CN105199643A - Cationic UV and heat dual deeply-curing adhesive and preparation method thereof - Google Patents

Cationic UV and heat dual deeply-curing adhesive and preparation method thereof Download PDF

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Publication number
CN105199643A
CN105199643A CN201510702233.0A CN201510702233A CN105199643A CN 105199643 A CN105199643 A CN 105199643A CN 201510702233 A CN201510702233 A CN 201510702233A CN 105199643 A CN105199643 A CN 105199643A
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parts
heat
epoxide group
resin
tackiness agent
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CN201510702233.0A
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CN105199643B (en
Inventor
宋彩雨
孙明明
王磊
赵明
李坚辉
薛刚
刘彩召
张绪刚
李奇力
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 CN201710274115.3A priority Critical patent/CN106928893B/en
Priority to CN201510702233.0A priority patent/CN105199643B/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

Abstract

A cationic UV and heat dual deeply-curing adhesive and its preparation method relate to a curing adhesive and its preparation method. The invention aims to solve the problem that an existing UV curing adhesive cannot achieve rapid deep curing and still needs subsequent heating after UV-irradiation. The UV and heat dual deeply-curing adhesive is prepared from, by weight, 60-100 parts of an oligomer resin mixture containing an epoxy group, 5-30 parts of a diluent, 5-15 parts of a coupling agent, 0.75-3 parts of a photoinitiator, 0.75-3 parts of a photosensitizer, 0.075-0.5 part of a thermal initiator and 0-0.2 part of a heat stabilizer. The method comprises the following steps: 1, weighing; and 2, mixing to obtain the cationic UV and heat dual deeply-curing adhesive. According to the invention, a cationic UV and heat dual deeply-curing adhesive and its preparation method can be obtained.

Description

A kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat 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, environmental protection, energy-saving tackiness agent, not only have containing solvent, the advantage that the storage time is long, also show curing speed fast, the advantage of instantaneous solidification can be realized.But because ultraviolet photo-curing cementing agent relies on UV-irradiation to cause solidification, therefore its curing depth is subject to the restriction of ultraviolet light irradiation, pigmented system is difficult to realize application, system shadow region is difficult to realize solidification process simultaneously, makes conventional ultra-violet curable adhesive be subject to application limitations at some special dimensions.
The curing depth of ultraviolet photo-curing cementing agent is subject to the impact of many factors, light source influence factor mainly comprises curing light source intensity, light source throw range from and throw according to the time, by improving UV-light light intensity, shorten throw range from, extend the curing depth thrown and relatively can improve ultraviolet photo-curing cementing agent according to means such as times, but promote limited extent.The impact of adhesive components on curing depth is mainly derived from the factor such as trigger rate, the viscosity of adhesive system, the apparent transparency of solidification glue of initiator, the combined influence of many factors makes the cured thickness of conventional ultra-violet curable adhesive very limited, is difficult to the particular requirement meeting some Application Areass.Cation type ultraviolet photo-curing can solve deeply-curing and the solid difficult problem of shade light relatively, but its curing speed is far below free radical type curing system, be difficult to the Light Curing realizing completing certain thickness requirement at short notice, make the researchdevelopment in this direction comparatively slow.
For realizing problem that is quick, deep cure, study the future development towards utilizing multiple solidification means to mix application.Cause solidification means with UV-light to serve as theme, cause the means such as curing reaction with the use of thermal initiation, moisture, while retaining instantaneous solidification advantage, improve the curing depth of tackiness agent further, thus improve its utility value and broaden application scope.
Summary of the invention
The object of the invention is to solve the solidification that existing ultraviolet photo-curing cementing agent can not realize rapid deep zone, still need the problem of carrying out subsequent heat after using UV-irradiation, and a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat and preparation method thereof are provided.
A kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat are prepared from containing the oligomeric resin mixture of epoxide group, 5 parts ~ 30 parts thinners, 5 parts ~ 15 parts coupling agents, 0.75 part ~ 3 parts light triggers, 0.75 part ~ 3 parts photosensitizerss, 0.075 part ~ 0.5 part thermal initiator and 0 part ~ 0.2 part thermo-stabilizers by 60 parts ~ 100 parts by weight.
The preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat is prepared by the following method:
One, take 60 parts ~ 100 parts by weight and contain the oligomeric resin mixture of epoxide group, 5 parts ~ 30 parts thinners, 5 parts ~ 15 parts coupling agents, 0.75 part ~ 3 parts light triggers, 0.75 part ~ 3 parts photosensitizerss, 0.075 part ~ 0.5 part thermal initiator and 0 part ~ 0.2 part thermo-stabilizers;
The oligomeric resin mixture containing epoxide group described in step one is prepared according to the following steps:
Be be heated to 60 DEG C ~ 80 DEG C from room temperature under the condition of 100r/min ~ 150r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 100r/min ~ 150r/min and temperature is again the oligopolymer added under the condition of 60 DEG C ~ 80 DEG C containing multi-functional epoxy group; Low whipping speed is 150r/min ~ 200r/min and temperature is again stirring reaction 6h ~ 18h under the condition of 60 DEG C ~ 80 DEG C, obtains the oligomeric resin mixture containing epoxide group;
The described resin containing difunctionality epoxide group is 100:(5 ~ 40 with the mass ratio of the oligopolymer containing multi-functional epoxy group);
The described resin containing difunctionality epoxide group is a kind of or wherein several mixture in cycloaliphatic epoxy resin, dibasic acid esters chain cycloaliphatic epoxy resin, aliphatic epoxy resin, bisphenol A epoxide resin and hydrogenated bisphenol A epoxy resin; Described cycloaliphatic epoxy resin is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; Dibasic acid esters chain cycloaliphatic epoxy resin is two ((3,4-epoxycyclohexyl) methyl) adipic acid esters; Aliphatic epoxy resin is ethylene glycol diglycidylether;
The described oligopolymer containing multi-functional epoxy group is 4,5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester, poly-[(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether, a kind of or wherein several mixture in tetramethylolmethane glycidyl ether;
Thinner described in step one is 3-ethyl-3-oxa-fourth ring methyl alcohol, 3,3'-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide, 1,2, a kind of or wherein several mixture in 8,9-bis-epoxy-4 vinyl cyclohexene, divinyl bis-epoxy and butylglycidyl ether;
Described coupling agent described in step one is a kind of or wherein several mixture in γ-glycidyl ether oxygen propyl trimethoxy silicane, 3,4-epoxycyclohexylethyl Trimethoxy silanes and γ-methacryloxypropyl trimethoxy silane;
Light trigger described in step one is triaryl sulfonium salts or diaryl group iodized salt; Described triaryl sulfonium salts is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator;
Photosensitizers described in step one is 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexyl-phenyl ketone, the derivative of 1-hydroxy-cyclohexyl-phenyl ketone, benzophenone, 2,4,6-trimethylbenzoy-dipheny phosphine oxide and 2, a kind of or wherein several mixture in the derivative of 4,6-trimethylbenzoy-dipheny phosphine oxide;
Thermal initiator described in step one is that superoxide causes solidifying agent or amine closes lewis acid; It is benzoyl peroxide BPO that described superoxide causes solidifying agent; It is VicbaseTC3630, VicbaseTC3632, VicbaseTC3633 or VicbaseTC3634 that described amine closes lewis acid;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, 60 parts ~ 100 parts that take in step one are contained the oligomeric resin mixture of epoxide group, 5 parts ~ 30 parts thinners and 5 parts ~ 15 parts coupling agents mix, add 0.75 part ~ 3 parts light triggers taken in step one more successively, 0.75 part ~ 3 parts photosensitizerss, 0.075 part ~ 0.5 part thermal initiator, low whipping speed is stirring reaction 20min ~ 40min under 100r/min ~ 150r/min again, add 0 part ~ 0.2 part thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 20min ~ 30min under 100r/min ~ 150r/min again, obtain a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
Advantage of the present invention:
One, a kind of cation type ultraviolet photo of preparing of the present invention and heat dual deep cure tackiness agent utilize the dual initiation means of ultraviolet light and heat to be cured, after UV-irradiation, rapid reaction, the heat simultaneously utilizing UV-light to produce causes thermofixation reaction process, thus realizes rapid deep zone solidification;
Two, a kind of cation type ultraviolet photo of preparing of the present invention and the dual deep cure tackiness agent of heat cause curing process without the need to carrying out post-heating, and the curing reaction time is short, and technological process is simple to operation, and meets deep cure requirement;
Three, the present invention is polymerized to principal reaction process with cationic epoxy ring-opening, epoxy resin is as main component, a kind of cation type ultraviolet photo of the preparation of preparing and heat dual deep cure tackiness agent have the viscosity number of lower scope, mobility is good, easy handling, the features such as the volumetric shrinkage degree that solidification produces is relatively low, and present cementability and the mechanicalness of epoxies tackiness agent excellence, there is good application performance;
Four, a kind of cation type ultraviolet photo of preparing of the present invention and the viscosity of the dual deep cure tackiness agent of heat at 25 DEG C are 750 ~ 3850cps, the bonding strength 10MPa at 25 DEG C ~ 18MPa, second-order transition temperature 65 DEG C ~ 90 DEG C;
Five, after a kind of cation type ultraviolet photo of preparing of the present invention and the dual deep cure tackiness agent of heat irradiate 1.5min ~ 3min under ultraviolet light, complete solidification process, cured thickness is 18.6mm ~ 32.3mm.
