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CN116622263A - Low-VOC high-stability environment-friendly engraving gravure ink and preparation method thereof - Google Patents

Low-VOC high-stability environment-friendly engraving gravure ink and preparation method thereof Download PDF

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Publication number
CN116622263A
CN116622263A CN202310578575.0A CN202310578575A CN116622263A CN 116622263 A CN116622263 A CN 116622263A CN 202310578575 A CN202310578575 A CN 202310578575A CN 116622263 A CN116622263 A CN 116622263A
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CN
China
Prior art keywords
ink
binder
alkyd resin
counterfeiting
pigment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310578575.0A
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Chinese (zh)
Inventor
滕尚君
孙明珠
孙军飞
杨惊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Banknote Ink Co ltd
China Banknote Printing and Minting Group Co Ltd
Original Assignee
China Banknote Ink Co ltd
China Banknote Printing and Minting Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Banknote Ink Co ltd, China Banknote Printing and Minting Group Co Ltd filed Critical China Banknote Ink Co ltd
Priority to CN202310578575.0A priority Critical patent/CN116622263A/en
Publication of CN116622263A publication Critical patent/CN116622263A/en
Pending legal-status Critical Current

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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
    • C09D11/104—Polyesters
    • C09D11/105—Alkyd resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/103—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds of aldehydes, e.g. phenol-formaldehyde resins
    • 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
    • C09D11/50—Sympathetic, colour changing or similar inks
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working

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

Abstract

The invention relates to the technical field of printing ink, in particular to low-VOC high-stability environment-friendly engraving gravure ink and a preparation method thereof. The raw materials of the engraving gravure printing ink comprise a binder, pigment, a metal anti-counterfeiting material, a filler, an auxiliary agent, a solvent and a drying agent. The VOC content of the ink is less than or equal to 6 percent, and the ink keeps bright and clean and does not get coarser in the constant temperature or variable temperature storage process which is obviously higher than the room temperature. Has better printing adaptability, physical and chemical resistance and binding fastness with a substrate. Meanwhile, the anti-counterfeiting ink with optical or magnetic anti-counterfeiting characteristics can be prepared by adding the metal anti-counterfeiting material according to the demands of customers, and the ink not only has low VOC (volatile organic compound) and high stability, but also has the following anti-counterfeiting characteristics: (1) engraving special anti-counterfeiting performance of gravure ink; (2) The optical/magnetic anti-counterfeiting feature can be used for printing paper money and enhancing the anti-counterfeiting function of the paper money.

Description

Low-VOC high-stability environment-friendly engraving gravure ink and preparation method thereof
Technical Field
The invention relates to the technical field of printing ink, in particular to low-VOC high-stability environment-friendly engraving gravure ink and a preparation method thereof.
Background
With the continuous enhancement of the environmental protection of the country, the environmental protection consciousness of the country is gradually improved. In recent years, related departments sequentially output standards and documents such as gravure ink and flexo ink which are technical requirements for environmental sign products, limit value of the content of Volatile Organic Compounds (VOCs) in the ink, and the like, clearly specify the type and the content of the VOCs in the ink, and put forward stricter requirements. Therefore, the improvement of the environmental protection performance of the ink, particularly the reduction of VOCs, is a necessary trend of development in terms of improving the competitiveness of the ink product, ensuring the long-term development of enterprises and fulfilling social responsibility of the enterprises.
The development of the banknote printing engraving gravure ink is to continuously improve the environmental protection performance and the printing adaptability. In the international range, regarding the aspect of engraving gravure ink by banknote printing, SICPA becomes a marker post type enterprise by virtue of yield and quality advantages, and group companies also introduce the engraving gravure ink technology, but VOCs of the engraving gravure ink are always higher, reaching 16-20%. According to the research of the method for detecting the content of Volatile Organic Compounds (VOCs) in the RMB, the research shows that two systems exist in the Chinese banknote printing gravure ink, and the VOCs are mainly distributed in the range of 9-15% and 11-15%. Although the overall VOCs are lower than the GB38507-2020 and SICPA company related products, there is still room for reduction. In addition, there is room for further improvement in the environmental protection or recyclability of the ink as a mixture of component materials, such as the use of an environmental protection type aqueous resin vehicle instead of a solvent type resin vehicle, the use of MDI (low toxicity) modified alkyd resin vehicle instead of TDI (highly toxic) modified alkyd resin vehicle, the use of renewable vegetable wax instead of mineral wax, the use of environmental protection type material instead of synthetic wax, the use of vegetable oil solvent instead of mineral oil solvent, the use of aqueous auxiliary agent, and the like. In the whole, the development and application of environment-friendly ink with low VOC, even zero VOC and the like are very necessary.
The banknote printing engraving gravure is large-area deep pattern, and the ink has special performance and generally has higher VOC. Low VOC engraved gravure inks generally require reduced binder molecular weight, reduced solvent usage, but tend to result in smearing, hardening, poor abrasion resistance, etc. of the print. To ensure the above properties, the ink needs to be increased in the amount of, for example, a wax auxiliary agent, but is liable to cause deterioration in stability. Therefore, it is critical to reduce the VOC of the ink while maintaining or even improving the printability, physical and chemical resistance and stability of the ink. In view of the development trend of the ink technology and the defects of the prior art, the invention aims to provide the low-VOC high-stability environment-friendly engraving gravure ink and the preparation method thereof, so that the requirements of banknote printing engraving gravure ink are met.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a low VOC high stability environment-friendly engraved gravure ink and a method for preparing the same, which are used for solving the problems in the prior art.
To achieve the above and other related objects, one aspect of the present invention provides an engraving gravure ink, which comprises the following raw materials in percentage by weight:
The sum of the percentages of the components is 100 percent.
The invention also provides a preparation method of the engraving gravure printing ink, which comprises the following steps:
1) Preparing Cheng Baiji from a binder, an auxiliary agent and a filler;
2) Rolling the binder, pigment and auxiliary agent into a chromophore;
3) Adding the white base in the step 1) into the chromophore for rolling, adding the solvent and the drying agent, and dispersing to obtain the engraving gravure printing ink.
In a further aspect the present invention provides the use of an engraved intaglio ink according to the present invention in the printing arts.
The engraving gravure printing ink provided by the invention has the following beneficial effects:
the invention provides the environment-friendly engraving gravure ink with low VOC and high stability, the VOC content of the ink is less than or equal to 6 percent, and the ink is kept bright and clean and does not get thicker in the constant temperature or variable temperature storage process which is obviously higher than the room temperature. Has better printing adaptability, physical and chemical resistance and binding fastness with a substrate. Meanwhile, the anti-counterfeiting ink with optical or magnetic anti-counterfeiting characteristics can be prepared by adding the metal anti-counterfeiting material according to the demands of customers, and the ink not only has low VOC (volatile organic compound) and high stability, but also has the following anti-counterfeiting characteristics: (1) engraving special anti-counterfeiting performance of gravure ink; (2) The optical/magnetic anti-counterfeiting feature can be used for printing paper money and enhancing the anti-counterfeiting function of the paper money.
Detailed Description
The following detailed description specifically discloses embodiments of an engraving gravure ink and a preparation method thereof.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
One aspect of the invention provides a low-VOC high-stability environment-friendly engraving gravure ink, which comprises raw materials including a binder, pigment, a metal anti-counterfeiting material, a filler, an auxiliary agent, a solvent, a drying agent and the like.
