CN111253883B - Ultrafast photon curing conductive adhesive and preparation method thereof - Google Patents
Ultrafast photon curing conductive adhesive and preparation method thereof Download PDFInfo
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- CN111253883B CN111253883B CN202010123372.9A CN202010123372A CN111253883B CN 111253883 B CN111253883 B CN 111253883B CN 202010123372 A CN202010123372 A CN 202010123372A CN 111253883 B CN111253883 B CN 111253883B
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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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- 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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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- 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
- C08K2201/001—Conductive additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention belongs to the field of micro-nano electronic packaging and semiconductor materials, and particularly discloses an ultrafast photon curing conductive adhesive and a preparation method thereof, wherein the preparation raw materials at least comprise the following components in parts by weight: 10-20 parts of vinyl ester resin, 2-10 parts of diluent, 0-0.5 part of coupling agent, 0-2 parts of photoinitiator, 0-2 parts of thermal initiator, 0-0.5 part of thixotropic agent, 0-2 parts of impact resistance agent and 70-90 parts of silver powder. The invention introduces functional double bond group into polymer chain of conductive gum base resin, and achieves ultra-fast curing by photon energy, wherein the radiation energy is 1-3J cm‑2The radiation time is 90-200ms, and the volume resistance of the conductive adhesive is low and is 6-20 mu omega cm, and the bonding strength is high and is 6-8 MPa.
Description
Technical Field
The invention relates to the field of micro-nano electronic packaging and semiconductor materials, in particular to an ultra-fast photon curing conductive adhesive and a preparation method thereof.
Background
The conductive adhesive is a material for micro-nano electronic packaging and semiconductor component interconnection, and is mainly prepared from conductive filler, matrix resin, diluent, solvent and additive. The curing of the conductive adhesive includes thermal curing and photo-curing. At present, most of conductive adhesives are of a heat curing type and an ultraviolet curing type, the curing temperature of the heat curing type conductive adhesive is 120-150 ℃, the curing time is 30-60min, and the curing time of the ultraviolet curing type conductive adhesive is from several minutes to dozens of minutes. In addition, the room temperature curing conductive adhesive has longer curing time, which generally needs more than 2 hours to reach the required electrical and mechanical properties. Obviously, high temperature curing, long time curing of conductive pastes has not been satisfactory for the increasingly developed micro-nano electronic packaging and semiconductor device interconnection, especially in the field of printed electronics based on flexible substrates, which require low temperature curing environments, ultra-fast curing and very short operating times. Therefore, the need for further improvement and enhancement of the curing conditions of the conductive paste has become a focus of researchers in the field.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides an ultrafast photon curing conductive adhesive, which comprises, by weight, at least 10-20 parts of vinyl ester resin, 2-10 parts of diluent, 0-0.5 part of coupling agent, 0-2 parts of photoinitiator, 0-2 parts of thermal initiator, 0-0.5 part of thixotropic agent, 0-2 parts of impact resistance agent and 70-90 parts of silver powder.
As a preferred embodiment of the present invention, the vinyl ester resin is selected from one or more of bisphenol a epoxy vinyl ester resin, novolac epoxy vinyl ester resin, flexible vinyl ester resin, urethane-modified epoxy vinyl ester resin, and acrylic vinyl ester resin.
In a preferred embodiment of the present invention, the diluent is selected from one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, styrene, bisphenol a acrylate, ethoxylated bisphenol a diacrylate, and bisphenol a dimethacrylate.
As a preferred technical scheme of the invention, the coupling agent is selected from one or more of vinyl silane, amino silane and epoxy silane.
In a preferred embodiment of the present invention, the photoinitiator is one or more selected from diaryliodonium salts, triaryliodonium salts, alkyl iodonium salts, and cumeneferrocene hexafluorophosphate.
As a preferable technical scheme of the invention, the thermal initiator is selected from one or more of peroxyketal, blocked hexafluoroantimonate and blocked Lewis acid salt.
As a preferred technical scheme of the invention, the thixotropic agent is selected from one or more of silicon dioxide, organic bentonite, polyamide wax and hydrogenated castor oil.
As a preferable technical scheme of the invention, the impact resistance agent is selected from one or more of poly (4-vinylphenol-co-methyl methacrylate), poly (dimethylsiloxane-co-diphenylsiloxane), polydimethylsiloxane diglycidyl ether, 1, 3-propylene glycol bis (4-aminobenzoate) and vinyl ether.
