JP6532850B2 - Adhesive composition, film adhesive, adhesive sheet, circuit connector, method of connecting circuit members, use of adhesive composition, use of film adhesive, and use of adhesive sheet - Google Patents

Description

  The present invention relates to an adhesive composition, a film adhesive, an adhesive sheet, a circuit connector, a method of connecting circuit members, use of an adhesive composition, use of a film adhesive, and use of an adhesive sheet.

  In semiconductor devices and liquid crystal display devices, various adhesive compositions are conventionally used for the purpose of bonding various members in the devices. The adhesive composition is, for example, a connection between a liquid crystal display element and TCP (Tape Carrier Package) or COF (Chip On Film), a connection between TCP or COF and a printed wiring board, FPC (Flexible Printed Circuit) and printed wiring It is used for connection with a board, mounting to the substrate of a semiconductor element, etc.

  Heretofore, as an adhesive composition for semiconductor devices and liquid crystal display devices, a thermosetting resin containing an epoxy resin exhibiting high adhesiveness and high reliability has been used (see, for example, Patent Document 1). As a component of the thermosetting resin, a curing agent such as an epoxy resin and a phenol resin having reactivity with the epoxy resin, and a heat latent catalyst which accelerates the reaction of the epoxy resin and the curing agent are generally used. The heat latent catalyst is a substance which does not react at storage temperatures such as room temperature and shows high reactivity when heated. It is also an important factor in determining the curing temperature and curing speed, and various compounds are used from the viewpoint of storage stability of the adhesive composition at room temperature and the curing speed upon heating. In the actual process, the desired adhesion is obtained by curing conditions in which curing is performed at a temperature of 170 ° C. to 250 ° C. for 1 to 3 hours.

  On the other hand, with the recent trend toward higher integration of semiconductor devices and higher definition of liquid crystal display, the pitch between devices and wires has been narrowed, and heating at the time of curing has a tendency to adversely affect peripheral members. It is required to cure the agent composition. Moreover, since it is necessary to improve the throughput for cost reduction, it is also required to cure the adhesive composition in a short time.

  However, in order to achieve low temperature and short time curing (low temperature fast curing) in thermosetting resin containing conventional epoxy resin, it is necessary to use a heat latent catalyst with low activation energy, In that case, there is a problem that the storage stability of the adhesive composition at room temperature is reduced.

  Instead, a radical curable adhesive composition in which a radically polymerizable compound such as a (meth) acrylate derivative and a peroxide which is a radical polymerization initiator are used in combination as an adhesive composition having a low temperature fast curing property is noted (See, for example, Patent Document 2). According to radical curing, since a radical which is a reactive species is rich in reactivity, curing at low temperature and in a short time is possible.

  However, since the adhesive composition using radical curing has a large cure shrinkage at the time of curing, it is inferior to the adhesive strength as compared with the case of using the epoxy resin, and in particular, the adhesive strength to the inorganic or metallic substrate There is a tendency to decline.

  In the case of connecting a semiconductor device using a glass substrate or the like, a printed circuit board using a liquid crystal display device or an FR4 substrate, and a flexible printed circuit (FPC) using a polymer film such as polyimide or polyester as a substrate There is a problem that internal stress based on the difference in thermal expansion coefficient becomes large, causing peeling of the adhesive composition and reduction in connection reliability.

  As a method of improving the adhesive strength, a method using an adhesive aid represented by a silane coupling agent (see, for example, Patent Document 3), a method of imparting flexibility of a cured product by ether bond and improving adhesive strength (See, for example, Patent Document 4), a method (see Patent Documents 5, 6, 7, etc.), etc., for improving adhesion strength by dispersing stress absorbing particles made of a rubber-based elastic material in an adhesive composition. It is done.

Unexamined-Japanese-Patent No. 1-113480 WO 98/044067 pamphlet Patent No. 3434886 Patent No. 3503740 Patent No. 3477367 WO 09/020005 pamphlet WO 09/051067 pamphlet

  Recently, circuit members including polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), cycloolefin polymer (COP), etc. for the purpose of reducing the thickness, weight and flexibility of touch panels, electronic paper etc. Application of is being considered. However, when using a low heat resistant organic substrate such as PET, PC, PEN, COP, etc., the adhesive composition at a lower temperature is more likely because heating during curing tends to adversely affect the organic substrate and peripheral members. It is required to cure the object. In addition, since the surfaces of PET, PC, PEN, COP and the like are smooth, the adhesion effect by the physical anchoring effect (anchor effect) is small.

  Therefore, in a radical curable adhesive composition having low temperature curing properties, it is desirable to improve the adhesive strength, but organic substrates such as PET, PC, PEN, COP, etc., which are thermoplastic resins, have benzene rings etc. It is difficult to form a covalent bond with a silane coupling agent, since it is easy to form a crystalline part by intermolecular interaction by Therefore, when these organic substrates are used, the method described in Patent Document 3 can not obtain a sufficient adhesive strength improvement effect.

  In addition, organic base materials such as PET, PC, PEN and COP have a thermal expansion coefficient larger than that of a glass substrate, and also have different surface energy. Therefore, it is necessary to impart sufficient flexibility to the adhesive composition in order to improve the wettability to the adherend and reduce the internal stress, but the method described in Patent Document 4 provides sufficient flexibility. It can not be applied, and a further improvement in adhesive strength is desired.

  Even by the method described in Patent Document 5, since the glass transition temperature of the stress absorbing particles is as high as 80 ° C. to 120 ° C., a sufficient stress relaxation effect can not be obtained, and adhesion strength and connection resistance after a high temperature and high humidity test are obtained. There is a problem that sufficient performance can not be obtained. Also by the method of dispersing the stress absorbing particles described in Patent Document 6, a sufficient adhesive strength improvement effect to organic substrates such as PET, PC, PEN, COP and the like can not be obtained. Further, in the methods described in Patent Documents 5, 6, and 7, since epoxy resin is used as a curing component of the adhesive composition, heating at relatively high temperature is required to obtain sufficient adhesion. There is a concern that the heat-resistant PET, PC, PEN, COP and other organic substrates may be adversely affected.

  Therefore, according to the present invention, an organic base material with low heat resistance such as polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), cycloolefin polymer (COP) and the like is cured even at low temperature Adhesive composition capable of obtaining excellent adhesive strength and maintaining stable performance (adhesive strength and connection resistance) even after long-term reliability test (high temperature and high humidity test) It is an object of the present invention to provide a film adhesive, an adhesive sheet, a circuit connector, a method of connecting circuit members, the use of an adhesive composition, the use of a film adhesive, and the use of an adhesive sheet.

  As a result of intensive studies to solve the above problems, the present inventors have found that thermoplastic resins having low heat resistance, such as polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), cycloolefin polymer (COP), etc. It has been found that the low adhesive strength in the connection between the organic base material of the above and the semiconductor element or liquid crystal display element is due to insufficient relaxation of the internal stress. As a result of further investigations to solve these, excellent adhesive strength can be obtained by using silicone fine particles having a specific structure, and stable performance even after a long time reliability test (high temperature high humidity test) It was found that (adhesive strength and connection resistance) could be maintained, leading to the completion of the present invention.

  That is, the present invention relates to 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. An adhesive composition for bonding the first circuit electrode and the second circuit electrode so as to electrically connect the first circuit electrode and the second circuit electrode, wherein at least the first circuit board and the second circuit board An adhesive composition, wherein one of the substrates is a substrate containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less, and a core-shell type silicone fine particle having a core layer and a shell layer provided to cover the core layer. Provide the goods.

  Since the adhesive composition contains silicone fine particles having the above-described specific structure, the interaction between the silicone fine particles is alleviated and the structural viscosity (non-Newtonian viscosity) is lowered, so that the silicone fine particles are dispersed in the resin. It is considered that the property is improved and the internal stress can be sufficiently relieved effectively. Thereby, the adhesive strength with respect to the base material (for example, PET, PC, PEN, COP etc.) containing a thermoplastic resin whose glass transition temperature is 200 degrees C or less can be improved, and the adhesive strength between circuit members can be improved. In addition, stable performance (adhesive strength and connection resistance) can be maintained even after long-term reliability tests.