In the engraving gravure ink provided by the invention, the raw materials of the engraving gravure ink comprise the following components in percentage by weight:
the sum of the percentages of the components is 100 percent.
In the engraving gravure ink provided by the invention, the weight percentage of the raw materials can be 25-50%, 25-40%, 40-50%, 25-35%, 35-45%, 45-50%, 25-30%, 30-35%, 35-40%, 40-45%, 45-50% or the like according to the weight percentage of the engraving gravure ink.
In some embodiments, the binder is selected from one or more of a first binder, a second binder, a macromolecular phenolic binder, and the like.
Wherein the first binder is selected from one or two of MDI modified alkyd resin and IPDI modified alkyd resin. Wherein MDI is diphenylmethane diisocyanate. IPDI is isophorone diisocyanate.
The second binder is selected from one or two of water-based alkyd resin and epoxy modified alkyd resin.
In some embodiments of the present invention, the vehicle comprises the following components in weight percent, based on the total amount of engraved gravure ink:
0.1-20% of a first connecting material;
0.1-20% of a second binder;
0.1-15% of macromolecular phenolic resin.
The weight percentage of the first binder, based on the total amount of engraved gravure ink, is for exampleCan be 0.1-20%, 0.1-1%, 1-10%, 10-20%, 1-5%, 5-10%, 10-15%, 15-20%, etc. In specific embodiments, the MDI modified alkyd resin may have a number average molecular weight of, for example, 5000 to 100000, 5000 to 10000, 10000 to 50000, or 50000 to 100000, etc. The viscosity of the MDI modified alkyd resin is 0.1-5Pa.s at 40 DEG C -1 、0.1-1Pa.s -1 、1-3Pa.s -1 、3-5Pa.s -1 、0.1-0.5Pa.s -1 、0.5-1Pa.s -1 、1-2Pa.s -1 、2-3Pa.s -1 、3-4Pa.s -1 Or 4-5Pa.s -1 Etc.
The second binder may be, for example, 0.1 to 20%, 0.1 to 1%, 1 to 8%, 8 to 20%, 1 to 5%, 5 to 10%, 10 to 20%, etc., by weight based on the total amount of engraved gravure ink. In particular embodiments, the number average molecular weight of the second binder may be, for example, 1000-50000, 1000-10000, 1000-5000, 5000-10000, 1000-3000, 3000-5000, 5000-8000, 8000-10000, 10000-30000, 30000-50000, or the like. The second binder has a viscosity of 0.1 to 20Pa.s at 40deg.C -1 、0.1-5Pa.s -1 、0.1-1Pa.s -1 、1-3Pa.s -1 、3-5Pa.s -1 、5-10Pa.s -1 、10-15Pa.s -1 、15-20Pa.s -1 、0.1-0.5Pa.s -1 、0.5-1Pa.s -1 、1-2Pa.s -1 、2-3Pa.s -1 、3-4Pa.s -1 Or 4-5Pa.s -1 Etc.
The weight percentage of the macromolecular phenolic resin based on the total amount of the engraving gravure ink can be, for example, 0.1-15%, 0.1-1%, 1-8%, 8-15%, 1-5%, 5-10%, or 10-15%. In specific embodiments, the macromolecular phenolic resin has a number average molecular weight of 50000-500000, 5000-10000, 10000-50000, 50000-100000, 100000-300000, 300000-500000, or the like. The viscosity of the macromolecular phenolic resin is 6-12Pa.s at 40 DEG C -1 、6-8Pa.s -1 、8-10Pa.s -1 Or 10-12Pa.s -1 Etc. In a specific embodiment, the macromolecular phenolic resin is selected from vegetable oil modified macromolecular phenolic resins. Wherein the vegetable oil in the vegetable oil modified macromolecular phenolic resin can be selected from tall oil and tung treeOne or more of oil, catalpa oil, linseed oil, castor oil, coconut oil, etc.
In a specific embodiment, the binder comprises the following components in percentage by weight, based on the total amount of the engraving gravure ink:
wherein:
the MDI modified alkyd resin may be, for example, 0 to 20%, 0.1 to 20%, 0 to 1%, 1 to 10%, 10 to 20%, 1 to 5%, 5 to 10%, 10 to 15%, or 15 to 20% by weight based on the total amount of the engraved gravure ink. In specific embodiments, the MDI modified alkyd resin may have a number average molecular weight of, for example, 5000 to 100000, 5000 to 10000, 10000 to 50000, or 50000 to 100000, etc. The viscosity of the MDI modified alkyd resin is 0.1-5Pa.s at 40 DEG C -1 、0.1-1Pa.s -1 、1-3Pa.s -1 、3-5Pa.s -1 、0.1-0.5Pa.s -1 、0.5-1Pa.s -1 、1-2Pa.s -1 、2-3Pa.s -1 、3-4Pa.s -1 Or 4-5Pa.s -1 Etc.
The weight percentage of IPDI modified alkyd resin may be, for example, 0.1-20%, 0-1%, 1-10%, 10-20%, 1-5%, 5-10%, 10-15%, or 15-20% based on the total amount of engraved gravure ink. In specific embodiments, the number average molecular weight of the IPDI modified alkyd resin may be, for example, 5000-100000, 5000-10000, 10000-50000, or 50000-100000, etc. The viscosity of the IPDI modified alkyd resin is 0.1-5Pa.s at 40 DEG C -1 、0.1-1Pa.s -1 、1-3Pa.s -1 、3-5Pa.s -1 、0.1-0.5Pa.s -1 、0.5-1Pa.s -1 、1-2Pa.s -1 、2-3Pa.s -1 、3-4Pa.s -1 Or 4-5Pa.s -1 Etc.
Water based on the total amount of the engraving gravure inkThe weight percentage of the alkyd resin may be, for example, 0.1 to 20%, 0.1 to 1%, 1 to 8%, 8 to 20%, 1 to 5%, 5 to 10%, 10 to 20%, etc. In specific embodiments, the number average molecular weight of the aqueous alkyd resin may be, for example, 1000-10000, 1000-5000, 5000-10000, 1000-3000, 3000-5000, 5000-8000, 8000-10000, or the like. The viscosity of the aqueous alkyd resin is 0.1-5Pa.s at 40 DEG C -1 、0.1-1Pa.s -1 、1-3Pa.s -1 、3-5Pa.s -1 、0.1-0.5Pa.s -1 、0.5-1Pa.s -1 、1-2Pa.s -1 、2-3Pa.s -1 、3-4Pa.s -1 Or 4-5Pa.s -1 Etc.
The epoxy-modified alkyd resin may be, for example, 0-20%, 0-1%, 1-10%, 10-20%, 1-5%, 5-10%, 10-15%, or 15-20% by weight based on the total amount of engraved gravure ink. In specific embodiments, the epoxy-modified alkyd resin may have a number average molecular weight of, for example, 5000 to 50000, 5000 to 10000, 10000 to 30000, 30000 to 50000, or the like. The viscosity of the epoxy modified alkyd resin is 5-20Pa.s at 40 DEG C -1 、5-10Pa.s -1 、10-15Pa.s -1 Or 15-20Pa.s -1 Etc. In a specific embodiment, the alkyd resin in the epoxy modified alkyd resin is selected from vegetable oil fatty acid modified m-phenylene alkyd resin. The vegetable oil fatty acid in the vegetable oil fatty acid modified m-benzene alkyd resin is selected from C1-C30 unsaturated fatty acid. Preferably, the vegetable oil fatty acid may be selected from one or more of tall oil acid, tung oil acid, catalpa oil acid, linoleic acid, linseed oil acid, ricinoleic acid, tall oil acid, coconut oil fatty acid, oleic acid, palmitic acid, and the like.
