KR20140082696A - Adhesive composition, adhesive film, adhesive sheet, circuitry connector, method for connecting circuitry member, use of adhesive composition, use of adhesive film, and use of adhesive sheet - Google Patents

Abstract

A first circuit member having a first circuit electrode formed on a main surface of the first circuit substrate and a second circuit member having a second circuit electrode formed on a main surface of the second circuit substrate, Wherein at least one of the first circuit substrate and the second circuit substrate is a substrate including a thermoplastic resin having a glass transition temperature of 200 DEG C or lower and is formed so as to cover the core layer and the core layer Shell-type silicon microparticles having an installed shell layer.

Description

TECHNICAL FIELD [0001] The present invention relates to an adhesive composition, a film-like adhesive, an adhesive sheet, a circuit connector, a circuit member connection method, a use of an adhesive composition, CONNECTING CIRCUITRY MEMBER, USE OF ADHESIVE COMPOSITION, USE OF ADHESIVE FILM, AND USE OF ADHESIVE SHEET}

The present invention relates to an adhesive composition, a film-like adhesive, an adhesive sheet, a circuit connecting member, a circuit member connecting method, a use of an adhesive composition, a use of a film-like adhesive, and use of an adhesive sheet.

BACKGROUND ART In semiconductor devices and liquid crystal display devices, various adhesive compositions have conventionally been used for the purpose of bonding various members in a device. For example, the adhesive composition can be used for connection of a liquid crystal display element with TCP (Tape Carrier Package) or COF (Chip On Film), connection between TCP or COF and a printed wiring board, connection between FPC (Flexible Printed Circuit) Or a semiconductor element is mounted on a substrate or the like.

BACKGROUND ART Conventionally, as an adhesive composition for a semiconductor element or a liquid crystal display element, a thermosetting resin including an epoxy resin exhibiting high adhesiveness and high reliability has been used (see, for example, Patent Document 1). As the constituent components of the thermosetting resin, a curing agent such as an epoxy resin, a phenol resin having reactivity with the epoxy resin, and a thermal latent catalyst for promoting the reaction between the epoxy resin and the curing agent are generally used. The thermal latent catalyst is a substance which does not react at a storage temperature such as room temperature and exhibits high reactivity when heated. In addition, various compounds have been used in view of the storage stability at room temperature of the adhesive composition and the curing rate at the time of heating since they are important factors for determining the curing temperature and curing rate. In the actual process, a desired adhesion property is obtained by curing conditions of 1 to 3 hours at a temperature of 170 ° C to 250 ° C.

On the other hand, along with recent high integration of semiconductor devices and high definition of liquid crystal displays, there has been a tendency that the inter-device pitch and inter-wiring pitch are narrowed and the heating at the time of curing tends to adversely affect peripheral members. Therefore, . Further, since it is necessary to improve the throughput in order to lower the cost, it is also required to cure the adhesive composition in a short time.

However, in a conventional thermosetting resin containing an epoxy resin, it is necessary to use a thermal latent catalyst having a low activation energy in order to achieve curing at a low temperature in a short time (low temperature curability). In this case, There is a problem that the storage stability at room temperature is lowered.

As an adhesive composition having a low-temperature curing property, a radical-curing adhesive composition using a radical polymerizing compound such as a (meth) acrylate derivative and a peroxide as a radical polymerization initiator has attracted attention (see, for example, Patent Document 2) . According to the radical curing, since radicals which are reaction active species are highly reactive, curing at a low temperature in a short time is possible.

However, since the adhesive composition using radical curing has a large curing shrinkage at the time of curing, the adhesive strength is lowered as compared with the case of using an epoxy resin, and the adhesive strength to a substrate made of an inorganic material or a metal material tends to be lowered .

In the case of connecting a flexible printed circuit board (FPC) made of a semiconductor element, a liquid crystal display element or a FR4 substrate using a glass substrate or the like and a polymer film such as polyimide or polyester to a substrate, There is a problem that the underlying internal stress is increased and separation of the adhesive composition and deterioration of the connection reliability occur.

As a method of improving the bonding strength, there have been proposed a method of using an adhesion assisting agent typified by a silane coupling agent (see, for example, Patent Document 3), a method of imparting flexibility of a cured product by ether bonding to improve the bonding strength (See Patent Document 4); and a method of improving the adhesive strength by dispersing stress-absorbing particles containing rubber-based elastic material in the adhesive composition (see Patent Documents 5, 6, 7, etc.).

Japanese Patent Laid-Open No. 1-113480 WO 98/044067 Pamphlet Japanese Patent No. 3344886 Japanese Patent No. 3503740 Japanese Patent No. 3477367 International Publication No. 09/020005 pamphlet International Publication No. 09/051067 pamphlet

(PET), polycarbonate (PC), polyethylene naphthalate (PEN), cycloolefin polymer (COP), and the like for the purpose of thinning, light weight, and flexibility of touch panels and electronic papers The application of the circuit member including the circuit board is being studied. However, in the case of using an organic substrate having low heat resistance such as PET, PC, PEN, or COP, heating at the time of curing tends to adversely affect the organic substrate and peripheral members, Is required. In addition, since the surfaces of PET, PC, PEN, COP and the like are smooth, the adhesive effect by physical anchoring effect (anchor effect) is small.

Therefore, it is desirable to improve the adhesive strength of the radical-curable adhesive composition having low-temperature curing properties. However, organic substrates such as PET, PC, PEN and COP, which are thermoplastic resins, It is difficult to form a covalent bond with the silane coupling agent. Therefore, when these organic substrates are used, the method described in Patent Document 3 fails to obtain a sufficient adhesive strength improving effect.

In addition, organic substrates such as PET, PC, PEN, COP and the like have a larger thermal expansion coefficient than the glass substrate and have different surface energies. Therefore, it is necessary to impart sufficient flexibility to the adhesive composition in order to improve the wettability of the adherend and reduce the internal stress. However, in the method described in Patent Document 4, sufficient flexibility can not be imparted, Is desired.

Even in the method described in Patent Document 5, since the glass transition temperature of the stress-absorbing particles is as high as 80 占 폚 to 120 占 폚, sufficient stress relaxation effect can not be obtained and sufficient performance such as adhesion strength and connection resistance after high- There is a problem that does not support. Even in the method of dispersing the stress absorbing particles described in Patent Document 6, a sufficient adhesive strength improving effect on organic substrates such as PET, PC, PEN, COP and the like can not be obtained. In the methods described in Patent Documents 5, 6, and 7, since an epoxy resin is used as a curing component of an adhesive composition, heating at a relatively high temperature is required in order to obtain a sufficient adhesive force. PET, PC, and PEN , An adverse effect on an organic substrate such as COP is worried.

Therefore, the present invention is also applicable to an organic substrate having low heat resistance such as polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN) and cycloolefin polymer (COP) (Adhesive strength and connection resistance) can be maintained even after a long time reliability test (high temperature and high humidity test), a film-like adhesive using the adhesive composition, an adhesive sheet, a circuit connecting member, A method of bonding, a use of an adhesive composition, a use of a film-like adhesive, and an application of an adhesive sheet.

The inventors of the present invention have made intensive investigations to solve the above problems and found that a thermoplastic resin such as polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), cycloolefin polymer It has been found that a low bonding strength in connection between an organic substrate and a semiconductor element or a liquid crystal display element is caused by insufficient relaxation of internal stress. As a result of further studies to solve these problems, it has been found that excellent adhesion strength can be obtained by using silicon fine particles having a specific structure, and stable performance (adhesive strength and connection resistance) can be maintained even after a long time reliability test And the present invention has been accomplished.

That is, the present invention is a circuit board comprising: a first circuit member having a first circuit electrode formed on a first circuit board; and a second circuit member having a second circuit electrode formed on the second circuit board, Wherein at least one of the first circuit board and the second circuit board comprises a thermoplastic resin having a glass transition temperature of 200 DEG C or lower, wherein the core layer and the core layer Shell-type silicon fine particles having a shell layer provided so as to cover at least one of the core-shell type silicon fine particles.

Since the adhesive composition contains the silicon fine particles having the specific structure, the interaction between the silicon fine particles is relaxed and the structural viscosity (non-Newtonian viscosity) is lowered. Therefore, the dispersibility of the silicone fine particles in the resin is improved, It is considered that the stress can be sufficiently relaxed. This improves the bonding strength to a substrate (for example, PET, PC, PEN, COP, etc.) containing a thermoplastic resin having a glass transition temperature of 200 占 폚 or less, and can improve the bonding strength between circuit members. In addition, stable performance (adhesive strength and connection resistance) can be maintained even after a long-term reliability test.

As used herein, the term " substrate comprising a thermoplastic resin having a glass transition temperature of 200 DEG C or lower " refers to a thermoplastic resin as a polymer handbook (Polymer Society Handbook: Polymer Data Handbook, Fundamentals, p.525, Baifukan, 1986) And a thermoplastic resin exhibiting a glass transition temperature of 200 DEG C or lower. Here, the thermoplastic resin is a resin having thermoplasticity, and usually does not have a crosslinked structure, but it also includes a thermoplastic resin having a slight crosslinking structure if it has thermoplasticity. The glass transition temperature of the thermoplastic resin can be determined by a measuring method described later.

