CN116144215A - High-gloss bright silver ink with transfer paper imitation effect and preparation method and application thereof - Google Patents
High-gloss bright silver ink with transfer paper imitation effect and preparation method and application thereof Download PDFInfo
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- CN116144215A CN116144215A CN202310306631.5A CN202310306631A CN116144215A CN 116144215 A CN116144215 A CN 116144215A CN 202310306631 A CN202310306631 A CN 202310306631A CN 116144215 A CN116144215 A CN 116144215A
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- silver ink
- dispersion liquid
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- transfer paper
- aluminum pigment
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 90
- 239000004332 silver Substances 0.000 title claims abstract description 90
- 238000012546 transfer Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 230000000694 effects Effects 0.000 title claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 91
- 238000007639 printing Methods 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 23
- 239000000049 pigment Substances 0.000 claims description 70
- 239000007788 liquid Substances 0.000 claims description 68
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 62
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 56
- 239000000123 paper Substances 0.000 claims description 53
- 229910052782 aluminium Inorganic materials 0.000 claims description 43
- 239000011230 binding agent Substances 0.000 claims description 40
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 32
- 229920001220 nitrocellulos Polymers 0.000 claims description 30
- 239000000020 Nitrocellulose Substances 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 239000012046 mixed solvent Substances 0.000 claims description 24
- 239000004925 Acrylic resin Substances 0.000 claims description 23
- 229920000178 Acrylic resin Polymers 0.000 claims description 23
- -1 modified aluminum silver Chemical class 0.000 claims description 18
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 15
- 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 15
- 239000000463 material Substances 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 230000001588 bifunctional effect Effects 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000007646 gravure printing Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 230000003746 surface roughness Effects 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 10
- 229940090181 propyl acetate Drugs 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
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- 238000010407 vacuum cleaning Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-M 2-ethylhexanoate Chemical compound CCCCC(CC)C([O-])=O OBETXYAYXDNJHR-UHFFFAOYSA-M 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000007756 gravure coating Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000000976 ink Substances 0.000 description 68
- 239000010410 layer Substances 0.000 description 13
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- 239000003513 alkali Substances 0.000 description 2
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- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
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Images
Classifications
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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
- C09D11/14—Printing inks based on carbohydrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/10—Intaglio printing ; Gravure 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
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
-
- 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
- C09D11/106—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)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a high-brightness silver ink with a transfer paper imitation effect, a preparation method and application thereof. The high-gloss bright silver ink prepared by the method provided by the invention has good dispersion stability, leveling property and transfer property, and the preparation method is simple; the silver printing paper produced by the process provided by the invention has the characteristics of high gloss, strong brightness, good flatness, good printability and the like, and the apparent metallic gloss and brightness of the silver printing paper are similar to the effect of transferring paper.
Description
Technical Field
The invention relates to the technical field of printing materials, in particular to a high-gloss bright silver ink with a transfer paper imitation effect, and a preparation method and application thereof.
Background
The transfer paper has the characteristics of good glossiness, high smoothness, attractive appearance and the like, and is widely used for packaging exquisite products such as cigarettes and wines, electronic products, foods, cosmetics and the like. The transfer paper is produced by mostly adopting wet process compounding, namely vacuum aluminizing the surface of a substrate (PET or BOPP) coated with a release layer and an information layer, compounding the aluminized layer with base paper, drying to enable the aluminized layer to be tightly adhered with paper surface, and stripping the base film to realize the transfer of the highlight aluminum layer. The process is complicated, the required equipment is expensive, the cost is higher, the environment-friendly pressure is inevitably caused by the use of the film material and the adhesive for compounding, faults such as paper scratch, layout crack, indentation burst and the like are easy to occur on the surface of transfer paper, the quality control difficulty is higher, and the process quality of printing, post-printing and the like is influenced.
The printing process for preparing the high-brightness silver printing paper replaces transfer paper, so that the cost can be greatly reduced, the production period can be shortened, and the product quality can be improved. The reduction of transfer paper consumption also can reduce the use of transfer film and adhesive from the source. However, the silver printing paper in the present stage has far difference from the transfer paper in glossiness, brightness and flatness, and aluminum powder has large specific surface area, high surface energy and poor compatibility with organic resin, and the silver ink prepared by the silver printing paper is easy to agglomerate and has poor adhesive force in practical application. In addition, aluminum powder is poor in self-orientation, and sliding and rolling are easy to generate in the ink film drying process. The gravure ink is mainly formed by solvent volatilization, particle extrusion, permeation, film forming and drying, and internal stress generated in the extrusion process is extremely easy to cause disordered aluminum powder particle arrangement.
Disclosure of Invention
In view of the defects existing at present, the invention provides the highlight bright silver ink with the imitated transfer paper effect, and the preparation method and the application thereof; the silver printing paper produced by the process provided by the invention has the characteristics of high gloss, strong brightness, good flatness, good printability and the like, and the apparent metallic gloss and brightness of the silver printing paper are similar to the effect of transferring paper.
