JP5855459B2 - Circuit member connection structure - Google Patents

Description

  The present embodiment relates to an adhesive composition, a connection structure, a manufacturing method of the connection structure, and an application of the adhesive composition.

In the semiconductor element and the liquid crystal display element, various adhesives are conventionally used for the purpose of bonding various members in the element. The demand for adhesives is diverse, including adhesiveness, heat resistance, and reliability in high temperature and high humidity conditions. In addition, adherends used for adhesion include printed wiring boards, organic substrates such as polyimide, polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), metals such as copper and aluminum, Substrates having various surface states such as ITO (complex oxide of indium and tin), SiN, SiO _{2 and the} like are used, and molecular design in accordance with each adherend is required.

  Conventionally, as an adhesive for the semiconductor element and the liquid crystal display element, a thermosetting resin using an epoxy resin having high adhesiveness and high reliability has been used (for example, see Patent Document 1). As a constituent component of the 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 upon heating, and is an important factor that determines the curing temperature and the curing rate. Various compounds have been used from the viewpoints of storage stability at room temperature and curing rate during heating. The curing conditions in the actual process were that desired adhesion was obtained by curing at a temperature of 170 to 250 ° C. for 1 to 3 hours.

  However, recently, semiconductor elements, liquid crystal display elements and wirings may be formed on organic substrates with low heat resistance such as PET, PC, PEN, etc., but the organic substrate and peripheral members are heated by curing. Since there is a possibility of adverse effects, adhesion at lower temperature curing is required. In order to achieve low-temperature rapid curing with the above-described epoxy resin or the like, it is necessary to use a thermal latent catalyst with low activation energy, but it is difficult to combine storage stability near room temperature.

Under such circumstances, a radical curable adhesive using a radical polymerizable compound such as an acrylate derivative or a methacrylate derivative in combination with a peroxide which is a radical polymerization initiator has attracted attention. Radical curing can be cured for a short time because radicals that are reactive species are rich in reactivity (see, for example, Patent Document 2). However, since the radical curing adhesive has a large curing shrinkage when heated, it is inferior in adhesive strength as compared with the case of using an epoxy resin. Regarding such a decrease in adhesive strength, a method has been proposed in which urethane acrylate is applied to provide flexibility and improve the adhesive strength (see, for example, Patent Document 3). Further, a method for improving the adhesive strength by adding an adhesion assistant such as a silane coupling agent to an inorganic base material whose adherend is ITO, SiN, SiO ₂ or the like has been proposed (for example, , See Patent Document 4).

Japanese Patent Laid-Open No. 1-113480 International Publication No. 98/44067 Pamphlet Japanese Patent No. 3503740 JP-A-62-62874

  However, organic substrates such as PET, PC, and PEN that are thermoplastic resins are straight-chain, and are easy to form crystal parts due to intermolecular interaction by benzene rings. Formation of a covalent bond with a silane coupling agent is extremely difficult. Therefore, the method described in Patent Document 4 described above cannot provide sufficient adhesive strength. Moreover, since the surface of PET, PC, PEN or the like is smooth, the adhesion effect due to the physical anchoring effect (anchor effect) is small. Therefore, it is necessary to apply an adhesive composition that provides wettability to the adherend and sufficient flexibility. However, in the method described in Patent Document 3 described above, sufficient wettability and flexibility to the adherend are required. The flexibility is not obtained.

  Therefore, the present invention can obtain excellent adhesive strength even under low temperature curing conditions for organic base materials such as polyethylene terephthalate, polycarbonate, polyethylene naphthalate, etc., and a long-term reliability test (high temperature and high humidity test). ) Adhesive composition that can maintain stable performance (adhesive strength and connection resistance) afterwards, circuit member connection structure using the same, connection structure manufacturing method, and application of adhesive composition The purpose is to provide.

  To achieve the above object, the present invention connects a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface. The first circuit member and / or the second circuit member is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower, and the adhesive composition is Urethane (meth) acrylate containing (a) thermoplastic resin, (b) radical polymerizable compound and (c) radical polymerization initiator, and (b) radical polymerizable compound having a critical surface tension of 25 to 40 mN / m An adhesive composition is provided.

  The adhesive composition contains a thermoplastic resin having a Tg of 200 ° C. or less by containing a (b) radical polymerizable compound containing urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m. The wettability with a material (for example, PET, PC, PEN, etc.) is improved, adhesion at low temperature is possible, and the adhesive strength between circuit members can be improved. In addition, stable performance can be maintained even after a long-term reliability test.

［式（Ａ）中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子またはメチル基を示し、Ｒ^３はエチレン基、プロピレン基、ε−カプロラクトンの開環化合物から誘導される基、または下記一般式（Ｂ）で表される基を示し、Ｒ^４は飽和脂肪族基または飽和脂環式基を示し、Ｒ^５は下記一般式（Ｂ）で表される基を示し、ａは１〜４０の整数を示す。］

［式（Ｂ）中、Ｒ^６及びＲ^７はそれぞれ独立に炭素数２〜１２の直鎖又は分岐鎖のアルキレン基を示し、ｂは１〜１０の整数を示し、ｃは１〜２５の整数を示す。なお、式中、Ｒ^６同士、Ｒ^７同士、ｂ同士及びｃ同士はそれぞれ同一でも異なってもよい。］ In the adhesive composition of the present invention, the urethane (meth) acrylate contained in the radically polymerizable compound (b) is preferably represented by the following general formula (A).

[In the formula (A), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: A group represented by (B), R ⁴ represents a saturated aliphatic group or a saturated alicyclic group , R ⁵ represents a group represented by the following general formula (B), and a represents 1 to 40 Indicates an integer. ]

[In formula (B), R ⁶ and R ⁷ each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R ^{6 s} , R ^{7 s} , b s, and c s may be the same or different. ]

  Since there is a proportional relationship between the critical surface tension and the cohesive energy density, it is considered that the critical surface tension is improved by introducing a functional group having a high cohesive energy density. Therefore, (b) the urethane (meth) acrylate contained in the radical polymerizable compound has a structure represented by the above general formula (A), whereby the cohesive energy density is improved, and the adhesive composition and Tg are 200. Adhesion between circuit members composed of a substrate containing a thermoplastic resin such as PET, PC, PEN, etc., with improved wettability with a substrate containing a thermoplastic resin at a temperature of ℃ or less (for example, PET, PC, PEN, etc.) Strength is improved and excellent connection reliability can be obtained. In addition, (b) the urethane (meth) acrylate contained in the radical polymerizable compound has a structure represented by the general formula (A), so that an appropriate flexibility is imparted to the adhesive composition. Adhesive strength between circuit members composed of a base material containing a thermoplastic resin such as PC and PEN is improved, and excellent connection reliability can be obtained.

［式（Ａ）中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子またはメチル基を示し、Ｒ^３はエチレン基、プロピレン基、ε−カプロラクトンの開環化合物から誘導される基、または下記一般式（Ｂ）で表される基を示し、Ｒ^４は飽和脂肪族基または飽和脂環式基を示し、Ｒ^５は下記一般式（Ｂ）で表される基を示し、ａは１〜４０の整数を示す。］

［式（Ｂ）中、Ｒ^６及びＲ^７はそれぞれ独立に炭素数２〜１２の直鎖又は分岐鎖のアルキレン基を示し、ｂは１〜１０の整数を示し、ｃは１〜２５の整数を示す。なお、式中、Ｒ^６同士、Ｒ^７同士、ｂ同士及びｃ同士はそれぞれ同一でも異なってもよい。］ The present invention also provides an adhesive composition for connecting a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface. The first circuit member and / or the second circuit member is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less, and the adhesive composition is (a) a thermoplastic resin. , (B) a radically polymerizable compound and (c) a radical polymerization initiator, and (b) a radically polymerizable compound containing a urethane (meth) acrylate represented by the following general formula (A) I will provide a.

