CN104371420B - A kind of water color ink and preparation method thereof and its application in PP decorating film - Google Patents
A kind of water color ink and preparation method thereof and its application in PP decorating film Download PDFInfo
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- CN104371420B CN104371420B CN201410608964.4A CN201410608964A CN104371420B CN 104371420 B CN104371420 B CN 104371420B CN 201410608964 A CN201410608964 A CN 201410608964A CN 104371420 B CN104371420 B CN 104371420B
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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
- C09D11/10—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
-
- 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
- B41M1/26—Printing on other surfaces than ordinary paper
- B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C5/00—Processes for producing special ornamental bodies
- B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
-
- 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
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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)
- Inorganic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Printing Methods (AREA)
Abstract
The invention discloses a kind of aqueous ink and preparation method thereof, this aqueous ink in the application of PP decorating film and the preparation method of its PP decorating film, the preparation method of this aqueous ink comprises the following steps that: a, preparation mill base；B, grinding；C, inking；Described PP decorating film is followed successively by PP substrate layer, aqueous ink printing layer, gloss oil coating layer from the bottom to top；Described preparation method comprises the following steps that: 1) PP film surface polarity processes；2) preparation of aqueous ink；3) aqueous ink printing；4) glazing coating；5) embossing.The present invention integrates, by selection and the process optimization of material, the printing effect making PP decorating film reach solvent type ink, printing is without water wave, and shallow-layer is clear, and texture is the most true to nature, there is nontoxic odorlessness, sun-proof, mar-proof, wear-resistant, the premium properties of disinfection simultaneously；The preparation method production process of the present invention is convenient and easy, and simple to operate, production cost is low, it is easier to industrialized production.
Description
Technical field
The present invention relates to a kind of decorating film, be specifically related to a kind of green environmental protection PP decorating film and preparation method thereof.
Background technology
Along with economic development, growth in the living standard, people are increasing, to quality of life to the demand of decoration household
And environment protection health focuses on day by day.The Wood-based Panel Furniture posting the exquisite pattern decorative film of printing is elegant in appearance, meets public aesthetic view,
Accept for increasing people.The decoration household industry decorating film used on the market at present, is adopted as base material with PVC (polrvinyl chloride)
Decorations layer is printed with solvent type ink.PVC film contains chlorine element, to light and thermally labile, can release venomous injurant during burning
Matter；The fusing point of the opposing party's surface and PVC is 70 DEG C, starts to soften when 40 DEG C, so oven temperature not can exceed that 50 during PVC film printing
DEG C, which limit the application in PVC film of the environment-friendly water-based ink, use the PVC facing film of solvent type ink printing to have solvent
Residual, product has abnormal flavour, endangers healthy.The PP decorating film traditional PVC decorative Film of replacement researching and developing a kind of environmental protection is to adapt to
Consumer demand, be decoration household industry value chain in the urgent need to, there is good economic benefit and social benefit.
Summary of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of green environmental protection PP decorating film and system thereof
Preparation Method, the present invention integrates, by selection and the process optimization of material, the printing effect making PP decorating film reach solvent type ink,
Printing is without water wave, and shallow-layer is clear, and texture is the most true to nature, has a nontoxic odorlessness simultaneously, sun-proof, mar-proof, wear-resistant, sterilize and kill
The premium properties of bacterium.
For solving the problems referred to above, the technical solution adopted in the present invention is as follows:
A kind of aqueous ink, it is prepared from by following raw material in parts by weight:
The preparation method of a kind of aqueous ink as above, it comprises the following steps that:
A, preparation mill base: weigh each component of formula as below amount, put in dispersion machine after mix homogeneously and disperse；
B, grinding: mixture step a obtained puts in the sand mill being filled with pure zirconia and grinds；
C, inking: the mixture obtained to step b adds the self-crosslinking styrene-acrylic emulsion of formula ratio, moistening flatting agent, froth breaking
Disperse after agent, polythene wax emulsion, transferring assistant, industrial alcohol and water mix homogeneously, adjust with non-ionic polyurethane thickening agent
Viscosity, adds PH regulator regulation pH value.
In the preparation method of above-mentioned a kind of aqueous ink, the rate of dispersion of step a is 1500r/min, and jitter time is 30
～50min；In step b, the grinding rate with 100kg/h grinds twice, until fineness≤5 μm of mixture；With 800 in step c
～after the Rate Dispersion 30min of 1000r/min, add PH regulator regulation pH value to 8.2～8.5.
