KR20130042017A - Adhesive composition, connection structure, and method for producing connection structure - Google Patents

Abstract

This invention is an adhesive composition for connecting the 1st circuit member which has a 1st connection terminal on a main surface, and the 2nd circuit member which has a 2nd connection terminal on a main surface, Comprising: A 1st circuit member and / or a 2nd circuit member Is composed of a substrate containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower, the adhesive composition contains (a) a thermoplastic resin, (b) a radical polymerizable compound and (c) a radical polymerization initiator, and (b A radically polymerizable compound relates to an adhesive composition comprising urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m.

Description

Adhesive composition, bonded structure, and manufacturing method of bonded structure {ADHESIVE COMPOSITION, CONNECTION STRUCTURE, AND METHOD FOR PRODUCING CONNECTION STRUCTURE}

This embodiment relates to the adhesive composition, the bonded structure, the manufacturing method of the bonded structure, and the use of an adhesive composition.

BACKGROUND OF THE INVENTION In a semiconductor device and a liquid crystal display device, various adhesives have been conventionally used for the purpose of bonding various members in the device. The demand for an adhesive is multifaceted including adhesiveness, heat resistance, reliability under high temperature and high humidity. In addition, the adherend used for adhesion includes organic substrates such as printed wiring boards, polyimide, polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), metals such as copper and aluminum, and ITO ( A substrate having various surface states such as indium and tin oxide), SiN, and SiO ₂ is used, and a molecular design suitable for each adherend is required.

Conventionally, as an adhesive agent for the said semiconductor element and a liquid crystal display element, the thermosetting resin using the epoxy resin which is high adhesiveness and shows high reliability has been used (for example, refer patent document 1). As the 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. The thermal latent catalyst is a substance that does not react at a storage temperature such as room temperature and exhibits high reactivity at the time of heating, and is an important factor for determining the curing temperature and curing rate, and the storage stability of the adhesive at room temperature and curing at heating. Various compounds have been used in terms of speed. The hardening conditions in the actual process obtained the desired adhesive by hardening for 1 to 3 hours at the temperature of 170-250 degreeC.

However, in recent years, semiconductor elements, liquid crystal display elements, and wirings are sometimes formed on organic substrates having low heat resistance, such as PET, PC, and PEN, which may adversely affect the organic substrate and the peripheral member by heating during curing. Since there exists, adhesion in low temperature hardening is calculated | required. In order to achieve low temperature fast curing with the above-mentioned epoxy resin, it is necessary to use a thermal latent catalyst having a low activation energy, but it is difficult to have a storage stability near room temperature.

Among these, attention is paid to radical curable adhesives which use together radical polymerizable compounds, such as an acrylate derivative and a methacrylate derivative, and a peroxide which is a radical polymerization initiator. Radical hardening can be hardened for a short time because the radical which is reactive active species is rich in reactivity (for example, refer patent document 2). However, since the radical shrinkage-type adhesive agent has large hardening shrinkage at the time of heating, adhesive strength is inferior compared with the case where an epoxy resin is used. About the fall of such adhesive strength, the method of providing flexibility and improving adhesive strength by applying urethane acrylate is proposed (for example, refer patent document 3). Further, for the body is deposited ITO, SiN, SiO ₂ or the like inorganic base material, a method for improving the bonding strength by adding an adhesion aid such as a silane coupling agent has been proposed (for example, see Patent Document 4).

Japanese Patent Laid-Open No. 1-13480 International Publication No. 98/44067 Japanese Patent No. 3503740 Japanese Patent Laid-Open No. 62-62874

However, organic substrates such as thermoplastic resins, such as PET, PC, and PEN, are linear and easily form crystal parts due to intermolecular interactions with a benzene ring. Therefore, covalent bonds with adhesive compositions or silane coupling agents Formation is very difficult. Therefore, in the method of patent document 4 mentioned above, sufficient adhesive strength is not obtained. In addition, since the surfaces of PET, PC, PEN and the like are smooth, the adhesion effect due to the physical anchoring effect (anchor effect) is small. Therefore, although it is necessary to apply the adhesive composition which obtains wettability and sufficient flexibility with respect to a to-be-adhered body, in the method of patent document 3 mentioned above, sufficient wettability and flexibility with respect to a to-be-adhered body are not acquired.

Therefore, this invention can obtain the outstanding adhesive strength with respect to organic base materials, such as polyethylene terephthalate, a polycarbonate, and a polyethylene naphthalate, even in low-temperature hardening conditions, and is stable even after a long time reliability test (high temperature, high humidity test) (adhesive strength) And (b) connection resistance), the connection structure of a circuit member using the same, the manufacturing method of a connection structure, and the use of an adhesive composition are provided.

In order to achieve the said objective, this invention is an adhesive composition for connecting the 1st circuit member which has a 1st connection terminal on a main surface, and the 2nd circuit member which has a 2nd connection terminal on a main surface, Comprising: 1st circuit member And / or the second circuit member is composed of a substrate comprising a thermoplastic resin having a glass transition temperature of 200 ° C. or less, and the adhesive composition comprises (a) a thermoplastic resin, (b) a radical polymerizable compound, and (c) radical polymerization. An adhesive composition is provided which comprises an urethane (meth) acrylate containing an initiator and (b) the radically polymerizable compound having a critical surface tension of 25 to 40 mN / m.

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

Moreover, in the adhesive composition of this invention, it is preferable that the urethane (meth) acrylate contained in (b) radically polymerizable compound is represented by following General formula (A).

[In Formula (A), R <^1> and R <^2> represents a hydrogen atom or a methyl group each independently, R <^3> is group derived from the ring-opening compound of ethylene group, a propylene group, (epsilon) -caprolactone, or following formula (B) Represents a group represented by R ⁴ represents a group represented by the following formula (B), R ⁵ represents a saturated aliphatic group or a saturated alicyclic group, and a represents an integer of 1 to 40.]

[In formula (B), R <^6> and R <^7> respectively independently represents the C2-C12 linear or branched alkylene group, b represents the integer of 1-10, c represents the integer of 1-25. , Wherein, R ⁶ , R ⁷ , b and c may be the same or different.

Since there is a proportional relationship between the critical surface tension and the aggregation energy density, it is considered that the critical surface tension is improved by introducing a functional group having a high aggregation energy density. Therefore, when (b) the urethane (meth) acrylate contained in a radically polymerizable compound is a structure represented by the said General formula (A), aggregation energy density improves and a thermoplastic resin whose adhesive composition and Tg are 200 degrees C or less. The wettability with the base material (for example, PET, PC, PEN, etc.) containing this improves, the adhesive strength between the circuit members comprised from the base material containing thermoplastic resins, such as PET, PC, and PEN, improves, and is excellent connection Reliability can be obtained. Moreover, when the urethane (meth) acrylate contained in the (b) radically polymerizable compound is a structure represented by the said general formula (A), appropriate flexibility is provided to adhesive composition, and thermoplastics, such as PET, PC, and PEN, are provided. The adhesive strength between the circuit members comprised of the base material containing resin improves, and the outstanding connection reliability can be obtained.

Moreover, this invention is an adhesive composition for connecting the 1st circuit member which has a 1st connection terminal on a main surface, and the 2nd circuit member which has a 2nd connection terminal on a main surface, Comprising: 1st circuit member and / or 2nd The circuit member is composed of a substrate containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower, the adhesive composition contains (a) a thermoplastic resin, (b) a radical polymerizable compound and (c) a radical polymerization initiator, (b) It provides the adhesive composition in which a radically polymerizable compound contains urethane (meth) acrylate represented by following General formula (A).

[In Formula (A), R <^1> and R <^2> represents a hydrogen atom or a methyl group each independently, R <^3> is group derived from the ring-opening compound of ethylene group, a propylene group, (epsilon) -caprolactone, or following formula (B) Represents a group represented by R ⁴ represents a group represented by the following formula (B), R ⁵ represents a saturated aliphatic group or a saturated alicyclic group, and a represents an integer of 1 to 40.]

[In formula (B), R <^6> and R <^7> respectively independently represents the C2-C12 linear or branched alkylene group, b represents the integer of 1-10, c represents the integer of 1-25. , Wherein, R ⁶ , R ⁷ , b and c may be the same or different.

