KR101788379B1 - Polymer resin having a chemical structure 1 or 2, adhesive film comprising the polymer resin, and semiconductive device connected by the adhesive film - Google Patents
Polymer resin having a chemical structure 1 or 2, adhesive film comprising the polymer resin, and semiconductive device connected by the adhesive film Download PDFInfo
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- KR101788379B1 KR101788379B1 KR1020150080958A KR20150080958A KR101788379B1 KR 101788379 B1 KR101788379 B1 KR 101788379B1 KR 1020150080958 A KR1020150080958 A KR 1020150080958A KR 20150080958 A KR20150080958 A KR 20150080958A KR 101788379 B1 KR101788379 B1 KR 101788379B1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
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Abstract
The present invention relates to a polymer resin of formula (1) or (2), an adhesive film containing the same, and a semiconductor device connected by the adhesive film.
[Chemical Formula 1]
(2)
In Formula 1 or 2, X is a unit derived from a bifunctional epoxy compound or a mesogenic compound-derived unit containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group,
Y is a unit derived from a bifunctional epoxy compound and Z is a mesogenic compound-derived unit containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group, or
Y is a unit derived from a mesogenic compound containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group, Z is a unit derived from a bifunctional epoxy compound, n 1 is an integer of 1 to 10, n 2 is 1 Lt; / RTI >
Description
The present invention relates to a polymer resin of formula (1) or (2), an adhesive film containing the same, and a semiconductor device connected by the adhesive film.
In recent years, in the field of electronic packaging, various kinds of film-shaped adhesives capable of easily connecting such terminals have been proposed as IC chips A flexible printed wiring board (FPC), a glass substrate on which an IC chip and an ITO (Indium-Tin-Oxide) electrode circuit are formed, and the like.
In the adhesive film containing conductive particles in the resin composition as one of the film-shaped adhesives, the resin in the adhesive flows by heating and pressing to seal the gaps between the electrodes which face each other on the connection object, and at the same time, And filled between the electrodes to enable electrical connection.
In general, the adhesive film is composed of an epoxy composition containing a thermosetting resin and a curing agent as essential components, but this epoxy resin composition (JP-A-2009-161755) has a problem that film formability and flexibility are insufficient . Particularly, as the substrate thickness is thinned together with the light and thin chips of electronic devices and thus the bonding heat and pressure are lowered, the film formability and flexibility are more important characteristics. Therefore, there is a need for a novel polymer resin excellent in fluidity, adhesion, adhesion property and reliability at low temperatures.
An object of the present invention is to provide a polymer resin which is excellent in heat resistance and fluidity, has a high film-forming property during film formation, and is excellent in flexibility, heat resistance and connection property. Another object of the present invention is to provide an adhesive film which is connectable even at a low temperature connection temperature, excellent in storage stability, adhesion and reliability, and a semiconductor device connected by the film.
In one embodiment of the present invention, a polymeric resin having units of formula (1) or (2) is provided.
[Chemical Formula 1]
(2)
In Formula 1 or 2, X is a unit derived from a bifunctional epoxy compound or a mesogenic compound-derived unit containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group,
Y is a unit derived from a bifunctional epoxy compound and Z is a mesogenic compound-derived unit containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group, or
Y is a unit derived from a mesogenic compound containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group and Z is a unit derived from a bifunctional epoxy compound, n 1 is 1 to 10, n 2 is 1 to 10 Lt; / RTI >
In another embodiment of the present invention, there is provided an adhesive film comprising a polymer resin having units of the above formula (1) or (2).
In another embodiment of the present invention, there is provided an adhesive film having a lowest melt viscosity at a temperature of 100 DEG C or lower and a lowest melt viscosity of 1000 cps to 40000 cps.
Still another embodiment of the present invention provides a semiconductor device connected by the adhesive film disclosed in the present application.
The polymer resin and the adhesive film containing the polymer resin according to one embodiment of the present invention are excellent in heat resistance and fluidity, and have excellent film formability at the time of film formation, and excellent flexibility, fluidity, heat resistance, and connection property. In addition, the adhesive film comprising the polymer resin according to one embodiment is excellent in storage stability, adhesion and reliability, while being connectable even at a low temperature connection temperature.
1 shows a first embodiment of the present invention in which a first connected
Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.
According to an embodiment of the present invention, there is provided a polymer resin having units of the general formula (1) or (2).
[Chemical Formula 1]
(2)
In Formula 1 or 2, X is a unit derived from a bifunctional epoxy compound or a mesogenic compound-derived unit containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group,
Y is a unit derived from a bifunctional epoxy compound and Z is a mesogenic compound-derived unit containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group, or
Y is a unit derived from a mesogenic compound containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group, Z is a unit derived from a bifunctional epoxy compound, n 1 is an integer of 1 to 10, n 2 is 1 Lt; / RTI > When the polymer resin of formula (1) or (2) is used, not only the film forming property at the time of film formation is high but also the flexibility, heat resistance, adhesion, or storage stability can be improved.
