A double-sided high-temperature-resistant and ultra-low-volatile adhesive film for dust-free oven and preparation method thereof

Abstract

The present invention relates to the field of adhesive films, and provides an adhesive film for a dust-free oven with high temperature resistance and ultra-low volatility on both sides and a preparation method thereof, wherein the adhesive film comprises, from top to bottom, a release film layer, a first adhesive layer, a high temperature resistant substrate layer, a second adhesive layer and a release film layer. The adhesive film provided by the present invention has the characteristics of excellent high temperature resistance and oxidation resistance, and can be widely used in high temperature baking devices.

Description

Technical Field

[0001] The present invention relates to the field of adhesive films, and in particular to an adhesive film for a dust-free oven with double-sided high temperature resistance and ultra-low volatility and a preparation method thereof. Background Art

[0002] Double-sided tape is a roll of adhesive tape made of paper, cloth, or plastic film as the base material, with elastomeric pressure-sensitive adhesive or resin-type pressure-sensitive adhesive evenly coated on the above base material. It is generally composed of three parts: base material, adhesive, and release layer. Double-sided tape is widely used and can be applied to many fields such as electronics and electrical appliances.

[0003] High-temperature heating and baking devices, such as ovens, especially high-temperature ovens, are subject to extremely important maintenance. Dust or corrosive substances adhering to the oven will affect the service life of the oven. Therefore, the development of high-temperature resistant double-sided adhesive films that can be used in ovens has become increasingly important.

[0004] At present, the adhesive part of double-sided tapes is mainly composed of acrylates, which are widely used in the field of double-sided tapes due to their excellent bonding performance and leveling properties and have good application prospects. Although acrylate tapes have the above-mentioned excellent characteristics, there are still some unresolved defects in the acrylate double-sided tapes on the market, such as the problem that acrylates are easy to age and have reduced viscosity at high temperatures; and in order to increase the high temperature resistance of the double-sided tape, some high temperature resistant fillers are often added, such as silicon dioxide, silicon carbide, etc., but these fillers often have the problem of poor dispersion, which leads to the high temperature resistance of the double-sided tape cannot achieve the ideal effect.

[0005] Patent CN 106675461A discloses a glue for double-sided tape and a preparation method thereof. The raw materials are composed of an acrylate prepolymer resin, a curing agent and ethyl acetate, wherein the acrylate prepolymer resin includes the following raw materials: butyl acrylate, isooctyl acrylate, acrylic acid, hydroxyethyl methacrylate, ethyl methacrylate, a tackifying resin and a solvent. The glue has good heat resistance, weather resistance and environmental friendliness. However, it does not mention the problem that acrylate substances may age at high temperatures, resulting in a decrease in viscosity, and there is a hidden danger of poor durability.

[0006] Therefore, there is an urgent need in the market for a dust-free oven adhesive film with excellent high temperature resistance and oxidation resistance. Summary of the invention

[0007] In view of the problems existing in the prior art, the present invention uses acrylic resin and epoxy resin as main components, and then adds fillers, curing agent accelerators, antioxidants and solvents to prepare a first adhesive layer; uses acrylic resin and epoxy resin as main components, and then adds fillers, organic peroxides, antioxidants and solvents to prepare a second adhesive layer; and then the release film layer, the first adhesive layer, the high temperature resistant substrate layer, the second adhesive layer and the release film layer are compounded from top to bottom to form a dust-free oven adhesive film with a five-layer structure, which has excellent high temperature resistance and oxidation resistance.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] On one hand, the present invention provides a double-sided high-temperature resistant and ultra-low-volatile dust-free oven adhesive film, the adhesive film comprising, from top to bottom, a release film layer, a first adhesive layer, a high-temperature resistant substrate layer, a second adhesive layer and a release film layer;

[0010] The first adhesive layer is prepared by the following raw materials in parts by weight: 30-40 parts of acrylic resin, 1-10 parts of epoxy resin, 2-5 parts of filler, 2-10 parts of curing agent accelerator, 1-3 parts of antioxidant, and 40-60 parts of solvent;

[0011] The second adhesive layer is prepared by the following raw materials in parts by weight: 40-60 parts of acrylic resin, 1-10 parts of epoxy resin, 2-5 parts of filler, 2-10 parts of organic peroxide, 1-3 parts of antioxidant, and 40-50 parts of solvent.

[0012] Wherein, the thickness of the release film layer is 50-100µm, the thickness of the first adhesive layer is 10-100µm, the thickness of the second adhesive layer is 10-100µm, and the thickness of the high temperature resistant substrate layer is 10-100µm.

[0013] In some embodiments of the present invention, the polymer used to prepare the release film layer is a thermosetting resin or a light-curing resin;

[0014] The polymer used to prepare the high temperature resistant substrate layer is any one of polyetherimide, polyetherimide, polyamideimide, polyphenylene sulfide and polytetrafluoroethylene.

