CN114456638A - Vegetable oil-based low-halogen environment-friendly ink and preparation method thereof - Google Patents
Vegetable oil-based low-halogen environment-friendly ink and preparation method thereof Download PDFInfo
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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
- C09D11/06—Printing inks based on fatty oils
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- 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
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Abstract
The invention discloses a vegetable oil-based low-halogen environment-friendly printing ink and a preparation method thereof, wherein the vegetable oil-based low-halogen environment-friendly printing ink is prepared from the following raw materials: pigment particles, polyethylene wax, a connecting material, soybean methyl oleate, a cobalt drying agent and a dispersing agent. The printing ink is refined by pure vegetable oil, is green and environment-friendly, is suitable for various offset printing presses, is quick in fixation, quick in drying, high in gloss, stable in printing on the printing press and good in wear resistance, is a product which has excellent printing performance and wide application range and meets the environment-friendly requirements of packaging and green printing of various industries; the preparation method comprises the steps of dispersion matching, rolling grinding, filtering and packaging; the modified short-oil alkyd resin is prepared by a double-bond copolymerization method, and the modified alkyd resin has excellent self-drying property; the self-made modified short-oil alkyd resin is put into the preparation process of the binder through a two-step method, and the prepared binder endows the ink with excellent flowing and printing capabilities, and enables an ink film to have high gloss and friction resistance.
Description
Technical Field
The invention relates to ink, in particular to vegetable oil-based low-halogen environment-friendly ink and a preparation method thereof.
Background
The low-halogen offset printing ink is refined from pure vegetable oil based on an advanced green environmental protection concept, almost does not contain volatile components such as mineral oil and the like, reaches the standards of low-halogen, no solvent and no aromatic hydrocarbon, and meets the control requirements of Europe on mineral oil (MOSH & MOAH) in the printing ink.
The NON VOC ink is suitable for quick-drying products which have strict requirements on printing environment and emission and good printing performance. NON VOC inks have been marketed for nearly 10 years, but the company that really mastered the technology did the Phoenix Linn horn. In the prior art, the performance of the VOC-free ink still has more defects: 1. the ink drying speed is slow; 2, the printing adaptability is poor.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the plant oil-based low-halogen environment-friendly ink and the preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the vegetable oil-based low-halogen environment-friendly ink is prepared from the following raw materials in parts by weight: 20-30 parts of pigment particles, 4-6 parts of polyethylene wax, 10-20 parts of a binder, 0.4-0.6 part of soybean methyl oleate A10-15 parts of a cobalt drying agent and 1-2 parts of a dispersing agent; the connecting material is prepared from 35-40 parts of modified short oil alkyd resin, 20-30 parts of tung oil, 10-15 parts of soybean oil, 78-30 parts of soybean methyl oleate B20, 0.5-0.7 part of gel and 0.1-0.3 part of 2, 6-di-tert-butyl-4-methylphenol; the modified short oil alkyd resin is prepared from 10-20 parts of soybean oil fatty acid, 10-20 parts of n-butyl methacrylate, 15-30 parts of refined soybean oil, 15-30 parts of glycerol, 20-30 parts of phthalic anhydride, 1-3 parts of lithium hydroxide and 3-5 parts of an initiator.
The ratio of the tung oil to the soybean oil is 2: 1.
The pigment particles are any one of phthalocyanine blue, phthalocyanine green, orange and lithol carmine.
The fineness of the pigment particles is 20-30 microns.
The cobalt drying agent is cobalt iso-octoate.
The dispersing agent is polyvinylpyrrolidone.
The initiator is any one of benzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide and dicetyl peroxydicarbonate.
A method of preparing an ink as described above, comprising the steps of:
(1) and dispersing and matching: adding the pigment particles, the polyethylene wax, the connecting material, the soybean methyl oleate A, the cobalt drying agent and the dispersing agent in parts by weight into a high-speed dispersion machine, uniformly mixing and dispersing to obtain a mixture A.
(2) Rolling and grinding: adding the obtained mixture A into a three-roller machine for fully grinding for 30 minutes to fully disperse the pigment in the resin; and (3) detecting the fineness of the ink by using a 25-micron scraper fineness meter after grinding, and discharging to obtain the base ink when the fineness of the ink is less than 5 microns.
(3) And filtering and packaging: filtering the obtained base ink by using a 200-mesh and 300-mesh filter, removing impurities, and packaging the obtained plant oil-based low-halogen environment-friendly ink.
The production process of the modified short oil alkyd resin comprises the following steps:
(1) adding the refined soybean oil and the glycerol in parts by weight into a reaction kettle A, heating to 120 ℃ while stirring, adding the lithium hydroxide in parts by weight when the temperature is increased to 120 ℃, then continuing heating to 210 ℃, and carrying out heat preservation reaction for 30 minutes to obtain the basic alkyd resin.
(2) Adding the above-mentioned portions of phthalic anhydride, soybean oil fatty acid, n-butyl methacrylate and half of initiator into reaction still B, uniformly mixing them in advance; and then diluting the basic alkyd resin with a proper amount of dimethylbenzene in a reaction kettle B, stirring and heating to 140 ℃, adding the basic alkyd resin at a constant speed, keeping for 3-4 hours until the basic alkyd resin is dripped, keeping the temperature at 135 ℃ for 2 hours after the basic alkyd resin is dripped, then adding the rest initiator, keeping the temperature for 1 hour, cooling, and filtering to obtain the modified short-oil alkyd resin.
