CN103160216B - Anisotropic conductive film and semiconductor device - Google Patents
Anisotropic conductive film and semiconductor device Download PDFInfo
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- CN103160216B CN103160216B CN201210253668.8A CN201210253668A CN103160216B CN 103160216 B CN103160216 B CN 103160216B CN 201210253668 A CN201210253668 A CN 201210253668A CN 103160216 B CN103160216 B CN 103160216B
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- conductive film
- anisotropic conductive
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- tricyclodecane dimethanol
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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 polyester urethane resin and Tricyclodecane Dimethanol diacrylate to have high storage modulus simultaneously, thus the height endurability presented pucker & bloat, produce less bubble, even and if also there is fabulous reliability in cohesive strength and connection after hot and humid lower standing storage.
Background technology
Usually, anisotropic conductive film (ACF) refers to film adhesive, wherein conductive particle, and the metallic particles or the metal-coated polymeric resin particles that such as comprise nickel particle or gold grain are dispersed in resin as in epoxy resin.Anisotropic conductive film represents to have and presents conduction property at its thickness direction and present the electrical anisotropy of insulating property and fusible polymer layer in its surface direction.When between anisotropic conductive film is placed in the circuit card be connected and when standing heating and pressurization under given conditions, the circuit terminal of circuit card is electrically connected by conductive particle, and the space between insulating binder resin filling adjacent circuit terminal is to make conductive particle insulated from each other, thus provides the high insulating property between circuit terminal.
Along with the rising tendency that large size panel and wiring expand, interelectrode spacing broadens.Therefore, because connection substrate owing to being heated and compacting under pressure and to expand and contraction after bonding recovers in bonding, so binder composition expands and is retracted to severity, a large amount of bubble is caused to produce, and deteriorated binder composition filling effect.
In order to solve problems, a kind of method uses 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, the tolerance that anisotropic conductive film improves expansion due to hardness and shrinks, but there is the Resin Flow for weakening impression (indentation) of reduction, 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 disclose a kind of anisotropic conductive film.This anisotropic conductive film fast setting at low temperatures, it comprises phenoxy resin and radical polymerization condensation material, and has fabulous switching performance.
These open disclosing by describing the Tricyclodecane Dimethanol diacrylate that uses together with phenoxy resin use Tricyclodecane Dimethanol diacrylate as radical polymerization condensation material.Particularly, the phenoxy resin with very high acid value used together with radical polymerization condensation material tends to accelerate metal attack.Thus, if there is this anisotropic conductive film constructed for connecting semiconductor device, the less reliable of device.Because phenoxy resin is incompatible with Tricyclodecane Dimethanol diacrylate, use the anisotropic conductive film of these materials can not have high reliability, hardness and the tolerance to shrink/expanded together.
Summary of the invention
For solving the problem, the present inventor have developed a kind of anisotropic conductive film, described anisotropic conductive film comprises polyester urethane resin and Tricyclodecane Dimethanol diacrylate to have high storage modulus simultaneously, thus the height endurability presented pucker & bloat, produce less bubble, even after hot and humid lower standing storage, in cohesive strength and connection, also there is fabulous reliability.
The present invention aims to provide a kind of anisotropic conductive film, and described anisotropic conductive film comprises polyester urethane resin and Tricyclodecane Dimethanol diacrylate to have hardness simultaneously, thus 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, thus not only suppress the initial generation of the bubble at film adhering zone, and the bubble area after hot and humid lower standing storage is suppressed to increase.
The present invention also aims to provide a kind of anisotropic conductive film presenting fabulous reliability in cohesive strength and hardness.
The present invention relates to a kind of anisotropic conductive film simultaneously comprising polyester urethane resin and Tricyclodecane Dimethanol diacrylate.
According to an aspect of the present invention, provide a kind of anisotropic conductive film, described anisotropic conductive film comprises:
A) adhesive composition of polyester urethane resin is comprised;
B) the radical polymerization condensation material of Tricyclodecane Dimethanol diacrylate is comprised;
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 comprising polyester urethane resin of 40 to 80 weight parts;
B) the radical polymerization condensation material comprising Tricyclodecane 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 Tricyclodecane Dimethanol diacrylate can be 5 to 30 weight parts.
According to another aspect of the present invention, described anisotropic conductive film can comprise organic granular or inorganic particle further.