The present invention is also characterized in that a first circuit member on which a first circuit electrode is formed on a first circuit board and a second circuit member on which a second circuit electrode is formed on a second circuit board are connected to the first circuit electrode, Wherein at least one of the first circuit board and the second circuit board is made of a material selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer Shell type silicon fine particles having a core layer and a shell layer provided so as to cover the core layer, wherein the substrate comprises at least one selected from the group consisting of the core-shell type silicon fine particles and the core layer.

Since the adhesive composition contains silicon fine particles having the specific structure, the interaction between the silicon fine particles is relaxed and the structural viscosity (non-Newtonian viscosity) is lowered. Therefore, the dispersibility of the silicone fine particles in the resin is improved, It is considered that the stress can be sufficiently relaxed. Thereby, the adhesive strength to a substrate comprising at least one kind selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer can be improved, and the bonding strength between circuit members can be improved . In addition, stable performance (adhesive strength and connection resistance) can be maintained even after a long-term reliability test.

The glass transition temperature of the core layer of the silicon microparticles is preferably -130 ° C to -20 ° C, more preferably -125 ° C to -40 ° C, and particularly preferably -120 ° C to -50 ° C. Thereby, since the internal stress can be sufficiently relaxed, the bonding strength between the circuit members can be improved. In addition, stable performance can be maintained even after a long-term reliability test. When the glass transition temperature is higher than -20 占 폚, it is impossible to sufficiently mitigate the internal stress, so that a sufficient adhesive strength improving effect tends not to be obtained. When the glass transition temperature is lower than -130 占 폚, sufficient cohesive strength can not be obtained, Is lowered.

The adhesive composition according to the present invention preferably further contains a radically polymerizable compound. As a result, adhesion at a lower temperature can be achieved.

It is preferable that the adhesive composition further contains conductive particles. By containing the conductive particles, good conductivity or anisotropic conductivity is imparted to the adhesive composition, so that it is more suitably used for bonding between circuit members having circuit electrodes (connection terminals). Further, by electrically connecting the circuit members through the adhesive composition containing the conductive particles, the connection resistance can be further reduced.

The present invention provides a film-like adhesive obtained by molding the above adhesive composition into a film. The present invention also provides an adhesive sheet comprising an adhesive layer comprising a substrate and the film-like adhesive formed on the substrate.

The present invention provides a circuit board comprising a first circuit member having a first circuit electrode formed on a first circuit board, a second circuit member having a second circuit electrode formed on the second circuit board, And a connecting portion which is interposed between a surface of the second circuit member on which the second circuit electrode is formed and a surface of the second circuit member on which the second circuit electrode is formed and electrically connects the first circuit electrode and the second circuit electrode, Wherein at least one of the first circuit board and the second circuit board is a substrate comprising a thermoplastic resin having a glass transition temperature of 200 DEG C or lower and the connecting part is a circuit board having a circuit connection Provide sieve.

In the circuit connecting member according to the present invention, even when a substrate comprising a thermoplastic resin having a glass transition temperature of 200 DEG C or lower is used, the adhesive portion according to the present invention includes a cured product, A stable performance (adhesive strength or connection resistance) can be obtained.

It is preferable that the thermoplastic resin includes at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer. Thereby, the wettability between the circuit board and the adhesive composition is improved, the bonding strength is further improved, and excellent connection reliability can be obtained.

It is preferable that one of the first circuit board and the second circuit board includes at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer, It is preferable that the other circuit board includes at least one member selected from the group consisting of polyimide resin, polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer. Thereby, wettability and adhesive strength between the circuit board and the adhesive composition are further improved, and excellent connection reliability can be obtained.

The present invention is also characterized in that it comprises a first circuit member having a first circuit electrode formed on a first circuit board, a second circuit member having a second circuit electrode formed on the second circuit board, And a connecting portion which is interposed between a surface of the second circuit member on which the circuit electrode is formed and a surface of the second circuit member on which the second circuit electrode is formed and which electrically connects the first circuit electrode and the second circuit electrode, Wherein at least one of the first circuit board and the second circuit board includes at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer, The adhesive composition according to the present invention comprises a cured product.

In the circuit connecting member, the connecting portion includes a cured product, and the adhesive composition according to the present invention includes a cured product, thereby forming a circuit board comprising at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer It is possible to obtain excellent adhesive strength and stable performance (bonding strength and connection resistance) after long-term reliability test.

Wherein at least one of the first circuit board and the second circuit board includes at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer, It is preferable that the circuit board of the circuit board includes at least one member selected from the group consisting of polyimide resin, polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer. Thereby, wettability and adhesive strength between the circuit board and the adhesive composition are further improved, and excellent connection reliability can be obtained.

The present invention is characterized in that an adhesive composition according to the present invention is interposed between a first circuit member on which a first circuit electrode is formed on a first circuit board and a second circuit member on which a second circuit electrode is formed on a second circuit substrate And the first circuit member and the second circuit member are bonded to each other so that the first circuit electrode and the second circuit electrode are electrically connected to each other by curing the first circuit member and the second circuit member, Wherein at least one of the circuit boards comprises a thermoplastic resin having a glass transition temperature of 200 DEG C or lower.

According to the connection method of a circuit member according to the present invention, even when low-temperature curing is suitably applied to a substrate including a thermoplastic resin having a glass transition temperature of 200 DEG C or lower, sufficient bonding strength and stable performance after long- ) Is obtained.

The present invention also provides an adhesive composition according to the present invention between a first circuit member having a first circuit electrode formed on a first circuit substrate and a second circuit member having a second circuit electrode formed on the second circuit substrate, Wherein the first circuit member and the second circuit member are bonded to each other such that the first circuit electrode and the second circuit electrode are electrically connected to each other by curing the first circuit member and the second circuit member, Wherein at least one of the second circuit substrates is a substrate comprising at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer.

According to the circuit member connecting method described above, even when the low temperature curing is suitably applied to the substrate comprising at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer, A circuit connector having a strength (bonding strength and connection resistance) after the strength and long-term reliability test can be obtained.

The present invention relates to the use of the adhesive composition of the present invention, which comprises a first circuit member having a first circuit electrode formed on a first circuit board and a second circuit member having a second circuit electrode formed on the second circuit substrate, Wherein at least one of the first circuit board and the second circuit board is used to adhere the first circuit electrode and the second circuit electrode so as to electrically connect them and the thermosetting resin is a substrate comprising a thermoplastic resin having a glass transition temperature of 200 DEG C or lower , And the use of the adhesive composition.

The present invention further relates to a use of the adhesive composition of the present invention, which comprises a first circuit member having a first circuit electrode formed on a first circuit board, and a second circuit member having a second circuit electrode formed on the second circuit board Wherein at least one of the first circuit board and the second circuit board is made of at least one material selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate And at least one member selected from the group consisting of a cycloolefin polymer, and the use of the adhesive composition.

The present invention relates to the use of the film-based adhesive of the present invention, which comprises a first circuit member having a first circuit electrode formed on a first circuit board, and a second circuit member having a second circuit electrode formed on the second circuit board, Wherein at least one of the first circuit board and the second circuit board is used for bonding the first circuit electrode and the second circuit electrode so as to be electrically connected to each other, ≪ / RTI > the use of an adhesive on the film.

The present invention also relates to the use of the film-based adhesive of the present invention, which comprises a first circuit member having a first circuit electrode formed on a first circuit substrate, a second circuit member having a second circuit electrode formed on the second circuit substrate, Wherein at least one of the first circuit substrate and the second circuit substrate is made of a material selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene terephthalate, Wherein the substrate is a substrate comprising at least one selected from the group consisting of phthalates and cycloolefin polymers.

The present invention relates to the use of the adhesive sheet of the present invention, wherein a first circuit member on which a first circuit electrode is formed on a first circuit board, and a second circuit member on which a second circuit electrode is formed on a second circuit board, Wherein at least one of the first circuit board and the second circuit board is used to adhere the first circuit electrode and the second circuit electrode so as to electrically connect them and the thermosetting resin is a substrate comprising a thermoplastic resin having a glass transition temperature of 200 DEG C or lower , And the use of the adhesive sheet.

The present invention further relates to a use of the adhesive sheet of the present invention, wherein a first circuit member having a first circuit electrode formed on a first circuit board and a second circuit member having a second circuit electrode formed on the second circuit board Wherein at least one of the first circuit board and the second circuit board is made of at least one material selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate And at least one member selected from the group consisting of a cycloolefin polymer, and the use of the adhesive sheet.

INDUSTRIAL APPLICABILITY According to the present invention, even when an organic base material having low heat resistance such as polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN) or cycloolefin polymer (COP) (Adhesive strength and connection resistance) can be maintained even after a long time reliability test (high temperature and high humidity test), a film-like adhesive using the adhesive composition, an adhesive sheet, a circuit connecting member, A connection method, use of an adhesive composition, use of a film-like adhesive, and use of an adhesive sheet.

1 is a cross-sectional view showing an embodiment of an adhesive sheet of the present invention.
2 is a cross-sectional view showing one embodiment of the silicon microparticle of the present invention.
3 is a cross-sectional view showing an embodiment of a circuit connector of the present invention.

Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid corresponding thereto, "(meth) acrylate" means acrylate or methacrylate corresponding thereto, Acryloyl group " means an acryloyl group or a corresponding methacryloyl group.

The glass transition temperature (Tg) of the thermoplastic resin or the circuit board was measured using a viscoelasticity analyzer "RSA-3" (trade name) manufactured by T.A. Refers to the value of tan? Peak temperature measured at 150 占 폚 to 300 占 폚. When the glass transition temperature of the circuit board is measured, if a base layer such as a glass layer, a hard coat layer such as an acrylic resin layer, a gas barrier layer, or the like is formed on the thermoplastic resin substrate, Measure the glass transition temperature of the circuit board including.

The term "glass transition temperature (Tg)" of the fine particles refers to a value obtained by dispersing fine particles in a known thermoplastic resin having a Tg and using the produced film as a viscoelasticity analyzer "RSA-3" (trade name) manufactured by T.A. Refers to the value of tan? Peak temperature measured at a rate of 5 占 폚 / min, a frequency of 10Hz, and a measurement temperature of -150 占 폚 to 300 占 폚.

The "average particle diameter" of fine particles refers to the average particle diameter (Z-value) measured by using Zetasizer Nano-S (manufactured by Malvern Instruments Ltd.) after diluting the fine particles with methyl ethyl ketone to 0.1 wt% average value). The fine particles having a particle diameter of a size that can not be accurately measured by the above measuring apparatus were measured using an average value measured by a Shimadzu laser diffraction particle size distribution analyzer SALD-2200 (trade name, manufactured by Shimadzu Corporation) The particle size can also be used.

The adhesive composition according to the present invention is characterized by containing silicon fine particles having a core-shell structure. As the core shoe type structure, there is a structure having a core layer and a shell layer provided so as to cover the core layer, and a surface layer (shell layer) having a glass transition temperature or elastic modulus higher than the glass transition temperature or elastic modulus of the surface of the core material And a graft layer (shell layer) provided outside the core material (core layer). Silicon microparticles having the same or different composition in the core layer and the shell layer can be used. Concretely, core-shell type silicon fine particles (for example, see Japanese Patent No. 2832143) obtained by adding an alkaline substance or alkaline aqueous solution and organotrialkoxysilane to an aqueous dispersion of spherical fine particles of silicone rubber and performing hydrolysis and condensation reaction, , Core-shell type silicon fine particles such as those described in WO 2009/051067 can also be used. In addition, a silicon fine particle containing a hydroxyl group, a functional group such as an epoxy group, a ketimine, a carboxyl group and a mercapto group in a molecular end or an intramolecular side chain can be used. Such silicone fine particles are preferred because they improve the dispersibility of the film-forming component or the radical polymerizable substance. In addition, the core layer and the shell layer need not necessarily have a clear boundary line.

The core layer constituting the core-shell type silicon fine particles is preferably silicon or silicone rubber from the viewpoint of the stress relaxation effect, and the shell layer can use the same kind of polymer as the core layer or another type of polymer. However, It is preferable that the physical properties (glass transition temperature, elastic modulus, etc.) of the shell layer are high. Thereby, the structure and shape of the core layer can be stabilized, and the performance thereof is effectively exhibited. Particularly, when silicone or silicone rubber is used as the core layer, the silicon or silicone rubber swells due to the constituent material of the solvent or the adhesive composition, and the fine particles are adhered to each other to form aggregates. By forming the shell layer, formation of the aggregate can be suppressed.

The glass transition temperature of the core layer of the silicon microparticles is preferably -130 DEG C to -20 DEG C, more preferably -125 DEG C to -40 DEG C, and particularly preferably -120 DEG C to -50 DEG C . Such silicon fine particles can sufficiently relax the internal stress of the adhesive composition.

From the viewpoint of alleviating the internal stress, the weight average molecular weight of the core layer of the silicon fine particles is preferably 1.5 million or less, more preferably 1.5 million or more and 500,000 or more, and particularly preferably 1.4 million or more and 800,000 or more.

The weight average molecular weight in the present embodiment is determined by gel permeation chromatography (GPC) analysis under the following conditions and converted by using a standard polystyrene calibration curve.

The GPC conditions are as follows.

Equipment: Hitachi L-6000 type (trade name, manufactured by Hitachi Seisakusho Co., Ltd.)

Detector: L-3300RI (trade name, manufactured by Hitachi, Ltd.)

Column: Gel pack GL-R420 + Gel pack GL-R430 + Gel pack GL-R440 (three in total) (trade name, manufactured by Hitachi Kasei Kogyo Co., Ltd.)

Eluent: tetrahydrofuran

Measuring temperature: 40 ° C

Flow rate: 1.75 ml / min

The shell layer in the core-shell type silicon fine particles preferably has a crosslinked structure in order to attain structural stability, shape retention and high functionality of the core layer, more preferably a crosslinked structure having a three-dimensional network structure And the shell layer is a crosslinked structure having a three-dimensional network structure. Further, more preferably, it is an organic compound such as polymethyl methacrylate copolymer or an inorganic compound such as silicon, silica, silsesquioxane and the like. This effectively alleviates internal stress caused by silicon.

As a method for confirming the structures of the silicon fine particles and the core-shell type silicon fine particles, it is possible to confirm the cross-section of the core-shell type silicon fine particles by observing the surface and analyzing the composition of the surface. As a specific method, it can be confirmed by carrying out a structural analysis by a transmission electron microscope (TEM) under the conditions shown below.

Resin casting: Epoxy resin (epo-mount base and curing agent manufactured by Refine Tech Co., Ltd.)

Heavy metal dyeing: A 2 mass% aqueous solution of OsO ₄ (osmium tetraoxide) is prepared, and the cast sample is bulk dyed for 24 hours.

Pretreatment: Cryo Ultramicrotome is pre-treated with a diamond knife at a blade speed of 0.6 mm / sec while cooling to -120 캜 to prepare a thin film.

TEM observation: STEM / EDX device manufactured by Hitachi High-Technologies Corporation; Using the HD-2700, the core layer, the type of shell layer, and the configuration are confirmed from the image or EDX mapping.

As another method, structural analysis by an atomic force microscope (AFM) can be performed under the conditions described below.

Resin casting: Epoxy resin (epo-mount base and curing agent manufactured by Refine Tech Co., Ltd.)

Pretreatment: Cryo ultra-microtome is pre-treated with a diamond knife at a blade speed of 0.6 mm / sec while cooling to -120 캜 to prepare a thin film.

Observation: The cross-section was observed using an atomic force microscope AFM manufactured by SII Nanotechnology Inc., and the shape of the core and the phase were measured in the DFM mode to confirm the core shell structure on the image.

The average particle diameter of the silicon fine particles is preferably 0.05 탆 or more and 25 탆 or less, more preferably 0.1 탆 or more and 20 탆 or less, and particularly preferably 0.6 탆 or more and 10 탆 or less. When the average particle diameter of the silicon fine particles is within the above range, compatibility between the fluidity of the adhesive composition and the relaxation of internal stress becomes easy.

The blending amount of the silicon fine particles is preferably 1% by mass or more and 50% by mass or less, more preferably 3% by mass or more and 30% by mass or less based on the mass of the adhesive component (adhesive composition excluding conductive particles) % Or more and 30 mass% or less. By making the blending amount of the silicon fine particles fall within the above range, the internal stress can be alleviated and the flexibility (elastic modulus, elongation) and adhesive strength of the adhesive composition can be sufficiently obtained.

The core-shell type silicon fine particles may be used alone or in combination of two or more. Insofar as the effect of the present invention is not impaired, other silicon fine particles may be used in combination.

From the viewpoint of dispersibility and alleviation of internal stress, the other silicon fine particles preferably have a weight average molecular weight of not more than 1.5 million, more preferably not less than 1.5 million, and more preferably not less than 1.4 million but not less than 800,000 Do. Further, the other silicon fine particles preferably have a three-dimensional crosslinked structure. "Having a three-dimensional crosslinked structure" means that the polymer chain has a three-dimensional network structure. The silicone fine particles having a three-dimensional crosslinked structure have high dispersibility to a resin and further excellent stress relaxation after curing. Silicone fine particles having a weight average molecular weight of not less than 1,000,000 and / or a three-dimensional crosslinked structure are less soluble in a polymer such as a thermoplastic resin, a monomer, a solvent, etc., so that the dispersibility and the stress relaxation effect can be obtained more remarkably.

Examples of other silicon fine particles include fine particles of polyorganosilsesquioxane resin having rubber elasticity, and spherical and amorphous silicon fine particles are used. Concretely, silicon fine particles obtained by reacting an organopolysiloxane containing at least two vinyl groups and an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms with a platinum-based catalyst (for example, Open No. 62-257939), organopolysiloxanes having an alkenyl group, organopolysiloxanes having a hydrosilyl group, and silicon fine particles obtained by using a platinum catalyst (see, for example, Japanese Patent Application Laid-Open No. 63-77942) (For example, see Japanese Patent Application Laid-Open No. 62-270660), methylsilanetriol and / or methylsilanetriol obtained by using a diorganosiloxane, a monoorganosilsesquioxane, a triorganosiloxane and a platinum- The water / alcohol solution of the partial condensate is added dropwise to the aqueous alkaline solution, and a polycondensation reaction is carried out. Cone particles and the like can be used (for example, see JP Patent No. 3970453). In addition, in order to improve the dispersibility and the adhesion with the substrate, it is also possible to use silicon fine particles (for example, see Japanese Patent Application Laid-Open No. 3-167228) or epoxy fine particles obtained by adding or copolymerizing an acrylic acid ester compound Etc. may be used.