In this adhesive composition, (b) the urethane (meth) acrylate contained in a radically polymerizable compound is a structure represented by the said General formula (A), and cohesion energy density improves and a thermoplastic composition whose adhesive composition and Tg are 200 degrees C or less. The wettability with the base material (for example, PET, PC, PEN, etc.) containing resin improves, the adhesive strength between the circuit members comprised from the base material containing thermoplastic resins, such as PET, PC, PEN, improves, and is excellent. Connection reliability can be obtained. Moreover, when the urethane (meth) acrylate contained in the (b) radically polymerizable compound is a structure represented by the said general formula (A), appropriate flexibility is provided to adhesive composition, and thermoplastics, such as PET, PC, and PEN, are provided. The adhesive strength between the circuit members comprised of the base material containing resin improves, and the outstanding connection reliability can be obtained. In addition, 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 one obtained using an aliphatic polyesterdiol. Since urethane (meth) acrylate is obtained using aliphatic polyesterdiol, the flexibility of the adhesive composition is improved, and the adhesion between circuit members composed of a substrate containing a thermoplastic resin such as PET, PC, or PEN The strength is 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. By the weight average molecular weight of a urethane (meth) acrylate being in the said range, adhesive strength with organic base materials, such as PET, PC, and PEN, can be improved more, and the outstanding connection reliability can be obtained.

Moreover, in the adhesive composition of this invention, it is preferable that (b) a radically polymerizable compound contains 1 or more types of radically polymerizable compounds other than the vinyl compound which has a phosphoric acid group, and the vinyl compound which has a phosphoric acid group, respectively. (b) When a radically polymerizable compound has such a structure, especially the adhesive strength with the base material which consists of metals improves more.

Moreover, in the adhesive composition of this invention, as (a) thermoplastic resin, at least 1 sort (s) chosen from the group which consists of a phenoxy resin, a polyurethane resin, polyesterurethane resin, butyral resin, an acrylic resin, and a polyimide resin. It is preferable to contain. (a) As thermoplastic resin, by containing such resin, the heat resistance and adhesiveness of an adhesive composition improve more.

Moreover, in the adhesive composition of this invention, it is also preferable to contain (d) electroconductive particle further. (d) Since good electroconductivity or anisotropic electroconductivity can be provided to an adhesive composition by containing electroconductive particle, it becomes possible to use more preferably for the adhesive use etc. of circuit members which have a connection terminal. Moreover, the connection resistance of the circuit member electrically connected through the said adhesive composition can be reduced more fully.

Moreover, this invention is a connection structure of 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 the circuit member provided with a connection member, 1st connection. The 1st circuit member and the 2nd connection terminal are arrange | positioned through the connection member which consists of said adhesive composition so that a terminal and a 2nd connection terminal may oppose, and the 1st connection terminal and the 2nd connection terminal are electrically connected, and the 1st A circuit member and / or the said 2nd circuit member provide the connection structure of the circuit member comprised from the base material containing a thermoplastic resin whose glass transition temperature is 200 degrees C or less.

When the first circuit member and / or the second circuit member are circuit members composed of a substrate containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower, the wettability with the adhesive composition is improved and the adhesive strength is further improved. Excellent connection reliability can be obtained.

It is preferable that the thermoplastic resin whose said glass transition temperature is 200 degrees C or less is at least 1 sort (s) chosen from the group which consists of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. By being a circuit member comprised from the base material containing polyethylene terephthalate etc., the wettability with an adhesive composition improves and adhesive strength improves more, and it is possible to obtain the excellent connection reliability.

Moreover, in the connection structure of the circuit member of this invention, the circuit member of one of a 1st circuit member or a 2nd circuit member contains at least 1 sort (s) chosen from the group which consists of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. It is preferable that it is comprised from a base material and the other circuit member of a 1st circuit member or a 2nd circuit member consists of a base material containing at least 1 sort (s) chosen from the group which consists of a polyimide resin and a polyethylene terephthalate. Since this 1st circuit member and a 2nd circuit member are comprised from the base material mentioned above, this connection structure can improve the wettability and adhesive strength with an adhesive composition, and can obtain the outstanding connection reliability.

The present invention provides a first circuit member having a first connection terminal on a main surface and a second circuit member having a second connection terminal on a main surface such that the first connection terminal and the second connection terminal face each other through the adhesive composition. The manufacturing method of the circuit member connection structure provided with the process of arrange | positioning, and the process of heating and hardening an adhesive composition and connecting a 1st circuit member and a 2nd circuit member are provided. According to this manufacturing method, the connection structure of the circuit member which has the outstanding connection reliability can be obtained by connecting a 1st circuit member and a 2nd circuit member with the said adhesive composition.

In addition, the present invention contains (a) a thermoplastic resin, (b) a radically polymerizable compound and (c) a radical polymerization initiator, and (b) the radically polymerizable compound has a critical surface tension of 25 to 40 mN / m. At least one circuit member is free as a 1st circuit member which has a 1st connection terminal on the main surface, and a 2nd circuit member which has a 2nd connection terminal on the main surface of the adhesive composition containing a urethane (meth) acrylate. The use as an adhesive composition for connecting a 1st circuit member and a 2nd circuit member comprised with the base material containing a thermoplastic resin of transition temperature 200 degrees C or less is provided. The present adhesive composition containing (b) a radically polymerizable compound comprising a urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m includes a substrate comprising a thermoplastic resin having a Tg of 200 ° C. or lower (eg, For example, since wettability with PET, PC, PEN, etc.) improves and adhesion in low-temperature hardening becomes possible, it is suitable for the use as an adhesive composition for connecting a circuit member.

In the said use, it is preferable that urethane (meth) acrylate is a urethane (meth) acrylate represented by following General formula (A). Since urethane (meth) acrylate is a structure represented by following General formula (A), the adhesive strength between circuit members can improve and the outstanding connection reliability can be obtained.

[In Formula (A), R <^1> and R <^2> represents a hydrogen atom or a methyl group each independently, R <^3> is group derived from the ring-opening compound of ethylene group, a propylene group, (epsilon) -caprolactone, or following formula (B) Represents a group represented by R ⁴ represents a group represented by the following formula (B), R ⁵ represents a saturated aliphatic group or a saturated alicyclic group, and a represents an integer of 1 to 40.]

[In formula (B), R <^6> and R <^7> respectively independently represents the C2-C12 linear or branched alkylene group, b represents the integer of 1-10, c represents the integer of 1-25. , Wherein, R ⁶ , R ⁷ , b and c may be the same or different.

Moreover, this invention contains urethane (meth) containing (a) a thermoplastic resin, (b) radically polymerizable compound, and (c) radical polymerization initiator, and (b) radically polymerizable compound is represented by following General formula (A) At least one circuit member has a glass transition temperature of 200 ° C. as a first circuit member having a first connection terminal on a main surface and a second circuit member having a second connection terminal on a main surface of an adhesive composition comprising an acrylate. The use as an adhesive composition for connecting the 1st circuit member and the 2nd circuit member comprised with the base material containing the following thermoplastic resins is provided. Since urethane (meth) acrylate is a structure represented by following General formula (A), the adhesive strength between circuit members can improve and the outstanding connection reliability can be obtained.

[In Formula (A), R <^1> and R <^2> represents a hydrogen atom or a methyl group each independently, R <^3> is group derived from the ring-opening compound of ethylene group, a propylene group, (epsilon) -caprolactone, or following formula (B) Represents a group represented by R ⁴ represents a group represented by the following formula (B), R ⁵ represents a saturated aliphatic group or a saturated alicyclic group, and a represents an integer of 1 to 40.]

[In formula (B), R <^6> and R <^7> respectively independently represents the C2-C12 linear or branched alkylene group, b represents the integer of 1-10, c represents the integer of 1-25. , Wherein, R ⁶ , R ⁷ , b and c may be the same or different.

In the said use, it is preferable that urethane (meth) acrylate is obtained using aliphatic polyesterdiol. Since urethane (meth) acrylate is obtained using aliphatic polyesterdiol, the flexibility of the adhesive composition is improved, and the adhesion between the circuit members composed of a substrate containing a thermoplastic resin such as PET, PC, or PEN The strength is improved, and excellent connection reliability can be obtained.

In the said use, it is preferable that the weight average molecular weights of urethane (meth) acrylates are 8000 or more and less than 25000. By the weight average molecular weight of a urethane (meth) acrylate being in the said range, adhesive strength with organic base materials, such as PET, PC, and PEN, can be improved more, and the outstanding connection reliability can be obtained.

In the said use, it is preferable that (b) radically polymerizable compound contains 1 or more types of radically polymerizable compounds other than the vinyl compound which has a phosphoric acid group, and the vinyl compound which has a phosphoric acid group, respectively. (b) When a radically polymerizable compound has such a structure, especially the adhesive strength with the base material which consists of metals improves more.

In the said use, 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, polyesterurethane resin, butyral resin, an acrylic resin, and a polyimide resin. Do. (a) As thermoplastic resin, by containing such resin, heat resistance and adhesiveness improve more.

In the said use, it is preferable that adhesive composition contains (d) electroconductive particle further. (d) By containing electroconductive particle, favorable electroconductivity or anisotropic electroconductivity can be provided to an adhesive composition, and the connection resistance of the circuit member electrically connected can be reduced more fully.

