CN108485372A - A kind of aqueous UV foam inks and preparation method thereof - Google Patents

A kind of aqueous UV foam inks and preparation method thereof Download PDF

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Publication number
CN108485372A
CN108485372A CN201810616525.6A CN201810616525A CN108485372A CN 108485372 A CN108485372 A CN 108485372A CN 201810616525 A CN201810616525 A CN 201810616525A CN 108485372 A CN108485372 A CN 108485372A
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nano
titanium dioxide
preparation
photoinitiator
aqueous
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汪国亮
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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
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention discloses a kind of aqueous UV foam inks and preparation method thereof, photoinitiator is used as using radical photoinitiator TPO and cationic photoinitiator diaryl iodonium salt compounding, it is effectively improved the spectral characteristic of salt, improve the light utilization efficiency to light source, it is reacted with calcium carbonate foaming agent with generating enough Bronsted acids, fully realize foamable reaction, ink film has extremely strong stereosopic printing effect after solidification；Use polyacrylate/nano-titanium dioxide lotion for binder simultaneously, since Nano filling has higher covering effect, it can stop that the oxygen in air participates in the contention of free radical, to make hardening time shorten, on the other hand silicone molecules chain is introduced into acrylate and forms securely crosslinked cubic network ink film, ink film is set to have many advantages, such as very strong water resistance and adhesive force, and clear with glossiness height, lines.

