High-speed spraying mouthpiece adhesive for self-breathable tipping paper and preparation method of high-speed spraying mouthpiece adhesive

Abstract

The invention belongs to the technical field of cigarette adhesives, and provides a high-speed spraying mouthpiece adhesive for self-breathable tipping paper and a preparation method thereof.The mouthpiece adhesive is mainly prepared from VAE emulsion, polyvinyl alcohol, a thixotropic additive, a plasticizer, a cross-linking agent, a defoaming agent, a pH value regulator, a bactericide and purified water, and the mass ratio of the VAE emulsion to the polyvinyl alcohol to the thixotropic additive to the cross-linking agent is 80: (6-12): (0.7-1.2): (0.5-1); the VAE emulsion is an emulsion with high ethylene content, and the ethylene content is 26-30%; the polyvinyl alcohol comprises 30%-70% by mass of carboxylic acid modified polyvinyl alcohol. The high-speed filter tip adhesive provided by the invention is excellent in dynamic rheological property, strong in adhesive strength, less in adhesive scale, good in air permeability and free of spinning and flying adhesive, and can meet the requirements of high-speed roller coating type equipment of self-breathable tipping paper cigarettes.

Description

Technical Field

[0001] This invention belongs to the field of cigarette adhesive technology, specifically relating to a high-speed spraying splice adhesive for self-breathing splicing paper and its preparation method. Background Technology

[0002] Tipping paper is a tobacco material used to wrap the cigarette filter tip, while tipping adhesive is an adhesive used in cigarette production to attach cigarettes to the filter tip.

[0003] In recent years, with the continuous development of cigarette technology, consumers have increasingly higher requirements for cigarette quality. At the same time, as environmental protection and health have become a focus of public attention, higher demands have been placed on the environmental friendliness and health benefits of cigarette products. Currently, the industry generally uses laser-perforated tipping paper or naturally breathable tipping paper to reduce tar and harm in cigarettes. The principle of tar reduction and harm reduction with naturally breathable tipping paper is similar to that of laser-perforated paper; both reduce tar hazards by increasing the overall ventilation rate of the cigarette and diluting the smoke.

[0004] Compared with ordinary tipping paper, self-breathing tipping paper has the following characteristics: (1) The paper has a large number of holes of varying sizes, with the main size between 0.001-0.02mm and a very small number of large holes between 0.05-0.1mm; (2) Since the natural breathable tipping paper does not contain short wood pulp fibers, the glue is slower to naturally wet the surface of the self-breathing tipping paper than the surface of ordinary tipping paper, resulting in a poorer anchoring effect during bonding. Therefore, the surface of the self-breathing tipping paper is more difficult to bond than that of ordinary tipping paper; (3) There is a glue-free area when the self-breathing tipping paper is rolled. Under high-speed twisting conditions, the adhesive force of the glued part needs to be stronger to resist the displacement tendency caused by external force during the twisting process.

[0005] In summary, due to the characteristics of self-permeable tipping paper, there are problems such as difficulty in bonding, difficulty in natural wetting, and easy glue leakage. In order to ensure that self-permeable tipping paper does not leak glue, has good twisting, and can complete cigarette rolling production normally on high-speed spray coating rolling equipment such as Protos M5 12K and 14k, the matching tipping adhesive must have suitable viscosity, good rheological properties, high adhesion and fast drying speed.

[0006] Patent No. CN201210400083.4 discloses a novel starch-based cigarette adhesive containing modified cellulose. It mainly uses pyrolytic dextrin, glucose, modified cellulose and other components. The prepared cigarette adhesive has good viscosity, fluidity and stability. It can be stored stably at room temperature for more than three months. It is suitable for faster cigarette rolling machines with a speed of more than 10,000 cigarettes / minute, but the speed of the cigarette rolling machine needs to be improved.

[0007] Patent CN201710903061.2 discloses a water-based ultra-high speed spraying tip adhesive and its preparation method. It has high paper adhesion, suitable drying speed, and can achieve uniform adhesive supply at a speed of 20,000 cigarettes / minute without interruption or clogging. The produced cigarettes have no defects such as air leakage, tip dropping, or wrinkling. However, it is not suitable for self-breathing tipping paper.

[0008] Patent CN201410428783.3 discloses a method for preparing a cigarette tip adhesive with a breathable function. The adhesive mainly increases the breathability and meets the normal rolling and splicing requirements of various cigarette rolling machines with a speed of 7,000 to 16,000 cigarettes per minute. However, the rolling and splicing speed of the cigarette rolling machine needs to be improved, and it is not used for self-permeable splicing paper.

[0009] The self-breathable splicing paper high-speed spraying splice adhesive provided by this invention has suitable drying speed, rheological properties and high adhesion, can maintain the normal operation of the equipment at a rate of more than 14,000 splices / min, and has a low frequency of downtime for cleaning and maintenance (cleaning interval of more than 4 hours), which can solve the industry problem of self-breathable splicing paper high-speed spraying splice adhesive. Summary of the Invention

[0010] To address the shortcomings of existing technologies, this invention provides a high-speed spray-coated splice adhesive for self-breathing splicing paper and its preparation method: Using ethylene-vinyl acetate copolymer emulsion as the main raw material, carboxylic acid-modified polyvinyl alcohol as a drying speed regulator, a titanate crosslinking agent is introduced, and a thixotropic agent is added to significantly improve the dynamic rheological properties and interfacial adhesion of the water-based adhesive. Simultaneously, polydimethylsiloxane defoamer, plasticizer, pH adjuster, purified water, and other auxiliary materials are added and mixed to obtain the product of this invention. The product exhibits suitable drying speed, rheological properties, and adhesion; it does not leak adhesive during machine application, exhibits good splicing, and can maintain a stable production rate of 14,000 splices / min, meeting the coating requirements of self-breathing splicing paper on most high-speed roller coating machines such as the PROTOS M5.