In the engraving gravure ink provided by the invention, the weight percentage of the raw materials can be 0.1-30%, 5-30%, 0.1-1%, 1-30%, 1-5%, 5-10%, 10-15%, 15-20%, 20-25%, 25-30%, 1-15%, 15-30% or the like according to the weight percentage of the engraving gravure ink. The pigment may be, for example, one or more of a phthalocyanine blue pigment, a phthalocyanine green pigment, a permanent red pigment, a permanent yellow pigment, a permanent orange pigment, a permanent violet pigment, a pigment carbon black pigment, a titanium white pigment, an effect pigment, and the like.
In the engraving gravure ink provided by the invention, the weight percentage of the raw materials according to the weight percentage of the engraving gravure ink can be 0-35%, 0.1-35%, 0-1%, 1-35%, 1-5%, 5-10%, 10-15%, 15-20%, 20-25%, 25-30%, 30-35%, 1-15%, 15-35% or the like. In a specific embodiment, the metal anti-counterfeiting material can be one or a combination of two of infrared absorption and magnetic anti-counterfeiting materials.
In the engraving gravure ink provided by the invention, the raw materials can be 0-40%, 0.1-40%, 0-1%, 1-40%, 1-5%, 5-10%, 10-15%, 15-20%, 20-25%, 25-30%, 30-35%, 35-40%, 1-10%, 10-20%, 20-30%, 30-40%, 10-20%, or 20-40% by weight of the engraving gravure ink, and the weight percentage of the filling material can be 0-40%. In a specific embodiment, the filler may be one or more of heavy calcium carbonate, barium sulfate, kaolin, aluminum silicate, nano barium sulfate, nano calcium carbonate, and fumed silica, for example. The particle size of the heavy calcium carbonate, barium sulfate, kaolin, and aluminum silicate is generally 800 mesh or more, preferably 1250 mesh or more, more preferably 2500 mesh or more, depending on the fineness of the ink.
In the engraving gravure ink provided by the invention, the weight percentage of the raw materials and the weight percentage of the auxiliary agents can be 0.1-20%, 0.1-1%, 1-20%, 1-5%, 5-10%, 10-15%, 15-20%, 1-10%, 10-20% or the like according to the weight percentage of the engraving gravure ink.
In some embodiments, the adjuvant may be selected from one or more of surfactants, leveling agents, vegetable waxes, whiskers, microsphere powders, talc, bentonite;
Preferably, the auxiliary agent comprises the following components in percentage by weight based on the total amount of the engraving gravure ink:
wherein:
the weight percentage of the surfactant may be, for example, 0 to 10%, 0.1 to 10%, 0 to 1%, 1 to 5%, 5 to 10%, 1 to 3%, 3 to 5%, 5 to 8%, or 8 to 10% based on the total amount of the engraved gravure ink. In a specific embodiment, the surfactant may be one or more selected from sodium fatty alcohol polyoxyethylene ether sulfate, sodium secondary alkyl sulfonate, ammonium dodecylbenzene sulfonate, APG1214, APG0810, APG0814, AEC-9Na, dodecyl propyl phosphate betaine, lauramidopropyl hydroxysulfobetaine, cocamidopropyl hydroxysulfobetaine, imidazoline, cocamidopropyl hydroxysulfobetaine, sodium dodecylbenzene sulfonate, and the like.
The leveling agent may be, for example, 0.1 to 5%, 0.1 to 1%, 1 to 5%, 1 to 3%, 3 to 5%, 1 to 2%, 2 to 3%, 3 to 4%, or 4 to 5% by weight based on the total amount of the engraved gravure ink. In a specific embodiment, the leveling agent is one or more selected from organosilicon leveling agents and polyacrylate leveling agents, and belongs to novel environment-friendly materials. The leveling agent is a commercial product. The addition of a leveling agent, 1) abrasion resistance; 2) Hardening resistance; 3) Anti-blocking; 4) Drying is promoted.
The plant wax may be, for example, 0.1 to 10%, 0.1 to 1%, 1 to 5%, 5 to 10%, 1 to 3%, 3 to 5%, 5 to 8%, or 8 to 10% by weight based on the total amount of the engraved gravure ink. In specific embodiments, the vegetable wax is selected from one or more of carnauba vegetable wax, rice bran wax, sugar cane wax, candelilla wax, lacquer wax, wood wax, and the like. All belong to renewable resources.
In particular, the vegetable wax has 0 to 210mg KOH/g, preferably 0 to 120mg KOH/g, particularly preferably 0 to 100mg KOH/g, measured according to GB/T5530-2005 acid value and acidity of animal and vegetable fats and oils.
The vegetable wax has a melting point of 40-100deg.C, preferably 50-90deg.C, particularly preferably 60-90deg.C, according to GB/T2559-2005 montan wax measurement method.
The weight percentage of whiskers based on the total amount of engraved gravure ink may be, for example, 0.1-10%, 0.1-5%, 5-10%, 0.1-1%, 1-5%, 1-3%, 3-5%, 1-2%, 2-3%, 3-4%, or 4-5%. In a specific embodiment, the whisker is one or more selected from calcium carbonate whisker, calcium sulfate whisker, potassium titanate and the like, and belongs to novel environment-friendly materials. Whisker is a commercial product. Whisker addition 1) reduces risk, 2) improves stability; 3) Reducing the viscosity; 4) The additional solvent is used less.
The weight percentage of talcum powder can be, for example, 0-5%, 0.1-5%, 0-1%, 1-5%, 1-3%, 3-5%, 1-2%, 2-3%, 3-4%, or 4-5% based on the total amount of engraved gravure ink. The talcum powder is a commercial product.
The weight percentage of the microsphere powder can be, for example, 0-5%, 0.1-5%, 0-1%, 1-5%, 1-3%, 3-5%, 1-2%, 2-3%, 3-4%, or 4-5% based on the total amount of the engraving gravure ink. In a specific embodiment, the microsphere powder is selected from one or more of silica microspheres, PET microspheres, PS microspheres, PTFE microspheres, PMMA microspheres and the like. The microsphere powder is a commercial product.
The bentonite may be, for example, 0-3%, 0.1-3%, 0-1%, 1-3%, 1-2%, or 2-3% by weight based on the total amount of the engraving gravure ink. In a specific embodiment, the bentonite is organic bentonite. The bentonite is a commercial product, and can be selected from one or more of Hamming organic bentonite series, feng Hong organic bentonite series and the like.
