A dual-cured epoxy acrylate resin for preparing a 3D curved screen protective film and a preparation method thereof

Abstract

The present invention provides a dual-cured epoxy acrylate resin for preparing a 3D curved screen protective film and a preparation method thereof, belonging to the technical field of curved screen protective films. The present invention changes the dual-cured resin formula, adjusts the cross-linking density in the thermal curing process, and then adjusts the modulus after thermal curing film formation, and directly applies the dual-cured resin to the non-hardened surface of the optical PET hardened film, first thermally cures the film and rolls it up, and then directly applies a silicone pressure-sensitive adhesive layer on the dual-cured layer, and adheres the lower protective PET release film layer to obtain a 3D curved screen protective film, which does not require other processes such as hot pressing, and can be directly applied to different curved display screens. At the same time, in order to meet different hardened surface treatment requirements, it can be used with different hardened surface treatments, such as: anti-static, anti-glare, anti-reflection or anti-fingerprint, etc.

Description

Technical Field

[0001] The present invention relates to the technical field of curved screen protective films, and in particular to a dual-cured epoxy acrylate resin for preparing a 3D curved screen protective film and a preparation method thereof. Background Art

[0002] CN202020015967.8 provides a 3D heat-bending hardened film, comprising: 1-optical PET (polyethylene terephthalate) layer, 2-organic silicon pressure-sensitive adhesive layer, 3-optical PET hardened film layer, 4-acrylate adhesive layer, 5-optical TPU (polyurethane) layer, 6-organic silicon pressure-sensitive adhesive layer, 7-PET release film layer. Among them, 1 and 2 constitute the upper protection, 7 is the lower protection, and 3, 4, 5, and 6 constitute the main body of the 3D heat-bending hardened film.

[0003] This type of 3D screen protective film is made by high-temperature hot pressing of a mold, so that the film material has a curvature corresponding to the 3D curved display screen, which is convenient for laminating with the 3D curved display screen. This type of protective film has problems such as complex preparation process, low hot pressing yield, and inability to adapt to large curvature 3D displays.

[0004] CN202221089207.7 discloses a heat-set 3D curved film, comprising: 1-PET layer, 2-organic silicone pressure-sensitive adhesive layer, 3-self-repairing layer, 4-heat-set layer, 5-lower adhesive layer, 6-PET release film layer. 1 and 2 form the upper protection, 6 is the lower protection, and 3, 4, and 5 form the main body of the heat-set 3D curved film.

[0005] This type of 3D curved surface protective film will soften at a certain high temperature, making it easier to fit the curved display screen. After cooling to room temperature, the film material will return to normal hardness and shape to protect the 3D curved display screen. Although this type of protective film can be well adapted to 3D displays of various curvatures, due to the limitations of the surface treatment of the self-repairing layer, it has problems such as low water contact angle, poor anti-fouling performance, severe nail marks, slow self-repair rate and other poor user experience.

[0006] CN202110381257.6 discloses a UV-3D curved screen protective film, including: 1-optical PET (polyethylene terephthalate) layer, 2-organic silicon pressure-sensitive adhesive layer, 3-optical PET hardened film layer, 4-UV-heat dual-curing layer, 5-optical TPU (polyurethane) layer, 6-organic silicon pressure-sensitive adhesive layer, 7-PET release film layer. Among them, 1 and 2 constitute the upper protection, 7 is the lower protection, and 3, 4, 5, and 6 constitute the main body of the rear UV-3D curved screen protective film.

[0007] After this type of 3D screen protective film is attached to the 3D curved display screen, it mainly relies on the characteristics of the UV-heat dual curing layer to cure and shape after UV irradiation to shape the film material. Although this type of protective film can better adapt to 3D displays of various curvatures, and the surface treatment is more diverse. However, this type of product has problems such as complex product structure, complex preparation process, and limited yield. Summary of the invention

[0008] The technical problem to be solved by the present invention is to overcome the technical problem in the prior art that the dual-cured layer material hydroxyl group needs to be matured after reacting with isocyanate, and to provide a dual-cured epoxy acrylate resin that does not require a curing treatment, a 3D curved screen protective film and a preparation method thereof.

[0009] In one aspect of the present invention, a 3D curved screen protective film is disclosed, comprising: an optical PET hardened film layer, a UV-heat dual-curing layer and a silicone pressure-sensitive adhesive layer.

[0010] Furthermore, the thickness of the UV-heat dual-curing layer is 20-100 μm.

[0011] Furthermore, the thickness of the organic silicone pressure-sensitive adhesive layer is 5-50 μm.

[0012] Furthermore, the 3D curved screen protective film may also include a PET release film layer, and the PET release film layer is laminated with the silicone pressure-sensitive adhesive layer to serve as a lower protector of the 3D curved screen protective film.

[0013] Furthermore, the 3D curved screen protective film may also include an upper protective layer composed of an optical PET layer and a silicone pressure-sensitive adhesive layer, and the upper protective layer is bonded to the optical PET hardened film layer.