[In the formula (A), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: A group represented by (B), R ⁴ represents a saturated aliphatic group or a saturated alicyclic group , R ⁵ represents a group represented by the following general formula (B), and a represents 1 to 40 Indicates an integer. ]

[In formula (B), R ⁶ and R ⁷ each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R ^{6 s} , R ^{7 s} , b s, and c s may be the same or different. ]

  This adhesive composition has a structure in which the urethane (meth) acrylate contained in the radically polymerizable compound (b) is represented by the general formula (A), whereby the cohesive energy density is improved, and the adhesive composition The wettability between the product and a base material containing a thermoplastic resin having a Tg of 200 ° C. or lower (for example, PET, PC, PEN, etc.) is improved, and the base material contains a thermoplastic resin such as PET, PC, PEN, etc. The adhesive strength between circuit members is improved, and excellent connection reliability can be obtained. In addition, (b) the urethane (meth) acrylate contained in the radical polymerizable compound has a structure represented by the general formula (A), so that an appropriate flexibility is imparted to the adhesive composition. Adhesive strength between circuit members composed of a base material containing a thermoplastic resin such as PC and PEN is improved, and excellent connection reliability can be obtained. Furthermore, stable performance can be maintained even after a long-term reliability test.

  In the adhesive composition of the present invention, the urethane (meth) acrylate is preferably obtained using an aliphatic polyester diol. Since the urethane (meth) acrylate is obtained using an aliphatic polyester diol, the flexibility of the adhesive composition is improved, and it is composed of a base material containing a thermoplastic resin such as PET, PC, or PEN. The adhesive strength between circuit members can be improved, and excellent connection reliability can be obtained.

  Moreover, in the adhesive composition of this invention, it is preferable that the weight average molecular weights of urethane (meth) acrylate are 8000 or more and less than 25000. When the weight average molecular weight of the urethane (meth) acrylate is within the above range, the adhesive strength with an organic base material such as PET, PC, PEN or the like is further improved, and excellent connection reliability can be obtained.

  In the adhesive composition of the present invention, the radically polymerizable compound (b) is a vinyl compound having a phosphate group and one or more radically polymerizable compounds other than the vinyl compound having a phosphate group. It is preferable to contain. (B) Since the radically polymerizable compound has such a configuration, the adhesive strength with a base material made of a metal is further improved.

  In the adhesive composition of the present invention, (a) the thermoplastic resin contains at least one selected from the group consisting of phenoxy resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin, and polyimide resin. It is preferable to do. (A) By containing such a resin as a thermoplastic resin, the heat resistance and adhesiveness of the adhesive composition are further improved.

  The adhesive composition of the present invention preferably further contains (d) conductive particles. (D) By containing conductive particles, it is possible to impart good conductivity or anisotropic conductivity to the adhesive composition. Therefore, it is preferably used for bonding applications between circuit members having connection terminals. It becomes possible. Moreover, the connection resistance of the circuit member electrically connected via the said adhesive composition can be reduced more fully.

Moreover, this invention is a circuit member provided with the 1st circuit member which has a 1st connection terminal on a main surface, the 2nd circuit member which has a 2nd connection terminal on a main surface, and a connection member a connection structure as the first connection terminal and second connection terminal are opposed, with the first circuit member and second circuit member is disposed through the connecting member, first The connection terminal and the second connection terminal are electrically connected, the connection member is a cured product of the adhesive composition, and the first circuit member and / or the second circuit member is made of glass. Provided is a circuit member connection structure comprising a base material containing a thermoplastic resin having a transition temperature of 200 ° C. or lower.

  The first circuit member and / or the second circuit member is a circuit member composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower, so that wetting with the adhesive composition As a result, the adhesive strength is further improved and excellent connection reliability can be obtained.

  The thermoplastic resin having a glass transition temperature of 200 ° C. or lower is preferably at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. By being a circuit member composed of a base material containing polyethylene terephthalate or the like, wettability with the adhesive composition is improved, adhesive strength is further improved, and excellent connection reliability can be obtained.

  In the circuit member connection structure of the present invention, one circuit member of the first circuit member or the second circuit member is at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. It is comprised from the base material to contain, and the other circuit member is comprised from the base material which contains at least 1 sort (s) chosen from the group which consists of a polyimide resin and a polyethylene terephthalate among 1st circuit members or 2nd circuit members. It is preferable. In this connection structure, the first circuit member and the second circuit member are composed of the above-described base materials, so that the wettability and adhesive strength with the adhesive composition are further improved, and an excellent connection is achieved. Reliability can be obtained.

  The present invention provides a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface through the adhesive composition. A step of disposing the first connection terminal and the second connection terminal so as to face each other, a step of heating and curing the adhesive composition, and connecting the first circuit member and the second circuit member; The manufacturing method of the connection structure of a circuit member provided with these is provided. According to this manufacturing method, the connection structure of the circuit member which has the outstanding connection reliability can be obtained by connecting the 1st circuit member and the 2nd circuit member with the said adhesive composition.

  The present invention also includes (a) a thermoplastic resin, (b) a radical polymerizable compound, and (c) a radical polymerization initiator, and (b) the radical polymerizable compound has a critical surface tension of 25 to 40 mN / m. A first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface of the adhesive composition containing urethane (meth) acrylate having As an adhesive composition for connecting the first circuit member and the second circuit member, wherein at least one circuit member is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less. Provide application. The adhesive composition containing (b) a radical polymerizable compound containing urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m is a base material containing a thermoplastic resin having a Tg of 200 ° C. or less (for example, PET, PC, PEN, etc.) are improved in wettability and can be bonded by low-temperature curing. Therefore, it is suitable for application as an adhesive composition for connecting circuit members.

［式（Ａ）中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子またはメチル基を示し、Ｒ^３はエチレン基、プロピレン基、ε−カプロラクトンの開環化合物から誘導される基、または下記一般式（Ｂ）で表される基を示し、Ｒ^４は飽和脂肪族基または飽和脂環式基を示し、Ｒ^５は下記一般式（Ｂ）で表される基を示し、ａは１〜４０の整数を示す。］

［式（Ｂ）中、Ｒ^６及びＲ^７はそれぞれ独立に炭素数２〜１２の直鎖又は分岐鎖のアルキレン基を示し、ｂは１〜１０の整数を示し、ｃは１〜２５の整数を示す。なお、式中、Ｒ^６同士、Ｒ^７同士、ｂ同士及びｃ同士はそれぞれ同一でも異なってもよい。］ In the said application, it is preferable that urethane (meth) acrylate is a urethane (meth) acrylate represented by the following general formula (A). When the urethane (meth) acrylate has a structure represented by the following general formula (A), the adhesive strength between the circuit members is improved, and excellent connection reliability can be obtained.

[In the formula (A), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: A group represented by (B), R ⁴ represents a saturated aliphatic group or a saturated alicyclic group , R ⁵ represents a group represented by the following general formula (B), and a represents 1 to 40 Indicates an integer. ]

[In formula (B), R ⁶ and R ⁷ each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R ^{6 s} , R ^{7 s} , b s, and c s may be the same or different. ]

［式（Ａ）中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子またはメチル基を示し、Ｒ^３はエチレン基、プロピレン基、ε−カプロラクトンの開環化合物から誘導される基、または下記一般式（Ｂ）で表される基を示し、Ｒ^４は飽和脂肪族基または飽和脂環式基を示し、Ｒ^５は下記一般式（Ｂ）で表される基を示し、ａは１〜４０の整数を示す。］

［式（Ｂ）中、Ｒ^６及びＲ^７はそれぞれ独立に炭素数２〜１２の直鎖又は分岐鎖のアルキレン基を示し、ｂは１〜１０の整数を示し、ｃは１〜２５の整数を示す。なお、式中、Ｒ^６同士、Ｒ^７同士、ｂ同士及びｃ同士はそれぞれ同一でも異なってもよい。］ The present invention also includes (a) a thermoplastic resin, (b) a radical polymerizable compound, and (c) a radical polymerization initiator, and (b) the radical polymerizable compound is represented by the following general formula (A). A first circuit member having a first connection terminal on a main surface of an adhesive composition containing urethane (meth) acrylate, and a second circuit member having a second connection terminal on the main surface. And an application as an adhesive composition for connecting the first circuit member and the second circuit member, wherein at least one circuit member is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower. I will provide a. When the urethane (meth) acrylate has a structure represented by the following general formula (A), the adhesive strength between the circuit members is improved, and excellent connection reliability can be obtained.