[0015] Preferably, the polymer used to prepare the release film layer is PET.

[0016] The applicant selected acrylic resin as the main component of the first adhesive layer, and used epoxy resin to improve high temperature resistance, mechanical toughness and cohesion, so as to ensure that the adhesive film has high peel strength, high initial adhesion and high lasting adhesion, and no residual adhesive after peeling; in the second adhesive layer, the applicant selected a relatively large amount of acrylic resin in the first adhesive layer as the main component, so that it has the characteristics of heat resistance, no VOC emission after multiple heating, and easy adsorption of dust and impurities in the oven.

[0017] In some embodiments of the present invention, the acrylic resin includes the following raw materials, measured in parts by weight: 1-2 parts of special acrylic ester monomers, 5-9 parts of ethyl acrylate, 2-5 parts of methyl methacrylate, 9-13 parts of butyl methacrylate, 1-5 parts of butyl acrylate, 0.5-1 parts of acrylic acid, 0.5-1 parts of initiator, and 65-82 parts of organic solvent.

[0018] Wherein, the special acrylate monomer is isotridecyl acrylate or 2-phenoxyethyl acrylate; the initiator is dibenzoyl peroxide or azobisisobutyronitrile; and the organic solvent is ethyl acetate.

[0019] In some embodiments of the present invention, the epoxy resin is one or a combination of two or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydantoin epoxy resin, glycidyl ether epoxy resin, glycidyl amine epoxy resin, and acetourea epoxy resin.

[0020] In some embodiments of the present invention, the method for preparing the filler comprises the following steps:

[0021] Ammonia water, anhydrous ethanol and deionized water are mixed and stirred to obtain an alkaline solution for use; tetraethyl orthosilicate and anhydrous ethanol are mixed, hydroxyethyl chitosan is added, and the solution is added to the alkaline solution after ultrasonic treatment, stirred, and centrifuged; the precipitate is added to deionized water, Tween 20 and silane coupling agent Si69 are added, stirred, centrifuged, washed, and dried to obtain a filler.

[0022] In some embodiments of the present invention, the mass ratio of tetraethyl orthosilicate, hydroxyethyl chitosan, Tween 20 and silane coupling agent Si69 is 1: (0.1-0.3): (0.05-0.15): (0.05-0.15).

[0023] Preferably, the mass ratio of tetraethyl orthosilicate, hydroxyethyl chitosan, Tween 20 and silane coupling agent Si69 is 1:0.2:0.1:0.1.

[0024] Silica has good high temperature resistance and stability. Adding it to the first adhesive layer and the first adhesive layer with acrylic resin as the main component can effectively improve the overall high temperature resistance of the film. However, silica has the problems of easy agglomeration and poor dispersion, which will seriously affect its effect on improving the high temperature resistance of the film.

[0025] The present application selects acrylic resin as the main component of the first adhesive layer, and uses epoxy resin to improve high temperature resistance, mechanical toughness and cohesion, so as to ensure that the adhesive film has high peel strength, high initial adhesion and high lasting adhesion, and no residual adhesive after peeling; in the second adhesive layer, the present application selects acrylic resin with a relatively higher content in the first adhesive layer as the main component, so that it has the characteristics of heat resistance, no VOC emission after multiple heating, and easy adsorption of dust and impurities in the oven.

[0026] In some embodiments of the present invention, the acrylic resin includes the following raw materials, measured in parts by weight: 1-2 parts of special acrylic ester monomers, 5-9 parts of ethyl acrylate, 2-5 parts of methyl methacrylate, 9-13 parts of butyl methacrylate, 1-5 parts of butyl acrylate, 0.5-1 parts of acrylic acid, 0.5-1 parts of initiator, and 65-82 parts of organic solvent.

[0027] Wherein, the special acrylate monomer is isotridecyl acrylate or 2-phenoxyethyl acrylate; the initiator is dibenzoyl peroxide or azobisisobutyronitrile; and the organic solvent is ethyl acetate.

[0028] In some embodiments of the present invention, the epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydantoin epoxy resin, glycidyl ether epoxy resin, glycidyl amine epoxy resin, and acetyl urea epoxy resin.

[0029] In some embodiments of the present invention, the method for preparing the filler comprises the following steps:

[0030] Ammonia water, anhydrous ethanol and deionized water are mixed and stirred to obtain an alkaline solution for use; tetraethyl orthosilicate and anhydrous ethanol are mixed, hydroxyethyl chitosan is added, and the solution is added to the alkaline solution after ultrasonic treatment, stirred, and centrifuged; the precipitate is added to deionized water, Tween 20 and silane coupling agent Si69 are added, stirred, centrifuged, washed, and dried to obtain a filler.

[0031] In some embodiments of the present invention, the mass ratio of tetraethyl orthosilicate, hydroxyethyl chitosan, Tween 20 and silane coupling agent Si69 is 1: (0.1-0.3): (0.05-0.15): (0.05-0.15).