The production process of the connecting material comprises the following steps: putting the modified alkyd resin, the tung oil and the soybean oil in parts by weight and half of the soybean methyl oleate B in parts by weight into a reaction kettle C, heating to 200 ℃, and preserving heat for 30 minutes after the resin is completely dissolved; and cooling to 90 ℃ after heat preservation, adding the gel, 2, 6-di-tert-butyl-4-methylphenol and the rest of the soybean methyl oleate B in parts by weight, heating to 180 ℃ while stirring, preserving heat for reaction for 30 minutes, and discharging to obtain the connecting material.
The invention has the beneficial effects that:
(1) the printing ink is refined by pure vegetable oil, is environment-friendly and low in halogen, has MOSH & MOAH content of less than 1%, is suitable for various offset printing machines, can be used under the conditions of alcohol and no alcohol, is suitable for the current high-speed multicolor printing conditions, has quick ink fixation, quick drying, high gloss, stable printing on a machine and good wear resistance, can be used for coated paper, matt powder paper, paperboard and offset printing, and can provide better printing effect; meanwhile, the ink disclosed by the invention is excellent in transferability, excellent in stability on a roller, not easy to plate up, excellent in printing performance, wide in application and capable of meeting the environmental protection requirements of packaging and green printing of various industries.
(2) The preparation method comprises the steps of dispersing and matching, rolling and grinding, filtering and packaging; the modified short-oil alkyd resin is prepared by a double-bond copolymerization method, and has excellent self-drying property; the self-made modified short-oil alkyd resin is put into the preparation process of the binder through a two-step method, and the prepared binder endows the ink with excellent flowing and printing capabilities, and enables an ink film to have high gloss and friction resistance.
Detailed Description
In all the examples of the present invention, the temperature and pressure are not particularly emphasized, and are both normal temperature and normal pressure, and the equipment use is not particularly described, and the equipment can be used according to the conventional setting.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be noted that the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
The vegetable oil-based low-halogen environment-friendly ink is prepared from the following raw materials in parts by weight: 20-30 parts of pigment particles, 4-6 parts of polyethylene wax, 10-20 parts of a binder, 0.4-0.6 part of soybean methyl oleate A10-15 parts of a cobalt drying agent and 1-2 parts of a dispersing agent; the connecting material comprises 35-40 parts of modified short oil alkyd resin, 20-30 parts of tung oil (the manufacturer is not limited and can buy the tung oil according to the requirement in the market), 10-15 parts of soybean oil (the manufacturer is not limited and can buy the soybean oil according to the requirement in the market), 10-15 parts of soybean methyl oleate B20-30 parts (replacing mineral oil), and a gel (selected from Jinxin chemical industry Limited public works)Department of sauce) 0.5-0.7 part and 2, 6-di-tert-butyl-4-methylphenol 0.1-0.3 part; the modified short oil alkyd resin is prepared from 10-20 parts of soybean oil fatty acid (produced by Jinan Xundali chemical Co., Ltd.) and n-butyl methacrylate (chemical formula C)8H14O2)10-20 parts of refined soybean oil (produced by Wuhan Haohan Cheng Shang trade Co., Ltd.), 15-30 parts of glycerol (produced by Shanghai Kangyin chemical Co., Ltd.), and phthalic anhydride (molecular formula C)8H4O3)20-30 parts of lithium hydroxide (chemical formula is LiOH)1-3 parts of initiator 3-5 parts of the composition.
The pigment particles are organic pigment particles, and are selected from one of phthalocyanine blue (produced by Shandong Polychemists, Inc.), phthalocyanine green (produced by Shandong Polychemists, Inc.), orange (produced by Shandong Polychemists, Inc.) and lithol carmine (produced by Shandong Polychemists, Inc.), and the like, and the pigment particles can be selected according to actual requirements. The fineness of the pigment particles directly affects the colors that the ink exhibits. Through research, when the fineness of the pigment particles is 20-30 microns, the color development effect of the ink is best
The polyethylene wax (produced by Shanghai Kayin chemical Co., Ltd.) is used as a friction-resistant additive, and can be floated on an ink film after being printed on a printing stock by being added into the ink to increase the friction resistance. The amount of polyethylene wax used is critical to the performance of the ink and directly affects the fluidity, transfer and gloss of the ink.
Soybean methyl oleate (including soybean methyl oleate a and soybean methyl oleate B, produced by ewing-witz chemical (shanghai) limited) is used in the present invention instead of conventional mineral oil. In the traditional printing ink, the common mineral oil has high boiling point and has the function of dissolving with resin and quickly separating from a film layer to enter between paper fibers, so that the film layer is thickened and tackified, and the stability of the printing ink on a printing machine is ensured. In order to achieve the effect of no VOC, the invention uses soybean methyl oleate to replace mineral oil, and it needs to be specifically described that: first, not all vegetable fats can be used as a substitute for mineral oil, since most vegetable fats have strong solubility and only cause printer failure if put into use blindly (because these fats swell rollers and blankets); secondly, the amount of the vegetable oil is also needed to be paid special attention, and excessive vegetable oil causes problems of ink flying, excessive emulsification and the like. The applicant tested other vegetable fats in sequence, and at present only soybean methyl oleate can replace mineral oil.
