An intaglio printing ink with dual functions of UV drying and natural oxidation drying and its application

Abstract

The application provides an engraved gravure printing ink with dual functions of UV drying and natural oxidation drying and application thereof, and belongs to the technical field of printing ink. The engraved gravure printing ink with dual functions of UV drying and natural oxidation drying comprises the following components in percentage by weight: functional resin 10-30%, active diluent 5-20%, pigment 8-40%, filler 15-40%, wax 3-8%, surfactant 1-5%, photoinitiator 2-8% and drier 0.5-3%. The functional resin has a molecular structure with dual curing functions of UV curing and natural oxidation crosslinking curing, and can meet the demand of water wiping engraved gravure printing mode, and completely solves the problems of incomplete drying of UV ink, poor materialized performance of hot air infrared ink and too slow surface drying of natural oxidation ink which cannot meet the requirement of roll printing.

Description

Technical Field

[0001] This invention relates to the field of printing ink technology, and in particular to an engraved gravure printing ink with dual functions of UV drying and natural oxidation drying, and its application. Background Technology

[0002] Most commonly used gravure printing inks rely on natural oxidation drying, requiring the printed material to dry naturally at room temperature for at least 24 hours before proceeding to the next processing stage. Often, this type of ink becomes unrecoverable after roll-to-roll printing due to adhesion. While hot-air infrared drying gravure inks can be used for roll-to-roll printing, the physical and chemical properties of the printed material cannot meet high requirements, and such drying systems are typically large and slow, impacting printing efficiency. Furthermore, because gravure printing usually involves deep engraving lines and thick ink layers, UV gravure inks using ordinary UV drying methods cannot completely dry the interior of the printed material, compromising its physical and chemical properties.

[0003] The related technology discloses a UV-oxidation mixed drying type engraving gravure ink, which is composed of a base ink that can be UV cured and a base ink that can be oxidized and dried. The UV curing resin and the oxidizing drying resin are physically mixed. The UV light cannot penetrate the bottom layer of the ink, so it cannot be completely cured, nor can it react with other resins through the curing method of oxidative cross-linking. It is difficult to form a dense polymer structure, thus making it difficult to meet the high performance requirements of engraving gravure ink. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide an engraving gravure printing ink with dual functions of UV drying and natural oxidation drying, and its application. The functional resin in the engraving gravure printing ink of this invention possesses both UV drying and natural oxidation drying functions, thus meeting the high-performance requirements of engraving gravure printing inks.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides an engraving gravure printing ink with both UV drying and natural oxidation drying functions, comprising the following components by weight percentage: Functional resin 10-30%, reactive diluent (UV-604 resin) 5-20%, pigment 8-40%, filler 15-40%, wax 3-8%, surfactant 1-5%, photoinitiator 2-8%, and drier 0.5-3%; The functional resin is either a first functional resin (UV-601 resin) or a second functional resin (UV-602 resin). The first functional resin is prepared by a method comprising the following steps: Tung oil and maleic anhydride were mixed and subjected to the first addition reaction to obtain the first addition product; The first addition product, hydroxyethyl acrylic acid and the first polymerization inhibitor are mixed and subjected to a first esterification reaction to obtain the first esterified product. The first esterification product and glycidyl methacrylate were mixed and subjected to a first ring-opening esterification to obtain the first ring-opening esterification product. The first ring-opening esterification product is mixed with epoxy resin to carry out an epoxy ring-opening reaction to obtain the first functional resin. The second functional resin is prepared by a method comprising the following steps: Linseed oil and maleic anhydride were mixed and subjected to a second addition reaction to obtain the second addition product; The second addition product and polyethylene glycol monomethyl ether were mixed and subjected to a second esterification reaction to obtain the second esterified product. The second esterification product, glycidyl methacrylate, and the second polymerization inhibitor are mixed and subjected to a second ring-opening esterification to obtain the second functional resin. The reactive diluent is prepared by a method comprising the following steps: The reactive diluent is obtained by mixing tung oil acid, glycidyl methacrylate, triethanolamine and a third polymerization inhibitor and then performing a third ring-opening esterification.

[0006] Preferably, when preparing the first functional resin, the mass ratio of tung oil, maleic anhydride, hydroxyethyl acrylic acid, glycidyl methacrylate and epoxy resin is 900:200:180:180:100.

