CN103160216A - Anisotropic conductive film and semiconductor device - Google Patents
Anisotropic conductive film and semiconductor device Download PDFInfo
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- CN103160216A CN103160216A CN2012102536688A CN201210253668A CN103160216A CN 103160216 A CN103160216 A CN 103160216A CN 2012102536688 A CN2012102536688 A CN 2012102536688A CN 201210253668 A CN201210253668 A CN 201210253668A CN 103160216 A CN103160216 A CN 103160216A
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- conductive film
- anisotropic conductive
- resin
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- urethane resin
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
- H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
Abstract
The invention discloses an anisotropic conductive film and a semiconductor device. The anisotropic conductive film comprises polyester type polyurethane resin and tricyclodecane dimethanol diacrylate. The anisotropic conductive film comprises the polyester type polyurethane resin and the tricyclodecane dimethanol diacrylate at the same time, therefore the conductive film is provided with the high energy storage modulus, the high tolerance to retraction and expansion, and less bubbles can be generated, in addition, the conductive film is provided with good bonding strength reliability and connecting reliability even after a long term storage under a high temperature and high humidity condition.
Description
Technical field
The present invention relates to a kind of anisotropic conductive film, relate more specifically to a kind of anisotropic conductive film, described anisotropic conductive film comprises that simultaneously polyester urethane resin and tristane dimethanol diacrylate are to have high storage modulus, thereby present the height endurability to pucker ﹠ bloat, produce less bubble, even and be connected with connection in cohesive strength and also have fabulous reliability after hot and humid lower standing storage.
Background technology
Usually, anisotropic conductive film (ACF) refers to film adhesive, and wherein conductive particle, for example comprise that the metallic particles of nickel particle or gold grain or metal-coated polymeric resin particles are dispersed in resin such as epoxy resin.Anisotropic conductive film represents to have at its thickness direction and presents conduction property and present electrical anisotropy and the fusible polymer layer of insulating property in its surface direction.When anisotropic conductive film is placed between the circuit card that will be connected and stands under given conditions heating and when pressurization, the circuit terminal of circuit card is electrically connected to by conductive particle, and the space between insulating binder resin filling adjacent circuit terminal is so that conductive particle is insulated from each other, thereby the high insulating property between circuit terminal is provided.
Along with the rising tendency that large size panel and wiring enlarge, interelectrode spacing broadens.Therefore, because connection substrate due in bonding be heated and pressure under compacting expand and contraction after bonding recovers, so binder composition expands and is retracted to severity, causes a large amount of Bubble formations, and deteriorated binder composition filling effect.
In order to solve problems, a kind of method is to use the adhesive resin (Japanese patent application publication No. 2011-159486, on August 8th, 2011 is open) with high second-order transition temperature (Tg).But, in this case, anisotropic conductive film still has the Resin Flow that is used for weakening impression (indentation) of reduction because hardness has been improved the tolerance that expands and shrink, cause the minimizing of conductive particle contact area, thus deteriorated connection reliability.
As prior art related to the present invention, Korean Patent Publication No. 10-2011-0095127(2011 August 24 is open) in a kind of anisotropic conductive film is disclosed.This anisotropic conductive film is fast setting at low temperatures, and it comprises phenoxy resin and radical polymerization condensation material, and has fabulous switching performance.
These open tristane dimethanol diacrylates that use together with phenoxy resin by description disclose use tristane dimethanol diacrylate as the radical polymerization condensation material.That uses together with the radical polymerization condensation material particularly, has very that the phenoxy resin of high acid value tends to accelerate metal attack.Thereby, be used for connecting semiconductor device, the reliability variation of device if having the anisotropic conductive film of this structure.Incompatible with tristane dimethanol diacrylate due to phenoxy resin, use together the anisotropic conductive film of these materials can not have high reliability, hardness and to the tolerance of shrink/expanded.
Summary of the invention
For addressing the above problem, the present inventor has developed a kind of anisotropic conductive film, described anisotropic conductive film comprises that simultaneously polyester urethane resin and tristane dimethanol diacrylate are to have high storage modulus, thereby present the height endurability to pucker ﹠ bloat, produce less bubble, even be connected with connection in cohesive strength after hot and humid lower standing storage and also have fabulous reliability.
The present invention aims to provide a kind of anisotropic conductive film, and described anisotropic conductive film comprises polyester urethane resin and tristane dimethanol diacrylate simultaneously having hardness, thereby prevents volume to be heated and change.
The present invention also aims to provide a kind of anisotropic conductive film, described anisotropic conductive film has height endurability to the pucker ﹠ bloat by heat, thereby not only be suppressed at the initial generation of the bubble of film adhering zone, and the bubble area that is suppressed at after hot and humid lower standing storage increases.