The cobalt drying agent is cobalt iso-octoate (chemical formula: C)16H30CoO4) The cobalt iso-octoate is an oxidation type drying agent, has strong drying capability and particularly promotes surface drying. The cobalt iso-octoate adopted by the invention plays a role in accelerating the drying of the ink oxidized film, is also called as a drier, and is one of the most important auxiliaries. The common drying agents also comprise metal drying agents such as manganese drying agents, but the drying effects of the drying agents are not ideal, and the drying agents are not generally used for printing ink. The drying mechanism of the cobalt iso-octoate of the present application: the cobalt iso-octoate can be dissociated into free radicals and receives hydrogen on the adjacent carbon atoms of the double bonds of the soybean methyl oleate molecules, so that the soybean methyl oleate molecules are dissociated into free radicals, and the free radicals are further oxidized into peroxide and generate new free radicals; in other words, the cobalt iso-octoate can promote the double bond opening in the soybean methyl oleate, form free radicals and further polymerize, and oxygen is not absorbed in the polymerization process. It should be noted that the cobalt isooctanoate of the present invention contains a small amount of mineral oil, but the content of the mineral oil in the final product is very small and can be ignored (no drying agent capable of replacing the cobalt isooctanoate can be found at present).
The dispersant is polyvinylpyrrolidone (chemical formula is (C)6H9NO)n). The vinylpyrrolidone can improve the dispersibility of the pigment in the binder, so that the finished product has better fluidity and the quality of the ink is improved. The vinylpyrrolidone can effectively improve the dispersibility of the pigment in the binder, so that the ink has better fluidity and higher color difference and gloss.
A method of preparing an ink as described above, comprising the steps of:
(1) and dispersed matching: adding the pigment particles, the polyethylene wax, the connecting material, the soybean methyl oleate A, the cobalt drying agent and the dispersing agent in parts by weight into a high-speed dispersion machine, uniformly mixing and dispersing to obtain a mixture A. The high-speed dispersion machine is arranged conventionally.
(2) Rolling and grinding: adding the obtained mixture A into a three-roller machine for fully grinding for 30 minutes to fully disperse the pigment in the resin; and (3) detecting the fineness of the ink by using a 25-micron scraper fineness meter after grinding, and discharging to obtain the base ink when the fineness of the ink is less than 5 microns.
(3) And filtering and packaging: filtering the obtained base ink by using a 200-mesh and 300-mesh filter, removing impurities, and packaging the obtained plant oil-based low-halogen environment-friendly ink.
The connecting material is prepared from 35-40 parts of modified short oil alkyd resin, 20-30 parts of tung oil, 10-15 parts of soybean oil, 20-30 parts of soybean methyl oleate B, 0.5-0.7 part of gel (produced by Heizhou Hengying technologies Co., Ltd.) and 0.1-0.3 part of 2, 6-di-tert-butyl-4-methylphenol;
the binder is a substance for connecting the pigment particles and the printing stock, is a mixed liquid with certain viscosity and fluidity, is an important component for forming the ink, and the quality of the ink is directly determined by the property of the binder. Conventional inks are generally composed of resins, vegetable oils, mineral oils and gelling agents.
As for the selection of the resin, the alkyd resin comprises short oil, medium oil and long oil according to the content of the vegetable oil, and the medium oil alkyd resin and the long oil alkyd resin have poor pigment wettability, so the short oil alkyd resin is selected and synthesized in the invention and is modified to prepare the modified short oil alkyd resin. The modified short oil alkyd resin has good wettability and ideal color development, and the prepared ink has good fluidity.
For the selection of vegetable oils, which are important components of the vehicle, common vegetable oils used in inks are: catalpa oil, tung oil, soybean oil, linseed oil, rapeseed oil, peanut oil and the like. The reason for choosing the tung oil and the soybean oil to be matched among a plurality of vegetable oils is that: the tung oil has conjugated double bonds in its molecular structure, and has excellent drying performance and filming performance, but because it is dried too fast, it is easy to crystallize and wrinkle, so it needs to select vegetable oil with slow oxidation speed to match it. Experiments show that the soybean oil and the tung oil are matched for use, the matching proportion is that the tung oil is 2 to 1 compared with the soybean oil, and the matching effect is far better than that of other vegetable oils which are singly used or mixed (the linseed oil is not used, so that the economy is improved).
Because the printing ink adopts the cobalt drying agent with strong drying property and the tung oil, the situation that the film is easy to form and the fine rolling is difficult to occur in the preparation process, 2, 6-di-tert-butyl-4-methylphenol (molecular formula C) is added into the binder11H16O) is used to retard oxidative polymerization. The action mechanism is as follows: the 2, 6-di-tert-butyl-4-methylphenol is easy to generate a stable compound by a free radical reaction, prevents a free radical chain growth reaction and delays an oxidation process.
The production process of the connecting material comprises the following steps: putting the modified alkyd resin, the tung oil and the soybean oil in parts by weight and half of the soybean methyl oleate B in parts by weight into a reaction kettle C, heating to 200 ℃, and preserving heat for 30 minutes after the resin is completely dissolved; and cooling to 90 ℃ after heat preservation, adding the gel, 2, 6-di-tert-butyl-4-methylphenol and the rest of the soybean methyl oleate B in parts by weight, heating to 180 ℃ while stirring, preserving heat for reaction for 30 minutes, and discharging to obtain the connecting material.