In the engraving gravure ink provided by the invention, the weight percentage of the raw materials and the solvent can be 0-3%, 0-1%, 1-3%, 1-2%, 2-3% or the like according to the weight percentage of the engraving gravure ink. In specific embodiments, the solvent may be selected from one or more of an ester solvent, an ether solvent, a mineral oil solvent, and the like. Preferably, the ester solvent may be one or more of methyl esters, butyl acetate, ethyl acetate, and the like. The ether solvent can be one or more of diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether and the like. The mineral oil solvent may be one or more of normal alkane, isoalkane, cycloalkane, arene, etc. More preferably, diethylene glycol monoethyl ether and diethylene glycol diethyl ether in the ether solvent are selected.
In the engraving gravure ink provided by the invention, the weight percentage of the raw materials can be 0.1-4%, 1-3%, 1-2%, 2-3% or 3-4% of the drying agent according to the weight percentage of the engraving gravure ink. In a specific embodiment, the desiccant may be selected from one or more of cobalt zero VOC iso-octoate, manganese zero VOC iso-octoate, zirconium zero VOC iso-octoate, combinations thereof, non-cobalt iron-halogen azabicyclo macrocyclic iron complexes, manganese-halogen azabicyclo macrocyclic manganese complexes, combinations thereof, and the like.
The zero-VOC cobalt iso-octoate, zero-VOC manganese iso-octoate, zero-VOC zirconium iso-octoate composition is defined as a zero-VOC cobalt iso-octoate/manganese/zirconium composition.
The zero-VOC manganese iso-octoate, zero-VOC zirconium iso-octoate composition is defined as a zero-VOC manganese iso-octoate/zirconium composition.
In another aspect, the present invention provides a method for preparing the engraving gravure ink, the method comprising the steps of:
1) Preparing Cheng Baiji from a binder, an auxiliary agent and a filler;
2) Rolling the binder, pigment and auxiliary agent into a chromophore;
3) Adding the white base in the step 1) into the chromophore, or adding the white base and the anti-counterfeiting ink into the chromophore for rolling, adding a solvent and a drying agent, and dispersing to obtain the engraving gravure ink.
In the preparation method of the engraving gravure printing ink provided by the invention, step 1) is to prepare Cheng Baiji from one or more of a first binder, a second binder, a surfactant, vegetable wax, whiskers and a filler. The first binder may be, for example, 0-10%, 0.1-10%, 0-1%, 1-5%, or 5-10% by weight, etc. The weight percentage of the second binder is 0.1-20%, 0.1-1%, 1-8%, 8-20%, 1-5%, 5-10%, or 10-20%. And satisfies a total weight percentage of binder (alkyd resin) of 10-25%.
In a particular embodiment of the white base, the aqueous alkyd may be 0.1-20%, 0.1-1%, 1-8%, 8-20%, 1-5%, 5-10%, 10-20%, etc. The weight percentage of the epoxy modified alkyd resin is 0-20%, 0.1-1%, 1-8%, 8-20%, 1-5%, 5-10%, or 10-20%. The weight percentage of the MDI modified alkyd resin is 0-10%, 0.1-10%, 0-1%, 1-5%, or 5-10%. The weight percentage of the IPDI modified alkyd resin is 0-10%, 0.1-10%, 0-1%, 1-5%, or 5-10%. And satisfies a total weight percentage of binder (alkyd resin) of 10-25%.
In another embodiment of the white base, the white base may further include a macromolecular phenolic resin, where the weight percentage of the macromolecular phenolic resin may be, for example, 0.1-15%, 0.1-1%, 1-8%, 8-15%, 1-5%, 5-10%, 10-15%, etc. The weight percentage of the aqueous alkyd resin can be 0.1-20%, 0.1-1%, 1-8%, 8-20%, 1-5%, 5-10%, 10-20%, etc. The weight percentage of the epoxy modified alkyd resin is 0-20%, 0.1-1%, 1-8%, 8-20%, 1-5%, 5-10%, or 10-20%. The weight percentage of the MDI modified alkyd resin is 0-10%, 0.1-10%, 0-1%, 1-5%, or 5-10%. The weight percentage of the IPDI modified alkyd resin is 0-10%, 0.1-10%, 0-1%, 1-5%, or 5-10%. And satisfies a total weight percentage of binder (alkyd resin) of 10-25%.
In the preparation method of the engraving gravure printing ink provided by the invention, step 2) is to roll a first binder, macromolecular phenolic resin, pigment and an auxiliary agent into a chromophore. Wherein the weight percentage of the macromolecular phenolic resin can be, for example, 0.1-15%, 0.1-1%, 1-8%, 8-15%, 1-5%, 5-10%, 10-15%, etc. The weight percentage of the first connecting material is 0.1-15%, 0.1-1%, 1-8%, 8-15%, 1-5%, 5-10%, or 10-15% and so on. And the total weight percentage of the binder is 5-25%.
In a specific embodiment of the chromophore, one or more of macromolecular phenolic resin, MDI modified alkyd resin, IPDI modified alkyd resin, pigment and auxiliary agent are rolled into the chromophore. Wherein the weight percent of the macromolecular phenolic resin can be 0.1-15%, 0.1-1%, 1-8%, 8-15%, 1-5%, 5-10%, 10-15% or the like, the weight percent of the MDI modified alkyd resin can be 0-15%, 0.1-1%, 1-8%, 8-15%, 1-5%, 5-10%, or 10-15% or the like, the weight percent of the IPDI modified alkyd resin can be 0.1-15%, 0.1-1%, 1-8%, 8-15%, 1-5%, 5-10%, or 10-15% or the like, and the total weight percent of the binder is 5-25%.
In another embodiment of the chromophore, a second binder may also be included in the chromophore. The weight percentage of the second binder is 0.1-20%, 0.1-1%, 1-8%, 8-20%, 1-5%, 5-10%, or 10-20%. Specifically, the weight percentage of the aqueous alkyd resin can be 0.1-20%, 0.1-1%, 1-8%, 8-20%, 1-5%, 5-10%, 10-20%, etc. The weight percentage of the epoxy modified alkyd resin is 0-20%, 0.1-1%, 1-8%, 8-20%, 1-5%, 5-10%, or 10-20%. The weight percent of the macromolecular phenolic resin can be 0.1-15%, 0.1-1%, 1-8%, 8-15%, 1-5%, 5-10%, or 10-15%, etc., the weight percent of the MDI modified alkyd resin can be 0-15%, 0.1-1%, 1-8%, 8-15%, 1-5%, 5-10%, or 10-15%, etc., the weight percent of the IPDI modified alkyd resin can be 0.1-15%, 0.1-1%, 1-8%, 8-15%, 1-5%, 5-10%, or 10-15%, etc., and the total weight percent of the binder is 5-25%.
In the preparation method of the engraving gravure printing ink provided by the invention, step 3) is to roll white base by adding the white base into the chromophore according to the proportion, wherein the proportion of the white base to the chromophore is, for example, 50-65: 35 to 45. Then adding solvent and drying agent, stirring at high speed, dispersing, and obtaining the ink product.
The preparation method of the engraving gravure printing ink provided by the invention further comprises the step of rolling the first connecting material, the second connecting material, the vegetable wax and the metal anti-counterfeiting material into anti-counterfeiting base ink; adding white base and anti-counterfeiting base ink into a chromophore for rolling, adding a solvent and a drying agent, and dispersing to obtain the engraving gravure printing ink. Wherein, the weight percentage of the first binder can be 0-10%, 0.1-10%, 0-1%, 1-5%, or 5-10%, etc.; the weight percent of the second binder may be 0.1-20%, 0.1-1%, 1-8%, 8-20%, 1-5%, 5-10%, or 10-20%, etc., and the total weight percent of the binder (alkyd) is 10-25%.
