CN114479551A - High-leveling photo-curing UV (ultraviolet) ink and preparation method thereof - Google Patents
High-leveling photo-curing UV (ultraviolet) ink and preparation method thereof Download PDFInfo
- Publication number
- CN114479551A CN114479551A CN202210051999.7A CN202210051999A CN114479551A CN 114479551 A CN114479551 A CN 114479551A CN 202210051999 A CN202210051999 A CN 202210051999A CN 114479551 A CN114479551 A CN 114479551A
- Authority
- CN
- China
- Prior art keywords
- leveling
- photo
- ink
- photoinitiator
- curing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 89
- 239000000463 material Substances 0.000 claims abstract description 55
- 239000000945 filler Substances 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 35
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000227 grinding Methods 0.000 claims abstract description 24
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000000049 pigment Substances 0.000 claims description 47
- 230000004048 modification Effects 0.000 claims description 33
- 238000012986 modification Methods 0.000 claims description 33
- 229920002101 Chitin Polymers 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000011268 mixed slurry Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims 4
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 66
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 18
- 238000007639 printing Methods 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 18
- 239000010703 silicon Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001723 curing Methods 0.000 description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
-
- 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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- 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
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
Landscapes
- 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 application relates to the field of photo-curing ink, and particularly discloses high-leveling photo-curing UV ink. The high-leveling photo-curing UV ink comprises the following substances in parts by weight: 65-75 parts of polyurethane resin, 20-30 parts of diluent, 3-5 parts of modified additive and 5-8 parts of composite filler; the modifying auxiliary agent comprises a leveling agent, and the leveling agent comprises a fluorocarbon leveling agent. The preparation method comprises the following steps: s1, pre-dispersing; s2, secondary mixing; and S3, grinding. The application optimizes the type of the leveling agent, adopts the fluorocarbon leveling agent to replace the traditional leveling agent material, and further reduces the surface energy of the ink surface, thereby effectively improving the fingerprint resistance of the photo-cured ink.
Description
Technical Field
The application relates to the field of photo-curing ink, in particular to photo-curing UV ink with high leveling property and a preparation method thereof.
Background
The photo-curing ink is a film-forming substance prepared from cross-linkable photo-polymerization resin, a pigment with good light transmittance is used as a coloring material, and a diluent monomer is used for dissolving and diluting the resin and promoting the photo-polymerization resin to be cured. Then adding photoinitiator, generating free radical under the irradiation of ultraviolet light with certain wavelength and power, and initiating photopolymerization resin to carry out crosslinking curing reaction.
The photocuring ink is high in curing speed, time is saved, and the photocuring ink can be cured only in a fraction of a second to a few seconds under the irradiation of UV light with a certain wavelength. Meanwhile, the light curing equipment occupies a small area, is printed in line production, saves labor and is economical and practical. Energy is saved compared to any other ink than solvent evaporation drying ink. With equal dry film thickness, the UV ink printed area was large. Has the performances of no net blocking, no viscosity change, no wire drawing and the like.
In view of the above-mentioned related art, the inventors believe that the leveling of the existing photocurable ink is not good during actual use, resulting in poor cap tack and fingerprint resistance of the photocurable ink.
Disclosure of Invention
In order to overcome the defect that the leveling property of the existing photo-curing ink is poor in the actual use process, the application provides the photo-curing UV ink with high leveling property and the preparation method thereof.
In a first aspect, the present application provides a high leveling photo-curing UV ink, which adopts the following technical scheme:
a high-leveling photo-curing UV ink comprises the following substances in parts by weight:
65-75 parts of polyurethane resin;
20-30 parts of a diluent;
3-5 parts of a modification auxiliary agent;
5-8 parts of a composite filler;
the modifying auxiliary agent comprises a leveling agent, and the leveling agent comprises a fluorocarbon leveling agent.
By adopting the technical scheme, the type of the leveling agent is optimized, the fluorocarbon leveling agent is adopted to replace the traditional leveling agent material, and the fluorine atoms contained in the fluorocarbon leveling agent have high electronegativity and low van der Waals radius, so that the surface energy of the fluorocarbon leveling agent is very low. The fluorine-containing surfactant can remarkably reduce the surface tension of a solution system, has excellent wetting and spreading performance, is beneficial to eliminating defects of the printing ink in a drying film-forming process, and forms a flat, smooth and uniform coating film.
