A reactive antistatic protective film adhesive and a preparation method thereof

Abstract

The application relates to the technical field of electronic device protective film materials, in particular to a reactive antistatic protective film glue and a preparation method thereof. The reactive antistatic protective film glue is prepared from the following raw materials in parts by weight: 100 parts of antistatic modified polyacrylate resin with a solid content of 38-50%, 2-5 parts of a crosslinking agent, 0.02-0.10 parts of an organic tin catalyst and 15-40 parts of a dilution solvent; the antistatic modified polyacrylate resin contains an antistatic functional monomer, and the antistatic functional monomer includes at least one of a quaternary ammonium salt type acrylate monomer, a sulfonate type acrylate monomer and a polyether phosphate type acrylate monomer. The application has excellent and durable antistatic value performance and high light transmission performance, and does not become white and misty during long-term use.

Description

Technical Field

[0001] This invention relates to the field of protective film materials for electronic devices, and in particular to a reactive antistatic protective film adhesive and its preparation method. Background Technology

[0002] Protective films are widely used in high-end electronic products such as consumer electronics, automotive electronics, and semiconductor packaging, and are indispensable functional consumables. Because electronic components in electronic products are relatively fragile, static electricity generated by the protective film can cause irreversible damage to these components, and the presence of static electricity can also affect the use of electronic products. Therefore, higher requirements are placed on the antistatic properties and durability of protective films.

[0003] Currently, the mainstream antistatic protective film solution involves physically blending small-molecule ionic antistatic agents or conductive fillers into adhesives. For example, the antistatic coating in publication CN111019550A mainly consists of polythiophene and carbon nanotubes, which have poor compatibility with acrylic resin. Over time, these substances migrate, precipitate, and run off to the surface, leading to increased surface resistance, decreased antistatic effect, and poor antistatic durability, failing to meet the requirements of high-end electronic products. Furthermore, conductive fillers such as graphene, carbon nanotubes, and lithium imide salt antistatic agents affect the light transmittance of the protective film. As these conductive fillers migrate and precipitate to the surface over time, problems such as fogging and whitening appear on the protective film surface, affecting its appearance and lifespan. Therefore, this invention provides a reactive antistatic protective film adhesive and its preparation method. Summary of the Invention

[0004] To address the issues of inconsistent antistatic durability and optical stability in existing antistatic protective films, this invention provides a reactive antistatic protective film adhesive and its preparation method.

[0005] The reactive antistatic protective film adhesive provided by this invention is achieved through the following technical solution: A reactive antistatic protective film adhesive is made from the following raw materials in parts by weight: 100 parts of antistatic modified polyacrylate resin with a solid content of 38-50%, 2-5 parts of crosslinking agent, 0.02-0.10 parts of organotin catalyst, and 15-40 parts of diluent; wherein the antistatic modified polyacrylate resin contains antistatic functional monomers, and the antistatic functional monomers include at least one of quaternary ammonium salt acrylate monomers, sulfonate acrylate monomers, and polyether phosphate acrylate monomers.

[0006] This invention has excellent antistatic properties and high light transmittance. It does not turn white or foggy even after long-term use, and can meet the needs of high-end electronic products.

[0007] Preferably, the structural formula of the quaternary ammonium salt type acrylate monomer is as follows: TFSI in the structural formula - It can also be other anions, such as Cl. - ,Br - CH3SO4 - Any one of the following, where R in the structural formula is either -H or -CH3.

[0008] Preferably, the sulfonate type acrylate monomer has the following structural formula: M in the structural formula + for Na + K + NH4 + Any one of the following; R in the structural formula is either -H or -CH3.

[0009] Preferably, the polyether phosphate type acrylate monomer has the following structural formula: The structural formula contains Na. + K + NH4 + Any one of the following; R in the structural formula is either -H or -CH3; EO in the structural formula is polyoxyethylene-CH2CH2O-; PO in the structural formula is polyoxypropylene-CH2CH(CH3)O-; the degree of polymerization n in the structural formula is 1~30; the degree of polymerization m in the structural formula is 0~20.

[0010] By employing the aforementioned antistatic functional monomers, the antistatic functional monomers can be introduced into the molecular chain of polyacrylate resin through covalent bonds, overcoming the problems of antistatic durability and optical stability deviations caused by the easy aging and precipitation of traditional antistatic agents.