In one embodiment of the anti-counterfeiting base ink, one or more of water-based alkyd resin, epoxy modified alkyd resin, MDI modified alkyd resin and IPDI modified alkyd resin, a surfactant and a metal anti-counterfeiting material are rolled into the anti-counterfeiting base ink. Wherein the weight percentage of the aqueous alkyd resin is 0.1-20%, 0.1-1%, 1-8%, 8-20%, 1-5%, 5-10%, or 10-20%. The weight percentage of the epoxy modified alkyd resin is 0-20%, 0.1-1%, 1-8%, 8-20%, 1-5%, 5-10%, or 10-20%. The weight percentage of the MDI modified alkyd resin is 0-10%, 0.1-10%, 0-1%, 1-5%, or 5-10%. The weight percentage of the IPDI modified alkyd resin is 0.1-10%, 0-1%, 1-5%, or 5-10%, etc., and the total weight percentage of the binder (alkyd resin) is 10-25%.
In another embodiment of the anti-counterfeiting base ink, the anti-counterfeiting base ink can further comprise macromolecular phenolic resin, wherein the weight percentage of the macromolecular phenolic resin can be 0.1-15%, 0.1-1%, 1-8%, 8-15%, 1-5%, 5-10%, 10-15% or the like. The weight percentage of the aqueous alkyd resin can be 0.1-20%, 0.1-1%, 1-8%, 8-20%, 1-5%, 5-10%, 10-20%, etc. The weight percentage of the epoxy modified alkyd resin is 0-20%, 0.1-1%, 1-8%, 8-20%, 1-5%, 5-10%, or 10-20%. The weight percentage of the MDI modified alkyd resin is 0-10%, 0.1-10%, 0-1%, 1-5%, or 5-10%. The weight percentage of the IPDI modified alkyd resin is 0-10%, 0.1-10%, 0-1%, 1-5%, or 5-10%. And satisfies a total weight percentage of binder (alkyd resin) of 10-25%.
In the specific embodiment of the invention, white base and anti-counterfeiting base ink are added into the chromophore according to the proportion, and the proportion of the white base, the anti-counterfeiting base ink and the chromophore is, for example, 0.1-10: 0.1 to 55: 35-45, adding solvent and drying agent, and stirring and dispersing at high speed to obtain the anti-counterfeiting ink product.
The viscosity of the engraving gravure ink obtained by the invention has a test value of (0.1-30) Pa.s, (0.1-10) Pa.s, (10-20) Pa.s, or (20-30) Pa.s at 40 ℃. Specifically, the viscosity is (0.1-30) Pa.s (40 ℃,1000 s) -1 ). In specific embodiments, the viscosity of the ink product or anti-counterfeit ink product is the same as described above.
In another aspect the invention provides the use of the engraved intaglio ink in printing. In particular, the low-VOC high-stability environment-friendly engraving gravure ink can be used for printing.
The engraving gravure printing ink provided by the invention has the following beneficial effects:
an environment-friendly engraving gravure ink with low VOC and high stability. The ink binder system consists of an IPDI (low toxicity) or MDI (low toxicity) modified resin binder, an aqueous resin binder and a resin binder with zero solvent content, and has higher environmental protection property. In addition, main assistants such as domestic green plant wax, novel environment-friendly wear-resistant materials, domestic drying agents with zero solvent content, water-based assistants and the like are creatively introduced and used, so that the environment-friendly performance is further improved. According to the invention, the content of the VOCs in the printing ink is lower than 6% by reducing the content of the solvent in the binder and the auxiliary agent and using the solvent with an excellent viscosity reduction effect, so that the content of the VOCs in the printing ink is obviously lower than that of the gravure printing ink for banknote printing and engraving in the existing system. The ink has good stability through the application of new materials and the optimization and adjustment of the formula, and the ink keeps smooth and non-thick in the constant temperature or variable temperature storage process which is obviously higher than the room temperature. The ink provided by the invention has good printing adaptability, physical and chemical resistance and binding fastness with various base materials. Meanwhile, the anti-counterfeiting ink with optical or magnetic anti-counterfeiting characteristics can be prepared by adding the metal anti-counterfeiting material according to the demands of customers, and the ink not only has low VOC and high stability, but also has anti-counterfeiting characteristics. The ink provided by the invention can be used for printing paper money and enhancing the anti-counterfeiting function of paper money.
According to the environment-friendly engraving gravure ink, the low VOC can be realized through the cooperation of the binder and the solvent, and the solvent can be reduced or not used in the combination of the binder. The stability can be improved significantly by the combination of the binder with adjuvants, especially vegetable waxes and whiskers. The whisker is used for replacing the wear-resistant wax, so that the risk can be reduced, the stability can be improved, the viscosity can be reduced, and the use of solvents can be reduced. By adding the leveling agent, the drying can be promoted while the wear resistance, the substrate hardening resistance and the adhesion resistance are ensured, and the drying time is reduced.
The advantageous effects of the present application are further illustrated below with reference to examples.
In order to make the objects, technical solutions and advantageous technical effects of the present application more clear, the present application is described in further detail below with reference to examples. However, it should be understood that the examples of the present application are merely for the purpose of explaining the present application and are not intended to limit the present application, and the examples of the present application are not limited to the examples given in the specification. The specific experimental or operating conditions were not noted in the examples and were made under conventional conditions or under conditions recommended by the material suppliers.
Furthermore, it is to be understood that the reference to one or more method steps in this disclosure does not exclude the presence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise indicated; it should also be understood that the combined connection between one or more devices/means mentioned in the present application does not exclude that other devices/means may also be present before and after the combined device/means or that other devices/means may also be interposed between these two explicitly mentioned devices/means, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the application in which the application may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the application without substantial modification to the technical matter.
In the examples described below, reagents, materials and equipment used were commercially available unless otherwise specified, except resins (MDI modified alkyd, IPDI modified alkyd, waterborne alkyd, epoxy modified alkyd, macromolecular phenolic, etc.) were developed and produced by and used only by the medium banknote ink company.
The MDI modified alkyd resin or IPDI modified alkyd resin synthesis method can refer to a polyurethane modified hydrophilic alkyd resin binder for water-jet engraving gravure ink disclosed in patent CN103204984B issued to the midnote ink company limited.
The synthetic method of the water-based alkyd resin or the epoxy modified alkyd resin can refer to the self-emulsifiable alkyd resin disclosed in the patent CN1580093B of the banknote ink Co-Ltd, and the preparation method is different from the method that the patent uses a surfactant or an epoxy modified material to replace polyethylene glycol in the CN 1580093B.
The macromolecular phenolic resin synthesis method can refer to a gelled high acid value phenolic resin disclosed in a patent CN1314751C issued by medium banknote ink Co-Ltd and a preparation method thereof, and is different from the fact that a gelling agent is not used in macromolecular phenolic resin synthesis in the patent, and the rosin modified phenolic resin has a self-gelling effect.