In order to achieve the above purpose, the invention provides a preparation method of high-gloss bright silver ink with a transfer paper imitation effect, which comprises the following steps:
s1: compounding propyl acetate, ethyl acetate and isopropanol to form a uniform mixed solvent; respectively dispersing nitrocellulose, acrylic resin and aluminum powder orientation agent in a certain amount of mixed solvent, and stirring and standing to form uniform and stable binder dispersion liquid A, binder dispersion liquid B and orientation dispersion liquid C;
s2: soaking the modified aluminum pigment in a mixed solvent for a certain time to obtain modified aluminum silver paste;
s3: dropwise adding the binder dispersion liquid A into the modified aluminum silver paste while stirring, continuing stirring for a certain time after the completion of the dropwise adding, dropwise adding the binder dispersion liquid B, and stirring for a certain time again after the completion of the dropwise adding to obtain a mixed system;
s4: sequentially adding the directional dispersion liquid C and the auxiliary agent into the mixed system, and stirring to obtain high-brightness silver ink;
the preparation method of the modified aluminum pigment comprises the following steps:
the preparation method comprises the steps of carrying out condensation reaction on aluminum pigment and bifunctional cage-type oligomeric silsesquioxane dispersion liquid, and carrying out vacuum suction filtration, cleaning and drying to obtain the bifunctional cage-type oligomeric silsesquioxane coated aluminum pigment; and sequentially adding isophorone diisocyanate and nitrocellulose dispersion liquid dropwise, grafting nitrocellulose on the surface of the difunctional cage-type oligomeric silsesquioxane coated aluminum pigment through gradual polymerization reaction, and obtaining the functionalized cage-type oligomeric silsesquioxane modified aluminum pigment after precipitation, centrifugation, cleaning and drying.
In accordance with one aspect of the present invention, in S1, the volume ratio of propyl acetate, ethyl acetate and isopropyl alcohol is 6:3:1, a step of; the mass ratio of the acrylic resin to the nitrocellulose is 3:1-5:1; the solid content of the binder dispersion liquid A, the binder dispersion liquid B and the directional dispersion liquid C is 20-40%.
According to one aspect of the invention, in S1, the stirring time is 30 to 60 minutes and the standing time is 30 to 60 minutes.
According to one aspect of the invention, in S2, the soaking time is 60 to 90 minutes.
According to one aspect of the invention, the S3 is specifically: dropwise adding the binder dispersion liquid A into the modified aluminum silver paste while stirring, continuing stirring for 30-60 min after the completion of dripping, dropwise adding the binder dispersion liquid B, and stirring for 60-120 min again after the completion of dripping to obtain a mixed system; in the step S4, the stirring time is 30-60 min, and the stirring speed is 800-1000 r/min.
In accordance with one aspect of the invention, in S4, the adjuvant comprises one or both of a leveling agent, an anti-settling agent.
According to one aspect of the invention, the preparation method of the modified aluminum pigment specifically comprises the following steps:
y1: vacuum filtering nanometer flake aluminum paste, soaking in solvent, stirring, standing, desolventizing and dispersing in alcohol ester solvent to obtain aluminum pigment dispersion; drying isophorone diisocyanate, difunctional cage-type oligomeric silsesquioxane, nitrocellulose and ethyl acetate for water removal;
y2: stirring the aluminum pigment dispersion under the protection of nitrogen, dropwise adding a catalyst and a bifunctional cage-type oligomeric silsesquioxane dispersion liquid, performing condensation reaction for 2-3 hours at the temperature of 40-50 ℃, and performing vacuum filtration, cleaning and drying to obtain the bifunctional cage-type oligomeric silsesquioxane coated aluminum pigment; the catalyst is triethylamine or ethylenediamine;
y3: dispersing the difunctional cage-type oligomeric silsesquioxane coated aluminum pigment in ethyl acetate, adding a catalyst and dropwise adding the iso-siliconeDispersion of isophorone diisocyanate at 45-55 ℃ and N 2 Reacting for 1.5-2.5 h under atmosphere; adding nitrocellulose dispersion drop by drop at 65-75 deg.C and N 2 Reacting for 1.5-2.5 h in the atmosphere, namely grafting nitrocellulose on the surface of the difunctional cage-type oligomeric silsesquioxane coated aluminum pigment; the catalyst is dibutyl tin dilaurate or stannous 2-ethyl caproate;
y4: and (3) precipitating, centrifuging, cleaning and drying the material obtained in the step (Y3) to obtain the functionalized cage-type oligomeric silsesquioxane modified aluminum pigment.
According to one aspect of the invention, the highlight silver ink comprises the following components in percentage by weight:
modified aluminum pigment: 5-15%; mixed solvent: 60-75%; binder resin: 10-20%; aluminum powder orientation agent: 0.05 to 5 percent; auxiliary agent: 0.01 to 1 percent;
wherein the binder resin comprises nitrocellulose and an acrylic resin.