According to the present invention, excellent adhesive strength can be obtained with respect to organic substrates such as polyethylene terephthalate, polycarbonate and polyethylene naphthalate even under low temperature curing conditions, and stable performance even after a long time reliability test (high temperature and high humidity test) (adhesive strength) (B) connection resistance), the connection structure of the circuit member using the same, the manufacturing method of the connection structure of a circuit member, and the use of an adhesive composition can be provided.

1: is a schematic cross section which shows one Embodiment of the connection structure of a circuit member using the adhesive composition of this embodiment.
FIG. 2: is a schematic cross section which shows a 1st circuit member, a 2nd circuit member, and an adhesive composition before manufacturing the connection structure of the circuit member shown in FIG.
FIG. 3: is a schematic cross section which shows one Embodiment of the connection structure of a circuit member using the adhesive composition (containing electroconductive particle) of this embodiment.
FIG. 4: is a schematic cross section which shows the 1st circuit member, the 2nd circuit member, and adhesive composition (containing electroconductive particle) before producing the connection structure of the circuit member shown in FIG.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail, referring drawings as needed. In addition, description which attaches | subjects the same code | symbol to the same or equivalent part in the drawing, and overlaps is abbreviate | omitted. In addition, in this embodiment, (meth) acrylic acid represents acrylic acid or methacrylic acid corresponding to it, (meth) acrylate means acrylate or methacrylate corresponding to it, and (meth) acryloyl group is acryl It means a loyl group or methacryloyl group.

"Glass transition temperature (Tg)" in this embodiment is measured using a viscoelastic analyzer "RSA-3" (trade name) manufactured by TA Instruments, Inc., at an elevated temperature of 5 deg. The value of tan-delta peak temperature in the vicinity of Tg is measured on the conditions of temperature -150-300 degreeC.

Note that when manufacturing "critical surface tension (γ _c)" refers to a urethane (meth) pure water, a wetting tension acrylate in the form of a film test mixture No.50, 60 (Wako Junya packed Kogyo Co., Ltd. according to the present embodiment When the angle (contact angle θ) formed with the urethane (meth) acrylate surface immediately after dropping 1 µl each at 23 ° C was measured, and the surface tension of each liquid was plotted on the x-axis and COSθ on the y-axis, The surface tension when the straight line passing through three points becomes Y = 1. In addition, when X becomes a negative value when the straight line which passes three points obtained by the said pure water and the measurement of No.50, 60 is Y = 1, the mixed solution No.60, 1 for pure water and a wet tension test The same measurement as described above is carried out using bromonaphthalene (manufactured by Wako Junyaku Kogyo Co., Ltd.), and the value of the surface tension when the straight line passing through the obtained three points becomes Y = 1 may be used.

In addition, in this embodiment, a "weight average molecular weight" and a "number average molecular weight" mean the value measured using the analytical curve by standard polystyrene from the gel permeation chromatograph (GPC) according to the conditions shown in Table 1.

The adhesive composition of this embodiment is an adhesive composition for connecting the 1st circuit member which has a 1st connection terminal on a main surface, and the 2nd circuit member which has a 2nd connection terminal on a main surface, Comprising: 1st circuit member and / or A 2nd circuit member is comprised from the base material containing the thermoplastic resin whose glass transition temperature is 200 degrees C or less, and an adhesive composition contains (a) thermoplastic resin, (b) radically polymerizable compound, and (c) radical polymerization initiator And (b) the radically polymerizable compound comprises a urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m.

The thermoplastic resin (a) contained in the adhesive composition of the present embodiment becomes a liquid state having a high viscosity by heating, and deforms freely by external force, and when cooled to remove the external force, becomes hard while maintaining its shape. It refers to resin (polymer) which has the property which can be performed repeatedly. Moreover, resin (polymer) which has a reactive functional group which has the above-mentioned property is also included. (a) 0-190 degreeC is preferable and, as for Tg of a thermoplastic resin, 20-170 degreeC is more preferable.

As such a thermoplastic resin, a polyimide resin, a polyamide resin, a phenoxy resin, a (meth) acrylic resin, a urethane resin, a polyester urethane resin, a polyvinyl butyral resin, or the like can be used. These may be used alone or in combination of two or more. In addition, these thermoplastic resins may contain a siloxane bond or a fluorine substituent. These resins can be suitably used as long as the resins to be mixed are completely compatible or have a microphase separation.

When the adhesive composition is used in the form of a film, the higher the molecular weight of the thermoplastic resin is, the better the film formability can be easily obtained, and the melt viscosity affecting the fluidity as the film adhesive composition can be set widely. (a) As a weight average molecular weight of a thermoplastic resin, 5000-150000 are preferable and 10000-80000 are more preferable. When this value is less than 5000, there exists a tendency for favorable film formability to be difficult to be obtained, and when it exceeds 150000, there exists a tendency for favorable compatibility with other components to be difficult to be obtained.

In the adhesive composition of this embodiment, it is preferable that it is 5-80 mass%, and, as for content of (a) thermoplastic resin, it is more preferable that it is 15-70 mass% based on adhesive composition whole quantity. When this content is less than 5 mass%, when using an adhesive composition in a film form, especially tends to be difficult to obtain favorable film formability, and when it exceeds 80 mass%, the tendency which the fluidity of a favorable adhesive composition is hard to be acquired is There is this.

The radically polymerizable compound (b) 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, which itself generates radicals by applying activation energy such as light or heat. It may be. (b) As a radically polymerizable compound, the compound which has a functional group superposing | polymerizing with active radicals, such as a vinyl group, a (meth) acryloyl group, an allyl group, and a maleimide group, can be used preferably, for example.

(b) As a radically polymerizable compound, specifically, oligomers, such as an epoxy (meth) acrylate oligomer, a urethane (meth) acrylate oligomer, a polyether (meth) acrylate oligomer, and a polyester (meth) acrylate oligomer, trimethylol Propane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, Neopentylglycoldi (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) acrylate, bisphenoxy Epoxy (meth) acrylic which added (meth) acrylic acid to glycidyl group of ethanol fluorene acrylate and bisphenol fluorene diglycidyl ether Glyci of epoxy (meth) acrylate and bisphenol fluorene diglycidyl ether which added (meth) acrylic acid to the glycidyl group of bisphenoxy ethanol fluorene acrylate and bisphenol fluorene diglycidyl ether The compound which introduce | transduced the (meth) acryloyloxy group into the compound which added ethylene glycol and propylene glycol to the diyl group, the compound represented by following formula (C) and (D), etc. are mentioned.

[In formula (C), R <^8> and R <^9> represents a hydrogen atom or a methyl group each independently, d and e represent the integer of 1-8 each independently.]

[In formula (D), R <^10> and R <^11> represents a hydrogen atom or a methyl group each independently, f and g represent the integer of 0-8 each independently.]

The radically polymerizable compound (b) may be used without particular limitation even when the mixture is left alone at 30 ° C. even if it exhibits a solid state without fluidity such as wax, lead, crystal, glass, or powder. Specifically as such a (b) radically polymerizable compound, N, N'-methylenebisacrylamide, diacetone acrylamide, N-methylol acrylamide, N-phenyl methacrylamide, 2-acrylamide-2-methylpropane Sulfonic 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-ethyl Maleimide, N-octylmaleimide, 4,4'-diphenylmethanebismaleimide, m-phenylenebismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-di Phenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, N-methacryloxymaleimide, N-acryloxymaleimide, 1,6-bismaleimide- (2,2,4- Trimethyl) hexane, N-methacryloyloxysuccinate N-acryloyloxysuccinimide, 2-naphthyl methacrylate, 2-naphthyl acrylate, pentaerythritol tetraacrylate, divinyl ethylene urea, divinyl propylene urea, 2-polytyryl ethyl meth Acrylate, N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N-phenyl-N'-(3-acryloyloxy-2-hydroxy Oxypropyl) -p-phenylenediamine, tetramethylpiperidyl methacrylate, tetramethylpiperidyl acrylate, pentamethylpiperidyl methacrylate, pentamethylpiperidyl acrylate, octadecyl acrylate, Nt -Butyl acrylamide, diacetone acrylamide, N- (hydroxymethyl) acrylamide, the compound represented by following General formula (E)-(N), etc. are mentioned.

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

[In formula (G), R <^12> and R <^13> represents a hydrogen atom or a methyl group each independently, and i represents the integer of 15-30.]

[In formula (H), R <^14> and R <^15> represents a hydrogen atom or a methyl group each independently, j represents the integer of 15-30.]

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

[In formula (J), R <^17> represents a hydrogen atom or a methyl group, k represents the integer of 1-10.]

Formula (K) of, R ¹⁸ represents an organic group represented by a hydrogen atom or the following formula (i) or (ii), l represents an integer of 1 to 10;

[In formula (L), R <^19> represents a hydrogen atom or the organic group represented by following General formula (iii) or (iv), and m represents the integer of 1-10.