The radical polymerizable compound contained in the adhesive composition refers to a compound that generates radical polymerization under the action of a radical polymerization initiator and may be a compound that generates its own radical by imparting activation energy such as light or heat. As the radical polymerizing compound, for example, a compound having a functional group polymerizable by an active radical such as a vinyl group, a (meth) acryloyl group, an aryl group or a maleimide group can be suitably used.

Specific examples of the radical polymerizable compound include oligomers such as epoxy (meth) acrylate oligomer, urethane (meth) acrylate oligomer, polyether (meth) acrylate oligomer and polyester (meth) acrylate oligomer, trimethylolpropane tri (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (Meth) acrylate, isocyanuric acid-modified trifunctional (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isocyanuric acid-modified bifunctional (meth) (Meth) acrylic acid having a (meth) acrylic acid added to the glycidyl group of bisphenol fluorene diglycidyl ether, Epoxy (meth) acrylate in which (meth) acrylic acid is added to the glycidyl group of bisphenol fluorene diglycidyl ether, glycidyl ether of bisphenol fluorenediglycidyl ether (Meth) acryloyloxy group is introduced into a compound obtained by adding ethylene glycol or propylene glycol to a silyl group, a compound represented by the following formula (A) or (B), and the like.

In the above formula (A), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and a and b each independently represent an integer of 1 to 8.

In the formula (B), R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and c and d each independently represent an integer of 0 to 8.

The radical polymerizing compound may be used without particular limitation, even if it exhibits a solid state without any fluidity such as a wax phase, a lead phase, a crystalline phase, a glass phase, and a powder phase when it is left alone at 30 캜. Specific examples of such radically polymerizable compounds include N, N'-methylenebisacrylamide, diacetone acrylamide, N-methylol acrylamide, N-phenylmethacrylamide, 2-acrylamide- N-phenylmaleimide, N- (o-methylphenyl) maleimide, N- (m-methylphenyl) maleimide, N- (p-methylphenyl) -maleimide , N- (m-methoxyphenyl) maleimide, N- (p-methoxyphenyl) -maleimide, N- methylmaleimide, N- ethylmaleimide, Octylmaleimide, 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bis Maleic anhydride, maleimide, 4-methyl-1,3-phenylene bismaleimide, N-methacryloxy maleimide, N-acryloxymaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) , N-methacryloyloxysuccinic acid imide , N-acryloyloxysuccinimide, 2-naphthyl methacrylate, 2-naphthyl acrylate, pentaerythritol tetraacrylate, divinylethylene element, divinylpropylene element, 2- polystyrylethyl methacrylate (3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N-phenyl-N ' Propyl) -p-phenylenediamine, tetramethylpiperidyl methacrylate, tetramethylpiperidyl acrylate, pentamethylpiperidyl methacrylate, pentamethylpiperidyl acrylate, octadecyl acrylate, Nt- Butyl acrylamide, diacetone acrylamide, N- (hydroxymethyl) acrylamide, and compounds represented by any of the following formulas (C) to (L).

In the above formula (C), e represents an integer of 1 to 10.

In the formula (E), R ⁵ and R ⁶ each independently represents a hydrogen atom or a methyl group, and f represents an integer of 15 to 30.

In the above formula (F), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and g represents an integer of 15 to 30.

In the above formula (G), R ⁹ represents a hydrogen atom or a methyl group.

In the above formula (H), R ¹⁰ represents a hydrogen atom or a methyl group, and h represents an integer of 1 to 10.

In the above formula (I), R ¹¹ represents a hydrogen atom or an organic group represented by the following formula (i) or (ii), and i represents an integer of 1 to 10.

In the above formula (J), R ¹² represents a hydrogen atom or an organic group represented by the following formula (iii) or (iv), and j represents an integer of 1 to 10. Each of R ¹² may be the same or different.

In the above formula (K), R ¹³ represents a hydrogen atom or a methyl group.

In the above formula (L), R ¹⁴ represents a hydrogen atom or a methyl group.

As the radical polymerizable compound, urethane (meth) acrylate can be used alone or in combination with other radical polymerizable compounds. The use of urethane (meth) acrylate improves flexibility and improves the adhesion strength to organic substrates such as PET, PC, PEN, and COP.

The urethane (meth) acrylate is not particularly limited, but it is preferable to use urethane (meth) acrylate represented by the following formula (M). Here, the urethane (meth) acrylate represented by the following formula (M) is a condensation reaction between an aliphatic or alicyclic diisocyanate and at least one aliphatic or alicyclic ester diol or an aliphatic or alicyclic carbonate diol Lt; / RTI >

In the formula (M), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a methyl group, R ¹⁷ represents an ethylene group or a propylene group, R ¹⁸ represents a saturated aliphatic group or a saturated alicyclic group, and R ¹⁹ represents an ester group And a saturated aliphatic group or a saturated alicyclic group containing a saturated alicyclic group or a carbonate group, and k represents an integer of 1 to 40, In the formula, R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different.

The aliphatic diisocyanate constituting the urethane (meth) acrylate is at least one selected from the group consisting of tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, Diisocyanate, 2,2,4-trimethylhexamethylene-1,6-diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, isophorone diisocyanate, cyclohexyldiisocyanate, hydrogenated xylene Diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated trimethyl xylylene diisocyanate, and the like.

The aliphatic ester diol constituting the urethane (meth) acrylate is at least one selected from the group consisting of ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, Glycol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2-methyl- Pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5- 1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,7-heptanediol, , 2-decanediol, 1,10-decanediol, 1,12-decanediol, dodecanediol, pinacol, 1,4-butynediol, triethylene glycol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol , And 1,4-cyclohexane dimethanol, and saturated low molecular glycols such as adipic acid, 3-methyladipic acid, 2,2,5,5-tetramethyladipic acid, maleic acid, fumaric acid, 2-methylsuccinic acid, 2,3-dimethylsuccinic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, butylmalonic acid, dimethylmalonic acid, glutaric acid, 2 -Methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 2,4-dimethylglutaric acid, pimelic acid, A polyester diol obtained by dehydration condensation of a dibasic acid such as sebacic acid or a corresponding acid anhydride thereof, a polyester diol obtained by ring-opening polymerization of a cyclic ester compound such as? -Caprolactone, and the like. The polyester diols obtained from the diols and dicarboxylic acids may be used alone or in combination with two or more kinds of polyester diols.

The polycarbonate diol constituting the urethane (meth) acrylate is selected from polycarbonate diols obtained by reaction of at least one of the above-mentioned glycols with phosgene. The polycarbonate diol obtained by the reaction of the glycols and phosgene may be used alone or in combination with two or more polycarbonate diols.

The weight average molecular weight of the urethane (meth) acrylate can be freely adjusted within a range of from 5000 to less than 30000 from the viewpoint of improvement of adhesion strength to a base material such as PET, PC, PEN, COP and the like. When the weight average molecular weight of the urethane (meth) acrylate is within the above range, both flexibility and cohesive force can be obtained, adhesion strength with organic substrates such as PET, PC, PEN, and COP is improved, Can be obtained. When the weight average molecular weight of the urethane (meth) acrylate is within the above range, it is easy for the adhesive composition to have both sufficient flexibility and fluidity. From the viewpoint of more fully obtaining such effects, the weight average molecular weight of the urethane (meth) acrylate is more preferably from 80,000 to less than 25,000, and particularly preferably from 10000 to less than 20,000.

The weight average molecular weight in the present embodiment is determined by gel permeation chromatography (GPC) analysis under the following conditions and converted by using a standard polystyrene calibration curve.

The GPC conditions are as follows.

Equipment: Hitachi L-6000 type (trade name, manufactured by Hitachi Seisakusho Co., Ltd.)

Detector: L-3300RI (trade name, manufactured by Hitachi, Ltd.)

Column: Gel pack GL-R420 + Gel pack GL-R430 + Gel pack GL-R440 (three in total) (trade name, manufactured by Hitachi Kasei Kogyo Co., Ltd.)

Eluent: tetrahydrofuran

Measuring temperature: 40 ° C

Flow rate: 1.75 ml / min

The blending amount of the urethane (meth) acrylate is preferably 5% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 80% by mass or less based on the mass of the adhesive component (adhesive composition excluding conductive particles) By mass, and particularly preferably from 15% by mass to 70% by mass. When the blending amount of the urethane (meth) acrylate is within the above range, sufficient heat resistance is obtained after curing, and when used as a film-like adhesive, it becomes easy to obtain good film formability.

