Wear-resistant and scratch-resistant transfer tipping paper ink and preparation method thereof

Abstract

The invention discloses wear-resistant and scratch-resistant transfer tipping paper ink and a preparation method of the wear-resistant and scratch-resistant transfer tipping paper ink. Comprising the following components in parts by weight: 35 to 60 parts of self-crosslinking fluorine modified acrylic emulsion, 8 to 15 parts of surface modified nano calcium hexaboride, 6 to 18 parts of pigment, 1.2 to 2.0 parts of silane coupling agent KH-550, 0.9 to 1.5 parts of dispersing agent, 0.6 to 1.8 parts of wetting leveling agent, 0.2 to 0.4 part of defoaming agent, 0.8 to 1.6 parts of pH regulator and 15 to 32 parts of deionized water. According to the invention, through formula optimization and raw material modification design, synergistic improvement of wear resistance, scratch resistance, flexibility and adhesive force of the ink film is realized, and high-end application requirements of transfer tipping paper are met.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of printing ink, in particular to a kind of wear-resistant and scratch-resistant transfer tipping paper ink. BACKGROUND

[0002] Transfer tipping paper is widely used in high-end tobacco packaging field due to its high light quality, environmental adaptability and cost advantage, and the printing quality of transfer tipping paper directly affects the appearance grade and use durability of product. The current mainstream printing ink of transfer tipping paper is water-based system, which meets the environmental requirements, but has key performance defects: the wear resistance and scratch resistance of ink film are insufficient, and scratches, wear and even pattern peeling are prone to occur during subsequent processing, packaging and transportation and use, which seriously affects the appearance integrity of product; meanwhile, the existing technology for improving the wear resistance of ink has obvious limitations, such as adding hard and brittle resin or excessive crosslinking agent, which will cause the flexibility of ink film to decrease and be prone to cracking, and adding nano inorganic particles will face the problems of unstable dispersion and easy agglomeration, which not only affects the printing smoothness (such as blocking screen), but also reduces the overall adhesion and durability of ink film.

[0003] In addition, the insufficient bonding force between the aluminum plating layer and the ink layer of transfer tipping paper is also an important reason for the attenuation of the wear resistance of printing ink, and traditional ink is difficult to simultaneously improve the hardness, toughness and interfacial adhesion of ink film. Therefore, it is of important practical application value to develop a kind of transfer tipping paper printing ink with excellent wear resistance and scratch resistance, good flexibility and interfacial bonding force, and stable process suitable for industrial production. SUMMARY

[0004] The present application relates to the field of printing ink, in particular to a kind of wear-resistant and scratch-resistant transfer tipping paper ink.

[0005] To achieve the above-mentioned purpose, the present application provides the following technical scheme: a kind of wear-resistant and scratch-resistant transfer tipping paper ink, according to weight fraction, it includes the following components: 35-60 parts of self-crosslinking type fluorine modified acrylic emulsion, 8-15 parts of surface modified nano calcium hexaboride, 6-18 parts of pigment, 1.2-2.0 parts of silane coupling agent KH-550, 0.9-1.5 parts of dispersing agent, 0.6-1.8 parts of wetting and leveling agent, 0.2-0.4 parts of defoaming agent, 0.8-1.6 parts of pH regulator, 15-32 parts of deionized water.

[0006] As a further scheme of the present application: the pigment is at least selected from one of rutile titanium dioxide R-706, fast scarlet 48:2, permanent yellow BHGS, phthalocyanine blue BGS and carbon black N330;

[0007] The dispersant is selected from BYK-190 or EFKA-4580;

[0008] The wetting and leveling agent is selected from BYK-346 or TEGO-270;

[0009] The defoaming agent is selected from BYK-024 or WT-082;

[0010] The pH regulator is selected from AMP-95 or triethylamine.

