Anti-burst and high anti-falling water-based transfer adhesive, and preparation method and application thereof

Abstract

The application discloses an anti-burst and high-anti-falling water-based transfer adhesive as well as a preparation method and application thereof. The water-based transfer adhesive comprises the following raw materials in parts by weight: 29-43 parts of a silicon-modified styrene-acrylic emulsion, 34-52 parts of a water-based butadiene-styrene emulsion, 0.3-1 part of cellulose nanofiber, 15-26 parts of deionized water, 0.1-1 part of a wetting agent, 0.1-1 part of a leveling agent and 0.05-0.9 part of a defoaming agent. The water-based transfer adhesive provided by the application has excellent anti-burst and anti-sticking properties and good adhesion.

Description

Technical Field

[0001] This invention relates to a method for recycling by-products, and more particularly to a crack-resistant and highly anti-reflective water-based transfer adhesive, its preparation method, and its application. Background Technology

[0002] Metallized transfer adhesives are primarily used in the tobacco packaging industry to transfer aluminum foil from metallized transfer film to white cardboard or inner lining paper. They are also gradually penetrating other industries, such as daily chemical product packaging and high-end gift box packaging. Water-based metallized transfer adhesives include acrylic emulsion systems, styrene-butadiene emulsion systems, and polyurethane emulsion systems. Due to inherent defects such as poor adhesion of water-based polyurethane emulsions, acrylic and styrene-butadiene emulsion systems are currently the main types used. Besides adhesion, transfer adhesives also primarily focus on burst resistance and anti-sticking properties. Bursting resistance assesses the flexibility of the adhesive film, while anti-sticking properties assess its stiffness. However, due to system limitations, traditional water-based acrylic and styrene-butadiene transfer adhesives cannot simultaneously achieve both burst resistance and anti-sticking properties. Therefore, it is crucial to develop a water-based transfer adhesive that combines excellent burst resistance and anti-sticking properties while ensuring sufficient adhesion. Summary of the Invention

[0003] To address the above technical problems, this invention proposes a crack-resistant and highly anti-reflective water-based transfer adhesive, its preparation method, and its application.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] A crack-resistant and highly anti-reflective water-based transfer adhesive, comprising the following raw materials in parts by weight:

[0006] Silicone-modified styrene-acrylic emulsion, 29-43 parts.

[0007] Aqueous styrene-butadiene emulsion, 34-52 parts,

[0008] Cellulose nanofibers, 0.3-1 part,

[0009] Deionized water, 15-26 parts

[0010] Wetting agent, 0.1-1 part.

[0011] Leveling agent, 0.1-1 part,

[0012] Defoamer, 0.05-0.9 parts.

[0013] In the above raw material formulation, silicone-modified styrene-acrylic emulsion and water-based styrene-butadiene emulsion serve as the main agents of the water-based transfer adhesive, which can meet the product requirements of high adhesion. At the same time, cellulose nanofibers are rich in polar groups such as hydroxyl and carboxyl groups, which have good compatibility with the system. Furthermore, the hydroxyl groups can react with the silanol groups in the silicone-modified styrene-acrylic emulsion, allowing the nanopolymer structure to be interspersed in the system and form a uniform and interconnected rigid network structure after film formation.

[0014] As a preferred embodiment of the present invention, the silicone-modified styrene-acrylic emulsion is a styrene-acrylate emulsion modified by organosiloxane copolymerization, wherein the content of organosiloxane is 1-5% of the total mass of styrene and acrylate;

[0015] Preferably, the organosiloxane is one or more selected from vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and octamethylcyclotetrasiloxane;

[0016] As a preferred embodiment of the present invention, the glass transition temperature of the silicon-modified styrene-acrylic emulsion is -1℃ to 24℃, the average particle size of the latex particles is 50-300nm, the emulsion viscosity is 100-300mPa.s, the solid content is 42-52%, and the pH value is 6.5-8.