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

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

Moreover, (b) N-vinyl type compound chosen from the group which consists of a phosphoric acid group containing vinyl compound which is a compound which belongs to a radically polymerizable compound, and an N-vinyl compound and an N, N-dialkylvinyl compound (b) ) Can be used in combination with a radically polymerizable compound. By using together a phosphoric acid group containing vinyl compound, it becomes possible to improve adhesiveness to the metal base material of an adhesive composition. Moreover, the crosslinking rate of an adhesive composition can be improved by using together N-vinyl type compound.

Although it will not restrict | limit especially if it is a compound which has a phosphoric acid group and a vinyl group as a phosphoric acid group containing vinyl compound, The compound represented by following formula (O)-(Q) is preferable.

In formula (O), R ²² represents a (meth) acryloyloxy group, R ²³ represents a hydrogen atom or a methyl group, n and o each independently represent an integer of 1 to 8, and in the formula, R ²² May be identical to or different from each other, R ²³ , n and o;

[In formula (P), R <^24> represents a (meth) acryloyloxy group, p and q respectively independently represent the integer of 1-8, In formula, R <^24> , p, and q are the same each, or May be different]

[In Formula (Q), R ²⁵ represents a (meth) acryloyloxy group, R ²⁶ represents a hydrogen atom or a methyl group, r and s each independently represent an integer of 1 to 8, and in the formula, R ²⁶ May be identical to or different from each other]

Specific examples of the phosphoric acid group-containing vinyl compound include acid phospho oxyethyl methacrylate, acid phospho oxyethyl acrylate, acid phospho oxypropyl methacrylate, and acid phospho oxy polyoxyethylene glycol monomethacrylate. Acid phosphooxy polyoxypropylene glycol monomethacrylate, 2,2'-di (meth) acryloyloxydiethyl phosphate, EO modified phosphate dimethacrylate, phosphoric acid modified epoxy acrylate, vinyl phosphate, etc. are mentioned. Can be.

The compounding amount of the phosphoric acid group-containing vinyl compound is preferably 0.2 to 300 parts by mass, and preferably 1 to 200 mass parts of the compounding amount of the (b) radically polymerizable compound other than the phosphoric acid group-containing vinyl compound independently (a) 100 parts by mass of the thermoplastic resin. It is more preferable to set it as a part, It is further more preferable to set it as 1-50 mass parts, It is especially preferable to set it as 1-15 mass parts. When the compounding quantity of a phosphate group containing vinyl compound is less than 0.2 mass part, it exists in the tendency for a high adhesive strength to be difficult to be obtained, and when it exceeds 300 mass parts, the physical property of the adhesive composition after hardening will fall easily, and it will become difficult to ensure reliability. .

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

It is preferable that the compounding quantity of the (b) radically polymerizable compound except the compound corresponding to the above-mentioned phosphoric acid group containing vinyl compound is 50-250 mass parts with respect to 100 mass parts of (a) thermoplastic resin, and it is more preferable that it is 60-150 mass parts. Do. When the said compounding quantity is less than 50 mass parts, there exists a tendency for sufficient heat resistance after hardening to be difficult to be obtained, and when it exceeds 250 mass parts, when using as a film, favorable film formability tends to be difficult to be obtained.

The adhesive composition of this embodiment is (b) a urethane (meth) acrylate having a critical surface tension of 25 to 40 mN / m as the radical polymerizable compound, and one of the urethane (meth) acrylates represented by the following general formula (A) or Urethane (meth) acrylate which satisfies both conditions is contained as an essential component. Among these, in this embodiment, urethane acrylate which satisfy | fills the said conditions is used more preferably. Here, the urethane (meth) acrylate represented by the following general formula (A) can be obtained by condensation reaction of aliphatic diisocyanate and polyesterdiol.

[In Formula (A), R <^1> and R <^2> represents a hydrogen atom or a methyl group each independently, R <^3> is group derived from the ring-opening compound of ethylene group, a propylene group, (epsilon) -caprolactone, or following formula (B) Represents a group represented by R ⁴ represents a group represented by the following formula (B), R ⁵ represents a saturated aliphatic group or a saturated alicyclic group, and a represents an integer of 1 to 40.]

[In formula (B), R <^6> and R <^7> respectively independently represents the C2-C12 linear or branched alkylene group, b represents the integer of 1-10, c represents the integer of 1-25. , Wherein, R ⁶ , R ⁷ , b and c 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 xylylene diisocyanate, etc. are chosen.

As the polyester diol constituting the urethane (meth) acrylate, for example, an aliphatic polyester diol or an aromatic polyester diol can be used, and it is preferable to use an aliphatic polyester diol. Aliphatic polyester diols are ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentylglycol, 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-octanediol, 1,8-octanediol, 1,7-heptanediol, 1,9-nonanediol, 1,2-decanediol, 1,10 Saturated low molecular glycols such as -decanediol, 1,12-decanediol, dodecanediol, pinacol, 1,4-butynediol, triethylene glycol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol, at least Polycarbonate diols obtained by the reaction of at least one of the above glycols and phosgene, and at least one of the above glycols as an initiator Diols such as polyetherdiol obtained by addition polymerization of one or more monomers such as ethylene oxide, propylene oxide and epichlorohydrin by a known method, 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, methyl Malonic acid, ethyl malonic acid, butyl malonic acid, dimethyl malonic acid, glutaric acid, 2-methyl glutaric acid, 3-methyl glutaric acid, 2,2-dimethyl glutaric acid, 3,3-dimethyl glutaric acid , Aliphatic polyester diols obtained by dehydrating and condensing dibasic acids such as 2,4-dimethylglutaric acid, pimelic acid, subic acid, azelaic acid, and sebacic acid or their corresponding anhydrides, ε-caprolactone, and the like From aliphatic polyester diols obtained by ring-opening polymerization of a cyclic ester compound of Is selected. 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 adjusted freely 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 used preferably. If the weight average molecular weight of the said urethane (meth) acrylate is in the said range, both flexibility and cohesion force can be obtained, adhesive strength with organic substrates, such as PET, PC, and PEN, will improve, and excellent connection reliability can be obtained. . Moreover, from a viewpoint of fully obtaining such an effect, it is more preferable that the weight average molecular weights of the said urethane (meth) acrylate are 10000 or more and less than 25000. Moreover, when this weight average molecular weight is less than 8000, there exists a tendency for sufficient flexibility not to be obtained, and when it is 25000 or more, there exists a tendency for the fluidity | liquidity of an adhesive composition to fall.

It is preferable that it is 25-40 mN / m, and, as for the critical surface tension of the said urethane (meth) acrylate, it is more preferable that it is 25-35 mN / m. When the critical surface tension of the urethane (meth) acrylate is 25 to 40 mN / m, it is close to the critical surface tension of PET, PC, and PEN as the adherend, and the wettability is improved, thereby improving the adhesive strength and obtaining excellent connection reliability. . Moreover, when this critical surface tension exceeds 25 mN / m or exceeds 40 mN / m, there exists a possibility that the wettability or compatibility with PET, PC, PEN, etc. may deteriorate. It is thought that the critical surface tension of the urethane (meth) acrylate can be adjusted by changing the number average molecular weight of the diol in relation to the urethane bond equivalent. For example, when the number average molecular weight of the diol is increased, the urethane bond equivalents tend to decrease, and the critical surface tension tends to decrease.

Moreover, it is preferable that it is 5-95 mass% on the basis of the adhesive composition whole quantity, and, as for the compounding quantity of the said urethane (meth) acrylate, it is more preferable that it is 10-80 mass%. When the compounding quantity is less than 5 mass%, there exists a tendency for heat resistance to fall easily, and when it exceeds 95 mass%, there exists a tendency for film formability to fall easily when using as a film.

As a (c) radical polymerization initiator contained in the adhesive composition of this embodiment, the compound which generate | occur | produces a radical by provision of energy from the exterior, such as a conventionally known organic peroxide and an azo compound, can be used. As the (c) radical polymerization initiator, an organic peroxide having a half-life temperature of 90 to 175 ° C and a molecular weight of 180 to 1,000 is preferable from the viewpoint of stability, reactivity and compatibility. When the half-life temperature is in this range for 1 minute, the storage stability is excellent, the radical polymerizability is sufficiently high, and the curing can be performed in a short time.

(c) As a radical polymerization initiator, 1,1,3,3- tetramethylbutyl peroxy neodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, and di (2-ethylhexyl) are specifically, mentioned. Peroxydicarbonate, cumylperoxy neodecanoate, 1,1,3,3-tetramethylbutylperoxy neodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethylperoxy neode Decanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-butyl peroxy pivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexano Acetate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy neoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexano 8, 3-hydroxy-1,1-dimeth Butylbutyl peroxy neodecanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy neodecanoate, t-amylperoxy-2-ethylhexa Noate, di (3-methylbenzoyl) peroxide, dibenzoylperoxide, di (4-methylbenzoyl) peroxide, t-hexylperoxyisopropylmonocarbonate, t-butylperoxymaleic acid, t-butylper Oxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) hexane, t-butylperoxy-2- Ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, dibutylperoxytrimethyl adipate, t-amyl Organic peroxides such as peroxy normal octoate, t-amyl peroxy isononanoate and t-amyl peroxy benzoate; 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis (1-acetoxy-1-phenylethane), 2,2'-azobisisobutyronitrile, 2, 2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), 1,1'-azo Azo compounds, such as bis (1-cyclohexanecarbonitrile), etc. are mentioned.

