CN106866875A - It is a kind of to can be used for toughness reinforcing microballoon of anisotropic conductive and preparation method thereof - Google Patents
It is a kind of to can be used for toughness reinforcing microballoon of anisotropic conductive and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- 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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
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Abstract
A kind of preparation method that can be used for the toughness reinforcing microballoon of anisotropic conductive includes：Step one：The seed microballoon of uniform particle diameter is prepared with dispersin polymerization, polymerization temperature is 60 100 DEG C, and polymerization time is 1h 24h；Step 2：Dispersion liquid is made into aqueous by dispersant is dispersed；Step 3：Seed microballoon dispersed with stirring is made into dilution in the dispersion liquid that step 2 is made；Step 4：Monofunctional monomer and multi-group crosslink agent, radical initiator are well mixed, reactant is configured to, reactant is dispersed in the dispersion liquid that step 2 is made, the solution ultrasonic agitation of gained is emulsified into 5 60min, obtain swelling emulsion；Step 5：Described swelling emulsion in step 4 is added into the dilute solution that step 3 is made in batches, the seed microballoon absorbs the swelling emulsion and grows up to the microballoon of target grain size；Step 6：The microballoon of the target grain size that step 5 is obtained is polymerized, be centrifuged to clean and obtain the toughness reinforcing microballoon.
Description
Technical field
The present invention provides a kind of toughness reinforcing polymer microsphere and preparation method thereof, and its component is by Monofunctional monomers and multifunctional
Group's crosslinking agent is polymerized the microballoon of copolymerization glass transition temperature, and particle diameter is 2um-100um.
Background technology
Toughener refers to the auxiliary agent that can increase adhesive toughness, and elongation is low after the solidification of some hot setting adhesives, fragility
Greatly, easily crack, and extend rapidly, cause glue-line to ftracture, not endurance, cause strength of glass low.Therefore must try to
The fragility of adhesive is reduced, increases its toughness, improve its peel strength, particularly in anisotropic conductive films, can significantly dropped
Low its stress and raising peel strength, to ensure the stability of electrical property.Toughener of the prior art mainly has toughness reinforcing to divide greatly
Bullet gonosome and toughness reinforcing core shell rubbers, above-mentioned both of which can form island structure in material of main part, to avoid causing stress collection
In, and reach toughening effect.But, there is also defect：(1) use of toughness reinforcing macromolecular elastomer can reduce the system degree of cross linking,
And influence the heat resistance of system etc.；(2) effective toughness reinforcing part --- the lower glass transition temperatures elastomer portion of core shell rubbers
Content it is restricted, and the shell degree of cross linking not enough, easily by solvent swell, cause core toughness reinforcing part be dissolved, cause island
Structure is reduced or disappeared, and causes toughening effect to weaken；(3) most of core shell rubbers particle size ranges are 30-1000nm, easily reunite,
Dispersion is difficult, the dispersiveness in material of main part is influenceed, is unstable product.
After hardening, everywhere, fragility is big, easily cracks, and extends rapidly, causes for elongation at break for adhesive coating
Glue-line ftractures, not endurance.Be badly in need of a kind of material for discharging internal stress and toughness reinforcing, European patent EP 0308664A1 and
EP0353190A2, United States Patent (USP) 5278257, United States Patent (USP) 5073601, United States Patent (USP) 5202390, this five patents
Describe comprising a kind of epoxy adhesive composition, it includes hycar and carrys out toughness reinforcing.Japanese clock deep pool asphalt mixtures modified by epoxy resin
Fat toughness reinforcing core shell rubbers MX series is that the capsule shape functional resin for being referred to as core shell rubbers evenly spreads to the heat such as epoxy resin
In hardening resin, there is product good with property, toughness, heat resistance and electric insulating quality.But because core shell rubbers hold
Easily reunite, therefore Japanese clock deep pool epoxy resin roughening core shell rubbers MX series is that core shell rubbers are dispersed in into epoxy resin in advance to work as
In be formed with the epoxy resin of certain content and the toughener of core shell rubbers.
The content of the invention
The technical problem to be solved in the present invention is：Overcome the defect of toughener in the prior art, there is provided one kind has core
The rubber toughened advantage of shell and the toughness reinforcing microballoon of solvent resistant and particle diameter in the range of 2-100um, and one kind is provided can be used for different side
The preparation method of the toughness reinforcing microballoon of property conducting resinl, toughness reinforcing microballoon can not reduce the system degree of cross linking and heat-resisting compared with toughness reinforcing macromolecular
Performance, there is more preferable solvent resistance and dispersiveness compared with nano core shell rubber.
