A cork paper water-based ink containing rare earth composite antibacterial material and its preparation method

Abstract

The present invention provides a cork paper water-based ink containing a rare earth composite antibacterial material and a preparation method thereof, belonging to the technical field of inks. In the present invention, a rare earth composite antibacterial material is prepared by using rare earth ions as antibacterial active substances and modified sepiolite as a carrier, and the antibacterial property of the rare earth composite antibacterial material is efficient and persistent; the rare earth composite antibacterial material is used to prepare a cork paper water-based ink, which is used in combination with acrylic resin, cellulose acetate butyrate, propylene glycol alginate, 1,4,5,8-naphthalenetetracarboxylic dianhydride, N-benzylethanolamine, additives, pigments and solvents. The obtained cork paper water-based ink is non-toxic and harmless, has good dispersibility, an efficient and persistent antibacterial effect, high adhesion fastness, good water resistance and good storage stability.

Description

Technical Field

[0001] The present invention belongs to the technical field of inks, and particularly relates to a tipping paper water-based ink containing rare earth composite antibacterial materials and a preparation method thereof. Background Art

[0002] Tipping paper is a packaging material for cigarettes, also known as tipping paper, and is one of the important materials for cigarette production. At present, most tipping paper printing uses alcohol-soluble and ester-soluble inks to print tipping paper. A large amount of volatile organic solvents during the printing process and solvent residues in the printed matter will have a certain impact on the environment and people's health. Water-based ink uses water as the main solvent. Water-based ink printing can reduce or even eliminate organic residues in the printed matter, ensuring the hygiene and safety of users. Therefore, the research on using water-based ink for tipping paper printing has received increasing attention.

[0003] Since tipping paper is in direct contact with the lips during use, the paper of tipping paper and the ink printed on tipping paper must be non-toxic and harmless to the human body, and the hygiene requirements are also very high, and it needs to have good antibacterial properties. At present, the research and development of water-based inks for tipping paper on the market mostly stay on non-toxic and harmless. Therefore, the research on how to improve the antibacterial properties of water-based inks is the current research focus of water-based inks for tipping paper. The commonly used method at present is to add antibacterial materials to the ink.

[0004] For example, Patent CN104725934A discloses a preparation method of a tipping paper water-based ink containing silver-loaded sepiolite antibacterial materials, including (1) preparation of silver-loaded sepiolite; (2) compounding the silane coupling agent-modified silver-loaded sepiolite with water-based resin solution A and water-based resin solution B, and then compounding the mixed resin solution with deionized water, ethanol, tea saponin, organic pigments, defoamers, leveling agents and buffers to prepare a tipping paper water-based ink containing silver-loaded sepiolite antibacterial materials. This water-based ink adds a variety of antibacterial components such as nano-silver, titanium dioxide and tea saponin, and has strong broad-spectrum bactericidal properties.

[0005] Another example is that Patent CN104946007A discloses a special antibacterial water-based ink for tipping paper, which consists of 40-70 parts of acrylic resin solution, 15-25 parts of pigments and fillers, 5-15 parts of ethanol, 5-10 parts of deionized water, 1 part of wetting and dispersing agent, 0.1 part of defoamer, 0-1 part of leveling agent, and 0-1.5 parts of antibacterial auxiliary agent. This water-based ink has antibacterial and bactericidal properties, and at the same time has a low VOC content, extremely low metal content and residue.

[0006] For another example, Patent CN112457707A discloses a tipping paper water-based ink containing a composite antibacterial material and a preparation method thereof. The water-based ink containing the composite antibacterial material comprises the following components: 35-40 parts by weight of water-based polyurethane, 10-20 parts by weight of polyethylene emulsion, 3-5 parts by weight of additives, 25-30 parts by weight of pigments and fillers, 15-20 parts by weight of deionized water, 6-15 parts by weight of ethyl acetate, and 5-8 parts by weight of a composite bacteriostatic agent. While ensuring the antibacterial effect, the antibacterial stability of this water-based ink is improved, and the stability of the water-based ink is also ensured.

[0007] Currently, commonly used antibacterial materials can be classified into three major types according to their composition: inorganic antibacterial materials, organic antibacterial materials, and natural antibacterial materials. Silver-loaded inorganic antibacterial agents are currently the most ideal and widely used antibacterial agents, but the cost of using silver as the active ingredient is too high, and it is prone to discoloration problems; moreover, the antibacterial stability of current antibacterial materials is poor. Rare earth ions have unique physicochemical properties, and rare earth salts can be used as anti-corrosion and bactericidal agents. Rare earth ions can be used as antibacterial active ingredients to prepare tipping paper water-based ink, but there is little research on using rare earth in tipping paper water-based ink currently. Summary of the Invention

[0008] In view of this, the present invention provides a tipping paper water-based ink containing a rare earth composite antibacterial material and a preparation method thereof. This tipping paper water-based ink is non-toxic, harmless, has good dispersibility, has an efficient and long-lasting antibacterial effect, high adhesion fastness, good water resistance, and good storage stability, making up for the shortcomings of the prior art.

[0009] To solve the above technical problems, the technical solutions provided by the present invention are as follows:

[0010] On the one hand, a rare earth composite antibacterial material, comprising an antibacterial active substance and a modified sepiolite carrier;

[0011] The antibacterial active substance is a rare earth ion, and the rare earth ion is Ce 3+ , Pr 3+ , Nd 3+ , La 3+ or Gd 3+ or at least one of them;

[0012] The modified sepiolite is sepiolite chemically modified with a silane coupling agent, cucurbit[n]uril, and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid.

