KR101293788B1 - Composition For Anisotropic Conductive Film And Anisotropic Conductive Film Using the Same - Google Patents
Composition For Anisotropic Conductive Film And Anisotropic Conductive Film Using the Same Download PDFInfo
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Abstract
The composition for anisotropic conductive films of the present invention has an elasticity modulus of 4000 MPa to 10000 MPa at 50 ° C. after curing, and a glass transition temperature (Tg) of 110 ° C. to 150 ° C. after curing. The composition for the anisotropic conductive film may withstand the stress generated at both ends of the connection substrate during the compression by heat and pressure.
Description
The present invention relates to a composition for an anisotropic conductive film and an anisotropic conductive film using the same. More specifically, the present invention provides a composition for anisotropic conductive films that can withstand the stress generated at both ends of the connection substrate when the elasticity and glass transition temperature of the anisotropic conductive film after curing to a specific range and the pressure caused by heat and pressure and anisotropic using the same It relates to a conductive film.
Anisotropic conductive films are used to electrically connect small electrical components such as semiconductor devices to substrates or to electrically connect between substrates in the manufacture of electronic products such as liquid crystal displays, personal computers, portable communication devices, and the like.
In recent years, as the panel becomes larger and the wiring becomes finer, the connection board becomes thinner and longer, which causes severe shrinkage / expansion of the connection board during crimping due to heat and pressure. The stress becomes large. As the stress increases in this way, internal breakage occurs, which causes adhesion failure.
FIG. 1 is a photograph showing that voids are formed due to internal breakdown caused by stress generated by shrinkage / expansion of a connection substrate during compression using heat and pressure using a conventional adhesive composition.
JP3342703 discloses an anisotropic conductive adhesive material having a modulus of elasticity of 100 to 2000 MPa at 40 ° C. after adhesion in a heat adhesive adhesive that electrically connects a circuit electrode by heat and pressure. However, the patent is also insufficient to solve the problem of poor adhesion due to the internal breakdown caused by stress during the compression by heat and pressure.
In order not to be destroyed by the stress caused by shrinkage / expansion of the connecting substrate during the compression by heat and pressure, the elastic modulus of the anisotropic conductive film after curing should be high, and the glass transition temperature must be high so that the stress expression by the elastic modulus of the anisotropic conductive film after curing This is facilitated. This is because the stress must be greater than the stress due to shrinkage / expansion of the connecting substrate so that internal breakage does not occur and adhesion can be maintained.
In general, the stress is very small because the elastic modulus is low in the rubbery state above the glass transition temperature, but the stress increases as the elastic modulus increases below the glass transition temperature. If the glass transition temperature of the composition is high, but the elastic modulus is low after curing, a problem may occur because the stress is small, and if the glass transition temperature is low, the fracture occurs before the stress due to the increase of the elastic modulus is expressed. The problem cannot be solved.
In addition, when the elastic modulus is high, it is difficult to express the adhesive force due to the ACF characteristics, and thus, it is necessary to adjust the elastic modulus after curing. Accordingly, in order to be able to withstand the stress generated at both ends of the connecting substrate during the compression by heat and pressure, and to develop adhesive force, an anisotropic conductive film satisfying the two characteristics is required.
An object of the present invention is to provide an anisotropic conductive film composition and an anisotropic conductive film using the same that can withstand the stress generated at both ends of the connection substrate when the compression by heat and pressure.
Another object of the present invention is to provide an anisotropic conductive film composition having excellent connection reliability and an anisotropic conductive film using the same.
One aspect of the present invention relates to a composition for an anisotropic conductive film. The composition has an elastic modulus of 4000 MPa to 10000 MPa at 50 ° C. after curing, and a glass transition temperature (Tg) of 110 ° C. to 150 ° C. after curing.
In an embodiment, the composition for the anisotropic conductive film may include an acrylate-modified urethane resin, a diene rubber resin, an elastic reinforcing resin, a radical polymerizable material, a polymerization initiator, and conductive particles.