Further, it is also possible to use an N-vinyl compound selected from the group consisting of a vinyl compound having a phosphoric acid group (a vinyl compound containing a phosphoric acid group), an N-vinyl compound and an N, N- And can be used in combination with other radical polymerizing compounds. By using the phosphoric acid group-containing vinyl compound in combination, it becomes possible to improve the adhesiveness of the adhesive composition to the metal substrate. Further, by using the N-vinyl compound in combination, the crosslinking ratio of the adhesive composition can be improved.

The phosphoric acid group-containing vinyl compound is not particularly limited as long as it is a compound having a phosphoric acid group and a vinylic group, but a compound represented by the following formulas (N) to (P) is preferable.

In the formula (N), R ²⁰ represents a (meth) acryloyloxy group, R ²¹ represents a hydrogen atom or a methyl group, and l and m each independently represent an integer of 1 to 8. In the formula, R ²⁰ , R ²¹ , l and m may be the same or different from each other.

In the formula (O), R ²² represents a (meth) acryloyloxy group, and n, o and p each independently represent an integer of 1 to 8. In the formula, R ²² may be the same or different from each other, and n, o and p may be the same or different.

In the above formula (P), R ²³ represents a (meth) acryloyloxy group, R ²⁴ represents a hydrogen atom or a methyl group, q and r each independently represent an integer of 1 to 8. In the formula, R ²³ , R ²⁴ , q and r may be the same or different from each other.

Specific examples of the phosphoric acid group-containing vinyl compound include acid phosphoxyethyl methacrylate, acid phosphoxyethyl acrylate, acid phosphoxypropyl methacrylate, acid phosphoxypolyoxyethylene glycol monomethacrylate, Polyoxypropylene glycol monomethacrylate, 2,2'-di (meth) acryloyloxydiethyl phosphate, EO-modified phosphoric acid dimethacrylate, phosphoric acid-modified epoxy acrylate, and vinyl phosphate.

Specific examples of the N-vinyl compound include N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4'- Bis (N, N-dimethylaniline), N-vinylacetamide, N, N-dimethylacrylamide and N, N-diethylacrylamide.

The compounding amount of the phosphoric acid group-containing vinyl compound and the N-vinyl compound is preferably 0.2% by mass or less based on the mass of the adhesive component (adhesive composition excluding conductive particles), independently of the compounding amount of the radically polymerizable compound other than the phosphoric acid group- Or more and 15 mass% or less, more preferably 0.3 mass% or more and 10 mass% or less, and particularly preferably 0.5 mass% or more and 5 mass% or less. When the blending amount of the phosphoric acid group-containing vinyl compound and the N-vinyl compound is within the above range, it becomes easy to make both the adhesive strength of the adhesive composition and the physical properties after curing of the adhesive composition easy to assure reliability.

The compounding amount of the radical polymerizing compound other than the phosphoric acid group-containing vinyl compound and the N-vinyl compound is preferably 5% by mass or more and 95% by mass or less based on the mass of the adhesive component (adhesive composition excluding conductive particles) More preferably not less than 80% by mass, and particularly preferably not less than 15% by mass and not more than 70% by mass. When the compounding amount of the radical polymerizing compound is within the above range, sufficient heat resistance can be obtained after curing, and when used as a film-like adhesive, it becomes easy to obtain good film formability.

As the radical polymerization initiator contained in the adhesive composition, conventionally known compounds such as organic peroxides and azo compounds capable of generating radicals by the application of external energy can be used. The radical polymerization initiator is preferably an organic peroxide having a half-life temperature for one minute of 90 占 폚 or more and 175 占 폚 or less and a molecular weight of 180 or more and 1,000 or less from the viewpoints of stability, reactivity and compatibility. When the one-minute half-life temperature is within this range, the storage stability is excellent, the radical polymerization is sufficiently high, and curing can be performed in a short time.

Specific examples of the radical polymerization initiator include 1,1,3,3-tetramethylbutyl peroxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) Oxydicarbonate, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, dilauryl peroxide, 1-cyclohexyl-1-methylethyl peroxyneo Decanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexa (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate , t-butylperoxyneoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexa Nonoate, 3-hydroxy-1,1-di Methyl butyl peroxyneodecanoate, 1,1,3,3-tetramethyl butyl peroxy-2-ethyl hexanoate, t-amyl peroxyneodecanoate, t-amyl peroxy-2-ethylhexa T-butyl peroxymaleic acid, t-butyl peroxymaleic acid, t-butyl peroxymaleic acid, t-butyl peroxymaleic acid, t-butyl peroxymaleic acid, Butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) hexane, 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoyl peroxy) hexane, t-butyl peroxybenzoate, dibutyl peroxytrimethyl adipate , t-amyl peroxynormal octoate, t-amyl peroxyisonanoate and t-amyl peroxybenzoate, organic peroxides such as 2,2'-azobis-2,4-dimethylvaleronitrile, 1 ' -azobis (1-acetoxy-1-phenyl) Azobisisobutyronitrile, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyronitrile, 4,4'- Azo compounds such as azobis (4-cyanovaleric acid) and 1,1'-azobis (1-cyclohexanecarbonitrile). These compounds may be used alone or in combination of two or more.

As the radical polymerization initiator, a compound capable of generating a radical by light irradiation at 150 nm or more and 750 nm or less can be used. As such a compound, for example, photoinitiation, Photopolymerization, and Photocuring, J.-P. Acetaminophenone derivatives or phosphine oxide derivatives described in Fouassier, Hanser Publishers (1995, p17 to p35)} are more preferable because of their high sensitivity to light irradiation. These compounds may be used alone or in combination with the organic peroxide or azo compound.

The blending amount of the radical polymerization initiator is preferably 0.5% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 30% by mass or less based on the mass of the adhesive component (adhesive composition excluding conductive particles) % Or more and 20 mass% or less. When the blending amount of the radical polymerization initiator is within the above range, it becomes easy to make both the curing property and the storage stability of the adhesive composition compatible.

The thermoplastic resin contained in the adhesive composition becomes a liquid state having a high viscosity by heating and is freely deformed by an external force. When the external force is removed by cooling, the thermoplastic resin becomes hard while maintaining its shape, (Polymer) can be suitably used. It also includes a resin (polymer) having a reactive functional group having the above properties. The Tg of the thermoplastic resin is preferably from -30 占 폚 to 190 占 폚, more preferably from -25 占 폚 to 170 占 폚, and particularly preferably from -20 占 폚 to 150 占 폚.

As such thermoplastic resin, polyimide resin, polyamide resin, phenoxy resin, (meth) acrylic resin, urethane resin, polyester urethane resin, polyvinyl butyral resin, vinyl acetate copolymer and the like can be used. These may be used alone or in combination of two or more. These thermoplastic resins may contain siloxane bonds or fluorine-substituted groups. These can be suitably used as long as the resins to be mixed are completely compatible with each other or in a state where they are opaque due to micro-phase separation.

When the adhesive composition is formed into a film and used as a film-like adhesive, the larger the molecular weight of the thermoplastic resin, the better the film formability can be easily obtained and the melt viscosity affecting the flowability as a film- have. The weight average molecular weight of the thermoplastic resin is preferably 5,000 to 150,000, more preferably 7,000 to 100,000, and particularly preferably 10000 to 80,000. When the weight average molecular weight of the thermoplastic resin is within the above range, it becomes easy to achieve both good film formation and good compatibility with other components.

The weight average molecular weight in the present embodiment is determined by gel permeation chromatography (GPC) analysis under the following conditions and converted by using a standard polystyrene calibration curve.

The GPC conditions are as follows.

Equipment: Hitachi L-6000 type (trade name, manufactured by Hitachi Seisakusho Co., Ltd.)

Detector: L-3300RI (trade name, manufactured by Hitachi, Ltd.)

Column: Gel pack GL-R420 + Gel pack GL-R430 + Gel pack GL-R440 (three in total) (trade name, manufactured by Hitachi Kasei Kogyo Co., Ltd.)

Eluent: tetrahydrofuran

Measuring temperature: 40 ° C

Flow rate: 1.75 ml / min

The content of the thermoplastic resin is preferably 5 mass% or more and 80 mass% or less, more preferably 15 mass% or more and 70 mass% or less, based on the mass of the adhesive component (adhesive composition excluding conductive particles). When the content of the thermoplastic resin is within the above range, when the adhesive composition is used as a film, it becomes easy to achieve good film formability and good flowability of the film-form adhesive.

It is preferable that the conductive particles contained in the adhesive composition are particles having conductivity on the whole or at least the surface thereof. When used for connection of circuit members having connection terminals (circuit electrodes), the average particle diameter Small is more preferable.

Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, Pd, and solder, and carbon. It is also possible to use a non-conductive glass, ceramic, plastic, or the like as a nucleus and coating the nucleus with the metal, metal particles, or carbon. In the case of the conductive particles coated with the metal, the metal particles or the carbon, or the hot molten metal particles with the plastic as a nucleus, since the conductive particles have deformability by heating and pressing, the contact area with the electrodes increases during connection, Is improved. The conductive particles may be, for example, particles in which silver is coated on metal particles containing copper. As the conductive particles, a metal powder having a shape in which a plurality of fine metal particles are connected in a chain, such as that described in Japanese Patent Application Laid-Open No. 2005-116291, may be used.

