High-speed spraying packaging adhesive for low-surface-energy packaging paper and preparation method of high-speed spraying packaging adhesive

Abstract

The invention belongs to the technical field of adhesives, and provides a high-speed spraying adhesive suitable for low-surface-energy packaging paper and a preparation method. The product is mainly prepared from the following raw materials: modified acrylic emulsion, EVA emulsion, polyvinyl alcohol, a plasticizer, emulsified silicone oil, a pH value regulator, a bactericide, pure water and the like, wherein the mass ratio of the modified acrylic emulsion to the EVA emulsion to the polyvinyl alcohol to the plasticizer to the emulsified silicone oil to the pH value regulator to the bactericide is (10-20): (62-72): (3-8): (2-4): (1-2): (0.1-0.5): 0.1; the modified acrylic emulsion is formed by copolymerization of acrylic acid, methyl methacrylate, 2-ethylhexyl acrylate, ethyl acrylate, phosphate adhesive force monomers, a silane coupling agent and the like. The product can stably operate on machines such as ZB48, FX2, FXS and the like through a small glue spraying nozzle, can adapt to most packaging materials difficult to adhere on the market, and is high in adhesion force to meet the packaging requirement.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of water-based adhesives, and particularly relates to a high-speed spray packaging adhesive for low-surface-energy packaging paper and a preparation method. BACKGROUND

[0002] The packaging adhesive is applied to a cigarette adhesive, and is one of main materials for cigarette packaging, and is mainly used for bonding packaging materials such as small box packaging, strip box packaging and seal tag paper. The amount of the cigarette packaging adhesive accounts for a small proportion of cigarette materials, but has a great influence on the quality of cigarette packaging, and affects the consumption of other cigarette materials and the production efficiency of cigarettes.

[0003] With the continuous development of the cigarette industry, the production rate of the packaging machine is increased from less than 150 packs / min to 500-800 packs / min or even the highest rate of 1000 packs / min. Main models include focke, G.D, ZB, BE and other series of medium and high-speed packaging machines. Fcoke700E and FXS machines are cigarette machine products of Germany Fock Company, and ZB48 machine is a cigarette machine product of Italy GD Company, and both are at the world leading level. Compared with traditional cigarette machines, the operation speed of the machine is adjusted, and the machine has the characteristics of high performance, waste reduction, high adaptability and low maintenance. The Fock700E, FXS and ZB48 machines introduced by China Tobacco Yunnan Company have a spraying type adhesive application mode, and are matched with the Germany HHS adhesive system, adopt point spraying, have a small nozzle diameter (0.35 mm), and the adhesive is easy to adhere to the nozzle to cause the nozzle to be blocked. In the process of adhesive spraying, the adhesive is easy to be thrown and splashed, and the equipment is dirty, so the production needs to be frequently stopped for maintenance and maintenance, which not only affects the quality of cigarettes, but also affects the overall production efficiency.

[0004] Moreover, with the increasing richness of cigarette products and the increasing market competition pressure, the cigarette as a high-end fashion consumer product has a continuously increasing requirement for the packaging fineness, and more and more new packaging materials are applied to the products. The packaging paper pays more attention to the selection of raw paper materials and the use of various colors in the design, and is supplemented by various printing processes (such as concave-convex, positioning and anti-fake, etc.), so as to achieve the requirements of good visual effect, good gloss and good texture of the appearance packaging. Therefore, the tobacco enterprises widely use the transfer aluminum plated card or composite aluminum foil card on some high-end products, which involves the materials of transfer aluminum, aluminum film and heavy light oil. These materials have poor water absorption and low surface energy (the dyne value is below 34). The traditional cigarette packaging adhesive has the disadvantages of low initial adhesion, slow drying rate, short storage period, large brittleness of the cured adhesive film and poor adhesion to the complex printed packaging materials, and cannot meet the speed requirement of the high-speed cigarette machine and the development requirement of the packaging materials.

[0005] In view of the above problems, it is urgent to develop a high-speed spraying packaging adhesive which can be used on the machine models of ZB48, FX2, FXS and the like equipped with small glue spraying nozzles, can stably run, has strong adhesive force and is not easy to block the glue spraying nozzle, can also adapt to the bonding requirements of low surface energy difficult-to-bond materials in the cigarette packaging market, and can meet the specific needs of users and production application. SUMMARY

[0006] In view of the deficiencies of the prior art, the purpose of the present application is to provide a high-speed spraying packaging adhesive suitable for low surface energy packaging paper and a preparation method thereof, which can be used on high-speed machine models such as ZB48, FX2, FXS, has strong adaptability, and in particular has good adhesive force for difficult-to-bond materials such as transfer aluminum-coated cardboard or composite aluminum foil cardboard, transfer aluminum, aluminum film and heavy material with light oil. The use of the high-speed spraying adhesive can ensure stable operation of the equipment, prevent nozzle blockage and glue throwing, significantly reduce the cleaning frequency of the equipment, and improve production efficiency. The high-speed spraying adhesive packaging adhesive of the present application is prepared by introducing a high-performance acrylic emulsion synthesized by copolymerization of phosphate adhesion monomers, silane coupling agents and acrylic esters, adding VAE emulsion, polyvinyl alcohol, plasticizer, and adding an appropriate amount of emulsified silicone oil to enhance the moisture retention and moisturizing performance. The high-speed spraying adhesive packaging adhesive is developed to effectively avoid the occurrence of nozzle blockage and glue throwing problems, and can stably run on machine models such as ZB48, FX2, FXS, can adapt to most difficult-to-bond packaging materials on the market, and has strong adhesive force to meet the packaging requirements.

[0007] To achieve the technical purpose of the application, the technical scheme of the present application is as follows:

[0008] The high-speed spraying packaging adhesive suitable for low surface energy packaging paper provided by the present application is mainly prepared from modified acrylic emulsion, VAE emulsion, polyvinyl alcohol, plasticizer, emulsified silicone oil, pH value regulator, bactericide and pure water, etc. The mass ratio of the modified acrylic emulsion, VAE emulsion, polyvinyl alcohol, plasticizer, emulsified silicone oil, pH value regulator and bactericide is (10-20):(62-72):(3-8):(2-4):(1-2):(0.1-0.5):0.1. The modified acrylic emulsion is a copolymer mainly composed of acrylic acid, methyl methacrylate, isooctyl acrylate, ethyl acrylate, phosphate adhesion monomers, silane coupling agents, etc. Since the emulsified silicone oil itself has defoaming and bubble suppressing effects, no additional defoaming agent needs to be added.

