Fluorinated modified polyurethane adhesive, functional protective film and application thereof

Abstract

The invention belongs to the field of preparation of protective films, and particularly relates to a fluorinated modified polyurethane adhesive, a functional protective film and application of the functional protective film. The fluorinated modified polyurethane adhesive is prepared from the following raw material components in parts by mass: 20 to 40 parts of fluorinated modified polyurethane; 5-20 parts of a plasticizer; 0.1 to 5 parts of a defoaming agent; 0.1-2 parts of a leveling agent; 0.1-2 parts of an antistatic agent; and 0.5-3 parts of an anti-degradation agent. The fluorine-containing amine substance is applied to preparation of the fluorinated modified polyurethane adhesive, no isocyanate is used in the process, the fluorinated modified polyurethane adhesive has good safety, and the antistatic property of the fluorinated modified polyurethane adhesive can be well improved by synthesizing the antistatic agent; in addition, an anti-degradation agent is obtained through compounding in a specific proportion, and the comprehensive performance of the fluorinated modified polyurethane adhesive and the protective film is improved. The electronic protective film is indispensable in the OLED laminating layer process, and is easy to remove and free of residues and prevents secondary pollution when the electronic protective film is completed in the later stage.

Description

Technical Field

[0001] The invention belongs to the field of protective film preparation, and specifically relates to a fluorinated modified polyurethane adhesive, a functional protective film and applications thereof. Background Art

[0002] Polyurethane protective film is a material used for screen protection of electronic devices. It has many advantages: (1) High transparency and flexibility: Polyurethane protective film can perfectly cover screens of various shapes and sizes, providing first-class transparency and flexibility, protecting devices from wear and tear in daily use; (2) Excellent fingerprint and touch sensitivity: Polyurethane material can provide excellent fingerprint and touch sensitivity, making it easier to unlock the device; (3) Anti-UV performance: Polyurethane protective film has excellent anti-ultraviolet performance, which can protect the screen content from ultraviolet rays and ensure the clarity of the screen; (3) Adhesion and anti-bubble performance: Polyurethane protective film has first-class adhesion and anti-bubble performance, and is compatible with silicone adhesives, making the film application process easier and reducing the generation of bubbles; (4) Anti-stain and scratch performance: Polyurethane protective film has excellent anti-stain and scratch performance, can resist various stains and scratches in daily life and is an ideal screen protector.

[0003] Patent CN 115785884 A discloses an adhesive for an electrostatic protective film and an electrostatic protective film with an ultra-low tearing voltage prepared based on the adhesive. The adhesive includes the following raw materials: polyester polyurethane; curing agent; plasticizer; antistatic agent; leveling agent; catalyst. The electrostatic protective film provided by the invention has an extremely low electrostatic tearing voltage for the screen of electronic products, which can effectively reduce the breakdown damage of electronic components caused by static electricity generated during the tearing process, and increase its versatility in electronic products. Patent CN 116536000 A discloses a PET protective film and its preparation method and application. First, a polyurethane pressure-sensitive adhesive is prepared, and then the polyurethane pressure-sensitive adhesive is coated on the surface of the PET film, and an adhesive layer is formed after drying. A release film is attached to the surface of the adhesive layer, and ripened to obtain the PET protective film. The polyurethane pressure-sensitive adhesive used does not contain silicone components, and will not leave residual adhesive in the surface protection of electronic products, and will not pollute electronic products. In addition, due to the introduction of ionic liquid composite graphene and polybutadiene reinforcing agents, it has good water resistance and antistatic properties.

[0004] However, in the preparation process of polyurethane protective film, isocyanate is usually used as a curing agent, which not only causes environmental problems, but also affects human health and safety. Therefore, it is of great significance to develop polyurethane with excellent performance that can be used in OLED protective film without using isocyanate. Summary of the invention

[0005] The present invention discloses a fluorinated polyurethane adhesive, a functional protective film and applications thereof. No isocyanate is used in the preparation process of the fluorinated polyurethane adhesive, which has good safety. By synthesizing an antistatic agent, the antistatic property of the fluorinated polyurethane adhesive can be improved. In addition, an anti-degradation agent is obtained by compounding in a specific ratio to improve the comprehensive performance of the fluorinated polyurethane adhesive and the protective film. The electronic protective film prepared by the present invention has excellent high temperature resistance and antistatic property, high transmittance, high refractive index, good adhesion, moderate release force, super yellowing resistance, and the number of folding times can reach more than 20,000 times, which can prevent the bending of the polyimide (PI) layer and the thin film encapsulation layer from being damaged by external factors. It is indispensable in the OLED lamination process. When the latter stage is completed, it is easy to remove without residue, and can prevent secondary pollution.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0007] The first aspect of the present invention provides a fluorinated modified polyurethane adhesive, which comprises the following raw material components in parts by mass:

[0008] 20-40 parts of fluorinated modified polyurethane; 5-20 parts of plasticizer; 0.1-5 parts of defoaming agent; 0.1-2 parts of leveling agent; 0.1-2 parts of antistatic agent; 0.5-3 parts of anti-deterioration agent.

