CN103160238B - Adhesive composite, film-like adhesive, adhesive sheet and connection structural bodies - Google Patents

Abstract

The present invention relates to an adhesive composition containing (a) a thermoplastic resin, (b) a radically polymerizable compound, (c) a film-like adhesive, an adhesive sheet, and a bonded structure. ) a free radical polymerization initiator, and (d) a boron-containing salt, wherein the (d) boron-containing salt is a compound represented by the following general formula (A), in formula (A), R ¹ , R ^{2. R3} and R4 each independently represent a hydrogen atom, an alkyl group with ¹ to 18 carbon atoms, or an aryl group, and X ⁺ represents a cation containing a quaternary phosphorus atom and/or a quaternary nitrogen atom.

Description

Adhesive composition, film adhesive, adhesive sheet, and bonded structure

technical field

The present invention relates to an adhesive composition, a film-like adhesive, an adhesive sheet, a bonded structure, a method for producing a bonded structure, and an application of the adhesive composition.

Background technique

In semiconductor elements and liquid crystal display elements, various adhesives have been used conventionally for the purpose of bonding various components in the elements. Requirements for adhesives include many aspects such as adhesiveness, heat resistance, and reliability under high-temperature and high-humidity conditions. The above-mentioned adhesive is used for the connection between liquid crystal display element and TCP (COF), the connection between FPC and TCP (COF), the connection between TCP (COF) and printed circuit board, the connection between FPC and printed circuit board, etc. Moreover, the said adhesive agent is also used when mounting a semiconductor element on a board|substrate.

As an adherend for bonding, a printed wiring board, or polyimide, polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate ( PEN), organic substrates such as cycloolefin polymer (COP), and metals such as copper and aluminum, or ITO (composite oxide of indium and tin), IZO (composite of indium oxide and zinc oxide), AZO (zinc aluminum oxide), SiN (silicon nitride), SiO ₂ (silicon dioxide) and other substrates with various surface states. Therefore, molecular design of an adhesive composition suitable for each adherend is required.

Recently, along with the high integration of semiconductor elements and the high-definition of liquid crystal display elements, the pitch between elements and the pitch between wirings have been narrowed. In addition, semiconductor elements, liquid crystal display elements, and touch panels using low-heat-resistant organic substrates such as PET, PC, and PEN are being used. If the heating temperature of the adhesive composition used for such a semiconductor element is high and the curing rate is slow, not only the desired connection part but also the surrounding parts will be overheated, which may cause damage to the surrounding parts. Therefore, for the adhesive composition, adhesion under low-temperature curing is required.

Conventionally, thermosetting resins using epoxy resins exhibiting high adhesiveness and high reliability have been used as adhesives for the semiconductor elements and liquid crystal display elements described above (for example, refer to Patent Document 1 below). As constituents of the resin, epoxy resins, curing agents such as phenolic resins reactive with the epoxy resins, and thermolatent catalysts that promote the reaction between the epoxy resins and the curing agents are generally used. A heat-latent catalyst is a substance that does not react at storage temperatures such as room temperature but exhibits high reactivity when heated, and becomes an important factor determining the curing temperature and curing speed. Various compounds are used from the viewpoint of the curing speed. In the actual process, the desired bonding is obtained by curing at a temperature of 170~250°C for 1~3 hours. However, in order to cure the above-mentioned adhesive at low temperature, it is necessary to use a thermolatent catalyst with low activation energy, but it is very difficult to achieve both storage stability.

In recent years, radically curable adhesives using a radically polymerizable compound such as an acrylate derivative or a methacrylate derivative in combination with a peroxide as a radical polymerization initiator have attracted attention. In radical curing, since radicals serving as reactive centers are highly reactive, curing can be achieved in a short time (for example, refer to Patent Document 2 below). For such a radical-curable adhesive, a method of using benzoyl peroxide (BPO), an amine compound, an organoboron compound, or the like in combination as a radical polymerization initiator has been proposed (see, for example, Patent Document 3 below).

prior art literature

Patent Document 1: Japanese Patent Application Laid-Open No. 1-113480

Patent Document 2: International Publication No. 98/44067

Patent Document 3: Japanese Patent Laid-Open Publication No. 2000-290121

Contents of the invention

The problem to be solved by the invention

In order to cure the above-mentioned radical curable adhesive at low temperature, it is necessary to use a radical polymerization initiator, but it is very difficult for conventional radical curable adhesives to achieve both low temperature curability and storage stability. For example, when the above-mentioned benzoyl peroxide (BPO), amine compound, organoboron compound, etc. are used as a radical polymerization initiator of radical polymerizable compounds such as acrylate derivatives or methacrylate derivatives, even in Curing reaction proceeds even at room temperature (25°C or below), so storage stability may decrease.

Accordingly, an object of the present invention is to provide an adhesive composition excellent in low-temperature curability and storage stability. In addition, an object of the present invention is to provide a film adhesive using such an adhesive composition, an adhesive sheet, a bonded structure, a method for producing a bonded structure, and an application of the adhesive composition.

Technical solution to the problem

As a result of intensive research to solve the above-mentioned technical problems, the present inventors found that excellent low-temperature curability and storage stability can be obtained by using a specific boron compound as a constituent of an adhesive composition, and completed the present invention.

That is, the adhesive composition of the present invention contains (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a radical polymerization initiator, and (d) a boron-containing salt, wherein (d) contains The boron salt is a compound represented by the following general formula (A).

【Chemical 1】

In formula (A), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group with 1 to 18 carbon atoms, or an aryl group, and X ⁺ represents a quaternary phosphorus atom and/or quaternary nitrogen atomic cations.

In the present invention, by making the adhesive composition contain (d) boron-containing salt, the decomposition of (c) the radical polymerization initiator at low temperature (for example, 80 to 120° C.) can be promoted, so the adhesive composition Excellent low temperature curability. In addition, in the present invention, since the above-mentioned (d) boron-containing salt is a compound represented by the general formula (A), the storage stability of the adhesive composition (for example, at around room temperature (for example, -20 to 25° C.) Storage stability) is excellent, and even when the adhesive composition is stored for a long time, excellent adhesive strength and connection resistance (for example, adhesive strength and connection in a connection structure of circuit components or a solar cell module) can be obtained. resistance). As described above, the adhesive composition of the present invention is excellent in low-temperature curability and storage stability.

Furthermore, in the present invention, excellent adhesive strength and connection resistance can be obtained regardless of whether the adhesive composition is stored for a long period of time. Furthermore, in the present invention, regardless of whether the adhesive composition is stored for a long period of time, stable performance (adhesive strength and connection resistance) can be maintained even after a long-term reliability test (high temperature and high humidity test).

The adhesive composition of the present invention may contain a compound represented by the following general formula (A1) as (d) a boron-containing salt. In this case, low-temperature curability and storage stability can be further improved. improve.

【Chemical 2】

In formula (A1), R ¹ , R ² , R ³ , R ⁴ , R ^5a , R ^6a , R ^7a , and R ^8a each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group.

Any one and only one of R ^5a , R ^6a , R ^7a and R ^8a in the above general formula (A) is preferably a hydrogen atom. In this case, low-temperature curability can be further improved.

The adhesive composition of the present invention may contain a compound represented by the following general formula (A2) as (d) a boron-containing salt. In this case, the low-temperature curability and storage stability can be further improved. improve.

【Chemical 3】

In formula (A2), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group with 1 to 18 carbon atoms, or an aryl group, and R ^5b , R ^6b , R ^7b , R ^8b and R ^9b each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group, and R ^8b and R ^9b may combine with each other to form a ring.

In addition, in the adhesive composition of the present invention, the (b) radically polymerizable compound may contain a vinyl compound having a phosphoric acid group and a radically polymerizable compound other than the vinyl compound. In this case, adhesion under low-temperature curing becomes easy, and at the same time, it is possible to further increase the adhesive strength with the substrate having the connection terminal.

In addition, (d) the melting point of the boron-containing salt may be not less than 60°C and not more than 300°C. In this case, stability (for example, stability around room temperature) is further improved, and storage stability is further improved.

In addition, (a) thermoplastic resins may contain phenoxy resins, urethane resins, polyester urethane resins, butyral resins, acrylic resins, polyimide resins, and polyamide resins, and those having vinyl acetate as structural units At least one selected from the group consisting of copolymers. In this case, heat resistance and adhesiveness are further improved, and these excellent characteristics can be easily maintained even after a long-term reliability test (high-temperature and high-humidity test).

Moreover, the adhesive composition of this invention may contain (e) electroconductive particle further. In this case, since favorable conductivity or anisotropic conductivity can be imparted to the adhesive composition, it can be more suitably used for bonding of circuit components having connection terminals, solar cell modules, and the like. Moreover, the connection resistance of the bonded structure electrically connected via the said adhesive composition can be further reduced sufficiently.

Furthermore, the present inventors found that the above-mentioned adhesive composition can be effectively used for connection of components having connection terminals. The adhesive composition of the present invention can be used to electrically connect the first connection terminal arranged on the main surface of the first substrate and the second connection terminal arranged on the main surface of the second substrate, and can also be used to connect The connection terminals of the solar cells having the connection terminals arranged on the main surface of the substrate are electrically connected to the wiring members.

The film adhesive according to the present invention includes the above-mentioned adhesive composition. The adhesive sheet according to the present invention includes a base material and the above-mentioned film adhesive, and the film adhesive is arranged on the base material.

A connection structure according to one aspect of the present invention includes: a first circuit component having a first substrate and first connection terminals arranged on a main surface of the first substrate; a second substrate and a terminal arranged on the second substrate; The second circuit part of the second connection terminal on the main surface, and the connection part arranged between the first circuit part and the second circuit part, the connection part contains the cured product of the above-mentioned adhesive composition, the first connection terminal and The second connection terminals are electrically connected. In the bonded structure according to one aspect of the present invention, the connection member contains a cured product of the above-mentioned adhesive composition, thereby improving the connection resistance and adhesive strength of the bonded structure.

In the bonded structure according to one aspect of the present invention, at least one of the first substrate and the second substrate may be composed of a base material containing a thermoplastic resin having a glass transition temperature of 200° C. or lower. In this case, the adhesive strength of the bonded structure using the adhesive composition can be further improved.

In the connection structure related to one aspect of the present invention, at least one of the first substrate and the second substrate may be made of polyethylene terephthalate, polycarbonate, polyethylene naphthalate The base material is composed of at least one selected from the group consisting of esters and cycloolefin polymers. In this case, even in the case of using the first circuit component or the second circuit component having a substrate made of the above-mentioned specific material, low-temperature curing can be achieved by using the adhesive composition according to the present invention described above, so , it is possible to reduce thermal damage to the first circuit component or the second circuit component. In addition, the wettability of the substrate composed of the above-mentioned specific material and the adhesive composition is improved, whereby the adhesive strength can be further improved. Accordingly, excellent connection reliability can be obtained when a substrate made of the above-mentioned specific material is used.

The connection structure that one aspect of the present invention relates to can be as follows: the first substrate is made of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer The second substrate is composed of at least one base material selected from the group consisting of polyimide resin and polyethylene terephthalate. . In this case, even in the case of using the first circuit component or the second circuit component having a substrate made of the above-mentioned specific material, low-temperature curing can be achieved by using the adhesive composition according to the present invention described above, so , it is possible to reduce thermal damage to the first circuit component or the second circuit component. In addition, the wettability of the substrate composed of the above-mentioned specific material and the adhesive composition can be improved, and the adhesive strength can be further improved. Accordingly, excellent connection reliability can be obtained when a substrate made of the above-mentioned specific material is used.

A connection structure according to another aspect of the present invention includes: a solar battery cell having a substrate and a connection terminal arranged on a main surface of the substrate, a wiring member, and a connecting member arranged between the solar battery cell and the wiring member, The connection member contains a cured product of the above-mentioned adhesive composition, and electrically connects the connection terminal and the wiring member. In the bonded structure according to another aspect of the present invention, the connection member contains a cured product of the above-mentioned adhesive composition, thereby improving the connection resistance and adhesive strength of the bonded structure.