[In the formula (A), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: A group represented by (B), R ⁴ represents a saturated aliphatic group or a saturated alicyclic group , R ⁵ represents a group represented by the following general formula (B), and a represents 1 to 40 Indicates an integer. ]

[In formula (B), R ⁶ and R ⁷ each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R ^{6 s} , R ^{7 s} , b s, and c s may be the same or different. ]

  In the above application, the urethane (meth) acrylate is preferably obtained using an aliphatic polyester diol. Since the urethane (meth) acrylate is obtained using an aliphatic polyester diol, the flexibility of the adhesive composition is improved, and it is composed of a base material containing a thermoplastic resin such as PET, PC, or PEN. The adhesive strength between circuit members can be improved, and excellent connection reliability can be obtained.

  In the said application, it is preferable that the weight average molecular weights of urethane (meth) acrylate are 8000 or more and less than 25000. When the weight average molecular weight of the urethane (meth) acrylate is within the above range, the adhesive strength with an organic base material such as PET, PC, PEN or the like is further improved, and excellent connection reliability can be obtained.

  In the said application, it is preferable that (b) radically polymerizable compound contains 1 or more types of vinyl compounds which have a phosphoric acid group, and radically polymerizable compounds other than the vinyl compound which has a phosphoric acid group, respectively. (B) Since the radically polymerizable compound has such a configuration, the adhesive strength with a base material made of a metal is further improved.

  In the said application, it is preferable that (a) thermoplastic resin contains at least 1 sort (s) chosen from the group which consists of a phenoxy resin, a polyurethane resin, a polyester urethane resin, a butyral resin, an acrylic resin, and a polyimide resin. (A) By containing such a resin as a thermoplastic resin, heat resistance and adhesiveness are further improved.

  In the said application, it is preferable that adhesive composition further contains (d) electroconductive particle. (D) By containing conductive particles, it is possible to impart good conductivity or anisotropic conductivity to the adhesive composition, and more sufficiently reduce the connection resistance of electrically connected circuit members. can do.

  According to the present invention, an excellent adhesive strength can be obtained even under low temperature curing conditions on an organic substrate such as polyethylene terephthalate, polycarbonate, and polyethylene naphthalate, and a long-term reliability test (high temperature and high humidity) can be achieved. Adhesive composition capable of maintaining stable performance (adhesive strength and connection resistance) even after test), circuit member connection structure using the same, circuit member connection structure manufacturing method, and adhesive composition Application of things can be provided.

It is a schematic cross section which shows one Embodiment of the connection structure of a circuit member using the adhesive composition of this embodiment. It is a schematic cross section which shows the 1st circuit member, the 2nd circuit member, and adhesive composition before producing the connection structure of the circuit member shown in FIG. It is a schematic cross section which shows one Embodiment of the connection structure of a circuit member using the adhesive composition (electroconductive particle containing) of this embodiment. It is a schematic cross section which shows the 1st circuit member, the 2nd circuit member, and adhesive composition (electroconductive particle containing) before producing the connection structure of the circuit member shown in FIG.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. In this embodiment, (meth) acrylic acid means acrylic acid or methacrylic acid corresponding thereto, (meth) acrylate means acrylate or methacrylate corresponding thereto, and (meth) acryloyl group means acryloyl. Means a group or a methacryloyl group.

  “Glass transition temperature (Tg)” in the present embodiment means a film-like organic base material using a viscoelasticity analyzer “RSA-3” (trade name) manufactured by TA Instruments, Inc. It means the value of tan δ peak temperature near Tg measured under conditions of 5 ° C./min, frequency 10 Hz, measurement temperature −150 to 300 ° C.

In addition, “critical surface tension (γ _c )” in the present embodiment is a film-like urethane (meth) acrylate mixed with pure water and a wet tension test mixed solution No. 50 and 60 (manufactured by Wako Pure Chemical Industries, Ltd.) were each measured at the angle (contact angle θ) formed with the urethane (meth) acrylate surface immediately after dropping 1 μl at 23 ° C., and the surface tension of each liquid was measured on the x-axis. The surface tension when the straight line passing through the three points becomes Y = 1 when COSθ is plotted on the y-axis. In addition, the pure water, No. When the straight line passing through the three points obtained by the measurements of 50 and 60 is Y = 1, X is a negative value. 60, 1-bromonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) is used for the same measurement as above, and the value of the surface tension when the obtained straight line passing through the three points becomes Y = 1 is used. You can also.

  In the present embodiment, “weight average molecular weight” and “number average molecular weight” refer to values measured from a gel permeation chromatograph (GPC) using a standard polystyrene calibration curve according to the conditions shown in Table 1.

  The adhesive composition of the present embodiment is for connecting a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface. An adhesive composition, wherein the first circuit member and / or the second circuit member is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less, and the adhesive composition comprises (a A) a thermoplastic resin, (b) a radical polymerizable compound and (c) a radical polymerization initiator, and (b) a urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m. An adhesive composition.

  The thermoplastic resin (a) contained in the adhesive composition of the present embodiment becomes a liquid state having a high viscosity by heating and is freely deformed by external force, and is hardened while maintaining its shape when cooled and removed. That is, it refers to a resin (polymer) having the property of repeating this process. In addition, a resin (polymer) having a reactive functional group having the above properties is also included. (A) Tg of the thermoplastic resin is preferably 0 to 190 ° C, more preferably 20 to 170 ° C.

  As such a thermoplastic resin, polyimide resin, polyamide resin, phenoxy resin, (meth) acrylic resin, urethane resin, polyester urethane resin, polyvinyl butyral resin, or 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 used in the form of a film, the higher the molecular weight of the thermoplastic resin, the easier it is to obtain good film formability, and the melt viscosity that affects the fluidity of the film-like adhesive composition. Can be set in a wide range. (A) As a weight average molecular weight of a thermoplastic resin, 5000-150,000 are preferable and 10000-80000 are more preferable. If this value is less than 5000, good film formability tends to be difficult to obtain, and if it exceeds 150,000, good compatibility with other components tends to be difficult to obtain.

  In the adhesive composition of the present embodiment, the content of the thermoplastic resin (a) is preferably 5 to 80% by mass, and preferably 15 to 70% by mass based on the total amount of the adhesive composition. More preferred. When this content is less than 5% by mass, particularly when the adhesive composition is used in the form of a film, good film formability tends to be difficult to obtain, and when it exceeds 80% by mass, good adhesion is obtained. The fluidity of the agent composition tends to be difficult to obtain.

  The (b) radical polymerizable compound contained in the adhesive composition of the present embodiment refers to a compound that generates radical polymerization by the action of a radical polymerization initiator, but by applying activation energy such as light and heat. It may be a compound that itself generates a radical. (B) 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 allyl group, or a maleimide group can be preferably used.

  (B) Specific examples of the radical polymerizable compound include epoxy (meth) acrylate oligomers, urethane (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polyester (meth) acrylate oligomers, 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, di Pentaerythritol hexa (meth) acrylate, isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) acrylate, bisphenoxyethanol (Meth) acrylic acid is 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 rufluorene acrylate or bisphenol fluorenediglycidyl ether. Epoxy (meth) acrylates, compounds obtained by adding (meth) acryloyloxy groups to compounds obtained by adding ethylene glycol or propylene glycol to the glycidyl groups of bisphenol fluorenediglycidyl ether, represented by the following general formulas (C) and (D) And the like.

