UV (ultraviolet) visbreaking acid-resistant adhesive tape for thinning flexible glass and preparation process of UV visbreaking acid-resistant adhesive tape

Abstract

The invention relates to the technical field of adhesive tapes, and particularly discloses a UV (ultraviolet) visbreaking anti-acid adhesive tape for thinning flexible glass and a preparation process of the UV visbreaking anti-acid adhesive tape. A UV viscosity-reducing acid-resistant adhesive tape for thinning flexible glass comprises a base material layer, a pressure-sensitive adhesive layer and a release film layer which are stacked in sequence, and the pressure-sensitive adhesive layer is prepared from the following raw materials: 85-120 parts by mass of an acrylate copolymer, 3-5 parts by mass of a cross-linking agent, 1.5-2.5 parts by mass of a photoinitiator, 2-5 parts by mass of an acid-resistant nano filler and 0.2-0.4 part by mass of an amine catalyst; the acrylate copolymer is prepared from the following raw materials in parts by mass: 20-30 parts of an imidazolinyl-containing monomer, 15-25 parts of a large-steric-hindrance alkyl-containing monomer, 45-55 parts of a flexible monomer and 5-10 parts of a carboxyl-containing monomer. The UV visbreaking acid-resistant agent prepared by the invention has relatively good acid resistance and reliable UV visbreaking and high initial bonding balance.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of adhesive tapes, in particular to a UV debonding acid-resistant adhesive tape for flexible glass thinning and a preparation process thereof. BACKGROUND

[0002] In the glass thinning process, mixed acid such as nitric acid, hydrofluoric acid and hydrochloric acid is used to corrode the glass, and an acid-resistant film is used to paste and seal the surface that does not need to be thinned, and the surface that needs to be thinned is chemically thinned from 200 μm to 30-50 μm through acid spraying. The existing protective adhesive tape or acid-resistant film faces two major challenges in the thinning process of ultra-thin flexible glass: firstly, it is difficult to maintain stable adhesion and integrity in a strong acid (especially hydrofluoric acid) environment for a long time, and acid penetration easily leads to failure of protection and corrosion of the glass; secondly, ordinary acid-resistant adhesive tapes rely on a highly cross-linked dense structure to achieve acid resistance, and it is difficult to achieve non-damage and low-stress peeling from the ultra-thin glass with extremely low mechanical strength after the thinning is completed.

[0003] The patent application file with the publication number CN111793449A discloses a UV-cured thermal debonding adhesive layer composition, the raw materials of which include: (I) an acrylic resin; (II) thermal expansion microspheres, accounting for 6.5-16.6 wt% of the acrylic resin; (III) a polymerization initiator, accounting for 0.1-2.5 wt% of the acrylic resin; wherein the acrylic resin (c) is an acrylic monomer without active groups, with a weight average molecular weight of 200-800 g / mol; (d) an acrylic monomer with active groups, with a weight average molecular weight of 150-650 g / mol, and (e) diisocyanate, which are formed by these raw materials. The active groups are reactive group structures.

[0004] In this technical solution, the acrylic resin with different weight average molecular weights and the thermal expansion microspheres are the core system, and the density of the structure is insufficient, which is specifically due to: firstly, the acrylic resin is composed of low molecular weight monomers, which can promote rapid cross-linking, but the formed molecular chain segments are short, and the three-dimensional network structure constructed has a large number of local pores and defects; secondly, the acrylic monomer without active groups in the formula can only rely on physical entanglement, and lacks stable chemical cross-linking, further aggravating the looseness of the network structure; thirdly, the thermal expansion microspheres as the key component for debonding are micrometer-level structures, which are much larger than the nanometer-level resin molecular chains, and it is difficult to achieve close interface bonding and effective space filling, which essentially introduces more structural porosity. This structural density deficiency directly leads to the lack of acid resistance. SUMMARY

[0005] In order to overcome the acid resistance defects directly caused by the insufficient compactness of the existing adhesive tape structure, and balance the initial high adhesion and the later UV adhesion reduction technical problems, the application provides a UV adhesion reduction acid-resistant adhesive tape for flexible glass thinning and a preparation process thereof.

