CN1613924A - Digital painting printing ink containing pigment and dye, preparation thereof - Google Patents
Digital painting printing ink containing pigment and dye, preparation thereof Download PDFInfo
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- CN1613924A CN1613924A CN 200410066363 CN200410066363A CN1613924A CN 1613924 A CN1613924 A CN 1613924A CN 200410066363 CN200410066363 CN 200410066363 CN 200410066363 A CN200410066363 A CN 200410066363A CN 1613924 A CN1613924 A CN 1613924A
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Abstract
A numerical-code spraying ink containing pigment and dyestuff is prepared by adding in the pigment and dyestuff, because the price of solvent dyestuff is cheaper than the organic dyestuff. So it will decrease the cost. Colors of the ink include bluish, fuchsin, yellow and black. The process is so simple enough to industrial production.
Description
Technical field
The present invention relates to a kind of solvent type ink, be specifically related to a kind of printing ink that is applicable to large-scale digit inkjet printer.
Background technology
Large-scale in recent years air brushing machine is along with swift and violent development has appearred in the development of computer industry, and the air brushing machine can be divided into heat foamable formula and piezo crystal according to the principle of work of shower nozzle.Heat foamable formula shower nozzle is mainly used on the ink jet unit of companies such as Hewlett-Packard (Hewlett Packard Corporation), Mimaki, and such shower nozzle mainly uses water color ink, and tinting material all is dyestuff usually; The piezo crystal shower nozzle is mainly used on the air brushing machine of companies such as Witter (Vutek), Ya Selan, and such shower nozzle mainly uses solvent type ink, and tinting material is a pigment dyestuff.The shower nozzle of different operating principle differs to the performance requriements of printing ink, and the ink viscosity that uses as heat foamable formula shower nozzle is at 3-5 centipoise (25 ℃), and the ink viscosity that the piezo crystal shower nozzle uses is then at 5-20 centipoise (25 ℃).
Tinting material in the water color ink (dyestuff) is dissolved in the ink composite, but contains the water color ink of soluble dye, has problems such as water dungeon degree, light fastness difference.Also there is a very big weak point in water color ink for industrial application, that is exactly dry problem, because the low rate of volatilization of water causes the drying process of water color ink to take long to, even use well heater still to need long time of drying.The operable ground of water color ink also has certain limitation simultaneously: must be the class that water can adsorb, the ground that can not adsorb for water then can't be suitable for;
Different with water color ink is solvent type ink, because the easy volatile of organic solvent, the drying of solvent type ink is very fast, and the ground that can use is also very wide.The tinting material of solvent type ink (pigment) has been compared many premium propertiess with the dyestuff in the water color ink, such as water dungeon degree, light fastness, thermostability, oxidative stability etc.But because pigment can not be dissolved in ink composite, but be present in the printing ink with little particle, this certainly will just produce a new problem: be the printing ink of pigment dyestuff for tinting material, how to guarantee the stability of printing ink, the homogeneity of guaranteed performance causes shower nozzle to stop up with the gathering that prevents granules of pigments.
On February 29th, 2000 Japanese Toyo Ink public affairs (Toyo Ink Manufacturing Co., people such as Uraki Ltd) disclose in US6031024 pigment dyestuff stable dispersion the method in ink mixture of median size at 50-300nm, and dispersion process has been carried out detailed description.In addition, also has US6406528 people such as () Macholdt of Clariant company to what the dispersion of pigment dyestuff and the stability in ink mixture were studied, US6409816 (people such as Weber of Clariant company), US6398858 (Cabot company), US6352340 (Eastman Kodak company) or the like.Another scheme that solves the colo(u)rant dispersion problem is to adopt the pre-dispersed thing of pigment dyestuff, and this is at US6113679 people such as () Adkins of 3M company, all is described among the US 6623702 people such as () Day of Sericol company.But because the complex manufacturing of the pre-dispersed thing of pigment, price is very high.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of digital painting printing ink that contains pigment and dyestuff and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
Technical conceive of the present invention is such:
In order to solve the problem of present existence, the present invention has added pre-dispersed thing of pigment and solvent dye simultaneously in digital painting printing ink.Because the price of solvent dye is generally low than the pre-dispersed thing of pigment dyestuff, its adding has significantly reduced the content of the pre-dispersed thing of pigment dyestuff, thereby has played the effect that reduces cost.