Based on the same inventive concept, the invention also provides the transfer paper-imitated high-gloss silver ink prepared by the transfer paper-imitated high-gloss silver ink preparation method, wherein the viscosity of the high-gloss silver ink is 10-25 s/4# En cup; the solid content of the high-gloss bright silver ink is 15-35%.
Based on the same inventive concept, the invention also provides the high-gloss silver ink with the imitated transfer paper effect prepared by any one of the preparation methods or the application of the high-gloss silver ink on the printing transfer paper, wherein the application comprises the following steps:
step 1: gravure printing or coating a layer of acrylic resin dispersion liquid on the surface of a single-sided coated white cardboard, drying, and regulating the moisture content of the coated white cardboard to 4-6%, wherein the surface roughness is not higher than 0.95 mu m;
step 2: preparing high-brightness silver ink by adopting the preparation method of any one of claims 1-8;
step 3: printing a designed image and text on the surface of the coated white cardboard in the step 1 by using the high-brightness silver ink through a gravure printing process.
Wherein the depth of the mesh holes of the image-text part of the intaglio printing is 35-55 mu m.
The invention has the beneficial effects that:
according to the invention, the functionalized POSS modified aluminum pigment is added into an ink system, acrylic resin and nitrocellulose are used as connecting materials, an alcohol ester compound solvent is selected, the high-brightness silver ink is prepared through processes such as dispersion, stirring and the like, and the high-brightness silver printing paper is obtained by printing on the surface of white cardboard coated with the acrylic resin.
(1) The double-functional POSS hybridized modified flaky aluminum pigment is coated with an organic-inorganic hybridized nano film. The hybridized nano film is interwoven into a network structure in a three-dimensional space, so that the blocking effect of the coating layer on light is weakened, and the coated aluminum pigment keeps better metallic luster; silicon hydroxyl on the surface of POSS is bonded with aluminum hydroxyl on the surface of the flaky pigment to form Si-O-Al bond, so that a firm coating layer is formed on the surface of the aluminum pigment; the organic chain segment on the inert group can improve the compatibility of the hybrid film and a resin system in the printing ink, and improve the adhesive force of the printing ink. The grafting of NC in the functional POSS modified aluminum pigment can improve the directional arrangement of the aluminum pigment and improve the metallic luster.
(2) The POSS grafted modified NC containing amino also improves the heat resistance of NC and the compatibility with main resin. Because the compatibility of the functional POSS modified aluminum pigment and the nitrocotton resin is good, the modified aluminum pigment can be better coated by the main resin (acrylic resin) to form a stable dispersion system, and the soft and hard resin is compounded and used to have obvious significance for improving the corrosion resistance, metallic luster, printability and flexibility of the silver ink.
(3) The volatilization rate of the compound solvent is in gradient distribution, so that the surface dryness of silver ink can be improved, the surface dryness is moderate, the re-arrangement of aluminum powder can be inhibited, and the special anchoring effect of the aluminum powder directing agent on the surface of the modified aluminum pigment can be achieved, so that the aluminum powder is restrained from moving and rolling in a wet film, the aluminum powder is kept in a uniformly dispersed and parallel arrangement state, the uneven surface of silver printing paper, the collapse of the ink film and even the bloom are avoided, and the apparent metallic luster and brightness are influenced.
(4) The compatibility of the surface treatment layer of the single-sided coated white cardboard and the high-brightness silver ink film forming resin is good, and the appearance quality such as metallic luster and brightness of the silver printing paper is prevented from being influenced by harmful interlayer migration or reaction while the better inner layer adhesive force is ensured.
In conclusion, the high-gloss bright silver ink prepared by the method provided by the invention has good dispersion stability, leveling property and transfer property, and the preparation method is simple; the silver printing paper produced by the process provided by the invention has the characteristics of high gloss, strong brightness, good flatness, good printability and the like, and the apparent metallic gloss and brightness of the silver printing paper are similar to the effect of transferring paper.
Drawings
Fig. 1 is a process flow diagram of a preparation method and application of a high-gloss bright silver ink with a transfer paper imitation effect according to an embodiment of the invention.
Detailed Description
In order that the invention may be more readily understood, the invention will be further described with reference to the following examples. It should be understood that these examples are intended to illustrate the invention and not to limit the scope of the invention, and that the described embodiments are merely some, but not all, of the embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Unless defined otherwise, the terms of art used hereinafter are consistent with the meanings understood by those skilled in the art; unless otherwise indicated, all the materials and reagents referred to herein are commercially available or may be prepared by well-known methods.
It should be noted that the cage-type oligomeric silsesquioxane is abbreviated as POSS in the application; isophorone diisocyanate is abbreviated as IPDI in the application; the nitrocellulose of the present application is abbreviated as NC.