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

In addition, as the (c) radical polymerization initiator, a compound which generates a radical by light irradiation of 150 to 750 nm can be used. As such a compound, for example, Photoinitiation, Photopolymerization, and Photocuring, J.-P. [Alpha] -acetaminophenone derivatives or phosphine oxide derivatives described in Fouassier, Hanser Publishers (1995, p17 to p35) are more preferred because of their high sensitivity to light irradiation.

These compounds may be used alone or in combination with the above organic peroxides and azo compounds.

0.1-500 mass parts is preferable with respect to 100 mass parts of (a) thermoplastic resins, As for the compounding quantity of the said (c) radical polymerization initiator, 1-300 mass parts is more preferable, 5-50 mass parts is still more preferable, 10-30 Part by mass is particularly preferred. (c) When the compounding quantity of a radical polymerization initiator is less than 0.1 mass part, it will become difficult to fully harden an adhesive composition, and when it exceeds 500 mass parts, there exists a tendency for storage stability to deteriorate.

Although (d) electroconductive particle contained in the adhesive composition of this embodiment should just be the particle | grains which have electroconductivity in the whole or the surface, when using for the connection of the circuit member which has a connection terminal, the average particle diameter is smaller than the distance between connection terminals. It is preferable.

(d) As electroconductive particle, metal particles, such as Au, Ag, Ni, Cu, a solder, carbon etc. are mentioned. It is also possible to use a non-conductive glass, ceramic, plastic, or the like as a nucleus and coating the nucleus with the metal, metal particles, or carbon. (d) In the case where the conductive particles are made of plastic as a nucleus, and the nucleus is coated with the metal, metal particles or carbon, or in the case of hot-melt metal particles, they are deformable by heating and pressing, so that the contact area with the electrode at the time of connection is reduced. It is preferable because it increases and reliability improves.

Moreover, the microparticles | fine-particles which further coat | covered the surface of these (d) electroconductive particle with a polymer resin etc. can suppress the short circuit by the contact of the particles when the compounding quantity of electroconductive particle is increased, and can improve the insulation between electrode circuits. Since it exists, it can also be used individually or in mixture with (d) electroconductive particle suitably.

It is preferable that the average particle diameter of this (d) electroconductive particle is 1-18 micrometers from a dispersible and electroconductive point. When it contains such (d) electroconductive particle, an adhesive composition can be used suitably as an anisotropically conductive adhesive agent.

(d) Although the usage-amount of electroconductive particle is not specifically limited, It is preferable to set it as 0.1-30 volume% with respect to the whole volume of adhesive composition, and it is more preferable to set it as 0.1-10 volume%. If this value is less than 0.1 volume%, there exists a tendency for electroconductivity to become low, and when it exceeds 30 volume%, there exists a tendency for a short circuit to occur easily. In addition, although the volume% is determined based on the volume of each component before hardening at 23 degreeC, the volume of each component can be converted from volume to volume using specific gravity. In addition, the volume of the component may be obtained as the volume of the component by adding the appropriate component (water, alcohol, or the like) into a measuring cylinder or the like without dissolving or swelling the component.

In addition, a stabilizer can be added to the adhesive composition of this embodiment in order to provide control of a curing rate, or to provide storage stability. As such a stabilizer, a well-known compound can be used without a restriction | limiting in particular, Quinone derivatives, such as benzoquinone and hydroquinone; Phenol derivatives such as 4-methoxy phenol and 4-t-butyl catechol; Aminoxyl derivatives such as 2,2,6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl; Hindered amine derivatives, such as tetramethyl piperidyl methacrylate, are preferable.

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 compounding amount is less than 0.01 part by mass, it is difficult to impart control or storage stability of the curing rate, and when it exceeds 30 parts by mass, it is easy to adversely affect the compatibility with other components.

Moreover, you may add suitably adhesion | attachment adjuvant, such as a coupling agent represented by an alkoxysilane derivative and a silazane derivative, an adhesion promoter and a leveling agent, to the adhesive composition of this embodiment. Specifically as a coupling agent, the compound represented by following General formula (R) is preferable, In addition to using independently, you may mix and use 2 or more types of compounds.

[In formula (R), R <^27> , R <^28> and R <^29> respectively independently represent a hydrogen atom, a C1-C5 alkyl group, a C1-C5 alkoxy group, a C1-C5 alkoxycarbonyl group, or an aryl group, R ³⁰ is a (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, urea Earthenware or glycidyl group, and t represents an integer of 1 to 10]

The adhesive composition of this embodiment can also use a rubber component together for the purpose of stress relaxation and an adhesive improvement. The rubber component refers to a component exhibiting rubber elasticity (JIS K6200) or a component exhibiting rubber elasticity by reaction under the same condition. The rubber component may be solid or liquid at room temperature (25 ° C.), but is preferably liquid in view of fluidity improvement. 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. Moreover, the rubber component which contains the cyano group and carboxyl group which are high polar groups in a side chain or the terminal from a viewpoint of adhesive improvement is preferable. Moreover, even if it has polybutadiene frame | skeleton, when it shows thermoplasticity, it classifies as (a) thermoplastic resin, and when it shows radically polymerizable, it classifies as (b) radically polymerizable compound.

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

Moreover, as a rubber component which has the said high polar group and is liquid at room temperature, Specifically, the liquid acrylonitrile- which contains a liquid acrylonitrile- butadiene rubber, a carboxyl group, a hydroxyl group, a (meth) acryloyl group, or a morpholine group at a polymer terminal- Butadiene rubber, liquid carboxylated nitrile rubber, etc. are mentioned, As for the acrylonitrile content which is a polar group, 10-60 mass% is preferable.

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

Moreover, organic fine particles can also be added to the adhesive composition of this embodiment for the purpose of stress relaxation and an adhesive improvement. The average particle diameter of the organic fine particles is preferably 0.05 to 1.0 m. In addition, when organic fine particles consist of the above-mentioned rubber component, it classifies not as organic microparticles but as rubber component, and when organic microparticles | fine-particles consist of the above-mentioned (a) thermoplastic resin, it classifies as (a) thermoplastic resin, not organic fine particles. do.

Specific examples of the organic fine particles include polyisoprene, polybutadiene, carboxyl terminal polybutadiene, hydroxyl terminal polybutadiene, 1,2-polybutadiene, carboxyl terminal 1,2-polybutadiene, acrylic rubber, styrene-butadiene rubber, acrylonitrile- Acrylonitrile-butadiene rubber containing a butadiene rubber, a carboxyl group, a hydroxyl group, a (meth) acryloyl group, or a morpholine group at the polymer terminal, a carboxylated nitrile rubber, a hydroxyl group-terminated poly (oxypropylene), an alkoxysilyl group-terminated poly (oxy Propylene), poly (oxytetramethylene) glycol, polyolefin glycol (meth) alkyl acrylate-butadiene-styrene copolymer, alkyl (meth) acrylate-silicone copolymer, or silicone (meth) -acryl copolymer or composite Can be mentioned.

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 paste form when it is liquid at normal temperature. In the case of a solid at room temperature, in addition to heating, it can also paste into a solvent. As a solvent which can be used, it is preferable that it is not reactive with an adhesive composition and an additive, and shows sufficient solubility, and it is preferable that the boiling point in normal pressure is 50-150 degreeC. When boiling point is less than 50 degreeC, when left at room temperature, there exists a possibility that it may volatilize and it becomes difficult to use in an open system. Moreover, when a boiling point exceeds 150 degreeC, it is difficult to volatilize a solvent and it tends to adversely affect the reliability after adhesion.

In addition, the adhesive composition of this embodiment can also be used as a film form. A solution obtained by adding a solvent or the like to the adhesive composition, if necessary, is applied onto a peelable substrate such as a fluororesin film, a polyethylene terephthalate film, a release paper, or impregnated with the solution to a substrate such as a non-woven fabric to release the peelable substrate. It can be used as a film by removing the solvent or the like onto the film. When used in the shape of a film, it is more convenient in terms of handling properties.

The adhesive composition of this embodiment can be bonded together using heating and pressurization. As for heating temperature, the temperature of 100-200 degreeC is preferable. The pressure is preferably in a range that does not cause damage to the adherend, and in general, 0.1 to 10 MPa is preferable. It is preferable to perform these heatings and pressurization in the range for 0.5 second-120 second, and can also adhere | attach by the heating of 120-190 degreeC, 3 MPa, and 10 second.