The component and the weight content of the digital painting printing ink that contains pigment and dyestuff of the present invention are as follows:
Organic solvent 70-90%
Pigment 1-10%
Dyestuff 1-10%
Cross-linked resin 1-10%
UV light absorber 0.1-2%
Tensio-active agent 0.1-2%.
Pigment of the present invention is the pre-dispersed thing of pigment dyestuff, promptly containing particle diameter is the vinylchlorid vinyl acetate resin of the pigment dyestuff of 0.05-0.6 micron, the Permajet series pigment dyestuff of producing as Clariant company (Clariant) (comprises Yellow H4G, Yellow HG, Yellow HR, Red E5B, Magenta E, Blue B2G, Black R etc.), the Microlith series of vapour Bagong department (Ciba) (comprises MICROLITH YELLOW 4G-K, YELLOW 3R-K, MAGENTA 5B-K, BLUE4G-K, BLACK C-K etc.) and the SKYSPERSE series of the high company in sky, Zhuhai, the yellow AAA-NC (Yellow 12) of preferred pigment preparations, the yellow 5GX-NC (Yellow 74) of pigment preparations, the yellow HR-NC (Yellow 83) of pigment preparations, the red 4B-NC of pigment preparations (Red 57:1), the blue BF-NC (Blue 15:3) of pigment preparations, the blue BFNF-NC (Blue 15:4) of pigment preparations, pigment preparations is deceived a kind of among B-NC (Black 7) or the green G-NC of pigment preparations (Green 7) etc., and their common feature is the pigment dyestuff of particle diameter at the 0.05-0.6 micron to be dispersed in the vinylchlorid vinyl acetate resin.
The dyestuff that the present invention adopts is a solvent dye, be selected from the Yellow 156 of BASF AG, Yellow157, Red 335, Black x-51, Orange 251, Orange 272, Blue 807, the solvent yellow 801 of the high company in sky, Zhuhai, solvent yellow 802, solvent red 8 05, solvent red 8 06, solvent red 8 08, solvent black 810, solvent black 811, solvent orange 815, solvent orange 816, solvent orchid 820, solvent brown 830, the MH. Huang 20 of bright brightness chemical industry (Wuxi) company limited, MH. yellow 57, MH. yellow KK, MH. the orange 10, MH. the orange 09, MH. red 04, MH. red 35Y, MH. red 06R, MH. red 95, MH. red 10, MH. red 16, MH. the palm fibre 02, MH. the palm fibre 05, MH. blue 03, MH. blue 06, MH. green 20, MH. green 575, MH. deceive 04, MH. deceive 27, MH. deceive 56, the metallized dye YELLOW J12 (Solvent Yellow21) of Guangzhou Jing Ze chemical industry company limited, RED J36 (SolventRed122), YELLOW J45 (Solvent Orange45), RED J31 (Solvent Red91), YELLOW J57 (Solvent Yellow82), RED J55 (Solvent Red119), GREEN J62 (Mixture), ORANGE J20 (Solvent Orange54), RED J95 (Solvent Red122), BLACK J92 (Solvent Black27), ORANGE J29 (Solvent Orange62), RED J42 (Solvent Red218), BLACK J93 (Solvent Black27), BLUE J76 (SolventBlue70), RED J34 (Solvent Red8), BROWN J52 (Mixture), BLACK J94 (Solvent Black34), RED J35 (Solvent Red122), BROWN J55 (Mixture), BLACK J56 (Solvent Black28), Guangzhou unit becomes the metal complex solvent dye solvent yellow GR of pigment chemical industry company limited, solvent yellow 2 RN, solvent yellow R, solvent orange O, solvent orange R, solvent orange 5A, solvent orange G, solvent red 3304, solvent red G, solvent red RL, solvent red BL, solvent red FB, solvent red B, purple 840, solvent blue EL, solvent green 520, solvent brown 2RL, solvent black RE or solvent black RB.