[0011] As a further scheme of the present application: the preparation method of the self-crosslinking fluorine-modified acrylic emulsion comprises the following steps:

[0012] Step 1: take 22-28 parts by weight of methyl methacrylate, 12-18 parts of butyl acrylate, 3-6 parts of fluorine-containing modified acrylamide, 1.2-1.8 parts of composite emulsifier, 0.3-0.6 parts of initiator ammonium persulfate, 0.08-0.12 parts of chain transfer agent dodecanethiol, 0.8-1.5 parts of crosslinking agent adipic acid dihydrazide and 48-62 parts of deionized water, the composite emulsifier is DNS-86 mixed with OP-10 in a weight ratio of 2:1;

[0013] Step 2: mix the composite emulsifier with deionized water, stir uniformly, then add methyl methacrylate, butyl acrylate, fluorine-containing modified acrylamide and chain transfer agent, stir at 250-350 r / min for 30 min to obtain a pre-emulsion;

[0014] Step 3: take 1 / 5 weight of the pre-emulsion, heat to 78-82°C under nitrogen protection, add 1 / 3 weight of the initiator, stir for 30 min to obtain a seed emulsion;

[0015] Step 4: add the remaining pre-emulsion and the remaining initiator to the seed emulsion at a uniform speed, the dropwise adding time is 2.5-3h, after the dropwise adding is completed, 78-82°C is kept for 1h, then cooled to room temperature, 200 mesh filtration is performed, the crosslinking agent is added and stirred for 30 min, the pH is adjusted to 7.8-8.2, and a self-crosslinking fluorine-modified acrylic emulsion is obtained.

[0016] As a further scheme of the present application: the preparation method of the surface-modified calcium hexaboride nanoparticles comprises the following steps:

[0017] Step 1: 10 parts of nano calcium hexaboride powder with a particle size of 80-100 nm are mixed with 12-13 parts of amino silane coupling agent KH-550 in a mixed solution of 165-175 ml of ethanol and 25-35 ml of water, ultrasonic dispersion is carried out, then 72-78 DEG C water bath reflux stirring is carried out for 3.5-4.5 h, the precipitate is collected by centrifugation, alcohol washing and drying are carried out to obtain aminated calcium hexaboride;

[0018] Step 2: 10 parts of aminated calcium hexaboride are dispersed in 120-180 ml of anhydrous ethanol, 7.8-8.8 parts of methacryloyl chloride and 4.0-4.5 parts of acid binding agent triethylamine are added, 72-78 DEG C water bath reflux stirring is carried out for 5-7 h, solvent is removed under reduced pressure, alcohol washing and drying are carried out to obtain surface modified nano calcium hexaboride.

[0019] Another object of the present application is to provide a preparation method of wear-resistant and scratch-resistant transfer tipping paper ink, comprising the following steps:

[0020] Step 1: according to the weight fraction, the corresponding weight of each component is weighed, the self-crosslinking fluorine modified acrylic emulsion is mixed with deionized water, 450-500 r / min stirring is carried out for 15 min, the surface modified nano calcium hexaboride is added, and 750-850 r / min stirring is carried out for 30 min;

[0021] Step 2: the pigment, silane coupling agent, dispersant, wetting and leveling agent and defoaming agent are added in sequence, 450-500 r / min stirring is carried out for 20 min, and the pH of the system is adjusted to 7.5-8.5 by dropwise adding a pH adjuster;

[0022] Step 3: filtering through a 200 mesh screen, a wear-resistant and scratch-resistant transfer tipping paper ink is obtained.

[0023] Compared with the prior art, the present application has the following advantages:

[0024] 1. The present application realizes the balanced improvement of the hardness and toughness of the ink film through the synergistic effect of the self-crosslinking fluorine modified acrylic emulsion and the surface modified nano calcium hexaboride: the crosslinking network formed by the fluorine modified acrylic emulsion has rigidity and flexibility, and the fluorine-containing groups enhance the hydrophobicity and durability of the ink film; the modified nano calcium hexaboride strengthens the scratch resistance by virtue of the high hardness, and the surface grafted groups form a firm covalent bond with the emulsion, solving the problem of poor compatibility between inorganic particles and organic phase and avoiding the agglomeration phenomenon;

[0025] 2. The introduction of the silane coupling agent further improves the interfacial bonding force between the ink film and the aluminum plated layer of the transfer tipping paper, and the self-crosslinking property of the emulsion makes the adhesion of the ink film significantly enhanced, effectively preventing peeling and falling off after printing; through testing, the wear-resistant times of the ink film can reach more than 500 times (500g weight friction), and the scratch resistance grade can reach more than 4H;

[0026] 3. The ink system is stable and dispersed, eliminating the risk of clogging the screen or printhead during printing. The preparation process is simple and controllable, requiring no special equipment, making it suitable for large-scale industrial production. It can be widely used in tobacco packaging, high-end gift packaging, and other fields with stringent requirements for the surface performance of transfer and splicing paper. Detailed Implementation

[0027] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] In this embodiment of the invention,

[0029] Example 1:

[0030] A wear-resistant and scratch-resistant transfer paper ink, by weight, comprises the following components: 35 parts of self-crosslinking fluorinated modified acrylic emulsion, 8 parts of surface-modified nano-calcium hexaboride, 6 parts of pigment, 1.2 parts of silane coupling agent KH-550, 0.9 parts of dispersant, 0.6 parts of wetting and leveling agent, 0.2 parts of defoamer, 0.8 parts of pH adjuster, and 15 parts of deionized water.

