CN105199643B - A kind of cation type ultraviolet photo and hot dual deep cure adhesive and preparation method thereof - Google Patents

A kind of cation type ultraviolet photo and hot dual deep cure adhesive and preparation method thereof Download PDF

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Publication number
CN105199643B
CN105199643B CN201510702233.0A CN201510702233A CN105199643B CN 105199643 B CN105199643 B CN 105199643B CN 201510702233 A CN201510702233 A CN 201510702233A CN 105199643 B CN105199643 B CN 105199643B
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parts
resin
epoxide group
agent
ultraviolet photo
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CN105199643A (en
Inventor
孙明明
宋彩雨
李奇力
王磊
赵明
李坚辉
薛刚
刘彩召
张绪刚
梅格
张斌
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Institute of Petrochemistry of Heilongjiang Academy of Sciences
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Institute of Petrochemistry of Heilongjiang Academy of Sciences
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Priority to CN201510702233.0A priority Critical patent/CN105199643B/en
Priority to CN201710274115.3A priority patent/CN106928893B/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A kind of cation type ultraviolet photo and hot dual deep cure adhesive and preparation method thereof, it is related to a kind of cured adhesive and preparation method thereof.The invention aims to solve existing ultraviolet photo-curing cementing agent to realize the solidification of rapid deep zone, using stilled need after ultraviolet light carry out subsequent heat the problem of.A kind of cation type ultraviolet photo and hot dual deep cure adhesive are prepared from by 60 parts~100 parts oligomeric resin mixtures containing epoxide group, 5 parts~30 parts diluents, 5 parts~15 parts coupling agents, 0.75 part~3 parts light triggers, 0.75 part~3 parts sensitising agents, 0.075 part~0.5 part thermal initiator and 0 part~0.2 part heat stabilizer by weight.Method：First, weigh；2nd, knead, obtain cation type ultraviolet photo and hot dual deep cure adhesive.The present invention can obtain a kind of cation type ultraviolet photo and hot dual deep cure adhesive and preparation method thereof.

Description

A kind of cation type ultraviolet photo and hot dual deep cure adhesive and preparation method thereof
Technical field
The present invention relates to a kind of cured adhesive and preparation method thereof.
Background technology
Ultraviolet photo-curing cementing agent is that a class is efficient, environmentally friendly, energy-saving adhesive, not only with without solvent, during storage Between long advantage, also show that curing rate is fast, the advantage instantaneously solidified can be achieved.But because ultraviolet photo-curing cementing agent is relied on Ultraviolet light triggers solidification, therefore its curing depth is limited by ultraviolet light irradiation, and pigmented system is difficult to application, together When system shadow region be difficult to solidification process so that conventional ultra-violet curable adhesive is applied in some special dimensions Limitation.
The curing depth of ultraviolet photo-curing cementing agent is affected by various factors, and light source influence factor mainly includes solidification The intensity of light source, light source throw range from and throw shine the time, by improve ultraviolet light light intensity, shorten throw range from, extension throwing shine when Between etc. means can the relative curing depth for improving ultraviolet photo-curing cementing agent, but lifting limited extent.Adhesive components are to solidification The influence of depth be mainly derived from trigger rate, the viscosity of adhesive system, apparent transparency of solidification glue of initiator etc. because Element, the combined influence of many factors make it that the cured thickness of conventional ultra-violet curable adhesive is extremely limited, it is difficult to meet The particular/special requirement of application field.Cation type ultraviolet photo-curing relative can solve deeply-curing and the solid problem of shade light, but Its curing rate is far below free radical type curing system, it is difficult to realize the photocuring mistake for completing certain thickness requirement in a short time Journey so that the research and development in this direction is more slow.
The problem of for realizing quick, deep cure, study towards the direction hair that application is mixed using a variety of solidification means Exhibition.Served as theme with ultraviolet light-initiated solidification means, the means such as curing reaction are triggered with the use of thermal initiation, moisture, retain instantaneous While solidification advantage, the curing depth of adhesive is further improved, so as to improve its value and widen application.
The content of the invention
The invention aims to solve existing ultraviolet photo-curing cementing agent to realize the solidification of rapid deep zone, purple is used The problem of stilling need to carry out subsequent heat after outer light irradiation, and a kind of cation type ultraviolet photo and hot dual deep cure glue are provided Stick and preparation method thereof.
A kind of cation type ultraviolet photo and hot dual deep cure adhesive contain ring by 60 parts~100 parts by weight The oligomeric resin mixture of oxygen groups, 5 parts~30 parts diluents, 5 parts~15 parts coupling agents, 0.75 part~3 parts light triggers, 0.75 part~3 parts sensitising agents, 0.075 part~0.5 part thermal initiator and 0 part~0.2 part heat stabilizer are prepared from.
The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive is prepared as follows：
First, weigh by weight 60 parts~100 parts oligomeric resin mixtures containing epoxide group, 5 parts~30 parts it is dilute Agent, 5 parts~15 parts coupling agents, 0.75 part~3 parts light triggers, 0.75 part~3 parts sensitising agents, 0.075 part~0.5 part heat is released to draw Send out agent and 0 part~0.2 part heat stabilizer；
The oligomeric resin mixture containing epoxide group described in step one is prepared according to the following steps：
It is from room under conditions of 100r/min~150r/min by the resin low whipping speed of the epoxide group containing bifunctionality Temperature is heated to 60 DEG C~80 DEG C；Low whipping speed is 100r/min~150r/min again and temperature is under conditions of 60 DEG C~80 DEG C Add the oligomer containing multi-functional epoxy group；Low whipping speed is 150r/min~200r/min again and temperature is 60 DEG C Stirring reaction 6h~18h under conditions of~80 DEG C, obtains the oligomeric resin mixture containing epoxide group；
The resin of the described epoxide group containing bifunctionality and the mass ratio of the oligomer containing multi-functional epoxy group For 100:(5~40)；
The resin of the described epoxide group containing bifunctionality be cycloaliphatic epoxy resin, dibasic acid esters chain cycloaliphatic epoxy resin, One kind or wherein several mixtures in aliphatic epoxy resin, bisphenol A epoxide resin and hydrogenated bisphenol A epoxy resin；Institute The cycloaliphatic epoxy resin stated is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters；Dibasic acid esters chain aliphatic ring oxygen tree Fat is double ((3,4- epoxycyclohexyls) methyl) adipate esters；Aliphatic epoxy resin is ethylene glycol diglycidylether；
The described oligomer containing multi-functional epoxy group shrinks sweet for 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two Grease, poly- [(2- Oxyranyles) -1,2- cyclohexanediols] 2- ethyls -2- (methylol) -1,3- propylene glycols, pentaerythrite contracting One kind or wherein several mixtures in water glycerin ether；
Diluent described in step one is 3- ethyl -3- oxa- fourth rings methanol, 3,3'- (epoxide dimethylene) double (3- Ethyl) in oxetanes, 1,2,8,9- bis-epoxies -4 vinyl cyclohexene, butadiene bis-epoxy and butyl glycidyl ether One kind or wherein several mixtures；
Described coupling agent described in step one is γ-glycidyl ether oxygen propyl trimethoxy silicane, 3,4- epoxies Cyclohexyl-ethyl trimethoxy silane and one kind or wherein several in γ-methacryloxypropyl trimethoxy silane Mixture；
Light trigger described in step one is triaryl sulfonium salts or diaryl group iodized salt；Described triaryl sulfonium salts For mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyclohexyl-phenyls Ketone, the derivative of 1- hydroxy-cyclohexyl-phenyl ketones, benzophenone, the oxidation of 2,4,6- trimethylbenzoy-diphenies One kind or wherein several mixtures in the derivative of phosphine and 2,4,6- trimethylbenzoy-dipheny phosphine oxides；
Thermal initiator described in step one triggers curing agent or amine closing lewis acid for peroxide；Described mistake It is benzoyl peroxide BPO that oxide, which triggers curing agent,；Described amine closing lewis acid be Vicbase TC3630, Vicbase TC3632, Vicbase TC3633 or Vicbase TC3634；
Heat stabilizer described in step one is epoxy resin composite stabilizer；Described epoxy resin composite is stable Agent is Vicbase TC3602H；
2nd, by weighed in step one 60 parts~100 parts oligomeric resin mixtures containing epoxide group, 5 parts~30 parts Diluent and 5 parts~15 parts coupling agents are well mixed, sequentially add weighed in step one 0.75 part~3 parts light triggers, 0.75 part~3 parts sensitising agents, 0.075 part~0.5 part thermal initiators, then low whipping speed be 100r/min~150r/min under stir Reaction 20min~40min is mixed, 0 part~0.2 part heat stabilizer weighed in step one is added, then low whipping speed is 100r/ Stirring reaction 20min~30min under min~150r/min, obtains a kind of cation type ultraviolet photo and hot dual deep cure glue Stick.