[0017] The silicon-modified styrene-acrylic emulsion can be synthesized using known techniques or purchased directly from commercially available products. As an example of a feasible solution provided by this invention, the silicon-modified styrene-acrylic emulsion can be purchased directly from XQ 97918, Archsol 8042A, and / or Acronal 5041.

[0018] As a preferred embodiment of the present invention, the glass transition temperature of the aqueous styrene-butadiene emulsion is -5°C to 8°C, the average particle size of the latex particles is 100-280 nm, and the solid content is 42-52%.

[0019] The aqueous styrene-butadiene emulsion can be synthesized using known techniques or purchased directly from commercially available finished products. As an example of a feasible solution provided by this invention, the aqueous styrene-butadiene emulsion can be purchased directly from Shengxi Ao XQ 97902, XQ 97912, and SD 516.

[0020] As a preferred embodiment of the present invention, the cellulose nanofibers are cellulose nanofibers prepared by one or more methods including mechanical grinding, enzyme catalysis and chemical pretreatment, with a carboxyl content of 0.3-1.0 mmol / g and a particle length of 0.4-7 μm.

[0021] This invention introduces cellulose nanofibers into the formulation, which facilitates the transfer of stress from the emulsion polymer to the cellulose nanofibers during film stretching, thereby making the film more robust. In the application of the transfer adhesive, this translates to improved anti-burst performance. Furthermore, during compression, due to the volume effect, the rigid network structure effectively prevents the free movement of the polymer molecules, maintaining a relatively stable state and thus imparting excellent anti-scratching properties to the transfer adhesive. Therefore, the prepared water-based transfer adhesive possesses both excellent anti-burst and anti-scratching properties, while also exhibiting excellent adhesion to aluminum foil.

[0022] In a preferred embodiment of the present invention, the wetting agent is one or more of OT-75, TEGO-245 and ST-83.

[0023] In a preferred embodiment of the present invention, the leveling agent is an organosilicon leveling agent, preferably one or more of BYK-333, RM2020 and TEGO-450.

[0024] In a preferred embodiment of the present invention, the defoamer is one or more of DF-691, ST-2410 and BYK-024.

[0025] This invention also proposes a method for preparing a crack-resistant and highly anti-reflective water-based transfer adhesive as described above, characterized by comprising the following steps:

[0026] Silicon-modified styrene-acrylic emulsion and aqueous styrene-butadiene emulsion were mixed and stirred to obtain solution A;

[0027] Cellulose nanofibers were optionally diluted with deionized water and then neutralized with alkali to obtain solution B;

[0028] Solution A and solution B are added to the reaction vessel, along with a wetting agent, leveling agent, and defoamer. The mixture is stirred until homogeneous, and the gel residue is filtered out before discharge to obtain the water-based transfer adhesive.

[0029] As a preferred preparation method, the mixing time of the silicon-modified styrene-acrylic emulsion and the aqueous styrene-butadiene emulsion is 10-30 min, and the stirring rate is 100-300 r / min.

[0030] As a preferred preparation method, the alkali is preferably one or more selected from ammonia, AMP-95, and caustic soda flakes. More preferably, the amount of alkali added is such that the pH of the solution is adjusted to 6.5-8; after adding the alkali, the solution is stirred at a speed of 500-1200 r / min for 30-60 min.

[0031] Preferably, the processing conditions after mixing solution A, solution B and other additives are: stirring time 20-30 min, stirring speed 200-500 r / min.

[0032] This invention also proposes the application of a crack-resistant and highly reflective water-based transfer adhesive, as described above, in the fields of tobacco packaging, daily chemical product packaging, and high-end gift box packaging.

[0033] The present invention has the following beneficial effects:

[0034] 1) The water-based transfer adhesive of the present invention introduces cellulose nanofibers as fillers, which act as rigid skeletons in the adhesive film, thereby improving the anti-cracking and anti-sticking properties of the transfer adhesive at the same time, and overcoming the disadvantage that the anti-cracking and anti-sticking properties of traditional transfer adhesives cannot be obtained at the same time.