Aqueous ink application in PP decorating film as above, PP decorating film is followed successively by PP substrate layer from the bottom to top, answers
With the printing layer of above-mentioned aqueous ink, gloss oil coating layer.
The preparation method of PP decorating film as above, it comprises the following steps:
1) PP film surface polarity processes: PP film surface uses high-voltage corona to process；
2) aqueous ink printing: three roller chromatographys, it is 16～22 seconds/painting to printing viscosity that aqueous ink mixed solvent is opened dilute
4 glasss 25 DEG C, use circulating pump inking；Being coated with scraper is ceramic blade, and scraper angle is 45 °；Dry by press oven；
3) glazing coating: being coated with gloss oil by the laser roller of 80 lines, coating speed is 60m/min；
4) embossing: embossing speed is 30m/min, and temperature is 180 DEG C.
Above-mentioned steps 2) in oven temperature scope be 90～120 DEG C；Described mixed solvent by water and ethanol with water: ethanol=
The proportions of 3:1 forms；Rubber roll pressure is 0.25～0.4MPa, and print speed printing speed is 80～120m/min.
Described dispersant is the organically-modified polyacrylate containing high pigment affinity groups；Described moistening flatting agent is
Acetylenic glycols Shuangzi based surfactants；Described defoamer is organic silicon modified by polyether oxygen alkanes；Described thickening agent be non-from
Sub-polyurethane thickener；Described PH regulator is AMP-95 multifunctional assistant.
Component and the proportioning of described gloss oil are as follows:
Described roller is electric carving intaglio plate, and its electric carving angle is 45 degree, netting twine density 60～100 lines/cm, and chromium plating is hard
Chromium, layers of chrome thickness is 10 μm, hardness 800～1000HV.
Compared to existing technology, the beneficial effects of the present invention is:
(1) printing is dried completely, and picture and text are clear, and dot reproduction is good, and adhesive force is strong；
(2) gloss oil adds kieselguhr, make PP decorating film have sterilizing ability；
(3) present invention integrates, by selection and the process optimization of material, the printing effect making PP decorating film reach solvent type ink
Really, printing is without water wave, and shallow-layer is clear, and texture is the most true to nature, has a nontoxic odorlessness simultaneously, sun-proof, mar-proof, wear-resistant, disappear
The premium properties of sterilization；
(4) the preparation method production process of the present invention is convenient and easy, and simple to operate, production cost is low, it is simple to industry metaplasia
Produce.
With detailed description of the invention, the present invention is described in further detail below in conjunction with the accompanying drawings.
Accompanying drawing explanation
Fig. 1 is the structure chart of a kind of green environmental protection PP decorating film of the present invention.
Wherein, 1, PP substrate layer；2, aqueous ink printing layer；3, gloss oil coating layer.
Detailed description of the invention
Specific embodiment 1～3:
A kind of aqueous ink, it is prepared from by following raw material in parts by weight:
The preparation method of the aqueous ink described in embodiment 1～3, concrete technology step is as follows:
A, preparation mill base: weigh each component of formula as below amount, put in dispersion machine after mix homogeneously and disperse；
B, grinding: mixture step a obtained puts in the sand mill being filled with pure zirconia and grinds；
C, inking: the mixture obtained to step b adds the self-crosslinking styrene-acrylic emulsion of formula ratio, moistening flatting agent, froth breaking
Disperse after agent, transferring assistant mix homogeneously, adjust viscosity with non-ionic polyurethane thickening agent, add PH regulator regulation pH value.
In above-mentioned steps, the rate of dispersion of step a is 1500r/min, and jitter time is 30～50min；In step b with
The grinding rate of 100kg/h grinds twice, until fineness≤5 μm of mixture；In step c with 800～1000r/min speed
After dispersion 30min, add PH regulator regulation pH value to 8.2～8.5.
Aqueous ink described in above example 1～3 is carried out performance test:
Detection method is as follows: viscosity: GB/T13217.4-91；Attachment fastness on PP film: GB/T131217.7-19.