The present invention can obtain a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat and preparation method thereof.
Embodiment
Embodiment one: present embodiment is that the dual deep cure tackiness agent of a kind of cation type ultraviolet photo and heat is prepared from containing the oligomeric resin mixture of epoxide group, 5 parts ~ 30 parts thinners, 5 parts ~ 15 parts coupling agents, 0.75 part ~ 3 parts light triggers, 0.75 part ~ 3 parts photosensitizerss, 0.075 part ~ 0.5 part thermal initiator and 0 part ~ 0.2 part thermo-stabilizers by 60 parts ~ 100 parts by weight.
The advantage of present embodiment:
One, a kind of cation type ultraviolet photo of preparing of present embodiment and heat dual deep cure tackiness agent utilize the dual initiation means of ultraviolet light and heat to be cured, after UV-irradiation, rapid reaction, the heat simultaneously utilizing UV-light to produce causes thermofixation reaction process, thus realizes rapid deep zone solidification;
Two, a kind of cation type ultraviolet photo of preparing of present embodiment and the dual deep cure tackiness agent of heat cause curing process without the need to carrying out post-heating, and the curing reaction time is short, and technological process is simple to operation, and meets deep cure requirement;
Three, present embodiment is polymerized to principal reaction process with cationic epoxy ring-opening, epoxy resin is as main component, a kind of cation type ultraviolet photo of the preparation of preparing and heat dual deep cure tackiness agent have the viscosity number of lower scope, mobility is good, easy handling, the features such as the volumetric shrinkage degree that solidification produces is relatively low, and present cementability and the mechanicalness of epoxies tackiness agent excellence, there is good application performance;
Four, a kind of cation type ultraviolet photo of preparing of present embodiment and the viscosity of the dual deep cure tackiness agent of heat at 25 DEG C are 750 ~ 3850cps, the bonding strength 10MPa at 25 DEG C ~ 18MPa, second-order transition temperature 65 DEG C ~ 90 DEG C;
Five, after a kind of cation type ultraviolet photo of preparing of present embodiment and the dual deep cure tackiness agent of heat irradiate 1.5min ~ 3min under ultraviolet light, complete solidification process, cured thickness is 18.6mm ~ 32.3mm.
Present embodiment can obtain a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat and preparation method thereof.
Embodiment two: present embodiment and embodiment one difference are: the described oligomeric resin mixture containing epoxide group is prepared according to the following steps:
Be be heated to 60 DEG C ~ 80 DEG C from room temperature under the condition of 100r/min ~ 150r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 100r/min ~ 150r/min and temperature is again the oligopolymer added under the condition of 60 DEG C ~ 80 DEG C containing multi-functional epoxy group; Low whipping speed is 150r/min ~ 200r/min and temperature is again stirring reaction 6h ~ 18h under the condition of 60 DEG C ~ 80 DEG C, obtains the oligomeric resin mixture containing epoxide group;
The described resin containing difunctionality epoxide group is 100:(5 ~ 40 with the mass ratio of the oligopolymer containing multi-functional epoxy group).Other steps are identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two difference is: the described resin containing difunctionality epoxide group is a kind of or wherein several mixture in cycloaliphatic epoxy resin, dibasic acid esters chain cycloaliphatic epoxy resin, aliphatic epoxy resin, bisphenol A epoxide resin and hydrogenated bisphenol A epoxy resin; Described cycloaliphatic epoxy resin is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; Dibasic acid esters chain cycloaliphatic epoxy resin is two ((3,4-epoxycyclohexyl) methyl) adipic acid esters; Aliphatic epoxy resin is ethylene glycol diglycidylether.Other steps are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three difference is: the described oligopolymer containing multi-functional epoxy group is 4,5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester, poly-[(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether, a kind of or wherein several mixture in tetramethylolmethane glycidyl ether.Other steps are identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four difference is: described thinner is 3-ethyl-3-oxa-fourth ring methyl alcohol, 3,3'-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide, 1,2, a kind of or wherein several mixture in 8,9-bis-epoxy-4 vinyl cyclohexene, divinyl bis-epoxy and butylglycidyl ether.Other steps are identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five difference is: described coupling agent is a kind of or wherein several mixture in γ-glycidyl ether oxygen propyl trimethoxy silicane, 3,4-epoxycyclohexylethyl Trimethoxy silanes and γ-methacryloxypropyl trimethoxy silane; Described light trigger is triaryl sulfonium salts or diaryl group iodized salt; Described triaryl sulfonium salts is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator.Other steps are identical with embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six difference is: described photosensitizers is 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexyl-phenyl ketone, the derivative of 1-hydroxy-cyclohexyl-phenyl ketone, benzophenone, 2; 4; 6-trimethylbenzoy-dipheny phosphine oxide and 2; a kind of or wherein several mixture in the derivative of 4,6-trimethylbenzoy-dipheny phosphine oxide.Other steps are identical with embodiment one to six.
The derivative of the 1-hydroxy-cyclohexyl-phenyl ketone described in present embodiment is bought from Double Bond Chemical Ind.,Co.,Ltd., and product type is Doublecure184L;
The derivative of 2,4,6-trimethylbenzoy-dipheny phosphine oxides described in present embodiment is bought from Double Bond Chemical Ind.,Co.,Ltd., and product type is double bond chemical industry DoublecureTPO-L.
Embodiment eight: one of present embodiment and embodiment one to seven difference is: described thermal initiator is that superoxide causes solidifying agent or amine closes lewis acid; It is benzoyl peroxide BPO that described superoxide causes solidifying agent; It is VicbaseTC3630, VicbaseTC3632, VicbaseTC3633 or VicbaseTC3634 that described amine closes lewis acid.Other steps are identical with embodiment one to seven.