The adhesive composition of this embodiment can be used as an adhesive agent of the heterogeneous to-be-adhered body from which a thermal expansion coefficient differs. Specifically, it can be used as a semiconductor device bonding material represented by a circuit connecting material such as an anisotropic conductive adhesive, a silver paste, or a silver film, an elastomer for CSP, an underfill material for CSP, an LOC tape or the like.

The adhesive composition of this embodiment is used as an adhesive composition for connecting the 1st circuit member which has a 1st connection terminal on a main surface, and the 2nd circuit member which has a 2nd connection terminal on a main surface. Here, the said 1st circuit member and / or the 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 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, the connection structure of the circuit member using the adhesive composition of this embodiment mentioned above is demonstrated. 1: is a schematic cross section which shows one Embodiment of the connection structure of a circuit member using the adhesive composition of this embodiment. FIG. 2: is a schematic cross section which shows a 1st circuit member, a 2nd circuit member, and an adhesive composition before manufacturing the connection structure of the circuit member shown in FIG.

The connection structure 100 of the circuit member shown in FIG. 1 is the 1st circuit member 30 which has the 1st connection terminal 32 on the main surface 31a of the 1st circuit board 31, and the 2nd circuit board. The first circuit board so that the second circuit member 40 having the second connection terminal 42 and the first connection terminal 32 and the second connection terminal 42 face each other on the main surface 41a of the 41. The connection member 10C which connects the main surface 31a of 31 and the main surface 41a of the 2nd circuit board 41 is provided. The 1st connection terminal 32 and the 2nd connection terminal 42 are electrically connected by contacting each other. In addition, the connection member 10C consists of hardened | cured material of the adhesive composition 10 of this embodiment.

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

First, as shown in FIG. 2, the 1st circuit member 30, the 2nd circuit member 40, and the adhesive composition 10 shape | molded in the film form are prepared. Next, the adhesive composition 10 is mounted on the main surface 41a in which the second connection terminal 42 in the second circuit member 40 is formed, and further the first connection terminal (on the adhesive composition 10). The first circuit member 30 is mounted so that the 32 faces the second connection terminal 42. Subsequently, the adhesive composition 10 is cured while the adhesive composition 10 is heated through the first circuit member 30 and the second circuit member 40, and simultaneously pressed in a direction perpendicular to the main surfaces 31a and 41a, thereby The connection member 10C is formed between the 1st and 2nd circuit members 30 and 40, and the connection structure 100 of the circuit member of FIG. 1 is obtained.

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 containing (d) electroconductive particle. FIG. 4: is a schematic cross section which shows the 1st circuit member, the 2nd circuit member, and adhesive composition (containing electroconductive particle) before producing the connection structure of the circuit member shown in FIG.

The connection structure 200 of the circuit member shown in FIG. 3 is the 1st circuit member 30 which has the 1st connection terminal 32 on the main surface 31a of the 1st circuit board 31, and the 2nd circuit board. The first circuit board so that the second circuit member 40 having the second connection terminal 42 and the first connection terminal 32 and the second connection terminal 42 face each other on the main surface 41a of the 41. The connection member 20C which connects the main surface 31a of 31 and the main surface 41a of the 2nd circuit board 41 is provided. In addition, the connection member 20C is hardened | cured material of the adhesive composition 20 in which the electroconductive particle 22 disperse | distributed in the component 21 other than electroconductive particle of an adhesive composition (that is, hardened | cured material of components other than electroconductive particle of an adhesive composition). Electroconductive particle 22 disperse | distributed in (21C), and the electroconductive particle 22 contacts both connecting terminals between the 1st connecting terminal 32 and the 2nd connecting terminal 42 which oppose, and electroconductivity. Both connection terminals are electrically connected through the particle | grains 22. As shown in FIG.

As shown in FIG. 4, the connection structure 200 of the circuit member shown in FIG. 3 is the adhesive composition formed into the 1st circuit member 30, the 2nd circuit member 40, and the film form, for example. 20) can be prepared and manufactured by the method similar to obtaining the connection structure 100 of the said circuit member.

Here, at least one of the 1st circuit member 30 and the 2nd circuit member 40 is comprised from the base material containing the thermoplastic resin whose glass transition temperature is 200 degrees C or less. That is, at least one of the 1st circuit board 31 and the 2nd circuit board 41 contains the thermoplastic resin whose glass transition temperature is 200 degrees C or less. Here, as a thermoplastic resin whose glass transition temperature is 200 degrees C or less, it is preferable that it is at least 1 sort (s) chosen from the group which consists of polyethylene terephthalate, a polycarbonate, and polyethylene naphthalate. If at least one of the 1st circuit member 30 and the 2nd circuit member 40 is a circuit member comprised from the base material containing at least 1 sort (s) chosen from the group which consists of a polyethylene terephthalate, a polycarbonate, and a polyethylene naphthalate, The wettability with an adhesive composition improves, and adhesive strength improves more. Therefore, the connection structure of such a circuit member can acquire more excellent connection reliability.

In addition, one of the 1st circuit member 30 and the 2nd circuit member 40 may be comprised from the base material which does not contain at least 1 sort (s) chosen from the group which consists of a polyethylene terephthalate, a polycarbonate, and a polyethylene naphthalate. have. As a base material which forms such a circuit member, the base material which consists of inorganic materials, such as a semiconductor, glass, and a ceramic, the base material which consists of organic materials, such as a polyimide, the base material which combined inorganic materials, such as glass / epoxy, and organic substance, etc. can be used.

In addition, it is preferable that at least one of the 1st connection terminal 32 and the 2nd connection terminal 42 is comprised by at least 1 sort (s) chosen from the group which consists of ITO and IZO. ITO and IZO are preferable as connection terminals because they are easy to etch and have excellent pattern workability. And by using the adhesive composition of this embodiment, corrosion of the connection terminal comprised from ITO and / or IZO can fully be suppressed.

In addition, one or both of the 1st connection terminal 32 and the 2nd connection terminal 42 may be comprised from materials other than ITO and IZO. As such a connection terminal, the connection terminal which consists of metals, such as copper, silver, aluminum, gold, palladium, nickel, and these alloys, can be used.

In addition, the adhesive composition of this embodiment used as a connection member does not need to be fully hardened (the highest hardening which can be achieved by predetermined hardening conditions), and may be in the state of partial hardening as long as the said characteristic is produced. have.

[Example]

EMBODIMENT OF THE INVENTION Although this embodiment is demonstrated concretely based on an Example below, this embodiment is not limited to this.

<Thermoplastic>

(Preparation of phenoxy resin)

40 mass parts of phenoxy resins (made by Toto Kasei Co., Ltd., YP-50 (brand name)) were melt | dissolved in 60 mass parts of methyl ethyl ketone, and it was set as the solution of 40 mass% of solid content.

(Preparation of polyester urethane resin)

Polyester urethane resin (Toyobo Co., Ltd. make, UR-1400 (brand name)) used the 1: 1 mixed solvent melt | dissolved product of methyl ethyl ketone and toluene of 30 mass% of resin powder.

(Synthesis of urethane resin)

In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube having a calcium chloride drying tube, and a nitrogen gas introduction tube, 450 parts by weight of polybutylene adipatediol having a weight average molecular weight of 2000 and a polyoxytetramethylene glycol 450 having a weight average molecular weight of 2000 Mass part and 100 mass parts of 1, 4- butylene glycol were mixed uniformly in 4000 mass parts of methyl ethyl ketone, 390 mass parts of diphenylmethane diisocyanate were added, and it reacted at 70 degreeC, and obtained the urethane resin of the weight average molecular weight 350,000.

<Radical Polymerizable Compound>

(Preparation of urethane acrylate (L-1600S))

Urethane acrylate (Mitsui Polyurethanes Co., Ltd. make, L-1600S (brand name)) whose weight average molecular weight is 15000 and critical surface tension is 15 mN / m was prepared. In addition, L-1600S uses ether type diol and does not satisfy said Formula (A).

(Synthesis of urethane acrylate (PE-UA1))

A poly (3-methylpentane adipate) diol (aliphatic polyesterdiol, aliphatic polyester diol, fluorocarbonic acid) having a number average molecular weight of 2000 in a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube with a calcium chloride drying tube, and a nitrogen gas introduction tube. 2000 mass parts (1.00 mol) of manufacture, Golapol P-2010 (brand name), and 5.53 mass parts of dibutyltin dilaurate (made by Aldrich Co., Ltd.) were prepared. After introducing nitrogen gas sufficiently, it heated at 70-75 degreeC, and dicyclohexyl methane 4,4'- diisocyanate (aliphatic diisocyanate, the product made by Evonik Degussa, VESTANAT H ₁₂ DMI (brand name)) 787 mass parts (3.00 mol) was uniformly added dropwise for 3 hours to react. After completion of the dropping, the reaction was continued for about 10 hours. 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich Co., Ltd.) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich Co., Ltd.) were added thereto, and the resulting mixture was allowed to react for 10 hours, followed by IR measurement. By confirming that the isocyanate disappeared by this, reaction was complete | finished and urethane acrylate was obtained. The critical surface tension of the obtained urethane acrylate (PE-UA1) was 30 mN / m, and the weight average molecular weight was 15300. In addition, PE-UA1 uses polyesterdiol and satisfies the above formula (A).