Description

A kind of aqueous UV foam inks and preparation method thereof
Technical field
The invention belongs to print technical field of ink, and in particular to a kind of aqueous UV foam inks and preparation method thereof.
Background technology
After traditional foam ink is by oven drying foamable, it is desirable to which obtaining has clearly lines effect, softness The specimen page of feel and excellent adhesive force, the control of oven drying temperature are to ensure the key parameter of foaming effect and lines effect.But It is extremely difficult to accurately control oven drying temperature in actual technical process, UV foam inks come into being.Its foaming mechanism is： Lipophilic salt photoinitiator is added in UV ink, salt is in UV（Ultraviolet light）By key homolysis and different under radiation effects It splits generation Bronsted acid and other photodestruction products, the Bronsted acid of generation is reacted with inorganic foaming agents such as calcium carbonate, discharge CO2I.e. Expandable generation micropore.
Diaryl iodonium salt and triaryl sulfonium salts are the aryl salt photoinitiators more early developed, the disadvantage is that absorbing wave Length is close to far-ultraviolet region, such as a length of 227nm of the maximum absorption wave of diaryl iodonium salt, the maximum absorption wave of triaryl sulfonium salts A length of 254nm.Current main ultraviolet curing equipment（Such as high-pressure sodium lamp）) wavelength that provides is usually all in middle ultraviolet band and close Ultra-violet (UV) band, be more than 280nm, this result in light source offer wavelength and photoinitiator absorbing wavelength mismatch, make using by Certain restrictions.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of aqueous UV foam inks and preparation method thereof, widen light Initiator absorbing wavelength range shortens the hardening time of UV ink, improves ink printing effect.
To reaching above-mentioned purpose, the present invention uses following technical scheme：
A kind of aqueous UV foam inks, including following raw material：Polyacrylate/nano-titanium dioxide complex emulsions connection 45-55 parts of material, 5-12 parts of photoinitiator, 15-20 parts of pigment, 4-8 parts of calcium carbonate, 0.5-3 parts of antifoaming agent, wetting dispersing agent 0.3- 2 parts；
The photoinitiator includes photoinitiator TPO, diaryl iodonium salt, and the two mass ratio is 1:1.5-3；
The polyacrylate/nano-titanium dioxide complex emulsions are then to be added third with KH-570 modified nano-titanium dioxides Olefin(e) acid ester monomer simultaneously carries out pre-emulsification, is prepared by in-situ emulsion polymerization.
The preparation method of the aqueous UV foam inks, the specific method is as follows：
（1）The surface modification of nano-titanium dioxide：
Weigh a certain amount of nano-TiO2It is added in toluene solvant, ultrasonic vibration disperses 20-30min, obtains the nanometer of 1-2% TiO2Dispersion liquid, and nano-TiO is added2 The Silane coupling reagent KH-570 of quality 10-15%, is vigorously stirred, and 45-55 DEG C of constant temperature is anti- 4-6h is answered, is cooled to room temperature, filtration drying obtains the nano-TiO of silane coupling agent surface modification2；
（2）Weigh 0.8-1.2g surfactants, 30-40g deionized waters, 12-18g methyl methacrylates, 32-40g propylene Acid butyl ester, high speed pre-emulsification 20-30min, obtains pre-emulsion, is placed in spare in constant pressure separatory funnel；
（3）Weigh 2.0-3.0g surfactants, 50-65g deionized waters, 32-38g methyl methacrylates, 12-20g third Olefin(e) acid butyl ester and quantitative KH570 are modified TiO2In reactor, high-speed stirred 10-15min, then disperse 10- with ultrasonic wave 20min is then transferred in the four-hole boiling flask equipped with blender, thermometer and condenser pipe, is heated to 68-75 DEG C, is then added 0.2-0.4g potassium peroxydisulfates are gradually heating to 70-80 DEG C, insulation reaction 1.5-2h；
By step（2）Pre-emulsion is slowly dropped evenly into reaction system in 1h, while adding suitable potassium peroxydisulfate water Then system is warming up to 80-85 DEG C by solution, react 2-3h, be cooled to room temperature after the completion of reaction, filtered with 300 mesh filter screens, and Its pH value is adjusted to 7-8 to get polyacrylate/nano-titanium dioxide complex emulsions with ammonium hydroxide；
（4）The preparation of foam ink：
Each component is weighed according to weight, above-mentioned polyacrylate/nano-titanium dioxide Composite Milk is added in the reactor Liquid, antifoaming agent, wetting dispersing agent stir 10-15min with the rotating speed of 500rpm-1000rpm, pigment, calcium carbonate are then added, With the rotating speed grinding distribution 25-40min of 2500rpm-3000rpm, it is being protected from light, is adding photoinitiator, Disperse 20-30min under the rotating speed of 1000rpm-1500rpm, 1-2h is ground in grinder, anti-light package is spare.