According to another aspect of the present invention, described organic granular can comprise and is selected from by acrylic resin, such as acrylate resin, ethylene-acrylate copolymer and ethylene-acrylic acid copolymer; Olefin resin, such as 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, ethylene-stryene-butylene block-copolymer; Rubber, such as divinyl rubber, nitrile-divinyl rubber, styrene butadiene rubbers and neoprene; Vinylite, such as vinyl butyral resin, vinyl formal resin; Ester resin, such as polyester and cyanate ester resin; Phenoxy resin; Silicon rubber; With the particle in the group of urethane resin composition.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 has the storage modulus of 100MPa or higher after solidification 90% or more at 40 DEG C.
According to another aspect of the present invention, suppress rear and after 85 DEG C and 85%RH store 500 hours interelectrode spatial area based on final, described anisotropic conductive film can have the bubble area of 20% or lower.
According to another aspect of the present invention, described anisotropic conductive film can have a cohesive strength of 500gf/cm or higher after final compacting after 85 DEG C 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 Tricyclodecane Dimethanol diacrylate, and wherein, described anisotropic conductive film has:
A) in the storage modulus of the 100MPa or higher of 40 DEG C; With
B) the interelectrode spatial area after final compacting and after 85 DEG C and 85%RH store 500 hours 20% or lower bubble area.
According to a further aspect of the invention, provide a kind of semiconductor device, described semiconductor device comprises: circuit board and semi-conductor chip, and wherein said semiconductor device is connected by described anisotropic conductive film.
As mentioned above, comprise polyester urethane resin and Tricyclodecane Dimethanol diacrylate to have high storage modulus according to anisotropic conductive film of the present invention simultaneously, thus the height endurability presented pucker & bloat, produce less bubble, even and if also there is fabulous reliability in cohesive strength and connection after hot and humid lower standing storage.
Particularly described anisotropic conductive film comprises polyester urethane resin and Tricyclodecane Dimethanol diacrylate to have hardness, thus controls the change that volume is heated.
In addition, the pucker & bloat of described anisotropic conductive film to heat has height endurability, thus not only suppresses the initial generation of the bubble at film adhering zone, and suppresses the bubble area after hot and humid lower standing storage to increase.
In addition, described anisotropic conductive film presents fabulous reliability in cohesive strength and hardness.
Embodiment
To describe illustrative embodiments of the present invention in detail now.The details that it will be apparent to those skilled in the art will be omitted herein.
According to an aspect of the present invention, provide a kind of anisotropic conductive film, described anisotropic conductive film comprises:
A) adhesive composition of polyester urethane resin is comprised;
B) the radical polymerization condensation material of Tricyclodecane Dimethanol diacrylate is comprised;
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 obtains by the reaction of polyester polyol and vulcabond.
Described polyester polyol refers to the polymkeric substance with multiple ester group and multiple hydroxyl.Described polyester polyol obtains 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.These aromatics of preferred use or aliphatic dicarboxylic acid.
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-trimethylammoniums-1,3-pentanediol, 1,4 cyclohexane dimethanol etc.These glycol of preferred 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 diisocyanates etc.These aromatics of preferred use, alicyclic or aliphatic vulcabond.
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, preferably 15 to 40 weight parts.Within the scope of this, maintain the balance between storage modulus and cohesive strength, thus this film can obtain solid performance and fabulous cohesive strength.
Be not specifically limited about the adhesive resin used together with polyester urethane resin in the present invention, and any resin conventional in this area can be used.The example of adhesive resin can comprise acrylic resin, urethane resin, paracril (NBR) resin etc.
acrylic resin
Acrylic resin available in the present invention obtains by Acrylic Acid Monomer and/or with being polymerized of the polymerisable monomer of Acrylic Acid Monomer.Such as, acrylic resin is selected from least one monomer preparation in group be made up of the Acrylic Acid Monomer of (methyl) acrylate of the alkyl with C2 to C10, (methyl) vinylformic acid, vinyl-acetic ester and modification thereof by polymerization.Polymerization process is without concrete restriction.
urethane resin
Urethane resin available in the present invention is the fluoropolymer resin with urethane bonds, and its polymerization by such as isophorone diisocyanate, polytetramethylene glycol etc. obtains, but is not limited thereto.Described urethane resin can have the weight-average molecular weight of 50000 to 100000g/mol.
nBR resin
NBR resin available in the present invention is the multipolymer obtained by the letex polymerization of acrylonitrile and butadiene.About the amount of acrylonitrile and butadiene in multipolymer without concrete restriction, about polymerization process also without concrete restriction.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, preferably 55 to 80 weight parts.Within the scope of this, maintain the balance between storage modulus and cohesive strength, thus this film can obtain hardness and fabulous cohesive strength.