[0031] The pigment shall be at least one of the following: rutile titanium dioxide R-706, fast red 48:2, permanent yellow BHGS, phthalocyanine blue BGS, and carbon black N330.

[0032] The dispersant is selected from BYK-190 or EFKA-4580;

[0033] The wetting and leveling agent to be selected is BYK-346 or TEGO-270;

[0034] Defoamer options include BYK-024 or WT-082;

[0035] pH adjusters to be selected include AMP-95 or triethylamine.

[0036] The preparation method of the self-crosslinking fluorinated modified acrylic emulsion includes the following steps:

[0037] Step 1: By weight, take 22 parts methyl methacrylate, 12 parts butyl acrylate, 3 parts fluorinated modified acrylamide, 1.2 parts composite emulsifier, 0.3 parts initiator ammonium persulfate, 0.08 parts chain transfer agent dodecyl mercaptan, 0.8 parts crosslinking agent adipic acid dihydrazide, and 48 parts deionized water. The composite emulsifier is a mixture of DNS-86 and OP-10 in a weight ratio of 2:1.

[0038] Step 2: Mix the composite emulsifier with deionized water, stir evenly, then add methyl methacrylate, butyl acrylate, fluorinated modified acrylamide and chain transfer agent, stir at 250-350 r / min for 30 min to obtain a pre-emulsion;

[0039] Step 3: Take 1 / 5 of the pre-emulsion by weight, heat it to 78-82℃ under nitrogen protection, add 1 / 3 of the initiator by weight, and stir for 30 minutes to obtain the seed emulsion;

[0040] Step 4: Add the remaining pre-emulsion and the remaining initiator separately to the seed emulsion at a uniform rate over a period of 2.5-3 hours. After the addition is complete, keep the mixture at 78-82℃ for 1 hour. After cooling to room temperature, filter through a 200-mesh filter, add the crosslinking agent and stir for 30 minutes. Adjust the pH to 7.8-8.2 to obtain a self-crosslinking fluorinated modified acrylic emulsion.

[0041] The preparation method of the surface-modified nano-calcium hexaboride includes the following steps:

[0042] Step 1: Take 10 parts of nano calcium hexaboride powder with a particle size of 80-100nm, mix it with 12 parts of aminosilane coupling agent KH-550 in a mixed solution of 165-175ml ethanol and 25-35ml water, disperse it by ultrasonication, reflux it in a water bath at 72-78℃ for 3.5-4.5h, collect the precipitate by centrifugation, wash it with alcohol and dry it to obtain amino-modified calcium hexaboride;

[0043] Step 2: Take 10 parts of amino-modified calcium hexaboride and disperse it in 120-180 ml of anhydrous ethanol. Add 7.8 parts of methacryloyl chloride and 4.0 parts of triethylamine as an acid binder. Reflux in a water bath at 72-78℃ for 5-7 hours. Remove the solvent under reduced pressure, wash with alcohol and dry to obtain surface-modified nano calcium hexaboride.

[0044] A method for preparing abrasion-resistant and scratch-resistant transfer splicing paper ink includes the following steps:

[0045] Step 1: Weigh the corresponding weight of each component according to the weight parts, mix the self-crosslinking fluorinated modified acrylic emulsion with deionized water, stir at 450-500 r / min for 15 min, add the surface modified nano calcium hexaboride, and stir at 750-850 r / min for 30 min.

[0046] Step 2: Add pigment, silane coupling agent, dispersant, wetting and leveling agent and defoamer in sequence, stir at 450-500 r / min for 20 min, and add pH adjuster dropwise to adjust the pH of the system to 7.5-8.5;

[0047] Step 3: After filtering through a 200-mesh sieve, a wear-resistant and scratch-resistant transfer splicing paper ink is obtained.