As a preferable technical scheme of the invention, the silver powder has the particle size of 1-20 μm and the thickness of 0.1-0.5 μm.
The second aspect of the invention provides a preparation method of an ultrafast photon-cured conductive adhesive, which comprises the following steps:
(1) preparing conductive adhesive: fully stirring and dispersing vinyl ester resin, a diluent, a coupling agent, a photoinitiator, a thermal initiator, a thixotropic agent, an impact resistance agent and silver powder, and then grinding and defoaming to obtain the conductive adhesive;
(2) curing the conductive adhesive: and (3) curing the conductive adhesive prepared in the step (1) by adopting a photon sintering system.
Has the advantages that: the invention provides an ultrafast photon curing conductive adhesive and a preparation method thereof, wherein functional double bond groups are introduced into polymer chains of conductive adhesive matrix resin, and ultrafast curing is realized by photon energy.
Drawings
To more clearly express the data results in the embodiments of the present invention, the drawings are described.
FIG. 1 is a DSC curve of examples 1-3, wherein 1 is the conductive paste prepared in example 1 and the radiation energy is 1.2J. cm-2The radiation time is 200 ms; 2 is the conductive paste prepared in example 2, which has a radiation energy of 2.4J. cm-2The radiation time is 140 ms; 3 is the conductive paste prepared in example 3, which has a radiation energy of 2.9 J.cm-2The irradiation time was 90 ms.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
In order to solve the above technical problems, a first aspect of the present invention provides an ultrafast photon-cured conductive adhesive, which comprises the following raw materials, by weight: 10-20 parts of vinyl ester resin, 2-10 parts of diluent, 0-0.5 part of coupling agent, 0-2 parts of photoinitiator, 0-2 parts of thermal initiator, 0-0.5 part of thixotropic agent, 0-2 parts of impact resistance agent and 70-90 parts of silver powder.
Vinyl ester resins
The vinyl resin is an unsaturated resin which is dissolved in styrene liquid and contains unsaturated double bonds and has a special structure.
In a preferred embodiment, the vinyl ester resin of the present invention is selected from one or more of bisphenol a epoxy vinyl ester resin, novolac epoxy vinyl ester resin, flexible vinyl ester resin, urethane-modified epoxy vinyl ester resin, and acrylic vinyl ester resin.
In a preferred embodiment, the novolac epoxy vinyl ester resin of the present invention is commercially available from a commercial source including, but not limited to, Ripoxy under the designation 630.
In a preferred embodiment, the urethane-modified epoxy vinyl ester resin of the present invention is commercially available from a commercial vendor including, but not limited to, Atlac, under the designation 580.
In a preferred embodiment, the flexible vinyl resin of the present invention is commercially available from a commercial vendor including, but not limited to, Derakane under the designation 8084.
In a preferred embodiment, the bisphenol A epoxy vinyl ester resin of the present invention is commercially available from a commercial source including, but not limited to, Ripoxy under the designation 806.
Diluent
The diluents of the present invention are also referred to as "fillers". Diluting inert substance can be added when the raw materials are processed into powder or in order to facilitate spraying.
In a preferred embodiment, the diluent of the present invention is selected from one or more of hydroxyethyl methacrylate (CAS: 868-77-9), hydroxypropyl methacrylate (CAS: 27813-02-1), 1, 6-hexanediol diacrylate (CAS: 13048-33-4), trimethylolpropane triacrylate (CAS: 15625-89-5), styrene (CAS: 100-42-5), bisphenol A acrylate, ethoxylated bisphenol A diacrylate (CAS: 64401-02-1), bisphenol A dimethacrylate (CAS: 3253-39-2).
Coupling agent
The coupling agent is a substance with two functional groups with different properties, and the molecular structure of the coupling agent is mainly characterized in that molecules contain two groups with different chemical properties, one group is an inorganophilic group and is easy to react with the surface of an inorganic substance; the other is an organophilic group which is capable of chemically reacting with or forming hydrogen bonds soluble in synthetic resins or other polymers. Therefore, the coupling agent is called as a molecular bridge and is used for improving the interface action between inorganic matters and organic matters, so that the properties of the composite material, such as physical properties, electrical properties, thermal properties, optical properties and the like, are greatly improved.
In a preferred embodiment, the coupling agent of the present invention is selected from one or more of vinyl silane, amino silane, and epoxy silane.