[0014] In another aspect of the present invention, a dual-curing epoxy acrylate resin is disclosed, comprising the following components in parts by weight:

[0015] 300-400 parts of epoxy acrylate monomer, 50-200 parts of alicyclic epoxy resin, 300-500 parts of bisphenol A epoxy resin, 6-10 parts of photoinitiator, 0.5-20 parts of catalyst, 0.1-60 parts of thermal cationic initiator, 1-20 parts of inhibitor, 0.5-10 parts of leveling agent and 300-600 parts of organic solvent.

[0016] Furthermore, the epoxy acrylate monomer includes one or more of glycidyl methacrylate (preferably Weber Technology), glycidyl ethacrylate, and methacrylate compounds having alicyclic epoxy groups (preferably Daicel CYCLOMERM100).

[0017] Furthermore, a guanidinopropoxy acrylate monomer is provided to replace part of the epoxy acrylate monomer. The dual-curing epoxy acrylate resin comprises the following components in parts by weight:

[0018] 250-300 parts of epoxy acrylate monomer, 50-100 parts of guanidinopropoxy acrylate monomer, 50-200 parts of alicyclic epoxy resin, 300-500 parts of bisphenol A epoxy resin, 6-10 parts of photoinitiator, 0.5-20 parts of catalyst, 0.1-60 parts of thermal cationic initiator, 1-20 parts of inhibitor, 0.5-10 parts of leveling agent and 300-600 parts of organic solvent.

[0019] Furthermore, the guanidine propoxy acrylate monomer is obtained by reacting Α, Ω-dimercapto polyethylene glycol, domain vinyl guanamine, and cerium acrylate, and then reacting with propoxy neopentyl alcohol diacrylate. The preparation method thereof is as follows:

[0020] According to the weight proportions, 1300-1600 parts of Α,Ω-dimercaptopolyethylene glycol, 0.8-6 parts of vinylguanamine, 0.01-0.2 parts of cerium acrylate and 20-50 parts of triethylamine are slowly added into a reaction kettle, nitrogen is introduced, the temperature is raised to 50-60° C., the temperature is kept for reaction for 30-100 minutes, and then 1000-1400 parts of propoxy neopentyl alcohol diacrylate are added, and the temperature is kept for reaction for 30-60 minutes to obtain a guanidine propoxy acrylate monomer.

[0021] Furthermore, the alicyclic epoxy resin is a low molecular weight compound containing two alicyclic epoxy groups, including TT297 (Tiantai Chemical), CELLOXIDE series (Daicel), and one or more of the EHPE and EPOLEAD series of multifunctional alicyclic epoxy resins (Daicel). CELLOXIDE 2000 is preferred.

[0022] Furthermore, the bisphenol A epoxy resin is a resin compound containing at least two reactive epoxy groups in the molecule, including one or more of the LOTADER series products (Arkema), with a number average molecular weight of 3700-7000. EA-1010N is preferred.

[0023] Further, the photoinitiator is any one or more of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl phosphonic acid ethyl ester, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 1,1'-(methylenedi-4,1-phenylene)bis[2-hydroxy-2-methyl-1-propanone], 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, 2-isopropylthioxanthone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone.

[0024] Furthermore, the catalyst is a tertiary amine catalyst, including one or more of bis(dimethylaminoethyl) ether, pentamethyldipropylenediamine, N-methylmorpholine or triethylenediamine.

[0025] Furthermore, the thermal cationic initiator includes one or more of blocked fluoromethanesulfonic acid, amine blocked hexafluoroantimonate, CTI thermal cationic initiator series (Uoyang Technology), and TC thermal cationic initiator series (Vicbase).

[0026] Furthermore, the inhibitor is one or more of p-hydroxyanisole, hydroquinone, methylhydroquinone, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, inhibitor-701, or inhibitor-705.

[0027] Furthermore, the leveling agent is one or more of polydimethylsiloxane solution modified with polypropylene functional groups, polyester-modified polydimethylsiloxane solution containing acrylic functional groups, and polyester-modified polydimethylsiloxane solution containing hydroxyl functional groups. Polyester-modified polydimethylsiloxane solution containing acrylic functional groups is preferred, and BYK330 is the most preferred.

[0028] Furthermore, the organic solvent includes any one or more of ethyl acetate, butanone, acetone, methyl isobutyl ketone, propylene glycol methyl ether, tetrahydrofuran, and dichloromethane.

[0029] The present invention also provides a method for preparing the 3D curved screen protective film as described above, comprising the following steps:

[0030] (1) coating the modified polyurethane acrylic resin on an optical PET substrate and curing the resin to obtain an optical PET hardened film layer;

[0031] (2) coating the dual-cured epoxy acrylate resin as described above on the non-cured surface of the optical PET hardened film layer, heating, baking, and curing to obtain a UV-heat dual-cured layer;

[0032] (3) coating the silicone onto the cured UV-heat dual-curing layer, heating and baking, and obtaining a silicone pressure-sensitive adhesive layer.