The present invention provides a method for producing a bonded structure by interposing the above-mentioned adhesive composition between a first circuit component having a first substrate and first connection terminals disposed on a main surface of the first substrate, and a first circuit component having Between the second substrate and the second circuit component of the second connection terminal arranged on the main surface of the second substrate, the adhesive composition is cured in such a state, thereby making the first connection terminal and the second circuit component The first circuit component and the second circuit component are bonded in a state where the second connection terminal is electrically connected. In addition, the present invention provides a method for producing a bonded structure by interposing the above-mentioned adhesive composition between a solar battery cell having a substrate and connection terminals disposed on the main surface of the substrate, and a wiring member. By curing the adhesive composition in such a state, the solar cell and the wiring member are bonded together in a state where the connection terminal and the wiring member are electrically connected.

The present invention provides an application of the above-mentioned adhesive composition for electrically connecting a first connection terminal arranged on a main surface of a first substrate with a second connection terminal arranged on a main surface of a second substrate. The present invention provides the application of the above-mentioned adhesive composition, which is used to manufacture a connection member for connecting a first connection terminal arranged on a main surface of a first substrate with a terminal arranged on a main surface of a second substrate. The second connection terminal is electrically connected.

The present invention provides the use of the above-mentioned adhesive composition for electrically connecting the connection terminals of a solar battery cell having the connection terminals arranged on the main surface of the substrate to a wiring member. The present invention provides the use of the above-mentioned adhesive composition for producing a connection member for electrically connecting the connection terminal of a solar battery cell having a connection terminal arranged on a main surface of a substrate with a wiring member. connect.

The present invention provides the above-mentioned adhesive composition used as a connecting member in a bonded structure including a first circuit having a first substrate and first connection terminals arranged on a main surface of the first substrate. Components, a second circuit component having a second substrate and a second connection terminal disposed on the main surface of the second substrate, and a connection component disposed between the first circuit component and the second circuit component, the first connection terminal and the second connection terminal are electrically connected. The present invention provides the above-mentioned adhesive composition used as a connecting member in a bonded structure comprising: a solar battery cell having a substrate and connection terminals arranged on a main surface of the substrate, a wiring member, and The connection member disposed between the solar cell and the wiring member is electrically connected to the connection terminal and the wiring member.

Beneficial effect

According to the present invention, an adhesive composition excellent in low-temperature curability and storage stability can be provided. Such an adhesive composition can improve storage stability compared to the case of using an alkyl boron compound described in Patent Document 3 above. In addition, the adhesive composition according to the present invention is excellent in balance between low-temperature curability and storage stability. Since the adhesive composition according to the present invention is excellent in storage stability, even when the adhesive composition is stored for a long period of time, excellent adhesive strength and connection resistance can be obtained. Furthermore, in the adhesive composition according to the present invention, excellent adhesive strength and connection resistance can be obtained regardless of whether the adhesive composition is stored for a long period of time. In addition, the adhesive composition according to the present invention can maintain stable performance (adhesive strength) even after a long-term reliability test (high temperature and high humidity test) regardless of whether the adhesive composition is stored for a long time or not. strength and connection resistance). The present invention can provide a film adhesive using such an adhesive composition, an adhesive sheet, a bonded structure, a method for producing a bonded structure, and an application of the adhesive composition.

Description of drawings

FIG. 1 is a schematic cross-sectional view showing a bonded structure according to a first embodiment of the present invention.

Fig. 2 is a schematic cross-sectional view showing a method of manufacturing the bonded structure shown in Fig. 1 .

Fig. 3 is a schematic cross-sectional view showing a bonded structure according to a second embodiment of the present invention.

Fig. 4 is a schematic cross-sectional view showing a method of manufacturing the bonded structure shown in Fig. 3 .

5 is a schematic cross-sectional view showing a bonded structure according to a third embodiment of the present invention.

Explanation of reference signs

10 is a circuit component (first circuit component); 12 is a circuit substrate (first substrate); 12a is a main surface; 14 is a connection terminal (first connection terminal); 20 is a circuit component (second circuit component); 22 is Circuit board (second board); 22a is the main surface; 24 is a connection terminal (second connection terminal); 30, 40 are connection members; 30a, 40a are adhesive compositions; 44 is conductive particles; 100, 200 300 is a solar battery module (connection structure); 310a, 310b are solar battery cells; 312 is a substrate; 312a is a surface (main surface); 312b is a back surface (main surface); 314 is a surface 316 is a back electrode; 320 is a wiring member; 330 is a connection member.

detailed description

Hereinafter, preferred embodiments of the present invention will be described in detail. Here, in this specification, "(meth)acrylic acid" means acrylic acid and its corresponding methacrylic acid, "(meth)acrylate" means acrylate and its corresponding methacrylate, "( "Meth)acryloyl" means acryloyl and methacryloyl, and "(meth)acryloyloxy" means acryloyloxy and its corresponding methacryloyloxy.

In addition, in this specification, "melting point" means: the temperature obtained according to the method described in JIS standard K0064, or, weighing 5.0 mg of a sample in a non-hermetic sample pan, and using a differential scanning calorimeter (DSC7 PERKIN (manufactured by Elmer Co., Ltd.) under nitrogen gas at the temperature of the peak endothermic peak measured at a heating rate of 10°C/min.

In addition, in this specification, "weight average molecular weight" means the value measured by gel permeation chromatography (GPC) using the calibration curve of standard polystyrene under the conditions shown below.

(measurement conditions)

Device: GPC-8020 manufactured by Tosoh Corporation

Detector: RI-8020 manufactured by Tosoh Corporation

Column: Hitachi Chemical Industries, Ltd. Gelpack GL-A-160-S + GL-A150

Sample concentration: 120mg/3ml

Solvent: THF

Injection volume: 60μl

Pressure: 30kgf/ ^cm2

Flow: 1.00ml/min

The adhesive composition of the present embodiment contains (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a radical polymerization initiator, and (d) a boron-containing salt.

((a) Thermoplastic resin)

(a) Thermoplastic resin refers to a resin (polymer) that has the following properties: it becomes a high-viscosity liquid state when heated, deforms freely with external force, and keeps its shape when it is cooled and the external force is removed. This process can be repeated. In addition, the (a) thermoplastic resin may be a resin (polymer) having a reactive functional group having the above-mentioned properties. (a) The glass transition temperature (Tg) of the thermoplastic resin is, for example, preferably -30°C or higher, more preferably -25°C or higher, even more preferably -20°C or higher. (a) The glass transition temperature (Tg) of the thermoplastic resin is, for example, preferably 190°C or lower, more preferably 170°C or lower, even more preferably 150°C or lower.

(a) Thermoplastic resins may include, for example, those made from phenoxy resins, urethane resins, polyester urethane resins, butyral resins (such as polyvinyl butyral resins), acrylic resins, polyimide resins, and polyamide resins. , and at least one selected from the group consisting of copolymers having vinyl acetate as a structural unit (vinyl acetate copolymers, such as ethylene-vinyl acetate copolymers). These can be used alone or in combination of two or more. Furthermore, these (a) thermoplastic resins may contain a siloxane bond or a fluorine substituent. For these, a state in which resins to be mixed are completely compatible with each other or a state in which microphase separation occurs and becomes cloudy is preferable.

When the adhesive composition is applied in the form of a film, (a) the greater the weight average molecular weight of the thermoplastic resin, the easier it is to obtain good film formability. In addition, the melt viscosity that affects the fluidity of the film adhesive composition can be reduced. Set in a wide range. (a) The weight average molecular weight of the thermoplastic resin is, for example, preferably 5,000 or more, more preferably 7,000 or more, and still more preferably 10,000 or more. (a) When the weight average molecular weight of a thermoplastic resin is 5000 or more, favorable film formability tends to be acquired easily. (a) The weight average molecular weight of the thermoplastic resin is, for example, preferably 150,000 or less, more preferably 100,000 or less, even more preferably 80,000 or less. (a) When the weight-average molecular weight of the thermoplastic resin is 150,000 or less, good compatibility with other components tends to be easily obtained.

The blending amount of (a) thermoplastic resin in the adhesive composition is based on the total mass of the adhesive components (components excluding conductive particles in the adhesive composition), for example, preferably 5% by mass or more, more preferably Preferably it is 15% by mass or more. When the compounding quantity of (a) thermoplastic resin is 5 mass % or more, especially when an adhesive composition is used in a film form, it exists in the tendency for favorable film formability to be obtained easily. (a) The blending amount of the thermoplastic resin is, for example, preferably 80% by mass or less, more preferably 70% by mass or less, based on the total mass of the adhesive component (component excluding conductive particles in the adhesive composition). When the compounding quantity of (a) thermoplastic resin is 80 mass % or less, favorable fluidity of an adhesive composition tends to be obtained easily.

((b) Radical polymerizable compound)

(b) The radically polymerizable compound refers to a compound that radically polymerizes under the action of a radical polymerization initiator, but may be a compound that itself generates radicals by imparting activation energy such as light or heat. As (b) the radically polymerizable compound, for example, a compound having a functional group polymerizable by living radicals such as a vinyl group, a (meth)acryloyl group, an allyl group, and a maleimide group can be suitably used.

Specific examples of (b) radically polymerizable compounds include epoxy (meth)acrylate oligomers, urethane (meth)acrylate oligomers, and polyether (meth)acrylate oligomers. , polyester (meth)acrylate oligomers and other oligomers, trimethylolpropane tri(meth)acrylate, polyethylene glycol di(meth)acrylate, polyalkylene glycol di( Meth)acrylate, Dicyclopentenyl (meth)acrylate, Dicyclopentenyloxyethyl (meth)acrylate, Neopentyl glycol di(meth)acrylate, Dipentaerythritol hexa(methyl) ) acrylate, isocyanuric acid modified difunctional (meth)acrylate, isocyanuric acid modified trifunctional (meth)acrylate, diphenoxyethanol fluorene acrylate, (meth)acrylic acid Epoxy (meth)acrylate obtained by forming the glycidyl group of bisphenol fluorene diglycidyl ether, and epoxy (meth)acrylate obtained by adding ethylene glycol or propylene glycol to the glycidyl group of bisphenol fluorene diglycidyl ether A compound obtained by introducing a (meth)acryloyloxy group into the compound, a compound represented by the following general formula (B) or general formula (C), and the like.

【Chemical 4】

In formula (B), R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group, and a and b each independently represent an integer of 1-8.

【Chemical 5】

In formula (C), R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, and c and d each independently represent an integer of 0-8.

In addition, as (b) the radically polymerizable compound, even if it is left alone at 30°C, it is wax-like (wax-like), wax-oily (ろう-like), crystalline, glass-like, powdery, etc. and has no fluidity. A substance in a solid state can also be used without particular limitation. Specific examples of such (b) radically polymerizable compounds include N,N'-methylene bisacrylamide, diacetone acrylamide, N-methylol acrylamide, N-phenylmethyl Acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, tris(2-acryloyloxyethyl)isocyanurate, N-phenylmaleimide, N-(o-methylphenyl ) maleimide, N-(m-methylphenyl)maleimide, N-(p-methylphenyl)maleimide, N-(o-methoxyphenyl)maleimide imine, N-(m-methoxyphenyl)maleimide, N-(p-methoxyphenyl)maleimide, N-methylmaleimide, N-ethylmaleimide Leimide, N-octylmaleimide, 4,4'-diphenylmethane dimaleimide, m-phenylene dimaleimide, 3,3'-dimethyl- 5,5'-diethyl-4,4'-diphenylmethane dimaleimide, 4-methyl-1,3-phenylene dimaleimide, N-methacryloxy phenylmaleimide, N-acryloyloxymaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, N-methacryloyl Oxysuccinimide, N-acryloyloxysuccinimide, 2-naphthyl methacrylate, 2-naphthyl acrylate, pentaerythritol tetraacrylate, divinylethylene urea, divinyl Propylene urea, 2-polystyryl ethyl methacrylate, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine, N-phenyl-N'-(3-acryloyloxy-2-hydroxypropyl)-p-phenylenediamine, tetramethylpiperidinyl methacrylate, tetramethylpiperidinyl acrylate, Pentamethylpiperidinyl methacrylate, pentamethylpiperidinyl acrylate, stearyl acrylate, N-tert-butylacrylamide, diacetoneacrylamide, N-(hydroxymethyl)acrylamide, Compounds represented by the following general formulas (D) to (M), etc.

【Chemical 6】

In formula (D), e represents the integer of 1-10.