As examples of vinylsilanes, mention may be made of: vinyltrichlorosilane, vinyltriethoxysilane, vinylsilane A-171, vinyltris (2-methoxysilane), vinyltriacetoxysilane, vinyltri-tert-butylperoxysilane, vinyltri-tert-butoxysilane, vinylmethyldichlorosilane.
In a most preferred embodiment, the vinyl silane of the present invention is vinyl silane A-171 (CAS: 2768-2-7).
As examples of aminosilanes, there may be cited: phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, aminoethylaminoethylaminopropyltrimethoxysilane, polyaminoalkyltrialkoxysilane, aminosilane KH-550, gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltriethoxysilane.
In a most preferred embodiment, the aminosilane according to the invention is the aminosilane KH-550, (CAS: 919-30-2).
As examples of the epoxysilane, there may be enumerated: gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltriethoxysilane, gamma- (beta-aminoethyl) aminopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, anilinomethyltrimethoxysilane and epoxysilane KH-560.
In a most preferred embodiment, the epoxysilane of the present invention is epoxysilane KH-560 (CAS: 2530-83-8).
Photoinitiator
The photoinitiator (also called photosensitizer) or photocuring agent (photocuring agent) is a compound which can absorb energy with a certain wavelength in an ultraviolet region (250-420 nm) or a visible light region (400-800 nm) to generate free radicals, cations and the like so as to initiate polymerization, crosslinking and curing of monomers.
In a preferred embodiment, the photoinitiator according to the invention is selected from: one or more of diaryl iodonium salt, triaryl iodonium salt, alkyl iodonium salt and cumeneferrocene hexafluorophosphate.
In a most preferred embodiment, the photoinitiator of the present invention is a triaryliodonium salt, commercially available from a manufacturer including, but not limited to, Bluesil PI, designation 2074.
Thermal initiators
The thermal initiator according to the present invention means a substance which is polymerized by activating a monomer with pure heat.
In a preferred embodiment, the thermal initiator is selected from one or more of peroxyketal, blocked hexafluoroantimonate and blocked lewis acid salt.
Thixotropic agent
The thixotropic agent of the present invention is a highly effective mineral rheological aid which can be used with cellulose ethers to improve workability and sag resistance in polymer mortar products. Compared with bentonite lubricant, the bentonite lubricant has better stability and higher rheological effect due to different structures, different sizes of platelets and different main components.
In a preferred embodiment, the thixotropic agent of the present invention is selected from one or more of silica, organobentonite, polyamide wax, hydrogenated castor oil.
Impact resistant agent
In a preferred embodiment, the impact modifier of the invention is selected from one or more of poly (4-vinylphenol-co-methylmethacrylate), poly (dimethylsiloxane-co-diphenylsiloxane), poly (dimethylsiloxane) diglycidyl ether, 1, 3-propanediol bis (4-aminobenzoate), vinyl ether, poly (dimethylsiloxane-co-diphenylsiloxane) terminal divinyl.
Silver powder
The silver powder is an important material in the electrical and electronic industries, and is a noble metal powder which is widely applied in the electronic industry.
In a preferred embodiment, the silver powder of the present invention has a particle size of 1 to 20 μm and a thickness of 0.1 to 0.5. mu.m.
The second aspect of the invention provides a preparation method of an ultrafast photon-cured conductive adhesive, which comprises the following steps:
(1) preparing the conductive adhesive: fully stirring and dispersing vinyl ester resin, a diluent, a coupling agent, a photoinitiator, a thermal initiator, a thixotropic agent, an impact resistance agent and silver powder, and then grinding and defoaming to obtain the conductive adhesive;
(2) curing the conductive adhesive: and (3) curing the conductive adhesive prepared in the step (1) by adopting a photon sintering system.
The inventor of the application finds that by introducing a functional double bond group into a polymer chain of the conductive adhesive body resin, under the condition of existence of a polyfunctional reactive diluent and silver powder, the conductive adhesive is helped to realize an ultra-fast curing effect by virtue of photon energy, and the conductive adhesive with low resistivity and high bonding strength can be obtained. The possible reason is that under the action of photon radiation, functional double bond groups can not only generate copolymerization crosslinking reaction with macromolecular resin containing unsaturated bonds, but also generate self-polymerization reaction among the unsaturated bonds of the functional double bond groups to cause crosslinking curing, thereby effectively accelerating the curing reaction speed, improving the reaction crosslinking density, and effectively promoting the increase of the reaction crosslinking density and further accelerating the curing speed of the conductive adhesive due to the existence of the optically active functional groups in the polyfunctional group reactive diluent.