  In the present specification, “a substrate containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less” means a polymer handbook as a thermoplastic resin (Polymer Science Society, edited by: Polymer Data Handbook, Basic, p. 525, Baifukan ( 1986)) and the like, and is a substrate comprising a thermoplastic resin having a glass transition temperature indicated by a value of 200 ° C. or less. Here, the thermoplastic resin is a resin having thermoplasticity and usually does not have a cross-linked structure, but includes thermoplastic resins having some cross-linked structure as long as it has thermoplasticity. The glass transition temperature of the thermoplastic resin can be determined by the measurement method described later.

  The present invention also provides 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. An adhesive composition for bonding the first circuit electrode and the second circuit electrode so as to electrically connect the first circuit electrode and the second circuit electrode, the adhesive composition comprising the first circuit board and the second circuit board At least one is a substrate comprising at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer, and having a core layer and a shell layer provided so as to cover the core layer. Provided is an adhesive composition containing core-shell type silicone microparticles.

  Since the adhesive composition contains silicone fine particles having the above-described specific structure, the interaction between the silicone fine particles is alleviated and the structural viscosity (non-Newtonian viscosity) is lowered, so that the silicone fine particles are dispersed in the resin. It is considered that the property is improved and the internal stress can be sufficiently relieved effectively. Thereby, the adhesive strength with respect to the base material containing at least 1 sort (s) chosen from the group which consists of a polyethylene terephthalate, a polycarbonate, polyethylene naphthalate, and a cycloolefin polymer can be improved, and the adhesive strength between circuit members can be improved. In addition, stable performance (adhesive strength and connection resistance) can be maintained even after long-term reliability tests.

  The glass transition temperature of the core layer of the silicone fine particles is preferably -130 ° C or more and -20 ° C or less, more preferably -125 ° C or more and -40 ° C or less, and particularly preferably -120 ° C or more. 50 ° C. or less. Thereby, the internal stress can be sufficiently relieved, and the adhesion strength between the circuit members can be improved. In addition, stable performance can be maintained even after long-term reliability tests. If the glass transition temperature is higher than -20 ° C, the internal stress can not be sufficiently relaxed, and a sufficient adhesive strength improvement effect tends not to be obtained. If the glass transition temperature is lower than -130 ° C, sufficient cohesion can not be obtained. Adhesive strength tends to decrease.

  The adhesive composition according to the present invention preferably further contains a radically polymerizable compound. This allows for lower temperature cure adhesion.

  The adhesive composition preferably further contains conductive particles. By containing the conductive particles, good conductivity or anisotropic conductivity is imparted to the adhesive composition, and hence it is more suitably used for bonding applications of circuit members having circuit electrodes (connection terminals). . Moreover, connection resistance can be further reduced by electrically connecting between the circuit members through the adhesive composition containing the conductive particles.

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

  The present invention relates to 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. The first circuit electrode is interposed between the surface of the first circuit member on which the first circuit electrode is formed and the surface of the second circuit member on which the second circuit electrode is formed. And a connection portion electrically connecting the second circuit electrode to the second circuit electrode, wherein at least one of the first circuit board and the second circuit board has a glass transition temperature of 200 It is a board | substrate containing the thermoplastic resin of ° C or less, and the said connection part provides the circuit connection body which consists of hardened | cured material of the adhesive composition concerning the said invention.

  In the circuit connection body according to the present invention, the connection portion is made of the cured product of the adhesive composition according to the present invention, so that the substrate having the glass transition temperature of 200 ° C. or less is excellent The adhesive strength and the stable performance (adhesive strength and connection resistance) after the long-term reliability test can be obtained.

  The thermoplastic resin preferably contains at least one 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 adhesive strength is further improved, and excellent connection reliability can be obtained.

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

  The present invention also provides 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. A first circuit member 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; It is a circuit connection body provided with the connection part which electrically connects an electrode and said 2nd circuit electrode, Comprising: At least one of said 1st circuit board and said 2nd circuit board is a polyethylene terephthalate, a polycarbonate, A circuit connecting body is provided, wherein the substrate includes at least one selected from the group consisting of polyethylene naphthalate and cycloolefin polymer, and the connecting portion is a cured product of the adhesive composition according to the present invention.

  In the above-mentioned circuit connector, a substrate comprising at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer when the connection portion is made of the cured product of the adhesive composition according to the present invention Even in the case where is used, it is possible to obtain excellent adhesive strength and stable performance (adhesive strength and connection resistance) after a long-term reliability test.

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

  The present invention relates to 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. Between the first circuit member and the first circuit member, the first circuit electrode and the second circuit electrode are electrically connected by interposing and curing the adhesive composition according to the present invention. A method of connecting circuit members, which adheres to two circuit members, wherein at least one of the first circuit board and the second circuit board includes a thermoplastic resin having a glass transition temperature of 200 ° C. or less The present invention provides a method of connecting circuit members.

  According to the method of connecting circuit members according to the present invention, sufficient adhesive strength and long-term reliability test can be performed even when low-temperature curing suitable for a substrate containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less is performed. A circuit connection having stable performance (adhesive strength and connection resistance) can be obtained.

  The present invention also provides 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. The first circuit member and the above-mentioned first circuit member and the above-mentioned second circuit electrode are electrically connected by interposing and curing the adhesive composition according to the present invention between them. A method of connecting circuit members, which adheres to a second circuit member, wherein at least one of the first circuit board and the second circuit board is made of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer. A method for connecting circuit members, which is a substrate comprising at least one selected from the group consisting of

  According to the method of connecting circuit members described above, sufficient adhesion is achieved even when a low temperature curing suitable for a substrate including at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer is performed. A circuit connection having stable performance (adhesive strength and connection resistance) after the strength and long-term reliability test can be obtained.

  The present invention is the use of the adhesive composition of the present invention, wherein the first circuit member has a first circuit electrode formed on a first circuit board, and a second circuit member on a second circuit board. The first circuit board is used to bond a second circuit member on which the first circuit electrode is formed to electrically connect the first circuit electrode and the second circuit electrode. The use of the adhesive composition is provided, wherein at least one of the second circuit boards is a substrate comprising a thermoplastic resin having a glass transition temperature of 200 ° C. or less.

  The present invention is also the use of the adhesive composition of the present invention, wherein the first circuit member has a first circuit electrode formed on a first circuit board, and a second circuit board on a second circuit board. The first circuit is used to bond a second circuit member, on which two circuit electrodes are formed, to electrically connect the first circuit electrode and the second circuit electrode. The use of the above adhesive composition is provided, wherein at least one of the substrate and the second circuit substrate is a substrate comprising at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer. .

  The present invention is the use of the film-like adhesive according to the present invention, wherein the first circuit member has a first circuit electrode formed on a first circuit board, and a second circuit board on a second circuit board. The first circuit board is used to bond a second circuit member on which the first circuit electrode is formed to electrically connect the first circuit electrode and the second circuit electrode. And the use of the film adhesive as described above, wherein at least one of the second circuit substrates is a substrate comprising a thermoplastic resin having a glass transition temperature of 200 ° C. or less.

  The present invention is also the use of the film-like adhesive according to the present invention, wherein the first circuit member has a first circuit electrode formed on a first circuit board, and a second circuit board on the second circuit board. The first circuit is used to bond a second circuit member, on which two circuit electrodes are formed, to electrically connect the first circuit electrode and the second circuit electrode. Provided is the use of the film adhesive as described above, wherein at least one of the substrate and the second circuit substrate comprises at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer. .

  The present invention is the use of the adhesive sheet of the present invention, wherein the first circuit member has a first circuit electrode formed on a first circuit board, and a second circuit on a second circuit board. It is used to bond a second circuit member on which an electrode is formed, so that the first circuit electrode and the second circuit electrode are electrically connected, and the first circuit board and the above The use of the above adhesive sheet is provided, wherein at least one of the second circuit boards is a substrate comprising a thermoplastic resin having a glass transition temperature of 200 ° C. or less.

  The present invention is also the use of the adhesive sheet of the present invention, wherein the first circuit member has a first circuit electrode formed on a first circuit board, and a second circuit member on a second circuit board. The first circuit board is used to bond a second circuit member on which a circuit electrode is formed to electrically connect the first circuit electrode and the second circuit electrode. The use of the adhesive sheet is provided, wherein at least one of the second circuit boards is a substrate comprising at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer.