[0011] Preferably, the antistatic modified polyacrylate resin is copolymerized from soft monomers, hard monomers, functional monomers, and antistatic functional monomers. The soft monomers account for 45-70% of the total mass of the antistatic modified polyacrylate resin, the hard monomers account for 10-30% of the total mass of the antistatic modified polyacrylate resin, the functional monomers account for 3-10% of the total mass of the antistatic modified polyacrylate resin, and the antistatic functional monomers account for 2-15% of the total mass of the antistatic modified polyacrylate resin.

[0012] Preferably, the soft monomer is at least one of butyl acrylate (BA), 2-ethylhexyl acrylate (2-EHA), and lauryl acrylate (LA); the hard monomer is at least one of methyl methacrylate (MMA), vinyl acetate (Vac), methyl acrylate (MA), and isobornyl methacrylate (IBOMA).

[0013] The use of the aforementioned soft monomers can provide initial tack and chain segment flexibility, and lower the overall glass transition temperature (Tg). The use of the aforementioned hard monomers can adjust cohesive strength and improve overall holding power and mechanical properties.

[0014] Preferably, the functional monomer is at least one of hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), acrylate (AA), hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA), methacrylate (MAA), glycidyl methacrylate (GMA), N-hydroxymethylacrylamide (N-MAN), N-hydroxymethylmethacrylamide (N-MMAA), acrylamide (AM), methacrylamide (MAAm), dimethylaminoethyl methacrylate (DMAEMA), and ethyl acetoacetate methacrylate (AAEM).

[0015] Functional monomers can provide -OH or -NH2 groups, offering crosslinking sites with -NCO to form a three-dimensional crosslinked network. This improves the overall mechanical properties, heat resistance, weather resistance, hydrolysis resistance, and abrasion and scratch resistance, while also enhancing the overall durable antistatic performance. The -NH2 groups provided by the functional monomers can undergo Michael addition or condensation reactions with the acetylacetoxy groups containing active methylene groups in AAEM, adjusting the crosslinking density of the three-dimensional crosslinked network and optimizing the overall comprehensive performance, thus improving the overall durable antistatic performance. DMAEMA, a functional monomer, introduces cationic groups; the tertiary amine groups can undergo quaternization reactions, transforming into a permanently cationic polymer, improving the overall antistatic effect. It can also serve as an active center for crosslinking and grafting, improving the crosslinking density of the overall three-dimensional crosslinked network and optimizing the overall comprehensive performance.

[0016] Preferably, the method for preparing the antistatic modified polyacrylate resin includes the following steps: S1, Ethyl acetate and butanone are mixed evenly at a mass ratio of 1:(0.8-2) to form the base material; Simultaneously, soft monomers, hard monomers, functional monomers, and antistatic functional monomers are mixed evenly according to a certain ratio to obtain a mixed monomer. Ethyl acetate and a thermal initiator are added to the mixed monomer. The mass ratio of ethyl acetate to the mixed monomer is (3-5):10, and the mass ratio of the thermal initiator to the mixed monomer is (0.3-0.8):100. The mixture is then mixed evenly to obtain a dropping solution. S2, under nitrogen protection, adjust the temperature of the base material to 60-80℃, add the dropping liquid to the base material at a dropping rate of 0.4-0.6 g / min, maintain the temperature at 60-80℃ for 90-150 min after the dropping is completed, add 0.2-0.4% of thermal initiator by mass of mixed monomers, and maintain the temperature at 60-80℃ for 300-400 min; S3, cool to below 30℃, add 0.02-0.05% of hydroquinone monomethyl ether MEHQ by mass of the mixed monomers and stir to mix evenly. Adjust the solid content to 38-50% with ethyl acetate. The discharged material is a slightly yellow, transparent, viscous liquid, which is the antistatic modified polyacrylate resin with a viscosity of 5000-10000 mPa·s.

[0017] Preferably, the crosslinking agent is at least one of HDI trimer, IPDI trimer, and NCO-terminated polyurethane oligomers with an NCO functional group degree of 3-5; the NCO-terminated polyurethane oligomers are prepared from small molecule polyols with a hydroxyl functional group degree of 3-5 and diisocyanates, wherein the small molecule polyol is at least one of glycerol, trimethylolpropane, tris(2-hydroxyethyl)isocyanurate, pentaerythritol, tetramethylolpropane, and di(trimethylolpropane); and the diisocyanate is at least one of HDI, IPDI, and NBDI.