［式（Ｃ）中、Ｒ^８及びＲ^９はそれぞれ独立に水素原子またはメチル基を示し、ｄ及びｅはそれぞれ独立に１〜８の整数を示す。］

[In Formula (C), R ⁸ and R ⁹ each independently represent a hydrogen atom or a methyl group, and d and e each independently represent an integer of 1 to 8. ]

［式（Ｄ）中、Ｒ^１０及びＲ^１１はそれぞれ独立に水素原子またはメチル基を示し、ｆ及びｇはそれぞれ独立に０〜８の整数を示す。］

[In Formula (D), R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a methyl group, and f and g each independently represent an integer of 0 to 8. ]

  The radically polymerizable compound (b) is a solid state having no fluidity such as waxy, waxy, crystalline, glassy or powdery when left alone at 30 ° C. However, it can be used without any particular limitation. Specific examples of the (b) radical polymerizable compound 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-fe Renbismaleimide, 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, Divinylethyleneurea, divinylpropyleneurea, 2-polystyrylethyl methacrylate, N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N-phenyl-N ′-(3-acryloyl) Oxy 2-hydroxypropyl) -p-phenylenediamine, tetramethylpiperidyl methacrylate, tetramethylpiperidyl acrylate, pentamethylpiperidyl methacrylate, pentamethylpiperidyl acrylate, octadecyl acrylate, Nt-butylacrylamide, diacetone acrylamide, N- (hydroxy) And methyl) acrylamide and compounds represented by the following general formulas (E) to (N).

［式（Ｅ）中、ｈは１〜１０の整数を示す。］

[In the formula (E), h represents an integer of 1 to 10. ]

［式（Ｇ）中、Ｒ^１２及びＲ^１３はそれぞれ独立に水素原子またはメチル基を示し、ｉは１５〜３０の整数を示す。］

[In Formula (G), R ¹² and R ¹³ each independently represent a hydrogen atom or a methyl group, and i represents an integer of 15 to 30. ]

［式（Ｈ）中、Ｒ^１４及びＲ^１５はそれぞれ独立に水素原子またはメチル基を示し、ｊは１５〜３０の整数を示す。］

[In formula (H), R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a methyl group, and j represents an integer of 15 to 30. ]

［式（Ｉ）中、Ｒ^１６は水素原子またはメチル基を示す。］

[In the formula (I), R ¹⁶ represents a hydrogen atom or a methyl group. ]

［式（Ｊ）中、Ｒ^１７は水素原子またはメチル基を示し、ｋは１〜１０の整数を示す。］

[In the formula (J), R ¹⁷ represents a hydrogen atom or a methyl group, and k represents an integer of 1 to 10. ]

［式（Ｋ）中、Ｒ^１８は水素原子または下記一般式（ｉ）もしくは（ｉｉ）で示される有機基を示し、ｌは１〜１０の整数を示す。］

[In formula (K), R ¹⁸ represents a hydrogen atom or an organic group represented by the following general formula (i) or (ii), and l represents an integer of 1 to 10. ]

［式（Ｌ）中、Ｒ^１９は水素原子または下記一般式（ｉｉｉ）もしくは（ｉｖ）で示される有機基を示し、ｍは１〜１０の整数を示す。］

[In formula (L), R ¹⁹ represents a hydrogen atom or an organic group represented by the following general formula (iii) or (iv), and m represents an integer of 1 to 10. ]

［式（Ｍ）中、Ｒ^２０は水素原子またはメチル基を示す。］

[In the formula (M), R ²⁰ represents a hydrogen atom or a methyl group. ]

［式（Ｎ）中、Ｒ^２１は水素原子またはメチル基を示す。］

[In formula (N), R ²¹ represents a hydrogen atom or a methyl group. ]

  In addition, (b) N-vinyl compounds selected from the group consisting of phosphate group-containing vinyl compounds, N-vinyl compounds and N, N-dialkylvinyl compounds, which are compounds belonging to radically polymerizable compounds, The (b) radical polymerizable compound can be used in combination. 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.

［式（Ｏ）中、Ｒ^２２は（メタ）アクリロイルオキシ基を示し、Ｒ^２３は水素原子またはメチル基を示し、ｎ及びｏはそれぞれ独立に１〜８の整数を示す。なお、式中、Ｒ^２２同士、Ｒ^２３同士、ｎ同士及びｏ同士はそれぞれ同一でも異なってもよい。］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 (O) to (Q) are preferable.

[In Formula (O), R ²² represents a (meth) acryloyloxy group, R ²³ represents a hydrogen atom or a methyl group, and n and o each independently represents an integer of 1 to 8. In the formula, R ^{22 s} , R ^{23 s} , n s, and o s may be the same or different. ]

［式（Ｐ）中、Ｒ^２４は（メタ）アクリロイルオキシ基を示し、ｐ及びｑはそれぞれ独立に１〜８の整数を示す。なお、式中、Ｒ^２４同士、ｐ同士及びｑ同士はそれぞれ同一でも異なってもよい。］

[In Formula (P), R ²⁴ represents a (meth) acryloyloxy group, and p and q each independently represent an integer of 1 to 8. In the formula, R ^{24 s} , p s, and q s may be the same or different. ]

［式（Ｑ）中、Ｒ^２５は（メタ）アクリロイルオキシ基を示し、Ｒ^２６は水素原子又はメチル基を示し、ｒ及びｓはそれぞれ独立に１〜８の整数を示す。なお、式中、Ｒ^２６同士及びｒ同士はそれぞれ同一でも異なってもよい。］

[In Formula (Q), R ²⁵ represents a (meth) acryloyloxy group, R ²⁶ represents a hydrogen atom or a methyl group, and r and s each independently represent an integer of 1 to 8. In the formulae, R ²⁶ and r 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.

  The blending amount of the phosphoric acid group-containing vinyl compound is, independently of the blending amount of the (b) radical polymerizable compound other than the phosphoric acid group-containing vinyl compound, (a) with respect to 100 parts by mass of the thermoplastic resin. It is preferable to set it as -300 mass parts, It is more preferable to set it as 1-200 mass parts, It is more preferable to set it as 1-50 mass parts, It is especially preferable to set it as 1-15 mass parts. If the amount of the phosphoric acid group-containing vinyl compound is less than 0.2 parts by mass, high adhesive strength tends to be difficult to obtain, and if it exceeds 300 parts by mass, the physical properties of the cured adhesive composition are likely to deteriorate. , Tend to be difficult to ensure reliability.

  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 radically polymerizable compound (b) excluding the compound corresponding to the phosphate group-containing vinyl compound described above is preferably 50 to 250 parts by mass with respect to 100 parts by mass of the (a) thermoplastic resin. 60 to 150 parts by mass is more preferable. If the blending amount is less than 50 parts by mass, sufficient heat resistance tends to be difficult to obtain after curing, and if it exceeds 250 parts by mass, good film formability is obtained when used as a film. It tends to be difficult.

［式（Ａ）中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子またはメチル基を示し、Ｒ^３はエチレン基、プロピレン基、ε−カプロラクトンの開環化合物から誘導される基、または下記一般式（Ｂ）で表される基を示し、Ｒ^４は飽和脂肪族基または飽和脂環式基を示し、Ｒ^５は下記一般式（Ｂ）で表される基を示し、ａは１〜４０の整数を示す。］ The adhesive composition of the present embodiment comprises (b) a urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m as a radical polymerizable compound, and a urethane (meth) represented by the following general formula (A). Urethane (meth) acrylate satisfying one or both conditions of acrylate is contained as an essential component. Among these, in this embodiment, the urethane acrylate which satisfy | fills the said conditions is used more suitably. Here, the urethane (meth) acrylate represented by the following general formula (A) can be obtained by a condensation reaction of an aliphatic diisocyanate and a polyester diol.

