JP2018188646A - Adhesive composition, film-like adhesive, adhesive sheet, circuit connection body, method for connecting circuit member, use of adhesive composition, use of film-like adhesive and use of adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition which can provide an excellent adhesive strength even when cured at low temperature and can maintain stable performance even after a long-time reliability test, a film-like adhesive, an adhesive sheet, a circuit connection body, a method for connecting a circuit member, a use of the adhesive composition, a use of the film-like adhesive, and a use of the adhesive sheet.SOLUTION: The adhesive composition is provided for bonding a first circuit member 30 in which a first circuit electrode 32 is formed on a main surface 31a of a first circuit board and a second circuit member 40 in which a second circuit electrode 42 is formed on a main surface 41a of a second circuit board so that the first circuit electrode and the second circuit electrode are electrically connected to each other, wherein at least one of the first circuit board 31 and the second circuit board 41 is a substrate including a thermoplastic resin having a glass transition temperature of 200°C or lower, and the adhesive composition contains core-shell type silicone fine particles having a core layer and a shell layer provided so as to cover the cover layer.SELECTED DRAWING: Figure 3

Description

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

  2. Description of the Related Art Various adhesive compositions have been conventionally used in semiconductor elements and liquid crystal display elements for the purpose of bonding various members in the element. The adhesive composition includes, 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 connecting to a board, mounting a semiconductor element on a substrate, and the like.

  Conventionally, as an adhesive composition for a semiconductor element or a liquid crystal display element, a thermosetting resin containing an epoxy resin exhibiting high adhesiveness and high reliability has been used (for example, see Patent Document 1). As a constituent component of the thermosetting resin, a curing agent such as an epoxy resin, a phenol resin having reactivity with the epoxy resin, and a thermal latent catalyst for promoting the reaction between the epoxy resin and the curing agent are generally used. A thermal latent catalyst is a substance that does not react at a storage temperature such as room temperature and exhibits high reactivity when heated. Further, it is an important factor for determining the curing temperature and the curing rate, and various compounds are used from the viewpoint of the storage stability of the adhesive composition at room temperature and the curing rate during heating. In an actual process, desired adhesiveness is obtained by curing conditions for curing at a temperature of 170 ° C. to 250 ° C. for 1 to 3 hours.

  On the other hand, with the recent high integration of semiconductor elements and high definition of liquid crystal displays, the pitch between elements and wirings has become narrower, and heating at the time of curing tends to adversely affect peripheral members. It is required to cure the agent composition. Moreover, since it is necessary to improve the throughput in order to reduce the cost, it is also required to cure the adhesive composition in a short time.

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

  Instead, a radical curable adhesive composition using a radical polymerizable compound such as a (meth) acrylate derivative and a peroxide as a radical polymerization initiator as an adhesive composition having a low temperature fast curing property has attracted attention. (For example, refer to Patent Document 2). According to radical curing, radicals that are reactive species are rich in reactivity, so that curing at a 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 in adhesive strength compared to the case of using an epoxy resin. There is a tendency to decrease.

  In addition, when a semiconductor element using a glass substrate or the like, a liquid crystal display element or a printed circuit board using an FR4 base material, and a flexible wiring board (FPC) using a polymer film such as polyimide or polyester as a base material are connected. In addition, the internal stress based on the difference in thermal expansion coefficient is increased, which causes a problem that peeling of the adhesive composition and a decrease in connection reliability occur.

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

Japanese Patent Laid-Open No. 1-113480 International Publication No. 98/044067 Pamphlet Japanese Patent No. 3344886 Japanese Patent No. 3503740 Japanese Patent No. 3477367 International Publication No. 09/020005 pamphlet WO09 / 051067 pamphlet

  Recently, circuit members containing polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), cycloolefin polymer (COP), etc. for the purpose of thinning, lightening, and flexibility of touch panels, electronic paper, etc. The application of is being considered. However, when using an organic base material with low heat resistance such as PET, PC, PEN, COP, etc., since the heat during curing tends to adversely affect the organic base material and peripheral members, the adhesive composition at a lower temperature. It is required to cure the object. Moreover, since the surfaces of PET, PC, PEN, COP, etc. are smooth, the adhesion effect due to the physical anchoring effect (anchor effect) is small.

  Therefore, it is desired to improve adhesive strength in a radical curable adhesive composition having low temperature curability, but organic substrates such as PET, PC, PEN, COP which are thermoplastic resins are benzene rings, etc. It is difficult to form a covalent bond with the silane coupling agent because a crystal part is easily formed by intermolecular interaction due to. Therefore, when these organic substrates are used, the method described in Patent Document 3 cannot provide a sufficient effect of improving the adhesive strength.

  Moreover, organic base materials, such as PET, PC, PEN, and COP, have a larger thermal expansion coefficient and different surface energy than glass substrates. Therefore, in order to improve wettability to the adherend and reduce internal stress, it is necessary to impart sufficient flexibility to the adhesive composition. However, the method described in Patent Document 4 provides sufficient flexibility. It cannot be imparted, and 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 cannot be obtained, such as the adhesive strength and connection resistance after the high temperature and high humidity test. There is a problem that sufficient performance cannot be obtained. Even by the method of dispersing the stress-absorbing particles described in Patent Document 6, it is not possible to obtain a sufficient effect of improving the adhesive strength to organic substrates such as PET, PC, PEN, and COP. Further, in the methods described in Patent Documents 5, 6 and 7, since an epoxy resin is used as a curing component of the adhesive composition, heating at a relatively high temperature is required in order to obtain a sufficient adhesive force. There is concern about adverse effects on organic base materials such as PET, PC, PEN, and COP having low heat resistance.

  Therefore, the present invention can be applied to an organic substrate having low heat resistance such as polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), and cycloolefin polymer (COP) even when cured at a low temperature. Adhesive composition that can obtain excellent adhesive strength and can maintain stable performance (adhesive strength and connection resistance) even after long-term reliability test (high temperature and high humidity test), and use thereof It is an object of the present invention to provide a film-like adhesive, an adhesive sheet, a circuit connector, a method for connecting circuit members, use of an adhesive composition, use of a film-like adhesive, and use of an adhesive sheet.

  As a result of diligent studies to solve the above problems, the present inventors have found that polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), cycloolefin polymer (COP), etc., which are thermoplastic resins having low heat resistance. It has been found that the low adhesive strength in the connection between the organic substrate and the semiconductor element or the liquid crystal display element is due to insufficient relaxation of internal stress. As a result of further studies to solve these problems, it was possible to obtain excellent adhesive strength by using silicone fine particles with a specific structure, and stable performance even after a long-term reliability test (high temperature and high humidity test). It was found that (adhesive strength and connection resistance) can be maintained, and the present invention was completed.