[0018] The present invention provides a method for preparing a reactive antistatic protective film adhesive, which is achieved through the following technical solution: A method for preparing a reactive antistatic protective film adhesive includes the following steps: Step 1: Preparation of antistatic modified polyacrylate resin; Step 2: Weigh 100 parts of the antistatic modified polyacrylate resin with a solid content of 38-50% prepared in Step 1, 2-5 parts of crosslinking agent, 0.02-0.10 parts of organotin catalyst, and 15-40 parts of diluent, mix them evenly and degas to obtain the antistatic protective film adhesive. Step 3: Apply the antistatic protective film adhesive from Step 2 to the PET base film, then dry it at 90±5℃ for 3-5 minutes, cover it with the release film, and cure it at 50±5℃ for 24-48 hours to obtain the finished antistatic protective film.

[0019] In summary, this invention has the following advantages: It overcomes the problem of poor antistatic durability and optical stability caused by the easy aging and precipitation of traditional antistatic agents by introducing antistatic functional monomers into the molecular chain of polyacrylate resin via covalent bonds. Furthermore, the use of functional monomers and crosslinking agents to form a three-dimensional crosslinked network structure improves the excellent mechanical properties, heat resistance, weather resistance, hydrolysis resistance, abrasion and scratch resistance, and durable antistatic performance of the prepared antistatic protective film. It does not whiten or fog after long-term use, meeting the requirements of high-end electronic products. In addition, both the synthetic monomers and crosslinking agents are aliphatic and / or alicyclic, endowing the antistatic protective film with excellent resistance to yellowing and UV aging, ensuring its superior optical performance. Detailed Implementation

[0020] To further understand the inventiveness and technical advancements of this invention, the preferred embodiments of this invention will be discussed in detail below with reference to examples and comparative examples.

[0021] Example: A reactive antistatic protective film adhesive is made from the following raw materials in parts by weight: 100 parts of antistatic modified polyacrylate resin with a solid content of 38-50%, 2-5 parts of crosslinking agent, 0.02-0.10 parts of organotin catalyst, and 15-40 parts of diluent.

[0022] The crosslinking agent is at least one of HDI trimer, IPDI trimer, and NCO-terminated polyurethane oligomers with an NCO functional group degree of 3-5. The NCO-terminated polyurethane oligomers are prepared from a small-molecule polyol with a hydroxyl functional group degree of 3-5 and a diisocyanate. The small-molecule polyol is at least one of glycerol, trimethylolpropane, tris(2-hydroxyethyl)isocyanurate, pentaerythritol, tetramethylolpropane, and di(trimethylolpropane). The diisocyanate is at least one of HDI, IPDI, and NBDI.

[0023] The organotin catalyst is at least one of dibutyltin dilaurate T12 and stannous octoate T9.

[0024] The diluent is at least one of methanol, ethanol, toluene, ethyl acetate, butyl acetate, and butanone.

[0025] Antistatic modified polyacrylate resin is made by copolymerization of soft monomers, hard monomers, functional monomers, antistatic functional monomers, thermal initiators, and organic solvents.

[0026] The soft monomer accounts for 45-70% of the total mass of the antistatic modified polyacrylate resin. The soft monomer is at least one of butyl acrylate (BA), 2-ethylhexyl acrylate (2-EHA), and lauryl acrylate (LA).

[0027] The hard monomer accounts for 10-30% of the total mass of the antistatic modified polyacrylate resin, and the hard monomer is at least one of methyl methacrylate (MMA), vinyl acetate (Vac), methyl acrylate (MA), and isobornyl methacrylate (IBOMA).

[0028] The functional monomer accounts for 3-10% of the total mass of the antistatic modified polyacrylate resin. The functional monomer is at least one of the following: hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), acrylate (AA), hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA), methacrylate (MAA), glycidyl methacrylate (GMA), N-hydroxymethylacrylamide (N-MAN), N-hydroxymethylmethacrylamide (N-MMAA), acrylamide (AM), methacrylamide (MAAm), dimethylaminoethyl methacrylate (DMAEMA), and ethyl acetoacetate methacrylate (AAEM).

[0029] Antistatic functional monomers account for 2-15% of the total mass of antistatic modified polyacrylate resin.

[0030] The antistatic functional monomers include at least one of quaternary ammonium salt acrylate monomers, sulfonate acrylate monomers, and polyether phosphate acrylate monomers.