(b) radical polymerization condensation material
The radical polymerization condensation material used in the present invention comprises Tricyclodecane Dimethanol diacrylate.
In the present invention, based on the anisotropic conductive film of the solid content of 100 weight parts, the amount of Tricyclodecane Dimethanol diacrylate can be 5 to 30 weight parts, preferably 10 to 25 weight parts.
Be not specifically limited about the radical polymerization condensation material used together with Tricyclodecane Dimethanol diacrylate in the present invention, and any radical polymerization condensation material conventional in this area can be used.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 thereto.
acrylate or methacrylic ester
Acrylate available in the present invention or the example of methacrylic ester can comprise methyl acrylate, ethyl propenoate, isopropyl acrylate, isobutyl acrylate, glycol diacrylate, diethylene glycol diacrylate, Viscoat 295, tetramethylol methane tetraacrylate, 2-hydroxyl-1, 3-bis-acryloxy propane, 2, two [4-(acryloxy polymethoxy) phenyl] propane of 2-, 2, two [4-(acryloxy polyethoxye) phenyl] propane of 2-, dicyclopentenyl acrylate, three ring decyl acrylate, three (acryloyl-oxyethyl) 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 thereto.These acrylate or methacrylic ester can their two or more uses alone or in combination.
maleimide
Maleimide compound available in the present invention can comprise the compound of at least two dimaleoyl iminos, such as 1-methyl-2,4-bismaleimides benzene, N, N'-meta-phenylene bismaleimide, N, N'-TOPOT 2,2′ p phenylenebis maleimide, tolylene bismaleimides between N, 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-(4-maleimidephenoxy) phenyl] propane of 2,2-, two [3-sec-butyl-4-8-(4-maleimidephenoxy) phenyl] propane of 2,2-, two [4-(4-maleimidephenoxy) phenyl] decane of 1,1-, 4,4'-cyclohexylidene-bis-[1-(4-maleimidephenoxy)-2-cyclohexyl] benzene, 2,2-pair [4-(4-maleimidephenoxy) phenyl) HFC-236fa etc., but be not limited thereto.These maleimide compounds can their two or more uses alone or in combination.
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, preferably 10 to 40 weight parts.If the amount of radical polymerization compound is less than 5 weight parts, owing to finally suppressing the minimizing of after fixing density, reliability and overall flow deterioration.As a result, the contact between conductive particle and circuit substrate can die down when bonding, and connection resistance can increase, thus reduces connection reliability.And if content is greater than 50 weight parts, be difficult to form anisotropic conductive film, and bond properties may deterioration.
(c) curing initiator
Be not specifically limited about the curing initiator used in the present invention, but any curing initiator conventional in this area can be comprised.Available curing initiator example can comprise peroxide initiator and azo initiator, but is not limited thereto.
peroxide initiator
In the present invention, the example of spendable peroxide initiator can comprise benzoyl peroxide, lauryl peroxide, tert-butylperoxylaurate, 1,1,3,3-tetramethyl butyl peroxy pivalate, cumyl hydroperoxide etc., but is not limited thereto.
azo-initiator
In the present invention, the example of spendable azo-initiator can comprise 2, two (the 4-methoxyl group-2 of 2'-azo, 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 thereto.
Based on the anisotropic conductive film of the solid content of 100 weight parts, the amount of the curing initiator used in the present invention is 0.1 to 10 weight part.
(d) conductive particle
The conductive particle used 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, such as Au, Ag, Ni, Cu and solder grain; Carbon granule; Metal-coated resin particle, such as polyethylene particle, polypropylene GRANULES, polyester granulate, granules of polystyrene, granule of polyvinyl alcohol and they scribble the modified resin particles thereof of Au, Ag, Ni etc.; And conductive particle scribbles insulated particle further.
The size of conductive particle can be determined in the scope of 2 to 30 μm according to the circuit spacing that will use and object.
