High-speed mouthpiece adhesive for PET (Polyethylene Terephthalate) tipping paper and preparation method of high-speed mouthpiece adhesive

Abstract

The invention relates to a preparation method of a high-speed mouthpiece adhesive for PET (polyethylene terephthalate) tipping paper, which is mainly prepared by adding EVA (ethylene-vinyl acetate) emulsion, polyvinyl alcohol, a plasticizer, a wetting agent, a defoaming agent, a pH (potential of hydrogen) regulator, a bactericide and the like into prefabricated acrylic emulsion. The preparation method is characterized in that the prefabricated acrylic emulsion has a high solid content of 65-70%, and is prepared by suspension polymerization of a soft-segment acrylate monomer, a hard-segment acrylate monomer, a crosslinking monomer, abietate and a reactive emulsifier with carbon-carbon double bonds; the mass ratio of the prefabricated acrylic emulsion to the EVA emulsion to the polyvinyl alcohol to the plasticizer to the wetting agent to the defoaming agent to the pH value regulator to the bactericide is (20-30) to (55-65) to (5-10) to (3-5) to (0.1-0.5) to (0.1-0.5) to (0.1-0.5) to 0.1. The high-speed mouthpiece adhesive for the PET tipping paper can meet the requirements of the high-speed mouthpiece adhesive for the PET tipping paper on the bonding force, the cohesive strength and the bonding stability.

Description

Technical Field

[0001] The invention relates to the technical field of adhesive preparation, and in particular to a high-speed nozzle adhesive for PET tipping paper and a preparation method thereof. Technical Background

[0002] The invention belongs to the field of cigarette adhesives and relates to a high-speed nozzle adhesive which is an adhesive used for bonding cigarette filters and cigarettes together in a high-speed production process of cigarettes.

[0003] PET film is a high temperature resistant polyester film, which is made by the dehydration condensation reaction of ethylene terephthalate. In recent years, it has been used in the field of cigarettes to replace ordinary tipping paper to wrap cigarette filter rods. The cigarettes produced have good optical transparency, stability, aesthetics and novelty, and are deeply loved by the public. However, PET film has the characteristics of low surface energy, weak polarity, and poor adhesion. When using ordinary adhesives, it is easy to have problems with weak adhesion. The ordinary tipping glue currently on the market is difficult to meet its bonding requirements.

[0004] In order to solve the above problems, the inventor's research aims to provide a high-speed nozzle glue for PET tipping paper and a preparation method thereof.

[0005] PVA commonly used in cigarette mouthpiece glue C 1. The surface tension of VAE emulsion is high and its wettability on the surface of PET film is poor. The emulsion is prone to shrinkage during coating, affecting the uniformity of coating and bonding strength.

[0006] Acrylic emulsion is an emulsion formed by copolymerization of acrylic ester monomers. It uses water as the dispersion medium and does not use organic solvents. It is safe and environmentally friendly. The molecules contain polar groups such as carboxyl and hydroxyl groups, and have high bonding strength and shear strength.

[0007] Rosin is a monocarboxylic acid with rosin acid as the main component, and is a mixture of isomers with different double bond positions. Rosin resin contains double chains and carboxyl active genes, has conjugated double bonds and typical carboxyl reactions, and is used in the adhesive industry to increase viscosity, change adhesive holding properties, cohesive properties, etc.

[0008] If rosin ester emulsion is added to polyacrylate pressure-sensitive adhesive, especially tackifying resin with low molecular polarity, low molecular weight and high softening point can reduce the interfacial tension between the base polymer and the adhered surface, increase the viscoelasticity and permeability of the adhesive, improve its peel strength and initial adhesion, and improve the adhesion of the adhesive to low surface energy and difficult-to-bond materials such as polyethylene, polypropylene, and PET. However, there are problems with compatibility and stability between tackifying resin and acrylic emulsion system, which easily leads to the instability of the emulsion. The inventors imagine that preparing a composite polymer emulsion by copolymerization and compounding it with a VAE emulsion may be an effective way to solve this type of problem. Summary of the invention

[0009] In view of the deficiencies of the prior art, the present invention provides a high-speed nozzle glue for PET tipping paper and a preparation method thereof, wherein the high-speed nozzle glue can have good adhesion to the PET film, generate high cohesive strength and have a suitable open time. The high-speed nozzle glue for PET tipping paper of the present invention introduces a high-solid content, high-performance polyacrylic acid composite emulsion synthesized by copolymerization of soft and hard monomers, polymerized rosin, etc., and then adds VAE emulsion and polyvinyl alcohol for compounding, and adds a substrate wetting agent to reduce the surface tension of the substrate, improve its wetting performance on the PET film, and finally prepare a high-performance high-speed nozzle glue for PET tipping paper with good adhesion and cohesive strength.

[0010] The technical problem to be solved by the present invention is to provide a high-speed nozzle glue for high-performance PET tipping paper with high safety, strong initial adhesion, high cohesive strength and interface adhesion, and a preparation method thereof. To achieve the purpose of the invention, the technical solution of the present invention is implemented as follows:

[0011] The high-speed nozzle glue for PET tipping paper provided by the present invention is mainly prepared by adding EVA emulsion, polyvinyl alcohol, plasticizer, wetting agent, defoamer, pH value regulator, bactericide and pure water into prefabricated acrylic emulsion; the characteristic is that the prefabricated acrylic emulsion has a high solid content of 65-70%, and is an emulsion prepared by polymerizing soft segment acrylic ester monomer, hard segment acrylic ester monomer, cross-linking monomer, rosin ester, and a composite emulsifier containing a reactive emulsifier and a conventional emulsifier. liquid, wherein the reactive emulsifier is a highly hydrophilic functional emulsifier having a carbon-carbon double bond; and when compounding the high-speed nozzle glue, the mass ratio of the prefabricated acrylic emulsion, EVA emulsion, polyvinyl alcohol, plasticizer, wetting agent, defoamer, pH regulator, bactericide and pure water is (20-30): (55-65): (5-10): (3-5): (0.1-0.5): (0.1-0.5): (0.1-0.5): 0.1: (1-5).