[0011] To achieve the technical objective of the invention, the technical solution of the present invention is implemented as follows:

[0012] The self-breathable splicing paper high-speed spraying splice adhesive provided by the present invention is made of VAE emulsion, polyvinyl alcohol and other additives, wherein the mass ratio of VAE emulsion, polyvinyl alcohol, thixotropic agent, plasticizer, crosslinking agent, defoamer, pH adjuster, bactericide and purified water is 80: (6~12): (0.7~1.2): (2~4): (0.5~1): (0.1~0.3): (0~0.05): 0.1: (1~10).

[0013] Preferably, the high-speed spray nozzle adhesive for self-breathing splicing paper provided by the present invention uses Celvolit® 1475 with a high ethylene content, wherein the ethylene content is 26-30%, more preferably 28%; compared with ordinary VAE emulsions (ethylene content is 14%-18%), it has the characteristics of soft film and strong wet adhesion, which can ensure good adhesion of products when running on high-speed equipment.

[0014] Preferably, the VAE emulsion used also has the following characteristics: glass transition temperature onset: -16~-20℃, solid content: 54.5~56.5%, pH value: 4.0~6.0, and viscosity: 1500~3000 mPa.s (25℃, BROOKFIELD RVT04#20RPM).

[0015] Preferably, the high-speed spray nozzle adhesive for self-breathing splicing paper provided by the present invention uses polyvinyl alcohol comprising a self-developed carboxylic acid-modified polyvinyl alcohol and ordinary polyvinyl alcohol. The carboxylic acid-modified polyvinyl alcohol has a raw material polyvinyl alcohol type 1788, a degree of polymerization of 1700, a degree of alcoholysis of 88%, and acrylic acid as the carboxylic acid. The solid content of the carboxylic acid-modified polyvinyl alcohol is 19-21%. The ordinary polyvinyl alcohol has a solid content of 30% and is of at least one of the types 0588, 1788, 2088, and 2488. More preferably, the polyvinyl alcohol used comprises 30% to 70% by mass of the self-developed carboxylic acid-modified polyvinyl alcohol.

[0016] Preferably, the high-speed spray nozzle adhesive for self-breathing splicing paper provided by the present invention uses ACRYSOLTMRM-8W and ACRYSOLTMRM-2020NPR as thixotropic agents. Both are low-odor, solvent-free, water-based nonionic associative rheology modifiers that provide excellent flow and leveling properties, uniform film-forming performance, and thickening efficiency. The combination of the two thixotropic agents achieves an ideal balance between high and low shear viscosity.

[0017] Preferably, the plasticizer used in the high-speed spray nozzle adhesive for self-breathing splicing paper provided by the present invention is selected from at least one of triacetin, tributyl acetyl citrate, and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.

[0018] Preferably, the high-speed spray nozzle adhesive for self-breathing splicing paper provided by the present invention uses a crosslinking agent of the titanate type, specifically at least one of TC-TE and AQ33.

[0019] Preferably, the self-breathing splicing paper high-speed spraying splice adhesive provided by the present invention uses polydimethylsiloxane as the defoamer; sodium bicarbonate as the pH adjuster; at least one of 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, and 1,2-benzisothiazol-3-one as the bactericide; and the pure water used is tertiary pure water that has undergone multi-stage reverse osmosis membrane filtration.

[0020] The present invention also provides a method for preparing the high-speed spraying adhesive for self-breathing splicing paper, comprising the following steps:

[0021] (1) Preparation of carboxylic acid modified polyvinyl alcohol aqueous solution: ① Add 70.8 parts of purified water to the reactor, turn on the stirrer, and while stirring at a speed of 44 r / min, add 19 parts of polyvinyl alcohol 1788 dry powder at a uniform speed. After adding, stir at room temperature for 15 minutes. ② Initially heat to 90℃, keep warm for 2 hours until completely dissolved, then cool to 35℃, add 1.5 parts acrylic acid and 0.1 parts cerium ammonium nitrate (dissolved in 2 parts purified water), and react for 90 minutes; ③ Heat to 80℃ (complete within 40 minutes), add 0.05 parts of ammonium persulfate (dissolved in 2.5 parts of water) dropwise over 10 minutes, and maintain the temperature for 60 minutes. ④ Heat to 90℃ (complete within 20 minutes), add 0.05 parts of tert-butyl hydrogen peroxide (dissolved in 2.5 parts of water), and maintain the temperature for 90 minutes; ⑤ Cool to room temperature, add 0.5 parts ammonia and 1 part purified water, and adjust the pH to between 4.9 and 5.1; ⑥ Pressurize and filter the material for later use;

[0022] (2) Preparation of a 30% (w / w) concentration aqueous solution of ordinary polyvinyl alcohol:

[0023] Add 70 parts of purified water to the reactor, start stirring, and add 30 parts of polyvinyl alcohol dry powder while stirring at a speed of 44 r / min. After the addition is complete, stir at room temperature for 15 minutes, then start heating to 90℃, keep warm for 2 hours until completely dissolved, then cool down to below 55℃, pressurize and filter to discharge the material for later use.