[0007] Preferably, when preparing the second functional resin, the mass ratio of linseed oil, maleic anhydride, polyethylene glycol monomethyl ether, and glycidyl methacrylate is 900:150:400:280.

[0008] Preferably, when preparing the reactive diluent, the mass ratio of tung oil acid, glycidyl methacrylate and triethanolamine is 300:100:0.5.

[0009] Preferably, the filler comprises calcium carbonate and / or talc.

[0010] Preferably, the surfactant comprises one or more of sodium dodecylbenzenesulfonate, amine dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium dibutylnaphthalenesulfonate, sodium fatty alcohol ether sulfate, fatty alcohol polyoxyethylene ether, alkyl glycoside, and cocamidopropyl betaine.

[0011] Preferably, the drying agent includes one or more of isooctanoate, naphthenate, and stearate, and the drying agent contains a metal element.

[0012] Preferably, the metallic element includes one or more of cobalt, manganese, vanadium, cerium, calcium, zinc, barium, zirconium, iron, and rare earth elements.

[0013] Preferably, the wax comprises one or more of paraffin wax, polyethylene wax, polypropylene wax, polyamide wax, Fischer-Tropsch wax, carnauba wax, and polytetrafluoroethylene wax.

[0014] The present invention also provides the application of the engraving gravure printing ink described above in the field of engraving gravure printing.

[0015] This invention provides an engraved gravure printing ink with dual functions of UV drying and natural oxidation drying, comprising the following components by weight percentage: 10-30% functional resin, 5-20% reactive diluent, 8-40% pigment, 15-40% filler, 3-8% wax, 1-5% surfactant, 2-8% photoinitiator, and 0.5-3% drier; wherein the functional resin is a first functional resin or a second functional resin; the first functional resin is prepared by a method comprising the following steps: mixing tung oil and maleic anhydride, performing a first addition reaction to obtain a first addition product; mixing the first addition product, hydroxyethyl acrylic acid, and a first polymerization inhibitor, performing a first esterification reaction to obtain a first esterified product; mixing the first esterified product with glycidyl methacrylate, and performing... The first ring-opening esterification yields a first ring-opening esterified product; the first ring-opening esterified product is mixed with an epoxy resin to undergo an epoxy group ring-opening reaction to obtain the first functional resin; the second functional resin is prepared by a method comprising the following steps: mixing linseed oil and maleic anhydride to undergo a second addition reaction to obtain a second addition product; mixing the second addition product with polyethylene glycol monomethyl ether to undergo a second esterification reaction to obtain a second esterified product; mixing the second esterified product, glycidyl methacrylate, and a second polymerization inhibitor to undergo a second ring-opening esterification to obtain the second functional resin; the reactive diluent is prepared by a method comprising the following steps: mixing tung oil acid, glycidyl methacrylate, triethanolamine, and a third polymerization inhibitor to undergo a third ring-opening esterification to obtain the reactive diluent.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: The functional resin described in this invention has a molecular structure with dual curing functions of UV curing and natural oxidation crosslinking curing. This functional resin is a high-molecular-weight resin formed by reacting drying vegetable oils (such as linseed oil and tung oil) with propylene-based raw materials, such as hydroxyethyl acrylate and glycidyl methacrylate. This resin has a certain acid value (20~70 mg KOH / g) or contains a hydrophilic surface-active structure (provided by polyethylene glycol monomethyl ether) to meet the requirements of water-based gravure printing. The reactive diluent is formed by reacting drying oleic acid (tung oil acid) with glycidyl methacrylate. The gravure printing ink of this invention simultaneously possesses both UV drying and natural oxidation drying functions, completely solving the shortcomings of incomplete drying of UV inks in gravure printing, poor physicochemical properties of hot air infrared inks, and slow surface drying of natural oxidation inks, which cannot meet the requirements of roll-to-roll printing. Using the ink manufactured according to this invention, the surface can be cured after printing by irradiation with a UV lamp, and it will no longer stick together even after rewinding, without affecting the next processing step. Ink that has not been completely UV dried inside the printed image can be oxidized and dried under natural conditions in the later stage, allowing the resin in the ink to fully cross-link, thereby obtaining the good physicochemical properties required for high-grade printed products. Attached Figure Description