[In the formula (A), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: A group represented by (B), R ⁴ represents a saturated aliphatic group or a saturated alicyclic group , R ⁵ represents a group represented by the following general formula (B), and a represents 1 to 40 Indicates an integer. ]

［式（Ｂ）中、Ｒ^６及びＲ^７はそれぞれ独立に炭素数２〜１２の直鎖又は分岐鎖のアルキレン基を示し、ｂは１〜１０の整数を示し、ｃは１〜２５の整数を示す。なお、式中、Ｒ^６同士、Ｒ^７同士、ｂ同士及びｃ同士はそれぞれ同一でも異なってもよい。］

[In formula (B), R ⁶ and R ⁷ each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R ^{6 s} , R ^{7 s} , b s, and c 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.

  Moreover, as polyester diol which comprises the said urethane (meth) acrylate, aliphatic polyester diol and aromatic polyester diol can be used, for example, It is preferable to use aliphatic polyester diol. Aliphatic polyester diols are ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,2-pentane. Diol, 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-octanediol, 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 Saturated low molecular glycols such as diethylene glycol, dipropylene glycol and cyclohexanedimethanol, polycarbonate diols obtained by the reaction of at least one kind of the above glycols with phosgene, and at least one kind of the above glycols as an initiator Diols such as polyether diol obtained by addition polymerization of one or more monomers such as ethylene oxide, propylene oxide and epichlorohydrin by a known method, adipic acid, 3-methyladipine 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 Acid, malonic acid, methylmalonic acid, ethylmalonic acid, butylmalonic acid, dimethylmalonic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid Aliphatic polyester diols obtained by dehydration condensation of dibasic acids such as acid, 2,4-dimethylglutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or the like and acid anhydrides corresponding thereto, and ε -It is selected from aliphatic polyester diols obtained by ring-opening polymerization of cyclic ester compounds such as caprolactone. The polyester diols obtained from the diols and dicarboxylic acids may be used alone or in combination of two or more polyester diols.

  Moreover, in the adhesive composition of this embodiment, the weight average molecular weight of the said urethane (meth) acrylate is in the range of 8000 or more and less than 25000 from a viewpoint of the adhesive strength improvement with respect to base materials, such as PET, PC, and PEN. It can be freely adjusted and used suitably. If the weight average molecular weight of the urethane (meth) acrylate is within the above range, both flexibility and cohesive force can be obtained, and the adhesive strength with organic base materials such as PET, PC, and PEN is improved and excellent. Connection reliability can be obtained. Moreover, from the viewpoint of obtaining such effects more sufficiently, the weight average molecular weight of the urethane (meth) acrylate is more preferably 10,000 or more and less than 25,000. In addition, when this weight average molecular weight is less than 8000, there exists a tendency for sufficient flexibility not to be acquired, and when it is 25000 or more, there exists a tendency for the fluidity | liquidity of an adhesive composition to fall.

  The urethane (meth) acrylate has a critical surface tension of preferably 25 to 40 mN / m, and more preferably 25 to 35 mN / m. When the critical surface tension of urethane (meth) acrylate is 25 to 40 mN / m, it becomes close to the critical surface tension of the adherends PET, PC and PEN, and the wettability is improved, thereby improving the adhesive strength. Excellent connection reliability can be obtained. Moreover, when this critical surface tension is less than 25 mN / m or more than 40 mN / m, the wettability with respect to PET, PC, PEN and the like may be deteriorated and the compatibility may deteriorate. It is considered that the critical surface tension of the urethane (meth) acrylate is related to the urethane bond equivalent and can be adjusted by changing the number average molecular weight of the diol. For example, when the number average molecular weight of the diol is increased, the urethane bond equivalent decreases, and the critical surface tension tends to decrease.

  Moreover, it is preferable that the compounding quantity of the said urethane (meth) acrylate is 5-95 mass% on the basis of adhesive agent whole quantity, and it is more preferable that it is 10-80 mass%. When the blending amount is less than 5% by mass, the heat resistance tends to decrease, and when it exceeds 95% by mass, the film formability tends to decrease when used as a film.

  As the (c) radical polymerization initiator contained in the adhesive composition of the present embodiment, conventionally known organic peroxides, azo compounds, and the like are compounds that generate radicals by applying external energy. Can be used. (C) The radical polymerization initiator is preferably an organic peroxide having a one-minute half-life temperature of 90 to 175 ° C. and a molecular weight of 180 to 1,000 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.

  (C) 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-methylethylperoxynoe Decanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexa Noate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t- Xylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t -Butylperoxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, 1,1,3,3- Tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, di (3-methylbenzoyl) peroxide, dibenzoylperoxide , Di (4-methylbenzoyl) peroxide, t-hexylperoxyisopropyl Carbonate, 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 dibutylperoxytrimethyladipate, t-amylperoxynormal octoate, t-amylperoxyisononanoate, t-amylperoxybenzoate; 2,2′-azobis-2,4-dimethylvalero Nitrile, 1,1′-azobis (1-acetoxy-1-phen Nylethane), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyronitrile, 4,4′-azobis 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 (c) radical polymerization initiator, the compound which generate | occur | produces a radical by 150-750 nm light irradiation 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 (c) radical polymerization initiator is preferably 0.1 to 500 parts by weight, more preferably 1 to 300 parts by weight, and 5 to 50 parts by weight with respect to 100 parts by weight of the (a) thermoplastic resin. More preferably, 10-30 mass parts is especially preferable. (C) When the blending amount of the radical polymerization initiator is less than 0.1 parts by mass, the adhesive composition tends to be hard to be cured sufficiently, and when it exceeds 500 parts by mass, the storage stability tends to deteriorate.

  The conductive particles (d) contained in the adhesive composition of the present embodiment may be particles having conductivity on the whole or on the surface, but when used for connecting circuit members having connection terminals, The average particle size is preferably smaller than the distance between the connection terminals.

  (D) Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, 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. (D) 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, they are deformable by heating and pressurization, so that they are in contact with the electrode at the time of connection. This is preferable because the area is increased and the reliability is improved.

  In addition, the fine particles obtained by coating the surface of the conductive particles (d) with a polymer resin or the like suppress a short circuit due to contact between the particles when the blending amount of the conductive particles is increased. Since insulation can be improved, it may be used alone or in admixture with (d) conductive particles.

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

  (D) The amount of the conductive particles used is not particularly limited, but is preferably 0.1 to 30% by volume, and preferably 0.1 to 10% by volume with respect to the total volume of the adhesive composition. Is more preferable. If this value is less than 0.1% by volume, the conductivity tends to be low, and if it exceeds 30% by volume, a short circuit tends to occur. 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 of the present embodiment in order to impart control of the curing rate and 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; , 6,6-tetramethylpiperidine-1-oxyl, aminoxyl derivatives such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl; hindered amine derivatives such as tetramethylpiperidyl methacrylate;

  0.01-30 mass parts is preferable with respect to 100 mass parts of adhesive compositions, and, as for the compounding quantity of a stabilizer, 0.05-10 mass parts is more preferable. When the blending amount is less than 0.01 parts by mass, it becomes difficult to control the curing rate and storage stability, and when it exceeds 30 parts by mass, the compatibility with other components tends to be adversely affected.

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

［式（Ｒ）中、Ｒ^２７、Ｒ^２８及びＲ^２９はそれぞれ独立に、水素原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、炭素数１〜５のアルコキシカルボニル基又はアリール基を示し、Ｒ^３０は（メタ）アクリロイル基、ビニル基、イソシアナート基、イミダゾール基、メルカプト基、アミノ基、メチルアミノ基、ジメチルアミノ基、ベンジルアミノ基、フェニルアミノ基、シクロヘキシルアミノ基、モルホリノ基、ピペラジノ基、ウレイド基又はグリシジル基を示し、ｔは１〜１０の整数を示す。］

[In the formula (R), R ²⁷ , R ²⁸ and R ²⁹ 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 an alkoxycarbonyl group having 1 to 5 carbon atoms. Or R ³⁰ represents (meth) acryloyl group, vinyl group, isocyanate group, imidazole group, mercapto group, amino group, methylamino group, dimethylamino group, benzylamino group, phenylamino group, cyclohexylamino group , Morpholino group, piperazino group, ureido group or glycidyl group, t represents an integer of 1 to 10. ]

  The adhesive composition of this embodiment may use a rubber component in combination for the purpose of stress relaxation and adhesive improvement. 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) a thermoplastic resin, and if it exhibits radical polymerizability, it is classified as (b) a radically 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.

