CN105504995A - Foaming ink for ink-jet printing and preparation method of foaming ink - Google Patents

Foaming ink for ink-jet printing and preparation method of foaming ink Download PDF

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Publication number
CN105504995A
CN105504995A CN201610068369.5A CN201610068369A CN105504995A CN 105504995 A CN105504995 A CN 105504995A CN 201610068369 A CN201610068369 A CN 201610068369A CN 105504995 A CN105504995 A CN 105504995A
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CN
China
Prior art keywords
ink
agent
foam
printing
acid
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Granted
Application number
CN201610068369.5A
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Chinese (zh)
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CN105504995B (en
Inventor
鄢腊梅
李黎
何宏
胡更生
陈梅
彭永昭
彭秋燕
周玲烽
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Tianjin bodrun Digital Printing Technology Co., Ltd
Zhu Bopeng
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Hangzhou Electronic Science and Technology University
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Priority to CN201610068369.5A priority Critical patent/CN105504995B/en
Priority to CN201810030714.5A priority patent/CN108084797B/en
Publication of CN105504995A publication Critical patent/CN105504995A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Abstract

The invention discloses foaming ink for ink-jet printing and a preparation method of the foaming ink. The foaming ink is prepared from a connecting material, a blowing agent, a photoinitiator, a foam stabilizing agent, a solvent, an ink stabilizing agent for yellowing resistance, a PH buffer solution, a dispersing agent, an emulsifying agent, a surfactant, a chelate agent, a preservative and a colorant. Through the adoption of the technical scheme, the performance of the prepared foaming ink completely meets the requirement of ink-jet printing, and besides, foaming at high temperature is not needed; the foaming ink can initiate a photoacid generator or sulfonium salt adopted in the foaming ink disclosed by the invention to generate protonic acid through bond homolysis and heterolysis under the action of UV-LED light, and then the generated protonic acid is subjected to chemical reaction with sodium carbonate to generate and give off CO2, therefore the purpose of foaming is achieved, and 3D micropores are formed in the ink.

Description

Foam ink of a kind of spray ink Printing and preparation method thereof
Technical field
The invention belongs to ink material technical field, especially relate to foam ink of a kind of spray ink Printing and preparation method thereof.
Background technology
Foaming printing technology has a wide range of applications, and foam ink is applied to book cover and binding and layout material is not only bright in colour, and picture and text are given prominence to; For books printed in braille printing, blind person according to the idea size of printing projection, some distance, character-spacing, line-spacing, can read with finger touch; Map printing and imitative carved gilded decoration printing etc. can also be applied to simultaneously.
The foam ink of prior art has two kinds: one is microballoon foam ink, and another kind is bottom of trench foam ink.Microballoon foam ink is the characteristic property utilizing microballoon, and be imprinted on the stock such as paper, textiles by method for printing screen, 120 ~ 140 DEG C are heated to through cryodrying, drying tunnel, microballoon after a few second in ink just can expand and form countless Minute pores, thus makes picture and text present stereoeffect.Whipping agent, mainly based on polyvinyl chloride (PVC) RESINS, is dissolved in liquid polymkeric substance by bottom of trench foam ink, and after ink is heated, whipping agent gasifies, and makes ink layer form countless small pore, and picture and text foaming is protruding.Above-mentioned two kinds of foam inks all adopt the method for silk screen printing, the bottleneck of silk screen printing is that its ink film thickness can have influence on the depth of picture and text and the reducing degree of look cabinet and colour cast size and silk screen printing can not can realize total digitalization printing as ink jet printing, can not the printed images of precise Printing customer requirement.The books simultaneously adopting existing silk screen printing foam ink to print and artwork etc., after a period of time can xanthochromia, and foam wherein can diminish or disappear.
Ink jet printing uses the ink of low-viscosity to spray from the nozzle of printhead, realizes image reproduction with certain speed by fine droplet jet to stock.But above-mentioned two kinds of foam ink formulas cannot directly apply to spray ink Printing, and spray ink Printing has special requirement to ink performance:
(1) ink for ink-jet print will have a low viscosity, and the viscosity of ink system can increase along with pigment content and increase gradually, so under the prerequisite meeting ink colors performance requirement, require that the content of pigment should be low as far as possible, its k value of ink for ink-jet print is generally (10 ~ 20) mPa.s;
(2) ink surface tension is that (30 ~ 50) mN/m is with the flowing property ensured and droplet morphology;
(3) pH value of ink must be suitable with the pH value of tinting material, and pH value is generally 7 ~ 9, and the pH value of ink is too low, and ink is that acidity can corrode print cartridge; Too high pH value can improve specific conductivity, reduces the work-ing life of print cartridge.
(4) particle size is less than 0.2 μm, and conductivity values < 25 μ s/cm is to avoid forming crystallization at nozzle.
Market in the urgent need to studying foam ink of a kind of new ink jet printing and preparation method thereof, fully to meet the performance requriements of ink jet inks, can realize total digitalization printing and the printing ink foam of printed matter can keep permanent.Therefore, for the above-mentioned defect existed in currently available technology, be necessary to study in fact, to provide a kind of scheme, solve the defect existed in prior art.