[0017] Figure 1 The image shows the back-side smudge test and smudge condition of the engraved gravure printing ink used in Example 1, directly after the proof was completed. Figure 2 The image shows the back-side smudge test and smudge condition of the engraved gravure printing ink after UV lamp curing in Example 1. Figure 3 The back-side adhesion test and adhesion status were performed on the engraved gravure printing ink of Example 1 after it had been naturally dried for 24 hours. Figure 4 To test the back adhesion and the adhesion status of the ordinary ink used in Comparative Example 1 after it was naturally dried for 24 hours; Figure 5 The image shows a back-side smudge test and smudge condition of the engraved gravure printing ink after UV lamp curing in Example 2. Detailed Implementation

[0018] This invention provides an engraving gravure printing ink with both UV drying and natural oxidation drying functions, comprising the following components by weight percentage: Functional resin 10-30%, reactive diluent 5-20%, pigment 8-40%, filler 15-40%, wax 3-8%, surfactant 1-5%, photoinitiator 2-8%, and drier 0.5-3%; The functional resin is a first functional resin or a second functional resin; The first functional resin is prepared by a method comprising the following steps: Tung oil and maleic anhydride were mixed and subjected to the first addition reaction to obtain the first addition product; The first addition product, hydroxyethyl acrylic acid and the first polymerization inhibitor are mixed and subjected to a first esterification reaction to obtain the first esterified product. The first esterification product and glycidyl methacrylate were mixed and subjected to a first ring-opening esterification to obtain the first ring-opening esterification product. The first ring-opening esterification product is mixed with epoxy resin to carry out an epoxy ring-opening reaction to obtain the first functional resin. The second functional resin is prepared by a method comprising the following steps: Linseed oil and maleic anhydride were mixed and subjected to a second addition reaction to obtain the second addition product; The second addition product and polyethylene glycol monomethyl ether were mixed and subjected to a second esterification reaction to obtain the second esterified product. The second esterification product, glycidyl methacrylate, and the second polymerization inhibitor are mixed and subjected to a second ring-opening esterification to obtain the second functional resin. The reactive diluent is prepared by a method comprising the following steps: The reactive diluent is obtained by mixing tung oil acid, glycidyl methacrylate, triethanolamine and a third polymerization inhibitor and then performing a third ring-opening esterification.

[0019] Unless otherwise specified, all raw materials used in this invention are commercially available products in the field.

[0020] The weight percentage of functional resin in the engraving gravure printing ink of the present invention can be 10%, 20%, 25% or 30%.

[0021] In this invention, the functional resin is a first functional resin or a second functional resin.

[0022] In this invention, the first functional resin is prepared by a method comprising the following steps: Tung oil and maleic anhydride were mixed and subjected to the first addition reaction to obtain the first addition product; The first addition product, hydroxyethyl acrylic acid and the first polymerization inhibitor are mixed and subjected to a first esterification reaction to obtain the first esterified product. The first esterification product and glycidyl methacrylate were mixed and subjected to a first ring-opening esterification to obtain the first ring-opening esterification product. The first ring-opening esterification product is mixed with epoxy resin to carry out an epoxy ring-opening reaction, thereby obtaining the first functional resin.

[0023] In this invention, when preparing the first functional resin, the preferred mass ratio of tung oil, maleic anhydride, hydroxyethyl acrylic acid, glycidyl methacrylate and epoxy resin is 900:200:180:180:100.

[0024] In this invention, the epoxy resin preferably includes epoxy resin E-51.

[0025] In this invention, tung oil and maleic anhydride are mixed and subjected to a first addition reaction to obtain a first addition product.

[0026] In this invention, the temperature of the first addition reaction is preferably 190~210℃, specifically 190, 200 or 210℃, and the time is preferably 3h.

[0027] After obtaining the first addition product, the present invention mixes the first addition product, hydroxyethyl acrylic acid and the first polymerization inhibitor, and performs a first esterification reaction to obtain the first esterified product.

[0028] In this invention, the first polymerization inhibitor preferably includes hydroquinone, and the mass ratio of tung oil to the first polymerization inhibitor is preferably 900:5.

[0029] In this invention, the temperature of the first esterification reaction is preferably 115~120℃, specifically 115, 118 or 120℃, and the time is preferably 2h.

[0030] After obtaining the first esterified product, the present invention mixes the first esterified product with glycidyl methacrylate and performs a first ring-opening esterification to obtain the first ring-opening esterified product.