Advantages of the present invention：
First, a kind of cation type ultraviolet photo and hot dual deep cure adhesive that prepared by the present invention utilize ultraviolet light and heat Dual initiation means are solidified, after ultraviolet light, rapid reaction, while the heat produced using ultraviolet light triggers thermosetting Change course of reaction, so as to realize that rapid deep zone solidifies；
2nd, a kind of cation type ultraviolet photo and hot dual deep cure adhesive that prepared by the present invention after carrying out without heating Trigger curing process, the curing reaction time is short, and technical process is simple to operation, and meets deep cure requirement；
3rd, the present invention key reaction process is polymerized to cationic epoxy ring-opening, epoxy resin as main component, A kind of cation type ultraviolet photo for the preparation prepared and hot dual deep cure adhesive have the viscosity number of relatively low scope, stream Dynamic property is good, it is easy to operate, and solidifies the features such as volume contraction degree produced is relatively low, and it is excellent to show epoxies adhesive Cementability and mechanicalness, with good application performance；
4th, the viscosity of a kind of cation type ultraviolet photo and hot dual deep cure adhesive prepared by the present invention at 25 DEG C For 750~3850cps, adhesive strength 10MPa~18MPa at 25 DEG C, 65 DEG C~90 DEG C of glass transition temperature；
5th, a kind of cation type ultraviolet photo and hot dual deep cure adhesive that prepared by the present invention irradiate under ultraviolet light After 1.5min~3min, solidification process is completed, cured thickness is 18.6mm~32.3mm.
The present invention can obtain a kind of cation type ultraviolet photo and hot dual deep cure adhesive and preparation method thereof.
Embodiment
Embodiment one：Present embodiment be a kind of cation type ultraviolet photo and hot dual deep cure adhesive by Parts by weight are by 60 parts~100 parts oligomeric resin mixtures containing epoxide group, 5 parts~30 parts diluents, 5 parts~15 parts idols Connection agent, 0.75 part~3 parts light triggers, 0.75 part~3 parts sensitising agents, 0.075 part~0.5 part thermal initiator and 0 part~0.2 part Heat stabilizer is prepared from.
The advantage of present embodiment：
First, a kind of cation type ultraviolet photo and hot dual deep cure adhesive that prepared by present embodiment utilize ultraviolet light Solidified with hot dual initiation means, after ultraviolet light, rapid reaction, while the heat produced using ultraviolet light is triggered Heat cure course of reaction, so as to realize that rapid deep zone solidifies；
2nd, after a kind of cation type ultraviolet photo and hot dual deep cure adhesive that prepared by present embodiment are without carrying out Heating triggers curing process, and the curing reaction time is short, and technical process is simple to operation, and meets deep cure requirement；
3rd, present embodiment is polymerized to key reaction process with cationic epoxy ring-opening, and epoxy resin is as main Composition, a kind of cation type ultraviolet photo for the preparation prepared and hot dual deep cure adhesive have the viscosity of relatively low scope Value, mobility is good, it is easy to operate, and solidifies the features such as volume contraction degree produced is relatively low, and it is gluing to show epoxies The excellent cementability of agent and mechanicalness, with good application performance；
4th, a kind of cation type ultraviolet photo and hot dual deep cure adhesive that prepared by present embodiment are at 25 DEG C Viscosity is 750~3850cps, adhesive strength 10MPa~18MPa at 25 DEG C, 65 DEG C~90 DEG C of glass transition temperature；
5th, a kind of cation type ultraviolet photo and hot dual deep cure adhesive that prepared by present embodiment are under ultraviolet light Irradiate after 1.5min~3min, complete solidification process, cured thickness is 18.6mm~32.3mm.
Present embodiment can obtain a kind of cation type ultraviolet photo and hot dual deep cure adhesive and preparation method thereof.
Embodiment two：Present embodiment is with the difference of embodiment one：Described contains epoxide group Oligomeric resin mixture prepare according to the following steps：
It is from room under conditions of 100r/min~150r/min by the resin low whipping speed of the epoxide group containing bifunctionality Temperature is heated to 60 DEG C~80 DEG C；Low whipping speed is 100r/min~150r/min again and temperature is under conditions of 60 DEG C~80 DEG C Add the oligomer containing multi-functional epoxy group；Low whipping speed is 150r/min~200r/min again and temperature is 60 DEG C Stirring reaction 6h~18h under conditions of~80 DEG C, obtains the oligomeric resin mixture containing epoxide group；
The resin of the described epoxide group containing bifunctionality and the mass ratio of the oligomer containing multi-functional epoxy group For 100:(5~40).Other steps are identical with embodiment one.
Embodiment three：One of present embodiment and embodiment one or two difference is：Described containing is double The resin of degree of functionality epoxide group is cycloaliphatic epoxy resin, dibasic acid esters chain cycloaliphatic epoxy resin, aliphatic epoxy resin, bis-phenol One kind or wherein several mixtures in A epoxy resin and hydrogenated bisphenol A epoxy resin；Described cycloaliphatic epoxy resin is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters；Dibasic acid esters chain cycloaliphatic epoxy resin is double ((3,4- epoxy hexamethylenes Base) methyl) adipate ester；Aliphatic epoxy resin is ethylene glycol diglycidylether.Other steps and embodiment one Or two is identical.
Embodiment four：One of present embodiment and embodiment one to three difference is：Described contains The oligomer of multi-functional epoxy group is 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl esters, poly- [(2- epoxy second Alkyl) -1,2- cyclohexanediols] 2- ethyls -2- (methylol) -1,3- propylene glycols, one kind in pentaerythrite glycidol ether Or wherein several mixture.Other steps are identical with embodiment one to three.
Embodiment five：One of present embodiment and embodiment one to four difference is：Described dilution Agent is 3- ethyl -3- oxa- fourth rings methanol, double (3- ethyls) oxetanes of 3,3'- (epoxide dimethylene), 1,2,8,9- are double Epoxy -4 vinyl cyclohexene, butadiene bis-epoxy and one kind or wherein several mixtures in butyl glycidyl ether.Its His step is identical with embodiment one to four.
Embodiment six：One of present embodiment and embodiment one to five difference is：Described coupling Agent is γ-glycidyl ether oxygen propyl trimethoxy silicane, 3,4- epoxycyclohexylethyls trimethoxy silane and γ-methyl-prop One kind or wherein several mixtures in alkene acryloxypropylethoxysilane trimethoxy silane；Described light trigger is triaryl sulphur Salt or diaryl group iodized salt；Described triaryl sulfonium salts trigger for mixed type triaryl hexafluoro-antimonic acid sulfonium salt cationic photopolymerization Agent.Other steps are identical with embodiment one to five.
Embodiment seven：One of present embodiment and embodiment one to six difference is：Described is photosensitive Agent is 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyclohexyl-phenyls ketone, 1- hydroxy-cyclohexyl-phenyl ketones Derivative, benzophenone, 2,4,6- trimethylbenzoy-diphenies phosphine oxide and 2,4,6- trimethylbenzoyls-two One kind or wherein several mixtures in the derivative of phenyl phosphine oxide.Other steps and the phase of embodiment one to six Together.
