CN112279989A - Alcohol-soluble polyurethane ink binder and preparation method thereof - Google Patents
Alcohol-soluble polyurethane ink binder and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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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
- C09D11/03—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
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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
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an alcohol-soluble polyurethane ink binder and a preparation method thereof, wherein the alcohol-soluble polyurethane ink binder comprises the following steps: adding polytetrahydrofuran ether glycol, isocyanate and stannous octoate into a reaction kettle, uniformly stirring, heating to 80-90 ℃, reacting for 2 hours, cooling to below 50 ℃, and adding an ester solvent for dilution to obtain a polyurethane prepolymer; and adding a micromolecular chain extender, an amine end-capping agent, an ester solvent and an isopropanol solvent into another reaction kettle, stirring uniformly, adding the polyurethane prepolymer, fully reacting for 1 hour, adding isocyanate, and continuously reacting for 1 hour to obtain the alcohol-soluble polyurethane ink binder. The invention is a single-component ink binder, has strong operability, simple preparation process and convenient use, and the solvent components in the binder mainly comprise alcohol solvents and can be used for preparing flexographic printing ink.
Description
Technical Field
The invention relates to the field of flexible package printing ink binder, in particular to an alcohol-soluble polyurethane ink binder and a preparation method thereof.
Background
The printing ink for plastic flexible package is used for printing on plastic film (such as PET, OPP, PE and other materials), and is widely applied to the packaging field of food, medicine, sanitary products and the like. At present, the printing ink for flexible package is mainly classified into solvent type ink and water-based ink according to different dispersion media. The water-based ink is printing ink taking water as a solvent, does not contain an organic solvent, has the advantages of small smell, high safety and the like, is environment-friendly ink, receives wide attention of people, is influenced by factors such as technology, cost, equipment and the like, and cannot be widely applied to the market.
The solvent-based ink has the advantages of high adhesion, good stability, easy drying, high temperature resistance, good printability and the like, and is widely applied to the field of flexible package printing. At present, the solvent-based inks commonly used in the market mainly include ester-soluble inks and alcohol-soluble inks. The domestic flexible package printing mode mainly adopts gravure printing, and the printing ink is required to have good drying speed, so that the ester-soluble printing ink occupies most markets of the flexible package printing ink in China. However, in recent years, with the progress of industrial technologies and the change of industrial packaging consciousness, the flexographic printing technology with lower printing cost and higher production efficiency is rapidly developed in China. The alcohol-soluble ink has the characteristics of moderate drying speed, high coloring power of the ink, no damage to a flexographic printing roller by a solvent and the like, and can be perfectly applied to flexographic printing equipment. Meanwhile, the alcohol solvent has lower smell and irritation than the ester solvent, so the alcohol-soluble ink is safer to use.
Because flexographic printing ink starts late in China, research on related ink vehicle technology is less. Polyurethane resin is used as a common ink binder resin and is widely applied to flexible package printing ink. The polyurethane is a high molecular resin which is composed of oligomer polyol as a soft segment and isocyanate and a micromolecule chain extender as a hard segment, and the polyurethane has good flexibility, adhesion fastness and alcohol solubility by adjusting the type of the polyol and the proportion of the soft segment and the soft segment. The Chinese patent application with publication number CN102746735A discloses an alcohol-soluble polyurethane ink binder, which does not contain unreacted isocyanate groups, has low toxicity and can be used in alcohol-soluble ink; however, the ink vehicle is divided into a component A and a component B, the proportion of the two components needs to be adjusted, and the use is troublesome.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an alcohol-soluble polyurethane ink binder and a preparation method thereof; the alcohol-soluble polyurethane ink binder is a single-component ink binder, has strong operability, simple preparation process and convenient use, and the solvent components in the alcohol-soluble polyurethane ink binder are mainly alcohol solvents and can be used for preparing flexographic printing ink.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an alcohol-soluble polyurethane ink binder comprises the following steps:
step A, adding 15-30 parts by weight of polytetrahydrofuran ether glycol, 5-15 parts by weight of isocyanate and 0.01-0.02 part by weight of stannous octoate into a reaction kettle, uniformly stirring, heating to 80-90 ℃, reacting for 2 hours, cooling to below 50 ℃, and adding 10-15 parts by weight of ester solvent for dilution to obtain a polyurethane prepolymer;
and step B, adding 1-4 parts by weight of a small molecular chain extender, 0.1-0.5 part by weight of an amine end-capping agent, 5-15 parts by weight of an ester solvent and 40-50 parts by weight of an isopropanol solvent into another reaction kettle, uniformly stirring, adding the polyurethane prepolymer obtained in the step A, fully reacting for 1 hour, adding 1-3 parts by weight of isocyanate, and continuously reacting for 1 hour to obtain the alcohol-soluble polyurethane ink binder.