In an embodiment, the composition for the anisotropic conductive film is 30 to 70% by weight of the acrylate-modified urethane resin, 5 to 25% by weight of the diene rubber resin, 5 to 40% by weight of the elastic reinforcing resin, 10 to 30% by weight of the radical polymerizable material , 1 to 5% by weight of a polymerization initiator, and 1 to 10% by weight of conductive particles.
The elastic reinforcing resin may be at least one of cellulose resin and styrene resin.
In one embodiment, the elastic reinforcing resin may include 20 to 50% by weight of cellulose-based resin and 50 to 80% by weight of styrene-based resin.
In another embodiment the composition may further comprise more than 0% to 15% by weight of the acrylic copolymer or styrene resin.
The acrylate-modified urethane resin may have a hydroxyl group / isocyanate group (NCO) molar ratio of 0.5 to 1.0 and a polyol content of up to 70%.
In a specific embodiment, the diene rubber resin is acrylonitrile-butadiene copolymer, styrene butadiene copolymer, (meth) acrylate-butadiene copolymer, (meth) acrylate-acrylonitrile-butadiene-styrene copolymer, carboxyl group modification Acrylonitrile-butadiene rubber and the like can be used.
The cellulose-based resin may have a weight average molecular weight of 12,000 to 80,000 g / mol.
The radically polymerizable substance may be urethane-based (meth) acrylate, epoxy-based (meth) acrylate, polyester-based (meth) acrylate, fluorine-based (meth) acrylate, fluorene-based (meth) acrylate, or silicone-based (meth) Acrylate, phosphate (meth) acrylate, maleimide modified (meth) acrylate, acrylate (methacrylate), (meth) acrylate monomer and the like can be used.
The polymerization initiator may be used ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, peroxy carbonate and the like.
The conductive particles may be metal particles including at least one of Au, Ag, Ni, Cu, Pd, Al, Cr, Sn, Ti, and Pb; Carbon particles; Particles coated with the metals of particles comprising resins containing at least one of benzoguanamine, polyolefins, polyesters, polystyrenes and polyvinyl alcohols or modified resins thereof; And particles insulated from the coated particles may be used.
The styrene resin may have a weight average molecular weight of 90,000 to 150,000 g / mol.
The acrylic copolymer may have a weight average molecular weight of 90,000 to 120,000 g / mol, and a glass transition temperature of 50 ° C. to 120 ° C.
The acrylic copolymer may have an acid value of 1 to 100 mg KOH / g.
The present invention also provides an anisotropic conductive film formed by the composition.
The present invention provides an anisotropic conductive film composition and an anisotropic conductive film composition using the same, which can express adhesive force while being able to withstand the stresses generated at both ends of the connecting substrate when pressed by heat and pressure. Have
1 is a photograph showing that voids are formed due to internal breakdown using a conventional adhesive composition.
2 is a photograph showing the adhesion state in the Examples and Comparative Examples.
Contents mentioned below are based on solids, unless otherwise specified. The acrylic resin includes both acrylate and methacrylate resins.
The composition for anisotropic conductive films of the present invention may have an elastic modulus of 4000 MPa to 10000 MPa, preferably 4500 MPa to 8500 MPa, and more preferably 5000 MPa to 8000 MPa at 50 ° C. after curing. In the elastic modulus range, it is not destroyed by stress caused by shrinkage / expansion of the connecting substrate during compression by heat and pressure.
In addition, the composition is characterized in that the glass transition temperature (Tg) after curing is 110 ℃ ~ 150 ℃, preferably 115 ℃ ~ 145 ℃, more preferably 120 ℃ ~ 140 ℃. After curing in the above range, it becomes easy to express stress by the elastic modulus of the anisotropic conductive film.