[0024] (3) Preparation of high-speed spray nozzle adhesive for self-breathing splicing paper: ① Add 80 parts of VAE emulsion with high ethylene content to the reactor; ② Turn on the stirrer and add 2-8 parts of the carboxylic acid modified polyvinyl alcohol solution prepared in step (1) and 4-10 parts of the ordinary polyvinyl alcohol solution prepared in step (2) at a speed of 35 r / min. Stir for 20 min. ③ Increase the stirring speed to 50 r / min, and slowly add 0.2 parts of ACRYSOLTMRM-8W and 0.5~1.0 parts of ACRYSOLTMRM-2020NPR thixotropic additive using a peristaltic pump (the thixotropic additives should be diluted with water at a ratio of 1:1 beforehand). Keep the stirring speed at 50 r / min and the entire dropping time is 30~60 minutes. After the addition is complete, continue stirring for 15 minutes. ④ Add 2-4 parts of plasticizer to step ③, and continue stirring for 10 minutes after adding. ⑤ Slowly add 0.5~1 part of titanate crosslinking agent to step ④ (using a peristaltic pump), while keeping the stirring rate at 50 r / min. The entire addition time is 20~40 minutes. After the addition is complete, continue stirring for 20 minutes. ⑥ Reduce the stirring speed to 35 r / min, add 0.1~0.3 parts of polydimethylsiloxane defoamer, and stir for 10 min; ⑦ Add 0.1 parts of bactericide to step ⑥ and stir for 10 minutes; ⑧ Add pH adjuster and 1-10 parts of pure water to adjust the viscosity to 500-2000 mPa.s (25℃, Brookfield 03# 20rpm), adjust the pH to 4.5-5.5, and the solid content ≥48%. Stir for 10 minutes and then discharge to obtain high-speed spray nozzle adhesive for self-breathing splicing paper.

[0025] This invention has produced good results:

[0026] (1) This invention addresses the problems of difficult bonding, difficulty in natural wetting, and easy glue leakage in the self-breathing tipping paper adhesive process. By rationally designing the tipping adhesive formula, the developed tipping adhesive has suitable viscosity, good stability under high and low speed rheology, high adhesion and fast drying speed, thereby avoiding problems such as wrinkling, poor bonding and low and unstable total ventilation rate in the production of self-breathing tipping paper. The application of the tipping adhesive of this invention has enabled self-breathing tipping paper to achieve no glue leakage, good twisting and moderate and stable total ventilation rate of cigarettes on high-speed spray coating type rolling equipment such as Protos M5 12K, 14k, etc., meeting the normal rolling production requirements of self-breathing tipping paper cigarettes.

[0027] (2) The high-speed splice adhesive of the present invention possesses excellent rheological properties. Rheological data shows that the viscosity of each embodiment is high, and the viscosity decreases only slightly with increasing shear rate. This indicates that the high-speed splice adhesive exhibits excellent dynamic rheological properties under high-speed roller coating, and is less prone to problems such as excessive adhesive residue, poor adhesion, and low overall ventilation rate due to the adhesive clogging the pores of the self-ventilating splicing paper caused by excessively fast flow. Its high-speed shear resistance characteristics are better suited to the operating requirements of high-speed roller coating cigarette machines.

[0028] (3) The self-breathable splicing paper high-speed spraying splice adhesive provided by the present invention has suitable drying speed, rheological properties and high adhesion, can maintain the equipment at a rate of more than 14,000 cigarettes / min for 4 hours, the cigarette defect rate is 0, the frequency of shutdown for cleaning and maintenance is low (cleaning interval time is more than 4 hours), and significantly improves production efficiency and cigarette product quality. Detailed Implementation

[0029] The present invention will be further described in detail below with reference to preparation examples, embodiments, and comparative examples, but the scope of the present invention is not limited to these preparation examples and embodiments.

[0030] Preparation Example 1

[0031] Preparation of carboxylic acid-modified polyvinyl alcohol aqueous solution: ① Add 70.8 parts of purified water to the reactor, turn on the stirrer, and while stirring at a speed of 44 r / min, add 19 parts of polyvinyl alcohol 1788 dry powder at a uniform speed. After adding, stir at room temperature for 15 minutes. ② Initially heat to 90℃, keep warm for 2 hours until completely dissolved, then cool to 35℃, add 1.5 parts acrylic acid and 0.1 parts cerium ammonium nitrate (pre-dissolved in 2 parts purified water), and react for 90 minutes; ③ Heat to 80℃ (complete within 40 minutes), add 0.05 parts of ammonium persulfate (pre-dissolved in 2.5 parts of water) dropwise over 10 minutes, and maintain the temperature for 60 minutes. ④ Heat to 90℃ (complete within 20 minutes), add 0.05 parts of tert-butyl hydrogen peroxide (pre-dissolved in 2.5 parts of water), and maintain the temperature for 90 minutes; ⑤ Cool to room temperature, add 0.5 parts ammonia and 1 part purified water, and adjust the pH to between 4.9 and 5.1; ⑥ The material is discharged under pressure and filtered to obtain carboxylic acid modified polyvinyl alcohol with a solid content of 20.5%, which is then set aside for later use.

[0032] Preparation Example 2

[0033] Preparation of a 30% aqueous solution of ordinary polyvinyl alcohol:

[0034] Add 70 parts of purified water to the reactor, start stirring, and while stirring at a speed of 44 r / min, add 30 parts of polyvinyl alcohol dry powder (model 0588) at a uniform speed. After adding, stir at room temperature for 15 minutes, start heating to 90℃, keep warm for 2 hours until completely dissolved, then cool down to below 55℃, pressurize and filter to discharge the material. The solid content is 30%, and it is ready for use.