Example 1
a. Ink preparation
The ink was prepared according to the following composition:
material Formula (%)
MDI modified alkyd resin 10
Water-based alkyd resin 15
Epoxy modified alkyd resin 10
Macromolecular phenolic resin 5
Sodium secondary alkyl sulfonate 3
Sugarcane wax 5
Calcium carbonate whisker 4
Polydimethylsiloxane leveling agent 1
PMMA microsphere powder 2
Phthalocyanine blue B 6
Heavy calcium carbonate 35
Diethylene glycol monoethyl ether 1
Zero VOC cobalt/manganese/zirconium isooctanoate compositions 3
Totalizing 100
According to the formula, MDI modified alkyd resin, water-based alkyd resin, secondary alkyl sodium sulfonate, sugar cane wax and heavy calcium carbonate (1500 meshes) are stirred and dispersed at high speed to prepare Cheng Baiji for later use; adding epoxy modified alkyd resin, macromolecular phenolic resin, phthalocyanine blue B, calcium carbonate whisker, polydimethylsiloxane flatting agent and PMMA microsphere powder, rolling to obtain a chromophore, adding white base, continuously rolling, adding a zero VOC cobalt iso-octoate/manganese/zirconium composition drying agent, dispersing and stirring at high speed, testing the viscosity after the ink is stable, and adjusting the viscosity to a proper range by using diethylene glycol monoethyl ether. The viscosity of the prepared ink is 15 Pa.s (40 ℃,0.5 DEG cone, and the shear rate is 1000 s) -1 ). In the formulation, zero VOC cobalt/manganese/zirconium isooctanoate compositionThe preparation method comprises the following steps of using zero-VOC cobalt iso-octoate, zero-VOC manganese iso-octoate and zero-VOC zirconium iso-octoate according to 5-15 percent: 25-35%:50-70% of the powder is prepared, wherein the content of the zero VOC cobalt iso-octoate metal ions is 8-15%, the content of the zero VOC manganese iso-octoate metal ions is 8-12%, and the content of the zero VOC zirconium iso-octoate metal ions is 15-20%.
b. Stability test
The experimental ink prepared in example 1a was compared with a comparative ink selected from the group of inks B described in example 1 of patent CN 106349809B. The specific formula is as follows: 30% of blue inorganic nano pigment, 17% of alkyd resin, 21% of phenolic resin, 5% of surfactant, 5% of wax, 8% of calcium carbonate, 4% of titanium white, 8% of mineral oil solvent and 2% of drier.
The experimental ink and the comparative ink sample were placed in a 60 ℃ oven and allowed to stand for 320h, followed by cooling to room temperature in the oven. After removal, two ink samples were taken for scraping. After the scratch sample Zhang Ziran was dried, it was rated as a comparison with the control sample, and the ink particle roughness was rated from 1 to 5 as high as low.
The test results of the experimental ink samples were rated 5 and the test results of the comparative ink samples were rated 3. The stability of the experimental ink was better than that of the comparative ink.
VOC detection
The VOC measurement is carried out on the experimental ink and the comparative ink according to the measurement method of the content of Volatile Organic Compounds (VOCs) in the GB/T38608-2020 4.2 ink.
The test ink sample was 3.5% VOC and the comparative ink sample was rated 10.6%. The VOC content of the experimental ink was significantly lower than the comparative ink.
Example 2
a. Ink preparation
The ink was prepared according to the following composition:
material Formula (%)
IPDI modified alkyd resin 12
Epoxy modified alkyd resin 20
Macromolecular phenolic resin 10
Dodecyl propyl phosphate betaine 5
Potassium titanate whisker 4
Rice bran wax 8
Polyacrylate copolymer leveling agent 2
4708 scarlet 5
Barium sulfate 2
Copper-containing infrared absorbing material 30
Non-cobalt iron-halogen aza-bicyclo macrocyclic iron complex 2
Totalizing 100
According to the formula, epoxy modified alkyd resin (8%), macromolecular phenolic resin (2%), rice bran wax, dodecyl propyl phosphate betaine and barium sulfate are stirred and dispersed at a high speed to prepare Cheng Baiji for later use; rolling epoxy modified alkyd resin (12%), macromolecular phenolic resin (3%) and copper-containing infrared absorption material into anti-counterfeiting base ink for later use, rolling IPDI modified alkyd resin, macromolecular phenolic resin (5%), 4708 scarlet, potassium titanate whisker and polyacrylate copolymer flatting agent into chromophore, adding white base and anti-counterfeiting base ink, continuing rolling, then adding zero VOC non-cobalt iron-halogen aza bicyclo macrocyclic iron complex, dispersing and stirring at high speed, testing viscosity after the ink is stable, and adjusting the viscosity to a proper range. The viscosity of the prepared ink is 13 Pa.s (40 ℃,0.5 DEG cone, and the shear rate is 1000 s) -1 ). Copper-containing infrared absorbing materials are commercially available, for example, from Shanghai banknote printing Inc. or as synthesized in CN 103242708B. The non-cobalt iron-halogen aza-bicyclo macrocyclic iron complex can be selected from environment-friendly drying agents disclosed in Chinese paper money ink limited patent CN 103602268B. The specific components are ligand 3, 7-diazabicyclo [3.3.1 ]]Mixed crystal or solid solution type of the reaction product of nonane and chloride of iron or manganese.
b. Stability test
The experimental ink prepared in example 2a was compared with a comparative ink selected from the group of inks B described in example 3 of patent CN 106349809B. The specific formula is as follows: 25% of blue inorganic nano pigment, 20% of copper-containing infrared absorption material, 0.3% of F5RK permanent red pigment, 15.7% of alkyd resin, 14% of phenolic resin, 4% of surfactant, 4% of wax, 2% of drier, 5% of calcium carbonate and 10% of mineral oil.
The experimental ink and the comparative ink sample were placed in a 90 ℃ oven which was slowly cooled to room temperature over 20 hours at a cooling rate. After taking out, two samples were taken for scraping. After natural drying, the ink particles were rated as 1-5 according to the level of the ink particle roughness from high to low, respectively, in comparison with the control.
The test results of the experimental ink samples were rated 5 and the test results of the comparative ink samples were rated 1. The stability of the experimental ink was better than that of the comparative ink.
VOC detection
The VOC measurement is carried out on the experimental ink and the comparative ink according to the measurement method of the content of Volatile Organic Compounds (VOCs) in the GB/T38608-2020 4.2 ink.
The test ink sample was tested for VOC at 4.5% and the comparative ink sample was rated for 14.5%. The VOC content of the experimental ink was significantly lower than the comparative ink.
Example 3
a. Ink preparation
The ink was prepared according to the following composition:
material Formula (%)
IPDI modified alkyd resin 12
Water-based alkyd resin 20
Macromolecular phenolic resin 8
Dodecylbenzenesulfonic acid ammonia 5
Calcium sulfate whisker 5
Rice bran wax 8
Polydimethylsiloxane leveling agent 2
Permanent red F5RK 6
Heavy calcium carbonate 30
Bentonite clay 1
Diethylene glycol diethyl ether 1
Non-cobalt iron-halogen aza-bicyclo macrocyclic iron complex 2
Totalizing 100
Stirring and dispersing the water-based alkyd resin, rice bran wax, dodecylbenzene sulfonic acid ammonia and heavy calcium carbonate (2500 meshes) at a high speed according to the formula, and preparing Cheng Baiji for later use; rolling IPDI modified alkyd resin, macromolecular phenolic resin, permanent red F5RK, calcium sulfate whisker, polydimethylsiloxane flatting agent and bentonite into a chromophore, adding white base for continuous rolling, then adding diethylene glycol diethyl ether and zero VOC non-cobalt iron-halogen aza bicyclo macrocyclic iron complex for high-speed dispersion stirring, testing viscosity after the ink is stable, and adjusting the viscosity To a suitable range. The viscosity of the prepared ink is 13 Pa.s (40 ℃,0.5 DEG cone, and the shear rate is 1000 s) -1 )。
b. Stability test
The experimental ink prepared in example 3a was compared to a comparative ink, which was prepared in 3a for wax conditioning with an equivalent replacement of rice bran wax with montan wax having an acid number of 125mg KOH/g.