  According to the present invention, an organic substrate with low heat resistance such as polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), cycloolefin polymer (COP), etc. is cured even at low temperature Adhesive composition capable of obtaining excellent adhesive strength and maintaining stable performance (adhesive strength and connection resistance) even after long-term reliability test (high temperature and high humidity test) It is possible to provide the film adhesive, the adhesive sheet, the circuit connector, the method of connecting the circuit members, the use of the adhesive composition, the use of the film adhesive, and the use of the adhesive sheet.

It is an end elevation which shows one Embodiment of the adhesive sheet of this invention. It is an end elevation showing one embodiment of silicone fine particles of the present invention. It is an end elevation showing one embodiment of the circuit connection object of the present invention.

  Hereinafter, modes for carrying out 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” indicates acrylic acid or corresponding methacrylic acid, “(meth) acrylate” means acrylate or corresponding methacrylate, and “(meth) acryloyl group” The term "acryloyl group" means an acryloyl group or a corresponding methacryloyl group.

  The “glass transition temperature (Tg)” of a thermoplastic resin or a circuit board is a temperature increase rate of 5 ° C./min using a viscoelastic analyzer “RSA-3” (trade name) manufactured by TA Instruments. The value of tan δ peak temperature is measured under the conditions of a frequency of 10 Hz and a measurement temperature of -150 ° C to 300 ° C. In the measurement of the glass transition temperature of the circuit substrate, when an underlayer such as a glass layer, a hard coat layer such as an acrylic resin layer, a gas barrier layer, etc. are formed on a thermoplastic resin substrate, they are included. Measure the glass transition temperature of the circuit board.

  The “glass transition temperature (Tg)” of the fine particles means that the fine particles are dispersed in a thermoplastic resin having a known Tg, and the produced film is a visco-elastic analyzer “RSA-3” manufactured by TA Instruments Co., Ltd. It is the value of tan δ peak temperature measured under the conditions of temperature rise rate of 5 ° C / min, frequency of 10 Hz and measurement temperature of -150 ° C to 300 ° C.

  The “average particle size” of the fine particles is the average particle diameter measured using Zetasizer Nano-S (trade name of Malvern Instruments Ltd.) after diluting the fine particles to 0.1 wt% (mass%) with methyl ethyl ketone Z-average value). Moreover, about the microparticles | fine-particles which have a particle size of the magnitude | size which can not measure correctly with the said measuring apparatus, it is an average measured using Shimadzu laser diffraction type | formula particle size distribution measuring apparatus SALD-2200 (The Shimadzu Corp. make, brand name) Particle sizes can also be used.

  The adhesive composition according to the present invention is characterized by containing silicone fine particles having a core-shell type structure. The core-shell structure includes a structure having a core layer and a shell layer provided to cover the core layer, and a glass transition temperature or a temperature higher than the glass transition temperature or elastic modulus of the surface of the core material (core layer) There are those having a surface layer (shell layer) having an elastic modulus, those having a graft layer (shell layer) outside the core material (core layer), etc., and silicone fine particles having the same or different compositions in the core layer and shell layer. Can be used. Specifically, an alkaline substance or an alkaline aqueous solution and an organotrialkoxysilane are added to an aqueous dispersion of silicone rubber spherical fine particles, followed by hydrolysis and condensation reaction (see, for example, Japanese Patent No. 2832143). It is also possible to use core-shell type silicone granules as described in WO 2009/051067. Further, silicone fine particles having a functional group such as a hydroxyl group, an epoxy group, a ketimine, a carboxyl group or a mercapto group at a molecular end or a molecular inner chain can be used. Such silicone fine particles are preferable because the dispersibility in the film forming component and the radically polymerizable substance is improved. The core layer and the shell layer described above may not necessarily have clear boundaries.

  The core layer constituting the above-mentioned core-shell type silicone fine particles is preferably silicone or silicone rubber from the viewpoint of the stress relaxation effect, and the shell layer can use the same kind of polymer of the core layer or other types of polymers. It is preferable that the physical properties (glass transition temperature, elastic modulus, etc.) of the shell layer be higher than that of the core layer. Thereby, the structure and shape of the core layer can be stabilized, and the performance thereof is effectively exhibited. In particular, when silicone, silicone rubber or the like is used as the core layer, the silicone or silicone rubber swells with the solvent or the constituent material of the adhesive composition, and these fine particles adhere to each other to easily form an aggregate. The formation of the aggregate can be suppressed by forming the shell layer.

  The glass transition temperature of the core layer of the silicone fine particles is preferably -130 ° C or more and -20 ° C or less, more preferably -125 ° C or more and -40 ° C or less, and particularly preferably -120 ° C or more. 50 ° C. or less. Such silicone particles can sufficiently relieve the internal stress of the adhesive composition.

  In addition, from the viewpoint of alleviating internal stress, the weight average molecular weight of the core layer of the silicone fine particles is preferably not more than 1,500,000, more preferably not more than 1,500,000 and not less than 500,000, and particularly preferably not less than 1.4 million and not less than 800,000.

In addition, the weight average molecular weight in this embodiment is measured by gel permeation chromatography (GPC) analysis under the following conditions, and is obtained by conversion using a standard polystyrene calibration curve.
The GPC conditions are as follows.
Equipment used: Hitachi L-6000 (manufactured by Hitachi, Ltd., trade name)
Detector: L-3300RI (manufactured by Hitachi, Ltd., trade name)
Column: gel pack GL-R420 + gel pack GL-R430 + gel pack GL-R440 (total three) (manufactured by Hitachi Chemical Co., Ltd., trade name)
Eluent: tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 1.75 ml / min

  The shell layer in the core-shell type silicone fine particles preferably has a crosslinked structure to achieve structural stabilization, shape maintenance, and high functionalization of the core layer, and has a three-dimensional network structure. It is more preferable that the structure be a structure, and it is particularly preferable that the shell layer be a crosslinked structure having a three-dimensional network structure. More preferably, it is an organic compound such as polymethyl methacrylate copolymer, or an inorganic compound such as silicone, silica, silsesquioxane or the like. Thereby, relaxation of internal stress by silicone is exhibited effectively.

As a method of confirming the structure of the silicone fine particle and the core-shell type silicone fine particle, the cross-section of the core-shell type silicone fine particle can be confirmed by surface observation and composition analysis of the surface. As a specific method, it can be confirmed by performing structural analysis by a transmission electron microscope (TEM) under the conditions shown below.
Resin casting: Epoxy resin (Epomount main agent and curing agent manufactured by Refintech Co., Ltd.)
Heavy metal staining: A 2% by mass aqueous solution of OsO ₄ (osmium tetraoxide) is prepared, and the bulk staining of the casted sample is performed in it for 24 hours.
Pretreatment: The film is pretreated with a diamond knife at a blade speed of 0.6 mm / sec while cooling to -120 ° C with a cryoultramicrotome to form a thin film.
TEM observation: Hitachi High-Technologies Corporation STEM / EDX apparatus; HD-2700 is used to confirm the type and configuration of the core layer and shell layer from the image or EDX mapping.

As another method, structural analysis by an atomic force microscope (AFM) can be performed under the conditions shown below.
Resin casting: Epoxy resin (Epomount main agent and curing agent manufactured by Refintech Co., Ltd.)
Pretreatment: The film is pretreated with a diamond knife at a blade speed of 0.6 mm / sec while cooling to -120 ° C with a cryoultramicrotome to form a thin film.
Observation: A cross section is observed using an atomic force microscope AFM manufactured by SII Nano Technology, and a shape image and a phase image are measured in the DFM mode to confirm the core-shell structure in the phase image.

  The average particle diameter of the silicone fine particles is preferably 0.05 μm or more and 25 μm or less, more preferably 0.1 μm or more and 20 μm or less, and particularly preferably 0.6 μm or more and 10 μm or less. By setting the average particle diameter of the silicone fine particles in the above range, it is easy to achieve both the fluidity of the adhesive composition and the relaxation of the internal stress.

  The amount of the silicone fine particles is preferably 1% by mass to 50% by mass, and more preferably 3% by mass to 30% by mass, based on the mass of the adhesive component (adhesive composition excluding conductive particles). And more preferably 5% by mass to 30% by mass. By setting the amount of the silicone fine particles in the above range, relaxation of internal stress, and flexibility (elastic modulus, elongation) and adhesive strength of the adhesive composition can be sufficiently obtained.