Test result is as shown in table 1:
Table 1 aqueous ink the performance test results
| Detection project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Viscosity (s) | 32s | 30s | 31s |
| Attachment fastness (100%) on PP film | 99% | 100% | 99.5% |
Application Example 1:
A kind of PP decorating film is followed successively by PP substrate layer, the print having the aqueous ink described in above-described embodiment 1 to prepare from the bottom to top
Brush layer, gloss oil coating layer.
Described PP decorating film is prepared from by following steps:
1) PP film surface polarity processes: PP film surface uses high-voltage corona to process；
2) aqueous ink printing: 200 mesh negative+1 complexion versions, three roller chromatographys of+No. 2 complexion versions, aqueous ink mixing is molten
It is 22 seconds/painting 4 glasss 25 DEG C to printing viscosity that agent is opened dilute, uses circulating pump inking；Being coated with scraper is ceramic blade, and scraper angle is
45°；Dry by press oven；
3) glazing coating: being coated with gloss oil by the laser roller of 80 lines, coating speed is 60m/min；
4) embossing: embossing speed is 30m/min, and temperature is 180 DEG C.
In the preparation method of above-mentioned PP decorating film, the first oven temperature of printer is 105 DEG C, and the second oven temperature is
115 DEG C, the 3rd oven temperature is 90 DEG C；Described mixed solvent by water and ethanol with water: the proportions of ethanol=3:1 forms；
Rubber roll pressure is 0.3MPa, and print speed printing speed is 80m/min.
Described dispersant is745W；Described moistening flatting agent is Surfynol 104E；Described froth breaking
Agent is organic silicon modified by polyether oxygen alkanes；Described thickening agent is non-ionic polyurethane thickening agent；Described PH regulator is AMP-
95 multifunctional assistants.
Component and the proportioning of described gloss oil are as follows:
Described roller is electric carving intaglio plate, and its electric carving angle is 45 degree, and netting twine density is 80 lines/cm, and chromium plating is hard chrome, chromium
Layer thickness is 10 μm, hardness 800HV.
Application Example 2:
A kind of PP decorating film is followed successively by PP substrate layer, the print having the aqueous ink described in above-described embodiment 2 to prepare from the bottom to top
Brush layer, gloss oil coating layer.
Described PP decorating film is prepared from by following steps:
1) PP film surface polarity processes: PP film surface uses high-voltage corona to process；
2) aqueous ink printing: 200 mesh negative+1 complexion versions, three roller chromatographys of+No. 2 complexion versions, aqueous ink mixing is molten
It is 20 seconds/painting 4 glasss 25 DEG C to printing viscosity that agent is opened dilute, uses circulating pump inking；Being coated with scraper is ceramic blade, and scraper angle is
45°；Dry by press oven；
3) glazing coating: being coated with gloss oil by the laser roller of 80 lines, coating speed is 60m/min；
4) embossing: embossing speed is 30m/min, and temperature is 180 DEG C.
In the preparation method of above-mentioned PP decorating film, the first oven temperature of printer is 109 DEG C, and the second oven temperature is
115 DEG C, the 3rd oven temperature is 90 DEG C；Described mixed solvent by water and ethanol with water: the proportions of ethanol=3:1 forms；
Rubber roll pressure is 0.3MPa, and print speed printing speed is 90m/min.
Described dispersant is745W；Described moistening flatting agent is Surfynol 104E；Described disappears
Infusion is organic silicon modified by polyether oxygen alkanes；Described thickening agent is non-ionic polyurethane thickening agent；Described PH regulator is
AMP-95 multifunctional assistant.
Component and the proportioning of described gloss oil are as follows:
Described roller is electric carving intaglio plate, and its electric carving angle is 45 degree, and netting twine density is 80 lines/cm, and chromium plating is hard chrome, chromium
Layer thickness is 10 μm, hardness 900HV.
Application Example 3:
A kind of PP decorating film is followed successively by PP substrate layer, the print having the aqueous ink described in above-described embodiment 3 to prepare from the bottom to top
Brush layer, gloss oil coating layer.
Described PP decorating film is prepared from by following steps:
1) PP film surface polarity processes: PP film surface uses high-voltage corona to process；
2) aqueous ink printing: 200 mesh negative+1 complexion versions, three roller chromatographys of+No. 2 complexion versions, aqueous ink mixing is molten
It is 18 seconds/painting 4 glasss 25 DEG C to printing viscosity that agent is opened dilute, uses circulating pump inking；Being coated with scraper is ceramic blade, and scraper angle is
45°；Dry by press oven；
3) glazing coating: being coated with gloss oil by the laser roller of 80 lines, coating speed is 60m/min；
4) embossing: embossing speed is 30m/min, and temperature is 180 DEG C.