Summary of the invention
An object of the present invention is to be for the deficiencies in the prior art, provide a kind of prepare simple and excellent property can direct foam ink of printing of spray ink Printing and preparation method thereof.
For achieving the above object, the present invention adopts following technical scheme:
A kind of foam ink of spray ink Printing, for blend, this blend comprises binder, whipping agent, light draw agent, suds-stabilizing agent, solvent, the agent of anti-yellowing change ink stability, PH damping fluid, dispersion agent, emulsifying agent, tensio-active agent, sequestrant, sanitas and tinting material; The mass percentage of above-mentioned each component in the foam ink of spray ink Printing is as follows:
Binder: 15 ~ 55%;
Whipping agent: 2 ~ 5%;
Light draws agent: 10 ~ 20%;
Suds-stabilizing agent: 1 ~ 3%;
Solvent: 20 ~ 25%;
Anti-yellowing change ink stability agent: 1 ~ 4 ﹪;
PH damping fluid: 1 ~ 5 ﹪;
Dispersion agent: 2 ~ 5%;
Emulsifying agent: 1 ~ 4%;
Tensio-active agent: 1 ~ 3%;
Sequestrant: 0.5 ~ 2%;
Sanitas: 0.1 ~ 0.5%;
Tinting material: 5 ~ 9%;
Wherein, described binder is one or more in hexamethylene diisocyanate, polyvinyl acetate, bisphenol A type epoxy resin;
Described whipping agent is sodium carbonate;
It is one in photo-acid agent, sulfosalt or two kinds that described light draws agent;
Described suds-stabilizing agent is dimethyl dodecyl amine oxide.
For achieving the above object, present invention also offers a kind of method preparing the foam ink of spray ink Printing as described above, the method comprises the following steps:
Step (1), ink mix
Each component following for mass percentage is mixed and uses FS-S type twin shaft dispersator within 45 ~ 60 minutes, to make each component mix formation ink mixture:
Binder: 15 ~ 55%;
Whipping agent: 2 ~ 5%;
Light draws agent: 10 ~ 20%;
Suds-stabilizing agent: 1 ~ 3%;
Solvent: 20 ~ 25%;
Anti-yellowing change ink stability agent: 1 ~ 4 ﹪;
PH damping fluid: 1 ~ 5 ﹪;
Dispersion agent: 2 ~ 5%;
Emulsifying agent: 1 ~ 4%;
Tensio-active agent: 1 ~ 3%;
Sequestrant: 0.5 ~ 2%;
Sanitas: 0.1 ~ 0.5%;
Tinting material: 5 ~ 9%;
Wherein, described binder is one or more in hexamethylene diisocyanate, polyvinyl acetate, bisphenol A type epoxy resin;
Described whipping agent is sodium carbonate;
It is one in photo-acid agent, sulfosalt or two kinds that described light draws agent;
Described suds-stabilizing agent is dimethyl dodecyl amine oxide;
Step (2), ink jet-printing
By above-mentioned ink mixture by printing of inkjet printer on high temperature resistant PET paper; The DimatixDMP2831 of FUJIFILM company of the U.S. selected by described ink-jet printer;
Step (3), ink foam
Sending complete continuous ultraviolet light belt by UV-LED curing light source makes the ink pattern on PET paper foam, in foaming process, by ultraviolet excitation light trigger, make photo-acid agent or/and sulfosalt produces protonic acid by key homolysis and heterolytic fission, described protonic acid and sodium carbonate carry out the CO that chemical reaction discharges 2multiple 3D micropore is produced in ink;
Step (4), ink solidification
In above-mentioned ink foaming process, make PET paper substrates temperature maintain 45 ~ 55 DEG C, then cooling at normal temperatures solidify to form foam ink in 24 hours with dry.
Preferably, it is characterized in that, described solvent is one or more in 2-Pyrrolidone, glycol ether, hexanaphthene, sebacic acid, methyl ethyl ketone, methyl iso-butyl ketone (MIBK).
Preferably, it is characterized in that, described PH damping fluid is one or more in lithium hydroxide, potassium hydroxide, sodium hydroxide, salt of wormwood.
Preferably, it is characterized in that, the agent of described anti-yellowing change ink stability be tetramethyl piperidine oxide compound, benzophenone, w-bromoacetophenone, one or more in phenylbenzene sulphur.
Preferably, described dispersion agent is German Lu Borun hyper-dispersant S-13940 and/or solsperse5000 hyper-dispersant;
Described sanitas is phenol and/or arsenous acid anhydride;
Described emulsifying agent is polyoxyethylene glycol cetyl ether and/or polyethylene glycol stearate;
Described tensio-active agent is acetylenic diols tensio-active agent;
Described sequestrant is one or more in D401 aminophosphonic acid chelate resin, D403 phosphoramidic acid type resin, C900 Amino phosphonic acid resin, C800 aminocarboxylic acid resin;
Described tinting material is in pigment dyestuff and/or mineral dye.
