative example that the content that obtains similarly to Example 4 solid substance is 16.6% is used.By obtained painted dispersion liquid dispersion liquid 3 as a comparison.
[comparative example 4～6]: relatively use the modulation of ink
After the painted dispersion liquid obtaining in 3 in comparative example example 1 is mixed with each composition of recording in following table 2, with the film filter filtration inclusion of 3 μ m, what obtain that evaluation test uses relatively uses red ink composition.
In following table 2, the numerical value of each composition refers to umber.
In addition, comparative example 5 and 6 is to obtain red ink composite by allocating yellow and pinkish red tinting material.The method of utilizing the allotment of these tinting materials and obtain red ink composition is well known to a person skilled in the art.
Table 2
[(A) ink-vapor recording]
The ink composite obtaining in above-described embodiment and comparative example is filled in respectively to the ink-jet printer that Seiko Epson company manufactures, and the magenta print cartridge of trade(brand)name PX101, has carried out ink-vapor recording to the senior common paper DL9084 of Mitsubishi's paper manufacture processed.
Ink-vapor recording is red 100% to become, 80%, the mode of the image of the 3 grade gray scales of 60%Duty carries out, and obtained the colouring agent by each ink composite record of above-described embodiment and comparative example.Using obtained colouring agent as test film, carry out following evaluation test.
[(B) colour examining of document image]
The color measurement instrument that the colour examining of each test film is used X-rite company to manufacture, trade(brand)name Spectro Eye carries out.Colour examining condition is concentration benchmark ANSI A, 2 °, visual angle, light source D50.
[(C) form and aspect evaluation test]
To by the above-mentioned each test film obtaining like that, the concentration hue angle (h) of the each concentration gray scale portion to 3 grades carries out colour examining, evaluates and whether is equivalent to red region.
And, in the region of this said redness, be defined as the hue angle (h) of L*a*b* color specification system 20 °≤h≤35 °, whether be equivalent to this scope with the numerical value of 2 following actual colour examinings of grade evaluation.To the results are shown in following table 3.
A: be equivalent to red region.
C: be not equivalent to red region.
[(D) color emissivity evaluation test]
Using the concentration of the 100%Duty portion of each test film as the colour examining of Dm value, evaluate with the metewand of 3 following grades: will the results are shown in following table 3.In addition large more excellent of the D value that obtains.
A:Dm value is more than 1.20
B:Dm value is more than 1.10 and less than 1.20
C:Dm value is less than 1.10
[(E) tone (color and taste) evaluation test]
The 100%Duty portion of visual each test film, evaluates tone with the metewand of 5 following grades.To the results are shown in following table 3.
AA: distinct and there is the redness of concentration sense
A: distinct redness
B: the redness with concentration sense
C: dull redness
D: reddish orange
Table 3
Known to the result from above-mentioned, confirm that ink composite of the present invention demonstrates excellent form and aspect and tone as red ink, and there is extremely excellent color emissivity.
[embodiment 9]: the modulation (3) of red painted dispersion liquid
The segmented copolymer that the synthesis example 3 that No. 2013/115071st, adjustment International Publication is recorded, is dissolved in 30 parts of 2-butanone 6 parts of obtained macromolecule dispersing agents, is allocated as uniform solution.Make the dissolution of sodium hydroxide of the 0.44 part solution after the ion exchanged water of 41 parts to adding in this liquid, stir 1 hour, modulated emulsified soln.Now, there is no separating out of crystallization.Add wherein C.I.Pigment Red48:1(35.6 part) and C.I.Pigment Orange16(1.9 part) 20 parts, in sand mill, disperse.Be dispersed under the condition of 1500rpm and carry out 15 hours., drip ion exchanged water 100 part, filter and remove dispersion pearl, then, after vaporizer underpressure distillation 2-butanone and water, obtained the red dispersion liquid of pigment solid substance 12.41% thereafter.During solid substance in the aqueous solution is measured, use A & D company of Co., Ltd. to produce MS-70, obtain by dry weight method.PH is now 8.6, and the median size of pigment is 92nm.Using obtained painted dispersion liquid as dispersion liquid 4.