[0009] Preferably, the high-speed spray packaging glue suitable for low surface energy packaging paper provided by the present application, wherein the modified acrylic emulsion is prepared from acrylic acid, methyl methacrylate, isooctyl acrylate, ethyl acrylate, phosphate adhesion monomer, silane coupling agent and the like raw materials in a mass ratio of (0.5-1.0):(15-20):(20-25):(5-8):(0.5-1.5):(0.5-1.5); the modified acrylic emulsion further has the following characteristics: solid content: 48-52%, viscosity: 1000-3000 mPa.s, pH value: 4.0-6.0, and glass transition temperature: -20℃ to -5℃.

[0010] Preferably, the high-speed spray packaging glue suitable for low surface energy packaging paper provided by the present application, wherein the phosphate adhesion monomer is phosphate functional monomer PAM200, which contains active phosphomethacrylate monomer. The phosphate adhesion monomer is PAM200, which is an active phosphomethacrylate monomer, can be easily polymerized into an emulsion system, can increase the stability of the latex, and can significantly improve the adhesion to the surface of metal materials such as aluminum and galvanized steel.

[0011] The acrylic emulsion type adhesive is copolymerized from acrylic ester and methacrylic ester and other monomers, uses water as a dispersion medium, does not use organic solvents, belongs to an environmentally friendly product, has strong initial adhesion, and is stable. In particular, the addition of phosphate monomer and silane coupling agent can effectively enhance the adhesion to metal, glass and other substrates.

[0012] Preferably, the high-speed spray packaging glue suitable for low surface energy packaging paper provided by the present application, wherein the VAE emulsion has the following characteristics: solid content: 54-56%, viscosity: 1500-2500 mPa.s, pH value: 4.0-6.0, and glass transition temperature: 0℃ to 10℃.

[0013] Preferably, the high-speed spray packaging glue suitable for low surface energy packaging paper provided by the present application, wherein the polyvinyl alcohol is PVA-1788. The PV-1788 has a polymerization degree of 1700 and an alcoholysis degree of 88%.

[0014] Silicone oil is a new green environmental protection material, has many excellent performance, such as outstanding high and low temperature resistance, very low glass transition temperature, very low surface tension and surface energy, high degree of hydrophobicity, very low solubility parameter and dielectric constant, etc., in textile finishing agent, leather finishing agent, cosmetics, waterproof material, paint and photosensitive material, etc. Field has obtained the wide application, but because its hydrophobicity increases its dispersion difficulty in water phase, makes its application in some aspects is limited, and the emergence of emulsified silicone oil solves this problem. Emulsified silicone oil refers to the silicone oil emulsion obtained by emulsifier, also known as silky, has excellent chemical stability, heat resistance, cold resistance, weather resistance, lubricity, hydrophobicity and low surface tension, good compatibility with emulsion. Appropriate amount of emulsified silicone oil is added into the emulsion, which can play a good lubricity and moisture retention during the glue spraying process. At the same time, emulsified silicone oil can also play a function of defoaming and inhibiting bubbles, which can avoid the normal operation of equipment due to a large number of bubbles generated during high speed operation, and the product bonding is affected by too many bubbles. At present, emulsified silicone oil has been listed in YQ / 5 tobacco materials license using material list.

[0015] Preferably, the high-speed spraying packaging glue suitable for low surface energy packaging paper provided by the application comprises 60% small particle size high molecular weight polydimethylsiloxane alcohol anion emulsion, the particle size is less than 1 microns, the solid content (105℃, 3H) is ≥60%, and the viscosity (25℃) is ≥3000 mPa.s. By reasonably selecting the small particle size high molecular weight emulsified silicone oil, the moisture retention and moisturizing performance of the high-speed spraying glue can be enhanced, and the problems of nozzle blockage and glue throwing can be effectively avoided.

[0016] Preferably, the high-speed spraying packaging glue suitable for low surface energy packaging paper provided by the application comprises 60% small particle size high molecular weight polydimethylsiloxane alcohol anion emulsion, the particle size is less than 1 microns, the solid content (105℃, 3H) is ≥60%, and the viscosity (25℃) is ≥3000 mPa.s. By reasonably selecting the small particle size high molecular weight emulsified silicone oil, the moisture retention and moisturizing performance of the high-speed spraying glue can be enhanced, and the problems of nozzle blockage and glue throwing can be effectively avoided.

[0017] Preferably, the present application provides a high-speed spray packaging glue suitable for low surface energy packaging paper, wherein the emulsifier is SE-10N, which is a low-foaming anionic reactive emulsifier: 1-allyloxy-3-(4-nonyl phenol)-2-2 propyl alcohol polyoxyethylene (10) ether, which can give the emulsion excellent stability and lower foam generation rate; the plasticizer is selected from one or more of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, acetyl citrate tributyl, glyceryl triacetate; the pH regulator is sodium bicarbonate; the bactericide is MBS, and the active ingredient is 2-methyl-4-isothiazolin-3-ketone, 1,2-benzisothiazolin-3-ketone; and the pure water is tertiary purified water filtered by multi-stage reverse osmosis membrane, and the conductivity is less than 10 µs / cm.