Preferably, in step (2), FUJIFILM company of adjustment U.S. model is the parameter of DimatixDMP2831 ink-jet printer: the Dimatix box arranging 16 nozzles makes a nozzle send a stream of liquid droplets; Print speed is 0.5 ~ 1.1m/s; Set single ink drop volumes and be not more than 50um, the temperature selecting print cartridge is 25 ~ 30 DEG C.
Preferably, in step (3), adopt Shenzhen Hai Sien Science and Technology Ltd. UV-LED light source solidification system.
Preferably, in ink foaming process, connect multiple UV-LED irradiation head and each UV-LED irradiation head sends the UV-LED light of different wave length simultaneously.
Preferably, the wavelength of described UV-LED irradiation head is any one in 365nm, 385nm or 395nm.
The invention has the beneficial effects as follows:
1, because the present invention adopts different formulas, under the effect of UV-LED light, photo-acid agent or sulfosalt in the present invention can be caused and produce protonic acid by key homolysis and heterolytic fission, then generate with sodium carbonate generation chemical reaction the CO discharged 2namely foam, in ink, produce 3D micropore.
2, in preparation method of the present invention, ink foaming and solidification are being carried out simultaneously, accelerate the solidification process of ink, improve the rate of drying of ink, and foamed gas is not volatile simultaneously, better can retain foamed gas.
3, the present invention adds suds-stabilizing agent and the agent of anti-yellowing change ink stability in formula, makes foam can keep permanent.
4, the performance of foam ink that prepared by the present invention meets the requirement of ink jet printing completely: particle diameter is less than 0.15 μm, viscosity is 10 ~ 20mPa.s (25 DEG C), surface tension is 35 ~ 40mN/m (25 DEG C), specific conductivity is < 15 μ s/cm, and pH value is between 7 ~ 9.
Accompanying drawing explanation
Fig. 1 embodiment of the present invention 2 foam ink compares with the solidification rate of common UV ink-jet ink.
Fig. 2 is the scanning electron microscope diagram that in embodiment 2, printed sample surface morphology is observed.
The scanning electron microscope diagram that the surface topography that in Fig. 3 Fig. 2, part is amplified is observed.
After Fig. 4 embodiment 2 sample deposits 1 day, the microscopic appearance figure of the surfactant foam ink utilizing AFM to characterize.
After Fig. 5 embodiment 2 sample deposits 180 days, the microscopic appearance figure of the surfactant foam ink utilizing AFM to characterize.
Embodiment
Below in conjunction with specific embodiment, the present invention is further analyzed.
A kind of foam ink of spray ink Printing, for blend, this blend comprises binder, whipping agent, light draw agent, suds-stabilizing agent, solvent, the agent of anti-yellowing change ink stability, PH damping fluid, dispersion agent, emulsifying agent, tensio-active agent, sequestrant, sanitas and tinting material; The mass percentage of above-mentioned each component in the foam ink of spray ink Printing is as follows:
Binder: 15 ~ 55%;
Whipping agent: 2 ~ 5%;
Light draws agent: 10 ~ 20%;
Suds-stabilizing agent: 1 ~ 3%;
Solvent: 20 ~ 25%;
Anti-yellowing change ink stability agent: 1 ~ 4 ﹪;
PH damping fluid: 1 ~ 5 ﹪;
Dispersion agent: 2 ~ 5%;
Emulsifying agent: 1 ~ 4%;
Tensio-active agent: 1 ~ 3%;
Sequestrant: 0.5 ~ 2%;
Sanitas: 0.1 ~ 0.5%;
Tinting material: 5 ~ 9%;
Wherein, binder is one or more in hexamethylene diisocyanate, polyvinyl acetate, bisphenol A type epoxy resin; Binder is the important component part of printing-ink, is the fluid section of ink.The wetting action of the solids component dependence binder in ink can in the fabrication process by porphyrize; rely on its viscosity to complete the transmission transfer of printing process, printed matter relies on the drying and forming-film of low-melting ink vehicle make trace form the ink film of the fastness of gloss and protect pigment.Above-mentioned binder hexamethylene diisocyanate; Polyvinyl acetate; The transparency of bisphenol A type epoxy resin is good, by rheological, viscosity, drying property, the good film-forming property of the printing-ink of this resin formulations.
Whipping agent and light draw the important formula that agent is foam ink of the present invention, just because of employing sodium carbonate as whipping agent, and adopt photo-acid agent and/or sulfosalt to draw agent as light, make the foam theory of foam ink of the present invention and prior art completely different.Ink is under the effect of UV-LED light, and light trigger photo-acid agent and sulfosalt are excited, and initiation photo-acid agent and sulfosalt produce protonic acid by key homolysis and heterolytic fission thus, then generates with sodium carbonate generation chemical reaction the CO discharged 2namely foam, in ink, produce 3D micropore.Draw unsaturated link(age) in trip base in agent or ion and hydroxyl polymers and monomer with the time to react, form monomeric groups, then these monomeric groups carry out chain reaction, complete solidification process, make the bubble of generation not volatile, improve the rate of drying of ink simultaneously.