Solvent dye is a very fast kind of development in the dyestuff, and it can be dissolved in the organic solvent, does not have organic dispersing of pigments problem, has good outdoor weatherability simultaneously.The people such as Zou of VideojetTechnologies company describe in detail using the digital marking ink of solvent dye (SolventBlack 29) making in US6726756, are characterized in that the solvent that adopts is butanone (MEK) and 1-methoxyl group 2-propyl alcohol (1-Methoxy-2-propanol).
Said cross-linked resin is act as solvents volatilization back and the pigment effect of formation ink lay and adjusting ink viscosity on ground together in printing ink, and the outdoor weatherability of printing ink also has confidential relation with cross-linked resin.Cross-linked resin of the present invention is acrylic resin or vinylchlorid vinyl acetate resin etc., the preferred acrylic resin that adopts is selected from A11, the B66 trade mark of ROHM AND HAAS (Room and Hass), the vinylchlorid vinyl acetate resin that adopts is selected from the VYHH of DOW Chemical, VYNS, the trades mark such as VYHD and VYGH.The content of cross-linked resin in printing ink is according to the difference of pigment and different, such as usually in magenta content minimum, higher in yellow and cyan.
Said organic solvent comprises pimelinketone, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate, a kind of or its mixture in 2-Butoxyethyl acetate, Diethylene Glycol monobutyl ether acetate, methylethylketone or the N-Methyl pyrrolidone etc., the proportioning logarithmic code painting printing ink Effect on Performance of relevant different evaporation rate organic solvents, the people such as Day of Sericol company have carried out sets forth in detail in US6663702, the surface tension of the solvent that adopts is at 25-35 dynes per centimeter (25 ℃).
The outdoor weatherability of painting printing ink is a very important index, it mainly is to cause because of the UV-irradiation in the sunlight that the picture of being drawn by printing ink fades, in order to improve outdoor weatherability, the present invention has added ultraviolet absorbers in printing ink, the ultraviolet absorbers that adopts comprises the ultraviolet absorbers Tinuvin900 (2-(2`-hydroxy phenyl) benzotriazole) of vapour Bagong department, UV-9 (2-hydroxyl-4-methoxy benzophenone) that Shenyang Fine Chemical Works and Yixing City foundation chemical industry company limited produce and UV-531 (Octabenzone) etc.
In printing ink, tensio-active agent plays the surface tension of regulating printing ink, and the contact angle when change printing ink contacts with ground strengthens the effects such as stability in storage of printing ink.Can the surface tension size of printing ink influence printing ink on the one hand spray from shower nozzle very unobstructedly, and whether China ink on ground occur drop down on the one hand if influencing printing ink again in addition.Because tinting material of the present invention comprises pigment dyestuff and solvent dye two classes, the tensio-active agent of interpolation not only will be regulated the surface tension of printing ink, will solve the stability in storage of printing ink simultaneously, and the latter is the key of option table surface-active agent especially.The tensio-active agent that is adopted among the present invention is a kind of tensio-active agent that contains the alkyne diol structure shown in the formula (1), and structural formula is as follows:
The adding of this tensio-active agent has obviously improved the stability, fluency of printing ink and to the wettability of ground.Can adopt the tensio-active agent of the SURFYNOL trade mark of U.S. gas products company (AIR PRODUCT) production.
As required, as at low temperature (being lower than 5 ℃) with occur should adding additives such as softening agent, defoamer and thermo-stabilizer simultaneously under the too much situation of foam in printing ink, the weight content of interpolation is 0.1-2%.Wherein, the softening agent that can select comprise dioctyl phthalate (DOP) (DOA) that German BASF AG produces and Shanghai China overflow the production of additives for plastics cooperative venture to dioctyl phthalate (DOP) (DOTP) etc.; the defoamer that can select comprises the AF9020 defoamer of U.S. GE company production and 1026 defoamers of Changfeng Chemical Plant, Shanghai's production etc., and thermo-stabilizer comprises the organo-tin het stabilizer that Changfeng Chemical Plant, Shanghai produces etc.