[0018] The present application also provides a preparation method of the high-speed spray packaging glue suitable for low surface energy packaging paper, comprising the following steps:

[0019] (1) Synthesis of modified acrylic emulsion:

[0020] 1.1 Pre-emulsification: The phosphate adhesion monomer PAM200 is pre-neutralized to a PH value of 7 with 0.1 mol / L sodium hydroxide to obtain a pre-adjusted phosphate adhesion monomer; 20-24 parts by weight of water are added to the emulsification kettle, 0.5-1.0 parts by weight of emulsifier SE-10N is added, stirred for 10 minutes, then 0.5-1.5 parts by weight of pre-adjusted phosphate adhesion monomer is added and stirred for 15 minutes, then 0.5-1.0 parts by weight of acrylic acid, 15-20 parts by weight of methyl methacrylate, 20-25 parts by weight of isooctyl acrylate, 5-8 parts by weight of ethyl acrylate, and 0.5-1.5 parts by weight of coupling agent A-172 are added in sequence, and high-speed stirring is carried out for 30 minutes to obtain a pre-emulsion;

[0021] 1.2 20-25 parts by weight of water and 0.1-0.2 parts by weight of pH regulator sodium bicarbonate are added to the reaction kettle, stirring is started, the stirring speed is controlled at 30-50 r / min, the temperature is raised to 85°C, 5 parts of the pre-emulsion prepared in step 1.1 and 0.05 parts of initiator ammonium persulfate are added, after blue fluorescence appears in the reaction kettle, the remaining pre-emulsion and 0.1 parts of ammonium persulfate are added at the same time, after the addition is completed, the temperature is kept for 2 hours, the temperature is lowered to 70°C, and 0.05 parts of tert-butyl hydroperoxide and 0.05 parts of sodium metabisulfite are added at the same time, and the temperature is kept for 30 minutes, and the temperature is lowered to room temperature. until there is no monomer smell, and then it is ready for use; the modified acrylic emulsion prepared in this way has the following characteristics: solid content: 48-52%, viscosity: 1000-3000 mpa.s, pH value: 4.0-6.0, glass transition temperature: -20℃ to -5℃;

[0022] (2) Preparation of polyvinyl alcohol solution:

[0023] 2.1 80 parts of water was added into the kettle, stirring was started, 20 parts of PVA-1788 was added while stirring at a speed of 50 r / min, after the addition, the temperature was increased to 90 DEG C, and the stirring was kept for 2 hours, then the temperature was cooled to room temperature for standby;

[0024] (3) High-speed spraying glue preparation

[0025] 3.1 62-72 parts of VAE emulsion was added into the kettle, stirring was started, 10-20 parts of modified acrylic emulsion prepared in step 1.2 was added while stirring at a speed of 40 r / min, and the stirring was kept for 10 min;

[0026] 3-8 parts of polyvinyl alcohol prepared in step 2.1 was added, and the stirring was kept for 20 min at a speed of 50 r / min;

[0027] 2-4 parts of plasticizer was added, and the stirring was kept for 10 min at a speed of 50 r / min;

[0028] 1-2 parts of emulsified silicone oil was added, and the stirring was kept for 20 min at a speed of 70 r / min;

[0029] 0.1 parts of bactericide MBS was added, and the stirring was kept for 10 min at a speed of 50 r / min;

[0030] pH value regulator was added, and the stirring was kept for 5 min at a speed of 50 r / min;

[0031] 3.2 Appropriate amount of pure water was added, the viscosity of the material prepared in step 3.1 was adjusted to 260-320 mpa.s, and the material was discharged to obtain high-speed spraying glue.

[0032] The present application has good effects:

[0033] 1. The present application designs and synthesizes high-performance acrylic emulsion copolymerized by phosphate adhesion monomer, silane coupling agent and acrylic acid and its ester, and is compounded with VAE emulsion, polyvinyl alcohol and plasticizer in a reasonable proportion, and a proper amount of emulsified silicone oil is added to enhance the moisture retention and moisturizing performance, and a packaging glue suitable for high-speed spraying is developed. The packaging glue has strong adhesion to low surface energy packaging materials, reasonable open time, good small diameter port flow performance, meets the safety and health requirements of YQ5 cigarette adhesive, and can meet the use requirements of ZB48, FX2 and FXS high-speed spraying packaging machines;

[0034] 2、The high performance modified acrylic emulsion synthesized by copolymerization of phosphate ester adhesion monomer, silane coupling agent and acrylic acid and its esters etc. can improve the adhesion strength of high speed spraying packaging glue to low surface energy packaging material. When the dosage of modified acrylic emulsion reaches the amount of comparative example 4, the machine speed can reach 800 boxes / min, the nozzle is not blocked for 12 hours, no glue is thrown, but the bonding is poor, the cigarette package rejection rate is high, and the rejection rate is 1.5%; when the dosage of modified acrylic emulsion reaches the amount of example 1, the machine speed can reach 800 boxes / min, the nozzle is not blocked for 12 hours, no glue is thrown, and the whole cigarette package is not damaged, and the cigarette package rejection rate is 0.

[0035] 3、The emulsified silicone oil containing 60% of small particle size high molecular weight polydimethylsiloxane alcohol anion emulsion is reasonably selected, and the emulsified silicone oil has good lubricity and moisture retention in the process of glue spraying. At the same time, the emulsified silicone oil also has the functions of defoaming and bubble suppression, so that the defoaming agent is not needed, and a large amount of bubbles generated in the high speed operation of the equipment can be avoided, thereby affecting the normal operation of the equipment.

[0036] 4、The high speed spraying machine of the present application has good on-machine adaptability, and is suitable for commonly used high speed spraying packaging machines for gluing low surface energy packaging materials. The ZB48 high speed spraying packaging machine is used as glue, the machine speed is 800-1000 boxes / min, the HHS D500 spray gun is used, the nozzle diameter is 0.35mm, and the low surface energy packaging box skin with an aluminum plating layer having a daun value of 28 is glued and bonded, so that good effects are achieved. The machine speed can be stabilized at 800 boxes / min, the nozzle is not blocked for 12 hours, and no glue is thrown. DETAILED DESCRIPTION

[0037] The present application will be further described in detail below in combination with examples, but the scope of the present application is not limited to these examples.

[0038] The high speed spraying packaging glue suitable for low surface energy packaging paper provided by the present application is mainly prepared from modified acrylic emulsion, VAE emulsion, polyvinyl alcohol, plasticizer, emulsified silicone oil, pH value regulator, bactericide and pure water, wherein, the mass ratio of the modified acrylic emulsion, VAE emulsion, polyvinyl alcohol, plasticizer, emulsified silicone oil, pH value regulator and bactericide is (10-20):(62-72):(3-8):(2-4):(1-2):(0.1-0.5):0.1; the modified acrylic emulsion is a copolymer mainly composed of acrylic acid, methyl methacrylate, isooctyl acrylate, ethyl acrylate, phosphate ester adhesion monomer, silane coupling agent, etc.