[0032] Preferably, the mass ratio of tetraethyl orthosilicate, hydroxyethyl chitosan, Tween 20 and silane coupling agent Si69 is 1:0.2:0.1:0.1.

[0033] Silica has good high temperature resistance and stability. Adding it to the first adhesive layer and the first adhesive layer with acrylic resin as the main component can effectively improve the overall high temperature resistance of the film. However, silica has the problems of easy agglomeration and poor dispersion, which will seriously affect its effect on improving the high temperature resistance of the film.

[0034] The present application adopts hydroxyethyl chitosan and tetraethyl orthosilicate as raw materials to prepare the product, thereby realizing the modification of silica by hydroxyethyl chitosan. The hydroxyl groups enriched on the surface of hydroxyethyl chitosan can form hydrogen bond complexes with silica, thereby weakening the surface energy of silica, thereby improving the dispersibility of silica; further, the present application selects Tween 20 and silane coupling agent Si69 to jointly modify the above-mentioned hydroxyethyl chitosan-modified silica, which plays a role in synergistically improving the dispersibility and stability of silica.

[0035] In some embodiments of the present invention, the curing agent accelerator includes one or more of imidazole compounds and their derivatives and salts, urea derivatives, organic guanidine derivatives, and phosphorus-containing compounds.

[0036] Preferably, the curing agent accelerator includes one or more of triphenylphosphine, diphosphomethane, N-(2-hydroxyphenyl)-N',N'-dimethylurea, N-(2-hydroxy-4-nitrobenzene)-N',N'-dimethylurea, N-(5-chloro-2-hydroxybenzene)-N',N'-dimethylurea, di-o-tolylguanidine, and o-tolylbiguanide.

[0037] In some embodiments of the present invention, the organic peroxide is benzoyl peroxide, tert-butyl perbenzoate, tert-amyl perbenzoate, tert-amyl peroxyacetate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxy-2-ethylhexyl carbonate, ethyl 3,3-bis(tert-butylperoxy)butyrate, ethyl 3,3-di(tert-amylperoxy)butyrate, 4,4-bis(tert-butylperoxy)butylate, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-amylperoxy)cyclohexane, 1,1-di-tert-amylperoxy-3,3, 5-trimethylcyclohexane, 1,1-di-tert-butylperoxy- Any one of 3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, 2,5-dimethyl-2,5-di-tert-butylperoxy-3-hexyne, di-tert-butyl peroxide, di-tert-amyl peroxide, tert-butylcumyl peroxide, di-tert-butylperoxycumyl, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, diisopropylbenzene peroxide and tert-butylperoxy-3,5,5-trimethylhexanoate.

[0038] In some embodiments of the present invention, the method for preparing the antioxidant comprises the following steps:

[0039] 1) Add chitosan to citric acid aqueous solution, heat to 45-55°C, stir to obtain solution 1 for use; add nano-montmorillonite to deionized water, heat to 45-55°C, stir to obtain solution 2 for use; mix solution 1 and solution 2, add glycerol, stir, and ultrasonicate to obtain a mixed solution for use;

[0040] 2) Adding tea polyphenols and vitamin C to the mixed solution of step 1), stirring, ultrasonicating, rotary evaporating and drying to obtain an antioxidant.

[0041] In some embodiments of the present invention, the mass ratio of tea polyphenols, vitamin C, chitosan and nano-montmorillonite is 1: (0.1-0.3): (1-1.5): (1.5-2.5).

[0042] Preferably, the mass ratio of the tea polyphenols, vitamin C, chitosan and nano-montmorillonite is 1:0.2:1.25:2.

[0043] Acrylic resin is prone to yellowing and discoloration during long-term use, affecting its appearance and performance. Especially in high temperature environments, acrylic resin is more prone to aging. Therefore, the appropriate use of antioxidants is crucial. In order to make the film safer and more environmentally friendly, this application uses bio-based tea polyphenols as the main component of the antioxidant. However, bio-based antioxidants generally have the problem of insufficient heat resistance.

[0044] The present application uses chitosan and nano-montmorillonite as carriers to load tea polyphenols and vitamin C. On the one hand, chitosan has good water solubility and biocompatibility, while nano-montmorillonite has good thermal stability, and both have a large specific surface area, making them good materials as carriers. Furthermore, chitosan, nano-montmorillonite, and tea polyphenols have strong interactions due to the presence of hydrogen bonds and hydroxyl groups, which can make the antioxidant have a dense network structure inside, thereby effectively improving the antioxidant activity of tea polyphenols. On the other hand, the present application combines tea polyphenols and vitamin C to play a coordinated antioxidant role, further enhancing the antioxidant activity of tea polyphenols.