Experiments show that the synergistic effect between the resin with the functional double bond group and the polyfunctional reactive diluent is beneficial to improving the toughness of the resin, and simultaneously has a protective effect on the silver powder, so that the silver powder is prevented from greatly migrating, and the dispersibility of the silver powder in the resin is effectively improved. The reason for this is probably that the long-chain structure contained in the system has a reinforcing effect on the resin, and secondly, the reaction system has a large amount of ether bonds, hydroxyl groups, epoxy groups and the like, and the ether bonds, the hydroxyl groups, the epoxy groups and the like are associated with polar groups on the surface of the silver powder, so that the surface tension of the silver powder can be effectively reduced, and the wettability of metal in the system can be improved. And when the particle size of the silver powder is 1-20 μm and the thickness is 0.1-0.5 μm, the effect is better. In addition, experimental tests show that the invention can be applied to different types of resin systems, and by applying the preparation method and the composition of the formula, the radiation energy is 1-3J-cm-2When the radiation time is 90-200ms, the conductive adhesive can be cured, the volume resistance is low and is 6-20 mu omega cm, and the bonding strength is high and is 6-8 MPa.
Examples
Example 1
Embodiment 1 provides an ultrafast photon curing conductive adhesive, which is prepared from 15 parts by weight of vinyl ester resin, 10 parts by weight of diluent, 0.5 part by weight of coupling agent, 2 parts by weight of photoinitiator, 0 part by weight of thermal initiator, 0.5 part by weight of thixotropic agent, 2 parts by weight of impact resistance agent and 70 parts by weight of silver powder.
The vinyl ester resin is novolac epoxy vinyl ester resin, which is commercially available, and the manufacturer is Ripoxy with the mark number of 630.
The diluent is hydroxyethyl methacrylate (CAS: 868-77-9).
The coupling agent is epoxy silane KH-560 (CAS: 2530-83-8).
The photoinitiator is triaryliodonium salt, can be obtained commercially, and is manufactured by Bluesil PI with the trade name of 2074.
The thixotropic agent is a polyamide wax, which is commercially available from Disparlon under the brand name of 6500.
The impact resistance agent is 1, 3-propylene glycol bis (4-aminobenzoate) CAS number 57609-64-0.
The silver powder purchasing manufacturer is Shanghai lane field nanometer material Co., Ltd, and the product number is XT-0801-4-3.
The preparation method of the ultrafast photon curing conductive adhesive comprises the following steps:
(1) preparing the conductive adhesive: fully stirring and dispersing vinyl ester resin, a diluent, a coupling agent, a photoinitiator, a thixotropic agent, an impact resistance agent and silver powder, and then grinding and defoaming to obtain the conductive adhesive;
(2) curing the conductive adhesive: and (2) curing the conductive adhesive prepared in the step (1) by using a PulseForge @3300(NCC Nano, LLC, USA) photon sintering system.
Example 2
The vinyl ester resin is polyurethane modified epoxy vinyl ester resin which can be obtained commercially, and is Atlac with the trade name of 580.
The diluent is 1, 6-hexanediol diacrylate (CAS: 13048-33-4).
The coupling agent is aminosilane KH-550 (CAS: 919-30-2).
The thermal initiator is a peroxyketal, commercially available from Trigonox under the designation 122-C80.
The thixotropic agent is silicon dioxide and is commercially available from Aerosil under the trade name R202.
The impact resistance agent is poly (dimethylsiloxane-co-diphenylsiloxane) terminated divinyl (CAS: 68951-96-2).
The silver powder purchasing manufacturer is Shanghai lane field nanometer material Co., Ltd, and the product number is XT-0801-4-3.
The preparation method of the ultrafast photon curing conductive adhesive comprises the following steps:
(1) preparing the conductive adhesive: fully stirring and dispersing vinyl ester resin, a diluent, a coupling agent, a thermal initiator, a thixotropic agent, an impact resistance agent and silver powder, and then grinding and defoaming to obtain the conductive adhesive;
(2) curing the conductive adhesive: and (2) curing the conductive adhesive prepared in the step (1) by using a PulseForge @3300(NCC Nano, LLC, USA) photon sintering system.
Example 3
The vinyl ester resin is a flexible vinyl ester resin commercially available from Derakane under the designation 8084.
The diluent is bisphenol A acrylate, and the model is EO 3-BPADA.