Suds-stabilizing agent is added in order to make the foam in ink of the present invention keep permanent.Dimethyl dodecyl amine oxide (lauryl dimethyl amine oxide) is colourless or micro-yellow transparent liquid at normal temperatures, it is a kind of tensio-active agent of specific type, be colourless or micro-yellow transparent liquid at normal temperatures, it becomes cationic in acidic medium, is then non-ionic type in neutrality or alkaline medium.Except there is general surfactant properties, also there is excellent solubilising, thickening, emulsification, foaming, steady bubble and mildew-proof function.
As pointed by background technology, the pH value of spray ink Printing ink is too low, and ink is that acidity can corrode print cartridge; If pH value is too high, then can improve specific conductivity, reduce the work-ing life of print cartridge.For ensureing ink satisfactory stability, the pH value of ink must be suitable with the pH value of tinting material, is generally 7 ~ 9.Therefore, when preparing ink, a small amount of buffer reagent or pH value conditioning agent need be added.Metal hydroxides generally in alkalescence, has alkaline lithium hydroxide; Potassium hydroxide, sodium hydroxide, electronegativity is less, and its oxyhydroxide easily discharges hydroxide radical in ink, and salt of wormwood is also in alkalescence, and low price.Or directly buy pH value be 10.00 PH standard buffer solution (APURE) regulate ink PH concentration to remain between 7 ~ 9.
In a preferred embodiment, the anti-yellowing change ink stability agent that composition for ink of the present invention adopts is tetramethyl piperidine oxide compound, benzophenone, w-bromoacetophenone, one or more in phenylbenzene sulphur, effectively can suppress the printed Yellowing of ink under action of ultraviolet radiation, effectively prevent the generation of the reduction of gloss, crackle, bubble, delamination, significantly improve the weathering resistance of product.
In a preferred embodiment, the sequestrant that composition for ink of the present invention adopts can buy D401 aminophosphonic acid chelate resin; D403 phosphoramidic acid type resin; C900 Amino phosphonic acid resin; One or more in C800 aminocarboxylic acid resin; Because above sequestrant has sequestering to metal ions such as sodium, effectively can stop the metal ions such as sodium that chemical reaction occurs in ink printing process and form throw out, the nozzle solidifying and block print cartridge of particle can be prevented, and can progressively remove original fouling.
In a preferred embodiment, composition for ink of the present invention comprises dispersion agent further, German Lu Borun hyper-dispersant S-13940 will be bought in the present invention, solsperse5000 hyper-dispersant, by the stability in the dispersiveness of raising pigment and liquid organic medium, make ink have better tinctorial property simultaneously.
The effect of the solvent in the present invention's formula is wetting agent thus can controls the viscosity of ink.In a preferred embodiment, 2-Pyrrolidone is used as solvent and organic synthesis intermediate, and hexanaphthene is solvent, stratographic analysis reference material and for organic synthesis, and sebacic acid is tenderizer and solvent.Methyl ethyl ketone is organic synthesis raw material, can make solvent, and can reduce the viscosity referring to ink, has quick-drying.Glycol ether, methyl iso-butyl ketone (MIBK) are solvents.
Sanitas in the present invention's formula storage and the use of protecting water color ink product, preferably, phenol, arsenous acid anhydride are used as the sanitas in this ink.
Tensio-active agent in the present invention's formula, for the affinity improving ink pigment and low-melting ink vehicle, it has the effect of two aspects.One is adsorb the location of pigment particles, prevents this suspension system of printing-ink because of the gathering sedimentation of disperse phase, and occurs the situation of Precipitation; Two is the wetting abilities improving low-melting ink vehicle, reduces its surface tension, makes it be less than the critical surface tension of solid, also reduce the interfacial energy of system simultaneously.
The effect of the tinting material in the present invention's formula is to provide color, directly adds one or more in pigment dyestuff or mineral dye in this ink.As: turmeric yellow, C.I. 42685, directly indigo plant, reactive black etc.
Present invention also offers a kind of preparation method of foam ink of spray ink Printing, comprise the following steps:
Step (1), ink mix
Each component as above for mass percentage is mixed and uses FS-S type twin shaft dispersator within 45 ~ 60 minutes, to make each component mix formation ink mixture;
Step (2), ink jet-printing
By above-mentioned ink mixture by printing of inkjet printer on high temperature resistant PET paper; The DimatixDMP2831 of FUJIFILM company of the U.S. selected by described ink-jet printer; The typography of foam ink utilizes conventional ink-jet printer to be difficult to realize, the DimatixDMP2831 ink-jet printer of the U.S. FUJIFILM of market release in recent years, the minisize fluid ink droplet that 10 skins rise size can be deposited, with ink droplet sighting disk and heated platen, carry the Dimatix box of multiple nozzle, a nozzle can send a stream of liquid droplets, for foam ink adopts the total digitalization of spray ink Printing to print the platform provided.