[0035] Example 1

[0036] Prepare a high-speed spray adhesive for self-breathing splicing paper by following the methods and steps: ① Add 80 parts of VAE emulsion with high ethylene content to the reactor; ② Turn on the stirrer and add 4 parts of the carboxylic acid modified polyvinyl alcohol solution prepared in Preparation Example 1 and 8 parts of the ordinary polyvinyl alcohol aqueous solution prepared in Preparation Example 2 (the polyvinyl alcohol dry powder is model 0588, solid content: 30%) at a speed of 35 r / min, and stir for 20 min; ③ Increase the stirring speed to 50 r / min, and slowly add 0.2 parts of ACRYSOLTMRM-8W and 0.5 parts of ACRYSOLTMRM-2020NPR polyurethane thixotropic additive (the polyurethane thixotropic additives should be diluted with water at a 1:1 ratio beforehand) using a peristaltic pump. Keep the stirring speed at 50 r / min, and the entire dropping time should be 30-60 minutes. After the addition is complete, continue stirring for 15 minutes. ④ Add 2.0 parts of acetylthiose tributyl citrate plasticizer to step ③, and continue stirring for 10 minutes after adding. ⑤ Use a peristaltic pump to slowly add 0.5 parts of titanate crosslinking agent TC-TE to step ④. The entire addition time is 20~40 minutes. After the addition is complete, continue stirring for 10 minutes. ⑥ Reduce the stirring speed to 35 r / min, add 0.10 parts of polydimethylsiloxane defoamer, and stir for 10 min; ⑦ Add 0.1 parts of bactericide to step ⑥ and stir for 10 minutes; ⑧ Add sodium bicarbonate (10% aqueous solution) and 4.55 parts of pure water to step ⑦, stir for 10 minutes, and then filter through a 300-mesh filter to obtain the self-breathing splicing paper high-speed spraying splice adhesive of the present invention. The physicochemical properties are: viscosity 1820 mPa·s, pH value 4.88, solid content 50.40%, and adhesion strength 1.25 N. The specific rheological properties are shown in Table 1 below:

[0037] Table 1. Rheological test data of Example 1

[0038]

[0039] Example 2

[0040] Prepare a high-speed spray adhesive for self-breathing splicing paper by following the methods and steps: ① Add 80 parts of VAE emulsion with high ethylene content to the reactor; ② Turn on the stirrer and add 6 parts of the carboxylic acid modified polyvinyl alcohol solution prepared in Preparation Example 1 and 6 parts of the ordinary polyvinyl alcohol aqueous solution prepared in Preparation Example 2 (the polyvinyl alcohol dry powder is model 0588, solid content: 30%) at a speed of 35 r / min, and stir for 20 min; ③ Increase the stirring speed to 50 r / min, and slowly add 0.2 parts of ACRYSOLTMRM-8W and 0.8 parts of ACRYSOLTMRM-2020NPR polyurethane thixotropic additive (the polyurethane thixotropic additives should be diluted with water at a 1:1 ratio beforehand) using a peristaltic pump. Keep the stirring speed at 50 r / min, and the entire dropping time should be 30-60 minutes. After the addition is complete, continue stirring for 15 minutes. ④ Add 3.0 parts of acetylthiose tributyl citrate plasticizer to step ③, and continue stirring for 10 minutes after adding. ⑤ Use a peristaltic pump to slowly add 0.8 parts of titanate crosslinking agent TC-TE to step ④. The entire addition time is 20~40 minutes. After the addition is complete, continue stirring for 10 minutes. ⑥ Reduce the stirring speed to 35 r / min, add 0.2 parts of polydimethylsiloxane defoamer, and stir for 10 min; ⑦ Add 0.1 parts of bactericide to step ⑥ and stir for 10 minutes; ⑧ Add sodium bicarbonate (10% aqueous solution) and 2.85 parts of pure water to step ⑦, stir for 10 minutes, and then filter through a 300-mesh filter to obtain the self-breathing splicing paper high-speed spraying splice adhesive of the present invention. The physicochemical properties are: viscosity 1860 mPa.s, pH value 4.85, solid content 51.82%, adhesion strength: 1.26 N. The specific rheological properties are shown in Table 2 below.

[0041] Table 2 Rheological test data of Example 2

[0042]

[0043] Example 3

[0044] Prepare a high-speed spray adhesive for self-breathing splicing paper by following the methods and steps: ① Add 80 parts of VAE emulsion with high ethylene content to the reactor; ② Turn on the stirrer and add 8 parts of the carboxylic acid modified polyvinyl alcohol solution prepared in Preparation Example 1 and 4 parts of the ordinary polyvinyl alcohol aqueous solution prepared in Preparation Example 2 (the polyvinyl alcohol dry powder is model 0588, solid content: 30%) at a speed of 35 r / min, and stir for 20 min. ③ Increase the stirring speed to 50 r / min, and slowly add 0.2 parts of ACRYSOLTMRM-8W and 1.0 part of ACRYSOLTMRM-2020NPR polyurethane thixotropic additive (the polyurethane thixotropic additives should be diluted with water at a ratio of 1:1 beforehand) using a peristaltic pump. Keep the stirring speed at 50 r / min, and the entire dropping time should be 30-60 minutes. After the addition is complete, continue stirring for 15 minutes. ④ Add 4.0 parts of acetylthiose tributyl citrate plasticizer to step ③, and continue stirring for 10 minutes after adding. ⑤ Use a peristaltic pump to slowly add 1.0 part of titanate crosslinking agent TC-TE to step ④. The entire addition time is 20~40 minutes. After the addition is complete, continue stirring for 10 minutes. ⑥ Reduce the stirring speed to 35 r / min, add 0.3 parts of polydimethylsiloxane defoamer, and stir for 10 min; ⑦ Add 0.1 parts of bactericide to step ⑥ and stir for 10 minutes; ⑧ Add sodium bicarbonate (10% aqueous solution) and 1.35 parts of pure water to step ⑦, stir for 10 minutes, and then filter through a 300-mesh filter to obtain the self-breathing splicing paper high-speed spraying splice adhesive of the present invention. The physicochemical properties are: viscosity 1910 mPa.s, pH value 4.92, solid content 53.04%, adhesion strength: 1.29 N. The specific rheological properties are shown in Table 3 below.