At present, the preparation process of transfer paper is complicated, required equipment is expensive, the cost is high, the use of a film material and a composite adhesive inevitably causes environmental protection pressure, faults such as paper scratch, layout cracks, indentation burst and the like are easy to occur on the surface of the transfer paper, the quality control difficulty is high, and the process quality of printing, post-printing and the like is influenced. The silver printing paper has far difference from the transfer paper in glossiness, brightness and flatness, and aluminum powder has large specific surface area, high surface energy and poor compatibility with organic resin, and the silver ink prepared by the silver printing paper is easy to agglomerate and has poor adhesive force in practical application. In addition, aluminum powder is poor in self-orientation, and sliding and rolling are easy to generate in the ink film drying process. The gravure ink is mainly formed by solvent volatilization, particle extrusion, permeation, film forming and drying, and internal stress generated in the extrusion process is extremely easy to cause disordered aluminum powder particle arrangement.
In order to solve the problems, the invention provides a preparation method and application of a high-gloss bright silver ink with a transfer paper imitation effect, wherein a process flow chart is shown in figure 1, and the preparation method comprises the following steps:
step 1: selection and treatment of printing materials. Gravure printing or coating a layer of acrylic resin dispersion liquid on the surface of a single-sided coated white cardboard, drying, and regulating the moisture content of the coated white cardboard to 4-6%, wherein the surface roughness is not higher than 0.95 mu m;
step 2: preparing the high-brightness silver ink.
S1: compounding propyl acetate, ethyl acetate and isopropanol to form a uniform mixed solvent; respectively dispersing nitrocellulose, acrylic resin and aluminum powder orientation agent in a certain amount of mixed solvent, and stirring and standing to form uniform and stable binder dispersion liquid A, binder dispersion liquid B and orientation dispersion liquid C;
s2: soaking the modified aluminum pigment in a mixed solvent for a certain time to obtain modified aluminum silver paste;
s3: dropwise adding the binder dispersion liquid A into the modified aluminum silver paste while stirring, continuing stirring for a certain time after the completion of the dropwise adding, dropwise adding the binder dispersion liquid B, and stirring for a certain time again after the completion of the dropwise adding to obtain a mixed system;
s4: sequentially adding the directional dispersion liquid C and the auxiliary agent into the mixed system, and stirring to obtain high-brightness silver ink;
the preparation method of the modified aluminum pigment comprises the following steps:
the preparation method comprises the steps of carrying out condensation reaction on aluminum pigment and bifunctional cage-type oligomeric silsesquioxane dispersion liquid, and carrying out vacuum suction filtration, cleaning and drying to obtain the bifunctional cage-type oligomeric silsesquioxane coated aluminum pigment; and sequentially adding isophorone diisocyanate and nitrocellulose dispersion liquid dropwise, grafting nitrocellulose on the surface of the difunctional cage-type oligomeric silsesquioxane coated aluminum pigment through gradual polymerization reaction, and obtaining the functionalized cage-type oligomeric silsesquioxane modified aluminum pigment after precipitation, centrifugation, cleaning and drying.
Preferably, in S1, the volume ratio of propyl acetate, ethyl acetate and isopropyl alcohol is 6:3:1, a step of; the mass ratio of the acrylic resin to the nitrocellulose is 3:1-5:1; the solid content of the binder dispersion liquid A, the binder dispersion liquid B and the directional dispersion liquid C is 20-40%.
Preferably, in S1, the stirring time is 30 to 60 minutes, and the standing time is 30 to 60 minutes.
Preferably, in S2, the soaking time is 60 to 90 minutes.
Preferably, the S3 specifically is: dropwise adding the binder dispersion liquid A into the modified aluminum silver paste while stirring, continuing stirring for 30-60 min after the completion of dripping, dropwise adding the binder dispersion liquid B, and stirring for 60-120 min again after the completion of dripping to obtain a mixed system; in the step S4, the stirring time is 30-60 min, and the stirring speed is 800-1000 r/min.
Preferably, in S4, the auxiliary agent includes one or both of a leveling agent and an anti-settling agent.