Unless defined otherwise herein, 'substituted' means that a hydrogen atom in the compound is replaced by a halogen atom (F, Br, Cl, I), a halogenated alkyl, a hydroxy group, an alkoxy group, a nitro group, a cyano group, A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C 1 to C 20 alkyl group, a C 2 to C 20 alkyl group, a substituted or unsubstituted C 2 to C 20 alkoxy group, to C 20 alkenyl groups, C 2 to C 20 alkynyl groups, C 6 to C 30 aryl groups, C 7 to C 30 arylalkyl group, C 1 to C 20 alkoxy group, C 1 to C 20 heterocyclic group, C 3 to C 20 heteroaryl group, a C 3 to C 20 cycloalkyl group, a (meth) acrylate groups, C 3 to C 20 cycloalkyl alkenyl, C 4 to C 20 cycloalkyl alkynyl group, C 2 to C 20 heterocycloalkyl group, and combinations thereof ≪ / RTI >
In addition, unless otherwise defined herein, "hetero" means containing one to three heteroatoms selected from N, O, S, and P;
In the definition of the above formula (1) or (2), the bifunctional epoxy compound is a substituted or unsubstituted, bifunctional, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol AD type epoxy compound, bisphenol S type epoxy compound, . Specifically, it may be a bisphenol A type epoxy compound or a bisphenol F type epoxy compound.
In the definition of the above general formula (1) or (2), a mesogenic compound having two or more aromatic or alicyclic ring compounds having a crosslinkable functional group is a compound having a crosslinkable functional group and being substituted or unsubstituted, Or a mesogenic compound of an alicyclic ring, and the mesogenic compound may have a rod-like or disk-like structure. Examples of the crosslinkable functional group include a hydroxy group, an epoxy group, an acrylate group, and a carboxyl group, and more specifically, a hydroxy group, which can react with an epoxy group to form a crosslinked structure.
Specific examples of the mesogenic compound-derived unit include the following formulas A1 to A7:
(A1)
(A2)
(A3)
(A4)
(A5)
[Formula A6]
(A7)
.
Wherein R < 1 > To R 24 may each independently be an alcohol, amine, or carboxylic acid containing 0 to 20 hydrogen atoms, fluorine, alkyl, a silyl group, a methylcyclic group, a nitro group or an alkyl group or a hydrogen atom, May contain an ether or ester linkage.
Another specific example of the mesogen compound is a compound having two or more aromatic hydrocarbons bonded to each other to form a condensed ring, or two or more aromatic rings having a structure directly connected to each other or connected by another connecting group, and having a crosslinkable functional group , And compounds.
The polymer resin having a unit represented by the formula (1) or (2) is preferably a polymer comprising a bifunctional epoxy compound, a phenylfluorene compound or a naphthylfluorene compound having a crosslinkable functional group, and an aromatic or alicyclic ring compound having a crosslinkable functional group Can be produced by the condensation reaction of a mesogen compound. Examples of the crosslinkable functional group include a hydroxy group, an epoxy group, an acrylate group, and a carboxyl group, and more specifically, a hydroxyl group or an epoxy group. Examples of the crosslinkable functional group include a hydroxyl group, have. Specifically, the polymer resin having the units of the general formula (1) or (2) is obtained by introducing the above compounds into a reactor in which nitrogen gas is refluxed, adding a solvent such as cyclohexanone and maintaining the temperature of the reactor at 100 ° C to 200 ° C Adding a reaction catalyst and polymerizing for 1 hour to 50 hours. The polymerization equivalent ratio of the phenylfluorene compound or naphthylfluorene compound having a crosslinkable functional group and the mesogen compound having a crosslinkable functional group is in the range of 1: 5 to 5: 1, specifically in the range of 1: 4 to 4: 1 Lt; / RTI > The polymerization equivalent ratio of the phenylfluorene compound or naphthylfluorene compound having a crosslinkable functional group and the difunctional epoxy compound may be in the range of 1: 5 to 5: 1, specifically 1: 4 to 3: 1 . The phenylfluorene compound or naphthylfluorene compound having a crosslinkable functional group can be obtained by reacting 9,9-bis (4-hydroxyphenyl) fluorene or 9,9-bis (6-hydroxy-2-naphthyl) .
The weight average molecular weight of the polymer resin having the unit represented by the formula (1) or (2) may be in the range of 1000 to 500,000, and may be in the range of 2,000 to 200,000, more specifically 10,000 to 100,000. The above range can be advantageous in terms of film formability, flexibility, heat resistance, and the like. The glass transition temperature of the polymer resin having the unit of the formula (1) or (2) may be in the range of 95 to 180 ° C, specifically in the range of 100 to 150 ° C. The polymer resin may be contained in an amount of 10% by weight to 50% by weight, specifically 15% by weight to 40% by weight, based on the solid content of the adhesive film.
Examples of the reaction catalyst which can be used in the production of the polymer resin having the unit of the formula (1) or (2) include an amine type or an imidazole type. Examples of the amine-based reaction catalyst include linear amines, aliphatic amines, modified aliphatic amines, aromatic amines, secondary amines, and tertiary amines, and specific examples thereof include benzyldimethylamine, triethanolamine, triethylenetetramine, Diethylenetriamine, triethylenamine, dimethylaminoethanol, and tri (dimethylaminomethyl) phenol.