The production of the traditional connecting material is a one-step method, and although the production mode has short working hours and convenient operation, the prepared connecting material is unstable because the resin is not completely dissolved in the preparation process and partial resin begins to perform chelation reaction. The preparation method of the binder adopts a two-step method, and the self-made modified short-oil alkyd resin is added into the preparation process of the binder through the two-step method, so that the prepared binder endows the ink with excellent flowing and printing capabilities, and enables an ink film to have high gloss and friction resistance.
The modified short oil alkyd resin is prepared from 10-20 parts of soybean oil fatty acid, 10-20 parts of n-butyl methacrylate, 15-30 parts of refined soybean oil, 15-30 parts of glycerol, 20-30 parts of phthalic anhydride, 1-3 parts of lithium hydroxide (catalyst) and 3-5 parts of initiator.
The alkyd resin has multidirectional conjugated double bonds, so that the viscosity of the alkyd resin is inferior to that of other resins, the conjugated double bonds of the alkyd resin are consumed by a double bond copolymerization method, and the viscosity of the alkyd resin is improved. Alkyd resins are polymers obtained by esterification of polyols and polyacids. Alkyd resins are slow to dry, have poor water resistance and poor corrosion resistance, and are therefore unsuitable for direct use in inks and require modification treatment. Modified alkyd resins are generally prepared by first forming monoglycerides by alcoholysis of vegetable oils and then esterifying the monoglycerides with a polybasic acid to form a polymer. The modified alkyd resin has ideal pigment wettability and color rendering property, and the prepared ink has good fluidity, good conjunctiva luster and good drying property. But its use in flexographic inks is limited due to the presence of larger hydroxyl groups in the system, resulting in poor water resistance. At present, the water resistance of modified alkyd resins is generally improved by increasing the relative molecular weight or by isocyanating (reacting a portion of the hydroxyl groups) or by reacting with solid hard resins. The invention uses a double-bond copolymerization method to synthesize the alkyd resin prepared by an alcoholysis method, n-butyl methacrylate and soybean oil fatty acid to obtain the modified alkyd resin (which is modified bilaterally by the n-butyl methacrylate and the soybean oil fatty acid). The properties were characterized by viscosity testing, infrared spectroscopy and differential scanning calorimetry analysis. The viscosity of the modified alkyd resin is increased by 67 percent; the acid value is reduced by 30 percent, and the self-drying property is better at normal temperature.
The initiator is benzoyl peroxide (molecular formula C)14H10O4) Dicumyl peroxide (chemical formula C)18H22O2) Tert-butyl hydroperoxide (formula C)4H10O2) And dicetyl peroxydicarbonate of formula C34H66O6) Any one of them.
The production process of the modified short oil alkyd resin comprises the following steps:
(1) adding the refined soybean oil and the glycerol in parts by weight into a reaction kettle A, heating to 120 ℃ while stirring, adding the lithium hydroxide in parts by weight when the temperature is increased to 120 ℃, then continuing heating to 210 ℃, and carrying out heat preservation reaction for 30 minutes to obtain the basic alkyd resin.
(2) Adding the above-mentioned portions of phthalic anhydride, soybean oil fatty acid, n-butyl methacrylate and half of initiator into reaction still B, uniformly mixing them in advance; and then diluting the basic alkyd resin with a proper amount of dimethylbenzene in a reaction kettle B, stirring and heating to 140 ℃, adding the basic alkyd resin at a constant speed, keeping for 3-4 hours until the basic alkyd resin is dripped, keeping the temperature at 135 ℃ for 2 hours after the basic alkyd resin is dripped, then adding the rest initiator, keeping the temperature for 1 hour, cooling, and filtering to obtain the modified short-oil alkyd resin.
Specific example 1: 20 parts of pigment particles, 4 parts of polyethylene wax, 10 parts of connecting material, 0.4 part of soybean oil methyl A10 part of cobalt drying agent and 1 part of dispersing agent. The connecting material is prepared from 38 parts of modified short oil alkyd resin, 26 parts of tung oil, 13 parts of soybean oil, 0.6 part of soybean methyl oleate B25 part, 0.2 part of gelling agent and 0.2 part of 2, 6-di-tert-butyl-4-methylphenol. The modified short oil alkyd resin is prepared from 15 parts of soybean oil fatty acid, 15 parts of n-butyl methacrylate, 25 parts of refined soybean oil, 25 parts of glycerol, 20 parts of phthalic anhydride, 2 parts of lithium hydroxide and 4 parts of an initiator.
Preparation step (1) of specific example 1, dispersion compounding: and adding the pigment particles, the polyethylene wax, the connecting material, the soybean methyl oleate A, the cobalt drying agent and the dispersing agent in parts by weight into a high-speed dispersion machine, uniformly mixing and dispersing to obtain a mixture.
(2) Rolling and grinding: adding the obtained mixture into a three-roller machine for fully grinding for 30 minutes to fully disperse the pigment in the resin; and (3) detecting the fineness of the ink by using a 25-micron scraper fineness meter after grinding, and discharging to obtain the base ink when the fineness of the ink is less than 5 microns.
(3) And filtering and packaging: filtering the obtained basement membrane by using a 200-mesh and 300-mesh filter, removing impurities, and packaging the obtained plant oil-based low-halogen environment-friendly ink A.