  That is, the present invention provides a first circuit member in which a first circuit electrode is formed on a first circuit board, and a second circuit member in which a second circuit electrode is formed on a second circuit board. An adhesive composition for electrically connecting the first circuit electrode and the second circuit electrode, wherein at least one of the first circuit board and the second circuit board. One is a substrate containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less, and contains a core-shell type silicone fine particle having a core layer and a shell layer provided so as to cover the core layer. Offer things.

  Since the adhesive composition contains the silicone fine particles having the specific structure described above, 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. Therefore, it is considered that the internal stress can be sufficiently relaxed effectively. Thereby, the adhesive strength with respect to the base material (for example, PET, PC, PEN, COP etc.) containing the 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 a long-term reliability test.

  In this specification, “a substrate containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower” means a polymer handbook (edited by the Society of Polymer Science: Polymer Data Handbook, Basics, p. 525, Baifukan ( 1986)) etc., and a glass substrate containing a thermoplastic resin having a value of 200 ° C. or less. Here, the thermoplastic resin is a resin having thermoplasticity, and usually does not have a crosslinked structure, but if it has thermoplasticity, it also includes those having a slight crosslinked structure. The glass transition temperature of a thermoplastic resin can be calculated | required with the measuring method mentioned 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 electrically connecting the first circuit electrode and the second circuit electrode, wherein the first circuit board and the second circuit board At least one is a substrate containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer, and has a core layer and a shell layer provided so as to cover the core layer An adhesive composition containing core-shell type silicone fine particles is provided.

  Since the adhesive composition contains the silicone fine particles having the specific structure described above, 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. Therefore, it is considered that the internal stress can be sufficiently relaxed 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, a 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 a long-term reliability test.

  The glass transition temperature of the core layer of the silicone fine particles is preferably −130 ° C. or higher and −20 ° C. or lower, more preferably −125 ° C. or higher and −40 ° C. or lower, and particularly preferably −120 ° C. or higher − It is 50 degrees C or less. Thereby, since internal stress can fully be relieved, the adhesive strength between circuit members can be improved. In addition, stable performance can be maintained even after a long-term reliability test. When the glass transition temperature is higher than −20 ° C., the internal stress cannot be sufficiently relaxed, and thus there is a tendency that a sufficient effect of improving the adhesive strength cannot be obtained. When the glass transition temperature is lower than −130 ° C., sufficient cohesive force cannot be obtained. There exists a tendency for adhesive strength to fall.

  The adhesive composition according to the present invention preferably further contains a radical polymerizable compound. Thereby, adhesion by lower temperature hardening is attained.

  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 therefore, it is more suitably used for bonding applications between circuit members having circuit electrodes (connection terminals). . Further, the connection resistance can be further reduced by electrically connecting the circuit members via the adhesive composition containing conductive particles.

  This invention provides the film adhesive obtained by shape | molding the said adhesive composition in a film form. Moreover, this invention provides an adhesive sheet provided with a base material and the adhesive bond layer which consists of the said film adhesive formed on this base material.

  The present invention includes a first circuit member having a first circuit electrode formed on a first circuit board, a second circuit member having a second circuit electrode formed on 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 part for electrically connecting the second circuit electrode, and at least one of the first circuit board and the second circuit board has a glass transition temperature of 200. Provided is a circuit connection body, which is a substrate containing a thermoplastic resin at a temperature of 0 ° C. or lower, and wherein the connection portion is made of a cured product of the adhesive composition according to the present invention.

  In the circuit connector according to the present invention, the connection portion is made of a cured product of the adhesive composition according to the present invention, so that even when a substrate containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower is used, it is excellent. In addition, stable performance (adhesive strength and connection resistance) after a 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.

  Further, one of the first circuit board and the second circuit board includes at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymer, and the other circuit board. The circuit board preferably contains at least one selected from the group consisting of polyimide resin, polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymer. Thereby, the wettability and adhesive strength of a circuit board and an adhesive composition improve more, and the outstanding connection reliability can be acquired.

  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 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. A connection part for electrically connecting the electrode and the second circuit electrode, wherein at least one of the first circuit board and the second circuit board is made of polyethylene terephthalate or polycarbonate There is provided a circuit connection body, wherein the substrate comprising at least one selected from the group consisting of polyethylene naphthalate and cycloolefin polymer, and the connection part is made of a cured product of the adhesive composition according to the present invention.

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

  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 adhesive strength of a circuit board and an adhesive composition improve more, and the outstanding connection reliability can be acquired.

  The present invention includes 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. By interposing and curing the adhesive composition according to the present invention, the first circuit member and the second circuit electrode are electrically connected to each other so that the first circuit electrode and the second circuit electrode are electrically connected. A circuit member connecting method for bonding a second circuit member, 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 lower. A circuit member connecting method is provided.

  According to the method for connecting circuit members according to the present invention, even when low-temperature curing suitable for a substrate containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower is performed, sufficient adhesive strength and long-term reliability test are performed. A circuit connector 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. Between the first circuit member and the second circuit electrode so that the first circuit electrode and the second circuit electrode are electrically connected by interposing and curing the adhesive composition according to the present invention between A circuit member connection method for bonding 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. Provided is a circuit member connection method which is a substrate including at least one selected from the group consisting of:

  According to the above circuit member connection method, sufficient adhesion can be obtained even when low-temperature curing suitable for a substrate containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer is performed. A circuit connector 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 the first circuit electrode formed on the first circuit board, and the second circuit board has the second circuit board. The first circuit board is used for bonding the second circuit member on which the circuit electrode is formed so that the first circuit electrode and the second circuit electrode are electrically connected to each other. And use of the said adhesive composition whose at least one of said 2nd circuit board is a board | substrate containing the thermoplastic resin whose glass transition temperature is 200 degrees C or less is provided.

  The present invention is also the use of the adhesive composition of the present invention, wherein the first circuit member has the first circuit electrode formed on the first circuit board, and the second circuit board has the first circuit member. A second circuit member on which two circuit electrodes are formed, and is used to bond the first circuit electrode and the second circuit electrode so that the first circuit electrode and the second circuit electrode are electrically connected to each other; Provided is the use of the adhesive composition, 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 above-described film-like adhesive of the present invention, wherein the first circuit member having the first circuit electrode formed on the first circuit board and the second circuit board on the second circuit board are used. The first circuit board is used for bonding the second circuit member on which the circuit electrode is formed so that the first circuit electrode and the second circuit electrode are electrically connected to each other. And at least one of said 2nd circuit board provides use of the said film adhesive which is a board | substrate containing the thermoplastic resin whose glass transition temperature is 200 degrees C or less.