Wherein, the step（2）Surfactant includes lauryl sodium sulfate, nonylphenol polyoxyethylene ether, the two matter Amount is than being 1.5-2:1.
Wherein, the solid content of the polyacrylate/nano-titanium dioxide complex emulsions is in 40-60%.
Wherein, in the foam ink nano-titanium dioxide additive amount be ink gross mass 4-10%.
Beneficial effects of the present invention are as follows：
（1）Conduct is compounded using radical photoinitiator TPO and cationic photoinitiator diaryl iodonium salt in the present invention Photoinitiator, initiator TPO can not only be used for the photosensitizer of cationic salt compounded of iodine photoinitiator, cause the free radical energy for decomposing and generating Salt compounded of iodine class initiator is restored, promotes salt cracking to generate super strong proton acid, is effectively improved the spectral characteristic of salt, improve to light The light utilization efficiency in source is reacted with generating enough Bronsted acids with calcium carbonate foaming agent, fully realizes foamable reaction, ink film after solidification With extremely strong stereosopic printing effect.
（2）But when receiving ultraviolet light, free radical type initiator TPO photodissociation is that free radical participates in system reaction, by Very thin in layer of ink, the oxygen in air easily penetrates into layer of ink and reacts with free radical, to reduce active group so that ink The hardening time of film extends.Therefore use polyacrylate/nano-titanium dioxide lotion for binder in the present invention, due to nanometer Filler has higher covering effect, can stop that the oxygen in air participates in the contention of free radical, to make hardening time shorten, On the other hand silicone molecules chain is introduced into acrylate and forms securely crosslinked cubic network ink film, ink film is made to have very Strong water resistance and adhesive force, and have many advantages, such as that glossiness is high, lines is clear.
Specific implementation mode
Embodiment 1
A kind of aqueous UV foam inks, including following raw material：Polyacrylate/nano-titanium dioxide complex emulsions connection 45-55 parts of material, 5-12 parts of photoinitiator, 15-20 parts of pigment, 4-8 parts of calcium carbonate, 0.5-3 parts of antifoaming agent, wetting dispersing agent 0.3- 2 parts；
The photoinitiator includes photoinitiator TPO, diaryl iodonium salt, and the two mass ratio is 1:1.5-3；
The polyacrylate/nano-titanium dioxide complex emulsions are then to be added third with KH-570 modified nano-titanium dioxides Olefin(e) acid ester monomer simultaneously carries out pre-emulsification, is prepared by in-situ emulsion polymerization.
The preparation method of the aqueous UV foam inks, the specific method is as follows：
（1）The surface modification of nano-titanium dioxide：
Weigh 0.5g nano-TiOs2It is added in 50mL toluene solvants, ultrasonic vibration disperses 30min, and it is even that 0.05g silane is added Join agent KH-570, be vigorously stirred, 50 DEG C of reaction 5h of constant temperature are cooled to room temperature, filtration drying, obtain silane coupling agent surface modification Nano-TiO2；
（2）Weigh 0.6g lauryl sodium sulfate, 0.3g nonylphenol polyoxyethylene ether, 30g deionized waters, 15g methacrylic acids Methyl esters, 35g butyl acrylates, high speed pre-emulsification 25min, obtain pre-emulsion, are placed in spare in constant pressure separatory funnel；
（3）Weigh 1.5g lauryl sodium sulfate, 0.6g nonylphenol polyoxyethylene ether, 50g deionized waters, 35g methacrylic acids Methyl esters, 15g butyl acrylates and 10g KH570 are modified TiO2In reactor, high-speed stirred 15min, then disperseed with ultrasonic wave 20min is then transferred in the four-hole boiling flask equipped with blender, thermometer and condenser pipe, is heated to 70 DEG C, 0.2g is then added Potassium peroxydisulfate is gradually heating to 75 DEG C, 1.5 h of insulation reaction；
Pre-emulsion is slowly added dropwise in 1h into reaction bulb, while adding suitable persulfate aqueous solution；Then by body System is warming up to 85 DEG C, reacts 2h, is cooled to room temperature, and is filtered with 300 mesh filter screens, is used in combination ammonium hydroxide that its pH value is adjusted to 7-8, i.e., Obtain polyacrylate/nano-titanium dioxide complex emulsions of the solid content 50%；
（4）The preparation of foam ink：
Each component is weighed according to weight, it is multiple that 50 parts of above-mentioned polyacrylate/nano-titanium dioxides are added in the reactor Lotion, 2 parts of antifoaming agent, 0.8 part of wetting dispersing agent are closed, 15min is stirred with the rotating speed of 800rpm, 18 parts of pigment, 6 are then added Part calcium carbonate is being protected from light with the rotating speed grinding distribution 30min of 3000rpm, adds 10 parts of photoinitiators, Disperse 30min under the rotating speed of 1500rpm, 1h is ground in grinder, anti-light package is spare.