The derivative purchase of 1- hydroxy-cyclohexyl-phenyl ketones described in present embodiment is limited from double bond chemical industry share Company, product type is Doublecure 184L；
The derivative of 2,4,6- trimethylbenzoy-dipheny phosphine oxides described in present embodiment is bought from double bond Work limited company, product type is double bond chemical industry Doublecure TPO-L.
Embodiment eight：One of present embodiment and embodiment one to seven difference is：Described heat is drawn It is that peroxide triggers curing agent or amine closing lewis acid to send out agent；It is benzoyl peroxide that described peroxide, which triggers curing agent, Formyl BPO；Described amine closing lewis acid is Vicbase TC3630, Vicbase TC3632, Vicbase TC3633 Or Vicbase TC3634.Other steps are identical with embodiment one to seven.
Vicbase TC3630, Vicbase TC3632, Vicbase TC3633 and Vicbase described in present embodiment TC3634 is bought from Kai Ji Applied Materials Inc of Shenzhen.
Embodiment nine：One of present embodiment and embodiment one to eight difference is：Described heat is steady Agent is determined for epoxy resin composite stabilizer；Described epoxy resin composite stabilizer is Vicbase TC3602H.Other steps Suddenly it is identical with embodiment one to eight.
Vicbase TC3602H described in present embodiment are enough bought from Kai Ji Applied Materials Inc of Shenzhen.
Embodiment ten：Present embodiment is a kind of cation type ultraviolet photo and hot dual deep cure adhesive Preparation method is prepared as follows：
First, weigh by weight 60 parts~100 parts oligomeric resin mixtures containing epoxide group, 5 parts~30 parts it is dilute Agent, 5 parts~15 parts coupling agents, 0.75 part~3 parts light triggers, 0.75 part~3 parts sensitising agents, 0.075 part~0.5 part heat is released to draw Send out agent and 0 part~0.2 part heat stabilizer；
The oligomeric resin mixture containing epoxide group described in step one is prepared according to the following steps：
It is from room under conditions of 100r/min~150r/min by the resin low whipping speed of the epoxide group containing bifunctionality Temperature is heated to 60 DEG C~80 DEG C；Low whipping speed is 100r/min~150r/min again and temperature is under conditions of 60 DEG C~80 DEG C Add the oligomer containing multi-functional epoxy group；Low whipping speed is 150r/min~200r/min again and temperature is 60 DEG C Stirring reaction 6h~18h under conditions of~80 DEG C, obtains the oligomeric resin mixture containing epoxide group；
The resin of the described epoxide group containing bifunctionality and the mass ratio of the oligomer containing multi-functional epoxy group For 100:(5~40)；
The resin of the described epoxide group containing bifunctionality be cycloaliphatic epoxy resin, dibasic acid esters chain cycloaliphatic epoxy resin, One kind or wherein several mixtures in aliphatic epoxy resin, bisphenol A epoxide resin and hydrogenated bisphenol A epoxy resin；Institute The cycloaliphatic epoxy resin stated is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters；Dibasic acid esters chain aliphatic ring oxygen tree Fat is double ((3,4- epoxycyclohexyls) methyl) adipate esters；Aliphatic epoxy resin is ethylene glycol diglycidylether；
The described oligomer containing multi-functional epoxy group shrinks sweet for 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two Grease, poly- [(2- Oxyranyles) -1,2- cyclohexanediols] 2- ethyls -2- (methylol) -1,3- propylene glycols, pentaerythrite contracting One kind or wherein several mixtures in water glycerin ether；
Diluent described in step one is 3- ethyl -3- oxa- fourth rings methanol, 3,3'- (epoxide dimethylene) double (3- Ethyl) in oxetanes, 1,2,8,9- bis-epoxies -4 vinyl cyclohexene, butadiene bis-epoxy and butyl glycidyl ether One kind or wherein several mixtures；
Described coupling agent described in step one is γ-glycidyl ether oxygen propyl trimethoxy silicane, 3,4- epoxies Cyclohexyl-ethyl trimethoxy silane and one kind or wherein several in γ-methacryloxypropyl trimethoxy silane Mixture；
Light trigger described in step one is triaryl sulfonium salts or diaryl group iodized salt；Described triaryl sulfonium salts For mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyclohexyl-phenyls Ketone, the derivative of 1- hydroxy-cyclohexyl-phenyl ketones, benzophenone, the oxidation of 2,4,6- trimethylbenzoy-diphenies One kind or wherein several mixtures in the derivative of phosphine and 2,4,6- trimethylbenzoy-dipheny phosphine oxides；
Thermal initiator described in step one triggers curing agent or amine closing lewis acid for peroxide；Described mistake It is benzoyl peroxide BPO that oxide, which triggers curing agent,；Described amine closing lewis acid be Vicbase TC3630, Vicbase TC3632, Vicbase TC3633 or Vicbase TC3634；
Heat stabilizer described in step one is epoxy resin composite stabilizer；Described epoxy resin composite is stable Agent is Vicbase TC3602H；
2nd, by weighed in step one 60 parts~100 parts oligomeric resin mixtures containing epoxide group, 5 parts~30 parts Diluent and 5 parts~15 parts coupling agents are well mixed, sequentially add weighed in step one 0.75 part~3 parts light triggers, 0.75 part~3 parts sensitising agents, 0.075 part~0.5 part thermal initiators, then low whipping speed be 100r/min~150r/min under stir Reaction 20min~40min is mixed, 0 part~0.2 part heat stabilizer weighed in step one is added, then low whipping speed is 100r/ Stirring reaction 20min~30min under min~150r/min, obtains a kind of cation type ultraviolet photo and hot dual deep cure glue Stick.
The derivative purchase of 1- hydroxy-cyclohexyl-phenyl ketones described in present embodiment is limited from double bond chemical industry share Company, product type is Doublecure 184L；
The derivative of 2,4,6- trimethylbenzoy-dipheny phosphine oxides described in present embodiment is bought from double bond Work limited company, product type is double bond chemical industry Doublecure TPO-L；
Vicbase TC3630, Vicbase TC3632, Vicbase TC3633 and Vicbase described in present embodiment TC3634 is bought from Kai Ji Applied Materials Inc of Shenzhen；
Vicbase TC3602H described in present embodiment are enough bought from Kai Ji Applied Materials Inc of Shenzhen.
The advantage of present embodiment：
First, a kind of cation type ultraviolet photo and hot dual deep cure adhesive that prepared by present embodiment utilize ultraviolet light Solidified with hot dual initiation means, after ultraviolet light, rapid reaction, while the heat produced using ultraviolet light is triggered Heat cure course of reaction, so as to realize that rapid deep zone solidifies；
2nd, after a kind of cation type ultraviolet photo and hot dual deep cure adhesive that prepared by present embodiment are without carrying out Heating triggers curing process, and the curing reaction time is short, and technical process is simple to operation, and meets deep cure requirement；
3rd, present embodiment is polymerized to key reaction process with cationic epoxy ring-opening, and epoxy resin is as main Composition, a kind of cation type ultraviolet photo for the preparation prepared and hot dual deep cure adhesive have the viscosity of relatively low scope Value, mobility is good, it is easy to operate, and solidifies the features such as volume contraction degree produced is relatively low, and it is gluing to show epoxies The excellent cementability of agent and mechanicalness, with good application performance；
4th, a kind of cation type ultraviolet photo and hot dual deep cure adhesive that prepared by present embodiment are at 25 DEG C Viscosity is 750~3850cps, adhesive strength 10MPa~18MPa at 25 DEG C, 65 DEG C~90 DEG C of glass transition temperature；
5th, a kind of cation type ultraviolet photo and hot dual deep cure adhesive that prepared by present embodiment are under ultraviolet light Irradiate after 1.5min~3min, complete solidification process, cured thickness is 18.6mm~32.3mm.