Meanwhile, compared with a small-molecular fluorine-containing surfactant, the fluorocarbon leveling agent has the characteristics of better film forming property, stability, smoothness, low foaming, good compatibility and the like, and has more advantages in the aspect of long-wave leveling, especially in the aspect of improving the final gloss of a coating film. The application has the advantages that through the introduction of a plurality of fluorocarbon chains, the fluorocarbon chains have sufficiently low surface tension and high migration rate. Improves the compatibility with matrix resin and solves the contradiction between the leveling rate and the compatibility of the common fluorine-containing leveling agent. Meanwhile, the fluorocarbon leveling agent adopted by the photo-curing ink can further reduce the surface energy of the surface of the ink, so that the fingerprint resistance of the photo-curing ink is effectively improved.
Preferably, the leveling agent further comprises an acrylate leveling agent and an organic silicon leveling agent, and the mass ratio of the acrylate leveling agent to the organic silicon leveling agent to the fluorocarbon leveling agent is 1: 2.5-3.3: 1.8 to 2.5.
By adopting the technical scheme, the composition of the leveling agent material is further optimized, and the composite leveling agent material is formed by compounding the acrylate leveling agent, the organic silicon leveling agent and the fluorocarbon leveling agent. The fluorocarbon leveling agent and the organic silicon leveling agent in the system mainly reduce the surface tension of the coating system to enable the coating film to tend to level, and the acrylic resin leveling agent mainly forms limited compatibility with resin and cosolvent in the system, and can migrate to a gas-liquid interface during film forming to play a role in leveling the surface of the coating film. According to the technical scheme, the composition mode of the leveling agent material is optimized, and the film layer formed by curing the photo-curing printing ink has good structural performance and leveling performance through mixing and compounding.
Preferably, the modification auxiliary agent comprises a photoinitiator material, and the photoinitiator material is a chitin nanowhisker graft photoinitiator.
By adopting the technical scheme, the components of the photoinitiator material are further optimized, and because the mobility and the volatility of the traditional micromolecule photoinitiator are high, fragments generated after the micromolecule photoinitiator is cracked are easy to remain on the surface of the coating film which slowly migrates and escapes in the middle and later periods, and the compatibility of the photoinitiator material and a photocuring system is poor, the problem that the compatibility of the photoinitiator and a polymer matrix is poor is improved by the chitin nano whisker grafted photoinitiator, and the mechanical strength and the mechanical property of the photocuring ink material are further improved.
Preferably, the chitin nanowhisker graft photoinitiator is prepared by adopting the following scheme:
adding chitin into hydrochloric acid, stirring, mixing, heating in oil bath for refluxing, standing, cooling to room temperature, standing, collecting supernatant, dialyzing to pH 7.0, collecting dialysate, ultrasonically dispersing, vacuum freeze drying, and collecting chitin nanowhiskers;
dispersing chitin nanowhiskers into acetone, adding isophorone diisocyanate and dibutyltin dilaurate, heating to react for 4 hours, adding a photoinitiator, controlling the adding ratio of the photoinitiator to the isophorone diisocyanate to be 1: 1.3-1.8, keeping the temperature to react, washing and drying to obtain the chitin nanowhisker grafting photoinitiator.
By adopting the technical scheme, the chitin is selected as the raw material, and the chitin surface contains abundant hydroxyl groups, so that chemical grafting modification can be performed through chemical reaction. This application forms into the structure of nano whisker through dialyzing it, can effectively fill to polymer base member inside, as the inside connection structure in photocuring printing ink layer, improve the mechanical properties of photocuring printing ink, can not only effectively improve the problem that the volatility of photoinitiator material is high, still further improve its molecular structure through graft modification, thereby improved chitin nano whisker and the not good problem of macromolecular material base member compatibility, further improved the levelling performance of photocuring printing ink.
Preferably, the photoinitiator includes at least two of photoinitiator TPO, photoinitiator 907, and photoinitiator 819.
By adopting the technical scheme, the type of the photoinitiator is further optimized, and the photoinitiator is selected to enable the photocuring ink to have good curing speed and stable curing efficiency during curing, so that the leveling performance of the photocuring ink is further improved.
Preferably, the composite filler comprises a pigment filler, the pigment filler comprises a pigment base layer and a coating modification layer coated on the surface of the pigment base layer, and the coating modification layer is prepared by adopting the following scheme:
taking a silane coupling agent, a sodium silicate solution and absolute ethyl alcohol, stirring and mixing, and collecting to obtain a mixed solution;
adding the pigment and the filler into the mixed solution, stirring, mixing, performing ultrasonic dispersion, collecting dispersed slurry, filtering, and performing vacuum drying to obtain the coating modified layer.
