JP2007231279A - Circuit-connecting material and method for producing circuit-connected product therewith - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive with a support, which effectively prevents the separation of the adhesive from an interface between the adhesive and the support, when slit, and can remarkably improve a yield, when massively produced, and to provide a circuit-connected structure using the same. <P>SOLUTION: This circuit-connecting material is characterized in that the circuit-connecting material has tensile breaking strength of 0.3 to 4.5 N/mm<SP>2</SP>and a tensile breaking elongation of 115 to 600%, before cured, and the circuit-connecting material has a Tg (glass transition temperature) of 80 to 200°C, after cured. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a circuit connection material and a method for manufacturing a circuit connection body using the same.

  A circuit connection material (hereinafter referred to as ACF) is used as a connection material for connecting a member to be connected having a large number of opposing electrodes. This ACF keeps the conductive state between the opposing electrodes when connecting substrates such as printed wiring boards, glass substrates for LCDs, flexible printed boards, semiconductor elements such as ICs and LSIs, and packages. It is a connection material that performs electrical connection and mechanical fixation so as to maintain insulation between electrodes.

  Many of such ACFs are formed in a film shape including an adhesive component containing a thermosetting resin and conductive particles blended as necessary, and are laminated on a support such as PET (polyethylene terephthalate). It is commercialized in a state. In use, after transferring the ACF to the member to be connected and temporarily press-bonding, the support is peeled off and thermo-compression is performed, the thermosetting resin is cured to obtain mechanical fixing between the members, and the opposing electrodes An electrical connection is obtained by contacting them directly or through conductive particles.

  The ACF as such a product is first formed on a support such as a PET film with a width of about 10 to 50 cm and a length of about 10 to 100 m, and is wound up once (this is called the original fabric). Is continuously cut using a cutter blade or the like into a narrow width of about 1 to 5 mm and wound up again (referred to as a slit process) to be supplied as an actual product.

  However, when the slit process is performed, the adhesive is peeled off from the interface between the ACF and the support, resulting in a problem that the yield during mass production is reduced. In addition, if the composition or type of the ACF constituent material is changed in order to improve the slit property, a problem occurs in which the adhesive strength and the electrical resistance of the circuit connection body, which are important characteristics of the ACF itself, increase. It was often difficult to do. The present invention effectively suppresses the peeling of the adhesive from the interface between the adhesive and the support at the time of slitting, can dramatically improve the yield during mass production, and the electrical resistance of the circuit connection body hardly increases, The present invention provides a circuit connecting material in which the adhesive strength is not easily lowered.

As a result of diligent examination of the above-mentioned problems, by controlling the tensile fracture strength and tensile fracture elongation of the circuit connection material before curing and the Tg of the circuit connection material after curing, the slit property, the adhesive strength, and the circuit connection body It was discovered that the electrical resistance can be satisfied at the same time, and the present invention has been achieved. The invention according to claim 1 is that the circuit connection material before curing has a tensile fracture strength of 0.1 to 5 N / mm ² and a tensile fracture elongation of 50 to 600%. Tg (Glass Transition Temperature) of 80 to 200 ° C., which is a circuit connection material, has a high slit yield at the time of manufacture, is less likely to increase the electrical resistance of the circuit connection body, and has a low adhesive strength It is intended to provide a circuit connection material that is difficult to perform. Invention of Claim 2 is a circuit connection material of Claim 1 in which a circuit connection material contains a film formation material (A), a radically polymerizable compound (B), and a radical generating agent (C), In addition to the invention described in item 1, it provides a circuit connecting material that is particularly excellent in adhesion in a short time. The invention according to claim 3 is the circuit connection material according to claim 1, wherein the circuit connection material includes a film forming material (A), an epoxy resin (D), and a latent curing agent (E). In addition to the invention described in 1, the present invention provides a circuit connecting material in which a decrease in adhesion strength particularly after adhesion is suppressed. The invention according to claim 4 is the circuit connection material according to any one of claims 1 to 3, wherein the circuit connection material further contains conductive particles (F). In addition to the invention described above, a circuit connection material having a remarkably low connection resistance when a circuit is connected is provided. In the fifth aspect of the invention, the circuit connecting material is interposed between the substrates having the circuit electrodes facing each other, and the substrates having the circuit electrodes facing each other are pressed to electrically connect the electrodes in the pressing direction. It is a connection structure, Comprising: It is a manufacturing method of the circuit connection body whose circuit connection material is the circuit connection material in any one of Claims 1 thru | or 4, The circuit in any one of Claims 1-4 A method for manufacturing a circuit connection structure using a connection material is provided.