  The core-shell type silicone fine particles may be used alone or in combination of two or more. Furthermore, as long as the effects of the present invention are not impaired, it may be used in combination with other silicone fine particles.

  From the viewpoint of dispersibility and relaxation of internal stress, the weight-average molecular weight of the silicone particles is preferably not more than 1,500,000, more preferably not more than 1,500,000 and not less than 500,000, and not less than 1.4 million and not less than 800,000. Particularly preferred. Moreover, it is preferable that other silicone microparticles have a three-dimensional crosslinked structure. "Having a three-dimensional crosslinked structure" indicates that the polymer chain has a three-dimensional network structure. The silicone fine particles having a three-dimensional crosslinked structure have high dispersibility in a resin and are further excellent in stress relaxation after curing. The fine particles of silicone having a weight average molecular weight of 1,000,000 or more and / or a three-dimensional crosslinked structure have low dispersibility in polymers, monomers, solvents, etc., such as thermoplastic resins, so the dispersibility and stress relaxation effect can be more remarkable. be able to.

  Other silicone microparticles include microparticles of polyorganosilsesquioxane resin having rubber elasticity, and spherical and amorphous silicone microparticles are used. Specifically, silicone microparticles obtained by the reaction of an organopolysiloxane having at least two vinyl groups, an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms, and a platinum-based catalyst (for example, JP-A-62-257939), organopolysiloxane having an alkenyl group, organopolysiloxane having a hydrosilyl group, silicone fine particles obtained using a platinum-based catalyst (see, for example, JP-A-63-77942), Silicone microparticles obtained using organosiloxane, monoorganosilsesquioxane, triorganosiloxane and platinum-based catalyst (see, for example, JP-A-62-270660), water of methylsilanetriol and / or partial condensate thereof / Alcohol dissolution The silicone particles obtained by performing the dropped polycondensation reaction in an aqueous alkaline solution (for example, see Patent JP No. 3970453), or the like can be used. In addition, in order to improve the dispersibility and the adhesion to the substrate, silicone fine particles to which an epoxy compound is added or copolymerized (for example, see JP-A-3-167228), or an acrylic ester compound is added or copolymerized. Also, fine particles of silicone may be used.

  The radically polymerizable compound contained in the adhesive composition refers to a compound which causes radical polymerization by the action of a radical polymerization initiator, but is a compound which itself generates radicals by applying activation energy such as light and heat. It may be. As a radically polymerizable compound, the compound which has a functional group which superposes | polymerizes by active radicals, such as a vinyl group, a (meth) acryloyl group, an aryl group, maleimide group, can be used suitably, for example.

  Specific examples of the radically polymerizable compound include epoxy (meth) acrylate oligomers, urethane (meth) acrylate oligomers, polyether (meth) acrylate oligomers, oligomers such as polyester (meth) acrylate oligomers, and trimethylolpropane tri (meth) acrylate , Polyethylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy ethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexahex (Meth) acrylate, isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) acrylate, bisphenoxyethanol Orene acrylate, epoxy (meth) acrylate obtained by adding (meth) acrylic acid to glycidyl group of bisphenol furan orange glycidyl ether, bis phenoxyethanol fluorene acrylate, glycidyl group of bisphenol furan orange glycidyl ether added (meth) acrylic acid Compounds obtained by introducing a (meth) acryloyloxy group to a compound obtained by adding ethylene glycol or propylene glycol to a glycidyl group of epoxy (meth) acrylate, bisphenol furan orange glycidyl ether, represented by the following general formula (A) or (B) Compounds and the like.

In the above general 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 above general 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.

  Moreover, as a radically polymerizable compound, there is no fluidity such as waxy, waxy, crystalline, glassy, powdery, etc. when it is left alone at 30 ° C., and it shows a solid state, especially, It can be used without restriction. Specific examples of such radically polymerizable compounds include N, N'-methylenebisacrylamide, diacetone acrylamide, N-methylol acrylamide, N-phenyl methacrylamide, 2-acrylamido-2-methylpropane sulfonic acid, tris ( 2-acryloyloxyethyl) isocyanurate, N-phenyl maleimide, N- (o-methylphenyl) maleimide, N- (m-methylphenyl) maleimide, N- (p-methylphenyl) -maleimide, N- (o-) Methoxyphenyl) maleimide, N- (m-methoxyphenyl) maleimide, N- (p-methoxyphenyl) -maleimide, N-methyl maleimide, N-ethyl maleimide, N-octyl maleimide, 4,4'-diphenylmethane bismaleimide, m-phenylene Smaleimide, 3,3′-Dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, N-methacryloxymaleimide, N-acryloxymaleimide, 1 , 6-Bismaleimide- (2,2,4-trimethyl) hexane, N-methacryloyloxysuccinimide, N-acryloyloxysuccinimide, 2-naphthyl methacrylate, 2-naphthyl acrylate, pentaerythritol tetraacrylate, divinyl ethylene Urea, divinylpropylene urea, 2-polystyrylethyl methacrylate, N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N-phenyl-N'-(3-acryloyloxy- 2- Droxypropyl) -p-phenylenediamine, tetramethyl piperidyl methacrylate, tetramethyl piperidyl acrylate, pentamethyl piperidyl methacrylate, pentamethyl piperidyl acrylate, octadecyl acrylate, N-t-butyl acrylamide, diacetone acrylamide, N- (hydroxy methyl) ) Acrylamide, a compound represented by any one of the following general formulas (C) to (L), and the like can be mentioned.

上記一般式（Ｃ）中、ｅは１〜１０の整数を示す。

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

In the general formula (E), ^{R 5} and ^{R 6} each independently represent a hydrogen atom or a methyl group, f is an integer of 15 to 30.

In the above general 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.

上記一般式（Ｇ）中、Ｒ^９は水素原子又はメチル基を示す。

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

上記一般式（Ｈ）中、Ｒ^１０は水素原子又はメチル基を示し、ｈは１〜１０の整数を示す。

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

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

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

上記一般式（Ｋ）中、Ｒ^１３は水素原子又はメチル基を示す。

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

上記一般式（Ｌ）中、Ｒ^１４は水素原子又はメチル基を示す。

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

  Also, as the radically polymerizable compound, urethane (meth) acrylate can be used alone or together with other radically polymerizable compounds. By using urethane (meth) acrylate, flexibility can be improved, and adhesion strength to organic substrates such as PET, PC, PEN, COP and the like can be improved.

  Although there is no restriction | limiting in particular as a urethane (meth) acrylate, It is preferable to use the urethane (meth) acrylate represented by the following general formula (M). Here, the urethane (meth) acrylate represented by the following general formula (M) is an aliphatic or alicyclic diisocyanate and at least one or more kinds of aliphatic or alicyclic ester diols or aliphatic or alicyclic It can be obtained by a condensation reaction with a carbonate-based diol.

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

  Aliphatic diisocyanates constituting the above urethane (meth) acrylate are tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2, 2,4-Trimethylhexamethylene-1,6-diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated trimethyl It is selected from xylylene diisocyanate and the like.

  Aliphatic ester-based diols constituting the above urethane (meth) acrylate are ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, Neopentyl glycol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2 2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2 -Ethyl-1,3-hexanediol, 2, 5-dimethyl-2, 5-hexanediol, 1,2- Cutandiol, 1,8-octanediol, 1,7-heptanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-decanediol, dodecanediol, pinacol, 1 Saturated low molecular weight glycols such as 2,4-butynediol, triethylene glycol, diethylene glycol, dipropylene glycol, cyclohexane dimethanol, 1,4-cyclohexane dimethanol, etc., and adipic acid, 3-methyl adipic acid, 2,2 , 5, 5- tetramethyladipic acid, maleic acid, fumaric acid, succinic acid, 2,2-dimethylsuccinic acid, 2-ethyl-2-methylsuccinic acid, 2,3-dimethylsuccinic acid, oxalic acid, malonic acid, Methyl malonic acid, ethyl malonic acid, butyl malonic acid, dimethyl malo Acid, glutaric acid, 2-methyl glutaric acid, 3-methyl glutaric acid, 2, 2- dimethyl glutaric acid, 3, 3- dimethyl glutaric acid, 2,4- dimethyl glutaric acid, pimelic acid, suberic acid, azelaic acid, It is selected from polyester diols obtained by dehydrating condensation of dibasic acids such as sebacic acid or acid anhydrides corresponding thereto and polyester diols obtained by ring-opening polymerization of cyclic ester compounds such as ε-caprolactone. The polyester diols obtained from the above diols and dicarboxylic acids may be used alone or in combination of two or more polyester diols.