[0045] On the other hand, the present invention also provides a method for preparing the double-sided high temperature resistant and ultra-low volatile dust-free oven adhesive film described in the above technical solution, comprising the following steps:

[0046] S1, prepare the first adhesive layer raw materials in proportion, add acrylic resin, epoxy resin, filler, antioxidant into solvent, heat, stir, cool, add curing agent accelerator, stir, and obtain glue solution 1 for standby use;

[0047] S2, prepare the raw materials for the second adhesive layer in proportion, add acrylic resin, epoxy resin, filler, and antioxidant into the solvent, heat, stir, cool, add organic peroxide, stir, and obtain glue solution 2 for standby use;

[0048] S3, applying the glue 1 of step S1 to the upper surface of the high temperature resistant substrate layer to form a first adhesive layer, attaching a release film layer on the first adhesive layer, and then applying the glue 2 of step S2 to the other surface of the high temperature resistant substrate layer to form a second adhesive layer, attaching a release film layer on the second adhesive layer, baking, and rolling up to obtain a double-sided high temperature resistant and ultra-low volatile dust-free oven adhesive film.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] (1) The present invention uses acrylic resin and epoxy resin as main components, and then adds fillers, curing agent accelerators, antioxidants and solvents to prepare a first adhesive layer. Use acrylic resin and epoxy resin as main components, and then add fillers, organic peroxides, antioxidants and solvents to prepare a second adhesive layer. Then, the release film layer, the first adhesive layer, the high temperature resistant substrate layer, the second adhesive layer and the release film layer are compounded from top to bottom to prepare a dust-free oven adhesive film with a five-layer structure. Through the synergistic effect of the various components, the dust-free oven adhesive film has excellent high temperature resistance and antioxidant properties.

[0051] (2) The present invention first uses hydroxyethyl chitosan to modify silica, and then introduces Tween 20 and silane coupling agent Si69 to jointly modify the hydroxyethyl chitosan-modified silica, thereby effectively improving the dispersibility of silica, thereby making the film have good high temperature resistance.

[0052] (3) The present invention uses chitosan and nano-montmorillonite as carriers to load tea polyphenols and vitamin C, which synergistically improves the antioxidant activity of tea polyphenols while also improving the thermal stability of tea polyphenols, so that the film can have better antioxidant activity, thereby making the film more durable.

[0053] (4) The adhesive film prepared by the present invention has the advantages of excellent high temperature resistance and oxidation resistance, can be widely used in the field of dust-free ovens, and has good commercial application value. DETAILED DESCRIPTION

[0054] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0055] In the following embodiments and comparative examples, except for fillers and antioxidants, the other compound monomers and related reagents used can be purchased from the market. Among them, bisphenol A epoxy resin and bisphenol F epoxy resin were purchased from Shandong Poly Chemical Co., Ltd.; hydroxyethyl chitosan was purchased from Hubei Xinyuhong Biomedicine Technology Co., Ltd.; chitosan was purchased from Qingdao Bozhihuili Biotechnology Co., Ltd., the release film layer was a PET film, and the high temperature resistant substrate layer was a polytetrafluoroethylene film.

[0056] Preparation Example 1

[0057] The synthetic method of filler A comprises the following steps:

[0058] Mix 20 ml of 28 wt% ammonia water, 35 ml of anhydrous ethanol and 50 ml of deionized water, stir for 5 min to obtain an alkaline solution for use, mix 10 g of tetraethyl orthosilicate and 90 ml of anhydrous ethanol, add 2 g of hydroxyethyl chitosan, add to the alkaline solution after ultrasonic treatment for 30 min, stir at 600 r / min for 3 h, centrifuge, add the precipitate into 50 ml of deionized water, add 1 g of Tween 20 and 1 g of silane coupling agent Si69, stir for 30 min, centrifuge, wash with deionized water 3 times, and dry at 60°C for 24 h to obtain filler A.

[0059] Preparation Example 2

[0060] Filler B, the specific implementation manner is the same as that of filler A, except that the mass of hydroxyethyl chitosan is replaced with 0.8 g.

[0061] Preparation Example 3

[0062] Filler C, the specific implementation manner is the same as that of filler A, except that the mass of Tween 20 is replaced with 0.3 g.

[0063] Preparation Example 4

[0064] Filler D, the specific implementation manner is the same as that of filler A, except that the mass of silane coupling agent Si69 is replaced with 0.3 g.

[0065] Preparation Example 5

[0066] The synthesis method of antioxidant A comprises the following steps:

[0067] 1) Add 5 g of chitosan to 40 ml of 1 wt% citric acid aqueous solution, heat to 50 ° C, stir for 2 h, and obtain solution 1 for use; add 8 g of nano-montmorillonite to 40 ml of deionized water, heat to 50 ° C, stir for 30 min, and obtain solution 2 for use; mix solution 1 and solution 2, add 10 g of glycerol, stir for 2 h, and ultrasonicate for 30 min to obtain a mixed solution for use;

[0068] 2) Add 4 g of tea polyphenols and 2 g of vitamin C to the mixed solution of step 1), stir for 1 h, ultrasonicate for 30 min, rotary evaporate, and dry at 30° C. for 48 h to obtain antioxidant A.