By adopting the technical scheme, the surface of the pigment and filler is further coated and modified by organic silicon and inorganic silicon, and the organic silicon and the inorganic silicon are combined with each other and tightly and firmly cover the surfaces of the pigment fine particles to form an effective barrier, so that the agglomeration of the pigment and filler particles can be prevented. The inorganic coating layer in the coating structure can be mutually bonded with the surface of the pigment through attractive force adsorption or functional groups, and the organosilicon material has good compatibility with a dispersion medium. The interaction between the pigment and filler particles is reduced, and a stable pigment dispersion is formed, so that the dispersion uniformity of the pigment and filler among the photo-curing printing ink is improved, and the leveling property of the photo-curing printing ink is further improved.
In a second aspect, the present application provides a method for preparing a high leveling photo-curing UV ink, comprising the following preparation steps:
s1, pre-dispersion treatment: firstly, stirring and mixing the composite filler and the polyurethane resin, performing ultrasonic dispersion, and collecting to obtain a pre-dispersed material;
s2, secondary mixing: stirring and mixing the pre-dispersed material, the diluent and the modified auxiliary agent, and collecting to obtain mixed slurry;
s3, grinding treatment: and (3) placing the mixed slurry into a grinding device, grinding, dispersing and collecting to obtain the grinding slurry, and thus preparing the high-leveling photocuring UV ink.
By adopting the technical scheme, the preparation method of the high leveling property photocuring UV ink is optimized, and the multi-stage mixing treatment is adopted, so that the components are more sufficiently dispersed and mixed, and the finally prepared photocuring UV ink has good leveling property.
Preferably, the particle size of the grinding slurry in the step S3 is less than 5 μm.
By adopting the technical scheme, the particle size of the grinding slurry is optimized, the prepared light-cured UV ink forms a fine slurry structure, and the light-cured UV ink after being ground and sieved is relatively uniform in particle size and has good leveling performance.
In summary, the present application has the following beneficial effects:
firstly, the application optimizes the type of the flatting agent, adopts the fluorocarbon flatting agent to replace the traditional flatting agent material, and has very low surface energy because fluorine atoms contained in the fluorocarbon flatting agent have high electronegativity and low van der Waals radius. The fluorine-containing surfactant can remarkably reduce the surface tension of a solution system, has excellent wetting and spreading performance, is beneficial to eliminating defects of the printing ink in a drying film-forming process, and forms a flat, smooth and uniform coating film.
Meanwhile, compared with a small-molecular fluorine-containing surfactant, the fluorocarbon leveling agent has the characteristics of better film forming property, stability, smoothness, low foaming, good compatibility and the like, and has more advantages in the aspect of long-wave leveling, especially in the aspect of improving the final gloss of a coating film. The application has the advantages that through the introduction of a plurality of fluorocarbon chains, the fluorocarbon chains have low enough surface tension and high migration rate. Improves the compatibility with matrix resin and solves the contradiction between the leveling rate and the compatibility of the common fluorine-containing leveling agent. Meanwhile, the fluorocarbon leveling agent adopted by the photo-curing ink can further reduce the surface energy of the surface of the ink, so that the fingerprint resistance of the photo-curing ink is effectively improved.
Secondly, the components of the photoinitiator material are further optimized, and because the conventional micromolecule photoinitiator has high mobility and volatility, fragments generated after the micromolecule photoinitiator is cracked are easy to remain on the surfaces of the coating film and slowly migrate out of the coating film in the middle and later periods, and the compatibility of the photoinitiator material and a photocuring system is poor, the problem that the compatibility of the photoinitiator and a polymer matrix is poor is solved by the chitin nano whisker grafted photoinitiator, and the mechanical strength and the mechanical property of the photocuring ink material are further improved.
And thirdly, the surfaces of the pigment and the filler are subjected to surface coating modification of organic silicon and inorganic silicon, and the organic silicon and the inorganic silicon are combined with each other and tightly and firmly cover the surfaces of the pigment fine particles to form an effective barrier, so that the agglomeration of pigment and filler particles can be prevented. The inorganic coating layer in the coating structure can be mutually bonded with the surface of the pigment through attractive force adsorption or functional groups, and the organosilicon material has good compatibility with a dispersion medium. The interaction between the pigment and filler particles is reduced, and a stable pigment dispersion is formed, so that the dispersion uniformity of the pigment and filler among the photo-curing printing ink is improved, and the leveling property of the photo-curing printing ink is further improved.
Detailed Description
The present application will be described in further detail with reference to examples.
