CN110483743A - A kind of modified epoxy acrylic ester resin, preparation method and its preparing the application in conductive adhesive - Google Patents
A kind of modified epoxy acrylic ester resin, preparation method and its preparing the application in conductive adhesive Download PDFInfo
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- CN110483743A CN110483743A CN201910577090.3A CN201910577090A CN110483743A CN 110483743 A CN110483743 A CN 110483743A CN 201910577090 A CN201910577090 A CN 201910577090A CN 110483743 A CN110483743 A CN 110483743A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/145—Compounds containing one epoxy group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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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
- C09J163/10—Epoxy resins modified by unsaturated compounds
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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Abstract
The invention discloses a kind of modified epoxy acrylic ester resin, preparation method and its application in conductive adhesive is being prepared, hydroxyl in Epocryl is changed into the acetal groups of-H containing α, obtains the modified epoxy acrylic ester resin by the present invention.The present invention reduces resin viscosity by consumption hydroxyl；The acetal groups of-the H containing α are generated simultaneously, and α-H is active hydrogen, can be used as hydrogen donor or peroxide and oxygen quencher, effectively inhibition oxygen inhibition, can be improved photocuring activity, is conducive to improve photo-curing rate, promotes photo-crosslinking.When the modified epoxy acrylic ester resin is used to prepare Photocurable composition, Photocurable composition obtained easily solidifies, and surface drying is fast.The present invention also provides use enol ethers to be reacted to obtain the preparation method of the acetal groups of-H containing α with the hydroxyl of Epocryl, and provides the modified epoxy acrylic ester resin and preparing the application in Photocurable composition especially conductive adhesive.
Description
Technical field
The present invention relates to photocuring technical field of polymer materials, more particularly, to a kind of modified epoxy acrylic ester
Resin, preparation method and its preparing the application in conductive adhesive.
Background technique
Photocuring technology is extensive because of the advantages that its curing rate is fast, energy conservation and environmental protection, economic benefit are good, and VOC free s is discharged
Applied to fields such as printing packaging, woodenware, plastics, dental material, adhesives.Ultraviolet-curing paint is generally by four part groups
At i.e. resin or oligomer, reactive diluent, photoinitiator, auxiliary agent.Wherein resin or oligomer are main in formula system
Formula is film forming matter, determines the subjectivity property of material.
Light-cured resin or oligomer mainly include (fragrance) epoxy acrylic resin, polyurethane acrylic resin, polyester
Acrylic resin, four major class of polyoxyalkylene acrylate resin also include macromolecular acrylate.Wherein, propylene oxide acids tree
Rouge is resin the most commonly used in curing field often with having high rigidity, high reactivity and excellent chemically-resistant property
One of.Epoxy Acrylates resin usually passes through epoxy compounds and (methyl) acrylic acid is opened under the action of catalyst
Ring esterification generates an acrylic acid ester bond and hydroxyl, and the presence of hydroxyl can enhance intermolecular force by hydrogen bond, thus
Increase system viscosity, reduces the water resistance of resin, usual Epocryl viscosity reaches 104cps@60℃。
Photocureable coating includes roller coating in actual work progress, and showering sprays, and different forms of construction work want system viscosity
It asks different, 30 DEG C of 4000cps@generally is less than to photocureable coating viscosity requirement, and actual Epoxy Acrylates resin is viscous
Degree is very big, needs to be added a large amount of reactive diluent to reach suitable viscosity.But the addition of Macrodilution agent will lead to coating
The performance of formula declines, so a small amount of solvent is added sometimes to adjust viscosity to reach construction requirement.
In addition, as terminal electronic device is towards small, light, Bao Fangxiang development, thin space between electronic component close draws
The fitting of foot becomes a main flow direction of current adhesive research.Anisotropy electroconductive resin film fine, patch by feat of its bonding
Fit away from it is thin the advantages that, be applied in the assembling of various portable electronic products.However, domestic different side used at present
Property electroconductive resin film still relies primarily on import.Ingredient one of of the Epocryl as conductive adhesive, it is existing
Epocryl viscosity is larger, is unfavorable for preparing conductive adhesive.