[0069] Preparation Example 6

[0070] The specific implementation manner of antioxidant B is the same as that of antioxidant filler A, except that in step 1), the mass of chitosan is replaced with 3.2 g.

[0071] Preparation Example 7

[0072] The specific implementation method of antioxidant C is the same as that of antioxidant A, except that in step 1), the mass of nano-montmorillonite is replaced with 5 g.

[0073] Preparation Example 8

[0074] Antioxidant D, the specific implementation method is the same as that of antioxidant A, except that: in step 2), the mass of vitamin C is replaced with 0.3 g. Example 1

[0075] A double-sided high-temperature resistant and ultra-low volatile dust-free oven adhesive film, the adhesive film comprises from top to bottom: a release film layer, a first adhesive layer, a high-temperature resistant substrate layer, a second adhesive layer and a release film layer;

[0076] The first adhesive layer is prepared by the following raw materials in parts by weight: 35 parts of acrylic resin, 5 parts of bisphenol A epoxy resin, 3.5 parts of filler A, 6 parts of triphenylphosphine, 2 parts of antioxidant A, and 50 parts of ethyl acetate;

[0077] The second adhesive layer is prepared by the following raw materials in parts by weight: 50 parts of acrylic resin, 5 parts of bisphenol A epoxy resin, 3.5 parts of filler A, 6 parts of benzoyl peroxide, 2 parts of antioxidant A, and 45 parts of ethyl acetate;

[0078] In terms of weight parts, the acrylic resin includes the following raw materials: 1.5 parts of 2-phenoxyethyl acrylate, 7 parts of ethyl acrylate, 3.5 parts of methyl methacrylate, 11 parts of butyl methacrylate, 4 parts of butyl acrylate, 0.7 parts of acrylic acid, 0.7 parts of azobisisobutyronitrile, and 71.6 parts of ethyl acetate.

[0079] The preparation method of acrylic resin comprises the following steps:

[0080] (1) 70 wt% of methyl methacrylate, 70 wt% of ethyl acrylate, 30 wt% of 2-phenoxyethyl acrylate, 30 wt% of butyl methacrylate, 30 wt% of butyl acrylate, 30 wt% of acrylic acid and azobisisobutyronitrile were uniformly mixed and divided into two equal parts by mass, which were respectively recorded as component A and component C;

[0081] (2) uniformly mixing the remaining methyl methacrylate, the remaining ethyl acrylate, the remaining 2-phenoxyethyl acrylate, the remaining butyl methacrylate, the remaining butyl acrylate and the remaining acrylic acid, which is recorded as component B;

[0082] (3) Heat ethyl acetate to 90°C, add component A dropwise for 1 hour, continue to add component B dropwise for 0.5 hour, continue to add component C dropwise for 1 hour, keep warm for 3 hours, cool to 60°C, filter, and obtain acrylic resin.

[0083] The preparation method of the double-sided high temperature resistant and ultra-low volatility dust-free oven adhesive film in this embodiment comprises the following steps:

[0084] S1, prepare the raw materials of the first adhesive layer according to the proportion, add acrylic resin, bisphenol A type epoxy resin, filler A, antioxidant A into ethyl acetate, heat to 65°C, stir for 30 minutes, cool to room temperature, add triphenylphosphine, stir for 30 minutes, and obtain glue solution 1 for standby use;

[0085] S2, prepare the raw materials for the second adhesive layer in proportion, add acrylic resin, bisphenol A epoxy resin, filler A, and antioxidant A into ethyl acetate, heat to 65° C., stir for 30 min, cool to room temperature, add benzoyl peroxide, stir for 30 min, and obtain glue solution 2 for standby use;

[0086] S3, applying the glue 1 of step S1 to the upper surface of the high temperature resistant substrate layer to form a first adhesive layer with a thickness of 50µm, laminating a release film layer with a thickness of 80µm on the first adhesive layer, and then applying the glue 2 of step S2 to the other surface of the high temperature resistant substrate layer to form a second adhesive layer with a thickness of 50µm, laminating a release film layer with a thickness of 80µm on the second adhesive layer, 60 o C for 4 hours and rolled up to obtain a double-sided high-temperature resistant and ultra-low volatile dust-free oven adhesive film. Example 2

[0087] A double-sided high-temperature resistant and ultra-low volatile dust-free oven adhesive film, the adhesive film comprises from top to bottom: a release film layer, a first adhesive layer, a high-temperature resistant substrate layer, a second adhesive layer and a release film layer;

[0088] The first adhesive layer is prepared by the following raw materials, calculated by weight: 30 parts of acrylic resin, 1 part of bisphenol F epoxy resin, 2 parts of filler A, 2 parts of N-(2-hydroxyphenyl)-N',N'-dimethylurea, 1 part of antioxidant A, and 40 parts of ethyl acetate;