[0033] In some embodiments of the present invention, in step (2), the dual-cured epoxy acrylate resin as described above is coated on the non-cured surface of the optical PET hardened film layer, and the epoxy group is used to heat-cure and cross-link under the action of a catalyst and a thermal cationic initiator to form a film surface that can be rolled up, and the acrylic double bond group is in an unreacted state. After the 3D product is attached, UV (2000-6000mJ / cm 2 ) Curing and hardness improvement. Bisphenol A epoxy resin containing multiple epoxy groups is used as a long chain, and alicyclic epoxy resin is used as a small molecule to adjust the cross-linking density of the film after thermosetting. The addition of epoxy acrylate monomer ensures that the film has sufficient hardness and shaping ability after UV curing.

[0034] In some embodiments of the present invention, the heating and baking in step (2) is carried out at a temperature of 110 to 135° C. and for a time of 5 to 8 minutes.

[0035] In some embodiments of the present invention, the aging temperature in step (2) is 40-60° C. and the time is 48-120 hours.

[0036] The upper surface of the optical PET hardened film layer of the present invention may be provided with an anti-glare structural layer, an anti-reflective coating or an anti-fingerprint coating. The anti-glare structural layer is provided with a plurality of protrusions protruding from the surface of the optical PET hardened film layer. The anti-glare structural layer forms a rough surface, and when light is reflected from the rough surface, it will scatter at different angles, thereby improving the anti-glare effect.

[0037] Furthermore, the anti-fingerprint coating is an oleophobic surface coating disposed on the surface of the optical PET hardened film layer, which can improve the anti-fingerprint property of the protective film, the surface is not easy to generate dirt and is easy to clean, and has a good touch feel.

[0038] Furthermore, the thickness of the optical PET hardened film layer is 50-75 μm, so that the optical PET hardened film layer has good protection performance for the curved screen, and at the same time helps to control the thickness of the curved film, does not affect the controllability of the touch screen, and is more convenient to use.

[0039] Furthermore, the thickness of the optical PET hardened film layer is preferably but not limited to 50, 55, 60, 65, 70 or 75 μm.

[0040] Basic principles of the present invention:

[0041] The UV-heat dual-curing layer of the present invention has two reaction mechanisms. In the early stage, the epoxy group reacts under the action of a catalyst and a thermal cationic initiator to form a three-dimensional structure under heat, and in the later stage, the photoinitiator initiates the polymerization of the acrylic double bonds of the epoxy acrylate monomer that has participated in the thermal curing. The secondary curing improves the cross-linking density of the material, and the curing, shaping and hardness performance of the 3D curved screen protective film are more stable.

[0042] Beneficial Effects

[0043] The present invention changes the dual-curing resin formula, adjusts the cross-linking density in the heat-curing process, and further adjusts the modulus after heat-curing film formation. The dual-curing resin is directly coated on the non-hardened surface of the optical PET hardened film layer 3, and the film is first heat-cured and rolled up, and then the silicone pressure-sensitive adhesive layer 5 is directly coated on the UV-heat dual-curing layer 4, and the lower protective PET release film layer 6 is attached to obtain a 3D curved screen protective film. No other processes such as hot pressing are required, and it can be directly applied to different curved display screens. At the same time, in order to meet different hardened surface treatment requirements, it can be used in combination with different hardened surface treatments, such as: anti-static, anti-glare, anti-reflection or anti-fingerprint. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 This is the 3D curved screen protective film structure described in the present invention.

[0045] In the figure: 1-optical PET layer, 2-organic silicon pressure-sensitive adhesive layer, 3-optical PET hardening film layer, 4-UV-heat dual curing layer, 5-organic silicon pressure-sensitive adhesive layer, 6-PET release film layer. 1 and 2 form the upper protection, 6 is the lower protection, and 3, 4, and 5 form the main body of the rear 3D curved screen protective film. DETAILED DESCRIPTION

[0046] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. If no specific techniques or conditions are specified in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. The reagents or instruments used that do not specify the manufacturer are all conventional products that can be obtained commercially.

[0047] Example 1

[0048] A dual-curing epoxy acrylate resin comprises the following components:

[0049] 350g of epoxy acrylate monomer, 150g of alicyclic epoxy resin, 380g of bisphenol A epoxy resin, 8g of photoinitiator, 5g of catalyst, 30g of thermal cationic initiator, 10g of inhibitor, 5g of leveling agent, and 400g of organic solvent.

[0050] The epoxy acrylate monomer is glycidyl methacrylate (Weber Technology).

[0051] The alicyclic epoxy resin is CELLOXIDE 2000.

[0052] The bisphenol A epoxy resin is EA-1010N.

[0053] The photoinitiator is 1-hydroxycyclohexyl phenyl ketone.

[0054] The catalyst is bis(dimethylaminoethyl) ether.

[0055] The thermal cationic initiator is blocked fluoromethanesulfonic acid.

[0056] The polymerization inhibitor is p-hydroxyanisole.

[0057] The leveling agent is BYK330 from BYK Chemical.

[0058] The organic solvent is ethyl acetate.