[0009] In some embodiments, a plasticizer, a defoamer, a leveling agent, an antistatic agent, and an anti-deterioration agent are added to the fluorinated modified polyurethane and stirred evenly to prepare a fluorinated modified polyurethane adhesive.

[0010] In some embodiments, the preparation method of the antistatic agent is:

[0011] Mix monomethyl ether and sodium bromide evenly, add sulfuric acid dropwise, stir and heat to react for 4-8 hours, then add ethyl acetate and continue to react for 2-4 hours; then add deionized water, mix evenly, add thiazole, stir and react at 10-30°C for 30-60 minutes, add sodium bicarbonate, stir and react at 10-30°C for 10-12 hours, reflux and react for 5-8 hours, filter, add ethyl bromide to the filtrate, react at 10-30°C for 3-4 hours, reflux and react for 3.5-4.5 hours, and stir and react at 10-30°C for 10-12 hours; then add α-olefin sulfonate, stir and react at 10-30°C for 10-12 hours, filter, distill under reduced pressure, purify, and obtain an antistatic agent.

[0012] In some embodiments, the monomethyl ether is selected from at least one of triethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and propylene glycol monomethyl ether.

[0013] Preferably, the monomethyl ether is triethylene glycol monomethyl ether.

[0014] In some embodiments, the molar ratio of the monomethyl ether, thiazole, ethyl bromide and α-olefin sulfonate is 1:(1-1.2):(1-1.2):(1-1.2).

[0015] Preferably, the molar ratio of monomethyl ether, thiazole, ethyl bromide and α-olefin sulfonate is 1:1.1:1.1:1.1.

[0016] In some embodiments, the heating temperature is 60-80°C.

[0017] Preferably, the heating temperature is 70-80°C.

[0018] In some embodiments, the anti-degradation agent includes at least one of an antioxidant, an ultraviolet absorber, and a light stabilizer.

[0019] Preferably, the antioxidant is selected from one or more of phenolic antioxidants, amine antioxidants, sulfur-containing antioxidants and phosphorus-containing antioxidants; the UV absorber is selected from one or more of benzophenone UV absorbers, benzotriazole UV absorbers, salicylic acid UV absorbers, oxalic acid aniline UV absorbers, cyanoacrylate UV absorbers and triazine UV absorbers; the light stabilizer is selected from hindered amine light stabilizers and / or UV stabilizers.

[0020] More preferably, the anti-degradation agent comprises an antioxidant, an ultraviolet absorber and a light stabilizer in a mass ratio of (0.5-1.5):(1-3):1.

[0021] In some embodiments, the preparation steps of the fluorinated modified polyurethane are:

[0022] (1) In an inert gas atmosphere, syringaldehyde is added to an aqueous sodium hydroxide solution, heated in a water bath at 75-85° C. with stirring for 1-1.5 h, 3-chloro-1,2-propanediol is then added dropwise thereto, the temperature is raised to 90-110° C., the reaction is stirred for 3.5-4.5 h, extraction, washing, and drying are performed to obtain syringaldehyde diol;

[0023] (2) mixing the syringaldehyde diol of step (1) with carbonate, adding a catalyst, reacting under reflux for 7-8 hours in an inert gas atmosphere, washing, filtering, and drying to obtain syringaldehyde carbonate;

[0024] (3) adding the syringaldehyde carbonate and amine substance of step (2) into a solvent, stirring and reacting at 40-90° C. for 4-18 hours, and drying to obtain a fluorinated modified polyurethane.

[0025] In some embodiments, in step (1), the molar ratio of syringaldehyde to 3-chloro-1,2-propanediol is 1:(1-1.2).

[0026] Preferably, in step (1), the molar ratio of syringaldehyde to 3-chloro-1,2-propanediol is 1:1.1.

[0027] In some embodiments, in step (2), the molar ratio of syringaldehyde diol to carbonate is 1:(5-9).

[0028] Preferably, in step (2), the molar ratio of syringaldehyde diol to carbonate is 1:(6-8).

[0029] In some embodiments, in step (3), the amine substance includes a fluorine-containing amine substance and a diamine substance.

[0030] Preferably, in step (3), the mass ratio of the fluorine-containing amine substance to the diamine substance is 1:(1-2).

[0031] More preferably, the diamine substance is one or more of alkyl diamine, aromatic diamine and cyclohexane diamine.