[0089] The second adhesive layer is prepared by the following raw materials in parts by weight: 40 parts of acrylic resin, 1 part of bisphenol F epoxy resin, 2 parts of filler A, 2 parts of tert-butyl perbenzoate, 1 part of antioxidant A, and 40 parts of ethyl acetate;

[0090] In parts by weight, the acrylic resin includes the following raw materials: 1 part of 2-phenoxyethyl acrylate, 5 parts of ethyl acrylate, 2 parts of methyl methacrylate, 9 parts of butyl methacrylate, 1 part of butyl acrylate, 0.5 parts of acrylic acid, 0.5 parts of azobisisobutyronitrile, and 81 parts of ethyl acetate.

[0091] The preparation method of acrylic resin is the same as that of Example 1.

[0092] The preparation method of the double-sided high temperature resistant and ultra-low volatility dust-free oven adhesive film in this embodiment comprises the following steps:

[0093] S1, prepare the raw materials of the first adhesive layer in proportion, add acrylic resin, bisphenol F epoxy resin, filler A, and antioxidant A into ethyl acetate, heat to 65° C., stir for 30 min, cool to room temperature, add N-(2-hydroxyphenyl)-N',N'-dimethylurea, stir for 30 min, and obtain glue solution 1 for standby use;

[0094] S2, prepare the raw materials for the second adhesive layer in proportion, add acrylic resin, bisphenol F epoxy resin, filler A, and antioxidant A into ethyl acetate, heat to 65° C., stir for 30 min, cool to room temperature, add tert-butyl peroxybenzoate, stir for 30 min, and obtain glue solution 2 for standby use;

[0095] S3, applying the glue 1 of step S1 to the upper surface of the high temperature resistant substrate layer to form a first adhesive layer with a thickness of 50µm, laminating a release film layer with a thickness of 80µm on the first adhesive layer, and then applying the glue 2 of step S2 to the other surface of the high temperature resistant substrate layer to form a second adhesive layer with a thickness of 50µm, laminating a release film layer with a thickness of 80µm on the second adhesive layer, 60 o C for 4 hours and rolled up to obtain a double-sided high-temperature resistant and ultra-low volatile dust-free oven adhesive film. Example 3

[0096] A double-sided high-temperature resistant and ultra-low volatile dust-free oven adhesive film, the adhesive film comprises from top to bottom: a release film layer, a first adhesive layer, a high-temperature resistant substrate layer, a second adhesive layer and a release film layer;

[0097] The first adhesive layer is prepared by the following raw materials in parts by weight: 40 parts of acrylic resin, 10 parts of bisphenol A epoxy resin, 5 parts of filler A, 10 parts of N-(2-hydroxy-4-nitrobenzene)-N',N'-dimethylurea, 3 parts of antioxidant A, and 60 parts of ethyl acetate;

[0098] The second adhesive layer is prepared by the following raw materials in parts by weight: 60 parts of acrylic resin, 10 parts of bisphenol A epoxy resin, 5 parts of filler A, 10 parts of tert-butyl peroxide-3,5,5-trimethylhexanoate, 3 parts of antioxidant A, and 50 parts of ethyl acetate;

[0099] The acrylic resin includes the following raw materials in parts by weight: 2 parts of 2-phenoxyethyl acrylate, 9 parts of ethyl acrylate, 5 parts of methyl methacrylate, 13 parts of butyl methacrylate, 4 parts of butyl acrylate, 1 part of acrylic acid, 1 part of azobisisobutyronitrile, and 65 parts of ethyl acetate.

[0100] The preparation method of acrylic resin is the same as that of Example 1.

[0101] The preparation method of the double-sided high temperature resistant and ultra-low volatility dust-free oven adhesive film in this embodiment comprises the following steps:

[0102] S1, prepare the raw materials of the first adhesive layer according to the proportion, add acrylic resin, bisphenol A type epoxy resin, filler A, antioxidant A into ethyl acetate, heat to 65°C, stir for 30 minutes, cool to room temperature, add N-(2-hydroxy-4-nitrobenzene)-N',N'-dimethylurea, stir for 30 minutes, and obtain glue solution 1 for standby use;

[0103] S2, prepare the raw materials for the second adhesive layer in proportion, add acrylic resin, bisphenol A epoxy resin, filler A, and antioxidant A into ethyl acetate, heat to 65° C., stir for 30 min, cool to room temperature, add tert-butyl peroxide-3,5,5-trimethylhexanoate, stir for 30 min, and obtain glue solution 2 for standby use;