The preparation method who contains the digital painting printing ink of pigment and dyestuff of the present invention comprises the steps:
The at first pigment of compounding high concentration and dye paste, with said pigment, dyestuff and organic solvent adopt the method for this area routine to mix, in mill base, add cross-linked resin then, UV light absorber and tensio-active agent, can further add softening agent as required, defoamer and thermo-stabilizer, stirred 30-60 minute, the ink viscosity that obtains is 5-15 centipoise (25 ℃), surface tension is at 25-35 dynes per centimeter (25 ℃), flash-point is more than 62 ℃, proportion is 0.90-1.00 under the room temperature, use millipore filtration at last printing ink is filtered, filtering accuracy is 0.1～1 micron, is preferably 0.1～0.45 micron.
Painting printing ink of the present invention comprises green grass or young crops (C), product (M), yellow (Y), black (K) and light greenish blue (LC), six kinds of colors of light product (LM), the shower nozzle that is suitable for comprises the SPECTRA256 that U.S. SPECTRA and Britain XAAR company produce, the XAAR128 shower nozzle, the air brushing machine that is suitable for comprises U.S. VUTEK5300 air brushing machine, Shanghai Ya Selan air brushing machine, Korea S DGI air brushing machine etc.
Printing ink of the present invention, characteristics such as production technique is simple, is convenient to suitability for industrialized production, and is cheap, the colour fastness height, and outdoor weatherability is good, and stable storing is strong, and ink-jet is unobstructed are suitable for applying.
Embodiment
Embodiment 1
The proportioning of cyan ink process for preparation and each component
At first the Microlith4G-K pigment preparation matter of vapour Bagong department and 2-Butoxyethyl acetate are mixed according to 20% and 80% composition by weight and high-speed stirring 30 minutes, make high density mill base A; Again Blue 807 solvent dyes of BASF AG and 2-Butoxyethyl acetate are mixed according to 20% and 80% composition by weight and high-speed stirring 60 minutes, make high density mill base B.Prepare burden according to the proportioning of table 1 at last:
Table 1. cyan (C) printing ink each component proportioning
| Component | Weight % |
| Mill base A | ?10％ |
| Mill base B | ?5％ |
| ROHM AND HAAS A11 acrylic resin | ?3％ |
| Pimelinketone | ?20％ |
| Dipropylene glycol methyl ether acetate | ?30％ |
| 2-Butoxyethyl acetate | ?28％ |
| Tensio-active agent SURFYNO104 | ?0.5％ |
| Ultraviolet absorbers UV-9 | ?0.5％ |
| The plasticizer phthalic acid dioctyl ester | ?2％ |
| Defoamer AF9020 | ?0.5％ |
| Organo-tin het stabilizer | ?0.5％ |
And, find relatively that through last machine test and with the cyan ink that American I NKWARE produces printing ink of the present invention has beautiful in colour, advantages such as spray picture smoothness with the 30 minutes after-filtration of printing ink high-speed stirring that are mixed with.According to actual detected, printing ink still can keep stable after storing 6 months under 10-20 ℃, and the wetting situation of printing ink on ground makes moderate progress simultaneously, particularly improved the ink-jet effect under low temperature (10 ℃).
Embodiment 2～4
Example 2-example 4 is proportionings of magenta M, yellow Y, three kinds of color inks of black K
According to preparation steps preparation M, the Y of example 1 cyan, the printing ink of K color, proportioning sees Table 2.
Table 2. magenta, yellow and black ink each component proportioning
| Example 2 magenta inks (M) | Example 3 Yellow inks (Y) | Example 4 black inks (K) | |
| Mill base A | 20 | ?10 | ?10 |
| Mill base B | 5 | ?5 | ?8 |
| ROHM AND HAAS A11 acrylic resin | 1 | ?5 | ?3 |
| Pimelinketone | 20 | ?20 | ?20 |
| Dipropylene glycol methyl ether acetate | 30 | ?30 | ?30 |
| 2-Butoxyethyl acetate | 22 | ?28 | ?27 |
| Tensio-active agent SURFYNO104 | 0.5 | ?0.5 | ?0.5 |
| Ultraviolet absorbers UV-9 | 0.5 | ?0.5 | ?0.5 |
| The softening agent dioctyl terephthalate | 0.6 | ?0.6 | ?0.6 |
| Defoamer 1026 | 0.2 | ?0.2 | ?0.2 |
| Organo-tin het stabilizer | 0.2 | ?0.2 | ?0.2 |
Wherein: a. magenta mill base A is that Microlith 5B-K of vapour Bagong department and 2-Butoxyethyl acetate were prepared according to 20: 80; Mill base B is that SOLVENT RED 808 of BASF AG and 2-Butoxyethyl acetate were prepared according to 20: 80.