Specific examples of the imidazole-based reaction catalyst include imidazole, isoimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, butylimidazole, 2- 2-methylimidazole, 2-undecenedimidazole, 1-vinyl-2-methylimidazole, 2-n-heptadecylimidazole, 2- 2-methylimidazole, 1-propyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-heptadecylimidazole, Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 2-methylimidazole, adduct of imidazole and methylimidazole, adduct of imidazole and trimellitic acid, 2-n-heptadecyl-4-methylimidazole, phenyl Methylimidazole, benzylimidazole, 2-methyl-4,5-diphenylimidazole, 2,3,5-triphenylimidazole, 2-styrylimidazole, 1- Benzyl) -2-methylimidazole, 2- (2-hydroxy-4-t-butylphenyl) -4,5-diphenylimidazole, 2- Diphenylimidazole, 2- (3-hydroxyphenyl) -4,5-diphenylimidazole, 2- (p-dimethyl- Diphenylimidazole, di (4,5-diphenyl-2-imidazole) -benzene-1,4,2-naphthyl-4,5- 2-methylimidazole, 2-p-methoxystyrylimidazole, and the like, but are not limited thereto.
The reaction catalyst may be used in an amount of about 0.5 wt% to about 20 wt%, for example, about 1 wt% to about 15 wt%, or about 1 wt% to about 10 wt%, based on the total weight of the polymeric resin- % ≪ / RTI > by weight.
Hereinafter, an adhesive film according to an embodiment of the present invention will be described. This embodiment relates to an adhesive film comprising a polymer resin having units of the above-mentioned formula (1) or (2). The adhesive film may further include a radical reactive substance, a radical reaction initiator and conductive particles, or a cationic polymerizable substance, a cationic polymerization initiator, and conductive particles, in addition to the polymer resin having the units of the above formula (1) or (2). Specifically, the adhesive film may further include a conductive particle, a cationic polymerizable substance, and a cationic polymerization initiator.
In one example, the adhesive film may comprise a polymer resin having units of formula (1) or (2), conductive particles, a radical reactive material, and a radical reaction initiator. Examples of the radical reactive material include (meth) acrylate-based polymeric materials such as (meth) acrylate oligomers or (meth) acrylate-based monomers. Examples of the (meth) acrylate monomer include 6-hexanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ) Acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol (meth) acrylate, 2- hydroxyalkyl (meth) acryloylphosphate, 4-hydroxycyclohexyl (Meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylol ethane di (meth) acrylate, trimethylol propane di (meth) acrylate and the like. Examples of the (meth) acrylate oligomer include epoxy (meth) acrylate type epoxy resins having an intermediate molecular structure such as bisphenol such as 2-bromohydroquinone, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol AD, (4-hydroxyphenyl) ether and the like, and those having a skeleton such as an alkyl group, an aryl group, a methylol group, an allyl group, a cyclic aliphatic group, a halogen (such as tetrabromobisphenol A), a nitro group, and the like may be used. However, the (meth) acrylate oligomer is not limited thereto.
The radical reactive material may be included in an amount of 10% by weight to 40% by weight, for example, 10% by weight to 30% by weight, based on the solid content. Within the above range, properties such as adhesion and appearance can be excellent, and reliability and stability can be obtained.
As examples of the radical reaction initiator, at least one of a photopolymerization initiator or a thermosetting reaction initiator may be used in combination. Examples of the photopolymerization type reaction initiator include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4-methyldiphenyl sulfide, isopropyl thioxanthone, diethyl thioxanthone, ethyl 4-diethylbenzoate, benzoin ether, Propyl ether, 2-hydroxy-2-methyl-1-phenylpropane-1-one, diethoxyacetophenone and the like can be used, but are not limited thereto. As the thermosetting type reaction initiator, a peroxide system and an azo system may be used, but the present invention is not limited thereto. As the peroxide system, benzoyl peroxide, lauryl peroxide, t-butyl peroxyl laurate, 1,1,3,3,4-methyl butyl peroxy-2-ethylhexanoate and the like can be used. Examples of azo compounds include azo compounds such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis Azobis (2-methylbutylonitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2'- Azobis [N- (2-propenyl) -2-methylpropionimide], 2,2'-azobis Azobis (cyclohexane-1-carbonitrile), 1 - [(cyano-1-methylethyl) azo] formamide And the like, but are not limited thereto.
The radical reaction initiator may be contained in an amount of 0.5 to 10% by weight, for example, 1 to 8% by weight, based on the solid content of the adhesive film. Within the above range, a sufficient reaction required for curing takes place, and excellent physical properties can be expected in adhesion strength, reliability, etc. after bonding through formation of an appropriate molecular weight.
In another example, the adhesive film may include a polymer resin having units of the above formula (1) or (2), a cationic polymerizable substance, a conductive particle and a cationic polymerization initiator.