[0006] In a first aspect, the application provides a UV adhesion reduction acid-resistant adhesive tape for flexible glass thinning, which adopts the following technical scheme: A UV adhesion reduction acid-resistant adhesive tape for flexible glass thinning comprises a substrate layer, a pressure-sensitive adhesive layer and a release film layer stacked in sequence, and the pressure-sensitive adhesive layer is prepared from the following raw materials: 85-120 parts by mass of an acrylate copolymer, 3-5 parts by mass of a crosslinking agent, 1.5-2.5 parts by mass of a photoinitiator, 2-5 parts by mass of an acid-resistant nano filler and 0.2-0.4 parts by mass of an amine catalyst; The acrylate copolymer is prepared from 20-30 parts by mass of an imidazoline group-containing monomer, 15-25 parts by mass of a large steric alkyl group-containing monomer, 45-55 parts by mass of a flexible monomer and 5-10 parts by mass of a carboxyl group-containing monomer.

[0007] In the technical scheme, a specific acrylate copolymer is used as the basis, a dense covalent network is formed by reaction with a crosslinking agent, and a stable foundation for resisting acid liquid erosion is constructed. The large steric alkyl group monomer serves as a physical toughening unit, and its bulky side group effectively prevents excessive close packing of polymer chains through steric hindrance effect, thereby introducing static free volume into the system. The flexible monomer serves as a kinetic adjustment unit, and the excellent chain segment movement ability provided by its long chain structure provides a kinetic channel for the migration and diffusion of free radicals after UV irradiation, thereby achieving a sharp drop in adhesion. In addition, the acid-resistant nano filler is uniformly dispersed in the polymer network, and plays a physical barrier role, further delaying the penetration path of the acid liquid.

[0008] In a second aspect, the application provides a preparation method of a UV adhesion reduction acid-resistant adhesive tape for flexible glass thinning, which comprises the following steps: S1: adding an acrylate copolymer mixed solution with a solid content of 85-120 parts by mass into a reactor, then adding 3-5 parts by mass of a crosslinking agent, 1.5-2.5 parts by mass of a photoinitiator, 2-5 parts by mass of an acid-resistant nano filler and 0.2-0.4 parts by mass of an amine catalyst, and mixing uniformly to obtain a uniform glue solution; S2: coating the uniform glue solution on a substrate layer, drying and curing to obtain a pressure-sensitive adhesive layer; S3: compounding a release film layer on the pressure-sensitive adhesive layer, and winding to obtain a UV adhesion reduction acid-resistant adhesive tape.

[0009] Preferably, in step S2, the drying and curing specifically comprises: a first zone of 60-70℃ for 3-5min; a second zone of 80-90℃ for 3-5min; and a third zone of 110-120℃ for 3-5min.

[0010] In the technical solution, the mixing stage uniformly disperses the components, avoids local defects, and regulates the concentration of the uniform glue solution; the drying and curing stage regulates the temperature and time, triggers the pre-crosslinking to form a preliminary dense structure, and controls the glue layer thickness to ensure the UV light penetration efficiency; and the compounding stage uses a low-surface-energy release film to ensure smooth release and protect the glue layer surface, maintaining the initial bonding stability.

[0011] Preferably, in step S1, the acrylic ester copolymer mixed solution with a solid content of 85-120 parts by mass is added to a reactor, 3-5 parts by mass of a crosslinking agent, 1.5-2.5 parts by mass of a photoinitiator, and 2-5 parts by mass of an acid-resistant nano filler are added and uniformly mixed, then 0.2-0.4 parts by mass of an amine catalyst is added and uniformly mixed to obtain a uniform glue solution.

[0012] Preferably, the preparation method of the acrylic ester copolymer mixed solution comprises the following steps: Under an inert atmosphere, 20-30 parts by mass of an imidazoline group-containing monomer, 15-25 parts by mass of a large steric alkyl group-containing monomer, 45-55 parts by mass of a flexible monomer, 5-10 parts by mass of a carboxyl-containing monomer, an initiator, and an organic solvent are uniformly mixed, heated to 60-80℃, and reacted for 4-6h, and then concentrated to obtain the acrylic ester copolymer mixed solution.

[0013] Preferably, in the acrylic ester copolymer mixed solution, the mass fraction of the acrylic ester copolymer is 30%-40%.

[0014] Preferably, the organic solvent comprises ethyl acetate and toluene, and the mass ratio of the ethyl acetate to the toluene is 1:(1-2).

[0015] Preferably, the imidazoline group-containing monomer is 2-methyl-2-propenoic acid-2-(2-oxo-1-imidazolinyl) ethyl ester.

[0016] Preferably, the flexible monomer is a long-chain alkyl acrylate with a carbon atom number of no less than 12.

[0017] Further preferably, the flexible monomer is selected from any one of lauryl acrylate and stearyl acrylate.

[0018] Preferably, the large steric alkyl group-containing monomer is selected from any one of 1,3-dimethyladamantyl acrylate and isobornyl methacrylate.