[0031] In this invention, the temperature of the first ring-opening esterification is preferably 115~120℃, specifically 115, 118 or 120℃, and the time is preferably 4h.

[0032] After obtaining the first ring-opening esterified product, the present invention mixes the first ring-opening esterified product with epoxy resin and performs an epoxy group ring-opening reaction to obtain the first functional resin.

[0033] In this invention, the preferred temperature for the ring-opening reaction of the epoxy group is 115~120℃, specifically 115, 118 or 120℃, and the preferred time is 2h.

[0034] In a specific embodiment of the present invention, preferably, tung oil and maleic anhydride are added to a reaction flask, and the first addition reaction is carried out by heating under stirring. Then, hydroquinone and hydroxyethyl acrylic acid are added after cooling to carry out the first esterification reaction. Then, glycidyl methacrylate is added to carry out the first ring-opening esterification. Finally, epoxy resin is added to carry out the epoxy ring-opening reaction to obtain the UV-601 resin.

[0035] In this invention, the second functional resin is prepared by a method comprising the following steps: Linseed oil and maleic anhydride were mixed and subjected to a second addition reaction to obtain the second addition product; The second addition product and polyethylene glycol monomethyl ether were mixed and subjected to a second esterification reaction to obtain the second esterified product. The second esterification product, glycidyl methacrylate, and the second polymerization inhibitor are mixed and subjected to a second ring-opening esterification to obtain the second functional resin.

[0036] In this invention, when preparing the second functional resin, the preferred mass ratio of linseed oil, maleic anhydride, polyethylene glycol monomethyl ether, and glycidyl methacrylate is 900:150:400:280.

[0037] In this invention, linseed oil and maleic anhydride are mixed and subjected to a second addition reaction to obtain a second addition product.

[0038] In this invention, the temperature of the second addition reaction is preferably 210~230℃, specifically 210, 220 or 230℃, and the time is preferably 4h.

[0039] After obtaining the second addition product, the present invention mixes the second addition product with polyethylene glycol monomethyl ether and carries out a second esterification reaction to obtain the second esterified product.

[0040] In this invention, the temperature of the second esterification reaction is preferably 190~210℃, specifically 190, 200 or 210℃, and the time is preferably 1h.

[0041] After obtaining the second esterification product, the present invention mixes the second esterification product, glycidyl methacrylate, and the second polymerization inhibitor to perform a second ring-opening esterification to obtain the second functional resin.

[0042] In this invention, the second polymerization inhibitor preferably includes hydroquinone, and the mass ratio of the linseed oil to the second polymerization inhibitor is preferably 900:5.

[0043] In this invention, the temperature of the second ring-opening esterification is preferably 70~90°C, specifically 70, 80 or 90°C, and the time is preferably 6h.

[0044] In a specific embodiment of the present invention, linseed oil and maleic anhydride are preferably added to a reaction flask, and the mixture is heated under stirring. The reaction is maintained at 210~230°C for 4 hours. Then, polyethylene glycol monomethyl ether is added at 200°C, and the reaction is maintained at 200°C for 1 hour. The temperature is then lowered to 80°C, and glycidyl methacrylate and hydroquinone are added. After the reaction is maintained at 200°C for 6 hours, the UV-602 resin is obtained.

[0045] In this invention, the functional resin is a molecular structure with dual curing functions of UV curing and natural oxidation crosslinking curing. The functional resin is a polymer resin formed by reacting drying vegetable oil (such as linseed oil and tung oil) with raw materials containing propylene groups, such as hydroxyethyl acrylate and glycidyl methacrylate. This resin has a certain acid value (20~70mg KOH / g, preferably 40~70mg KOH / g) or contains a hydrophilic (including hydroxyl and carboxyl groups) surface-active structure (provided by polyethylene glycol monomethyl ether) to meet the requirements of water-rubbed engraving gravure printing.

[0046] The weight percentage of the reactive diluent in the engraved gravure printing ink of the present invention can be 5%, 10%, 15% or 20%.

[0047] In this invention, the reactive diluent is prepared by a method comprising the following steps: The reactive diluent is obtained by mixing tung oil acid, glycidyl methacrylate, triethanolamine and a third polymerization inhibitor and then performing a third ring-opening esterification.

[0048] In this invention, when preparing the active diluent, the preferred mass ratio of tung oil acid, glycidyl methacrylate, and triethanolamine is 300:100:0.5.