[0045] Table 3. Rheological test data of Example 3

[0046]

[0047] Comparative Example 1

[0048] Compared to Example 1, only 2 parts of a carboxylic acid-modified polyvinyl alcohol solution were added, and the following methods and steps were followed to prepare a high-speed spray nozzle adhesive for self-breathing splicing paper: ① Add 80 parts of VAE emulsion with high ethylene content to the reactor; ② Turn on the stirrer and add 2 parts of the carboxylic acid modified polyvinyl alcohol solution prepared in Preparation Example 1 and 10 parts of the ordinary polyvinyl alcohol aqueous solution prepared in Preparation Example 2 (the polyvinyl alcohol dry powder is model 0588, solid content: 30%) at a speed of 35 r / min, and stir for 20 min; ③ Increase the stirring speed to 50 r / min, and slowly add 0.2 parts of ACRYSOLTMRM-8W and 0.5 parts of ACRYSOLTMRM-2020NPR polyurethane thixotropic additive (the polyurethane thixotropic additives should be diluted with water at a 1:1 ratio beforehand) using a peristaltic pump. Keep the stirring speed at 50 r / min, and the entire dropping time should be 30-60 minutes. After the addition is complete, continue stirring for 15 minutes. ④ Add 2.0 parts of acetylthiose tributyl citrate plasticizer to the mixture from step ③, and continue stirring for 10 minutes after adding. ⑤ Use a peristaltic pump to slowly add 0.5 parts of titanate crosslinking agent TC-TE to step ④. The entire addition time is 20~40 minutes. After the addition is complete, continue stirring for 10 minutes. ⑥ Reduce the stirring speed to 35 r / min, add 0.1 parts of polydimethylsiloxane defoamer, and stir for 10 min; ⑦ Add 0.1 parts of bactericide to step ⑥ and stir for 10 minutes; ⑧ Add sodium bicarbonate (10% aqueous solution) and 4.55 parts of pure water to step ⑦, stir for 10 minutes, and then filter through a 300-mesh filter to obtain the self-breathing splicing paper high-speed spraying splice adhesive of the present invention. The physicochemical properties are: viscosity 1640 mPa.s, pH value 4.85, solid content 50.58%, adhesion strength: 1.16 N. The specific rheological properties are shown in Table 4 below.

[0049] Table 4 Comparative Example 1 Rheological Test Data

[0050]

[0051] Comparative Example 2

[0052] Compared with Example 1, a high-speed spray nozzle adhesive was prepared from a polyvinyl alcohol solution without carboxylic acid modification according to the following methods and steps.

[0053] ① Add 80 parts of VAE emulsion with high ethylene content to the reactor; ② Turn on the stirrer and add 12 portions of the ordinary polyvinyl alcohol aqueous solution prepared in Preparation Example 2 (polyvinyl alcohol dry powder model is 0588, solid content: 30%) at a speed of 35 r / min, and stir for 20 min; ③ Increase the stirring speed to 50 r / min, and slowly add 0.2 parts of ACRYSOLTMRM-8W and 0.5 parts of ACRYSOLTMRM-2020NPR polyurethane thixotropic additive (the polyurethane thixotropic additives should be diluted with water at a 1:1 ratio beforehand) using a peristaltic pump. Keep the stirring speed at 50 r / min, and the entire dropping time should be 30-60 minutes. After the addition is complete, continue stirring for 15 minutes. ④ Add 2.0 parts of acetylthiose tributyl citrate plasticizer to step ③, and continue stirring for 10 minutes after adding. ⑤ Use a peristaltic pump to slowly add 0.5 parts of titanate crosslinking agent TC-TE to step ④. The entire addition time is 20~40 minutes. After the addition is complete, continue stirring for 10 minutes. ⑥ Reduce the stirring speed to 35 r / min, add 0.10 parts of polydimethylsiloxane defoamer, and stir for 10 min; ⑦ Add 0.1 parts of bactericide to step ⑥ and stir for 10 minutes; ⑧ Add sodium bicarbonate (10% aqueous solution) and 4.55 parts of pure water to step ⑦, stir for 10 minutes, and then filter through a 300-mesh filter to obtain the self-breathing splicing paper high-speed spraying splice adhesive of the present invention. The physicochemical properties are: viscosity 1310 mPa.s, pH value 4.78, solid content 50.75%, adhesion strength: 1.05 N. The specific rheological properties are shown in Table 5 below.