[0039] As a specific embodiment, the high-speed spray packaging glue suitable for low surface energy packaging paper provided by the present application comprises a modified acrylic emulsion, a VAE emulsion, polyvinyl alcohol, a plasticizer, emulsified silicone oil, a pH regulator, and a bactericide, and the mass ratio of the modified acrylic emulsion, the VAE emulsion, the polyvinyl alcohol, the plasticizer, the emulsified silicone oil, the pH regulator, and the bactericide is (10-20):(62-72):(3-8):(2-4):(1-2):(0.1-0.5):0.1. The mass ratio can be specifically selected from (10, 12, 15, 17.5, 20):(62, 65, 67, 70, 72):(3, 4.5, 6, 8):(2, 3, 4):(1, 1.5, 2):(0.1, 0.25, 0.4, 0.5):0.1, but is not limited thereto.

[0040] As a specific embodiment, the high-speed spray packaging glue suitable for low surface energy packaging paper provided by the present application comprises a modified acrylic emulsion, a VAE emulsion, polyvinyl alcohol, a plasticizer, emulsified silicone oil, a pH regulator, and a bactericide, and the mass ratio of the modified acrylic emulsion, the VAE emulsion, the polyvinyl alcohol, the plasticizer, the emulsified silicone oil, the pH regulator, and the bactericide is (10-20):(62-72):(3-8):(2-4):(1-2):(0.1-0.5):0.1. The mass ratio can be specifically selected from (10, 12, 15, 17.5, 20):(62, 65, 67, 70, 72):(3, 4.5, 6, 8):(2, 3, 4):(1, 1.5, 2):(0.1, 0.25, 0.4, 0.5):0.1, but is not limited thereto.

[0041] The modified acrylic emulsion also has the following characteristics: solid content: 48-52%, viscosity: 1000-3000 mPa.s, pH value: 4.0-6.0, and glass transition temperature: -20℃ to -5℃.

[0042] The following examples and comparative examples are used to illustrate the advantages and disadvantages of the specific embodiments of the present application.

[0043] Example 1

[0044] The high-speed spray packaging glue is prepared according to the following methods and steps:

[0045] (1) Synthesis of the modified acrylic emulsion:

[0046] 1.1 Pre-emulsification: the phosphate adhesion monomer PAM200 is pre-neutralized with 0.1 mol / L sodium hydroxide to a pH value of 7 to obtain a pre-prepared phosphate adhesion monomer; 22 parts of pure water are added to an emulsification kettle, 0.7 parts of emulsifier SE-10N are added, stirred for 10 minutes, 1.0 parts of the pre-prepared phosphate adhesion monomer are added and stirred for 15 minutes, and then 0.5 parts of acrylic acid, 18.49 parts of methyl methacrylate, 22.19 parts of isooctyl acrylate, 6.29 parts of ethyl acrylate, and 1 part of coupling agent A-172 are sequentially added, and high-speed stirring is carried out for 30 minutes to obtain a pre-emulsion;

[0047] 1.2 21 parts of pure water and 0.1 parts of pH regulator sodium bicarbonate are added to a reaction kettle, stirring is started, the stirring speed is controlled at 30-50 r / min, the temperature is raised to 85°C, 5 parts of the pre-emulsion in step 1.1 and 0.05 parts of initiator ammonium persulfate are added, after blue fluorescence appears in the reaction kettle, the remaining pre-emulsion and 0.1 parts of ammonium persulfate are added dropwise, after the addition is completed, the temperature is kept for 2 hours, the temperature is lowered to 70°C, 0.05 parts of tert-butyl hydroperoxide and 0.05 parts of sodium metabisulfite are added dropwise, and the temperature is kept for another 30 minutes until no monomer odor is detected, and then the temperature is lowered for use; the modified acrylic emulsion prepared in this way has the following characteristics: solid content: 49.8%, viscosity: 2520 mpa.s, pH value: 4.5, and glass transition temperature: -13.5°C;

[0048] (2) Preparation of polyvinyl alcohol solution:

[0049] 2.1 According to the weight, 80 parts of pure water are added to the kettle, stirring is started, and 20 parts of PVA-1788 are added while stirring at a speed of 50 r / min, after addition, the temperature is raised to 90°C, and the temperature is kept for 2 hours, then cooled to room temperature for use;

[0050] (3) Preparation of high-speed spraying glue

[0051] 3.1 70 parts of VAE emulsion are added to the kettle, stirring is started, and 12 parts of the modified acrylic emulsion prepared in step 1.2 are added at a speed of 40 r / min, and stirred for 10 min;

[0052] 5 parts of polyvinyl alcohol prepared in step 2.1 are added, and stirred at a speed of 50 r / min for 20 min;

[0053] 2 parts of plasticizer acetyl tri-butyl citrate are added, and stirred at a speed of 50 r / min for 10 min;

[0054] 1 part of emulsified silicone oil is added, and stirred at a speed of 70 r / min for 20 min;

[0055] Add 0.1 part of fungicide MBS, stir at a speed of 50 r / min for 10 min;

[0056] Add pH regulator to adjust the pH value to 5.1, and continue to stir at a speed of 50 r / min for 5 min;

[0057] 3.2 Add appropriate amount of pure water to adjust the viscosity of the material prepared in step 3.1 to 285 mpa.s, and discharge to obtain a high-speed spray adhesive.

[0058] Example 2

[0059] A high-speed spray adhesive packaging glue was prepared according to the following methods and steps:

[0060] (1) Synthesis of modified acrylic emulsion:

[0061] 1.1 Pre-emulsification: The phosphate adhesion monomer PAM200 was pre-neutralized to a pH value of 7 with 0.1 mol / L sodium hydroxide to obtain a pre-prepared phosphate adhesion monomer; 22 parts by weight of pure water were added to the emulsification kettle, 0.7 parts by weight of emulsifier SE-10N was added, stirred for 10 minutes, then 0.8 parts by weight of the pre-prepared phosphate adhesion monomer was added and stirred for 15 minutes, and then 0.5 parts by weight of acrylic acid, 18.49 parts by weight of methyl methacrylate, 22.19 parts by weight of isooctyl acrylate, 6.29 parts by weight of ethyl acrylate, and 1.5 parts by weight of coupling agent A-172 were added in sequence. After high-speed stirring for 30 minutes, a pre-emulsion was obtained;