[0059] The method for preparing the 3D curved screen protective film comprises the following steps:

[0060] (1) The modified polyurethane acrylic resin (Huizhixing R0310 resin) is coated on a 23 μm optical PET, heated and baked to evaporate the solvent, and UV cured to obtain an optical PET hardened film layer 3.

[0061] (2) The UV-heat dual-curing material (dual-curing epoxy acrylate resin) as described above is coated on the non-curing surface of the optical PET hardening film layer 3, heated and baked, and cured to obtain a UV-heat dual-curing layer 4.

[0062] The heating and baking temperature is 110° C. and the time is 8 minutes.

[0063] The aging temperature is 40° C. and the aging time is 120 hours.

[0064] (3) directly coating silica gel (Dow 7685) onto the cured UV-heat dual-curing layer 4, heating and baking to form an organic silicone pressure-sensitive adhesive layer 5.

[0065] The thickness of the UV-heat dual-curing layer is 60 μm.

[0066] The thickness of the organic silicone pressure-sensitive adhesive layer is 5 μm.

[0067] The thickness of the optical PET hardened film layer 3 is 50 μm.

[0068] Example 2

[0069] A dual-curing epoxy acrylate resin comprises the following components:

[0070] 380g of epoxy acrylate monomer, 120g of alicyclic epoxy resin, 400g of bisphenol A epoxy resin, 10g of photoinitiator, 5g of catalyst, 50g of thermal cationic initiator, 10g of inhibitor, 5g of leveling agent, and 400g of organic solvent.

[0071] The epoxy acrylate monomer is glycidyl ethyl acrylate.

[0072] The alicyclic epoxy resin is CELLOXIDE 2000.

[0073] The bisphenol A epoxy resin is EA-1010N.

[0074] The photoinitiator is 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone.

[0075] The catalyst is pentamethyldipropylenediamine.

[0076] The thermal cationic initiator is amine-blocked hexafluoroantimonate.

[0077] The polymerization inhibitor is hydroquinone.

[0078] The leveling agent is BYK330 from BYK Chemical.

[0079] The organic solvent is butanone.

[0080] The method for preparing the 3D curved screen protective film comprises the following steps:

[0081] (1) The modified polyurethane acrylic resin (Huizhixing R0310 resin) is coated on a 23 μm optical PET, heated and baked to evaporate the solvent, and UV cured to obtain an optical PET hardened film layer 3.

[0082] (2) The UV-heat dual-curing material (dual-curing epoxy acrylate resin) as described above is coated on the non-curing surface of the optical PET hardening film layer 3, heated and baked, and cured to obtain a UV-heat dual-curing layer 4.

[0083] The heating and baking temperature is 115° C. and the time is 8 minutes.

[0084] The aging temperature is 45° C. and the aging time is 100 h.

[0085] (3) directly coating silica gel (Dow 7685) onto the cured UV-heat dual-curing layer 4, heating and baking to form an organic silicone pressure-sensitive adhesive layer 5.

[0086] The thickness of the UV-heat dual-curing layer is 60 μm.

[0087] The thickness of the organic silicone pressure-sensitive adhesive layer is 15 μm.

[0088] The thickness of the optical PET hardened film layer 3 is 55 μm.

[0089] Example 3

[0090] A dual-curing epoxy acrylate resin comprises the following components:

[0091] 260g of epoxy acrylate monomer, 60g of guanidinopropoxy acrylate monomer, 150g of alicyclic epoxy resin, 360g of bisphenol A epoxy resin, 7g of photoinitiator, 5g of catalyst, 10g of thermal cationic initiator, 10g of inhibitor, 5g of leveling agent, and 400g of organic solvent.

[0092] The preparation method of the guanidinopropoxy acrylate monomer is as follows:

[0093] 1300g of Α,Ω-dimercaptopolyethylene glycol, 0.8g of vinylguanamine, 0.01g of cerium acrylate, and 20g of triethylamine were slowly added to a reaction kettle, nitrogen was introduced, and the temperature was raised to 50°C. The reaction was kept warm for 100min, and then 1000g of propoxy neopentyl alcohol diacrylate was added. The reaction was kept warm for 60min to obtain guanidine propoxy acrylate monomer.

[0094] The epoxy acrylate monomer is CYCLOMER M100 from Daicel.

[0095] The alicyclic epoxy resin is CELLOXIDE 2000.

[0096] The bisphenol A epoxy resin is EA-1010N.

[0097] The photoinitiator is 1,1'-(methylenebis-4,1-phenylene)bis[2-hydroxy-2-methyl-1-propanone].

[0098] The catalyst is N-methylmorpholine.

[0099] The thermal cationic initiator is CTI-100 (Uoyang Technology).

[0100] The polymerization inhibitor is methyl hydroquinone.

[0101] The leveling agent is BYK330 from BYK Chemical.

[0102] The organic solvent is acetone.

[0103] The method for preparing the 3D curved screen protective film comprises the following steps:

[0104] (1) The modified polyurethane acrylic resin (Huizhixing R0310 resin) is coated on a 23 μm optical PET, heated and baked to evaporate the solvent, and UV cured to obtain an optical PET hardened film layer 3.