[0013] In the present invention, the rare earth ions are added using rare earth chloride salts or rare earth nitrate salts, and the rare earth ions account for 3-50% of the total mass of the rare earth composite antibacterial material. The present invention prepares an antibacterial material using rare earth ions as the active ingredient and modified sepiolite as the carrier. The rare earth ions are dispersed in the micropores of sepiolite and the three-dimensional network structure formed on the surface of sepiolite, thereby obtaining high-efficiency and stable antibacterial properties. When this antibacterial material is used to prepare water-based ink, it not only imparts excellent antibacterial properties but also helps improve the overall stability of the ink.

[0014] In the present invention, the modified sepiolite is prepared by the following method:

[0015] (1) Dissolve the silane coupling agent in water to prepare a silane coupling agent solution. After grinding and sieving sepiolite, add it to the silane coupling agent solution for treatment. After the treatment is completed, filter, and wash the filter residue with water to obtain silane coupling agent-modified sepiolite;

[0016] (2) Disperse cucurbit[n]uril in sufficient water, add potassium persulfate and potassium sulfate, and treat at 80-90 °C for 10-16 h. Cool to room temperature, filter to collect the filtrate, perform rotary evaporation at 50-60 °C, extract with concentrated hydrochloric acid, filter and wash with methanol, and dry to obtain activated cucurbit[n]uril;

[0017] (3) Disperse the activated cucurbit[n]uril obtained in step (2) in dimethyl sulfoxide, add the silane coupling agent-modified sepiolite obtained in step (1) and mix well, then add 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid, and react at room temperature for 2-5 h. After the reaction is completed, filter with ether, wash, and dry to obtain modified sepiolite.

[0018] The present invention first uses a silane coupling agent to modify the surface of sepiolite so that the surface of sepiolite is loaded with the silane coupling agent, and then uses cucurbit[n]uril and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid to further modify sepiolite to obtain modified sepiolite. Using it as a carrier to load the antibacterial active substance rare earth ions to prepare an antibacterial material, the obtained antibacterial material has more efficient and stable antibacterial properties. This may be because, on the one hand, cucurbit[n]uril and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid are introduced onto the surface of sepiolite, forming intermolecular forces with sepiolite, forming a certain uniform and stable three-dimensional network structure on the surface, increasing the loading of rare earth ions, thereby exerting the long-term and stable antibacterial properties of rare earth ions; on the other hand, the introduced 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid also has antibacterial properties. Through the synergistic effect of rare earth ions and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid, the antibacterial properties of the antibacterial agent are improved. The antibacterial material has good affinity with other components in the water-based ink and high dispersion uniformity, and can better exert its antibacterial properties, so that the water-based ink obtains high-efficiency and long-lasting antibacterial properties. In addition, it is also found that controlling the dosage of cucurbit[n]uril and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid also has a certain beneficial effect on the overall stability of the water-based ink.

[0019] Further, in step (1), the silane coupling agent is an amino-silane coupling agent, selected from at least one of N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane (KH-602), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AEAPS), or 3-aminopropyltriethoxysilane (APTES).

[0020] Further, in step (1), the mass ratio of the sepiolite to the silane coupling agent is 10:0.4 - 0.8; preferably, the mass ratio of the sepiolite to the silane coupling agent is 10:0.7.

[0021] Further, in step (1), the temperature of the treatment is 50 - 60°C, and the time is 1.5 - 3 h; preferably, the temperature of the treatment is 55°C, and the time is 2.5 h.

[0022] Further, in step (2), in the cucurbit[n]uril, n = 6, 7, or 8; preferably, in the cucurbit[n]uril, n = 7.

[0023] Further, in step (2), the mass ratio of potassium persulfate, potassium sulfate, and cucurbit[n]uril is 0.1 - 0.2:0.5 - 0.6:1; preferably, the mass ratio of potassium persulfate, potassium sulfate, and cucurbit[n]uril is 0.14:0.55:1.

[0024] Further, in step (3), the addition amount of the cucurbit[n]uril is 10 - 20% of the mass of the sepiolite modified by the silane coupling agent, and the addition amount of 4-hydroxyethylpiperazineethanesulfonic acid is 3 - 5% of the mass of the sepiolite modified by the silane coupling agent; preferably, the addition amount of the cucurbit[n]uril is 4.4% of the mass of the sepiolite modified by the silane coupling agent, and the addition amount of 4-hydroxyethylpiperazineethanesulfonic acid is 18% of the mass of the sepiolite modified by the silane coupling agent. Experiments have found that in the process of preparing the modified sepiolite, controlling the addition amounts of cucurbit[n]uril and 4-hydroxyethylpiperazineethanesulfonic acid not only ensures high-efficiency and stable antibacterial properties but also has a certain beneficial effect on improving the overall stability of the water-based ink.

[0025] The preparation method of the above rare earth composite antibacterial material includes the following steps:

[0026] Disperse rare earth chloride salt or rare earth nitrate salt in water to form a solution, add the modified sepiolite according to the formula amount, stir for 0.5 - 1 h, then heat up to 40 - 50°C and adjust the pH = 5 - 6, stir and react for 6 - 12 h, filter, wash the filter residue with water, and dry to obtain the rare earth composite antibacterial material.