VicbaseTC3630, VicbaseTC3632, VicbaseTC3633 and VicbaseTC3634 described in present embodiment all buy from Kai Ji Applied Materials Inc of Shenzhen.
Embodiment nine: one of present embodiment and embodiment one to eight difference is: described thermo-stabilizer is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H.Other steps are identical with embodiment one to eight.
VicbaseTC3602H described in present embodiment enough buys from Kai Ji Applied Materials Inc of Shenzhen.
Embodiment ten: present embodiment is that the preparation method of the dual deep cure tackiness agent of a kind of cation type ultraviolet photo and heat is prepared by the following method:
One, take 60 parts ~ 100 parts by weight and contain the oligomeric resin mixture of epoxide group, 5 parts ~ 30 parts thinners, 5 parts ~ 15 parts coupling agents, 0.75 part ~ 3 parts light triggers, 0.75 part ~ 3 parts photosensitizerss, 0.075 part ~ 0.5 part thermal initiator and 0 part ~ 0.2 part thermo-stabilizers;
The oligomeric resin mixture containing epoxide group described in step one is prepared according to the following steps:
Be be heated to 60 DEG C ~ 80 DEG C from room temperature under the condition of 100r/min ~ 150r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 100r/min ~ 150r/min and temperature is again the oligopolymer added under the condition of 60 DEG C ~ 80 DEG C containing multi-functional epoxy group; Low whipping speed is 150r/min ~ 200r/min and temperature is again stirring reaction 6h ~ 18h under the condition of 60 DEG C ~ 80 DEG C, obtains the oligomeric resin mixture containing epoxide group;
The described resin containing difunctionality epoxide group is 100:(5 ~ 40 with the mass ratio of the oligopolymer containing multi-functional epoxy group);
The described resin containing difunctionality epoxide group is a kind of or wherein several mixture in cycloaliphatic epoxy resin, dibasic acid esters chain cycloaliphatic epoxy resin, aliphatic epoxy resin, bisphenol A epoxide resin and hydrogenated bisphenol A epoxy resin; Described cycloaliphatic epoxy resin is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; Dibasic acid esters chain cycloaliphatic epoxy resin is two ((3,4-epoxycyclohexyl) methyl) adipic acid esters; Aliphatic epoxy resin is ethylene glycol diglycidylether;
The described oligopolymer containing multi-functional epoxy group is 4,5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester, poly-[(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether, a kind of or wherein several mixture in tetramethylolmethane glycidyl ether;
Thinner described in step one is 3-ethyl-3-oxa-fourth ring methyl alcohol, 3,3'-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide, 1,2, a kind of or wherein several mixture in 8,9-bis-epoxy-4 vinyl cyclohexene, divinyl bis-epoxy and butylglycidyl ether;
Described coupling agent described in step one is a kind of or wherein several mixture in γ-glycidyl ether oxygen propyl trimethoxy silicane, 3,4-epoxycyclohexylethyl Trimethoxy silanes and γ-methacryloxypropyl trimethoxy silane;
Light trigger described in step one is triaryl sulfonium salts or diaryl group iodized salt; Described triaryl sulfonium salts is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator;
Photosensitizers described in step one is 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexyl-phenyl ketone, the derivative of 1-hydroxy-cyclohexyl-phenyl ketone, benzophenone, 2,4,6-trimethylbenzoy-dipheny phosphine oxide and 2, a kind of or wherein several mixture in the derivative of 4,6-trimethylbenzoy-dipheny phosphine oxide;
Thermal initiator described in step one is that superoxide causes solidifying agent or amine closes lewis acid; It is benzoyl peroxide BPO that described superoxide causes solidifying agent; It is VicbaseTC3630, VicbaseTC3632, VicbaseTC3633 or VicbaseTC3634 that described amine closes lewis acid;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, 60 parts ~ 100 parts that take in step one are contained the oligomeric resin mixture of epoxide group, 5 parts ~ 30 parts thinners and 5 parts ~ 15 parts coupling agents mix, add 0.75 part ~ 3 parts light triggers taken in step one more successively, 0.75 part ~ 3 parts photosensitizerss, 0.075 part ~ 0.5 part thermal initiator, low whipping speed is stirring reaction 20min ~ 40min under 100r/min ~ 150r/min again, add 0 part ~ 0.2 part thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 20min ~ 30min under 100r/min ~ 150r/min again, obtain a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
The derivative of the 1-hydroxy-cyclohexyl-phenyl ketone described in present embodiment is bought from Double Bond Chemical Ind.,Co.,Ltd., and product type is Doublecure184L;
The derivative of 2,4,6-trimethylbenzoy-dipheny phosphine oxides described in present embodiment is bought from Double Bond Chemical Ind.,Co.,Ltd., and product type is double bond chemical industry DoublecureTPO-L;
VicbaseTC3630, VicbaseTC3632, VicbaseTC3633 and VicbaseTC3634 described in present embodiment all buy from Kai Ji Applied Materials Inc of Shenzhen;
VicbaseTC3602H described in present embodiment enough buys from Kai Ji Applied Materials Inc of Shenzhen.
The advantage of present embodiment:
One, a kind of cation type ultraviolet photo of preparing of present embodiment and heat dual deep cure tackiness agent utilize the dual initiation means of ultraviolet light and heat to be cured, after UV-irradiation, rapid reaction, the heat simultaneously utilizing UV-light to produce causes thermofixation reaction process, thus realizes rapid deep zone solidification;
Two, a kind of cation type ultraviolet photo of preparing of present embodiment and the dual deep cure tackiness agent of heat cause curing process without the need to carrying out post-heating, and the curing reaction time is short, and technological process is simple to operation, and meets deep cure requirement;
Three, present embodiment is polymerized to principal reaction process with cationic epoxy ring-opening, epoxy resin is as main component, a kind of cation type ultraviolet photo of the preparation of preparing and heat dual deep cure tackiness agent have the viscosity number of lower scope, mobility is good, easy handling, the features such as the volumetric shrinkage degree that solidification produces is relatively low, and present cementability and the mechanicalness of epoxies tackiness agent excellence, there is good application performance;
Four, a kind of cation type ultraviolet photo of preparing of present embodiment and the viscosity of the dual deep cure tackiness agent of heat at 25 DEG C are 750 ~ 3850cps, the bonding strength 10MPa at 25 DEG C ~ 18MPa, second-order transition temperature 65 DEG C ~ 90 DEG C;
Five, after a kind of cation type ultraviolet photo of preparing of present embodiment and the dual deep cure tackiness agent of heat irradiate 1.5min ~ 3min under ultraviolet light, complete solidification process, cured thickness is 18.6mm ~ 32.3mm.
Present embodiment can obtain a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat and preparation method thereof.