In the present invention, the circuit connection material before curing has a tensile fracture strength of 0.3 to 4.5 N / mm ² and a tensile fracture elongation of 115 to 600%, and the Tg of the circuit connection material after curing is It is related with the circuit connection material characterized by being 80-200 degreeC. Moreover, this invention relates to the circuit connection material containing a film formation material (A), a radically polymerizable compound (B), and a radical generating agent (C). Moreover, this invention relates to the circuit connection material characterized by including a film formation material (A), an epoxy resin (D), and a latent hardening agent (E). The present invention further relates to a circuit connecting material containing conductive particles (F). Further, the present invention provides a connection structure in which a circuit connecting material is interposed between substrates having circuit electrodes facing each other, and the substrates having circuit electrodes facing each other are pressed to electrically connect the electrodes in the pressing direction. It relates to a manufacturing method.

  The invention according to claim 1 can provide a circuit connection material that has a high slit yield at the time of manufacture, is unlikely to cause an increase in electrical resistance of the circuit connection body, and is less likely to have a decrease in adhesive strength. In addition to the invention described in claim 1, the invention described in claim 2 can provide an adhesive having excellent adhesion in a short time. In addition to the invention described in claim 1, the invention described in claim 3 can provide an adhesive in which a decrease in adhesion strength particularly after adhesion is suppressed. In addition to the inventions described in claims 1 to 3, the invention described in claim 4 can provide an adhesive having a remarkably low connection resistance when a circuit is connected. The invention according to claim 5 can provide a method of manufacturing a circuit connection assembly using the adhesive according to claims 1 to 4.

The circuit connection material of the present invention is an adhesive that is interposed between substrates having circuit electrodes facing each other, and can press the substrate having circuit electrodes facing each other to electrically connect the electrodes in the pressing direction. It refers to the agent material, preferably in the form of a film. The circuit connection material before curing of the present invention does not cause a rapid chemical change when stored at room temperature (20 to 25 ° C.) or refrigerated, but external energy such as heating or irradiation with actinic rays or ultrasonic waves Is a circuit connecting material in a state where it can undergo a curing reaction. The tensile breaking strength and tensile breaking elongation of the circuit connecting material before curing according to the present invention can be measured at a test speed of 200 mm ± 20 mm per minute based on JIS K7127-1989. Tensile breaking strength of the circuit connecting material prior to curing of the present invention is preferably a 0.1~5N / mm ^2, more desirably 0.3~4.5N / mm ^2, 0.5~ Most desirably, it is 4 N / mm ² . When the tensile fracture strength of the circuit connection material before curing is less than 0.1 N / mm ² , the performance of the circuit connection material is low, and the electrical resistance and adhesion strength of the circuit connection body tend to decrease, When it exceeds 5 N / mm ² , the circuit connection material tends to peel from the support film at the time of slitting. The tensile breaking elongation of the circuit connecting material before curing of the present invention is desirably 50 to 600%, more desirably 70 to 550%, and most desirably 100 to 500%. When the tensile breaking elongation of the circuit connection material before curing is less than 50%, the circuit connection material tends to peel off from the support film at the time of slitting. On the other hand, when it exceeds 600%, the performance of the circuit connection material is low, and the circuit There exists a tendency for the electrical resistance of a connection body to raise and the adhesive strength to fall.

  The circuit connection material after curing of the present invention is obtained by subjecting the circuit connection material before curing to a curing reaction by heating, irradiation with actinic rays or supply of external energy such as ultrasonic waves. Conditions for allowing the curing reaction to proceed can be easily found from the end temperature of the observed exothermic peak by measuring the circuit connecting material by DSC. The reaction rate of the circuit connection material after curing according to the present invention is 20% or less, that is, the reaction rate is 80% or more when the calorific value of the circuit connection material before curing is 100%. The Tg (glass transition temperature) of the circuit connection material after curing can be measured as its tan δ peak temperature by performing a DMA (Dynamic Mechanical Analyzer) measurement. The Tg of the circuit connection material after curing according to the present invention is desirably 80 to 200 ° C, more desirably 90 to 180 ° C, and most desirably 100 to 160 ° C. When the Tg of the circuit connection material before curing is less than 80 ° C., the performance of the circuit connection material is low, and the electrical resistance of the circuit connection body tends to increase and the adhesive strength tends to decrease. There is a tendency that the circuit connection material is peeled off from the support film at the time of slitting.