[0105] (2) The UV-heat dual-curing material (dual-curing epoxy acrylate resin) as described above is coated on the non-curing surface of the optical PET hardening film layer 3, heated and baked, and cured to obtain a UV-heat dual-curing layer 4.

[0106] The heating and baking temperature is 120° C. and the time is 8 minutes.

[0107] The aging temperature is 50° C. and the aging time is 80 hours.

[0108] (3) directly coating silica gel (Dow 7685) onto the cured UV-heat dual-curing layer 4, heating and baking to form an organic silicone pressure-sensitive adhesive layer 5.

[0109] The thickness of the UV-heat dual-curing layer is 60 μm.

[0110] The thickness of the organic silicone pressure-sensitive adhesive layer is 30 μm.

[0111] The thickness of the optical PET hardened film layer 3 is 60 μm.

[0112] Example 4

[0113] A dual-curing epoxy acrylate resin comprises the following components:

[0114] 280g of epoxy acrylate monomer, 70g of guanidinopropoxy acrylate monomer, 120g of alicyclic epoxy resin, 370g of bisphenol A epoxy resin, 9g of photoinitiator, 5g of catalyst, 60g of thermal cationic initiator, 10g of inhibitor, 5g of leveling agent, and 400g of organic solvent.

[0115] The preparation method of the guanidinopropoxy acrylate monomer is as follows:

[0116] 1450 g of Α, Ω-dimercaptopolyethylene glycol, 3.2 g of vinylguanamine, 0.1 g of cerium acrylate, and 35 g of triethylamine were slowly added to a reactor, nitrogen was introduced, and the temperature was raised to 55° C. and kept warm for 65 minutes. Then 1150 g of propoxy neopentyl alcohol diacrylate was added and kept warm for 45 minutes to obtain guanidine propoxy acrylate monomer.

[0117] The epoxy acrylate monomer is DACIDL CYCLOMERM100.

[0118] The alicyclic epoxy resin is CELLOXIDE 2000.

[0119] The bisphenol A epoxy resin is EA-1010N.

[0120] The photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0121] The catalyst is triethylenediamine.

[0122] The thermal cationic initiator is CTI-200 (Uoyang Technology).

[0123] The polymerization inhibitor is 2-tert-butylhydroquinone.

[0124] The leveling agent is BYK330 from BYK Chemical.

[0125] The organic solvent is methyl isobutyl ketone.

[0126] The method for preparing the 3D curved screen protective film comprises the following steps:

[0127] (1) The modified polyurethane acrylic resin (Huizhixing R0310 resin) is coated on a 23 μm optical PET, heated and baked to evaporate the solvent, and UV cured to obtain an optical PET hardened film layer 3.

[0128] (2) The UV-heat dual-curing material (dual-curing epoxy acrylate resin) as described above is coated on the non-curing surface of the optical PET hardening film layer 3, heated and baked, and cured to obtain a UV-heat dual-curing layer 4.

[0129] The heating and baking temperature is 130° C. and the time is 8 minutes.

[0130] The aging temperature is 55° C. and the aging time is 60 h.

[0131] (3) directly coating silica gel (Dow 7685) onto the cured UV-heat dual-curing layer 4, heating and baking to form an organic silicone pressure-sensitive adhesive layer 5.

[0132] The thickness of the UV-heat dual-curing layer is 60 μm.

[0133] The thickness of the organic silicone pressure-sensitive adhesive layer is 40 μm.

[0134] The thickness of the optical PET hardened film layer 3 is 65 μm.

[0135] Example 5

[0136] A dual-curing epoxy acrylate resin comprises the following components:

[0137] 300g of epoxy acrylate monomer, 60g of guanidinopropoxy acrylate monomer, 160g of alicyclic epoxy resin, 410g of bisphenol A epoxy resin, 8g of photoinitiator, 5g of catalyst, 50g of thermal cationic initiator, 10g of inhibitor, 5g of leveling agent, and 400g of organic solvent.

[0138] The preparation method of the guanidinopropoxy acrylate monomer is as follows:

[0139] 1600g of Α,Ω-dimercaptopolyethylene glycol, 6g of vinylguanamine, 0.2g of cerium acrylate, and 50g of triethylamine were slowly added to a reaction kettle, nitrogen was introduced, and the temperature was raised to 60°C and kept warm for 30min. Then, 1400g of propoxy neopentyl alcohol diacrylate was added and kept warm for 30min to obtain guanidine propoxy acrylate monomer.

[0140] The epoxy acrylate monomer is CYCLOMER M100 from Daicel.

[0141] The alicyclic epoxy resin is CELLOXIDE 2000.

[0142] The bisphenol A epoxy resin is EA-1010N.

[0143] The photoinitiator is 2-isopropylthioxanthone.

[0144] The catalyst is bis(dimethylaminoethyl) ether.

[0145] The thermal cationic initiator is TC3634 (Vicbase).