The composition for anisotropic conductive films of the present invention having such characteristics may include an acrylate-modified urethane resin, a diene rubber resin, a styrene resin, a cellulose resin, and conductive particles.
In another embodiment, the composition for the anisotropic conductive film may include an acrylate-modified urethane resin, a diene rubber resin, a styrene resin, a cellulose resin, a radical polymerizable material, a polymerization initiator, and conductive particles.
In another embodiment, the composition for the anisotropic conductive film may include an acrylate-modified urethane resin, a diene rubber resin, an acrylic copolymer, a styrene resin, a cellulose resin, a radical polymerizable material, a polymerization initiator, and conductive particles. .
Acrylate Modified urethane resin
The acrylate-modified urethane resin has a low glass transition temperature and therefore has excellent flowability and high adhesiveness due to urethane groups in the molecular chain. In particular, when used in a conductive film, the curing performance can be improved to lower the temperature of the connection process.
The acrylate modified urethane resin comprises a component of a diisocyanate, a polyol, a diol and an acrylate. The diisocyanate may be aromatic, aliphatic, alicyclic diisocyanate, combinations thereof, or the like. The polyol has two or more hydroxyl groups in the molecular chain Polyester polyols, polyether polyols, polycarbonate polyols, and the like. Diols include 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, Glycol, tetraethylene glycol, and the like. As the acrylate, hydroxy acrylate or amine acrylate can be used.
The acrylate-modified urethane resin including the above four components has a hydroxy group (OH) / diisocyanate group (NCO) molar ratio of 0.5 to 1.0, and the content of polyol is 70% of the three components except for acrylate. A polyaddition polymerization reaction is carried out so that the hydroxy acrylate or amine acrylate is reacted with any one of diisocyanate groups which are terminal functional groups of the urethane synthesized by the polyaddition polymerization reaction in a molar ratio of 0.1 to 2.1. do. In addition, the residual isocyanate groups can be reacted with alcohols to produce the final acrylate modified urethane resin. At this time, in the middle polymerization step, a known central polymerization method may be used. In the above step, the reaction temperature may be 90 ° C, the reaction pressure may be 1 atm, the time may be 5 hours, and the catalyst may be prepared using a tin-based catalyst, but is not limited thereto.
The acrylate modified urethane resin prepared as described above has a weight average molecular weight of 1,000 to 50,000 g / mol, and at least one end functional group may be composed of acrylate. At least one of the two glass transition temperatures (Tg) of the acrylate modified urethane resin may be 0 ° C or more.
That is, the acrylate-modified urethane resin has a single glass transition temperature of 0 ° C or higher or a glass transition temperature of 0 ° C or higher at 0 ° C or higher by phase mixing of a soft segment polyol and a hard segment diisocyanate The curing reaction proceeds along with the acrylate groups of the cured portion through the acrylate groups present in the terminal functional groups and also acts as a curing portion, Reliability is shown.
The acrylate-modified urethane resin of the present invention may be included in 30 to 70% by weight, preferably 40 to 60% by weight of the composition for the anisotropic conductive film. It is possible to implement desirable film properties and increase reliability within the above range.
Diene rubber resin
The diene rubber resin is acrylonitrile-butadiene copolymer, styrene butadiene copolymer, (meth) acrylate-butadiene copolymer, (meth) acrylate-acrylonitrile-butadiene-styrene copolymer, carboxyl group-modified acrylonitrile Butadiene rubber or the like may be used, but is not necessarily limited thereto. These may be used alone or in combination of two or more. Among these, carboxyl group-modified acrylonitrile-butadiene rubbers are preferred which increase the stability of the resin mixture, improve the adhesive strength by increasing the polarity, and improve physical properties such as moisture resistance and heat resistance.
In the specific examples, a carboxyl group-modified acrylonitrile butadiene rubber having a weight average molecular weight of 2,000 to 200,000 g / mol, and preferably 3,000 to 200,000 g / mol may be used. At this time, the acrylonitrile content may be 10 to 60% by weight, preferably 20 to 50% by weight, and the carboxyl group content may be 1 to 20% by weight.