  The circuit connection material of the present invention preferably contains a film forming material (A), a radical polymerizable compound (B), and a radical generator (C) as essential components. Examples of the film forming material (A) include phenoxy resin, polyvinyl formal resin, polystyrene resin, polyvinyl butyral resin, polyester resin, polyamide resin, xylene resin, polyurethane resin and the like. The film-forming material is a material that solidifies a liquid material and forms a constituent composition into a film shape, so that the film is easy to handle and imparts mechanical properties that are not easily torn, cracked, or sticky. Yes, it can be handled as a film in a normal state. Among the film-forming materials (A), a phenoxy resin is preferable because of excellent adhesion, compatibility, heat resistance, and mechanical strength. The phenoxy resin is a resin obtained by reacting a bifunctional phenol and epihalohydrin to a high molecular weight or by polyaddition of a bifunctional epoxy resin and a bifunctional phenol. Specifically, 1 mol of a bifunctional phenol and 0.985 to 1.015 mol of epihalohydrin are reacted at a temperature of 40 to 120 ° C. in a non-reactive solvent in the presence of a catalyst such as an alkali metal hydroxide. Can be obtained. Further, from the viewpoint of the mechanical properties and thermal properties of the resin, the blending equivalent ratio of the bifunctional epoxy resin and the bifunctional phenols is particularly preferably epoxy group / phenol hydroxyl group = 1 / 0.9 to 1 / 1.1. In the presence of a catalyst such as an alkali metal compound, an organic phosphorus compound, or a cyclic amine compound, the reaction solid content in an organic solvent such as an amide, ether, ketone, lactone, or alcohol having a boiling point of 120 ° C. or higher Is preferably obtained by heating to 50 to 200 ° C. and causing a polyaddition reaction at 50 parts by weight or less. Examples of the bifunctional epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, biphenyl diglycidyl ether, and methyl-substituted biphenyl diglycidyl ether. Bifunctional phenols have two phenolic hydroxyl groups, such as hydroquinones, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, bisphenol fluorene, methyl substituted bisphenol fluorene, dihydroxy biphenyl, methyl substituted dihydroxy biphenyl, etc. Bisphenols and the like. The phenoxy resin may be modified with a radical polymerizable functional group or other reactive compound. A phenoxy resin may be used independently or may be used in mixture of 2 or more types.

  The radical polymerizable compound (B) used in the present invention is a substance having a functional group that is polymerized by radicals, and examples thereof include acrylates, methacrylates, maleimide compounds, and styrene derivatives. The radical polymerizable compound can be used in either a monomer or oligomer state, and the monomer and oligomer can be used in combination. Specific examples of the acrylate (methacrylate) include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, 2-hydroxy-1,3. -Diacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, dicyclopentynyl acrylate, tricyclodeca Nyl acrylate, isocyanuric acid ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified triacrylate, urethane acrylate, these Methacrylate corresponding to acrylate. These can be used alone or in combination. If necessary, a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be appropriately used. Moreover, when it has a dicyclopentynyl group and / or a tricyclodecanyl group and / or a triazine ring, since heat resistance improves, it is preferable.

  The maleimide compound contains at least two maleimide groups in the molecule. For example, 1-methyl-2,4-bismaleimidebenzene, N, N′-m-phenylenebismaleimide, N, N′— p-phenylene bismaleimide, N, N′-m-toluylene bismaleimide, N, N′-4,4-biphenylene bismaleimide, N, N′-4,4- (3,3′-dimethyl-biphenylene) Bismaleimide, N, N′-4,4- (3,3′-dimethyldiphenylmethane) bismaleimide, N, N′-4,4- (3,3′-diethyldiphenylmethane) bismaleimide, N, N′- 4,4-diphenylmethane bismaleimide, N, N′-4,4-diphenylpropane bismaleimide, N, N′-3,3′-diphenylsulfone bismaleimide, N, N′-4,4-dipheni Ruether bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-s-butyl-4,8- (4-maleimidophenoxy) phenyl) propane, 1, 1-bis (4- (4-maleimidophenoxy) phenyl) decane, 4,4′-cyclohexylidene-bis (1- (4-maleimidophenoxy) -2-cyclohexylbenzene, 2,2-bis (4 -(4-maleimidophenoxy) phenyl) hexafluoropropane, etc. These may be used alone or in combination.

  For the circuit connection material of the present invention, a polymer or copolymer containing at least one of acrylic acid, acrylic acid ester, methacrylic acid ester or acrylonitrile as a monomer component can be used, and contains a glycidyl ether group. When a copolymer acrylic rubber containing glycidyl acrylate or glycidyl methacrylate is used in combination, stress relaxation is excellent, which is preferable. The molecular weight (weight average) of these acrylic rubbers is preferably 200,000 or more from the viewpoint of increasing the cohesive strength of the circuit connecting material.

  The circuit connection material of the present invention further contains a coupling agent, a filler, a softener, an accelerator, an anti-aging agent, a flame retardant, a dye, a thixotropic agent, a phenol resin, a melamine resin, an isocyanate, and the like. You can also

  The radical generator (C) used in the present invention generates free radicals by being decomposed by heating a peroxide compound, an azo compound, etc., depending on the intended connection temperature, connection time, pot life, etc. An organic peroxide having a half-life of 10 hours at a temperature of 40 ° C. or higher and a half-life of 1 minute at a temperature of 180 ° C. or lower is preferred from the viewpoint of high reactivity and pot life. An organic peroxide having a time temperature of 60 ° C. or higher and a half-life of 1 minute is 170 ° C. or lower is more preferable. When the connection time is 10 seconds or less, the blending amount of the radical generator (C) is based on a total of 100 parts by weight of the radical polymerizable compound (B) and the film forming material (A) in order to obtain a sufficient reaction rate. The content is preferably 0.1 to 30 parts by weight, and more preferably 1 to 20 parts by weight. When the blending amount of the radical generator (C) is less than 0.1 parts by weight, a sufficient reaction rate cannot be obtained, and good adhesive strength and small connection resistance tend to be difficult to obtain. When the blending amount of the radical generator (C) exceeds 30 parts by weight, the fluidity of the circuit connecting material decreases, the connection resistance increases, or the pot life of the adhesive composition tends to be shortened.