[0146] The polymerization inhibitor is 2,5-di-tert-butylhydroquinone.

[0147] The leveling agent is BYK330 from BYK Chemical.

[0148] The organic solvent is propylene glycol methyl ether.

[0149] The method for preparing the 3D curved screen protective film comprises the following steps:

[0150] (1) The modified polyurethane acrylic resin (Huizhixing R0310 resin) is coated on a 23 μm optical PET, heated and baked to evaporate the solvent, and UV cured to obtain an optical PET hardened film layer 3.

[0151] (2) The UV-heat dual-curing material (dual-curing epoxy acrylate resin) as described above is coated on the non-curing surface of the optical PET hardening film layer 3, heated and baked, and cured to obtain a UV-heat dual-curing layer 4.

[0152] The heating and baking temperature is 135° C. and the time is 8 minutes.

[0153] The aging temperature is 60° C. and the aging time is 48 hours.

[0154] (3) directly coating silica gel (Dow 7685) onto the cured UV-heat dual-curing layer 4, heating and baking to form an organic silicone pressure-sensitive adhesive layer 5.

[0155] The thickness of the UV-heat dual-curing layer is 60 μm.

[0156] The thickness of the organic silicone pressure-sensitive adhesive layer is 50 μm.

[0157] The thickness of the optical PET hardened film layer 3 is 70 μm.

[0158] Comparative Example 1

[0159] A dual-curing epoxy acrylate resin comprises the following components:

[0160] Epoxy acrylate monomer 200g, alicyclic epoxy resin 150g, bisphenol A type epoxy resin 300g, photoinitiator 6g, catalyst 5g, thermal cationic initiator 30g, inhibitor 10g, leveling agent 5g, organic solvent 400g.

[0161] The epoxy acrylate monomer is glycidyl methacrylate (Weber Technology).

[0162] The alicyclic epoxy resin is CELLOXIDE 2000.

[0163] The bisphenol A epoxy resin is EA-1010N.

[0164] The photoinitiator is 1-hydroxycyclohexyl phenyl ketone.

[0165] The catalyst is bis(dimethylaminoethyl) ether.

[0166] The thermal cationic initiator is blocked fluoromethanesulfonic acid.

[0167] The polymerization inhibitor is p-hydroxyanisole.

[0168] The leveling agent is BYK330 from BYK Chemical.

[0169] The organic solvent is ethyl acetate.

[0170] The method for preparing the 3D curved screen protective film comprises the following steps:

[0171] (1) The modified polyurethane acrylic resin (Huizhixing R0310 resin) is coated on a 23 μm optical PET, heated and baked to evaporate the solvent, and UV cured to obtain an optical PET hardened film layer 3.

[0172] (2) The UV-heat dual-curing material (dual-curing epoxy acrylate resin) as described above is coated on the non-curing surface of the optical PET hardening film layer 3, heated and baked, and cured to obtain a UV-heat dual-curing layer 4.

[0173] The heating and baking temperature is 110° C. and the time is 8 minutes.

[0174] The aging temperature is 40° C. and the aging time is 120 hours.

[0175] (3) directly coating silica gel (Dow 7685) onto the cured UV-heat dual-curing layer 4, heating and baking to form an organic silicone pressure-sensitive adhesive layer 5.

[0176] The thickness of the UV-heat dual-curing layer is 60 μm.

[0177] The thickness of the organic silicone pressure-sensitive adhesive layer is 5 μm.

[0178] The thickness of the optical PET hardened film layer 3 is 50 μm.

[0179] Comparative Example 2

[0180] A dual-curing epoxy acrylate resin comprises the following components:

[0181] Epoxy acrylate monomer 300g, alicyclic epoxy resin 150g, bisphenol A type epoxy resin 900g, photoinitiator 8g, catalyst 5g, thermal cationic initiator 30g, inhibitor 10g, leveling agent 5g, organic solvent 400g.

[0182] The epoxy acrylate monomer is glycidyl methacrylate (Weber Technology).

[0183] The alicyclic epoxy resin is CELLOXIDE 2000.

[0184] The bisphenol A epoxy resin is EA-1010N.

[0185] The photoinitiator is 1-hydroxycyclohexyl phenyl ketone.

[0186] The catalyst is bis(dimethylaminoethyl) ether.

[0187] The thermal cationic initiator is blocked fluoromethanesulfonic acid.

[0188] The polymerization inhibitor is p-hydroxyanisole.

[0189] The leveling agent is BYK330 from BYK Chemical.

[0190] The organic solvent is ethyl acetate.

[0191] The method for preparing the 3D curved screen protective film comprises the following steps:

[0192] (1) The modified polyurethane acrylic resin (Huizhixing R0310 resin) is coated on a 23 μm optical PET, heated and baked to evaporate the solvent, and UV cured to obtain an optical PET hardened film layer 3.

[0193] (2) The UV-heat dual-curing material (dual-curing epoxy acrylate resin) as described above is coated on the non-curing surface of the optical PET hardening film layer 3, heated and baked, and cured to obtain a UV-heat dual-curing layer 4.