[0019] Preferably, the carboxyl-containing monomer is at least one of methacrylic acid and acrylic acid.

[0020] In the technical solution, the acid-resistant skeleton is constructed by using the imidazoline group-containing monomer, the synergistic effect of the large steric alkyl group-containing monomer and the flexible monomer is utilized, and the synergistic effect of each component is strengthened by using the small molecule carboxyl-containing monomer; the static free volume for maintaining toughness and the dynamic free volume for realizing UV viscosity reduction are simultaneously introduced into the polymer network, and finally the unification of the material acid erosion resistance and the controllable peeling is realized at the molecular level.

[0021] Preferably, the acid-resistant nano filler is a silanized nano filler.

[0022] Preferably, the preparation method of the silanized nano filler comprises the following steps: The nano filler is uniformly dispersed in an ethanol aqueous solution, a silane coupling agent is added and uniformly mixed, the pH is adjusted to 4-5, the temperature is raised to 50-70 DEG C, the reaction is carried out for 3-5 hours, cooling, solid-liquid separation, washing, and drying to obtain the silanized nano filler.

[0023] Preferably, the mass ratio of the nano filler, the silane coupling agent and the ethanol aqueous solution is 15: (2-4): (96-98).

[0024] Preferably, the silane coupling agent is an epoxy silane coupling agent.

[0025] Further preferably, the silane coupling agent is silane coupling agent KH560.

[0026] Preferably, the silanized nano filler is selected from at least one of silanized nano cerium dioxide and silanized nano barium sulfate.

[0027] Further preferably, the silanized nano filler is silanized nano cerium dioxide with a particle size of 10-30 nm.

[0028] In the technical solution, the nano cerium dioxide can be closely embedded in the polymer network due to its stable chemical properties and high surface energy, and physically blocks the penetration and diffusion of acid liquor.

[0029] Preferably, the crosslinking agent is selected from at least one of isocyanuric acid triglycidyl ester and dioxazoline.

[0030] In the technical solution, the isocyanuric acid triglycidyl ester contains multiple epoxy groups, providing a rigid skeleton with high crosslinking density, while the dioxazoline forms a flexible and hydrolysis-resistant crosslinking point, and this rigid and flexible composite network can more effectively resist the penetration and swelling of acid liquor, and at the same time endows the adhesive layer with excellent toughness, significantly improving the durability and reliability of the adhesive tape in long-term acid erosion environment.

[0031] Preferably, the amine catalyst is N,N-dimethylbenzylamine.

[0032] Preferably, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone.

[0033] Preferably, the substrate layer is a polyolefin film.

[0034] Further preferably, the substrate layer is a polyethylene film with a thickness of 40-60 microns.

[0035] Preferably, the release film is a fluorine release film with a thickness of 50-75 microns.

[0036] Preferably, the fluorine release film has a release force of 3-5 g / in.

[0037] Preferably, the pressure-sensitive adhesive layer has a thickness of 20-40 microns.

[0038] Preferably, the pressure-sensitive adhesive layer further comprises 0.5-1 parts by mass of an antioxidant and 0.1-0.5 parts by mass of a light stabilizer.

[0039] Preferably, the pressure-sensitive adhesive layer further comprises 5-15 parts by mass of a hydrogenated terpene resin.

[0040] Preferably, in step S1, after the acid-resistant nano-filler is added, the process further comprises the steps of adding 0.5-1 parts by mass of an antioxidant and 0.1-0.5 parts by mass of a light stabilizer.

[0041] Preferably, in step S1, after the acrylic ester copolymer mixture is added, the process further comprises the step of adding 5-15 parts by mass of a hydrogenated terpene resin.

[0042] In the present technical solution, the hydrogenated terpene resin, through its unique modulus adjustment behavior, synergistically improves the initial bonding strength and promotes the interface peeling after UV irradiation.

[0043] In summary, the present application has the following beneficial effects: The present application adopts the synergistic effect of a specific acrylic ester copolymer, a crosslinking agent, and an acid-resistant nano-filler to construct a dense composite structure with rigid backbone and flexible segment. The rigid heterocycle containing imidazoline-based monomer, the dense network of the crosslinking agent, and the acid-resistant nano-filler synergistically form a triple protection against acid erosion; meanwhile, the static free volume created by the bulky alkyl monomer and the dynamic segment motion realized by the flexible monomer are combined to ensure the conversion of the adhesive tape from firm bonding to fast and clean peeling. DETAILED DESCRIPTION

[0044] The present application is further described below in conjunction with examples.