  Specific examples of the radical generator (C) can be selected from diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, hydroperoxide, silyl peroxide, and the like. Moreover, in order to suppress the corrosion of the circuit electrode of a circuit connection material, it is preferable that the chlorine ion and organic acid which are contained in a hardening | curing agent are 5000 ppm or less. Specifically, it is more preferably selected from peroxyesters, peroxyketals, peroxyketals, dialkyl peroxides, hydroperoxides, and silyl peroxides, and from peroxyesters and peroxyketals that provide high reactivity. The said hardening | curing agent can be mixed suitably and used.

  Diacyl peroxide includes isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide , Benzoylperoxytoluene, benzoyl peroxide and the like.

  Examples of peroxydicarbonate include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, di- (2-ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate, di (3-methyl-3methoxybutylperoxy) dicarbonate, and the like.

  Peroxyesters include cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxynodecanoate, t -Hexylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di ( 2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2 -Ethylhexanoate, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, -Hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoyl par Oxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, t-butylperoxyacetate and the like.

  As peroxyketals, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1- Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) decane, etc. It is done.

  Examples of the dialkyl peroxide include α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t- Examples thereof include butyl cumyl peroxide.

  Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

  Examples of silyl peroxide include t-butyltrimethylsilyl peroxide, bis (t-butyl) dimethylsilyl peroxide, t-butyltrivinylsilyl peroxide, bis (t-butyl) divinylsilyl peroxide, and tris (t-butyl). Examples thereof include vinylsilyl peroxide, t-butyltriallylsilyl peroxide, bis (t-butyl) diallylsilyl peroxide, and tris (t-butyl) allylsilyl peroxide.

These curing agents that generate free radicals upon heating can be used alone or in combination, and a decomposition accelerator, an inhibitor, and the like may be used in combination. In addition, those encapsulating these curing agents with polyurethane-based or polyester-based polymeric substances and the like and microencapsulated are preferable because the pot life is extended.

  The circuit connecting material of the present invention preferably contains a film forming material (A), an epoxy resin (D), and a latent curing agent (E) as essential components. The epoxy resin (D) used in the present invention includes bisphenol type epoxy resins derived from epichlorohydrin and bisphenol A, F, AD, etc., epoxy novolac resins derived from epichlorohydrin and phenol novolac or cresol novolac, and naphthalene rings. Naphthalene-based epoxy resin having a skeleton, glycidylamine, glycidyl ether, biphenyl, alicyclic and other epoxy compounds having two or more glycidyl groups in one molecule alone or in combination of two or more It is possible to use. For these epoxy resins, it is preferable to use a high-purity product in which impurity ions (Na +, Cl-, etc.), hydrolyzable chlorine, etc. are reduced to 300 ppm or less.

  Examples of the latent curing agent (E) used in the present invention include imidazole series, hydrazide series, amine imide, dicyandiamide and the like. These can be used alone or in combination, and may be used by mixing a decomposition accelerator, an inhibitor and the like. In addition, those encapsulating these curing agents with polyurethane-based or polyester-based polymeric substances and the like and microencapsulated are preferable because the pot life is extended. The blending amount of the latent curing agent (E) is 0.1 to 60 parts by weight with respect to 100 parts by weight in total of the film forming material (A) and the epoxy resin (D) in order to obtain a sufficient reaction rate. 1 to 20 parts by weight is more preferable. When the blending amount of the latent curing agent (E) is less than 0.1 parts by weight, a sufficient reaction rate cannot be obtained, and good adhesive strength and small connection resistance tend to be hardly obtained. When the blending amount of the latent curing agent (E) exceeds 60 parts by weight, the fluidity of the circuit connection material is lowered, the connection resistance is increased, or the pot life of the circuit connection material tends to be shortened.