In order to solve the above-mentioned technical problem, the present invention proposes following technical scheme：A kind of anisotropic conductive of can be used for
The preparation method of toughness reinforcing microballoon, described toughness reinforcing microballoon be by monofunctional monomer, multi-group crosslink agent, radical initiator,
Toughened polymer of the copolymer glass transition temperature of the uniform particle diameter that dispersant is prepared by seed swelling polymerization less than 0 DEG C
Compound microballoon；
The preparation method comprises the following steps：
Step one：The seed microballoon of uniform particle diameter is prepared with dispersin polymerization, polymerization temperature is 60-100 DEG C, and polymerization time is
1h-24h；
Step 2：Dispersion liquid is made into aqueous by dispersant is dispersed；
Step 3：Seed microballoon dispersed with stirring is made into dilution in the dispersion liquid that step 2 is made；
Step 4：Monofunctional monomer and multi-group crosslink agent, radical initiator are well mixed, reaction is configured to
Thing, reactant is dispersed in the dispersion liquid that step 2 is made, and the solution ultrasonic agitation of gained is emulsified into 5-60min, obtains molten
Swollen emulsion；
Step 5：Described swelling emulsion in step 4 is added into the dilute solution that step 3 is made in batches,
The seed microballoon absorbs the swelling emulsion and grows up to the microballoon of target grain size；
Step 6：The microballoon of the target grain size that step 5 is obtained is polymerized, be centrifuged to clean and obtain glass transition temperature
Solvent-proof described toughness reinforcing microballoon of the degree less than 0 DEG C；
Monofunctional monomer is 99 with the amount ratio of multi-group crosslink agent:1~75:25；
The monofunctional monomer is the mixture of one or more in following material：Ethyl acrylate；The positive fourth of acrylic acid
Ester；Isobutyl acrylate；N-propyl；Lauryl acrylate；Acrylic acid-2-ethyl caproite；Lauryl methacrylate；
Ethoxyethoxyethyl acrylate；AAEM；
The multi-group crosslink agent is the mixture of one or more in following material：Ethylene glycol dimethacrylate
Ester；1,3 butanediol dimethylacrylates；1,6 hexanediol diacrylate；Tri (propylene glycol) diacrylate；Three hydroxyl first
Base propane triacrylate.
The further restriction of above-mentioned technical proposal is that the radical initiator is one or more in following material
Mixture：Azodiisobutyronitrile, dibenzoyl peroxide, dilauroyl peroxide.
The further restriction of above-mentioned technical proposal is that the dispersant is by surfactant and macromolecule stabilizer group
Into the surfactant is the mixture of one or more in following material：Lauryl sodium sulfate, detergent alkylate sulphur
Sour sodium or dodecyltriethanolamine sulfate；The macromolecule stabilizer is the mixture of one or more in following material：
Polyvinylpyrrolidone, polyvinyl alcohol or polyethylene glycol.
In order to solve the above-mentioned technical problem, the present invention proposes following technical scheme：A kind of anisotropic conductive of can be used for
The preparation method of toughness reinforcing microballoon, described toughness reinforcing microballoon be by monofunctional monomer, multi-group crosslink agent, radical initiator,
Dispersant emulsifies increasing of the uniform particle diameter copolymer glass transition temperature less than 0 DEG C that suspension polymerisation is prepared by glass-film
Tough polymer microballoon；
The preparation method comprises the following steps：
Step one：Monofunctional monomer and multi-group crosslink agent, radical initiator are well mixed, reaction is configured to
Thing；
Step 2：Dispersion liquid is made into aqueous by dispersant is dispersed；
Step 3：The reactant that step one is made is emulsified into hanging drop by glass-film, step 2 is dispersed in and is made
Dispersion liquid in；
Step 4：Dispersion liquid containing hanging drop be polymerized, and it is resistance to molten less than 0 DEG C to obtain glass transition temperature
The toughness reinforcing microballoon of agent；
Monofunctional monomer is 99 with the amount ratio of multi-group crosslink agent:1~75:25；
The monofunctional monomer is the mixture of one or more in following material：Ethyl acrylate；The positive fourth of acrylic acid
Ester；Isobutyl acrylate；N-propyl；Lauryl acrylate；Acrylic acid-2-ethyl caproite；Lauryl methacrylate；
Ethoxyethoxyethyl acrylate；AAEM；
The multi-group crosslink agent is the mixture of one or more in following material：Ethylene glycol dimethacrylate
Ester；1,3 butanediol dimethylacrylates；1,6 hexanediol diacrylate；Tri (propylene glycol) diacrylate；Three hydroxyl first
Base propane triacrylate.