[0035] 2) This invention uses a blend of silicone-modified styrene-acrylic emulsion and styrene-butadiene emulsion. Combining the excellent adhesion of styrene-butadiene with the flexible and controllable properties of silicone-modified styrene-acrylic emulsion, a water-based transfer adhesive with excellent anti-cracking, anti-sticking properties and good adhesion is prepared.

[0036] 3) This invention adopts a water-based resin system. Biomass-based cellulose nanofibers can be extracted in large quantities from plants, which responds to the call for green development and low-carbon transformation and solves the problem of volatile organic compound pollution in the environment from the source. Detailed Implementation

[0037] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.

[0038] Unless otherwise specified, all raw materials and reagents used in the following embodiments of the present invention were obtained through commercially available channels. Among them:

[0039] Silicon-modified styrene-acrylic emulsion XQ 97918: Tg 24℃, solid content 50%, viscosity 100mPa.s, Shengxi'ao;

[0040] Silicon-modified styrene-acrylic emulsion Archsol 8042A: Tg 20℃, solid content 45%, viscosity 270 mPa.s, Wanhua;

[0041] Silicon-modified styrene-acrylic emulsion Acronal 5041: Tg 0℃, solid content 52%, viscosity 160 mPa.s, BASF;

[0042] Waterborne styrene-butadiene emulsion XQ 97902: Tg 2℃, average latex particle size 160nm, Shengxi'ao;

[0043] Waterborne styrene-butadiene emulsion XQ 97912: Tg 8℃, average latex particle size 120nm, Shengxi'ao;

[0044] Aqueous styrene-butadiene emulsion SD 516: Tg-2℃, average latex particle size 250nm, BASF;

[0045] Cellulose nanofibers A: Purchased from Tianjin Wood Elf Biotechnology Co., Ltd., with a particle length of 6.5 μm and a carboxyl content of 0.3 mmol / g;

[0046] Cellulose nanofibers B: Purchased from Tianjin Wood Elf Biotechnology Co., Ltd., with a particle length of 3.0 μm and a carboxyl content of 0.6 mmol / g;

[0047] Cellulose nanofibers C: Purchased from Tianjin Wood Elf Biotechnology Co., Ltd., with a particle length of 0.6 μm and a carboxyl content of 1.0 mmol / g.

[0048] The main testing methods involved in this invention are as follows:

[0049] (1) Crack resistance test: The water-based transfer adhesive was directly applied to the aluminum transfer adhesive, and the sample was folded 180° in both directions. The number of folds and whether it broke were recorded.

[0050] (2) Anti-sticking test: The water-based transfer adhesive was directly applied to the aluminized transfer adhesive. The sample was made into a 4cm*4cm paper sample and 4kg / cm was applied. 2 The samples were placed in a constant temperature and humidity chamber at 60℃*80%RH for 24 hours under pressure. After that, the samples were taken out and the changes in surface flatness were observed. The samples were divided into 5 levels according to the degree of embossing. Samples with basically no damage were classified as level 5, and samples with more than 20 spots on the surface were classified as level 1.

[0051] (3) Adhesion test: Water-based transfer adhesive was used for aluminum transfer adhesive, and 3M tape was used to quickly peel it off at a 45° angle to observe the changes on the surface of the aluminum layer.

[0052]

Example 1

[0053] A crack-resistant and highly anti-reflective water-based transfer adhesive, comprising the following raw materials in parts by weight:

[0054] Silicone-modified styrene-acrylic emulsion Acronal 5041, 36 parts.

[0055] Aqueous styrene-butadiene emulsion XQ 97902, 44 parts

[0056] Cellulose nanofibers A, 0.9 parts,

[0057] Deionized water, 18.55 parts.

