UV (ultraviolet) delayed curing adhesive and preparation method thereof

Abstract

The invention provides a UV delayed curing adhesive and a preparation method thereof. The UV delayed curing adhesive is prepared from the following raw materials in parts by weight: alicyclic epoxy resin, modified alicyclic epoxy resin, polycaprolactone polyol, a reactive diluent, a photoinitiator, a silane coupling agent and gaseous silicon. According to the prepared UV delayed curing adhesive, the formula is optimized, the defects of performance of traditional curing adhesives can be overcome, the performance of the adhesive is improved, the post-curing time is shortened, the bonding performance is improved, application in many scenes can be met, and the important research value is achieved.

Description

Technical Field

[0001] This application relates to the technical field of solidifying adhesives, and particularly relates to a UV delayed-curing adhesive and a preparation method thereof. Background Art

[0002] At present, almost all composite adhesives in the flexible packaging industry are solvent-based adhesives, with the solvent mass > 70%. The composite process includes the technological steps of coating, solvent volatilization, lamination, storage, and curing. Besides being flammable and explosive, having high emissions, a long production process, and low efficiency, there are still solvents remaining in the composite film. During peak holiday seasons when there is a strong demand for delicate packaging and urgent delivery, many composite packaging films are delivered for use without fully reacting and thoroughly volatilizing the solvents. The remaining solvents and incompletely reacted chemical substances may penetrate and contaminate food, which is a major reason why the health indicators of many pharmaceutical and food packaging materials still do not meet the standards. Although water-based adhesives are solvent-free, they have a slow drying speed, low production efficiency, and unsatisfactory adhesion performance to plastics.

[0003] Replacing solvent-based adhesives with UV adhesives can not only greatly improve the production efficiency of composite films, reducing the production process from several hours to one minute; UV adhesives are solvent-free, have no volatilization, and no harmful residues, and can better ensure that composite films meet the health and hygiene requirements of packaging materials such as food and medicine. When waiting for the solvent to volatilize for several or even dozens of hours during which the construction site cannot be used, there is no such problem with the use of photocuring adhesives. The photocuring adhesive can be first coated on the ground, leveled by self-leveling, and then cured by irradiating with ultraviolet light. The surface has adhesiveness, and then the PVC floor can be laid and used immediately. This not only greatly shortens the construction period, but also there is no solvent volatilization during the entire production process, and it does not pollute the indoor air.

[0004] A UV delayed-curing adhesive is a material suitable for bonding opaque substrates. A photoinitiator (or photosensitizer) is added to a resin with a special formula. This adhesive is usually liquid, can be applied at the desired position during use, and can initiate the curing reaction by irradiating with a UV light source at an appropriate time, or after absorbing the high-intensity ultraviolet light (300nm - 400nm) in a UV light-curing device, generating active free radicals or ionic groups, thereby initiating polymerization, crosslinking, and grafting reactions, converting the resin from liquid to solid within seconds, thus achieving the bonding of substrates. It not only has high bonding strength, high transparency, no yellowing, no whitening, and good weather resistance, but also has a moderate viscosity, and has high strength for bonding plastic to plastic and plastic to metal. It has good application effects for bonding, reinforcing, and strengthening various plastics such as metal to PMMA, PC, ABS, and PVC, and is widely used in industries such as microelectronics, optical communication, optoelectronics, medical treatment, household, and aerospace.

[0005] The quality of UV glue is measured in many aspects: positioning time, curing depth, strength, flexibility of the glue film, etc. are all important factors for evaluating the quality of UV glue. However, the existing UV delayed curing agents have disadvantages such as weak adhesion and long post-curing time.

[0006] Therefore, it is of great significance to develop a high-strength UV delayed curing glue system with delayed curing characteristics and improved bonding strength after curing. Summary of the Invention

[0007] In view of this, it is necessary to provide a UV delayed curing glue and its preparation method. The raw materials for preparing the UV delayed curing glue include specific parts by weight of alicyclic epoxy resin, modified alicyclic epoxy resin, polycaprolactone polyol, reactive diluent, photoinitiator, silane coupling agent, and fumed silica. The UV delayed curing glue prepared by the present invention optimizes the formula, can make up for the deficiencies of traditional curing glue performance, improves the performance of the adhesive, shortens the post-curing time, improves the bonding performance, and can meet the applications in many scenarios, and has important research value.