As the cationic polymerizable substance, an epoxy resin, specifically, a thermosetting epoxy resin can be used. For example, an epoxy resin having an epoxy equivalent of about 90 to 5000 g / eq and having two or more epoxy groups in the molecule can be used . More specifically, it may include at least one epoxy resin selected from the group consisting of hydrogenated, bisphenol-type, novolak-type, glycidyl-type, aliphatic and alicyclic epoxy resins. For example, a naphthalene-based epoxy resin can be used. The cationic polymerizable material may be from 10% to 50% by weight, specifically from 15% to 45% by weight, more specifically from 15% to 35% by weight, based on the solids content of the adhesive film.
More specifically, a hydrogenated epoxy resin or a propylene oxide-based epoxy resin can be used. Use of a hydrogenated epoxy resin or a propylene oxide-based epoxy resin enables rapid curing at a low temperature and secures good stability.
The hydrogenated epoxy resin is specifically an alicyclic hydrogenated epoxy resin such as a hydrogenated bisphenol A type epoxy resin or a cycloaliphatic system. As the cycloaliphatic epoxy resin, resins having a structure such as alicyclic diepoxyacetal, alicyclic diepoxy adipate, alicyclic diepoxy carboxyate, or vinylcyclohexene dioxide may be used. The hydrogenated bisphenol A type epoxy resin is generally obtained by using a hydrogenated bisphenol A derivative and epichlorohydrin, and may be a structure in which a double bond in a bisphenol A molecular structure is substituted with a hydrogen molecule.
As the hydrogenated bisphenol A type epoxy resin, for example, a hydrogenated bisphenol A type epoxy monomer represented by the following
(3)
[Chemical Formula 4]
In the above formula (4), n is 0.1 to 13.
Specifically, the hydrogenated epoxy resin may have an epoxy equivalent of 150 g / eq to 1,200 g / eq and a viscosity of 900 cps / 25 ° C to 12,000 cps / 25 ° C.
The cationic polymerization initiator is not limited as long as it can catalyze the curing of the epoxy resin, and for example, sulfone, imidazole, isocyanate, amine, amide, phenol or acid anhydride curing agents can be used These may be used alone or in combination of two or more.
The conductive particles include, for example, metal particles including Au, Ag, Ni, Cu, and Pb, carbon particles, particles coated with a metal on the polymer resin, particles coated with a metal on a polymer resin, Etc. may be used. As the polymer resin, polyethylene, polypropylene, polyester, polystyrene, polyvinyl alcohol and the like can be used, but the present invention is not limited thereto. Examples of the metal coating the polymer resin include, but are not limited to, Au, Ag, Ni, Cu, and Pb. Specifically, in the case of OLB (Outer Lead Bonding), since the adherend is an ITO (Indium Tin Oxide) glass surface, the core portion is made of a plastic material so that the ITO is not damaged by the pressure generated in the connection process of the anisotropic conductive film Metal particles such as Ni can be used to connect a PCB substrate. In the case of a PDP (Plasma Display Panel), a voltage applied to a circuit is very high, so that gold (Au) ). In the case of COG (Chip On Glass) or COF (Chip On Film) having a narrow pitch, insulated conductive particles coated with a thermoplastic resin on the surface of the conductive particles can be used. The conductive particles may be included in the adhesive film in an amount of 10 wt% to 40 wt%, 15 wt% to 35 wt%, for example, 15 wt% to 25 wt%.
In another example, the adhesive film may further include a binder resin in addition to the polymer resin having the units of the formula (1) or (2). Examples of the binder resin that can be used include at least one selected from the group consisting of acrylonitrile-based, phenoxystyrene, butadiene-based, acrylate-based, urethane-based, polyamide-based, silicone-based and NBR (nitrilebutadiene rubber) But is not limited thereto. Alternatively, as the binder resin, an olefin resin, an acrylonitrile butadiene copolymer, a carboxyl terminal acrylonitrile butadiene copolymer, a polyimide resin, a polyester resin, a polyvinyl butyral resin, an ethylene-vinyl acetate copolymer, At least one of a styrene-butylene-styrene (SBS) resin, a styrene-ethylene-butylene-styrene (SEBS) resin, an epoxy resin or a phenoxy resin can be used.
The adhesive film may be an anisotropic conductive adhesive film in one example. The anisotropically conductive adhesive film may have a single-layer structure containing conductive particles, a polymer resin of Formula (1) or (2) and a cured portion, or a structure of two or more layers of a conductive layer containing conductive particles and an insulating resin layer containing no conductive particles. The composition of the conductive layer and the insulating resin layer may be the same only in the presence or absence of the conductive particles. Therefore, the conductive layer and the insulating resin layer in the above two-layer structure or more may independently include the polymer resin of formula (1) or (2). For example, the anisotropic conductive film may have a two-layer structure in which a conductive layer and an insulating resin layer are laminated or a three-layer structure in which a first insulating resin layer and a second insulating resin layer are laminated on both surfaces of the conductive layer, Layer structure in which a first insulating resin layer and a second insulating resin layer are laminated on both surfaces and a third insulating resin layer is laminated on any one of the insulating resin layers.