In the preparation method of above-mentioned PP decorating film, the first oven temperature of printer is 108 DEG C, and the second oven temperature is
116 DEG C, the 3rd oven temperature is 98 DEG C；Described mixed solvent by water and ethanol with water: the proportions of ethanol=3:1 forms；
Rubber roll pressure is 0.3MPa, and print speed printing speed is 100m/min.
Described dispersant is745W；Described moistening flatting agent is Surfynol 104E；Described froth breaking
Agent is organic silicon modified by polyether oxygen alkanes；Described thickening agent is non-ionic polyurethane thickening agent；Described PH regulator is AMP-
95 multifunctional assistants.
Component and the proportioning of described gloss oil are as follows:
Described roller is electric carving intaglio plate, and its electric carving angle is 45 degree, and netting twine density is 65 lines/cm, and chromium plating is hard chrome, chromium
Layer thickness is 10 μm, hardness 900HV.
PP decorating film described in use above embodiment 1～3 is carried out performance test:
Detection method is as follows: light fastness: GB/P250-208；Abrasivity: GB1768-79；Attachment fastness: GB/
T131217.7-19。
Test result is as shown in table 2:
Table 2PP decorating film the performance test results
| Detection project | Application Example 1 | Application Example 2 | Application Example 3 |
| Light fastness | 6.5 level | 6.5 level | 6.5 level |
| Abrasivity | 380r | 385r | 380r |
| Attachment fastness | 99% | 98% | 99% |
Above-mentioned embodiment is only the preferred embodiment of the present invention, it is impossible to limit the scope of protection of the invention with this,
The change of any unsubstantiality that those skilled in the art is done on the basis of the present invention and replacement belong to institute of the present invention
Claimed scope.
Claims (10)
1. an aqueous ink, it is characterised in that: described aqueous ink is prepared from by following raw material in parts by weight:
The preparation method of a kind of aqueous ink the most as claimed in claim 1, it is characterised in that: it comprises the following steps that:
A, preparation mill base: weigh each component of formula as below amount, put in dispersion machine after mix homogeneously and disperse；
B, grinding: mixture step a obtained puts in the sand mill being filled with pure zirconia and grinds；
C, inking: the mixture obtained to step b adds the self-crosslinking styrene-acrylic emulsion of formula ratio, moistening flatting agent, defoamer, gathers
Disperse after ethylene waxes emulsion, transferring assistant, industrial alcohol, water mix homogeneously, adjust viscosity with non-ionic polyurethane thickening agent, add
Enter pH adjusting agent regulation pH value.
Preparation method the most according to claim 2, it is characterised in that: the rate of dispersion in step a is 1500r/min, point
The scattered time is 30～50min；In step b, the grinding rate with 100kg/h grinds twice, until fineness≤5 μm of mixture；Step
In rapid c with the Rate Dispersion 30min of 800～1000r/min after, add pH adjusting agent regulation pH value to 8.2～8.5.
4. aqueous ink application in preparing PP decorating film as claimed in claim 1.
5. a PP decorating film, it is characterised in that: described PP decorating film is followed successively by PP substrate layer, from the bottom to top by claim 2
Printing layer prepared by the aqueous ink that the preparation method of described aqueous ink is obtained, gloss oil coating layer.
6. the preparation method of PP decorating film as claimed in claim 5, it is characterised in that: it comprises the following steps:
1) PP film surface polarity processes: PP film surface uses high-voltage corona to process；
2) aqueous ink printing: three roller chromatographys, it is 16～22 seconds/painting 4 glasss to printing viscosity that aqueous ink mixed solvent is opened dilute
25 DEG C, use circulating pump inking；Being coated with scraper is ceramic blade, and scraper angle is 45 °；Dry by press oven；
3) glazing coating: being coated with gloss oil by the laser roller of 80 lines, coating speed is 60m/min；
4) embossing: embossing speed is 30m/min, and temperature is 180 DEG C.