[0008] In a first aspect, an embodiment of the present application provides a UV delayed curing glue. The raw materials for preparing the UV delayed curing glue include the following components in parts by weight:

[0009]

[0010]

[0011] In one embodiment, the alicyclic epoxy resin is one or more of EHPE-3150CE, 2021p, TT386A, YDH184, CY179, TT284.

[0012] In one embodiment, the modified alicyclic epoxy resin is one or more of organosilicon-modified alicyclic epoxy, carboxyl-terminated polyester-modified alicyclic epoxy resin, and etherified alicyclic epoxy resin.

[0013] In one embodiment, the polycaprolactone polyol is PCL-305.

[0014] In one embodiment, the reactive diluent is one or more of polypropylene glycol diglycidyl ether, trimethylolpropane glycidyl ether, phenyl glycidyl ether, 3-ethyl-3-hydroxymethyloxetane, and propylene glycol butyl ether.

[0015] In one embodiment, the photoinitiator is one or more of triaryl sulfonium salts, diaryl iodonium salts, alkyl sulfonium salts, and hexafluoroantimonates.

[0016] In one embodiment, the silane coupling agent is one or more of propyl methacrylate trimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, or γ-mercaptopropyltrimethoxysilane.

[0017] Second, an embodiment of the present application provides a method for preparing a UV-delay curing adhesive, which is applied to a UV-delay curing adhesive described in the first aspect. The preparation method includes the following steps:

[0018] (1) Take a certain amount of alicyclic epoxy resin, modified alicyclic epoxy resin, polycaprolactone polyol, and photoinitiator and add them to a mixing container in sequence. Among them, the alicyclic epoxy resin is one combination or multiple combinations of EHPE-3150CE, 2021p, TT386A, YDH184, CY179, TT284, and is adjusted according to the weight ratio. The modified alicyclic epoxy resin is one or more of organosilicon-modified alicyclic epoxy, carboxyl-terminated polyester-modified alicyclic epoxy resin, and etherified alicyclic epoxy resin;

[0019] (2) Start stirring and fully mix the raw materials in the mixer to form a uniform mixture;

[0020] (3) Gradually add fumed silica, reactive diluent, photoinitiator, and silane coupling agent during the stirring process, and defoam after stirring evenly to obtain the adhesive.

[0021] In one embodiment, the preparation method of the carboxyl-terminated polyester-modified aliphatic epoxy resin includes the following steps: Weigh a certain amount of epoxy resin, carboxyl-terminated polyester as a modifier, and triphenylphosphine into a round-bottom flask, stir in an oil bath at 120 °C until the epoxy value of the resin reaches the theoretical value, and cool to room temperature to obtain the modified alicyclic epoxy resin; where n(epoxy resin):n(carboxyl-terminated polyester)=4:1, and the epoxy resin is one or more of EHPE-3150CE, 2021p, TT386A, YDH184, CY179, TT284.

[0022] In one embodiment, the preparation method of the modified etherified alicyclic epoxy resin includes the following steps: Weigh a certain amount of epoxy resin and a Lewis base as an etherification catalyst into a round-bottom flask, stir in an oil bath at 100 °C until the epoxy value of the resin reaches the theoretical value; raise the temperature of the oil bath to 130 °C, add CTBN as a modifier while stirring, and continue stirring until the epoxy value of the resin reaches the theoretical value, and cool to room temperature to obtain the modified etherified alicyclic epoxy resin; where n(etherified epoxy resin):n(CTBN)=4:1, and the epoxy resin is one or more of EHPE-3150CE, 2021p, TT386A, YDH184, CY179, TT284.

[0023] A UV delayed-curing adhesive and a preparation method thereof provided by an embodiment of the present application optimize the formula, can improve the performance of the adhesive, shorten the post-curing time, and improve the bonding performance. Specific embodiments

[0024] The principles and features of the present invention are described below. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention. The present invention is described more specifically by way of example in the following paragraphs. The advantages and features of the present invention will be clearer according to the following description and claims..

[0025] It should be noted that unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the description of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0026] Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts are within the scope of protection of the present application.

