A water-resistant white water-based adhesive tape film, a preparation method and application thereof

Abstract

The application belongs to the technical field of films, and discloses a water-white water-based adhesive film, a preparation method and application thereof. The water-based adhesive film comprises a base film, a water-resistant functional coating and a water-based water-resistant pressure-sensitive adhesive layer, the water-resistant functional coating is arranged on one surface of the base film, and the water-based water-resistant pressure-sensitive adhesive layer is arranged on the other opposite surface of the base film. The raw material components of the water-resistant functional coating comprise 35-40 parts of an organic solvent, 12-20 parts of an acrylic resin, 1-2 parts of organic silane A, 1-2 parts of organic silane B and 0.1-0.2 parts of an organic acid catalyst according to mass fractions. The organic silane A comprises tetraethoxysilane. The organic silane B comprises 3-methacryloyloxypropyl trimethoxysilane and / or 3-acryloyloxypropyl trimethoxysilane. The water-based adhesive film has high transparency, excellent water resistance and bonding performance.

Description

Technical Field

[0001] This invention belongs to the field of thin film technology, and specifically relates to a water-resistant white water-based adhesive film for lamination, its preparation method, and its application. Background Technology

[0002] With the upgrading of the packaging and printing industry, the demand for product transparency and applicability is constantly increasing. While traditional water-based laminating films possess good optical properties, they are prone to problems such as water absorption and fogging, whitening, loss of gloss, bubbling, and peeling in humid, cold chain transportation, and outdoor environments. Their poor water resistance makes them unsuitable for high-humidity applications. Traditional solvent-based laminating films, although water-resistant, have high emissions of volatile organic compounds (VOCs) and strong odors, which are inconsistent with environmental trends and are gradually being phased out. Therefore, the industry urgently needs a water-based laminating film with high transparency and good water resistance to meet the application needs of environmentally friendly lamination, cold chain labels, outdoor labels, and surface protection for bathroom product labels. Summary of the Invention

[0003] This invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the object of this invention is to provide a water-resistant, white, water-based adhesive laminating film, its preparation method, and its application. The water-based adhesive laminating film of this invention has high transparency and excellent water resistance and adhesion properties.

[0004] In a first aspect, the present invention provides a water-based adhesive laminating film, comprising a base film, a water-resistant functional coating, and a water-based water-resistant pressure-sensitive adhesive layer, wherein the water-resistant functional coating is disposed on one surface of the base film, and the water-based water-resistant pressure-sensitive adhesive layer is disposed on the other opposite surface of the base film; by weight, the raw material components of the water-resistant functional coating include 35-40 parts of organic solvent, 12-20 parts of acrylic resin, 1-2 parts of organosilane A, 1-2 parts of organosilane B, and 0.1-0.2 parts of organic acid catalyst; wherein organosilane A includes tetraethoxysilane; and wherein organosilane B includes 3-methacryloyloxypropyltrimethoxysilane and / or 3-acryloyloxypropyltrimethoxysilane.

[0005] Specifically, the water-resistant functional coating of this invention is a continuous film formed by the entanglement of organic polymer chain segments. It achieves water resistance while maintaining high transparency through the synergistic effect of organosilane A and organosilane B. Tetraethoxysilane provides a dispersion anchoring structure, while organosilane B provides interfacial compatibility and dispersion. The silane component exists in the coating as a dispersed interfacial anchoring structure, and its content and reaction conditions are insufficient to form a continuous inorganic silicon-oxygen network. The coating's water resistance does not stem from preventing water from entering the coating, but rather from regulating the state of water in the coating through a film-forming structure with organic polymer (acrylic resin) as the continuous phase, combined with the dispersed silane anchoring structure. This allows water to exist in a confined adsorption state rather than forming a free water phase, thus maintaining the structural stability and optical continuity of the coating even in the presence of water, resulting in water-resistant whitening. Furthermore, the water-based water-resistant pressure-sensitive adhesive layer has hydrophobic properties and also exhibits good water resistance.

[0006] In some embodiments of the present invention, the raw material components of the water-resistant functional coating further include 0.2-0.3 parts of defoamer, 0.2-0.3 parts of flow control agent, 0.4-0.6 parts of pH adjuster, and 25-30 parts of water.

[0007] In some embodiments of the present invention, the organic solvent includes anhydrous ethanol.

[0008] In some embodiments of the present invention, the organic acid catalyst includes one or both of formic acid and acetic acid. The selection of organic acids yields a more stable hydrolysis rate and better transparency.