[0049] In this invention, the third polymerization inhibitor preferably includes hydroquinone, and the mass ratio of tung oil acid to the third polymerization inhibitor is preferably 300:0.8.

[0050] In this invention, the temperature of the third ring-opening esterification is preferably 100~120℃, specifically 100, 110 or 120℃, and the time is preferably 6h.

[0051] In a specific embodiment of the present invention, tung oil acid, glycidyl methacrylate, triethanolamine and hydroquinone are preferably added to a reaction flask, and the mixture is heated under stirring. The reaction is maintained at 100~120°C for 6 hours to obtain the UV-604 active diluent.

[0052] The weight percentage of pigment in the engraved gravure printing ink of the present invention can be 10%, 14%, 15%, 16.5%, 20%, 30% or 40%.

[0053] In this invention, the pigment preferably includes one or more of organic pigments, inorganic pigments, and natural pigments.

[0054] The weight percentage of filler in the engraved gravure printing ink of the present invention can be 15%, 24%, 25.5%, 27%, 29.5%, 35% or 40%.

[0055] In this invention, the filler preferably comprises calcium carbonate and / or talc.

[0056] In this invention, the calcium carbonate preferably comprises light calcium carbonate and / or heavy calcium carbonate.

[0057] In this invention, the calcium carbonate preferably includes nano-calcium carbonate.

[0058] The weight percentage of wax in the engraved gravure printing ink of the present invention can be 3%, 5%, 7% or 8%.

[0059] In this invention, the wax preferably includes one or more of paraffin wax, polyethylene wax, polypropylene wax, polyamide wax, Fischer-Tropsch wax, carnauba wax, and polytetrafluoroethylene wax.

[0060] The specific weight percentage of surfactant in the engraved gravure printing ink of the present invention can be 1%, 3% or 5%.

[0061] In this invention, the surfactant preferably includes one or more of sodium dodecylbenzenesulfonate, dodecylbenzenesulfonate amine, sodium dodecyl sulfate, sodium dibutylnaphthalenesulfonate, sodium fatty alcohol ether sulfate, fatty alcohol polyoxyethylene ether, alkyl glycoside and cocamidopropyl betaine.

[0062] The weight percentage of photoinitiator in the engraved gravure printing ink of the present invention can be 2.5%, 4%, 5%, 6%, 7% or 8%.

[0063] In this invention, the photoinitiator preferably includes one or more of 2-hydroxy-2-methyl-1-phenylpropanone (1173), 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO-L), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (819-L), benzophenone, and thioxanthone photoinitiators, wherein the thioxanthone photoinitiator is preferably ITX (2-isopropylthioxanthone) and / or DETX (2,4-diethylthioxanthone).

[0064] The weight percentage of the drier in the engraved gravure printing ink of the present invention can be 0.5%, 1.5%, 2.5% or 3%.

[0065] In this invention, the drying agent preferably includes one or more of isooctanoate, naphthenate and stearate, and the drying agent preferably contains a metal element.

[0066] In this invention, the metallic element preferably includes one or more of cobalt, manganese, vanadium, cerium, calcium, zinc, barium, zirconium, iron, and rare earth elements.

[0067] In this invention, the rare earth elements preferably include one or more of cerium, lanthanum, praseodymium, and rubidium.

[0068] The present invention also provides a method for preparing the engraved gravure printing ink described in the above technical solution. The present invention does not have any special limitation on the preparation method of the engraved gravure printing ink, and it can be prepared by a composition preparation method well known to those skilled in the art.

[0069] The engraved gravure printing ink of the present invention has the following advantages: 1. Environmental friendliness: The volatile organic compound (VOC) content in the ink is less than 5 wt%; 2. Better printing effect and higher anti-counterfeiting value: The functional resin has a molecular structure with dual curing functions of UV curing and natural oxidation cross-linking curing. The printed images and text are quickly cured and shaped on the surface, and its film-forming content is ≥95%. Due to the high solid content and rapid curing characteristics of the ink, the printed imprint is not easy to penetrate deep into the substrate. At the same time, the low volatile matter content will not cause the imprint to collapse, thus obtaining a thicker ink layer. The images and text are more three-dimensional, the tactile sensation is more obvious, and the anti-counterfeiting performance is better.