[0012] Preferably, in the high-speed nozzle glue for PET tipping paper provided by the present invention, when the prefabricated acrylic emulsion is prepared, the mass ratio of main raw materials is soft segment acrylic ester monomer: hard segment acrylic ester monomer: cross-linking monomer: rosin ester = 8∽10: 22∽26:: 0.5∽1.5: 3∽5.

[0013] Preferably, in the high-speed nozzle glue for PET tipping paper provided by the present invention, the hard segment acrylate monomer is methyl methacrylate; and the soft segment acrylate monomer is butyl acrylate.

[0014] Preferably, in the high-speed nozzle glue for PET tipping paper provided by the present invention, the cross-linking monomer is a functional monomer containing vinyl, hydroxyl and acrylamide groups.

[0015] Preferably, the high-speed nozzle glue for PET tipping paper provided by the present invention, the prefabricated acrylic emulsion has the following characteristics: solid content: 65∽70%, viscosity: 800∽1500mPa.s, pH value: 4.0∽6.0, and glass transition temperature: -30°C∽-20°C.

[0016] Preferably, in the high-speed nozzle glue for PET tipping paper provided by the present invention, the reactive emulsifier is COPS-1.

[0017] Preferably, in the high-speed nozzle glue for PET tipping paper provided by the present invention, the mass ratio of the reactive emulsifier to the conventional emulsifier is 0.7 to 1.3.

[0018] Preferably, when compounding the high-speed nozzle glue for PET tipping paper provided by the present invention, the VAE emulsion used has the following characteristics: solid content: 59-61%, viscosity: 1500-2000mPa.s, pH value: 4.0-6.0, and glass transition temperature: 0°C-10°C.

[0019] Preferably, in the high-speed nozzle glue for PET tipping paper provided by the present invention, the wetting agent is BYK-347; the plasticizer is selected from one or more of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, acetyl tributyl citrate, and triacetin; the defoamer is a mineral oil defoamer, and the pH adjuster is: sodium bicarbonate; the bactericide is selected from one or more of 2-methyl-4-isothiazoline-3-one, 5-chloro-2-methyl-4-isothiazoline-3-one, and 1,2-benzisothiazol-3-one; the pure water is tertiary pure water treated by multi-stage reverse osmosis membrane filtration, and its conductivity is less than 10μs / cm.

[0020] The high-speed nozzle glue for PET tipping paper provided by the present invention uses a specially designed acrylic emulsion which is an acrylic ester copolymer polymerized by hard monomer methyl methacrylate, soft monomer butyl acrylate and a crosslinking agent; the emulsifier used is a combination of a reactive emulsifier and a conventional emulsifier, and the ratio used is 0.7-1.3:1, wherein the reactive emulsifier is a highly hydrophilic functional emulsifier containing a carbon-carbon double bond, for example, a sodium salt of propenyl ether sulfonic acid, and in a specific embodiment, it is 3-allyloxy-1-hydroxy-1-propane sulfonate (commonly known as COPS-1). This type of reactive emulsifier does not contain alkylphenol polyoxyethylene ethers (i.e., APEO), and can significantly improve the adhesion of the emulsion and the stability of the emulsion system; the conventional emulsifier is, for example, sodium dodecyl diphenyl ether disulfonate (DSB); the crosslinking agent used is a crosslinking monomer HA, and the crosslinking monomer HA ( HA) is a trademark of Hanko Chemical, a functional monomer containing vinyl, hydroxyl and acrylamide groups; the initiator used is ammonium persulfate; the rosin ester used is PENSEL GB-75 of Arakawa Chemical; when preparing the polyacrylic acid emulsion, the ratio of soft and hard monomers (methyl methacrylate, butyl acrylate and cross-linking monomer HA) is controlled to achieve the glass transition temperature (-30℃~-20℃) required to achieve the purpose of the invention. If the glass transition temperature is too high, the bonding strength will be significantly reduced; if the glass transition temperature is too low, it will cause more adhesive scale to be generated when the product is used, which is easy to dirty the equipment and is not conducive to equipment cleaning; the use of rosin ester can improve the bonding strength and reduce the interfacial tension between the base polymer and the bonded surface (the contact angle becomes smaller). Too much rosin ester will affect the stability of the system, and too little rosin ester will not achieve a satisfactory bonding effect.

[0021] If too much acrylic emulsion is added, there will be too much adhesive scale when the product is used, which will dirty the equipment, make cleaning difficult and reduce production efficiency; if too little is added, the bonding strength effect cannot be achieved.

[0022] Preferably, the polyvinyl alcohol used in the high-speed nozzle glue for PET tipping paper provided by the present invention is KL318, which is a carboxyl-modified structure, has excellent cross-linking reactivity, good water solubility, excellent dispersibility and rheological properties, and has anti-skinning performance and low foaming performance. The use of carboxyl-modified polyvinyl alcohol can improve the bonding strength on the one hand, and improve the rheological properties on the other hand, so that the nozzle glue has high-speed shear resistance.

[0023] The rosin ester used in the present invention has excellent properties, such as low polarity and good adhesion to materials with low surface tension.