Therefore, it is necessary to develop the lower Epocryl of viscosity.
Summary of the invention
The present invention is to overcome the biggish defect of viscosity described in the above-mentioned prior art, provides a kind of modified epoxy acrylic ester
Resin, the modified epoxy acrylic ester resin provided, which is changed into have by hydroxyl in Epocryl, promotes photopolymerization living
It is obtained after the acetal groups of-H containing α of property, viscosity is lower, can effectively facilitate photo-crosslinking.
Another object of the present invention is to provide the preparation method of above-mentioned modified epoxy acrylic ester resin
Another object of the present invention is to provide above-mentioned modified epoxy acrylic ester resin in preparing Photocurable composition
Application.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
Hydroxyl in Epocryl is changed into the acetal radical of-H containing α by a kind of modified epoxy acrylic ester resin
Group, obtains the modified epoxy acrylic ester resin.
Hydroxyl in Epocryl is changed into the acetal groups of-H containing α by the present invention, obtains modified epoxy propylene
Acid ester resin consumes hydroxyl, reduces resin viscosity；The acetal groups of-the H containing α are generated simultaneously, and α-H is active hydrogen, can be used as hydrogen
Donor or peroxide and oxygen quencher, effectively inhibition oxygen inhibition, can be improved photocuring activity, be conducive to improve light
Solidification rate promotes photo-crosslinking.
When the modified epoxy acrylic ester resin is used to prepare Photocurable composition, Photocurable composition obtained is easily solid
Change, surface drying is fast.
In addition, low viscosity epoxy resin facilitates broader formula design and to conductive particle when being applied to conductive adhesive
The dispersion of son, so the modified epoxy acrylic ester resin helps to prepare conductive adhesive.
Preferably, the structure of the acetal groups is
Wherein, R1The straight chained alkyl or branched alkyl for being 1~6 for carbon atom number；
R2The straight chained alkyl or branched alkyl for being 1~5 for H or carbon atom number；
R3For alkyl, R3 and adjacent oxygen and another two carbon atom form five-membered ring or hexatomic ring.
Preferably, the modified epoxy acrylic ester resin containsGroup orGroup；Wherein, R4For H or methyl.
Preferably, hydroxyl in Epocryl is reacted to the acetal groups for being changed into-H containing α with enol ether.
The present invention also protects the preparation method of above-mentioned modified epoxy acrylic ester resin, and the preparation method includes following step
It is rapid:
S1. Epocryl is prepared, the Epocryl contains hydroxyl；
S2. the hydroxyl of the Epocryl of step S1. and enol ether are subjected to nucleophilic addition, obtained described
Modified epoxy acrylic ester resin.
The Epocryl containsGroup.
This field generally uses epoxide to react with acrylic acid progress esterification by ring opening, generates hydroxyl, obtains epoxy third
Alkene acid ester resin.The hydroxyl and enol ether of Epocryl carry out nucleophilic addition, consume hydroxyl, and it is viscous to reduce resin
Degree；The acetal groups for generating-H containing α simultaneously can be improved photocuring activity, is conducive to improve photo-curing rate, light is promoted to hand over
Connection.
Step S1. is specifically as follows: under catalysts conditions open loop is occurred for epoxy compounds and (methyl) acrylic acid
Esterification obtains Epocryl, in T1DEG C when, catalyst, polymerization inhibitor, (first are added into epoxy compounds
Base) acrylic acid, at this temperature react 1h~1.5h, after in T2The reaction was continued at DEG C, until acid value is lower than 3mg KOH/g sample
When, reaction is completed.
In the application, (methyl) acrylic acid refers to acrylic or methacrylic acid.
Preferably, T1DEG C be 80~90 DEG C, T2DEG C be 105~110 DEG C.
Preferably, the catalyst is that one of tertiary amine, pyridine derivate, quaternary ammonium salt or lewis acid are two or more
Combination.
It is highly preferred that the catalyst is triphenylphosphine, antimony triphenyl, 2- picoline, tetra-n-butyl ammonium bromide or second
The two or more combination of one of acyl acetone chromium (III) metal-organic complex.