The present invention also aims to provide a kind of anisotropic conductive film that presents fabulous reliability on cohesive strength and hardness.
The present invention relates to a kind of anisotropic conductive film that comprises simultaneously polyester urethane resin and tristane dimethanol diacrylate.
According to an aspect of the present invention, provide a kind of anisotropic conductive film, described anisotropic conductive film comprises:
A) comprise the adhesive composition of polyester urethane resin;
B) comprise the radical polymerization condensation material of tristane dimethanol diacrylate;
C) curing initiator; With
D) conductive particle.
According to another aspect of the present invention, provide a kind of anisotropic conductive film, based on the anisotropic conductive film of the solid content of 100 weight parts, described anisotropic conductive film comprises:
A) adhesive composition that comprises polyester urethane resin of 40 to 80 weight parts;
B) the radical polymerization condensation material that comprises tristane dimethanol diacrylate of 5 to 50 weight parts;
C) curing initiator of 0.1 to 10 weight part; With
D) conductive particle of 0.1 to 10 weight part.
According to a further aspect of the invention, based on the anisotropic conductive film of the solid content of 100 weight parts, the amount of polyester urethane resin can be 5 to 40 weight parts.
According to a further aspect of the invention, based on the anisotropic conductive film of the solid content of 100 weight parts, the amount of tristane dimethanol diacrylate can be 5 to 30 weight parts.
According to another aspect of the present invention, described anisotropic conductive film can further comprise organic granular or inorganic particle.
According to another aspect of the present invention, described organic granular can comprise and select free acrylic resin, for example acrylate resin, ethylene-acrylate copolymer and ethylene-acrylic acid copolymer; Olefin resin, for example ethenoid resin and ethylene-propylene copolymer; Butadiene resin, the styrene-ethylene-butadiene-styrene block copolymer of acrylonitrile butadiene copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, carboxylation, ethene-vinylbenzene-butylene block-copolymer; Rubber, for example divinyl rubber, nitrile-divinyl rubber, styrene butadiene rubbers and neoprene; Vinylite, for example vinyl butyral resin, vinyl alcohol methylal resin; Ester resin, for example polyester and cyanate ester resin; Phenoxy resin; Silicon rubber; Particle in the group that forms with urethane resin.These organic granulars can use separately or as mixture.
According to another aspect of the present invention, described inorganic particle can include but not limited to silicon-dioxide.
According to another aspect of the present invention, based on the anisotropic conductive film of the solid content of 100 weight parts, the amount of described organic granular or inorganic particle is 1 to 20 weight part.
According to another aspect of the present invention, described anisotropic conductive film solidify 90% or more after have 100MPa or higher storage modulus at 40 ℃.
According to another aspect of the present invention, based on after final compacting and the interelectrode spatial area after 85 ℃ and 85%RH store 500 hours, described anisotropic conductive film can have 20% or lower bubble area.
According to another aspect of the present invention, described anisotropic conductive film can have 500gf/cm or higher cohesive strength after final compacting and after 85 ℃ and 85%RH store 500 hours.
According to another aspect of the present invention, provide a kind of anisotropic conductive film, described anisotropic conductive film comprises polyester urethane resin and tristane dimethanol diacrylate, and wherein, described anisotropic conductive film has:
A) in the 100MPa of 40 ℃ or higher storage modulus; With
B) 20% or lower bubble area of the interelectrode spatial area after storing 500 hours with 85%RH after final compacting and at 85 ℃.
According to a further aspect of the invention, provide a kind of semiconductor device, described semiconductor device comprises: circuit board and semi-conductor chip, wherein said semiconductor device connects by described anisotropic conductive film.
As mentioned above, comprise simultaneously that according to anisotropic conductive film of the present invention polyester urethane resin and tristane dimethanol diacrylate are in order to have high storage modulus, thereby present the height endurability to pucker ﹠ bloat, produce less bubble, even and be connected with connection in cohesive strength and also have fabulous reliability after hot and humid lower standing storage.
Particularly described anisotropic conductive film comprises polyester urethane resin and tristane dimethanol diacrylate having hardness, thereby controls the variation that volume is heated.
In addition, described anisotropic conductive film has height endurability to the pucker ﹠ bloat of heat, thereby not only is suppressed at the initial generation of the bubble of film adhering zone, and the bubble area that is suppressed at after hot and humid lower standing storage increases.
In addition, described anisotropic conductive film presents fabulous reliability on cohesive strength and hardness.
Embodiment
To describe illustrative embodiments of the present invention in detail now.The details that herein omission be it will be apparent to those skilled in the art.