Present embodiment can obtain a kind of cation type ultraviolet photo and hot dual deep cure adhesive and preparation method thereof.
Embodiment one：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive is by following step Suddenly prepare：
First, 70 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents, 10 parts of couplings are weighed by weight Agent, 0.7 part of light trigger, 0.7 part of sensitising agent, 0.14 part of thermal initiator and 0.07 part of heat stabilizer；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 80 under conditions of 100r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 100r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 80 DEG C Thing；Low whipping speed is 150r/min again and temperature is stirring reaction 12h under conditions of 80 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls Formic acid esters；The described oligomer containing multi-functional epoxy group is poly- [(2- Oxyranyles) -1,2- cyclohexanediols] 2- Ethyl -2- (methylol) -1,3- propylene glycols；The resin of the described epoxide group containing bifunctionality is with containing multi-functional epoxy The mass ratio of the oligomer of group is 100:10；
Diluent described in step one is 3- ethyl -3- oxa- fourth ring methanol；
Coupling agent described in step one is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 1- hydroxy-cyclohexyl-phenyl ketones；
Thermal initiator described in step one closes lewis acid for amine；Described amine closing lewis acid Vicbase TC3632；
Heat stabilizer described in step one is epoxy resin composite stabilizer；Described epoxy resin composite is stable Agent is Vicbase TC3602H；
2nd, by weighed in step one 70 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents and 10 parts Coupling agent is well mixed, and sequentially adds the 0.7 part of light trigger weighed in step one, 0.7 part of sensitising agent, 0.14 part of thermal initiation Agent, then low whipping speed are stirring reaction 20min under 100r/min, add the 0.07 part of heat stabilizer weighed in step one, Low whipping speed is stirring reaction 30min under 100r/min again, obtains a kind of cation type ultraviolet photo and hot dual deep cure Adhesive.
Vicbase TC3632 described in embodiment one are bought from Kai Ji Applied Materials Inc of Shenzhen；
Vicbase TC3602H described in embodiment one are enough bought from Kai Ji Applied Materials Inc of Shenzhen.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by embodiment one irradiates under ultraviolet light Solidification is completed after 1.5min；Through measuring the cation type ultraviolet photo of the preparation of embodiment one and consolidating for hot dual deep cure adhesive Change thickness is 20.5mm.
Embodiment two：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive, is by following Prepared by step：
First, 70 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents, 10 parts of couplings are weighed by weight Agent, 0.7 part of light trigger, 0.7 part of sensitising agent, 0.14 part of thermal initiator and 0.07 part of heat stabilizer；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 80 under conditions of 100r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 100r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 80 DEG C Thing；Low whipping speed is 200r/min again and temperature is stirring reaction 15h under conditions of 80 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls Formic acid esters；The described oligomer containing multi-functional epoxy group is poly- [(2- Oxyranyles) -1,2- cyclohexanediols] 2- Ethyl -2- (methylol) -1,3- propylene glycols；The resin of the described epoxide group containing bifunctionality is with containing multi-functional epoxy The mass ratio of the oligomer of group is 100:20；
Diluent described in step one is butadiene bis-epoxy；
Coupling agent described in step one is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 1- hydroxy-cyclohexyl-phenyl ketones；
Thermal initiator described in step one closes lewis acid for amine；Described amine closing lewis acid Vicbase TC3634；
Heat stabilizer described in step one is epoxy resin composite stabilizer；Described epoxy resin composite is stable Agent is Vicbase TC3602H；
2nd, by weighed in step one 70 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents and 10 parts Coupling agent is well mixed, and sequentially adds the 0.7 part of light trigger weighed in step one, 0.7 part of sensitising agent, 0.14 part of thermal initiation Agent, then low whipping speed are stirring reaction 20min under 100r/min, add the 0.07 part of heat stabilizer weighed in step one, Low whipping speed is stirring reaction 30min under 100r/min again, obtains a kind of cation type ultraviolet photo and hot dual deep cure Adhesive.
Vicbase TC3634 described in embodiment two are bought from Kai Ji Applied Materials Inc of Shenzhen；
Vicbase TC3602H described in embodiment two are enough bought from Kai Ji Applied Materials Inc of Shenzhen.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by embodiment two irradiates 2min under ultraviolet light Solidification is completed afterwards；Through measuring the cation type ultraviolet photo of the preparation of embodiment two and the cured thickness of hot dual deep cure adhesive For 21.4mm.
Embodiment three：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive, is by following Prepared by step：
First, 70 parts of oligomeric resin mixtures containing epoxide group, 25 parts of diluents, 5 parts of couplings are weighed by weight Agent, 0.7 part of light trigger, 0.7 part of sensitising agent, 0.07 part of thermal initiator and 0.035 part of heat stabilizer；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 80 under conditions of 150r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 150r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 80 DEG C Thing；Low whipping speed is 150r/min again and temperature is stirring reaction 15h under conditions of 80 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls Formic acid esters；The described oligomer containing multi-functional epoxy group is poly- [(2- Oxyranyles) -1,2- cyclohexanediols] 2- Ethyl -2- (methylol) -1,3- propylene glycols；The resin of the described epoxide group containing bifunctionality is with containing multi-functional epoxy The mass ratio of the oligomer of group is 100:20；
Diluent described in step one is 3- ethyl -3- oxa- fourth ring methanol；
Coupling agent described in step one is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 2- hydroxy-2-methyl -1- phenyl -1- acetone；
Thermal initiator described in step one closes lewis acid for amine；Described amine closing lewis acid Vicbase TC3632；
Heat stabilizer described in step one is epoxy resin composite stabilizer；Described epoxy resin composite is stable Agent is Vicbase TC3602H；
2nd, by weighed in step one 70 parts of oligomeric resin mixtures containing epoxide group, 25 parts of diluents and 5 parts of idols Join agent to be well mixed, sequentially add the 0.7 part of light trigger weighed in step one, 0.7 part of sensitising agent, 0.07 part of thermal initiation Agent, then low whipping speed are stirring reaction 20min under 100r/min, add the 0.035 part of heat stabilizer weighed in step one, Low whipping speed is stirring reaction 20min under 150r/min again, obtains a kind of cation type ultraviolet photo and hot dual deep cure Adhesive.
Vicbase TC3632 described in embodiment three are bought from Kai Ji Applied Materials Inc of Shenzhen；
Vicbase TC3602H described in embodiment three are enough bought from Kai Ji Applied Materials Inc of Shenzhen.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by embodiment three irradiates under ultraviolet light Solidification is completed after 1.5min；Through measuring the cation type ultraviolet photo of the preparation of embodiment three and consolidating for hot dual deep cure adhesive Change thickness is 19.7mm.
Example IV：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive, is by following Prepared by step：
First, 80 parts of oligomeric resin mixtures containing epoxide group, 15 parts of diluents, 5 parts of couplings are weighed by weight Agent, 0.8 part of light trigger, 0.8 part of sensitising agent, 0.08 part of thermal initiator and 0.024 part of heat stabilizer；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 60 under conditions of 120r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 120r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 60 DEG C Thing；Low whipping speed is 250r/min again and temperature is stirring reaction 6h under conditions of 60 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls Formic acid esters；The described oligomer containing multi-functional epoxy group shrinks sweet for 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two OilEster；The mass ratio of the resin and the oligomer containing multi-functional epoxy group of the described epoxide group containing bifunctionality is 100:15；
Diluent described in step one is 3- ethyl -3- oxa- fourth ring methanol；
Coupling agent described in step one is 3,4- epoxycyclohexylethyl trimethoxy silanes；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 2- hydroxy-2-methyl -1- phenyl -1- acetone；
Thermal initiator described in step one closes lewis acid for amine；Described amine closing lewis acid Vicbase TC3632；
Heat stabilizer described in step one is epoxy resin composite stabilizer；Described epoxy resin composite is stable Agent is Vicbase TC3602H；
2nd, by weighed in step one 80 parts of oligomeric resin mixtures containing epoxide group, 15 parts of diluents and 5 parts of idols Join agent to be well mixed, sequentially add the 0.8 part of light trigger weighed in step one, 0.8 part of sensitising agent, 0.08 part of thermal initiation Agent, then low whipping speed are stirring reaction 20min under 100r/min, add the 0.024 part of heat stabilizer weighed in step one, Low whipping speed is stirring reaction 30min under 100r/min again, obtains a kind of cation type ultraviolet photo and hot dual deep cure Adhesive.