[0024] The wetting agent used in the present invention is BYK-347, which can effectively reduce the surface tension of the water-based system and improve its wettability and leveling properties on the substrate.

[0025] The present invention also provides a method for preparing a high-speed nozzle glue for PET tipping paper, comprising the following steps:

[0026] Step 1: Prepare high solid content acrylic emulsion using secondary nucleation method:

[0027] 1.1 First, mix Mixing is performed;

[0028] 1.2 Add by weight to the reactor 1 cup water, Mixed monomers (methyl methacrylate, butyl acrylate and crosslinking monomers HA, rosin ester), 0.8∽1.2 parts of emulsifier (COPS-1:DSB=0.7~1.3:1) and 0.05 parts of initiator are added to the reactor in sequence, stirring is started, the stirring speed is controlled at 30∽50r / min, the temperature is raised to 75°C, kept warm for 1 hour, and then raised to 80°C. After blue fluorescence appears in the reactor, 0.25 parts of initiator and the remaining monomers are added dropwise at the same time, and the secondary nucleation method is used. , 0.4∽0.7 parts of emulsifier (COPS-1:DSB=0.7~1.3:1) was added intermittently during the polymerization process, and the total dropwise addition time was 4 hours. After the dropwise addition was completed, the mixture was kept warm for 1 hour, and the temperature was continued to rise to 90°C for maturation until there was no monomer odor, and then the temperature was lowered for standby use; the acrylic emulsion thus prepared had the following characteristics: solid content: 65∽70%, viscosity: 800∽1500mpa.s, pH value: 4.0∽6.0, and glass transition temperature: -30°C∽-20°C;

[0029] Step 2 Preparation of polyvinyl alcohol solution

[0030] Add 75-80 parts of water into the kettle by mass percentage, start stirring, keep stirring at 50r / min and add 20-25 parts of polyvinyl alcohol KL318. After adding, heat to 90℃, keep stirring for 2 hours, and then cool to room temperature for use;

[0031] Step 3: Compound high-speed nozzle glue

[0032] 3.1 Add 50∽60 parts of VAE emulsion into the kettle, start stirring, add the acrylic emulsion prepared in step 1.2 at a speed of 40r / min, and stir for 10min;

[0033] 3.2 Add 5-10 parts of polyvinyl alcohol prepared in step 2 and stir at a speed of 50r / min for 20min;

[0034] 3.3 Add 3-5 parts of plasticizer to step 3.2 and stir at 50r / min for 10min;

[0035] Add 0.1-0.5 parts of wetting agent and stir at 50r / min for 5 minutes;

[0036] Then add 0.1 part of fungicide and 0.1 part of mineral oil defoamer, and stir at 50r / min for 10min;

[0037] Then add pH adjuster and continue stirring at 50r / min for 5min;

[0038] The viscosity of the material obtained in step 3.3 is adjusted to 5000-6000 mpa.s, and the material is discharged to obtain a high-speed nozzle glue for PET tipping paper.

[0039] For high-speed nozzle glue products for PET tipping paper, the higher the solid content, the more conducive it is to improving the comprehensive bonding performance. Therefore, the preparation method of the present invention adopts a secondary nucleation method to increase the solid content of the nozzle glue latex.

[0040] The present invention produces beneficial effects:

[0041] 1. The present invention forms a high-solid content, high-performance acrylic emulsion by copolymerizing soft and hard monomers, polymerized rosin, crosslinking agent and reactive emulsifier in optimized proportions, which gives the nozzle glue greater initial viscosity and stronger cohesive force; VAE emulsion, carboxyl-modified polyvinyl alcohol, plasticizer and the like are then added for compounding, and a substrate wetting agent is added to reduce the surface tension of the substrate and improve its wetting performance on the PET film. The nozzle glue prepared in this way has stronger bonding performance than conventional nozzle glue, high cohesive strength, and is particularly suitable for low surface energy and difficult-to-bond materials such as polyethylene, polypropylene, and PET;

[0042] 2. The present invention uses a highly hydrophilic functional reactive emulsifier containing a carbon-carbon double bond. This type of reactive emulsifier does not contain alkylphenol polyoxyethylene ethers, which can significantly improve the adhesion of the emulsion and improve the stability of the emulsion system. The cross-linking agent containing a functional monomer containing vinyl, hydroxyl and acrylamide groups can improve the compatibility of acrylate and rosin ester, and improve the stability and bonding performance of the system.

[0043] 3. When preparing polyacrylic acid emulsion, the ratio of soft and hard monomers (the ratio of methyl methacrylate, butyl acrylate and cross-linking monomer HA) is controlled to achieve the reasonable glass transition temperature range (-30°C to -20°C) required to achieve the purpose of the invention. This not only avoids the reduction of bonding strength caused by too high a glass transition temperature, but also eliminates the disadvantages of too much glue scale generated when using the nozzle glue product due to too low a glass transition temperature, which easily stains the equipment and is not conducive to equipment cleaning;

[0044] 4. The use of rosin ester can improve the bonding strength, reduce the interfacial tension between the base polymer and the bonded surface, and reduce the contact angle; a reasonable amount of rosin ester can not only ensure the stability of the nozzle glue during high-speed gluing, but also achieve a satisfactory bonding effect;

[0045] 5. Reasonable selection of the compounding ratio of acrylic emulsion and EVA emulsion avoids excessive addition of acrylic emulsion, which will cause excessive adhesive scale when the product is used, dirty equipment, and be unfavorable for cleaning the working surface, reducing production efficiency; it also avoids too little acrylic emulsion to achieve the bonding strength effect;