[0062] 1.2 Add 21 parts by weight of pure water and 0.1 parts by weight of pH regulator sodium bicarbonate to the reaction kettle, start stirring, and control the stirring speed at 30-50 r / min, heat to 85°C, add 5 parts of the pre-emulsion prepared in step 1.1 and 0.05 parts of initiator ammonium persulfate, and then add the remaining pre-emulsion and 0.1 parts of ammonium persulfate after the blue fluorescence appears in the reaction kettle. After the addition is completed, keep warm for 2 hours, cool to 70°C, and then add 0.05 parts of tert-butyl hydroperoxide and 0.05 parts of sodium metabisulfite dropwise, continue to keep warm for 30 minutes, and mature until there is no monomer odor. Cool down for standby; the modified acrylic emulsion prepared in this way has the following characteristics: solid content: 50.1%, viscosity: 2680 mpa.s, pH value: 4.6, glass transition temperature: -13.2°C;

[0063] (2) Preparation of polyvinyl alcohol solution:

[0064] 2.1 According to the weight, 80 parts of pure water were added to the kettle, and stirring was started at a speed of 50 r / min. 20 parts of PVA-1788 were added while stirring, and after addition, the temperature was raised to 90°C, and the stirring was kept for 2 hours, and then cooled to room temperature for standby;

[0065] (3) Preparation of high-speed spray adhesive

[0066] 3.1 Add 66 parts of VAE emulsion into the kettle, start stirring, add 16 parts of modified acrylic emulsion prepared in step 1.2 at a speed of 40 r / min, stir for 10 min;

[0067] Add 7 parts of polyvinyl alcohol prepared in step 2.1, stir at a speed of 50 r / min for 20 min;

[0068] Add 3 parts of plasticizer 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, stir at a speed of 50 r / min for 10 min;

[0069] Add 1.6 parts of emulsified silicone oil, stir at a speed of 70 r / min for 20 min;

[0070] Add 0.1 parts of bactericide MBS, stir at a speed of 50 r / min for 10 min;

[0071] Adjust the pH value to 5.0 by adding pH adjuster, continue to stir at a speed of 50 r / min for 5 min;

[0072] 3.2 Add appropriate amount of pure water to adjust the viscosity of the material prepared in step 3.1 to 302 mpa.s, discharge to obtain a high-speed spraying adhesive.

[0073] Comparative Example 1

[0074] Compared with Example 1, the difference is that no emulsified silicone oil is added. That is, a high-speed spraying adhesive packaging adhesive is prepared according to the following method and steps:

[0075] (1) Synthesis of modified acrylic emulsion:

[0076] 1.1 Pre-emulsification: The phosphate adhesion monomer PAM200 is pre-neutralized to a pH value of 7 with 0.1 mol / L sodium hydroxide to obtain a pre-adjusted phosphate adhesion monomer; add 22 parts of pure water to the emulsification kettle by weight, add 0.7 parts of emulsifier SE-10N, stir for 10 minutes, then add 1.0 parts of pre-adjusted phosphate adhesion monomer and stir for 15 minutes, then add acrylic acid 0.5 parts, methyl methacrylate 18.49 parts, isooctyl acrylate 22.19 parts, ethyl acrylate 6.29 parts, 1 part of coupling agent A-172, and high-speed stirring for 30 minutes to obtain a pre-emulsion;

[0077] 1.2 Into the reactor, 21 parts of pure water and 0.1 part of pH regulator sodium bicarbonate were added by weight, and stirring was started with a stirring speed of 30-50 r / min. The temperature was raised to 85°C, and 5 parts of the pre-emulsion prepared in step 1.1 and 0.05 part of initiator ammonium persulfate were added. After blue fluorescence appeared in the reactor, the remaining pre-emulsion and 0.1 part of ammonium persulfate were added dropwise. After the dropwise addition was completed, the temperature was kept for 2 hours, and then the temperature was lowered to 70°C. At the same time, 0.05 part of tert-butyl hydroperoxide and 0.05 part of sodium metabisulfite were added dropwise, and the temperature was kept for another 30 minutes. The aging was continued until no monomer odor was detected. The modified acrylic emulsion thus prepared had the following characteristics: solid content: 49.4%, viscosity: 2500 mpa.s, pH value: 4.5, and glass transition temperature: -13.4°C.

[0078] (2) Preparation of polyvinyl alcohol solution:

[0079] 2.1 Into the reactor, 80 parts of pure water were added by weight, and stirring was started with a stirring speed of 50 r / min. Then 20 parts of PVA-1788 were added while stirring. After the addition was completed, the temperature was raised to 90°C, and the temperature was kept for 2 hours. Then the temperature was lowered to room temperature for standby.

[0080] (3) Preparation of high-speed sprayable adhesive

[0081] 3.1 Into the reactor, 70 parts of VAE emulsion were added, and stirring was started with a stirring speed of 40 r / min. Then 12 parts of the modified acrylic emulsion prepared in step 1.2 were added, and stirring was continued for 10 minutes.

[0082] Then 5 parts of the polyvinyl alcohol prepared in step 2.1 were added, and stirring was continued for 20 minutes at a stirring speed of 50 r / min.

[0083] Then 2 parts of plasticizer acetyl tri-butyl citrate were added, and stirring was continued for 10 minutes at a stirring speed of 50 r / min.

[0084] Then 0.1 part of bactericide MBS was added, and stirring was continued for 10 minutes at a stirring speed of 50 r / min.

[0085] Then the pH value was adjusted to 5.1 by adding a pH regulator, and stirring was continued for 5 minutes at a stirring speed of 50 r / min.

[0086] 3.2 An appropriate amount of pure water was added to adjust the viscosity of the material prepared in step 3.1 to 280 mpa.s, and the material was discharged to obtain the high-speed sprayable adhesive.