Preferably, the molecular weight of the polytetrahydrofuran ether glycol is 1000-4000.
Preferably, the isocyanate is at least one of isophorone diisocyanate and 4, 4' -dicyclohexylmethane diisocyanate.
Preferably, the ester solvent is at least one of ethyl acetate, n-propyl acetate and n-butyl acetate.
Preferably, the small-molecule chain extender adopts at least one of hydroxyethyl ethylenediamine, ethylenediamine and isophorone diamine.
Preferably, the amine blocking agent is at least one of di-n-butylamine, ethanolamine and diethanolamine.
An alcohol soluble polyurethane ink binder is prepared by the preparation method of the alcohol soluble polyurethane ink binder.
According to the technical scheme provided by the invention, the preparation method of the alcohol-soluble polyurethane ink binder provided by the invention obtains a high-hardness polyurethane prepolymer by adjusting the proportion of polyether polyol and isocyanate, and simultaneously improves the carbamido content in resin by means of secondary chain extension, and the increase of polar groups such as carbamido is beneficial to improving the alcohol solubility of the resin, the dispersibility of the resin to pigment and the adhesive force to a plastic film. The alcohol-soluble polyurethane ink binder prepared by the invention has simple preparation process and convenient operation. The flexographic printing ink prepared from the alcohol-soluble polyurethane ink binder has the characteristics of strong ink tinting strength, high substrate adhesion, good ink drying performance and the like, can be applied to high-speed printing, and improves the production efficiency.
Detailed Description
The technical solutions in the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The alcohol-soluble polyurethane ink vehicle and the preparation method thereof provided by the invention are described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art.
A preparation method of an alcohol-soluble polyurethane ink binder comprises the following steps:
step A, adding 15-30 parts by weight of polytetrahydrofuran ether glycol, 5-15 parts by weight of isocyanate and 0.01-0.02 part by weight of stannous octoate into a reaction kettle, uniformly stirring, slowly heating to 80-90 ℃, reacting for 2 hours, cooling to below 50 ℃, and adding 10-15 parts by weight of ester solvent for dilution to obtain a polyurethane prepolymer;
and step B, adding 1-4 parts by weight of a small molecular chain extender, 0.1-0.5 part by weight of an amine end-capping agent, 5-15 parts by weight of an ester solvent and 40-50 parts by weight of an isopropanol solvent into another reaction kettle, stirring uniformly, slowly adding the polyurethane prepolymer in the step A, fully reacting for 1 hour, adding 1-3 parts by weight of isocyanate, and continuously reacting for 1 hour to obtain the alcohol-soluble polyurethane ink binder.
Specifically, the preparation method of the alcohol-soluble polyurethane ink binder comprises the following embodiments:
(1) the molecular weight of the polytetrahydrofuran ether glycol is 1000-4000.
(2) The isocyanate is at least one of isophorone diisocyanate and 4, 4' -dicyclohexylmethane diisocyanate.