The diene rubber resin may be included in 5 to 25% by weight, preferably 10 to 20% by weight of the composition. In the above range, the composition is not phase separated and the connection reliability is good.
Elastic reinforced resin
As the elastic reinforcement resin One or more types of styrene resin and cellulose resin can be used. In one embodiment, a styrene resin may be used, and in another embodiment, a cellulose resin may be applied. In another embodiment, styrene resin and cellulose resin may be applied together.
Preferably, 20 to 50% by weight of the cellulose resin and 50 to 80% by weight of the styrene resin may be mixed and applied. In the above range, there is an advantage in that voids are not formed by maintaining stress generated by shrinkage / expansion when pressed.
As the styrene-based resin, polystyrene (GPPS) and styrene-based resin may be preferably applied.
The styrene resin may have a weight average molecular weight of 90,000 to 150,000 g / mol, preferably 100,000 to 135,000 g / mol. When the weight average molecular weight of the styrene-based resin is within the above range, the contact is excellent when ACF compression is not caused to cause a poor contact.
The cellulose resin is Cellulose-acetate-butylate resins, cellulose-acetate resins, cellulose-acetate-propionate resins, and the like.
The cellulose-based resin may have a weight average molecular weight of 12,000 to 80,000 g / mol. Preferably from 20,000 to 75,000 g / mol. When the weight average molecular weight of the cellulose-based resin is in the above range, the crude liquid stability is excellent, and it is easy to adhere to the contact substrate during compression.
The elastic resin may be included in 5 to 40% by weight, preferably 10 to 35% by weight of the composition. In the above composition, the elastic modulus is increased to maintain the stress generated by shrinkage / expansion during press bonding, thereby preventing void formation.
Radical Polymerizable matter
The radically polymerizable material acts as a component of the cured part to perform a radical curing reaction, thereby assuring adhesion and connection reliability between the connection layers.
The radically polymerizable material in the connection material of the present invention is a radically polymerizable material having at least one vinyl group in the molecule, and includes (meth) acrylate oligomer, (meth) acrylate monomer, or a mixture thereof.
(Meth) acrylate oligomer may be used. For example, urethane (meth) acrylate having an average molecular weight in the range of about 1,000 to 100,000, epoxy (meth) acrylate, polyester Based (meth) acrylate, maleimide-modified (meth) acrylate, acrylate (meth) acrylate, Methacrylate) and the like can be used.
Specifically, the urethane-based (meth) acrylate has a structure in which the intermediate structure of the molecule is a polyester polyol, a polyether polyol, a polycarbonate polyol, a polycarprolactone polyol, Propylene oxide ring opening copolymer, polybutadiene diol, polydimethylsiloxane diol, ethylene glycol, propylene glycol, 1, 2-butanediol, 2-ethylhexyl acrylate, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-butanediol, Cyclohexane dimethanol, bisphenol A, hydrogenated bisphenol A, 2,4-toluene diisocyanate, 1,4-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, 3- Examples of the diisocyanate include 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, 1,6-hexane diisocyanate, (1,6-hexanediisocyanate), isophorone diisocyanate, and bisphenol A-propylene oxide-modified diacrylate. Examples of the epoxy (meth) acrylate-based resin include bisphenols such as 2-bromohydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol AD and bisphenol S, (Tetrabromobisphenol A), a nitro group, and the like, which are constituted of a skeleton such as an alkyl group, a cyclohexylphenyl group, a cyclohexylphenyl group, Methacrylate oligomer group can be used. Other examples of the (meth) acrylate oligomer of the present invention include at least two maleimide groups in the molecule such as 1-methyl-2,4-bismaleimide benzene, N, N'-m- Maleimide, N, N'-p-phenylene bismaleimide, N, N'-m-tolylenbismaleimide, N, N'- N, N'-4,4- (3,3'-dimethyldiphenylmethane) bismaleimide, N, N'- N, N'-4,4-diphenylmethane bismaleimide, N, N'-4,4-diphenylpropane bismaleimide, N, N, N'-4,4-diphenyl ether bismaleimide, N, N'-3,3'-diphenylsulfonylbismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl ) Propane, 2,2-bis (3-s-butyl-4-8 (4-maleimidophenoxy) phenyl) propane, 1,1- Phenyl) decane, 4,4'-cyclohexylidene bis (1- (4-maleimidophenoxy) -2-cyclohexylbenzene, 2,2-bis (4- (4-maleimidophenoxy) Hexafluoropropane and the like can be used.