[0054] Table 5 Comparative Example 2 Rheological Test Data

[0055]

[0056] Comparative Example 3

[0057] Compared with Example 1, without the addition of thixotropic additives, the high-speed spray nozzle adhesive was prepared according to the following methods and steps: ① Add 80 parts of VAE emulsion with high ethylene content to the reactor; ② Turn on the stirrer and add 4 parts of the carboxylic acid modified polyvinyl alcohol solution prepared in Preparation Example 1 and 8 parts of the ordinary polyvinyl alcohol aqueous solution prepared in Preparation Example 2 (the polyvinyl alcohol dry powder is model 0588, solid content: 30%) at a speed of 35 r / min, and stir for 20 min; ③ Add 2.0 parts of acetylthiose tributyl citrate plasticizer to step ②, and continue stirring for 10 minutes after adding. ④ Use a peristaltic pump to slowly add 0.5 parts of titanate crosslinking agent TC-TE to step ③. The entire addition time is 20~40 minutes. After the addition is complete, continue stirring for 10 minutes. ⑤ Reduce the stirring speed to 35 r / min, add 0.10 parts of polydimethylsiloxane defoamer, and stir for 10 min; ⑥ Add 0.1 parts of bactericide to the mixture and stir for 10 minutes; ⑦ Add sodium bicarbonate (10% aqueous solution) and 5.25 parts of pure water to step ⑥, stir for 10 minutes, and then filter through a 300-mesh filter to obtain the high-speed spraying nozzle adhesive for self-breathing splicing paper of the present invention. The physicochemical properties are: viscosity 1280 mPa.s, pH value 4.88, solid content 49.70%, and adhesion strength 1.26 N. The specific rheological properties are shown in Table 6 below.

[0058] Table 6. Rheological test data for Comparative Example 3

[0059]

[0060] Comparative Example 4

[0061] Compared with Example 1, without the addition of a titanate crosslinking agent, the high-speed spray nozzle adhesive was prepared according to the following methods and steps: ① Add 80 parts of VAE emulsion with high ethylene content to the reactor; ② Turn on the stirrer and add 4 parts of the carboxylic acid modified polyvinyl alcohol solution prepared in Preparation Example 1 and 8 parts of the ordinary polyvinyl alcohol aqueous solution prepared in Preparation Example 2 (the polyvinyl alcohol dry powder is model 0588, solid content: 30%) at a speed of 35 r / min, and stir for 20 min; ③ Increase the stirring speed to 50 r / min, and slowly add 0.2 parts of ACRYSOLTMRM-8W and 0.5 parts of ACRYSOLTMRM-2020NPR polyurethane thixotropic additive (the polyurethane thixotropic additives should be diluted with water at a 1:1 ratio beforehand) using a peristaltic pump. Keep the stirring speed at 50 r / min, and the entire dropping time should be 30-60 minutes. After the addition is complete, continue stirring for 15 minutes. ④ Add 2.0 parts of acetylthiose tributyl citrate plasticizer to step ③, and continue stirring for 10 minutes after adding. ⑤ Reduce the stirring speed to 35 r / min, add 0.10 parts of polydimethylsiloxane defoamer, and stir for 10 min; ⑥ Add 0.1 parts of bactericide to step ⑤ and stir for 10 minutes; ⑦ Add sodium bicarbonate (10% aqueous solution) and 5.05 parts of pure water to step ⑥, stir for 10 minutes, and then filter through a 300-mesh filter to obtain the self-breathing splicing paper high-speed spraying splice adhesive of the present invention. The physicochemical properties are: viscosity 1480 mPa.s, pH value 4.88, solid content 49.90%, adhesion strength: 1.01 N. The specific rheological properties are shown in Table 7 below.

[0062] Table 7 Comparative Example 4 Rheological Test Data

[0063]

[0064] Comparative Example 5

[0065] Compared to Example 1, a common emulsion was used instead of the high-ethylene-content VAE emulsion. The common VAE emulsion selected was Celvolit® 1491, a plasticizer-free vinyl acetate-ethylene copolymer emulsion with an ethylene content of approximately 16%. The high-speed spray nozzle adhesive was prepared according to the following methods and steps: ① Add 80 parts of ordinary VAE emulsion (ethylene content 16%) to the reactor. ② Turn on the stirrer and add 4 parts of the carboxylic acid modified polyvinyl alcohol solution prepared in Preparation Example 1 and 8 parts of the ordinary polyvinyl alcohol aqueous solution prepared in Preparation Example 2 (the polyvinyl alcohol dry powder is model 0588, solid content: 30%) at a speed of 35 r / min, and stir for 20 min; ③ Increase the stirring speed to 50 r / min, and slowly add 0.2 parts of ACRYSOLTMRM-8W and 0.5 parts of ACRYSOLTMRM-2020NPR polyurethane thixotropic additive (the polyurethane thixotropic additives should be diluted with water at a 1:1 ratio beforehand) using a peristaltic pump. Keep the stirring speed at 50 r / min, and the entire dropping time should be 30-60 minutes. After the addition is complete, continue stirring for 15 minutes. ④ Add 2.0 parts of acetylthiose tributyl citrate plasticizer to step ③, and continue stirring for 10 minutes after adding. ⑤ Use a peristaltic pump to slowly add 0.5 parts of titanate crosslinking agent TC-TE to step ④. The entire addition time is 20~40 minutes. After the addition is complete, continue stirring for 10 minutes. ⑥ Reduce the stirring speed to 35 r / min, add 0.10 parts of polydimethylsiloxane defoamer, and stir for 10 min; ⑦ Add 0.1 parts of bactericide to step ⑥ and stir for 10 minutes; ⑧ Add sodium bicarbonate (10% aqueous solution) and 4.55 parts of pure water to step ⑦, stir for 10 minutes, and then filter through a 300-mesh filter to obtain the self-breathing splicing paper high-speed spraying splice adhesive of the present invention. The physicochemical properties are: viscosity 1770 mPa·s, pH value 4.96, solid content 50.22%, and adhesion strength 1.12 N. The specific rheological properties are shown in Table 1 below:

[0066] Table 1. Rheological test data of Comparative Example 5

[0067]

[0068] Raw material information

[0069] The relevant raw material parameters and sources in each preparation example, embodiment, and comparative example are as follows:

[0070] The high-ethylene-content VAE emulsion is Celvolit® 1475, a plasticizer-free vinyl acetate-ethylene copolymer emulsion with an ethylene content of 28%. Its glass transition temperature is -16 to -20°C, solids content is 54.5% to 56.5%, pH is 4.0 to 6.0, and viscosity is 1500 to 3000 mPa·s (25°C, BROOKFIELD RVT 04# 20 RPM). Source: Celanese (China) Investment Co., Ltd.

[0071] The standard VAE emulsion is Celvolit® 1491, a plasticizer-free vinyl acetate-ethylene copolymer emulsion with an ethylene content of approximately 16%. Its glass transition temperature is onset: 2~6℃, solids content is 54.5~56.5%, pH is 4.0~5.0, and viscosity is 4000~6000 mPa·s (25℃, BROOKFIELD RVT 04# 20 RPM). Source: Celanese (China) Investment Co., Ltd.

[0072] Acrysol RM8W: A low-odor, solvent-free, water-based nonionic associative rheology modifier (hydrophobic modified polyurethane); Source: ROHMHAAS.

[0073] ACRYSOL RM-2020NPR: Solvent-free nonionic polyurethane rheology modifier; Source: Dow Chemical;

[0074] Titanate crosslinking agent TC-TE, source: Tianchang Tianchen Chemical Co., Ltd.

[0075] Titanium catalyst AQ33, source: Zhuhai Weiken Chemical Co., Ltd.

[0076] The testing indicators for each product are as follows:

[0077]

[0078] The following is a comparison of the machine performance of various embodiments and comparative examples of the high-speed sprayed splice adhesive for self-breathing splicing paper:

[0079]

[0080] Based on the machine testing, Examples 1, 2, and 3 all met the customer's requirements. In Comparative Example 1, the amount of carboxylic acid-modified polyvinyl alcohol added was relatively small, resulting in a slightly longer open time, lower adhesion, and slight wrinkling of the cigarette, preventing the machine speed from reaching the expected requirements. In Comparative Example 2, without carboxylic acid-modified polyvinyl alcohol, the open time was significantly longer, adhesion was lower, leading to severe wrinkling of the cigarette, a high air leakage rejection rate, and a total ventilation rate below the standard lower limit (27±8%), making normal winding impossible at a machine speed of 10,000. In Comparative Example 3, the absence of a thixotropic agent resulted in high-speed shearing... The viscosity of the cigarettes was significantly lower than expected, resulting in glue leakage and dripping at the nozzles. The splicing paper detached and accumulated at the corrugated board, causing machine shutdowns and preventing normal winding. Comparative Example 4, without crosslinking agent, showed significantly weak adhesion, resulting in leaky cigarettes with a leakage rejection rate of approximately 0.7%. The overall ventilation rate of the cigarettes was also high, indicating poor cigarette bonding quality. Comparative Example 5 also exhibited leaky cigarettes. Increasing the glue amount improved the situation, reducing the leakage rejection rate to 0.08%. However, the increased glue amount led to a low overall ventilation rate and increased glue residue, resulting in poor operational quality. Comparative Examples 1, 2, and 3 all showed low overall ventilation rates, while Comparative Example 4 had a high overall ventilation rate due to insufficient adhesion. Comparative Example 5 also suffered from leaky cigarettes due to insufficient adhesion. Increasing the glue amount improved the cigarette quality, but excess glue overflowed, resulting in a low overall ventilation rate and increased glue residue.

[0081] The rheological data show that the viscosity of each embodiment is high, and the viscosity decreases only slightly with the increase of shear rate. This indicates that the high-speed splice adhesive has excellent dynamic rheological properties under high-speed roller coating and is not prone to problems such as excessive adhesive residue, poor adhesion, and low total ventilation rate caused by the adhesive clogging the pores of the self-ventilating splice paper due to excessive flow.

[0082] Furthermore, the physicochemical indicators and machine tests of each embodiment meet the requirements of high-speed coating production for self-breathable tipping paper cigarettes. The high-speed spraying tipping adhesive for self-breathable tipping paper provided by this invention has suitable drying speed, good rheological properties, and high adhesion, and can be stably used in the coating production of self-breathable paper cigarettes. The equipment operating speed reaches 14,000 cigarettes / min, and after running for more than 4 hours, the defect rate of cigarette product quality is 0. The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A high-speed spraying tip joint glue for self-breathable tipping paper, prepared mainly from VAE emulsion, polyvinyl alcohol, thixotropic agent, plasticizer, crosslinking agent, defoaming agent, pH regulator, bactericide and pure water, wherein, VAE emulsion, polyvinyl alcohol, thixotropic agent, crosslinking agent, the mass ratio of 80: (6~12): (0.7~1.2): (0.5~1); the VAE emulsion is a high ethylene content emulsion, wherein the ethylene content is 26~30%; the polyvinyl alcohol comprises 30%~70% mass fraction of carboxylic acid modified polyvinyl alcohol.

2. A high speed spray tip for tipping paper for use in making self-venting tipping paper, according to claim 1, wherein The mass ratio of the VAE emulsion, polyvinyl alcohol, thixotropic agent, plasticizer, crosslinking agent, defoaming agent, pH regulator, bactericide and pure water is 80: (6~12): (0.7~1.2): (2~4): (0.5~1): (0.1~0.3): (0~0.05): 0.1: (1~10).