According to an aspect of the present invention, provide a kind of anisotropic conductive film, described anisotropic conductive film comprises:
A) comprise the adhesive composition of polyester urethane resin;
B) comprise the radical polymerization condensation material of tristane dimethanol diacrylate;
C) curing initiator; With
D) conductive particle.
Adhesive composition can comprise polyester urethane resin.
Polyester urethane resin
The polyester urethane resin that the present invention uses can obtain by the reaction of polyester polyol and vulcabond.
Described polyester polyol refers to have the polymkeric substance of a plurality of ester groups and a plurality of hydroxyls.Described polyester polyol can obtain by the reaction of dicarboxylic acid and glycol.
The example of dicarboxylic acid can comprise phthalic acid, terephthalic acid, m-phthalic acid, hexanodioic acid, SA, succsinic acid, pentanedioic acid, suberic acid, nonane diacid, dodecanedioic acid, hexahydrophthalic acid, phthalic acid, tetrachlorophthalic acid, 1,5-naphthalene dicarboxylic acids, fumaric acid, toxilic acid, methylene-succinic acid, citraconic acid, methylfumaric acid, tetrahydrophthalic acid etc.Preferred these aromatics or the aliphatic dicarboxylic acid of using.
The example of glycol can comprise ethylene glycol, propylene glycol, hexylene glycol, neopentyl glycol, Diethylene Glycol, triethylene glycol, 1, ammediol, 1,3-butyleneglycol, BDO, 1,5-PD, 1,6-hexylene glycol, dipropylene glycol, dibutylene glycol, 2-methyl isophthalic acid, 3-pentanediol, 2,2,4-trimethylammonium-1,3-pentanediol, 1,4 cyclohexane dimethanol etc.Preferred these glycol that use.
The example of vulcabond can comprise isophorone diisocyanate (IPDI), 4,4'-diphenylmethanediisocyanate (MDI), 1, the diphenylmethanediisocyanate of 6-hexamethylene diisocyanate (HDI), Xylene Diisocyanate, hydrogenation, naphthalene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate etc.Preferred these aromatics, the alicyclic or aliphatic vulcabond of using.
Polyester urethane resin can have 10000g/mol to 100000g/mol, the weight-average molecular weight of preferred 25000g/mol to 70000g/mol.
Based on the anisotropic conductive film of the solid content of 100 weight parts, the amount of polyester urethane resin can be 5 to 40 weight parts, preferred 15 to 40 weight parts.In this scope, kept the balance between storage modulus and cohesive strength, thereby this film can obtain solid performance and fabulous cohesive strength.
Be not specifically limited about the adhesive resin that uses together with polyester urethane resin in the present invention, and can use any resin commonly used in this area.The example of adhesive resin can comprise acrylic resin, urethane resin, paracril (NBR) resin etc.
Acrylic resin
In the present invention, available acrylic resin can obtain by Acrylic Acid Monomer and/or with the polymerization of the polymerisable monomer of Acrylic Acid Monomer.For example, acrylic resin can select at least a monomer preparation in the group that the Acrylic Acid Monomer of (methyl) acrylate, (methyl) vinylformic acid, vinyl-acetic ester and the modification thereof of the alkyl that freely has C2 to C10 forms by polymerization.Polymerization process is without concrete restriction.
Urethane resin
In the present invention, available urethane resin is the fluoropolymer resin with urethane bonds, and it can obtain by the polymerization such as isophorone diisocyanate, polytetramethylene glycol etc., but is not limited to this.Described urethane resin can have 50000 to 100000g/mol weight-average molecular weight.
The NBR resin
In the present invention, available NBR resin is the multipolymer by the letex polymerization acquisition of acrylonitrile and butadiene.About the amount of acrylonitrile and butadiene in multipolymer without concrete restriction, about polymerization process also without concrete restriction.The NBR resin can have the weight-average molecular weight of 50000g/mol to 2000000g/mol.
Based on the anisotropic conductive film of the solid content of 100 weight parts, the amount of adhesive composition of the present invention can be 40 to 80 weight parts, preferred 55 to 80 weight parts.In this scope, kept the balance between storage modulus and cohesive strength, thereby this film can obtain hardness and fabulous cohesive strength.
(b) radical polymerization condensation material
The radical polymerization condensation material that uses in the present invention comprises tristane dimethanol diacrylate.
In the present invention, based on the anisotropic conductive film of the solid content of 100 weight parts, the amount of tristane dimethanol diacrylate can be 5 to 30 weight parts, preferred 10 to 25 weight parts.