  The present invention is also the use of the film-like adhesive of the present invention, wherein the first circuit member having the first circuit electrode formed on the first circuit board and the second circuit board on the second circuit board are used. A second circuit member on which two circuit electrodes are formed, and is used to bond the first circuit electrode and the second circuit electrode so that the first circuit electrode and the second circuit electrode are electrically connected to each other; Provided is the use of the film adhesive, wherein at least one of the substrate and the second circuit substrate is a substrate containing 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 above adhesive sheet of the present invention, wherein the first circuit member having the first circuit electrode formed on the first circuit board and the second circuit on the second circuit board are provided. The second circuit member on which the electrode is formed is used for bonding so that the first circuit electrode and the second circuit electrode are electrically connected to each other. There is provided use of the above adhesive sheet, wherein at least one of the second circuit boards is a board containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower.

  The present invention is also the use of the above adhesive sheet of the present invention, wherein the first circuit member has the first circuit electrode formed on the first circuit board, and the second circuit board has the second circuit board. Used to bond the second circuit member on which the circuit electrode is formed so that the first circuit electrode and the second circuit electrode are electrically connected, and the first circuit board and There is provided use of the above adhesive sheet, wherein at least one of the second circuit boards is a board containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer.

  According to the present invention, even when cured at a low temperature on an organic substrate having low heat resistance such as polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), and cycloolefin polymer (COP). Adhesive composition that can obtain excellent adhesive strength and can maintain stable performance (adhesive strength and connection resistance) even after long-term reliability test (high temperature and high humidity test), and use thereof Film adhesives, adhesive sheets, circuit connectors, circuit member connection methods, use of adhesive compositions, use of film adhesives and use of adhesive sheets can be provided.

It is an end view which shows one Embodiment of the adhesive sheet of this invention. It is an end view which shows one Embodiment of the silicone fine particle of this invention. It is an end view which shows one Embodiment of the circuit connection body of this invention.

  Hereinafter, embodiments 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” means acrylic acid or methacrylic acid corresponding to it, “(meth) acrylate” means acrylate or the corresponding methacrylate, and “(meth) acryloyl group” Means an acryloyl group or a corresponding methacryloyl group.

  “Glass transition temperature (Tg)” of a thermoplastic resin or a circuit board is a temperature rise rate of 5 ° C./min using a viscoelasticity analyzer “RSA-3” (trade name) manufactured by TA Instruments. Tan δ peak temperature 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 board, when a base layer such as a glass layer, a hard coat layer such as an acrylic resin layer, a gas barrier layer, or the like is formed on the thermoplastic resin substrate, these are also included. Measure the glass transition temperature of the circuit board.

  “Glass transition temperature (Tg)” of fine particles means that the fine particles are dispersed in a thermoplastic resin having a known Tg, and the produced film is a viscoelasticity analyzer “RSA-3” (product of TA Instruments) Name), and the value of tan δ peak temperature measured under conditions of a temperature rising rate of 5 ° C./min, a frequency of 10 Hz, and a measurement temperature of −150 ° C. to 300 ° C.

  The “average particle diameter” of the fine particles refers to an average particle diameter (measured using a product manufactured by Malvern Instruments Ltd., trade name) after diluting the fine particles to 0.1 wt% (mass%) with methyl ethyl ketone. Z-average value). In addition, for the fine particles having a particle size that cannot be accurately measured by the measuring device, an average measured using a Shimadzu laser diffraction particle size distribution measuring device SALD-2200 (trade name, manufactured by Shimadzu Corporation). The particle size can also be used.

  The adhesive composition according to the present invention includes silicone fine particles having a core-shell structure. Examples of the core-shell type structure include a structure having a core layer and a shell layer provided so as to cover the core layer, and a glass transition temperature higher than the glass transition temperature or elastic modulus of the surface of the core material (core layer) or Silicone fine particles that have a surface layer (shell layer) having an elastic modulus and those that have a graft layer (shell layer) outside the core material (core layer), and the core layer and shell layer have the same or different composition Can be used. Specifically, core-shell type silicone fine particles obtained by adding an alkaline substance or an alkaline aqueous solution and an organotrialkoxysilane to an aqueous dispersion of silicone rubber spherical fine particles, followed by hydrolysis and condensation reaction (see, for example, Japanese Patent No. 2832143), Core-shell type silicone fine particles as described in International Publication No. 2009/051067 pamphlet can also be used. Further, silicone fine particles containing a functional group such as a hydroxyl group, an epoxy group, a ketimine, a carboxyl group, or a mercapto group at the molecular terminal or inner molecular chain can be used. Such silicone fine particles are preferable because dispersibility in film-forming components and radical polymerizable substances is improved. The core layer and the shell layer do not necessarily have a clear boundary line.

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

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

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

The weight average molecular weight in the present embodiment is determined by gel permeation chromatography (GPC) analysis under the following conditions and converted using a standard polystyrene calibration curve.
The GPC conditions are as follows.
Equipment used: Hitachi L-6000 type (manufactured by Hitachi, Ltd., trade name)
Detector: L-3300RI (trade name, manufactured by Hitachi, Ltd.)
Column: Gel pack GL-R420 + Gel pack GL-R430 + Gel pack GL-R440 (3 in total) (trade name, manufactured by Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 1.75 ml / min

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

As a method for confirming the structure of the silicone fine particles and the core-shell type silicone fine particles, the cross section of the core-shell type silicone fine particles can be confirmed by surface observation and surface composition analysis. As a specific method, it can be confirmed by conducting a structural analysis with a transmission electron microscope (TEM) under the following conditions.
Resin casting: Epoxy resin (Epomount main agent and curing agent by Refine Tech Co., Ltd.)
Heavy metal dyeing: A 2% by weight aqueous solution of OsO ₄ (osmium tetroxide) is prepared, and the cast sample is bulk dyed therein for 24 hours.
Pretreatment: While cooling to −120 ° C. with a cryoultramicrotome, pretreatment is performed with a diamond knife at a blade speed of 0.6 mm / second to form a thin film.
TEM observation: STEM / EDX apparatus manufactured by Hitachi High-Technologies Corporation; using HD-2700, the type and configuration of the core layer and shell layer are confirmed from the image or EDX mapping.

As another method, structural analysis by an atomic force microscope (AFM) can be performed under the following conditions.
Resin casting: Epoxy resin (Epomount main agent and curing agent by Refine Tech Co., Ltd.)
Pretreatment: While cooling to −120 ° C. with a cryoultramicrotome, pretreatment is performed with a diamond knife at a blade speed of 0.6 mm / second to form a thin film.
Observation: A cross section is observed using an atomic force microscope AFM manufactured by SII Nanotechnology, and a shape image and a phase image are measured in a DFM mode, and a core-shell structure is confirmed by the phase image.