  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 terminal. Examples thereof include liquid acrylonitrile-butadiene rubber and liquid carboxylated nitrile rubber. The content of acrylonitrile which is a polar group is preferably 10 to 60% by mass.

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

  Moreover, you may add organic fine particles to the adhesive composition of this embodiment for the purpose of stress relaxation and adhesive improvement. The average particle size of the organic fine particles is preferably 0.05 to 1.0 μm. In addition, when organic fine particles consist of the above-mentioned rubber component, it classify | categorizes into a rubber component instead of organic fine particles, and when organic fine particles consist of the above-mentioned (a) thermoplastic resin, it is not organic fine particle (a) thermoplastic resin. Classify into:

  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.

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

  The adhesive composition of this embodiment 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. As the solvent that can be used, those that are not reactive with the adhesive composition and additives and that exhibit sufficient solubility are preferred, and those having a boiling point of 50 to 150 ° C. at normal pressure are preferred. When the boiling point is less than 50 ° C., it tends to volatilize when left at room temperature, and it tends to be difficult to use in an open system. On the other hand, if the boiling point exceeds 150 ° C., it is difficult to volatilize the solvent, and the reliability after adhesion tends to be adversely affected.

  Moreover, the adhesive composition of this embodiment can also be used in the form of a film. 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 placed on a peelable substrate and used as a film after removing the solvent and the like. Use in the form of a film is more convenient from the viewpoint of handleability.

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

  The adhesive composition of the present embodiment can be used as an adhesive for different types of adherends having different thermal expansion coefficients. Specifically, it is used as a semiconductor element adhesive material typified by anisotropic conductive adhesive, silver paste, silver film, etc., circuit connection material, CSP elastomer, CSP underfill material, LOC tape, etc. Can do.

  The adhesive composition of the present embodiment is for connecting a first circuit member having a first connection terminal on the main surface and a second circuit member having a second connection terminal on the main surface. Used as an adhesive composition. Here, said 1st circuit member and / or said 2nd circuit member are comprised from the base material containing the thermoplastic resin whose glass transition temperature is 200 degrees C or less. Although it does not specifically limit as a thermoplastic resin whose glass transition temperature is 200 degrees C or less, For example, a polyethylene terephthalate, a polycarbonate, a polyethylene naphthalate, etc. are mentioned.

  Next, a circuit member connection structure using the above-described adhesive composition of the present embodiment will be described. FIG. 1 is a schematic cross-sectional view showing an embodiment of a circuit member connection structure using the adhesive composition of the present embodiment. FIG. 2 is a schematic cross-sectional view showing the first circuit member, the second circuit member, and the adhesive composition before producing the circuit member connection structure shown in FIG. 1.

  A circuit member connection structure 100 shown in FIG. 1 includes a first circuit member 30 having a first connection terminal 32 on a main surface 31 a of a first circuit board 31, and a main surface of a second circuit board 41. The main surface 31a of the first circuit board 31 so that the second circuit member 40 having the second connection terminal 42 on 41a and the first connection terminal 32 and the second connection terminal 42 face each other. 10C of connection members which connect the main surface 41a of the 2nd circuit board 41. The first connection terminal 32 and the second connection terminal 42 are electrically connected by being in contact with each other. Moreover, 10C of connection members consist of hardened | cured material of the adhesive composition 10 of this embodiment.

  The circuit member connection structure 100 shown in FIG. 1 can be manufactured, for example, as follows.

  First, as shown in FIG. 2, the first circuit member 30, the second circuit member 40, and the adhesive composition 10 formed into a film are prepared. Next, the adhesive composition 10 is placed on the main surface 41a of the second circuit member 40 on which the second connection terminals 42 are formed, and the first connection terminals are further formed on the adhesive composition 10. The first circuit member 30 is placed so that 32 faces the second connection terminal 42. Subsequently, the adhesive composition 10 is cured while being heated through the first circuit member 30 and the second circuit member 40, and simultaneously pressurized in a direction perpendicular to the main surfaces 31a and 41a. A connection member 10C is formed between the second circuit members 30 and 40 to obtain the circuit member connection structure 100 of FIG.

  FIG. 3: is a schematic cross section which shows one Embodiment of the connection structure of a circuit member using the adhesive composition of this embodiment containing (d) electroconductive particle. FIG. 4 is a schematic cross-sectional view showing the first circuit member, the second circuit member, and the adhesive composition (containing conductive particles) before producing the circuit member connection structure shown in FIG. 3.

  A circuit member connection structure 200 shown in FIG. 3 includes a first circuit member 30 having a first connection terminal 32 on a main surface 31 a of a first circuit board 31, and a main surface of a second circuit board 41. The main surface 31a of the first circuit board 31 so that the second circuit member 40 having the second connection terminal 42 on 41a and the first connection terminal 32 and the second connection terminal 42 face each other. A connecting member 20C for connecting the main surface 41a of the second circuit board 41. The connecting member 20C is a cured product of the adhesive composition 20 in which the conductive particles 22 are dispersed in the component 21 other than the conductive particles of the adhesive composition (that is, the components other than the conductive particles of the adhesive composition). The conductive particles 22 are dispersed in the cured product 21C), and the conductive particles 22 are in contact with both connection terminals between the first connection terminal 32 and the second connection terminal 42 facing each other. Both connection terminals are electrically connected through the conductive particles 22.

  The circuit member connection structure 200 shown in FIG. 3 includes, for example, as shown in FIG. 4, a first circuit member 30, a second circuit member 40, and an adhesive composition 20 formed into a film shape, The circuit member connection structure 100 can be manufactured by the same method as described above.

  Here, at least one of the first circuit member 30 and the second circuit member 40 is composed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less. That is, at least one of the first circuit board 31 and the second circuit board 41 contains a thermoplastic resin having a glass transition temperature of 200 ° C. or lower. Here, the thermoplastic resin having a glass transition temperature of 200 ° C. or lower is preferably at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. A circuit member in which at least one of the first circuit member 30 and the second circuit member 40 is composed of a base material containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. If it exists, the wettability with an adhesive composition will improve and adhesive strength will improve more. Therefore, such a connection structure of circuit members can obtain better connection reliability.

  One of the first circuit member 30 and the second circuit member 40 may be composed of a base material that does not contain at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. . As a base material for forming such a circuit member, a base material made of an inorganic material such as a semiconductor, glass or ceramic, a base material made of an organic material such as polyimide, a base material combining an inorganic material such as glass / epoxy and an organic material, etc. Can be used.

  Moreover, it is preferable that at least one of the first connection terminal 32 and the second connection terminal 42 is composed of at least one selected from the group consisting of ITO and IZO. ITO and IZO are suitable as connection terminals because they are easily etched and have excellent pattern processability. And the corrosion of the connection terminal comprised by ITO and / or IZO can fully be suppressed by using the adhesive composition of this embodiment.

  One or both of the first connection terminal 32 and the second connection terminal 42 may be made of a material other than ITO and IZO. As such a connection terminal, a connection terminal made of a metal such as copper, silver, aluminum, gold, palladium, nickel, or an alloy thereof can be used.

  Note that the adhesive composition of the present embodiment used as a connection member does not need to be completely cured (the highest degree of curing that can be achieved under predetermined curing conditions) and is in a partially cured state as long as the above characteristics are produced. May be.

  Hereinafter, the present embodiment will be specifically described based on examples, but the present embodiment is not limited thereto.

<Thermoplastic resin>
(Adjustment of phenoxy resin)
40 parts by mass of phenoxy resin (manufactured by Toto Kasei Co., Ltd., YP-50 (trade name)) was dissolved in 60 parts by mass of methyl ethyl ketone to obtain a solution having a solid content of 40% by mass.