Based on the anisotropic conductive film of the solid content of 100 weight parts, the amount of the conductive particle used in the present invention can be 0.1 to 10 weight part.Within the scope of this, connection and/or insulation defect can be prevented to obtain fabulous switching performance.
Another aspect of the present invention provides the anisotropic conductive film comprising organic granular or inorganic particle except component (a) and (b), (c) and (d) further.
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, such as acrylate resin, ethylene-acrylate copolymer and ethylene-acrylic acid copolymer; Olefin resin, such as 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, ethylene-stryene-butylene block-copolymer; Rubber, such as divinyl rubber, nitrile-divinyl rubber, styrene butadiene rubbers and and neoprene; Vinylite, such as vinyl butyral resin and vinyl formal resin; Ester resin, such as 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 thereto.
Described organic granular or inorganic particle can have 0.1 to 10 μm, preferably the size of 0.1 to 5 μm.Within the scope of this, particle can disperse suitably, and can prevent the film adhesive power owing to reducing and cause the deterioration in pre-bonded 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.Within the scope of this, this particle can provide sufficient effect, and prevents the excessive increase of film toughness, thus prevents adhesive power from reducing.
According to another aspect of the present invention, the anisotropic conductive film at 40 DEG C with the storage modulus of 100MPa or higher is provided.
Storage modulus is measured by any method usually used in this field, is not specifically limited.Such as, the evaluation of high energy storage mould is as follows: the sheet (such as 5mm is wide and 30mm long) anisotropic conductive film being cut into suitable size, then Dynamic Mechanical Analyzer (DMA is used, Q800, TA Instruments) with the frequency of 10Hz, measure storage modulus from-30 DEG C to 170 DEG C with the intensification of 4 DEG C/min.
Anisotropic conductive film according to the present invention can have the storage modulus of 100MPa or higher at 40 DEG C.Within the scope of this, film has sufficient hardness and to be heated change to control volume.
Another aspect of the present invention provides anisotropic conductive film, and suppress rear and after 85 DEG C and 85%RH store 500 hours interelectrode spatial area based on final, described anisotropic conductive film can have the bubble area of 20% or lower.
Above-mentioned final compacting can carry out 4 seconds under 185 DEG C and 4.5MPa.
The physicals of film after 85 DEG C and 85%RH store 500 hours can be measured for reliability evaluation.
Interelectrode space is the interelectrode gap being filled with anisotropic conductive film in compacting.
Bubble area is measured by any method usually used in this field, and is not specifically limited.Such as, bubble area, by observing with microscope (or photography) the interelectrode space being filled with film, then calculates bubble area with image analyzer or mesh coordinate and calculates.
If anisotropic conductive film has the bubble area being greater than 20%, the semiconductor device using film to connect can not use for a long time, and has short life.
Another aspect of the present invention to provide after final compacting and can have the anisotropic conductive film of the cohesive strength of 500gf/cm or higher after 85 DEG C and 85%RH stores 500 hours.
Final compacting can be carried out under condition same as described above.
Cohesive strength by any method evaluation usually used in this field, and limits without concrete.
Such as, cohesive strength can be suppressed and be measured with the peeling rate of the peel angle of 90 ° and 50mm/min by peel strength tester (H5KT, Tinius Olsen) afterwards for 4 seconds under 185 ° of C and 4.5MPa.
If anisotropic conductive film has the cohesive strength being less than 500gf/cm, the semiconductor device using this film to connect can not use for a long time, and has short life.
The method forming 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.Such as, anisotropic conductive film obtains by following process: dissolve in organic solvent and liquified binder resin, add remaining ingredient to it, and stirred solution certain period, by this solution coat to release film to suitable thickness, such as 10 to 50 μm, and drying solution is with volatile organic solvent.
Another aspect of the present invention provides the semiconductor device connected 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 fixing semi-conductor chip on the membrane.
The circuit board used in the present invention and semi-conductor chip are not specifically limited, and can comprise any circuit board generally known in the art and semi-conductor chip.
The method manufacturing semiconductor device of the present invention is not specifically limited, and can comprise any method generally known in the art.
Below, with reference to embodiment, comparative example and experimental example, the present invention is described in detail.But provide these embodiments only for illustration of object, and should not be construed as the scope limiting each embodiment.