(3) The ester solvent is at least one of ethyl acetate, n-propyl acetate and n-butyl acetate.
(4) The micromolecular chain extender adopts at least one of hydroxyethyl ethylenediamine, ethylenediamine and isophorone diamine.
(5) The amine blocking agent is at least one of di-n-butylamine, ethanolamine and diethanolamine.
Furthermore, the alcohol-soluble polyurethane ink binder prepared by the invention has good film forming property, good temperature resistance, excellent adhesion fastness to plastic films, and good alcohol solubility and pigment dispersibility. The alcohol-soluble polyurethane ink binder is used for preparing the polyurethane ink for flexographic printing, and can obviously improve the printability of the ink.
In conclusion, the embodiment of the invention is a single-component ink vehicle, the operability is strong, the preparation process is simple, the use is convenient, and the solvent component is mainly alcohol solvent, so that the vehicle can be used for preparing flexographic printing ink.
In order to more clearly show the technical solutions and the technical effects provided by the present invention, the alcohol-soluble polyurethane ink vehicle and the preparation method thereof provided by the embodiments of the present invention are described in detail with specific embodiments below.
Example 1
An alcohol-soluble polyurethane ink binder, the preparation method comprises the following steps:
step a1, adding 250kg of polytetrahydrofuran ether glycol with the molar molecular weight of 2000, 50kg of isophorone diisocyanate and 0.12kg of catalyst stannous octoate into a No. 1 reaction kettle, stirring uniformly, slowly heating to 90 ℃ for reaction for 2 hours, cooling to below 50 ℃, and adding 150kg of ethyl acetate for dilution to obtain the polyurethane prepolymer.
Step b1, adding 28kg of isophorone diamine, 3kg of diethanolamine, 76kg of ethyl acetate and 410kg of isopropanol solvent into a No. 2 reaction kettle, stirring uniformly, slowly adding the polyurethane prepolymer in the step a1, reacting for 1 hour sufficiently, adding 12kg of isophorone diisocyanate, and continuing to react for 1 hour to obtain the alcohol-soluble polyurethane ink binder.
Example 2
An alcohol-soluble polyurethane ink binder, the preparation method comprises the following steps:
step a2, putting 500kg of polytetrahydrofuran ether glycol with the molar molecular weight of 2000, 118kg of 4, 4' -dicyclohexylmethane diisocyanate and 0.24kg of stannous octoate serving as a catalyst into a reaction kettle No. 1, uniformly stirring, slowly heating to 80 ℃ for reaction for 2 hours, cooling to below 50 ℃, and adding 300kg of n-propyl acetate for dilution to obtain the polyurethane prepolymer.
Step b2, adding 30kg of isophorone diamine, 8kg of ethylenediamine, 8kg of diethanolamine, 152kg of n-propyl acetate and 820kg of isopropanol solvent into a No. 2 reaction kettle, stirring uniformly, slowly adding the polyurethane prepolymer in the step a2, reacting for 1 hour, adding 25kg of isophorone diisocyanate, and continuing to react for 1 hour to obtain the alcohol-soluble polyurethane ink binder.
Example 3
An alcohol-soluble polyurethane ink binder, the preparation method comprises the following steps:
step a3, adding 25kg of polytetrahydrofuran ether glycol with the molar molecular weight of 1000, 5kg of isophorone diisocyanate, 6kg of 4, 4' -dicyclohexylmethane diisocyanate and 0.12kg of catalyst stannous octoate into a No. 1 reaction kettle, stirring uniformly, slowly heating to 90 ℃ for reacting for 2 hours, cooling to below 50 ℃, and adding 15kg of n-butyl acetate for dilution to obtain the polyurethane prepolymer.