B. yellow mill base A is that yellow HR-NC of the high company in sky, Zhuhai pigment preparations and 2-Butoxyethyl acetate were prepared according to 20: 80; Mill base B is that the YELLOW J12 and the 2-Butoxyethyl acetate of Guangzhou Jing Ze chemical industry company limited prepared according to 20: 80.
C. black color paste A is that black B-NC of the high company in sky, Zhuhai pigment preparations and 2-Butoxyethyl acetate were prepared according to 20: 80; Mill base B is that the BLACK J93 and the 2-Butoxyethyl acetate of Guangzhou Jing Ze chemical industry company limited prepared according to 20: 80.
Embodiment 5-6
Example 5-example 6 is proportionings of nattierblue and light magenta ink
Prepared nattierblue and light magenta ink according to the process for preparation of example 1 cyan, wherein used mill base A of nattierblue and mill base B are with the used mill base of cyan in the example 1, and used mill base A of light magenta and mill base B are with the used mill base of magenta in the example 2, and proportioning sees Table 3.
Each proportioning of table 3. nattierblue and light magenta ink
| Example 5 pale cyan ink | Example 6 light product color inks | |
| Mill base A | 5％ | 10％ |
| Mill base B | 2％ | 4％ |
| ROHM AND HAAS A11 acrylic resin | 6％ | 3％ |
| Pimelinketone | 15％ | 15％ |
| Dipropylene glycol methyl ether acetate | 20％ | 20％ |
| 2-Butoxyethyl acetate | 50.5％ | 46.5％ |
| Tensio-active agent SURFYNO104 | 0.15％ | 0.15％ |
| Ultraviolet absorbers UV-9 | 0.8％ | 0.8％ |
| The plasticizer phthalic acid dioctyl ester | 0.15％ | 0.15％ |
| Defoamer 1026 | 0.2％ | 0.2％ |
| Organo-tin het stabilizer | 0.2％ | 0.2％ |
Embodiment 7
The index of the Witter former factory of the VUTEK5300 air brushing machine Yellow ink of each color ink of example 1～4 CMYK and excellent property (being produced by American I NKWARE company) sees the following form after tested.
Table 4.CMYK printing ink and INKWARE Yellow ink test index
| C | ?M | ?Y | ?K | The INKWARE Yellow ink | |
| Viscosity (25 ℃ of centipoises) | 9.9 | ?9.8 | ?10 | ?9.6 | ?10 |
| Surface tension (25 ℃ of dynes per centimeter) | 27.5 | ?28 | ?28 | ?27.5 | ?27 |
| Flash-point (℃) | 62.5 | ?62.5 | ?63 | ?62.8 | ?62.6 |
| Proportion | 0.97 | ?0.96 | ?0.97 | ?0.97 | ?0.97 |
The conclusion that CMYK four color inks of example 1-example 4 preparations draw after test on the VUTEK5300 air brushing machine is: ink-jet smoothness, picture lifelike image.Characteristics such as the digital painting printing ink that has pigment and dyestuff concurrently of the present invention has easily manufactured, with low cost, the colour fastness height, and outdoor weatherability is good, and stable storing is strong, and ink-jet is unobstructed are suitable for applying.