Specific example 2: 25 parts of pigment particles, 5 parts of polyethylene wax, 15 parts of connecting material, 12 parts of soybean methyl oleate A, 0.5 part of cobalt drying agent and 1.5 parts of dispersing agent. The connecting material is prepared from 38 parts of modified short oil alkyd resin, 26 parts of tung oil, 13 parts of soybean oil, 0.6 part of soybean methyl oleate B25 part, 0.2 part of gelling agent and 0.2 part of 2, 6-di-tert-butyl-4-methylphenol. The modified short oil alkyd resin is prepared from 15 parts of soybean oil fatty acid, 15 parts of n-butyl methacrylate, 25 parts of refined soybean oil, 25 parts of glycerol, 20 parts of phthalic anhydride, 2 parts of lithium hydroxide and 4 parts of an initiator.
Preparation step (1) of specific example 2, dispersive compounding: and adding the pigment particles, the polyethylene wax, the connecting material, the soybean methyl oleate A, the cobalt drying agent and the dispersing agent in parts by weight into a high-speed dispersion machine, uniformly mixing and dispersing to obtain a mixture.
(2) Rolling and grinding: adding the mixture A obtained in the previous step into a three-roller machine for fully grinding for 30 minutes to ensure that the pigment is fully dispersed in the resin; and (3) detecting the fineness of the ink by using a 25-micron scraper fineness meter after grinding, and discharging to obtain the base ink when the fineness of the ink reaches below 5 microns.
(3) And filtering and packaging: filtering the obtained basement membrane by using a filter with 200 meshes and 300 meshes, removing impurities, and packaging the obtained plant oil-based low-halogen environment-friendly ink B.
Specific example 3: 30 parts of pigment particles, 6 parts of polyethylene wax, 20 parts of connecting material, 15 parts of soybean methyl oleate A, 0.6 part of cobalt drying agent and 2 parts of dispersing agent. The connecting material is prepared from 38 parts of modified short oil alkyd resin, 26 parts of tung oil, 13 parts of soybean oil, 0.6 part of soybean methyl oleate B25 part, 0.2 part of gelling agent and 0.2 part of 2, 6-di-tert-butyl-4-methylphenol. The modified short oil alkyd resin is prepared from 15 parts of soybean oil fatty acid, 15 parts of n-butyl methacrylate, 25 parts of refined soybean oil, 25 parts of glycerol, 20 parts of phthalic anhydride, 2 parts of lithium hydroxide and 4 parts of an initiator.
The preparation procedure of specific example 3: (1) and dispersed matching: and adding the pigment particles, the polyethylene wax, the connecting material, the soybean methyl oleate A, the cobalt drying agent and the dispersing agent in parts by weight into a high-speed dispersion machine, uniformly mixing and dispersing to obtain a mixture.
(2) Rolling and grinding: adding the obtained mixture A into a three-roller machine for fully grinding for 30 minutes to ensure that the pigment is fully dispersed in the resin; and (3) detecting the fineness of the ink by using a 25-micron scraper fineness meter after grinding, and discharging to obtain the base ink when the fineness of the ink is less than 5 microns.
(3) And filtering and packaging: filtering the obtained basement membrane by using a 200-mesh and 300-mesh filter, removing impurities, and packaging the obtained plant oil-based low-halogen environment-friendly ink C.
Comparative example 1: 20 parts of pigment particles, 4 parts of polyethylene wax, 10 parts of connecting materials, 10 parts of mineral oil, 0.4 part of cobalt drying agent and 1 part of dispersing agent. The connecting material is prepared from 38 parts of rosin modified alkyd resin, 26 parts of tung oil, 13 parts of soybean oil, 0.6 part of soybean methyl oleate B25 part, 0.2 part of gelling agent and 0.2 part of 2, 6-di-tert-butyl-4-methylphenol.
Preparation step (1) of comparative example 1, dispersion compounding: and adding the pigment particles, the polyethylene wax, the connecting material, the soybean methyl oleate A, the cobalt drying agent and the dispersing agent in parts by weight into a high-speed dispersion machine, uniformly mixing and dispersing to obtain a mixture.
(2) Rolling and grinding: adding the obtained mixture into a three-roller machine for fully grinding for 30 minutes to fully disperse the pigment in the resin; and (3) detecting the fineness of the ink by using a 25-micron scraper fineness meter after grinding, and discharging to obtain the base ink when the fineness of the ink is less than 5 microns.
(3) And filtering and packaging: filtering the obtained basement membrane by using a 200-mesh and 300-mesh filter, removing impurities, and packaging the obtained plant oil-based low-halogen environment-friendly ink D.
Comparative example 2: 20 parts of pigment particles, 4 parts of polyethylene wax, 10 parts of connecting material, 10 parts of mineral oil, 0.4 part of cobalt drying agent and 1 part of dispersing agent. The connecting material is prepared from 38 parts of rosin modified phenolic resin, 26 parts of tung oil, 13 parts of soybean oil, 25 parts of soybean methyl oleate B, 0.6 part of gel and 0.2 part of 2, 6-di-tert-butyl-4-methylphenol.
Preparation step (1) of comparative example 2, dispersed compounding: and adding the pigment particles, the polyethylene wax, the connecting material, the soybean methyl oleate A, the cobalt drying agent and the dispersing agent in parts by weight into a high-speed dispersion machine, uniformly mixing and dispersing to obtain a mixture.