[0194] The heating and baking temperature is 110° C. and the time is 8 minutes.

[0195] The aging temperature is 40° C. and the aging time is 120 hours.

[0196] (3) directly coating silica gel (Dow 7685) onto the cured UV-heat dual-curing layer 4, heating and baking to form an organic silicone pressure-sensitive adhesive layer 5.

[0197] The thickness of the UV-heat dual-curing layer is 60 μm.

[0198] The thickness of the organic silicone pressure-sensitive adhesive layer is 5 μm.

[0199] The thickness of the optical PET hardened film layer 3 is 50 μm.

[0200] Comparative Example 3

[0201] A dual-curing epoxy acrylate resin comprises the following components:

[0202] Epoxy acrylate monomer 300g, alicyclic epoxy resin 20g, bisphenol A type epoxy resin 380g, photoinitiator 8g, catalyst 5g, thermal cationic initiator 30g, inhibitor 10g, leveling agent 5g, organic solvent 400g.

[0203] The epoxy acrylate monomer is glycidyl methacrylate (Weber Technology).

[0204] The alicyclic epoxy resin is CELLOXIDE 2000.

[0205] The bisphenol A epoxy resin is EA-1010N.

[0206] The photoinitiator is 1-hydroxycyclohexyl phenyl ketone.

[0207] The catalyst is bis(dimethylaminoethyl) ether.

[0208] The thermal cationic initiator is blocked fluoromethanesulfonic acid.

[0209] The polymerization inhibitor is p-hydroxyanisole.

[0210] The leveling agent is BYK330 from BYK Chemical.

[0211] The organic solvent is ethyl acetate.

[0212] The method for preparing the 3D curved screen protective film comprises the following steps:

[0213] (1) The modified polyurethane acrylic resin (Huizhixing R0310 resin) is coated on a 23 μm optical PET, heated and baked to evaporate the solvent, and UV cured to obtain an optical PET hardened film layer 3.

[0214] (2) The UV-heat dual-curing material (dual-curing epoxy acrylate resin) as described above is coated on the non-curing surface of the optical PET hardening film layer 3, heated and baked, and cured to obtain a UV-heat dual-curing layer 4.

[0215] The heating and baking temperature is 110° C. and the time is 8 minutes.

[0216] The aging temperature is 40° C. and the aging time is 120 hours.

[0217] (3) directly coating silica gel (Dow 7685) onto the cured UV-heat dual-curing layer 4, heating and baking to form an organic silicone pressure-sensitive adhesive layer 5.

[0218] The thickness of the UV-heat dual-curing layer is 60 μm.

[0219] The thickness of the organic silicone pressure-sensitive adhesive layer is 5 μm.

[0220] The thickness of the optical PET hardened film layer 3 is 50 μm.

[0221] The 3D curved screen protective films prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were tested under the following test conditions:

[0222] Transmittance (%)——Tested according to standard GB 2410-2008 "Test method for light transmittance and haze of transparent plastics".

[0223] Haze (%)——Tested according to standard GB 2410-2008 "Test method for light transmittance and haze of transparent plastics".

[0224] UV layer modulus before UV (KPa) - Test the modulus of the corresponding material according to the modulus test method in standard ASTM D1004.

[0225] No offset load after UV> 200g (HB pencil) - in accordance with Chapter 4 of standard GB / 6739, the hardness of the optical film coating is tested by a pencil hardness tester (QHQ-A, manufactured by Tianjin Jingke Material Testing Machine Factory).

[0226] Pressure-holding lamination and embossing - simulating the operation of a mobile phone assembly plant, the film material is attached to the mobile phone, and the mobile phone is pressed for 30 seconds using the pressure-holding lamination equipment. Then, the film surface of the mobile phone is observed for deformation during pressure-holding lamination. If it is deformed, it is NG.

[0227] High temperature and high humidity (60℃ / RH90%) - stick the film material on the corresponding 3D curved screen mobile phone and place it in a high temperature and high humidity test box at 60℃ / RH90% for 72 hours. The warping on the left and right sides is required to be ≤0.5mm, and the warping on the top and bottom is ≤1.0mm. The test quantity is 10pcs, and the failure probability is ≤2 / 10 ​​is OK.

[0228] Table 1 shows the composition ratios of the optical composite films prepared in Examples 1 to 5 and Comparative Examples 1 to 3 and the related performance test results:

[0229] Table 1

[0230]

[0231]

[0232] As can be seen from Table 1, the 3D curved screen protective films without curing described in Examples 1 to 5 of the present invention have good workability and excellent shaping ability, and have good offset printing effect after shaping. The 3D curved screen protective films described in Comparative Examples 1 to 3 cannot have both workability and excellent shaping ability.