The coupling agent is vinylsilane A-171.
The thermal initiator is a closed hexafluoroantimonate, which is commercially available under the designation CXC-1612.
The thixotropic agent is hydrogenated castor oil, commercially available from basf under the trademark Kolliwax HCO.
The impact resistance agent is poly (dimethylsiloxane-co-diphenylsiloxane) (CAS: 130167-23-6).
The silver powder purchasing manufacturer is Shanghai lane field nanometer material Co., Ltd, and the product number is XT-0801-4-3.
The preparation method of the ultrafast photon curing conductive adhesive comprises the following steps:
(1) preparing the conductive adhesive: the vinyl ester resin, the diluent, the coupling agent, the thermal initiator, the thixotropic agent, the impact resistance agent and the silver powder are fully stirred and dispersed, and then are ground and defoamed to obtain the conductive adhesive.
(2) Curing the conductive adhesive: and (2) curing the conductive adhesive prepared in the step (1) by using a PulseForge @3300(NCC Nano, LLC, USA) photon sintering system.
Example 4
Embodiment 4 provides an ultrafast photon-cured conductive adhesive, which is prepared from, by weight, 13 parts of vinyl ester resin, 2 parts of diluent, 0 part of coupling agent, 0 part of photoinitiator, 0 part of thermal initiator, 0 part of thixotropic agent, 0 part of impact resistance agent and 85 parts of silver powder.
The vinyl ester resin is bisphenol A epoxy vinyl ester resin which can be obtained commercially, and the manufacturer is Ripoxy with the brand number of 806.
The diluent is ethoxylated bisphenol A diacrylate with the model number EO 4-BPADA.
The silver powder purchasing manufacturer is Shanghai lane field nanometer material Co., Ltd, and the product number is XT-0801-4-3.
The preparation method of the ultrafast photon curing conductive adhesive comprises the following steps:
(1) preparing the conductive adhesive: fully stirring and dispersing vinyl ester resin, a diluent and silver powder, and then grinding and defoaming to obtain the conductive adhesive;
(2) curing the conductive adhesive: and (2) curing the conductive adhesive prepared in the step (1) by using a PulseForge @3300(NCC Nano, LLC, USA) photon sintering system.
Example 5
Embodiment 5 provides an ultrafast photon-cured conductive adhesive, which is prepared from, by weight, 10 parts of a vinyl ester resin, 10 parts of a diluent, 0 part of a coupling agent, 0 part of a photoinitiator, 0 part of a thermal initiator, 0 part of a thixotropic agent, 0 part of an impact resistance agent, and 80 parts of silver powder.
The vinyl ester resin is bisphenol A epoxy vinyl ester resin which can be obtained commercially, and the manufacturer is Ripoxy with the brand number of 806.
The diluent is ethoxylated bisphenol A diacrylate with the model number EO 4-BPADA.
The silver powder purchasing manufacturer is Shanghai lane field nanometer material Co., Ltd, and the product number is XT-0801-4-3.
The preparation method of the ultrafast photon curing conductive adhesive comprises the following steps:
(1) preparing the conductive adhesive: fully stirring and dispersing vinyl ester resin, a diluent and silver powder, and then grinding and defoaming to obtain the conductive adhesive;
(2) curing the conductive adhesive: and (2) curing the conductive adhesive prepared in the step (1) by using a PulseForge @3300(NCC Nano, LLC, USA) photon sintering system.
Example 6
Embodiment 6 provides an ultrafast photon-cured conductive adhesive, which is prepared from, by weight, 20 parts of a vinyl ester resin, 10 parts of a diluent, 0 part of a coupling agent, 0 part of a photoinitiator, 0 part of a thermal initiator, 0 part of a thixotropic agent, 0 part of an impact resistance agent, and 70 parts of silver powder.
The vinyl ester resin is bisphenol A epoxy vinyl ester resin which can be obtained commercially, and the manufacturer is Ripoxy with the brand number of 806.
The diluent is ethoxylated bisphenol A diacrylate with the model number EO 4-BPADA.
The silver powder purchasing manufacturer is Shanghai lane field nanometer material Co., Ltd, and the product number is XT-0801-4-3.
The preparation method of the ultrafast photon curing conductive adhesive comprises the following steps:
(1) preparing the conductive adhesive: fully stirring and dispersing vinyl ester resin, a diluent and silver powder, and then grinding and defoaming to obtain the conductive adhesive;
(2) curing the conductive adhesive: and (2) curing the conductive adhesive prepared in the step (1) by using a PulseForge @3300(NCC Nano, LLC, USA) photon sintering system.