[0046] 6. The high-speed nozzle glue for PET tipping paper provided by the present invention uses KL318 polyvinyl alcohol, which is a carboxyl-modified structure, has excellent cross-linking reactivity, good water solubility, excellent dispersibility and rheological properties, and has anti-skinning and low foaming properties. The use of carboxyl-modified polyvinyl alcohol can improve the bonding strength on the one hand, and improve the rheological properties on the other hand, so that the nozzle glue has high-speed shear resistance;

[0047] 7. The high-speed nozzle glue for PET tipping paper developed by the present invention has good performance: good safety and hygiene, centrifugal stability test, dilution stability, freeze-thaw stability meet the requirements, strong bonding strength, short surface drying time; and on a PROTOS 70 machine, using a PET smooth film with a dyne value of 36 as the tipping paper, the nozzle gluing test was carried out at a high speed of 3000-4000 pieces / minute. The results showed that there was no abnormality in the continuous operation time of 8 hours, and the machine speed could be increased to 3600 pieces / minute, showing good bonding, normal operation of the equipment, and a defect rate of 0, which fully met the use requirements of high-speed nozzle glue for smooth films such as PET tipping paper. DETAILED DESCRIPTION

[0048] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0049] The present invention will be further described in detail below with reference to the embodiments, but the scope of the present invention is not limited to these embodiments.

[0050] Example 1

[0051] According to the following method and steps, high-speed nozzle glue for PET tipping paper is prepared:

[0052] (1) Mixing by weight according to the ratio of methyl methacrylate: butyl acrylate: crosslinking monomer HA: rosin ester = 9.5:24.8:1:3.5;

[0053] (2) By weight, 23 parts of water, 4.5 parts of mixed monomers (methyl methacrylate, butyl acrylate and cross-linking monomers HA, rosin ester), 1 part of composite emulsifier (COPS-1:DSB=1:1) and 0.05 parts of initiator were added to the reactor in sequence, stirring was started, the stirring speed was controlled at 40r / min, the temperature was raised to 75°C, kept warm for 1 hour, and then raised to 80°C. After blue fluorescence appeared in the reactor, 0.25 parts of initiator were added dropwise at the same time. and the remaining 65.5 parts of monomers, using the secondary nucleation method, intermittently adding 0.5 parts of composite emulsifier (COPS-1:DSB=1:1) during the polymerization process, the total dropwise addition time is 4 hours, after the dropwise addition is completed, the temperature is kept for 1 hour, and the temperature is continued to rise to 90°C for maturation until there is no monomer odor, and the temperature is cooled for standby use; the prepared acrylic emulsion has the following characteristics: solid content: 68.1%, viscosity: 1100mpa.s, pH value: 4.2, glass transition temperature: -24.8°C;

[0054] (3) Preparation of polyvinyl alcohol solution. Add 75 parts of water into the kettle according to the mass percentage, start stirring, keep stirring at a speed of 50r / min, add 25 parts of KL318, after adding, heat to 90°C, keep stirring for 2 hours, and then cool to room temperature for use;

[0055] (4) Add 63 parts of VAE emulsion into the kettle, start stirring, add 25 parts of self-prepared acrylic emulsion at a speed of 40 r / min, and continue stirring for 10 minutes;

[0056] (5) adding 3.5 parts of plasticizer tributyl acetyl citrate to step (4) and stirring at a speed of 50 r / min for 10 min;

[0057] (6) Add 7 parts of polyvinyl alcohol solution to step (5) and stir at a speed of 50 r / min for 10 min;

[0058] (7) Add 0.2 parts of wetting agent and stir at 50 r / min for 5 min;

[0059] (8) Add 0.1 part of fungicide and 0.1 part of mineral oil defoamer and stir at 50 r / min for 5 min;

[0060] (9) Add pH adjuster and continue stirring at 50 r / min for 5 min;

[0061] (10) The viscosity of the material obtained in step (9) is adjusted to 5100 mPa.s, the pH value is 4.8, and the material is discharged to obtain the high-speed nozzle glue for PET tipping paper of the present invention.

[0062] Example 2

[0063] According to the following method and steps, high-speed nozzle glue for PET tipping paper is prepared:

[0064] (1) Mixing by weight according to the ratio of methyl methacrylate: butyl acrylate: crosslinking monomer HA: rosin ester = 8.5:25.2:1.2:4.5;

[0065] (2) By weight, 22 parts of water, 4.9 parts of mixed monomers (methyl methacrylate, butyl acrylate and crosslinking monomers HA: rosin ester), 1 part of composite emulsifier (COPS-1:DSB=1:1) and 0.05 parts of initiator were added to the reactor in sequence, stirring was started, the stirring speed was controlled at 40r / min, the temperature was raised to 75°C, kept warm for 1 hour, and then raised to 80°C. After blue fluorescence appeared in the reactor, 0.25 parts of initiator were added dropwise at the same time. and the remaining 65.1 parts of monomers, using the secondary nucleation method, intermittently adding 0.8 parts of composite emulsifier (COPS-1:DSB=1:1) during the polymerization process, the total dropwise addition time is 4 hours, after the dropwise addition is completed, the temperature is kept for 1 hour, and the temperature is continued to rise to 90°C for maturation until there is no monomer odor, and the temperature is cooled for standby use; the acrylic emulsion prepared in this way has the following characteristics: solid content: 68.5%, viscosity: 1050mpa.s, pH value: 4.1, glass transition temperature: -26.5°C

[0066] (3) Preparation of polyvinyl alcohol solution. Add 75 parts of water into the kettle according to mass percentage, start stirring, keep stirring at a speed of 50r / min, add 25 parts of KL318, after adding, heat to 90 degrees, keep stirring for 2 hours, and cool to room temperature for use;

[0067] (4) Add 58 parts of VAE emulsion into the kettle, start stirring, add 29 parts of self-prepared acrylic emulsion at a speed of 40 r / min, and continue stirring for 10 minutes;

[0068] (5) adding 5 parts of plasticizer 2,2,4-trimethyl-1,3-pentanediol diisobutyrate to step (4) and stirring at a speed of 50 r / min for 10 min;

[0069] (6) Add 6.5 parts of polyvinyl alcohol solution to step (5) and stir at a speed of 50 r / min for 10 min.