Preferably, the preparation method of the modified aluminum pigment specifically comprises the following steps:
y1: vacuum filtering nanometer flake aluminum paste, soaking in solvent, stirring, standing, desolventizing and dispersing in alcohol ester solvent to obtain aluminum pigment dispersion; drying isophorone diisocyanate, difunctional cage-type oligomeric silsesquioxane, nitrocellulose and ethyl acetate for water removal;
y2: stirring the aluminum pigment dispersion under the protection of nitrogen, dropwise adding a catalyst and a bifunctional cage-type oligomeric silsesquioxane dispersion liquid, performing condensation reaction for 2-3 hours at the temperature of 40-50 ℃, and performing vacuum filtration, cleaning and drying to obtain the bifunctional cage-type oligomeric silsesquioxane coated aluminum pigment; the catalyst is triethylamine or ethylenediamine;
y3: dispersing the difunctional cage-type oligomeric silsesquioxane coated aluminum pigment in ethyl acetate, adding a catalyst, dropwise adding isophorone diisocyanate dispersion liquid, and carrying out N at 45-55 DEG C 2 Reacting for 1.5-2.5 h under atmosphere; adding nitrocellulose dispersion drop by drop at 65-75 deg.C and N 2 Reacting for 1.5-2.5 h in the atmosphere, namely grafting nitrocellulose on the surface of the difunctional cage-type oligomeric silsesquioxane coated aluminum pigment; the catalyst is dibutyl tin dilaurate or stannous 2-ethyl caproate;
y4: and (3) precipitating, centrifuging, cleaning and drying the material obtained in the step (Y3) to obtain the functionalized cage-type oligomeric silsesquioxane modified aluminum pigment.
Preferably, the high-gloss bright silver ink comprises the following components in percentage by weight:
modified aluminum pigment: 5-15%; mixed solvent: 60-75%; binder resin: 10-20%; aluminum powder orientation agent: 0.05 to 5 percent; auxiliary agent: 0.01 to 1 percent;
wherein the binder resin comprises nitrocellulose and an acrylic resin.
Preferably, the viscosity of the high-gloss bright silver ink is 10-25 s/4# alpha-D enrobed cup; the solid content of the high-gloss bright silver ink is 15-35%.
Step 3: and (5) silver ink printing. And (3) printing the designed image and text on the surface of the coated white cardboard in the step (1) by adopting the high-brightness silver ink prepared in the step (2) through a gravure printing process.
Preferably, the depth of the mesh holes of the image-text part of the intaglio printing is 35-55 mu m.
Further details are provided below in connection with specific examples.
Example 1
A preparation method and application (printing transfer paper) of high-gloss bright silver ink with a transfer paper-like effect comprise the following steps:
step 1: selection and treatment of printing materials. And gravure printing a layer of acrylic resin dispersion liquid on the surface of the single-sided coated white cardboard, drying, and carrying out humidity conditioning treatment to ensure that the water content of the coated white cardboard is 5 percent and the surface roughness is 0.82 mu m.
Step 2: and (5) preparing high-brightness silver ink.
S1: compounding 75 parts of solvent (the volume ratio of propyl acetate to ethyl acetate to isopropyl alcohol is 6:3:1) to form a uniform mixed solvent; dispersing 2.5 parts of nitrocellulose, 12.5 parts of acrylic resin and 5 parts of aluminum powder orienting agent in a certain amount of mixed solvent, stirring at the speed of 800r/min for 60min, and standing for 30min to form a uniform and stable binder dispersion liquid A, a binder dispersion liquid B and an oriented dispersion liquid C with the solid content of 30 percent;
s2: immersing 5 parts of modified aluminum pigment in 28 parts of mixed solvent for 60min to obtain modified aluminum silver paste;
s3: dropwise adding the binder dispersion liquid A into the modified aluminum silver paste prepared in the step S2 while stirring (the speed is 800 r/min), continuously stirring for 60min after the completion of the dropwise adding, dropwise adding the binder dispersion liquid B, and stirring for 120min again at the speed of 800r/min after the completion of the dropwise adding;
s4: adding the directional dispersion liquid C and 0.01 part of auxiliary agents such as: leveling agent, anti-settling agent, etc.), stirring at 800r/min for 30min to obtain the high-brightness silver ink.
Step 3: and (5) silver ink printing. And (2) coating the white cardboard surface full-page printing in the step (S1) by adopting the high-brightness silver ink prepared in the step (2) through a gravure printing process. The depth of the net hole of the graph-text part of the gravure printing plate is 55 mu m.
The modified aluminum pigment is prepared by the following method:
y1: vacuum filtering 30 parts of nano lamellar aluminum paste (with the solid content of 10 percent), soaking in a solvent, stirring, standing, desolventizing, and dispersing in an alcohol ester solvent to obtain an aluminum pigment dispersion; drying and dewatering the raw materials such as IPDI, difunctional POSS, NC, ethyl acetate and the like;
y2: taking the raw materials in the step Y1, stirring the aluminum pigment dispersion under the protection of nitrogen, dropwise adding 0.01 part of catalyst triethylamine and bifunctional POSS dispersion liquid, performing condensation reaction for 2.5 hours at the temperature of 45 ℃, and performing vacuum filtration, cleaning and drying to obtain the bifunctional POSS coated aluminum pigment;
y3: dispersing 7 parts of the difunctional POSS-coated aluminum pigment from step Y2 in ethyl acetate, adding 0.02 part of dibutyltin dilaurate as catalyst and adding 1 part of IPDI dropwise in a dispersion at 50℃N 2 Reacting for 2h under atmosphere; adding 12 parts of NC dispersion liquid dropwise at 70deg.C under N 2 Reacting for 2h in atmosphere, namely grafting NC on the surface of the difunctional POSS coated aluminum pigment; the volume fraction of the ethyl acetate is 40%;
y4: and (3) precipitating, centrifuging, cleaning and drying the material obtained by the Y3 to obtain the functional POSS modified aluminum pigment.