(2) Rolling and grinding: adding the obtained mixture into a three-roller machine for fully grinding for 30 minutes to fully disperse the pigment in the resin; and (3) detecting the fineness of the ink by using a 25-micron scraper fineness meter after grinding, and discharging to obtain the base ink when the fineness of the ink reaches below 5 microns.
(3) And filtering and packaging: filtering the obtained basement membrane by using a 200-mesh and 300-mesh filter, removing impurities, and packaging the obtained plant oil-based low-halogen environment-friendly ink E.
Comparative example 3: 20 parts of pigment particles, 4 parts of polyethylene wax, 10 parts of connecting material, 10 parts of mineral oil, 0.4 part of manganese drying agent and 1 part of dispersing agent. The connecting material is prepared from 38 parts of modified short oil alkyd resin, 26 parts of tung oil, 13 parts of soybean oil, 25 parts of soybean methyl oleate B, 0.6 part of gelling agent and 0.2 part of 2, 6-di-tert-butyl-4-methylphenol. The modified short oil alkyd resin is prepared from 15 parts of soybean oil fatty acid, 15 parts of n-butyl methacrylate, 25 parts of refined soybean oil, 25 parts of glycerol, 20 parts of phthalic anhydride, 2 parts of lithium hydroxide and 4 parts of an initiator.
Preparation step (1) of comparative example 3, dispersed compounding: adding the pigment particles, the polyethylene wax, the connecting material, the soybean methyl oleate A, the manganese drying agent and the dispersing agent in parts by weight into a high-speed dispersion machine, uniformly mixing and dispersing to obtain a mixture.
(2) Rolling and grinding: adding the obtained mixture into a three-roller machine for fully grinding for 30 minutes to fully disperse the pigment in the resin; and (3) detecting the fineness of the ink by using a 25-micron scraper fineness meter after grinding, and discharging to obtain the base ink when the fineness of the ink is less than 5 microns.
(3) And filtering and packaging: filtering the obtained basement membrane by using a 200-mesh and 300-mesh filter, removing impurities, and packaging the obtained plant oil-based low-halogen environment-friendly ink F.
The inks a, B, C, D, E and F obtained above were tested for their ink properties, and the test results were as follows:
the data analysis shows that the VOC-free ink developed by the invention solves the problems of low fixing speed and poor printing adaptability of the traditional NON VOC ink, and other indexes are similar to those of the existing common ink. Therefore, the printing ink is refined by pure vegetable oil, is environment-friendly and low in halogen, has MOSH & MOAH content of less than 1 percent, is suitable for various offset printing presses, can be used under the condition of alcohol and no alcohol, is suitable for the current high-speed multicolor printing conditions, has quick ink fixation, quick drying, high gloss, stable printing on a machine and good wear resistance, can be used for coated paper, matt powder paper, paperboard and offset printing, and can provide better printing effect; meanwhile, the ink disclosed by the invention is excellent in transferability, excellent in stability on a roller, not easy to plate up, excellent in printing performance, wide in application and capable of meeting the environmental protection requirements of packaging and green printing of various industries.
As seen from comparative examples 1 and 2, since the rosin-modified alkyd resin and the rosin-modified phenolic resin have a reduced molecular weight compared to the modified short-oil alkyd resin of the present invention, at the same weight fraction, too much vegetable oil is caused, causing problems of ink misting, excessive emulsification, etc. In sum, comparative example 1, comparative example 2 and comparative example 3, cobalt driers are the best choice for the present invention with the modified short oil alkyds of the present invention.
It can also be seen from specific examples 1-3 that the viscosity of the system shows a tendency to decrease with increasing amounts of modified short oil alkyd resin. Through preliminary analysis, the polyvinyl pyrrolidone is probably related to the type of the dispersing agent, and the polyvinyl pyrrolidone is easy to agglomerate with the modified short-oil alkyd resin.
Countering: calculated, when the tung oil in the binder: when soybean oil is 3:2, theoretically the performance of the prepared connecting material is the best, but when the ratio of tung oil: soybean oil 3:2 instead without tung oil: the effect obtained when the soybean oil is 2:1 is good, the viscosity of the ink is more than 70000, the viscosity is still very low no matter how other components in the connecting material are adjusted, the specific reason is not found up to now, and preliminary analysis may be related to the modified short-oil alkyd resin.
In the description herein, the description of the terms "one embodiment," "some embodiments," "specific embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the claims and their equivalents.
Claims (10)
1. The vegetable oil-based low-halogen environment-friendly ink is characterized by being prepared from the following raw materials in parts by weight: 20-30 parts of pigment particles, 4-6 parts of polyethylene wax, 10-20 parts of a binder, 0.4-0.6 part of soybean methyl oleate A10-15 parts of a cobalt drying agent and 1-2 parts of a dispersing agent; the connecting material is prepared from 35-40 parts of modified short oil alkyd resin, 20-30 parts of tung oil, 10-15 parts of soybean oil, 78-30 parts of soybean methyl oleate B20, 0.5-0.7 part of gel and 0.1-0.3 part of 2, 6-di-tert-butyl-4-methylphenol; the modified short oil alkyd resin is prepared from 10-20 parts of soybean oil fatty acid, 10-20 parts of n-butyl methacrylate, 15-30 parts of refined soybean oil, 15-30 parts of glycerol, 20-30 parts of phthalic anhydride, 1-3 parts of lithium hydroxide and 3-5 parts of an initiator.