[0027] In a first aspect, the present invention provides a UV delayed-curing adhesive, and the raw materials for preparing the UV delayed-curing adhesive include the following components by weight:

[0028]

[0029] Specifically, the alicyclic epoxy resin is one or more of EHPE-3150CE, 2021p, TT386A, YDH184, CY179, TT284.

[0030] Specifically, the modified alicyclic epoxy resin is one or more of organosilicon-modified alicyclic epoxy, carboxyl-terminated polyester-modified alicyclic epoxy resin, and etherified alicyclic epoxy resin.

[0031] Specifically, the polycaprolactone polyol is PCL-305.

[0032] Specifically, the active diluent is one or more of polypropylene glycol diglycidyl ether, trimethylolpropane glycidyl ether, phenyl glycidyl ether, 3-ethyl-3-hydroxymethyloxetane, and propylene glycol butyl ether.

[0033] Specifically, the photoinitiator is one or more of triarylsulfonium salts, diaryliodonium salts, alkylsulfonium salts, hexafluoroantimonates. Preferably, the photoinitiator is selected from UVI-6992 or UVI-6979.

[0034] The typical structural formula of the triarylsulfonium salt is: Ph3S + MF n - , and the typical structural formula of the diaryliodonium salt is: Ph2I + MF n - , where MF n - is BF4 - , PF6 - , AsF6 - , SbF6 - , CF5SO3 - and other non-nucleophilic anions.

[0035] Specifically, the silane coupling agent is one or more of methacrylic acid propyl ester trimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane or γ-mercaptopropyltrimethoxysilane.

[0036] In a second aspect, an embodiment of the present application provides a method for preparing a UV delayed curing adhesive, which is applied to the UV delayed curing adhesive described in the first aspect. The preparation method is as follows:

[0037] Step 1: Take a certain amount of alicyclic epoxy resin, modified alicyclic epoxy resin, polycaprolactone polyol, and photoinitiator and add them to a mixing container in sequence. Among them, the alicyclic epoxy resin is one combination or multiple combinations of EHPE-3150CE, 2021p, TT386A, YDH184, CY179, TT284, and is adjusted according to the weight ratio. The modified alicyclic epoxy resin is one or more of organosilicon-modified alicyclic epoxy, carboxyl-terminated polyester-modified alicyclic epoxy resin, and etherified alicyclic epoxy resin;

[0038] Step 2: Start stirring and fully mix the raw materials in the mixer to form a uniform mixture;

[0039] Step 3: Gradually add fumed silica, reactive diluent, photoinitiator, and silane coupling agent during the stirring process, and defoam after stirring evenly to obtain the adhesive.

[0040] To obtain an acceptable curing time under the baking temperature of 160 - 200 °C, a curing catalyst is often added to the hybrid powder coating system. The polyester resin manufacturer adds the catalyst during resin production, and this method can make the dispersion of the catalyst in the powder coating more uniform. The catalysts used to accelerate the reaction rate are tertiary amines or quaternary ammonium salts.

[0041] Specifically, in one embodiment, the preparation method of the carboxyl - terminated polyester - modified aliphatic epoxy resin comprises the following steps: Weigh a certain amount of epoxy resin, hydroxyl - terminated polyester as a modifier, and triphenylphosphine into a round - bottom flask, stir in an oil bath at 120 °C until the epoxy value of the resin reaches the theoretical value, and cool to room temperature to obtain the modified alicyclic epoxy resin; where n(epoxy resin):n(hydroxyl - terminated polyester)=4:1, and the epoxy resin is preferably one or more of EHPE - 3150CE, 2021p, TT386A, YDH184, CY179, TT284, etc.

[0042] Specifically, the carboxyl - terminated polyester - modified aliphatic epoxy resin prepared by the above method has a molecular weight of about 1000, an acid value of 120 - 140 mg / g, is a tea - colored paste at room temperature, has a melting point of about 65 °C, and its main component has the following structure:

[0043]

[0044] Adding a curing agent containing carboxyl - terminated polyester - modified aliphatic epoxy resin has the following significances: (1) The introduction of a certain proportion of low - price carboxyl - terminated polyester can greatly reduce the production cost of the polyamide curing agent; (2) The aliphatic saturated polyester chain introduced by the carboxyl - terminated polyester increases the flexibility of the epoxy cured product; (3) The aliphatic saturated polyester chain introduced by the carboxyl - terminated polyester provides better weather resistance for the epoxy cured product; (4) The aliphatic saturated polyester chain introduced by the carboxyl - terminated polyester improves the compatibility between the polyamide curing agent and the low - molecular - weight epoxy resin; (5) Compared with the traditional polyamide curing agent, the mechanical strength of the carboxyl - terminated polyester - modified polyamide curing agent has no significant difference, and it can be used as a substitute in most fields.