[0009] In some embodiments of the present invention, the pH adjuster includes ammonia.

[0010] In some embodiments of the present invention, the thickness of the water-resistant functional coating is 1-3 μm.

[0011] In some embodiments of the present invention, the thickness of the water-based water-resistant pressure-sensitive adhesive layer is 5-15 μm.

[0012] In some embodiments of the present invention, the thickness of the base film is 19-35 μm.

[0013] In some embodiments of the present invention, the base film comprises a biaxially oriented polypropylene film or a cast polypropylene film.

[0014] A second aspect of the present invention provides a method for preparing the aqueous film for lamination as described in the first aspect of the present invention, comprising the following steps: The raw material components of the water-resistant functional coating are mixed and reacted to obtain the water-resistant functional coating liquid; The water-resistant functional coating is applied to one surface of the base film, pre-dried, and then dried a second time to form a water-resistant functional coating. The pre-drying temperature is 50-60℃ and the pre-drying time is 30-40s. The secondary drying temperature is 90-120℃ and the secondary drying time is 30-40s.

[0015] A water-based water-resistant pressure-sensitive adhesive is coated on the other opposite surface of the base film and dried to form a water-based water-resistant pressure-sensitive adhesive layer, thus obtaining the water-based adhesive film.

[0016] In some embodiments of the present invention, before coating, both surfaces of the base film are pre-treated with plasma activation, resulting in a surface dyne value of 40-45. Plasma activation treatment can increase the surface roughness of the base film and enhance its surface tension, thereby improving the adhesion between the water-resistant functional coating, the water-based water-resistant pressure-sensitive adhesive layer, and the base film surface, making the coating firm and less prone to peeling.

[0017] In some embodiments of the present invention, the drying temperature is 60-120°C.

[0018] In some embodiments of the present invention, the specific preparation process of the water-resistant functional coating liquid includes the following steps: S1. Mix the organic solvent, a portion of the acrylic resin, organosilane A and organosilane B to obtain mixture A; S2. Mix water and organic acid catalyst to obtain mixture B; S3. Mix mixture A and mixture B, allow them to react, then add the remaining acrylic resin and stir. Next, add defoamer, flow control agent, and pH adjuster to adjust the pH of the system to neutral or weakly alkaline, thus obtaining the water-resistant functional coating. Adjusting the pH of the system to neutral or weakly alkaline terminates the hydrolysis reaction of silane and stabilizes the system.

[0019] In some embodiments of the present invention, the specific process of step S1 includes: mixing an organic solvent and a portion of an acrylic resin, stirring for 15-20 minutes, then adding organosilane A and organosilane B, and stirring for 10-15 minutes.

[0020] In some embodiments of the present invention, the reaction time is 30-60 min.

[0021] In some embodiments of the present invention, the pH value is 7.0-8.0.

[0022] In some embodiments of the present invention, the acrylic resin accounts for 45%-55% of the total acrylic resin by mass, preferably 50%.

[0023] A third aspect of the present invention provides the application of the water-based adhesive laminating film described in the first aspect of the present invention in the surface lamination of labels and packaging materials.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows: The water-based adhesive laminating film provided by this invention, by having a water-resistant functional coating and a water-based water-resistant pressure-sensitive adhesive layer respectively on both surfaces of the base film, avoids the slow penetration of water or water vapor during use, which causes whitening and loss of adhesion on the adhesive surface, affecting the appearance and use of the label. This invention solves the technical problem of whitening and loss of adhesion of traditional water-based adhesive laminating films under humid and water-based processing conditions, improving the applicability of water-based adhesive laminating films. It can replace traditional solvent-based laminating films in similar environments and is environmentally friendly, in line with the trend of environmental protection. In addition, the preparation method of the water-based adhesive laminating film of this invention is simple, highly operable, and can be mass-produced. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the structure of the water-based adhesive film of the present invention.

[0026] Reference numerals: 100 - Water-resistant functional coating; 200 - Base film; 300 - Water-based water-resistant pressure-sensitive adhesive layer. Detailed Implementation

[0027] The present invention will be further described in detail below through specific embodiments. Unless otherwise specified, the raw materials, reagents, or apparatus used in the embodiments can be obtained from conventional commercial sources or by existing technical methods. Unless otherwise specified, the experimental or testing methods are conventional methods in the art.

[0028] Example 1 Reference Figure 1 A water-based adhesive film, comprising, from top to bottom, a water-resistant functional coating 100, a base film 200, and a water-based water-resistant pressure-sensitive adhesive layer 300.