[0031] The structural formulas of quaternary ammonium salt type acrylate monomers are as follows: TFSI in the structural formula - It could also be other anions, such as Cl. - ,Br - CH3SO4 - Any one of the following, where R in the structural formula is either -H or -CH3.

[0032] The structural formulas of sulfonate-type acrylate monomers are as follows: M in the structural formula + for Na + K + NH4 + Any one of the following; R in the structural formula is either -H or -CH3.

[0033] Preparation Example 1: A method for synthesizing sulfonate-type acrylate monomers, comprising the following steps: Step 1: Sodium 2-ethanesulfonate methacrylate SSEM-Na (CAS: 1804-87-1), potassium 3-sulfonate methacrylate SPMA-K (CAS: 31098-21-2), and sodium 2-acrylamide-2-methylpropanesulfonate AMPSNa (CAS: 5165-97-9) are mixed evenly in a molar ratio of 1 / 1 / 1 and then subjected to vacuum dehydration. Simultaneously, anhydrous triethylamine (CAS: 121-44-8) and butyl acetate were subjected to vacuum dehydration treatment; Step 2: The reactor is heated to 100℃ and dried, then nitrogen is used to purge moisture. The uniformly mixed SSEM-Na / SPMA-K / AMPSNa powder is dispersed in dry butyl acetate. An equimolar amount (total molar amount of SSEM-Na+SPMA-K+AMPSN) of anhydrous triethylamine is slowly added dropwise at 0.5 mL / min under controlled temperature of 30℃. The reaction is carried out under magnetic stirring at 120 rpm for 4.0 h. A white precipitate of NaCl / KCl is precipitated in the system. The precipitate is then filtered to remove the metal salt solid by vacuum filtration, yielding crude short-chain sulfonate triethylamine containing solvent. Step 3, vacuum desolventizing: Butyl acetate is completely evaporated under high vacuum at 45°C to obtain a pale yellow transparent oily monomer, which is the preparation of sulfonate type acrylate monomer.

[0034] The structural formula of polyether phosphate type acrylate monomers is as follows: The structural formula contains Na. + K + NH4 + Any one of the following; R in the structural formula is either -H or -CH3; EO in the structural formula is polyoxyethylene-CH2CH2O-; PO in the structural formula is polyoxypropylene-CH2CH(CH3)O-; the degree of polymerization n in the structural formula is 1~30; the degree of polymerization m in the structural formula is 0~20.

[0035] Preparation Example 2: Polyether phosphate type acrylate monomer, including the following steps: Step 1, raw material dehydration pretreatment: MPEG500MA / MPEG750MA (methoxy polyethylene glycol methacrylate, CAS: 26915-72-0) is put into the reactor and dehydrated under vacuum at 100℃ for 2 hours, with the moisture content controlled at ≤0.05%. Then, the inhibitor p-hydroxyanisole (MEHQ, CAS: 150-76-5) is added, with MEHQ accounting for 0.5% of the total mass of MPEG500MA / MPEG750MA. The air in the reactor is replaced with nitrogen 3 times. Step 2, Low-temperature controlled feeding: The kettle temperature is reduced to 68℃, and phosphorus pentoxide (P2O5) is slowly added in five batches. The phosphorus pentoxide (P2O5) accounts for 0.8% of the total mass of MPEG500MA / MPEG750MA. The interval between each batch of phosphorus pentoxide (P2O5) is 5 minutes. The entire process is carried out under nitrogen atmosphere and in the dark. After the phosphorus pentoxide (P2O5) is added, the temperature is maintained at 120 rpm and 65℃ for 8.0 hours.

[0036] Step 3, hydrolysis to eliminate byproducts: a small amount of ice water is slowly added dropwise to the reaction vessel to hydrolyze the byproduct pyrophosphate diester into monophosphate ester; after standing and separating into layers, the organic phase is taken and dichloroethane is removed under vacuum at 40°C to obtain a pale yellow transparent viscous free phosphoric acid. Step 4: Neutralize the acidic groups of the free acid polyether phosphate acrylate in the reactor with anhydrous triethylamine. Dry the reactor and replace it with nitrogen. Add the free acid phosphate and dry butyl acetate, and stir at 35°C until a completely transparent homogeneous phase is formed. Control the temperature at 45°C to prevent triethylamine from oxidizing and turning yellow, and the double bonds from gelling. Add 1.03 equivalents of anhydrous triethylamine dropwise at a uniform rate over 3 hours until the anhydrous triethylamine is completely added. The pH value is measured to be 7.35, thus obtaining the polyether phosphate acrylate monomer.