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

  The weight average molecular weight of the above urethane (meth) acrylate may be freely adjusted within the range of 5,000 or more and less than 30,000 from the viewpoint of improving the adhesive strength to a substrate such as PET, PC, PEN, COP etc. it can. If the weight average molecular weight of the urethane (meth) acrylate is within the above range, both flexibility and cohesion can be obtained, and adhesion strength with organic substrates such as PET, PC, PEN, COP and the like is improved. You can get excellent connection reliability. Furthermore, when the weight average molecular weight of the urethane (meth) acrylate is in the above range, it becomes easy to achieve both sufficient flexibility and fluidity of the adhesive composition. Further, from the viewpoint of obtaining such effects more sufficiently, the weight average molecular weight of the urethane (meth) acrylate is more preferably 80000 or more and less than 25000, and particularly preferably 10000 or more and less than 20000.

In addition, the weight average molecular weight in this embodiment is measured by gel permeation chromatography (GPC) analysis under the following conditions, and is obtained by conversion using a standard polystyrene calibration curve.
The GPC conditions are as follows.
Equipment used: Hitachi L-6000 (manufactured by Hitachi, Ltd., trade name)
Detector: L-3300RI (manufactured by Hitachi, Ltd., trade name)
Column: gel pack GL-R420 + gel pack GL-R430 + gel pack GL-R440 (total three) (manufactured by Hitachi Chemical Co., Ltd., trade name)
Eluent: tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 1.75 ml / min

  The content of the urethane (meth) acrylate 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), and is 10% by mass or more and 80% by mass. % Or less is more preferable, and 15% by mass or more and 70% by mass or less is particularly preferable. When the compounding amount of the urethane (meth) acrylate is in the above range, sufficient heat resistance is obtained after curing, and when used as a film adhesive, it becomes easy to obtain good film formability .

  In addition, N-vinyl selected from the group consisting of vinyl compounds having phosphoric acid groups (phosphoric acid group-containing vinyl compounds), N-vinyl compounds and N, N-dialkylvinyl compounds, which are compounds belonging to radically polymerizable compounds The compounds can be used in combination with other radically polymerizable compounds. The combined use of a phosphoric acid group-containing vinyl compound makes it possible to improve the adhesion of the adhesive composition to a metal substrate. Moreover, the crosslinking rate of an adhesive composition can be improved by combined use of a N-vinyl type compound.

  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 vinyl group, but compounds represented by the following general formulas (N) to (P) are preferable.

In the above general 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 formulae, R ^20's , R ^21's , l's and m may be the same or different.

In the above general 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 formulae, R ^22's , n's, o's and p's may be the same or different.

In the general 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 1-8 integer. In the formulae, R ^{23 's} , R ^{24' s} , q 's and r's may be the same or different.

  Specific examples of the phosphoric acid group-containing vinyl compound include acid phosphooxyethyl methacrylate, acid phosphooxyethyl acrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol monomethacrylate, 2,2'-di (meth) acryloyloxy diethyl phosphate, EO modified phosphoric acid dimethacrylate, phosphoric acid modified epoxy acrylate, vinyl phosphate etc. are mentioned.

  On the other hand, as N-vinyl compounds, specifically, N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4'-vinylidene bis (N, N) Dimethylaniline), N-vinylacetamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and the like.

  The compounding amount of the phosphoric acid group-containing vinyl compound and the N-vinyl compound is an adhesive component (adhesive composition excluding conductive particles) independently of the compounding amount of the radically polymerizable compound other than the phosphoric acid group-containing vinyl compound. It is preferable that it is 0.2 mass% or more and 15 mass% or less, more preferably 0.3 mass% or more and 10 mass% or less, and 0.5 mass% or more and 5 mass% or less based on the mass of Particularly preferred. When the compounding amount of the phosphoric acid group-containing vinyl compound and the N-vinyl compound is within the above range, it becomes easy to simultaneously achieve high adhesive strength of the adhesive composition and physical properties after curing of the adhesive composition. , It will be easier to ensure reliability.

  The blending amount of the radically polymerizable compound excluding the above-mentioned phosphoric acid group-containing vinyl compound and N-vinyl compound is 5% by mass or more and 95% by mass based on the mass of the adhesive component (adhesive composition excluding conductive particles) It is preferable that it is the following, It is more preferable that it is 10 to 80 mass%, 15 to 70 mass% is especially preferable. When the compounding amount of the radically polymerizable compound is in 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.

  As a radical polymerization initiator contained in an adhesive composition, the compound which generate | occur | produces a radical by provision of the energy from the outside, such as an organic peroxide known conventionally, and an azo compound, can be used. The radical polymerization initiator is preferably an organic peroxide having a one-minute half-life temperature of 90 ° C. or more and 175 ° C. or less and a molecular weight of 180 or more and 1,000 or less from the viewpoint of stability, reactivity, and compatibility. When the one-minute half-life temperature is in this range, the storage stability is excellent, the radical polymerization property is sufficiently high, and curing can be performed in a short time.

  Specific examples of the radical polymerization initiator include 1,1,3,3-tetramethylbutylperoxy neodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, and di (2-ethylhexyl). Peroxydicarbonate, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethylperoxyneodecanoate T-Hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-butyl peroxy pivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexene Peroxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t-butyl Peroxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxy neodecanoate, 1,1,3,3-tetramethyl Butylperoxy-2-ethylhexanoate, t-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, di (3-methylbenzoyl) peroxide, dibenzoyl peroxide, di-butyl peroxide (4-Methylbenzoyl) peroxide, t-hexylperoxyisopropyl monocar , T-butyl peroxymaleic acid, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy laurate, 2,5-dimethyl-2,5-di (3-methyl Benzoylperoxy) hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, Organic peroxides such as dibutylperoxytrimethyl adipate, t-amyl peroxy normal octoate, t-amyl peroxy isononanoate, t-amyl peroxybenzoate, 2,2'-azobis-2,4-dimethyl valero Nitrile, 1,1′-azobis (1-acetoxy-1-phenyl ester) Tan), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyronitrile, 4,4′-azobis Azo compounds such as (4-cyanovaleric acid), 1,1′-azobis (1-cyclohexanecarbonitrile) and the like can be mentioned. These compounds may be used alone or in combination of two or more.

  Moreover, as a radical polymerization initiator, the compound which generate | occur | produces a radical by light irradiation of 150 nm or more and 750 nm or less can be used. Such compounds include, for example, Photoinitiation, Photopolymerization, and Photocuring, J. Am. -P. The α-acetoaminophenone derivatives and phosphine oxide derivatives described in Fouassier and Hanser Publishers (1995, p17 to p35) are more preferable because they have high sensitivity to light irradiation. These compounds may be used alone or in combination with the above organic peroxide or azo compound.

  The compounding amount of the radical polymerization initiator is preferably 0.5% by mass or more and 40% by mass or less, and is 1% by mass or more and 30% by mass based on the mass of the adhesive component (adhesive composition excluding conductive particles). % Or less is more preferable, and 2% by mass or more and 20% by mass or less is particularly preferable. It becomes easy to make compatible the curability and storage stability of an adhesive agent composition as the compounding quantity of a radical polymerization initiator is in the said range.

  The thermoplastic resin contained in the adhesive composition turns into a liquid state with high viscosity by heating and is freely deformed by external force, and when it is cooled and removed from the external force, it becomes hard with its shape maintained, and this process is repeated to repeat Resins (polymers) having properties that can be used can be suitably used. Moreover, the resin (polymer | macromolecule) which has the reactive functional group which has said property is also included. The Tg of the thermoplastic resin is preferably −30 ° C. or more and 190 ° C. or less, more preferably −25 ° C. or more and 170 ° C. or less, and particularly preferably −20 ° C. or more and 150 ° C. or less.

  As such a 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 can be used individually or in mixture of 2 or more types. Furthermore, these thermoplastic resins may contain a siloxane bond or a fluorine substituent. These can be suitably used, as long as the resins to be mixed are completely compatible with each other, or microphase separation occurs to cause white turbidity.