[0032] In some embodiments, in step (3), the amount of the amine substance used is 5-10 wt % of the syringaldehyde carbonate.

[0033] Preferably, the amount of the amine substance used can be selected according to the desired performance of the product.

[0034] In some embodiments, the preparation steps of the fluorine-containing amine substance are:

[0035] The fluorine-containing acrylate is dissolved in an organic solvent, stirred evenly at 30-80° C., and a triamine substance is added under an inert gas atmosphere to react for 18-48 hours to obtain a fluorine-containing amine substance.

[0036] In some embodiments, the fluorine-containing acrylate is selected from one or more of trifluoroethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl acrylate, and hexafluorobutyl methacrylate.

[0037] In some embodiments, the triamine substance is selected from one or more of tris(2-aminoethyl)amine, tris[2-(methylamino)ethyl]amine, and polyetheramine.

[0038] In some embodiments, the molar ratio of the fluorinated acrylate to the triamine substance is 1:(1-1.1).

[0039] Preferably, the molar ratio of the fluorine-containing acrylate to the triamine substance is 1:1.05.

[0040] In some embodiments, the carbonate is selected from dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and propylene carbonate.

[0041] In some embodiments, the solvent is preferably one of DMF, THF, and DCM.

[0042] The second aspect of the present invention provides a functional protective film, which comprises a release film with a thickness of 10-300 μm, an adhesive layer with a thickness of 10-300 μm and a substrate with a thickness of 5-300 μm in sequence; the adhesive used in the adhesive layer is the fluorinated modified polyurethane adhesive described in the above scheme.

[0043] In some embodiments, the functional protective film is prepared by coating a fluorinated modified polyurethane adhesive on the surface of a substrate, drying to form an adhesive layer, laminating a release film on the surface of the adhesive layer, and then aging to obtain the functional protective film.

[0044] Finally, the present invention provides an application of the functional protective film described in the above scheme in the surface protection of electronic products.

[0045] In the synthesis process of the antistatic agent, sulfuric acid reacts with sodium bromide to generate hydrogen bromide, and the generated hydrogen bromide may undergo nucleophilic substitution reaction with monomethyl ether, providing an active intermediate for subsequent reactions; ethyl acetate, deionized water and thiazole are then added, the polarity of the system changes, thiazole may undergo nucleophilic substitution or addition reaction with the previously generated active intermediate, and the thiazole structure is introduced into the reaction product, and sodium bicarbonate is then added to neutralize the excess acid in the reaction system to promote the formation of the antistatic agent structure; ethyl bromide is then added to react with the nucleophilic reagent (such as an intermediate containing nitrogen or sulfur atoms) in the reaction system to undergo nucleophilic substitution reaction, and the reaction conditions are controlled to make the reaction more complete, thereby constructing a complex structure of the antistatic agent; finally, α-olefin sulfonate is added, and the α-olefin sulfonate may react with the active site in the reaction system to combine with it, playing a key role in the final structure formation of the antistatic agent, thereby preparing a new antistatic agent, which can be used in polyurethane adhesives to significantly improve the antistatic properties and mechanical properties of polyurethane adhesives.

[0046] On the one hand, the antistatic agent molecules can generate intermolecular forces with the fluorinated modified polyurethane molecules in the adhesive, and the thiazole ring of the antistatic agent may form hydrogen bonds with the fluorinated segments or other polar groups in the fluorinated modified polyurethane, which helps the two to be better dispersed and combined in the system, so that they can work together; on the other hand, the antistatic agent may also affect the molecular chain arrangement of the fluorinated modified polyurethane in the system. Due to the presence of fluorine atoms, the molecular chain of the fluorinated modified polyurethane has certain particularities, and the addition of the antistatic agent may adjust the mobility and stacking mode of its segments, so that when the two act together, a more favorable microstructure can be formed, while improving the flexibility, it can also reduce the internal gap and improve the isolation ability of water and oxygen from the outside. In addition, the role of the antistatic agent is to reduce the resistivity of the material surface, so that it can quickly conduct away the electrostatic charge, and the fluorinated modified polyurethane has good film-forming properties and adhesion to the substrate. When the two are used together, the conductive channel formed by the antistatic agent on the material surface can be combined with the continuous film structure formed by the fluorinated modified polyurethane. On the one hand, the antistatic agent ensures the effective conduction of static electricity. On the other hand, the membrane structure of the fluorinated modified polyurethane helps to maintain the stability of this conductive property. While providing good bonding properties, it will not hinder the function of the antistatic agent, thereby achieving the effect of synergistically improving the overall performance of the material.