Vicbase TC3632 described in example IV are bought from Kai Ji Applied Materials Inc of Shenzhen；
Vicbase TC3602H described in example IV are enough bought from Kai Ji Applied Materials Inc of Shenzhen.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by example IV irradiates under ultraviolet light Solidification is completed after 1.5min；Through measuring the cation type ultraviolet photo of example IV preparation and consolidating for hot dual deep cure adhesive Change thickness is 25.1mm.
Embodiment five：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive, is by following Prepared by step：
First, 70 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents, 10 parts of couplings are weighed by weight Agent, 0.7 part of light trigger, 0.7 part of sensitising agent, 0.14 part of thermal initiator and 0.07 part of heat stabilizer；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 60 under conditions of 120r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 120r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 60 DEG C Thing；Low whipping speed is 150r/min again and temperature is stirring reaction 6h under conditions of 60 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls Formic acid esters；The described oligomer containing multi-functional epoxy group shrinks sweet for 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two OilEster；The mass ratio of the resin and the oligomer containing multi-functional epoxy group of the described epoxide group containing bifunctionality is 100:25；
Diluent described in step one is 1,2,8,9- bis-epoxies -4 vinyl cyclohexene；
Coupling agent described in step one is 3,4- epoxycyclohexylethyl trimethoxy silanes；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 2- hydroxy-2-methyl -1- phenyl -1- acetone；
Thermal initiator described in step one closes lewis acid for amine；Described amine closing lewis acid Vicbase TC3630；
Heat stabilizer described in step one is epoxy resin composite stabilizer；Described epoxy resin composite is stable Agent is Vicbase TC3602H；
2nd, by weighed in step one 70 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents and 10 parts Coupling agent is well mixed, and sequentially adds the 0.7 part of light trigger weighed in step one, 0.7 part of sensitising agent, 0.14 part of thermal initiation Agent, then low whipping speed are stirring reaction 20min under 120r/min, add the 0.07 part of heat stabilizer weighed in step one, Low whipping speed is stirring reaction 25min under 120r/min again, obtains a kind of cation type ultraviolet photo and hot dual deep cure Adhesive.
Vicbase TC3630 described in embodiment five are bought from Kai Ji Applied Materials Inc of Shenzhen；
Vicbase TC3602H described in embodiment five are enough bought from Kai Ji Applied Materials Inc of Shenzhen.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by embodiment five irradiates 2min under ultraviolet light Solidification is completed afterwards；Through measuring the cation type ultraviolet photo of the preparation of embodiment five and the cured thickness of hot dual deep cure adhesive For 18.6mm.
Embodiment six：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive, is by following Prepared by step：
First, 70 parts of oligomeric resin mixtures containing epoxide group, 25 parts of diluents, 10 parts of couplings are weighed by weight Agent, 0.7 part of light trigger, 0.7 part of sensitising agent, 0.07 part of thermal initiator and 0.035 part of heat stabilizer；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 60 under conditions of 150r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 150r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 60 DEG C Thing；Low whipping speed is 150r/min again and temperature is stirring reaction 6h under conditions of 60 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls Formic acid esters；The described oligomer containing multi-functional epoxy group shrinks sweet for 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate two OilEster；The mass ratio of the resin and the oligomer containing multi-functional epoxy group of the described epoxide group containing bifunctionality is 100:25；
Diluent described in step one is 1,2,8,9- bis-epoxies -4 vinyl cyclohexene；
Coupling agent described in step one is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 1- hydroxy-cyclohexyl-phenyl ketones；
Thermal initiator described in step one closes lewis acid for amine；Described amine closing lewis acid Vicbase TC3633；
Heat stabilizer described in step one is epoxy resin composite stabilizer；Described epoxy resin composite is stable Agent is Vicbase TC3602H；
2nd, by weighed in step one 70 parts of oligomeric resin mixtures containing epoxide group, 25 parts of diluents and 10 parts Coupling agent is well mixed, and sequentially adds the 0.7 part of light trigger weighed in step one, 0.7 part of sensitising agent, 0.07 part of thermal initiation Agent, then low whipping speed are stirring reaction 20min under 150r/min, add the 0.035 part of heat stabilizer weighed in step one, Low whipping speed is stirring reaction 30min under 150r/min again, obtains a kind of cation type ultraviolet photo and hot dual deep cure Adhesive.
Vicbase TC3633 described in embodiment six are bought from Kai Ji Applied Materials Inc of Shenzhen；
Vicbase TC3602H described in embodiment six are enough bought from Kai Ji Applied Materials Inc of Shenzhen.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by embodiment six irradiates under ultraviolet light Solidification is completed after 1.5min；Through measuring the cation type ultraviolet photo of the preparation of embodiment six and consolidating for hot dual deep cure adhesive Change thickness is 32.3mm.
Embodiment seven：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive is by following step Suddenly prepare：
First, 80 parts of oligomeric resin mixtures containing epoxide group, 15 parts of diluents, 5 parts of couplings are weighed by weight Agent, 1.2 parts of light triggers, 1.2 parts of sensitising agents and 0.08 part of thermal initiator；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 80 under conditions of 100r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 100r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 80 DEG C Thing；Low whipping speed is 180r/min again and temperature is stirring reaction 15h under conditions of 80 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls Formic acid esters；The described oligomer containing multi-functional epoxy group is poly- [(2- Oxyranyles) -1,2- cyclohexanediols] 2- Ethyl -2- (methylol) -1,3- propylene glycols；The resin of the described epoxide group containing bifunctionality is with containing multi-functional epoxy The mass ratio of the oligomer of group is 100:20；
Diluent described in step one is double (3- ethyls) oxetanes of 3,3'- (epoxide dimethylene)；
Coupling agent described in step one is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 1- hydroxy-cyclohexyl-phenyl ketones；
Thermal initiator described in step one closes lewis acid for amine；Described amine closing lewis acid Vicbase TC3632；
2nd, by weighed in step one 80 parts of oligomeric resin mixtures containing epoxide group, 15 parts of diluents and 5 parts of idols Join agent to be well mixed, sequentially add the 1.2 parts of light triggers weighed in step one, 1.2 parts of sensitising agents, 0.08 part of thermal initiation Agent, then low whipping speed are stirring reaction 30min under 150r/min, obtain a kind of cation type ultraviolet photo and hot dual deep layer is solid Change adhesive.
Vicbase TC3632 described in embodiment seven are bought from Kai Ji Applied Materials Inc of Shenzhen.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by embodiment seven irradiates under ultraviolet light Solidification is completed after 2.5min；Through measuring the cation type ultraviolet photo of the preparation of embodiment seven and consolidating for hot dual deep cure adhesive Change thickness is 28.7mm.