[0058] Wetting agent OT-75, 0.3 parts.

[0059] Leveling agent BYK-333, 0.2 parts,

[0060] Defoamer DF-691, 0.8 parts.

[0061] Silicon-modified styrene-acrylic emulsion Acronal 5041 and waterborne styrene-butadiene emulsion XQ 97902 were mixed and stirred for 25 min at a stirring rate of 200 r / min to obtain solution A. Cellulose nanofibers A were diluted with 18.55 parts of deionized water and neutralized with ammonia water to pH 7. The mixture was stirred at 1000 r / min for 60 min to obtain solution B. Solutions A and B were added to a reaction vessel, along with a wetting agent, leveling agent, and defoamer. The mixture was stirred at 450 r / min for 30 min until homogeneous. After filtering out the gel residue, the waterborne transfer adhesive was obtained.

[0062]

Example 2

[0063] A crack-resistant and highly anti-reflective water-based transfer adhesive, comprising the following raw materials in parts by weight:

[0064] Silicon-modified styrene-acrylic emulsion Archsol 8042A, 29 parts.

[0065] Aqueous styrene-butadiene emulsion XQ 97912, 34 parts

[0066] Cellulose nanofibers B, 0.3 parts

[0067] Deionized water, 15 parts

[0068] Wetting agent TEGO-245, 0.1 parts.

[0069] Leveling agent RM2020, 0.55 parts

[0070] Defoamer ST-2410, 0.6 parts.

[0071] Silicon-modified styrene-acrylic emulsion Archsol 8042A and waterborne styrene-butadiene emulsion XQ 97912 were mixed and stirred for 10 min at a stirring rate of 100 r / min to obtain solution A. Cellulose nanofibers A were diluted with 15 parts of deionized water and neutralized to pH 6.5 with AMP-95. The mixture was stirred at 500 r / min for 30 min to obtain solution B. Solutions A and B were added to a reaction vessel, along with a wetting agent, leveling agent, and defoamer. The mixture was stirred at 250 r / min for 28 min. After stirring until homogeneous, the gel residue was filtered off and the product was discharged to obtain the waterborne transfer adhesive.

[0072]

Example 3

[0073] Silicon-modified styrene-acrylic emulsion XQ 97918, 43 parts.

[0074] Aqueous styrene-butadiene emulsion SD 516, 52 parts

[0075] Cellulose nanofibers C, 1 part

[0076] Deionized water, 24 parts

[0077] Wetting agent ST-83, 0.6 parts.

[0078] Leveling agent TEGO-450, 1 part

[0079] Defoamer BYK-024, 0.3 parts.

[0080] Silicon-modified styrene-acrylic emulsion XQ 97918 and waterborne styrene-butadiene emulsion SD 516 were mixed and stirred for 20 minutes at a stirring rate of 150 r / min to obtain solution A. Cellulose nanofibers A were diluted with 24 parts of deionized water and neutralized with caustic soda flakes to a pH of 7.4. The mixture was stirred at 700 r / min for 45 minutes to obtain solution B. Solutions A and B were added to a reaction vessel, along with a wetting agent, leveling agent, and defoamer. The mixture was stirred at 200 r / min for 20 minutes until homogeneous. After filtering out the gel residue, the waterborne transfer adhesive was obtained.

[0081]

Example 4

[0082] Silicon-modified styrene-acrylic emulsion Archsol 8042A, 32 parts.

[0083] Aqueous styrene-butadiene emulsion XQ 97902, 40 parts

[0084] Cellulose nanofibers C, 0.5 parts

[0085] Deionized water, 19 parts

[0086] Wetting agent ST-83, 0.5 parts.

[0087] Leveling agent BYK-333, 0.6 parts.

[0088] Defoamer ST-2410, 0.1 parts.