  When the adhesive composition is formed into a film and used as a film adhesive, the larger the molecular weight of the thermoplastic resin, the better the film formability can be easily obtained, and the fluidity as a film adhesive The melt viscosity that affects the The weight average molecular weight of the thermoplastic resin is preferably 5,000 or more and 150000 or less, more preferably 7,000 or more and 100000 or less, and particularly preferably 10,000 or more and 80000 or less. When the weight average molecular weight of the thermoplastic resin is in the above range, it becomes easy to achieve both good film formation and good compatibility with other components.

In addition, the weight average molecular weight in this embodiment is measured by gel permeation chromatography (GPC) analysis under the following conditions, and is obtained by conversion using a standard polystyrene calibration curve.
The GPC conditions are as follows.
Equipment used: Hitachi L-6000 (manufactured by Hitachi, Ltd., trade name)
Detector: L-3300RI (manufactured by Hitachi, Ltd., trade name)
Column: gel pack GL-R420 + gel pack GL-R430 + gel pack GL-R440 (total three) (manufactured by Hitachi Chemical Co., Ltd., trade name)
Eluent: tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 1.75 ml / min

  The content of the thermoplastic resin is preferably 5% by mass or more and 80% by mass or less, and is 15% by mass or more and 70% by mass or less based on the mass of the adhesive component (adhesive composition excluding conductive particles). It is more preferable that When the content of the thermoplastic resin is in the above range, when the adhesive composition is formed into a film and used, both good film formation and good fluidity of the film-like adhesive can be achieved. It becomes easy.

  The conductive particles contained in the adhesive composition are preferably particles having conductivity on the whole or at least the surface, and when used for connection of a circuit member having a connection terminal (circuit electrode), between the connection terminals More preferably, the average particle size is smaller than the distance.

  Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, Pd, solder, and carbon. In addition, nonconductive glass, ceramic, plastic or the like may be used as a core, and the core may be coated with the above metal, metal particles or carbon. In the case where the conductive particles have plastic as a core and these nuclei are coated with the above metal, metal particles or carbon, or heat melting metal particles, they have deformability by heating and pressing, so the contact area with the electrode increases at the time of connection It is preferable because the reliability is improved. Also, the conductive particles may be, for example, particles obtained by coating metal particles made of copper with silver. Furthermore, as the conductive particles, metal powders having a shape in which a large number of fine metal particles are connected in a chain shape as described in JP-A-2005-116291 can also be used.

  Further, fine particles obtained by further covering the surface of these conductive particles with insulating particles, or fine particles provided with an insulating layer made of an insulating material on the surface of the conductive particles by a method such as hybridization are the conductive particles. A short circuit due to contact between particles when the compounding amount is increased can be suppressed, and the insulation between the electrode circuits can be improved. Therefore, it may be used alone or in combination with other conductive particles.

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

  The use amount of the conductive particles is not particularly limited, but is preferably 0.1% by volume to 30% by volume with respect to the total volume of the adhesive composition, and 0.1% by volume to 10% by volume It is more preferable to do. When the amount of the conductive particles used is in the above range, a short circuit in the circuit can be sufficiently suppressed while sufficient conductivity can be obtained. Although the volume% is determined based on the volume of each component before curing at 23 ° C., the volume of each component can be converted from weight to volume using specific gravity. In addition, the volume of the component can be increased by adding the component to an appropriate solvent (water, alcohol, etc.) that well wets the component without dissolving or swelling the component in a measuring cylinder or the like. It can also be determined as volume.

  In addition, a stabilizer can 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, and quinone derivatives such as benzoquinone and hydroquinone, phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol, 2, 2 Preferred are aminoxyl derivatives such as 6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and hindered amine derivatives such as tetramethyl piperidyl methacrylate.

  The compounding amount of the stabilizer is preferably 0.005% by mass or more and 10% by mass or less, 0.01% by mass or more and 8% by mass or less, based on the mass of the adhesive component (adhesive composition excluding conductive particles). It is more preferable that it is mass% or less, and 0.02 mass% or more and 5 mass% or less are especially preferable. When the compounding amount of the stabilizer is in the above range, control of the curing rate and provision of storage stability can be performed without adversely affecting the compatibility with other components.

  Moreover, you may add suitably adhesion | attachment adjuvants, such as a coupling agent represented by an alkoxysilane derivative and a silazane derivative, an adhesion improving agent, and a leveling agent, to an adhesive composition. Specifically as a coupling agent, the compound represented by the following general formula (Q) is preferable, and may be used in mixture of 2 or more types of compounds other than using independently.

In the above general 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, or 1 to 5 carbon atoms R ²⁸ represents a (meth) acryloyl group, a vinyl group, an isocyanate group, an imidazole 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 morpholino group, a piperazino group, a ureido group or a glycidyl group, and s represents an integer of 1 to 10;

  The adhesive composition may use a rubber component in combination for the purpose of improving adhesion. The rubber component refers to a component that exhibits rubber elasticity (JIS K6200) as it is or a component that exhibits rubber elasticity by reaction. The rubber component may be solid or liquid at room temperature (25 ° C.), but is preferably liquid from the viewpoint of improving fluidity. As a 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. Further, from the viewpoint of improving adhesion, a rubber component containing a cyano group which is a highly polar group and a carboxyl group in the side chain or at the end is preferable. In addition, even if it has a polybutadiene skeleton, it is classified as a thermoplastic resin when it exhibits thermoplasticity, and it is classified as a radical polymerizable compound when it exhibits radical polymerization.

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

  The rubber component having a high polar group and being liquid at room temperature specifically includes liquid acrylonitrile-butadiene rubber, carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer terminal. Liquid acrylonitrile-butadiene rubber, liquid carboxylated nitrile rubber and the like can be mentioned, and 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 be added with organic fine particles other than the core-shell type silicone fine particles according to the present invention for the purpose of stress relaxation and adhesion improvement. The average particle diameter of the organic fine particles is preferably 0.05 μm or more and 1.0 μm or less. When the organic fine particles consist of the above-mentioned rubber component, they are classified not as organic fine particles but as rubber components, and when the organic fine particles consist of the above-mentioned thermoplastic resin, they are classified not as organic fine particles but as thermoplastic resin.

  Specific examples of the organic fine particles include polyisoprene, polybutadiene, carboxyl group-terminated polybutadiene, hydroxyl group-terminated polybutadiene, 1,2-polybutadiene, carboxyl group-terminated 1,2-polybutadiene, acrylic rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, Acrylonitrile-butadiene rubber having carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at polymer terminal, carboxylated nitrile rubber, hydroxyl group-terminated poly (oxypropylene), alkoxysilyl group-terminated poly (oxypropylene), poly (oxy) Tetramethylene) glycol, polyolefin glycol (meth) acrylate alkyl-butadiene-styrene copolymer, (meth) acrylate alkyl-silicone copolymer or silicone Corn (meth) - include organic fine particles of acrylic copolymer or complex.

  The adhesive composition can be used in the form of a paste when it is liquid at normal temperature. In the case of solid at room temperature, it may be used by heating or pasted using a solvent. As the solvent which can be used, those which do not react with the adhesive composition and the additive and exhibit sufficient solubility are preferable, and those having a boiling point of 50 ° C. or more and 150 ° C. or less at normal pressure are preferable. When the boiling point of the solvent is in the above range, it is difficult to volatilize even when left at room temperature, and it is easy to use in an open system, and the solvent can be sufficiently volatilized in order to secure sufficient reliability after adhesion. .

  The adhesive composition of the present invention can also be formed into a film and used as a film adhesive. Apply a solution prepared by adding a solvent or the like to the adhesive composition if necessary, on a releasable substrate such as a fluororesin film, a polyethylene terephthalate film, or a release paper, or impregnate the solution into a substrate such as a nonwoven fabric. It can be placed on a releasable substrate, and the solvent and the like can be removed to use as a film adhesive. When used in the form of a film, it is more convenient in terms of handleability and the like.

  The adhesive composition of the present invention can be adhered using heating and pressure in combination. The heating temperature is preferably a temperature of 100 ° C. or more and 200 ° C. or less. The pressure is preferably in a range that does not damage the adherend, and in general, is preferably 0.1 MPa or more and 10 MPa or less. It is preferable to perform these heating and pressurization in the range of 0.5 seconds or more and 120 seconds or less, and it is possible to bond even heating of 110 ° C. or more and 190 ° C. or less, 3 MPa, and 10 seconds.