The further restriction of above-mentioned technical proposal is that the radical initiator is one or more in following material
Mixture：Azodiisobutyronitrile, dibenzoyl peroxide, dilauroyl peroxide.
The further restriction of above-mentioned technical proposal is that the dispersant is by surfactant and macromolecule stabilizer group
Into the surfactant is the mixture of one or more in following material：Lauryl sodium sulfate, detergent alkylate sulphur
Sour sodium or dodecyltriethanolamine sulfate；The macromolecule stabilizer is the mixture of one or more in following material：
Polyvinylpyrrolidone, polyvinyl alcohol or polyethylene glycol.
In order to solve the above-mentioned technical problem, the present invention proposes following technical scheme：A kind of preparation method as mentioned is made
Can be used for the toughness reinforcing microballoon of anisotropic conductive for what is obtained.
Compared with prior art, the present invention has following beneficial effect：(1) relatively large molecular flexibility body toughness reinforcing, the present invention
The system degree of cross linking will not be reduced and system heat resistance etc. is not influenceed；(2) toughness reinforcing of relative core shell rubbers, microballoon of the present invention easily divides
Dissipate, will not reunite；(3) microspherulite diameter of the present invention is controllable, and the degree of cross linking can adjust.
Brief description of the drawings
Fig. 1 is the bulb electromicroscopic photograph that embodiment one is prepared.
Fig. 2 is the toughness reinforcing microballoon electromicroscopic photograph that embodiment one is prepared.
Fig. 3 is the toughness reinforcing microballoon electromicroscopic photograph that embodiment three is prepared.
Fig. 4 is test adhesive peel strength schematic diagram.
Specific embodiment
The present invention proposes a kind of preparation method that can be used for the toughness reinforcing microballoon of anisotropic conductive (referred to as：Seed swelling
Method), described toughness reinforcing microballoon is molten by seed by monofunctional monomer, multi-group crosslink agent, radical initiator, dispersant
The toughening polymer microballoon of the copolymer glass transition temperature less than 0 DEG C of the swollen uniform particle diameter for preparing that is polymerized；The system
Preparation Method comprises the following steps：
Step one：The seed microballoon of uniform particle diameter is prepared with dispersin polymerization, polymerization temperature is 60-100 DEG C, and polymerization time is
1h-24h, adds nitrogen protection；
Step 2：Dispersion liquid is made into aqueous by dispersant is dispersed；
Step 3：Seed microballoon dispersed with stirring is made into dilution in the dispersion liquid that step 2 is made；
Step 4：Monofunctional monomer and multi-group crosslink agent, radical initiator are well mixed, reaction is configured to
Thing, reactant is dispersed in the dispersion liquid that step 2 is made, and the solution ultrasonic agitation of gained is emulsified into 5-60min, obtains molten
Swollen emulsion；
Step 5：Described swelling emulsion in step 4 is added into the dilute solution that step 3 is made in batches,
The seed microballoon absorbs the swelling emulsion and grows up to the microballoon of target grain size；
Step 6：The microballoon of the target grain size that step 5 is obtained is polymerized, be centrifuged to clean and obtain glass transition temperature
Solvent-proof described toughness reinforcing microballoon of the degree less than 0 DEG C.
The present invention also proposes a kind of preparation method that can be used for the toughness reinforcing microballoon of anisotropic conductive (referred to as：Glass-film breast
Change method), described toughness reinforcing microballoon is to pass through glass by monofunctional monomer, multi-group crosslink agent, radical initiator, dispersant
Toughening polymer microballoon of the uniform particle diameter copolymer glass transition temperature less than 0 DEG C that film emulsification suspension polymerisation is prepared；
The preparation method comprises the following steps：
Step one：Monofunctional monomer and multi-group crosslink agent, radical initiator are well mixed, reaction is configured to
Thing；
Step 2：Dispersion liquid is made into aqueous by dispersant is dispersed；
Step 3：The reactant that step one is made is emulsified into hanging drop by glass-film, step 2 is dispersed in and is made
Dispersion liquid in；
Step 4：Dispersion liquid containing hanging drop be polymerized, and it is resistance to molten less than 0 DEG C to obtain glass transition temperature
The toughness reinforcing microballoon of agent.
In above two preparation method, monofunctional monomer is 99 with the amount ratio of multi-group crosslink agent:1~75:25.