[0070] (7) Add 0.25 parts of wetting agent and stir for 5 minutes;

[0071] (8) Add 0.1 part of fungicide and 0.1 part of mineral oil defoamer and stir at 50 r / min for 5 min;

[0072] (9) Add pH adjuster and continue stirring at 50 r / min for 5 min;

[0073] (10) adjusting the viscosity of the material obtained in step (9) to 5400 mPa.s and the pH value to 5.0, discharging the material to obtain the high-speed nozzle glue for PET tipping paper of the present invention;

[0074] Comparative Example 1

[0075] The nozzle glue products currently sold on the market (product name: high-speed nozzle glue) are also evaluated for their applicability on the machine.

[0076] Comparative Example 2

[0077] The other parts are the same as Example 2, except that: the amount of methyl methacrylate is less, 6.5; the amount of butyl acrylate is more, 27.2; Comparative Example 2 prepares high-speed nozzle glue for PET tipping paper according to the following method and steps:

[0078] (1) Mixing by weight according to the ratio of methyl methacrylate: butyl acrylate: crosslinking monomer HA: rosin ester = 6.5:27.2:1.2:4.5;

[0079] (2) By weight, 23 parts of water, 4.9 parts of mixed monomers (methyl methacrylate, butyl acrylate and crosslinking monomers HA: rosin ester), 1 part of emulsifier (COPS-1:DSB=1:1) and 0.05 parts of initiator were added to the reactor in sequence, stirring was started, the stirring speed was controlled at 40r / min, the temperature was raised to 75°C, kept warm for 1 hour, and then raised to 80°C. After blue fluorescence appeared in the reactor, 0.25 parts of initiator were added dropwise. The emulsifier and the remaining monomer 65.1 parts were added to the mixture by the secondary nucleation method. 0.8 parts of emulsifier (COPS-1:DSB=1:1) were added intermittently during the polymerization. The total dropwise addition time was 4 hours. After the dropwise addition was completed, the mixture was kept warm for 1 hour, and the temperature was continued to rise to 90°C for maturation until there was no monomer odor. The mixture was cooled for standby use. The acrylic emulsion thus prepared had the following characteristics: solid content: 67.4%, viscosity: 980mpa.s, pH value: 4.1, and glass transition temperature: -36.5°C

[0080] (3) Preparation of polyvinyl alcohol solution. Add 75 parts of water into the kettle according to mass percentage, start stirring, keep stirring at a speed of 50r / min, add 25 parts of KL318, after adding, heat to 90 degrees, keep stirring for 2 hours, and cool to room temperature for use;

[0081] (4) Add 58 parts of VAE emulsion into the kettle, start stirring, add 29 parts of self-prepared acrylic emulsion at a speed of 40 r / min, and continue stirring for 10 minutes;

[0082] (5) adding 5 parts of plasticizer 2,2,4-trimethyl-1,3-pentanediol diisobutyrate to step (4) and stirring at a speed of 50 r / min for 10 min;

[0083] (6) Add 6.5 parts of polyvinyl alcohol solution to step (5) and stir at a speed of 50 r / min for 10 min.

[0084] (7) Add 0.25 parts of wetting agent and stir for 5 minutes;

[0085] (8) Add 0.1 part of fungicide and 0.1 part of mineral oil defoamer and stir at 50 r / min for 5 min;

[0086] (9) Add pH adjuster and continue stirring at 50 r / min for 5 min;

[0087] (10) adjusting the viscosity of the material obtained in step (9) to 5080 mPa.s and the pH value to 5.0, discharging the material to obtain the high-speed nozzle glue for PET tipping paper of this comparative example;

[0088] Comparative Example 3

[0089] The other parts are the same as Example 2, except that the amount of cross-linking monomer HA is relatively small, which is 0.2; Comparative Example: A high-speed nozzle glue for PET tipping paper is prepared according to the following method and steps:

[0090] (1) Mixing by weight according to the ratio of methyl methacrylate: butyl acrylate: crosslinking monomer HA: rosin ester = 8.5:25.2:0.2:4.5;

[0091] (2) By weight, 22 parts of water, 4.9 parts of mixed monomers (methyl methacrylate, butyl acrylate and crosslinking monomers HA: rosin ester), 1 part of emulsifier (COPS-1:DSB=1:1) and 0.05 parts of initiator were added to the reactor in sequence, stirring was started, the stirring speed was controlled at 40r / min, the temperature was raised to 75°C, kept warm for 1 hour, and then raised to 80°C. After blue fluorescence appeared in the reactor, 0.25 parts of initiator were added dropwise. The emulsifier and the remaining monomer 65.1 parts were added intermittently by the secondary nucleation method during the polymerization process. 0.8 parts of emulsifier (COPS-1:DSB=1:1) were added intermittently. The total dropwise addition time was 4 hours. After the dropwise addition was completed, the mixture was kept warm for 1 hour, and the temperature was continued to rise to 90°C for maturation until there was no monomer odor. The mixture was cooled for standby use. The acrylic emulsion thus prepared had the following characteristics: solid content: 66.8%, viscosity: 820mpa.s, pH value: 4.1, and glass transition temperature: -22.5°C