Claims (8)
1. a digital painting printing ink that contains pigment and dyestuff is characterized in that, component and weight content comprise:
Organic solvent 70-90%
Pigment 1-10%
Dyestuff 1-10%
Cross-linked resin 1-10%
UV light absorber 0.1-2%
Tensio-active agent 0.1-2%;
Said pigment is to have to contain the vinylchlorid vinyl acetate resin that particle diameter is the pigment dyestuff of 0.05-0.6 micron;
Said solvent dye is the dyestuff that can be dissolved in the organic solvent;
Said cross-linked resin is acrylic resin or vinylchlorid vinyl acetate resin;
Said organic solvent comprises pimelinketone, 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate, a kind of or its mixture in 2-Butoxyethyl acetate, Diethylene Glycol monobutyl ether acetate, methylethylketone or the N-Methyl pyrrolidone.
2. the digital painting printing ink that contains pigment and dyestuff according to claim 1, it is characterized in that, said pigment is selected from Permajet Yellow H4G, Permajet Yellow HG, PermajetYellow HR, Permajet Red E5B, Permajet Magenta E, Permajet Blue B2G, Permajet Black R and Microlith YELLOW 4G-K, Microlith YELLOW 3R-K, Microlith MAGENTA 5B-K, Microlith BLUE 4G-K, a kind of in the pigment preparations such as Microlith BLACK C-K.
3. the digital painting printing ink that contains pigment and dyestuff according to claim 1, it is characterized in that, said solvent dye is selected from Yellow 156, Yellow 157, Red 335, Black x-51, Orange 251, Orange 272, Blue 807, solvent yellow 801, solvent yellow 802, solvent red 8 05, solvent red 8 06, solvent red 8 08, solvent black 810, solvent black 811, solvent orange 815, solvent orange 816, solvent orchid 820, solvent brown 830, MH. yellow 20, MH. yellow 57, MH. yellow KK, MH. the orange 10, MH. the orange 09, MH. red 04, MH. red 35Y, MH. red 06R, MH. red 95, MH. red 10, MH. red 16, MH. the palm fibre 02, MH. the palm fibre 05, MH. blue 03, MH. blue 06, MH. green 20, MH. green 575, MH. deceive 04, MH. deceive 27, MH. deceive 56, YELLOW J12, RED J36, YELLOW J45, RED J31, YELLOW J57, RED J55, GREEN J62, ORANGEJ20, RED J95, BLACK J92, ORANGE J29, RED J42, BLUE J76, RED J34, BROWN J52, BLACK J94, RED J35, BROWN J55, BLACK J56, the yellow GR of dye solvent, solvent yellow 2 RN, solvent yellow R, solvent orange O, solvent orange R, solvent orange 5A, solvent orange G, solvent red 3304, solvent red G, solvent red RL, solvent red BL, solvent red FB, solvent red B, purple 840, solvent blue EL, solvent green 520, solvent brown 2RL, a kind of among solvent black RE or the solvent black RB.
4. the digital painting printing ink that contains pigment and dyestuff according to claim 1 is characterized in that, said tensio-active agent is a kind of tensio-active agent that contains the alkyne diol structure shown in the formula (1), and structural formula is as follows:
Surfactant structure formula (1)
5. the digital painting printing ink that contains pigment and dyestuff according to claim 1 is characterized in that, ultraviolet absorbers is selected from 2-(2`-hydroxy phenyl) benzotriazole, 2-hydroxyl-4-methoxy benzophenone or Octabenzone.
6. the digital painting printing ink that contains pigment and dyestuff according to claim 1 is characterized in that, also contains softening agent, defoamer, flow agent and thermo-stabilizer in the printing ink, and the weight content of its interpolation is 0.1-2%.
7. each described method that contains the digital painting printing ink of pigment and dyestuff of preparation claim 1～6 is characterized in that, comprises the steps:
The at first pigment of compounding high concentration and dye paste, adopt the method for this area routine to mix said pigment, dyestuff and organic solvent, in mill base, add cross-linked resin, UV light absorber and tensio-active agent then, with millipore filtration printing ink is filtered at last, promptly obtain said printing ink.
8. method according to claim 7 is characterized in that, adds softening agent, defoamer and thermo-stabilizer in mill base.
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| CN103555043B (en) * | 2013-10-15 | 2015-07-08 | 绍兴虎彩激光材料科技有限公司 | Pigment formulation process for golden product |
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