Examples of the (meth) acrylate monomer include (meth) acrylate monomers such as 1,6-hexanediol mono (meth) acrylate, 2-hydroxyethyl (meth) (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- Acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylol ethanediol (Meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (metha) acrylate, dipentaerythritol hexa (metha) acrylate, (Meth) acrylate, glycerin di (meth) acrylate, t-hydroperfuryl (meth) acrylate, iso-decyl (meth) acrylate, 2- (Meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tridecyl Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, t-ethylene glycol di (Meth) acrylate, 3-butylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethoxy type bisphenol-A di (meth) acrylate, cyclohexanedimethanol di t-glycol (Meth) acrylate, 2-methacryloyloxyethyl phosphate, dimethyloltricyclodecane di (meth) acrylate, trimethylolpropane benzoate acrylate, fluorene (meth) acrylate, Methacrylate, and the like.
The radically polymerizable material may be included in 10 to 30% by weight of the connection material composition of the present invention. In the case of the above content, the reliability and the overall flowability after the pressing of the present process are excellent, and the connection resistance is not increased.
Polymerization initiator
The polymerization initiator used in the present invention acts as a curing agent that generates free radicals by heating or light, and organic peroxides can be preferably applied.
The organic peroxide is not particularly limited and various kinds of ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, peroxycarbonate and the like can be used, A plurality of peroxides may be used in combination from the viewpoint of storage stability of the product.
Specific examples include t-butyl peroxylaurate, 1,1,3,3-t-methylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoyl 2-ethylhexanoate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxy T-butyl peroxybenzoate, t-butyl peroxyacetate, dicumyl peroxide, 2,5, -dimethyl-2,5-di (t-butylperoxy) hexane, t-butyl cumyl peroxide, t-hexyl peroxyneodecanoate, t-hexyl peroxy-2-ethyl hexanonate, Butyl peroxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy- Trimethyl hexanoate, t-butyl peroxy pivalate, cumyl Hexanoyl peroxide, hexanoyl peroxide, hexanoyl peroxide, hexanoyl peroxide, oxyethylene decanoate, diisopropylbenzene hydroperoxide, cumene hydroperoxide, isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, , Lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxytoluene, 1,1,3,3-tetramethylbutyl peroxide Di-n-propyl peroxydicarbonate, di-isopropyl peroxycarbonate, bis (4-t-butylcyclohexyl) ) Di (2-ethylhexyl peroxy) dicarbonate, dimethoxybutyl peroxy dicarbonate, di (3-methyl-3-methoxybutyl Peroxy) dicarbonate, 1,1- Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1- (T-butylperoxy) decane, t-butyltrimethylsilyl peroxide, bis (t-butyl) But are not limited to, dimethylsilyl peroxide, t-butyltriallylsilyl peroxide, bis (t-butyl) diallylsilyl peroxide, and tris (t-butyl) arylsilyl peroxide.
Particularly, it is preferable to use the organic peroxide having a half-life temperature of from 5 to 15 hours at 40 to 100 < 0 > C. There is no problem in room temperature storage property in the above range, and it is suitable for fast curing type.