In the embodiments of the present application, the selected materials are as follows, but not limited to:
materials: photoinitiator 819, guangzhou guangdi electronics ltd;
a photoinitiator 907, guangzhou electronic materials ltd;
photoinitiator TPO, hubeijianzhu biomedical ltd;
an acrylate leveling agent OP-8035, Shanghai Kahn chemical Co., Ltd;
AKN-3600 fluorocarbon leveling agent, Qianzhi chemical Limited company;
s401, an organic silicon leveling agent, Scinula angustifolia New Material science and technology Co., Ltd;
large red pigment 254 PR254, deluxe gemini new materials ltd.
Preparation example
Preparation of leveling agent
Preparation example 1
A leveling agent 1: and AKN-3600 fluorocarbon leveling agent.
Preparation example 2
A leveling agent 2: and (3) stirring and mixing 1.8kg of fluorocarbon leveling agent AKN-3600, 2.5kg of S401 organic silicon leveling agent and 1kg of acrylate leveling agent OP-8035 to prepare the leveling agent 2.
Preparation example 3
A leveling agent 3: and 2.1kg of fluorocarbon leveling agent AKN-3600, 2.9kg of S401 organic silicon leveling agent and 1kg of acrylate leveling agent OP-8035 are stirred and mixed to prepare the leveling agent 3.
Preparation example 4
A leveling agent 4: 12.5kg of fluorocarbon leveling agent AKN-3600, 3.3kg of S401 organic silicon leveling agent and 1kg of acrylate leveling agent OP-8035 are stirred and mixed to prepare the leveling agent 4.
Preparation example 5
A photoinitiator 1: 100g of photoinitiator TPO and 100g of photoinitiator 907 were mixed with stirring to prepare photoinitiator 1.
Preparation example 6
A photoinitiator 2: 100g of photoinitiator 819 and 100g of photoinitiator 907 are stirred and mixed to prepare the photoinitiator 2.
Preparation example 7
A photoinitiator 3: 100g of photoinitiator TPO and 100g of photoinitiator 819 are stirred and mixed to prepare the photoinitiator 3.
Preparation example 8
A photoinitiator material 1: adding 1kg of chitin into 60kg of 1.5mol/L hydrochloric acid, stirring, mixing, heating and refluxing in an oil bath at 140 ℃, standing and cooling to room temperature, standing to obtain a supernatant, dialyzing until the pH of the solution in a dialysis bag is 7.0, taking a dialysate, placing the dialysate under 300W for ultrasonic dispersion, and carrying out vacuum freeze drying to obtain chitin nano whiskers;
dispersing 0.5kg of chitin nanowhiskers into 30kg of acetone, adding 10kg of isophorone diisocyanate and 60g of dibutyltin dilaurate, heating to react for 4h, adding 7.7kg of photoinitiator 1, keeping the temperature at 60 ℃ for reaction for 5h, washing and drying to obtain the chitin nanowhisker grafting photoinitiator 1.
Preparation example 9
A photoinitiator material 2: adding 1kg of chitin into 60kg of 1.5mol/L hydrochloric acid, stirring, mixing, heating and refluxing in an oil bath at 140 ℃, standing and cooling to room temperature, standing to obtain a supernatant, dialyzing until the pH of the solution in a dialysis bag is 7.0, taking a dialysate, placing the dialysate under 300W for ultrasonic dispersion, and carrying out vacuum freeze drying to obtain chitin nano whiskers;
dispersing 0.5kg of chitin nanowhiskers into 30kg of acetone, adding 10kg of isophorone diisocyanate and 60g of dibutyltin dilaurate, heating to react for 4h, adding 6.7kg of photoinitiator 1, keeping the temperature at 60 ℃ to react for 5h, washing and drying to prepare the chitin nanowhisker grafting photoinitiator 2.
Preparation example 10
A photoinitiator material 3: adding 1kg of chitin into 60kg of 1.5mol/L hydrochloric acid, stirring, mixing, heating and refluxing in an oil bath at 140 ℃, standing and cooling to room temperature, standing to obtain a supernatant, dialyzing until the pH of the solution in a dialysis bag is 7.0, taking a dialysate, placing the dialysate under 300W for ultrasonic dispersion, and carrying out vacuum freeze drying to obtain chitin nano whiskers;
dispersing 0.5kg of chitin nanowhiskers into 30kg of acetone, adding 10kg of isophorone diisocyanate and 60g of dibutyltin dilaurate, heating to react for 4h, adding 5.5kg of photoinitiator 1, keeping the temperature at 60 ℃ to react for 5h, washing and drying to obtain the chitin nanowhisker grafting photoinitiator 3.