Further, need to regulate U.S. FUJIFILM company model be the parameter of DimatixDMP2831 ink-jet printer to obtain optimum ink print effect, design parameter is: the Dimatix box arranging 16 nozzles makes a nozzle send a stream of liquid droplets; Print speed is 0.5 ~ 1.1m/s; Set single ink drop volumes and be not more than 50um, the temperature selecting print cartridge is 25 ~ 30 DEG C.
Step (3), ink foam
Sending complete continuous ultraviolet light belt by UV-LED curing light source makes the ink pattern on PET paper foam, in foaming process, by ultraviolet excitation light trigger, make photo-acid agent or/and sulfosalt produces protonic acid by key homolysis and heterolytic fission, described protonic acid and sodium carbonate carry out the CO that chemical reaction discharges 2multiple 3D micropore is produced in ink; In foaming process, also carry out ink solidification process simultaneously, wherein, light draws unsaturated link(age) in trip base in agent or ion and hydroxyl polymers and monomer and reacts, form monomeric groups, then these monomeric groups carry out chain reaction, owing to completing solidification process in foaming process simultaneously, make the bubble of generation not volatile, bubble can keep permanent.
In order to enhanced foaming and solidification effect, allow UV-LED send a complete continuous ultraviolet light belt, because the LED light source solidification effect of different wave length is different, short wavelength is conducive to the surface cure of ink, and long wavelength is conducive to the deep cure of ink.Therefore, in actual fabrication process, a kind of preferred implementation is: be first cured with the surface of shortwave UV-LED light to ink, the bubble that foaming process is produced can not vapor away from ink; After foaming completes, then at employing long wave UV-LED light, deep cure is carried out to ink, thus bubble can remain in ink for a long time.
Step (3) ink foaming process, can adopt Shenzhen Hai Sien Science and Technology Ltd. UV-LED light source solidification system, this system can select multiple wave band, such as wavelength 365nm/385nm/395nm; Four-way main frame: simultaneously can connect 4 LED illumination heads; Adopt 3.5 cun of colored technical grade liquid crystal displays, coordinate resistive touch screen, each channel current adopts the stepless control of constant current, and fluctuation of current is less than 1%.
Step (4), ink solidification
In above-mentioned ink foaming process, make PET paper substrates temperature maintain 45 ~ 55 DEG C, temperature is too low, and ink is difficult to drying and moulding, and temperature is too high, CO in invention 2gas easily volatilizees, and is difficult to form foam.Cooling at normal temperatures and drying solidify to form foam ink in 24 hours again.
Embodiment 1
Prepared by ink: first by binder 40.4g hexamethylene diisocyanate, whipping agent: sodium carbonate 2g, and light draws agent: photo-acid agent 15g; Suds-stabilizing agent: dimethyl dodecyl amine oxide 2g; The PH damping fluid of 1g: lithium hydroxide; 2g anti-yellowing change ink stability agent: tetramethyl piperidine oxide compound, 1g dispersion agent: German Lu Borun hyper-dispersant S-13940,1g emulsifying agent: polyoxyethylene glycol cetyl ether; Tensio-active agent 2g: acetylenic diols tensio-active agent, sequestrant 0.5g:D401 aminophosphonic acid chelate resin, solvent 25g:2-pyrrolidone, sanitas 0.1g: phenol; Tinting material 8g: turmeric yellow 73,
With FS-S type twin shaft dispersator 45 ~ 60 minutes, namely prepare the foam ink of the spray ink Printing of the present invention.
Spray ink Printing: adopt Shenzhen Hai Sien Science and Technology Ltd. UV-LED light source solidification system, select wave band 365nm; Four-way main frame: simultaneously can connect 4 LED illumination heads; Adopt 3.5 cun of colored technical grade liquid crystal displays, coordinate resistive touch screen, each channel current adopts the stepless control of constant current, and fluctuation of current is less than 1%.
Select the DimatixDMP2831 ink-jet printer of the U.S. FUJIFILM adopting energy continous inkjet, select the Dimatix box of 16 nozzles, a nozzle sends a stream of liquid droplets.Select to guide ink to be 16 kilo hertzs by the radio frequency of nozzle, voltage is 16 volts, and print speed is 0.5m/s; Set single ink drop volumes and be not more than 50um, the temperature selecting print cartridge is 25 DEG C, and in experiment, printed substrates adopts the PET paper of the certain high temperature of ability, during printing, PET paper substrates temperature maintains 45 DEG C, and temperature is too low, and ink is difficult to drying and moulding, temperature is too high, CO in invention 2gas easily volatilizees, and is difficult to form foam.Printed PET paper is cooled at normal temperatures and within 24 hours, laboratory sample 1 can be obtained with dry.