[0027] On the other hand, the application of the above rare earth composite antibacterial material in the preparation of water-based ink.

[0028] On the other hand, a water-based ink for tipping paper contains the above-mentioned rare earth composite antibacterial material, as well as acrylic resin, cellulose acetate butyrate, propylene glycol alginate, 1,4,5,8-naphthalenetetracarboxylic dianhydride, N-benzylethanolamine, additives, pigments and solvents.

[0029] In the present invention, acrylic resin, cellulose acetate butyrate and propylene glycol alginate are used as the matrix materials of the water-based ink for tipping paper, and a rare earth composite antibacterial material is added as an antibacterial component, and 1,4,5,8-naphthalenetetracarboxylic dianhydride, N-benzylethanolamine and additives are added to obtain the water-based ink for tipping paper. The obtained water-based ink for tipping paper is non-toxic and harmless, has good dispersibility, high and lasting antibacterial effect, high adhesion fastness, good water resistance and good storage stability, making up for the shortcomings of the prior art.

[0030] Furthermore, the water-based ink for tipping paper, by weight fraction, contains 50-60 parts of acrylic resin, 15-25 parts of cellulose acetate butyrate, 5-8 parts of propylene glycol alginate, 3-5 parts of 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2-5 parts of N-benzylethanolamine, 3-5 parts of rare earth composite antibacterial material, 0.5-5 parts of additives, 10-20 parts of pigments and 10-30 parts of solvents.

[0031] Preferably, the water-based ink for tipping paper, by weight fraction, contains 58 parts of acrylic resin, 20 parts of cellulose acetate butyrate, 7 parts of propylene glycol alginate, 4 parts of 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4 parts of N-benzylethanolamine, 4 parts of rare earth composite antibacterial material, 2 parts of additives, 16 parts of pigments and 22 parts of solvents.

[0032] In the present invention, a certain amount of 1,4,5,8-naphthalenetetracarboxylic dianhydride and N-benzylethanolamine are added to the water-based ink for tipping paper. It is found that by controlling the mass ratio of 1,4,5,8-naphthalenetetracarboxylic dianhydride and N-benzylethanolamine added in the water-based ink within the range of 1-1.5:1, the two components can synergistically significantly improve the water resistance and stability of the water-based ink and improve the adhesion fastness. This may be because the addition of 1,4,5,8-naphthalenetetracarboxylic dianhydride and N-benzylethanolamine introduces active groups, which can increase the intermolecular force between the water-based ink and the tipping paper, and can improve the adhesion fastness between the water-based ink and the tipping paper; the two components can also react to form a certain network structure, making the network structure of the water-based ink more stable, stabilizing the active ingredients in the water-based ink in the system, and improving the overall stability and water resistance.

[0033] Furthermore, the solvent is a mixture of water and ethanol, and the mixing volume ratio of water and ethanol is 55-70:30-45. Preferably, the mixing volume ratio of water and ethanol is 68:32.

[0034] Furthermore, the additives include but are not limited to at least one of defoamers, leveling agents, and dispersants. Among them, the defoamers include but are not limited to at least one of dimethyl silicone oil, polyethylene ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, and Tween series; the leveling agents include but are not limited to at least one of ethylene oxide, propylene oxide, ethyl polyacrylate, butyl polyacrylate, 2-ethylhexyl polyacrylate, copolymer of ethyl acrylate and butyl acrylate, urea-formaldehyde resin, melamine-formaldehyde resin, polydimethylsiloxane, silicone oil, polyether polyester modified silicone oxide, alkyl modified silicone oxide, and end-group modified silicone; the dispersants include but are not limited to at least one of sodium dodecyl sulfate, cellulose derivatives, polyacrylamide, acrylic acid / sodium acrylate polymer, and methyl amyl alcohol. Preferably, the additives include defoamers, leveling agents, and dispersants, and the mass ratio of the defoamers, leveling agents, and dispersants is 0.1-10:0.1-5:1-10. Most preferably, the mass ratio of the defoamers, leveling agents, and dispersants is 3:2:5.

[0035] Furthermore, pigments can be added to the tipping paper water-based ink according to customer needs, and inorganic pigments and / or organic pigments can be selected as the pigments. Tipping paper prints generally present specific colors according to customer requirements. For example, cigarette tipping paper prints are required to present a specific yellow color. Generally, inorganic pigments and / or organic pigments are added to make the tipping paper show color. Inorganic pigments have a large specific gravity and are unevenly dispersed, and the brightness and gloss of prints are not as good as those of organic pigments. Currently, organic pigments or a combination of inorganic pigments and organic pigments are mostly used to improve the color of prints while meeting the hue requirements. The pigments include but are not limited to at least one of iron oxide red, iron oxide yellow, carbon black, phthalocyanine blue, phthalocyanine green, titanium dioxide, lithopone, benzidine yellow, lemon yellow, and aniline black.