Step b3, adding 2kg of hydroxyethyl ethylene diamine, 0.4kg of ethylene diamine, 0.5kg of ethanolamine, 9kg of ethyl acetate and 48kg of isopropanol solvent into a No. 2 reaction kettle, stirring uniformly, slowly adding the polyurethane prepolymer in the step a3, reacting for 1 hour fully, adding 1.5kg of isophorone diisocyanate, and continuing to react for 1 hour to obtain the alcohol-soluble polyurethane ink binder.
In conclusion, the embodiment of the invention is a single-component ink vehicle, the operability is strong, the preparation process is simple, the use is convenient, and the solvent component is mainly alcohol solvent, so that the vehicle can be used for preparing flexographic printing ink.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are 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 (7)
1. The preparation method of the alcohol-soluble polyurethane ink binder is characterized by comprising the following steps of:
step A, adding 15-30 parts by weight of polytetrahydrofuran ether glycol, 5-15 parts by weight of isocyanate and 0.01-0.02 part by weight of stannous octoate into a reaction kettle, uniformly stirring, heating to 80-90 ℃, reacting for 2 hours, cooling to below 50 ℃, and adding 10-15 parts by weight of ester solvent for dilution to obtain a polyurethane prepolymer;
and step B, adding 1-4 parts by weight of a small molecular chain extender, 0.1-0.5 part by weight of an amine end-capping agent, 5-15 parts by weight of an ester solvent and 40-50 parts by weight of an isopropanol solvent into another reaction kettle, uniformly stirring, adding the polyurethane prepolymer obtained in the step A, fully reacting for 1 hour, adding 1-3 parts by weight of isocyanate, and continuously reacting for 1 hour to obtain the alcohol-soluble polyurethane ink binder.
2. The method of preparing an alcohol based polyurethane ink vehicle of claim 1, wherein the polytetrahydrofuran ether glycol has a molecular weight of 1000 to 4000.
3. The method for preparing alcohol-soluble polyurethane ink vehicle according to claim 1 or 2, wherein the isocyanate is at least one of isophorone diisocyanate and 4, 4' -dicyclohexylmethane diisocyanate.
4. The method of preparing an alcohol-soluble polyurethane ink vehicle of claim 1 or 2, wherein the ester solvent is at least one of ethyl acetate, n-propyl acetate, and n-butyl acetate.
5. The method for preparing the alcohol-soluble polyurethane ink vehicle according to claim 1 or 2, wherein the small molecular chain extender is at least one of hydroxyethyl ethylenediamine, ethylenediamine and isophorone diamine.
6. The method for preparing an alcohol-soluble polyurethane ink vehicle according to claim 1 or 2, wherein the amine-based capping agent is at least one of di-n-butylamine, ethanolamine, and diethanolamine.
7. An alcohol soluble polyurethane ink vehicle, characterized in that it is prepared by the method of any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011188531.XA CN112279989A (en) | 2020-10-30 | 2020-10-30 | Alcohol-soluble polyurethane ink binder and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011188531.XA CN112279989A (en) | 2020-10-30 | 2020-10-30 | Alcohol-soluble polyurethane ink binder and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403725A (en) * | 2022-08-15 | 2022-11-29 | 黄山中泽新材料有限公司 | Polyurethane binder for high-solid low-viscosity ink, and preparation method and device thereof |
| JP7411156B1 (en) | 2022-08-30 | 2024-01-11 | 東洋インキＳｃホールディングス株式会社 | Water-based flexo ink and printed matter |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403725A (en) * | 2022-08-15 | 2022-11-29 | 黄山中泽新材料有限公司 | Polyurethane binder for high-solid low-viscosity ink, and preparation method and device thereof |
| CN115403725B (en) * | 2022-08-15 | 2023-12-15 | 黄山中泽新材料有限公司 | Polyurethane binder for high-solid low-viscosity ink, and preparation method and device thereof |
| JP7411156B1 (en) | 2022-08-30 | 2024-01-11 | 東洋インキＳｃホールディングス株式会社 | Water-based flexo ink and printed matter |
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Application publication date: 20210129 |