Preparation example 11
A photoinitiator material 4: compared with preparation example 8, the photoinitiator material prepared in the preparation example uses the photoinitiator 2, and other preparation steps and preparation methods are the same as those of the preparation example 8.
Preparation example 12
A photoinitiator material 5: compared with preparation example 8, the photoinitiator material prepared in the preparation example uses the photoinitiator 3, and other preparation steps and preparation methods are the same as those of the preparation example 8.
Preparation example 13
A modification assistant 1: 0.5kg of photoinitiator material 1, 0.5kg of flatting agent 1 and 1kg of p-hydroxyanisole are taken to be stirred and mixed to prepare the modification auxiliary agent 1.
Preparation example 14
A modification assistant 2: 0.5kg of photoinitiator material 2, 0.5kg of flatting agent 1 and 1kg of p-hydroxyanisole are taken to be stirred and mixed to prepare the modification auxiliary agent 2.
Preparation example 15
A modification assistant 3: 0.5kg of photoinitiator material 3, 0.5kg of flatting agent 1 and 1kg of p-hydroxyanisole are taken to be stirred and mixed to prepare the modification auxiliary agent 3.
Preparation example 16
A modification assistant 4: 0.5kg of photoinitiator material 4, 0.5kg of flatting agent 1 and 1kg of p-hydroxyanisole are taken to be stirred and mixed to prepare the modification auxiliary agent 4.
Preparation example 17
A modification assistant 5: 0.5kg of photoinitiator material 5, 0.5kg of flatting agent 1 and 1kg of p-hydroxyanisole are taken to be stirred and mixed to prepare the modification auxiliary agent 5.
Preparation example 18
A modification assistant 6: 0.5kg of photoinitiator material 1, 0.5kg of flatting agent 2 and 1kg of p-hydroxyanisole are taken to be stirred and mixed to prepare the modification auxiliary agent 6.
Preparation example 19
A modification assistant 7: 0.5kg of photoinitiator material 1, 0.5kg of flatting agent 3 and 1kg of p-hydroxyanisole are taken to be stirred and mixed to prepare the modification auxiliary agent 7.
Preparation example 20
A modification assistant 8: 0.5kg of photoinitiator material 1, 0.5kg of flatting agent 4 and 1kg of p-hydroxyanisole are taken to be stirred and mixed to prepare the modification auxiliary agent 8.
Preparation example 21
A pigment and filler 1: taking 0.5kg of silane coupling agent, 10kg of sodium silicate solution with the mass fraction of 5% and 50kg of absolute ethyl alcohol, stirring and mixing, and collecting to obtain a mixed solution;
adding 5kg of pigment and filler into 50kg of mixed solution, stirring and mixing, placing under 200W for ultrasonic dispersion, collecting dispersed slurry, filtering, taking a filter cake, and drying in vacuum to obtain the pigment and filler 1.
Preparation example 22
A pigment and filler 2: taking 0.7kg of silane coupling agent, 15kg of sodium silicate solution with the mass fraction of 5% and 50kg of absolute ethyl alcohol, stirring and mixing, and collecting to obtain a mixed solution;
adding 5kg of pigment and filler into 50kg of mixed solution, stirring and mixing, placing under 200W for ultrasonic dispersion, collecting dispersed slurry, filtering, taking a filter cake, and drying in vacuum to obtain the pigment and filler 2.
Preparation example 23
A pigment and filler 3: 1kg of silane coupling agent, 20kg of sodium silicate solution with the mass fraction of 5% and 50kg of absolute ethyl alcohol are stirred and mixed, and mixed liquor is obtained;
adding 5kg of pigment and filler into 50kg of mixed solution, stirring and mixing, placing under 200W for ultrasonic dispersion, collecting dispersion slurry, filtering, taking a filter cake, and drying in vacuum to obtain the pigment and filler 3.
Examples
Example 1
A high leveling photo-curing UV printing ink: the polyurethane resin comprises 65kg of polyurethane resin, 20kg of diluent, 3kg of modification auxiliary agent 1 and 5kg of pigment and filler 1.
A preparation method of a high-leveling photocuring UV ink comprises the following steps:
s1, pre-dispersion treatment: firstly, stirring and mixing the pigment filler 1 serving as a composite filler with polyurethane resin, performing ultrasonic dispersion at 200W, and collecting to obtain a pre-dispersed material;
s2, secondary mixing: stirring and mixing the pre-dispersed material, the diluent and the modified auxiliary agent, and collecting to obtain mixed slurry;
s3, grinding treatment: and (3) placing the mixed slurry in a grinding device, grinding and dispersing the mixed slurry through a 5-micron screen, and collecting the grinding slurry to obtain the high-leveling photocuring UV ink.