Embodiment one: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat is prepared according to the following steps:
One, take 70 parts by weight and contain the oligomeric resin mixture of epoxide group, 20 parts of thinners, 10 parts of coupling agents, 0.7 part of light trigger, 0.7 part of photosensitizers, 0.14 part of thermal initiator and 0.07 part of thermo-stabilizer;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 80 DEG C from room temperature under the condition of 100r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 100r/min and temperature is again the oligopolymer added under the condition of 80 DEG C containing multi-functional epoxy group; Low whipping speed is 150r/min and temperature is again stirring reaction 12h under the condition of 80 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; The described oligopolymer containing multi-functional epoxy group is poly-[(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether; The described resin containing difunctionality epoxide group is 100:10 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is 3-ethyl-3-oxa-fourth ring methyl alcohol;
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;
Photosensitizers described in step one is 1-hydroxy-cyclohexyl-phenyl ketone;
Thermal initiator described in step one is that amine closes lewis acid; Described amine closes lewis acid VicbaseTC3632;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, contain the oligomeric resin mixture of epoxide group, 20 parts of thinners and 10 parts of coupling agents by take in step one 70 parts to mix, add the 0.7 part of light trigger taken in step one, 0.7 part of photosensitizers, 0.14 part of thermal initiator more successively, low whipping speed is stirring reaction 20min under 100r/min again, add the 0.07 part of thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 30min under 100r/min again, obtains a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
VicbaseTC3632 described in embodiment one buys from Kai Ji Applied Materials Inc of Shenzhen;
VicbaseTC3602H described in embodiment one enough buys from Kai Ji Applied Materials Inc of Shenzhen.
Solidification is completed after cation type ultraviolet photo prepared by embodiment one and the dual deep cure tackiness agent of heat irradiate 1.5min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment one preparation is 20.5mm.
Embodiment two: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat, prepare according to the following steps:
One, take 70 parts by weight and contain the oligomeric resin mixture of epoxide group, 20 parts of thinners, 10 parts of coupling agents, 0.7 part of light trigger, 0.7 part of photosensitizers, 0.14 part of thermal initiator and 0.07 part of thermo-stabilizer;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 80 DEG C from room temperature under the condition of 100r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 100r/min and temperature is again the oligopolymer added under the condition of 80 DEG C containing multi-functional epoxy group; Low whipping speed is 200r/min and temperature is again stirring reaction 15h under the condition of 80 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; The described oligopolymer containing multi-functional epoxy group is poly-[(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether; The described resin containing difunctionality epoxide group is 100:20 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is divinyl 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;
Photosensitizers described in step one is 1-hydroxy-cyclohexyl-phenyl ketone;
Thermal initiator described in step one is that amine closes lewis acid; Described amine closes lewis acid VicbaseTC3634;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, contain the oligomeric resin mixture of epoxide group, 20 parts of thinners and 10 parts of coupling agents by take in step one 70 parts to mix, add the 0.7 part of light trigger taken in step one, 0.7 part of photosensitizers, 0.14 part of thermal initiator more successively, low whipping speed is stirring reaction 20min under 100r/min again, add the 0.07 part of thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 30min under 100r/min again, obtains a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
VicbaseTC3634 described in embodiment two buys from Kai Ji Applied Materials Inc of Shenzhen;
VicbaseTC3602H described in embodiment two enough buys from Kai Ji Applied Materials Inc of Shenzhen.
Solidification is completed after cation type ultraviolet photo prepared by embodiment two and the dual deep cure tackiness agent of heat irradiate 2min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment two preparation is 21.4mm.
Embodiment three: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat, prepare according to the following steps:
One, take 70 parts by weight and contain the oligomeric resin mixture of epoxide group, 25 parts of thinners, 5 parts of coupling agents, 0.7 part of light trigger, 0.7 part of photosensitizers, 0.07 part of thermal initiator and 0.035 part of thermo-stabilizer;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 80 DEG C from room temperature under the condition of 150r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 150r/min and temperature is again the oligopolymer added under the condition of 80 DEG C containing multi-functional epoxy group; Low whipping speed is 150r/min and temperature is again stirring reaction 15h under the condition of 80 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; The described oligopolymer containing multi-functional epoxy group is poly-[(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether; The described resin containing difunctionality epoxide group is 100:20 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is 3-ethyl-3-oxa-fourth ring methyl alcohol;
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;
Photosensitizers described in step one is 2-hydroxy-2-methyl-1-phenyl-1-acetone;
Thermal initiator described in step one is that amine closes lewis acid; Described amine closes lewis acid VicbaseTC3632;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, contain the oligomeric resin mixture of epoxide group, 25 parts of thinners and 5 parts of coupling agents by take in step one 70 parts to mix, add the 0.7 part of light trigger taken in step one, 0.7 part of photosensitizers, 0.07 part of thermal initiator more successively, low whipping speed is stirring reaction 20min under 100r/min again, add the 0.035 part of thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 20min under 150r/min again, obtains a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
VicbaseTC3632 described in embodiment three buys from Kai Ji Applied Materials Inc of Shenzhen;
VicbaseTC3602H described in embodiment three enough buys from Kai Ji Applied Materials Inc of Shenzhen.
Solidification is completed after cation type ultraviolet photo prepared by embodiment three and the dual deep cure tackiness agent of heat irradiate 1.5min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment three preparation is 19.7mm.
Embodiment four: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat, prepare according to the following steps:
One, take 80 parts by weight and contain the oligomeric resin mixture of epoxide group, 15 parts of thinners, 5 parts of coupling agents, 0.8 part of light trigger, 0.8 part of photosensitizers, 0.08 part of thermal initiator and 0.024 part of thermo-stabilizer;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 60 DEG C from room temperature under the condition of 120r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 120r/min and temperature is again the oligopolymer added under the condition of 60 DEG C containing multi-functional epoxy group; Low whipping speed is 250r/min and temperature is again stirring reaction 6h under the condition of 60 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; The described oligopolymer containing multi-functional epoxy group is 4,5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester; The described resin containing difunctionality epoxide group is 100:15 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is 3-ethyl-3-oxa-fourth ring methyl alcohol;
Coupling agent described in step one is 3,4-epoxycyclohexylethyl Trimethoxy silane;
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator;
Photosensitizers described in step one is 2-hydroxy-2-methyl-1-phenyl-1-acetone;
Thermal initiator described in step one is that amine closes lewis acid; Described amine closes lewis acid VicbaseTC3632;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, contain the oligomeric resin mixture of epoxide group, 15 parts of thinners and 5 parts of coupling agents by take in step one 80 parts to mix, add the 0.8 part of light trigger taken in step one, 0.8 part of photosensitizers, 0.08 part of thermal initiator more successively, low whipping speed is stirring reaction 20min under 100r/min again, add the 0.024 part of thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 30min under 100r/min again, obtains a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
VicbaseTC3632 described in embodiment four buys from Kai Ji Applied Materials Inc of Shenzhen;
VicbaseTC3602H described in embodiment four enough buys from Kai Ji Applied Materials Inc of Shenzhen.
Solidification is completed after cation type ultraviolet photo prepared by embodiment four and the dual deep cure tackiness agent of heat irradiate 1.5min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment four preparation is 25.1mm.
Embodiment five: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat, prepare according to the following steps:
One, take 70 parts by weight and contain the oligomeric resin mixture of epoxide group, 20 parts of thinners, 10 parts of coupling agents, 0.7 part of light trigger, 0.7 part of photosensitizers, 0.14 part of thermal initiator and 0.07 part of thermo-stabilizer;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 60 DEG C from room temperature under the condition of 120r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 120r/min and temperature is again the oligopolymer added under the condition of 60 DEG C containing multi-functional epoxy group; Low whipping speed is 150r/min and temperature is again stirring reaction 6h under the condition of 60 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; The described oligopolymer containing multi-functional epoxy group is 4,5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester; The described resin containing difunctionality epoxide group is 100:25 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is 1,2,8,9-bis-epoxy-4 vinyl cyclohexene;
Coupling agent described in step one is 3,4-epoxycyclohexylethyl Trimethoxy silane;
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator;
Photosensitizers described in step one is 2-hydroxy-2-methyl-1-phenyl-1-acetone;
Thermal initiator described in step one is that amine closes lewis acid; Described amine closes lewis acid VicbaseTC3630;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, contain the oligomeric resin mixture of epoxide group, 20 parts of thinners and 10 parts of coupling agents by take in step one 70 parts to mix, add the 0.7 part of light trigger taken in step one, 0.7 part of photosensitizers, 0.14 part of thermal initiator more successively, low whipping speed is stirring reaction 20min under 120r/min again, add the 0.07 part of thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 25min under 120r/min again, obtains a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
VicbaseTC3630 described in embodiment five buys from Kai Ji Applied Materials Inc of Shenzhen;
VicbaseTC3602H described in embodiment five enough buys from Kai Ji Applied Materials Inc of Shenzhen.