3. A high speed spray tip for tipping paper according to claim 1 or 2, wherein The VAE emulsion also has the following characteristics: the glass transition temperature is onset: -16~-20℃, the solid content is 54.5~56.5%, the pH value is 4.0~6.0, and the BROOKFIELD RVT viscosity under the condition of 25℃, 04# rotor and 20RPM rotation speed is 1500~3000mPa.s.

4. A high speed spray tip for tipping paper according to claim 1 or 2, wherein The polyvinyl alcohol comprises carboxylic acid modified polyvinyl alcohol and ordinary polyvinyl alcohol; wherein, the carboxylic acid modified polyvinyl alcohol: solid content is 19-21%, carboxylic acid is acrylic acid, the type of polyvinyl alcohol raw material is 1788, the polymerization degree is 1700, and the alcoholysis degree is 88%; the ordinary polyvinyl alcohol: solid content is 30%, and is selected from at least one of polyvinyl alcohol with type 0588, 1788, 2088 and 2488.

5. A high speed spray tip for tipping paper according to claim 1 or 2, wherein The thixotropic agent is a low odor, solvent-free aqueous non-ionic associated rheological modifier, which is a compound of ACRYSOLTMRM-8W and ACRYSOLTMRM-2020NPR.

6. A high speed spray tip for tipping paper according to claim 1 or 2, wherein The crosslinking agent is a titanate, and is selected from at least one of TC-TE and AQ33.

7. A high speed spray tip for tipping paper according to claim 1 or 2, wherein The plasticizer is selected from at least one of glyceryl triacetate, acetyl tri-butyl citrate and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.

8. A high speed spray tip for tipping paper according to claim 1 or 2, wherein The defoaming agent is a polydimethylsiloxane defoaming agent; the pH regulator used is sodium bicarbonate; the bactericide used is selected from at least one of 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one and 1,2-benzisothiazolin-3-one; and the pure water used is tertiary pure water treated by multi-stage reverse osmosis membrane filtration.

9. The method of claim 1 to 8, wherein the method is characterized in that, Comprise the following steps: (1) preparing a carboxylic acid modified polyvinyl alcohol aqueous solution: ①Take 70.8 parts of pure water into the reaction kettle, start stirring, keep the stirring speed at 44r / min, add 19 parts of polyvinyl alcohol 1788 dry powder at a uniform speed while stirring, after adding, stir at room temperature for 15 minutes; ②Start heating to 90℃, keep for 2 hours until completely dissolved, then cool to 35℃, add 1.5 parts of acrylic acid and 0.1 part of cerium nitrate ammonium (dissolved in 2 parts of pure water), react for 90min; ③Heat to 80℃ (control within 40min), add 0.05 parts of ammonium persulfate (dissolved in 2.5 parts of water), drop for 10min, keep for 60min; (4) warming to 90°C (control in 20 min to complete), drop 0.05 parts of tert-butyl hydroperoxide (using 2.5 parts of water to dissolve), keep warm reaction 90 min; (5) cooling to room temperature, add 0.5 parts of ammonia and 1 parts of pure water, adjust the pH value to 4.9-5.1; ⑥ pressurized filtration out of the material, ready for use; (2) preparation of 30% mass concentration of ordinary polyvinyl alcohol aqueous solution: Take 70 parts of pure water into the reaction kettle, open the stirring, keep the speed of 44r / min, add 30 parts of polyvinyl alcohol dry powder at a constant speed, after adding, stir for 15 minutes at room temperature, start to warm up to 90°C, keep warm for 2 hours until completely dissolved, cool down to below 55°C, pressurized filtration out of the material, ready for use; (3) preparation of high-speed spraying of filter tip paper with self-breathable filter tip paper with filter tip paper: ① add 80 parts of VAE emulsion with high ethylene content into the reaction kettle; ② open the stirring, add 2~8 parts of carboxylic acid modified polyvinyl alcohol solution prepared in step (1) and 4~10 parts of ordinary polyvinyl alcohol solution prepared in step (2) at a speed of 35r / min, stir for 20 min; ③ increase the stirring speed to 50r / min, slowly add 0.2 parts of ACRYSOLTMRM-8W, 0.5~1.0 parts of ACRYSOLTMRM-2020NPR thixotropic agent (thixotropic agent is diluted with 1:1 water first) by peristaltic pump, the stirring speed is still controlled at 50r / min, the whole drop adding time is 30~60 minutes, after adding, continue to stir for 15 min; ④ add 2~4 parts of plasticizer to step ③, after adding, continue to stir for 10 min; ⑤ slowly drop 0.5~1 parts of titanium ester crosslinking agent into step ④ (drop by peristaltic pump), the stirring speed is still controlled at 50r / min, the whole drop adding time is 20~40 minutes, after adding, continue to stir for 20 min; ⑥ reduce the stirring speed to 35r / min, add 0.1~0.3 parts of polydimethylsiloxane defoaming agent, stir for 10 min; ⑦ add 0.1 parts of bactericide to step ⑥, stir for 10 min; ⑧ add pH value regulator and 1~10 parts of pure water, adjust the viscosity to 500-2000 mPa.s (25°C, Brookfield 03# 20 rpm), adjust the pH to 4.5~5.5, solid content ≥48%, stir for 10 min, then discharge, get high-speed spraying of filter tip paper with self-breathable filter tip paper with filter tip paper.

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