2. The ink of claim 1, wherein the tung oil to soybean oil ratio is 2: 1.
3. The ink according to claim 1, wherein the pigment particles are any one of phthalocyanine blue, phthalocyanine green, orange, and lithol carmine.
4. An ink according to claim 1, characterised in that the fineness of the pigment particles is 20-30 microns.
5. The ink of claim 1, wherein the cobalt drier is cobalt iso-octoate.
6. An ink according to claim 1, characterised in that the dispersant is polyvinylpyrrolidone.
7. The ink of claim 1, wherein the initiator is any one of benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, and dicetyl peroxydicarbonate.
8. A process for the preparation of an ink according to any of claims 1 to 7, characterized by the following steps:
(1) and dispersed matching: adding the pigment particles, the polyethylene wax, the connecting material, the soybean methyl oleate A, the cobalt drying agent and the dispersing agent in parts by weight into a high-speed dispersion machine, uniformly mixing and dispersing to obtain a mixture A;
(2) rolling and grinding: adding the obtained mixture A into a three-roller machine for fully grinding for 30 minutes to fully disperse the pigment in the resin; detecting the fineness of the ink by using a 25-micron scraper fineness meter after grinding, and discharging to obtain base ink when the fineness of the ink reaches below 5 microns;
(3) and filtering and packaging: filtering the obtained base ink by a filter with 200-300 meshes, removing impurities, and packaging the obtained plant oil-based low-halogen environment-friendly ink.
9. The preparation method according to claim 8, wherein the modified short oil alkyd resin is prepared by the following steps:
(1) adding the refined soybean oil and the glycerol in parts by weight into a reaction kettle A, heating to 120 ℃ while stirring, adding the lithium hydroxide in parts by weight when the temperature is increased to 120 ℃, then continuing heating to 210 ℃, and carrying out heat preservation reaction for 30 minutes to obtain a basic alkyd resin;
(2) adding the above-mentioned portions of phthalic anhydride, soybean oil fatty acid, n-butyl methacrylate and half of initiator into reaction still B, uniformly mixing them in advance; and then diluting the basic alkyd resin with a proper amount of dimethylbenzene in a reaction kettle B, stirring and heating to 140 ℃, adding the basic alkyd resin at a constant speed, keeping for 3-4 hours until the basic alkyd resin is dripped, keeping the temperature at 135 ℃ for 2 hours after the basic alkyd resin is dripped, then adding the rest initiator, keeping the temperature for 1 hour, cooling, and filtering to obtain the modified short-oil alkyd resin.
10. The production method according to claim 8, characterized in that the binder is produced by a process comprising: putting the modified alkyd resin, the tung oil and the soybean oil in parts by weight and half of the soybean methyl oleate B in parts by weight into a reaction kettle C, heating to 200 ℃, and preserving heat for 30 minutes after the resin is completely dissolved; and cooling to 90 ℃ after heat preservation, adding the gel, 2, 6-di-tert-butyl-4-methylphenol and the rest of the soybean methyl oleate B in parts by weight, heating to 180 ℃ while stirring, preserving heat for reaction for 30 minutes, and discharging to obtain the connecting material.
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| CN202210281503.5A CN114456638B (en) | 2022-03-21 | 2022-03-21 | Vegetable oil-based low-halogen environment-friendly ink and preparation method thereof |
| PCT/CN2022/126750 WO2023179008A1 (en) | 2022-03-21 | 2022-10-21 | Vegetable oil-based low-halogen environmentally friendly ink and preparation method therefor |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114958078A (en) * | 2022-06-08 | 2022-08-30 | 中山市富日印刷材料有限公司 | High-viscosity low-viscosity pure vegetable oil ink and preparation method thereof |
| WO2023179008A1 (en) * | 2022-03-21 | 2023-09-28 | 中山市富日印刷材料有限公司 | Vegetable oil-based low-halogen environmentally friendly ink and preparation method therefor |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002074871A1 (en) * | 2001-03-19 | 2002-09-26 | Guanbao Fan | Optically-variable ink composition and the use thereof |
| CN101831234A (en) * | 2010-05-25 | 2010-09-15 | 北京化工大学 | Method for preparing aqueous acrylic acid modified alkyd resin coating |
| CN102532991A (en) * | 2011-12-17 | 2012-07-04 | 张家港市威迪森油墨有限公司 | Soybean oil-based offset printing ink binder and preparation method thereof |
| CN102746738A (en) * | 2012-05-29 | 2012-10-24 | 兰州理工大学 | Alkyd acrylic graft copolymer printing ink and preparation method thereof |
| CN102993424A (en) * | 2012-11-27 | 2013-03-27 | 上海振华重工（集团）常州油漆有限公司 | Novel acrylic acid modified alkyd resin and method for preparing same |