Embodiment eight：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive is by following step Suddenly prepare：
First, 80 parts of oligomeric resin mixtures containing epoxide group, 16 parts of diluents, 5 parts of couplings are weighed by weight Agent, 0.8 part of light trigger, 0.8 part of sensitising agent, 0.08 part of thermal initiator and 0.04 part of heat stabilizer；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 70 under conditions of 150r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 150r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 70 DEG C Thing；Low whipping speed is 150r/min again and temperature is stirring reaction 6h under conditions of 70 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls Formic acid esters；The described oligomer containing multi-functional epoxy group is hydrogenated bisphenol A epoxy resin；Described contains bifunctionality The resin of epoxide group is 100 with the mass ratio of the oligomer containing multi-functional epoxy group:20；
Diluent described in step one is double (3- ethyls) oxetanes of 3,3'- (epoxide dimethylene)；
Coupling agent described in step one is 3,4- epoxycyclohexylethyl trimethoxy silanes；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 1- hydroxy-cyclohexyl-phenyl ketones；
Thermal initiator described in step one closes lewis acid for amine；Described amine closing lewis acid Vicbase TC3632；
Heat stabilizer described in step one is epoxy resin composite stabilizer；Described epoxy resin composite is stable Agent is Vicbase TC3602H；
2nd, by weighed in step one 80 parts of oligomeric resin mixtures containing epoxide group, 16 parts of diluents and 5 parts of idols Join agent to be well mixed, sequentially add the 0.8 part of light trigger weighed in step one, 0.8 sensitising agent, 0.08 part of thermal initiator, Low whipping speed is stirring reaction 20min under 150r/min again, adds the 0.04 part of heat stabilizer weighed in step one, then Mixing speed is stirring reaction 25min under 150r/min, obtains a kind of dual deep cure adhesive of cation type ultraviolet photo heat.
Vicbase TC3632 described in embodiment eight are bought from Kai Ji Applied Materials Inc of Shenzhen；
Vicbase TC3602H described in embodiment eight are enough bought from Kai Ji Applied Materials Inc of Shenzhen.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by embodiment eight irradiates under ultraviolet light Solidification is completed after 1.5min；Through measuring the cation type ultraviolet photo of the preparation of embodiment eight and consolidating for hot dual deep cure adhesive Change thickness is 26.8mm.
Embodiment nine：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive is by following step Suddenly prepare：
First, 70 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents, 10 parts of couplings are weighed by weight Agent, 0.7 part of light trigger, 0.7 part of sensitising agent, 0.07 part of thermal initiator and 0.035 part of heat stabilizer；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 70 under conditions of 120r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 120r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 70 DEG C Thing；Low whipping speed is 200r/min again and temperature is stirring reaction 8h under conditions of 70 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls Formic acid esters；The described oligomer containing multi-functional epoxy group is bisphenol A epoxide resin E51；Described contains bifunctionality The resin of epoxide group is 100 with the mass ratio of the oligomer containing multi-functional epoxy group:20；
Diluent described in step one is double (3- ethyls) oxetanes of 3,3'- (epoxide dimethylene)；
Coupling agent described in step one is 3,4- epoxycyclohexylethyl trimethoxy silanes；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 1- hydroxy-cyclohexyl-phenyl ketones；
Thermal initiator described in step one closes lewis acid for amine；Described amine closing lewis acid Vicbase TC3630；
Heat stabilizer described in step one is epoxy resin composite stabilizer；Described epoxy resin composite is stable Agent is Vicbase TC3602H；
2nd, by weighed in step one 70 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents and 10 parts Coupling agent is well mixed, and sequentially adds the 0.7 part of light trigger weighed in step one, 0.7 sensitising agent, 0.07 part of thermal initiation Agent, then low whipping speed are stirring reaction 20min under 120r/min, add the 0.035 part of heat stabilizer weighed in step one, Low whipping speed is stirring reaction 30min under 120r/min again, obtains a kind of cation type ultraviolet photo and hot dual deep cure Adhesive.
Vicbase TC3630 described in embodiment nine are bought from Kai Ji Applied Materials Inc of Shenzhen；
Vicbase TC3602H described in embodiment nine are enough bought from Kai Ji Applied Materials Inc of Shenzhen.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by embodiment nine irradiates under ultraviolet light Solidification is completed after 1.5min；Through measuring the cation type ultraviolet photo of the preparation of embodiment nine and consolidating for hot dual deep cure adhesive Change thickness is 29.6mm.
Embodiment ten：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive is by following step Suddenly prepare：
First, 70 parts of oligomeric resin mixtures containing epoxide group, 15 parts of diluents, 5 parts of couplings are weighed by weight Agent, 0.7 part of light trigger, 0.7 part of sensitising agent, 0.07 part of thermal initiator and 0.035 part of heat stabilizer；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 60 under conditions of 150r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 150r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 60 DEG C Thing；Low whipping speed is 150r/min again and temperature is stirring reaction 8h under conditions of 60 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls The mixture of formic acid esters and double ((3,4- epoxycyclohexyls) methyl) adipic acids；Described 3,4- epoxycyclohexyl-methyl 3,4- rings Oxygen hexahydrobenzoid acid ester is 2 with the mass ratio of the mixture of double ((3,4- epoxycyclohexyls) methyl) adipic acids:1；Described contains The oligomer for having multi-functional epoxy group is pentaerythrite glycidol ether；The resin of the described epoxide group containing bifunctionality Mass ratio with the oligomer containing multi-functional epoxy group is 100:30；
Diluent described in step one is 3- ethyl -3- oxa- fourth ring methanol；
Coupling agent described in step one is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is benzophenone；
Thermal initiator described in step one closes lewis acid for amine；Described amine closing lewis acid Vicbase TC3634；
Heat stabilizer described in step one is epoxy resin composite stabilizer；Described epoxy resin composite is stable Agent is Vicbase TC3602H；
2nd, by weighed in step one 70 parts of oligomeric resin mixtures containing epoxide group, 15 parts of diluents and 5 parts of idols Join agent to be well mixed, sequentially add the 0.7 part of light trigger weighed in step one, 0.7 sensitising agent, 0.07 part of thermal initiator, Low whipping speed is stirring reaction 20min under 150r/min again, adds the 0.035 part of heat stabilizer weighed in step one, then Low whipping speed is stirring reaction 25min under 150r/min, obtains a kind of cation type ultraviolet photo and hot dual deep cure glue Stick.
Vicbase TC3634 described in embodiment ten are bought from Kai Ji Applied Materials Inc of Shenzhen；
Vicbase TC3602H described in embodiment ten are enough bought from Kai Ji Applied Materials Inc of Shenzhen.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by embodiment ten irradiates under ultraviolet light Solidification is completed after 1.8min；Through measuring the cation type ultraviolet photo of the preparation of embodiment ten and consolidating for hot dual deep cure adhesive Change thickness is 20.2mm.
Embodiment 11：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive is by following Prepared by step：
First, 70 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents, 10 parts of couplings are weighed by weight Agent, 0.7 part of light trigger, 0.7 part of sensitising agent, 0.14 part of thermal initiator and 0.07 part of heat stabilizer；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 60 under conditions of 150r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 150r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 60 DEG C Thing；Low whipping speed is 150r/min again and temperature is stirring reaction 8h under conditions of 60 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls The mixture of formic acid esters and double ((3,4- epoxycyclohexyls) methyl) adipate esters；The tree of the described epoxide group containing bifunctionality 3,4- epoxycyclohexyl-methyls 3,4- epoxycyclohexyls formic acid esters and double ((3,4- epoxycyclohexyls) methyl) adipate esters in fat Mass ratio be 2:1；The described oligomer containing multi-functional epoxy group is pentaerythrite glycidol ether；Described contains The resin of bifunctionality epoxide group is 100 with the mass ratio of the oligomer containing multi-functional epoxy group:30；
Diluent described in step one is 3- ethyls -3- oxa-s fourth ring methanol and 3,3'- (epoxide dimethylene) double (3- Ethyl) oxetanes mixture；3- ethyls -3- oxa-s fourth ring methanol and 3,3'- (the double methylenes of epoxide in described diluent Base) double (3- ethyls) oxetanes mass ratio be 1:1；
Coupling agent described in step one is γ-glycidyl ether oxygen propyl trimethoxy silicane；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 1- hydroxy-cyclohexyl-phenyl ketone derivatives；
Thermal initiator described in step one closes lewis acid for amine；Described amine closing lewis acid Vicbase TC3632；
Heat stabilizer described in step one is epoxy resin composite stabilizer；Described epoxy resin composite is stable Agent is Vicbase TC3602H；
2nd, by weighed in step one 70 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents and 10 parts Coupling agent is well mixed, and sequentially adds the 0.7 part of light trigger weighed in step one, 0.7 sensitising agent, 0.14 part of thermal initiation Agent, then low whipping speed are stirring reaction 20min under 150r/min, add the 0.07 part of heat stabilizer weighed in step one, Low whipping speed is stirring reaction 30min under 150r/min again, obtains a kind of cation type ultraviolet photo and hot dual deep cure Adhesive.