Solidification is completed after cation type ultraviolet photo prepared by embodiment five and the dual deep cure tackiness agent of heat irradiate 2min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment five preparation is 18.6mm.
Embodiment six: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat, prepare according to the following steps:
One, take 70 parts by weight and contain the oligomeric resin mixture of epoxide group, 25 parts of thinners, 10 parts of coupling agents, 0.7 part of light trigger, 0.7 part of photosensitizers, 0.07 part of thermal initiator and 0.035 part of thermo-stabilizer;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 60 DEG C from room temperature under the condition of 150r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 150r/min and temperature is again the oligopolymer added under the condition of 60 DEG C containing multi-functional epoxy group; Low whipping speed is 150r/min and temperature is again stirring reaction 6h under the condition of 60 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; The described oligopolymer containing multi-functional epoxy group is 4,5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester; The described resin containing difunctionality epoxide group is 100:25 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is 1,2,8,9-bis-epoxy-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;
Photosensitizers described in step one is 1-hydroxy-cyclohexyl-phenyl ketone;
Thermal initiator described in step one is that amine closes lewis acid; Described amine closes lewis acid VicbaseTC3633;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, contain the oligomeric resin mixture of epoxide group, 25 parts of thinners and 10 parts of coupling agents by take in step one 70 parts to mix, add the 0.7 part of light trigger taken in step one, 0.7 part of photosensitizers, 0.07 part of thermal initiator more successively, low whipping speed is stirring reaction 20min under 150r/min again, add the 0.035 part of thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 30min under 150r/min again, obtains a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
VicbaseTC3633 described in embodiment six buys from Kai Ji Applied Materials Inc of Shenzhen;
VicbaseTC3602H described in embodiment six enough buys from Kai Ji Applied Materials Inc of Shenzhen.
Solidification is completed after cation type ultraviolet photo prepared by embodiment six and the dual deep cure tackiness agent of heat irradiate 1.5min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment six preparation is 32.3mm.
Embodiment seven: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat is prepared according to the following steps:
One, take 80 parts by weight and contain the oligomeric resin mixture of epoxide group, 15 parts of thinners, 5 parts of coupling agents, 1.2 parts of light triggers, 1.2 parts of photosensitizerss and 0.08 part of thermal initiator;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 80 DEG C from room temperature under the condition of 100r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 100r/min and temperature is again the oligopolymer added under the condition of 80 DEG C containing multi-functional epoxy group; Low whipping speed is 180r/min and temperature is again stirring reaction 15h under the condition of 80 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; The described oligopolymer containing multi-functional epoxy group is poly-[(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether; The described resin containing difunctionality epoxide group is 100:20 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is 3,3'-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide;
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;
Photosensitizers described in step one is 1-hydroxy-cyclohexyl-phenyl ketone;
Thermal initiator described in step one is that amine closes lewis acid; Described amine closes lewis acid VicbaseTC3632;
Two, contain the oligomeric resin mixture of epoxide group, 15 parts of thinners and 5 parts of coupling agents by take in step one 80 parts to mix, add the 1.2 parts of light triggers taken in step one, 1.2 parts of photosensitizerss, 0.08 part of thermal initiator more successively, low whipping speed is stirring reaction 30min under 150r/min again, obtains a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
VicbaseTC3632 described in embodiment seven buys from Kai Ji Applied Materials Inc of Shenzhen.
Solidification is completed after cation type ultraviolet photo prepared by embodiment seven and the dual deep cure tackiness agent of heat irradiate 2.5min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment seven preparation is 28.7mm.
Embodiment eight: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat is prepared according to the following steps:
One, take 80 parts by weight and contain the oligomeric resin mixture of epoxide group, 16 parts of thinners, 5 parts of coupling agents, 0.8 part of light trigger, 0.8 part of photosensitizers, 0.08 part of thermal initiator and 0.04 part of thermo-stabilizer;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 70 DEG C from room temperature under the condition of 150r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 150r/min and temperature is again the oligopolymer added under the condition of 70 DEG C containing multi-functional epoxy group; Low whipping speed is 150r/min and temperature is again stirring reaction 6h under the condition of 70 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; The described oligopolymer containing multi-functional epoxy group is hydrogenated bisphenol A epoxy resin; The described resin containing difunctionality epoxide group is 100:20 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is 3,3'-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide;
Coupling agent described in step one is 3,4-epoxycyclohexylethyl Trimethoxy silane;
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator;
Photosensitizers described in step one is 1-hydroxy-cyclohexyl-phenyl ketone;
Thermal initiator described in step one is that amine closes lewis acid; Described amine closes lewis acid VicbaseTC3632;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, contain the oligomeric resin mixture of epoxide group, 16 parts of thinners and 5 parts of coupling agents by take in step one 80 parts to mix, add the 0.8 part of light trigger, 0.8 photosensitizers, the 0.08 part of thermal initiator that take in step one more successively, low whipping speed is stirring reaction 20min under 150r/min again, add the 0.04 part of thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 25min under 150r/min again, obtains the dual deep cure tackiness agent of a kind of cation type ultraviolet photo heat.
VicbaseTC3632 described in embodiment eight buys from Kai Ji Applied Materials Inc of Shenzhen;
VicbaseTC3602H described in embodiment eight enough buys from Kai Ji Applied Materials Inc of Shenzhen.
Solidification is completed after cation type ultraviolet photo prepared by embodiment eight and the dual deep cure tackiness agent of heat irradiate 1.5min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment eight preparation is 26.8mm.
Embodiment nine: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat is prepared according to the following steps:
One, take 70 parts by weight and contain the oligomeric resin mixture of epoxide group, 20 parts of thinners, 10 parts of coupling agents, 0.7 part of light trigger, 0.7 part of photosensitizers, 0.07 part of thermal initiator and 0.035 part of thermo-stabilizer;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 70 DEG C from room temperature under the condition of 120r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 120r/min and temperature is again the oligopolymer added under the condition of 70 DEG C containing multi-functional epoxy group; Low whipping speed is 200r/min and temperature is again stirring reaction 8h under the condition of 70 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; The described oligopolymer containing multi-functional epoxy group is bisphenol A epoxide resin E51; The described resin containing difunctionality epoxide group is 100:20 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is 3,3'-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide;
Coupling agent described in step one is 3,4-epoxycyclohexylethyl Trimethoxy silane;
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator;
Photosensitizers described in step one is 1-hydroxy-cyclohexyl-phenyl ketone;
Thermal initiator described in step one is that amine closes lewis acid; Described amine closes lewis acid VicbaseTC3630;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, contain the oligomeric resin mixture of epoxide group, 20 parts of thinners and 10 parts of coupling agents by take in step one 70 parts to mix, add the 0.7 part of light trigger, 0.7 photosensitizers, the 0.07 part of thermal initiator that take in step one more successively, low whipping speed is stirring reaction 20min under 120r/min again, add the 0.035 part of thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 30min under 120r/min again, obtains a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
VicbaseTC3630 described in embodiment nine buys from Kai Ji Applied Materials Inc of Shenzhen;
VicbaseTC3602H described in embodiment nine enough buys from Kai Ji Applied Materials Inc of Shenzhen.