[0037] A method for preparing antistatic modified polyacrylate resin includes the following steps: S1, Ethyl acetate and butanone are mixed evenly at a mass ratio of 1:(0.8-2) to form the base material; Simultaneously, soft monomers, hard monomers, functional monomers, and antistatic functional monomers are mixed evenly according to a certain ratio to obtain a mixed monomer. Ethyl acetate and a thermal initiator are added to the mixed monomer. The mass ratio of ethyl acetate to the mixed monomer is (3-5):10, and the mass ratio of the thermal initiator to the mixed monomer is (0.3-0.8):100. The mixture is then mixed evenly to obtain a dropping solution. S2, under nitrogen protection, adjust the temperature of the base material to 60-80℃, add the dropping liquid to the base material at a dropping rate of 0.4-0.6 g / min, maintain the temperature at 60-80℃ for 90-150 min after the dropping is completed, add 0.2-0.4% of thermal initiator by mass of mixed monomers, and maintain the temperature at 60-80℃ for 300-400 min; S3, cool to below 30℃, add 0.02-0.05% of hydroquinone monomethyl ether MEHQ by mass of the mixed monomers and stir to mix evenly. Adjust the solid content to 38-50% with ethyl acetate. The product is a slightly yellow, transparent, viscous liquid, which is the antistatic modified polyacrylate resin with a viscosity of 5000-10000 mPa•s.

[0038] A method for preparing a reactive antistatic protective film adhesive includes the following steps: Step 1: Preparation of antistatic modified polyacrylate resin; Step 2: Weigh 100 parts of the antistatic modified polyacrylate resin with a solid content of 38-50% prepared in Step 1, 2-5 parts of crosslinking agent, 0.02-0.10 parts of organotin catalyst, and 15-40 parts of diluent, mix them evenly and degas to obtain the antistatic protective film adhesive. Step 3: Apply the antistatic protective film adhesive from Step 2 to the PET base film, then dry it at 90±5℃ for 3-5 minutes, cover it with the release film, and cure it at 50±5℃ for 24-48 hours to obtain the finished antistatic protective film.

[0039] Example 1: A reactive antistatic protective film adhesive is made from the following raw materials in parts by weight: 100 parts of antistatic modified polyacrylate resin with a solid content of 45%, 3.2 parts of HDI trimer (Bayer N3600), 0.06 parts of dibutyltin dilaurate T12, and 25 parts of ethyl acetate BA.

[0040] The antistatic modified polyacrylate resin is made from 64g butyl acrylate (BA), 20g methyl methacrylate (MMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 8g [2-(methacryloyloxy)ethyl]trimethylammonium chloride (CAS: 5039-78-1, Beijing Bailingwei Technology Co., Ltd.), 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0041] A method for preparing a reactive antistatic protective film adhesive includes the following steps: Step 1: Preparation of antistatic modified polyacrylate resin; S1.1 In a four-necked flask equipped with a stirrer, reflux condenser, thermometer and N2 inlet tube, add 30g of ethyl acetate and 25g of butanone as the base liquid, heat to 50℃ and set aside. Simultaneously, 60g of butyl acrylate (BA), 20g of methyl methacrylate (MMA), 6g of hydroxyethyl acrylate (HEA), 2g of acrylic acid (AA), and 12g of quaternary ammonium salt-TFSI type antistatic functional monomers are mixed evenly to obtain a mixed monomer. 40g of ethyl acetate and 0.3g of thermal initiator AIBN are added to the mixed monomer and mixed evenly to obtain a dropping solution. S1.2, under nitrogen protection, adjust the temperature of the base material to 72℃, add the dropping liquid to the base material at a dropping rate of 0.5g / min at a speed of 200rpm, maintain the temperature at 72℃ for 2h after the dropping is completed, add 0.2g of thermal initiator AIBN, adjust the temperature to 78℃ and maintain the temperature for 4.0h. S1.3, cool to below 30℃, add 5.02g of hydroquinone monomethyl ether / ethyl acetate solution (containing 0.02g of hydroquinone monomethyl ether MEHQ), stir at 200rpm for 5min, add 11.72g of ethyl acetate to adjust the solid content to 45%, and the viscosity of the discharged product is 8.05*10. 4 A slightly yellow, transparent, viscous liquid at mPa•s is an antistatic modified polyacrylate resin. Step 2: Weigh 100 parts of the antistatic modified polyacrylate resin with a solid content of 45% prepared in S1.3, 3.2 parts of HDI trimer N3600, 0.06 parts of dibutyltin dilaurate T12, and 25 parts of ethyl acetate BA. Stir at 320 rpm for 8 min, then degas under vacuum for 15 min, and discharge to obtain the antistatic protective film adhesive. Step 3: Apply the antistatic protective film adhesive from Step 2 to the PET base film, then dry it at 90℃ for 3 minutes, laminate with the release film, and cure at 50℃ for 48 hours to obtain the finished antistatic protective film.