[0045] The raw materials of the examples and comparative examples of the present application are all ordinary commercially available, except for special instructions.

[0046] Preparation Example 1~3 Acrylate copolymer Preparation Example 1 The preparation method of the acrylate copolymer of the present preparation example comprises the following steps: Under the nitrogen atmosphere, 2-methyl-2-acrylate-2-(2-oxo-1-imidazolinyl) ethyl ester 40 g, 1,3-dimethyl adamantyl acrylate 30 g, lauryl acrylate 90 g, acrylic acid 10 g, azobisisobutyronitrile 1.7 g and organic solvent 450 g were stirred and mixed uniformly, transferred to a reaction container, warmed to 60℃, stirred for 6h, and then concentrated by reduced pressure distillation at 80℃ to obtain an acrylate copolymer mixture with a mass fraction of 30%.

[0047] The organic solvent comprises ethyl acetate and toluene, and the mass ratio of ethyl acetate to toluene is 1:1.

[0048] Preparation Example 2 The preparation method of the acrylate copolymer of the present preparation example comprises the following steps: Under the nitrogen atmosphere, 2-methyl-2-acrylate-2-(2-oxo-1-imidazolinyl) ethyl ester 40 g, 1,3-dimethyl adamantyl acrylate 30 g, lauryl acrylate 90 g, acrylic acid 10 g, azobisisobutyronitrile 1.7 g and organic solvent 450 g were stirred and mixed uniformly, transferred to a reaction container, warmed to 60℃, stirred for 6h, and then concentrated by reduced pressure distillation at 80℃ to obtain an acrylate copolymer mixture with a mass fraction of 30%.

[0049] The organic solvent comprises ethyl acetate and toluene, and the mass ratio of ethyl acetate to toluene is 1:2.

[0050] Preparation Example 3 The preparation method of the acrylate copolymer of the present preparation example comprises the following steps: Under the nitrogen atmosphere, 2-methyl-2-acrylate-2-(2-oxo-1-imidazolinyl) ethyl ester 40 g, 1,3-dimethyl adamantyl acrylate 30 g, lauryl acrylate 90 g, acrylic acid 10 g, azobisisobutyronitrile 1.7 g and organic solvent 450 g were stirred and mixed uniformly, transferred to a reaction container, warmed to 60℃, stirred for 6h, and then concentrated by reduced pressure distillation at 80℃ to obtain an acrylate copolymer mixture with a mass fraction of 30%.

[0051] The organic solvent comprises ethyl acetate and toluene, and the mass ratio of ethyl acetate to toluene is 1:1.5.

[0052] Preparation Example 4~6 Preparation Example 4 The preparation method of the silanized nano filler of the present preparation example comprises the following steps: 15g of nano barium sulfate was added into 98g of an ethanol aqueous solution, and was transferred into an ultrasonic device. The ultrasonic treatment was performed at a power of 300W and a frequency of 20KHz for 30min. Then, 2g of silane coupling agent KH560 was added, and was stirred and mixed uniformly at a rotating speed of 200r / min. After that, a 5% acetic acid solution was used to adjust the pH to 5, and the temperature was increased to 50℃. The stirring reaction was performed for 5h. After filtration, the product was washed with deionized water for 3 times, and was dried at 80℃ until the constant weight was reached, so as to obtain the silanized nano filler.

[0053] The particle size distribution of the nano barium sulfate is 20-40nm. The volume ratio of ethanol to water in the ethanol aqueous solution is 9:1.

[0054] Preparation Example 5 The preparation method of the silanized nano filler of the present preparation example comprises the following steps: 10g of nano barium sulfate and 5g of nano cerium dioxide were added into 97g of an ethanol aqueous solution, and were transferred into an ultrasonic device. The ultrasonic treatment was performed at a power of 300W and a frequency of 20KHz for 30min. Then, 3g of silane coupling agent KH560 was added, and was stirred and mixed uniformly at a rotating speed of 200r / min. After that, a 5% acetic acid solution was used to adjust the pH to 4.5, and the temperature was increased to 70℃. The stirring reaction was performed for 3h. After filtration, the product was washed with deionized water for 3 times, and was dried at 80℃ until the constant weight was reached, so as to obtain the silanized nano filler.

[0055] The particle size distribution of the nano barium sulfate is 20-40nm. The particle size distribution of the nano cerium dioxide is 10-30nm. The volume ratio of ethanol to water in the ethanol aqueous solution is 8:1.