[0087] Comparative Example 2

[0088] Compared with Example 1, 0.5 parts of emulsified silicone oil were added to the formula, and the high-speed sprayable adhesive packaging adhesive was prepared according to the following methods and steps:

[0089] (1) Synthesis of modified acrylic emulsion:

[0090] 1.1 Pre-emulsification: the phosphate adhesion monomer PAM200 is pre-neutralized with 0.1 mol / L sodium hydroxide to a pH value of 7 to obtain a pre-prepared phosphate adhesion monomer; 22 parts of pure water are added to an emulsification kettle, 0.7 parts of emulsifier SE-10N are added, stirred for 10 minutes, 1.0 parts of the pre-prepared phosphate adhesion monomer are added and stirred for 15 minutes, and then 0.5 parts of acrylic acid, 18.49 parts of methyl methacrylate, 22.19 parts of isooctyl acrylate, 6.29 parts of ethyl acrylate, and 1 part of coupling agent A-172 are sequentially added, and high-speed stirring is carried out for 30 minutes to obtain a pre-emulsion;

[0091] 1.2 21 parts of pure water and 0.1 parts of pH regulator sodium bicarbonate are added to a reaction kettle, stirring is started, the stirring speed is controlled at 30-50 r / min, the temperature is raised to 85°C, 5 parts of the pre-emulsion prepared in step 1.1 and 0.05 parts of initiator ammonium persulfate are added, after blue fluorescence appears in the reaction kettle, the remaining pre-emulsion and 0.1 parts of ammonium persulfate are added at the same time, after the addition is completed, the temperature is kept for 2 hours, the temperature is lowered to 70°C, 0.05 parts of tert-butyl hydroperoxide and 0.05 parts of sodium metabisulfite are added at the same time, and the temperature is kept for another 30 minutes, until there is no monomer smell, and then the temperature is lowered for standby; the modified acrylic emulsion prepared in this way has the following characteristics: solid content: 49.8%, viscosity: 2600 mpa.s, pH value: 4.85, glass transition temperature: -13.3°C;

[0092] (2) Preparation of polyvinyl alcohol solution:

[0093] 2.1 According to the weight, 80 parts of pure water are added to the kettle, stirring is started, and 20 parts of PVA-1788 are added while stirring at a speed of 50 r / min, after addition, the temperature is raised to 90°C, and the temperature is kept for 2 hours, then cooled to room temperature for standby;

[0094] (3) Preparation of high-speed spraying glue

[0095] 3.1 70 parts of VAE emulsion are added to the kettle, stirring is started, and 12 parts of the modified acrylic emulsion prepared in step 1.2 are added at a speed of 40 r / min, and stirred for 10 min;

[0096] 5 parts of polyvinyl alcohol prepared in step 2.1 are added, and stirred at a speed of 50 r / min for 20 min;

[0097] 2 parts of plasticizer acetyl tri-butyl citrate are added, and stirred at a speed of 50 r / min for 10 min;

[0098] 0.5 parts of emulsified silicone oil are added, and stirred at a speed of 70 r / min for 20 min;

[0099] Add 0.1 part of fungicide MBS, stir at a speed of 50 r / min for 10 min;

[0100] Add pH regulator to adjust the pH value to 5.0, continue to stir at a speed of 50 r / min for 5 min;

[0101] 3.2 Add appropriate amount of pure water to adjust the viscosity of the material prepared in step 3.1 to 301 mpa.s, discharge, and obtain a high-speed spraying adhesive.

[0102] Comparative Example 3

[0103] Compared with Example 1, the difference is that the self-made modified acrylic emulsion is not added in the formula, and the proportion is replaced by VAE emulsion. That is, a high-speed spraying adhesive packaging adhesive is prepared according to the following method and steps:

[0104] (1) Preparation of polyvinyl alcohol solution:

[0105] 1.1 According to the weight, 80 parts of pure water are added into the kettle, the stirring is started, and 20 parts of PVA-1788 are added while stirring at a speed of 50 r / min. After adding, the temperature is raised to 90℃, and the stirring is kept for 2 hours, and then cooled to room temperature for standby;

[0106] (2) Preparation of high-speed spraying adhesive

[0107] 2.1 Add 82 parts of VAE emulsion into the kettle, start stirring, and stir at a speed of 40 r / min for 10 min;

[0108] Add 5 parts of polyvinyl alcohol prepared in step 1.1, stir at a speed of 50 r / min for 20 min;

[0109] Add 2 parts of plasticizer acetyl tri-butyl citrate, stir at a speed of 50 r / min for 10 min;

[0110] Add 1 part of emulsified silicone oil, stir at a speed of 70 r / min for 20 min;

[0111] Add 0.1 part of fungicide MBS, stir at a speed of 50 r / min for 10 min;

[0112] Add pH regulator to adjust the pH value to 5.1, continue to stir at a speed of 50 r / min for 5 min;

[0113] 2.2 Add appropriate amount of pure water to adjust the viscosity of the material prepared in step 3.1 to 290 mpa.s, discharge, and obtain a high-speed spraying adhesive.

[0114] Comparative Example 4

[0115] The self-made modified acrylic emulsion is less added in the formula, and the reduced acrylic emulsion is replaced by VAE emulsion. That is, the high-speed spray adhesive packaging adhesive is prepared according to the following methods and steps:

[0116] (1) Synthesis of modified acrylic emulsion:

[0117] 1.1 Pre-emulsification: The phosphate adhesion monomer PAM200 is pre-neutralized to a PH value of 7 with 0.1 mol / L sodium hydroxide to obtain a pre-adjusted phosphate adhesion monomer; 22 parts of pure water are added to the emulsification kettle by weight, 0.7 parts of emulsifier SE-10N are added, stirred for 10 minutes, 1.0 parts of pre-adjusted phosphate adhesion monomer are added and stirred for 15 minutes, and then 0.5 parts of acrylic acid, 18.49 parts of methyl methacrylate, 22.19 parts of isooctyl acrylate, 6.29 parts of ethyl acrylate, and 1 part of coupling agent A-172 are added in sequence, and high-speed stirring is carried out for 30 minutes to obtain a pre-emulsion;

[0118] 1.2 21 parts of pure water and 0.1 parts of pH regulator sodium bicarbonate are added to the reaction kettle by weight, stirring is started, the stirring speed is controlled at 30-50 r / min, the temperature is raised to 85℃, 5 parts of the pre-emulsion prepared in step 1.1 and 0.05 parts of initiator ammonium persulfate are added, after blue fluorescence appears in the reaction kettle, the remaining 95 parts of pre-emulsion and 0.1 parts of ammonium persulfate are added at the same time, after the addition is completed, the temperature is kept for 2 hours, the temperature is lowered to 70℃, and 0.05 parts of tert-butyl hydroperoxide and 0.05 parts of sodium metabisulfite are added at the same time, and the temperature is kept for 30 minutes. Continue to mature until there is no monomer odor, and cool down for standby; the modified acrylic emulsion prepared in this way has the following characteristics: solid content: 49.7%, viscosity: 2670 mpa.s, pH value: 4.8, glass transition temperature: -13.4℃;

