Light-cured resin as well as preparation method and application thereof

Abstract

The invention relates to the technical field of light-cured materials, in particular to light-cured resin as well as a preparation method and application thereof. The structural general formula of the light-cured resin is as shown in formula 1, wherein R1 is selected from one of C1-C20 straight-chain alkyl, branched-chain alkyl and cyclic alkyl; r2 is selected from hydrogen or methyl; r3 is selected from one of ethylene, propylene and butylidene; r4 is selected from one of hydrogen, methyl and cyclohexyl; n1 is an integer selected from 1-40, and n2 is an integer selected from 10-60. The resin is a multi-block polymer containing phosphorus oxide, organic silicon chain segments and unsaturated double bonds, has light curing activity and low stripping performance, and meanwhile has good adhesive force and does not generate migration; and when being applied to the optical UV imprinting adhesive, the high-precision transfer printing of the optical film with special textures and fine patterns can be obviously improved, the mold residue is reduced, the service life is prolonged, and the high quality, high yield and long-term stability of the optical film are ensured.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of light-cured materials, in particular to a light-cured resin and a preparation method and application thereof. BACKGROUND

[0002] UV imprinting is a surface micro-nano processing technology. By imprinting a mold with micro-fine concave and convex textures on the surface of resin, and curing under ultraviolet irradiation and then demolding, the microstructure pattern on the substrate film surface can be accurately replicated. This technology is distinguished from thermal imprinting process by its low-temperature and low-pressure curing characteristics, and is particularly suitable for batch manufacturing of sub-micron structures with high aspect ratio, and has high efficiency and energy saving. Its core advantage is that it can achieve large-area, high-precision microstructure replication through a simple process, and is widely used in optical brightening film, anti-glare film, decorative film and other fields. However, the control of the demolding process is crucial to the accuracy, clarity and stability of the final structure. High aspect ratio microstructures are prone to deformation or damage due to interfacial adhesion during demolding.

[0003] Chinese patent application CN105038392A discloses a UV imprinting coating composition and its application. A surface smoothing aid is used, which is selected from one of polysiloxane, modified polysiloxane, polyester modified polysiloxane, polyether modified polysiloxane, fluorine-containing polyacrylic copolymer. However, the polyfluoroalkane / silicone polymer has poor compatibility with the resin matrix, and the demolding force is still high when a small amount is added, and excessive addition will cause phase separation, resulting in turbidity of the system and destruction of optical uniformity. At the same time, the physical addition method is limited by the application environment, especially in high temperature and high humidity environment, the additive is easy to migrate and precipitate on the film surface, causing optical performance degradation. SUMMARY

[0004] The first aspect of the present application provides a light-cured resin, the structure general formula is shown as formula 1:

[0005] 1; wherein R1 is selected from one of C1-C 20 straight-chain alkyl, branched alkyl, cyclic alkyl; R2 is selected from hydrogen or methyl; R3 is selected from one of ethylene, propylene, butylene; R4 is selected from one of hydrogen, methyl, cyclohexyl; n1 is an integer selected from 1-40, and n2 is an integer selected from 10-60.

[0006] The preparation raw materials of the light-cured resin include, by weight parts, 30-55 parts of fatty alcohol polyether, 3-10 parts of hydroxy acrylate monomer, 3-10 parts of phosphorus oxide, 30-60 parts of epoxy polysiloxane, 0.1-0.5 parts of polymerization inhibitor, and 0.05-0.4 parts of catalyst.

[0007] The application effectively balances the adhesion, surface tension and release force of the photocuring resin by designing a specific structure of the resin. The phosphate block serves as a rigid unit, and its strong P=O bond forms directional adsorption with the substrate to improve adhesion; the polyether chain segment and the organic silicon chain segment constitute a flexible unit, and the molecular chain movement ability is given. During curing, the rigid phosphate segment preferentially anchors the substrate interface, and the flexible polyether / siloxane segment migrates to the gas-mold interface. The ether bond of polyether can buffer stress through intramolecular rotation, and the methyl / cyclohexyl of siloxane can effectively reduce the surface energy. The two are connected by chemical bonds to form a microphase separation structure: the phosphate-polyether block forms a continuous phase to ensure overall strength, and the epoxy polysiloxane as a dispersed phase is enriched on the surface. When the external release force is applied, the flexible chain segment effectively reduces the release force through conformational change, avoids damage to the microstructure, and the rigid segment maintains the pattern anchoring without falling off, realizing the dynamic balance of adhesion and release.

[0008] Optionally, the raw materials for preparing the photocuring resin include, by weight parts: fatty alcohol polyether 35-55 parts, hydroxy acrylate monomer 3-5 parts, phosphorus oxide 3-7 parts, epoxy polysiloxane 35-60 parts, polymerization inhibitor 0.1-0.3 parts, catalyst 0.2-0.4 parts.