【Chemical 7】

【chemical 8】

In formula (F), R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a methyl group, and f represents an integer of 15-30.

【Chemical 9】

In formula (G), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a methyl group, and g represents an integer of 15-30.

【chemical 10】

In formula (H), R ¹⁷ represents a hydrogen atom or a methyl group.

【chemical 11】

In the formula (I), R ¹⁸ represents a hydrogen atom or a methyl group, and h represents an integer of 1-10.

【Chemical 12】

In formula (J), R ¹⁹ represents a hydrogen atom or an organic group represented by the following general formula (i) or (ii), and i represents an integer of 1 to 10.

【chemical 13】

【Chemical 14】

【chemical 15】

In the formula (K), R ²⁰ represents a hydrogen atom or an organic group represented by the following general formula (iii) or (iv), and j represents an integer of 1 to 10.

【Chemical 16】

【Chemical 17】

【chemical 18】

In formula (L), R ²¹ represents a hydrogen atom or a methyl group.

【chemical 19】

In formula (M), R ²² represents a hydrogen atom or a methyl group.

Moreover, urethane acrylate can be used as (b) radically polymerizable compound. Urethane acrylate may be used alone or in combination with (b) radically polymerizable compounds other than urethane acrylate. By using urethane acrylate alone or in combination with (b) a radically polymerizable compound other than urethane acrylate, flexibility is improved, and adhesive strength can be further improved.

The urethane acrylate is not particularly limited, but is preferably a urethane acrylate represented by the following general formula (N). Here, the urethane acrylate represented by the following general formula (N) can be obtained by aliphatic diisocyanate or alicyclic diisocyanate, aliphatic ester diol, alicyclic ester diol and fatty It is obtained by condensation reaction of at least one selected from the group consisting of aliphatic carbonate-based diols and alicyclic carbonate-based diols.

【chemical 20】

In formula (N), R ²³ and R ²⁴ each independently represent a hydrogen atom or a methyl group, R ²⁵ represents an ethylene or propylene group, R ²⁶ represents a saturated aliphatic group or a saturated alicyclic group, and R ²⁷ represents a A saturated aliphatic group or a saturated alicyclic group of an ester group, or a saturated aliphatic group or a saturated alicyclic group containing a carbonate group, k represents an integer of 1 to 40. Here, in formula (N), R ²⁵ and R ²⁶ may be the same or different from each other.

The aliphatic diisocyanate constituting the above-mentioned urethane acrylate can be selected from 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 xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated trimethylxylene diisocyanate, etc.

In addition, the aliphatic ester diol constituting the above polyurethane acrylate can be selected from ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol Diol, neopentyl glycol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol Diol, 2,4-dimethyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-hexanediol, 1,5-hexane Diol, 1,6-hexanediol, 2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1, 2-octanediol, 1,8-octanediol, 1,7-heptanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12- Dodecanediol, dodecanediol, pinacol, 1,4-butynediol, triethylene glycol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol, 1,4-cyclohexanediol Saturated low-molecular-weight diols such as methanol, 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-methylsuccinic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, butylpropane Diacid, dimethylmalonic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid dibasic acid, 2,4-dimethylglutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and other dibasic acids or polyester diols obtained by dehydration condensation of their corresponding anhydrides, ε - Polyester diols obtained by ring-opening polymerization of cyclic ester compounds such as caprolactone. The aforementioned aliphatic ester diols may be used alone or in combination of two or more.

In addition, the aliphatic carbonate-based diol constituting the above-mentioned urethane acrylate may be selected from polycarbonate diols obtained by reacting at least one or more of the above-mentioned diols with phosgene. The polycarbonate-based diols obtained by reacting the above-mentioned diols with phosgene can be used alone or in combination of two or more.

The weight average molecular weight of the above-mentioned urethane acrylate is, for example, preferably 5,000 or more, more preferably 8,000 or more, and still more preferably 10,000 or more. The weight average molecular weight of the urethane acrylate is, for example, preferably less than 30,000, more preferably less than 25,000, even more preferably less than 20,000. Moreover, the said urethane acrylate can freely adjust a weight average molecular weight in the range of 5000-30000 from a viewpoint of further improving adhesive strength, and can use it suitably. If the weight-average molecular weight of the above-mentioned urethane acrylate is within the above-mentioned range, both flexibility and cohesion can be sufficiently obtained, and the bonding strength with organic substrates such as PET, PC, and PEN can be further improved, and more excellent connection reliability can be obtained. . Moreover, the weight average molecular weight of the said urethane acrylate is, for example, preferably 8,000 or more and less than 25,000, and more preferably 10,000 or more and less than 20,000 from the viewpoint of obtaining such an effect more sufficiently. Moreover, it is preferable that the weight average molecular weight of the said urethane acrylate is 10000 or more and less than 25000 from a viewpoint of obtaining such an effect more fully. Here, when the weight average molecular weight is 5,000 or more, sufficient flexibility tends to be easily obtained, and when the weight average molecular weight is less than 30,000, it tends to be possible to suppress a decrease in fluidity of the adhesive composition.

In addition, the compounding amount of the above-mentioned urethane acrylate is based on the total mass of the adhesive component (component excluding the conductive particles in the adhesive composition), for example, preferably 5% by mass or more, more preferably 10% by mass above, more preferably 15% by mass or more. When the above compounding amount is 5% by mass or more, sufficient heat resistance after curing tends to be easily obtained. In addition, the compounding amount of the above-mentioned urethane acrylate is, for example, preferably 95% by mass or less, more preferably 80% by mass, based on the total mass of the adhesive component (component excluding conductive particles in the adhesive composition). or less, more preferably 70% by mass or less. When the said compounding quantity is 95 mass % or less, when using an adhesive composition as a film adhesive agent, it exists in the tendency for favorable film formability to be acquired easily.

(b) The radically polymerizable compound may contain a phosphoric acid group-containing vinyl compound (a vinyl compound having a phosphoric acid group) and one or more radically polymerizable compounds other than the phosphoric acid group-containing vinyl compound. (b) The radically polymerizable compound may also contain N-vinyl compounds selected from the group consisting of N-vinyl compounds and N,N-dialkylvinyl compounds, and the N-vinyl compounds One or more radically polymerizable compounds other than the compound. By using a phosphoric acid group-containing vinyl compound in combination, the adhesiveness of the adhesive composition to a substrate having a connection terminal can be further improved. In addition, the crosslinking rate of the adhesive composition can be increased by using an N-vinyl compound in combination.

The vinyl compound containing a phosphoric acid group is not particularly limited as long as it is a compound having a phosphoric acid group and a vinyl group, but compounds represented by the following general formulas (O) to (Q) are preferred.

【Chemical 21】

In the formula (O), R ²⁸ represents a (meth)acryloyloxy group, R ²⁹ represents a hydrogen atom or a methyl group, and 1 and m each independently represent an integer of 1 to 8. Here, in the formula (O), ^R28 , ^R29 , l, and m are the same or different from each other.

【Chemical 22】

In the formula (P), R ³⁰ represents a (meth)acryloyloxy group, and n, o, and p each independently represent an integer of 1-8. Here, in formula (P), R ³⁰ each other, n each other, o each other, and p each each other are the same or different.

【Chemical 23】

In the formula (Q), R ³¹ represents a (meth)acryloyloxy group, R ³² represents a hydrogen atom or a methyl group, and q and r each independently represent an integer of 1 to 8.

Specific examples of vinyl compounds containing phosphoric acid groups include acid phosphooxy ethyl methacrylate, acid phosphoethyl acrylate, acid phosphopropylmethyl Acrylates, polyoxyethylene glycol monomethacrylate acid phosphate, polyoxypropylene glycol monomethacrylate acid phosphate, 2,2'-di(meth)acryloyloxydiethyl phosphate , EO modified phosphoric acid dimethacrylate, phosphoric acid modified epoxy acrylate, 2-(meth)acryloxyethyl phosphate, vinyl phosphate, etc.

Specific examples of N-vinyl compounds include N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4' - Vinylidene bis(N,N-dimethylaniline), N-vinylacetamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, etc.

Regarding the compounding amounts of the above-mentioned phosphoric acid group-containing vinyl compound and N-vinyl compound, independently of the compounding amounts of the phosphoric acid group-containing vinyl compound and the compounding amount of radically polymerizable compounds other than the N-vinyl compound, The total mass of the adhesive component (component excluding the conductive particles in the adhesive composition) is preferably, for example, 0.2% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5% by mass or more. When the above compounding amount is 0.2% by mass or more, high adhesive strength tends to be easily obtained. The compounding amount of the above-mentioned phosphate group-containing vinyl compound and N-vinyl compound is based on the total mass of the adhesive components (components excluding conductive particles in the adhesive composition), for example, preferably 15 mass % or less, more preferably 10 mass % or less, still more preferably 5 mass % or less. When the above compounding amount is 15% by mass or less, the physical properties of the adhesive composition after curing tend to be less likely to decrease, and reliability tends to be easily ensured.

In addition, regarding the compounding amount of (b) radically polymerizable compound other than the compounds corresponding to the above-mentioned phosphoric acid group-containing vinyl compound or N-vinyl compound, the adhesive component (excluding Based on the total mass of the components of the conductive particles), for example, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. When the above compounding amount is 5% by mass or more, sufficient heat resistance after curing tends to be easily obtained. The compounding amount of (b) radically polymerizable compound other than the compound corresponding to the above-mentioned vinyl compound is based on the total mass of the adhesive component (component excluding conductive particles in the adhesive composition), for example Preferably it is 95 mass % or less, More preferably, it is 80 mass % or less, More preferably, it is 70 mass % or less. When the said compounding quantity is 95 mass % or less, when using an adhesive composition as a film adhesive agent, it exists in the tendency for favorable film formability to be acquired easily.

((c) Radical polymerization initiator)

As the (c) radical polymerization initiator, compounds that generate radicals by applying external energy, such as conventionally known organic peroxides and azo compounds, can be used. As the (c) radical polymerization initiator, an organic peroxide having a half-life temperature of 90 to 175° C. and a weight average molecular weight of 180 to 1,000 in one minute is preferable from the viewpoint of stability, reactivity, and compatibility. When the 1-minute half-life temperature is within this range, the storage stability is more excellent, the radical polymerizability is also sufficiently high, and curing is possible in a short time.

Specific examples of (c) radical polymerization initiators include 1,1,3,3-tetramethylbutylperoxyneodecanoate, bis(4-tert-butylcyclohexyl)peroxydicarbonate , Di(2-ethylhexyl)peroxydicarbonate, cumenyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, dilauroyl peroxide 1-cyclohexyl-1-methylethylperoxyneodecanoate, tert-hexylperoxyneodecanoate, tert-butylperoxyneodecanoate, tert-butylperoxypivalate, 1 ,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert Hexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneheptanoate, tert-amylperoxy-2-ethylhexanoate, Di-tert-butylperoxyhexahydroterephthalate, tert-amylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxide Decanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxyneodecanoate, tert-amylperoxy-2-ethylhexanoate Esters, bis(3-methylbenzoyl) peroxide, dibenzoyl peroxide, bis(4-methylbenzoyl) peroxide, tert-hexylperoxyisopropyl monocarbonate, tert- Butyl peroxymaleic acid, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, 2,5-dimethyl-2,5-di( 3-methylbenzoylperoxy)hexane, tert-butylperoxy-2-ethylhexyl monocarbonate, tert-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (Benzoyl peroxide) hexane, tert-butylperoxybenzoate, dibutylperoxytrimethyladipate, tert-amylperoxy-n-octanoate, tert-amylperoxide isononyl peroxide Organic peroxides such as esters, tert-amyl peroxybenzoate, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(1-acetoxy base-1-phenylethane), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azo Azo compounds such as diisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(1-cyclohexanenitrile), etc. These compounds may be used alone or in combination of two or more.

Moreover, as (c) radical polymerization initiator, the compound which generate|occur|produces a radical by 150-750 nm light irradiation can be used. Such a compound has high sensitivity to light irradiation, for example, α-aminoacetophenone described in Photoinitiation, Photopolymerization, and Photocuring, J.-P.Fouassier, Hanser Publishers (1995, p17-p35) derivatives and phosphine oxide derivatives. These compounds may be used alone or in combination with the above-mentioned organic peroxides or azo compounds.