Preferably, the polymerization inhibitor is hydroquinone, p methoxy phenol, 2,5- dimethyl hydroquinones, Isosorbide-5-Nitrae-naphthalene two
The two or more combination of one of phenol or its corresponding quinone.
Preferably, catalyst amount is 0.1wt%~3wt% of reaction system gross mass.Preferably, polymerization inhibitor dosage is
0.01wt%~1wt% of reaction system gross mass.Preferably, acrylic acid and epoxide molar ratio be 1:1~
1.05。
Preferably, the chemical structure of the enol ether is
Wherein, R5The straight chained alkyl or branched alkyl for being 1~5 for H or carbon atom number；
R6The straight chained alkyl or branched alkyl for being 1~5 for H or carbon atom number；
R7For alkyl,Form five-membered ring or hexatomic ring.
Preferably, the enol ether is methoxy ethylene, vinyl-n-butyl ether, methyl-1-propylene base ether, vinyl isopropyl
The combination of one or more of ether, 2,3 dihydro furan or 3,4- dihydropyran.
Epocryl inventory is calculated according to the hydroxyl value of measurement.
Preferably, the ratio of the hydroxyl moles of the molal quantity and Epocryl of the enol ether be 1~
1.5。
It is highly preferred that the ratio of the hydroxyl moles of the molal quantity and Epocryl of the enol ether be 1~
1.05。
Preferably, the reaction temperature of step S2. be 30~80 DEG C, the reaction time be 3~for 24 hours.
The present invention also protects above-mentioned modified epoxy acrylic ester resin in preparing Photocurable composition or conductive adhesive
Application.
Compared with prior art, the beneficial effects of the present invention are:
Hydroxyl in Epocryl is changed into the acetal groups of-H containing α by the present invention, obtains modified epoxy propylene
Acid ester resin consumes hydroxyl, reduces resin viscosity；The acetal groups of-the H containing α are generated simultaneously, and α-H is active hydrogen, can be used as hydrogen
Donor or peroxide and oxygen quencher, effectively inhibition oxygen inhibition, can be improved photocuring activity, be conducive to improve light
Solidification rate promotes photo-crosslinking.When the modified epoxy acrylic ester resin is used to prepare Photocurable composition, photocuring obtained
Composition easily solidifies, and surface drying is fast.The modified epoxy acrylic ester resin helps to prepare conductive adhesive.
In addition, the present invention specifically uses enol ether to be reacted to obtain-the H's containing α with the hydroxyl of Epocryl
Acetal groups consume hydroxyl, reduce viscosity, promote photo-crosslinking.
Specific embodiment
The present invention is further illustrated With reference to embodiment.
Raw material in embodiment can be by being commercially available；
Unless stated otherwise, the present invention uses reagent, method and apparatus for the art conventional reagent, method and are set
It is standby.
Embodiment 1
A kind of modified epoxy acrylic ester resin, the preparation method is as follows:
S1. gained Epocryl A after epoxy bisphenol-A and acrylic acid esterification by ring opening1, chemical structure is as follows:
Concrete operations: thermometer, agitating paddle are equipped in 500mL four-hole boiling flask.By 200g standard epoxy bisphenol-A, (epoxy is worked as
Measure 192g/ equivalent) it is added in 500mL four-hole boiling flask, 0.27g polymerization inhibitor p methoxy phenol, 0.82g catalyst triphenyl is added
Phosphine, after be added dropwise 74g acrylic acid, increase temperature to 80 DEG C, can obviously observe exothermic heat of reaction, react 1h.After increase temperature
To 110 DEG C, an acid value is surveyed every 1h, until when acid value is lower than 3mg KOH/g sample, reaction terminating reacts 6~8h of duration.
Gained Epocryl A1Viscosity is 30 DEG C of 8500cps@, acid value 1.58mg KOH/g, hydroxyl value 304.12mg KOH/g
Sample.