Be not specifically limited about the radical polymerization condensation material that uses together with tristane dimethanol diacrylate in the present invention, and can use any radical polymerization condensation material commonly used in this area.The example of this type of radical polymerization condensation material can comprise acrylate, methacrylic ester and maleimide compound.They can be used as the combination of monomer, oligopolymer or monomer and oligopolymer, but are not limited to this.
Acrylate or methacrylic ester
in the present invention, available acrylate or the example of methacrylic ester can comprise methyl acrylate, ethyl propenoate, isopropyl acrylate, isobutyl acrylate, glycol diacrylate, diethylene glycol diacrylate, Viscoat 295, the tetramethylol methane tetraacrylate, 2-hydroxyl-1, 3-two propylene acyloxy propane, 2, two [4-(acryloxy polymethoxy) phenyl] propane of 2-, 2, two [4-(acryloxy polyethoxye) phenyl] propane of 2-, the dicyclopentenyl acrylate, three ring decyl acrylate, three (acryloxy ethyl) isocyanic ester, tricyclic decane dimethanol diacrylate, 2-methacryloxy phosphoric acid ester (2-methacryloyloxy phosphate), tetramethylolmethane three (methyl) acrylate or 2-hydroxyethyl (methyl) acrylate, but be not limited to this.Their two or more uses alone or in combination of these acrylate or methacrylic ester.
Maleimide
in the present invention, available maleimide compound can comprise the compound of at least two dimaleoyl iminos, 1-methyl-2 for example, 4-bismaleimides benzene, N, the N'-meta-phenylene bismaleimide, N, N'-TOPOT 2,2′ p phenylenebis maleimide, N, tolylene bismaleimides between N'-, N, N'-4,4-biphenylene bismaleimides, N, N'-4,4-(3,3'-dimethyl biphenylene) bismaleimides, N, N'-4,4-(3,3'-dimethyl diphenyl methane) bismaleimides, N, N'-4,4-(3,3'-diethyl ditane) bismaleimides, N, N'-4,4-diphenyl methane dimaleimide, N, N'-4,4-diphenyl propane bismaleimides, N, N'-4,4-diphenyl ether bismaleimides, N, N'-3,3'-sulfobenzide bismaleimides, two [4-(the 4-maleimide phenoxy group) phenyl] propane of 2,2-, two [3-sec-butyl-4-8-(the 4-maleimide phenoxy group) phenyl] propane of 2,2-, two [4-(the 4-maleimide phenoxy group) phenyl] decane of 1,1-, 4,4'-cyclohexylidene-two [1-(4-maleimide phenoxy group)-2-cyclohexyl] benzene, 2,2-pair [4-(4-maleimide phenoxy group) phenyl) HFC-236fa etc., but be not limited to this.Their two or more uses alone or in combination of these maleimide compounds.
Based on the anisotropic conductive film of the solid content of 100 weight parts, the amount of radical polymerization condensation material of the present invention can be 5 to 50 weight parts, preferred 10 to 40 weight parts.If the amount of radical polymerization compound is less than 5 weight parts, due to the minimizing of final compacting after fixing density, reliability and overall flow are deteriorated.As a result, the contact meeting between conductive particle and circuit substrate dies down when bonding, and connection resistance can increase, thereby reduces connection reliability.And if content is difficult to form anisotropic conductive film greater than 50 weight parts, and bond properties may be deteriorated.
(c) curing initiator
Be not specifically limited about the curing initiator that uses in the present invention, but can comprise any curing initiator commonly used in this area.Available curing initiator example can comprise peroxide initiator and azo initiator, but is not limited to this.
Peroxide initiator
In the present invention, the example of spendable peroxide initiator can comprise benzoyl peroxide, lauryl peroxide, the peroxide lauric acid tert-butyl ester, 1,1,3,3-tetramethyl butyl peroxidation pivalate, cumyl hydroperoxide etc., but be not limited to this.
Azo-initiator
In the present invention, the example of spendable azo-initiator can comprise 2,2'-azo two (4-methoxyl group-2,4-methyl pentane nitrile), dimethyl-2,2'-azo two (2 Methylpropionic acid ester), 2,2'-azo two (N-cyclohexyl-2-methyl propanamide) etc., but be not limited to this.
Based on the anisotropic conductive film of the solid content of 100 weight parts, the amount of the curing initiator that uses in the present invention is 0.1 to 10 weight part.
(d) conductive particle
The conductive particle that uses in the present invention can comprise any particle usually used in this field, and is not specifically limited.
The example of conductive particle can comprise metallic particles, for example Au, Ag, Ni, Cu and solder grain; Carbon granule; Metal-coated resin particle scribbles the modified resin particles thereof of Au, Ag, Ni etc. such as polyethylene particle, polypropylene GRANULES, polyester granulate, granules of polystyrene, granule of polyvinyl alcohol and they; And conductive particle further scribbles insulated particle.