[0042] The difference between Example 2 and Example 1 is that the [2-(methacryloyloxy)ethyl]trimethylammonium chloride in the antistatic modified polyacrylate resin formulation is replaced in equal amounts with the sulfonate type acrylate monomer in Preparation Example 1.

[0043] The difference between Example 3 and Example 1 is that the [2-(methacryloyloxy)ethyl]trimethylammonium chloride in the antistatic modified polyacrylate resin formulation is replaced in equal amounts with the polyether phosphate type acrylate monomer in Preparation Example 2.

[0044] The difference between Example 4 and Example 2 is that the antistatic modified polyacrylate resin is made from 70g butyl acrylate (BA), 20g methyl methacrylate (MMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 2g sulfonate type acrylate monomer as in Preparation Example 1, 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0045] The difference between Example 5 and Example 2 is that the antistatic modified polyacrylate resin is made from 70g butyl acrylate (BA), 20g methyl methacrylate (MMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 5g sulfonate-type acrylate monomers as in Preparation Example 1, 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0046] The difference between Example 6 and Example 2 is that the antistatic modified polyacrylate resin is made from 70g butyl acrylate (BA), 20g methyl methacrylate (MMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 15g sulfonate-type acrylate monomer as in Preparation Example 1, 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0047] The difference between Example 7 and Example 3 is that the antistatic modified polyacrylate resin is made from 67g butyl acrylate (BA), 20g methyl methacrylate (MMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 2g polyether phosphate type acrylate monomer as in Preparation Example 2, 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0048] The difference between Example 8 and Example 3 is that the antistatic modified polyacrylate resin is made from 67g butyl acrylate (BA), 20g methyl methacrylate (MMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 5g polyether phosphate type acrylate monomer as in Preparation Example 2, 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0049] The difference between Example 9 and Example 3 is that the antistatic modified polyacrylate resin is made from 60g butyl acrylate (BA), 20g methyl methacrylate (MMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 15g polyether phosphate type acrylate monomer as in Preparation Example 2, 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0050] The difference between Example 10 and Example 2 is that the antistatic modified polyacrylate resin is made from 64g butyl acrylate (BA), 10g methyl methacrylate (MMA), 10g isobornyl methacrylate (IBOMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 8g of the sulfonate type acrylate monomer from Preparation Example 1, 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0051] The difference between Example 11 and Example 3 is that the antistatic modified polyacrylate resin is made from 64g butyl acrylate (BA), 10g methyl methacrylate (MMA), 10g isobornyl methacrylate (IBOMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 8g of the polyether phosphate type acrylate monomer from Preparation Example 2, 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0052] The difference between Example 12 and Example 3 is that the antistatic modified polyacrylate resin is made from 62g butyl acrylate (BA), 10g methyl methacrylate (MMA), 10g isobornyl methacrylate (IBOMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 2g dimethylaminoethyl methacrylate (DMAEMA), 8g of the sulfonate type acrylate monomer from Preparation Example 1, 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0053] The difference between Example 13 and Example 1 is that the antistatic modified polyacrylate resin is made from 62g butyl acrylate (BA), 10g methyl methacrylate (MMA), 10g isobornyl methacrylate (IBOMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 2g dimethylaminoethyl methacrylate (DMAEMA), 8g of the polyether phosphate type acrylate monomer from Preparation Example 2, 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0054] The difference between Example 14 and Example 1 is that 3.2 parts of HDI trimer were replaced with 4.8 parts of NCO-terminated polyurethane oligomer with an NCO functional group degree of 4.