[0036] The preparation method of the above-mentioned tipping paper water-based ink includes the following steps:

[0037] Disperse the rare earth composite antibacterial material in the solvent according to the formula amount, add 1,4,5,8-naphthalenetetracarboxylic dianhydride and N-benzylethanolamine, adjust the pH to 5-6, heat up to 70-80 °C and stir for 2-4 h; cool to room temperature, add acrylic resin, cellulose acetate butyrate, propylene glycol alginate, additives, and add pigments and mix evenly to obtain the tipping paper water-based ink.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] 1. The present invention prepares a cork paper water-based ink using acrylic resin, cellulose acetate butyrate, propylene glycol alginate, rare earth composite antibacterial material, 1,4,5,8-naphthalenetetracarboxylic dianhydride, N-benzylethanolamine, additives and solvents as raw materials. The components cooperate with each other, making the cork paper water-based ink have high and lasting antibacterial effect, high adhesion fastness, good water resistance, good storage stability, non-toxic and harmless, and good dispersibility.

[0040] 2. In the rare earth composite antibacterial material of the present invention, rare earth ions are used as active ingredients and are prepared with modified sepiolite as a carrier. The synergistic effect of rare earth ions and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid endows the antibacterial material with high antibacterial property. Moreover, the modified sepiolite as a carrier can endow the material with long-lasting antibacterial property and also has a certain enhancing effect on improving the overall stability of the water-based ink. Experiments have found that the water-based ink prepared with the rare earth composite antibacterial material has high antibacterial property against Staphylococcus aureus and Escherichia coli, with the antibacterial rate reaching more than 99%, and still maintaining an antibacterial rate of more than 95% after 1 year.

[0041] 3. The present invention adds a certain proportion of 1,4,5,8-naphthalenetetracarboxylic dianhydride and N-benzylethanolamine to the cork paper water-based ink. The two components synergistically can significantly improve the water resistance and stability of the water-based ink and enhance the adhesion fastness. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 It is the infrared spectrum diagram of the modified sepiolite in Example 1 of the present invention; in the figure, (a) represents unmodified sepiolite, (b) represents sepiolite modified with silane coupling agent, and (c) represents modified sepiolite. DETAILED DESCRIPTION OF THE INVENTION

[0043] The following non-limiting examples can enable those of ordinary skill in the art to more comprehensively understand the present invention, but do not limit the present invention in any way. The following content is only an exemplary illustration of the scope claimed by the present invention. Those skilled in the art can make various changes and modifications to the invention of the present invention according to the disclosed content, and it should also fall within the scope claimed by the present invention.

[0044] The present invention will be further described below by way of specific examples. All chemical reagents used in the examples of the present invention are obtained through conventional commercial channels unless otherwise specified.

[0045] Example 1

[0046] The formula of the cork paper water-based ink is as follows:

[0047] 50 parts of acrylic resin;

[0048] 25 parts of cellulose acetate butyrate;

[0049] 8 parts of propylene glycol alginate;

[0050] 3 parts of 1,4,5,8-naphthalenetetracarboxylic dianhydride;

[0051] 2 parts of N-benzylethanolamine;

[0052] 3 parts of composite rare earth antibacterial material;

[0053] Organic pigment: 16 parts;

[0054] 2 parts of auxiliary agents: polyethylene ether, butyl acrylate, polyacrylamide (mass ratio 3:2:5); and

[0055] 20 parts of solvent: water and ethanol with a volume ratio of 68:32.

[0056] The composite rare earth antibacterial material is prepared by the following method:

[0057] (1) Preparation of modified sepiolite

[0058] Dissolve the silane coupling agent KH-602 in water to prepare a solution with a mass concentration of 10%. Grind sepiolite and pass it through a 400-mesh sieve, then add it to the solution. After treating at 50 °C for 3 h, filter, and wash the filter residue with water to obtain silane coupling agent-modified sepiolite; the mass ratio of sepiolite to silane coupling agent is 10:0.4;

[0059] Disperse cucurbit[6]uril in sufficient water, add potassium persulfate and potassium sulfate, treat at 80 °C for 16 h, cool to room temperature, filter to collect the filtrate, rotary evaporate at 50 °C, extract with concentrated hydrochloric acid, filter with methanol and wash, and dry to obtain activated cucurbit[6]uril; the mass ratio of potassium persulfate, potassium sulfate, and cucurbit[6]uril is 0.1:0.5:1;

[0060] Disperse activated cucurbit[6]uril in dimethyl sulfoxide, add silane coupling agent-modified sepiolite and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid, react at room temperature for 2 h. After the reaction, filter with ether, wash, and dry to obtain modified sepiolite; the addition amounts of cucurbit[6]uril and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid are 10% and 3% of the mass of silane coupling agent-modified sepiolite respectively. Test the modified sepiolite with a Fourier transform infrared spectrometer at a test wavelength of 4000 - 400 cm -1 , and the test results are as Figure 1 shown. As shown in the figure, curve (a) in the figure represents unmodified sepiolite, (b) represents silane coupling agent-modified sepiolite, and (c) represents modified sepiolite. Comparing the three curves, it is found that compared with curve (a), the stretching vibration absorption peak of curve (b) near 1215 cm -1 weakens, indicating that the silane coupling agent is coated on the surface of sepiolite; compared with curves (a) and (b), curve (c) has a stretching vibration absorption peak at 1150 - 1200 cm -1There is a characteristic absorption peak of sulfonic acid group within the range, 2545 cm -1 There is a stretching vibration of mercapto - SH near it. The above results indicate that cucurbit[6]uril and 4 - hydroxyethylpiperazine ethanesulfonic acid have successfully modified sepiolite.