Vicbase TC3632 described in embodiment 11 are bought from Kai Ji Applied Materials Inc of Shenzhen；
Vicbase TC3602H described in embodiment 11 are enough bought from Kai Ji Applied Materials Inc of Shenzhen.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by embodiment 11 irradiates under ultraviolet light Solidification is completed after 2min；Through measuring the cation type ultraviolet photo of the preparation of embodiment 11 and consolidating for hot dual deep cure adhesive Change thickness is 31.5mm.
Embodiment 12：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive is by following Prepared by step：
First, 70 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents, 5 parts of couplings are weighed by weight Agent, 0.7 part of light trigger, 0.7 part of sensitising agent, 0.07 part of thermal initiator and 0.07 part of heat stabilizer；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 60 under conditions of 100r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 100r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 60 DEG C Thing；Low whipping speed is 150r/min again and temperature is stirring reaction 8h under conditions of 60 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls The mixture of formic acid esters and double ((3,4- epoxycyclohexyls) methyl) adipate esters；The tree of the described epoxide group containing bifunctionality 3,4- epoxycyclohexyl-methyls 3,4- epoxycyclohexyls formic acid esters and double ((3,4- epoxycyclohexyls) methyl) adipate esters in fat Mass ratio be 4:3；The described oligomer containing multi-functional epoxy group is [(2- Oxyranyles) -1,2- hexamethylenes two Alcohol] 2- ethyls -2- (methylol) -1,3- propylene glycols；The resin of the described epoxide group containing bifunctionality is multifunctional with containing The mass ratio for spending the oligomer of epoxide group is 100:35；
Diluent described in step one is 3- ethyls -3- oxa-s fourth ring methanol and 3,3'- (epoxide dimethylene) double (3- Ethyl) oxetanes mixture；3- ethyls -3- oxa-s fourth ring methanol and 3,3'- (the double methylenes of epoxide in described diluent Base) double (3- ethyls) oxetanes mass ratio be 1:1；
Coupling agent described in step one is 3,4- epoxycyclohexylethyl trimethoxy silanes；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 1- hydroxy-cyclohexyl-phenyl ketone derivatives；
Thermal initiator described in step one closes lewis acid for amine；Described amine closing lewis acid Vicbase TC3632；
Heat stabilizer described in step one is epoxy resin composite stabilizer；Described epoxy resin composite is stable Agent is Vicbase TC3602H；
2nd, by weighed in step one 70 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents and 5 parts of idols Join agent to be well mixed, sequentially add the 0.7 part of light trigger weighed in step one, 0.7 part of sensitising agent, 0.07 part of thermal initiation Agent, then low whipping speed are stirring reaction 20min under 150r/min, add the 0.07 part of heat stabilizer weighed in step one, Low whipping speed is stirring reaction 25min under 150r/min again, obtains a kind of cation type ultraviolet photo and hot dual deep cure Adhesive.
The derivative purchase of 1- hydroxy-cyclohexyl-phenyl ketones described in embodiment 12 is limited from double bond chemical industry share Company, product type is Doublecure 184L；
Vicbase TC3632 described in embodiment 12 are bought from Kai Ji Applied Materials Inc of Shenzhen；
Vicbase TC3602H described in embodiment 12 are enough bought from Kai Ji Applied Materials Inc of Shenzhen.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by embodiment 12 irradiates under ultraviolet light Solidification is completed after 2.5min；Cation type ultraviolet photo and hot dual deep cure adhesive through the measurement preparation of embodiment 12 Cured thickness is 23.8mm.
Embodiment 13：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive is by following Prepared by step：
First, 80 parts of oligomeric resin mixtures containing epoxide group, 15 parts of diluents, 5 parts of couplings are weighed by weight Agent, 1.2 parts of light triggers, 1.2 parts of sensitising agents and 0.4 part of thermal initiator；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 60 under conditions of 120r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 120r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 60 DEG C Thing；Low whipping speed is 200r/min again and temperature is stirring reaction 8h under conditions of 60 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls The mixture of formic acid esters and double ((3,4- epoxycyclohexyls) methyl) adipate esters；The tree of the described epoxide group containing bifunctionality 3,4- epoxycyclohexyl-methyls 3,4- epoxycyclohexyls formic acid esters and double ((3,4- epoxycyclohexyls) methyl) adipate esters in fat Mass ratio be 4:3；The described oligomer containing multi-functional epoxy group is hydrogenated bisphenol A epoxy resin and [(2- epoxies Ethyl group) -1,2- cyclohexanediols] 2- ethyls -2- (methylol) -1,3- propylene glycols mixture；Described containing is multifunctional Spend hydrogenated bisphenol A epoxy resin and [(2- Oxyranyles) -1,2- cyclohexanediols] 2- ethyls -2- in the oligomer of epoxide group The mass ratio of (methylol) -1,3- propylene glycols is 1:1；The resin of the described epoxide group containing bifunctionality is multifunctional with containing The mass ratio for spending the oligomer of epoxide group is 100:30；
Diluent described in step one is 3- ethyls -3- oxa-s fourth ring methanol and 3,3'- (epoxide dimethylene) double (3- Ethyl) oxetanes；
Coupling agent described in step one is γ-methacryloxypropyl trimethoxy silane；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 2,4,6- trimethylbenzoy-dipheny phosphine oxides；
Thermal initiator described in step one closes lewis acid for amine；Described amine closing lewis acid Vicbase TC3630；
Heat stabilizer described in step one is epoxy resin composite stabilizer；Described epoxy resin composite is stable Agent is Vicbase TC3602H；
2nd, by weighed in step one 80 parts of oligomeric resin mixtures containing epoxide group, 15 parts of diluents and 5 parts of idols Join agent to be well mixed, sequentially add the 1.2 parts of light triggers weighed in step one, 1.2 parts of sensitising agents, 0.4 part of thermal initiator, Low whipping speed is stirring reaction 20min under 150r/min again, adds the 0.4 part of heat stabilizer weighed in step one, then Mixing speed is stirring reaction 30min under 150r/min, obtains a kind of cation type ultraviolet photo and hot dual deep cure is gluing Agent.
Vicbase TC3630 described in embodiment 13 are bought from Kai Ji Applied Materials Inc of Shenzhen；
Vicbase TC3602H described in embodiment 13 are enough bought from Kai Ji Applied Materials Inc of Shenzhen.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by embodiment 13 irradiates under ultraviolet light Solidification is completed after 2min；Through measuring the cation type ultraviolet photo of the preparation of embodiment 13 and consolidating for hot dual deep cure adhesive Change thickness is 30.5mm.