The compounding amount of the above-mentioned (c) radical polymerization initiator is based on the total mass of the adhesive component (component excluding the conductive particles in the adhesive composition), for example, preferably 0.5% by mass or more, and more preferably 0.5% by mass or more. 1% by mass or more, more preferably 2% by mass or more. When the above compounding amount is 0.5% by mass or more, the adhesive composition tends to be easily cured sufficiently. The compounding amount of the above-mentioned (c) radical polymerization initiator is based on the total mass of the adhesive component (component excluding the conductive particles in the adhesive composition), for example, preferably 40% by mass or less, more preferably 30% by mass or less, more preferably 20% by mass or less. When the above compounding amount is 40% by mass or less, the storage stability tends to be difficult to decrease.

(d) Boron-containing salts

(d) A boron-containing salt (hereinafter referred to as "(d) component") is a compound represented by the following general formula (A). (d) The component contains a borate compound and a counter cation X ⁺ of the borate compound.

【Chemical 24】

In formula (A), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group with 1 to 18 carbon atoms, or an aryl group, and X ⁺ represents a quaternary phosphorus atom and/or quaternary nitrogen atomic cations.

Examples of borate compounds contained in the component (d) include tetraalkyl borates, tetraaryl borates, trialkylaryl borates, dialkyldiaryl borates, Alkyl triaryl borates. The borate compound is preferably a borate containing an aryl group, more preferably a tetraaryl borate. As the borate compound, a compound having a plurality of these compounds in the molecule, or a compound having the above-mentioned compounds in the main chain and/or side chain of the polymer may be used.

As the alkyl group bonded to the boron atom in the borate compound, a linear, branched or cyclic alkyl group can be used. Specific examples of alkyl groups having 1 to 18 carbon atoms include methyl, trifluoromethyl, ethyl, butyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, Octadecyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, isopentyl, heptyl, nonyl , undecyl, tert-octyl, etc. The number of carbon atoms in the alkyl group can be 1-12.

In addition, specific examples of the aryl group bonded to the boron atom in the borate compound include phenyl, p-tolyl, m-tolyl, Base, xylyl, p-tert-butylphenyl, p-methoxyphenyl, biphenyl, naphthyl, p-fluorophenyl, pentafluorophenyl, p-chlorophenyl, o-chlorophenyl, 3,5 - bis(trifluoromethyl)phenyl and the like. Among these aryl groups, phenyl is preferred.

In addition, the alkyl group and aryl group bonded to the boron atom in the borate compound are each the same as or different from each other.

As a cation containing a quaternary phosphorus atom, a phosphonium ion etc. are mentioned. Examples of the cation containing a quaternary nitrogen atom include ammonium ions, imidazolium ions, imidazolinium ions, and the like.

The adhesive composition according to the present embodiment preferably contains a compound represented by the following general formula (A1) and/or a compound represented by the following general formula (A2) as the component (d). The compound represented by the general formula (A1) contains a phosphonium compound as a counter cation of the borate compound. The compound represented by the general formula (A2) contains an imidazolium compound as a counter cation of the borate compound.

【Chemical 25】

In formula (A1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group. In addition, R ^5a , R ^6a , R ^7a and R ^8a each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group. Here, the aryl group may have a substituent.

【Chemical 26】

In formula (A2), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group with 1 to 18 carbon atoms, or an aryl group, and R ^5b , R ^6b , R ^7b , R ^8b and R ^9b each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group, and R ^8b and R ^9b may combine with each other to form a ring. The aryl group may have a substituent.

Examples of phosphonium compounds used as counter cations in component (d) include trialkylphosphonium, dialkylarylphosphonium, alkyldiarylphosphonium, triarylphosphonium, tetraalkylphosphonium, tetraarylphosphonium , Trialkylarylphosphonium, dialkyldiarylphosphonium, alkyltriarylphosphonium. As the phosphonium compound, a compound having a plurality of these compounds in the molecule, or a compound having the above-mentioned compounds in the main chain and/or side chain of the polymer may be used.

In particular, among the above-mentioned phosphonium compounds, it is preferable to use compounds selected from the group consisting of trialkylphosphonium, dialkylarylphosphonium, and alkyldiarylphosphonium from the viewpoint of excellent low-temperature curability and storage stability. at least one trisubstituted phosphonium. That is, it is preferable that any one and only one of R ⁵ , R ⁶ , R ⁷ and R ⁸ is a hydrogen atom. By using a trisubstituted phosphonium, the reactivity with a borate compound can be improved, and low-temperature curability can be further improved.

In addition, the phosphonium compound is preferably an alkylphosphonium, more preferably a trialkylphosphonium among the above-mentioned trisubstituted phosphoniums.

As the alkyl group used as the substituent of the phosphonium compound, a linear, branched or cyclic alkyl group can be used. Specific examples of alkyl groups having 1 to 18 carbon atoms include methyl, trifluoromethyl, ethyl, butyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, Octadecyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, isopentyl, heptyl, nonyl , undecyl, tert-octyl, etc. The number of carbon atoms in the alkyl group can be 1-12. Among these alkyl groups, tert-butyl is preferred.

Specific examples of the aryl group used as a substituent of the phosphonium compound include phenyl, p-tolyl, m-tolyl, Base, xylyl, p-tert-butylphenyl, p-methoxyphenyl, biphenyl, naphthyl, p-fluorophenyl, pentafluorophenyl, p-chlorophenyl, o-chlorophenyl, etc.

In addition, the alkyl group and aryl group which are the substituents of the phosphonium compound are each the same as or different from each other.

Examples of the imidazolium compound used as a counter cation in the component (d) include imidazolium and imidazolium derivatives. Examples of imidazolium derivatives include 2-methylimidazolium, 2-phenylimidazolium, 2-ethyl-4-methylimidazolium, benzimidazolium, 1-methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium, 1-ethyl-5,6-dichlorobenzimidazolium, and the like. As the imidazolium compound, a compound having a plurality of these compounds in the molecule, or a compound having the above-mentioned compounds in the main chain and/or side chain of the polymer may be used.

Among imidazolium compounds, those having an alkyl group or phenyl group bonded to the imidazolium ring are preferred, more preferably 2-methylimidazolium, 2-phenylimidazolium, 2-ethyl-4-methylimidazolium.

Bromine, chlorine, fluorine, etc. are mentioned as a halogen atom used as a substituent of an imidazolium compound. Examples of the alkyl group include methyl, trifluoromethyl, ethyl, butyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, octadecyl, propyl, isopropyl Base, isobutyl, sec-butyl, tert-butyl, pentyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, isopentyl, heptyl, nonyl, undecyl, tert-octyl, etc. . Examples of the aryl group include phenyl, p-tolyl, m-tolyl, Base, xylyl, p-tert-butylphenyl, p-methoxyphenyl, biphenyl, naphthyl, p-fluorophenyl, pentafluorophenyl, p-chlorophenyl, o-chlorophenyl, 3,5 - bis(trifluoromethyl)phenyl and the like. Examples of the alkoxy group include methoxy, ethoxy, butoxy and the like. R ^8b and R ^9b can combine with each other to form aromatic ring, heterocyclic ring, alicyclic ring, etc. The substituents of the imidazolium compounds are the same or different from each other.

The (d) component is preferably a combination of an aryl group-containing borate and an alkylphosphonium, or a combination of an aryl group-containing borate and an imidazolium compound. A more balanced combination of adhesives can be obtained by making the component (d) a salt consisting of an aryl group-containing borate and an alkylphosphonium, or a salt consisting of an aryl group-containing borate and an imidazolium compound. The improvement of the low-temperature curability of the product and the improvement of the storage stability.

Concretely, as (d) component, the salt obtained by the conventional synthesis method can be used. For example, in a mixture of alkali metals or alkaline earth metals, and alkyl halides or aryl halides, after dropping the etherate solution of boron trifluoride, sodium hydroxide is added dropwise to form tetraalkyl borate sodium salt Or tetraaryl borate sodium salt, and then through the displacement reaction with phosphonium, borate-phosphonium salt can be obtained. Also, for example, a borate-imidazolium salt can be obtained by adding an aqueous solution in which sodium aryl borate or sodium alkyl borate is dissolved to a solution of 10 mol (10 mol) of methylimidazole hydrochloric acid to perform salt exchange.

The salts obtained from these compounds can be used alone or in combination of two or more.

The melting point of the component (d) is, for example, preferably 60° C. or higher, more preferably 70° C. or higher, and still more preferably 80° C. or higher from the viewpoint of further improving storage stability. The melting point of the component (d) is, for example, preferably 300° C. or lower, more preferably 270° C. or lower, and even more preferably 250° C. or lower from the viewpoint of further improving storage stability. When the adhesive composition contains multiple types of (d) components, it is preferable that the melting point of at least one salt satisfies the above-mentioned range, and it is more preferable that the melting points of all the salts satisfy the above-mentioned range.

The amount of the component (d) is, for example, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the adhesive component (component excluding the conductive particles in the adhesive composition). When the compounding quantity of (d) component is 0.1 mass % or more, it exists in the tendency which fully acquires the effect of promoting the reactivity of a radical polymerization initiator easily. The amount of the component (d) is, for example, preferably 20% by mass or less, more preferably 15% by mass or less, based on the total mass of the adhesive component (component excluding conductive particles in the adhesive composition), More preferably, it is 10 mass % or less. When the compounding quantity of (d) component is 20 mass % or less, there exists a tendency for the storage stability of an adhesive composition to fall hard.

((e) Conductive particles)

(e) The conductive particles may be particles as long as they are conductive in their entirety or on the surface, but when used for connection of components having connection terminals, particles having an average particle diameter smaller than the distance between connection terminals are preferable.

As (e) electroconductive particle, the metal particle which consists of metals, such as Au, Ag, Ni, Cu, Pd, or solder, and the particle which consists of carbon etc. are mentioned. Moreover, (e) electroconductive particle may use nonconductive glass, ceramics, plastics, etc. as a core, and the said metal, metal particle, or carbon particle may be coat|covered on this core. As (e) conductive particles, the above-mentioned metals, metal particles or carbon particles coated on the plastic core, and hot-melt metal particles are deformable by heat and pressure, so the contact area with the electrode increases when connected On the other hand, reliability is improved, so it is preferable. (e) Electroconductive particle may be the particle which coat|covered silver on the metal particle which consists of copper, for example. Moreover, as (e) electroconductive particle, the metal powder which has many fine metal particles connected in chain form as described in Unexamined-Japanese-Patent No. 2005-116291 can be used.

In addition, by using fine particles further coated with polymer resin or the like on the surface of these (e) conductive particles, or by providing (e) conductive particles made of an insulating substance on the surface by a method such as hybridization (hybridization) The fine particles of the insulating layer can suppress the short circuit caused by the contact of the particles when the compounding amount of the conductive particles is increased, and improve the insulation between electrode circuits, so they can be used alone or mixed with (e) conductive particles.

(e) The average particle size of the electroconductive particle is preferably 1 to 18 μm, for example, from the viewpoint of dispersibility and conductivity. When such (e) electroconductive particle is contained, an adhesive composition can be used suitably as an anisotropic electroconductive adhesive. (e) The average particle diameter of electroconductive particle can be measured using the laser diffraction type particle size distribution analyzer (for example, the laser diffraction type SALD-2100 by Shimadzu Corporation).

(e) The compounding amount of conductive particles is not particularly limited, but based on the entire volume of the adhesive component (components excluding conductive particles in the adhesive composition), for example, it is preferably 0.1% by volume or more, more preferably Preferably it is 0.2 volume % or more. When the above-mentioned compounding quantity is 0.1 volume % or more, it exists in the tendency which can suppress electroconductivity from becoming low. (e) The amount of conductive particles is based on the entire volume of the adhesive component (components excluding conductive particles in the adhesive composition), for example, preferably 30% by volume or less, more preferably 10% by volume the following. When the above compounding amount is 30% by volume or less, it tends to be difficult to generate a short circuit. Here, "volume %" is determined based on the volume of each component before curing at 23° C., and the volume of each component can be converted from weight to volume using specific gravity. In addition, it is also possible to add an appropriate solvent (water, alcohol, etc.) that does not dissolve or swell the component and fully wet the component in a graduated cylinder, put the component in it, and use the increased volume as the volume of the component. Find out.