  Even if the circuit connection material of the present invention is free of conductive particles (F), the connection can be obtained by direct contact of the circuit electrodes facing each other at the time of connection. However, when the conductive particles (F) are contained, A stable connection can be obtained by absorbing variations in the height of the circuit electrode due to deformation, increasing the contact area, and breaking through and contacting the oxide layer and passive layer on the surface of the circuit electrode. As conductive particles (F), there are metal particles such as Au, Ag, Ni, Cu, and solder, carbon, etc., and in order to obtain a sufficient pot life, the surface layer is not a transition metal such as Ni or Cu. Au, Ag and white metal noble metals are preferred, and Au is more preferred. Further, the surface of a transition metal such as Ni may be coated with a noble metal such as Au. Further, the conductive layer described above may be formed by coating or the like on non-conductive glass, ceramic, plastic, or the like, and the outermost layer may be a noble metal. When a conductive layer is formed on a plastic by coating, etc., or because it is deformable by heating and pressurization of hot molten metal particles, the contact area with the electrode increases at the time of connection, resulting in variations in the thickness of the circuit electrode of the circuit connection material. Absorption is improved and reliability is improved. The thickness of the noble metal coating layer is preferably 100 angstroms or more in order to obtain good resistance. However, when a noble metal layer is formed on a transition metal such as Ni, free radicals are generated by redox action caused by a deficiency in the noble metal layer or a deficiency in the noble metal layer generated when the conductive particles (F) are mixed and dispersed. Is more likely to cause a decrease in storage stability, and is preferably 300 angstroms or more. When the thickness is increased, these effects are saturated, so that the maximum thickness is preferably 1 μm, but is not limited. The conductive particles (F) are composed of the circuit connecting material resin component (that is, the total of the film forming material (A), the epoxy resin (D), and the latent curing agent (E), the film forming material (A), and the radical polymerizable property. The total amount of the compound (B) and radical generator (C)) is 100 to 100 parts by volume, and is properly used in the range of 0.1 to 30 parts by volume. In order to prevent an adjacent circuit from being short-circuited by excessive conductive particles (F), the amount is more preferably 0.1 to 10 parts by volume.

  The circuit connection material of the present invention can also be used as a circuit connection material between a flexible tape or a glass substrate and an IC chip in COG (chip on glass) mounting or COF (chip on film) mounting. That is, the first circuit member having the first connection terminal and the second circuit member having the second connection terminal are arranged so that the first connection terminal and the second connection terminal are opposed to each other, and the opposing The circuit connection material of the present invention is interposed between the arranged first connection terminal and the second connection terminal, and the first connection terminal and the second connection terminal arranged to face each other are electrically connected by heating and pressing. Can be made. These circuit members are usually provided with a large number of connection terminals (or a single connection terminal in some cases), and at least one set of the circuit members is arranged so that at least a part of the connection terminals provided on the circuit members are opposed to each other. Then, the circuit connection material of the present invention is interposed between the connection terminals arranged opposite to each other, and the connection terminals arranged opposite to each other by heating and pressing are electrically connected to form a circuit board. By heating and pressurizing at least one set of circuit members, the connection terminals arranged to face each other can be electrically connected by direct contact or through the conductive particles (F) in the circuit connection material.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
(Synthesis Experiment Example 1) Synthesis of Film Forming Material (A) Synthesis of Phenoxy Resin (Ph-1) 4,4- (9-Fluorenylidene) -diphenol 45g, 3,3 ', 5,5'-tetramethylbiphenol 50 g of diglycidyl ether was dissolved in 1000 ml of N-methylpyrrolidione, 21 g of potassium carbonate was added thereto, and the mixture was stirred at 110 ° C. After stirring for 3 hours, it was added dropwise to a large amount of methanol, and the produced precipitate was collected by filtration to obtain 75 g of a phenoxy resin (Ph-1). The molecular weight was measured by GPC8020 manufactured by Tosoh Corporation, the columns were measured by TSKgel G3000HXL and TSKgel G4000HXL manufactured by Tosoh Corporation, and the flow rate was 1.0 ml / min. .42.

(Synthesis Experimental Example 2) Synthesis of Film Forming Material (A) Synthesis of Phenoxy Resin (Ph-2) Tetrabromobisphenol was added to a 2 liter four-necked flask equipped with a nitrogen introduction tube, a thermometer, a cooling tube and a mechanical stirrer. A (FG-2000, trade name, manufactured by Teijin Chemicals Ltd.) 333.83 g, bisphenol A type epoxy resin (YD-8125, molecularly distilled product, epoxy equivalent 172 g / equivalent, trade name, manufactured by Toto Kasei Co., Ltd.) 205.56 g and 1257 g of N, N-dimethylacetamide was added and mixed under stirring in a nitrogen atmosphere until uniform. Next, 0.94 g of lithium hydroxide was added and reacted at 120 ° C. for 9 hours while gradually raising the temperature. The reaction was monitored by measuring the viscosity of the reaction solution at regular time intervals until the viscosity did not increase. After completion of the reaction, the reaction solution was allowed to cool, and about 420 g of activated alumina (200 mesh) was added thereto and left overnight. The activated alumina was filtered to obtain an N, N-dimethylacetamide solution of phenoxy resin. Subsequently, 807.62 g of N, N-dimethylacetamide solution of the obtained phenoxy resin and terminal carboxyl group-containing butadiene-acrylonitrile were added to a 1 liter four-necked flask equipped with a nitrogen introduction tube, a thermometer, a cooling tube and a mechanical stirrer. A copolymer (Hycar CTBNX1009-SP, trade name, manufactured by Ube Industries, Ltd.) (50.88 g) was added, and the mixture was sufficiently purged with nitrogen while being stirred and mixed. Next, the mixture was stirred and mixed in a nitrogen atmosphere, and heated for 8.5 hours in a state where the solvent was refluxed while gradually raising the temperature. After cooling, it was added dropwise to a large amount of methanol, and the produced precipitate was collected by filtration to obtain 470 g of a phenoxy resin (Ph-2).