Embodiment 14：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive is by following Prepared by step：
First, 70 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents, 10 parts of couplings are weighed by weight Agent, 0.7 part of light trigger, 0.7 part of sensitising agent and 0.035 part of thermal initiator；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 60 under conditions of 150r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 150r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 60 DEG C Thing；Low whipping speed is 150r/min again and temperature is stirring reaction 8h under conditions of 60 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls Formic acid esters；The described oligomer containing multi-functional epoxy group is organosilicon bisphenol A epoxide resin 665 and [(2- epoxy second Alkyl) -1,2- cyclohexanediols] 2- ethyls -2- (methylol) -1,3- propylene glycols mixture；Described contains polyfunctionality Organosilicon bisphenol A epoxide resin 665 and [(2- Oxyranyles) -1,2- cyclohexanediols] 2- second in the oligomer of epoxide group The mass ratio of base -2- (methylol) -1,3- propylene glycols is 1:1；The resin of the described epoxide group containing bifunctionality is with containing The mass ratio of the oligomer of multi-functional epoxy group is 100:40；
Diluent described in step one is double (3- ethyls) oxetanes of 3,3'- (epoxide dimethylene)；
Coupling agent described in step one is γ-methacryloxypropyl trimethoxy silane；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 2,4,6- trimethylbenzoy-dipheny phosphine oxides；
Thermal initiator described in step one is benzoyl peroxide；
2nd, by weighed in step one 70 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents and 10 parts Coupling agent is well mixed, and sequentially adds the 0.7 part of light trigger weighed in step one, 0.7 part of sensitising agent, 0.4 part of thermal initiation Agent, then low whipping speed are stirring reaction 25min under 150r/min, add the 0.035 part of heat stabilizer weighed in step one, Low whipping speed is stirring reaction 30min under 150r/min again, obtains a kind of cation type ultraviolet photo and hot dual deep cure Adhesive.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by embodiment 14 irradiates under ultraviolet light Solidification is completed after 1.5min；Cation type ultraviolet photo and hot dual deep cure adhesive through the measurement preparation of embodiment 14 Cured thickness is 22mm.
Embodiment 15：The preparation method of a kind of cation type ultraviolet photo and hot dual deep cure adhesive is by following Prepared by step：
First, 60 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents, 10 parts of couplings are weighed by weight Agent, 0.6 part of light trigger, 0.6 part of sensitising agent, 0.12 part of thermal initiator and 0.06 part of heat stabilizer；
The oligomeric resin mixture containing epoxide group is prepared according to the following steps in step one：
It is from room temperature to be heated to 60 under conditions of 150r/min by the resin low whipping speed of the epoxide group containing bifunctionality ℃；Low whipping speed is 150r/min again and temperature is to add containing the oligomeric of multi-functional epoxy group under conditions of 60 DEG C Thing；Low whipping speed is 200r/min again and temperature is stirring reaction 8h under conditions of 60 DEG C, is obtained containing the low of epoxide group Poly resin mixture；The resin of the described epoxide group containing bifunctionality is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyls Formic acid esters；The described oligomer containing multi-functional epoxy group is organosilicon bisphenol A epoxide resin 665 and [(2- epoxy second Alkyl) -1,2- cyclohexanediols] 2- ethyls -2- (methylol) -1,3- propylene glycols mixture；Described contains polyfunctionality Organosilicon bisphenol A epoxide resin 665 and [(2- Oxyranyles) -1,2- cyclohexanediols] 2- second in the oligomer of epoxide group The mass ratio of base -2- (methylol) -1,3- propylene glycols is 1:1；The resin of the described epoxide group containing bifunctionality is with containing The mass ratio of the oligomer of multi-functional epoxy group is 100:40；
Diluent described in step one is double (3- ethyls) oxetanes of 3,3'- (epoxide dimethylene)；
Coupling agent described in step one is γ-methacryloxypropyl trimethoxy silane；
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator；
Sensitising agent described in step one is 2,4,6- trimethylbenzoy-dipheny phosphine oxides；
Thermal initiator described in step one is benzoyl peroxide；
2nd, by weighed in step one 60 parts of oligomeric resin mixtures containing epoxide group, 20 parts of diluents and 10 parts Coupling agent is well mixed, and sequentially adds the 0.6 part of light trigger weighed in step one, 0.6 part of sensitising agent, 0.12 part of thermal initiation Agent, then low whipping speed are stirring reaction 30min under 150r/min, add the 0.06 part of heat stabilizer weighed in step one, Low whipping speed is stirring reaction 25min under 150r/min again, obtains a kind of cation type ultraviolet photo and hot dual deep cure Adhesive.
Cation type ultraviolet photo and hot dual deep cure adhesive prepared by embodiment 15 irradiates under ultraviolet light Solidification is completed after 1.5min；Cation type ultraviolet photo and hot dual deep cure adhesive through the measurement preparation of embodiment 15 Cured thickness is 27.3mm.

Claims (1)

1. a kind of cation type ultraviolet photo and hot dual deep cure adhesive, it is characterised in that a kind of cation type ultraviolet photo and The dual deep cure adhesive of heat by weight by 60 parts~100 parts oligomeric resin mixtures containing epoxide group, 5 parts~ 30 parts of diluents, 5 parts~15 parts coupling agents, 0.75 part~3 parts light triggers, 0.75 part~3 parts sensitising agents, 0.075 part~0.5 Part thermal initiator and 0 part~0.2 part heat stabilizer are prepared from；
The described oligomeric resin mixture containing epoxide group is prepared according to the following steps：
By the resin low whipping speed of the epoxide group containing bifunctionality be 100r/min~150r/min under conditions of add from room temperature Heat is to 60 DEG C~80 DEG C；Low whipping speed is 100r/min~150r/min again and temperature is addition under conditions of 60 DEG C~80 DEG C Oligomer containing multi-functional epoxy group；Low whipping speed is 150r/min~200r/min again and temperature is 60 DEG C~80 Stirring reaction 6h~18h under conditions of DEG C, obtains the oligomeric resin mixture containing epoxide group；
The mass ratio of the resin and the oligomer containing multi-functional epoxy group of the described epoxide group containing bifunctionality is 100:(5~40)；
The resin of the described epoxide group containing bifunctionality is cycloaliphatic epoxy resin, dibasic acid esters chain cycloaliphatic epoxy resin, fat One kind or wherein several mixtures in race's epoxy resin, bisphenol A epoxide resin and hydrogenated bisphenol A epoxy resin；Described Cycloaliphatic epoxy resin is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters；Dibasic acid esters chain cycloaliphatic epoxy resin is Double ((3,4- epoxycyclohexyls) methyl) adipate esters；Aliphatic epoxy resin is ethylene glycol diglycidylether；
The described oligomer containing multi-functional epoxy group is 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate 2-glycidyls Ester, poly- [(2- Oxyranyles) -1,2- cyclohexanediols] 2- ethyls -2- (methylol) -1,3- propylene glycols, pentaerythrite shrink One kind or wherein several mixtures in glycerin ether；
Described diluent is 3- ethyl -3- oxa- fourth rings methanol, double (3- ethyls) the oxa- ring fourths of 3,3'- (epoxide dimethylene) Alkane, 1,2,8,9- bis-epoxies -4 vinyl cyclohexene, butadiene bis-epoxy and one kind or wherein several in butyl glycidyl ether The mixture planted；
Described coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane, 3,4- epoxycyclohexylethyl trimethoxies Silane and one kind or wherein several mixtures in γ-methacryloxypropyl trimethoxy silane；Described light draws It is triaryl sulfonium salts or diaryl group iodized salt to send out agent；Described triaryl sulfonium salts are mixed type triaryl hexafluoro-antimonic acid sulfonium Salt cation light trigger；
Described sensitising agent be 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyclohexyl-phenyls ketone, 1- hydroxyls - Derivative, benzophenone, 2,4,6- trimethylbenzoy-diphenies phosphine oxide and the 2,4,6- tri- of cyclohexyl-phenyl ketone One kind or wherein several mixtures in the derivative of methyl benzoyl-diphenyl phosphine oxide；
Described thermal initiator is that peroxide triggers curing agent or amine closing lewis acid；Described peroxide triggers solid Agent is benzoyl peroxide BPO；Described amine closing lewis acid be Vicbase TC3630, Vicbase TC3632, Vicbase TC3633 or Vicbase TC3634；
Described heat stabilizer is epoxy resin composite stabilizer；Described epoxy resin composite stabilizer is Vicbase TC3602H。
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