  The average particle size 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 making the average particle diameter of the silicone fine particles within the above range, it becomes easy to achieve both the fluidity of the adhesive composition and the relaxation of the internal stress.

  The blending amount of the silicone fine particles is preferably 1% by mass or more and 50% by mass or less, preferably 3% by mass or more and 30% by mass or less based on the mass of the adhesive component (adhesive composition excluding conductive particles). More preferably, it is 5 mass% or more and 30 mass% or less. By making the compounding quantity of the said silicone fine particle in the said range, relaxation of an internal stress and the flexibility (elastic modulus, elongation) and adhesive strength of an adhesive composition can fully be obtained.

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

  From the viewpoint of dispersibility and relaxation of internal stress, the silicone fine particles preferably have a weight average molecular weight of 1.5 million or less, more preferably 1.5 million or less and 500,000 or more, and 1.4 million or less and 800,000 or more. Particularly preferred. Further, the other silicone fine particles preferably have a three-dimensional crosslinked structure. “Having a three-dimensional crosslinked structure” means that the polymer chain has a three-dimensional network structure. Silicone fine particles having a three-dimensional crosslinked structure have high dispersibility in the resin and are further excellent in stress relaxation after curing. Silicone fine particles having a weight average molecular weight of 1 million or more and / or a three-dimensional cross-linked structure have low solubility in polymers such as thermoplastic resins, monomers, solvents, etc., so that the dispersibility and the stress relaxation effect are more remarkably obtained. be able to.

  Other silicone fine particles include fine particles of polyorganosilsesquioxane resin having rubber elasticity, and spherical and amorphous silicone fine particles are used. Specifically, silicone fine particles obtained by reaction of an organopolysiloxane containing at least two vinyl groups and an organohydropolyene polysiloxane having at least two hydrogen atoms bonded to silicon atoms and a platinum-based catalyst (for example, No. 62-257939), organopolysiloxane having an alkenyl group, organopolysiloxane having a hydrosilyl group, and a silicone fine particle obtained using a platinum-based catalyst (see, for example, JP-A-63-77742) and di Silicon fine particles obtained using organosiloxane, monoorganosilsesquioxane, triorganosiloxane, and platinum-based catalyst (for example, see JP-A-62-270660), water of methylsilane triol and / or partial condensate thereof / Alcohol soluble 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. Further, in order to improve dispersibility and adhesion to the substrate, silicone fine particles to which an epoxy compound is added or copolymerized (for example, see JP-A-3-167228), an acrylate compound is added or copolymerized. Silicone fine particles can also be used.

  The radically polymerizable compound contained in the adhesive composition is a compound that generates radical polymerization by the action of a radical polymerization initiator, and is a compound that itself generates radicals by applying activation energy such as light and heat. There may be. As the radically polymerizable compound, for example, a compound having a functional group that is polymerized by an active radical such as a vinyl group, a (meth) acryloyl group, an aryl group, or a maleimide group can be preferably used.

  Specific examples of the radical polymerizable compound include epoxy (meth) acrylate oligomers, urethane (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and trimethylolpropane tri (meth) acrylate. , Polyethylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) acrylate, bisphenoxyethanol (Meth) acrylic acid was added to the glycidyl group of epoxy (meth) acrylate, bisphenoxyethanol fluorene acrylate, or bisphenol fluorenediglycidyl ether with (meth) acrylic acid added to the glycidyl group of olene acrylate or bisphenol fluorenediglycidyl ether Epoxy (meth) acrylate, a compound in which ethylene glycol or propylene glycol is added to a glycidyl group of bisphenol fluorenediglycidyl ether, a compound in which a (meth) acryloyloxy group is introduced, represented by the following general formula (A) or (B) And the like.

In the 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 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.

  In addition, as a radically polymerizable compound, even when it is left alone at 30 ° C., it has no fluidity such as wax, wax, crystal, glass, powder, etc. Can be used without limitation. Specific examples of such radically polymerizable compounds include N, N′-methylenebisacrylamide, diacetone acrylamide, N-methylolacrylamide, N-phenylmethacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, tris ( 2-acryloyloxyethyl) isocyanurate, N-phenylmaleimide, 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-methylmaleimide, N-ethylmaleimide, N-octylmaleimide, 4,4′-diphenylmethane bismaleimide, m-phenylene Sumerimide, 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, divinylethylene Urea, divinylpropylene urea, 2-polystyrylethyl methacrylate, N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N-phenyl-N ′-(3-acryloyloxy- 2- (Droxypropyl) -p-phenylenediamine, tetramethylpiperidyl methacrylate, tetramethylpiperidyl acrylate, pentamethylpiperidyl methacrylate, pentamethylpiperidyl acrylate, octadecyl acrylate, Nt-butylacrylamide, diacetone acrylamide, N- (hydroxymethyl) ) Acrylamide, compounds represented by any of the following general formulas (C) to (L), and the like.

上記一般式（Ｃ）中、ｅは１〜１０の整数を示す。

In the 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, and f represents an integer of 15 to 30.

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

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

  Moreover, urethane (meth) acrylate can be used individually or with another radically polymerizable compound as a radically polymerizable compound. By using urethane (meth) acrylate, flexibility is improved and adhesion strength to organic base materials such as PET, PC, PEN and COP can be improved.

  Although there is no restriction | limiting in particular as 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 aliphatic or alicyclic ester diol or aliphatic or alicyclic. It can be obtained by a condensation reaction with a carbonate type diol.

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

  The aliphatic diisocyanate constituting the urethane (meth) acrylate is 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.

  The aliphatic ester diol constituting the urethane (meth) acrylate is 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 , 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- Kutandiol, 1,8-octanediol, 1,7-heptanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-decanediol, dodecanediol, pinacol, 1 , 4-butynediol, triethylene glycol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and the like, as well as adipic acid, 3-methyladipic 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, Methylmalonic acid, ethylmalonic acid, butylmalonic acid, dimethylmalo Acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 2,4-dimethylglutaric acid, pimelic acid, suberic acid, azelaic acid, It is selected from polyester diols obtained by ring-opening polymerization of polyester diols obtained by dehydrating condensation of dibasic acids such as sebacic acid or acid anhydrides corresponding thereto, and ε-caprolactone, and the like. The polyester diols obtained from the 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 reaction of at least one kind of the glycols with phosgene. The polycarbonate diols obtained by the reaction of the glycols and phosgene may be used alone or in combination of two or more polycarbonate diols.

  The weight average molecular weight of the urethane (meth) acrylate can be freely adjusted within the range of 5000 or more and less than 30000 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 the adhesive strength with organic base materials such as PET, PC, PEN, and COP is improved. Excellent connection reliability can be obtained. Furthermore, when the weight average molecular weight of the urethane (meth) acrylate is within 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 10,000 or more and less than 20000.