In the case of a two-layer structure, the thickness of the insulating resin layer may be larger than the thickness of the conductive layer, and specifically, the thickness of the insulating resin layer may be in the range of one to four times the thickness of the conductive layer. In this range, the insulating resin is sufficiently filled between adjacent circuits, so that good insulation and adhesion can be exhibited.
In the case of a three-layer structure, the thickness of the first insulating resin layer may be 2 占 퐉 or less, the thickness of the second insulating resin layer may be in a range of 7 to 18 占 퐉, and the thickness of the conductive layer may be 0.5 to Can be doubled. More specifically, the thickness of the first insulating resin layer may be 1 占 퐉 or less, and the thickness of the second insulating resin layer may be in the range of 7 to 15 占 퐉.
The adhesive film comprising the polymer resin of Formula 1 or Formula 2 according to the above embodiments has a lowest melt viscosity at a temperature of 100 ° C or lower and a lowest melt viscosity of 1000 cps to 40000 cps. Thus, in one embodiment, an adhesive film having a lowest melt viscosity at a temperature of 100 DEG C or less and a minimum melt viscosity of 1000 cps to 40000 cps is provided. When the melt viscosity is in the above range, it may be advantageous from the standpoint of pressure-bonding ability and indentation uniformity. Specifically, the lowest melt viscosity may range from 1000 cps to 20000 cps, for example, from 1000 cps to 10000 cps. The method of measuring the lowest melt viscosity is as follows:
The lowest melt viscosity of the adhesive film was measured using ARES G2 (TA Instruments) at 30 ° C to 180 ° C at a heating rate of 10 ° C / min, a strain of 5% and a frequency of 1 rad / s, And the lowest melt viscosity. The diameter of the parallel plate and the aluminum disposable plate used was 8 mm.
In the adhesive film, the rate of change in calorific value of the following formula 1 on the thermal differential scanning calorimeter is
30% or less.
[Formula 1]
Heating rate change rate (%) = [(T 0 -T 1 ) / T 0 ] × 100
T 0 is an initial heating value measured at 10 ° C / 1 min and -50 to 250 ° C in the temperature range of 10 ° C / 1 min for the adhesive film, T 1 is the adhesive temperature at 25 ° C for 70 hours, It is the calorific value measured at 10 ° C / 1min and -50 to 250 ° C temperature range of the scanning calorimeter. The rate of change in calorific value may be specifically 20% or less.
The method of measuring the rate of change of the calorific value is not particularly limited and can be measured according to a method commonly used in the art. 1 mg of the adhesive film is dispensed at 25 ° C, and a differential scanning calorimeter (for example, TA 20 Q 20 model) is used to measure the rate of change of the calorific value at a rate of 10 ° C / (T 0 ) is measured at the temperature range of 0 ° C to 70 ° C, and then the film is allowed to stand at 25 ° C for 70 hours, and the calorific value is measured (T 1 ) by the same method. When the rate of change of the calorific value is within the above range, the storage stability of the adhesive film is good and the adhesive strength or the connection resistance can be prevented from increasing.
Another example of the present invention also provides an adhesive film having a connection resistance of 5? Or less after reliability evaluation. Specifically, the connection resistance after the reliability evaluation may be 3? Or less. In this range, it is possible to maintain a low connection resistance while being able to be cured at a low temperature, thereby improving the connection reliability, and also there is an advantage that the storage stability can be maintained for a long period of time.
The method of measuring the connection resistance after the above reliability evaluation is not particularly limited, and a non-limiting example is as follows.
Five specimens were respectively prepared by pressurization at 60 ° C and 1.0 MPa for 1 second and final compression at 130 ° C and 60 MPa for 5 seconds. Each specimen was held at 85 ° C and 85% relative humidity for reliability evaluation. After storing the circuit connections in a high temperature and high humidity chamber for 500 hours, measure the resistance using the 4 point probe method. The resistance measuring device applies 1mA and the resistance is calculated by the measured voltage.
The adhesive film disclosed herein has a bubble-forming area of not more than 5% at a pressure-adhering bonding site under a pressure of 1 MPa to 3 MPa for 1 second to 3 seconds at 55 to 70 캜, Under the condition of 1 second to 5 seconds, the indentation can be uniform during the compression.
In one embodiment of the present invention,
A first connected member containing a first electrode;
A second connected member containing a second electrode; And
And a connecting film as described herein, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode.
In one aspect, the first and second connected members may be structurally similar in terms of material, thickness, dimension, and physical interconnectivity. The thickness of the first and second connected members is about 20 to 100 탆. In another aspect, the first connected member and the second connected member may not be structurally and functionally similar in terms of material, thickness, dimension, and physical interconnectivity. Examples of the first connected member and the second connected member include, but are not limited to, glass, printed circuit board (PCB), FPCB, COF, TCP, ITO glass and the like. The first electrode or the second electrode may be in the form of a protruding electrode or a planar electrode. In the case of the protruding electrode, the height H of the electrode, the width W, and the gap G between the electrode and the electrode exist, the height H of the electrode is about 2.50 μm to 10 μm, About 10 to 90 占 퐉, and the gap G between the electrode and the electrode may be in a range of about 10 to 110 占 퐉. Preferably, the height H of the electrode is about 2.50 to 9 占 퐉, the width W of the electrode is about 5 to 80 占 퐉, and the gap G between the electrode and the electrode is about 5 to 80 占 퐉.