Example 2
A high leveling photo-curing UV printing ink: comprises 70kg of polyurethane resin, 25kg of diluent, 4kg of modification auxiliary agent 1 and 6kg of pigment and filler 1.
A preparation method of high-leveling photo-curing UV ink comprises the following steps:
s1, pre-dispersion treatment: firstly, mixing the pigment filler 1 serving as a composite filler with polyurethane resin, stirring and mixing, performing ultrasonic dispersion at 200W, and collecting to obtain a pre-dispersion material;
s2, secondary mixing: stirring and mixing the pre-dispersed material, the diluent and the modified auxiliary agent, and collecting to obtain mixed slurry;
s3, grinding treatment: and (3) placing the mixed slurry in a grinding device, grinding and dispersing the mixed slurry through a 5-micron screen, and collecting the grinding slurry to obtain the high-leveling photocuring UV ink.
Example 3
A high leveling photo-curing UV printing ink: comprises 75kg of polyurethane resin, 30kg of diluent, 5kg of modification auxiliary agent 1 and 8kg of pigment and filler 1.
A preparation method of high-leveling photo-curing UV ink comprises the following steps:
s1, pre-dispersion treatment: firstly, mixing the pigment filler 1 serving as a composite filler with polyurethane resin, stirring and mixing, performing ultrasonic dispersion at 200W, and collecting to obtain a pre-dispersion material;
s2, secondary mixing: stirring and mixing the pre-dispersed material, the diluent and the modified additive, and collecting mixed slurry;
s3, grinding treatment: and (3) placing the mixed slurry in a grinding device, grinding and dispersing the mixed slurry through a 5-micron screen, and collecting the grinding slurry to obtain the high-leveling photocuring UV ink.
Examples 4 to 12 are high leveling photo-curable UV inks, which are different from example 1 in that the components in examples 4 to 12 are shown in table 1 below, and the rest of the preparation steps and preparation conditions are the same as those in example 1.
Table 1, examples 4 to 12, selection of the raw materials and their amounts (Kg)
Comparative example
Comparative example 1
A high leveling photo-curing UV ink is different from example 1 in that an equal-quality S401 organic silicon leveling agent is adopted in comparative example 1 to replace a fluorocarbon leveling agent AKN-3600.
Comparative example 2
A high leveling photo-curing UV ink is different from example 1 in that an equal-quality acrylate leveling agent OP-8035 is adopted in comparative example 2 to replace a fluorocarbon leveling agent AKN-3600.
Performance test
The leveling property of the high-leveling photocuring UV ink prepared in the examples 1-12 and the comparative examples 1-2 is tested according to a paint leveling property scratch test method of JB-T3998-; the test results are shown in table 2 below.
Curing the ink layer in a UV curing machine according to GB/T9286-1998 for 15s, and testing the adhesive force of the cured ink layer, wherein the detection effects are shown in the following table 2;
TABLE 2 Performance test Table
By combining the performance test tables of examples 1 to 12, comparative examples 1 to 2 and table 2, comparison can be found out that:
now, examples 1 to 3, examples 4 to 7, examples 8 to 10, examples 11 to 12 and comparative examples 1 to 2 are used as comparison groups, and the comparison is specifically as follows:
(1) firstly, the performance of the examples 1-3 is compared with that of the comparative examples 1-2, and as can be seen from the data in the table 2, the data of the examples 1-3 is obviously superior to that of the comparative examples 1-2, which shows that the technical scheme of the application optimizes the type of the leveling agent, and the fluorocarbon leveling agent is adopted to replace the traditional leveling agent material, and the fluorine atoms contained in the fluorocarbon leveling agent have high electronegativity and low van der Waals radius. The fluorine-containing compound has low surface energy, and the fluorine-containing surfactant can obviously reduce the surface tension of a solution system, has excellent wetting and spreading performance, is favorable for eliminating defects of the ink in a drying film-forming process, and forms a flat, smooth and uniform coating film. Improves the compatibility with matrix resin and solves the contradiction between the leveling rate and the compatibility of the common fluorine-containing leveling agent. Meanwhile, the fluorocarbon leveling agent adopted by the photo-curing ink can further reduce the surface energy of the surface of the ink, so that the fingerprint resistance of the photo-curing ink is effectively improved.