[0056] Preparation Example 6 The preparation method of the silanized nano filler of the present preparation example comprises the following steps: 15g of nano cerium dioxide was added into 96g of an ethanol aqueous solution, and was transferred into an ultrasonic device. The ultrasonic treatment was performed at a power of 300W and a frequency of 20KHz for 30min. Then, 4g of silane coupling agent KH560 was added, and was stirred and mixed uniformly at a rotating speed of 200r / min. After that, a 5% acetic acid solution was used to adjust the pH to 4, and the temperature was increased to 60℃. The stirring reaction was performed for 4h. After filtration, the product was washed with deionized water for 3 times, and was dried at 80℃ until the constant weight was reached, so as to obtain the silanized nano filler.

[0057] The particle size distribution of the nano cerium dioxide is 10-30nm. The volume ratio of ethanol to water in the ethanol aqueous solution is 8:1.

[0058] Example 1 The flexible glass thinning UV adhesion-reducing acid-resistant tape of the embodiment comprises a substrate layer, a pressure-sensitive adhesive layer and a release film layer which are sequentially stacked, and the pressure-sensitive adhesive layer is prepared from the following raw materials by mass fraction: acrylate copolymer 85 g, crosslinking agent 3 g, photoinitiator 1.5 g, acid-resistant nano filler 2 g, N,N-dimethylbenzylamine 0.2 g.

[0059] Among them, the acrylate copolymer is from the acrylate copolymer mixed solution in Preparation Example 1; the crosslinking agent is trioxantriazine glycidyl ester; the photoinitiator is 1-hydroxy cyclohexyl phenyl ketone; and the acid-resistant nano filler is from Preparation Example 4.

[0060] The preparation method of the flexible glass thinning UV adhesion-reducing acid-resistant tape of the embodiment comprises the following steps: S1: 283.3 g of acrylate copolymer mixed solution (about 85 g of acrylate copolymer) is added to a reactor, the stirring device is turned on, the rotating speed is 300 r / min, 3 g of crosslinking agent, 1.5 g of photoinitiator, 2 g of acid-resistant nano filler are sequentially added, and stirred and mixed for 35 min, then 0.2 g of N,N-dimethylbenzylamine is added, and the stirring and mixing is continued for 10 min to obtain a uniform glue solution; S2: the uniform glue solution is roll-coated on the substrate layer, then a one-zone temperature of 70°C for 3 min, a two-zone temperature of 90°C for 3 min, and a three-zone temperature of 120°C for 3 min are set, and a pressure-sensitive adhesive layer is obtained; S3: a release film layer is compounded on the pressure-sensitive adhesive layer, and then wound to obtain a UV adhesion-reducing acid-resistant tape.

[0061] Among them, the solid content of the uniform glue solution is about 32%; and the thickness of the pressure-sensitive adhesive layer is about 20 μm; The substrate layer is a polyethylene film with a thickness of 40 μm; The release film is a fluorine release film with a thickness of 50 μm and a release force of about 3-5 g / in.

[0062] Example 2 The flexible glass thinning UV adhesion-reducing acid-resistant tape of the embodiment comprises a substrate layer, a pressure-sensitive adhesive layer and a release film layer which are sequentially stacked, and the pressure-sensitive adhesive layer is prepared from the following raw materials by mass fraction: acrylate copolymer 120 g, crosslinking agent 5 g, photoinitiator 2.5 g, acid-resistant nano filler 5 g, antioxidant 1010 1 g, light stabilizer UV-944 0.5 g, N,N-dimethylbenzylamine 0.4 g.

[0063] Among them, the acrylate copolymer is from the acrylate copolymer mixed solution in Preparation Example 2; the crosslinking agent is trioxantriazine glycidyl ester; the photoinitiator is 1-hydroxy cyclohexyl phenyl ketone; and the acid-resistant nano filler is from Preparation Example 5.

[0064] The preparation method of the flexible glass thinning UV adhesion-reducing acid-resistant adhesive tape of the embodiment comprises the following steps: S1: 300g of the acrylate copolymer mixed solution (about 120g of acrylate copolymer) is added to a reactor, the stirring device is turned on at a speed of 300r / min, 5g of crosslinking agent, 2.5g of photoinitiator, 5g of acid-resistant nano filler, 1g of antioxidant 1010, and 0.5g of light stabilizer UV-944 are sequentially added, and stirring and mixing are performed for 50min, then 0.4g of N,N-dimethylbenzylamine is added, and stirring and mixing are continuously performed for 10min to obtain a uniform glue solution; S2: The uniform glue solution is roll-coated on a substrate layer, then a first zone at 60℃ for 5min, a second zone at 80℃ for 5min, and a third zone at 110℃ for 5min are set, and a pressure-sensitive adhesive layer is obtained; S3: A release film layer is compounded on the pressure-sensitive adhesive layer, and winding is performed to obtain the UV adhesion-reducing acid-resistant adhesive tape.