For planar electrodes, the thickness may range from 500 to 1200 angstroms.
As the first electrode or the second electrode, ITO, copper, silicon, IZO, or the like may be used, but the present invention is not limited thereto.
Preferably, the thickness of the planar electrode is 800 to 1200 ANGSTROM, and the height of the protruding electrode is 6 to 10 mu m. At this time, if the thickness of the insulating layer is 4 to 20 占 퐉, sufficient adhesion can be exhibited. More preferably, the height of the planar electrode is 1000 占 and the height of the protruding electrode is 8 占 퐉, wherein the thickness of the insulating layer is 6-12 占 퐉.
Hereinafter, the present invention will be described in more detail by describing Production Examples, Examples, Comparative Examples and Experimental Examples. However, the following Production Examples, Examples, Comparative Examples and Experimental Examples are merely examples of the present invention, and the present invention should not be construed as being limited thereto.
Example
Manufacturing example
[Production Example 1 of Polymer Resin]
64.5 g of 4,4'-biphenol and 35 g of 9,9-bis (4-hydroxyphenyl) fluorene were dissolved in 120 ml of cyclohexanone in a 500 ml separable round round flask equipped with a stirrer, 186.5 g of an epoxy resin and 0.18 g of an imidazole catalyst 2E4MZ were added and reacted for 5 hours while maintaining the temperature at 145 캜 in a nitrogen atmosphere to obtain a polymer resin 1 (weight average molecular weight 48400, glass transition temperature 103 캜).
[Production Example 2 of Polymeric Resin]
In the same manner as in Production Example 1, except that 64.5 g of 4,4'-biphenol and 35.9 g of 9,9-bis (4-hydroxyphenyl) fluorene were used, 55.9 g of 4,4'- (Weight average molecular weight: 47,600, glass transition temperature: 125 占 폚) was obtained in the same manner as in Preparation Example 1,
[Production Example 3 of Polymeric Resin]
In the same manner as in Production Example 1, except that 64.5 g of 4,4'-biphenol and 35 g of 9,9-bis (4-hydroxyphenyl) fluorene were used instead of 37.2 g of 4,4'- (Weight average molecular weight: 47,000, glass transition temperature: 130 占 폚) was obtained in the same manner as in Preparation Example 1, except that the polymerization initiator was used.
[Production Example 4 of Polymer Resin]
In the same manner as in Production Example 1, except that 64.5 g of 4,4'-biphenol and 35 g of 9,9-bis (4-hydroxyphenyl) fluorene were used instead of 18.6 g of 4,4'-biphenol and 9,9- (Weight average molecular weight: 42,600, glass transition temperature: 140 占 폚) was obtained in the same manner as in Preparation Example 1,
[Production Example 5 of Polymeric Resin]
In Production Example 1, except that 65 g of 2,3-dihydroxynaphthalene was used in place of 64.5 g of 4,4'-biphenol, polymerization was carried out in the same manner as in Production Example 1 to obtain Polymer Resin 5 (weight average molecular weight: 48600, 113 < 0 > C).
[Production Example 6 of Polymeric Resin]
64.5 g of 4,4'-biphenol was used instead of 64.5 g of 4,4'-biphenol and 35 g of 9,9-bis (4-hydroxyphenyl) fluorene was used instead of 64.5 g of 4,4'- 2-naphthyl) fluorene was used as the initiator in the same manner as in Preparation Example 1 to obtain Polymer Resin 6 (weight average molecular weight: 29200, glass transition temperature: 95 ° C).
[Production Example 7 of Polymeric Resin]
Except that 93.2 g of 4,4'-biphenol was used instead of 64.5 g of 4,4'-biphenol and 35 g of 9,9-bis (4-hydroxyphenyl) fluorene in Production Example 1, To obtain Polymer Resin 7 (weight average molecular weight: 50,200, glass transition temperature: 93 占 폚).
The polymerization equivalent ratios of the polymer resins of Production Examples 1 to 7 are shown in Table 1 below.
Preparation of anisotropic conductive adhesive film
[Conductive layer production example 1]
Based on the solid weight of the entire film, 1, 20% by weight of the polymer resin obtained in Production Example 1 was dissolved in the same amount of PGMEA (propylene glycol monomethyl ether acetate) solvent as a binder resin part serving as a matrix for film formation, 30% by weight of a hydrogenated epoxy resin (YX8000, epoxy equivalent: 205, viscosity: 1800 mPs), 5% by weight of a cationic polymerization catalyst Benzyl (4-hydroxyphenyl) methylsulfonium hexafluorophosphate, 4% by weight of nano silica R972, 1 wt% of a coupling agent KBM403, 40 wt% of conductive particles (AUL-704, average particle size: 4 袖 m, SEKISUI, Japan) as a filler for imparting a conductive property was insulated and mixed to prepare a conductive layer composition.