[embodiment 10]: the modulation of ink
After the painted dispersion liquid obtaining is mixed with each composition of recording in following table 4, with the film filter filtration mishmash of 3 μ m, obtained the red ink composition of the present invention that evaluation test is used in embodiment 9.
In following table 4, the numerical value of each composition refers to umber.
Table 4
| Composition | Embodiment 10 |
| Dispersion liquid 4 | 40.3 |
| Glycerine | 20 |
| Glycol ether | 5 |
| サ mono-Off ィ mono-Le TM465 | 0.2 |
| プロキセルGXL(s) | 0.1 |
| Ion exchanged water | Residue umber |
| Add up to | 100 |
Use by the ink composite of the above-mentioned embodiment obtaining like that 10, by similarly carrying out " (A) ink-vapor recording ", " (C) form and aspect evaluation test ", " (D) color emissivity evaluation test " and " (E) tone evaluation test " with above-mentioned, evaluate its performance.As a result, above-mentioned 3 kinds of evaluations of having confirmed the ink composite of embodiment 10 are all " A ".
Industrial usability
Painted dispersion liquid of the present invention, the ink composite that contains this painted dispersion liquid demonstrate excellent form and aspect and tone, and have extremely excellent color emissivity, thereby the red ink of using as ink-vapor recording is exceedingly useful.
Claims (14)
1. a painted dispersion liquid, contains the tinting material being represented by following formula (1):
In formula (1), R
1and R
2represent independently respectively hydrogen atom, chlorine atom or methyl, M represents to be selected from the atom in Ba, Ca, Sr and Mn.
2. painted dispersion liquid according to claim 1, is characterized in that, in above-mentioned formula (1), and R
1for methyl, R
2for chlorine atom.
3. painted dispersion liquid according to claim 1, is characterized in that, in above-mentioned formula (1), M is Ba.
4. painted dispersion liquid according to claim 1, is characterized in that, in above-mentioned formula (1), and R
1for methyl, R
2for chlorine atom, M is Ba.
5. painted dispersion liquid according to claim 1, is characterized in that, also contains carbon black as tinting material.
6. painted dispersion liquid according to claim 1, is characterized in that, also contains C.I. pigment orange as tinting material.
7. painted dispersion liquid according to claim 6, is characterized in that, C.I. pigment orange is at least one pigment selecting in the group that free C.I. pigment orange 16, C.I. pigment orange 36, C.I. pigment orange 43 and C.I. pigment orange 64 form.
8. an ink composite, it contains painted dispersion liquid and organic solvent described in any one in claim 1 to 7.
9. ink composite according to claim 8, is characterized in that, described organic solvent is at least one polyvalent alcohol.
10. ink composite according to claim 8, is characterized in that, the median size of the tinting material in described ink composite is below the above 200nm of 50nm.
11. 1 kinds of ink jet recording methods, it carries out record by making the drop of the ink composite described in any one in claim 8 to 10 spray according to recording signal and being attached to be recorded on material.
12. ink jet recording methods according to claim 11, is characterized in that, described in to be recorded material be information transmission thin slice.
13. 1 kinds of colouring agenies, it is painted by ink composite claimed in claim 8.
14. 1 kinds of ink-jet printers, it is filled with the container that comprises ink composite claimed in claim 8.
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| JP2013-072060 | 2013-03-29 | ||
| JP2013072060 | 2013-03-29 | ||
| JP2013167514A JP2014208744A (en) | 2013-03-29 | 2013-08-12 | Colored dispersion, ink composition, inkjet recording method, and colored matter |
| JP2013-167514 | 2013-08-12 |
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| CN104073025A true CN104073025A (en) | 2014-10-01 |
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