[0061] (2) Loading rare earth ions

[0062] Disperse lanthanum chloride in 15 times the mass of water to prepare a solution. Add the modified sepiolite according to the formula amount and stir for 0.5 h. Then raise the temperature to 40 °C and adjust the pH = 5. Stir and react for 12 h, filter, wash the filter residue with water, and dry to obtain the rare earth composite antibacterial material.

[0063] The preparation method of the above - mentioned tipping - paper water - based ink includes the following steps:

[0064] Disperse the rare earth composite antibacterial material in a solvent according to the formula amount. Add 1,4,5,8 - naphthalenetetracarboxylic dianhydride and N - benzylethanolamine, adjust the pH to 5, raise the temperature to 70 °C and stir for 4 h; cool to room temperature, add acrylic resin, cellulose acetate butyrate, propylene glycol alginate, additives, organic pigments, and mix well with the pigments as required to obtain the tipping - paper water - based ink.

[0065] Example 2

[0066] The tipping - paper water - based ink has the following formula:

[0067] 58 parts of acrylic resin;

[0068] 20 parts of cellulose acetate butyrate;

[0069] 7 parts of propylene glycol alginate;

[0070] 4 parts of 1,4,5,8 - naphthalenetetracarboxylic dianhydride;

[0071] 4 parts of N - benzylethanolamine;

[0072] 4 parts of composite rare earth antibacterial material;

[0073] Organic pigment: 16 parts;

[0074] 2 parts of additives: polyethylene ether, butyl acrylate, polyacrylamide (mass ratio 3:2:5); and

[0075] 22 parts of solvent: water and ethanol with a volume ratio of 68:32.

[0076] The composite rare earth antibacterial material is prepared by the following method:

[0077] (1) Preparation of modified sepiolite

[0078] The silane coupling agent AEAPS was dissolved in water to prepare a solution with a mass concentration of 10%. After sepiolite was ground and passed through a 400-mesh sieve, it was added to the solution. After treatment at 60 °C for 1.5 h, it was filtered, and the filter residue was washed with water to obtain silane coupling agent-modified sepiolite; the mass ratio of sepiolite to silane coupling agent was 10:0.7;

[0079] Cucurbit[7]uril was dispersed in sufficient water, potassium persulfate and potassium sulfate were added, and it was treated at 90 °C for 10 h. After cooling to room temperature, the filtrate was collected by filtration, rotary evaporation was carried out at 60 °C, concentrated hydrochloric acid was used for extraction, methanol was added for suction filtration and washing, and drying was carried out to obtain activated cucurbit[7]uril; the mass ratio of potassium persulfate, potassium sulfate to cucurbit[7]uril was 0.14:0.55:1;

[0080] The activated cucurbit[7]uril was dispersed in dimethyl sulfoxide, the silane coupling agent-modified sepiolite and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid were added, and the reaction was carried out at room temperature for 5 h. After the reaction, suction filtration was carried out with ether, washing was carried out, and drying was carried out to obtain modified sepiolite; the addition amounts of cucurbit[7]uril and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid were 18% and 4.4% of the mass of the silane coupling agent-modified sepiolite, respectively.

[0081] (2) Loading rare earth ions

[0082] Cerium nitrate was dispersed in 30 times the mass of water to prepare a solution. After adding the modified sepiolite according to the formula amount and stirring for 1 h, the temperature was raised to 50 °C and the pH was adjusted to 6, and the stirring reaction was carried out for 6 h. After filtration, the filter residue was washed with water and dried to obtain the rare earth composite antibacterial material.

[0083] The preparation method of the above-mentioned tipping paper water-based ink includes the following steps:

[0084] According to the formula amount, the rare earth composite antibacterial material was dispersed in a solvent, 1,4,5,8-naphthalenetetracarboxylic dianhydride and N-benzylethanolamine were added, the pH was adjusted to 5, and the temperature was raised to 70 °C and stirred for 4 h; after cooling to room temperature, acrylic resin, cellulose acetate butyrate, propylene glycol alginate, additives and organic pigments were added, and the pigments were mixed evenly as required to obtain the tipping paper water-based ink.

[0085] Example 3

[0086] The tipping paper water-based ink has the following formula:

[0087] 60 parts of acrylic resin;

[0088] 15 parts of cellulose acetate butyrate;

[0089] 5 parts of propylene glycol alginate;

[0090] 5 parts of 1,4,5,8-naphthalenetetracarboxylic dianhydride;

[0091] 4 parts of N-benzylethanolamine;

[0092] 5 parts of composite rare earth antibacterial material;

[0093] Organic pigment: 16 parts;

[0094] 2 parts of additives: polyethylene ether, butyl acrylate, polyacrylamide (mass ratio 3:2:5); and

[0095] 18 parts of solvent: water and ethanol with a volume ratio of 68:32.