[0047] In addition, the present invention also compounds an antioxidant, an ultraviolet absorber and a light stabilizer in a specific ratio to obtain an anti-degradation agent, which is used together with fluorinated modified polyurethane to improve the performance of the adhesive protective film. First, the light stabilizer and the ultraviolet absorber can produce a synergistic effect, and deal with the light degradation problem from different links. The two complement each other. The light stabilizer can also protect the antioxidant from being destroyed by photochemical reactions to a certain extent, so that it can continue to play an antioxidant role; and when combined with the fluorinated modified polyurethane adhesive, the light stabilizer can penetrate into the molecular structure of the adhesive and maintain the performance stability of the adhesive under the light environment together with the other two anti-degradation agents. The ultraviolet absorber focuses on absorbing ultraviolet energy, while the light stabilizer focuses on inhibiting the subsequent steps of the photochemical reaction, such as inhibiting the cross-linking of the molecular chain, photolysis and other reactions. The three work together to more comprehensively protect the adhesive from light degradation. And when combined with fluorinated modified polyurethane, the antioxidant can play a role at the molecular level of the adhesive, protecting its fluorinated segments and other easily oxidized functional groups. When working in synergy with UV absorbers and light stabilizers, they can protect the adhesive system from all angles, since UV absorbers and light stabilizers mainly target light-induced degradation processes, while antioxidants target oxidation processes.

[0048] The present invention also prepares a fluorine-containing amine substance for use in the synthesis of polyurethane. The fluorine-containing acrylate and the alkyl triamine substance are reacted under certain conditions to generate a fluorine-containing amine substance, which has good low surface energy, water resistance and thermal stability, and also has an amino active site for subsequent reaction with syringaldehyde carbonate to generate polyurethane; under alkaline conditions, the hydrogen atoms of the phenolic hydroxyl groups in the syringaldehyde molecules will be taken away by sodium hydroxide to form phenol oxide anions with stronger nucleophilicity and reaction activity, forming an active intermediate; then under specific reaction conditions, 3-chloro-1,2-propanediol is added dropwise, and its chlorine atoms react with syringaldehyde carbonate to form an active intermediate. The active intermediate of aldehyde undergoes nucleophilic substitution reaction to generate syringaldehyde diol with higher reactivity, which then combines with carbonyl carbon to generate syringaldehyde carbonate; finally, the active carbonate group in syringaldehyde carbonate reacts with the amino group in diamine substances and the amino group in fluorine-containing amine substances to generate a fluorine-containing amine substance, which can be used in the preparation process of polyurethane to introduce fluorine-containing groups into the polyurethane structure, and finally form a multifunctional fluorinated modified polyurethane, which gives it good softness and excellent water and oxygen isolation properties and thermal stability, etc., and can be well used in the field of OLED protective films.

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

[0050] 1. The present invention applies a fluorine-containing amine substance to the preparation of a fluorinated modified polyurethane adhesive. No isocyanate is used in the process, which has good safety. In addition, an antistatic agent is synthesized to improve the antistatic property of the fluorinated modified polyurethane adhesive.

[0051] 2. The present invention mixes an antioxidant, an ultraviolet absorber and a light stabilizer in a specific ratio to obtain an anti-deterioration agent, and uses the anti-deterioration agent together with a fluorinated modified polyurethane to improve the performance of the adhesive protective film.

[0052] 3. The present invention also uses bio-based syringaldehyde as a raw material, and converts it into syringaldehyde carbonate by controlling the process conditions of the chemical reaction, and then reacts with amine substances to generate a multifunctional fluorinated modified polyurethane with excellent comprehensive performance, which can meet the requirements of some special scenarios for polyurethane and further expand the application scope of non-isocyanate polyurethane. DETAILED DESCRIPTION

[0053] Now describe in detail various exemplary embodiments of the present invention, this detailed description should not be considered as limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the present invention. It should be understood that the terms described in the present invention are only for describing a particular embodiment, and are not used to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the range.

[0054] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. Various modifications and variations may be made to the specific embodiments of the present invention specification without departing from the scope or spirit of the present invention, which will be apparent to those skilled in the art. Other embodiments obtained from the present invention specification will be apparent to the technician. The present application specification and examples are exemplary only.

[0055] The words “include,” “including,” “have,” or “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0056] It should be noted that the post-processing steps such as "extraction", "distillation under reduced pressure" and "stirring" appearing in the following embodiments are routine operations for those skilled in the art and can be selected according to actual operations.

[0057] The mass fractions described in the following embodiments may be grams, kilograms, tons or other mass units.

[0058] The catalyst used in the present invention is anhydrous potassium carbonate; the leveling agent used is polydimethylsiloxane with a number average molecular weight of 10,000; the defoamer used is heptadecafluorodecyltrimethoxysilane; the plasticizer used is dibutyl phthalate; the release film and substrate used are both made of PET. The remaining reagents used can be purchased.