The polymerization initiator may be included in 1 to 5% by weight, preferably 1.5 to 3% by weight of the composition. In the above range, the pressure bonding property and reworkability are excellent, and bubbles are not generated.
Conductive particle
The anisotropic conductive film composition of this invention contains electroconductive particle in order to improve the electroconductive performance at the time of a circuit connection.
Such conductive particles may include metal particles including at least one of Au, Ag, Ni, Cu, Pd, Al, Cr, Sn, Ti, and Pb; Carbon particles; Particles comprising at least one of benzoguanamine, polyethylene, polyester, polystyrene and polyvinyl alcohol, or particles of modified resins thereof, coated with the metal particles; Insulated particles coated with insulating particles; And the like.
The size of the said electroconductive particle can be selected and used according to a use in 0.1-30 micrometers range by the pitch of the circuit applied. Preferably 0.5 to 15 mu m.
In the present invention, the conductive particles are used in the range of 1 to 10% by weight based on the total composition (solid content). Insulation defects and conductivity are not generated in the above range. Preferably 2 to 8% by weight, more preferably 3 to 6% by weight.
Acrylic copolymer
The acrylic copolymer may be optionally contained.
Specific examples include acrylates, acrylic acid esters, methacrylic acid esters, methyl methacrylate, vinyl acetate, methacrylic acid and the like, which are composed of ethyl, methyl, propyl, butyl, hexyl, oxyl, dodecyl, lauryl acrylate, And acrylic copolymers obtained by polymerizing acrylic monomers such as acrylic monomers modified from the acrylic monomers. However, the present invention is not limited thereto. The acrylic copolymer preferably has a glass transition temperature (Tg) of 50 to 120 ° C. When the glass transition temperature of the acrylic copolymer is in the above range, the connection reliability is improved and the film is formed well.
The acrylic copolymer essentially contains a hydroxyl group or a carboxyl group and has an acid value of 1 to 100 mgKOH / g, and may further optionally contain an epoxy group or an alkyl group. Sufficient adhesion can be exhibited within the above range, and connection reliability is excellent.
In particular, the acrylic copolymer preferably has a glass transition temperature of 90 DEG C and an acid value of 3.4 mgKOH / g in order to realize strong film characteristics, and can only serve as a binder. Since the urethane binder has a relatively low glass transition temperature, the acrylic copolymer as a binder to be blended together is advantageous in connection reliability as the glass transition temperature is higher. However, if the glass transition temperature of the acrylic copolymer is excessively high, the film may not be properly formed due to the characteristic of being broken due to the characteristics of acrylic.
The acrylic copolymer is 0 to 15% by weight, preferably 5 to 10% by weight of the total composition.
The composition for anisotropic conductive films of this invention can further mix | blend a coloring pigment, dye, a polymerization inhibitor, a silane coupling agent, etc. in consideration of the property at the time of productization and workability, in order to acquire the target hardened | cured material characteristic. These addition amounts are well known to those skilled in the art.
The anisotropic conductive film of this invention can be manufactured easily using the composition for anisotropic conductive films of this invention, without a special apparatus or installation. For example, after dissolving the composition of the present invention in an organic solvent such as toluene and liquefying, the conductive particles are stirred for a predetermined time within a speed range in which the conductive particles are not crushed, and then applied to a release film at a thickness of 10 to 50 μm, and then The anisotropic conductive film can be obtained by drying for evaporating time and evaporating an organic solvent.
The invention can be better understood by the following examples, which are intended to illustrate the invention and are not intended to limit the scope of protection defined by the appended claims.