[0048] Example 2:

[0049] A wear-resistant and scratch-resistant transfer paper ink, by weight, comprises the following components: 43 parts of self-crosslinking fluorinated modified acrylic emulsion, 12 parts of surface-modified nano-calcium hexaboride, 12 parts of pigment, 1.6 parts of silane coupling agent KH-550, 1.2 parts of dispersant, 1.2 parts of wetting and leveling agent, 0.3 parts of defoamer, 1.2 parts of pH adjuster, and 24 parts of deionized water.

[0050] The pigment shall be at least one of the following: rutile titanium dioxide R-706, fast red 48:2, permanent yellow BHGS, phthalocyanine blue BGS, and carbon black N330.

[0051] The dispersant is selected from BYK-190 or EFKA-4580;

[0052] The wetting and leveling agent to be selected is BYK-346 or TEGO-270;

[0053] Defoamer options include BYK-024 or WT-082;

[0054] pH adjusters to be selected include AMP-95 or triethylamine.

[0055] The preparation method of the self-crosslinking fluorinated modified acrylic emulsion includes the following steps:

[0056] Step 1: By weight, take 25 parts methyl methacrylate, 15 parts butyl acrylate, 4 parts fluorinated modified acrylamide, 1.5 parts composite emulsifier, 0.5 parts initiator ammonium persulfate, 0.1 parts chain transfer agent dodecyl mercaptan, 1.2 parts crosslinking agent adipic acid dihydrazide, and 55 parts deionized water. The composite emulsifier is a mixture of DNS-86 and OP-10 in a weight ratio of 2:1.

[0057] Step 2: Mix the composite emulsifier with deionized water, stir evenly, then add methyl methacrylate, butyl acrylate, fluorinated modified acrylamide and chain transfer agent, stir at 250-350 r / min for 30 min to obtain a pre-emulsion;

[0058] Step 3: Take 1 / 5 of the pre-emulsion by weight, heat it to 78-82℃ under nitrogen protection, add 1 / 3 of the initiator by weight, and stir for 30 minutes to obtain the seed emulsion;

[0059] Step 4: Add the remaining pre-emulsion and the remaining initiator separately to the seed emulsion at a uniform rate over a period of 2.5-3 hours. After the addition is complete, keep the mixture at 78-82℃ for 1 hour. After cooling to room temperature, filter through a 200-mesh filter, add the crosslinking agent and stir for 30 minutes. Adjust the pH to 7.8-8.2 to obtain a self-crosslinking fluorinated modified acrylic emulsion.

[0060] The preparation method of the surface-modified nano-calcium hexaboride includes the following steps:

[0061] Step 1: Take 10 parts of nano calcium hexaboride powder with a particle size of 80-100nm, mix it with 12.5 parts of aminosilane coupling agent KH-550 in a mixed solution of 165-175ml ethanol and 25-35ml water, disperse it by ultrasonication, reflux it in a water bath at 72-78℃ for 3.5-4.5h, collect the precipitate by centrifugation, wash it with alcohol and dry it to obtain amino-modified calcium hexaboride;

[0062] Step 2: Take 10 parts of amino-modified calcium hexaboride and disperse it in 120-180 ml of anhydrous ethanol. Add 8.2 parts of methacryloyl chloride and 4.25 parts of triethylamine as an acid binder. Reflux in a water bath at 72-78℃ for 5-7 hours. Remove the solvent under reduced pressure, wash with alcohol and dry to obtain surface-modified nano calcium hexaboride.

[0063] A method for preparing abrasion-resistant and scratch-resistant transfer splicing paper ink includes the following steps:

[0064] Step 1: Weigh the corresponding weight of each component according to the weight parts, mix the self-crosslinking fluorinated modified acrylic emulsion with deionized water, stir at 450-500 r / min for 15 min, add the surface modified nano calcium hexaboride, and stir at 750-850 r / min for 30 min.

[0065] Step 2: Add pigment, silane coupling agent, dispersant, wetting and leveling agent and defoamer in sequence, stir at 450-500 r / min for 20 min, and add pH adjuster dropwise to adjust the pH of the system to 7.5-8.5;

[0066] Step 3: After filtering through a 200-mesh sieve, a wear-resistant and scratch-resistant transfer splicing paper ink is obtained.

[0067] Example 3:

[0068] A wear-resistant and scratch-resistant transfer paper ink, by weight, comprises the following components: 60 parts of self-crosslinking fluorinated modified acrylic emulsion, 15 parts of surface-modified nano-calcium hexaboride, 18 parts of pigment, 2.0 parts of silane coupling agent KH-550, 1.5 parts of dispersant, 1.8 parts of wetting and leveling agent, 0.4 parts of defoamer, 1.6 parts of pH adjuster, and 32 parts of deionized water.