Example 2
The preparation method application of the high-gloss bright silver ink (printing transfer paper) with the transfer paper-like effect is different from example 1 with reference to example 1 in that:
step 1: selection and treatment of printing materials. And (3) coating a layer of acrylic resin dispersion on the surface of the single-sided coated white cardboard, drying, and carrying out humidity conditioning treatment to ensure that the water content of the coated white cardboard is 6%, and the surface roughness is 0.89 mu m.
Step 2: and (5) preparing high-brightness silver ink.
S1: mixing 65 parts of mixed solvent (the volume ratio of propyl acetate, ethyl acetate and isopropanol is 6:3:1) to form a uniform mixed solvent; dispersing 5 parts of nitrocellulose, 15 parts of acrylic resin and 4 parts of aluminum powder orienting agent in a certain amount of mixed solvent, stirring at a speed of 1000r/min for 60min, and standing for 30min to form a uniform and stable binder dispersion liquid A, a binder dispersion liquid B and an oriented dispersion liquid C with the solid content of 35%;
s2: immersing 10 parts of modified aluminum pigment in 20 parts of mixed solvent for 90min to obtain modified aluminum silver paste;
s3: dropwise adding the binder dispersion liquid A into the modified aluminum silver paste prepared in the step S2 while stirring (the speed is 1000 r/min), continuously stirring for 60min after the completion of the dropwise adding, dropwise adding the binder dispersion liquid B, and stirring for 60min again at the speed of 800r/min after the completion of the dropwise adding;
s4: and (3) adding the directional dispersion liquid C and 1 part of auxiliary agent (such as leveling agent, anti-settling agent and the like) into the mixed system of the S3 in sequence, and stirring at the speed of 1000r/min for 120min to obtain the high-brightness silver ink.
The preparation method of the modified aluminum pigment described above is different from example 1 with reference to example 1 in that: in Y3, 2 parts of the dispersion of IPDI and 11 parts of the dispersion of NC were added dropwise.
Example 3
The difference between the transfer paper-imitated high-gloss silver ink and the preparation method and application (printing transfer paper) of the transfer paper-imitated high-gloss silver ink with reference to the embodiment 1 and the embodiment 1 is that:
step 1: selection and treatment of printing materials. And gravure printing a layer of acrylic resin dispersion on the surface of the single-sided coated white cardboard, drying, and regulating the moisture content of the coated white cardboard to be 4% and the surface roughness to be 0.84 mu m.
Step 2: and (5) preparing high-brightness silver ink.
S1: taking 70 parts of mixed solvent (the volume ratio of propyl acetate, ethyl acetate and isopropanol is 6:3:1) for compounding to form a uniform mixed solvent; 2 parts of nitrocellulose, 8 parts of acrylic resin and 0.05 part of aluminum powder orientation agent are respectively dispersed in a certain amount of mixed solvent, stirred at the speed of 800r/min for 60min and then kept stand for 30min, so as to form a connecting material dispersion liquid A, a connecting material dispersion liquid B and an orientation dispersion liquid C which are uniform and stable and have the solid content of 20%;
s2: 15 parts of modified aluminum pigment is soaked in 30 parts of mixed solvent for 90min to obtain modified aluminum silver paste;
s3: dropwise adding the binder dispersion liquid A into the modified aluminum silver paste prepared in the step S2 while stirring (the speed is 800 r/min), continuously stirring for 60min after the completion of the dropwise adding, dropwise adding the binder dispersion liquid B, and stirring for 120min again at the speed of 800r/min after the completion of the dropwise adding;
s4: and (3) adding the directional dispersion liquid C and 0.02 part of auxiliary agent (such as leveling agent, anti-settling agent and the like) into the mixed system of the S3 in sequence, and stirring at the speed of 800r/min for 30min to obtain the high-brightness silver ink.
The preparation method of the modified aluminum pigment described above is different from example 1 with reference to example 1 in that: in Y3, a dispersion of 0.5 part of IPDI and a dispersion of 11.5 parts of NC were added dropwise.
Comparative example 1
And gravure printing a layer of acrylic resin dispersion on the surface of the single-sided coated white cardboard, drying, and carrying out humidity-adjusting treatment to obtain the coated white cardboard with the water content of 4% and the surface roughness of 0.84 mu m. 50 parts of commercial aluminum silver paste (solid content=10%), 5 parts of NC resin, 15 parts of acrylic resin, 5 parts of aluminum powder directing agent, 25 parts of mixed solvent (the volume ratio of propyl acetate, ethyl acetate and isopropanol is 6:3:1) and 0.01 part of auxiliary agent (such as leveling agent and anti-settling agent) are mixed at room temperature and stirred uniformly to prepare silver ink, and the silver ink is subjected to full-page printing on the surface of the coated white cardboard through a gravure printing process.