(other ingredients)

A stabilizer may be added to the adhesive composition according to the present embodiment in order to control the curing rate and further improve storage stability. As such a stabilizer, known compounds can be used without particular limitation, preferably quinone derivatives such as benzoquinone and hydroquinone; phenol derivatives such as 4-methoxyphenol and 4-tert-butylcatechol; 2,2,6,6-tetramethylpiperidin-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl and other aminooxyl derivatives ; Tetramethylpiperidine methacrylate and other hindered amine derivatives. The stabilizers can be used alone or in combination of two or more.

The compounding amount of the stabilizer is based on the total mass of the adhesive component (the component excluding the conductive particles in the adhesive composition), for example, preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and furthermore Preferably it is 0.02 mass % or more. When the above compounding amount is 0.005% by mass or more, it tends to be easy to control the curing rate and to improve the storage stability. The compounding amount of the stabilizer is, for example, preferably 10% by mass or less, more preferably 8% by mass or less, and further Preferably it is 5% by mass or less. When the above compounding amount is 10% by mass or less, the compatibility with other components tends to be difficult to decrease.

In addition, in the adhesive composition according to this embodiment, a coupling agent represented by alkoxysilane derivatives and silazane derivatives, an adhesion promoter, and a leveling agent, etc., can also be appropriately added for adhesion. Auxiliary. Specifically, as the coupling agent, a compound represented by the following general formula (R) is preferable. A coupling agent can be used individually by 1 type or in mixture of 2 or more types.

【Chemical 27】

In formula (R), R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, an alkane with 1 to 5 carbon atoms Oxycarbonyl or aryl, R ³⁶ represents (meth)acryloyl, vinyl, isocyanate, imidazolyl, mercapto, amino, methylamino, dimethylamino, benzylamino, phenylamino, cyclohexylamino, morpholino group, piperazinyl group, ureido group or glycidyl group, and s represents an integer of 1 to 10.

The adhesive composition according to this embodiment may contain a rubber component for the purpose of stress relaxation and adhesive improvement. The rubber component refers to a component that expresses rubber elasticity (JIS K6200) in its own state or a component that expresses rubber elasticity by reaction. The rubber component may be solid or liquid at room temperature (25° C.), but is preferably liquid from the viewpoint of improving fluidity. As the rubber component, a compound having a polybutadiene skeleton is preferable. The rubber component may have a cyano group, a carboxyl group, a hydroxyl group, a (meth)acryloyl group or a morpholino group. In addition, from the viewpoint of improving adhesiveness, a rubber component containing a cyano group or a carboxyl group as a highly polar group in a side chain or a terminal is preferable. Among them, even if it has a polybutadiene skeleton, it is classified as (a) a thermoplastic resin when it exhibits thermoplasticity, and it is classified as (b) a radical polymerizable compound when it exhibits radical polymerizability.

Specific examples of the rubber component include polyisoprene, polybutadiene, carboxy-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1,2 -Polybutadiene, hydroxyl-terminated 1,2-polybutadiene, acrylic rubber, styrene-butadiene rubber, hydroxyl-terminated styrene-butadiene rubber, acrylonitrile-butadiene rubber, at polymer ends Acrylonitrile-butadiene rubber containing carboxyl, hydroxyl, (meth)acryloyl or morpholino groups, carboxylated nitrile rubber, hydroxyl-terminated poly(propylene oxide), alkoxysilyl-terminated poly(oxypropylene) , poly(tetramethylene ether) glycol, polyolefin glycol, etc.

In addition, examples of rubber components that have the above-mentioned highly polar groups and are liquid at room temperature include liquid acrylonitrile-butadiene rubber, polymer terminals containing carboxyl groups, hydroxyl groups, and (meth)acryloyl groups. Or morpholine-based liquid acrylonitrile-butadiene rubber, liquid carboxylated nitrile rubber, etc., the blending amount of acrylonitrile as a polar group is preferably 10 to 60% by mass.

These rubber components can be used alone or in combination of two or more.

In addition, organic fine particles may be added to the adhesive composition according to the present embodiment for the purpose of stress relaxation and adhesive improvement. The average particle diameter of the organic fine particles is preferably, for example, 0.05 to 1.0 μm. Here, when the organic fine particles are composed of the above rubber component, they are classified into the rubber component instead of the organic fine particles, and when the organic fine particles are composed of the above (a) thermoplastic resin, they are classified into the (a) thermoplastic resin instead of the organic fine particles.

Specific examples of organic fine particles include polyisoprene, polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1, 2-polybutadiene, acrylic rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylonitrile-butadiene rubber containing carboxyl, hydroxyl, (meth)acryloyl or morpholinyl groups at the end of the polymer Diene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly(propylene oxide), alkoxysilyl-terminated poly(propylene oxide), poly(tetramethylene ether) glycol, polyolefin glycol, (methyl ) organic particles composed of alkyl acrylate-butadiene-styrene copolymer, alkyl (meth)acrylate-silicone copolymer or silicone-(meth)acrylic acid copolymer, or their composites.

In addition, the adhesive composition that can be used for the bonded structure described later may also contain silicone particles. In the above bonded structure, the substrate is made of polyethylene terephthalate, polycarbonate, poly The substrate is composed of at least one selected from the group consisting of ethylene naphthalate and cycloolefin polymer.

Connection by making the substrate consist of a base material containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymers The adhesive composition used in the structure contains silicone microparticles, which can sufficiently relax the internal stress, so for polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin The adhesive strength of the polymer is further improved, and the adhesive strength to a member having a connection terminal can be further improved. In addition, further stable performance can be maintained even after a long-term reliability test.

As the aforementioned silicone fine particles, fine particles of polyorganosilsesquioxane resin having rubber elasticity are known, and spherical or amorphous silicone fine particles can be used. Furthermore, from the viewpoint of dispersibility and relaxation of internal stress, it is preferable that the silicone fine particles have a weight average molecular weight of 1 million or more. In addition, it is preferable that the silicone microparticles have a three-dimensional crosslinked structure. Such silicone fine particles have high dispersibility in resin and are further excellent in stress relaxation after curing. Silicone microparticles having a weight-average molecular weight of 1 million or more and/or silicone microparticles having a three-dimensional crosslinked structure have low solubility in polymers such as thermoplastic resins, monomers, and solvents, so the above-mentioned effects can be more remarkably obtained . Here, "having a three-dimensional crosslinked structure" means that the polymer chain has a three-dimensional network structure. In addition, the glass transition temperature of the silicone fine particles is, for example, preferably -130°C or higher and -20°C or lower, more preferably -120°C or higher and -40°C or lower. Such silicone fine particles can sufficiently relax the internal stress of the adhesive composition as a circuit connection material.

As silicone microparticles having such a structure, specifically, silicone microparticles obtained by making organopolysiloxane having at least two vinyl groups, organic polysiloxane having at least two hydrogen atoms bonded to silicon atoms, Silicone particles obtained by the reaction of hydrogen polysiloxane and a platinum catalyst (for example, Japanese Patent Laid-Open No. 62-257939); Silicone microparticles obtained by siloxane and platinum-based catalysts (for example, Japanese Patent Laid-Open No. 63-77942); diorganosiloxane, monoorganosilsesquioxane, triorganosilsesquioxane, and platinum-based catalysts Silicone microparticles obtained (for example, Japanese Patent Application Laid-Open No. 62-270660); a silicone obtained by dropping a water/alcohol solution of methylsilanetriol and/or a partial condensate thereof into an aqueous alkali solution for polycondensation Fine particles (for example, Japanese Patent No. 3970453) and the like. In addition, in order to improve the dispersibility and the adhesion to the substrate, it is also possible to use silicone microparticles to which epoxy compounds are added or copolymerized (for example, Japanese Patent Application Laid-Open No. 3-167228), and silicone microparticles to which acrylate compounds are added or copolymerized. Ketone particles, etc.

In addition, in order to further improve dispersibility, it is preferable to use silicone fine particles having a core-shell structure. As the core-shell structure, there are structures in which a surface layer (shell) having a glass transition temperature higher than that of the surface of the core material (core layer) is formed, and a structure having For the structure of the graft layer (shell layer), silicone particles with different compositions of the core layer and the shell layer can be used. Specifically, it is possible to use core-shell type silicone microparticles ( For example, Japanese Patent No. 2832143), core-shell silicone microparticles as described in WO2009/051067. In addition, silicone microparticles containing functional groups such as hydroxyl, epoxy, ketimine, carboxyl, and mercapto groups at the end of the molecule or in the inner chain of the molecule can be used. Such silicone microparticles are preferable because they have improved dispersibility with respect to film-forming components and radically polymerizable substances.

The average particle diameter of the silicone fine particles is, for example, preferably 0.05 to 25 μm, more preferably 0.1 to 20 μm. When the average particle diameter is 0.05 μm or more, the decrease in the fluidity of the adhesive composition tends to be suppressed due to the increase in the surface area. In addition, when the average particle diameter is 25 μm or less, the effect of alleviating internal stress tends to be sufficiently exhibited.

The blending amount of the silicone microparticles is, for example, preferably 3% by mass or more, more preferably 5% by mass or more, based on the total mass of the adhesive component (component excluding conductive particles in the adhesive composition). . When the blending amount of the silicone fine particles is 3% by mass or more, the internal stress tends to be sufficiently relaxed. The blending amount of the silicone fine particles is, for example, preferably 40% by mass or less, more preferably 30% by mass or less, based on the total mass of the adhesive component (component excluding the conductive particles in the adhesive composition). When the blending amount of the silicone fine particles is 40% by mass or less, the decrease in the flexibility (elastic modulus, elongation) of the adhesive composition tends to be suppressed, and the adhesive strength tends to be less likely to decrease.

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

The adhesive composition according to the present embodiment can be used in a paste form when the adhesive composition is liquid at room temperature. When the adhesive composition is solid at room temperature, it may be used by heating, or gelatinized using a solvent. The solvent that can be used is preferably a solvent that has no reactivity with the adhesive composition and additives and exhibits sufficient solubility, and is preferably a solvent that has a boiling point of 50 to 150° C. under normal pressure. When the boiling point is 50° C. or higher, volatilization decreases when left standing at room temperature, and the use in an open system tends to be easier. In addition, when the boiling point is 150° C. or lower, the solvent tends to volatilize easily, and the reliability after bonding tends to be difficult to decrease.

In addition, the adhesive composition according to the present embodiment may be formed into a film and used as a film adhesive. The film adhesive according to this embodiment contains the above-mentioned adhesive composition. A solution obtained by adding a solvent or the like to the adhesive composition as needed is applied on a release substrate such as a fluororesin film, polyethylene terephthalate film, or release paper, or on an Substrates such as woven fabrics are dipped in the solution and mounted on a peelable substrate, and the solvent and the like are removed and used as a film. If it is used in the form of a film, it is more convenient from the viewpoints of operability and the like. According to this embodiment, an adhesive sheet including a base material and a film-like adhesive can be provided. In the adhesive sheet, the film-like adhesive is disposed on the substrate, for example, to form an adhesive layer.

The adhesive composition according to this embodiment can be bonded by using heat and pressure in combination. The heating temperature is preferably a temperature of 100 to 200°C. The pressure is preferably within a range that does not damage the adherend, and generally, it is preferably 0.1 to 10 MPa. These heating and pressurization are preferably carried out in the range of 0.5 to 120 seconds, and bonding may be performed under heating at 120 to 190° C., 3 MPa, and 10 seconds.

The adhesive composition according to this embodiment can be used to electrically connect the first connection terminal arranged on the main surface of the first substrate and the second connection terminal arranged on the main surface of the second substrate. According to this embodiment, there are provided an adhesive composition, a film-shaped Application of adhesive or bonding sheet. According to the present embodiment, there is provided an adhesive combination for preparing a connection member for electrically connecting a first connection terminal arranged on a main surface of a first substrate and a second connection terminal arranged on a main surface of a second substrate. application of materials, film adhesives or adhesive sheets.