[0092] (3) Preparation of polyvinyl alcohol solution. Add 75 parts of water into the kettle according to mass percentage, start stirring, keep stirring at a speed of 50r / min, add 25 parts of KL318, after adding, heat to 90 degrees, keep stirring for 2 hours, and cool to room temperature for use;

[0093] (4) Add 58 parts of VAE emulsion into the kettle, start stirring, add 29 parts of self-prepared acrylic emulsion at a speed of 40 r / min, and continue stirring for 10 minutes;

[0094] (5) adding 5 parts of plasticizer 2,2,4-trimethyl-1,3-pentanediol diisobutyrate to step (4) and stirring at a speed of 50 r / min for 10 min;

[0095] (6) Add 6.5 parts of polyvinyl alcohol solution to step (5) and stir at a speed of 50 r / min for 10 min.

[0096] (7) Add 0.25 parts of wetting agent and stir for 5 minutes;

[0097] (8) Add 0.1 part of fungicide and 0.1 part of mineral oil defoamer and stir at 50 r / min for 5 min;

[0098] (9) Add pH adjuster and continue stirring at 50 r / min for 5 min;

[0099] (10) adjusting the viscosity of the material obtained in step (9) to 4650 mPa.s and the pH value to 4.8, discharging the material to obtain the high-speed nozzle glue for PET tipping paper of this comparative example;

[0100] Comparative Example 4

[0101] The other parts are the same as those in Example 2, except that: no reactive emulsifier is used in the synthesis of acrylic emulsion, and all ordinary emulsifiers are used; Comparative Example 4 prepares high-speed nozzle glue for PET tipping paper according to the following method and steps:

[0102] (1) Mixing by weight according to the ratio of methyl methacrylate: butyl acrylate: crosslinking monomer HA: rosin ester = 8.5:25.2:1.2:4.5;

[0103] (2) 22 parts of water, 4.9 parts of mixed monomers (methyl methacrylate, butyl acrylate and crosslinking monomer HA: rosin ester), 1 part of emulsifier (DSB) and 0.05 parts of initiator were added to the reactor in sequence, stirring was started, the stirring speed was controlled at 40 r / min, the temperature was raised to 75°C, kept warm for 1 hour, and then raised to 80°C. After blue fluorescence appeared in the reactor, 0.25 parts of initiator and the remaining 65.1 parts of monomers were added dropwise at the same time. 0.8 parts of emulsifier (DSB) were added intermittently during the polymerization process by the secondary nucleation method. The total dropwise addition time was 4 hours. After the dropwise addition was completed, the temperature was kept warm for 1 hour, and the temperature was continued to be raised to 90°C for maturation until there was no monomer odor, and then the temperature was cooled for use. The acrylic emulsion prepared in this way had the following characteristics: solid content: 58.5%, viscosity: 630 mPa.s, pH value: 4.1, glass transition temperature: -20.5°C

[0104] (3) Preparation of polyvinyl alcohol solution. Add 75 parts of water into the kettle according to mass percentage, start stirring, keep stirring at a speed of 50r / min, add 25 parts of KL318, after adding, heat to 90 degrees, keep stirring for 2 hours, and cool to room temperature for use;

[0105] (4) Add 58 parts of VAE emulsion into the kettle, start stirring, add 29 parts of self-prepared acrylic emulsion at a speed of 40 r / min, and continue stirring for 10 minutes;

[0106] (5) adding 5 parts of plasticizer 2,2,4-trimethyl-1,3-pentanediol diisobutyrate to step (4) and stirring at a speed of 50 r / min for 10 min;

[0107] (6) Add 6.5 parts of polyvinyl alcohol solution to step (5) and stir at a speed of 50 r / min for 10 min.

[0108] (7) Add 0.25 parts of wetting agent and stir for 5 minutes;

[0109] (8) Add 0.1 part of fungicide and 0.1 part of mineral oil defoamer and stir at 50 r / min for 5 min;

[0110] (9) Add pH adjuster and continue stirring at 50 r / min for 5 min;

[0111] (10) adjusting the viscosity of the material obtained in step (9) to 4150 mPa.s and the pH value to 4.6, discharging the material to obtain the high-speed nozzle glue for PET tipping paper of this comparative example;

[0112] Comparative Example 5

[0113] The other parts are the same as those in Example 1, except that when preparing the nozzle glue product, the amount of acrylic emulsion is low, 20 parts; the amount of VAE is increased to 68 parts. Comparative Example 5: High-speed nozzle glue for PET tipping paper is prepared according to the following method and steps:

[0114] (1) Mixing by weight according to the ratio of methyl methacrylate: butyl acrylate: crosslinking monomer HA: rosin ester = 9.5:24.8:1:3.5;

[0115] (2) By weight, 23 parts of water, 4.5 parts of mixed monomers (methyl methacrylate, butyl acrylate and crosslinking monomers HA, rosin), 1 part of emulsifier (COPS-1:DSB=1:1) and 0.05 parts of initiator were added to the reactor in sequence, stirring was started, the stirring speed was controlled at 40r / min, the temperature was raised to 75°C, kept warm for 1 hour, and then raised to 80°C. After blue fluorescence appeared in the reactor, 0.25 parts of initiator were added dropwise at the same time. and the remaining 65.5 parts of monomers, using the secondary nucleation method, intermittently adding 0.5 parts of emulsifier (COPS-1:DSB=1:1) during the polymerization process, the total dropwise addition time is 4 hours, after the dropwise addition is completed, the temperature is kept for 1 hour, and the temperature is continued to rise to 90°C for maturation until there is no monomer odor, and the temperature is cooled for standby use; the prepared acrylic emulsion has the following characteristics: solid content: 68.1%, viscosity: 1100mpa.s, pH value: 4.2, glass transition temperature: -24.8°C;