[0069] The pigment shall be at least one of the following: rutile titanium dioxide R-706, fast red 48:2, permanent yellow BHGS, phthalocyanine blue BGS, and carbon black N330.

[0070] The dispersant is selected from BYK-190 or EFKA-4580;

[0071] The wetting and leveling agent to be selected is BYK-346 or TEGO-270;

[0072] Defoamer options include BYK-024 or WT-082;

[0073] pH adjusters to be selected include AMP-95 or triethylamine.

[0074] The preparation method of the self-crosslinking fluorinated modified acrylic emulsion includes the following steps:

[0075] Step 1: By weight, take 28 parts methyl methacrylate, 18 parts butyl acrylate, 6 parts fluorinated modified acrylamide, 1.8 parts composite emulsifier, 0.6 parts initiator ammonium persulfate, 0.12 parts chain transfer agent dodecyl mercaptan, 1.5 parts crosslinking agent adipic acid dihydrazide, and 62 parts deionized water. The composite emulsifier is a mixture of DNS-86 and OP-10 in a weight ratio of 2:1.

[0076] Step 2: Mix the composite emulsifier with deionized water, stir evenly, then add methyl methacrylate, butyl acrylate, fluorinated modified acrylamide and chain transfer agent, stir at 250-350 r / min for 30 min to obtain a pre-emulsion;

[0077] Step 3: Take 1 / 5 of the pre-emulsion by weight, heat it to 78-82℃ under nitrogen protection, add 1 / 3 of the initiator by weight, and stir for 30 minutes to obtain the seed emulsion;

[0078] Step 4: Add the remaining pre-emulsion and the remaining initiator separately to the seed emulsion at a uniform rate over a period of 2.5-3 hours. After the addition is complete, keep the mixture at 78-82℃ for 1 hour. After cooling to room temperature, filter through a 200-mesh filter, add the crosslinking agent and stir for 30 minutes. Adjust the pH to 7.8-8.2 to obtain a self-crosslinking fluorinated modified acrylic emulsion.

[0079] The preparation method of the surface-modified nano-calcium hexaboride includes the following steps:

[0080] Step 1: Take 10 parts of nano calcium hexaboride powder with a particle size of 80-100nm, mix it with 13 parts of aminosilane coupling agent KH-550 in a mixed solution of 165-175ml ethanol and 25-35ml water, disperse it by ultrasonication, reflux it in a water bath at 72-78℃ for 3.5-4.5h, collect the precipitate by centrifugation, wash it with alcohol and dry it to obtain amino-modified calcium hexaboride;

[0081] Step 2: Take 10 parts of amino-modified calcium hexaboride and disperse it in 120-180 ml of anhydrous ethanol. Add 8.8 parts of methacryloyl chloride and 4.5 parts of triethylamine as an acid binder. Reflux in a water bath at 72-78℃ for 5-7 hours. Remove the solvent under reduced pressure, wash with alcohol and dry to obtain surface-modified nano calcium hexaboride.

[0082] A method for preparing abrasion-resistant and scratch-resistant transfer splicing paper ink includes the following steps:

[0083] Step 1: Weigh the corresponding weight of each component according to the weight parts, mix the self-crosslinking fluorinated modified acrylic emulsion with deionized water, stir at 450-500 r / min for 15 min, add the surface modified nano calcium hexaboride, and stir at 750-850 r / min for 30 min.

[0084] Step 2: Add pigment, silane coupling agent, dispersant, wetting and leveling agent and defoamer in sequence, stir at 450-500 r / min for 20 min, and add pH adjuster dropwise to adjust the pH of the system to 7.5-8.5;

[0085] Step 3: After filtering through a 200-mesh sieve, a wear-resistant and scratch-resistant transfer splicing paper ink is obtained.

[0086] Test experiment:

[0087] The abrasion resistance and scratch resistance of the ink layer were tested, mainly using GB / T7706 for abrasion resistance and GB / T6739 for scratch resistance. In addition to the inks involved in this invention, commercially available alcohol-soluble and ester-soluble inks for tipping paper produced in Jiangsu, and water-based inks for tipping paper produced in Guangdong were also compared. Specific results are as follows:

[0088]

[0089] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A wear and scratch resistant tipping paper ink, characterized in that: According to the weight parts, including the following components: 35-60 parts of self-crosslinking fluorine modified acrylic emulsion, 8-15 parts of surface modified nano calcium hexaboride, 6-18 parts of pigment, 1.2-2.0 parts of silane coupling agent KH-550, 0.9-1.5 parts of dispersant, 0.6-1.8 parts of wet leveling agent, 0.2-0.4 parts of defoaming agent, 0.8-1.6 parts of pH regulator, 15-32 parts of deionized water.