Solidification is completed after cation type ultraviolet photo prepared by embodiment nine and the dual deep cure tackiness agent of heat irradiate 1.5min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment nine preparation is 29.6mm.
Embodiment ten: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat is prepared according to the following steps:
One, take 70 parts by weight and contain the oligomeric resin mixture of epoxide group, 15 parts of thinners, 5 parts of coupling agents, 0.7 part of light trigger, 0.7 part of photosensitizers, 0.07 part of thermal initiator and 0.035 part of thermo-stabilizer;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 60 DEG C from room temperature under the condition of 150r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 150r/min and temperature is again the oligopolymer added under the condition of 60 DEG C containing multi-functional epoxy group; Low whipping speed is 150r/min and temperature is again stirring reaction 8h under the condition of 60 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is the mixture of 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate and two ((3,4-epoxycyclohexyl) methyl) hexanodioic acid; 3,4-described epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate are 2:1 with the mass ratio of the mixture of two ((3,4-epoxycyclohexyl) methyl) hexanodioic acid; The described oligopolymer containing multi-functional epoxy group is tetramethylolmethane glycidyl ether; The described resin containing difunctionality epoxide group is 100:30 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is 3-ethyl-3-oxa-fourth ring methyl alcohol;
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;
Photosensitizers described in step one is benzophenone;
Thermal initiator described in step one is that amine closes lewis acid; Described amine closes lewis acid VicbaseTC3634;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, contain the oligomeric resin mixture of epoxide group, 15 parts of thinners and 5 parts of coupling agents by take in step one 70 parts to mix, add the 0.7 part of light trigger, 0.7 photosensitizers, the 0.07 part of thermal initiator that take in step one more successively, low whipping speed is stirring reaction 20min under 150r/min again, add the 0.035 part of thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 25min under 150r/min again, obtains a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
VicbaseTC3634 described in embodiment ten buys from Kai Ji Applied Materials Inc of Shenzhen;
VicbaseTC3602H described in embodiment ten enough buys from Kai Ji Applied Materials Inc of Shenzhen.
Solidification is completed after cation type ultraviolet photo prepared by embodiment ten and the dual deep cure tackiness agent of heat irradiate 1.8min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment ten preparation is 20.2mm.
Embodiment 11: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat is prepared according to the following steps:
One, take 70 parts by weight and contain the oligomeric resin mixture of epoxide group, 20 parts of thinners, 10 parts of coupling agents, 0.7 part of light trigger, 0.7 part of photosensitizers, 0.14 part of thermal initiator and 0.07 part of thermo-stabilizer;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 60 DEG C from room temperature under the condition of 150r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 150r/min and temperature is again the oligopolymer added under the condition of 60 DEG C containing multi-functional epoxy group; Low whipping speed is 150r/min and temperature is again stirring reaction 8h under the condition of 60 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is the mixture of 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate and two ((3,4-epoxycyclohexyl) methyl) adipic acid ester; Described is 2:1 containing 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate in the resin of difunctionality epoxide group and the mass ratio of two ((3,4-epoxycyclohexyl) methyl) adipic acid ester; The described oligopolymer containing multi-functional epoxy group is tetramethylolmethane glycidyl ether; The described resin containing difunctionality epoxide group is 100:30 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is the mixture of 3-ethyl-3-oxa-fourth ring methyl alcohol and 3,3'-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide; In described thinner, the mass ratio of 3-ethyl-3-oxa-fourth ring methyl alcohol and 3,3'-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide is 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;
Photosensitizers described in step one is 1-hydroxy-cyclohexyl-phenyl ketone derivatives;
Thermal initiator described in step one is that amine closes lewis acid; Described amine closes lewis acid VicbaseTC3632;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, contain the oligomeric resin mixture of epoxide group, 20 parts of thinners and 10 parts of coupling agents by take in step one 70 parts to mix, add the 0.7 part of light trigger, 0.7 photosensitizers, the 0.14 part of thermal initiator that take in step one more successively, low whipping speed is stirring reaction 20min under 150r/min again, add the 0.07 part of thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 30min under 150r/min again, obtains a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
VicbaseTC3632 described in embodiment 11 buys from Kai Ji Applied Materials Inc of Shenzhen;
VicbaseTC3602H described in embodiment 11 enough buys from Kai Ji Applied Materials Inc of Shenzhen.
Solidification is completed after cation type ultraviolet photo prepared by embodiment 11 and the dual deep cure tackiness agent of heat irradiate 2min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment 11 preparation is 31.5mm.
Embodiment 12: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat is prepared according to the following steps:
One, take 70 parts by weight and contain the oligomeric resin mixture of epoxide group, 20 parts of thinners, 5 parts of coupling agents, 0.7 part of light trigger, 0.7 part of photosensitizers, 0.07 part of thermal initiator and 0.07 part of thermo-stabilizer;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 60 DEG C from room temperature under the condition of 100r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 100r/min and temperature is again the oligopolymer added under the condition of 60 DEG C containing multi-functional epoxy group; Low whipping speed is 150r/min and temperature is again stirring reaction 8h under the condition of 60 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is the mixture of 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate and two ((3,4-epoxycyclohexyl) methyl) adipic acid ester; Described is 4:3 containing 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate in the resin of difunctionality epoxide group and the mass ratio of two ((3,4-epoxycyclohexyl) methyl) adipic acid ester; The described oligopolymer containing multi-functional epoxy group is [(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether; The described resin containing difunctionality epoxide group is 100:35 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is the mixture of 3-ethyl-3-oxa-fourth ring methyl alcohol and 3,3'-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide; In described thinner, the mass ratio of 3-ethyl-3-oxa-fourth ring methyl alcohol and 3,3'-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide is 1:1;
Coupling agent described in step one is 3,4-epoxycyclohexylethyl Trimethoxy silane;
Light trigger described in step one is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator;
Photosensitizers described in step one is 1-hydroxy-cyclohexyl-phenyl ketone derivatives;
Thermal initiator described in step one is that amine closes lewis acid; Described amine closes lewis acid VicbaseTC3632;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, contain the oligomeric resin mixture of epoxide group, 20 parts of thinners and 5 parts of coupling agents by take in step one 70 parts to mix, add the 0.7 part of light trigger taken in step one, 0.7 part of photosensitizers, 0.07 part of thermal initiator more successively, low whipping speed is stirring reaction 20min under 150r/min again, add the 0.07 part of thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 25min under 150r/min again, obtains a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
The derivative of the 1-hydroxy-cyclohexyl-phenyl ketone described in embodiment 12 is bought from Double Bond Chemical Ind.,Co.,Ltd., and product type is Doublecure184L;
VicbaseTC3632 described in embodiment 12 buys from Kai Ji Applied Materials Inc of Shenzhen;
VicbaseTC3602H described in embodiment 12 enough buys from Kai Ji Applied Materials Inc of Shenzhen.
Solidification is completed after cation type ultraviolet photo prepared by embodiment 12 and the dual deep cure tackiness agent of heat irradiate 2.5min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment 12 preparation is 23.8mm.