The size of conductive particle can be determined in the scope of 2 to 30 μ m according to circuit spacing and the purpose that will use.
Based on the anisotropic conductive film of the solid content of 100 weight parts, the amount of the conductive particle that uses in the present invention can be 0.1 to 10 weight part.In this scope, can prevent from connecting and/or insulation defect to obtain fabulous switching performance.
Another aspect of the present invention provides except component (a) and (b), (c) and has further comprised the anisotropic conductive film of organic granular or inorganic particle (d).
Described organic granular or inorganic particle can comprise any particle usually used in this field, and are not specifically limited.
The example of organic granular can comprise acrylic resin, for example acrylate resin, ethylene-acrylate copolymer and ethylene-acrylic acid copolymer; Olefin resin, for example ethenoid resin and ethylene-propylene copolymer; Butadiene resin, the styrene-ethylene-butadiene-styrene block copolymer of acrylonitrile butadiene copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, carboxylation, ethene-vinylbenzene-butylene block-copolymer; Rubber, for example divinyl rubber, nitrile-divinyl rubber, styrene butadiene rubbers and and neoprene; Vinylite, for example vinyl butyral resin and vinyl alcohol methylal resin; Ester resin, for example polyester and cyanate ester resin; Phenoxy resin; Silicon rubber; Or the particle of urethane resin.These organic granulars can use separately or as mixture.
The example of inorganic particle can comprise silica dioxide granule, but is not limited to this.
Described organic granular or inorganic particle can have 0.1 to 10 μ m, the size of preferred 0.1 to 5 μ m.In this scope, particle can disperse suitably, and can prevent because the film adhesive power that reduces causes deteriorated on pre-bonding processibility.
Based on the anisotropic conductive film of the solid content of 100 weight parts, the amount of organic granular or inorganic particle can be 1 to 20 weight part.In this scope, this particle can provide sufficient effect, and prevents the excessive increase of film toughness, thereby prevents that adhesive power from reducing.
According to another aspect of the present invention, provide the anisotropic conductive film that has 100MPa or higher storage modulus at 40 ℃.
Storage modulus can be measured by any method usually used in this field, is not specifically limited.For example, high energy storage mould is estimated as follows: the sheet (for example 5mm is wide and 30mm length) that anisotropic conductive film is cut into suitable size, then use dynamic mechanical analysis instrument (DMA, Q800, TA Instruments) with the frequency of 10Hz, storage modulus is measured in the intensification from-30 ℃ to 170 ℃ with 4 ℃/min.
Anisotropic conductive film according to the present invention can have 100MPa or higher storage modulus at 40 ℃.In this scope, film has sufficient hardness to control the volume variation of being heated.
Another aspect of the present invention provides anisotropic conductive film, and based on after final compacting and the interelectrode spatial area after 85 ℃ and 85%RH store 500 hours, described anisotropic conductive film can have 20% or lower bubble area.
Above-mentioned final compacting can be carried out 4 seconds under 185 ℃ and 4.5MPa.
Can measure the physicals of film after 85 ℃ and 85%RH store 500 hours to be used for reliability evaluation.
Interelectrode space is to be filled with the interelectrode gap of anisotropic conductive film in compacting.
Bubble area can be measured by any method usually used in this field, and is not specifically limited.For example, bubble area can by observing with microscope (or photography) the interelectrode space that is filled with film, then be calculated bubble area with image analyzer or mesh coordinate and calculate.
If anisotropic conductive film has the bubble area greater than 20%, the semiconductor device that uses film to connect can not use for a long time, and has short life.
Another aspect of the present invention provides in the anisotropic conductive film that can have 500gf/cm or higher cohesive strength after final compacting and after 85 ℃ and 85%RH store 500 hours.
Final compacting can be carried out under condition same as described above.
Cohesive strength can be passed through any method evaluation usually used in this field, and without concrete restriction.
For example, cohesive strength can be suppressed under 185 ° of C and 4.5MPa and be measured with the peeling rate of the peel angle of 90 ° and 50mm/min by peel strength tester (H5KT, Tinius Olsen) afterwards in 4 seconds.
If anisotropic conductive film has the cohesive strength less than 500gf/cm, the semiconductor device that uses this film to connect can not use for a long time, and has short life.
Form the method for anisotropic conductive film without concrete restriction, can use any method usually used in this field.
Do not need special device or equipment to form above-mentioned anisotropic conductive film.For example, anisotropic conductive film can obtain by following process: dissolve in organic solvent and the adhesive resin that liquefies, it is added remaining ingredient, and certain period of stirred solution, to release film to suitable thickness, for example 10 to 50 μ m, and drying solution are with the volatilization organic solvent with this solution coat.