[0065] The solid content of the uniform glue solution is about 43%, and the thickness of the pressure-sensitive adhesive layer is about 40μm; The substrate layer is a polyethylene film with a thickness of 60μm; The release film is a fluorine release film with a thickness of 75μm and a release force of about 3~5g / in.

[0066] Embodiment 3 The UV adhesion-reducing acid-resistant adhesive tape for flexible glass thinning of the embodiment comprises a substrate layer, a pressure-sensitive adhesive layer, and a release film layer which are sequentially stacked, and the pressure-sensitive adhesive layer is prepared from the following raw materials by mass fraction: 100g of acrylate copolymer, 4g of crosslinking agent, 2g of photoinitiator, 3.5g of acid-resistant nano filler, 0.5g of antioxidant 1010, 0.1g of light stabilizer UV-944, and 0.3g of N,N-dimethylbenzylamine.

[0067] The acrylate copolymer is from the acrylate copolymer mixed solution in the preparation example 3; the crosslinking agent is trioxan triglycidyl ester; the photoinitiator is 1-hydroxycyclohexyl phenyl ketone; and the acid-resistant nano filler is from the preparation example 6.

[0068] The preparation method of the UV adhesion-reducing acid-resistant adhesive tape for flexible glass thinning of the embodiment comprises the following steps: S1: 285.7g of the acrylate copolymer mixed solution (about 100g of acrylate copolymer) is added to a reactor, the stirring device is turned on at a speed of 300r / min, 4g of crosslinking agent, 2g of photoinitiator, 3.5g of acid-resistant nano filler, 0.5g of antioxidant 1010, and 0.1g of light stabilizer UV-944 are sequentially added, and stirring and mixing are performed for 45min, then 0.3g of N,N-dimethylbenzylamine is added, and stirring and mixing are continuously performed for 10min to obtain a uniform glue solution; S2: roll coating the uniform glue liquid on the substrate layer, then at a first zone 60℃ for 4min, a second zone 80℃ for 4min, and a third zone 110℃ for 4min, to obtain the pressure-sensitive adhesive layer; S3: laminating the release film layer on the pressure-sensitive adhesive layer, and winding to obtain the UV adhesion-reducing acid-resistant adhesive tape.

[0069] The solid content of the uniform glue liquid is about 37%, and the thickness of the pressure-sensitive adhesive layer is about 30μm. The substrate layer is a polyethylene film with a thickness of 50μm. The release film is a fluorine release film with a thickness of 75μm and a release force of about 3-5g / in.

[0070] Example 4 The UV adhesion-reducing acid-resistant adhesive tape for thinning flexible glass in this example comprises a substrate layer, a pressure-sensitive adhesive layer and a release film layer which are sequentially stacked, and the pressure-sensitive adhesive layer is prepared from the following raw materials by mass: 100g of the acrylate copolymer, 5g of the hydrogenated terpene resin, 4g of the crosslinking agent, 2g of the photoinitiator, 3.5g of the acid-resistant nano-filler, 0.5g of the antioxidant 1010, 0.3g of the light stabilizer UV-944, and 0.3g of N,N-dimethylbenzylamine.

[0071] The acrylate copolymer is from the acrylate copolymer mixed solution in the preparation example 3; the crosslinking agent is 4g, which comprises 3g of isocyanuric acid triglycidyl ester and 1g of dioxazoline; the photoinitiator is 1-hydroxycyclohexyl phenyl ketone; and the acid-resistant nano-filler is from the preparation example 5.

[0072] The preparation method of the UV adhesion-reducing acid-resistant adhesive tape for thinning flexible glass in this example comprises the following steps: S1: 285.7g of the acrylate copolymer mixed solution (about 100g of the acrylate copolymer) is added into a reactor, the stirring device is turned on at a speed of 300r / min, 5g of the hydrogenated terpene resin, 4g of the crosslinking agent, 2g of the photoinitiator, 3.5g of the acid-resistant nano-filler, 0.5g of the antioxidant 1010, 0.3g of the light stabilizer UV-944 are sequentially added, and stirred and mixed for 45min, then 0.3g of N,N-dimethylbenzylamine is added, and the stirring and mixing is continued for 10min to obtain a uniform glue liquid; S2: roll coating the uniform glue liquid on the substrate layer, then at a first zone 60℃ for 4min, a second zone 80℃ for 4min, and a third zone 110℃ for 4min, to obtain the pressure-sensitive adhesive layer; S3: laminating the release film layer on the pressure-sensitive adhesive layer, and winding to obtain the UV adhesion-reducing acid-resistant adhesive tape.