| CN105802325A (en) * | 2014-12-30 | 2016-07-27 | 天津天女化工集团股份有限公司 | Plant oil-based offset lithographic printing ink formula and preparation method thereof |
| CN106833120A (en) * | 2017-03-03 | 2017-06-13 | 苏州市博来特油墨有限公司 | The stainless coloring agent printing ink of high osmosis wearable environment protection |
| CN108059908A (en) * | 2018-01-04 | 2018-05-22 | 山东齐鲁漆业有限公司 | A kind of acrylic modified waterborne alkyd lacquer type organic coating and preparation method thereof |
| CN108342124A (en) * | 2017-01-23 | 2018-07-31 | 上海杰易森股份有限公司 | A kind of environmental protection offset ink and preparation method thereof |
| CN108997818A (en) * | 2018-08-15 | 2018-12-14 | 芜湖扬展新材料科技服务有限公司 | A kind of environment protecting plant oil type ink and its preparation process |
| CN111138906A (en) * | 2020-01-18 | 2020-05-12 | 东昌工业（临海）有限公司 | Acrylate high-gloss gravure plastic surface printing ink and preparation method thereof |
| WO2020110501A1 (en) * | 2018-11-30 | 2020-06-04 | サカタインクス株式会社 | Ink composition for offset printing, method for producing same, and method for producing printed matter in which same is used |
| CN111393902A (en) * | 2020-03-26 | 2020-07-10 | 深圳市雅图燊印刷包装有限公司 | Biodegradable green printing ink binder, printing ink and preparation method thereof |
| CN112250850A (en) * | 2020-11-05 | 2021-01-22 | 韶关德瑞化学工业有限公司 | Environment-friendly alkyd resin and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105385229A (en) * | 2015-11-30 | 2016-03-09 | 苏州市博来特油墨有限公司 | Quick-dry high-gloss environment-friendly offset printing ink |
| CN107793834B (en) * | 2017-11-20 | 2021-05-04 | 武汉红金龙印务股份有限公司 | Preparation method and application of single-sheet paper offset printing ink with low VOC content |
| CN114456638B (en) * | 2022-03-21 | 2023-03-10 | 中山市富日印刷材料有限公司 | Vegetable oil-based low-halogen environment-friendly ink and preparation method thereof |
-
2022
- 2022-03-21 CN CN202210281503.5A patent/CN114456638B/en active Active
- 2022-10-21 WO PCT/CN2022/126750 patent/WO2023179008A1/en unknown
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002074871A1 (en) * | 2001-03-19 | 2002-09-26 | Guanbao Fan | Optically-variable ink composition and the use thereof |
| CN101831234A (en) * | 2010-05-25 | 2010-09-15 | 北京化工大学 | Method for preparing aqueous acrylic acid modified alkyd resin coating |
| CN102532991A (en) * | 2011-12-17 | 2012-07-04 | 张家港市威迪森油墨有限公司 | Soybean oil-based offset printing ink binder and preparation method thereof |
| CN102746738A (en) * | 2012-05-29 | 2012-10-24 | 兰州理工大学 | Alkyd acrylic graft copolymer printing ink and preparation method thereof |
| CN102993424A (en) * | 2012-11-27 | 2013-03-27 | 上海振华重工（集团）常州油漆有限公司 | Novel acrylic acid modified alkyd resin and method for preparing same |
| CN105802325A (en) * | 2014-12-30 | 2016-07-27 | 天津天女化工集团股份有限公司 | Plant oil-based offset lithographic printing ink formula and preparation method thereof |
| CN108342124A (en) * | 2017-01-23 | 2018-07-31 | 上海杰易森股份有限公司 | A kind of environmental protection offset ink and preparation method thereof |
| CN106833120A (en) * | 2017-03-03 | 2017-06-13 | 苏州市博来特油墨有限公司 | The stainless coloring agent printing ink of high osmosis wearable environment protection |
| CN108059908A (en) * | 2018-01-04 | 2018-05-22 | 山东齐鲁漆业有限公司 | A kind of acrylic modified waterborne alkyd lacquer type organic coating and preparation method thereof |
| CN108997818A (en) * | 2018-08-15 | 2018-12-14 | 芜湖扬展新材料科技服务有限公司 | A kind of environment protecting plant oil type ink and its preparation process |
| WO2020110501A1 (en) * | 2018-11-30 | 2020-06-04 | サカタインクス株式会社 | Ink composition for offset printing, method for producing same, and method for producing printed matter in which same is used |
| CN111138906A (en) * | 2020-01-18 | 2020-05-12 | 东昌工业（临海）有限公司 | Acrylate high-gloss gravure plastic surface printing ink and preparation method thereof |
| CN111393902A (en) * | 2020-03-26 | 2020-07-10 | 深圳市雅图燊印刷包装有限公司 | Biodegradable green printing ink binder, printing ink and preparation method thereof |
| CN112250850A (en) * | 2020-11-05 | 2021-01-22 | 韶关德瑞化学工业有限公司 | Environment-friendly alkyd resin and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 丁艳丽;: "大豆油在胶印油墨中的应用与发展" * |
| 肖志红,胡静波,张玉军,陈杰: "植物油基印刷油墨研究进展" * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023179008A1 (en) * | 2022-03-21 | 2023-09-28 | 中山市富日印刷材料有限公司 | Vegetable oil-based low-halogen environmentally friendly ink and preparation method therefor |
| CN114958078A (en) * | 2022-06-08 | 2022-08-30 | 中山市富日印刷材料有限公司 | High-viscosity low-viscosity pure vegetable oil ink and preparation method thereof |
| CN114958078B (en) * | 2022-06-08 | 2023-03-10 | 中山市富日印刷材料有限公司 | High-viscosity low-viscosity pure vegetable oil ink and preparation method thereof |
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| CN114456638B (en) | 2023-03-10 |
| WO2023179008A1 (en) | 2023-09-28 |
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