[0070] 3. Diverse printing methods: The engraving gravure ink manufactured by this invention can be applied to sheet or roll printing.

[0071] 4. Diverse printing materials: It can be used for printing on paper and composite materials such as polymer films with (pre-coated) surface treatment.

[0072] The present invention also provides the application of the engraving gravure printing ink described above in the field of engraving gravure printing.

[0073] In this invention, the preferred parameters for the engraved gravure printing include: printing speed: 50~100m / min, mercury lamp power of 5000W or more, and emission spectrum wavelength of 365~440nm.

[0074] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0075] In the embodiments and comparative examples of this invention: The preparation process of UV-601 resin is as follows: Add 900g of tung oil and 200g of maleic anhydride to a reaction flask, heat to 200℃ with stirring, and maintain the temperature at 190℃ for 3 hours; cool to 110℃ and add 5g of hydroquinone and 180g of hydroxyethyl acrylic acid, and maintain the temperature at 115℃ for 2 hours; add 180g of glycidyl methacrylate and continue the reaction for 4 hours; add 100g of epoxy resin (E-51) and continue the reaction for 2 hours to complete the preparation of UV-601 resin.

[0076] The preparation process of UV-602 resin is as follows: Add 900g of linseed oil and 150g of maleic anhydride to a reaction flask, heat with stirring, and maintain the temperature at 230℃ for 4 hours; add 400g of polyethylene glycol monomethyl ether at 200℃ and maintain the temperature for 1 hour; cool down to 80℃, add 280g of glycidyl methacrylate and 5g of hydroquinone, and maintain the temperature for 6 hours to complete the preparation of UV-602 resin.

[0077] The preparation process of UV-604 reactive diluent is as follows: Add 300g of tung oil acid, 100g of glycidyl methacrylate, 0.5g of triethanolamine and 0.8g of hydroquinone to the reaction flask, stir and heat, and keep the reaction at 100℃ for 6 hours to complete the preparation of UV-604 reactive diluent.

[0078] Example 1 A type of engraving gravure printing ink with dual UV and natural drying functions, comprising, by weight percentage: 30% UV-601 resin, 20% UV-604 resin, 10% pigment (Mitsubishi Carbon Black MA100 from Japan), 27% filler (light calcium carbonate), 5% wax (carnauba wax), 3% surfactant (sodium dodecylbenzene sulfonate), 2.5% photoinitiator (TPO-L), and 2.5% drier (Shanghai Changfeng Chemical Plant HD-610). The preparation method includes the following steps: mixing UV-601 resin, UV-604 resin, pigment, filler, wax, surfactant, photoinitiator, and drier.

[0079] Example 2 Same as Example 1, except that UV-601 resin is replaced with UV-602 resin.

[0080] Example 3 Same as Example 1, except that the components by weight percentage are: 25% UV-601 resin, 20% UV-604 resin, 15% pigment (phthalocyanine blue), 25.5% filler (nano-calcium carbonate), 5% wax (polyethylene wax), 3% surfactant (ammonia dodecylbenzenesulfonate), 4% photoinitiator (1173), and 2.5% drier (Shanghai Changfeng Chemical Plant HD-610).

[0081] Example 4 Same as Example 1, except that the components by weight percentage are: 25% UV-601 resin, 20% UV-604 resin, 16.5% pigment (phthalocyanine green), 24% filler (nano-calcium carbonate), 5% wax (paraffin), 3% surfactant (ammonia dodecylbenzenesulfonate), 4% photoinitiator (819-L), and 2.5% drier (Shanghai Changfeng Chemical Plant HD-610).

[0082] Example 5 Same as Example 1, except that the components by weight percentage are: 20% UV-601 resin, 20% UV-604 resin, 14% pigment (titanium dioxide R-996), 29.5% filler (light calcium carbonate), 5% wax (carnauba wax), 3% surfactant (AEO), 6% photoinitiator (TPO-L), and 2.5% drier (Shanghai Changfeng Chemical Plant HD-610).

[0083] Example 6 Same as Example 1, except that the components by weight percentage are: 20% UV-601 resin, 20% UV-604 resin, 20% pigment (181 Yellow), 25.5% filler (light calcium carbonate), 5% wax (polyethylene wax), 3% surfactant (ammonia dodecylbenzenesulfonate), 4% photoinitiator (TPO-L), and 2.5% drier (Shanghai Changfeng Chemical Plant HD-610).