Embodiment 2
Prepared by ink: first binder 45g polyvinyl acetate, whipping agent 3g sodium carbonate and 12g light are drawn agent sulfosalt; 3g suds-stabilizing agent dimethyl dodecyl amine oxide; The PH damping fluid potassium hydroxide of 2g, 2g anti-yellowing change ink stability agent benzophenone, 2g dispersion agent: German Lu Borun hyper-dispersant S-13940,3g emulsifying agent: polyoxyethylene glycol cetyl ether; Tensio-active agent 2g: acetylenic diols tensio-active agent, sequestrant 0.5g:C900 Amino phosphonic acid resin; Solvent 20.3g: methyl ethyl ketone; Sanitas 0.2g: phenol; Tinting material 5g: directly indigo plant 199,
Use FS-S type twin shaft dispersator 50 minutes again.Namely the foam ink of the spray ink Printing of the present invention has been prepared.
Spray ink Printing: adopt Shenzhen Hai Sien Science and Technology Ltd. UV-LED light source solidification system, select wave band 385nm; Four-way main frame: simultaneously can connect 4 LED illumination heads; Adopt 3.5 cun of colored technical grade liquid crystal displays, coordinate resistive touch screen, each channel current adopts the stepless control of constant current, and fluctuation of current is less than 1%.Select the DimatixDMP2831 ink-jet printer of the U.S. FUJIFILM adopting energy continous inkjet, select the Dimatix box of 16 nozzles, a nozzle sends a stream of liquid droplets.Select to guide ink to be 16 kilo hertzs by the radio frequency of nozzle, voltage is 16 volts, and print speed is 0.8m/s; Set single ink drop volumes and be not more than 50um, the temperature selecting print cartridge is 25 DEG C, and in experiment, printed substrates adopts the PET paper of the certain high temperature of ability, and during printing, PET paper substrates temperature maintains 50 DEG C.Temperature is too low, and ink is difficult to drying and moulding, and temperature is too high, CO in invention 2gas easily volatilizees, and is difficult to form foam, is cooled at normal temperatures by printed PET paper and within 24 hours, can obtain laboratory sample 2 with dry.
Embodiment 3
Prepared by ink: first by binder 21.5g polyvinyl acetate; 23.5g bisphenol A type epoxy resin, whipping agent 4g sodium carbonate and 15g light draw agent sulfosalt; 1g suds-stabilizing agent dimethyl dodecyl amine oxide; The pH value of 1g is PH standard buffer solution (APURE) potassium hydroxide of 10.00,1g anti-yellowing change ink stability agent phenylbenzene sulphur, 1g dispersion agent: solsperse5000 hyper-dispersant; 2g emulsifying agent: polyoxyethylene glycol cetyl ether; The C900 Amino phosphonic acid resin of tensio-active agent 1g: acetylenic diols tensio-active agent, sequestrant: 0.5g; The C800 aminocarboxylic acid resin of 0.5g; The methyl ethyl ketone of solvent 9g, the methyl iso-butyl ketone (MIBK) of 12.9g; Sanitas 0.1g: arsenous acid anhydride; Tinting material 6g: reactive black 81.
Use FS-S type twin shaft dispersator 55 minutes again.Namely the foam ink of the spray ink Printing of the present invention has been prepared.
Spray ink Printing: adopt Shenzhen Hai Sien Science and Technology Ltd. UV-LED light source solidification system, select wave band 385nm; Four-way main frame: simultaneously can connect 4 LED illumination heads; Adopt 3.5 cun of colored technical grade liquid crystal displays, coordinate resistive touch screen, each channel current adopts the stepless control of constant current, and fluctuation of current is less than 1%.Select the DimatixDMP2831 ink-jet printer of the U.S. FUJIFILM adopting energy continous inkjet, select the Dimatix box of 16 nozzles, a nozzle sends a stream of liquid droplets.Select to guide ink to be 16 kilo hertzs by the radio frequency of nozzle, voltage is 16 volts, and print speed is 1.1m/s; Set single ink drop volumes and be not more than 50um, the temperature selecting print cartridge is 30 DEG C, and in experiment, printed substrates adopts the PET paper of the certain high temperature of ability, and during printing, PET paper substrates temperature maintains 55 DEG C.Temperature is too low, and ink is difficult to drying and moulding, and temperature is too high, CO in invention 2gas easily volatilizees, and is difficult to form foam, is cooled at normal temperatures by printed PET paper and within 24 hours, can obtain laboratory sample 3 with dry.
Embodiment 4
Prepared by ink: first binder 54g bisphenol A type epoxy resin, whipping agent 2g sodium carbonate and 10g light are drawn agent photo-acid agent; 1g suds-stabilizing agent dimethyl dodecyl amine oxide; The pH value of 1g is the PH standard buffer solution (APURE) of 10.00,1g anti-yellowing change ink stability agent benzophenone, 2g dispersion agent: solsperse5000 hyper-dispersant; 1g emulsifying agent: polyethylene glycol stearate; Tensio-active agent 1g: acetylenic diols tensio-active agent, 1g sequestrant: D403 phosphoramidic acid type resin; The sebacic acid of solvent 20.9g:10g, the glycol ether of 10.9g; Sanitas 0.1g: arsenous acid anhydride; Tinting material 5g: acid fuchsin 6b.
Use FS-S type twin shaft dispersator 60 minutes again.Namely the foam ink of the spray ink Printing of the present invention has been prepared.