[0045] Optionally, the chemical structure of the alicyclic epoxy resin is alicyclic diglycidyl ether and its modified products, the product is colorless and odorless, and has a low viscosity. Due to the presence of saturated six - membered rings in the molecular structure, compared with basic epoxy products, it has excellent chemical properties. Because of its good thermal stability, excellent resistance to ultraviolet irradiation, resistance to damp - heat aging, resistance to thermal shock, and resistance to arc, it is widely used in the insulation casting and encapsulation of electronic and electrical components for outdoor use, such as dry - type transformers, instrument transformers, insulator casting insulation, outdoor coatings, etc.

[0046] Specifically, in one embodiment, the preparation method of the modified etherified alicyclic epoxy resin comprises the following steps: Weigh a certain amount of epoxy resin and Lewis base as the etherification catalyst into a round-bottom flask, stir in an oil bath at 100 °C until the epoxy value of the resin reaches the theoretical value; raise the temperature of the oil bath to 130 °C, add CTBN as the modifier while stirring, continue stirring until the epoxy value of the resin reaches the theoretical value, and cool to room temperature to obtain the modified etherified alicyclic epoxy resin; where n(etherified epoxy resin):n(CTBN) = 4:1, and the epoxy resin is preferably one or more of EHPE-3150CE, 2021p, TT386A, YDH184, CY179, TT284, etc.

[0047] Experiments show that the characteristics of the modified etherified alicyclic epoxy resin are: having high compression and tensile strength, still maintaining good mechanical properties after being exposed to high temperature conditions for a long time, having good arc resistance, ultraviolet light aging resistance and weather resistance, high purity, low viscosity, good operability, high heat resistance, small shrinkage rate, stable electrical properties and good weather resistance, etc. It is especially suitable for the requirements of high-performance electronic packaging materials such as low viscosity, high heat resistance, low water absorption and excellent electrical properties, and is a very promising electronic packaging material.

[0048] Furthermore, the following formula shows the reaction process of the specific application of a new type of modified etherified alicyclic epoxy resin. The alicyclic olefin diol and the halogenated hydrocarbon are subjected to an etherification reaction to generate an alicyclic triene ether compound, and then it can be obtained by epoxidation.

[0049]

[0050] Furthermore, when there is no accelerator, first, the hydroxyl group in the epoxy resin opens the acid anhydride ring to generate a monoester and a carboxylic acid:

[0051]

[0052] The carboxylic acid adds to the epoxy group to generate a diester and a hydroxyl group:

[0053]

[0054] The hydroxyl group generated by esterification undergoes an etherification reaction with the epoxy group:

[0055]

[0056] In this way, the ring-opening - esterification - etherification reaction continues until the epoxy adhesive crosslinks and thermally cures.

[0057] Example 1:

[0058] Add 20 parts of TT284, 20 parts of 2021p, 35 parts of 2021p modified with hydroxyl-terminated polyester, 15 parts of PCL-305, and 2 parts of triaryliodonium salt into the mixing container in sequence.

[0059] Start stirring, fully mix the raw materials in the mixer to form a uniform mixture. During the stirring process, gradually add 1 part of fumed silica, 5 parts of trimethylolpropane glycidyl ether, 1 part of hexafluoroantimonate, and 0.5 part of 3-glycidoxypropyltrimethoxysilane. After stirring evenly, defoam to obtain the adhesive.

[0060] Example 2:

[0061] Add 20 parts of TT284, 20 parts of 2021p, 35 parts of 2021p modified with hydroxyl-terminated polyester, 15 parts of PCL-305, and 3 parts of triaryliodonium salt into the mixing container in sequence.