Embodiment 1: the preparation comprising the anisotropic conductive film of polyester urethane resin and Tricyclodecane 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 (NPC8750, NanuxInc.) of 30 weight parts; With the acrylic resin (AOF-7003, Aekyung Chemical) of 27 weight parts,
B) as radical polymerization condensation material, the Tricyclodecane Dimethanol diacrylate of 14 weight parts; The urethane acrylate (NPC7007, Nanux Inc.) of 12 weight parts; The 2-methyacryloxyethyl phosphoric 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 (Sekisui Chemical) of 3 μm of 3 weight parts.
Said mixture solution is stirred 60 minutes under the speed not pulverizing conductive particle and room temperature (25 ° of C).Use casting cutter, this solution is formed in the polyethylene based film through the process of silicone release surface the film of 16 μm of thickness.By this film 60 ° of C dryings 5 minutes.
Embodiment 2: not only comprise polyester urethane resin and Tricyclodecane Dimethanol diacrylate, also comprise the preparation of the anisotropic conductive film of organic granular
Manufacture anisotropic conductive film by the method identical with embodiment 1, difference is the polyester urethane resin of use 23 weight part and the urethane pearl (MM-101-MS, Negami) of 5 weight parts.
Embodiment 3: not only comprise polyester urethane resin and Tricyclodecane Dimethanol diacrylate, also comprise the preparation of the anisotropic conductive film of organic granular
Manufacture anisotropic conductive film by the method identical with embodiment 1, difference is the polyester urethane resin of use 15 weight part; The NBR resin (N-34, Nippon Zeon) of 5 weight parts; The acrylic resin of 20 weight parts; The Tricyclodecane Dimethanol diacrylate of 25 weight parts; The 2-hydroxyethylisocyanurate 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: the preparation comprising the anisotropic conductive film of polyester urethane resin and Tricyclodecane Dimethanol diacrylate
Manufacture anisotropic conductive film by the method identical with embodiment 3, difference is the polyester urethane resin of use 40 weight part; The Tricyclodecane Dimethanol diacrylate of 10 weight parts; The urethane acrylate of 5 weight parts; The 2-hydroxyethylisocyanurate diacrylate of 13 weight parts; With the conductive particle of 3 weight parts, and do not add urethane pearl.
Comparative example 1: comprise polyester urethane resin but do not comprise the preparation of the anisotropic conductive film of Tricyclodecane Dimethanol diacrylate
Manufacture anisotropic conductive film by the method identical with embodiment 1, difference is that use three (2-hydroxyethyl) isocyanuric acid ester diacrylate replaces Tricyclodecane Dimethanol diacrylate.
Comparative example 2: comprise Tricyclodecane Dimethanol diacrylate but do not comprise the preparation of the anisotropic conductive film of polyester urethane resin
Manufacture anisotropic conductive film by the method identical with embodiment 1, difference is to use polyatomic alcohol polyurethane resin (NPC7007T, Nanux Inc.) to replace polyester urethane resin.
Comparative example 3: the preparation not comprising the anisotropic conductive film of polyester urethane resin and Tricyclodecane Dimethanol diacrylate
Anisotropic conductive film is manufactured by 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 Tricyclodecane Dimethanol diacrylate.
Composition according to the anisotropic conductive film of embodiment 1 to 4 and comparative example 1 to 3 is listed in table 1 and table 2 with weight part.
Table 1
Table 2
Experimental example 1: the measurement of storage modulus
Following evaluate root according to each anisotropic conductive film of embodiment 1 to 4 and comparative example 1 to 3 the storage modulus of 40 DEG C.
Often kind of anisotropic conductive film is formed the lamination with 200 μm of thickness, be cut into the sheet (such as 5mm is wide and 30mm long) of suitable size, then place 3 hours in the baking box of 200 DEG C.Then DMA(Q800 is used, TA Instruments) with the frequency of 10Hz, the storage modulus measuring sample after all solidstate from-30 DEG C to 170 DEG C with the intensification of 4 DEG C/min.
Experimental example 2: the measurement of the cohesive strength after initial bond strength and reliability detect
To pre-bonded 1 second under the observed temperature of 70 DEG C be passed through according to often kind of anisotropic conductive film of embodiment 1 to 4 and comparative example 1 to 3 and suppress 4 seconds under 185 DEG C and 4.5MPa and be connected to metal electrode glass (Mo/Al/Mo structure, Samsung Electronics) and film on chip (COF, Samsung Electronics), thus 10 samples of preparation often kind of film.