(Synthesis of urethane acrylate (PE-UA2))

Polycaprolactone diol (aliphatic polyesterdiol, trade name: Flaccel 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 cooling tube with a calcium chloride drying tube, and a nitrogen gas introduction tube. 2000 parts by mass (1.00 mol) of dibutyl tin dilaurate (manufactured by Aldrich Co., Ltd.) was added thereto. After sufficiently introducing nitrogen gas, the mixture was heated to 70 to 75 ° C, and 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) were added dropwise to react for 3 hours. After completion of the dropping, the reaction was continued for about 10 hours. 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich Co., Ltd.) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich Co., Ltd.) were added thereto, and the resulting mixture was allowed to react for 10 hours, followed by IR measurement. By confirming that the isocyanate disappeared by this, reaction was complete | finished and urethane acrylate was obtained. The critical surface tension of the obtained urethane acrylate (PE-UA2) was 25 mN / m, and the weight average molecular weight was 13500. In addition, PE-UA2 uses polyesterdiol and satisfies the above formula (A).

(Synthesis of urethane acrylate (PE-UA3))

238 parts by mass of 2-hydroxyethyl acrylate (manufactured by Aldrich Co., Ltd.) and hydroquinone monomethyl ether in a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube having a calcium chloride drying tube, and a nitrogen gas introduction tube. (Manufactured by Aldrich Co., Ltd.) 2000 parts by mass (2.00 mol) of 0.53 parts by mass of polycaprolactone diol (aliphatic polyesterdiol, trade name: Flaccel 210N, manufactured by Daicel Kagaku Kogyo Co., Ltd.) of number average molecular weight 1000, 5.53 parts by mass of dibutyltin dilaurate (manufactured by Aldrich Co., Ltd.) was added. After sufficiently introducing nitrogen gas, the mixture was heated to 70 to 75 ° C, and 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) were added dropwise to react for 3 hours. After completion of the dropwise addition, the reaction was continued for about 10 hours, confirmed that the isocyanate disappeared by IR measurement, and the reaction was terminated to obtain urethane acrylate. The critical surface tension of the obtained urethane acrylate (PE-UA3) was 28 mN / m, and the weight average molecular weight was 14500. In addition, PE-UA3 uses polyester diol and satisfies the above formula (A).

(Synthesis of urethane acrylate (PE-UA4))

1650 parts by mass (14 mol) of 3-methyl-1,5-pentanediol and 1660 parts by mass of isophthalic acid (10 mol) in a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube having a calcium chloride drying tube, and a nitrogen gas introduction tube. ), Nitrogen gas was introduced under normal pressure, and then the esterification reaction was carried out while distilling out water generated at about 170 ° C out of the system. When the acid value of polyester became 0.3 mgKOH / g or less, vacuum degree was gradually raised by the vacuum pump and the reaction was completed. The aromatic polyester diol (ED-1) thus obtained had a number average molecular weight 2000.

Further, 2000 parts by mass (1.00 mol) of aromatic polyesterdiol (ED-1) obtained in a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube having a calcium chloride drying tube, and a nitrogen gas introduction tube, and dibutyltin dilau 5.53 mass parts of rates (made by Aldrich Co., Ltd.) were prepared. After sufficiently introducing nitrogen gas, the mixture was heated to 70 to 75 ° C, and 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) were added dropwise to react for 3 hours. After completion of the dropwise addition, the reaction was continued for about 15 hours. 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich Co., Ltd.) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich Co., Ltd.) were added thereto, and the resulting mixture was allowed to react for 7 hours to carry out IR measurement. By confirming that the isocyanate disappeared by this, reaction was complete | finished and urethane acrylate was obtained. The critical surface tension of the obtained urethane acrylate (PE-UA4) was 42 mN / m, and the weight average molecular weight was 11500. In addition, PE-UA4 uses polyester diol and satisfies the above formula (A).

(Synthesis of urethane acrylate (PE-UA5))

Poly (1,6-hexanediol carbonate) diol (aliphatic polycarbonate diol, Asahi Kasei Chemicals) having a number average molecular weight of 2000 in a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube with a calcium chloride drying tube, and a nitrogen gas introduction tube. 4000 parts by mass (2.00 mol) of PCDL T5652 (trade name), and 5.53 parts by mass of dibutyltin dilaurate (manufactured by Aldrich Co., Ltd.) were charged. After sufficiently introducing nitrogen gas, the mixture was heated to 70 to 75 ° C, and 666 parts by mass (3.00 mol) of isophorone diisocyanate (aliphatic diisocyanate, manufactured by Aldrich Co., Ltd.) were added dropwise to react for 3 hours. After completion of the dropwise addition, the reaction was continued for about 15 hours. 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich Co., Ltd.) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich Co., Ltd.) were added thereto, and the resulting mixture was allowed to react for 10 hours, followed by IR measurement. By confirming that the isocyanate disappeared by this, reaction was complete | finished and urethane acrylate was obtained. The critical surface tension of the obtained urethane acrylate (PE-UA5) was 21 mN / m, and the weight average molecular weight was 30000. In addition, PE-UA5 uses polycarbonate diol and does not satisfy the above formula (A).

(Preparation of isocyanuric acid modified bifunctional acrylate (M-215))

Isocyanuric acid modified bifunctional acrylate (made by Toagosei Co., Ltd., M-215 (brand name)) was prepared.

(Preparation of vinyl compound (P-2M) which has a phosphate group)

2- (meth) acryloyloxyethyl phosphate (brand name: Light ester P-2M, Kyoisha Chemical Co., Ltd. make) was prepared.

&Lt; Radical polymerization initiator &

Dibenzoyl peroxide (brand name: Naper BW, Nichiyu Corp.) was prepared as a radical polymerization initiator.

<Conductive Particles>

(Production of conductive particles)

A nickel layer having a thickness of 0.2 μm was provided on the surface of the particles containing polystyrene as a nucleus, and a gold layer having a thickness of 0.02 μm was provided on the outside of the nickel layer to prepare conductive particles having an average particle diameter of 10 μm and a specific gravity of 2.5.

[Examples 1 to 10 and Comparative Examples 1 to 5]

As shown in Table 2 by a solid mass ratio, a thermoplastic resin, a radically polymerizable compound, and a radical polymerization initiator were mix | blended, and the electroconductive particle was mix | blended and disperse | distributed 1.5 volume%, and the adhesive composition was obtained. The obtained adhesive composition was apply | coated on the 80-micrometer-thick fluororesin film using the coating apparatus, and the film adhesive composition of 20 micrometers in thickness of an adhesive bond layer was obtained by 70 degreeC and hot air drying for 10 minutes.

[Measurement of connection resistance, adhesive strength]

The flexible adhesive circuit board (FPC) which has 80 copper circuits of 150 micrometers in width, 300 micrometers in pitch, and 8 micrometers in thickness on the polyimide film (Tg 350 degreeC) of the film adhesive composition of Examples 1-10 and Comparative Examples 1-5. ) And a PET substrate (0.1 mm thick) in which a thin layer of Ag paste having a thickness of 5 µm was formed. Further, the film adhesive compositions of Examples 1 to 10 and Comparative Examples 1 to 5 were 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 interposed between the board | substrate which formed Ag paste circuit of 150 micrometers of line width, 300 micrometers of pitch, and 10 micrometers in thickness on a film. These were heated and pressurized at 150 degreeC and 2 MPa for 10 second using the thermocompression bonding apparatus (heating method: a constant heat type, Toray Engineering Co., Ltd.), respectively, and were connected over 2 mm in width, and the connection body was produced. The resistance value between the adjacent circuits of these connection bodies was measured by a multimeter immediately after adhesion | attachment, and hold | maintained for 240 hours (after test) in 85 degreeC and the high temperature high humidity tank of 85% RH (after test). The resistance value was represented by the average of 37 resistance points between adjacent circuits.

In addition, the adhesive strength of each connection body was measured and evaluated by the 90 degree peeling method according to JIS-Z0237. Here, Tensilon UTM-4 (peel rate 50 mm / min, 25 degreeC) by Toyo Baldwin Co., Ltd. was used for the measurement apparatus of adhesive strength. The result of the measurement of the connection resistance and adhesive strength of the film adhesive composition performed as mentioned above is shown in Table 3 below.

The adhesive compositions of Examples 1 to 7 had a good connection resistance of about 1.2 Ω or less and 600 N at the heating temperature of 150 ° C. immediately after adhesion and after holding for 240 hours in a high temperature and high humidity bath at 85 ° C. and 85% RH (after the test). good adhesion strength of at least / m.