The experimental ink and the comparative ink sample were placed in a 90 ℃ oven which was slowly cooled to room temperature over 20 hours at a cooling rate. After taking out, two samples were taken for scraping. After natural drying, the ink particles were rated as 1-5 according to the level of the ink particle roughness from high to low, respectively, in comparison with the control.
The test results of the experimental ink samples were rated 5 and the test results of the comparative ink samples were rated 1. The stability of the experimental ink was better than that of the comparative ink.
VOC detection
The VOC measurement is carried out on the experimental ink and the comparative ink according to the measurement method of the content of Volatile Organic Compounds (VOCs) in the GB/T38608-2020 4.2 ink. The VOC test result of the experimental ink sample is 5.5%, and the VOC content of the experimental ink is lower than 6.0%.
d. Abrasion resistance experiment 1
The experimental ink prepared in example 3a was compared with a comparative ink, which was whisker modified ink from the ink prepared in 3a, with the modification scheme being 5% whisker replaced with 5% ground calcium carbonate.
The experimental ink and the comparative ink sample were subjected to 500 Rub tests using Rub abrasion instrument, and the level of the Rub fading of the ink was 5-1 respectively from low to high.
The test ink sample test results were rated 4.5 and the comparative ink sample test results were rated 3.5. The abrasion resistance of the experimental ink is better than that of the comparative ink.
e. Abrasion resistance experiment 2
The experimental ink prepared in example 3a was compared to a comparative ink, which was whisker modified with 5% whisker corresponding replacement with 5% oxidized polyethylene wax for the ink prepared in 3 a.
The experimental ink and the comparative ink sample were subjected to 500 Rub tests using Rub abrasion instrument, and the level of the Rub fading of the ink was 5-1 respectively from low to high.
The test ink sample test results were rated 4.5 and the comparative ink sample test results were rated 3.5. The abrasion resistance of the experimental ink is better than that of the comparative ink.
Example 4
a. Ink preparation
The ink was prepared according to the following composition:
according to the formula, water-based alkyd resin, carnauba wax, sodium dodecyl benzene sulfonate and heavy calcium carbonate (2000 meshes) are stirred and dispersed at high speed to prepare Cheng Baiji for later use; rolling MPDI modified alkyd resin, macromolecular phenolic resin, permanent peach red FBB, calcium sulfate whisker and polydimethylsiloxane flatting agent into a chromophore, adding white base for continuous rolling, then adding diethylene glycol diethyl ether and zero VOC manganese/zirconium isooctanoate composition for high-speed dispersion stirring, testing viscosity after the ink is stable, and adjusting the viscosity to a proper range. The viscosity of the prepared ink is 13 Pa.s (40 ℃,0.5 DEG cone, and the shear rate is 1000 s) -1 ). In the formula, the preparation method of the zero-VOC manganese iso-octoate/zirconium composition comprises the steps of using zero-VOC manganese iso-octoate and zero-VOC zirconium iso-octoate according to 30-40 percent: 60-70% of the powder is prepared, wherein the content of the zero VOC manganese iso-octoate metal ions is 8-12%, and the content of the zero VOC zirconium iso-octoate metal ions is 15-20%.
b. Stability test
The experimental ink prepared in example 4a was compared to a comparative ink, which was prepared in 4a for wax conditioning with equal replacement of carnauba wax with montan wax having an acid number of 125mg KOH/g.
The experimental ink and the comparative ink sample were placed in a 90 ℃ oven which was slowly cooled to room temperature over 20 hours at a cooling rate. After taking out, two samples were taken for scraping. After natural drying, the ink particles were rated as 1-5 according to the level of the ink particle roughness from high to low, respectively, in comparison with the control.
The test results of the experimental ink samples were rated 5 and the test results of the comparative ink samples were rated 1. The stability of the experimental ink was better than that of the comparative ink.
VOC detection
The VOC measurement is carried out on the experimental ink and the comparative ink according to the measurement method of the content of Volatile Organic Compounds (VOCs) in the GB/T38608-2020 4.2 ink. The VOC test result of the experimental ink sample is 5.0%, and the VOC content of the experimental ink is lower than 6.0%.
The experimental ink prepared in example 4a was compared with another comparative ink. In the experimental ink, the viscosity of the MDI modified alkyd resin is adjusted by using diethylene glycol diethyl ether in synthesis, and the viscosity of the ink is adjusted by using diethylene glycol diethyl ether in ink preparation; the MDI modified alkyd resin in the comparative ink used n-undecane in the synthesis to adjust the viscosity of the resin and n-undecane in the ink preparation to adjust the viscosity of the ink. At a desired ink viscosity of 13 Pa.s (40 ℃ C., plate, shear rate of 300 s) -1 ) On the premise that the dosage of diethylene glycol diethyl ether in the experimental ink comprising the MDI modified alkyd resin (2.1%) is 3.1%, and the dosage of n-undecane in the comparative ink comprising the MDI modified alkyd resin (3%) is 5%. The diethylene glycol diethyl ether is used as a solvent for reducing the viscosity of the MDI or IPDI modified alkyd resin and the ink, the effect is obviously better than that of solvents such as n-undecane and the like, and the use amount of the solvent in the resin or the ink can be effectively reduced, so that the VOC content of the ink is reduced.
d. Anti-blocking experiment
The experimental ink prepared in example 4a was compared with a comparative ink, which was prepared in 4a for leveling agent adjustment of the ink, the adjustment scheme being that the corresponding amount of leveling agent was replaced with 3% heavy calcium carbonate.
And (3) performing printing verification on the experimental ink and the comparative ink sample, respectively printing 1000 large sheets by using a designated banknote printing machine, stacking and placing for 3 days, and respectively setting the separation difficulty between the large sheets to be 1-5 grades according to the low-to-high grade of the separation difficulty between the large sheets.
The test ink sample test results were rated 1 and the comparative ink sample test results were rated 3. The anti-blocking performance of the experimental ink is superior to that of the comparative ink.
f. Drying experiment
The experimental ink prepared in example 4a was compared to a comparative ink in which the ink prepared in 4a was leveling agent adjusted in such a way that the corresponding amount of leveling agent was replaced with MDI modified alkyd resin.
And (3) scraping the sample of the experimental ink and the comparative ink, putting the sample into a constant temperature and constant humidity environment (23 ℃ and RH 50%), naturally drying the sample of the experimental ink for 12 hours, and naturally drying the sample of the comparative ink for 24 hours. The experimental ink naturally dries faster than the comparative ink.