Claims (5)

1. a kind of aqueous UV foam inks, which is characterized in that including following raw material：Polyacrylate/nanometer titanium dioxide 45-55 parts of titanium complex emulsions binder, 5-12 parts of photoinitiator, 15-20 parts of pigment, 4-8 parts of calcium carbonate, 0.5-3 parts of antifoaming agent, 0.3-2 parts of wetting dispersing agent；
The photoinitiator includes photoinitiator TPO, diaryl iodonium salt, and the two mass ratio is 1:1.5-3；
The polyacrylate/nano-titanium dioxide complex emulsions are then to be added third with KH-570 modified nano-titanium dioxides Olefin(e) acid ester monomer simultaneously carries out pre-emulsification, is prepared by in-situ emulsion polymerization.
2. a kind of preparation method of aqueous UV foam inks according to claim 1, which is characterized in that specific preparation method It is as follows：
（1）The surface modification of nano-titanium dioxide：
Weigh a certain amount of nano-TiO2It is added in toluene solvant, ultrasonic vibration disperses 20-30min, obtains the nano-TiO of 1-2%2 Dispersion liquid, and nano-TiO is added2 The Silane coupling reagent KH-570 of quality 10-15%, is vigorously stirred, 45-55 DEG C of reaction 4- of constant temperature 6h is cooled to room temperature, filtration drying, obtains the nano-TiO of silane coupling agent surface modification2；
（2）Weigh 0.8-1.2g surfactants, 30-40g deionized waters, 12-18g methyl methacrylates, 32-40g propylene Acid butyl ester, high speed pre-emulsification 20-30min, obtains pre-emulsion, is placed in spare in constant pressure separatory funnel；
（3）Weigh 2.0-3.0g surfactants, 50-65g deionized waters, 32-38g methyl methacrylates, 12-20g third Olefin(e) acid butyl ester and quantitative KH570 are modified TiO2In reactor, high-speed stirred 10-15min, then disperse 10- with ultrasonic wave 20min is then transferred in the four-hole boiling flask equipped with blender, thermometer and condenser pipe, is heated to 68-75 DEG C, is then added 0.2-0.4g potassium peroxydisulfates are gradually heating to 70-80 DEG C, insulation reaction 1.5-2h；
By step（2）Pre-emulsion is slowly dropped evenly into reaction system in 1h, while adding suitable potassium peroxydisulfate water Then system is warming up to 80-85 DEG C by solution, react 2-3h, be cooled to room temperature after the completion of reaction, filtered with 300 mesh filter screens, and Its pH value is adjusted to 7-8 to get polyacrylate/nano-titanium dioxide complex emulsions with ammonium hydroxide；
（4）The preparation of foam ink：
Each component is weighed according to weight, above-mentioned polyacrylate/nano-titanium dioxide Composite Milk is added in the reactor Liquid, antifoaming agent, wetting dispersing agent stir 10-15min with the rotating speed of 500rpm-1000rpm, pigment, calcium carbonate are then added, With the rotating speed grinding distribution 25-40min of 2500rpm-3000rpm, it is being protected from light, is adding photoinitiator, Disperse 20-30min under the rotating speed of 1000rpm-1500rpm, 1-2h is ground in grinder, anti-light package is spare.
3. a kind of preparation method of aqueous UV foam inks according to claim 2, which is characterized in that the step（2） Surfactant includes lauryl sodium sulfate, nonylphenol polyoxyethylene ether, and the two mass ratio is 1.5-2:1.
4. a kind of preparation method of aqueous UV foam inks according to claim 2, which is characterized in that the polyacrylic acid The solid content of ester/nano-titanium dioxide complex emulsions is in 40-60%.
5. a kind of preparation method of aqueous UV foam inks according to claim 2, which is characterized in that the foam ink The additive amount of middle nano-titanium dioxide is the 4-10% of ink gross mass.
CN201810616525.6A 2018-06-15 2018-06-15 A kind of aqueous UV foam inks and preparation method thereof Pending CN108485372A (en)

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Application Number Priority Date Filing Date Title
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516477A (en) * 2011-11-23 2012-06-27 华南理工大学 Nano titanium dioxide/ acrylate composite emulsion and preparation method thereof
CN104312260A (en) * 2014-10-24 2015-01-28 东莞智源彩印有限公司 Novel environment-friendly UV foamed ink and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516477A (en) * 2011-11-23 2012-06-27 华南理工大学 Nano titanium dioxide/ acrylate composite emulsion and preparation method thereof
CN104312260A (en) * 2014-10-24 2015-01-28 东莞智源彩印有限公司 Novel environment-friendly UV foamed ink and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
赵秀萍等: "《柔性版印刷技术》", 31 August 2013, 中国轻工业出版社 *
陈海生: "填料对UV胶印油墨性能的影响", 《包装工程》 *

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