[0089] Silicon-modified styrene-acrylic emulsion Archsol 8042A and waterborne styrene-butadiene emulsion XQ 97902 were mixed and stirred for 15 min at a stirring rate of 120 r / min to obtain solution A. Cellulose nanofibers A were diluted with 19 parts of deionized water and neutralized with ammonia water to pH 6.8. The mixture was stirred at 1200 r / min for 35 min to obtain solution B. Solutions A and B were added to a reaction vessel, along with a wetting agent, leveling agent, and defoamer. The mixture was stirred at 300 r / min for 22 min until homogeneous. After filtering out the gel residue, the product was discharged to obtain the waterborne transfer adhesive.

[0090]

Example 5

[0091] Silicone-modified styrene-acrylic emulsion XQ 97918, 38 parts.

[0092] Waterborne styrene-butadiene emulsion XQ 97912, 50 parts

[0093] Cellulose nanofibers B, 0.4 parts

[0094] Deionized water, 16 parts

[0095] Wetting agent TEGO-245, 0.8 parts.

[0096] Leveling agent TEGO-450, 0.8 parts.

[0097] Defoamer BYK-024, 0.5 parts.

[0098] Silicon-modified styrene-acrylic emulsion XQ 97918 and waterborne styrene-butadiene emulsion XQ 97912 were mixed and stirred for 30 minutes at a stirring rate of 300 r / min to obtain solution A. Cellulose nanofibers A were diluted with 16 parts of deionized water and neutralized to pH 8 with caustic soda flakes. The mixture was stirred at 800 r / min for 50 minutes to obtain solution B. Solutions A and B were added to a reaction vessel, along with a wetting agent, leveling agent, and defoamer. The mixture was stirred at 400 r / min for 25 minutes until homogeneous. After filtering out the gel residue, the product was discharged to obtain the waterborne transfer adhesive.

[0099]

Example 6

[0100] Silicon-modified styrene-acrylic emulsion Acronal 5041, 40 parts.

[0101] Aqueous styrene-butadiene emulsion SD 516, 48 parts

[0102] Cellulose nanofibers A, 0.7 parts

[0103] Deionized water, 25 parts

[0104] Wetting agent OT-75, 1 part

[0105] Leveling agent RM2020, 0.1 parts

[0106] Defoamer DF-691, 0.05 parts.

[0107] Silicon-modified styrene-acrylic emulsion Acronal 5041 and waterborne styrene-butadiene emulsion SD 516 were mixed and stirred for 27 min at a stirring rate of 120 r / min to obtain solution A. Cellulose nanofibers A were diluted with 25 parts of deionized water and neutralized to pH 7.8 with AMP-95 and stirred at 1100 r / min for 60 min to obtain solution B. Solutions A and B were added to a reaction vessel, along with a wetting agent, leveling agent, and defoamer, and stirred at 500 r / min for 28 min. After stirring until homogeneous, the gel residue was filtered off and the product was discharged to obtain the waterborne transfer adhesive.

[0108] Comparative Example 1

[0109] The water-based transfer gel was prepared using essentially the same raw material formulation and method as in Example 1, except that cellulose nanofibers A were not added.

[0110] Comparative Example 2

[0111] The waterborne transfer adhesive was prepared using essentially the same raw material formulation and method as in Example 1, except that the amount of silicone-modified styrene-acrylic emulsion Acronal 5041 was changed to 80 parts, and the waterborne styrene-butadiene emulsion XQ 97902 was not added.

[0112] Comparative Example 3

[0113] Commercially available product 3562F (Fustar) was used as the water-based transfer adhesive.