[0055] The preparation method of NCO-terminated polyurethane oligomers with NCO functionality of 4 is as follows: Under nitrogen atmosphere, 13.62g of pentaerythritol (CAS: 115-77-5), 88.92g of isophorone diisocyanate (IPDI), and 0.02g of 0.06 parts of dibutyltin dilaurate (T12) are mixed evenly, heated to 80℃, and reacted for 1.5h until the NCO content reaches the theoretical value. The mixture is then cooled to below 40℃ to obtain the final product.

[0056] The difference between Comparative Example 1 and Example 1 is that the antistatic modified polyacrylate resin was made from 72g butyl acrylate (BA), 20g methyl methacrylate (MMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0057] The difference between Comparative Example 2 and Example 1 is that the antistatic modified polyacrylate resin was made from 71g butyl acrylate (BA), 20g methyl methacrylate (MMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 1g of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0058] The difference between Comparative Example 3 and Example 1 is that the antistatic modified polyacrylate resin was made from 71g butyl acrylate (BA), 20g methyl methacrylate (MMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 1g of sulfonate-type acrylate monomer from Preparation Example 1, 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0059] The difference between Comparative Example 4 and Example 1 is that the antistatic modified polyacrylate resin was made from 71g butyl acrylate (BA), 20g methyl methacrylate (MMA), 6g hydroxyethyl acrylate (HEA), 2g acrylic acid (AA), 1g of polyether phosphate type acrylate monomer as in Preparation Example 2, 80g ethyl acetate, 0.5g azobisisobutyronitrile (AIBN), and 25g butanone.

[0060] Performance testing: 1. The transmittance and haze of the protective film@PET were determined according to ASTM D1003-21. 2. The surface resistivity of the protective film was determined using the four-probe method. 3. Weather resistance: The sample (protective film@PET) was placed in a 1000W high-pressure mercury lamp at a distance of 0.5m for UV aging for 168 hours. After being removed and allowed to warm for 2 hours, its transmittance, haze, and ΔE value (measured using a WF30 plastic film colorimeter) were tested.

[0061] Table 1: Test parameters of the cured protective films in Examples 1-14 and Comparative Examples 1-4 As can be seen from Examples 1-14 and Comparative Examples 1-4 and Table 1, the protective film prepared by the antistatic modified polyacrylate resin provided in this invention has excellent antistatic durability and high light transmittance. It does not turn white or foggy after long-term use, and overcomes the problems of antistatic durability and optical stability deviation caused by the easy aging and precipitation of traditional antistatic agents. It can meet the needs of high-end electronic products.

[0062] Based on Examples 1, 4-9, and Comparative Examples 2-4, and in conjunction with Table 1, it can be seen that the polyether phosphate type acrylate monomer in Preparation Example 2 has the most significant impact on the antistatic properties of the protective film; the addition amount of the antistatic functional monomer is controlled at 2-15% to ensure the antistatic properties of the protective film; the optimal addition amount of the antistatic functional monomer is controlled at 8±0.5%, which can both ensure the antistatic properties of the protective film and improve its weather resistance.

Claims

1. A reactive antistatic protective film adhesive, characterized in that: The resin is made from the following raw materials in parts by weight: 100 parts of antistatic modified polyacrylate resin with a solid content of 38-50%, 2-5 parts of crosslinking agent, 0.02-0.10 parts of organotin catalyst, and 15-40 parts of diluent; the antistatic modified polyacrylate resin contains antistatic functional monomers, including at least one of quaternary ammonium salt type acrylate monomers, sulfonate type acrylate monomers, and polyether phosphate type acrylate monomers; the antistatic modified polyacrylate resin is copolymerized from soft monomers, hard monomers, functional monomers, and antistatic functional monomers, wherein the soft monomers account for 45-70% of the total mass of the antistatic modified polyacrylate resin, the hard monomers account for 10-30% of the total mass of the antistatic modified polyacrylate resin, the functional monomers account for 3-10% of the total mass of the antistatic modified polyacrylate resin, and the antistatic functional monomers account for 2-15% of the total mass of the antistatic modified polyacrylate resin.

2. The reactive antistatic protective film adhesive according to claim 1, characterized in that: The structural formula of the quaternary ammonium salt type acrylate monomer is as follows: TFSI in the structural formula - It can also be other anions, such as Cl. - ,Br - CH3SO4 - Any one of the following, where R in the structural formula is either -H or -CH3.