Embodiment 13: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat is prepared according to the following steps:
One, take 80 parts by weight and contain the oligomeric resin mixture of epoxide group, 15 parts of thinners, 5 parts of coupling agents, 1.2 parts of light triggers, 1.2 parts of photosensitizerss and 0.4 part of thermal initiator;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 60 DEG C from room temperature under the condition of 120r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 120r/min and temperature is again the oligopolymer added under the condition of 60 DEG C containing multi-functional epoxy group; Low whipping speed is 200r/min and temperature is again stirring reaction 8h under the condition of 60 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is the mixture of 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate and two ((3,4-epoxycyclohexyl) methyl) adipic acid ester; Described is 4:3 containing 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate in the resin of difunctionality epoxide group and the mass ratio of two ((3,4-epoxycyclohexyl) methyl) adipic acid ester; The described oligopolymer containing multi-functional epoxy group is the mixture of hydrogenated bisphenol A epoxy resin and [(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether; Described is 1:1 containing the mass ratio of hydrogenated bisphenol A epoxy resin and [(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether in the oligopolymer of multi-functional epoxy group; The described resin containing difunctionality epoxide group is 100:30 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is 3-ethyl-3-oxa-fourth ring methyl alcohol and 3,3'-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide;
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;
Photosensitizers described in step one is 2,4,6-trimethylbenzoy-dipheny phosphine oxide;
Thermal initiator described in step one is that amine closes lewis acid; Described amine closes lewis acid VicbaseTC3630;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, contain the oligomeric resin mixture of epoxide group, 15 parts of thinners and 5 parts of coupling agents by take in step one 80 parts to mix, add the 1.2 parts of light triggers taken in step one, 1.2 parts of photosensitizerss, 0.4 part of thermal initiator more successively, low whipping speed is stirring reaction 20min under 150r/min again, add the 0.4 part of thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 30min under 150r/min again, obtains a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
VicbaseTC3630 described in embodiment 13 buys from Kai Ji Applied Materials Inc of Shenzhen;
VicbaseTC3602H described in embodiment 13 enough buys from Kai Ji Applied Materials Inc of Shenzhen.
Solidification is completed after cation type ultraviolet photo prepared by embodiment 13 and the dual deep cure tackiness agent of heat irradiate 2min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment 13 preparation is 30.5mm.
Embodiment 14: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat is prepared according to the following steps:
One, take 70 parts by weight and contain the oligomeric resin mixture of epoxide group, 20 parts of thinners, 10 parts of coupling agents, 0.7 part of light trigger, 0.7 part of photosensitizers and 0.035 part of thermal initiator;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 60 DEG C from room temperature under the condition of 150r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 150r/min and temperature is again the oligopolymer added under the condition of 60 DEG C containing multi-functional epoxy group; Low whipping speed is 150r/min and temperature is again stirring reaction 8h under the condition of 60 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; The described oligopolymer containing multi-functional epoxy group is the mixture of organosilicon bisphenol A epoxide resin 665 and [(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether; Described is 1:1 containing the mass ratio of organosilicon bisphenol A epoxide resin 665 and [(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether in the oligopolymer of multi-functional epoxy group; The described resin containing difunctionality epoxide group is 100:40 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is 3,3'-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide;
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;
Photosensitizers described in step one is 2,4,6-trimethylbenzoy-dipheny phosphine oxide;
Thermal initiator described in step one is benzoyl peroxide;
Two, contain the oligomeric resin mixture of epoxide group, 20 parts of thinners and 10 parts of coupling agents by take in step one 70 parts to mix, add the 0.7 part of light trigger taken in step one, 0.7 part of photosensitizers, 0.4 part of thermal initiator more successively, low whipping speed is stirring reaction 25min under 150r/min again, add the 0.035 part of thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 30min under 150r/min again, obtains a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
Solidification is completed after cation type ultraviolet photo prepared by embodiment 14 and the dual deep cure tackiness agent of heat irradiate 1.5min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment 14 preparation is 22mm.
Embodiment 15: the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat is prepared according to the following steps:
One, take 60 parts by weight and contain the oligomeric resin mixture of epoxide group, 20 parts of thinners, 10 parts of coupling agents, 0.6 part of light trigger, 0.6 part of photosensitizers, 0.12 part of thermal initiator and 0.06 part of thermo-stabilizer;
Oligomeric resin mixture containing epoxide group in step one is prepared according to the following steps:
Be be heated to 60 DEG C from room temperature under the condition of 150r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 150r/min and temperature is again the oligopolymer added under the condition of 60 DEG C containing multi-functional epoxy group; Low whipping speed is 200r/min and temperature is again stirring reaction 8h under the condition of 60 DEG C, obtains the oligomeric resin mixture containing epoxide group; The described resin containing difunctionality epoxide group is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; The described oligopolymer containing multi-functional epoxy group is the mixture of organosilicon bisphenol A epoxide resin 665 and [(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether; Described is 1:1 containing the mass ratio of organosilicon bisphenol A epoxide resin 665 and [(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether in the oligopolymer of multi-functional epoxy group; The described resin containing difunctionality epoxide group is 100:40 with the mass ratio of the oligopolymer containing multi-functional epoxy group;
Thinner described in step one is 3,3'-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide;
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;
Photosensitizers described in step one is 2,4,6-trimethylbenzoy-dipheny phosphine oxide;
Thermal initiator described in step one is benzoyl peroxide;
Two, contain the oligomeric resin mixture of epoxide group, 20 parts of thinners and 10 parts of coupling agents by take in step one 60 parts to mix, add the 0.6 part of light trigger taken in step one, 0.6 part of photosensitizers, 0.12 part of thermal initiator more successively, low whipping speed is stirring reaction 30min under 150r/min again, add the 0.06 part of thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 25min under 150r/min again, obtains a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
Solidification is completed after cation type ultraviolet photo prepared by embodiment 15 and the dual deep cure tackiness agent of heat irradiate 1.5min under ultraviolet light; The cured thickness of cation type ultraviolet photo and the dual deep cure tackiness agent of heat through measuring embodiment 15 preparation is 27.3mm.

Claims (10)

1. cation type ultraviolet photo and the dual deep cure tackiness agent of heat, is characterized in that a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat are prepared from containing the oligomeric resin mixture of epoxide group, 5 parts ~ 30 parts thinners, 5 parts ~ 15 parts coupling agents, 0.75 part ~ 3 parts light triggers, 0.75 part ~ 3 parts photosensitizerss, 0.075 part ~ 0.5 part thermal initiator and 0 part ~ 0.2 part thermo-stabilizers by 60 parts ~ 100 parts by weight.
2. a kind of cation type ultraviolet photo according to claim 1 and the dual deep cure tackiness agent of heat, is characterized in that the described oligomeric resin mixture containing epoxide group is prepared according to the following steps:
Be be heated to 60 DEG C ~ 80 DEG C from room temperature under the condition of 100r/min ~ 150r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 100r/min ~ 150r/min and temperature is again the oligopolymer added under the condition of 60 DEG C ~ 80 DEG C containing multi-functional epoxy group; Low whipping speed is 150r/min ~ 200r/min and temperature is again stirring reaction 6h ~ 18h under the condition of 60 DEG C ~ 80 DEG C, obtains the oligomeric resin mixture containing epoxide group;
The described resin containing difunctionality epoxide group is 100:(5 ~ 40 with the mass ratio of the oligopolymer containing multi-functional epoxy group).