[0029] The water-resistant functional coating 100 is prepared by coating the upper surface of the base film 200 with a coating solution composed of organic solvent, acrylic resin, 3-methacryloyloxypropyltrimethoxysilane, tetraethoxysilane (TEOS), deionized water, organic acid catalyst, defoamer, flow control agent and ammonia; the thickness of the water-resistant functional coating 100 is 1μm.

[0030] Among them, the organic solvent is anhydrous ethanol from Xilong Scientific Co., Ltd.; the acrylic resin is P59400 from Shanghai Jizhi Biochemical Technology Co., Ltd.; 3-methacryloyloxypropyltrimethoxysilane (MPTS) is SCA-R74M from Nanjing Nengde New Material Technology Co., Ltd.; TEOS is 131903TEOS from Merck Group, Germany; the organic acid catalyst is 695092 acetic acid from Merck Group, Germany; the defoamer is FOMATO MO2190 AC from BASF (China) Co., Ltd.; the flow control agent is DHB-2022 flow control agent from Foshan Shunde Bibian Industry and Trade Co., Ltd.; and the ammonia water is ammonia water from Guangdong Lianfa Additives Factory Co., Ltd.

[0031] Among them, the base film 200 is a cast polypropylene film from Guangdong Maosen Film Technology Co., Ltd., with a thickness of 30μm.

[0032] The water-based water-resistant pressure-sensitive adhesive layer 300 is prepared by coating the lower surface of the base film 200 with a water-based water-resistant pressure-sensitive adhesive; the thickness of the water-based water-resistant pressure-sensitive adhesive layer 300 is 5μm. The water-based water-resistant pressure-sensitive adhesive is PSA932 adhesive from Kaiping Qiyu Adhesive Products Technology Co., Ltd.

[0033] The preparation method of the water-based adhesive laminating film in this embodiment is as follows: 1) Premix 400g of anhydrous ethanol with 60g of acrylic resin and stir for 20 minutes; then add 10g of MPTS and 20g of TEOS and stir for 15 minutes to obtain mixture A; 2) Mix 300g of deionized water with 1g of acetic acid to obtain mixture B; 3) Under stirring conditions, slowly add mixture B to mixture A and react for 30 minutes. Then add 60g of acrylic resin and stir for 15 minutes. Then add 2g of defoamer, 2g of flow control agent and 4g of ammonia water to adjust the pH of the system to 7.2. Filter and let stand for 4 hours to obtain the water-resistant functional coating. 4) The cast polypropylene film was activated on both sides using a plasma cleaner, and the surface dyne value after treatment was 42. 5) Apply a water-resistant functional coating to the upper surface of the activated cast polypropylene film using a coating device, pre-dry at 50°C for 30 seconds, and then dry again at 90°C for 30 seconds to form a water-resistant functional coating. 6) Finally, a water-based water-resistant pressure-sensitive adhesive is coated on the lower surface of the cast polypropylene film, dried at 60°C to form a water-based water-resistant pressure-sensitive adhesive layer, and then wound up to form the product.

[0034] The plasma cleaning machine used was the TS-AP-02 model product from Shenzhen Dongxin Gaoke Automation Equipment Co., Ltd., the coating device used was the KV-DB-350 laboratory wire bar coater from Zhuhai Kaiwei Instrument Equipment Co., Ltd., and the drying equipment used was the electric thermostatic drying oven from Guangzhou Kangheng Instrument Co., Ltd.

[0035] Example 2 Reference Figure 1 A water-based adhesive film, comprising, from top to bottom, a water-resistant functional coating 100, a base film 200, and a water-based water-resistant pressure-sensitive adhesive layer 300.

[0036] The water-resistant functional coating 100 is prepared by coating the upper surface of the base film 200 with a coating solution composed of organic solvent, acrylic resin, 3-methacryloyloxypropyltrimethoxysilane, tetraethoxysilane (TEOS), deionized water, organic acid catalyst, defoamer, flow control agent and ammonia; the thickness of the water-resistant functional coating 100 is 3μm.

[0037] Among them, the organic solvent is anhydrous ethanol from Xilong Scientific Co., Ltd.; the acrylic resin is P59400 from Shanghai Jizhi Biochemical Technology Co., Ltd.; 3-methacryloyloxypropyltrimethoxysilane (MPTS) is SCA-R74M from Nanjing Nengde New Material Technology Co., Ltd.; TEOS is 131903TEOS from Merck Group, Germany; the organic acid catalyst is 695092 acetic acid from Merck Group, Germany; the defoamer is FOMATO MO2190 AC from BASF (China) Co., Ltd.; the flow control agent is DHB-2022 flow control agent from Foshan Shunde Bibian Industry and Trade Co., Ltd.; and the ammonia water is ammonia water from Guangdong Lianfa Additives Factory Co., Ltd.