[0009] The number average molecular weight of the fatty alcohol polyether is 500-4000.

[0010] Optionally, the fatty alcohol polyether is selected from C5-C 18 fatty alcohol polyoxyethylene ether or C5-C 18 fatty alcohol polyoxypropylene ether.

[0011] The number average molecular weight of the epoxy polysiloxane is 500-3000.

[0012] Optionally, the epoxy polysiloxane includes one of single-end mono-epoxy polysiloxane, single-end di-epoxy polysiloxane, and side-chain epoxy polysiloxane.

[0013] Optionally, the number average molecular weight of the epoxy polysiloxane is 500-3000.

[0014] Optionally, the epoxy polysiloxane is selected from one of the following grades: Silok 3590F4, Silok 3591, Silok 3596, Silok 3596F2, Silok 3597, IOTA 105-2, IOTA 105-3, IOTA 105-4.

[0015] The hydroxy acrylate monomer includes at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate.

[0016] The hydroxy acrylate monomer includes hydroxyethyl acrylate or hydroxybutyl acrylate.

[0017] The phosphorus oxide compound includes diphosphorus pentoxide or polyphosphoric acid.

[0018] The polymerization inhibitor includes a phenolic polymerization inhibitor selected from one or more of hydroquinone, p-methoxyphenol, p-hydroxyphenyl ether, p-tert-butyl catechol, di-tert-amyl hydroquinone, di-nitro-sec-butyl phenol, p-tert-butyl catechol, di-tert-butyl p-ethyl phenol.

[0019] Optionally, the polymerization inhibitor includes p-hydroxyphenyl ether.

[0020] The catalyst includes one or more of triphenylphosphine, triethylamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, and tetraethylammonium bromide.

[0021] Optionally, the catalyst includes triphenylphosphine or triethylamine.

[0022] The second aspect of the present application provides a preparation method of a photocuring resin, including the following steps: uniformly mixing a fatty alcohol polyether, a hydroxy acrylate monomer, and a polymerization inhibitor, and then performing heat preservation to obtain a first mixture; adding a phosphorus oxide compound to the first mixture, and performing a first reaction under an inert gas atmosphere to obtain a second mixture; adding a catalyst to the second mixture, and then adding dropwise an epoxy-based polysiloxane to perform a second reaction to obtain the photocuring resin.

[0023] The temperature of the first reaction is 40-70℃, and the time is 2-4h.

[0024] Optionally, the temperature of the first reaction is 40-50℃, and the time is 2-3h.

[0025] The temperature of the second reaction is 100-120℃, and the time is 2-4h.

[0026] Optionally, the temperature of the second reaction is 100-110℃, and the time is 3-4h.

[0027] The dropwise adding time is 1-2h.

[0028] The third aspect of the present application provides an application of the photocuring resin, which is applied to the preparation of optical UV imprinting glue.

[0029] Advantages

[0030] 1. The present application effectively balances the adhesion, surface tension, and release force of the photocuring resin by designing a resin with a specific structure.

[0031] 2. By limiting the composition of the raw materials for preparing the photocuring resin, the photocuring resin has an adhesion ≥ 4B, a surface tension ≥ 24 mN / m, and a release force of 28-35 N.

[0032] 3. The photocuring resin prepared by the method has low release force and avoids migration of small molecule compounds.

[0033] 4. The photocuring resin prepared by the method is simple to prepare and can be produced on a large scale.

[0034] 5. The photocuring resin can significantly improve the high-precision transfer of special textures and fine patterns of optical films, reduce mold residue, prolong the service life, ensure high quality and high yield of optical films, and have long-term stability when applied in optical UV imprinting glue. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 The infrared spectrum of the photocuring resin prepared in Example 1.

[0036] Figure 2 The surface three-dimensional structure observed by super-depth microscope after the optical UV imprinting glue of the photocuring resin prepared in Example 1 is imprinted. DETAILED DESCRIPTION

[0037] Example 1

[0038] A photocuring resin, the raw materials for preparing the photocuring resin are: fatty alcohol polyether (fatty alcohol polyoxyethylene ether, brand: O-3) 39.5 g, hydroxy acrylate monomer 3.7 g (hydroxypropyl acrylate), phosphorus oxide (phosphorus pentoxide) 4 g, epoxy polysiloxane (brand: Silok3596F2) 52.45 g, polymerization inhibitor (p-hydroxyphenyl ether) 0.3 g, catalyst (triphenylphosphine) 0.35 g.