[0059] Preparation Example 1

[0060] The preparation steps of fluorine-containing amine substances are as follows:

[0061] 0.1 mol of trifluoroethyl acrylate was dissolved in 200 mL of THF, and the mixture was stirred at 30° C., and 0.1 mol of tris(2-aminoethyl)amine was added under a nitrogen atmosphere. The mixture was refluxed for 48 hours to obtain fluorine-containing amine substances.

[0062] Preparation Example 2

[0063] The preparation steps of fluorinated modified polyurethane are:

[0064] (1) Under a nitrogen atmosphere, 0.2 mol of syringaldehyde was added to 100 mL of a 7.5 wt% sodium hydroxide aqueous solution, heated in a water bath at 80° C. with stirring for 1.25 h, and then 0.22 mol of 3-chloro-1,2-propanediol was added dropwise thereto, the temperature was raised to 100° C., and the mixture was stirred for 4 h. The mixture was extracted with an equal volume of n-butanol, and the organic phase was washed with 20 mL of deionized water, concentrated by rotary evaporation to half of the original volume, and then dried with a mixed solvent (ethyl acetate and n-hexane in a mass ratio of 1:1), allowed to stand for 15 min, and dried at 45° C. to constant weight to obtain syringaldehyde diol;

[0065] (2) 0.15 mol of syringaldehyde diol from step (1) was mixed with 1 mol of dimethyl carbonate, 0.25 wt% of the catalyst in the system was added, and the mixture was refluxed for 7.5 h under a nitrogen atmosphere, washed with anhydrous ethanol three times, filtered, and dried at 45° C. to constant weight to obtain syringaldehyde carbonate;

[0066] (3) 30 g of syringaldehyde carbonate and 2.1 g of amine substance in step (2) were added to 65 g of DMF, stirred and reacted at 60° C. for 12 h, and dried to obtain fluorinated modified polyurethane.

[0067] The amine substance used comprises the fluorine-containing amine substance obtained in Preparation Example 1 and 4,4'-diaminodiphenylmethane in a mass ratio of 1:1.5.

[0068] Preparation Example 3

[0069] The preparation method of the antistatic agent is:

[0070] 0.1 mol of triethylene glycol monomethyl ether and 0.125 mol of sodium bromide were mixed evenly, 0.125 mol of AR grade sulfuric acid was added dropwise within 15 minutes, and the mixture was heated at 150 rpm and 75°C for 6 hours, and then 0.08 mol of ethyl acetate was added to continue the reaction for 3 hours; 10 g of deionized water was added, and 0.11 mol of thiazole was added after mixing evenly, and the mixture was stirred at 20°C for 45 minutes, 0.025 mol of sodium bicarbonate (a total of 0.1 mol) was added every 1 hour, and the mixture was stirred at 20°C and 150 rpm for 11 hours, and then the mixture was heated to reflux for 6 hours, filtered, 0.11 mol of ethyl bromide was added to the filtrate, the mixture was reacted at 20°C for 3.5 hours, and then the mixture was refluxed for 4 hours, and then stirred at 20°C for 11 hours; 0.11 mol of sodium α-olefin sulfonate was added thereto, the mixture was stirred at 20°C for 11 hours, filtered, the filtrate was distilled under reduced pressure, and purified by silica gel chromatography to obtain an antistatic agent.

[0071] Preparation Example 4

[0072] The preparation method of the antistatic agent is the same as that of Preparation Example 3, except that 0.09 mol of thiazole is used.

[0073] Preparation Example 5

[0074] The preparation method of the antistatic agent is the same as that of Preparation Example 3, except that 0.09 mol of ethyl bromide is used.

[0075] Preparation Example 6

[0076] The preparation method of the antistatic agent is:

[0077] 0.1 mol of triethylene glycol monomethyl ether and 0.125 mol of sodium bromide were mixed evenly, 0.125 mol of AR grade sulfuric acid was added dropwise within 15 minutes, and the mixture was heated at 150 rpm and 75°C for 6 hours, and then 0.08 mol of ethyl acetate was added to continue the reaction for 3 hours; 10 g of deionized water was added, and the mixture was mixed evenly, and then 0.11 mol of thiazole was added, and the mixture was stirred and reacted at 20°C for 45 minutes. 0.025 mol of sodium bicarbonate (a total of 0.1 mol) was added every 1 hour, and the mixture was stirred and reacted at 20°C and 150 rpm for 11 hours, and then the mixture was heated to reflux for 6 hours, filtered, 0.11 mol of ethyl bromide was added to the filtrate, and the mixture was reacted at 20°C for 3.5 hours, and then refluxed for 4 hours, and then stirred and reacted at 20°C for 11 hours, filtered, and the filtrate was distilled under reduced pressure, and purified by silica gel chromatography to obtain an antistatic agent.