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

  In the case of connecting a circuit member using the adhesive composition of the present invention, for example, the first circuit member having a first circuit electrode formed on a first circuit board, and a second circuit board Between the first circuit electrode and the second circuit electrode by interposing and curing the adhesive composition of the present invention between the second circuit member on which the second circuit electrode is formed. By bonding the first circuit member and the second circuit member so as to connect to each other, the circuit members can be connected to each other to obtain a circuit connection body.

  At least one of the first circuit board and the second circuit board is 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 ° C. or less. It is preferable to include. By including such a thermoplastic resin, the wettability with the adhesive composition of the present invention is improved, and the adhesive strength and the connection reliability are improved.

  Furthermore, of the first circuit board and the second circuit board, one circuit board includes at least one selected from the group consisting of polyethylene terephthalate, polycarbonate and polyethylene naphthalate, and the other circuit board is polyimide. It is preferable to include at least one selected from the group consisting of a 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 adhesive strength and the connection reliability are further improved.

  Besides the above, as the circuit substrate, a semiconductor, an inorganic substrate such as glass or ceramic, an organic substrate or the like can be used in combination.

  The adhesive composition of the present invention does not have to reach complete curing (the highest degree of curing that can be achieved under predetermined curing conditions), and may be partially cured as long as the above-mentioned properties are produced.

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

[Preparation of conductive particles]
A 0.2 μm thick nickel layer is provided on the surface of particles having polystyrene as a core, a 0.02 μm thick gold layer is provided on the outside of this nickel layer, and conductive particles having an average particle diameter of 10 μm and a specific gravity of 2.5 are provided. Made.

[Preparation of Adhesive Composition]
Each component shown in Table 1 is compounded at a solid mass ratio shown in Table 1, and further, the conductive particles are compounded and dispersed by 1.5% by volume, and the adhesives of Examples 1 to 5 and Comparative Examples 1 to 11 are prepared. The composition was prepared. Hereinafter, each component shown in Table 1 will be described in detail.

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

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

(EV 40 W: ethylene-vinyl acetate copolymer)
A toluene solution of ethylene-vinyl acetate copolymer (solid content: 30% by mass) (EV40W (trade name) manufactured by Mitsui / Dupont Polychemicals Co., Ltd.) was used.

<Radical polymerizable compound>
(UA1: Urethane (Meth) Acrylate 1)
Poly (1,6-hexanediol carbonate) with a number average molecular weight of 1000 in a reaction vessel equipped with a stirrer, thermometer, a reflux condenser with a calcium chloride drying pipe, and a nitrogen gas inlet pipe (trade name: Duranol T5652, Asahi Kasei Corporation Add 2500 parts by mass (2.50 mol) of Chemicals (product) and 666 parts by mass (3.00 mol) of isophorone diisocyanate (manufactured by Sigma Aldrich Co.) uniformly over 3 hours, and sufficiently add nitrogen gas. After the introduction, the mixture was heated to 70 to 75 ° C. to react.

  Next, 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Sigma Aldrich) and 5.53 parts by mass of dibutyltin dilaurate (manufactured by Sigma Aldrich) are added, and further, 238 parts by mass of 2-hydroxyethyl acrylate (manufactured by Sigma Aldrich) A part (2.05 mol) was added and reacted at 70 ° C. for 6 hours under an air atmosphere to obtain urethane (meth) acrylate 1 (UA1).

(UA2: Urethane (Meth) Acrylate 2)
1000 parts by mass of methyl ethyl ketone, polycaprolactone diol having a number average molecular weight of 1000 (trade name: PLACEL 210N, Daicel Chemical Industries, Ltd.) in a reaction vessel equipped with a stirrer, thermometer, a reflux condenser with a calcium chloride drying pipe, and a nitrogen gas inlet pipe 2500 parts by mass (2.50 mol) of Co., Ltd. and 666 parts by mass (3.00 mol) of isophorone diisocyanate (manufactured by Sigma Aldrich Co.) were dropped uniformly over 3 hours, and nitrogen gas was sufficiently introduced. After that, the mixture was heated to 70 to 75 ° C. to be reacted.

  Next, 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Sigma Aldrich) and 5.53 parts by mass of dibutyltin dilaurate (manufactured by Sigma Aldrich) are added, and further, 238 parts by mass of 2-hydroxyethyl acrylate (manufactured by Sigma Aldrich) A part (2.05 mol) was added and reacted at 70 ° C. for 6 hours under an air atmosphere to obtain urethane (meth) acrylate 2 (UA2).

<Organic fine particles>
(KMP-600)
Core-shell type silicone fine particles (trade name: KMP-600, average particle diameter: 5 μm) manufactured by Shin-Etsu Chemical Co., Ltd. were used. The glass transition temperature of the core layer of the silicone fine particles was -110 ° C.

(BR: crosslinked polybutadiene fine particles)
Pure water was placed in a stainless steel autoclave, and polyvinyl alcohol (manufactured by Kanto Chemical Co., Ltd.) was added and dissolved as a suspending agent. Into this, butadiene (manufactured by Sigma Aldrich Co.) was added and dispersed by stirring. Furthermore, benzoyl peroxide (trade name: Cadox CH-50L, manufactured by Kayaku Akzo Co., Ltd.) as a radical polymerization initiator was dissolved and stirred. The autoclave was then heated to 60-65 ° C. and polymerized under stirring for 45 minutes. After releasing the unreacted monomer, the produced 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 Zetasizer Nano-S (manufactured by Malvern Instruments Ltd.). The average particle diameter was 0.5 μm.

(KMP 594: Silicone rubber fine particles)
A silicone rubber fine particle (trade name: KMP 594, average particle diameter 5 μm, glass transition temperature: −70 ° C.) manufactured by Shin-Etsu Chemical Co., Ltd. was used.

(W-5500)
A core-shell type acrylic fine particle (trade name: METABRENE W-5500, average particle diameter: 0.6 μm) manufactured by Mitsubishi Rayon Co., Ltd. was used.

(BTA-712)
A core-shell type acrylic acid alkyl ester-butadiene-styrene copolymer fine particle (trade name: Paraloid BTA-712) manufactured by Rohm and Haas Co., Ltd. was used.

<A vinyl compound having a phosphoric acid group>
(P-2M)
A 2- (meth) acryloyloxyethyl phosphate (trade name: light ester P-2M) manufactured by Kyoeisha Chemical Co., Ltd. was used.

<Radical polymerization initiator>
(Nyper BW)
A dibenzoyl peroxide (trade name: Nyper BW) manufactured by NOF Corporation was used.

[Preparation of film adhesive]
The adhesive compositions of Examples 1 to 5 and Comparative Examples 1 to 14 are coated on a 80 μm thick fluororesin film (substrate) using a coating apparatus, and dried by hot air at 70 ° C. for 10 minutes, The adhesive sheet in which the 20-micrometer-thick adhesive layer was formed on the base material was obtained. Let the thing which peeled the base material from the said adhesive sheet be the film adhesive of Examples 1-10 and Comparative Examples 1-11. However, in the film-like adhesives of Comparative Examples 4, 8 and 12, it was found that irregularities of the surface of the adhesive layer were generated due to the aggregates of KMP 594 used, and it was not possible to evaluate the characteristics.

[Measurement of connection resistance and adhesive strength]
(Reference Examples 1 to 9)
The film-like adhesives of Examples 1, 2 and 5 and Comparative Examples 3, 5 to 7, 9 and 10 have 500 copper circuits with a line width of 25 μm, a pitch of 50 μm and a thickness of 18 μm on a polyimide film (Tg 350 ° C.) It was interposed between a flexible circuit board (FPC) and glass (thickness 1.1 mm, surface resistance 20 Ω / □) on which a thin layer of 0.2 μm ITO was formed. This was heated and pressurized for 10 seconds at 150 ° C. and 2 MPa using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.) to bond over a width of 2 mm, to produce a circuit connected body.

  The resistance value between adjacent circuits of the above-mentioned circuit connection body was measured with a multimeter immediately after bonding and after being held in a high-temperature, high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test). The resistance value is shown as an average of 37 points of resistance between adjacent circuits.