[0039] A method for preparing a photocuring resin, comprising the following steps: mixing fatty alcohol polyether, hydroxy acrylate monomer, and polymerization inhibitor uniformly, and then performing heat preservation (30°C) to obtain a first mixture; adding phosphorus oxide to the first mixture, controlling the reaction temperature between 40-50°C under a nitrogen atmosphere, and reacting for 2.5 h to obtain a second mixture; adding a catalyst to the second mixture, heating to 80-90°C, then adding epoxy polysiloxane dropwise (dropwise time 1.5 h), and controlling the reaction temperature between 100-110°C for 3 h to obtain the photocuring resin, and the infrared spectrum of the photocuring resin is as follows.

[0040] Example 2

[0041] A photocurable resin is prepared from the following raw materials: 46 g of fatty alcohol polyether (fatty alcohol polyoxyethylene ether, brand: O-5), 3.6 g of hydroxy acrylate monomer (hydroxybutyl acrylate), 3.6 g of phosphorus oxide (phosphorus pentoxide), 46.15 g of epoxy polysiloxane (brand: Silok3596F2), 0.3 g of polymerization inhibitor (p-hydroxyphenyl ether), and 0.35 g of catalyst (triphenylphosphine).

[0042] A method for preparing a photocurable resin comprises the following steps: uniformly mixing a fatty alcohol polyether, a hydroxy acrylate monomer, and a polymerization inhibitor, and then heat-insulating the mixture at 30° C. to obtain a first mixture; adding phosphorus oxide to the first mixture, controlling the reaction temperature at 40-50° C. under a nitrogen atmosphere, and reacting for 2.5 hours to obtain a second mixture; adding a catalyst to the second mixture, heating the mixture to 80-90° C., and then dropwise adding epoxy polysiloxane (dropwise addition time 1.5 hours), controlling the reaction temperature at 100-110° C., and reacting for 3 hours to obtain the photocurable resin.

[0043] Example 3

[0044] A photocurable resin is prepared from the following raw materials: 35.9 g of fatty alcohol polyether (fatty alcohol polyoxyethylene ether, brand: O-5), 3.6 g of hydroxy acrylate monomer (hydroxybutyl acrylate), 6.5 g of phosphorus oxide (polyphosphoric acid, general product name: 8017-16-1), 53.65 g of epoxy polysiloxane (brand: Silok3591), 0.3 g of polymerization inhibitor (p-hydroxyphenyl ethyl ether), and 0.35 g of catalyst (triethylamine).

[0045] A method for preparing a photocurable resin comprises the following steps: uniformly mixing a fatty alcohol polyether, a hydroxy acrylate monomer, and a polymerization inhibitor, and then heat-insulating the mixture at 30° C. to obtain a first mixture; adding phosphorus oxide to the first mixture, controlling the reaction temperature at 40-50° C. under a nitrogen atmosphere, and reacting for 2.5 hours to obtain a second mixture; adding a catalyst to the second mixture, heating the mixture to 80-90° C., and then dropwise adding epoxy polysiloxane (dropwise addition time 1.5 hours), controlling the reaction temperature at 100-110° C., and reacting for 3 hours to obtain the photocurable resin.

[0046] Example 4

[0047] A photocurable resin is prepared from the following raw materials: 53.8 g of fatty alcohol polyether (fatty alcohol polyoxyethylene ether, brand: O-9), 3.5 g of hydroxy acrylate monomer (hydroxybutyl acrylate), 6.5 g of phosphorus oxide (polyphosphoric acid), 35.55 g of epoxy polysiloxane (brand: Silok3596F2), 0.3 g of polymerization inhibitor (p-hydroxyphenyl ether), and 0.35 g of catalyst (triphenylphosphine).

[0048] A method for preparing a photocurable resin comprises the following steps: uniformly mixing a fatty alcohol polyether, a hydroxy acrylate monomer, and a polymerization inhibitor, and then heat-insulating the mixture at 30° C. to obtain a first mixture; adding phosphorus oxide to the first mixture, controlling the reaction temperature between 40° C. and 50° C. under a nitrogen atmosphere for a reaction of 2.5 hours to obtain a second mixture; adding a catalyst to the second mixture, and then dropwise adding epoxy polysiloxane (dropwise addition time 1.5 hours), controlling the reaction temperature between 100° C. and 110° C. for a reaction of 3 hours to obtain the photocurable resin.

[0049] Example 5

[0050] A photocurable resin is prepared from the following raw materials: 37.4 g of fatty alcohol polyether (fatty alcohol polyoxyethylene ether, brand: O-3), 4.3 g of hydroxy acrylate monomer (hydroxyethyl acrylate), 8.9 g of phosphorus oxide (polyphosphoric acid), 48.75 g of epoxy polysiloxane (brand: IOTA105-4), 0.3 g of polymerization inhibitor (p-hydroxyphenyl ethyl ether), and 0.35 g of catalyst (triphenylphosphine).