[0119] (2) Preparation of polyvinyl alcohol solution:

[0120] 2.1 According to the weight, 80 parts of pure water are added to the kettle, stirring is started, and 20 parts of PVA-1788 are added while stirring at a speed of 50 r / min, after addition, the temperature is raised to 90℃, and the temperature is kept stirring for 2 hours, then cooled to room temperature for standby;

[0121] (3) Preparation of high-speed spray adhesive

[0122] 3.1 77 parts of VAE emulsion are added to the kettle, stirring is started, 5 parts of modified acrylic emulsion prepared in step 1.2 are added at a speed of 40 r / min, and stirring is carried out for 10 min;

[0123] 5 parts of polyvinyl alcohol prepared in step 2.1 are added, and stirring is carried out at a speed of 50 r / min for 20 min;

[0124] Then, 2 parts of plasticizer acetyl tri-butyl citrate were added, and stirring was carried out at a speed of 50 r / min for 10 min;

[0125] Then, 1 part of emulsified silicone oil was added, and stirring was carried out at a speed of 70 r / min for 20 min;

[0126] Then, 0.1 part of bactericide MBS was added, and stirring was carried out at a speed of 50 r / min for 10 min;

[0127] Then, pH regulator was added to adjust the pH value to 5.1, and stirring was continued at a speed of 50 r / min for 5 min;

[0128] 3.2 A proper amount of pure water was added to adjust the viscosity of the material prepared in step 3.1 to 298 mpa.s, and the material was discharged to obtain a high-speed spraying adhesive.

[0129] Raw material information

[0130] The raw material related information of each example and comparative example is as follows:

[0131] VAE emulsion: solid content: 54-56%, viscosity: 1500-2500 mPa.s, pH value: 4.0-6.0, glass transition temperature: 0℃-10℃;

[0132] The phosphate adhesion monomer is PAM200, which is an active phosphomethyl acrylate monomer;

[0133] The silane coupling agent is A-172, and the chemical name is vinyl tri (2-methoxyethoxy) silane;

[0134] PVA-1788 is polyvinyl alcohol, and the polymerization degree is 1700 and the alcoholysis degree is 88%;

[0135] The emulsified silicone oil is DC1785; it is a small particle size high molecular weight polydimethylsiloxane alcohol anion emulsion containing 60%, and the particle size is less than 1 micron;

[0136] The pH regulator is sodium bicarbonate.

[0137] The bactericide is MBS, and the active ingredient is 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one.

[0138] The beneficial effects of the present application are further illustrated by experimental tests and machine data as follows.

[0139] The physical and chemical indexes of the high-speed spraying adhesive for packaging of the present application are as shown in Table 1:

[0140] Table 1 Physical and chemical index test of high-speed spraying adhesive for packaging

[0141]

[0142] The on-machine adaptability index of the high-speed sprayable packaging adhesive of the present application is tested as shown in Table 2 below:

[0143] The on-machine adaptability refers to providing an evaluation system and method for a cigarette production enterprise to pre-judge the use effect of the high-speed sprayable packaging adhesive on the machine through the tests of open time and bonding force. The open time is the time required for the film formation of the water-based adhesive for cigarettes under the specified drying conditions; the bonding force refers to the intermolecular bonding force on the interface between the adhesive and the bonded object, which represents the bonding strength and peel strength of the adhesive; the present application tests the related on-machine adaptability indexes of Example 1, Example 2, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4, mainly testing the bonding force and open time of the packaging adhesive.

[0144] Table 2 Test of on-machine adaptability index of high-speed sprayable packaging adhesive

[0145]

[0146] From the test data in Table 2, Comparative Example 1 does not add emulsified silicone oil, and the open time is faster than that of Example 1 and Example 2, so it is easy to block the glue nozzle; Comparative Example 2 only adds 0.5 parts of emulsified silicone oil, and the open time is still faster than that of Example 1 and Example 2; Comparative Example 3 does not add acrylic emulsion, and the bonding force decreases obviously; Comparative Example 4 has a small amount of acrylic emulsion, and the bonding performance is not obviously improved.

[0147] The safety index test is shown in Table 3 below:

[0148] Table 3 Test of safety and health index of high-speed sprayable packaging adhesive

[0149]

[0150] From the data in Table 3, all samples meet the safety and health standard requirements of YQ 5 adhesive for cigarettes.

[0151] The on-machine situation of the high-speed sprayable packaging adhesive of the present application is shown in Table 4 below:

[0152] The machine used in this on-machine use is ZB48, the machine speed is 800-1000 boxes / min, and HHS D500 spray gun is used. The nozzle diameter is 0.35mm, and the packaging box skin is coated with an aluminum plating layer (which belongs to a low surface energy packaging material with a dyne value of 28).

[0153] Table 4 On-machine use situation of high-speed sprayable packaging adhesive

[0154]

[0155] From the machine running condition, it can be seen that the machine running condition of Example 1 and Example 2 is obviously better than that of each comparative example; Comparative Example 1 needs to clean the nozzle frequently due to the problem of nozzle blockage, and the missing of glue point will affect bonding; Comparative Example 2 still has the problem of nozzle blockage, and occasionally appears the phenomenon of nozzle deviation, and the cleaning frequency is slightly less than that of Comparative Example 1; Comparative Example 3 does not have the problem of nozzle blockage, but appears the phenomenon of poor bonding of cigarette packets, and the rejection rate of cigarette packets is high; Comparative Example 4 has slightly insufficient bonding strength, and the bottom of the cigarette packet and the inner liner paper appear the phenomenon of poor bonding.