[0096] The composite rare earth antibacterial material is prepared by the following method:

[0097] (1) Preparation of modified sepiolite

[0098] Dissolve the silane coupling agent APTES in water to prepare a solution with a mass concentration of 10%. After grinding sepiolite and passing it through a 400-mesh sieve, add it to the solution. After treating at 60 °C for 1.5 h, filter, and wash the filter residue with water to obtain silane coupling agent-modified sepiolite; the mass ratio of sepiolite to silane coupling agent is 10:0.8;

[0099] Disperse cucurbit[8]uril in sufficient water, add potassium persulfate and potassium sulfate, treat at 90 °C for 10 h, cool to room temperature, filter to collect the filtrate, rotary evaporate at 60 °C, extract with concentrated hydrochloric acid, filter with methanol and wash, and dry to obtain activated cucurbit[8]uril; the mass ratio of potassium persulfate, potassium sulfate, and cucurbit[8]uril is 0.2:0.6:1;

[0100] Disperse activated cucurbit[8]uril in dimethyl sulfoxide, add silane coupling agent-modified sepiolite and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid, react at room temperature for 5 h, after the reaction, filter with ether, wash, and dry to obtain modified sepiolite; the addition amounts of cucurbit[8]uril and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid are 20% and 5% of the mass of silane coupling agent-modified sepiolite respectively.

[0101] (2) Loading rare earth ions

[0102] Disperse neodymium nitrate in 30 mass times of water to prepare a solution. Add the modified sepiolite according to the formula amount and stir for 1 h, then raise the temperature to 50 °C and add NaOH to adjust the pH = 6, stir and react for 6 h, filter, wash the filter residue with water, and dry to obtain the rare earth composite antibacterial material.

[0103] The preparation method of the above water pine paper water-based ink includes the following steps:

[0104] Disperse the rare earth composite antibacterial material in a solvent according to the formulation amount, add 1,4,5,8-naphthalenetetracarboxylic dianhydride and N-benzylethanolamine, adjust the pH to 5, raise the temperature to 70 °C and stir for 4 h; cool to room temperature, add acrylic resin, cellulose acetate butyrate, propylene glycol alginate, additives, and organic pigments, and mix well according to the required addition of pigments to obtain the water-based ink for tipping paper.

[0105] Comparative Example 1

[0106] The difference from Example 2 is that in the preparation process of the modified sepiolite, the addition amounts of cucurbit[7]uril and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid are 8% and 7% of the mass of the silane coupling agent-modified sepiolite, respectively.

[0107] Comparative Example 2

[0108] The difference from Example 2 is that in the preparation process of the modified sepiolite, the addition amounts of cucurbit[7]uril and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid are 22% and 2% of the mass of the silane coupling agent-modified sepiolite, respectively.

[0109] Comparative Example 3

[0110] The difference from Example 2 is that the sepiolite is only modified with a silane coupling agent, that is, the modified sepiolite is prepared by the following method: Dissolve the silane coupling agent AEAPS in water to form a solution with a mass concentration of 10%, add the ground sepiolite sieved through 400 meshes to the solution, treat it at 60 °C for 1.5 h, then filter, and wash the filter residue with water to obtain the modified sepiolite; the mass ratio of the sepiolite to the silane coupling agent is 10:0.7;

[0111] Comparative Example 4

[0112] The difference from Example 2 is that the sepiolite is only modified with a silane coupling agent and cucurbit[n]uril, that is, the modified sepiolite is prepared by the following method:

[0113] Dissolve the silane coupling agent AEAPS in water to form a solution with a mass concentration of 10%, add the ground sepiolite sieved through 400 meshes to the solution, treat it at 60 °C for 1.5 h, then filter, and wash the filter residue with water to obtain the silane coupling agent-modified sepiolite; the mass ratio of the sepiolite to the silane coupling agent is 10:0.7;

[0114] Disperse cucurbit[7]uril in sufficient water, add potassium persulfate and potassium sulfate, treat it at 90 °C for 10 h, cool to room temperature, filter and collect the filtrate, rotary evaporate at 60 °C, extract with concentrated hydrochloric acid, filter with methanol, wash, and dry to obtain the activated cucurbit[7]uril; the mass ratio of potassium persulfate, potassium sulfate, and cucurbit[7]uril is 0.14:0.55:1;

[0115] The activated cucurbit[7]uril is dispersed in dimethyl sulfoxide, and the sepiolite modified with a silane coupling agent is added, and the reaction is carried out at room temperature for 5 h. After the reaction is completed, it is filtered by suction with ether, washed, and dried to obtain the modified sepiolite; the addition amount of the cucurbit[7]uril is 18% of the mass of the sepiolite modified with the silane coupling agent.

[0116] Comparative Example 5

[0117] The difference from Example 2 is that the modified sepiolite is replaced with an equal amount of unmodified sepiolite.

[0118] Comparative Example 6

[0119] The difference from Example 2 is that in the tipping paper water-based ink, the mass ratio of 1,4,5,8-naphthalenetetracarboxylic dianhydride to N-benzylethanolamine is 0.5:1; the total amount of 1,4,5,8-naphthalenetetracarboxylic dianhydride and N-benzylethanolamine remains unchanged.

[0120] Comparative Example 7

[0121] The difference from Example 2 is that in the tipping paper water-based ink, the mass ratio of 1,4,5,8-naphthalenetetracarboxylic dianhydride to N-benzylethanolamine is 2:1; the total amount of 1,4,5,8-naphthalenetetracarboxylic dianhydride and N-benzylethanolamine remains unchanged.

[0122] Comparative Example 8

[0123] The difference from Example 2 is that 1,4,5,8-naphthalenetetracarboxylic dianhydride is not added to the tipping paper water-based ink.

[0124] Comparative Example 9

[0125] The difference from Example 2 is that N-benzylethanolamine is not added to the tipping paper water-based ink.