[0073] The solid content of the uniform glue liquid is about 37%, and the thickness of the pressure-sensitive adhesive layer is about 30μm. The substrate layer is a polyethylene film with a thickness of 50μm. The release film is a fluorine release film, with a thickness of 75 μm and a release force of about 3-5 g / in.

[0074] Example 5 The difference between this example and Example 4 is that: The amount of hydrogenated terpene resin used is 15 g; The rest is the same as Example 4.

[0075] Comparative Example 1 The difference between this comparative example and Example 1 is that: The preparation method of the acrylate copolymer of this preparation example comprises the following steps: Under a nitrogen atmosphere, methyl methacrylate 40 g, isobornyl methacrylate 30 g, lauryl acrylate 90 g, acrylic acid 10 g, azobisisobutyronitrile 1.7 g and organic solvent 450 g are stirred and mixed uniformly, transferred to a reaction container, heated to 60°C, stirred for 6 h, and then concentrated by reduced pressure distillation at 80°C to obtain an acrylate copolymer mixture with a mass fraction of 30%.

[0076] The organic solvent includes ethyl acetate and toluene, and the mass ratio of ethyl acetate to toluene is 1:1.

[0077] The rest is the same as Example 1.

[0078] Comparative Example 2 The difference between this comparative example and Example 1 is that: The preparation method of the acrylate copolymer of this preparation example comprises the following steps: Under a nitrogen atmosphere, 2-methyl-2-acrylic acid-2-(2-oxo-1-imidazolinyl) ethyl ester 40 g, methyl methacrylate 30 g, lauryl acrylate 90 g, acrylic acid 10 g, azobisisobutyronitrile 1.7 g and organic solvent 450 g are stirred and mixed uniformly, transferred to a reaction container, heated to 60°C, stirred for 6 h, and then concentrated by reduced pressure distillation at 80°C to obtain an acrylate copolymer mixture with a mass fraction of 30%.

[0079] The organic solvent includes ethyl acetate and toluene, and the mass ratio of ethyl acetate to toluene is 1:1.

[0080] The rest is the same as Example 1.

[0081] Comparative Example 3 The difference between this comparative example and Example 1 is that: No acid-resistant nano-filler is added.

[0082] The rest is the same as Example 1.

[0083] Performance detection test The UV adhesion-reducing acid-resistant tapes prepared from Examples 1-5 and Comparative Examples 1-3 were uniformly cut to prepare standard samples, which were then subjected to the following performance tests, and the test results are shown in Table 1.

[0084] Acid resistance: According to the actual working conditions of flexible glass thinning, a mixed acid etching solution (HF 5%, HNO315%, HCl 10%, and the rest deionized water) was prepared. The tape sample was attached to a clean glass substrate and placed in a constant temperature environment at (50±2) °C. A spraying device was used to continuously spray the surface of the tape for 200 min. During the spraying process, whether the tape edge was raised, blistered, or peeled off was observed. Thickness uniformity test: A high-precision thickness gauge was used to measure 10 points on each sample, and the standard deviation of the thickness was calculated. Initial bonding strength: A 25 mm wide tape was attached to an alkali-free glass, and a 180° peeling test was performed at a speed of 300 mm / min according to GB / T 2792-2014 standard. The strength value (unit: N / 25 mm) was recorded. UV adhesion-reducing performance: The sample was irradiated with a UV lamp with a wavelength of 365 nm and an intensity of 100 mW / cm 2 for a total dose of 500 mJ / cm 2 . The 180° peeling force was tested immediately after irradiation and recorded as the UV post-irradiation peeling force.

[0085] Table 1 Performance test of UV adhesion-reducing acid-resistant tapes prepared from Examples 1-5 and Comparative Examples 1-3

[0086] As can be seen from Examples 1 and Comparative Examples 1-3, the acrylate copolymer and acid-resistant nanofiller used in the present application form an indispensable synergistic acid-resistant system. Although the initial bonding strength of Comparative Example 1 and Comparative Example 3 is better than that of some examples, their acid resistance has completely failed, proving that the imidazoline group-containing monomer is the basis for building an acid-resistant chemical skeleton; the large steric alkyl monomer is the key to maintaining the toughness and crack resistance of the adhesive layer; and the physical barrier effect of the acid-resistant nanofiller is indispensable for delaying acid liquid penetration.