[0051] A method for preparing a photocurable resin comprises the following steps: uniformly mixing a fatty alcohol polyether, a hydroxy acrylate monomer, and a polymerization inhibitor, and then heat-insulating the mixture at 30° C. to obtain a first mixture; adding phosphorus oxide to the first mixture, controlling the reaction temperature between 40° C. and 50° C. under a nitrogen atmosphere for a reaction of 2.5 hours to obtain a second mixture; adding a catalyst to the second mixture, and then dropwise adding epoxy polysiloxane (dropwise addition time 1.5 hours), controlling the reaction temperature between 100° C. and 110° C. for a reaction of 3 hours to obtain the photocurable resin.

[0052] Performance testing methods and data

[0053] 1. The photocurable resin prepared in Example 1 was subjected to infrared testing. Figure 1 As shown in the infrared spectrum, at 1635cm -1 The infrared characteristic absorption peak of acryloyloxy-C=C- is at 1261cm -1 The strong absorption peak of stretching vibration of phosphate group -P=O- is at 1193cm -1 The peak at 1093 cm is the characteristic peak of -COC- stretching vibration in the polyoxyethylene ether segment; -1 The absorption peak of -Si-O-Si- in the polysiloxane chain segment is shown in FIG1 , indicating that the photocurable resin was successfully prepared according to the designed molecular structure.

[0054] 2. The photocuring resin prepared in Examples 1-5 was added in a fixed ratio to 3.5% photoinitiator, coated on a PET film at a film thickness of 8 μm, and after UV irradiation and curing, the curing energy was LED lamp, 365 nm, 900 mj / cm2, and the adhesion, surface tension, and release force were tested, wherein the adhesion was tested in accordance with GB / T 9286-2021 "Paint Film Gravure Test for Pigment and Varnish", the surface tension was tested in accordance with GB / T 22237-2008 "Determination of Surface Tension of Surface Active Agents", and the release force was tested in accordance with GB / T 25256-2010 "Test Method for 180° Peel Force and Residual Adhesion of Release Film for Optical Functional Film", and the results are shown in Table 1.

[0055] 3. The photocuring resin of Example 1 was subjected to optical UV imprinting using a super-depth microscope, and the surface three-dimensional structure was analyzed, as shown in Figure 2 , and the micro-nano texture structure was clear and had no residual glue profile.

[0056] Table 1

[0057]

Claims

1. A light-curing resin, characterized in that: The general structural formula is shown in Formula 1: wherein R1 is selected from C1-C 20 Straight chain alkyl, C1-C 20 Branched alkyl, C1-C 20 R2 is selected from hydrogen or methyl; R3 is selected from ethylene, propylene and butylene; R4 is selected from hydrogen, methyl and cyclohexyl; n1 is selected from an integer of 1-40, and n2 is selected from an integer of 10-60.

2. The photocurable resin according to claim 1, wherein The raw materials for preparing the photocurable resin include, by weight, 30-55 parts of fatty alcohol polyether, 3-10 parts of hydroxy acrylate monomer, 3-10 parts of phosphorus oxide, 30-60 parts of epoxy polysiloxane, 0.1-0.5 parts of polymerization inhibitor, and 0.05-0.4 parts of catalyst.

3. The light-curable resin according to claim 2, wherein The fatty alcohol polyether is selected from C5-C 18 Fatty alcohol polyoxyethylene ether or C5-C 18 Fatty alcohol polyoxypropylene ether.

4. The photocurable resin according to claim 2 or 3, characterized in that: The epoxy polysiloxane includes one of single-end monoepoxy polysiloxane, single-end diepoxy polysiloxane and side-chain epoxy polysiloxane.

5. The light-curable resin according to claim 4, characterized in that The hydroxyacrylate monomer includes at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate.

6. A method for preparing the light-curable resin according to any one of claims 2 to 5, characterized in that: The following steps are involved: Fatty alcohol polyether, hydroxy acrylate monomer, and polymerization inhibitor are mixed evenly and then kept warm to obtain a first mixture; phosphorus oxide is added to the first mixture and a primary reaction is carried out under an inert gas atmosphere to obtain a second mixture; a catalyst is added to the second mixture, and epoxy polysiloxane is then added dropwise to carry out a secondary reaction to obtain a light-curing resin.

7. The method for preparing a light-curable resin according to claim 6, wherein: The temperature of the primary reaction is 40-70° C., and the time is 2-4 hours.

8. The method for preparing a light-curable resin according to claim 6, wherein: The temperature of the secondary reaction is 100-120° C., and the time is 2-4 hours.

9. The method for preparing a light-curable resin according to claim 6, wherein: The time of the dropwise addition is 1-2 hours.

10. A use of the light-curable resin according to any one of claims 1 to 5, characterized in that: Used in the preparation of optical UV embossing adhesives.

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