The weight average molecular weight in the present embodiment is determined by gel permeation chromatography (GPC) analysis under the following conditions and converted using a standard polystyrene calibration curve.
The GPC conditions are as follows.
Equipment used: Hitachi L-6000 type (manufactured by Hitachi, Ltd., trade name)
Detector: L-3300RI (trade name, manufactured by Hitachi, Ltd.)
Column: Gel pack GL-R420 + Gel pack GL-R430 + Gel pack GL-R440 (3 in total) (trade name, manufactured by Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 1.75 ml / min

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

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

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

In the general formula (N), R ²⁰ represents a (meth) acryloyloxy group, R ²¹ represents a hydrogen atom or a methyl group, l and m each independently represent an 1-8 integer. In the formula, R ^{20 s} , R ^{21 s} , l s, and m s may be the same or different.

In said general formula (O), R < ²² > shows a (meth) acryloyloxy group, n, o, and p show the integer of 1-8 each independently. In the formula, 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 formula, 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, Examples include 2,2′-di (meth) acryloyloxydiethyl phosphate, EO-modified phosphate dimethacrylate, phosphate-modified epoxy acrylate, and vinyl phosphate.

  On the other hand, specific examples of N-vinyl compounds include N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4′-vinylidenebis (N, N -Dimethylaniline), N-vinylacetamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and the like.

  The blending amount of the phosphoric acid group-containing vinyl compound and the N-vinyl compound is independent of the blending amount of the radical polymerizable compound other than the phosphoric acid group-containing vinyl compound, and is an adhesive component (adhesive composition excluding conductive particles). Is preferably 0.2% by mass or more and 15% by mass or less, more preferably 0.3% by mass or more and 10% by mass or less, and 0.5% by mass or more and 5% by mass or less. Particularly preferred. When the blending amount of the phosphate group-containing vinyl compound and the N-vinyl compound is within the above range, it becomes easy to achieve both high adhesive strength of the adhesive composition and physical properties after curing of the adhesive composition. , Making it easier to ensure reliability.

  The blending amount of the radical polymerizable compound excluding the phosphate group-containing vinyl compound and the 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 preferably 10% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 70% by mass or less. When the blending amount of the radical polymerizable compound is within the above range, sufficient heat resistance is obtained after curing, and it is easy to obtain good film formability when used as a film adhesive.

  As the radical polymerization initiator contained in the adhesive composition, conventionally known compounds such as organic peroxides and azo compounds that generate radicals by external energy application can be used. The radical polymerization initiator is preferably an organic peroxide having a 1 minute half-life temperature of 90 ° C. or more and 175 ° C. or less and a molecular weight of 180 or more and 1000 or less from the viewpoints of stability, reactivity, and compatibility. When the 1-minute half-life temperature is within this range, the storage stability is excellent, the radical polymerizability is sufficiently high, and the composition can be cured in a short time.

  Specific examples of the radical polymerization initiator include 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, and di (2-ethylhexyl). Peroxydicarbonate, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethylperoxyneodecanoate T-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hex 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-dimethylbutylperoxyneodecanoate, 1,1,3,3-tetramethyl Butyl peroxy-2-ethylhexanoate, t-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, di (3-methylbenzoyl) peroxide, dibenzoyl peroxide, di (4-Methylbenzoyl) peroxide, t-hexylperoxyisopropyl monocar Nate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 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 dibutyl peroxytrimethyl adipate, t-amyl peroxy normal octoate, t-amyl peroxy isononanoate, t-amyl peroxybenzoate, 2,2′-azobis-2,4-dimethylvalero 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 And azo compounds such as (4-cyanovaleric acid) and 1,1′-azobis (1-cyclohexanecarbonitrile). These compounds may be used alone or in admixture of two or more compounds.

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

  The blending amount of the radical polymerization initiator is preferably 0.5% by mass or more and 40% by mass or less, preferably 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. When the blending amount of the radical polymerization initiator is within the above range, it becomes easy to achieve both curability and storage stability of the adhesive composition.

  The thermoplastic resin contained in the adhesive composition becomes a high-viscosity liquid state by heating and deforms freely by external force, and when cooled and removed, the shape becomes hard while maintaining its shape, and this process is repeated. Resins (polymer) having properties that can be used can be suitably used. In addition, a resin (polymer) having a reactive functional group having the above properties is also included. Tg of the thermoplastic resin is preferably −30 ° C. or higher and 190 ° C. or lower, more preferably −25 ° C. or higher and 170 ° C. or lower, and particularly preferably −20 ° C. or higher and 150 ° C. or lower.

  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 alone or in admixture of two or more. Further, 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 and becomes cloudy.

  When the adhesive composition is formed into a film and used as a film adhesive, the higher the molecular weight of the thermoplastic resin, the easier it is to obtain good film formability and the fluidity as a film adhesive. The melt viscosity that affects the viscosity can be set in a wide range. The weight average molecular weight of the thermoplastic resin is preferably from 5,000 to 150,000, more preferably from 7,000 to 100,000, and particularly preferably from 10,000 to 80,000. When the weight average molecular weight of the thermoplastic resin is within the above range, it becomes easy to achieve both good film formability and good compatibility with other components.

The weight average molecular weight in the present embodiment is determined by gel permeation chromatography (GPC) analysis under the following conditions and converted using a standard polystyrene calibration curve.
The GPC conditions are as follows.
Equipment used: Hitachi L-6000 type (manufactured by Hitachi, Ltd., trade name)
Detector: L-3300RI (trade name, manufactured by Hitachi, Ltd.)
Column: Gel pack GL-R420 + Gel pack GL-R430 + Gel pack GL-R440 (3 in total) (trade name, manufactured by Hitachi Chemical Co., Ltd.)
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 preferably 15% by mass or more and 70% by mass or less, based on the mass of the adhesive component (adhesive composition excluding conductive particles). More preferably. When the content of the thermoplastic resin is within the above range, when the adhesive composition is used in the form of a film, it is possible to achieve both good film formability and good fluidity of the film adhesive. It becomes easy.

  The conductive particles contained in the adhesive composition are preferably particles having conductivity on the whole or at least on the surface, and when used for connecting circuit members having connection terminals (circuit electrodes), 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, and solder, and carbon. Further, non-conductive glass, ceramic, plastic or the like may be used as a core, and the core may be coated with the metal, metal particles, or carbon. In the case where the conductive particles are made of plastic as a core and the core is coated with the above metal, metal particles or carbon, or hot-melt metal particles, the contact area with the electrode is increased during connection because it is deformable by heating and pressing. This is preferable because reliability is improved. Further, the conductive particles may be, for example, particles obtained by coating silver on copper metal particles. Further, as the conductive particles, a metal powder 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 be used.