S2. modified epoxy acrylic ester resin M is prepared1, chemical structure is as follows:
Concrete operations: step S1. reaction gained Epocryl A in 100g embodiment 11, 40g 2,3- is added
Dihydrofuran is stirred in 40 DEG C, until stopping reaction when hydroxyl value is lower than 3mg KOH/g sample, when reaction is about 12h.Gained changes
Property Epocryl M1Parameters: hydroxyl value 1.56mg KOH/g sample, 30 DEG C of viscosity 5340cps@.The result shows that 2,
Hydroxyl reacts after 3- dihydrofuran is esterified with epoxy acrylic, and the viscosity of Epoxy Acrylates resin is effectively reduced.
Embodiment 2
The modified epoxy acrylic ester resin of the present embodiment the preparation method is as follows:
S1. novolac epoxy resin and gained Epocryl A after acrylic acid esterification by ring opening2, chemical structure is as follows:
Concrete operations: thermometer, agitating paddle are equipped in 500mL four-hole boiling flask.By 200g epoxy novolac (epoxide equivalent
175g/ equivalent) it is added in 500mL four-hole boiling flask, 0.28g polymerization inhibitor p methoxy phenol, 0.84g catalyst n, N- diformazan is added
Base benzylamine, after be added dropwise 80g acrylic acid, increase temperature to 80 DEG C, can obviously observe exothermic heat of reaction, react 1h.After increase
Temperature surveys an acid value to 110 DEG C, every 1h, until when acid value is lower than 3mg KOH/g sample, reaction terminating, reaction duration 6~
7h.Gained Epocryl A2Viscosity is 30 DEG C of 18500cps@, acid value 1.58mg KOH/g, hydroxyl value 335mg KOH/g
Sample.
S2. modified epoxy acrylic ester resin M is prepared2, chemical structure is as follows:
Concrete operations: step S1 reaction gained Epocryl A in 100g embodiment 22, 60g vinyl is added
N-butyl ether is stirred in 45 DEG C, until stopping reaction when hydroxyl value is lower than 3mg KOH/g sample, when reaction is about 14h.Gained is modified
Epocryl M2Parameters: hydroxyl value 1.68mgKOH/g sample, 30 DEG C of viscosity 10860cps@.The result shows that ethylene
Hydroxyl reacts after base n-butyl ether is esterified with epoxy acrylic, and the viscosity of Epoxy Acrylates resin is effectively reduced.
Embodiment 3
The modified epoxy acrylic ester resin of the present embodiment the preparation method is as follows:
S1. epoxide and gained Epocryl A after acrylic acid esterification by ring opening3, chemical structure is as follows:
Concrete operations: thermometer, agitating paddle are equipped in 500mL four-hole boiling flask.By 150g 1,2,9,10- diepoxy certain herbaceous plants with big flowers alkane
Be added 500mL four-hole boiling flask in, be added 0.28g polymerization inhibitor p methoxy phenol, 0.86g catalyst triphenylphosphine, after dropwise plus
Enter 127g acrylic acid, increases temperature to 80 DEG C, can obviously observe exothermic heat of reaction, react 1h.Temperature is increased afterwards to 110 DEG C, often
An acid value is surveyed every 1h, until when acid value is lower than 3mgKOH/g sample, reaction terminating reacts 6~7h of duration.Gained propylene oxide
Acid ester resin A3Viscosity is 30 DEG C of 2300cps@, acid value 1.58mg KOH/g, hydroxyl value 380mg KOH/g sample
S2. modified epoxy acrylic ester resin M is prepared3, chemical structure is as follows:
Concrete operations: 3 step S1 of 100g embodiment reaction gained Epocryl A3, 57.21g 2,3- is added
Dihydropyran is stirred in 45 DEG C, until stopping reaction when hydroxyl value is lower than 3mg KOH/g sample, when reaction is about 12h.Gained changes
Property Epocryl M3Parameters: hydroxyl value 1.43mg KOH/g sample, 30 DEG C of viscosity 500cps@.The result shows that 2,
Hydroxyl reacts after 3- dihydropyran is esterified with epoxy acrylic, and epoxy acrylic esterification product viscosity is effectively reduced.