The engraving gravure ink prepared by the embodiments 1, 2, 3 and 4 can meet the printing requirements of different engraving gravure machines, and has good printing adaptability, clear printed product lines, and excellent physical and chemical resistances such as acid resistance, alkali resistance, acetone resistance, ethanol resistance, soap resistance, saturated sodium sulfide resistance and the like through printing verification.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.

Claims (10)

1. The engraving gravure printing ink comprises the following raw materials in percentage by weight:
the sum of the percentages of the components is 100 percent.
2. The engraving gravure ink of claim 1, wherein the binder is selected from one or more of a first binder, a second binder, a macromolecular phenolic binder; preferably, the binder comprises the following components in weight percent, based on the total amount of engraved gravure ink:
0.1-20% of a first connecting material;
0.1-20% of a second binder;
0.1-15% of macromolecular phenolic resin.
3. The engraving gravure ink of claim 2, wherein the first vehicle is selected from one or a combination of two of MDI modified alkyd resin, IPDI modified alkyd resin;
And/or the number average molecular weight of the first connecting materials is 5000-100000;
and/or the viscosity of the first connecting material is 0.1-5Pa.s at 40 DEG C -1 ；
And/or the number average molecular weight of the second binder is controlled to be 1000-50000;
and/or the second binder has a viscosity of 0.1 to 20Pa.s at 40deg.C -1 ；
And/or the second binder is selected from one or a combination of two of water-based alkyd resin and epoxy modified alkyd resin;
and/or the macromolecular phenolic resin is selected from vegetable oil modified macromolecular phenolic resins;
and/or the number average molecular weight of the macromolecular phenolic resin is 50000-500000; the viscosity at 40 ℃ is 6-12Pa.s -1 。
4. The engraving ink of claim 3, wherein the MDI modified alkyd resin or the IPDI modified alkyd resin each has a number average molecular weight of 5000 to 100000;
and/or the viscosity of the MDI modified alkyd resin or the IPDI modified alkyd resin is 0.1-5Pa.s at 40 DEG C -1 ；
And/or the number average molecular weight of the water-based alkyd resin is controlled to be 1000-10000; the viscosity at 40 ℃ is 0.1-5Pa.s -1 ；
And/or, the alkyd resin in the epoxy modified alkyd resin is selected from vegetable oil fatty acid modified m-benzene alkyd resin; preferably, the vegetable oil fatty acid in the vegetable oil fatty acid modified meta-benzene alkyd resin is selected from C1-C30 unsaturated fatty acids; more preferably, the vegetable oil fatty acid may be selected from one or more of tall oil acid, tung oil acid, catalpa oil acid, linoleic acid, linseed oil acid, ricinoleic acid, tall oil acid, coconut oil fatty acid, oleic acid or palmitic acid;
And/or the number average molecular weight of the epoxy modified alkyd resin is 5000-50000; the viscosity at 40 ℃ is 5-20Pa.s -1 ；
And/or the vegetable oil in the vegetable oil modified macromolecular phenolic resin is one or more selected from tall oil, tung oil, catalpa oil, linseed oil, castor oil and coconut oil.
5. The engraving gravure ink of claim 1, wherein the auxiliary agent is selected from one or more of surfactants, leveling agents, vegetable waxes, whiskers, talc, microsphere powders, bentonite; preferably, the auxiliary agent comprises the following components in percentage by weight based on the total amount of the engraving gravure ink:
6. the engraving gravure ink of claim 5, wherein the surfactant is selected from one or more of sodium fatty alcohol-polyoxyethylene ether sulfate, sodium secondary alkyl sulfonate, ammonium dodecylbenzene sulfonate, APG1214, APG0810, APG0814, AEC-9Na, dodecyl propyl phosphate betaine, lauramidopropyl hydroxysulfobetaine, cocoamidopropyl hydroxysulfobetaine, imidazoline, cocoamidopropyl hydroxysulfobetaine, or sodium dodecylbenzene sulfonate;
and/or the leveling agent is selected from one or more of organosilicon leveling agents and polyacrylate leveling agents;
And/or the vegetable wax is selected from one or more of carnauba vegetable wax, rice bran wax, sugarcane wax, candelilla wax, lacquer wax, wood wax;
and/or the whisker is selected from one or more of calcium carbonate whisker, calcium sulfate whisker and potassium titanate;
and/or the microsphere powder is selected from one or more of silicon dioxide microspheres, PET microspheres, PS microspheres, PTFE microspheres and PMMA microspheres;
and/or, the bentonite is organic bentonite.
7. The engraving gravure ink of claim 1, wherein the pigment is selected from one or more of a phthalocyanine blue pigment, a phthalocyanine green pigment, a permanent red pigment, a permanent yellow pigment, a permanent orange pigment, a permanent violet pigment, a pigment carbon black pigment, a titanium white pigment, an effect pigment, and the like;
and/or the metal anti-counterfeiting material is selected from one or two of infrared absorption anti-counterfeiting material and magnetic anti-counterfeiting material; and/or the filling material is selected from one or more of heavy calcium carbonate, barium sulfate, kaolin, aluminum silicate, nano barium sulfate, nano calcium carbonate and aerosil;
and/or the solvent is one or more selected from an ester solvent, an ether solvent and a mineral oil solvent; preferably, the ester solvent is selected from one or more of methyl esters, butyl acetate and ethyl acetate; the ether solvent is selected from one or more of diethylene glycol monoethyl ether, diethylene glycol diethyl ether and dipropylene glycol dimethyl ether; the mineral oil solvent is selected from one or more of normal alkane, isoalkane, cycloalkane and arene;
And/or the drying agent is selected from one or more of cobalt zero-VOC iso-octoate, manganese zero-VOC iso-octoate, zirconium zero-VOC iso-octoate and combinations thereof, non-cobalt iron-halogen aza-bicyclo-type macrocyclic iron complexes, manganese-halogen aza-bicyclo-type macrocyclic manganese complexes and combinations thereof.
8. A method of preparing the engraved gravure ink of any one of claims 1 to 7 comprising the steps of:
1) Preparing Cheng Baiji from a binder, an auxiliary agent and a filler;
2) Rolling the binder, pigment and auxiliary agent into a chromophore;
3) Adding the white base in the step 1) into the chromophore for rolling, adding the solvent and the drying agent, and dispersing to obtain the engraving gravure printing ink.
9. The method for preparing the engraving ink as recited in claim 8, wherein the step 1) is to prepare Cheng Baiji from a first binder, a second binder, a surfactant, a vegetable wax, whiskers, and a filler;
and/or rolling the first binder, the macromolecular phenolic resin, the pigment and the auxiliary agent into a chromophore;
and/or rolling the first binder, the second binder, the vegetable wax and the metal anti-counterfeiting material into anti-counterfeiting base ink; adding white base and anti-counterfeiting base ink into a chromophore for rolling, adding a solvent and a drying agent, and dispersing to obtain engraving gravure ink;
And/or the viscosity of the engraved gravure ink obtained is measured at 40 ℃ to be (0.1-30) pa·s.
10. Use of the engraved intaglio ink of any of claims 1 to 7 in the printing arts.
CN202310578575.0A 2023-05-22 2023-05-22 Low-VOC high-stability environment-friendly engraving gravure ink and preparation method thereof Pending CN116622263A (en)

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