  In addition, fine particles in which the surface of these conductive particles is further coated with insulating particles, or fine particles in which an insulating layer made of an insulating material is provided on the surface of the conductive particles by a method such as hybridization, Since short-circuiting due to contact between particles when the blending amount is increased can be suppressed and insulation between the electrode circuits can be improved, this may be used alone or mixed with other conductive particles as appropriate.

  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 amount of conductive particles used is not particularly limited, but is preferably 0.1% by volume or more and 30% by volume or less, and 0.1% by volume or more and 10% by volume or less with respect to the total volume of the adhesive composition. More preferably. When the amount of the conductive particles used is within the above range, a short circuit can be sufficiently suppressed while sufficient conductivity is obtained. In addition, although volume% is determined based on the volume of each component before 23 degreeC hardening, the volume of each component can be converted into a volume from a weight using specific gravity. In addition, do not dissolve or swell the component in a graduated cylinder, etc., and put the component in a suitable solvent (water, alcohol, etc.) that wets the component well. It can also be determined as a 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, but 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 1,6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and hindered amine derivatives such as tetramethylpiperidyl methacrylate.

  The blending amount of the stabilizer is preferably 0.005% by mass or more and 10% by mass or less based on the mass of the adhesive component (adhesive composition excluding the conductive particles), and 0.01% by mass or more and 8% by mass or less. More preferably, it is 0.02 mass% or less and 5 mass% or less is especially preferable. When the blending amount of the stabilizer is within the above range, the curing rate can be controlled and storage stability can be imparted without adversely affecting the compatibility with other components.

  Moreover, you may add suitably adhesion assistants, such as a coupling agent represented by the alkoxysilane derivative and the silazane derivative, an adhesion improving agent, and a leveling agent, to an adhesive composition. Specifically, the compound represented by the following general formula (Q) is preferable as the coupling agent, and two or more compounds may be mixed and used in addition to the compound used alone.

In the general formula (Q), R ²⁵ , R ²⁶ and R ²⁷ are each independently 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, a mercapto group, an amino group, a methylamino group, a dimethylamino group, a benzylamino group, or 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 adhesiveness. 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 the rubber component, a compound having a polybutadiene skeleton is preferable. The rubber component may have a cyano group, a carboxyl group, a hydroxyl group, a (meth) acryloyl group, or a morpholine group. From the viewpoint of improving adhesiveness, a rubber component containing a cyano group or a carboxyl group, which is a highly polar group, in the side chain or terminal is preferable. In addition, even if it has a polybutadiene skeleton, if it exhibits thermoplasticity, it is classified as a thermoplastic resin, and if it exhibits radical polymerizability, it is classified as a radical polymerizable compound.

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

  In addition, the rubber component having a high polar group and being liquid at room temperature specifically includes a liquid acrylonitrile-butadiene rubber, a carboxyl group, a hydroxyl group, a (meth) acryloyl group or a morpholine group at the polymer end. Examples thereof include liquid acrylonitrile-butadiene rubber and liquid carboxylated nitrile rubber, 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 admixture of two or more compounds.

  The adhesive composition may contain 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 size of the organic fine particles is preferably 0.05 μm or more and 1.0 μm or less. In addition, when organic fine particles consist of the above-mentioned rubber component, it classifies into a rubber component instead of organic fine particles, and when organic fine particles consist of the above-mentioned thermoplastic resin, it classifies into a thermoplastic resin instead of organic fine particles.

  Specific examples of 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, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene), alkoxysilyl-terminated poly (oxypropylene), poly (oxypropylene) containing carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer end Tetramethylene) glycol, polyolefin glycol (meth) acrylic acid alkyl-butadiene-styrene copolymer, (meth) acrylic acid 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 room temperature. In the case of a solid at room temperature, it may be used by heating, or may be pasted using a solvent. Solvents that can be used are preferably those that are not reactive with the adhesive composition and additives and that exhibit sufficient solubility, and those having a boiling point of 50 ° C. or higher and 150 ° C. or lower at normal pressure. When the boiling point of the solvent is within the above range, it is difficult to volatilize even if it is left at room temperature, it is easy to use in an open system, and the solvent can be sufficiently volatilized to ensure sufficient reliability after bonding. .

  Moreover, the adhesive composition of the present invention can be formed into a film and used as a film adhesive. A solution in which a solvent or the like is added to the adhesive composition as necessary is applied onto a peelable substrate such as a fluororesin film, a polyethylene terephthalate film or a release paper, or a substrate such as a nonwoven fabric is impregnated with the above solution. It can be used as a film adhesive by placing on a peelable substrate and removing the solvent. Use in the form of a film is more convenient from the viewpoint of handleability.

  The adhesive composition of the present invention can be bonded using heating and pressurization together. The heating temperature is preferably 100 ° C. or higher and 200 ° C. or lower. The pressure is preferably in a range that does not damage the adherend, and is generally from 0.1 MPa to 10 MPa. These heating and pressurization are preferably performed in the range of 0.5 second or more and 120 seconds or less, and can be bonded by heating at 110 ° C. or more and 190 ° C. or less, 3 MPa, or 10 seconds.

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

  When connecting circuit members using the adhesive composition of the present invention, for example, a first circuit member in which a first circuit electrode is formed on a first circuit board, and a second circuit board. The first circuit electrode and the second circuit electrode are electrically connected by being cured by interposing the adhesive composition of the present invention between the second circuit member on which the second circuit electrode is formed. By connecting the first circuit member and the second circuit member so as to be connected to each other, the circuit members can be connected to obtain a circuit connection body.

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

  Furthermore, one of the first circuit board and the second circuit board includes at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate, 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, wettability with the adhesive composition of the present invention is further improved, and adhesive strength and connection reliability are further improved.

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

  The adhesive composition of the present invention does not need to reach full curing (the highest degree of curing that can be achieved under predetermined curing conditions), and may be in a partially cured state as long as the above characteristics are produced.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

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

[Preparation of adhesive composition]
Each component shown in Table 1 is blended at a solid mass ratio shown in Table 1, and further, the conductive particles are blended and dispersed by 1.5% by volume, and the adhesives of Examples 1 to 5 and Comparative Examples 1 to 11 are used. A 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 digalbonic acid, neopentyl glycol (manufactured by Aldrich) as diol, 4,4'-diphenylmethane diisocyanate (manufactured by Aldrich) as isocyanate, terephthalic acid A polyester urethane resin A having a molar ratio of / isolutaric acid / neopentyl glycol / 4,4′-diphenylmethane diisocyanate of 0.34 / 0.66 / 1.1 / 0.33 was prepared. The number average molecular weight of the obtained polyester urethane resin A was 25000. 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 Toto Kasei Co., Ltd. was dissolved in methyl ethyl ketone and used as a solution having a solid content of 40% by mass.