The fine particles in which the surfaces of these conductive particles are further coated with insulating particles or the insulating layer containing an insulating material is provided on the surfaces of the conductive particles by a method such as hybridization, It may be suitably used alone or in combination with other conductive particles since it is possible to suppress a short circuit due to contact between particles in the case of increasing the blending amount and to improve the insulating property between the electrode circuits.

The average particle diameter of the conductive particles is preferably 1 占 퐉 or more and 18 占 퐉 or less from the viewpoints of dispersibility and conductivity. When such conductive particles are contained, the adhesive composition can be suitably used as an anisotropic conductive adhesive.

The amount of the conductive particles to be used is not particularly limited, but is preferably 0.1% by volume or more and 30% by volume or less based on the total volume of the adhesive composition, more preferably 0.1% by volume or more and 10% by volume or less. When the amount of the conductive particles used is within the above range, sufficient conductivity can be obtained, and short circuit of the circuit can be sufficiently suppressed. The volume% is determined based on the volume of each component before curing at 23 ° C, but the volume of each component can be converted from weight to volume using the specific gravity. Further, by adding a suitable solvent (water, alcohol, or the like) which does not dissolve or swell the components thereof in a graduated cylinder or the like, the increased volume of the component can be obtained as the volume of the component .

In addition, a stabilizer may be added to the adhesive composition in order to control the curing rate and impart storage stability. As such a stabilizer, known compounds can be used without particular limitation, but quinone derivatives such as benzoquinone and hydroquinone, phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol, 2,2,6,6,6 Aminoxyl derivatives such as tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, hexamers such as tetramethylpiperidyl methacrylate A dodamine derivative and the like are preferable.

The blending amount of the stabilizer is preferably 0.005 mass% or more and 10 mass% or less, more preferably 0.01 mass% or more and 8 mass% or less, more preferably 0.02 mass% or less, based on the mass of the adhesive component (adhesive composition excluding conductive particles) By mass or more and 5% by mass or less. When the blending amount of the stabilizer is within the above range, compatibility with other components is not adversely affected, and control of the curing rate and storage stability can be imparted.

Adhesion aids such as coupling agents, adhesion improving agents and leveling agents typified by alkoxysilane derivatives and silazane derivatives may be suitably added to the adhesive composition. As the coupling agent, specifically, a compound represented by the following formula (Q) is preferable, and in addition to being used alone, two or more compounds may be mixed and used.

In the above formula (Q), R ²⁵ , R ²⁶ and R ²⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms Or an aryl group, and R ²⁸ represents a (meth) acryloyl group, a vinyl group, an isocyanate group, an imidazole group, a mercapto group, an amino group, a methylamino group, a dimethylamino group, a benzylamino group, a phenylamino group, a cyclohexylamino group, A piperazino group, an ureido group or a glycidyl group, and s represents an integer of 1 to 10.

The adhesive composition may be used in combination with a rubber component for the purpose of improving the adhesiveness. The rubber component refers to a component exhibiting rubber elasticity (JIS K6200) or a component exhibiting rubber elasticity by reaction under the same condition. The rubber component may be solid at room temperature (25 占 폚) or may be liquid, but it is preferably liquid in view of improvement of flowability. As the rubber component, a compound having a polybutadiene skeleton is preferable. The rubber component may have a cyano group, a carboxyl group, a hydroxyl group, a (meth) acryloyl group or a morpholine group. From the viewpoint of improvement in adhesion, a rubber component containing a cyano group or a carboxyl group having a high polar group at the side chain or terminal is preferable. Even if the polybutadiene skeleton is present, it is classified as a thermoplastic resin when it exhibits thermoplasticity, and is classified as a radical polymerizable compound when it exhibits radical polymerization.

Specific examples of the rubber component include polyisoprene, polybutadiene, carboxyl terminated polybutadiene, hydroxyl terminated polybutadiene, 1,2-polybutadiene, carboxyl terminated 1,2-polybutadiene, hydroxyl terminated 1,2-polybutadiene, Butadiene rubber, acrylonitrile-butadiene rubber, carboxyl group, hydroxyl group, acrylonitrile-butadiene rubber containing a (meth) acryloyl group or a morpholine group at the polymer terminal, a carboxylated nitrile rubber , Hydroxyl-terminated poly (oxypropylene), alkoxysilyl-terminated poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol and the like.

Specific examples of the rubber component having a high polar group and being liquid at room temperature include liquid acrylonitrile-butadiene rubber, liquid acrylonitrile containing carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the end of the polymer -Butadiene rubber, and liquid carboxyxylated nitrile rubber. The content of acrylonitrile as a polar group is preferably 10% by mass or more and 60% by mass or less.

These compounds may be used alone or in combination of two or more.

The adhesive composition may also contain organic fine particles other than the core-shell type silicon fine particles according to the present invention for the purpose of improving stress relaxation and adhesion. The average particle diameter of the organic fine particles is preferably 0.05 탆 or more and 1.0 탆 or less. When the organic fine particles include the above-mentioned rubber component, they are classified into a rubber component other than the organic fine particles. When the organic fine particles include the above-mentioned thermoplastic resin, they are classified as thermoplastic resins that are not organic fine particles.

Specific examples of the organic fine particles include polyisoprene, polybutadiene, carboxyl terminated polybutadiene, hydroxyl terminated polybutadiene, 1,2-polybutadiene, carboxyl terminated 1,2-polybutadiene, acrylic rubber, styrene-butadiene rubber, acrylonitrile Acrylonitrile-butadiene rubber, carboxyxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene), alkoxysilyl-terminated poly (meth) acrylate containing a butadiene rubber, carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer terminal Styrene copolymers, alkyl (meth) acrylate-silicone copolymers, or silicone (meth) -acrylic copolymers or complexes, such as poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol Fine particles.

The adhesive composition can be used in the form of a paste when it is liquid at room temperature. In the case of a solid at room temperature, in addition to being used by heating, a paste may be formed using a solvent. As the solvent which can be used, it is preferable that it has no reactivity with the adhesive composition and the additive and exhibits sufficient solubility, and it is preferable that the solvent has a boiling point of 50 캜 or more and 150 캜 or less at normal pressure. When the boiling point of the solvent is within the above range, it is difficult to volatilize even if left at room temperature, easy to use in an open system, and the solvent can be sufficiently volatilized to secure sufficient reliability after bonding.

The adhesive composition of the present invention may be molded into a film and used as an adhesive on a film. A solution such as a solvent or the like is added to the adhesive composition if necessary, or the solution is applied to a releasable substrate such as a fluororesin film, a polyethylene terephthalate film, or a release paper, or the substrate is impregnated with a solution such as a non- And the solvent or the like may be removed and used as an adhesive on a film. When used in the form of a film, it is more convenient in view of handleability and the like.

The adhesive composition of the present invention can be bonded together by heating and pressurization. The heating temperature is preferably 100 deg. C or higher and 200 deg. C or lower. The pressure is preferably within a range that does not cause damage to the adherend, and is generally preferably 0.1 MPa or more and 10 MPa or less. The heating and pressing are preferably performed in a range of 0.5 second or more and 120 seconds or less, and it is possible to perform bonding even at a heating temperature of 110 DEG C or more and 190 DEG C or less at 3 MPa for 10 seconds.

The adhesive composition of the present invention can be used as an adhesive composition of a different adherend having a different thermal expansion coefficient. Specifically, it can be used as a circuit connecting material represented by an anisotropic conductive adhesive, a silver paste, a silver film and the like.

When the circuit member is connected using the adhesive composition of the present invention, for example, a first circuit member having a first circuit electrode formed on a first circuit substrate and a second circuit member having a second circuit electrode formed on the second circuit substrate The first circuit member and the second circuit member are bonded to each other so that the first circuit electrode and the second circuit electrode are electrically connected to each other with the adhesive composition of the present invention interposed therebetween, The members are connected to each other to obtain a circuit connecting body.

Wherein at least one of the first circuit board and the second circuit board includes at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate as a thermoplastic resin having a glass transition temperature of 200 캜 or lower . By including such a thermoplastic resin, the wettability with the adhesive composition of the present invention is improved, and the bonding strength and the connection reliability are improved.

It is preferable that one of the first circuit board and the second circuit board includes at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate, and the other circuit board And at least one member selected from the group consisting of polyimide resin, polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer. By using such a circuit board, the wettability with the adhesive composition of the present invention is further improved, and the bonding strength and the connection reliability are further improved.

As the circuit substrate, an inorganic substrate such as semiconductor, glass, or ceramic, an organic substrate, or the like may be used in combination.

In addition, the adhesive composition of the present invention does not need to reach full curing (maximum curing that can be achieved under predetermined curing conditions), and may be in a partially cured state as long as the above properties are generated.

Example

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples.

[Production of conductive particles]

A nickel layer having a thickness of 0.2 占 퐉 was provided on the surface of particles made of polystyrene as nuclei and a gold layer having a thickness of 0.02 占 퐉 was provided on the outer side of the nickel layer to prepare conductive particles having an average particle diameter of 10 占 퐉 and a specific gravity of 2.5.