Preparation method the most according to claim 6, it is characterised in that: oven temperature scope is 90～120 DEG C；Described mixing
Solvent by water and ethanol with water: the proportions of ethanol=3:1 forms；The pressure of described three rollers is 0.25～0.4MPa,
Print speed printing speed is 80～120m/min.
Preparation method the most according to claim 6, it is characterised in that: described dispersant is containing high pigment affinity groups
Organically-modified polyacrylate；Described moistening flatting agent is acetylenic glycols Shuangzi based surfactants；Described defoamer is poly-
Ether modified organic silicon oxygen alkanes；Described pH adjusting agent is AMP-95 multifunctional assistant.
Preparation method the most according to claim 6, it is characterised in that: component and the proportioning of described gloss oil are as follows:
Preparation method the most according to claim 6, it is characterised in that: described three rollers are electric carving intaglio plate, its electric carving
Angle is 45 degree, netting twine density 60～100 lines/cm, and chromium plating is hard chrome, and layers of chrome thickness is 10 μm, hardness 800～1000HV.
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| CN201410608964.4A CN104371420B (en) | 2014-10-30 | 2014-10-30 | A kind of water color ink and preparation method thereof and its application in PP decorating film |
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|---|---|---|---|
| CN201410608964.4A CN104371420B (en) | 2014-10-30 | 2014-10-30 | A kind of water color ink and preparation method thereof and its application in PP decorating film |
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| CN104371420B true CN104371420B (en) | 2017-01-04 |
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| CN106700746A (en) * | 2015-11-17 | 2017-05-24 | 洋紫荆油墨（浙江）有限公司 | Water-based pre-printing varnish and preparation method thereof |
| CN105482548B (en) * | 2015-12-28 | 2019-01-04 | 广东天元汇邦新材料股份有限公司 | A kind of environment-friendly PVC decorating film and preparation method thereof |
| CN106956528A (en) * | 2017-03-30 | 2017-07-18 | 桶天下环保科技有限公司 | The gravure printing technique of water-based ink |
| CN107160696A (en) * | 2017-05-11 | 2017-09-15 | 安徽天安新材料有限公司 | Environmental-protection decorative film and preparation method thereof |
| CN107696654A (en) * | 2017-09-07 | 2018-02-16 | 佛山市联盛堂装饰材料有限公司 | A kind of environmentally friendly low smell solvent-borne type PVC decorative Film and its preparation technology |
| CN108623967A (en) * | 2018-05-25 | 2018-10-09 | 高阳 | A kind of preparation method of wax emulsion additive |
| CN109021690B (en) * | 2018-08-15 | 2021-08-06 | 北京裕金科技有限公司 | Graphene modified acrylic water-based ink and preparation method thereof |
| WO2020097817A1 (en) * | 2018-11-14 | 2020-05-22 | 广东天安新材料股份有限公司 | Decorative material and manufacturing method therefor |
| CN111301019A (en) * | 2018-12-11 | 2020-06-19 | 广东欧克水墨有限公司 | Environment-friendly ink-water color printing packaging film and manufacturing method thereof |
| CN114163957A (en) * | 2019-04-08 | 2022-03-11 | 浙江云峰莫干山地板有限公司 | Soybean formaldehyde-free glue |
| CN111688380A (en) * | 2020-06-16 | 2020-09-22 | 美盈森集团股份有限公司 | Printed matter glazing method |
| CN112391082B (en) * | 2020-11-16 | 2021-11-23 | 常州市天方印刷有限公司 | Waterborne polyurethane printing ink and printing process thereof |
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| CN102229764B (en) * | 2011-06-20 | 2013-08-21 | 袁建穗 | Ink for soft package intaglio printing and preparation method thereof |
| JP6083221B2 (en) * | 2012-02-06 | 2017-02-22 | セイコーエプソン株式会社 | Inkjet recording method |
| CN102604498B (en) * | 2012-02-29 | 2014-06-25 | 中山蓝海洋水性涂料有限公司 | High-pollution-resistant high weatherproof water-based external wall emulsion paint and preparation method thereof |
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Denomination of invention: A water-based ink, its preparation method and application in PP decorative film Effective date of registration: 20221215 Granted publication date: 20170104 Pledgee: Bank of China Limited by Share Ltd. Foshan branch Pledgor: FOSHAN NANHAI TIANYUAN MAOXIN NEW MATERIAL CO.,LTD. Registration number: Y2022980027497 |