(EV40W: ethylene-vinyl acetate copolymer)
Ethylene-vinyl acetate copolymer dissolved in toluene (solid content 30% by mass) (Mitsui / DuPont Polychemical Co., Ltd., EV40W (trade name)) was used.

<Radically polymerizable compound>
(UA1: Urethane (meth) acrylate 1)
Poly (1,6-hexanediol carbonate) with a number average molecular weight of 1000 (trade name: DURANOL T5652, Asahi Kasei) in a reaction vessel equipped with a stirrer, thermometer, reflux condenser with calcium chloride drying tube, and nitrogen gas introduction tube Chemicals Co., Ltd.) 2500 parts by mass (2.50 mol) and isophorone diisocyanate (Sigma Aldrich) 666 parts by mass (3.00 mol) are uniformly added dropwise over 3 hours, and nitrogen gas is sufficiently added. After the introduction, the reaction was performed by heating to 70 to 75 ° C.

  Subsequently, 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) were added, and further 238 masses of 2-hydroxyethyl acrylate (manufactured by Sigma Aldrich). Part (2.05 mol) was added and reacted at 70 ° C. in an air atmosphere for 6 hours to obtain urethane (meth) acrylate 1 (UA1).

(UA2: Urethane (meth) acrylate 2)
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser with calcium chloride drying tube, and nitrogen gas introduction tube, 1000 parts by mass of methyl ethyl ketone and polycaprolactone diol having a number average molecular weight of 1000 (trade name: Plaxel 210N, Daicel Chemical Industries) Co., Ltd.) 2500 parts by mass (2.50 mol) and isophorone diisocyanate (Sigma Aldrich) 666 parts by mass (3.00 mol) were uniformly added dropwise over 3 hours, and nitrogen gas was sufficiently introduced. Then, it heated to 70-75 degreeC and made it react.

  Subsequently, 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) were added, and further 238 masses of 2-hydroxyethyl acrylate (manufactured by Sigma Aldrich). Part (2.05 mol) was added and reacted at 70 ° C. in an air atmosphere for 6 hours to obtain urethane (meth) acrylate 2 (UA2).

<Organic fine particles>
(KMP-600)
Core-shell type silicone fine particles (trade name: KMP-600, average particle size: 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 put into a stainless steel autoclave, and polyvinyl alcohol (manufactured by Kanto Chemical Co., Inc.) was added and dissolved as a suspending agent. Butadiene (manufactured by Sigma Aldrich) was put into this and dispersed by stirring. Furthermore, benzoyl peroxide (trade name: Cadox CH-50L, manufactured by Kayaku Akzo Co., Ltd.) was dissolved as a radical polymerization initiator and stirred. The autoclave was then heated to 60-65 ° C. and polymerized for 45 minutes with stirring. After releasing unreacted monomers, 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 size of the particles was measured using Zetasizer Nano-S (manufactured by Malvern Instruments Ltd.). The average particle size was 0.5 μm.

(KMP594: silicone rubber fine particles)
Silicone rubber fine particles (trade name: KMP594, average particle size 5 μm, glass transition temperature: −70 ° C.) manufactured by Shin-Etsu Chemical Co., Ltd. were used.

(W-5500)
Core-shell type acrylic fine particles (trade name: Methabrene W-5500, average particle size: 0.6 μm) manufactured by Mitsubishi Rayon Co., Ltd. were used.

(BTA-712)
Core-shell type alkyl acrylate-butadiene-styrene copolymer fine particles (trade name: Paraloid BTA-712) manufactured by Rohm & Haas were used.

<Vinyl compound having a phosphate group>
(P-2M)
2- (Meth) acryloyloxyethyl phosphate (trade name: Light Ester P-2M) manufactured by Kyoeisha Chemical Co., Ltd. was used.

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

[Production of film adhesive]
By applying the adhesive compositions of Examples 1 to 5 and Comparative Examples 1 to 14 on a fluororesin film (base material) having a thickness of 80 μm using a coating apparatus and drying with hot air at 70 ° C. for 10 minutes, An adhesive sheet in which an adhesive layer having a thickness of 20 μm was formed on the substrate was obtained. What peeled the base material from the said adhesive sheet is made into 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 the KMP594 aggregate used produced irregularities on the surface of the adhesive layer, and the characteristics could not be evaluated.

[Measurement of connection resistance and adhesive strength]
(Reference Examples 1-9)
The film adhesives of Examples 1, 2, 5 and Comparative Examples 3, 5-7, 9, 10 have 500 copper circuits having 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 20Ω / □) on which a thin layer of 0.2 μm ITO was formed. This was heat-pressed at 150 ° C. and 2 MPa for 10 seconds using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.) and bonded over a width of 2 mm to produce a circuit connection body.

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

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

  As shown in Table 2, the circuit connection bodies of Reference Examples 1 to 9 had a good connection resistance of 4.0Ω or less and 560 N / m immediately after bonding and after the test under the condition of a heating temperature of 150 ° C. The above good adhesive strength was exhibited. That is, it was confirmed that the difference in the type of organic fine particles does not significantly affect the connection resistance and the adhesive strength in the adhesion between the flexible circuit board made of polyimide film and the glass on which the ITO thin film is formed.

(Examples 1-5 and Comparative Examples 1-14)
A flexible circuit board (FPC) having 80 copper circuits having a line width of 150 μm, a pitch of 300 μm, and a thickness of 8 μm on the polyimide film (Tg 350 ° C.) of the film adhesives of Examples 1 to 5 and Comparative Examples 1 to 14; It was interposed between a PET substrate (thickness 0.1 μm) on which a thin layer of 5 μm thick Ag paste was formed. Subsequently, using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.), the film was bonded by heating and pressing at 150 ° C. and 2 MPa for 20 seconds over a width of 2 mm to prepare a circuit connection body.

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

  Moreover, the board | substrate which formed the Ag paste circuit of the line width 150 micrometers, the pitch 300 micrometers, and the thickness 10 micrometers on the 0.1-micrometer-thick PET, PC, or PEN film about the film-form adhesive of Examples 1-5 and Comparative Examples 1-14. And the FPC. Subsequently, using the said thermocompression bonding apparatus, it heat-pressed for 20 second at 150 degreeC and 2 Mpa, it adhere | attached over width 2mm, and the circuit connection body was produced.

  The adhesive strength of the circuit connector was measured and evaluated by a 90-degree peeling method according to JIS-Z0237. As a measuring device for adhesive strength, “Tensilon UTM-4” (trade name) (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used. Table 3 shows the measurement results.