Example 7
Embodiment 7 provides an ultrafast photon-cured conductive adhesive, which is prepared from, by weight, 5 parts of a vinyl ester resin, 5 parts of a diluent, 0 part of a coupling agent, 0 part of a photoinitiator, 0 part of a thermal initiator, 0 part of a thixotropic agent, 0 part of an impact resistance agent, and 90 parts of silver powder.
The vinyl ester resin is bisphenol A epoxy vinyl ester resin which can be obtained commercially, and the manufacturer is Ripoxy with the brand number of 806.
The diluent is ethoxylated bisphenol A diacrylate with the model number EO 4-BPADA.
The silver powder purchasing manufacturer is Shanghai lane field nanometer material Co., Ltd, and the product number is XT-0801-4-3.
The preparation method of the ultrafast photon curing conductive adhesive comprises the following steps:
(1) preparing the conductive adhesive: fully stirring and dispersing vinyl ester resin, a diluent and silver powder, and then grinding and defoaming to obtain the conductive adhesive;
(2) curing the conductive adhesive: and (2) curing the conductive adhesive prepared in the step (1) by using a PulseForge @3300(NCC Nano, LLC, USA) photon sintering system.
Evaluation of Performance
1. And (3) curing test: the conductive pastes prepared in examples 1 to 7, the photon curing time and the required energy are shown in table 1 below.
After the conductive pastes prepared in examples 1 to 3 were photo-cured, the degree of curing was measured using a NETZSCH 204F1DSC differential scanning calorimeter (NETZSCH, Germany) under Ar gas at an air flow rate of 25 mL-min-1The temperature range is 40-300 ℃, and the heating rate is 10 ℃ min-1The results are shown in FIG. 1.
2. Volume resistance: the conductive pastes prepared in examples 1 to 7 were printed on a glass plate as a conductive paste film (30mm × 10mm × 0.05mm), and after being cured by photons, the resistance was measured by an Agilent 34401a 61/2 Digit Multimeter using a four-point probe method, and the volume resistance was calculated, and the results thereof are shown in table 3 below.
3. Bonding strength: printing the conductive adhesive prepared in the embodiments 1 to 7 on a glass sheet to form a conductive adhesive film (5mm × 5mm × 0.05mm), and then placing a glass sheet (5mm × 5mm × 1mm) on the conductive adhesive film, wherein two glass sheets and one conductive adhesive film form a sandwich structure; after photon curing, the material was tested using a Nordson Dage Series 4000 multifunctional bond tester (Nordson, USA) in the DS 100kg SK chip shear mode with a pusher width of 4mm and a thrust rate of 100 μm s-1The results are shown in Table 3 below.
TABLE 1
TABLE 2
| Examples | Example 1 | Example 2 | Example 3 |
| Degree of cure | Complete curing | Complete curing | Complete curing |
TABLE 3
Claims (3)
1. The ultrafast photon curing conductive adhesive is characterized by comprising the following raw materials, by weight, 15.5 parts of vinyl ester resin, 2 parts of diluent, 0.25 part of coupling agent, 0 part of photoinitiator, 1 part of thermal initiator, 0.25 part of thixotropic agent, 1 part of impact resistance agent and 80 parts of silver powder;
the vinyl ester resin is a flexible vinyl ester resin;
the diluent is bisphenol A acrylate;
the coupling agent is vinyl silane A-171;
the thermal initiator is closed hexafluoroantimonate;
the thixotropic agent is hydrogenated castor oil;
the impact resistance agent is poly (dimethylsiloxane-co-diphenylsiloxane).
2. The ultrafast photon-curable conductive paste according to claim 1, wherein the silver powder has a particle size of 1-20 μm and a thickness of 0.1-0.5 μm.
3. The preparation method of the ultrafast photon-cured conductive adhesive according to any one of claims 1 to 2, wherein the preparation method comprises the following steps:
(1) preparing the conductive adhesive: fully stirring and dispersing vinyl ester resin, a diluent, a coupling agent, a photoinitiator, a thermal initiator, a thixotropic agent, an impact resistance agent and silver powder, and then grinding and defoaming to obtain the conductive adhesive;
(2) curing the conductive adhesive: and (3) curing the conductive adhesive prepared in the step (1) by adopting a photon sintering system.
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