In above two preparation method, the monofunctional monomer is the mixture of one or more in following material：Third
Olefin(e) acid ethyl ester (homopolymers Tg, -22 DEG C)；N-butyl acrylate (homopolymers Tg, -56 DEG C)；Isobutyl acrylate (homopolymers Tg ,-
40℃)；N-propyl (homopolymers Tg, -25 DEG C)；Lauryl acrylate (homopolymers Tg, -17 DEG C)；Acrylic acid-2-ethyl
Own ester (homopolymers Tg, -67 DEG C)；Lauryl methacrylate (homopolymers Tg, -65 DEG C)；Ethoxyethoxyethyl acrylic acid
Ester (homopolymers Tg, -54 DEG C)；AAEM (homopolymers Tg, -18 DEG C).
In above two preparation method, the multi-group crosslink agent is the mixing of one or more in following material
Thing：GDMA (homopolymers Tg, 58 DEG C)；1,3 butanediol dimethylacrylates (homopolymers Tg, 85
℃)；1,6 hexanediol diacrylate (homopolymers Tg, 43 DEG C)；Tri (propylene glycol) diacrylate (homopolymers Tg, 62
℃)；Trimethylolpropane trimethacrylate (homopolymers Tg, 62 DEG C).
In above two preparation method, the radical initiator is the mixture of one or more in following material：
Azodiisobutyronitrile, dibenzoyl peroxide, dilauroyl peroxide.
In above two preparation method, the dispersant is made up of surfactant and macromolecule stabilizer, surface-active
Between 3%-8% weight ratio, macromolecule stabilizer consumption is between 0.1%-1% weight ratio for agent consumption.The surface-active
Agent is the mixture of one or more in following material：Lauryl sodium sulfate, neopelex or dodecyl
Sulfuric acid triethanolamine；The macromolecule stabilizer is the mixture of one or more in following material：Polyvinylpyrrolidone,
Polyvinyl alcohol or polyethylene glycol.
Table one：Raw material used in following several embodiments and comparative example
Prepare embodiment 1 (seed swelling method)
By 10g methyl methacrylates, 2.3g polyvinylpyrrolidones, 0.1g azodiisobutyronitriles, 40g methyl alcohol, 60g water
Add in four-hole bottle, under nitrogen protection, stir, the isothermal reaction 2h at 65 DEG C of temperature, centrifugation is cleaned, vacuum drying, system
Polymer bulb is obtained, its particle diameter is about 920nm.
The polymer bulb for taking the above-mentioned 920nm of 3g is distributed to and is gone containing 1g lauryl sodium sulfate, 5g polyvinyl alcohol, 100g
In ionized water, ultrasonic agitation is uniform, is configured to bulb dilution, and bulb dilution is poured into 500ml there-necked flasks at the uniform velocity
Stirring, 150 turns/min of rotating speed.
3.2g benzoyl peroxides are dissolved in into 6.4g GDMAs (to write a Chinese character in simplified form：EGDMA, homopolymers Tg,
58 DEG C), 57.6g AAEMs (write a Chinese character in simplified form：AAEMA, homopolymers Tg, -18 DEG C) mix monomer in.
120g deionized waters, 6g lauryl sodium sulfate, 6g polyethylene glycol, ultrasonic emulsification 15min is added to be emulsified into white in reactant
The swelling emulsion of nanoscale.
The swelling emulsion of white nanometer that will be obtained is added in seed microballoon dilution in batches, is allowed seed microballoon to absorb and is received
The swelling emulsion of rice and uniformly grow up.
After seed microspheres swell 24h, wherein 100ml polymer fluids and 200ml deionized waters, 0.03g MEHQs are taken
Constant temperature carries out polymerization 8h at 95 DEG C in 500ml four-hole boiling flasks, obtains the lower glass transition temperatures solvent resistant of particle diameter 2.5um
Toughness reinforcing microballoon.
Prepare embodiment 2 (seed swelling method)
By 10g methyl methacrylates, 1.8g polyvinylpyrrolidones, 0.2g azodiisobutyronitriles, 60g methyl alcohol, 40g water
Add in four-hole bottle, under nitrogen protection, stir, the isothermal reaction 2h at 65 DEG C of temperature, centrifugation is cleaned, vacuum drying, system
Polymer bulb is obtained, its particle diameter is about 1.5um.
The polymer bulb for taking the above-mentioned 1.5um of 0.4g is distributed to and contains 1g lauryl sodium sulfate, 5g polyvinyl alcohol, 100g
In deionized water, ultrasonic agitation is uniform, is configured to bulb dilution, and bulb dilution is poured into even in 1000ml there-necked flasks
Speed stirring, 150 turns/min of rotating speed.