(Preparation of polyester urethane resin)
As the polyester urethane resin (Toyobo Co., Ltd., UR-1400 (trade name)), a 1: 1 mixed solvent dissolved product of methyl ethyl ketone and toluene having a resin content of 30% by mass was used.

(Synthesis of urethane resin)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube, 450 parts by weight of polybutylene adipate diol having a weight average molecular weight of 2000 and polyoxytetramethylene glycol having a weight average molecular weight of 2000 450 parts by mass and 100 parts by mass of 1,4-butylene glycol are uniformly mixed in 4000 parts by mass of methyl ethyl ketone, 390 parts by mass of diphenylmethane diisocyanate is added and reacted at 70 ° C., and urethane having a weight average molecular weight of 350,000 A resin was obtained.

<Radically polymerizable compound>
(Preparation of urethane acrylate (L-1600S))
A urethane acrylate having a weight average molecular weight of 15000 and a critical surface tension of 15 mN / m (manufactured by Mitsui Polyurethane Co., Ltd., L-1600S (trade name)) was prepared. L-1600S uses an ether diol and does not satisfy the general formula (A).

(Synthesis of urethane acrylate (PE-UA1))
A poly (3-methylpentane adipate) diol (aliphatic polyester diol, Kuraray Co., Ltd.) having a number average molecular weight of 2000 was added to a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube and a nitrogen gas introduction tube Kurapol P-2010 (trade name) 2000 parts by mass (1.00 mol) and dibutyltin dilaurate (manufactured by Aldrich) 5.53 parts by mass were added. After sufficiently introducing nitrogen gas, the mixture was heated to 70 to 75 ° C. and dicyclohexylmethane 4,4′-diisocyanate (aliphatic diisocyanate, manufactured by Evonik Degussa, VESTANAT H ₁₂ DMI (trade name)) 787 parts by mass ( 3.00 mol) was uniformly added dropwise over 3 hours to react. The reaction was continued for about 10 hours after the completion of the dropwise addition. To this, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich) were further reacted for 10 hours. After confirming that the isocyanate had disappeared, the reaction was terminated to obtain urethane acrylate. The urethane acrylate (PE-UA1) obtained had a critical surface tension of 30 mN / m and a weight average molecular weight of 15,300. PE-UA1 uses a polyester diol and satisfies the above general formula (A).

(Synthesis of urethane acrylate (PE-UA2))
Polycaprolactone diol (aliphatic polyester diol, trade name: Plaxel 220EB, Daicel Chemical Industries, Ltd.) having a number average molecular weight of 2000 in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube Co., Ltd.) 2000 parts by mass (1.00 mol) and dibutyltin dilaurate (Aldrich Co., Ltd.) 5.53 parts by mass were added. After sufficiently introducing nitrogen gas, the mixture is heated to 70 to 75 ° C., and 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) is uniformly added dropwise over 3 hours to be reacted. It was. The reaction was continued for about 10 hours after the completion of the dropwise addition. To this, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich) were further reacted for 10 hours. After confirming that the isocyanate had disappeared, the reaction was terminated to obtain urethane acrylate. The obtained urethane acrylate (PE-UA2) had a critical surface tension of 25 mN / m and a weight average molecular weight of 13,500. PE-UA2 uses a polyester diol and satisfies the above general formula (A).

(Synthesis of urethane acrylate (PE-UA3))
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich), hydroquinone monomethyl 0.53 parts by mass of ether (manufactured by Aldrich), polycaprolactone diol having a number average molecular weight of 1000 (aliphatic polyester diol, trade name: Plaxel 210N, manufactured by Daicel Chemical Industries, Ltd.), 2000 parts by mass (2.00 mol), Dibutyltin dilaurate (Aldrich Co., Ltd.) 5.53 parts by mass was added. After sufficiently introducing nitrogen gas, the mixture is heated to 70 to 75 ° C., and 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) is uniformly added dropwise over 3 hours to be reacted. It was. The reaction was continued for about 10 hours after completion of the dropping, and the reaction was terminated after confirming that the isocyanate had disappeared by IR measurement, to obtain urethane acrylate. The urethane acrylate (PE-UA3) obtained had a critical surface tension of 28 mN / m and a weight average molecular weight of 14,500. PE-UA3 uses a polyester diol and satisfies the above general formula (A).

(Synthesis of urethane acrylate (PE-UA4))
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube, 1650 parts by mass of 3-methyl-1,5-pentanediol (14 mol) and 1660 parts by mass of isophthalic acid (10 mol) was charged, nitrogen gas was sufficiently introduced under normal pressure, and the esterification reaction was carried out while distilling off the water produced at about 170 ° C. out of the system. When the acid value of the polyester became 0.3 mgKOH / g or less, the degree of vacuum was gradually increased by a vacuum pump to complete the reaction. The aromatic polyester diol (ED-1) thus obtained had a number average molecular weight of 2000.

  Furthermore, 2000 parts by mass (1.00 mol) of the obtained aromatic polyester diol (ED-1) was added to a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube. ), 5.53 parts by mass of dibutyltin dilaurate (manufactured by Aldrich). After sufficiently introducing nitrogen gas, the mixture is heated to 70 to 75 ° C., and 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) is uniformly added dropwise over 3 hours to be reacted. It was. After completion of the dropwise addition, the reaction was continued for about 15 hours. To this, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich) were further reacted for 7 hours. After confirming that the isocyanate had disappeared, the reaction was terminated to obtain urethane acrylate. The urethane acrylate (PE-UA4) obtained had a critical surface tension of 42 mN / m and a weight average molecular weight of 11,500. PE-UA4 uses polyester diol and satisfies the above general formula (A).

(Synthesis of urethane acrylate (PE-UA5))
Poly (1,6-hexanediol carbonate) diol (aliphatic polycarbonate diol, Asahi Kasei) with a number average molecular weight of 2000 in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube Chemicals Co., Ltd., PCDL T5652 (trade name) 4000 parts by mass (2.00 mol) and dibutyltin dilaurate (Aldrich Co., Ltd.) 5.53 parts by mass were added. After sufficiently introducing nitrogen gas, the mixture is heated to 70 to 75 ° C., and 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) is uniformly added dropwise over 3 hours to be reacted. It was. The reaction was continued for about 15 hours after the completion of the dropwise addition. To this, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich) were further reacted for 10 hours. After confirming that the isocyanate had disappeared, the reaction was terminated to obtain urethane acrylate. The obtained urethane acrylate (PE-UA5) had a critical surface tension of 21 mN / m and a weight average molecular weight of 30000. PE-UA5 uses polycarbonate diol and does not satisfy the general formula (A).

(Preparation of isocyanuric acid-modified bifunctional acrylate (M-215))
Isocyanuric acid-modified bifunctional acrylate (manufactured by Toagosei Co., Ltd., M-215 (trade name)) was prepared.

(Preparation of vinyl compound having phosphoric acid group (P-2M))
2- (Meth) acryloyloxyethyl phosphate (trade name: Light Ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd.) was prepared.

<Radical polymerization initiator>
Dibenzoyl peroxide (trade name: Nyper BW, manufactured by NOF Corporation) was prepared as a radical polymerization initiator.

<Conductive particles>
(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. Was made.

[Examples 1 to 10 and Comparative Examples 1 to 5]
As shown in Table 2 in terms of solid mass ratio, a thermoplastic resin, a radical polymerizable compound, and a radical polymerization initiator were blended, and 1.5% by volume of conductive particles were blended and dispersed to obtain an adhesive composition. The obtained adhesive composition was applied on a fluororesin film having a thickness of 80 μm using a coating apparatus, and a film-like adhesive composition having an adhesive layer thickness of 20 μm was dried by hot air at 70 ° C. for 10 minutes. Obtained.