(Reference Example 1) Preparation of circuit connecting material (# 1) before curing Phenoxy resin (Ph-1) (Ph-1 / toluene / ethyl acetate = 40/30/30 parts by weight) as film forming material (A) 100 parts by weight of a solution, 20 parts by weight of a phenoxy resin (Ph-2) (Ph-2 / methyl ethyl ketone = 50/50 parts by weight) solution, and a radical polymerizable compound (B), isocyanuric acid ethylene oxide modified diacrylate (M -215, 30 parts by weight manufactured by Toagosei Co., Ltd., 15 parts by weight of urethane acrylate (NK oligo UA512, product name manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,1-bis as the radical generator (C) (T-hexylperoxy) -3,5,5-trimethylcyclohexane (Perhexa TMH, trade name of NOF Corporation), 5 parts by weight, conductivity 10 parts by weight of Ni / Au plated polystyrene particles (average particle size 4 μm) as the child (F), 10 parts by weight of γ-methacryloxypropyltrimethoxysilane as a silane coupling agent, and 10% by weight aqueous solution of methyl ethyl ketone 10 The parts by weight were mixed to prepare a mixed solution (SS1). This was coated on a PET (polyethylene terephthalate) film having a thickness of 50 μm and dried at 70 ° C. for 5 minutes to obtain a circuit connection material (# 1) before curing having a thickness of 25 μm.

(Example 2) Preparation of circuit connection material (# 2) before curing Phenoxy resin (Ph-1) (Ph-1 / toluene / ethyl acetate = 40/30/30 parts by weight) as a film forming material (A) Liquid epoxy (HX3941HP, trade name manufactured by Asahi Kasei Kogyo Co., Ltd., epoxy equivalent 185) 60 containing a microcapsule type latent curing agent as a mixture of 100 parts by weight of the solution and the epoxy resin (D) and the latent curing agent (E) 10 parts by weight of Ni / Au plated polystyrene particles (average particle size 4 μm) as conductive particles (F), 10 parts by weight of γ-methacryloxypropyltrimethoxysilane as a silane coupling agent, and methyl ethyl ketone 10 parts by weight of a 1% by weight aqueous solution was mixed to prepare a mixed solution (SS2). This was coated on a 50 μm thick PET film and dried at 70 ° C. for 5 minutes to obtain a circuit connection material (# 2) before curing having a film thickness of 25 μm.

(Example 3) Preparation of circuit connection material (# 3) before curing 15 parts by weight of urethane acrylate (NK Oligo UA512, trade name of Shin-Nakamura Chemical Co., Ltd.) is 20 parts by weight, and γ-methacryloxypropyltrimethoxy A circuit connection material (# 3) before curing was obtained in the same manner as in Reference Example 1 except that 10 parts by weight of silane was changed to 5 parts by weight.

(Example 4) Preparation of circuit connection material (# 4) before curing Circuit before curing was carried out in the same manner as in Example 2 except that 10 parts by weight of γ-methacryloxypropyltrimethoxysilane was changed to 5 parts by weight. A connection material (# 4) was obtained.

(Comparative example 1) Preparation of circuit connection material (# 1 ') before curing Phenoxy resin (Ph-1) (Ph-1 / toluene / ethyl acetate = 40/30/30 parts by weight) 110 parts by weight of 100 parts by weight of solution Circuit connection material before curing by operating in the same manner as in Reference Example 1 except that 20 parts by weight of the phenoxy resin (Ph-2) (Ph-2 / methyl ethyl ketone = 50/50 parts by weight) solution is 30 parts by weight. (# 1 ′) was obtained.

(Comparative example 2) Preparation of circuit connection material (# 2 ') before curing Phenoxy resin (Ph-1) (Ph-1 / toluene / ethyl acetate = 40/30/30 parts by weight) Instead of 100 parts by weight of solution 50 parts by weight of a mixed solution of bisphenol A type phenoxy resin (PKHC, trade name of Union Carbide Co., Ltd., weight average molecular weight 45000) of PKHC / toluene / ethyl acetate = 40/30/30 parts by weight was used to prepare a phenoxy resin (Ph- 2) (Ph-2 / methyl ethyl ketone = 50/50 parts by weight) 20 parts by weight of the solution is 50 parts by weight, and 30 parts by weight of isocyanuric acid ethylene oxide-modified diacrylate (M-215, trade name, manufactured by Toagosei Co., Ltd.) A circuit connection material (# 2 ′) before curing was obtained in the same manner as in Example 3 except that the weight parts were used.