Embodiment 4
The modified epoxy acrylic ester resin of the present embodiment the preparation method is as follows:
S1. epoxidized soybean oil and gained Epocryl A after acrylic acid esterification by ring opening4, chemical structure is as follows:
Concrete operations: thermometer, agitating paddle are equipped in 500mL four-hole boiling flask.500mL tetra- is added in 200g epoxidized soybean oil
In mouthful flask, be added 0.29g polymerization inhibitor p methoxy phenol, 0.88g catalyst triphenylphosphine, after 88g acrylic acid is added dropwise,
Temperature is increased to 80 DEG C, can obviously observe exothermic heat of reaction, reacts 1h.Temperature is increased afterwards to 110 DEG C, surveys a hypo acid every 1h
Value, until when acid value is lower than 3mg KOH/g sample, reaction terminating reacts 6~7h of duration.Gained Epocryl A4
Viscosity is 30 DEG C of 15000cps@, acid value 1.52mg KOH/g, hydroxyl value 267mg KOH/g sample.
S2. modified epoxy acrylic ester resin M is prepared4, chemical structure is as follows:
Concrete operations: 4 step S1 of 100g embodiment reaction gained Epocryl A4, 48g vinyl is being added just
Butyl ether is stirred in 50 DEG C, until stopping reaction when hydroxyl value is lower than 3mg KOH/g sample, when reaction is about 14h.Gained is modified ring
Oxypropylene acid ester resin M4Parameters: hydroxyl value 1.98mg KOH/g sample, 30 DEG C of viscosity 7800cps@.The result shows that vinyl
Hydroxyl reacts after n-butyl ether is esterified with epoxy acrylic, and epoxy acrylic esterification product viscosity is effectively reduced.
Test example 1~8 and reference examples 1~2
Photocurable composition is prepared, as shown in table 1, test example 1~8 is with modified epoxy acrylic acid made from Examples 1 to 4
Ester resin M1~M4As matrix resin, reference examples 1~2 using bisphenol A epoxy acrylate resin B-100 as matrix resin,
Middle reference examples 2 also added auxiliary agent B DMA (N, N- dimethyl benzylamine).
Step: reactive diluent tripropylene glycol double methacrylate TPGDA 50g, reactive diluent polyethylene glycol 200 are taken
Double methacrylate PEGDA-200 50g, modified epoxy acrylic ester resin 150g, photoinitiator isopropyl thioxanthone ITX
2.5g (1wt%), auxiliary agent B DMA 2.5g (1wt%) are stirred evenly, and on bar coated glass plate, control about 25 μm of film thickness.Respectively
With the solidification of different light irradiations, 1000W medium pressure mercury lamp irradiates light intensity 24.9mW/cm2, 375UV LED irradiation light intensity 260mW/cm2,
Irradiation time 10sec.Surface cure situation is detected with fingers-touch method, there is fingerprint impression in coating surface, with × indicate, show exist
Significant surface oxygen inhibition；Coating surface does not occur fingerprint impression, is indicated with ⊙, shows that photocuring surface oxygen inhibition is overcome,
Show that surface layer photo-crosslinking is preferable.Test result is as shown in table 1.
Photoinitiator used by the above test example 1~8 and reference examples 1~2 is isopropyl thioxanthone ITX, the light
Initiator is II type photoinitiator of Type, and the hydrogen donor auxiliary agent such as tertiary amines that need to arrange in pairs or groups use, and just can quickly and effectively generate activity
Free radical causes double-bond polymerization.The modified epoxy acrylic ester resin of Examples 1 to 4 preparation has the acetal containing active α-hydrogen
Group can be used as hydrogen donor, and collocation ITX is used, and without adding additional hydrogen donor auxiliary agent, effectively improve the initiation of light initiation system
Performance, promotion system photo-crosslinking.
According to the result of table 1 it is found that Examples 1 to 4 preparation modified epoxy acrylic ester resin viscosity it is low and have can
The feature of photocuring activity is improved, Photocurable composition obtained easily solidifies, surface drying is fast, can effectively solve surface oxygen inhibition and ask
Topic promotes photo-crosslinking.
Influence of the 1 different subjects resin of table to system surface oxygen inhibition
Test example 9~12
Test example 9~12 is application of the modified epoxy acrylic ester resin of preparation in conductive adhesive.