3. The reactive antistatic protective film adhesive according to claim 1, characterized in that: The structural formula of the sulfonate type acrylate monomer is as follows: M in the structural formula + for Na + K + NH4 + Any one of the following; R in the structural formula is either -H or -CH3.

4. The reactive antistatic protective film adhesive according to claim 1, characterized in that: The structural formula of the polyether phosphate type acrylate monomer is as follows: The structural formula contains Na. + K + NH4 + Any one of the following; R in the structural formula is either -H or -CH3; EO in the structural formula is polyoxyethylene-CH2CH2O-; PO in the structural formula is polyoxypropylene-CH2CH(CH3)O-; the degree of polymerization n in the structural formula is 1~30; the degree of polymerization m in the structural formula is 0~20.

5. The reactive antistatic protective film adhesive according to claim 1, characterized in that: The soft monomer is at least one of butyl acrylate (BA), 2-ethylhexyl acrylate (2-EHA), and lauryl acrylate (LA); the hard monomer is at least one of methyl methacrylate (MMA), vinyl acetate (Vac), methyl acrylate (MA), and isobornyl methacrylate (IBOMA).

6. The reactive antistatic protective film adhesive according to claim 1, characterized in that: The functional monomer is at least one of the following: hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), acrylate (AA), hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA), methacrylate (MAA), glycidyl methacrylate (GMA), N-hydroxymethylacrylamide (N-MAN), N-hydroxymethylmethacrylamide (N-MMAA), acrylamide (AM), methacrylamide (MAAm), dimethylaminoethyl methacrylate (DMAEMA), and ethyl acetoacetate methacrylate (AAEM).

7. The reactive antistatic protective film adhesive according to claim 1, characterized in that: The preparation method of the antistatic modified polyacrylate resin includes the following steps: S1, Ethyl acetate and butanone are mixed evenly at a mass ratio of 1:(0.8-2) to form the base material; Simultaneously, soft monomers, hard monomers, functional monomers, and antistatic functional monomers are mixed evenly according to a certain ratio to obtain a mixed monomer. Ethyl acetate and a thermal initiator are added to the mixed monomer. The mass ratio of ethyl acetate to the mixed monomer is (3-5):10, and the mass ratio of the thermal initiator to the mixed monomer is (0.3-0.8):

100. The mixture is then mixed evenly to obtain a dropping solution. S2, under nitrogen protection, adjust the temperature of the base material to 60-80℃, add the dropping liquid to the base material at a dropping rate of 0.4-0.6 g / min, maintain the temperature at 60-80℃ for 90-150 min after the dropping is completed, add 0.2-0.4% of thermal initiator by mass of mixed monomers, and maintain the temperature at 60-80℃ for 300-400 min; S3, cool to below 30℃, add 0.02-0.05% of hydroquinone monomethyl ether MEHQ by mass of the mixed monomers and stir to mix evenly. Adjust the solid content to 38-50% with ethyl acetate. The discharged material is a slightly yellow, transparent, viscous liquid, which is the antistatic modified polyacrylate resin with a viscosity of 5000-10000 mPa·s.

8. The reactive antistatic protective film adhesive according to claim 1, characterized in that: The crosslinking agent is at least one of HDI trimer, IPDI trimer, and NCO-terminated polyurethane oligomers with a functional group degree of 3-5; the NCO-terminated polyurethane oligomers are prepared from small molecule polyols with a hydroxyl functional group degree of 3-5 and diisocyanates, wherein the small molecule polyol is at least one of glycerol, trimethylolpropane, tris(2-hydroxyethyl)isocyanurate, pentaerythritol, tetramethylolpropane, and di(trimethylolpropane); and the diisocyanate is at least one of HDI, IPDI, and NBDI.

9. A method for preparing a reactive antistatic protective film adhesive according to any one of claims 1-8, characterized in that: Includes the following steps: Step 1: Preparation of antistatic modified polyacrylate resin; Step 2: Weigh 100 parts of the antistatic modified polyacrylate resin with a solid content of 38-50% prepared in Step 1, 2-5 parts of crosslinking agent, 0.02-0.10 parts of organotin catalyst, and 15-40 parts of diluent, mix them evenly and degas to obtain the antistatic protective film adhesive. Step 3: Apply the antistatic protective film adhesive from Step 2 to the PET base film, then dry it at 90±5℃ for 3-5 minutes, cover it with the release film, and cure it at 50±5℃ for 24-48 hours to obtain the finished antistatic protective film.

Images