[0078] Preparation Example 7

[0079] The preparation method of the antistatic agent is the same as that of Preparation Example 3, except that an equal amount of diethylene glycol monomethyl ether is used instead of diethylene glycol monomethyl ether.

[0080] Example 1

[0081] A fluorinated modified polyurethane adhesive comprises the following raw material components in parts by mass:

[0082] 20 parts of fluorinated modified polyurethane; 5 parts of plasticizer; 0.1 parts of defoaming agent; 0.1 parts of leveling agent; 0.1 parts of antistatic agent; 0.5 parts of anti-deterioration agent.

[0083] The fluorinated modified polyurethane used is obtained from Preparation Example 2; the antistatic agent used is obtained from Preparation Example 3.

[0084] The anti-degradation agent used is a mixture containing butylated hydroxyanisole, 2,4-dihydroxybenzophenone and bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate in a mass ratio of 0.5:1:1.

[0085] A plasticizer, a defoamer, a leveling agent, an antistatic agent and an anti-deterioration agent are added into the fluorinated modified polyurethane, and the mixture is stirred evenly to prepare a fluorinated modified polyurethane adhesive.

[0086] Example 2

[0087] A fluorinated modified polyurethane adhesive comprises the following raw material components in parts by mass:

[0088] 40 parts of fluorinated modified polyurethane; 20 parts of plasticizer; 5 parts of defoamer; 2 parts of leveling agent; 2 parts of antistatic agent; 3 parts of anti-deterioration agent.

[0089] The fluorinated modified polyurethane used is obtained from Preparation Example 2; the antistatic agent used is obtained from Preparation Example 3.

[0090] The anti-degradation agent used was methylene bis(4-methyl-6-tert-butylphenol), p-tert-butyl salicylate, and bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate in a mass ratio of 1.5:3:1.

[0091] A plasticizer, a defoamer, a leveling agent, an antistatic agent and an anti-deterioration agent are added into the fluorinated modified polyurethane, and the mixture is stirred evenly to prepare a fluorinated modified polyurethane adhesive.

[0092] Example 3

[0093] A fluorinated modified polyurethane adhesive comprises the following raw material components in parts by mass:

[0094] 30 parts of fluorinated modified polyurethane; 15 parts of plasticizer; 2 parts of defoamer; 0.5 parts of leveling agent; 1 part of antistatic agent; 2 parts of anti-deterioration agent.

[0095] The fluorinated modified polyurethane used is obtained from Preparation Example 2; the antistatic agent used is obtained from Preparation Example 3.

[0096] The anti-degradation agent used is 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2-hydroxy-4-oxybenzophenone and bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate in a mass ratio of 1:2:1.

[0097] A plasticizer, a defoamer, a leveling agent, an antistatic agent and an anti-deterioration agent are added into the fluorinated modified polyurethane, and the mixture is stirred evenly to prepare a fluorinated modified polyurethane adhesive.

[0098] Example 4

[0099] A fluorinated modified polyurethane adhesive, the specific implementation method is the same as that of Example 3, except that the antistatic agent used is obtained from Preparation Example 4.

[0100] Example 5

[0101] A fluorinated modified polyurethane adhesive, the specific implementation method is the same as that of Example 3, except that the antistatic agent used is obtained from Preparation Example 5.

[0102] Example 6

[0103] A fluorinated modified polyurethane adhesive, the specific implementation method is the same as that of Example 3, except that the antistatic agent used is obtained from Preparation Example 6.

[0104] Example 7

[0105] A fluorinated modified polyurethane adhesive, the specific implementation method is the same as that of Example 3, except that the antistatic agent used is obtained from Preparation Example 7.

[0106] Example 8

[0107] A fluorinated modified polyurethane adhesive, the specific implementation method is the same as that of Example 3, except that the anti-degradation agent used is 1,3,5-trimethyl 2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and 2-hydroxy-4-oxybenzophenone in a mass ratio of 1:2.

[0108] Example 9

[0109] A fluorinated modified polyurethane adhesive, the specific implementation method is the same as that of Example 3, except that the anti-deterioration agent used is 2-hydroxy-4-oxybenzophenone and bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate in a mass ratio of 2:1.

[0110] Example 10

[0111] A fluorinated modified polyurethane adhesive, the specific implementation method is the same as that of Example 3, except that the anti-degradation agent used is 1,3,5-trimethyl 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate in a mass ratio of 1:1.

[0112] Comparative Example 1

[0113] A fluorinated modified polyurethane adhesive, the specific implementation method is the same as that of Example 3, except that no anti-deterioration agent is added.

[0114] Comparative Example 2

[0115] A fluorinated modified polyurethane adhesive, the specific implementation method is the same as that of Example 3, except that no antistatic agent is added.