3. a kind of cation type ultraviolet photo according to claim 2 and the dual deep cure tackiness agent of heat, is characterized in that the described resin containing difunctionality epoxide group is a kind of or wherein several mixture in cycloaliphatic epoxy resin, dibasic acid esters chain cycloaliphatic epoxy resin, aliphatic epoxy resin, bisphenol A epoxide resin and hydrogenated bisphenol A epoxy resin; Described cycloaliphatic epoxy resin is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; Dibasic acid esters chain cycloaliphatic epoxy resin is two ((3,4-epoxycyclohexyl) methyl) adipic acid esters; Aliphatic epoxy resin is ethylene glycol diglycidylether.
4. a kind of cation type ultraviolet photo according to claim 2 and the dual deep cure tackiness agent of heat, it is characterized in that the described oligopolymer containing multi-functional epoxy group is 4,5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester, poly-[(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether, a kind of or wherein several mixture in tetramethylolmethane glycidyl ether.
5. a kind of cation type ultraviolet photo according to claim 1 and the dual deep cure tackiness agent of heat, it is characterized in that described thinner is 3-ethyl-3-oxa-fourth ring methyl alcohol, 3,3 '-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide, 1,2, a kind of or wherein several mixture in 8,9-bis-epoxy-4 vinyl cyclohexene, divinyl bis-epoxy and butylglycidyl ether.
6. a kind of cation type ultraviolet photo according to claim 1 and the dual deep cure tackiness agent of heat, it is characterized in that described coupling agent is a kind of or wherein several mixture in γ-glycidyl ether oxygen propyl trimethoxy silicane, 3,4-epoxycyclohexylethyl Trimethoxy silanes and γ-methacryloxypropyl trimethoxy silane; Described light trigger is triaryl sulfonium salts or diaryl group iodized salt; Described triaryl sulfonium salts is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator.
7. a kind of cation type ultraviolet photo according to claim 1 and the dual deep cure tackiness agent of heat; it is characterized in that described photosensitizers is 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexyl-phenyl ketone, the derivative of 1-hydroxy-cyclohexyl-phenyl ketone, benzophenone, 2; 4; 6-trimethylbenzoy-dipheny phosphine oxide and 2; a kind of or wherein several mixture in the derivative of 4,6-trimethylbenzoy-dipheny phosphine oxide.
8. a kind of cation type ultraviolet photo according to claim 1 and the dual deep cure tackiness agent of heat, is characterized in that described thermal initiator is that superoxide causes solidifying agent or amine closes lewis acid; It is benzoyl peroxide BPO that described superoxide causes solidifying agent; It is VicbaseTC3630, VicbaseTC3632, VicbaseTC3633 or VicbaseTC3634 that described amine closes lewis acid.
9. a kind of cation type ultraviolet photo according to claim 1 and the dual deep cure tackiness agent of heat, is characterized in that described thermo-stabilizer is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H.
10. a preparation method for cation type ultraviolet photo and the dual deep cure tackiness agent of heat, is characterized in that the preparation method of a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat is prepared by the following method:
One, take 60 parts ~ 100 parts by weight and contain the oligomeric resin mixture of epoxide group, 5 parts ~ 30 parts thinners, 5 parts ~ 15 parts coupling agents, 0.75 part ~ 3 parts light triggers, 0.75 part ~ 3 parts photosensitizerss, 0.075 part ~ 0.5 part thermal initiator and 0 part ~ 0.2 part thermo-stabilizers;
The oligomeric resin mixture containing epoxide group described in step one is prepared according to the following steps:
Be be heated to 60 DEG C ~ 80 DEG C from room temperature under the condition of 100r/min ~ 150r/min by the resin low whipping speed containing difunctionality epoxide group; Low whipping speed is 100r/min ~ 150r/min and temperature is again the oligopolymer added under the condition of 60 DEG C ~ 80 DEG C containing multi-functional epoxy group; Low whipping speed is 150r/min ~ 200r/min and temperature is again stirring reaction 6h ~ 18h under the condition of 60 DEG C ~ 80 DEG C, obtains the oligomeric resin mixture containing epoxide group;
The described resin containing difunctionality epoxide group is 100:(5 ~ 40 with the mass ratio of the oligopolymer containing multi-functional epoxy group);
The described resin containing difunctionality epoxide group is a kind of or wherein several mixture in cycloaliphatic epoxy resin, dibasic acid esters chain cycloaliphatic epoxy resin, aliphatic epoxy resin, bisphenol A epoxide resin and hydrogenated bisphenol A epoxy resin; Described cycloaliphatic epoxy resin is 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexyl manthanoate; Dibasic acid esters chain cycloaliphatic epoxy resin is two ((3,4-epoxycyclohexyl) methyl) adipic acid esters; Aliphatic epoxy resin is ethylene glycol diglycidylether;
The described oligopolymer containing multi-functional epoxy group is 4,5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester, poly-[(2-Oxyranyle)-1,2-cyclohexanediol] 2-ethyl-2-(methylol)-1,3-PD ether, a kind of or wherein several mixture in tetramethylolmethane glycidyl ether;
Thinner described in step one is 3-ethyl-3-oxa-fourth ring methyl alcohol, 3,3 '-(oxygen base dimethylene) two (3-ethyl) trimethylene oxide, 1,2, a kind of or wherein several mixture in 8,9-bis-epoxy-4 vinyl cyclohexene, divinyl bis-epoxy and butylglycidyl ether;
Described coupling agent described in step one is a kind of or wherein several mixture in γ-glycidyl ether oxygen propyl trimethoxy silicane, 3,4-epoxycyclohexylethyl Trimethoxy silanes and γ-methacryloxypropyl trimethoxy silane;
Light trigger described in step one is triaryl sulfonium salts or diaryl group iodized salt; Described triaryl sulfonium salts is mixed type triaryl hexafluoro-antimonic acid sulfonium salt cation light initiator;
Photosensitizers described in step one is 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexyl-phenyl ketone, the derivative of 1-hydroxy-cyclohexyl-phenyl ketone, benzophenone, 2,4,6-trimethylbenzoy-dipheny phosphine oxide and 2, a kind of or wherein several mixture in the derivative of 4,6-trimethylbenzoy-dipheny phosphine oxide;
Thermal initiator described in step one is that superoxide causes solidifying agent or amine closes lewis acid; It is benzoyl peroxide BPO that described superoxide causes solidifying agent; It is VicbaseTC3630, VicbaseTC3632, VicbaseTC3633 or VicbaseTC3634 that described amine closes lewis acid;
Thermo-stabilizer described in step one is epoxy resin composite stablizer; Described epoxy resin composite stablizer is VicbaseTC3602H;
Two, 60 parts ~ 100 parts that take in step one are contained the oligomeric resin mixture of epoxide group, 5 parts ~ 30 parts thinners and 5 parts ~ 15 parts coupling agents mix, add 0.75 part ~ 3 parts light triggers taken in step one more successively, 0.75 part ~ 3 parts photosensitizerss, 0.075 part ~ 0.5 part thermal initiator, low whipping speed is stirring reaction 20min ~ 40min under 100r/min ~ 150r/min again, add 0 part ~ 0.2 part thermo-stabilizer taken in step one again, low whipping speed is stirring reaction 20min ~ 30min under 100r/min ~ 150r/min again, obtain a kind of cation type ultraviolet photo and the dual deep cure tackiness agent of heat.
CN201510702233.0A 2015-10-26 2015-10-26 A kind of cation type ultraviolet photo and hot dual deep cure adhesive and preparation method thereof Expired - Fee Related CN105199643B (en)

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