[Preparation of adhesive composition]

The adhesive compositions of Examples 1 to 5 and Comparative Examples 1 to 11 were prepared by blending each component shown in Table 1 at a solid mass ratio shown in Table 1 and further mixing and dispersing 1.5% by volume of the conductive particles. Each component shown in Table 1 will be described in detail below.

≪ Thermoplastic resin &

(Polyester urethane resin A)

4,4'-diphenylmethane diisocyanate (manufactured by Aldrich) was added to the isocyanate using terephthalic acid (manufactured by Aldrich), isophthalic acid (manufactured by Aldrich), and neopentyl glycol (manufactured by Aldrich) , A polyester urethane resin A in which the molar ratio of terephthalic acid / isophthalic acid / neopentyl glycol / 4,4'-diphenylmethane diisocyanate was 0.34 / 0.66 / 1.1 / 0.33 was prepared. The number average molecular weight of the obtained polyester urethane resin A was 25,000. The resultant polyester urethane resin A (PEU-A) was dissolved in a ratio of 1: 1 of methyl ethyl ketone and toluene to a solid content of 40% by mass.

(YP-50: phenoxy resin)

A phenoxy resin (trade name: YP-50) manufactured by Tokto Kasei Co., Ltd. was dissolved in methyl ethyl ketone and used as a solution having a solid content of 40 mass%.

(EV40W: ethylene-vinyl acetate copolymer)

(Solids content 30% by mass) (EV40W (trade name), manufactured by Mitsui DuPont Polychemical Co., Ltd.) of ethylene-vinyl acetate copolymer was used.

<Radical Polymerizable Compound>

(UA1: urethane (meth) acrylate 1)

(1,6-hexanediol carbonate) having a number average molecular weight of 1000 (trade name: Dulanol T5652, manufactured by Asahi Kasei Corporation) was charged in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, 2500 parts by mass (2.50 moles) of isophorone diisocyanate (manufactured by Sigma Chemical Co., Ltd.) and 666 parts by mass (3.00 moles) of isophorone diisocyanate (Sigma Aldrich) were uniformly added dropwise over 3 hours, Thereafter, the mixture was heated at 70 to 75 ° C for reaction.

Subsequently, 0.53 parts by mass of hydroquinone monomethyl ether (Sigma Aldrich) and 5.53 parts by mass of dibutyltin dilaurate (Sigma Aldrich) were added, and then 2-hydroxyethyl acrylate (Sigma Aldrich) 238 parts by mass (2.05 mol) were added and the mixture was allowed to react at 70 캜 for 6 hours in an air atmosphere to obtain urethane (meth) acrylate 1 (UA1).

(UA2: urethane (meth) acrylate 2)

In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introducing tube, 1000 parts by mass of methyl ethyl ketone, 100 parts by mass of polycaprolactone diol having a number average molecular weight of 1,000 (trade name: , 2,500 parts by mass (2.50 mol) of isophorone diisocyanate (manufactured by Sigma Chemical Co., Ltd.) and 666 parts by mass (3.00 mol) of isophorone diisocyanate (Sigma Aldrich) were uniformly added dropwise over 3 hours, Thereafter, the mixture was heated at 70 to 75 ° C for reaction.

Subsequently, 0.53 parts by mass of hydroquinone monomethyl ether (Sigma Aldrich) and 5.53 parts by mass of dibutyltin dilaurate (Sigma Aldrich) were added, and then 2-hydroxyethyl acrylate (Sigma Aldrich) 238 parts by mass (2.05 mol) were added, and the mixture was reacted at 70 캜 for 6 hours under an air atmosphere to obtain urethane (meth) acrylate 2 (UA2).

&Lt; Organic fine particles &

(KMP-600)

Core-shell type silicon fine particles (trade name: KMP-600, manufactured by Shinetsu Chemical Industry Co., Ltd., average particle size: 5 μm) were used. The glass transition temperature of the core layer of the silicon fine particles was -110 deg.

(BR: crosslinked polybutadiene fine particles)

Pure water was added to a stainless steel autoclave, and polyvinyl alcohol (manufactured by KANTO CHEMICAL Co., Ltd.) as a suspending agent was added and dissolved. Among them, butadiene (manufactured by Sigma Aldrich) was added and dispersed by stirring. Subsequently, benzoyl peroxide (trade name: CARDOS CH-50L, manufactured by Kayaku Co., Ltd.) was dissolved as a radical polymerization initiator and stirred. Subsequently, the temperature of the autoclave was raised to 60 to 65 占 폚 and polymerization was carried out for 45 minutes under stirring. After releasing unreacted monomers, the resultant crosslinked polybutadiene particles were filtered, washed with water, and washed with ethanol, and the obtained crosslinked polybutadiene particles were dried under vacuum to obtain crosslinked polybutadiene fine particles (BR). The obtained crosslinked polybutadiene fine particles were dispersed in methyl ethyl ketone, and the average particle diameter of the particles was measured using a Zetasizer Nano-S (manufactured by Malvern Instruments Ltd.). The average particle diameter was 0.5 탆.

(KMP594: silicone rubber fine particles)

(Trade name: KMP594, average particle diameter 5 占 퐉, glass transition temperature: -70 占 폚) manufactured by Shin-Etsu Chemical Co., Ltd. was used.

(W-5500)

Core-shell type acrylic fine particles (trade name: Metablen W-5500, average particle diameter: 0.6 mu m) manufactured by Mitsubishi Rayon Co., Ltd. were used.

(BTA-712)

Core-shell acrylic acid alkyl ester-butadiene-styrene copolymer microparticles (trade name: Paraloid BTA-712) manufactured by Rohm and Haas Co. was used.

&Lt; Vinyl compound having phosphoric acid group >

(P-2M)

2- (meth) acryloyloxyethylphosphate (trade name: Liteester P-2M) manufactured by Kyoeisha Chemical Co., Ltd. was used.

&Lt; Radical polymerization initiator &

(Knife BW)

Dibenzoyl peroxide (trade name: Knife BW) manufactured by Nichiyu Corporation was used.

[Production of film-like adhesive]

The adhesive compositions of Examples 1 to 5 and Comparative Examples 1 to 14 were applied to a fluorine resin film (substrate) having a thickness of 80 占 퐉 using a coating apparatus and dried by hot air at 70 占 폚 for 10 minutes, An adhesive sheet having an adhesive layer of 20 mu m was obtained. The film-like adhesives of Examples 1 to 10 and Comparative Examples 1 to 11 were used in which the substrate was peeled from the adhesive sheet. However, in the case of the film-like adhesives of Comparative Examples 4, 8 and 12, it was found that the agglomerates of the KMP594 used produced irregularities on the surface of the adhesive layer, and the evaluation of the properties could not be performed.

[Measurement of connection resistance and adhesive strength]

(Reference Examples 1 to 9)

A film-like adhesive of Examples 1, 2, 5 and Comparative Examples 3, 5 to 7, 9 and 10 was laminated on a polyimide film (Tg 350 DEG C) with a copper wire having a line width of 25 mu m, a pitch of 50 mu m, (Having a thickness of 1.1 mm and a surface resistance of 20? /?) On which a thin film of ITO of 0.2 占 퐉 was formed. This was heated and pressed at 150 DEG C and 2 MPa for 10 seconds using a thermocompression bonding apparatus (heating system: Constant heat type, manufactured by Dore Engineering Co., Ltd.) and bonded over a width of 2 mm to prepare a circuit connector.

The resistance value between the adjacent circuits of the circuit connecting body was measured by a multimeter immediately after bonding and after holding for 240 hours in a high temperature and high humidity bath at 85 캜 and 85% RH (after the test). The resistance value was expressed as an average of 37 points of resistance between adjacent circuits.

Further, the adhesive strength of the connector was measured by a 90 degree peeling method according to JIS-Z0237, and evaluated. As a bonding strength measuring device, "Tensilon UTM-4" (trade name) (peeling speed: 50 mm / min, 25 ° C) manufactured by Toyo Baldwin Co., Ltd. was used. The measurement results are shown in Table 2.

As shown in Table 2, the circuit connecting bodies of Reference Examples 1 to 9 exhibited good connection resistance of 4.0 Ω or less and good bonding strength of 560 N / m or more, both at the heating temperature of 150 ° C. immediately after bonding and after the test, Respectively. That is, it was confirmed that the difference in the kind of the organic fine particles did not greatly affect the connection resistance and the bonding strength in the adhesion between the flexible circuit board including the polyimide film and the glass on which the ITO thin film was formed.

(Examples 1 to 5 and Comparative Examples 1 to 14)

The film-like adhesives of Examples 1 to 5 and Comparative Examples 1 to 14 were laminated on a polyimide film (Tg 350 ° C) with a flexible circuit board (FPC (polytetrafluoroethylene)) having 80 copper circuits with a line width of 150 μm, a pitch of 300 μm and a thickness of 8 μm ) And a PET substrate (thickness: 0.1 mu m) on which a thin layer of Ag paste with a thickness of 5 mu m was formed. Subsequently, the laminate was heated and pressed at 150 DEG C and 2 MPa for 20 seconds using a thermocompression bonding apparatus (heating method: Constant heat type, manufactured by Dore Engineering Co., Ltd.) and bonded over a width of 2 mm.