[0038] Among them, the base film 200 is a biaxially oriented polypropylene film from Zhongshan Yongning Film Materials Co., Ltd., with a thickness of 25μm.

[0039] The water-based water-resistant pressure-sensitive adhesive layer 300 is prepared by coating the lower surface of the base film 200 with a water-based water-resistant pressure-sensitive adhesive; the thickness of the water-based water-resistant pressure-sensitive adhesive layer 300 is 15μm. The water-based water-resistant pressure-sensitive adhesive is PSA932 adhesive from Kaiping Qiyu Adhesive Products Technology Co., Ltd.

[0040] The preparation method of the water-based adhesive laminating film in this embodiment is as follows: 1) Premix 350g of anhydrous ethanol with 100g of acrylic resin and stir for 20 minutes; then add 20g of MPTS and 10g of TEOS and stir for 20 minutes to obtain mixture A; 2) Mix 250g of deionized water with 2g of acetic acid to obtain mixture B; 3) Under stirring conditions, slowly add mixture B to mixture A and react for 60 minutes. Then add 100g of acrylic resin and stir for 20 minutes. Then add 3g of defoamer, 3g of flow control agent and 6g of ammonia water to adjust the pH of the system to 7.6. Filter and let stand for 4 hours to obtain the water-resistant functional coating. 4) The cast polypropylene film was activated on both sides using a plasma cleaner, and the surface dyne value after treatment was 42. 5) Apply a water-resistant functional coating to the upper surface of the activated cast polypropylene film using a coating device, pre-dry at 60°C for 40s, and then dry again at 120°C for 40s to form a water-resistant functional coating. 6) Finally, a water-based water-resistant pressure-sensitive adhesive is coated on the lower surface of the cast polypropylene film, dried at 120°C to form a water-based water-resistant pressure-sensitive adhesive layer, and then wound up to form the product.

[0041] The production equipment used in this embodiment is the same as in Embodiment 1.

[0042] Comparative Example 1 The only difference between this comparative example and Example 1 is that MPTS is not added in step 1) and the amount of TEOS is adjusted to 30g. The other raw material components, amounts and preparation methods are the same as in Example 1.

[0043] Comparative Example 2 The only difference between this comparative example and Example 1 is that TEOS is not added in step 1) and the amount of MPTS is adjusted to 30g. The other raw material components, amounts and preparation methods are the same as in Example 1.

[0044] Comparative Example 3 The only difference between this comparative example and Example 1 is that the acetic acid in step 2) is replaced with an equal amount of hydrochloric acid (31% hydrochloric acid from Guangdong Qiming Chemical Technology Co., Ltd.), while the other raw material components, dosages, and preparation methods are the same as in Example 1.

[0045] The surface of the water-based adhesive film prepared in Comparative Example 3 has a whitening problem, which does not meet the appearance requirements of the film.

[0046] Comparative Example 4 The only difference between this comparative example and Example 1 is that the pre-drying temperature in step 5) is adjusted to 45°C and the secondary drying temperature is adjusted to 85°C. The other raw material components, dosages, and preparation methods are the same as in Example 1.

[0047] In Comparative Example 4, after drying in step 5), the water-resistant functional coating was not completely dried and the coating surface had a whitening problem, which did not meet the appearance requirements of the film to be mounted.

[0048] Comparative Example 5 The only difference between this comparative example and Example 1 is that the pre-drying temperature in step 5) is adjusted to 65°C and the secondary drying temperature is adjusted to 125°C. The other raw material components, dosages, and preparation methods are the same as in Example 1.

[0049] The surface of the water-resistant coating of the water-based adhesive film prepared in Comparative Example 5 has small pits, which does not meet the appearance requirements of the film.

[0050] Performance testing of water-based adhesive laminating film The testing instruments used were: 1) 180° peel force tester: computer-controlled tape tensile testing machine, model AT-980B, accuracy 0.01 N / cm, Dongguan Zhangmutou Autong Instrument Equipment Factory; 2) Initial tack tester: inclined groove ball device as shown in 8.1 of GB / T 4852-2002, accuracy 0.1 cm; 3) Holding power tester: room temperature holding power tester, accuracy 1 s, Dongguan Zhangmutou Autong Instrument Equipment Factory.