[0116] (3) Preparation of polyvinyl alcohol solution. Add 75 parts of water into the kettle according to the mass percentage, start stirring, keep stirring at a speed of 50r / min, add 25 parts of KL318, after adding, heat to 90°C, keep stirring for 2 hours, and then cool to room temperature for use;

[0117] (4) Add 68 parts of VAE emulsion into the kettle, start stirring, add 20 parts of self-prepared acrylic emulsion at a speed of 40 r / min, and continue stirring for 10 min;

[0118] (5) adding 3.5 parts of plasticizer tributyl acetyl citrate to step (4) and stirring at a speed of 50 r / min for 10 min;

[0119] (6) Add 7 parts of polyvinyl alcohol solution to step (5) and stir at a speed of 50 r / min for 10 min;

[0120] (7) Add 0.2 parts of wetting agent and stir at 50 r / min for 5 min;

[0121] (8) Add 0.1 part of fungicide and 0.1 part of mineral oil defoamer and stir at 50 r / min for 5 min;

[0122] (9) Add pH adjuster and continue stirring at 50 r / min for 5 min;

[0123] (10) The viscosity of the material obtained in step (9) was adjusted to 5280 mPa.s and the pH value was 4.8, and the material was discharged to obtain the high-speed nozzle glue for PET tipping paper of this comparative example.

[0124] The raw materials involved in the above examples and comparative examples are as follows: cross-linking monomer HA ( HA) is the trademark of products produced by Hanko Chemical. This product is a functional monomer containing vinyl, hydroxyl and acrylamide groups; KL-318 is Kuraray modified PVA polyvinyl alcohol resin; COPS-1 is propenyl ether sulfonic acid sodium salt, chemical name 3-allyloxy-1-hydroxy-1-propane sulfonate; DSB is the emulsifier sodium dodecyl diphenyl ether disulfonate; the rosin ester used is PENSEL GB-75 of Arakawa Chemical.

[0125] The beneficial effects of the present invention are further illustrated below through experimental test data and machine tests.

[0126] Experimental test data:

[0127] The physical and chemical indicators of the high-speed nozzle glue for PET tipping paper of the present invention are as follows in Table 1:

[0128] Table 1

[0129]

[0130] The stability test is shown in Table 2 and Table 3:

[0131] Table 2

[0132]

[0133] Table 3

[0134]

[0135]

[0136] From the above stability test, it can be seen that the centrifugal stability test, dilution stability and freeze-thaw stability of comparative example 4 are all unqualified, indicating that the stability effect of the mouthpiece glue prepared by using a single emulsifier is worse than that of the mouthpiece glue prepared by using a mixed emulsifier.

[0137] The on-machine adaptability index test is shown in Table 4:

[0138] The present invention conducts relevant machine adaptability index tests on Example 1, Example 2, and various comparative examples, mainly testing the adhesion, open time, and contact angle of the nozzle glue on the PET film.

[0139] Table 4

[0140]

[0141] From the test data in Table 4, it can be seen that the adhesion of Examples 1 and 2 is stronger than that of Comparative Example 1, and the surface drying time is significantly faster than that of Comparative Example 1. At the same time, the contact angle is significantly lower than that of Comparative Example 1, indicating that the wettability and leveling properties of Examples 1 and 2 on the PET film are significantly better than those of Comparative Example 1. Due to stability issues, the relevant properties of Comparative Example 4 are significantly deteriorated.

[0142] The safety index test is shown in Table 5:

[0143] Table 5

[0144]

[0145]

[0146] It can be seen from Table 5 that Examples 1 and 2 of the present invention fully meet the tobacco industry standard requirements, while Comparative Example 4 uses a single emulsifier, resulting in incomplete reaction and excessive residual monomers.

[0147] The test results of the high-speed nozzle glue on the machine of each embodiment and comparative example are as follows in Table 6:

[0148] The machine model used in the test is PROTOS 70, with a normal machine speed of 3000-4000 pcs / min, a paper heating temperature of 60°C, a washboard temperature of 100°C, and a PET film with a dyne value of 36 as the tipping paper.

[0149] Table 6

[0150]

[0151]

[0152] From the test operation on the machine, it can be seen that the machine conditions of Example 1 and Example 2 are obviously better than Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 5 are better than Comparative Example 1, and Comparative Example 4 is the worst. After being placed for 2 months, the cigarettes produced by Example 1, Example 2, Comparative Example 2 and Comparative Example 5 have no poor bonding phenomenon, but the cigarettes produced by Comparative Example 1 and Comparative Example 3 have poor bonding at the joint part and will obviously bounce off, and Comparative Example 4 does not meet the use requirements at all.