[0084] Comparative Example 1 Ordinary engraving and gravure ink (sample from Langfang Anding New Material Technology Co., Ltd.)

[0085] The test methods and results for the performance of engraving gravure inks are as follows: Ink resistance to back-side smudging test method: The front side of the printed sample (the ink to be tested is evenly applied to the engraved gravure using a rubber squeegee, the gravure is fixed on the wiping table, and excess ink on the surface of the gravure is wiped off with special wiping paper, then the gravure is fixed face up on the printing machine (produced by Beijing Hengyin Machinery Manufacturing Co., Ltd.), a sheet of paper to be printed is placed on top, the rollers of the printing machine are rotated, so that the gravure and the paper to be printed pass through the pressure roller at a certain speed, so that the pattern on the gravure is printed on the special paper, and the printed sample is prepared by UV curing and leaving it at room temperature for 7 days) is attached to the front side of an A4 sheet of paper, and placed horizontally between two wooden boards the size of two A4 sheets of paper, with two 500g weights placed on top separately. After pressing for 24 hours, the test printed sample is taken out and the smudging on the front side of the A4 paper is observed.

[0086] Ink physicochemical property test items and methods: 1. Abrasion resistance test: Place the printed sample horizontally on a flat abrasive and rub it 50 times, then observe the ink loss.

[0087] 2. Alkali resistance test: Immerse the sample in a 2wt% sodium hydroxide solution for 30 minutes, then rinse with clean water and air dry on filter paper.

[0088] 3. Acid resistance test: Immerse the sample in 2wt% hydrochloric acid solution for 30 minutes, then rinse with clean water and air dry on filter paper.

[0089] 4. Rub resistance test: Roll the print into a small roll and put it into the steel tube. Press it 50 times with the matching piston, take it out and flatten it. Turn the print over and roll it into a small roll again and put it into the steel tube. Press it 50 times with the matching piston, take it out and flatten it.

[0090] 5. Heat resistance test of soap solution: Immerse the sample in a mixed soap solution (2wt% Na2CO3 + 1wt% laundry detergent + 97wt% water) at a temperature of 90℃ for 30 minutes, then remove it, wash it with clean water, and place it on filter paper to dry.

[0091] 6. Alcohol resistance test: Immerse the sample in 95 vol% ethanol for 30 minutes, then rinse with water and air dry on filter paper.

[0092] 7. Acetone resistance test: Immerse the print in acetone for 30 minutes, then remove it and let it air dry on filter paper.

[0093] Figure 1 The image shows a back-side smudge test and smudge condition of the engraved gravure printing ink used in Example 1, directly after the proof was completed. Figure 2 The image shows a back-side smudge test and smudge condition of the engraved gravure printing ink after UV lamp curing in Example 1. Figure 3The back-side adhesion test and adhesion status were performed on the engraved gravure printing ink of Example 1 after it had been naturally dried for 24 hours. Figure 4 To test the back adhesion and the adhesion status of the ordinary ink used in Comparative Example 1 after it was naturally dried for 24 hours; Figure 5 The image shows a back-side smudge test and smudge condition of the engraved gravure printing ink after UV lamp curing in Example 2. Test conclusions: 1. The engraved gravure printing ink of the present invention, after UV curing, showed the following results in the back-side smudging test: no smudging and no ink loss. 2. The results of the back-side smudging test of the engraved gravure printing ink of the present invention under the drying condition of natural air drying for 24 hours show that the smudging effect is better than that of ordinary engraved gravure printing ink.

[0094] 3. The engraving gravure printing ink of the present invention has dual curing functions of UV curing and natural oxidation drying, which can solve the problem of easy smudging and sticking on the back of the printing plate in high-speed engraving gravure printing machines.

[0095] Table 1 compares the test results of the inks in the embodiments and comparative examples of the present invention. It can be seen that the performance of the ink of the present invention is better than that of the comparative example, and the curing speed of the ink of Example 1 is faster than that of Example 2. The surface drying time (finger touch method) of the ink of Example 1 is 2 days faster than that of the ink of Example 2. The reasons are: tung oil has better drying properties than linseed oil, and the drying and curing speed of the resin prepared with tung oil as the main raw material is also faster than that of the resin prepared with linseed oil as the main raw material; the larger the amount of resin in the formulations of Examples 1 and 2, the better the physicochemical properties of the ink, especially the abrasion resistance and rubbing resistance; Examples 1 (black ink) and Examples 5 (white ink) require more photoinitiator; the viscosity and tack of the inks prepared in Examples 3 and 4 are higher than those of the inks in other examples; the selection of wax in the examples can be adjusted according to the depth of the printing pattern during actual printing, and different types and amounts of wax can be used.