In contrast, the adhesive compositions of Comparative Examples 1 and 3 exhibited good connection resistance immediately after adhesion and after 240 hours of storage at 85 ° C. and a high temperature and high humidity bath at 85% RH (after the test), but the adhesive strength was lowered. In addition, the adhesive compositions of Comparative Examples 2, 4 and 5 had a high connection resistance immediately after adhesion and after holding for 240 hours in a high temperature and high humidity bath at 85 ° C. and 85% RH (after the test), and the adhesive strengths of Examples 1 to 7 were also high. Compared to low.

On the other hand, the adhesive composition of Examples 8-10 shows favorable connection resistance of about 1.2 (ohm) or less immediately after adhesion | attachment, and after hold | maintaining for 240 hours (after test) in 85 degreeC and the high temperature high humidity tank of 85% RH, and also Comparative Example 1 And the adhesive strength was excellent compared with 3.

[Examples 11 to 13 and Comparative Examples 6 and 7]

Moreover, the flexible adhesive circuit board (FPC) which has 80 copper circuits of 150 micrometers of line width, 300 micrometers of pitch, and 8 micrometers in thickness of the film adhesive composition of Examples 3, 4 and 7 and Comparative Examples 3 and 4 on a polyimide film And a PET film (thickness 0.1 mm, Tg 120 degreeC), a PC film (thickness 0.1 mm, Tg 150 degreeC), and a PEN film (thickness 0.1 mm, Tg 160 degreeC), respectively. These were each heat-pressurized 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 pressed into a width of 2 mm to prepare a connecting body.

In addition, the adhesive strength of each connector was measured similarly to the said method. The measurement result of the adhesive strength of the film adhesive composition performed as mentioned above is shown in Table 4 below.

The adhesive compositions used in Examples 11 to 13 were held at a heating temperature of 150 ° C. for both substrates immediately after adhesion and after 240 hours in a high temperature and high humidity bath at 85 ° C. and 85% RH (after the test). good adhesion strength of at least m. In contrast, the adhesive compositions used in Comparative Examples 6 and 7 had a low adhesive strength immediately after adhesion and after holding for 240 hours in a high temperature and high humidity bath at 85 ° C. and 85% RH (after testing).

[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 were formed on a polyimide film with 500 copper circuits having a line width of 25 μm, a pitch of 50 μm, and a thickness of 8 μm. It interposed between the circuit board FPC and the glass (thickness 1.1 mm, surface resistance 20 ohms / square) in which the thin layer of ITO of 0.2 micrometer was formed. This was heated and pressurized at 150 degreeC and 2 MPa for 10 second using the thermocompression bonding apparatus (heating system: constant heat type, Toray Engineering Co., Ltd.), and it connected over 2 mm in width, and produced the connection body. The resistance value between adjacent circuits of this connection body was measured with a multimeter immediately after adhesion | attachment, and hold | maintained for 240 hours in 85 degreeC and the high temperature, high humidity tank of 85% RH (after test). The resistance value was represented by the average of 37 resistance points between adjacent circuits.

Moreover, the adhesive strength of this connector was measured and evaluated by the 90 degree peeling method according to JIS-Z0237. Here, Tensilon UTM-4 (peel rate 50 mm / min, 25 degreeC) by Toyo Baldwin Co., Ltd. was used for the measurement apparatus of adhesive strength. The result of the measurement of the connection resistance and adhesive strength of the film adhesive composition performed as mentioned above is shown in Table 5 below.

As shown above, in the adhesive composition of the comparative example, when an adherend was a PET film, a PC film, and a PEN film, connection resistance and adhesive strength were inferior. However, as shown in Table 5, when the to-be-adhered body is glass with ITO, in all the reference examples 1-6 including the case where the adhesive composition of the comparative example was used, immediately after adhesion and high temperature, high humidity of 85 degreeC and 85% RH After holding for 240 hours in the tank (after the test), it was confirmed that good connection resistance of 2.5 Ω or less and good adhesive strength of 680 N / m or more can be obtained.

According to the present embodiment, excellent adhesive strength can be obtained with respect to organic substrates such as polyethylene terephthalate, polycarbonate and polyethylene naphthalate even under low temperature curing conditions, and stable performance even after a long time reliability test (high temperature and high humidity test). Strength and connection resistance), the connection structure of the circuit member using the same, the manufacturing method of a connection structure, and the use of an adhesive composition can be provided.

10, 20: adhesive composition
10C, 20C: connection member
21: adhesive composition containing no conductive particles
22: conductive particles
21C: Cured product of adhesive composition not containing conductive particles
30: first circuit member
31: first circuit board
31a:
32: first connection terminal
40: second circuit member
41: second circuit board
41a: state
42: second connection terminal
100, 200: connection structure of a circuit member

Claims (12)

As an adhesive composition for connecting the 1st circuit member which has a 1st connection terminal on a main surface, and the 2nd circuit member which has a 2nd connection terminal on a main surface,
The first circuit member and / or the second circuit member are composed of a substrate containing a thermoplastic resin having a glass transition temperature of 200 ° C. or less,
The adhesive composition contains (a) a thermoplastic resin, (b) a radically polymerizable compound and (c) a radical polymerization initiator, wherein the (b) radically polymerizable compound has a critical surface tension of 25 to 40 mN / m. Adhesive composition containing urethane (meth) acrylate. As an adhesive composition for connecting the 1st circuit member which has a 1st connection terminal on a main surface, and the 2nd circuit member which has a 2nd connection terminal on a main surface,
The first circuit member and / or the second circuit member is composed of a substrate including at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate,
The adhesive composition contains (a) a thermoplastic resin, (b) a radically polymerizable compound and (c) a radical polymerization initiator, wherein the (b) radically polymerizable compound has a critical surface tension of 25 to 40 mN / m. Adhesive composition containing urethane (meth) acrylate. The adhesive composition of Claim 1 or 2 whose said urethane (meth) acrylate is a urethane (meth) acrylate represented by following General formula (A).

[In Formula (A), R <^1> and R <^2> represents a hydrogen atom or a methyl group each independently, R <^3> is group derived from the ring-opening compound of ethylene group, a propylene group, (epsilon) -caprolactone, or following formula (B) Represents a group represented by R ⁴ represents a saturated aliphatic group or a saturated alicyclic group, R ⁵ represents a group represented by the following formula (B), and a represents an integer of 1 to 40].

[In formula (B), R <^6> and R <^7> respectively independently represents the C2-C12 linear or branched alkylene group, b represents the integer of 1-10, c represents the integer of 1-25. , Wherein, R ⁶ , R ⁷ , b and c may be the same or different. The adhesive composition according to claim 1 or 2, wherein the urethane (meth) acrylate is obtained using aliphatic polyesterdiol. The adhesive composition of Claim 1 or 2 whose weight average molecular weights of the said urethane (meth) acrylate are 8000 or more and less than 25000. The adhesive composition of Claim 1 or 2 in which the said (b) radically polymerizable compound contains the vinyl compound which has a phosphoric acid group, and 1 or more types of radically polymerizable compounds other than the vinyl compound which has the said phosphoric acid group, respectively. The said (a) thermoplastic resin is at least 1 sort (s) of Claim 1 or 2 chosen from the group which consists of a phenoxy resin, a polyurethane resin, polyesterurethane resin, butyral resin, an acrylic resin, and a polyimide resin. An adhesive composition containing a. The adhesive composition of Claim 1 or 2 which further contains (d) electroconductive particle. As a connection structure of 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 the circuit member provided with a connection member,
The first circuit member and the second circuit member are disposed through the connection member made of the adhesive composition according to claim 1 or 2 so that the first connection terminal and the second connection terminal face each other. A first connection terminal and the second connection terminal are electrically connected;
The said 1st circuit member and / or the said 2nd circuit member are the connection structures of a circuit member comprised from the base material containing a thermoplastic resin whose glass transition temperature is 200 degrees C or less. The connecting member for a circuit member according to claim 9, wherein the thermoplastic resin having a glass transition temperature of 200 ° C or less is at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. The circuit member according to claim 9, wherein the circuit member of the first circuit member or the second circuit member is composed of a substrate containing at least one member selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. ,
The other structural member of the said 1st circuit member or the 2nd circuit member consists of a base material containing at least 1 sort (s) chosen from the group which consists of a polyimide resin and a polyethylene terephthalate. The 1st circuit member which has a 1st connection terminal on a main surface, and the 2nd circuit member which has a 2nd connection terminal on a main surface are made into the said 1st connection terminal and the said agent via the adhesive composition of Claim 1 or 2. The process of arrange | positioning so that 2 connection terminals oppose,
Heating and curing the adhesive composition to connect the first circuit member and the second circuit member
The manufacturing method of the bonded structure of a circuit member provided with the.

Images