[0104] S3, applying the glue 1 of step S1 to the upper surface of the high temperature resistant substrate layer to form a first adhesive layer with a thickness of 50µm, laminating a release film layer with a thickness of 80µm on the first adhesive layer, and then applying the glue 2 of step S2 to the other surface of the high temperature resistant substrate layer to form a second adhesive layer with a thickness of 50µm, laminating a release film layer with a thickness of 80µm on the second adhesive layer, 60 o C for 4 hours and rolled up to obtain a double-sided high-temperature resistant and ultra-low volatile dust-free oven adhesive film. Example 4

[0105] This embodiment provides a double-sided high-temperature resistant and ultra-low-volatile dust-free oven adhesive film and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that filler B replaces filler A in equal amounts. Example 5

[0106] This embodiment provides a double-sided high-temperature resistant and ultra-low-volatile dust-free oven adhesive film and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that filler C replaces filler A in equal amounts. Example 6

[0107] This embodiment provides a double-sided high-temperature resistant and ultra-low-volatile dust-free oven adhesive film and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that filler D replaces filler A in equal amounts. Example 7

[0108] This embodiment provides a double-sided high-temperature resistant and ultra-low-volatile dust-free oven adhesive film and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that antioxidant A is replaced by antioxidant B in equal amounts. Example 8

[0109] This embodiment provides a double-sided high-temperature resistant and ultra-low-volatile dust-free oven adhesive film and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that antioxidant A is replaced by antioxidant C in equal amounts. Example 9

[0110] This embodiment provides a double-sided high-temperature resistant and ultra-low-volatile dust-free oven adhesive film and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the antioxidant A is replaced by an antioxidant D in an equal amount. Example 10

[0111] This embodiment provides a double-sided high-temperature resistant and ultra-low-volatile dust-free oven adhesive film and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that filler A is replaced by an equal amount of silicon dioxide. Embodiment 11

[0112] This embodiment provides a double-sided high-temperature resistant and ultra-low-volatile dust-free oven adhesive film and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that tea polyphenols are used instead of antioxidant A.

[0113] The high temperature resistance and oxidation resistance of the double-sided high temperature resistant and ultra-low volatility dust-free oven adhesive films of the above-mentioned Examples 1-11 were tested, and the test results are shown in Table 1.

[0114] (1) High temperature resistance

[0115] The film was placed in a constant temperature box at 200°C for 80 hours, and then the peel strength was tested.

[0116] Peel strength: According to the standard GB / T2792-2014, the film (width 25mm, length 100mm) was attached to a stainless steel plate wiped clean with alcohol, pressed back and forth with a 2kg roller, left at room temperature for 24 hours, and tested with a peel strength tester. Measure more than three times and calculate the average value. Take the second adhesive layer as an example.

[0117] (2) Antioxidant properties

[0118] The anti-oxidation property is judged by the yellowing degree. After 30 hours of exposure with a carbon rod lamp-type sunlight irradiation atmospheric climate tester, the yellowing degree of the film is measured with a colorimeter and expressed as the yellowing value (YI). The larger the yellowing value, the worse the anti-aging performance.

[0119] Table 1

[0120] Group Peel strength after 200℃ high temperature (N / 25mm) Yellowing Index (YI) Example 1 15.6 20 Example 2 15.3 21 Example 3 15.4 21 Example 4 12.6 23 Example 5 12.8 24 Example 6 12.9 23 Example 7 14.9 29 Example 8 14.7 31 Example 9 14.8 32 Example 10 11.0 25 Embodiment 11 14.5 35

[0121] It can be seen from the data in Table 1 that the adhesive film in Examples 1-3 of the present invention has good high temperature resistance and antioxidant properties as a whole. Among them, Examples 4-6 respectively changed the modification ratio of hydroxyethyl chitosan, Tween 20 and silane coupling agent Si69 to silica in the filler, so that the dispersibility of silica was not well improved, resulting in a decrease in the peel strength of the adhesive film at high temperature, that is, a decrease in high temperature resistance, but little effect on antioxidant properties; Examples 7-9 changed the ratio of the key components in the modification of tea polyphenols when synthesizing antioxidants, so that the heat resistance and antioxidant properties of tea polyphenols were not well improved, that is, the yellowing value of the adhesive film was significantly increased, but little effect on the overall high temperature resistance of the adhesive film; Examples 10-11 respectively selected silica and tea polyphenols to replace filler A and antioxidant A, and the test found that the high temperature resistance and antioxidant properties of the tape showed poor results.