Comparative example 2
The glossy silver ink in example 1 was taken and full-printed on the untreated white cardboard surface by the gravure printing process.
Performance detection and result analysis:
the functionalized POSS-modified aluminum pigments prepared in examples 1-3 were stored for 2 months at room temperature in an acid solution at ph=1 and an alkali solution at ph=11, respectively, without H 2 The apparent color of the aluminum pigment is not changed obviously, and the commercial aluminum pigment (such as the group ZC 905) has a large amount of H after being stored for 15 days at room temperature in an alkaline solution with pH=9 or 5 days at room temperature in an acid solution with pH=1 2 Generating and gradually changing the appearance color into off-white; under the observation of a microscope, the prepared aluminum pigment particles are provided with a layer of compact coating film on the surfaces, and further the functional POSS modified aluminum pigment for the high-brightness silver ink has the advantages of better acid and alkali resistance and better storage stability.
Comparative examples 1 and 2 were tested against the high-gloss silver inks and prints prepared in examples 1-3, respectively:
storage stability test: and (3) hermetically storing the silver ink for one month at normal temperature, and observing whether layering, agglomeration, sinking and the like are visible to naked eyes.
Gloss test: the gloss meter was used to measure at 20 ° incidence angle and the average was taken from three measurements. A black glass plate with a polished refractive index of 1.567 was used as a glossiness standard.
Brightness test: the brightness value of the ink film is tested by an integrating sphere spectrophotometer, namely, the recorded brightness value L under the specular reflection mode is recorded, and the average value is obtained by three times of measurement.
Attachment fastness test: the 3M adhesive tape is stuck on the ink film, the adhesive tape and the substrate are prevented from wrinkling by pressing with fingers or a rubber, then the adhesive tape is torn off at 180 degrees, the adhesion fastness is represented by the proportion of the ink falling area on the sample, and the average value is obtained by three measurements.
Roughness test: the surface roughness is measured by a printing surface roughness meter, i.e. the sample is clamped between the measuring head and the elastic pad and subjected to the same pressure as the nip pressure in actual printing, and the surface roughness is calculated from the average cube root of the air flow in the slit.
The above detection results are shown in table 1:
TABLE 1 different silver inks and their printing performance
It should be noted that the above silver transferring card paper, its process and performance are all common knowledge in the art, and are not described herein.
As can be seen from Table 1, the storage stability test results show that the highlight bright silver ink has no obvious change after being stored for one month, which indicates that the compatibility among the components of the ink system is good, and the stability of the silver ink is good; the adhesion fastness of the printing product prepared by the high-gloss silver ink and the printing process thereof can meet the printing requirement, the glossiness and the brightness of the printing product are respectively 90-100% and 96-100% of the transfer paper, and the glossiness and the brightness of the printing product are far higher than those of the printing product of commercial aluminum silver paste ink or other process printing products; in addition, the surface roughness of the printing product prepared by the high-gloss silver ink and the printing process thereof is close to that of transfer paper. To sum up, the following description is provided: the high-gloss silver ink and the printing process thereof can lead the printing product to obtain better ink transfer performance and flatness, and can better reproduce the brightness of the aluminum pigment.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the highlight bright silver ink with the transfer paper imitation effect is characterized by comprising the following steps of:
s1: compounding propyl acetate, ethyl acetate and isopropanol to form a uniform mixed solvent; respectively dispersing nitrocellulose, acrylic resin and aluminum powder orientation agent in a certain amount of mixed solvent, and stirring and standing to form uniform and stable binder dispersion liquid A, binder dispersion liquid B and orientation dispersion liquid C;
s2: soaking the modified aluminum pigment in a mixed solvent for a certain time to obtain modified aluminum silver paste;
s3: dropwise adding the binder dispersion liquid A into the modified aluminum silver paste while stirring, continuing stirring for a certain time after the completion of the dropwise adding, dropwise adding the binder dispersion liquid B, and stirring for a certain time again after the completion of the dropwise adding to obtain a mixed system;
s4: sequentially adding the directional dispersion liquid C and the auxiliary agent into the mixed system, and stirring to obtain high-brightness silver ink;
the preparation method of the modified aluminum pigment comprises the following steps:
the preparation method comprises the steps of carrying out condensation reaction on aluminum pigment and bifunctional cage-type oligomeric silsesquioxane dispersion liquid, and carrying out vacuum suction filtration, cleaning and drying to obtain the bifunctional cage-type oligomeric silsesquioxane coated aluminum pigment; and sequentially adding isophorone diisocyanate and nitrocellulose dispersion liquid dropwise, grafting nitrocellulose on the surface of the difunctional cage-type oligomeric silsesquioxane coated aluminum pigment through gradual polymerization reaction, and obtaining the functionalized cage-type oligomeric silsesquioxane modified aluminum pigment after precipitation, centrifugation, cleaning and drying.