Another aspect of the present invention provides the semiconductor device that connects by anisotropic conductive film.
Described semiconductor device can comprise circuit board; Be attached to the anisotropic conductive film of the chip fixation side of this circuit board; With the semi-conductor chip that is fixed on described film.
The circuit board and the semi-conductor chip that use in the present invention are not specifically limited, and can comprise any circuit board and semi-conductor chip generally known in the art.
The method of making semiconductor device of the present invention is not specifically limited, and can comprise any method generally known in the art.
Below, the present invention is described in detail with reference to embodiment, Comparative Examples and experimental example.But provide these embodiment only to be used for illustration purpose, and should not be construed as the scope that limits each embodiment.
Embodiment 1: comprise the preparation of the anisotropic conductive film of polyester urethane resin and tristane dimethanol diacrylate
Anisotropic conductive film is by being mixed with.
Based on the anisotropic conductive film of the solid content of 100 weight parts,
A) as adhesive composition, the polyester urethane resin of 30 weight parts (NPC8750, Nanux Inc.); With the acrylic resin (AOF-7003, Aekyung Chemical) of 27 weight parts,
B) as the radical polymerization condensation material, the tristane dimethanol diacrylate of 14 weight parts; The urethane acrylate of 12 weight parts (NPC7007, Nanux Inc.); The 2-methacryloyl oxygen ethyl phosphonic acid ester of 1 weight part; Tetramethylolmethane three (methyl) acrylate of 5 weight parts; With 2-hydroxyethyl (methyl) acrylate of 5 weight parts,
C) as curing initiator, the lauryl peroxide of 3 weight parts, and
D) as conductive particle, the conductive particle of 3 μ m of 3 weight parts (Sekisui Chemical).
Stirred said mixture solution 60 minutes under the speed of not pulverizing conductive particle and room temperature (25 ° of C).Use the casting cutter, this solution is formed the film of 16 μ m thickness on the polyethylene based film of processing through the silicone release surface.With this film dry 5 minutes of 60 ° of C.
Embodiment 2: not only comprise polyester urethane resin and tristane dimethanol diacrylate, also comprise the preparation of the anisotropic conductive film of organic granular
Make anisotropic conductive film with the method identical with embodiment 1, difference is to use the urethane pearl (MM-101-MS, Negami) of polyester urethane resin and 5 weight parts of 23 weight parts.
Embodiment 3: not only comprise polyester urethane resin and tristane dimethanol diacrylate, also comprise the preparation of the anisotropic conductive film of organic granular
Make anisotropic conductive film with the method identical with embodiment 1, difference is to use the polyester urethane resin of 15 weight parts; The NBR resin of 5 weight parts (N-34, Nippon Zeon); The acrylic resin of 20 weight parts; The tristane dimethanol diacrylate of 25 weight parts; The 2-hydroxyethyl isocyanuric acid ester diacrylate of 10 weight parts; The conductive particle of 2 weight parts, and the urethane pearl (MM-101-MS, Negami) of 7 weight parts, and do not add tetramethylolmethane three (methyl) acrylate and 2-hydroxyethyl (methyl) acrylate.
Embodiment 4: comprise the preparation of the anisotropic conductive film of polyester urethane resin and tristane dimethanol diacrylate
Make anisotropic conductive film with the method identical with embodiment 3, difference is to use the polyester urethane resin of 40 weight parts; The tristane dimethanol diacrylate of 10 weight parts; The urethane acrylate of 5 weight parts; The 2-hydroxyethyl isocyanuric acid ester diacrylate of 13 weight parts; With the conductive particle of 3 weight parts, and do not add the urethane pearl.
Comparative Examples 1: comprise polyester urethane resin but do not comprise the preparation of the anisotropic conductive film of tristane dimethanol diacrylate
Make anisotropic conductive film with the method identical with embodiment 1, difference is to use three (2-hydroxyethyl) isocyanuric acid ester diacrylate to replace tristane dimethanol diacrylate.
Comparative Examples 2: comprise tristane dimethanol diacrylate but do not comprise the preparation of the anisotropic conductive film of polyester urethane resin
Make anisotropic conductive film with the method identical with embodiment 1, difference is to use polyatomic alcohol polyurethane resin (NPC7007T, Nanux Inc.) to replace polyester urethane resin.
Comparative Examples 3: do not comprise the preparation of the anisotropic conductive film of polyester urethane resin and tristane dimethanol diacrylate
Make anisotropic conductive film with the method identical with embodiment 1, difference is to use polyatomic alcohol polyurethane resin (NPC7007T, Nanux Inc.) replace polyester urethane resin, and use three (2-hydroxyethyl) isocyanuric acid ester diacrylate to replace tristane dimethanol diacrylate.