[0122] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A double-sided high temperature resistant and ultra-low volatile dust-free oven adhesive film, characterized in that: The adhesive film includes, from top to bottom, a release film layer, a first adhesive layer, a high temperature resistant substrate layer, a second adhesive layer and a release film layer; The first adhesive layer is prepared by the following raw materials in parts by weight: 30-40 parts of acrylic resin, 1-10 parts of epoxy resin, 2-5 parts of filler, 2-10 parts of curing agent accelerator, 1-3 parts of antioxidant, and 40-60 parts of solvent; The second adhesive layer is prepared by the following raw materials, calculated by weight: 40-60 parts of acrylic resin, 1-10 parts of epoxy resin, 2-5 parts of filler, 2-10 parts of organic peroxide, 1-3 parts of antioxidant, and 40-50 parts of solvent; The preparation method of the filler comprises the following steps: Ammonia water, anhydrous ethanol and deionized water are mixed and stirred to obtain an alkaline solution for use; ethyl orthosilicate and anhydrous ethanol are mixed, hydroxyethyl chitosan is added, and the mixture is added to the alkaline solution after ultrasonic treatment, stirred, and centrifuged; the precipitate is added to deionized water, Tween 20 and silane coupling agent Si69 are added, stirred, centrifuged, washed, and dried to obtain a filler; The mass ratio of tetraethyl orthosilicate, hydroxyethyl chitosan, Tween 20 and silane coupling agent Si69 is 1: (0.1-0.3): (0.05-0.15): (0.05-0.15); The preparation method of the antioxidant comprises the following steps: 1) Add chitosan to citric acid aqueous solution, heat to 45-55°C, stir to obtain solution 1 for use; add nano-montmorillonite to deionized water, heat to 45-55°C, stir to obtain solution 2 for use; mix solution 1 and solution 2, add glycerol, stir, and ultrasonicate to obtain a mixed solution for use; 2) adding tea polyphenols and vitamin C to the mixed solution of step 1), stirring, ultrasonicating, rotary evaporating, and drying to obtain an antioxidant; The mass ratio of the tea polyphenols, vitamin C, chitosan and nano-montmorillonite is 1:0.5:(1-1.5):(1.5-2.5).

2. The double-sided high temperature resistant and ultra-low volatility dust-free oven adhesive film according to claim 1, characterized in that: The acrylic resin comprises the following raw materials in parts by weight: 1-2 parts of special acrylic ester monomer, 5-9 parts of ethyl acrylate, 2-5 parts of methyl methacrylate, 9-13 parts of butyl methacrylate, 1-5 parts of butyl acrylate, 0.5-1 parts of acrylic acid, 0.5-1 parts of initiator, and 65-82 parts of organic solvent. Wherein, the special acrylate monomer is isotridecyl acrylate or 2-phenoxyethyl acrylate.

3. The double-sided high temperature resistant and ultra-low volatility dust-free oven adhesive film according to claim 1, characterized in that: The epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydantoin epoxy resin, and glycidylamine epoxy resin.

4. The double-sided high temperature resistant and ultra-low volatile dust-free oven adhesive film according to claim 1, characterized in that: The curing agent accelerator is one or a combination of two or more of triphenylphosphine, diphosphomethane, N-(2-hydroxyphenyl)-N',N'-dimethylurea, N-(2-hydroxy-4-nitrobenzene)-N',N'-dimethylurea, N-(5-chloro-2-hydroxybenzene)-N',N'-dimethylurea, di-o-tolylguanidine, and o-tolylbiguanide.

5. The double-sided high temperature resistant and ultra-low volatile dust-free oven adhesive film according to claim 1, characterized in that: The organic peroxide is benzoyl peroxide, tert-butyl perbenzoate, tert-amyl perbenzoate, tert-amyl peracetate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxy-2-ethylhexyl carbonate, ethyl 3,3-bis(tert-butylperoxy)butyrate, ethyl 3,3-di(tert-amylperoxy)butyrate, n-butyl 4,4-bis(tert-butylperoxy)valerate, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-amylperoxy)cyclohexane, 1,1-di-tert-amylperoxy-3,3, 5-trimethylcyclohexane, 1,1-di-tert-butylperoxy- Any one of 3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, 2,5-dimethyl-2,5-di-tert-butylperoxy-3-hexyne, di-tert-butyl peroxide, di-tert-amyl peroxide, tert-butylcumyl peroxide, di-tert-butylperoxycumyl, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, diisopropylbenzene peroxide and tert-butylperoxy-3,5,5-trimethylhexanoate.

6. A method for preparing a double-sided high temperature resistant ultra-low volatility dust-free oven adhesive film according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1, prepare the first adhesive layer raw materials in proportion, add acrylic resin, epoxy resin, filler, antioxidant into solvent, heat, stir, cool, add curing agent accelerator, stir, and obtain glue solution 1 for standby use; S2, prepare the raw materials for the second adhesive layer in proportion, add acrylic resin, epoxy resin, filler, and antioxidant into the solvent, heat, stir, cool, add organic peroxide, stir, and obtain glue solution 2 for standby use; S3, applying the glue 1 of step S1 to the upper surface of the high temperature resistant substrate layer to form a first adhesive layer, attaching a release film layer on the first adhesive layer, and then applying the glue 2 of step S2 to the other surface of the high temperature resistant substrate layer to form a second adhesive layer, attaching a release film layer on the second adhesive layer, baking, and rolling up to obtain a double-sided high temperature resistant and ultra-low volatile dust-free oven adhesive film.