With peel strength tester (H5KT, Tinius Olsen) with the cohesive strength of the peeling rate of the peel angle of 90 ° and 50mm/min in assess sample, and calculating mean value.
10 of often kind of film samples (are stored 500 hours at 85 DEG C and 85%RH) under hot and humid and carries out reliability detection, the cohesive strength after then detecting by method evaluation reliability same as described above, and calculating mean value.
Experimental example 3: the measurement of the contact resistance after initial contact resistance and reliability testing
Be placed in room temperature (25 DEG C) lower 1 hour by according to often kind of anisotropic conductive film of embodiment 1 to 4 and comparative example 1 to 3, then by pre-bonded 1 second under the observed temperature of 70 DEG C and under 185 DEG C and 4.5MPa compacting 4 seconds and be connected to
the 0.5t pattern-free glass of tin indium oxide (ITO) the layer coating of thickness being formed four point probe can mapping case and the COF(Samsung Electronics that obtains), thus 10 samples of preparation often kind of film.With the initial contact resistance (according to ASTM F43-64T) of four probe method assess sample, and calculating mean value.
By 10 of often kind of film samples under hot and humid, store 500 hours at 85 DEG C and 85%RH and carry out reliability detection, then evaluate 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
Be placed in room temperature (25 DEG C) lower 1 hour by according to often kind of anisotropic conductive film of embodiment 1 to 4 and comparative example 1 to 3, be then incorporated in compacting 4 seconds under 185 DEG C and 4.5MPa by pre-bonding under the observed temperature of 70 DEG C and be connected to
the 0.5t pattern-free glass of tin indium oxide (ITO) the layer coating of thickness being formed four point probe can mapping case and the COF(Samsung Electronics that obtains), thus 10 samples of preparation often kind of film.With opticmicroscope take pictures each sample 10 points after, by the bubble area in the space between image analyzer potential electrode, and calculating mean value.
By 10 of often kind of film samples under hot and humid, store under 85 DEG C and 85%RH and carry out reliability testing in 500 hours, by the bubble area after method evaluation reliability testing same as described above, and calculating mean value.
The result of experimental example 1 to 4 is shown in Table 3.
Table 3
As shown in table 3, with according to the anisotropic conductive film not containing polyester urethane resin and Tricyclodecane Dimethanol diacrylate of comparative example 3 with according to comparative example 1 with 2 the anisotropic conductive film containing polyester urethane resin or Tricyclodecane Dimethanol diacrylate compare, anisotropic conductive film according to comprising polyester urethane resin and Tricyclodecane Dimethanol diacrylate while embodiment 1 ~ 4 has fabulous physical properties in every respect, such as, cohesive strength, contact resistance and bubble area after initial bond strength, reliability testing.
Especially the anisotropic conductive film simultaneously comprising polyester urethane resin and Tricyclodecane Dimethanol diacrylate presents obviously high cohesive strength after reliability detects, and there is the bubble area of 20% or lower after reliability testing, based on this, think and maintain reliability in life-time service.
Compare embodiment 1 and embodiment 2, when organic granular adds fashionable with polyester urethane resin further together with Tricyclodecane Dimethanol diacrylate, cohesive strength and the suppression to bubble generation even more strengthen.This is that organic granular owing to being considered to relieve stresses and/or inorganic particle work in the pucker & bloat of anisotropic conductive film.
Although provide some embodiments in specification sheets of the present invention, but to it will be apparent to one skilled in the art that, each embodiment only proposes by way of illustration, and can carry out various amendment, change, replacement and equivalent implementations and not deviate from the spirit and scope of the present invention.Scope of the present invention should only be defined by the appended claims.
Claims (12)
1. an anisotropic conductive film, wherein, based on the described anisotropic conductive film of the solid content of 100 weight parts, described anisotropic conductive film comprises:
A) adhesive composition comprising polyester urethane resin of 40 to 80 weight parts;
B) the radical polymerization condensation material comprising Tricyclodecane 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,
Wherein, the amount of described polyester urethane resin is 5 to 40 weight parts, and the amount of described Tricyclodecane Dimethanol diacrylate is 5 to 30 weight parts.
2. anisotropic conductive film as claimed in claim 1, wherein, described anisotropic conductive film has the storage modulus of 100 MPa or higher at 40 DEG C.