List in table 1 and table 2 with weight part according to the composition of the anisotropic conductive film of embodiment 1 to 4 and Comparative Examples 1 to 3.
Table 1
Table 2
Experimental example 1: the measurement of storage modulus
Following evaluate root is according to each anisotropic conductive film of embodiment 1 to 4 and Comparative Examples 1 to 3 storage modulus at 40 ℃.
Every kind of anisotropic conductive film is formed the lamination with 200 μ m thickness, be cut into the sheet (for example 5mm is wide and 30mm length) of suitable size, then placed 3 hours in the baking box of 200 ℃.Then use DMA(Q800, TA Instruments) measure with the intensification of 4 ℃/min with the frequency of 10Hz, from-30 ℃ to 170 ℃ and solidify the storage modulus of sample afterwards fully.
Experimental example 2: the measurement of the cohesive strength after initial adhesion intensity and reliability detect
Will according to every kind of anisotropic conductive film of embodiment 1 to 4 and Comparative Examples 1 to 3 by under the observed temperature of 70 ℃ pre-bonding 1 second and under 185 ℃ and 4.5MPa compacting be connected to metal electrode glass (Mo/Al/Mo structure in 4 seconds, Samsung Electronics) chip (COF and on film, Samsung Electronics), thus prepare 10 samples of every kind of film.
With peel strength tester (H5KT, Tinius Olsen) with the peeling rate of the peel angle of 90 ° and the 50mm/min cohesive strength in assess sample, and calculating mean value.
10 samples of every kind of film (are stored 500 hours at 85 ℃ and 85%RH) under hot and humid carry out reliability and detect, then with the cohesive strength after method evaluation reliability detection same as described above, and calculating mean value.
Experimental example 3: the measurement of the contact resistance after initial contact resistance and reliability testing
To be placed in room temperature (25 ℃) lower 1 hour according to every kind of anisotropic conductive film of embodiment 1 to 4 and Comparative Examples 1 to 3, then by under the observed temperature of 70 ℃ pre-bonding 1 second and under 185 ℃ and 4.5MPa compacting be connected in 4 seconds by using
The tin indium oxide of thickness (ITO) but the 0.5t pattern-free formation four point probe on glass mapping case of layer coating and the COF(Samsung Electronics that obtains), thereby prepare 10 samples of every kind of film.With the initial contact resistance (according to ASTM F43-64T) of four probe method assess sample, and calculating mean value.
With 10 samples of every kind of film under hot and humid, store 500 hours and carry out reliability at 85 ℃ and 85%RH and detect, then estimate the contact resistance (according to ASTM D117) after reliability testing, and calculating mean value.
Experimental example 4: the measurement of the bubble area after incipient bubble area and reliability testing
To be placed in room temperature (25 ℃) lower 1 hour according to every kind of anisotropic conductive film of embodiment 1 to 4 and Comparative Examples 1 to 3, then by being incorporated in pre-sticking under the observed temperature of 70 ℃ that under 185 ℃ and 4.5MPa, compacting was connected to by using in 4 seconds
The tin indium oxide of thickness (ITO) but the 0.5t pattern-free formation four point probe on glass mapping case of layer coating and the COF(Samsung Electronics that obtains), thereby prepare 10 samples of every kind of film.Take pictures after 10 points of each sample with opticmicroscope, with the bubble area in the space between the image analyzer potential electrode, and calculating mean value.
With 10 samples of every kind of film under hot and humid, storage was carried out reliability testing in 500 hours under 85 ℃ and 85%RH, with the bubble area after method evaluation reliability testing same as described above, and calculating mean value.
The results are shown in table 3 of experimental example 1 to 4.
Table 3
As shown in table 3, with according to the anisotropic conductive film that does not contain polyester urethane resin and tristane dimethanol diacrylate of Comparative Examples 3 with compare with 2 the anisotropic conductive film that contains polyester urethane resin or tristane dimethanol diacrylate according to Comparative Examples 1, comprise that the anisotropic conductive film of polyester urethane resin and tristane dimethanol diacrylate has fabulous physical properties in every respect in the time of according to embodiment 1 ~ 4, for example cohesive strength, contact resistance and the bubble area after initial adhesion intensity, reliability testing.
Especially simultaneously the anisotropic conductive film that comprises polyester urethane resin and tristane dimethanol diacrylate presents obviously high cohesive strength after reliability detects, and have 20% or lower bubble area after reliability testing, based on this, think and kept reliability in life-time service.