[0062] Start stirring, fully mix the raw materials in the mixer to form a uniform mixture. During the stirring process, gradually add 1 part of fumed silica, 5 parts of trimethylolpropane glycidyl ether, 1 part of hexafluoroantimonate, and 0.5 part of 3-glycidoxypropyltrimethoxysilane. After stirring evenly, defoam to obtain the adhesive.

[0063] Example 3:

[0064] Add 30 parts of YDH184, 15 parts of 2021p, 20 parts of modified etherified 2021p, 10 parts of PCL-305, and 2 parts of diaryliodonium salt into the mixing container in sequence.

[0065] Start stirring, fully mix the raw materials in the mixer to form a uniform mixture

[0066] During the stirring process, gradually add 1 part of fumed silica, 5 parts of trimethylolpropane glycidyl ether, 1 part of hexafluoroantimonate, and 0.5 part of 3-glycidoxypropyltrimethoxysilane. After stirring evenly, defoam to obtain the adhesive.

[0067] Example 4:

[0068] Add 20 parts of YDH184, 20 parts of 2021p, 35 parts of modified etherified 2021p, 15 parts of PCL-305, and 2 parts of diaryliodonium salt into the mixing container in sequence.

[0069] Start stirring, fully mix the raw materials in the mixer to form a uniform mixture. During the stirring process, gradually add 1 part of fumed silica, 5 parts of trimethylolpropane glycidyl ether, 1 part of hexafluoroantimonate, and 0.5 part of 3-glycidoxypropyltrimethoxysilane. After stirring evenly, defoam to obtain the adhesive.

[0070] Specifically, in terms of economy, compared with thermal curing, the energy utilization rate of ultraviolet curing is high, saving up to 90% of the energy; in terms of time, the curing speed is fast, and curing can be completed in a few seconds to dozens of seconds, which is beneficial to the automated production line and improves labor productivity. It has good adhesion to materials and can be combined with materials sensitive to temperature and humidity; the molecular weight and cross-linking degree of the resin can be adjusted through raw materials and light. The equipment is simple and easy to use, suitable for both large-scale production in factories and small-scale use at home.

[0071] Test conditions:

[0072] Delay time: Drop 0.5 mL of glue on a glass slide, irradiate it with a light intensity of 2000 mJ / cm 2 for 5 seconds respectively, start timing, and the time when the glue loses fluidity is regarded as the delay time.

[0073] Open time: Drop 0.5 mL of glue on a glass slide, irradiate it with a light intensity of 2000 mJ / cm 2 for 5 seconds respectively, start timing, test its surface stickiness with fingers, and the time when the surface loses stickiness is regarded as the surface drying time.

[0074] Full curing time: Drop 0.5 mL of glue on a glass slide, irradiate it with a light intensity of 2000 mJ / cm 2 for 5 seconds respectively, place it at room temperature, and the time when it no longer releases heat measured by DSC is the full curing time.

[0075] Shear strength: Drop a certain amount of glue on a stainless steel substrate, irradiate it with a 365 nm light source for 5 seconds, bond an aluminum substrate, the bonding area is 12.5 mm * 5 mm, after preliminary bonding, place it at room temperature and cure for 24 hours, and then test the shear strength.

[0076] Aging test: Place the bonded substrate in an aging environment (temperature: 85 °C, humidity: 85%) for 1000 hours continuously, cool it to room temperature, and test its bonding strength.

[0077] Test results:

[0078]

[0079]

[0080] As can be seen from the test results in the table, the UV delayed-curing glue provided by the embodiments of the present invention and the new manufacturing method have achieved excellent results in terms of delay effect, curing speed, adhesion, aging test, etc. The components of the present invention optimize the formula, have an extremely wide application range, and have excellent bonding effects when bonding with plastics or various materials; the bonding strength is high, and through the test of the destructive test, it can reach the rupture of the plastic body without debonding. The UV glue can be positioned in a few seconds, reach the highest strength in one minute, greatly improving the working efficiency; compared with traditional instant adhesives, it has the advantages of being resistant to environmental testing, non-whitening, and good flexibility; it is resistant to low temperature, high temperature and high humidity, and has excellent performance. It can make up for the deficiencies of the performance of traditional curing glues, improve the performance of adhesives, shorten the post-curing time, and improve the bonding performance, and can meet the applications in many scenarios, having important research value.