3. anisotropic conductive film as claimed in claim 1, wherein, suppress rear and after 85 DEG C and 85%RH store 500 hours interelectrode spatial area based on final, described anisotropic conductive film has the bubble area of 20% or lower.
4. an anisotropic conductive film, described anisotropic conductive film comprises
A) adhesive composition comprising the polyester urethane resin of 5 to 40 weight parts of 40 to 80 weight parts;
B) the radical polymerization condensation material comprising the Tricyclodecane Dimethanol diacrylate of 5 to 30 weight parts 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;
Wherein, described anisotropic conductive film has:
A) in the storage modulus of the 100MPa or higher of 40 DEG C; With
B) based on 20% or less bubble area of the interelectrode spatial area after final compacting and after 85 DEG C and 85%RH store 500 hours.
5. the anisotropic conductive film as described in claim 1 or 4, wherein, described anisotropic conductive film comprises organic granular or inorganic particle further.
6. anisotropic conductive film as claimed in claim 5, wherein, described organic granular comprises the particle of at least one in the group being selected from and being made up of the styrene ethylene butadiene-styrene block copolymer of acrylic resin, olefin resin, acrylonitrile butadiene copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, carboxylation, ethylene-stryene-butylene block-copolymer, neoprene, silicon rubber, Vinylite, phenoxy resin, urethane resin, vibrin and cyanate ester resin.
7. anisotropic conductive film as claimed in claim 6, wherein, described acrylic resin is acrylate resin.
8. anisotropic conductive film as claimed in claim 6, wherein, described olefin resin is selected from ethenoid resin or butadiene resin.
9. anisotropic conductive film as claimed in claim 5, wherein, described inorganic particle is silica dioxide granule.
10. anisotropic conductive film as claimed in claim 5, 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.
11. anisotropic conductive film as described in claim 1 or 4, wherein, described anisotropic conductive film is after final compacting and after 85 DEG C and 85%RH store 500 hours, have the cohesive strength of 500gf/cm or higher.
12. 1 kinds of semiconductor devices, described semiconductor device comprises:
A) circuit board;
B) anisotropic conductive film described in any one in the claim 1 to 11 of the chip fixation side of described circuit board is attached to; With
C) fixing semi-conductor chip on the membrane.
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| KR1020110136328A KR101355854B1 (en) | 2011-12-16 | 2011-12-16 | Anisotropic conductive film |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7348079B2 (en) * | 2002-12-03 | 2008-03-25 | Fujifilm Corporation | Magnetic recording medium |
| CN101241207A (en) * | 2008-03-13 | 2008-08-13 | 长兴光学材料（苏州）有限公司 | Reflecting film |
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| JP2002184487A (en) * | 2000-12-15 | 2002-06-28 | Sony Chem Corp | Anisotropic conductive adhesive |
| US20070116961A1 (en) * | 2005-11-23 | 2007-05-24 | 3M Innovative Properties Company | Anisotropic conductive adhesive compositions |
| KR101289511B1 (en) * | 2006-10-27 | 2013-07-24 | 주식회사 씨씨텍 | UV cured adhesive, keypad structure for mobole phone and method for bonding key to keypad |
| TWI354807B (en) * | 2007-06-12 | 2011-12-21 | Eternal Chemical Co Ltd | Optical film |
| TW200937043A (en) * | 2008-02-29 | 2009-09-01 | Eternal Chemical Co Ltd | Brightness enhancement reflective film |
| CN102171306B (en) * | 2008-09-30 | 2014-08-13 | 迪睿合电子材料有限公司 | Anisotropic electroconductive adhesive and method for manufacturing connected structure using the anisotropic electroconductive adhesive |
| KR101246683B1 (en) * | 2009-12-14 | 2013-03-21 | 제일모직주식회사 | Composition for anisotropic conductive film having improved compatibility and film formed therefrom |
| KR101202045B1 (en) * | 2009-12-24 | 2012-11-16 | 제일모직주식회사 | Low temperature and fast curable anisotropic conductive film composition, and low temperature and fast curable anisotropic conductive film using the same |
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| US7348079B2 (en) * | 2002-12-03 | 2008-03-25 | Fujifilm Corporation | Magnetic recording medium |
| CN101241207A (en) * | 2008-03-13 | 2008-08-13 | 长兴光学材料（苏州）有限公司 | Reflecting film |
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| KR101355854B1 (en) | 2014-01-29 |
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