(Comparative example 3) Preparation of circuit connection material (# 3 ') before curing Phenoxy resin (Ph-2) (Ph-2 / methyl ethyl ketone = 50/50 parts by weight) solution without using phenoxy resin (Ph-1) 20 parts by weight is 100 parts by weight, isocyanuric acid ethylene oxide modified diacrylate (M-215, trade name of Toagosei Co., Ltd.) is 30 parts by weight, urethane acrylate (NK Oligo UA512, Shin-Nakamura Chemical Co., Ltd.) A circuit connection material (# 3 ′) before curing was obtained in the same manner as in Example 3 except that the company trade name was not used.

(Comparative example 4) Preparation of circuit connection material (# 4 ') before curing Phenoxy resin (Ph-1) (Ph-1 / toluene / ethyl acetate = 40/30/30 parts by weight) 100 parts by weight of solution is 80 parts by weight Parts, 20 parts by weight of a phenoxy resin (Ph-2) (Ph-2 / methyl ethyl ketone = 50/50 parts by weight) solution, 16 parts by weight, isocyanuric acid ethylene oxide-modified diacrylate (M-215, manufactured by Toagosei Co., Ltd.) Product name) A circuit connection material (# 4 ′) before curing was obtained in the same manner as in Example 3 except that 30 parts by weight was changed to 35 parts by weight.

(Comparative example 5) Preparation of circuit connection material (# 5 ') before curing Liquid epoxy (HX3941HP, Asahi Kasei) containing a microcapsule type latent curing agent as a mixture of epoxy resin (D) and latent curing agent (E) Kogyo Co., Ltd. trade name, epoxy equivalent 185) A circuit connection material (# 5 ′) before curing was obtained in the same manner as in Example 4 except that 60 parts by weight was changed to 25 parts by weight.

(Comparative Example 6) Preparation of circuit connecting material (# 6 ') before curing Phenoxy resin (Ph-1) (Ph-1 / toluene / ethyl acetate = 40/30/30 parts by weight) as film forming material (A) ) The same as in Comparative Example 5 except that 300 parts by weight of a 20 wt% toluene solution of 2,6-dimethyl-p-phenylene oxide (PPO, manufactured by Aldrich) was used instead of 100 parts by weight of the solution before curing. Circuit connection material (# 6 ') was obtained.

(Measurement of tensile fracture strength and tensile elongation of circuit connection material before curing)
It measured based on JIS K7127-1989. The circuit connection material before curing obtained in Reference Example 1, Examples 2 to 4 and Comparative Examples 1 to 6 was cut into a rectangular shape (No. 1 type test piece) having a width of 10 mm and a length of 50 mm. Produced. After removing the 50 μm thick PET film, using STROGRAPH ES (trade name, manufactured by Toyo Seiki Co., Ltd.) at 25 ° C., the distance between the marked lines is 20 mm, the distance between the grips is 30 mm, and the pulling speed is 200 mm ± 20 mm per minute. Measurements were made to calculate the tensile fracture strength (N / mm ² ) and the tensile fracture elongation from the average value of the five pieces. The measurement results are summarized in Table 1.

(Tg measurement of circuit connection material after curing)
The circuit connection material before curing obtained in Reference Example 1, Examples 2 to 4, and Comparative Examples 1 to 6 was cut into a rectangular shape having a width of 5 mm and a length of 40 mm. This film was heated at 170 ° C. for 2 hours using a hot air dryer to produce a cured circuit connection material. After peeling off the 50 μm-thick PET film, the viscoelastic spectrum was measured with a DMA measuring device (RSA II, trade name, manufactured by Rheometrics), and the value of the tan δ peak was defined as Tg. The measurement results are summarized in Table 1.

(Slit experiment of circuit connection material before curing)
Cutter blades obtained by cutting the circuit connection material before curing obtained in Reference Example 1, Examples 2 to 4 and Comparative Examples 1 to 6 into a length of 10 m and a width of 20 mm and arranging them at a width of 2.0 mm at equal intervals Was used to slit the circuit connection material before curing toward the blade surface of the cutter at 1 m / min. The slit surface of the circuit connection material before curing after the slit is visually observed. When all 10 pieces are in close contact with the PET film and the circuit connection material, ○, part of the PET film and the circuit connection material peels off. The case was marked with x. The measurement results are summarized in Table 1.

(Circuit connection-1)
ITO substrate (surface resistance, ≦ 20Ω) formed by vapor deposition of indium-tin oxide (ITO) on an IC chip having a bump area of 50 μm × 50 μm, a pitch of 100 μm and a height of 20 μm and a glass of 1.1 mm thickness / □) was sandwiched between quartz glass and a pressure head using the above-mentioned slit circuit connection material, and connected by heating and pressing at 200 ° C. and 100 MPa (in terms of bump area) for 10 seconds. At this time, the circuit connection material is heated on the ITO substrate in advance for 5 seconds at 70 ° C. and 0.5 MPa (bump area conversion) on the adhesive surface of the circuit connection material (# 1, # 3, # 1 ′ to # 4 ′). Then, the PET film was peeled off and connected to the IC chip. Ten circuit connection bodies were produced for each type of circuit connection material.