[0126] Comparative Example 10

[0127] The difference from Example 2 is that neither 1,4,5,8-naphthalenetetracarboxylic dianhydride nor N-benzylethanolamine is added to the tipping paper water-based ink.

[0128] Performance Test

[0129] The following performance tests were carried out on the tipping paper water-based inks obtained in Examples 1-3, Comparative Examples 1-10 of the present invention and commercially available ordinary water-based inks:

[0130] Test 1, Adhesion Fastness: The adhesion fastness was tested with reference to GB / T13217.7-2009, and the results are shown in Table 1.

[0131] Test 2, water resistance: After printing the water-based ink sample and baking it in an oven at 55°C for 10 minutes, wet a paper towel with clear water until it is just wet enough that water does not drip when lifted. Wipe back and forth 5 times on 5 areas of the sample respectively, and observe whether there is color on the paper towel and whether the surface of the sample changes. The results are shown in Table 1.

[0132] Test 3, stability:

[0133] (1) Place the water-based ink in an environment at -10°C for 24 hours, and observe whether there is precipitation in the water-based environmentally friendly ink composition. Test 10 samples of each water-based ink. If there is precipitation in 0 - 1 sample, the stability is recorded as excellent; if there is precipitation in 2 - 3 samples, the stability is recorded as good; if there is precipitation in more than 3 samples, the stability is recorded as poor. The results are shown in Table 1.

[0134] (2) After placing the water-based ink at room temperature for 1 year, test its adhesion fastness. The results are shown in Table 1.

[0135] Test 4, antibacterial property:

[0136] Refer to GB / T21866-2008, and use the film sticking method to test the antibacterial performance of the water-based ink. The experimental strains selected are Staphylococcus aureus and Escherichia coli. Also test the antibacterial property of the water-based ink after being placed at room temperature for 1 year to evaluate the antibacterial stability. The results are shown in Table 2 below.

[0137] Table 1

[0138]

[0139] As shown in the table, the adhesion fastness of the water-based inks obtained in Examples 1 - 3 of the present invention reaches more than 97%. Compared with the commercially available water-based inks, the water-based inks obtained in the present invention have higher adhesion fastness. Compared with Example 2, the adhesion fastness of the water-based inks obtained in Comparative Examples 6 and 7 is slightly lower than that of Example 2, and there is a large gap between the water-based inks obtained in Comparative Examples 8 - 10 and Example 2. It can be seen that adding 1,4,5,8-naphthalenetetracarboxylic dianhydride and N-benzylethanolamine to the water-based ink helps to improve the adhesion fastness of the water-based ink.

[0140] It can also be seen that after printing the water-based inks obtained in Examples 1 - 3, they do not fade or peel off after being wiped with a wet paper towel, and have good water resistance; the water-based inks obtained in Comparative Examples 8 - 10 and the commercially available water-based inks show fading or peeling off phenomena, and their water resistance is relatively poor. It can be seen that adding 1,4,5,8-naphthalenetetracarboxylic dianhydride and N-benzylethanolamine to the water-based ink helps to improve the water resistance of the water-based ink.

[0141] It can also be seen that the water-based inks obtained in Examples 1-3 did not show precipitation after being placed in an environment of -10°C for 24 hours, and the adhesion was still not lower than 92% after being placed for 1 year, with high storage stability; the water-based inks obtained in Comparative Examples 1-5 showed precipitation after being placed in an environment of -10°C for 24 hours, and the adhesion was significantly lower than that of Example 2 after being placed for 1 year. It can be seen that the modification treatment of sepiolite and the use of cucurbit[n]uril and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid in the modification process have an obvious beneficial effect on improving the stability of the water-based ink. After the water-based inks obtained in Comparative Examples 6-10 were placed in an environment of -10°C for 24 hours, a large number of samples showed precipitation, and the adhesion after being placed for 1 year decreased to 73-81%, which was significantly lower than that of Example 2. In particular, the adhesion of the water-based inks obtained in Comparative Examples 8 and 10 was lower than that of the commercially available products after being placed for 1 year. It can be seen that adding 1,4,5,8-naphthalenetetracarboxylic dianhydride and N-benzylethanolamine to the water-based ink of the present invention helps to improve the stability of the water-based ink.

[0142] Table 2

[0143]

[0144] As shown in Table 2, the water-based inks obtained in Examples 1-3 of the present invention have excellent antibacterial properties, and the antibacterial rates against Staphylococcus aureus and Escherichia coli reach more than 99%, with strong antibacterial properties, and the antibacterial rates against Staphylococcus aureus and Escherichia coli still remain above 95% after being placed for 1 year; compared with Example 2, in Comparative Examples 1 and 2, the amounts of cucurbit[n]uril and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid used in the preparation of modified sepiolite were different, and the antibacterial properties of the obtained water-based inks did not change significantly, but the antibacterial rate after 1 year was significantly lower than that of Example 2. It can be seen that controlling the amounts of cucurbit[n]uril and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid in the preparation of modified sepiolite helps to further improve the antibacterial stability of the material.

[0145] Compared with Example 2, the sepiolite in Comparative Example 3 was not modified with cucurbit[n]uril and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid, 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid was not added during the modification of sepiolite in Comparative Example 4, and the sepiolite in Comparative Example 5 was not modified. It can be seen from the data in the table that the antibacterial rates of the water-based inks in Comparative Examples 3-5 were significantly lower than that of Example 2, and there was an obvious difference in the antibacterial rate after 1 year compared with Example 2. It can be seen that the modification of sepiolite with cucurbit[n]uril and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid, and the combination of cucurbit[n]uril and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid has a certain synergistic effect, which helps to improve the antibacterial property and antibacterial stability.