In addition, the adhesive composition according to the present embodiment can be used to electrically connect the connection terminal of a solar battery cell having the connection terminal arranged on the main surface of the substrate to a wiring member. According to the present embodiment, there is provided an adhesive composition, a film adhesive, or an adhesive sheet for electrically connecting the connection terminals of a solar battery cell having the connection terminals arranged on the main surface of the substrate to a wiring member. material application. According to the present embodiment, there are provided an adhesive composition and a film-like adhesive for manufacturing a connecting member for electrically connecting the connecting terminal of a solar battery cell having the connecting terminal arranged on the main surface of the substrate and a wiring member. Or adhesive sheet applications.

The adhesive composition according to this embodiment can be used as an adhesive for a homogeneous adherend, and can also be used as an adhesive for a heterogeneous adherend having a different coefficient of thermal expansion. Specifically, the adhesive composition according to this embodiment can be used as an anisotropic conductive adhesive, a circuit connection material represented by silver paste, silver film, etc., an elastomer for CSP, an underfill material for CSP, Semiconductor element adhesive materials represented by LOC tape and the like.

For example, a first circuit component having a first circuit board and first connection terminals disposed on the main surface of the first circuit board, and a second circuit board having a first connection terminal disposed on the main surface of the second circuit board The second circuit component of the second connection terminal is disposed via the adhesive composition of the present embodiment in a state where the first connection terminal and the second connection terminal face each other and the first connection terminal and the second connection terminal are electrically connected. , thereby forming a connection structure of circuit components. In this case, the adhesive composition according to this embodiment can be effectively used as an adhesive for circuit connection.

(connection structure)

Next, the bonded structure using the said adhesive composition and its manufacturing method are demonstrated. According to the present embodiment, there is provided a method of manufacturing a bonded structure by interposing an adhesive composition between a first circuit component having a first substrate and first connection terminals disposed on a main surface of the first substrate, and Between the second circuit component having the second substrate and the second connection terminals disposed on the main surface of the second substrate, the adhesive composition is cured in such a state, thereby making the first connection terminal The first circuit component and the second circuit component are bonded in a state of being electrically connected to the second connection terminal. In addition, according to the present embodiment, there is provided a method of manufacturing a bonded structure by interposing an adhesive composition between a solar cell having a substrate and connection terminals disposed on the main surface of the substrate, and a wiring member, By curing the adhesive composition in such a state, the solar cell and the wiring member are bonded together in a state where the connection terminal and the wiring member are electrically connected.

FIG. 1 is a schematic cross-sectional view showing a bonded structure according to a first embodiment. Fig. 2 is a schematic cross-sectional view showing a method of manufacturing the bonded structure shown in Fig. 1 . The connection structure 100 of circuit components shown in FIG. 1 is obtained using the adhesive composition which does not contain (e) electroconductive particle.

The circuit component connection structure 100 shown in FIG. 1 includes a circuit component (first circuit component) 10 , a circuit component (second circuit component) 20 , and a connection component 30 . The circuit component 10 has a circuit board (first board) 12 and connection terminals (first connection terminals) 14 arranged on the main surface 12 a of the circuit board 12 . The circuit component 20 has a circuit board (second board) 22 and connection terminals (second connection terminals) 24 arranged on the main surface 22 a of the circuit board 22 .

The connection member 30 is disposed between the circuit member 10 and the circuit member 20 . The connecting member 30 connects the circuit component 10 and the circuit component 20 such that the main surface 12 a and the main surface 22 a are substantially parallel to each other and face each other. In the connection structure 100, the connection terminal 14 and the connection terminal 24 are arrange|positioned facing each other, and are electrically connected by mutual contact. The connecting member 30 is composed of a cured product of an adhesive composition 30a described later.

The bonded structure 100 can be manufactured as follows, for example. First, as shown in FIG. 2, the adhesive composition 30a which consists of the circuit component 10, the circuit component 20, and the said adhesive composition is prepared. The adhesive composition 30a is obtained by molding the above-mentioned adhesive composition into a film shape, for example. Next, the adhesive composition 30 a is placed on the main surface 22 a of the circuit component 20 on which the connection terminal 24 is formed. And the circuit component 10 is mounted on the adhesive composition 30a so that the connection terminal 14 and the connection terminal 24 may oppose. Next, while heating the adhesive composition 30a through the circuit component 10 and the circuit component 20, the adhesive composition 30a is cured, and pressure is applied in the direction perpendicular to the main surfaces 12a, 22a, and the circuit component 10, 20 to form a connection part 30 . Thus, bonded structure 100 is obtained.

When the above-mentioned adhesive composition contains conductive particles, by interposing an anisotropic conductive film produced using such an adhesive composition between opposing connection terminals and applying heat and pressure, the connections are made via the conductive particles. The terminals are electrically connected to each other, and the circuit components are bonded to each other, whereby a connected structure of circuit components can be obtained. Fig. 3 is a schematic cross-sectional view showing a bonded structure according to a second embodiment. Fig. 4 is a schematic cross-sectional view showing a method of manufacturing the bonded structure shown in Fig. 3 . The connection structure 200 of circuit components shown in FIG. 3 is obtained using the adhesive composition containing (e) electroconductive particle.

The connection structure 200 of circuit components shown in FIG. In the connection structure 200, the connection terminal 14 and the connection terminal 24 are arrange|positioned facing each other in the state separated from each other.

The connection member 40 is arranged between the circuit member 10 and the circuit member 20 . The connecting member 40 is composed of a cured product of an adhesive composition 40 a described later, and has an adhesive component 42 and conductive particles 44 dispersed in the adhesive component 42 . The adhesive component 42 is composed of a cured product of an adhesive component 42a described later. In connection structure 200 , between opposing connection terminal 14 and connection terminal 24 , conductive particle 44 contacts connection terminal 14 , 24 , whereby connection terminal 14 , 24 is electrically connected to each other via conductive particle 44 .

The bonded structure 200 can be manufactured as follows, for example. First, as shown in FIG. 4, the circuit component 10, the circuit component 20, and the adhesive composition 40a which consists of the said adhesive composition are prepared. The adhesive composition 40a is obtained by molding the above-mentioned adhesive composition into a film shape, for example. The adhesive composition 40a has an adhesive component 42a, and the electroconductive particle 44 dispersed in the adhesive component 42a. Thereafter, the circuit component 10 and the circuit component 20 are connected via the adhesive composition 40 a by the same method as the method for obtaining the above-mentioned bonded circuit component structure 100 . Thus, the bonded structure 200 is obtained.

At least one of the circuit board 12 and the circuit board 22 of the connection structures 100 and 200 of circuit components may be formed of a base material containing a thermoplastic resin having a glass transition temperature of 200° C. or lower. For example, at least one of the circuit board 12 and the circuit board 22 may be selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate and cycloolefin polymer. The selected at least one organic substrate constitutes. Therefore, when using organic substrates such as polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymers, the wettability of the circuit board and the adhesive composition As a result, excellent adhesive strength can be obtained even under low temperature curing conditions. Therefore, even after a long-term reliability test (high temperature and high humidity test), stable performance (adhesive strength and connection resistance) can be maintained, and excellent connection reliability can be obtained.

In addition, one of the circuit board 12 and the circuit board 22 is made of a material selected from the group consisting of polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and cycloolefin polymer. When at least one of the above-mentioned substrates is formed, the other circuit substrate of the circuit substrate 12 and the circuit substrate 22 may be composed of a material selected from the group consisting of polyimide and polyethylene terephthalate. At least one kind of base material constitutes. Thereby, the wettability and adhesive strength of a circuit board and an adhesive composition improve further, and it becomes possible to obtain more excellent connection reliability.

Here, the circuit boards 12 and 22 may be made of inorganic substances such as semiconductors, glass or ceramics, polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymers, polyimides, or polycarbonate. Organic materials such as esters, and composite materials such as glass/epoxy, etc. In addition, the circuit boards 12, 22 may be flexible boards.

5 is a schematic cross-sectional view showing a bonded structure according to a third embodiment. The solar battery module 300 shown in FIG. 5 includes solar battery cells 310 a and 310 b , a wiring member 320 , and a connection member 330 .

The solar cells 310 a and 310 b have a substrate 312 , surface electrodes (connection terminals) 314 arranged on the surface (main surface) 312 a of the substrate 312 , and back electrodes (connection terminals) arranged on the back surface (main surface) 312 b of the substrate 312 . ) 316. The substrate 312 is made of, for example, a semiconductor, an inorganic material such as glass or ceramics, or a composite material such as glass/epoxy. In addition, the substrate 312 may be a flexible substrate. The surface 312a is a light receiving surface.

The wiring member 320 is a member for electrically connecting the solar battery cell 310a to another member, for example, electrically connecting one solar battery cell to another solar battery cell. In FIG. 5 , the front electrode 314 of the solar cell 310 a is electrically connected to the back electrode 316 of the solar cell 310 b through the wiring member 320 .

Connection members 330 are disposed between solar battery cells 310 a and wiring member 320 and between solar battery cells 310 b and wiring member 320 , and connect solar battery cells 310 a and 310 b to wiring member 320 . The connecting member 330 contains a cured product of the above-mentioned adhesive composition and an insulating substance. The connection member 330 may further contain conductive particles, or may not contain conductive particles. When the connection member 330 contains conductive particles, the surface electrodes 314 of the solar cell 310a and the wiring member 320 can be electrically connected via the conductive particles. In addition, the back electrode 316 of the solar cell 310b and the wiring member 320 may be electrically connected via conductive particles. When the connection member 330 does not contain conductive particles, for example, the surface electrode 314 of the solar cell 310 a and/or the back electrode 316 of the solar cell 310 b may be in contact with the wiring member 320 .

In the solar cell module 300 , the connection member 330 is composed of a cured product of the above-mentioned adhesive composition. Thereby, the adhesive strength of the connection member 330 between the solar cell 310a and the wiring member 320 and between the solar cell 310b and the wiring member 320 is sufficiently high, and the connection resistance between the solar cell 310a and the wiring member 320 is sufficient. Small. In addition, even when left for a long time in a high-temperature and high-humidity environment, a decrease in adhesive strength and an increase in connection resistance can be sufficiently suppressed. Furthermore, the connecting member 330 may be formed by heat treatment at a low temperature and for a short time. Accordingly, the solar battery module shown in FIG. 5 can be manufactured without deteriorating the solar battery cells 310a and 310b at the time of connection, and can have higher reliability than conventional ones.

The solar cell module 300 can replace the circuit component 10 and the circuit component 20 in the manufacturing method of the above-mentioned bonded structure 100, 200 with the solar cell unit 310a, 310b and the wiring member 320, with the same manufacturing method as the above-mentioned bonded structure. method to manufacture.

Here, in the connection structure 100, 200 and the solar cell module 300, the above-mentioned adhesive composition used as a connection member does not need to be completely cured (the highest degree of curing that can be achieved under specified curing conditions), as long as the above-mentioned Traits can be in a partially cured state.

Example

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

＜Thermoplastic resin＞

(Preparation of Polyester Polyurethane)

Prepare the resin by dissolving polyester-type polyurethane resin (manufactured by Toyobo Co., Ltd., UR-4800 (trade name), weight-average molecular weight: 32,000, glass transition temperature: 106°C) in a 1:1 mixed solvent of methyl ethyl ketone and toluene A mixed solvent solution with a component of 30% by mass.

(Preparation of phenoxy resin)

Dissolve 40 parts by mass of phenoxy resin (trade name: YP-50 (manufactured by Tohto Kasei Co., Ltd.), weight average molecular weight: 60000, glass transition temperature: 80°C) in 60 parts by mass of methyl ethyl ketone to prepare 40 parts by mass of solid content %The solution.

＜Radical polymerizable compound＞

(Synthesis of Urethane Acrylate (UA1))

In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser with a calcium chloride drying tube, and a nitrogen gas introduction tube, poly(1,6-hexanediol carbonate with a number average molecular weight of 1000) was evenly added dropwise for 3 hours ) (trade name: Duranol T5652, manufactured by Asahi Kasei Chemical Co., Ltd.) 2500 parts by mass (2.50 mol) and isophorone diisocyanate (manufactured by Sigma-Aldrich) 666 parts by mass (3.00 mol), and nitrogen gas was sufficiently introduced into the reaction vessel Afterwards, heat at 70~75°C for reaction. After adding 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Sigma-Aldrich) and 5.53 parts by mass of dibutyltin dilaurate (manufactured by Sigma-Aldrich), 2-hydroxyethyl acrylate (manufactured by Sigma-Aldrich) was added to the reaction vessel. Aldrich) 238 parts by mass (2.05 mol) were reacted at 70° C. for 6 hours in an air environment to obtain urethane acrylate (UA1). The weight average molecular weight of urethane acrylate was 15,000.