[0116] Embodiment 11

[0117] A functional protective film comprises a release film with a thickness of 20 μm, an adhesive layer with a thickness of 75 μm and a substrate with a thickness of 50 μm in sequence; the adhesive used in the adhesive layer is the fluorinated modified polyurethane adhesive obtained in Example 1.

[0118] The preparation method of the functional protective film is as follows: coating the fluorinated modified polyurethane adhesive on the surface of the substrate, drying at 130°C for 2 minutes to form an adhesive layer, attaching a release film to the surface of the adhesive layer, and then aging at 50°C for 24 hours to obtain the functional protective film.

[0119] Example 12

[0120] A functional protective film, the specific implementation method is the same as that of Example 11, except that the adhesive used in the adhesive layer is the fluorinated modified polyurethane adhesive obtained in Example 2.

[0121] Example 13

[0122] A functional protective film, the specific implementation manner is the same as that of Example 11, except that the adhesive used in the adhesive layer is the fluorinated modified polyurethane adhesive obtained in Example 3.

[0123] Embodiment 14

[0124] A functional protective film, the specific implementation manner is the same as that of Example 11, except that the adhesive used in the adhesive layer is the fluorinated modified polyurethane adhesive obtained in Example 4.

[0125] Embodiment 15

[0126] A functional protective film, the specific implementation method is the same as that of Example 11, except that the adhesive used in the adhesive layer is the fluorinated modified polyurethane adhesive obtained in Example 5.

[0127] Example 16

[0128] A functional protective film, the specific implementation manner is the same as that of Example 11, except that the adhesive used in the adhesive layer is the fluorinated modified polyurethane adhesive obtained in Example 6.

[0129] Embodiment 17

[0130] A functional protective film, the specific implementation manner is the same as that of Example 11, except that the adhesive used in the adhesive layer is the fluorinated modified polyurethane adhesive obtained in Example 7.

[0131] Embodiment 18

[0132] A functional protective film, the specific implementation manner is the same as that of Example 11, except that the adhesive used in the adhesive layer is the fluorinated modified polyurethane adhesive obtained in Example 8.

[0133] Embodiment 19

[0134] A functional protective film, the specific implementation manner is the same as that of Example 11, except that the adhesive used in the adhesive layer is the fluorinated modified polyurethane adhesive obtained in Example 9.

[0135] Embodiment 20

[0136] A functional protective film, the specific implementation method is the same as that of Example 11, except that the adhesive used in the adhesive layer is the fluorinated modified polyurethane adhesive obtained in Example 10.

[0137] Embodiment 21

[0138] A functional protective film, the specific implementation manner is the same as that of Example 11, except that the adhesive used in the adhesive layer is the fluorinated modified polyurethane adhesive obtained in Comparative Example 1.

[0139] Embodiment 22

[0140] A functional protective film, the specific implementation manner is the same as that of Example 11, except that the adhesive used in the adhesive layer is the fluorinated modified polyurethane adhesive obtained in Comparative Example 2.

[0141] Performance Testing

[0142] The refractive index test is carried out in accordance with ISO 21395-1:2020. The peel force test is carried out in accordance with GB / T2792 2014. The tearing voltage test method is as follows: stick the protective film on the OLED screen, fix the electrostatic field meter on the machine, place the sample 10cm below the instrument, peel off the protective film from the OLED screen at a speed of 20cm / s, and record the tearing static voltage. The high temperature and high humidity peel force test is as follows: place it at 60℃ for 72h, then place it at 85%, 85℃ for 250h, place it at room temperature for 30min, and then place it in accordance with GB / T 27922014 was tested; the contamination test was as follows: the protective film was attached to the surface of the OLED, placed at 25°C for 30 days, then the protective film was torn off to observe whether the OLED was contaminated; the scratch resistance test was as follows: the steel wool #0000 produced by Japan Steel Wool Co., Ltd. was installed on a cardboard abrasion tester (produced by Xiong Geli Industrial Co., Ltd.), and the protective film was rubbed back and forth 100 times under a load of 250g. The specific test results are shown in Table 1.

[0143] Table 1

[0144]

[0145] It can be seen from Table 1 that the protective films prepared in Examples 11-13 and Example 17 have excellent comprehensive properties, moderate refractive index, good antistatic performance, moderate peeling force, no pollution and scratch resistance.

[0146] Compared with Example 13, the preparation process of the antistatic agent used in Examples 14-16 has changed, which may change the structure of the effective ingredient of the antistatic agent, thereby affecting the antistatic performance of the adhesive and deteriorating the antistatic property of the protective film; the composition of the anti-degradation agent used in Examples 18-20 has changed, the interaction between the components of the anti-degradation agent has changed, and the synergistic effect with other components in the adhesive system (especially fluorinated modified polyurethane) has decreased, affecting the comprehensive performance of the adhesive and the protective film, and the scratch resistance, peel force and contamination resistance of the protective film under the test conditions have obviously deteriorated; no anti-degradation agent was added in Example 21, and the performance of the prepared protective film was worse; no antistatic agent was added in Example 22, and the prepared protective film had the worst antistatic performance.