  The circuit connection body produced using the film adhesives of Examples 1 to 5 had a good connection resistance of about 2.6Ω or less immediately after bonding and after the test under the condition of a heating temperature of 150 ° C. Good adhesive strength of about 600 N / m or more was exhibited.

  On the other hand, although the circuit connection body produced using the film adhesives of Comparative Examples 1 to 14 (excluding Comparative Examples 4, 8, and 12) not containing silicone fine particles exhibits good connection resistance, Immediately after, the adhesive strength was as low as 590 N / m or less, and the adhesive strength after the test was as low as 510 N / m or less.

  From the above results, when at least one circuit board adheres a pair of circuit members containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less, the adhesive composition containing the silicone fine particles according to the present invention is used. It is clear that excellent adhesive strength can be obtained even under low temperature curing conditions, and that stable performance (adhesive strength and connection resistance) can be maintained even after a 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 cured at a low temperature for a circuit board containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower. It is suitably used for adhesion between a semiconductor element and an FPC using an organic substrate having low heat resistance such as PEN and COP.

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 ... Share layer, 20 ... conductive particles, 30 ... first circuit member, 31 ... first circuit board, 31a ... main surface of the first circuit board, 32 ... first circuit electrode, 40 ... second circuit member, 41 ... 2nd circuit board, 41a ... main surface of 2nd circuit board, 42 ... 2nd circuit electrode, 50 ... connection part, 100 ... circuit connection body.

Claims (20)

A first circuit member having a first circuit electrode formed on a first circuit board; and a second circuit member having a second circuit electrode formed on a second circuit board. An adhesive composition for adhering the circuit electrode and the second circuit electrode so as to be electrically connected,
At least one of the first circuit board and the second circuit board is a board containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less,
An adhesive composition comprising core-shell type silicone fine particles having a core layer and a shell layer provided so as to cover the core layer. A first circuit member having a first circuit electrode formed on a first circuit board; and a second circuit member having a second circuit electrode formed on a second circuit board. An adhesive composition for adhering the circuit electrode and the second circuit electrode so as to be electrically connected,
At least one of the first circuit board and the second circuit board is a board containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer,
An adhesive composition comprising core-shell type silicone fine particles having a core layer and a shell layer provided so as to cover the core layer.   The adhesive composition according to claim 1 or 2, wherein a glass transition temperature of the core layer of the silicone fine particles is -130 ° C or higher and -20 ° C or lower.   The adhesive composition according to any one of claims 1 to 3, further comprising a radical polymerizable compound.   The adhesive composition according to any one of claims 1 to 4, further comprising conductive particles.   The film adhesive obtained by shape | molding the adhesive composition as described in any one of Claims 1-5 in a film form.   An adhesive sheet provided with a base material and the adhesive bond layer which consists of a film adhesive of Claim 6 formed on this base material. A first circuit member having a first circuit electrode formed on a first circuit board;
A second circuit member having a second circuit electrode formed on the second circuit board;
The first circuit electrode 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 part for electrically connecting the second circuit electrode, and a circuit connection body comprising:
At least one of the first circuit board and the second circuit board is a board containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less,
The circuit connection body which the said connection part consists of the hardened | cured material of the adhesive composition as described in any one of Claims 1-5.   The circuit connector according to claim 8, wherein the thermoplastic resin includes at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymer. Of the first circuit board and the second circuit board, one circuit board contains at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer,
The circuit connection body according to claim 8, wherein the other circuit board includes at least one selected from the group consisting of polyimide resin, polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymer. A first circuit member having a first circuit electrode formed on a first circuit board;
A second circuit member having a second circuit electrode formed on the second circuit board;
The first circuit electrode 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 part for electrically connecting the second circuit electrode, and a circuit connection body comprising:
At least one of the first circuit board and the second circuit board is a board containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer,
The circuit connection body which the said connection part consists of the hardened | cured material of the adhesive composition as described in any one of Claims 1-5. Of the first circuit board and the second circuit board, one circuit board contains at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer,
The circuit connector according to claim 11, wherein the other circuit board includes at least one selected from the group consisting of polyimide resin, polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymer. A first circuit member having a first circuit electrode formed on a first circuit board;
By interposing and curing the adhesive composition according to any one of claims 1 to 5 between the second circuit member having the second circuit electrode formed on the second circuit board. A circuit member connection method for bonding the first circuit member and the second circuit member so that the first circuit electrode and the second circuit electrode are electrically connected,
A method for connecting circuit members, wherein at least one of the first circuit board and the second circuit board is a board containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower. A first circuit member having a first circuit electrode formed on a first circuit board;
By interposing and curing the adhesive composition according to any one of claims 1 to 5 between the second circuit member having the second circuit electrode formed on the second circuit board. A circuit member connection method for bonding the first circuit member and the second circuit member so that the first circuit electrode and the second circuit electrode are electrically connected,
A circuit member connection method, wherein at least one of the first circuit board and the second circuit board is a board containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymer. . Use of the adhesive composition according to any one of claims 1 to 5,
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 be electrically connected;
Use of the said adhesive composition whose at least one of said 1st circuit board and said 2nd circuit board is a board | substrate containing the thermoplastic resin whose glass transition temperature is 200 degrees C or less. Use of the adhesive composition according to any one of claims 1 to 5,
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 be electrically connected;
The adhesive composition, wherein at least one of the first circuit board and the second circuit board is a board containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymer. Use of. Use of the film adhesive according to claim 6,
A first circuit member having a first circuit electrode formed on the main surface of the first circuit board, and a second circuit member having a second circuit electrode formed on the main surface of the second circuit board And
Used to bond the first circuit electrode and the second circuit electrode so as to be electrically connected;
Use of the said film adhesive whose at least one of said 1st circuit board and said 2nd circuit board is a board | substrate containing the thermoplastic resin whose glass transition temperature is 200 degrees C or less. Use of the film adhesive according to claim 6,
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 be electrically connected;
The film adhesive, wherein at least one of the first circuit board and the second circuit board is a board containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymer. Use of. Use of the adhesive sheet according to claim 7,
A first circuit member having a first circuit electrode formed on the main surface of the first circuit board, and a second circuit member having a second circuit electrode formed on the main surface of the second circuit board And
Used to bond the first circuit electrode and the second circuit electrode so as to be electrically connected;
Use of the said adhesive sheet whose at least one of said 1st circuit board and said 2nd circuit board is a board | substrate containing the thermoplastic resin whose glass transition temperature is 200 degrees C or less. Use of the adhesive sheet according to claim 7,
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 be electrically connected;
Use of the adhesive sheet, wherein at least one of the first circuit board and the second circuit board is a board containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymer. .

Images