3.2g benzoyl peroxides are dissolved in into 32g1,3 butanediol dimethylacrylates (to write a Chinese character in simplified form：BDDMA, homopolymers
Tg, 85 DEG C), 96g ethoxyethoxyethyl acrylate (writes a Chinese character in simplified form：EOEOEA, homopolymers Tg, -54 DEG C) mix monomer in.
120g deionized waters, 6g lauryl sodium sulfate, 6g polyethylene glycol, ultrasonic emulsification 15min is added to be emulsified into white in reactant
The swelling emulsion of color nanoscale.
The swelling emulsion of white nanometer that will be obtained is added in seed microballoon dilution in batches, is allowed seed microballoon to absorb and is received
The swelling emulsion of rice and uniformly grow up.
After seed microspheres swell 24h, wherein 100ml polymer fluids and 200ml deionized waters, 0.03g MEHQs are taken
Constant temperature carries out polymerization 8h at 95 DEG C in 500ml four-hole boiling flasks, and the lower glass transition temperatures for obtaining particle diameter 10.2um are resistance to molten
The toughness reinforcing microballoon of agent
Prepare embodiment 3 (glass membrane emulsification)
2.5g benzoyl peroxides are dissolved in into 5g1,6- hexanediyl esters (to write a Chinese character in simplified form：HDDA, homopolymers Tg, 43
DEG C), 45g n-butyl acrylates (write a Chinese character in simplified form：N-BA, homopolymers Tg, -56 DEG C) mix monomer in.
15g lauryl sodium sulfate/5g polyethylene glycol is dispersed in 100g deionized waters.
Mix monomer is emulsified into there is a deionized water of dispersant with SPG membrane emulsifiers, suspension emulsion is obtained, wherein having
Particle diameter is about the suspension monomer droplet of 32um
Wherein suspension emulsion 100ml and 200ml deionized waters, 0.03g MEHQs are taken in 500ml four-hole boiling flasks
Constant temperature carries out polymerization 8h at 95 DEG C, obtains the solvent-proof toughness reinforcing microballoon of lower glass transition temperatures of particle diameter 30um.
Comparative example 1 (seed swelling method)
The polymer bulb for taking 920nm in 2g above-described embodiments 1 is distributed to and contains 1g lauryl sodium sulfate, 5g polyethylene
In alcohol, 100g deionized waters, ultrasonic agitation is uniform, is configured to bulb dilution, and bulb dilution is poured into tri- mouthfuls of burnings of 500ml
At the uniform velocity stirred in bottle, 150 turns/min of rotating speed.
3.2g benzoyl peroxides are dissolved in into 64g GDMAs (to write a Chinese character in simplified form：EGDMA, homopolymers Tg,
58 DEG C) in crosslinking agent.120g deionized waters, 6g lauryl sodium sulfate, 6g polyethylene glycol, ultrasonic emulsification are added in reactant
15min, is emulsified into the swelling emulsion of white nanoscale.
The swelling emulsion of white nanometer that will be obtained is added in seed microballoon dilution in batches, is allowed seed microballoon to absorb and is received
The swelling emulsion of rice and uniformly grow up.
After seed microspheres swell 24h, wherein 100ml polymer fluids and 200ml deionized waters, 0.03g MEHQs are taken
Constant temperature carries out polymerization 8h at 95 DEG C in 500ml four-hole boiling flasks, obtains the high glass-transition temperature crosslinking high of particle diameter 2.5um
The polymer microballoon of degree
Comparative example 2 (seed swelling method)
The polymer bulb for taking 1.5um in 0.4g above-described embodiments 2 is distributed to and contains 1g lauryl sodium sulfate, the poly- second of 5g
In enol, 100g deionized waters, ultrasonic agitation is uniform, is configured to bulb dilution, and bulb dilution is poured into 1000ml tri-
At the uniform velocity stirred in mouth flask, 150 turns/min of rotating speed.
3.2g benzoyl peroxides are dissolved in into the butanediol dimethylacrylates of 64g 1,3 (to write a Chinese character in simplified form：BDDMA, homopolymers
Tg, 85 DEG C), 96g styrene (writes a Chinese character in simplified form：ST, homopolymers Tg, 105 DEG C) mix monomer in.In reactant add 120g go from
Sub- water, 6g lauryl sodium sulfate, 6g polyethylene glycol, ultrasonic emulsification 15min are emulsified into the swelling emulsion of white nanoscale.
The swelling emulsion of white nanometer that will be obtained is added in seed microballoon dilution in batches, is allowed seed microballoon to absorb and is received
The swelling emulsion of rice and uniformly grow up.