Compare embodiment 1 and embodiment 2, when organic granular further add together with polyester urethane resin and tristane dimethanol diacrylate fashionable, cohesive strength and the inhibition of Bubble formation is even more strengthened.This is to work in the pucker ﹠ bloat of anisotropic conductive film due to the organic granular that is considered to relieve stresses and/or inorganic particle.
Although some embodiments are provided in specification sheets of the present invention, but to it will be apparent to one skilled in the art that, each embodiment only proposes in the mode of explanation, and can carry out various modifications, change, replacement and equivalent embodiment and do not deviate from the spirit and scope of the present invention.Scope of the present invention should only be limited by appended claims.
Claims (13)
1. anisotropic conductive film comprises:
A) comprise the adhesive composition of polyester urethane resin;
B) comprise the radical polymerization condensation material of tristane dimethanol diacrylate;
C) curing initiator; With
D) conductive particle.
2. anisotropic conductive film as claimed in claim 1, wherein, based on the described anisotropic conductive film of the solid content of 100 weight parts, described anisotropic conductive film comprises:
A) the described adhesive composition that comprises described polyester urethane resin of 40 to 80 weight parts;
B) the described radical polymerization condensation material that comprises described tristane dimethanol diacrylate of 5 to 50 weight parts;
C) the described curing initiator of 0.1 to 10 weight part; With
D) the described conductive particle of 0.1 to 10 weight part.
3. anisotropic conductive film as claimed in claim 2, wherein, based on the described anisotropic conductive film of the solid content of 100 weight parts, the amount of described polyester urethane resin is 5 to 40 weight parts.
4. anisotropic conductive film as claimed in claim 2, wherein, based on the described anisotropic conductive film of the solid content of 100 weight parts, the amount of described tristane dimethanol diacrylate is 5 to 30 weight parts.
5. anisotropic conductive film as described in any one in claim 1 to 4, wherein, described anisotropic conductive film has 100MPa or higher storage modulus at 40 ℃
6. anisotropic conductive film as described in any one in claim 1 to 4, wherein, based on after final compacting and the interelectrode spatial area after 85 ℃ and 85%RH store 500 hours, described anisotropic conductive film has 20% or lower bubble area.
7. anisotropic conductive film, described anisotropic conductive film comprises polyester urethane resin and tristane dimethanol diacrylate, wherein, described anisotropic conductive film has:
A) in the 100MPa of 40 ℃ or higher storage modulus; With
B) based on after final compacting and 20% or still less bubble area of the interelectrode spatial area after 85 ℃ and 85%RH store 500 hours.
8. anisotropic conductive film as described in claim 1 or 7, wherein, described anisotropic conductive film further comprises organic granular or inorganic particle.
9. anisotropic conductive film as claimed in claim 8, wherein, described organic granular comprises and selects free acrylate resin, acrylic resin, ethenoid resin, olefin resin, butadiene resin, acrylonitrile butadiene copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-ethylene-the butadiene-styrene block copolymer of carboxylation, ethene-vinylbenzene-butylene block-copolymer, divinyl rubber, neoprene, silicon rubber, Vinylite, the ester resin, at least a particle in the group that phenoxy resin and urethane resin form.
10. anisotropic conductive film as claimed in claim 8, wherein, described inorganic particle is silica dioxide granule.
11. anisotropic conductive film as claimed in claim 8, wherein, based on the anisotropic conductive film of the solid content of 100 weight parts, the amount of described organic granular or inorganic particle is 1 to 20 weight part.
12. anisotropic conductive film as described in claim 1 or 7, wherein, described anisotropic conductive film has 500gf/cm or higher cohesive strength after storing 500 hours with 85%RH after final compacting and at 85 ℃.
13. a semiconductor device, described semiconductor device comprises:
A) circuit board;
B) be attached to the described anisotropic conductive film of any one in the claim 1 to 12 of chip fixation side of described circuit board; With
C) be fixed on semi-conductor chip on described film.
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| KR1020110136328A KR101355854B1 (en) | 2011-12-16 | 2011-12-16 | Anisotropic conductive film |
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| CN104461117A (en) * | 2013-09-12 | 2015-03-25 | 迪睿合电子材料有限公司 | Connection structure and anisotropic conductive adhesive |
| CN110964468A (en) * | 2019-12-18 | 2020-04-07 | 西安英诺维特新材料有限公司 | Single-component acrylic resin conductive adhesive and preparation method thereof |
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Also Published As
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| TWI464230B (en) | 2014-12-11 |
| TW201326353A (en) | 2013-07-01 |
| KR20130068890A (en) | 2013-06-26 |
| KR101355854B1 (en) | 2014-01-29 |
| CN103160216B (en) | 2015-03-11 |
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