Spray ink Printing: adopt Shenzhen Hai Sien Science and Technology Ltd. UV-LED light source solidification system, select wave band 395nm; Four-way main frame: simultaneously can connect 4 LED illumination heads; Adopt 3.5 cun of colored technical grade liquid crystal displays, coordinate resistive touch screen, each channel current adopts the stepless control of constant current, and fluctuation of current is less than 1%.Select the DimatixDMP2831 ink-jet printer of the U.S. FUJIFILM adopting energy continous inkjet, select the Dimatix box of 16 nozzles, a nozzle sends a stream of liquid droplets.Select to guide ink to be 16 kilo hertzs by the radio frequency of nozzle, voltage is 16 volts, and print speed is 1.1m/s; Set single ink drop volumes and be not more than 50um, the temperature selecting print cartridge is 30 DEG C, and in experiment, printed substrates adopts the PET paper of the certain high temperature of ability, and during printing, PET paper substrates temperature maintains 55 DEG C.Temperature is too low, and ink is difficult to drying and moulding, and temperature is too high, CO in invention 2gas easily volatilizees, and is difficult to form foam, is cooled at normal temperatures by printed PET paper and within 24 hours, can obtain laboratory sample 3 with dry.
Below the foam ink prepared above-described embodiment again and common foam ink carry out contrast test analysis:
1. the foam ink of preparation in embodiment 2 and common foam ink are coated with on a pet film respectively, its ink film thicknesses is 10 μm, adopt Shenzhen Hai Sien Science and Technology Ltd. UV-LED light source solidification system, select power 1.18W/cm2, wave band is 365nm respectively, 385nm, 395nm, power is all adjusted to 1.2W/cm2), after the light source curing 5s of UV-LED, adopt interval infrared spectroscopy, the solidification rate of UV-LED ink is characterized with double bond turnover ratio, relatively in the present invention, foam ink is compared common UV ink-jet ink and is had solidification rate faster, its result shows foam ink of the present invention and has solidification rate faster.
2. ink performance test
The ink performance prepared experiment 1,2,3,4 is tested.As can be seen from Table 1, the performance of the foam ink of spray ink Printing prepared by embodiment 1-4 meets the requirement of ink jet printing completely, and wherein during test, temperature is 25 DEG C, and ink viscosity tester NDJ-8S carries out viscosimetric analysis.As shown in table 1: particle diameter is less than 0.15 μm, viscosity is 10 ~ 20mPa.s, and surface tension is 35 ~ 40mN/m, and specific conductivity is < 15 μ s/cm, and pH value is between 7 ~ 9;
Table 1 embodiment 1 ~ 4 foam ink performance test results
3.. morphology analysis is carried out to example 2
Sample printed in example 2 is analyzed.The morphology observation of sample adopts Hitachi S-4800 scanning electron microscope, and Fig. 2 is the SEM photo of printed sample in embodiment 2, and Fig. 3 is that in Fig. 2, part amplifies SEM photo.As can be seen from the figure: the intensive abscess be separated from each other in ink, and present a kind of orderly three-dimensional structure, its shape subglobular, foam size is between 40 ~ 110nm.Because PET printing sample is dry, scheme at SEM the agglomeration that edge can observe some particles.
4. MFP-3DTM standard type atomic force microscope is selected in experiment, and Fig. 4 is after embodiment 2 sample deposits 1 day, the microscopic appearance photo of the surfactant foam ink utilizing AFM to characterize; Fig. 5 is after embodiment 2 sample deposits 180 days, the microscopic appearance photo of the surfactant foam ink utilizing AFM to characterize; Be uneven for reference plane, it is protruding next that the place higher than reference plane represents relative to reference plane, otherwise then represents dented.Comparison diagram 4 and Fig. 5 can find out: the foam ink of embodiment 2 sample does not change substantially, and the sign that the sample surfaces that detects by an unaided eye does not turn to be yellow and fades, prove keep permanent with the printing ink foam of the printed product of undertaking the printing of of the inventive method.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.

Claims (10)

1. the foam ink of a spray ink Printing, for blend, it is characterized in that, this blend comprises binder, whipping agent, light draws agent, suds-stabilizing agent, solvent, the agent of anti-yellowing change ink stability, PH damping fluid, dispersion agent, emulsifying agent, tensio-active agent, sequestrant, sanitas and tinting material; The mass percentage of above-mentioned each component in the foam ink of spray ink Printing is as follows:
Binder: 15 ~ 55%;
Whipping agent: 2 ~ 5%;
Light draws agent: 10 ~ 20%;
Suds-stabilizing agent: 1 ~ 3%;
Solvent: 20 ~ 25%;
Anti-yellowing change ink stability agent: 1 ~ 4 ﹪;
PH damping fluid: 1 ~ 5 ﹪;
Dispersion agent: 2 ~ 5%;
Emulsifying agent: 1 ~ 4%;
Tensio-active agent: 1 ~ 3%;
Sequestrant: 0.5 ~ 2%;
Sanitas: 0.1 ~ 0.5%;
Tinting material: 5 ~ 9%;
Wherein, described binder is one or more in hexamethylene diisocyanate, polyvinyl acetate, bisphenol A type epoxy resin;
Described whipping agent is sodium carbonate;
It is one in photo-acid agent, sulfosalt or two kinds that described light draws agent;
Described suds-stabilizing agent is dimethyl dodecyl amine oxide.