The conductive layer composition was coated on a white release film and the solvent was evaporated in a drier at 60 캜 for 5 minutes to obtain a dried conductive layer film having a thickness of 6 탆.
[Insulating resin layer production example 1]
An insulating resin layer having a thickness of 12 占 퐉 and containing no conductive particles was prepared in the same manner as in the conductive layer production example 1 except that the conductive particles were not included.
[Example 1]
A conductive layer and an insulating resin layer obtained in the conductive layer production example 1 and the insulating resin layer production example 1 were laminated and laminated to produce a two-layer anisotropic conductive adhesive film.
[Example 2]
In Example 1, an anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 1, except that the polymer resin 2 of Production Example 2 was used instead of the polymer resin 1 of Production Example 1.
[Example 3]
In Example 1, an anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 1, except that the
[Example 4]
In Example 1, an anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 1, except that the polymer resin 4 of Production Example 4 was used instead of the polymer resin 1 of Production Example 1.
[Example 5]
In Example 1, an anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 1, except that the polymer resin 5 of Production Example 5 was used instead of the polymer resin 1 of Production Example 1.
[Example 6]
In Example 1, an anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 1, except that the polymer resin 6 of Production Example 6 was used instead of the polymer resin 1 of Production Example 1.
[Comparative Example 1]
In Example 1, an anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 1, except that PKHH (manufactured by InChem), which is a phenoxy resin, was used in place of the polymer resin 1 of Production Example 1 .
[Comparative Example 2]
The same procedure as in Example 1 was carried out except that the fluorene resin FX-293 (manufactured by Shinil Chemical Co., Ltd.) was used in place of the polymer resin 1 of Production Example 1 in Example 1 to obtain an anisotropic conductive To prepare an adhesive film.
[Comparative Example 3]
In Example 1, an anisotropic conductive adhesive film having a two-layer structure was produced in the same manner as in Example 1, except that the polymer resin 7 of Production Example 7 was used instead of the polymer resin 1 of Production Example 1.
Experimental Example
With respect to the anisotropically conductive adhesive films prepared in Examples 1 to 6 and Comparative Examples 1 to 3, the following methods were used to measure the adhesiveness, the indentation uniformity after bonding, the connection resistance after the initial and reliability evaluation, the rate of change in calorific value, The lowest melt viscosity was measured and the results are shown in Table 2 below.
[Pressure-bonding type]
In order to evaluate the adhesion of the anisotropic conductive adhesive film, an IC chip (Samsung LSI) having a bump area of 1430 mu m and a glass substrate having an indium tin oxide circuit having a thickness of 5000 ANGSTROM (manufacturer: Neoview Kolon Co., ) Were used. The anisotropic conductive adhesive film thus prepared was placed on the organic substrate and pressed at 60 DEG C for 1 second at 1 MPa. After pressurization, the release film was removed, and the presence or absence of bubbles between terminals and terminals was observed with a microscope (manufactured by Olympus). A very good image (O) when the area ratio of the bubble formation is less than 0 to 5% with respect to the three observation positions, a good image when less than 6 to 10%, and a bad image (X) Respectively.
[Uniformity of indentation after bonding]
After press-bonding, the specimens squeezed at 130 ° C for 5 seconds and 60 MPa were prepared and the indentation uniformity of the specimens was visually observed. Specifically, when the indentations on both side portions of the driver IC are clear to the extent equivalent to the indentations on the central portion, it is determined that the indentations are uniform, so that the indentations on both side portions of the driver IC are blurry or unclear (X).
[Rate of change in calorific value]
The adhesive film was measured for an initial calorific value (T 0 ) measured at 10 ° C / 1 min and a temperature range of -50 to 250 ° C using a thermal differential scanning calorimeter. The adhesive film was left at 25 ° C for 70 hours, (△), 30% (△) and 30% (△) when the DSC calorific value is within 20% of the initial value by measuring the calorific value (T 1 ) (X). ≪ / RTI >
[Adhesive strength]
Bond tester Dage Series-4000 was tested under the conditions of maximum load (200kgf) and test speed (100um / sec) at a pressure of 1 MPa at 60 ° C for 1 second, Were measured at least three times per each specimen. The adhesive strength was evaluated to be 10 MPa or more (⊚), 5 MPa or more and 10 MPa or less (◯), 1 MPa or more and 5 MPa or less (Δ)
[Initial connection resistance]
The initial resistance at 60 ° C for 1 second and 1 MPa and the initial resistance after the main pressing at 130 ° C for 5 seconds and 60 MPa were measured and then evaluated as good (O) when the resistance was 0.1Ω or less, , And when it was more than that, it was evaluated as poor (X).
[Connection resistance after reliability evaluation]
In order to evaluate the reliability, the circuit connections of five each for each sample were stored for 500 hours in a high-temperature and high-humidity chamber maintained at 85 ° C and 85% relative humidity. Then, the connection resistance was measured and the connection resistance after the reliability evaluation was measured Good (?) When the resistance was 5 Ω or less, and poor (×) when the resistance was 5 Ω or less. After the initial and reliability evaluation, the connection resistance measurement is a 4-point probe method, which can use a resistance measuring device. The resistance between four points is measured by using four probes connected to the device. The resistance measuring device applies 1mA and the resistance is calculated by the measured voltage.