(Preparation of vinyl compound (P-2M) with phosphoric acid group)

As a vinyl compound having a phosphate group, 2-(meth)acryloyloxyethyl phosphate (trade name: Light Ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd.) was prepared.

＜Preparation of boron compound＞

As boron compounds, tri-tert-butylphosphonium tetraphenyl borate (abbreviation: TBPTB, manufactured by Tokyo Chemical Industry Co., Ltd., melting point: 261°C), di-tert-butylmethylphosphonium tetraphenyl borate (abbreviation: DBMPTB, Tokyo Kasei Kogyo Co., Ltd., melting point: 158°C).

In addition, as a boron compound, 2-ethyl-4-methylimidazolium tetraphenyl borate (EMI-B) was synthesized as follows. First, a stirring device, a thermometer, and a reflux device were assembled in a 30 ml four-necked flask. Next, a solution obtained by dissolving 3.4 g (10 mmol) of sodium tetraphenylborate (manufactured by Aldrich) in 100 ml of distilled water was added to 1.1 g (manufactured by Aldrich) of 2-ethyl-4-methylimidazole ( 10mmol) of 1mol/l hydrochloric acid 10mol (10mol) solution. After stirring for 1 hour at 25°C, an oily substance separated. The obtained oily substance was diluted with methyl ethyl ketone (MEK), washed with water, and concentrated by a rotary evaporator. The obtained solid was washed with hexane to obtain 2-ethyl-4-methylimidazolium tetraphenylborate (melting point: 200° C.) as a white solid in a yield of 35%.

＜Preparation of amine compound＞

As an amine compound, N,N-dimethylaniline (abbreviation: DMA, manufactured by Aldrich) was prepared.

＜Radical polymerization initiator＞

As a radical polymerization initiator, dibenzoyl peroxide (trade name: NYPER BW, manufactured by NOF Corporation) and dilauroyl peroxide (trade name: PEROYL L, manufactured by NOF Corporation) were prepared.

＜Conductive Particles＞

(Production of conductive particles)

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

[Examples 1 to 8 and Comparative Examples 1 to 4]

(Production of adhesives for circuit connection)

Compound thermoplastic resin, radical polymerizable compound and radical polymerization initiator, and boron compound or amine compound according to solid mass such as shown in Table 1, and further, use adhesive agent (conductive conductivity is excluded in the adhesive for circuit connection) Based on the total volume of the particle components), 1.5% by volume of dispersed conductive particles was blended to obtain an adhesive for circuit connection. The obtained adhesive for circuit connection was coated on a fluororesin film with a thickness of 80 μm by a coating device, and dried by hot air at 70° C. for 10 minutes to obtain a film-shaped circuit connection adhesive with an adhesive layer thickness of 20 μm. Adhesive.

Table 1

UR-4800 YP-50 UA1 P-2M TBPTB DBMPTB EMI-B DMA NYPER BW PEROYLL Example 1 50 - 50 3 5 - - - 8 - Example 2 50 - 50 3 - 5 - - 8 - Example 3 50 - 50 3 5 - - - - 8 Example 4 50 - 50 3 - 5 - - - 8 Example 5 - 50 50 3 3 - - - 8 - Example 6 - 50 50 3 - 3 - - - 8 Example 7 50 - 50 3 - - 5 - 8 - Example 8 50 - 50 3 - - 5 - - 8 Comparative example 1 50 - 50 3 - - - 3 8 - Comparative example 2 50 - 50 3 - - - 3 - 8 Comparative example 3 50 - 50 3 - - - - 8 - Comparative example 4 50 - 50 3 - - - - - 8

(Measurement of connection resistance and adhesive strength)

A flexible circuit board (FPC) having 500 copper circuits with a line width of 25 μm, a pitch of 50 μm, and a thickness of 8 μm on a polyimide film was interposed between the adhesives for circuit connection of Examples 1 to 8 and Comparative Examples 1 to 4 , and glass (ITO, surface resistance 20Ω/□) having a thickness of 1.1 mm formed with a thin layer of ITO of 0.2 μm. Using a thermocompression bonding device (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.), heating and pressurizing at 120° C. and 2 MPa for 10 seconds were performed to connect with a width of 2 mm to produce a bonded structure A. Immediately after connection and after holding in a constant temperature and humidity chamber at 85° C. and 85% RH for 240 hours (after a high temperature and high humidity test), the resistance value between adjacent circuits of the connection structure A was measured with a multimeter. The resistance value is expressed as an average of 37 points of resistance between adjacent circuits.

In addition, the adhesive strength of the bonded structure A was measured by the 90-degree peeling method according to JIS-Z0237 immediately after connection and after the high-temperature, high-humidity test. Here, as a measuring device of the adhesive strength, Toyo Baldwin Co., Ltd. TENSILO NUTM-4 (peeling speed 50 mm/min, 25° C.) was used.

A flexible circuit having 80 copper circuits with a line width of 150 μm, a pitch of 300 μm, and a thickness of 8 μm on a polyimide film (Tg 350°C) interposed the circuit-connecting adhesives of Examples 1 to 8 and Comparative Examples 1 to 4 Between the plate (FPC) and the PET substrate (Ag) with a thickness of 0.1 μm on which a thin layer of Ag paste with a thickness of 5 μm was formed. Using a thermocompression bonding device (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.), heat and pressurize at 120° C. and 2 MPa for 20 seconds to perform connection with a width of 2 mm to produce a bonded structure B. Immediately after connection and after holding in a constant temperature and humidity chamber at 85°C and 85%RH for 240 hours (after a high-temperature and high-humidity test), the resistance of the FPC and the PET substrate on which a thin layer of Ag paste was formed was measured with a multimeter. The resistance value between adjacent circuits of the connection structure B. The resistance value is expressed as an average of 37 points of resistance between adjacent circuits.

In addition, immediately after the connection and after the high-temperature, high-humidity test, the adhesive strength of the bonded structure B was measured and evaluated under the same conditions as the bonded structure A described above.

The measurement results of connection resistance and adhesive strength of the connection structures A and B measured as above are shown in Table 2 below.

Table 2

(storage stability test)

Add the adhesives for circuit connection of Examples 1 to 2, 7 and Comparative Examples 1 to 2 into a gas barrier container (manufactured by Asahi Kasei PAX Co., Ltd., trade name: Polyflexbag (ポリフレッックスバッグ), model: N- 9. Material: nylon·thickness 15μm/PE·thickness 60μm, size: 200mm×300mm), after removing the air in the gas-barrier container, seal it with a heat sealer, and then place it at 40°C for 48 hours. By storing in the above-mentioned environment, it is equivalent to storing in a -10°C environment for 5 months. Thereafter, each of the circuit connection adhesives of Examples 1 to 2 and 7 and Comparative Examples 1 to 2 was interposed between the same FPC as above and the glass on which the thin layer of ITO was formed, and between the FPC and the glass on which the Ag paste was formed. between thin layers of PET substrates. This was subjected to thermocompression bonding under the same method and conditions as in the measurement of the above-mentioned connection resistance and adhesive strength to produce a bonded structure. The connection resistance and adhesive strength of this bonded structure were measured by the same method as above.

The measurement results of connection resistance and adhesive strength of the connection structure measured as above are shown in Table 3 below.

table 3

In addition, for the connection structure using the adhesive for circuit connection obtained in Examples 3-6, 8, the same test as Examples 1-2, 7 was also performed, and the result was the same as that of Examples 1-2, 7. , Good low temperature curing and storage stability.

The connection structure A of FPC/ITO using the adhesive for circuit connection obtained in Examples 1 to 8, regardless of whether the storage stability test is performed, immediately after connection at a heating temperature of 120°C, and at 85°C and 85%RH After being kept in a constant temperature and humidity chamber for 240 hours (after a high temperature and high humidity test), a good connection resistance of about 4.0Ω or less and a good adhesive strength of 580N/m or more were exhibited. In addition, in the FPC/Ag bonded structure B, immediately after bonding at a heating temperature of 120°C, and after holding in a constant temperature and humidity chamber at 85°C and 85%RH for 240 hours (after a high-temperature and high-humidity test), it also exhibited Good connection resistance below about 1.6Ω, and good bonding strength above 590N/m. It was confirmed that the adhesives for circuit connection obtained in Examples 1 to 8 were excellent in low-temperature curability and storage stability.

On the other hand, the bonded structures using the circuit-connecting adhesives obtained in Comparative Examples 1 and 2 had good connection properties when using the circuit-connecting adhesives before the storage stability test, but the circuit Since the connection adhesive does not contain (d) boron-containing salt, when using the circuit connection adhesive after the storage stability test, it can be confirmed that after 240 hours in a constant temperature and humidity chamber (after the high temperature and high humidity test ) of the connection resistance increases. In addition, in the bonded structures using the circuit connection adhesives obtained in Comparative Examples 3 to 4, since the circuit connection adhesives did not contain (d) boron-containing salts, even in the case where the storage stability test was not performed, In some cases, it can also be confirmed that the connection resistance increases after being kept in a constant temperature and humidity chamber for 240 hours (after a high temperature and high humidity test).

Claims (85)

1. an adhesive composite, it contains (a) thermoplastic resin, (b) free-radical polymerised compound, (c) radical polymerization Close initiator and the salt of (d) boracic,

Wherein, the salt of described (d) boracic is the compound shown in following formula (A),

In formula (A), R¹、R²、R³And R⁴Represent hydrogen atom, the alkyl of carbon number 1～18 or aryl, X independently of one another⁺Represent Comprise the cation of quaternary nitrogen atoms.

Adhesive composite the most according to claim 1, wherein, described cation X⁺Comprise quaternary phosphonium atom further.

Adhesive composite the most according to claim 1, wherein, the salt of described (d) boracic comprises from by ammonium ion, imidazoles Ion and imidazoline select in molecular group at least one as the described cation comprising quaternary nitrogen atoms.

Adhesive composite the most according to claim 2, wherein, the salt of described (d) boracic comprises from by ammonium ion, imidazoles Ion and imidazoline select in molecular group at least one as the described cation comprising quaternary nitrogen atoms.

Adhesive composite the most according to claim 1, wherein, as the salt of described (d) boracic, containing following formula (A2) compound shown in,

In formula (A2), R¹、R²、R³And R⁴Represent hydrogen atom, the alkyl of carbon number 1～18 or aryl, R independently of one another^5b、 R^6b、R^7b、R^8bAnd R^9bRepresent hydrogen atom, halogen atom, alkyl, aryl or alkoxyl, R independently of one another^8bAnd R^9bCan be mutual In conjunction with and form ring.

Adhesive composite the most according to claim 2, wherein, as the salt of described (d) boracic, containing following formula (A2) compound shown in,

In formula (A2), R¹、R²、R³And R⁴Represent hydrogen atom, the alkyl of carbon number 1～18 or aryl, R independently of one another^5b、 R^6b、R^7b、R^8bAnd R^9bRepresent hydrogen atom, halogen atom, alkyl, aryl or alkoxyl, R independently of one another^8bAnd R^9bCan be mutual In conjunction with and form ring.

7. according to the adhesive composite according to any one of claim 1～6, wherein, the salt of described (d) boracic comprise from by Tetraalkyl borate, four aromatic yl acid salts, trialkyl aromatic yl acid salt, dialkyl group diarylborinic acid salt and alkyl triaryl boric acid At least one selected in the group of salt composition is as borate compound.

8. according to the adhesive composite according to any one of claim 1～6, wherein, the salt of described (d) boracic comprises and has The borate of aryl is as borate compound.

9. according to the adhesive composite according to any one of claim 1～6, wherein, the salt of described (d) boracic comprises four virtues Ylboronic acid salt is as borate compound.

10. according to the adhesive composite according to any one of claim 1～6, wherein, the fusing point of the salt of described (d) boracic It it is more than 60 DEG C less than 300 DEG C.

11. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of the salt of described (d) boracic is more than 0.1 mass %.

12. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of the salt of described (d) boracic is more than 0.5 mass %.

13. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of the salt of described (d) boracic is below 20 mass %.

14. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of the salt of described (d) boracic is below 15 mass %.

15. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of the salt of described (d) boracic is below 10 mass %.

16. according to the adhesive composite according to any one of claim 1～6, wherein, described (b) free-radical polymerisedization Compound comprises the free-radical polymerised compound having beyond the vinyl compound of phosphate and this vinyl compound.

17. adhesive composites according to claim 16, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, described in there is phosphate the use level of vinyl compound be more than 0.2 mass %.

18. adhesive composites according to claim 16, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, described in there is phosphate the use level of vinyl compound be more than 0.3 mass %.

19. adhesive composites according to claim 16, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, described in there is phosphate the use level of vinyl compound be more than 0.5 mass %.

20. adhesive composites according to claim 16, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, described in there is phosphate the use level of vinyl compound be below 15 mass %.

21. adhesive composites according to claim 16, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, described in there is phosphate the use level of vinyl compound be below 10 mass %.

22. adhesive composites according to claim 16, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, described in there is phosphate the use level of vinyl compound be below 5 mass %.

23. according to the adhesive composite according to any one of claim 1～6, wherein, described (b) free-radical polymerisedization Compound comprises from by N-vinyl compound and N, the N-ethylene base system selected in the group of N-dialkyl group vinyl compound composition Free-radical polymerised compound beyond compound and this N-vinyl compound.

24. adhesive composites according to claim 23, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, the use level of described N-vinyl compound is more than 0.2 mass %.

25. adhesive composites according to claim 23, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, the use level of described N-vinyl compound is more than 0.3 mass %.

26. adhesive composites according to claim 23, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, the use level of described N-vinyl compound is more than 0.5 mass %.

27. adhesive composites according to claim 23, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, the use level of described N-vinyl compound is below 15 mass %.

28. adhesive composites according to claim 23, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, the use level of described N-vinyl compound is below 10 mass %.

29. adhesive composites according to claim 23, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, the use level of described N-vinyl compound is below 5 mass %.

30. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, except meeting the vinyl compound with phosphate or N-ethylene base system The use level of described (b) free-radical polymerised compound beyond the compound of compound is more than 5 mass %.

31. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, except meeting the vinyl compound with phosphate or N-ethylene base system The use level of described (b) free-radical polymerised compound beyond the compound of compound is more than 10 mass %.

32. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, except meeting the vinyl compound with phosphate or N-ethylene base system The use level of described (b) free-radical polymerised compound beyond the compound of compound is more than 15 mass %.

33. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, except meeting the vinyl compound with phosphate or N-ethylene base system The use level of described (b) free-radical polymerised compound beyond the compound of compound is below 95 mass %.

34. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, except meeting the vinyl compound with phosphate or N-ethylene base system The use level of described (b) free-radical polymerised compound beyond the compound of compound is below 80 mass %.

35. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, except meeting the vinyl compound with phosphate or N-ethylene base system The use level of described (b) free-radical polymerised compound beyond the compound of compound is below 70 mass %.

36. according to the adhesive composite according to any one of claim 1～6, wherein, as described (b) radical polymerization Property compound, containing urethane acrylate.

37. adhesive composites according to claim 36, wherein, as described urethane acrylate, containing following Urethane acrylate shown in formula (N),

In formula (N), R²³And R²⁴Represent hydrogen atom or methyl, R independently of one another²⁵Represent ethylidene or propylidene, R²⁶Represent saturated Fatty group or saturated fat cyclic group, R²⁷Represent the representative examples of saturated aliphatic base containing ester group or saturated fat cyclic group or containing carbon The representative examples of saturated aliphatic base of perester radical or saturated fat cyclic group, k represents the integer of 1～40, here, in formula (N), R²⁵Each other, R²⁶That This can be the most identical or different.

38. adhesive composites according to claim 36, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, the use level of described urethane acrylate is more than 5 mass %.

39. adhesive composites according to claim 36, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, the use level of described urethane acrylate is more than 10 mass %.

40. adhesive composites according to claim 36, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, the use level of described urethane acrylate is more than 15 mass %.

41. adhesive composites according to claim 36, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, the use level of described urethane acrylate is below 95 mass %.

42. adhesive composites according to claim 36, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, the use level of described urethane acrylate is below 80 mass %.

43. adhesive composites according to claim 36, wherein, to eliminate electroconductive particle in adhesive composite Composition all-mass on the basis of, the use level of described urethane acrylate is below 70 mass %.

44. according to the adhesive composite according to any one of claim 1～6, wherein, as described (c) radical polymerization Initiator, is 90～175 DEG C and organic peroxide that weight average molecular weight is 180～1000 containing 1 minute half life temperature.

45. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of described (c) radical polymerization initiator be 0.5 mass % with On.

46. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of described (c) radical polymerization initiator be 1 mass % with On.

47. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of described (c) radical polymerization initiator be 2 mass % with On.

48. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of described (c) radical polymerization initiator be 40 mass % with Under.

49. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of described (c) radical polymerization initiator be 30 mass % with Under.

50. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of described (c) radical polymerization initiator be 20 mass % with Under.

51. according to the adhesive composite according to any one of claim 1～6, and wherein, described (a) thermoplastic resin comprises From by phenoxy resin, polyurethane resin, butyral resin, acrylic resin, polyimide resin and polyamide and tool At least one selected in the group being made up of as the copolymer of construction unit vinylacetate.

52. according to the adhesive composite according to any one of claim 1～6, and wherein, described (a) thermoplastic resin comprises Polyester urethane resin.

53. according to the adhesive composite according to any one of claim 1～6, wherein, the weight of described (a) thermoplastic resin Average molecular weight is more than 5000.

54. according to the adhesive composite according to any one of claim 1～6, wherein, the weight of described (a) thermoplastic resin Average molecular weight is more than 7000.

55. according to the adhesive composite according to any one of claim 1～6, wherein, the weight of described (a) thermoplastic resin Average molecular weight is more than 10000.

56. according to the adhesive composite according to any one of claim 1～6, wherein, the weight of described (a) thermoplastic resin Average molecular weight is less than 150000.

57. according to the adhesive composite according to any one of claim 1～6, wherein, the weight of described (a) thermoplastic resin Average molecular weight is less than 100000.

58. according to the adhesive composite according to any one of claim 1～6, wherein, the weight of described (a) thermoplastic resin Average molecular weight is less than 80000.

59. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of described (a) thermoplastic resin is more than 5 mass %.

60. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of described (a) thermoplastic resin is more than 15 mass %.

61. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of described (a) thermoplastic resin is below 80 mass %.

62. according to the adhesive composite according to any one of claim 1～6, wherein, to eliminate in adhesive composite On the basis of the all-mass of the composition of electroconductive particle, the use level of described (a) thermoplastic resin is below 70 mass %.

63. according to the adhesive composite according to any one of claim 1～6, wherein, contains (e) electric conductivity grain further Son.

64. adhesive composites according to claim 63, wherein, to eliminate electroconductive particle in adhesive composite Composition whole volumes on the basis of, the use level of described (e) electroconductive particle is 0.1 more than volume %.

65. adhesive composites according to claim 63, wherein, to eliminate electroconductive particle in adhesive composite Composition whole volumes on the basis of, the use level of described (e) electroconductive particle is 0.2 more than volume %.

66. adhesive composites according to claim 63, wherein, to eliminate electroconductive particle in adhesive composite Composition whole volumes on the basis of, the use level of described (e) electroconductive particle is 30 below volume %.

67. adhesive composites according to claim 63, wherein, to eliminate electroconductive particle in adhesive composite Composition whole volumes on the basis of, the use level of described (e) electroconductive particle is 10 below volume %.

68. according to the adhesive composite according to any one of claim 1～6, and it is for making to be configured at the master of first substrate The first connection terminal on face is connected terminal with second on the interarea being configured at second substrate and is electrically connected.

69. according to the adhesive composite according to any one of claim 1～6, and it is for making have the master being configured at substrate This connection terminal of the solar battery cell connecting terminal on face is electrically connected with distribution component.

70. according to the adhesive composite according to any one of claim 1～6, and it becomes the connecting portion in connection structural bodies Part, described connection structural bodies possesses: have first substrate and the first connection terminal being configured on the interarea of this first substrate First circuit block, have second substrate and be configured on the interarea of this second substrate second connection terminal second circuit portion Part and be configured at the described connection member between described first circuit block and described second circuit parts, described first even Connecting terminal and described second connects terminal and is electrically connected.

71. according to the adhesive composite according to any one of claim 1～6, and it becomes the connecting portion in connection structural bodies Part, described connection structural bodies possesses: have substrate and the solaode list connecting terminal being configured on the interarea of this substrate Unit, distribution component and the described connection member being configured between described solar battery cell and described distribution component, described Connect terminal and described distribution component is electrically connected.

72. 1 kinds of film-like adhesives, it comprises the adhesive composite according to any one of claim 1～67.

73. 1 kinds of adhesive sheets, it possesses the film-like adhesive described in base material and claim 72, wherein, described membranaceous bonding Agent is configured on described base material.

74. 1 kinds of anisotropic conductive film, it comprises the adhesive composite according to any one of claim 1～67.

75. 1 kinds of connection structural bodies, it possesses: have first substrate and the first connection being configured on the interarea of this first substrate First circuit block of terminal, there is second substrate and be configured on the interarea of this second substrate the second of the second connection terminal Circuit block and be configured at the connection member between described first circuit block and described second circuit parts,

Described connection member contains the solidfied material of the adhesive composite according to any one of claim 1～67,

Described first connection terminal and described second connects terminal and is electrically connected.

76. according to the connection structural bodies described in claim 75, wherein, in described first substrate and described second substrate at least One side is made up of the base material comprising the thermoplastic resin that glass transition temperature is less than 200 DEG C.

77. according to the connection structural bodies described in claim 75, wherein, in described first substrate and described second substrate at least One side is by comprising from by polyethylene terephthalate, Merlon, PEN and cyclic olefin polymer The base material of at least one selected in the group of composition is constituted.

78. according to the connection structural bodies described in claim 75, and wherein, described first substrate is by comprising from by poly terephthalic acid At least one selected in the group of glycol ester, Merlon, PEN and cyclic olefin polymer composition Base material is constituted, and described second substrate is by comprising choosing from the group being made up of polyimide resin and polyethylene terephthalate The base material of at least one gone out is constituted.

79. 1 kinds of connection structural bodies, it possesses: have substrate and the solar energy connecting terminal being configured on the interarea of this substrate Battery unit, distribution component and be configured at the connection member between described solar battery cell and described distribution component,

Described connection member contains the solidfied material of the adhesive composite according to any one of claim 1～67,

Described connection terminal and described distribution component are electrically connected.

The manufacture method of 80. connection structural bodies, the method combines by making the bonding agent according to any one of claim 1～67 Thing between have first substrate and be configured on the interarea of this first substrate first connection terminal the first circuit block and tool Have second substrate and be configured on the interarea of this second substrate second connection terminal second circuit parts between, such Make described adhesive composite solidify under state, thus make described first to connect terminal and described second connection terminal electrical connection State under bonding described first circuit block and described second circuit parts.

The manufacture method of 81. connection structural bodies, the method combines by making the bonding agent according to any one of claim 1～67 Thing between have substrate and be configured on the interarea of this substrate connect terminal solar battery cell and distribution component between, Make described adhesive composite solidify in such a state, thus make described connection terminal and the electrical connection of described distribution component State under bonding described solar battery cell and described distribution component.

Adhesive composite according to any one of 82. claim 1～67 is for making to be configured at the interarea of first substrate First connection terminal be connected the application during terminal is electrically connected with second on the interarea being configured at second substrate.

Adhesive composite according to any one of 83. claim 1～67 makes to be configured at the master of first substrate for manufacture The first connection terminal on face is connected, with second on the interarea being configured at second substrate, the connection member that terminal is electrically connected In application.

Adhesive composite according to any one of 84. claim 1～67 is being configured at the interarea of substrate for making to have This connection terminal and the distribution component of the solar battery cell connecting terminal be electrically connected in application.

Adhesive composite according to any one of 85. claim 1～67 is being configured at the master of substrate for manufacturing to make to have In the connection member that this connection terminal of the solar battery cell connecting terminal on face and distribution component are electrically connected Application.