[Measurement of connection resistance and adhesive strength]
A flexible circuit board (FPC) having the film-like adhesive compositions of Examples 1 to 10 and Comparative Examples 1 to 5 having 80 copper circuits having a line width of 150 μm, a pitch of 300 μm, and a thickness of 8 μm on a polyimide film (Tg 350 ° C.). And a PET substrate (thickness 0.1 mm) on which a thin layer of 5 μm thick Ag paste was formed. In addition, the film-like adhesive compositions of Examples 1 to 10 and Comparative Examples 1 to 5 are FPC having 80 copper circuits having a line width of 150 μm, a pitch of 300 μm, and a thickness of 18 μm on a polyimide film, and PET (thickness 0. 1 mm) It was interposed between a substrate on which an Ag paste circuit having a line width of 150 μm, a pitch of 300 μm and a thickness of 10 μm was formed on a film. These were each connected by heating and pressing 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.) to produce a connection body. The resistance value between adjacent circuits of these connected bodies was measured with a multimeter immediately after bonding and after being kept in a high-temperature and high-humidity bath 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 each connection body was measured and evaluated by a 90-degree peeling method according to JIS-Z0237. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as a measuring device for adhesive strength. The results of measurement of the connection resistance and adhesive strength of the film adhesive composition performed as described above are shown in Table 3 below.

  The adhesive compositions of Examples 1 to 7 were about 1.2Ω or less immediately after bonding at a heating temperature of 150 ° C. and after being held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test). And good adhesive strength of 600 N / m or more.

  On the other hand, the adhesive compositions of Comparative Examples 1 and 3 show good connection resistance 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 adhesive strength was low. Further, the adhesive compositions of Comparative Examples 2, 4, and 5 have high connection resistance immediately after connection and after being held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test), and the adhesive strength was also implemented. It became low compared with Examples 1-7.

  On the other hand, the adhesive compositions of Examples 8 to 10 were good connections of about 1.2Ω or less 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). Resistance was exhibited and the adhesive strength was superior to Comparative Examples 1 and 3.

[Examples 11 to 13 and Comparative Examples 6 and 7]
Further, the film-like adhesive compositions of Examples 3, 4 and 7 and Comparative Examples 3 and 4 are flexible circuit boards (FPC) having 80 copper circuits having a line width of 150 μm, a pitch of 300 μm and a thickness of 8 μm on a polyimide film. And a PET film (thickness 0.1 mm, Tg 120 ° C.), a PC film (thickness 0.1 mm, Tg 150 ° C.) and a PEN film (thickness 0.1 mm, Tg 160 ° C.). These were each 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 pressure-bonded over a width of 2 mm to prepare a connected body.

  Moreover, the adhesive strength of each connection body was measured similarly to the said method. The measurement results of the adhesive strength of the film adhesive composition performed as described above are shown in Table 4 below.

  The adhesive compositions used in Examples 11 to 13 were heated at 150 ° C. for any substrate, immediately after bonding, and after being kept in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours. In (after test), good adhesive strength of 600 N / m or more was exhibited. On the other hand, the adhesive composition used in Comparative Examples 6 and 7 has low adhesive strength immediately after bonding and after being kept in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test). became.

[Reference Examples 1 to 6]
As a reference example, the film-like adhesive compositions of Examples 3, 4, 6 and 7 and Comparative Examples 1 and 3 are flexible circuits having 500 copper circuits having a line width of 25 μm, a pitch of 50 μm and a thickness of 8 μm on a polyimide film. It was interposed between a plate (FPC) and glass (thickness 1.1 mm, surface resistance 20Ω / □) on which a thin layer of 0.2 μm ITO was formed. Using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.), this was heated and pressurized at 150 ° C. and 2 MPa for 10 seconds to be connected over a width of 2 mm to produce a connected body. The resistance value between adjacent circuits of this connection body was measured with a multimeter immediately after bonding and after being held in a high-temperature and high-humidity bath 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 this connection body was measured by a 90-degree peeling method according to JIS-Z0237 and evaluated. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as a measuring device for adhesive strength. Table 5 below shows the results of the measurement of the connection resistance and the adhesive strength of the film adhesive composition performed as described above.

  As previously indicated, the adhesive composition of the comparative example was inferior in connection resistance and adhesive strength when the adherend was a PET film, a PC film and a PEN film. However, as shown in Table 5, when the adherend is a glass with ITO, in all of Reference Examples 1 to 6 including the case where the adhesive composition of the comparative example was used, immediately after bonding and at 85 ° C., 85 It was confirmed that a good connection resistance of 2.5Ω or less and a good adhesive strength of 680 N / m or more can be obtained after being kept in a high-temperature, high-humidity tank of% RH for 240 hours (after the test).

  According to this embodiment, it is possible to obtain excellent adhesive strength even under low-temperature curing conditions for organic base materials such as polyethylene terephthalate, polycarbonate, and polyethylene naphthalate, and a long-term reliability test (high temperature high Of an adhesive composition capable of maintaining stable performance (adhesion strength and connection resistance) even after a wet test), a connection structure for a circuit member using the same, a method for producing the connection structure, and an adhesive composition Application can be provided.

  DESCRIPTION OF SYMBOLS 10,20 ... Adhesive composition, 10C, 20C ... Connection member, 21 ... Adhesive composition which does not contain electroconductive particle, 22 ... Conductive particle, 21C ... Hardened | cured material of adhesive composition which does not contain electroconductive particle 30 ... first circuit member, 31 ... first circuit board, 31a ... main surface, 32 ... first connection terminal, 40 ... second circuit member, 41 ... second circuit board, 41a ... main surface 42, second connection terminals, 100, 200, connection structure for circuit members.

Claims (6)

A circuit member connection structure comprising: a first circuit member having a first connection terminal on a main surface; a second circuit member having a second connection terminal on a main surface; and a connection member. And
The first circuit member and the second circuit member are arranged via the connection member so that the first connection terminal and the second connection terminal face each other, and the first connection terminal And the second connection terminal is electrically connected,
The connecting member contains (a) a thermoplastic resin, (b) a radical polymerizable compound, and (c) a radical polymerization initiator, and the (b) radical polymerizable compound is represented by the following general formula (A). It is a cured product of an adhesive composition containing urethane (meth) acrylate ,
Said first circuit section Zaimata one of the circuit members of said second circuit member is constructed from a base material containing at least one polyethylene terephthalate, selected from the group consisting of polycarbonate and polyethylene naphthalate, the Circuit member connection structure , wherein the other circuit member of the first circuit member or the second circuit member is composed of a base material containing at least one selected from the group consisting of polyimide resin and polyethylene terephthalate body.

[In the formula (A), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ represents a group derived from a ring-opening compound of ethylene group, propylene group or ε-caprolactone, or the following general formula: A group represented by (B), R ⁴ represents a saturated aliphatic group or a saturated alicyclic group, R ⁵ represents a group represented by the following general formula (B), and a represents 1 to 40 Indicates an integer. ]

[In formula (B), R ⁶ and R ⁷ each independently represents a linear or branched alkylene group having 2 to 12 carbon atoms, b represents an integer of 1 to 10, and c represents an integer of 1 to 25. Indicates. In the formula, R ^{6 s} , R ^{7 s} , b s, and c s may be the same or different. ] The connection structure according to claim 1, wherein the urethane (meth) acrylate is obtained using an aliphatic polyester diol. The connection structure according to claim 1 or 2 , wherein the urethane (meth) acrylate has a weight average molecular weight of 8000 or more and less than 25,000. Wherein (b) a radical polymerizable compound, and a vinyl compound having a phosphoric acid group, containing one or more thereof and a radical polymerizable compound other than the vinyl compound, a having a phosphoric acid group, any of claim 1-3 The connection structure according to claim 1. The said (a) thermoplastic resin contains at least 1 sort (s) chosen from the group which consists of a phenoxy resin, a polyurethane resin, a polyester urethane resin, a butyral resin, an acrylic resin, and a polyimide resin, Any one of Claims 1-4. The connection structure described in 1. (D) The connection structure according to any one of claims 1 to 5 , further comprising conductive particles.

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