(2) Comparing examples 4-7 with example 1, the data of examples 4-7 is significantly higher than that of example 1, and since examples 4-7 optimize the composition of the photoinitiator, it is shown that chitin is selected as the raw material in the present application, and since the surface of chitin contains abundant hydroxyl groups, it can be chemically grafted and modified through chemical reaction. This application forms into the structure of nanowhisker through dialyzing it, can effectively fill to inside the polymer base member, as the inside connection structure of photocuring printing ink layer, improves the mechanical properties of photocuring printing ink, can not only effectively improve the high problem of volatility of photoinitiator material, still further improves its molecular structure through graft modification to the problem that chitin nanowhisker and macromolecular material base member compatibility are not good has been improved, thereby further improved the levelling performance of photocuring printing ink.
(3) Comparing examples 8-10 with example 1, the data of examples 8-10 is significantly higher than that of example 1, and since the types of the leveling agents are further optimized in examples 8-10, it is demonstrated that the composition of the leveling agent material is optimized, so that the film layer formed by curing the photo-curing ink has good structural performance and leveling performance.
(4) Comparing examples 11-12 with example 1, it can be found by combining the data in table 2 that the optimized pigment and filler composition adopted in the solutions of examples 11-12 indicates that the solution of the present application combines organosilicon and inorganic silicon by surface coating modification, and the two are tightly and firmly covered on the surface of the pigment fine particles to form an effective barrier, which can prevent the aggregation between the pigment and filler particles. The inorganic coating layer in the coating structure can be mutually bonded with the surface of the pigment through attractive force adsorption or functional groups, and the organosilicon material has good compatibility with a dispersion medium. The interaction between the pigment and filler particles is reduced, and a stable pigment dispersion is formed, so that the dispersion uniformity of the pigment and filler among the photo-curing printing ink is improved, and the leveling property of the photo-curing printing ink is further improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. The high-leveling photo-curing UV ink is characterized by comprising the following components in parts by weight:
65-75 parts of polyurethane resin;
20-30 parts of a diluent;
3-5 parts of a modification auxiliary agent;
5-8 parts of a composite filler;
the modifying auxiliary agent comprises a leveling agent, and the leveling agent comprises a fluorocarbon leveling agent.
2. The high leveling photocuring UV ink according to claim 1, wherein the leveling agent further comprises an acrylate leveling agent and an organosilicon leveling agent, and the mass ratio of the acrylate leveling agent to the organosilicon leveling agent to the fluorocarbon leveling agent is 1: 2.5-3.3: 1.8 to 2.5.
3. The high leveling photocuring UV ink as claimed in claim 1, wherein the modification auxiliary agent comprises a photoinitiator material, and the photoinitiator material is a chitin nanowhisker graft photoinitiator.
4. The high leveling photo-curing UV ink according to claim 3, wherein the chitin nanowhisker graft photoinitiator is prepared by the following scheme:
adding chitin into hydrochloric acid, stirring, mixing, heating in oil bath for refluxing, standing, cooling to room temperature, standing, collecting supernatant, dialyzing to pH 7.0, collecting dialysate, ultrasonically dispersing, vacuum freeze drying, and collecting chitin nanowhiskers;
dispersing chitin nanowhiskers into acetone, adding isophorone diisocyanate and dibutyltin dilaurate, heating to react for 4 hours, adding a photoinitiator, controlling the adding ratio of the photoinitiator to the isophorone diisocyanate to be 1: 1.3-1.8, keeping the temperature to react, washing and drying to obtain the chitin nanowhisker grafting photoinitiator.
5. The high leveling photo-curing UV ink according to claim 4, wherein the photo-initiator comprises at least two of photo-initiator TPO, photo-initiator 907 and photo-initiator 819.
6. The high leveling photo-curing UV ink as claimed in claim 1, wherein the composite filler comprises a pigment filler, the pigment filler comprises a pigment base layer and a coating modification layer coated on the surface of the pigment base layer, and the coating modification layer is prepared by adopting the following scheme:
taking a silane coupling agent, a sodium silicate solution and absolute ethyl alcohol, stirring and mixing, and collecting to obtain a mixed solution;
adding the pigment and the filler into the mixed solution, stirring, mixing, performing ultrasonic dispersion, collecting dispersed slurry, filtering, and performing vacuum drying to obtain the coating modified layer.
7. The preparation method of the photo-curing UV ink with high leveling property according to any one of claims 1 to 6, characterized by comprising the following preparation steps:
s1, pre-dispersion treatment: firstly, stirring and mixing the composite filler and the polyurethane resin, performing ultrasonic dispersion, and collecting to obtain a pre-dispersed material;
s2, secondary mixing: stirring and mixing the pre-dispersed material, the diluent and the modified auxiliary agent, and collecting to obtain mixed slurry;
s3, grinding treatment: and (3) placing the mixed slurry into a grinding device, grinding, dispersing and collecting to obtain the grinding slurry, and thus preparing the high-leveling photocuring UV ink.