Claims

1. A method for preparing a dual-cured epoxy acrylate resin for preparing a 3D curved screen protective film, characterized in that: A dual-curing epoxy acrylate resin, comprising the following components in parts by weight: 300-400 parts of epoxy acrylate monomer, 50-200 parts of alicyclic epoxy resin, 300-500 parts of bisphenol A epoxy resin, 6-10 parts of photoinitiator, 0.5-20 parts of catalyst, 0.1-60 parts of thermal cationic initiator, 1-20 parts of polymerization inhibitor, 0.5-10 parts of leveling agent, 300-600 parts of organic solvent; Provided is a guanidine propoxy acrylate monomer that replaces part of the epoxy acrylate monomer. The dual-curing epoxy acrylate resin comprises the following components in parts by weight: 250-300 parts of epoxy acrylate monomer, 50-100 parts of guanidino propoxy acrylate monomer, 50-200 parts of alicyclic epoxy resin, 300-500 parts of bisphenol A epoxy resin, 6-10 parts of photoinitiator, 0.5-20 parts of catalyst, 0.1-60 parts of thermal cationic initiator, 1-20 parts of inhibitor, 0.5-10 parts of leveling agent and 300-600 parts of organic solvent.

2. A method for preparing a dual-cured epoxy acrylate resin for preparing a 3D curved screen protective film as claimed in claim 1, characterized in that: The epoxy acrylate monomers include one or more of glycidyl methacrylate, glycidyl ethyl acrylate, and methacrylate compounds with alicyclic epoxy groups; the alicyclic epoxy resin is a low molecular weight compound containing two alicyclic epoxy groups; the bisphenol A type epoxy resin is a resin compound containing at least two reactive epoxy groups in the molecule, and the number average molecular weight is 3700-7000.

3. A method for preparing a dual-cured epoxy acrylate resin for preparing a 3D curved screen protective film as claimed in claim 1, characterized in that: The photoinitiator is any one or more of 1-hydroxycyclohexyl phenyl ketone, ethyl 2,4,6-trimethylbenzoylphosphonate, 2-hydroxy-4"-(2-hydroxyethoxy)-2-methylpropiophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1,1"-(methylenebis-4,1-phenylene)bis[2-hydroxy-2-methyl-1-propanone], 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, 2-isopropylthioxanthone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone; the thermal cationic initiator includes one or more of blocked fluoromethanesulfonic acid, amine-blocked hexafluoroantimonate, CTI thermal cationic initiator series, and TC thermal cationic initiator series.

4. The method for preparing a dual-cured epoxy acrylate resin for preparing a 3D curved screen protective film according to claim 1, characterized in that: The catalyst is a tertiary amine catalyst, including one or more of bis(dimethylaminoethyl) ether, pentamethyldipropylenediamine, N-methylmorpholine or triethylenediamine; the inhibitor is one or more of p-hydroxyanisole, hydroquinone, methylhydroquinone, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, inhibitor-701, or inhibitor-705.

5. A method for preparing a dual-cured epoxy acrylate resin for preparing a 3D curved screen protective film as claimed in claim 1, characterized in that: The leveling agent is one or more of polydimethylsiloxane solution modified with polypropylene functional groups, polyester-modified polydimethylsiloxane solution containing acrylic functional groups, and polyester-modified polydimethylsiloxane solution containing hydroxyl functional groups.

6. A method for preparing a dual-cured epoxy acrylate resin for preparing a 3D curved screen protective film as claimed in claim 1, characterized in that: The organic solvent includes any one or more of ethyl acetate, butanone, acetone, methyl isobutyl ketone, propylene glycol methyl ether, tetrahydrofuran and dichloromethane.

7. The method for preparing a dual-cured epoxy acrylate resin for preparing a 3D curved screen protective film according to claim 1, characterized in that: include: Optical PET hardened film layer, UV-heat dual-curing layer and silicone pressure-sensitive adhesive layer; The thickness of the UV-heat dual-curing layer is 20-100 μm; The thickness of the organic silicone pressure-sensitive adhesive layer is 5-50 μm.

8. The method for preparing a dual-cured epoxy acrylate resin for preparing a 3D curved screen protective film according to claim 1, characterized in that: The method for preparing the 3D curved screen protective film comprises the following steps: (1) coating the modified polyurethane acrylic resin on an optical PET substrate and curing the resin to obtain an optical PET hardened film layer; (2) coating the dual-cured epoxy acrylate resin described in claim 1 on the non-cured surface of the optical PET hardened film layer, heating, baking, and ripening to obtain a UV-heat dual-cured layer; (3) coating the silicone onto the cured UV-heat dual-curing layer, heating and baking, and obtaining a silicone pressure-sensitive adhesive layer.

9. The method for preparing a dual-cured epoxy acrylate resin for preparing a 3D curved screen protective film according to claim 8, characterized in that: The dual-cured epoxy acrylate resin in step (2) is coated on the non-hardened surface of the optical PET hardened film layer, and the epoxy group is thermally cured and cross-linked under the action of a catalyst and a thermal cationic initiator to form a film surface that is dry and can be rolled up, and the acrylic double bond group is in an unreacted state. After bonding to the 3D product, it is irradiated with UV at 2000-6000mJ / cm2 to cure and improve the hardness.

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