(Circuit connection-2)
When circuit connection materials (# 2, # 4, # 5 ′, # 6 ′) were used, the connection was made at 220 ° C. and 100 MPa (in terms of bump area) for 5 seconds. Other than that, it operated similarly to the connection-1 of a circuit.

(Connection reliability measurement method)
The connection resistance immediately after connection of the sample for connection reliability measurement and the connection resistance after being left in a moisture resistance test (85 ° C., 85% RH) for 500 hours were measured by the four-terminal method. The connection resistance (Ω) of 10 samples was measured and indicated by the average value. In addition, even if one of the 10 samples could not measure the connection resistance, it was determined as an OPEN failure. The results are summarized in Table 1.

(Adhesive strength measurement method-1)
Circuit connection material (# 1, # 3) described above using an IC chip (1.0 mm × 10 mm × 0.55 mm) with gold plating bumps (50 μm × 50 μm, bump height 15 μm, space 10 μm) and 0.7 mm thick glass , # 1 ′ to # 4 ′), and after connecting at 200 ° C. and 100 MPa (in terms of bump area) for 3 seconds, using a bond tester (manufactured by Dyge) immediately after bonding and after 168 hours of moisture resistance test Table 1 shows the average values of 10 samples.

(Adhesive strength measurement method-2)
When circuit connection materials (# 2, # 4, # 5 ′, # 6 ′) were used, they were connected at 220 ° C. and 100 MPa (in terms of bump area) for 5 seconds. Other than that, it operated similarly to the adhesive strength measuring method-1, and the measurement result was shown in Table 1.

(Appearance inspection after moisture resistance)
The connection surface after the moisture resistance test of the connection reliability measurement sample described above was observed with a metal microscope. Among the produced 10 samples, those where peeling did not occur were marked with ◯, those where peeling was observed were marked with ×, and the number of each sample is shown in Table 1.

In the circuit connection material of the present invention, the tensile strength of the circuit connection material before curing is 0.1 to 5 N / mm ² and the tensile fracture elongation is 50 to 600%, and the Tg of the circuit connection material after curing is In Reference Example 1 and Examples 2 to 4 at 80 to 200 ° C., the slit property of the circuit connection material is good, and furthermore, all the samples exhibit good connection resistance and high adhesive strength, and even after a moisture resistance test. The adhesion strength did not decrease, and the appearance of the adhesion surface after the moisture resistance test was also good. On the other hand, Comparative Examples 1, 5 and 5 in which the tensile fracture strength of the circuit connection material before curing exceeds 5 N / mm ² , the tensile fracture elongation is less than 50%, or the Tg of the circuit connection material after curing exceeds 200 ° C. In No. 6, the slit property is poor, and the tensile fracture strength of the circuit connection material before curing is less than 0.1 N / mm ² , the tensile elongation at break exceeds 600%, or the Tg of the circuit connection material after curing is less than 80 ° C. In Comparative Examples 2 to 4, the connection resistance after the moisture resistance test was particularly deteriorated, and the appearance of the adhesive surface after the moisture resistance test was deteriorated in some samples.

Claims (6)

The circuit connection material before curing has a tensile fracture strength of 0.3 to 4.5 N / mm ² and a tensile fracture elongation of 115 to 600%, and Tg (glass transition temperature) of the circuit connection material after curing. Is a circuit connecting material, characterized in that it is 80 to 200 ° C.   The circuit connection material according to claim 1, wherein the circuit connection material includes a film forming material (A), a radical polymerizable compound (B), and a radical generator (C).   The circuit connection material according to claim 1, wherein the circuit connection material includes a film forming material (A), an epoxy resin (D), and a latent curing agent (E).   The circuit connection material according to any one of claims 1 to 3, wherein the circuit connection material further contains conductive particles (F).   A connection structure in which a circuit connection material is interposed between substrates having circuit electrodes facing each other, the substrates having circuit electrodes facing each other are pressurized, and the electrodes in the pressing direction are electrically connected. The manufacturing method of the circuit connection body whose material is the circuit connection material in any one of Claim 1 thru | or 4. A circuit connection material having a tensile fracture strength before curing of 0.1 to 5 N / mm ² , a tensile fracture elongation of 50 to 600%, and a glass transition temperature after curing of 80 to 200 ° C. was used. A method for manufacturing a circuit connection body, comprising:
The first circuit member having the first connection terminal and the second circuit member having the second connection terminal are arranged so that the first connection terminal and the second connection terminal are opposed to each other, and the opposite arrangement is made. The circuit connection material is interposed between the first connection terminal and the second connection terminal, and the first connection terminal and the second connection terminal arranged to face each other are electrically connected by heating and pressing. The manufacturing method of a circuit connection body.