[0156] The above description is merely preferred embodiments of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A high-speed spray coating packaging glue suitable for low surface energy packaging paper, which is prepared from modified acrylic emulsion, EVA emulsion, polyvinyl alcohol, plasticizer, emulsified silicone oil, pH regulator, bactericide and pure water, characterized in that, The mass ratio of the modified acrylic emulsion, EVA emulsion, polyvinyl alcohol, plasticizer, emulsified silicone oil, pH regulator, bactericide is (10-20):(62-72):(3-8):(2-4):(1-2):(0.1-0.5):0.1; the modified acrylic emulsion is a copolymer mainly composed of acrylic acid, methyl methacrylate, isooctyl acrylate, ethyl acrylate, phosphate adhesion monomer, silane coupling agent, etc.

2. A high speed sprayable packaging adhesive suitable for low surface energy packaging paper as claimed in claim 1 or 2, wherein, The modified acrylic emulsion is prepared from acrylic acid, methyl methacrylate, isooctyl acrylate, ethyl acrylate, phosphate adhesion monomer, silane coupling agent, etc. with a mass ratio of (0.5-1.0):(15-20):(20-25):(5-8):(0.5-1.5):(0.5-1.5); the modified acrylic emulsion also has the following characteristics: solid content: 48-52%, viscosity: 1000-3000 mPa.s, pH value: 4.0-6.0, glass transition temperature: -20℃ to -5℃.

3. A high speed sprayable packaging adhesive suitable for low surface energy packaging paper according to claim 1 or 2, characterized in that, The phosphate adhesion monomer is phosphate functional monomer PAM200, which contains active phosphomethacrylate monomer.

4. A high speed sprayable packaging adhesive suitable for low surface energy packaging paper according to claim 1 or 2, characterized in that, The EVA emulsion has the following characteristics: solid content: 54-56%, viscosity: 1500-2500 mPa.s, pH value: 4.0-6.0, glass transition temperature: 0℃ to 10℃.

5. A high speed sprayable packaging adhesive suitable for low surface energy packaging paper according to claim 1 or 2, characterized in that, The polyvinyl alcohol is PVA-1788, with a polymerization degree of 1700 and an alcoholysis degree of 88%.

6. A high speed sprayable packaging adhesive suitable for low surface energy packaging paper according to claim 1 or 2, characterized in that, The emulsified silicone oil is a small particle size high molecular weight polydimethylsiloxane alcohol anion emulsion containing 60%, with a particle size less than 1 micron, a solid content (105℃, 3H): ≥60%, and a viscosity (25℃): ≥3000 mPa.s.

7. A high speed sprayable packaging adhesive suitable for low surface energy packaging paper according to claim 1 or 2, characterized in that, The silane coupling agent is vinyl tri(2-methoxyethoxy) silane.

8. A high speed sprayable packaging adhesive suitable for low surface energy packaging paper according to claim 1 or 2, characterized in that, The emulsifier is a low-foaming anionic reactive emulsifier: 1-allyloxy-3-(4-nonylphenol)-2-2 propyl alcohol polyoxyethylene (10) ether; the plasticizer is selected from one or more of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, acetyl citric acid tributyl ester, and glyceryl triacetate; the pH regulator is sodium bicarbonate; the bactericide is MBS, with active ingredients of 2-methyl-4-isothiazolin-3-one and 1,2-benzisothiazolin-3-one; the pure water is tertiary purified water treated by multi-stage reverse osmosis membrane filtration, with an electrical conductivity lower than 10 µs / cm.

9. The method of claim 1 to 8, wherein The method comprises the following steps: (1) synthesis of modified acrylic emulsion: 1.1 Pre-emulsification: the phosphate adhesion monomer PAM200 is pre-neutralized with 0.1 mol / L sodium hydroxide to a pH value of 7 to obtain a pre-prepared phosphate adhesion monomer; a certain amount of pure water is added to an emulsification kettle, a certain amount of emulsifier SE-10N is added, stirred for 10 minutes, a certain amount of pre-prepared phosphate adhesion monomer is added and stirred for 15 minutes, and then acrylate, methyl methacrylate, isooctyl acrylate, ethyl acrylate, and coupling agent A-172 are added in their respective formula amounts, and high-speed stirring is carried out for 30 minutes to obtain a pre-emulsion; 1.2 A certain amount of pure water and a certain amount of pH adjuster sodium bicarbonate are added to a reaction kettle, stirring is started, the stirring speed is controlled at 30-50 r / min, the temperature is raised to 85°C, 5 parts of the pre-emulsion prepared in step 1.1 and 0.05 parts of initiator ammonium persulfate are added, and after a blue fluorescence appears in the reaction kettle, the remaining pre-emulsion and 0.1 parts of ammonium persulfate are added dropwise, after the dropwise addition is completed, the temperature is kept for 2 hours, the temperature is lowered to 70°C, and 0.05 parts of tert-butyl hydroperoxide and 0.05 parts of sodium metabisulfite are added dropwise, and the temperature is kept for another 30 minutes. until there is no monomer smell, and then cool down for use; the modified acrylic emulsion prepared in this way has the following characteristics: solid content: 48-52%, viscosity: 1000-3000 mpa.s, pH value: 4.0-6.0, glass transition temperature: -20°C to -5°C; (2) Preparation of polyvinyl alcohol solution: 2.1 According to the weight, a certain amount of pure water is added to the kettle, stirring is started, and 20 parts of PVA-1788 are added while stirring at a speed of 50 r / min, then the temperature is raised to 90°C, and the mixture is stirred for 2 hours, and then cooled to room temperature for use; (3) Preparation of high-speed spraying adhesive 3.1 Add the formula amount of VAE emulsion to the kettle, start stirring, and add 10-20 parts of the modified acrylic emulsion prepared in step 1.2 at a speed of 40 r / min, and stir for 10 min; Add 3-8 parts of polyvinyl alcohol prepared in step 2.1, and stir at a speed of 50 r / min for 20 min; Then add 2-4 parts of plasticizer, and stir at a speed of 50 r / min for 10 min; Then add 1-2 parts of emulsified silicone oil, and stir at a speed of 70 r / min for 20 min; Then add 0.1 parts of bactericide MBS, and stir at a speed of 50 r / min for 10 min; Then add the pH adjuster, and continue to stir at a speed of 50 r / min for 5 min; 3.2 Add a certain amount of water to adjust the viscosity of the material prepared in step 3.1 to 260-320 mpa.s, and then discharge to obtain a high-speed spraying adhesive.

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