[0087] As can be seen from Examples 1-5, by synergistic copolymerization of imidazoline group-containing monomers, large steric alkyl monomers, and flexible long-chain monomers, a polymer network with rigid skeleton and moderate free volume is constructed. While the network forms a dense covalent structure with the crosslinking agent to resist acid liquid erosion, the inherent flexible segments provide a key reaction space for UV light-triggered secondary crosslinking and adhesion reduction. In addition, the introduction of hydrogenated terpene resin effectively improves the initial bonding strength of the system without compromising the overall acid resistance and UV adhesion-reducing performance.

[0088] The embodiments are only illustrative of the present application, and are not intended to limit the present application, and those skilled in the art can make modifications to the embodiments without creative contribution after reading the specification, but as long as the modifications are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A flexible glass thinning UV-debonding acid-resistant tape, characterized by, The UV anti-adhesion acid-resistant adhesive tape comprises a substrate layer, a pressure-sensitive adhesive layer and a release film layer which are sequentially stacked, and the pressure-sensitive adhesive layer is prepared from the following raw materials: 85-120 parts by mass of an acrylate copolymer, 3-5 parts by mass of a crosslinking agent, 1.5-2.5 parts by mass of a photoinitiator, 2-5 parts by mass of acid-resistant nano-filler and 0.2-0.4 parts by mass of an amine catalyst; The acrylate copolymer is prepared from the following raw materials: 20-30 parts by mass of an imidazoline group-containing monomer, 15-25 parts by mass of a large steric alkyl group-containing monomer, 45-55 parts by mass of a flexible monomer and 5-10 parts by mass of a carboxyl group-containing monomer.

2. A method of making a flexible glass thinning UV-debonding acid-resistant tape according to claim 1, characterized in that, The method comprises the following steps: S1: adding an acrylate copolymer mixed solution with a solid content of 85-120 parts by mass into a reactor, and then adding 3-5 parts by mass of a crosslinking agent, 1.5-2.5 parts by mass of a photoinitiator, 2-5 parts by mass of acid-resistant nano-filler and 0.2-0.4 parts by mass of an amine catalyst, and mixing them uniformly to obtain a uniform glue solution; S2: coating the uniform glue solution on a substrate layer, drying and curing to obtain a pressure-sensitive adhesive layer; S3: combining a release film layer on the pressure-sensitive adhesive layer, and winding to obtain a UV anti-adhesion acid-resistant adhesive tape.

3. The method of making a flexible glass thinning UV-debonding acid-resistant tape according to claim 2, wherein, The preparation method of the acrylate copolymer mixed solution comprises the following steps: In an inert atmosphere, 20-30 parts by mass of an imidazoline group-containing monomer, 15-25 parts by mass of a large steric alkyl group-containing monomer, 45-55 parts by mass of a flexible monomer, 5-10 parts by mass of a carboxyl group-containing monomer, an initiator and an organic solvent are mixed uniformly, heated to 60-80℃, reacted for 4-6 hours, and concentrated to obtain an acrylate copolymer mixed solution.

4. The method of making a flexible glass thinning UV-debonding acid-resistant tape according to claim 3, wherein, The imidazoline group-containing monomer is 2-methyl-2-acrylic acid-2-(2-oxo-1-imidazolinyl) ethyl ester.

5. The method of making a flexible glass thinning UV-debonding acid-resistant tape according to claim 3, wherein, The flexible monomer is a long-chain alkyl acrylate with a carbon atom number of no less than 12.

6. The method of making a flexible glass thinning UV-debonding acid-resistant tape according to claim 3, wherein, The large steric alkyl group-containing monomer is selected from any one of 1,3-dimethyl adamantyl acrylate and isobornyl methacrylate.

7. The method of making a flexible glass thinning UV-debonding acid-resistant tape according to claim 3, wherein, The carboxyl group-containing monomer is selected from at least one of methacrylic acid and acrylic acid.

8. The method of making a flexible glass thinning UV-debonding acid-resistant tape according to claim 2, wherein, The acid-resistant nano-filler is a silanized nano-filler.

9. The method of making a flexible glass thinning UV-debonding acid-resistant tape according to claim 8, wherein, The silanized nano-filler is selected from at least one of silanized nano-cerium dioxide and silanized nano-barium sulfate.

10. The method of making a flexible glass thinning UV-debonding acid-resistant tape according to claim 2, wherein, In step S1, after the acrylate copolymer mixed solution is added, the step of adding 5-15 parts by mass of a hydrogenated terpene resin is further included.

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