Example
The specification of each component used for the following Example and the comparative example is as follows:
* Acrylate modified urethane resin 1: 50% by volume of methyl ethyl ketone as a solvent, polyol content of 60%, hydroxy / isocyanate molar ratio = 0.5 temperature 90 ℃, pressure 1 atmosphere, reaction time 5 hours, dibutyl tin Polyurethane acrylate synthesized by polyaddition polymerization using ilaurate as a catalyst (weight average molecular weight 25,000 g / mol)
* Acrylate modified urethane resin 2: 50% by volume of methyl ethyl ketone as solvent, polyol content of 60%, hydroxy / isocyanate molar ratio = 1, temperature 90 DEG C, pressure 1 atm, reaction time 5 hours, dibutyl tin Polyurethane acrylate synthesized by polyaddition polymerization using ilaurate as a catalyst (weight average molecular weight 28,000 g / mol)
Rubber component: Acrylonitrile butadiene copolymer dissolved in toluene / methyl ethyl ketone at 25% by volume (1072CGX, Zeon Chemical)
* Acrylic copolymer: Acrylic resin having a weight average molecular weight of 100,000 g / mol dissolved in toluene / methyl ethyl ketone at 40% by volume (AOF7003, Aekyung Chemical)
* Styrene-based resin: Acrylonitrile-alpha-methylstyrene resin (AP-TJ, Cheil Industries) with a weight average molecular weight of 133,000 g / mol dissolved in toluene / methyl ethyl ketone at 40% by volume.
* Cellulose resin: Cellulose-acetate-butylate resin having a weight average molecular weight of 57,000 g / mol dissolved in toluene / methyl ethyl ketone at 25% by volume (CAB-500, Eastman)
* Radical polymerizable material: epoxy acrylate polymer (SP1509, Showa polymer)
Organic Peroxide: Benzoyl Peroxide (Hansol)
* Conductive particle: Conductive particle (Ni particle) of 5㎛ size
Example 1 to 6
Each compounding material was added to the content of Table 1 and stirred for 60 minutes at room temperature (25 ℃) within the speed range in which the conductive particles are not crushed. The combination solution was formed into a 35 μm thick film on a silicone release surface treated polyethylene base film using a casting knife, and dried at 60 ° C. for 5 minutes.
Samples for measuring the elastic modulus and Tg were obtained by placing a 35 μm thick anisotropic conductive film on a heat press, placing a 0.2 mm thick silicone rubber thereon, heating / pressing 190 ° C.-30 MPa-15 min to cure the connecting material, and then releasing the release film. Removed and used.
Comparative Example 1-2
Each blending material was carried out in the same manner as in Example except that the contents of Table 2 were added.
How to measure property
(1) Elastic modulus: The elastic modulus of the cured sample was measured by TA's Dynamic Mechanical Analyzer (DMA). The measurement sample was cured by using a hot press, it was confirmed that the cured sufficiently by DSC, the elastic modulus was observed while increasing the temperature from -40 ℃ to 200 ℃ at a rate of 10 ℃ / min.
(2) Glass transition temperature: TA TMA (Thermal Mechanical Analyzer) was used to measure the Tg of the cured sample. The measurement sample was cured by using a hot press, it was confirmed that the cured sufficiently by DSC, Tg was measured while increasing the temperature from -40 ℃ to 200 ℃ at a rate of 10 ℃ / min.
(3) Adhesion and poor adhesion: Each film is printed on PCB (Pitch 200㎛, Terminal width 100㎛, Distance between terminals 100㎛, Terminal height 35㎛) and COF film (Pitch 200㎛, Terminal width 100㎛, between terminals Distance 100 µm and terminal height 8 µm) were used under the following conditions.
1) pressing condition; 70 DEG C, 1 second, 1.0 MPa
2) main compression conditions; Five specimens of 150 ° C., 4 seconds, 4.0 MPa (condition 1), 200 ° C., 4 seconds, and 4.0 MPa (condition 2) were prepared. Adhesion was measured with the specimens prepared under condition 1 and shown in the tables, respectively. In addition, the specimen prepared under the condition 2, the adhesion was observed under a microscope.