[0114] The performance tests of the water-based transfer adhesives provided in each embodiment and comparative example were performed as shown in Table 1, and the results are as follows:

[0115] Table 1. Performance Test Results

[0116] Example 1 >25 times, no breakage. 5 No aluminum layer peeling was observed. Example 2 >25 times, no breakage. 5 No aluminum layer peeling was observed. Example 3 >25 times, no breakage. 5 No aluminum layer peeling was observed. Example 4 >25 times, no breakage. 5 No aluminum layer peeling was observed. Example 5 >25 times, no breakage. 5 No aluminum layer peeling was observed. Example 6 >25 times, no breakage. 5 No aluminum layer peeling was observed. Comparative Example 1 12 times, fracture 3 No aluminum layer peeling was observed. Comparative Example 2 20 times, fracture 4 Small amount of aluminum loss Comparative Example 3 13 times, fracture 3 No aluminum layer peeling was observed.

[0117] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.

Claims

1. A water-based transfer adhesive with anti-cracking and high anti-reflection properties, characterized in that, The ingredients include the following parts by weight: Silicone-modified styrene-acrylic emulsion, 29-43 parts. Aqueous styrene-butadiene emulsion, 34-52 parts, Cellulose nanofibers, 0.3-1 part, Deionized water, 15-26 parts Wetting agent, 0.1-1 part, Leveling agent, 0.1-1 part, Defoamer, 0.05-0.9 parts.

2. The anti-cracking and high anti-reflective water-based transfer adhesive according to claim 1, characterized in that, The silicone-modified styrene-acrylic emulsion is a styrene-acrylate emulsion modified by organosiloxane copolymerization, wherein the content of organosiloxane is 1-5% of the total mass of styrene and acrylate.

3. The anti-cracking and high anti-reflective water-based transfer adhesive according to claim 2, characterized in that, The organosiloxane is one or more of vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and octamethylcyclotetrasiloxane.

4. The anti-cracking and high anti-reflective water-based transfer adhesive according to claim 2, characterized in that, The silicon-modified styrene-acrylic emulsion has a glass transition temperature of -1℃ to 24℃, an average latex particle size of 50-300nm, an emulsion viscosity of 100-300mPa.s, a solid content of 42-52%, and a pH value of 6.5-8.

5. The anti-cracking and high anti-reflective water-based transfer adhesive according to any one of claims 1-4, characterized in that, The aqueous styrene-butadiene emulsion has a glass transition temperature of -5°C to 8°C, a solid content of 42-52%, and an average latex particle size of 100-280 nm.

6. The anti-cracking and high anti-reflective water-based transfer adhesive according to any one of claims 1-4, characterized in that, The cellulose nanofibers have a carboxyl content of 0.3-1.0 mmol / g and a particle length of 0.4-7 μm.

7. The anti-cracking and high anti-reflective water-based transfer adhesive according to any one of claims 1-4, characterized in that, The wetting agent is one or more of OT-75, TEGO-245 and ST-83.

8. The anti-cracking and high anti-reflective water-based transfer adhesive according to any one of claims 1-4, characterized in that, The leveling agent is an organosilicon-based leveling agent.

9. The anti-cracking and high anti-reflective water-based transfer adhesive according to claim 8, characterized in that, The leveling agent is one or more of BYK-333, RM2020 and TEGO-450.

10. The anti-cracking and high anti-reflective water-based transfer adhesive according to any one of claims 1-4, characterized in that, The defoamer is one or more of DF-691, ST-2410 and BYK-024.

11. A method for preparing a crack-resistant and highly anti-reflective waterborne transfer adhesive as described in any one of claims 1-10, characterized in that, Includes the following steps: Silicon-modified styrene-acrylic emulsion and aqueous styrene-butadiene emulsion were mixed and stirred to obtain solution A; Cellulose nanofibers were diluted with deionized water and then neutralized with alkali to obtain solution B. Solution A and solution B are added to the reaction vessel, along with a wetting agent, leveling agent, and defoamer. The mixture is stirred until homogeneous, and the gel residue is filtered out before discharge to obtain the water-based transfer adhesive.

12. The application of a burst-resistant and highly reflective water-based transfer adhesive as described in any one of claims 1-10 in the fields of tobacco packaging, daily chemical product packaging, and high-end gift box packaging.