After seed microspheres swell 24h, wherein 100ml polymer fluids and 200ml deionized waters, 0.03g MEHQs are taken
Constant temperature carries out polymerization 8h at 95 DEG C in 500ml four-hole boiling flasks, obtains the high glass-transition temperature friendship high of particle diameter 10.2um
The polymer microballoon of connection degree
Comparative example 3 (dispersion copolymerization method)
20g n-butyl acrylates (are write a Chinese character in simplified form：N-BA, homopolymers Tg, -56 DEG C), 1.0g polyvinylpyrrolidones, 0.8g idols
Nitrogen bis-isobutyronitrile, 70g methyl alcohol, 30g water are added in four-hole bottle, under nitrogen protection, are stirred, the isothermal reaction at 65 DEG C of temperature
2h, centrifugation is cleaned, vacuum drying, and polymer bulb is obtained, and its particle diameter is about 3.0um.
Synthesis result such as following table two
Table two
Embodiment 1 and embodiment 2 are prepared with seed swelling method, but its key is that Monofunctional monomers and polyfunctional group are handed over
The composition for joining agent is different with consumption, and the microballoon of preparation is also differed.
DSC is determined
Temperature range of the microballoon prepared for embodiment 1, embodiment 2, comparative example 1, comparative example 2 at -70-200 DEG C
(with the heating rate of 10 DEG C/min) carries out the measure of microballoon glass transition temperature.Differential scanning calorimetry (DSC) is used during measure
(DSC：The DSC8000 of PerkinElmer companies manufacture).Following table three shows glass transition temperature measurement result.
Table three
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Tg(℃) | -10 | -25 | -45 | 58 | 98 | -56 |
As shown in Table 1, embodiment 1, embodiment 2, glass transition temperature measured by the microballoon of comparative example 3 are below often
Temperature；Comparative example 1, glass transition temperature measured by the microballoon of comparative example 2 are far above normal temperature.
Solvent resistance is determined.
Taken for the microballoon that embodiment 1-2, comparative example 1-3 are prepared respectively take two parts of 1g microballoons be dispersed in 10ml acetone and
In 10ml toluene, the change of size of basis of microscopic observation microballoon after heated sealed to 50 DEG C/2h.Following table four shows that microspherulite diameter becomes
Change result
Table four
As shown in Table 2, embodiment 1, embodiment 2, comparative example 1, the microspherulite diameter of comparative example 2 do not change, comparative example
3 microballoon is dissolved in a solvent, in clear transparent solutions.Therefore embodiment 1, embodiment 2, comparative example 1, the microballoon of comparative example 2
Solvent resistance is excellent, and the degree of cross linking of comparative example 3 is too low, not solvent resistant, is dissolved in acetone and toluene, therefore is not suitable for doing microballoon increasing
Tough dose.
Using the preparation method that can be used for the toughness reinforcing microballoon of anisotropic conductive obtained in the inventive method, can be prepared into
To thermoset epoxy adhesive.
Above-mentioned thermosetting epoxy resin adhesive is main by the mass parts of phenoxy resin 40, the mass parts of epoxy resin 33, nanometer
The mass parts of aerosil 5, the mass parts of polyurethane 5, the mass parts of cation system curing agent 5, the matter of part silane coupler 2
Amount part, 30 μm of mass parts of conductive gold spacer 10 of monodispersity are uniformly prepared by mixing into thermosetting epoxy resin adhesive.
Being described below with can be used for the toughness reinforcing microballoon of anisotropic conductive obtained in the inventive method as raw material, being prepared into
To several embodiments of thermoset epoxy adhesive, and comparative example.
Embodiment 4
The mass parts of microballoon 6 of the appropriate degree of cross linking lower glass transition temperatures that will be obtained in embodiment 1 add thermosetting ring
The mass parts of oxygen resin adhesive 94 obtain toughness reinforcing adhesive, and adhesive uniform coating 35um is standby.
Embodiment 5
The mass parts of microballoon 6 of the appropriate degree of cross linking lower glass transition temperatures that will be obtained in embodiment 2 add thermosetting ring
The mass parts of oxygen resin adhesive 94 obtain toughness reinforcing adhesive, and adhesive uniform coating 35um is standby.
Embodiment 6
The mass parts of microballoon 6 of the appropriate degree of cross linking lower glass transition temperatures that will be obtained in embodiment 2 add thermosetting ring
The mass parts of oxygen resin adhesive 94 obtain toughness reinforcing adhesive, and adhesive uniform coating 35um is standby.