2. The method for preparing the transfer paper effect imitated high gloss silver ink according to claim 1, wherein in S1, a volume ratio of propyl acetate, ethyl acetate and isopropyl alcohol is 6:3:1, a step of; the mass ratio of the acrylic resin to the nitrocellulose is 3:1-5:1; the solid content of the binder dispersion liquid A, the binder dispersion liquid B and the directional dispersion liquid C is 20-40%.
3. The method for producing a transfer paper effect imitated high gloss silver ink according to claim 1, wherein in S1, the stirring time is 30 to 60min, and the standing time is 30 to 60min.
4. The method for preparing a transfer paper effect imitated high gloss silver ink according to claim 1, wherein in S2, the soaking time is 60-90 min.
5. The method for preparing the transfer paper effect imitated high gloss silver ink according to claim 1, wherein the S3 specifically comprises: dropwise adding the binder dispersion liquid A into the modified aluminum silver paste while stirring, continuing stirring for 30-60 min after the completion of dripping, dropwise adding the binder dispersion liquid B, and stirring for 60-120 min again after the completion of dripping to obtain a mixed system; in the step S4, the stirring time is 30-60 min, and the stirring speed is 800-1000 r/min.
6. The method for preparing a transfer paper effect imitated high gloss silver ink according to claim 1, wherein in S4, the auxiliary agent comprises one or two of leveling agent and anti-settling agent.
7. The method for preparing the transfer paper effect imitated high gloss silver ink according to claim 1, wherein the method for preparing the modified aluminum pigment specifically comprises the following steps:
y1: vacuum filtering nanometer flake aluminum paste, soaking in solvent, stirring, standing, desolventizing and dispersing in alcohol ester solvent to obtain aluminum pigment dispersion; drying isophorone diisocyanate, difunctional cage-type oligomeric silsesquioxane, nitrocellulose and ethyl acetate for water removal;
y2: stirring the aluminum pigment dispersion under the protection of nitrogen, dropwise adding a catalyst and a bifunctional cage-type oligomeric silsesquioxane dispersion liquid, performing condensation reaction for 2-3 hours at the temperature of 40-50 ℃, and performing vacuum filtration, cleaning and drying to obtain the bifunctional cage-type oligomeric silsesquioxane coated aluminum pigment; the catalyst is triethylamine or ethylenediamine;
y3: dispersing the difunctional cage-type oligomeric silsesquioxane coated aluminum pigment in ethyl acetate, adding a catalyst, dropwise adding isophorone diisocyanate dispersion liquid, and carrying out N at 45-55 DEG C 2 Reacting for 1.5-2.5 h under atmosphere; adding nitrocellulose dispersion drop by drop at 65-75 deg.C and N 2 Reacting for 1.5-2.5 h in the atmosphere, namely grafting nitrocellulose on the surface of the difunctional cage-type oligomeric silsesquioxane coated aluminum pigment; the catalyst is dibutyl tin dilaurate or stannous 2-ethyl caproate;
y4: and (3) precipitating, centrifuging, cleaning and drying the material obtained in the step (Y3) to obtain the functionalized cage-type oligomeric silsesquioxane modified aluminum pigment.
8. The method for preparing the transfer paper-imitated high-gloss silver ink according to claim 1, wherein the high-gloss silver ink comprises the following components in percentage by weight:
modified aluminum pigment: 5-15%; mixed solvent: 60-75%; binder resin: 10-20%; aluminum powder orientation agent: 0.05 to 5 percent; auxiliary agent: 0.01 to 1 percent;
wherein the binder resin comprises nitrocellulose and an acrylic resin.
9. The transfer paper effect imitated high-brightness silver ink prepared by the transfer paper effect imitated high-brightness silver ink preparation method according to any one of claims 1-8, wherein the viscosity of the high-brightness silver ink is 10-25 s/4# enrobed cup; the solid content of the high-gloss bright silver ink is 15-35%.
10. Use of a transfer paper imitated effect highlight bright silver ink prepared by a preparation method according to any one of claims 1-8 or a transfer paper imitated effect highlight bright silver ink according to claim 9 for printing transfer paper, the use comprising the following steps:
step 1: gravure printing or coating a layer of acrylic resin dispersion liquid on the surface of a single-sided coated white cardboard, drying, and regulating the moisture content of the coated white cardboard to 4-6%, wherein the surface roughness is not higher than 0.95 mu m;
step 2: preparing high-brightness silver ink by adopting the preparation method of any one of claims 1-8;
step 3: printing a designed image and text on the surface of the coated white cardboard in the step 1 by using high-brightness silver ink through a gravure printing process;
wherein the depth of the mesh holes of the image-text part of the intaglio printing is 35-55 mu m.
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