[0146] Compared with Example 2, the antibacterial rates of the aqueous inks obtained in Comparative Example 9 and Comparative Example 10 after being placed for 1 year are lower than that of Example 2, and the antibacterial stability is poor. This may be because 1,4,5,8-naphthalenetetracarboxylic dianhydride and N-benzylethanolamine are not added to the aqueous ink, resulting in sedimentation and other phenomena of the antibacterial components therein after long-term placement, uneven dispersion, and thus the antibacterial property decreases.

[0147] The above description of the embodiments is for the convenience of those of ordinary skill in the art to understand and use the invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative labor. Therefore, the present invention is not limited to the above embodiments, and the improvements and modifications made by those skilled in the art without departing from the scope of the present invention according to the disclosure of the present invention should be within the protection scope of the present invention.

Claims

1. A rare earth composite antibacterial material, characterized in that, It contains an antibacterial active substance and a modified sepiolite carrier; The antibacterial active substance is a rare earth ion, and the rare earth ion is Ce 3+ , Pr 3+ , Nd 3+ , La 3+ or Gd 3+ or at least one of them; The modified sepiolite is sepiolite chemically modified with a silane coupling agent, cucurbit[n]uril, and 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid; the silane coupling agent is an amino silane coupling agent; the modified sepiolite is prepared by the following method: (1) Dissolve the silane coupling agent in water to prepare a silane coupling agent solution, add the ground and sieved sepiolite to the silane coupling agent solution for treatment, filter after the treatment is completed, and wash the filter residue with water to obtain the silane coupling agent-modified sepiolite; (2) Disperse cucurbit[n]uril in sufficient water, add potassium persulfate and potassium sulfate, treat at 80 - 90 °C for 10 - 16 h, cool to room temperature, filter to collect the filtrate, rotary evaporate at 50 - 60 °C, extract with concentrated hydrochloric acid, filter with methanol and wash, and dry to obtain the activated cucurbit[n]uril; (3) Disperse the activated cucurbit[n]uril obtained in step (2) in dimethyl sulfoxide, add the silane coupling agent-modified sepiolite obtained in step (1) and mix well, then add 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid, react at room temperature for 2 - 5 h, filter with ether after the reaction is completed, wash, and dry to obtain the modified sepiolite.

2. The rare earth composite antibacterial material according to claim 1, wherein The rare earth ions are added with rare earth chloride salts or rare earth nitrate salts as raw materials, and the rare earth ions account for 3 - 50% of the total mass of the rare earth composite antibacterial material.

3. The rare earth composite antibacterial material according to claim 2, wherein In step (3), the addition amount of cucurbit[n]uril is 10 - 20% of the mass of the silane coupling agent-modified sepiolite, and the addition amount of 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid is 3 - 5% of the mass of the silane coupling agent-modified sepiolite.

4. The preparation method of the rare earth composite antibacterial material according to any one of claims 1-3, characterized in that, It includes the following steps: Disperse the rare earth chloride salt or rare earth nitrate salt in water to prepare a solution, add the modified sepiolite according to the formula amount and stir for 0.5 - 1 h, then raise the temperature to 40 - 50 °C and adjust the pH = 5 - 6, stir and react for 6 - 12 h, filter, wash the filter residue with water, and dry to obtain the rare earth composite antibacterial material.

5. Use of the rare earth composite antibacterial material according to any one of claims 1 - 3 in the preparation of tipping paper water-based ink.

6. A tipping paper water-based ink, characterized in that, It contains the rare earth composite antibacterial material according to any one of claims 1 - 3, as well as acrylic resin, cellulose acetate butyrate, propylene glycol alginate, 1,4,5,8-naphthalenetetracarboxylic dianhydride, N-benzylethanolamine, additives, pigments, and solvents.

7. The aqueous gravure ink for tipping paper according to claim 6, characterized in that, By weight fraction, it contains 50 - 60 parts of acrylic resin, 15 - 25 parts of cellulose acetate butyrate, 5 - 8 parts of propylene glycol alginate, 3 - 5 parts of 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2 - 5 parts of N-benzylethanolamine, 3 - 5 parts of the rare earth composite antibacterial material, 0.5 - 5 parts of additives, 10 - 20 parts of pigments, and 10 - 30 parts of solvents.

8. The tipping paper water-based ink according to claim 6 or 7, characterized in that, The mass ratio of 1,4,5,8-naphthalenetetracarboxylic dianhydride to N-benzylethanolamine is 1 - 1.5:

1.

9. The preparation method of the tipping paper water-based ink according to any one of claims 6-7, characterized in that, It includes the following steps: According to the formula amount, disperse the rare earth composite antibacterial material in the solvent, add 1,4,5,8-naphthalenetetracarboxylic dianhydride and N-benzylethanolamine, adjust the pH to 5 - 6, raise the temperature to 70 - 80 °C and stir for 2 - 4 h; cool to room temperature, add acrylic resin, cellulose acetate butyrate, propylene glycol alginate, additives, and add pigments and mix well to obtain the tipping paper water-based ink.

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