Comparative example 4
The mass parts of microballoon 6 of the high-crosslinking-degree high glass-transition temperature that will be obtained in comparative example 1 add thermoset epoxy
The mass parts of resin adhesive 96 obtain toughness reinforcing adhesive, and adhesive uniform coating 35um is standby.
Comparative example 5
The mass parts of microballoon 6 of the high-crosslinking-degree high glass-transition temperature that will be obtained in comparative example 2 add thermoset epoxy
The mass parts of resin adhesive 96 obtain toughness reinforcing adhesive, and adhesive uniform coating 35um is standby.
The measure of adhesive strength：
To assess the adhesive strength of each anisotropic-electroconductive adhesive film prepared in embodiment and comparative example, make
With 500 μm of ito glass substrates and corresponding FPC flexible PCBs of spacing, first by adhesive film in 70 DEG C/1MPa precompressed
On FPC, then it is heating and curing under 170 DEG C/15s/3MPa again.With universal tensile test machine special fixture with
The bonding peel strength of FPC flexible PCBs and glass is determined under the extension test speed of 50mm/min, embodiment 4, reality is determined
Apply the average data such as following table five of example 5, embodiment 6, comparative example 4, comparative example 5：
Table five
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 4 | Comparative example 5 | |
| Adhesive strength (mN/cm) | 636 | 604 | 667 | 457 | 423 |
As shown in Table 3, the film-like adhesive obtained by the embodiment 6 of 4/ embodiment of embodiment 5/, 170 DEG C of heating-up temperature,
Under the Sticking condition of 15 seconds time, good bonding intensity is all shown, there is good toughening effect.In contrast, do not use
In the comparative example 5 of comparative example 4/ of lower glass transition temperatures microballoon of the invention, poor adhesive strength is all shown.The present invention
Microballoon be easily dispersed, do not reunite；Secondly microballoon solvent-resisting of the invention can be excellent, can be kept in acetone and toluene not by
It is swelling, the peel strength of adhesive secondly can be effectively improved, the degree of cross linking and heat resistance are not reduced.
Claims (7)
1. a kind of preparation method that can be used for the toughness reinforcing microballoon of anisotropic conductive, it is characterised in that described toughness reinforcing microballoon is
The particle diameter prepared by seed swelling polymerization by monofunctional monomer, multi-group crosslink agent, radical initiator, dispersant
Toughening polymer microballoon of the homogeneous copolymer glass transition temperature less than 0 DEG C；
The preparation method comprises the following steps：
Step one：The seed microballoon of uniform particle diameter is prepared with dispersin polymerization, polymerization temperature is 60-100 DEG C, and polymerization time is 1h-
24h；
Step 2：Dispersion liquid is made into aqueous by dispersant is dispersed；
Step 3：Seed microballoon dispersed with stirring is made into dilution in the dispersion liquid that step 2 is made；
Step 4：Monofunctional monomer and multi-group crosslink agent, radical initiator are well mixed, reactant is configured to, will
Reactant is dispersed in the dispersion liquid that step 2 is made, and the solution ultrasonic agitation of gained is emulsified into 5-60min, obtains swelling emulsification
Liquid；
Step 5：Described swelling emulsion in step 4 is added into the dilute solution that step 3 is made in batches, it is described
Seed microballoon absorbs the swelling emulsion and grows up to the microballoon of target grain size；
Step 6：The microballoon of the target grain size that step 5 is obtained is polymerized, be centrifuged and clean that to obtain glass transition temperature low
In 0 DEG C of solvent-proof described toughness reinforcing microballoon；
Monofunctional monomer is 99 with the amount ratio of multi-group crosslink agent:1~75:25；
The monofunctional monomer is the mixture of one or more in following material：Ethyl acrylate；N-butyl acrylate；Third
Olefin(e) acid isobutyl ester；N-propyl；Lauryl acrylate；Acrylic acid-2-ethyl caproite；Lauryl methacrylate；Ethoxy
Base oxethyl ethyl propylene acid esters；AAEM；
The multi-group crosslink agent is the mixture of one or more in following material：GDMA；
1,3 butanediol dimethylacrylates；1,6 hexanediol diacrylate；Tri (propylene glycol) diacrylate；Trihydroxy methyl
Propane triacrylate.
2. a kind of preparation method that can be used for the toughness reinforcing microballoon of anisotropic conductive according to claim 1, its feature exists
In the radical initiator is the mixture of one or more in following material：Azodiisobutyronitrile, diphenyl peroxide first
Acyl, dilauroyl peroxide.