[0147] The overall performance of the functional protective film prepared by the present invention is shown in Table 2.

[0148] Table 2

[0149]

[0150] As can be seen from Table 1 and Table 2, the functional electronic protective film prepared by the present invention has a soft texture, good wettability, good high temperature resistance, antistatic property, high transmittance, good refractive index and adhesion, moderate release force, super yellowing resistance, and can be folded more than 20,000 times. It also has excellent protective effect, can prevent the bending of the polyimide (PI) layer and the thin film encapsulation layer from being damaged by external factors; the functional electronic protective film is also easy to remove when the latter stage is completed, without residue, and can prevent secondary pollution.

[0151] The above is only a preferred embodiment of the present invention and does not constitute any form of limitation to the present application. Although the present application is disclosed as above in the preferred embodiment, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution.

Claims

1. A fluorinated modified polyurethane adhesive, characterized in that: According to the weight percentage, it includes the following raw material components: Fluorinated modified polyurethane 20-40 parts; plasticizer 5-20 parts; defoamer 0.1-5 parts; leveling agent 0.1-2 parts; antistatic agent 0.1-2 parts; Anti-degradation agent 0.5-3 parts.

2. The fluorinated modified polyurethane adhesive according to claim 1, characterized in that: The preparation method of the antistatic agent is: Mix monomethyl ether and sodium bromide evenly, add sulfuric acid dropwise, stir and heat to react for 4-8 hours, then add ethyl acetate and continue to react for 2-4 hours; then add deionized water, mix evenly, add thiazole, stir and react at 10-30°C for 30-60 minutes, add sodium bicarbonate, stir and react at 10-30°C for 10-12 hours, reflux and react for 5-8 hours, filter, add ethyl bromide to the filtrate, react at 10-30°C for 3-4 hours, reflux and react for 3.5-4.5 hours, stir and react at 10-30°C for 10-12 hours; then add α-olefin sulfonate, stir and react at 10-30°C for 10-12 hours, filter, distill under reduced pressure, purify, and obtain an antistatic agent.

3. The fluorinated modified polyurethane adhesive according to claim 2, characterized in that: The monomethyl ether is selected from at least one of triethylene glycol monomethyl ether, diethylene glycol monomethyl ether and propylene glycol monomethyl ether.

4. The fluorinated modified polyurethane adhesive according to claim 2, characterized in that: The molar ratio of the monomethyl ether, thiazole, ethyl bromide and α-olefin sulfonate is 1:(1-1.2):(1-1.2):(1-1.2).

5. The fluorinated modified polyurethane adhesive according to claim 2, characterized in that: The heating temperature is 60-80°C.

6. The fluorinated modified polyurethane adhesive according to claim 1, characterized in that: The anti-degradation agent includes at least one of an antioxidant, an ultraviolet absorber, and a light stabilizer.

7. The fluorinated modified polyurethane adhesive according to claim 1, characterized in that: The preparation steps of the fluorinated modified polyurethane are: (1) In an inert gas atmosphere, syringaldehyde is added to an aqueous sodium hydroxide solution, heated in a water bath at 75-85° C. with stirring, 3-chloro-1,2-propanediol is then added dropwise thereto, the temperature is raised to 90-110° C., the reaction is stirred, extracted, washed, and dried to obtain syringaldehyde diol; (2) mixing the syringaldehyde diol of step (1) with carbonate, adding a catalyst, reacting under reflux for 7-8 hours in an inert gas atmosphere, washing, filtering, and drying to obtain syringaldehyde carbonate; (3) adding the syringaldehyde carbonate and amine substance of step (2) into a solvent, stirring and reacting at 40-90° C. to obtain a fluorinated modified polyurethane.

8. A functional protective film, characterized in that: The invention comprises a release film with a thickness of 10-300 μm, an adhesive layer with a thickness of 10-300 μm and a substrate with a thickness of 5-300 μm in sequence; the adhesive used in the adhesive layer is the fluorinated modified polyurethane adhesive according to any one of claims 1-7.

9. The functional protective film of rhizosphere claim 8, characterized in that: The preparation method of the functional protective film is as follows: coating a fluorinated modified polyurethane adhesive on the surface of a substrate, drying to form an adhesive layer, laminating a release film on the surface of the adhesive layer, and then aging to obtain the protective film.

10. Use of the functional protective film according to claim 8 or 9 in surface protection of electronic products.

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