[0096] Table 1. Comparison of test results for the inks in the examples and comparative examples.

[0097] In summary: The engraving gravure printing ink of this invention is UV cured, achieving rapid surface drying and allowing the printed matter to quickly proceed to the next process without sticking or smudging; it meets the high-performance requirements of advanced engraving gravure printing inks; through secondary curing, it not only meets the process requirements for rapid transfer on the production line but also achieves the high-performance requirements of engraving gravure printing inks.

[0098] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A gravure printing ink with dual functions of UV drying and natural oxidation drying, characterized in that, Includes the following components by weight percentage: Functional resin 10-30%, reactive diluent 5-20%, pigment 8-40%, filler 15-40%, wax 3-8%, surfactant 1-5%, photoinitiator 2-8%, and drier 0.5-3%; The functional resin is a first functional resin or a second functional resin; The first functional resin is prepared by a method comprising the following steps: Tung oil and maleic anhydride were mixed and subjected to the first addition reaction to obtain the first addition product; The first addition product, hydroxyethyl acrylic acid and the first polymerization inhibitor are mixed and subjected to a first esterification reaction to obtain the first esterified product. The first esterification product and glycidyl methacrylate were mixed and subjected to a first ring-opening esterification to obtain the first ring-opening esterification product. The first ring-opening esterification product is mixed with epoxy resin to carry out an epoxy ring-opening reaction to obtain the first functional resin. The second functional resin is prepared by a method comprising the following steps: Linseed oil and maleic anhydride were mixed and subjected to a second addition reaction to obtain the second addition product; The second addition product and polyethylene glycol monomethyl ether were mixed and subjected to a second esterification reaction to obtain the second esterified product. The second esterification product, glycidyl methacrylate, and the second polymerization inhibitor are mixed and subjected to a second ring-opening esterification to obtain the second functional resin. The reactive diluent is prepared by a method comprising the following steps: The reactive diluent is obtained by mixing tung oil acid, glycidyl methacrylate, triethanolamine and a third polymerization inhibitor and then performing a third ring-opening esterification.

2. The engraving gravure printing ink according to claim 1, characterized in that, When preparing the first functional resin, the mass ratio of tung oil, maleic anhydride, hydroxyethyl acrylic acid, glycidyl methacrylate and epoxy resin is 900:200:180:180:

100.

3. The engraving gravure printing ink according to claim 1, characterized in that, When preparing the second functional resin, the mass ratio of linseed oil, maleic anhydride, polyethylene glycol monomethyl ether and glycidyl methacrylate is 900:150:400:

280.

4. The engraving gravure printing ink according to claim 1, characterized in that, When preparing the reactive diluent, the mass ratio of tung oil acid, glycidyl methacrylate and triethanolamine is 300:100:0.

5.

5. The engraving gravure printing ink according to claim 1, characterized in that, The filler includes calcium carbonate and / or talc.

6. The engraving gravure printing ink according to claim 1, characterized in that, The surfactant includes one or more of sodium dodecylbenzenesulfonate, amine dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium dibutylnaphthalenesulfonate, sodium fatty alcohol ether sulfate, fatty alcohol polyoxyethylene ether, alkyl glycoside, and cocamidopropyl betaine.

7. The engraving gravure printing ink according to claim 1, characterized in that, The drying agent includes one or more of isooctanoate, naphthenate, and stearate, and contains a metal element.

8. The engraving gravure printing ink according to claim 7, characterized in that, The metallic elements include one or more of cobalt, manganese, vanadium, cerium, calcium, zinc, barium, zirconium, iron, and rare earth elements.

9. The engraving gravure printing ink according to claim 1, characterized in that, The wax includes one or more of paraffin wax, polyethylene wax, polypropylene wax, polyamide wax, Fischer-Tropsch wax, carnauba wax, and polytetrafluoroethylene wax.

10. The application of the engraving gravure printing ink according to any one of claims 1 to 9 in the field of engraving gravure printing.

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