3. a kind of preparation method that can be used for the toughness reinforcing microballoon of anisotropic conductive according to claim 1, its feature exists
In the dispersant is made up of surfactant and macromolecule stabilizer, and the surfactant is the one kind in following material
Or various mixtures：Lauryl sodium sulfate, neopelex or dodecyltriethanolamine sulfate；The high score
Sub- stabilizer is the mixture of one or more in following material：Polyvinylpyrrolidone, polyvinyl alcohol or polyethylene glycol.
4. a kind of preparation method that can be used for the toughness reinforcing microballoon of anisotropic conductive, it is characterised in that described toughness reinforcing microballoon is
Suspension polymerisation is emulsified by glass-film and is prepared by monofunctional monomer, multi-group crosslink agent, radical initiator, dispersant
Uniform particle diameter copolymer glass transition temperature less than 0 DEG C of toughening polymer microballoon；
The preparation method comprises the following steps：
Step one：Monofunctional monomer and multi-group crosslink agent, radical initiator are well mixed, reactant is configured to；
Step 2：Dispersion liquid is made into aqueous by dispersant is dispersed；
Step 3：The reactant that step one is made is emulsified into hanging drop by glass-film, be dispersed in that step 2 is made point
In dispersion liquid；
Step 4：Dispersion liquid containing hanging drop be polymerized, and it is solvent-proof less than 0 DEG C to obtain glass transition temperature
The toughness reinforcing microballoon；
Monofunctional monomer is 99 with the amount ratio of multi-group crosslink agent:1~75:25；
The monofunctional monomer is the mixture of one or more in following material：Ethyl acrylate；N-butyl acrylate；Third
Olefin(e) acid isobutyl ester；N-propyl；Lauryl acrylate；Acrylic acid-2-ethyl caproite；Lauryl methacrylate；Ethoxy
Base oxethyl ethyl propylene acid esters；AAEM；
The multi-group crosslink agent is the mixture of one or more in following material：GDMA；
1,3 butanediol dimethylacrylates；1,6 hexanediol diacrylate；Tri (propylene glycol) diacrylate；Trihydroxy methyl
Propane triacrylate.
5. a kind of preparation method that can be used for the toughness reinforcing microballoon of anisotropic conductive according to claim 1, its feature exists
In the radical initiator is the mixture of one or more in following material：Azodiisobutyronitrile, diphenyl peroxide first
Acyl, dilauroyl peroxide.
6. a kind of preparation method that can be used for the toughness reinforcing microballoon of anisotropic conductive according to claim 1, its feature exists
In the dispersant is made up of surfactant and macromolecule stabilizer, and the surfactant is the one kind in following material
Or various mixtures：Lauryl sodium sulfate, neopelex or dodecyltriethanolamine sulfate；The high score
Sub- stabilizer is the mixture of one or more in following material：Polyvinylpyrrolidone, polyvinyl alcohol or polyethylene glycol.
7. a kind of preparation method as described in claim any one of 1-6 is preparation-obtained can be used for the increasing of anisotropic conductive
Tough microballoon.
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| PCT/CN2017/076031 WO2018157414A1 (en) | 2017-03-01 | 2017-03-09 | Toughening macromolecular microspheres for adhesives and preparation method therefor |
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| CN112391021A (en) * | 2020-11-05 | 2021-02-23 | 浙江精通科技股份有限公司 | Preparation method of modified soft polyacrylic resin microspheres |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245120A (en) * | 2008-03-17 | 2008-08-20 | 烟台大学 | Process for producing cross-linked polymer microsphere with even grain diameter |
| CN104347192A (en) * | 2014-10-17 | 2015-02-11 | 深圳市飞世尔实业有限公司 | Method for preparing electronic conductive micro-sphere for producing anisotropic conductive film by simply absorbing metal palladium ions |
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| CN1927899A (en) * | 2006-09-01 | 2007-03-14 | 烟台硕德新材料有限公司 | Preparation method of micron-sized monodisperse copolymerized microspheres |
| CN101250245B (en) * | 2008-04-03 | 2011-06-29 | 金小刚 | Polymer phase-change microsphere and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245120A (en) * | 2008-03-17 | 2008-08-20 | 烟台大学 | Process for producing cross-linked polymer microsphere with even grain diameter |
| CN104347192A (en) * | 2014-10-17 | 2015-02-11 | 深圳市飞世尔实业有限公司 | Method for preparing electronic conductive micro-sphere for producing anisotropic conductive film by simply absorbing metal palladium ions |
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| CN112391021A (en) * | 2020-11-05 | 2021-02-23 | 浙江精通科技股份有限公司 | Preparation method of modified soft polyacrylic resin microspheres |
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