  Moreover, the adhesive strength of the said connection body was measured and evaluated by the 90 degree peeling method according to JIS-Z0237. As a measuring apparatus of adhesive strength, Toyo Baldwin Co., Ltd. product "Tensilon UTM-4" (brand name) (peeling speed 50 mm / min, 25 degreeC) was used. The measurement results are shown in Table 2.

  As shown in Table 2, the circuit assemblies of Reference Examples 1 to 9 had good connection resistances of not more than 4.0 Ω and 560 N / m both immediately after bonding and after the test at a heating temperature of 150 ° C. It showed the above-mentioned good adhesive strength. That is, in the adhesion between the flexible circuit board made of a polyimide film and the glass on which the ITO thin film was formed, it was confirmed that the difference in the type of organic fine particles has no significant influence on the connection resistance and the adhesive strength.

(Examples 1 to 5 and Comparative Examples 1 to 14)
A film-like adhesive according to each of Examples 1 to 5 and Comparative Examples 1 to 14 is a flexible circuit board (FPC) having 80 copper circuits with a line width of 150 μm, a pitch of 300 μm, and a thickness of 8 μm on a polyimide film (Tg 350 ° C.); It was interposed between a PET substrate (0.1 μm in thickness) on which a thin layer of Ag paste with a thickness of 5 μm was formed. Next, using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.), heat and pressure were applied at 150 ° C. and 2 MPa for 20 seconds to bond over a width of 2 mm to produce a circuit connector.

  The resistance value between adjacent circuits of the above-mentioned circuit connection body was measured with a multimeter immediately after bonding and after being held in a high-temperature, high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test). The resistance value is shown as an average of 37 points of resistance between adjacent circuits. The measurement results are shown in Table 3.

  Moreover, the board | substrate which formed Ag paste circuit with a line width of 150 micrometers, a pitch of 300 micrometers, and a thickness of 10 micrometers on PET, PC or PEN film with a thickness of 0.1 micrometer on the film adhesive of Examples 1-5 and Comparative Examples 1-14. And the FPC. Next, using the above-mentioned thermocompression bonding apparatus, heating and pressing were performed at 150 ° C. and 2 MPa for 20 seconds, and bonding was performed over a width of 2 mm to produce a circuit connector.

  The adhesive strength of the above-mentioned circuit connection body was measured and evaluated by the 90 degree peeling method according to JIS-Z0237. As a measuring apparatus of adhesive strength, Toyo Baldwin Co., Ltd. product "Tensilon UTM-4" (brand name) (peeling speed 50 mm / min, 25 degreeC) was used. The measurement results are shown in Table 3.

  The circuit connection produced using the film adhesive of Examples 1 to 5 has a good connection resistance of about 2.6 Ω or less both immediately after bonding and after the test at a heating temperature of 150 ° C. It showed a good adhesive strength of about 600 N / m or more.

  On the other hand, although the circuit connection object produced using the film-form adhesive of Comparative Examples 1-14 (except Comparative Example 4, 8, 12) which does not contain a silicone particle shows favorable connection resistance, it adheres. The adhesive strength immediately after that showed a low value of 590 N / m or less, and the adhesive strength after the test showed a still lower value of 510 N / m or less.

  From the above results, in the case where at least one circuit substrate adheres a pair of circuit members including a thermoplastic resin having a glass transition temperature of 200 ° C. or less, by using the adhesive composition containing silicone fine particles according to the present invention It is clear that excellent adhesive strength can be obtained even under low temperature curing conditions, and stable performance (adhesive strength and connection resistance) can be maintained even after long-term reliability test (high temperature and high humidity test) It became.

  The adhesive composition according to the present invention can obtain excellent adhesive strength even when it is cured at a low temperature to a circuit board containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less. It is suitably used, for example, in the adhesion of a semiconductor element using a low heat resistant organic base material such as PEN or COP to an FPC.

  DESCRIPTION OF SYMBOLS 5 ... Adhesive sheet, 6 ... Base material, 8 ... Adhesive layer (adhesive composition), 9 ... Adhesive component, 10 ... Silicone fine particle, 10a ... Core-shell type silicone fine particle, 11 ... Core layer, 12 ... Shear layer, 20: conductive particles, 30: first circuit member, 31: first circuit board, 31a: main surface of first circuit board, 32: first circuit electrode, 40: second circuit member, 41: Second circuit board, 41a: main surface of second circuit board, 42: second circuit electrode, 50: connection portion, 100: circuit connection body.

Claims (17)

A first circuit member having a first circuit electrode formed on a first circuit board;
An adhesive composition is interposed between the second circuit member on which the second circuit electrode is formed on the second circuit board, and the adhesive composition is cured to form the first circuit electrode and the second circuit. A method of connecting circuit members, wherein the first circuit member and the second circuit member are bonded so that electrodes are electrically connected.
Among the first circuit board and the second circuit board , one circuit board is a substrate including at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer, One circuit substrate is a substrate including at least one selected from the group consisting of polyimide resin, polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer,
Wherein the adhesive composition is one that contains a radically polymerizable compound, and a core-shell type silicone fine particles having a provided shell layer to cover the core layer and the core layer,
Method of connecting circuit members. Bonding the said second circuit member and said first circuit member at a heating temperature of 100 ° C. or higher 200 ° C. or less, the connection method of the circuit member according to claim 1. Bonding the said second circuit member and said first circuit member at a heating temperature of 100 ° C. or higher 0.99 ° C. or less, the connection method of the circuit member according to claim 1. The method for connecting circuit members according to any one of claims 1 to 3 , wherein the glass transition temperature of the core layer of the silicone fine particles is -130 ° C or more and -20 ° C or less. The method for connecting circuit members according to any one of claims 1 to 4 , wherein the adhesive composition further contains conductive particles. The connection method of the circuit member as described in any one of Claims 1-5 whose said adhesive composition is a film form. A radical polymerizable compound, a use of an adhesive composition containing a core-shell type silicone fine particles having a provided shell layer to cover the core layer and 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,
Used to bond the first circuit electrode and the second circuit electrode so as to electrically connect them,
Among the first circuit board and the second circuit board , one circuit board is a substrate including at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer, The use of the adhesive composition, wherein one circuit substrate is a substrate comprising at least one selected from the group consisting of polyimide resin, polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer . The use of the adhesive composition according to claim 7 , wherein the first circuit member and the second circuit member are bonded at a heating temperature of 100 ° C or more and 200 ° C or less. The use of the adhesive composition according to claim 7 , wherein the first circuit member and the second circuit member are bonded at a heating temperature of 100 ° C or more and 150 ° C or less. The use of the adhesive composition according to any one of claims 7 to 9 , wherein the glass transition temperature of the core layer of the silicone fine particles is -130 ° C or more and -20 ° C or less. 11. Use of an adhesive composition according to any one of claims 7 to 10 , wherein the adhesive composition further comprises conductive particles. The use of the adhesive composition according to any one of claims 7 to 11 , wherein the adhesive composition is in the form of a film. A substrate,
Formed on the substrate, and the radical polymerizable compound, and the adhesive layer containing the core-shell type silicone fine particles, a and a shell layer provided so as to cover the core layer and the core layer,
Use of an adhesive sheet, 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 a second circuit board; Used to bond the circuit electrode of the second circuit electrode and the second circuit electrode to electrically connect them,
Among the first circuit board and the second circuit board , one circuit board is a substrate including at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer, Use of the said adhesive sheet whose one circuit board is a board | substrate containing at least 1 sort (s) chosen from the group which consists of a polyimide resin, a polyethylene terephthalate, a polycarbonate, polyethylene naphthalate, and a cycloolefin polymer . The use of the adhesive sheet according to claim 13 , wherein the first circuit member and the second circuit member are bonded at a heating temperature of 100 ° C. or more and 200 ° C. or less. The use of the adhesive sheet according to claim 13 , wherein the first circuit member and the second circuit member are bonded at a heating temperature of 100 ° C or more and 150 ° C or less. The use of the adhesive sheet according to any one of claims 13 to 15 , wherein the glass transition temperature of the core layer of the silicone fine particles is -130 ° C or more and -20 ° C or less. The use of the adhesive sheet according to any one of claims 13 to 16 , wherein the adhesive layer further contains conductive particles.

Images