[0153] The above contents are merely examples and explanations of the concept of the present invention. Personnel in the technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A high-speed nozzle glue for PET tipping paper, which is mainly prepared by adding EVA emulsion, polyvinyl alcohol, plasticizer, wetting agent, defoamer, pH regulator, bactericide and pure water to prefabricated acrylic emulsion; characterized in that: The prefabricated acrylic emulsion has a high solid content of 65-70%, and is an emulsion prepared by polymerizing a soft segment acrylic ester monomer, a hard segment acrylic ester monomer, a cross-linking monomer, and a rosin ester under the condition of a composite emulsifier containing a reactive emulsifier and a conventional emulsifier, wherein the reactive emulsifier is a highly hydrophilic functional emulsifier having a carbon-carbon double bond; and when compounding the high-speed nozzle glue, the mass ratio of the prefabricated acrylic emulsion, EVA emulsion, polyvinyl alcohol, plasticizer, wetting agent, defoamer, pH value regulator, bactericide and pure water is (20-30): (55-65): (5-10): (3-5)：(0.1-0.5)：(0.1-0.5)：(0.1-0.5)：0.1：(1-5)。 2. A high-speed nozzle glue according to claim 1, characterized in that: When the prefabricated acrylic emulsion is prepared, the mass ratio of the main raw materials is soft segment acrylic ester monomer: hard segment acrylic ester monomer: cross-linking monomer: rosin ester = 8∽10: 22∽26:: 0.5∽1.5: 3∽5.

3. A high-speed nozzle glue according to claim 1 or 2, characterized in that: The high-speed nozzle glue according to claim 1 is characterized in that the hard segment acrylate monomer is methyl methacrylate; and the soft segment acrylate monomer is butyl acrylate.

4. A high-speed nozzle glue according to claim 1 or 2, characterized in that: The cross-linking monomer is a functional monomer containing vinyl, hydroxyl and acrylamide groups.

5. A high-speed nozzle glue according to claim 1 or 2, characterized in that: The prefabricated acrylic emulsion has the following characteristics: solid content: 65-70%, viscosity: 800-1500 mPa.s, pH value: 4.0-6.0, and glass transition temperature: -30°C-20°C.

6. A high-speed nozzle glue according to claim 1 or 2, characterized in that: The reactive emulsifier is COPS-1.

7. A high-speed nozzle glue according to claim 1 or 2, characterized in that: The mass ratio of the reactive emulsifier to the conventional emulsifier is 0.7 to 1.

3.

8. A high-speed nozzle glue according to claim 1 or 2, characterized in that: When compounding high-speed nozzle glue, the VAE emulsion used has the following characteristics: solid content: 59-61%, viscosity: 1500-2000mPa.s, pH value: 4.0-6.0, glass transition temperature: 0℃~10℃.

9. A high-speed nozzle glue according to claim 1 or 2, characterized in that: The wetting agent is BYK-347; the plasticizer is selected from one or more of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, acetyl tributyl citrate, and triacetin; the defoamer is a mineral oil defoamer, and the pH adjuster is sodium bicarbonate; the bactericide is selected from one or more of 2-methyl-4-isothiazoline-3-one, 5-chloro-2-methyl-4-isothiazoline-3-one, and 1,2-benzisothiazol-3-one; and the pure water is tertiary pure water treated by multi-stage reverse osmosis membrane filtration, and its conductivity is less than 10μs / cm.

10. A method for preparing the high-speed nozzle glue for PET tipping paper according to claims 1 to 9, characterized in that: The specific steps include: Step 1: Prepare high solid content acrylic emulsion using secondary nucleation method: 1.1 First, mix methyl methacrylate: butyl acrylate: cross-linking monomer HA: rosin ester according to the ratio of 8∽10:22∽26:0.5∽1.5:3∽5; 1.2 By weight, add 20-25 parts of water, 5-7% mixed monomers (methyl methacrylate, butyl acrylate and crosslinking monomers HA, rosin ester), 0.8-1.2 parts of emulsifier (COPS-1:DSB=0.7-1.3:1) and 0.05 parts of initiator to the reactor in sequence, start stirring, control the stirring speed at 30-50r / min, heat to 75°C, keep warm for 1 hour, then heat to 80°C, and add 0.25 parts of initiator dropwise when blue fluorescence appears in the reactor. and the remaining monomers, using the secondary nucleation method, intermittently adding 0.4∽0.7 parts of emulsifier (COPS-1:DSB=0.7~1.3:1) during the polymerization process, the total dropwise addition time is 4 hours, after the dropwise addition is completed, the temperature is kept for 1 hour, and the temperature is continued to be raised to 90°C for maturation until there is no monomer odor, and the temperature is cooled for standby use; the acrylic emulsion prepared in this way has the following characteristics: solid content: 65∽70%, viscosity: 800∽1500mPa.s, pH value: 4.0∽6.0, glass transition temperature: -30°C∽-20°C; Step 2 Preparation of polyvinyl alcohol solution Add 75-80 parts of water into the kettle by mass percentage, start stirring, keep stirring at 50r / min and add 20-25 parts of polyvinyl alcohol KL318. After adding, heat to 90℃, keep stirring for 2 hours, and then cool to room temperature for use; Step 3: Compound high-speed nozzle glue 3.1 Add 50∽60 parts of VAE emulsion into the kettle, start stirring, add the acrylic emulsion prepared in step 1.2 at a speed of 40r / min, and stir for 10min; 3.2 Add 5-10 parts of polyvinyl alcohol prepared in step 2 and stir at a speed of 50r / min for 20min; 3.3 Add 3-5 parts of plasticizer to step 3.2 and stir at 50r / min for 10min; Add 0.1-0.5 parts of wetting agent and stir at 50r / min for 5 minutes; Then add 0.1 part of fungicide and 0.1 part of mineral oil defoamer, and stir at 50r / min for 10min; Then add pH adjuster and continue stirring at 50r / min for 5min; The viscosity of the material obtained in step 3.3 is adjusted to 5000-6000 mpa.s, and the material is discharged to obtain a high-speed nozzle glue for PET tipping paper.

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