[0081] The present invention uses the above embodiments to illustrate a UV delayed-curing glue, its preparation method and its application, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope of the present invention.

Claims

1. A UV delayed-curing adhesive, characterized in that, The raw materials for preparing the UV delayed curing adhesive include the following components by weight:

2. The UV delayed-curing adhesive according to claim 1, characterized in that, The alicyclic epoxy resin is one or more of EHPE-3150CE, 2021p, TT386A, YDH184, CY179, and TT284.

3. The UV delayed-curing adhesive according to claim 1, wherein The modified alicyclic epoxy resin is one or more of silicone-modified alicyclic epoxy, carboxyl-terminated polyester-modified alicyclic epoxy resin, and etherified alicyclic epoxy resin.

4. A UV delayed-curing adhesive according to claim 1, wherein, The polycaprolactone polyol is PCL-305.

5. The UV delayed curing adhesive according to claim 1, characterized in that, The active diluent is one or more of polypropylene glycol diglycidyl ether, trimethylolpropane glycidyl ether, phenyl glycidyl ether, 3-ethyl-3-hydroxymethyloxetane, and propylene glycol butyl ether.

6. The UV delayed-curing adhesive according to claim 1, wherein The photoinitiator is one or more of triarylsulfonium salts, diaryliodonium salts, alkylsulfonium salts, and hexafluoroantimonate. Preferably, the photoinitiator is selected from UVI-6992 or UVI-6979.

7. The UV delayed-curing adhesive according to claim 1, wherein The silane coupling agent is one or more of propyl methacrylate trimethoxysilane, vinyl triethoxysilane, γ-aminopropyl triethoxysilane, 3-glycidyloxypropyl trimethoxysilane or γ-mercaptopropyl trimethoxysilane.

8. A preparation method of a UV delayed-curing adhesive, which is applied to a UV delayed-curing adhesive as described in any one of claims 1 to 7, characterized in that, The preparation method comprises the following steps: (1) taking a certain amount of alicyclic epoxy resin, modified alicyclic epoxy resin, polycaprolactone polyol, and photoinitiator and adding them into a mixing container in sequence, wherein the alicyclic epoxy resin is one or more combinations of EHPE-3150CE, 2021p, TT386A, YDH184, CY179, and TT284, and the weight ratio is adjusted; and the modified alicyclic epoxy resin is one or more of silicone-modified alicyclic epoxy, carboxyl-terminated polyester-modified alicyclic epoxy resin, and etherified alicyclic epoxy resin; (2) Start stirring to fully mix the raw materials in the mixer to form a uniform mixture; (3) During the stirring process, gas silicon, reactive diluent, photoinitiator and silane coupling agent are gradually added, and after stirring evenly, the mixture is degassed to obtain an adhesive.

9. A method for preparing a UV delayed curing adhesive according to claim 8, characterized in that, The preparation method of the carboxyl-terminated polyester modified aliphatic epoxy resin comprises the following steps: weighing a certain amount of epoxy resin, hydroxyl-terminated polyester as a modifier and triphenylphosphine into a round-bottom flask, stirring in an oil bath at 120° C. until the epoxy value of the resin reaches a theoretical value, cooling to room temperature, and obtaining a modified alicyclic epoxy resin; wherein n (epoxy resin): n (hydroxyl-terminated polyester) = 4:1, and the epoxy resin is one or more of EHPE-3150CE, 2021p, TT386A, YDH184, CY179, and TT284.

10. A method for preparing a UV delayed curing adhesive according to claim 8, characterized in that, The preparation method of the modified etherified alicyclic epoxy resin comprises the following steps: Weigh a certain amount of epoxy resin and a Lewis base as an etherification catalyst into a round-bottom flask, stir in an oil bath at 100 °C until the epoxy value of the resin reaches the theoretical value; Raise the temperature of the oil bath to 130 °C, add CTBN as a modifier while stirring, continue stirring until the epoxy value of the resin reaches the theoretical value, and cool to room temperature to obtain the modified etherified alicyclic epoxy resin; Wherein n(etherified epoxy resin):n(CTBN)=4:1, and the epoxy resin is one or more of EHPE-3150CE, 2021p, TT386A, YDH184, CY179, TT284.

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