Formula: graphene package plating copper particle 5wt%, resin 30wt%, photoinitiator TPO 5wt%, polyurethane propylene
Acid esters 2111 50wt%, dispersing aid Lu Borun 24000 4wt%, monomer propylene morpholide 5wt%.Test example 9~12 uses
The modified acrylic ester resin of Examples 1 to 4 preparation, reference examples 3 use bisphenol A epoxy acrylate resin B-100.
Experimental implementation: successively that resin, dispersing aid, graphene package plating copper particle addition dispersing agent dispersion 1~2 is small
When, photoinitiator, urethane acrylate and monomer are added later, stirs 30min.
Conducting resistance test: said mixture film-forming, is tested by CHT3540 D.C. resistance by 50 microns of film thickness
Instrument test；
According to table 2, modified epoxy acrylic ester resin prepared by the present invention facilitates point of graphene package plating copper particle
It dissipates, further, graphene package plating copper particle is in the system of modified epoxy acrylic ester resin prepared by Examples 1 to 2
Long-time stable.
Influence of the 2 different resins system of table when preparing conductive adhesive
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention
Protection scope within.
Claims (10)
1. a kind of modified epoxy acrylic ester resin, which is characterized in that hydroxyl in Epocryl is changed into the-H containing α
Acetal groups, obtain the modified epoxy acrylic ester resin.
2. modified epoxy acrylic ester resin according to claim 1, which is characterized in that the structure of the acetal groups is
Wherein, R1The straight chained alkyl or branched alkyl for being 1~6 for carbon atom number；
R2The straight chained alkyl or branched alkyl for being 1~5 for H or carbon atom number；
R3For alkyl, R3Five-membered ring or hexatomic ring are formed with adjacent oxygen and another two carbon atom.
3. modified epoxy acrylic ester resin according to claim 2, which is characterized in that the modified epoxy acrylic ester
Resin containsGroup orGroup；
Wherein, R4For H or methyl.
4. modified epoxy acrylic ester resin according to claim 1, which is characterized in that will be in Epocryl
Hydroxyl reacts the acetal groups for being changed into-H containing α with enol ether.
5. the preparation method of any one of Claims 1 to 4 modified epoxy acrylic ester resin, which is characterized in that including such as
Lower step:
S1. Epocryl is prepared, the Epocryl contains hydroxyl；
S2. the hydroxyl of the Epocryl of step S1. and enol ether are subjected to nucleophilic addition, obtain the modification
Epocryl.
6. preparation method according to claim 5, which is characterized in that the chemical structure of the enol ether is
Wherein, R5The straight chained alkyl or branched alkyl for being 1~5 for carbon atom number；
R6The straight chained alkyl or branched alkyl for being 1~5 for H or carbon atom number；
R7For alkyl,Form five-membered ring or hexatomic ring.
7. preparation method according to claim 6, which is characterized in that the enol ether is methoxy ethylene, vinyl fourth
One or both of ether, methyl-1-propylene base ether, vinyl isopropyl ether, 2,3 dihydro furan or 3,4- dihydropyran with
On combination.
8. preparation method according to claim 5, which is characterized in that the molal quantity and epoxy acrylate of the enol ether
The ratio of the hydroxyl moles of resin is 1~1.5.
9. preparation method according to claim 5, which is characterized in that the reaction temperature of step S2. is 30~80 DEG C, reaction
Time be 3~for 24 hours.
10. any one of Claims 1 to 4 modified epoxy acrylic ester resin is preparing Photocurable composition or conductive gluing
Application in agent.
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| CN114479009A (en) * | 2021-05-27 | 2022-05-13 | 广东新华粤石化集团股份公司 | Modified epoxy acrylate resin and preparation method thereof |
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| CN114479009A (en) * | 2021-05-27 | 2022-05-13 | 广东新华粤石化集团股份公司 | Modified epoxy acrylate resin and preparation method thereof |
| CN114479009B (en) * | 2021-05-27 | 2023-11-10 | 广东希必达新材料科技有限公司 | Modified epoxy acrylate resin and preparation method thereof |
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