The resistance value between the adjacent circuits of the circuit connecting member was measured by a multimeter immediately after bonding and after holding for 240 hours in a high temperature and high humidity bath at 85 캜 and 85% RH (after the test). The resistance value was expressed as an average of 37 points of resistance between adjacent circuits. The measurement results are shown in Table 3.

Further, the film-like adhesives of Examples 1 to 5 and Comparative Examples 1 to 14 were formed by forming an Ag paste circuit having a line width of 150 mu m, a pitch of 300 mu m, and a thickness of 10 mu m on a PET, PC or PEN film having a thickness of 0.1 mu m The substrate and the FPC. Subsequently, the laminate was heated and pressed at 150 DEG C and 2 MPa for 20 seconds by using the thermocompression bonding apparatus, and bonded over a width of 2 mm to prepare a circuit connecting body.

The bonding strength of the circuit connecting member was measured by a 90 degree peeling method according to JIS-Z0237 and evaluated. As a bonding strength measuring device, "Tensilon UTM-4" (trade name) (peeling speed: 50 mm / min, 25 ° C) manufactured by Toyo Baldwin Co., Ltd. was used. The measurement results are shown in Table 3.

The circuit connecting material manufactured using the film-like adhesive of Examples 1 to 5 had a good connection resistance of about 2.6 Ω or less and a tensile strength of about 600 N / m or more And a good adhesive strength was exhibited.

On the other hand, the circuit connecting material produced using the film-like adhesive of Comparative Examples 1 to 14 (excluding Comparative Examples 4, 8 and 12) containing no silicon fine particles exhibited good connection resistance, The adhesive strength was as low as 590 N / m or less, and the adhesive strength after the test was lower than 510 N / m.

From the above results, it was found that when a pair of circuit members including a thermoplastic resin having a glass transition temperature of 200 DEG C or lower is adhered to at least one of the circuit boards, by using the adhesive composition containing the silicon fine particles according to the present invention, Excellent adhesion strength can be obtained even under curing conditions, and it has become clear that stable performance (adhesive strength and connection resistance) can be maintained even after a long time reliability test (high temperature and high humidity test).

&Lt; Industrial applicability >

The adhesive composition according to the present invention has excellent heat resistance such as PRT, PC, PEN and COP because it can obtain excellent adhesive strength even when cured at a low temperature on a circuit board containing a thermoplastic resin having a glass transition temperature of 200 DEG C or lower It is suitably used in adhesion between a semiconductor element using a low organic substrate and an FPC.

5 ... Adhesive sheet, 6 ... Equipment, 8 ... Adhesive layer (adhesive composition), 9 ... Adhesive component, 10 ... Silicon fine particles, 10a ... Core shell type silicon fine particles, 11 ... Core layer, 12 ... Share Floor, 20 ... Conductive particles, 30 ... The first circuit member, 31 ... The first circuit board 31a, The main surface of the first circuit board, 32 ... The first circuit electrode, 40 ... A second circuit member, 41 ... The second circuit board, 41a ... The main surface of the second circuit board, 42 ... The second circuit electrode, 50 ... Connection, 100 ... Circuit connections.

Claims (20)

A first circuit member having a first circuit electrode formed on a first circuit board and a second circuit member having a second circuit electrode formed on a second circuit board are arranged such that the first circuit electrode and the second circuit electrode are electrically The adhesive composition comprising:
Wherein at least one of the first circuit board and the second circuit board comprises a thermoplastic resin having a glass transition temperature of 200 DEG C or lower,
Shell type silicon fine particles having a core layer and a shell layer provided so as to cover the core layer. A first circuit member having a first circuit electrode formed on a first circuit board and a second circuit member having a second circuit electrode formed on a second circuit board are arranged such that the first circuit electrode and the second circuit electrode are electrically The adhesive composition comprising:
Wherein at least one of the first circuit board and the second circuit board includes at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymer,
Shell type silicon fine particles having a core layer and a shell layer provided so as to cover the core layer. The adhesive composition according to claim 1 or 2, wherein the core layer of the silicone fine particles has a glass transition temperature of -130 캜 or higher and -20 캜 or lower. The adhesive composition according to any one of claims 1 to 3, further comprising a radically polymerizable compound. The adhesive composition according to any one of claims 1 to 4, further comprising conductive particles. A film-like adhesive obtained by molding the adhesive composition according to any one of claims 1 to 5 into a film. An adhesive sheet comprising: a base material; and an adhesive layer comprising the film-like adhesive material according to claim 6 formed on the base material. A first circuit member having a first circuit electrode formed on a first circuit board,
A second circuit member having a second circuit electrode formed on the second circuit board,
The first circuit electrode and the second circuit electrode are interposed between a surface of the first circuit member on which the first circuit electrode is formed and a surface of the second circuit member on which the second circuit electrode is formed, A circuit connecting body having a connecting portion to be connected,
Wherein at least one of the first circuit board and the second circuit board comprises a thermoplastic resin having a glass transition temperature of 200 DEG C or lower,
Wherein the connecting portion comprises a cured product of the adhesive composition as claimed in any one of claims 1 to 5. The circuit connector according to claim 8, wherein the thermoplastic resin comprises at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymer. 9. The circuit board according to claim 8, wherein one of the first circuit board and the second circuit board comprises at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer Including,
And the other circuit board comprises at least one member selected from the group consisting of polyimide resin, polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer. A first circuit member having a first circuit electrode formed on a first circuit board,
A second circuit member having a second circuit electrode formed on the second circuit board,
The first circuit electrode and the second circuit electrode are interposed between a surface of the first circuit member on which the first circuit electrode is formed and a surface of the second circuit member on which the second circuit electrode is formed, A circuit connecting body having a connecting portion to be connected,
Wherein at least one of the first circuit board and the second circuit board includes at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymer,
Wherein the connecting portion comprises a cured product of the adhesive composition as claimed in any one of claims 1 to 5. 12. The circuit board according to claim 11, wherein one of the first circuit board and the second circuit board comprises at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer Including,
And the other circuit board comprises at least one member selected from the group consisting of polyimide resin, polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer. A first circuit member having a first circuit electrode formed on a first circuit board,
And the second circuit member having the second circuit electrode formed on the second circuit substrate are cured by interposing the adhesive composition according to any one of claims 1 to 5, The first circuit member and the second circuit member are bonded to each other so that the two circuit electrodes are electrically connected to each other,
Wherein at least one of the first circuit board and the second circuit board is a substrate including a thermoplastic resin having a glass transition temperature of 200 占 폚 or less. A first circuit member having a first circuit electrode formed on a first circuit board,
And the second circuit member having the second circuit electrode formed on the second circuit substrate are cured by interposing the adhesive composition according to any one of claims 1 to 5, The first circuit member and the second circuit member are bonded to each other so that the two circuit electrodes are electrically connected to each other,
Wherein at least one of the first circuit board and the second circuit board is a substrate including at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymer Connection method. A use of the adhesive composition according to any one of claims 1 to 5,
A first circuit member on which a first circuit electrode is formed on a first circuit board and a second circuit member on which a second circuit electrode is formed on a second circuit board,
The first circuit electrode and the second circuit electrode are electrically connected to each other,
Wherein at least one of the first circuit substrate and the second circuit substrate is a substrate comprising a thermoplastic resin having a glass transition temperature of 200 DEG C or lower. A use of the adhesive composition according to any one of claims 1 to 5,
A first circuit member on which a first circuit electrode is formed on a first circuit board and a second circuit member on which a second circuit electrode is formed on a second circuit board,
The first circuit electrode and the second circuit electrode are electrically connected to each other,
Wherein at least one of the first circuit board and the second circuit board is a substrate comprising at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer, Use of. The use of the film-like adhesive according to claim 6,
A first circuit member having a first circuit electrode formed on a main surface of the first circuit substrate and a second circuit member having a second circuit electrode formed on a main surface of the second circuit substrate,
The first circuit electrode and the second circuit electrode are electrically connected to each other,
Wherein at least one of the first circuit board and the second circuit board is a substrate comprising a thermoplastic resin having a glass transition temperature of 200 DEG C or lower. The use of the film-like adhesive according to claim 6,
A first circuit member on which a first circuit electrode is formed on a first circuit board and a second circuit member on which a second circuit electrode is formed on a second circuit board,
The first circuit electrode and the second circuit electrode are electrically connected to each other,
Wherein at least one of the first circuit board and the second circuit board is a substrate comprising at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer, Uses of adhesives. A use of the adhesive sheet according to claim 7,
A first circuit member having a first circuit electrode formed on a main surface of the first circuit substrate and a second circuit member having a second circuit electrode formed on a main surface of the second circuit substrate,
The first circuit electrode and the second circuit electrode are electrically connected to each other,
Wherein at least one of the first circuit board and the second circuit board is a substrate comprising a thermoplastic resin having a glass transition temperature of 200 DEG C or lower. A use of the adhesive sheet according to claim 7,
A first circuit member on which a first circuit electrode is formed on a first circuit board and a second circuit member on which a second circuit electrode is formed on a second circuit board,
The first circuit electrode and the second circuit electrode are electrically connected to each other,
Wherein at least one of the first circuit board and the second circuit board is a substrate including at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer, Use of.

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