2. prepare the method for the foam ink of a kind of spray ink Printing as claimed in claim 1, it is characterized in that, the method comprises the following steps:
Step (1), ink mix
Each component following for mass percentage is mixed and uses FS-S type twin shaft dispersator within 45 ~ 60 minutes, to make each component mix formation ink mixture:
Binder: 15 ~ 55%;
Whipping agent: 2 ~ 5%;
Light draws agent: 10 ~ 20%;
Suds-stabilizing agent: 1 ~ 3%;
Solvent: 20 ~ 25%;
Anti-yellowing change ink stability agent: 1 ~ 4 ﹪;
PH damping fluid: 1 ~ 5 ﹪;
Dispersion agent: 2 ~ 5%;
Emulsifying agent: 1 ~ 4%;
Tensio-active agent: 1 ~ 3%;
Sequestrant: 0.5 ~ 2%;
Sanitas: 0.1 ~ 0.5%;
Tinting material: 5 ~ 9%;
Wherein, described binder is one or more in hexamethylene diisocyanate, polyvinyl acetate, bisphenol A type epoxy resin;
Described whipping agent is sodium carbonate;
It is one in photo-acid agent, sulfosalt or two kinds that described light draws agent;
Described suds-stabilizing agent is dimethyl dodecyl amine oxide;
Step (2), ink jet-printing
By above-mentioned ink mixture by printing of inkjet printer on high temperature resistant PET paper; The DimatixDMP2831 of FUJIFILM company of the U.S. selected by described ink-jet printer;
Step (3), ink foam
Sending complete continuous ultraviolet light belt by UV-LED curing light source makes the ink pattern on PET paper foam, in foaming process, by ultraviolet excitation light trigger, make photo-acid agent or/and sulfosalt produces protonic acid by key homolysis and heterolytic fission, described protonic acid and sodium carbonate carry out the CO that chemical reaction discharges 2multiple 3D micropore is produced in ink;
Step (4), ink solidification
In above-mentioned ink foaming process, make PET paper substrates temperature maintain 45 ~ 55 DEG C, then cooling at normal temperatures solidify to form foam ink in 24 hours with dry.
3. the foam ink of a kind of spray ink Printing as claimed in claim 1 or method as claimed in claim 2, it is characterized in that, described solvent is one or more in 2-Pyrrolidone, glycol ether, hexanaphthene, sebacic acid, methyl ethyl ketone, methyl iso-butyl ketone (MIBK).
4. the foam ink of a kind of spray ink Printing as claimed in claim 1 or method as claimed in claim 2, is characterized in that, described PH damping fluid is one or more in lithium hydroxide, potassium hydroxide, sodium hydroxide, salt of wormwood.
5. the foam ink of a kind of spray ink Printing as claimed in claim 1 or method as claimed in claim 2, it is characterized in that, the agent of described anti-yellowing change ink stability is tetramethyl piperidine oxide compound, benzophenone, w-bromoacetophenone, one or more in phenylbenzene sulphur.
6. the foam ink of a kind of spray ink Printing as claimed in claim 1 or method as claimed in claim 2, it is characterized in that, described dispersion agent is German Lu Borun hyper-dispersant S-13940 and/or solsperse5000 hyper-dispersant;
Described sanitas is phenol and/or arsenous acid anhydride;
Described emulsifying agent is polyoxyethylene glycol cetyl ether and/or polyethylene glycol stearate;
Described tensio-active agent is acetylenic diols tensio-active agent;
Described sequestrant is one or more in D401 aminophosphonic acid chelate resin, D403 phosphoramidic acid type resin, C900 Amino phosphonic acid resin, C800 aminocarboxylic acid resin;
Described tinting material is in pigment dyestuff and/or mineral dye.
7. method as claimed in claim 2, it is characterized in that, in step (2), FUJIFILM company of adjustment U.S. model is the parameter of DimatixDMP2831 ink-jet printer: the Dimatix box arranging 16 nozzles makes a nozzle send a stream of liquid droplets; Print speed is 0.5 ~ 1.1m/s; Set single ink drop volumes and be not more than 50um, the temperature selecting print cartridge is 25 ~ 30 DEG C.
8. method as claimed in claim 2, is characterized in that, in step (3), adopts Shenzhen Hai Sien Science and Technology Ltd. UV-LED light source solidification system.
9. method as claimed in claim 8, is characterized in that, in ink foaming process, connects multiple UV-LED irradiation head and each UV-LED irradiation head sends the UV-LED light of different wave length simultaneously.
10. method as claimed in claim 9, is characterized in that, the wavelength of described UV-LED irradiation head is any one in 365nm, 385nm or 395nm.
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