8. The method for preparing high leveling photo-curing UV ink according to claim 7, wherein the particle size of the grinding slurry of step S3 is less than 5 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210051999.7A CN114479551A (en) | 2022-01-18 | 2022-01-18 | High-leveling photo-curing UV (ultraviolet) ink and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210051999.7A CN114479551A (en) | 2022-01-18 | 2022-01-18 | High-leveling photo-curing UV (ultraviolet) ink and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114479551A true CN114479551A (en) | 2022-05-13 |
Family
ID=81511895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210051999.7A Pending CN114479551A (en) | 2022-01-18 | 2022-01-18 | High-leveling photo-curing UV (ultraviolet) ink and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114479551A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749689A (en) * | 2016-11-14 | 2017-05-31 | 嘉宝莉化工集团股份有限公司 | Whisker modified difunctional light trigger of nano-cellulose and preparation method thereof |
| CN109762397A (en) * | 2019-01-21 | 2019-05-17 | 长沙新宇高分子科技有限公司 | A kind of UV Photocurable composition containing amino ketone photoinitiator |
| CN110643203A (en) * | 2019-10-15 | 2020-01-03 | 湖州师范学院 | Easily-dispersible iron oxide green pigment and preparation method thereof |
-
2022
- 2022-01-18 CN CN202210051999.7A patent/CN114479551A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749689A (en) * | 2016-11-14 | 2017-05-31 | 嘉宝莉化工集团股份有限公司 | Whisker modified difunctional light trigger of nano-cellulose and preparation method thereof |
| CN109762397A (en) * | 2019-01-21 | 2019-05-17 | 长沙新宇高分子科技有限公司 | A kind of UV Photocurable composition containing amino ketone photoinitiator |
| CN110643203A (en) * | 2019-10-15 | 2020-01-03 | 湖州师范学院 | Easily-dispersible iron oxide green pigment and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈思瑜等: "《聚氨酯/甲壳素纳米晶须复合材料的制备与表征》", 《合成技术及应用》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20210079193A1 (en) | Functionalized graphene oxide curable formulations | |
| CN110527404B (en) | Composite material modified wear-resistant anticorrosive paint and preparation method thereof | |
| CN110951385B (en) | Epoxy resin modified polyurethane waterproof coating and preparation method thereof | |
| CN110698971B (en) | Water-based UV (ultraviolet) dirt-resistant self-cleaning coating and preparation method and application thereof | |
| CN111440496B (en) | Water-based UV silver powder coating and preparation method and application thereof | |
| CN109517433B (en) | Recoatable high-coverage UV ink and preparation method and application thereof | |
| CN108276889B (en) | Single-component water-based black paint for automobiles and preparation method thereof | |
| CN111363405A (en) | Environment-friendly water-based printing ink and preparation method thereof | |
| CN114479551A (en) | High-leveling photo-curing UV (ultraviolet) ink and preparation method thereof | |
| CN112662247B (en) | High-toughness water-based acrylic coating and preparation method thereof | |
| CN112341923B (en) | Water-based color modifier and preparation method thereof | |
| CN116445035B (en) | Flexible plate water-based ink and preparation method thereof | |
| CN112795297A (en) | Double-component polyurethane finish varnish and preparation method thereof | |
| CN111978768A (en) | Preparation method of high-toughness UV finishing varnish | |
| CN112341886B (en) | Anti-sagging polyurethane modified asphalt waterproof bonding coating for side wall | |
| CN114752266A (en) | UV wood lacquer and preparation method thereof | |
| CN113801539A (en) | Preparation method of graphene epoxy resin coating | |
| CN113698734A (en) | Epoxy resin composite material and preparation method thereof | |
| CN113444416A (en) | Anti-static plate and preparation method thereof | |
| CN111718628A (en) | Water-based multicolor paint and preparation method thereof | |
| CN115011101B (en) | High-suspension-property double-component polyurethane slurry and preparation method thereof | |
| CN114369406B (en) | Graphene zinc powder anticorrosion primer for high-flash-point steel structure and preparation method thereof | |
| CN115926600B (en) | Water-based polyurethane coating and preparation method thereof | |
| CN116656173B (en) | High-wear-resistance quick-drying ink and preparation method thereof | |
| CN116239930A (en) | Epoxy resin paint and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220513 |