2. A wear and scratch resistant tipping paper ink according to claim 1, characterized in that: The pigment is at least selected from one of rutile titanium dioxide R-706, sun-resistant big red 48:2, permanent yellow BHGS, phthalocyanine blue BGS, and carbon black N330; The dispersant is selected from BYK-190 or EFKA-4580; The wet leveling agent is selected from BYK-346 or TEGO-270; The defoaming agent is selected from BYK-024 or WT-082; The pH regulator is selected from AMP-95 or triethylamine.

3. A wear and scratch resistant tipping paper ink according to claim 1, wherein: The preparation method of the self-crosslinking fluorine modified acrylic emulsion comprises the following steps: Step 1: according to the weight parts, take 22-28 parts of methyl methacrylate, 12-18 parts of butyl acrylate, 3-6 parts of fluorine-containing modified acrylamide, 1.2-1.8 parts of composite emulsifier, 0.3-0.6 parts of initiator ammonium persulfate, 0.08-0.12 parts of chain transfer agent dodecanethiol, 0.8-1.5 parts of crosslinking agent adipic acid dihydrazide, and 48-62 parts of deionized water, wherein the composite emulsifier is a mixture of DNS-86 and OP-10 in a weight ratio of 2:1; Step 2: mix the composite emulsifier with deionized water, stir uniformly, then add methyl methacrylate, butyl acrylate, fluorine-containing modified acrylamide and chain transfer agent, and stir at 250-350 r / min for 30 min to obtain a pre-emulsion; Step 3: take 1 / 5 weight of the pre-emulsion, heat to 78-82℃ under nitrogen protection, add 1 / 3 weight of the initiator, and stir for 30 min to obtain a seed emulsion; Step 4: add the remaining pre-emulsion and the remaining initiator to the seed emulsion at a constant speed, the dropping time is 2.5-3h, after the dropping is completed, 78-82℃ is kept for 1h, then cooled to room temperature, filtered through a 200 mesh screen, stirred for 30 min after adding the crosslinking agent, and adjust the pH to 7.8-8.2 to obtain the self-crosslinking fluorine modified acrylic emulsion.

4. A wear and scratch resistant tipping paper ink according to claim 1, wherein: The preparation method of the surface modified nano calcium hexaboride comprises the following steps: Step 1: take 10 parts of nano calcium hexaboride powder with a particle size of 80-100nm, mix with 12-13 parts of amino silane coupling agent KH-550 in a mixed solution of 165-175ml of ethanol and 25-35ml of water, ultrasonic dispersion, then 72-78℃ water bath reflux stirring for 3.5-4.5h, centrifugal collection of the precipitate, alcohol washing and drying to obtain aminated calcium hexaboride; Step 2: 10 parts of amino calcium hexaboride was dispersed in 120-180 ml of anhydrous ethanol, 7.8-8.8 parts of methacryloyl chloride and 4.0-4.5 parts of acid binding agent triethylamine were added, and the mixture was stirred under reflux at 72-78°C for 5-7 h. The solvent was removed under reduced pressure, and the product was washed with alcohol and dried to obtain surface-modified nanometer calcium hexaboride.

5. A method of preparing a wear and scratch resistant transfer tipping paper ink as claimed in any one of claims 1 to 4, characterised in that: The method comprises the following steps: Step 1: According to the weight parts, the corresponding weight of each component is weighed, the self-crosslinking fluorine-modified acrylic emulsion is mixed with deionized water, and stirred at 450-500 r / min for 15 min, then the surface-modified nanometer calcium hexaboride is added and stirred at 750-850 r / min for 30 min; Step 2: The pigment, silane coupling agent, dispersant, wetting and leveling agent, and defoaming agent are added in sequence, and stirred at 450-500 r / min for 20 min, then the pH regulator is added dropwise to adjust the pH of the system to 7.5-8.5; Step 3: Filtered through a 200-mesh screen to obtain the wear-resistant and scratch-resistant transfer tipping paper ink.

Images