[Minimum melt viscosity]
The lowest melt viscosity was measured as follows:
The melt viscosity of the adhesive film was measured using a ARES G2 (manufactured by TA Instruments) at 30 ° C. to 180 ° C. at a heating rate of 10 ° C./min, a strain of 5% and a frequency of 1 rad / s, And its value were confirmed. The diameter of the parallel plate and the aluminum disposable plate used was 8 mm.
A case where the measured lowest melt viscosity is 1000 cps or more and 3000 cps or less (⊚), the case where the viscosity is more than 3000 cps is less than 10000 cps (◯), the case where the melt viscosity is more than 10000 cps (△) ×).
One
2
3
4
5
6
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that such detail is solved by the person skilled in the art without departing from the scope of the invention. will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (18)
[Chemical Formula 1]
(2)
In Formula 1 or 2, X is a unit derived from a bifunctional epoxy compound or a mesogenic compound-derived unit containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group,
Y is a unit derived from a bifunctional epoxy compound and Z is a mesogenic compound-derived unit containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group, or
Y is a unit derived from a mesogenic compound containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group, Z is a unit derived from a bifunctional epoxy compound, n 1 is an integer of 1 to 10, n 2 is 1 Lt; / RTI >
(A1)
(A2)
(A3)
(A4)
(A5)
[Formula A6]
(A7)
.
Wherein R 1 to R 24 are each independently an alcohol, amine, or carboxylic acid comprising 0 to 20 hydrogen or fluorine, alkyl, a silyl group, a methylcyclic group, a nitro group, The terminal linkage includes an ether or an ester linkage.
[Chemical Formula 1]
(2)
In Formula 1 or 2, X is a unit derived from a bifunctional epoxy compound or a mesogenic compound-derived unit containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group,
Y is a unit derived from a bifunctional epoxy compound and Z is a mesogenic compound-derived unit containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group, or
Y is a unit derived from a mesogenic compound containing two or more aromatic or alicyclic ring compounds having a crosslinkable functional group, Z is a unit derived from a bifunctional epoxy compound, n 1 is an integer of 1 to 10, n 2 is 1 Lt; / RTI >
[Formula 1]
Heating rate change rate (%) = [(T 0 -T 1 ) / T 0 ] × 100
T 0 is an initial heating value measured at 10 ° C / 1 min and -50 to 250 ° C in the temperature range of 10 ° C / 1 min for the adhesive film, T 1 is the adhesive temperature at 25 ° C for 70 hours, It is the calorific value measured at 10 ° C / 1min and -50 to 250 ° C temperature range of the scanning calorimeter.
A second connected member containing a second electrode; And
And an adhesive film according to any one of claims 9 and 11 to 13, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode. Device.
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CN201580080614.8A CN107614568B (en) | 2015-06-09 | 2015-09-30 | Fluoropolymer resin with formula 1 or formula 2, the then film containing it and the display device that is connected by then film |
PCT/KR2015/010304 WO2016199983A1 (en) | 2015-06-09 | 2015-09-30 | Macromolecular resin of chemical formula 1 or 2, adhesive film comprising same, and display device connected by means of the adhesive film |
TW105113259A TWI607031B (en) | 2015-06-09 | 2016-04-28 | Polymer resin having formula 1 or 2, adhesive film comprising the same, and display device connected by adhesive film |
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KR100673773B1 (en) | 2005-10-18 | 2007-01-24 | 제일모직주식회사 | Anisotropic conductive film composition using fluoren-based (meth)acrylate |
JP2012001689A (en) | 2010-06-21 | 2012-01-05 | Adeka Corp | Photocurable resin composition |
JP2015212367A (en) | 2014-04-16 | 2015-11-26 | 三菱化学株式会社 | Oligofluorene epoxy resin, epoxy resin composition, and cured product thereof |
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JP2008007555A (en) * | 2006-06-27 | 2008-01-17 | Three M Innovative Properties Co | Adhesive composition containing polyhydroxyether and organic particle and method for connecting circuit board using the same |
KR20100020029A (en) * | 2007-06-13 | 2010-02-19 | 히다치 가세고교 가부시끼가이샤 | Filmy adhesive for circuit connection |
JP5542833B2 (en) * | 2008-11-04 | 2014-07-09 | エルジー・ケム・リミテッド | Polymer electrolyte membrane |
JP4888482B2 (en) | 2008-12-22 | 2012-02-29 | 日立化成工業株式会社 | Anisotropic conductive adhesive composition, circuit terminal connection method and connection structure using the same |
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KR100673773B1 (en) | 2005-10-18 | 2007-01-24 | 제일모직주식회사 | Anisotropic conductive film composition using fluoren-based (meth)acrylate |
JP2012001689A (en) | 2010-06-21 | 2012-01-05 | Adeka Corp | Photocurable resin composition |
JP2015212367A (en) | 2014-04-16 | 2015-11-26 | 三菱化学株式会社 | Oligofluorene epoxy resin, epoxy resin composition, and cured product thereof |
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