[0051] Adhesion performance test methods: 1) Test the 180° peel force according to standard GB / T 2792-2014; 2) Test the initial tack force according to the skew groove rolling ball method in standard GB / T 4852-2002; 3) Test the holding power (12mm x 12mm, 1Kg weight) according to standard GB / T 4851-2014.

[0052] Water resistance whitening test: Apply water-based adhesive film to synthetic paper labels and place them in water at 25°C for a period of time to observe whether whitening or loss of adhesion occurs.

[0053] Transmittance test: The transmittance was tested according to the standard GB / T 2410-2008.

[0054] The performance test results of the water-based laminating films prepared in Examples 1-2 and Comparative Examples 1-2, as well as the ordinary water-based laminating films, are shown in Table 1. The ordinary water-based laminating films are LC82024 (adhesive thickness 5μm) and LC85040 (adhesive thickness 15μm) products from Kaiping Qiyu Adhesive Products Technology Co., Ltd.

[0055] Table 1

[0056] As shown in Table 1, compared with Comparative Examples 1-2 and ordinary water-based laminating films, the water-based laminating films prepared in the embodiments of the present invention have significantly better water-whitening resistance; they also have good adhesion properties.

[0057] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the embodiments described. Those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of the present invention, and these equivalent modifications or substitutions are all included within the scope defined by the claims of this application.

Claims

1. A water-based adhesive laminating film, characterized in that, The material comprises a base film, a water-resistant functional coating, and a water-based water-resistant pressure-sensitive adhesive layer. The water-resistant functional coating is disposed on one surface of the base film, and the water-based water-resistant pressure-sensitive adhesive layer is disposed on the other opposite surface of the base film. By mass, the raw material components of the water-resistant functional coating include 35-40 parts of organic solvent, 12-20 parts of acrylic resin, 1-2 parts of organosilane A, 1-2 parts of organosilane B, and 0.1-0.2 parts of organic acid catalyst. The organosilane A includes tetraethoxysilane, and the organosilane B includes 3-methacryloyloxypropyltrimethoxysilane and / or 3-acryloyloxypropyltrimethoxysilane.

2. The water-based adhesive laminating film according to claim 1, characterized in that, The raw material components of the water-resistant functional coating also include 0.2-0.3 parts of defoamer, 0.2-0.3 parts of flow control agent, 0.4-0.6 parts of pH adjuster, and 25-30 parts of water.

3. The water-based adhesive laminating film according to claim 1, characterized in that, The organic solvent includes anhydrous ethanol; and / or the organic acid catalyst includes one or both of formic acid and acetic acid.

4. The water-based adhesive laminating film according to claim 1, characterized in that, The thickness of the water-resistant functional coating is 1-3 μm.

5. The water-based adhesive laminating film according to claim 1, characterized in that, The thickness of the water-based water-resistant pressure-sensitive adhesive layer is 5-15 μm.

6. The water-based adhesive laminating film according to claim 1, characterized in that, The thickness of the base film is 19-35 μm.

7. A method for preparing an aqueous adhesive laminating film as described in any one of claims 1-6, characterized in that, Includes the following steps: The raw material components of the water-resistant functional coating are mixed and reacted to obtain the water-resistant functional coating liquid; The water-resistant functional coating is applied to one surface of the base film, pre-dried, and then dried a second time to form a water-resistant functional coating. The pre-drying temperature is 50-60℃ and the pre-drying time is 30-40s. The secondary drying temperature is 90-120℃ and the secondary drying time is 30-40s. A water-based water-resistant pressure-sensitive adhesive is coated on the other opposite surface of the base film and dried to form a water-based water-resistant pressure-sensitive adhesive layer, thus obtaining the water-based adhesive film.

8. The preparation method according to claim 7, characterized in that, Before coating, the two surfaces of the base film are pre-treated with plasma activation, and the surface dyne value after treatment is 40-45.

9. The preparation method according to claim 7, characterized in that, The specific preparation process of the water-resistant functional coating liquid includes the following steps: S1. Mix the organic solvent, a portion of the acrylic resin, organosilane A and organosilane B to obtain mixture A; S2. Mix water and organic acid catalyst to obtain mixture B; S3. Mix mixture A and mixture B, react, then add the remaining acrylic resin, stir, and then add defoamer, flow control agent and pH adjuster to adjust the pH value of the system to neutral or weakly alkaline to obtain the water-resistant functional coating.

10. The application of a water-based adhesive laminating film as described in any one of claims 1-6 in the coating of labels and packaging materials.

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