As shown in Table 1 and 2 and Figure 2 and in the case of Examples 1 to 6 according to the present invention, the adhesive state is good, and satisfies the adhesive force of 600gf / cm or more. In Comparative Example 1, the elastic modulus and the Tg value are not satisfactory, so that the number of poor adhesive strength due to the stress decreases. In the case of Comparative Example 2, the elastic modulus is good, but the Tg value is low so that the shrinkage of the PCB after crimping cannot be prevented. Lifting between adhesives occurs, resulting in poor adhesion.
Claims (13)
Carbon particles;
Particles coated with the metals of particles comprising resins containing at least one of benzoguanamine, polyolefins, polyesters, polystyrenes and polyvinyl alcohols or modified resins thereof; And
Particles coated with the coated particles;
Composition for anisotropic conductive film, characterized in that at least one selected from.
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| KR1020100117553A KR101293788B1 (en) | 2010-11-24 | 2010-11-24 | Composition For Anisotropic Conductive Film And Anisotropic Conductive Film Using the Same |
| CN201110231123.2A CN102477263B (en) | 2010-11-24 | 2011-08-12 | Composition for anisotropy conducting film, anisotropy conducting film, and semiconductor device |
| TW100142552A TWI510593B (en) | 2010-11-24 | 2011-11-21 | Composition for anisotropic conductive film, anisotropic conductive film and semiconductor device |
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| KR101583691B1 (en) | 2012-10-10 | 2016-01-08 | 제일모직주식회사 | Anisotropic conductive adhesive compositions and anisotropic conductive films using them |
| KR101541115B1 (en) * | 2012-10-26 | 2015-07-31 | 제일모직주식회사 | Composition for anisotropic conductive film and anisotropic conductive film using the same |
| KR101535600B1 (en) * | 2012-11-06 | 2015-07-09 | 제일모직주식회사 | Anisotropic conductive film and semiconductor device |
| KR101551758B1 (en) * | 2012-12-11 | 2015-09-09 | 제일모직주식회사 | Composition for use of an anisotropic conductive film and an anisotropic conductive film thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002246413A (en) | 2000-12-14 | 2002-08-30 | Hitachi Chem Co Ltd | Heat/electric conductive film for connecting and its application |
| JP2005184022A (en) | 2000-12-14 | 2005-07-07 | Hitachi Chem Co Ltd | Heat for connection/electrical conductive film, and application thereof |
| KR20070013473A (en) * | 2005-07-26 | 2007-01-31 | 새한미디어주식회사 | Anisotropic conductive film, and method for preparing the same |
| KR20100067559A (en) * | 2008-12-11 | 2010-06-21 | 제일모직주식회사 | Anisotropic conductive film composition and anisotropic conductive film using it |
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| JP2002356658A (en) * | 2001-05-31 | 2002-12-13 | Nippon Carbide Ind Co Inc | Acrylic overlay film |
| JP2005320455A (en) * | 2004-05-10 | 2005-11-17 | Hitachi Chem Co Ltd | Adhesive composition, material for connecting circuit, connecting structure of circuit member and semiconductor device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002246413A (en) | 2000-12-14 | 2002-08-30 | Hitachi Chem Co Ltd | Heat/electric conductive film for connecting and its application |
| JP2005184022A (en) | 2000-12-14 | 2005-07-07 | Hitachi Chem Co Ltd | Heat for connection/electrical conductive film, and application thereof |
| KR20070013473A (en) * | 2005-07-26 | 2007-01-31 | 새한미디어주식회사 | Anisotropic conductive film, and method for preparing the same |
| KR20100067559A (en) * | 2008-12-11 | 2010-06-21 | 제일모직주식회사 | Anisotropic conductive film composition and anisotropic conductive film using it |
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| CN102477263B (en) | 2014-12-03 |
| CN102477263A (en) | 2012-05-30 |
| TW201229192A (en) | 2012-07-16 |
| TWI510593B (en) | 2015-12-01 |
| KR20120056044A (en) | 2012-06-01 |
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