TWI705117B - Adhesive composition and connection structure - Google Patents

Abstract

式（A）中，R¹ 、R² 及R³ 分別獨立地表示氫原子、碳數1～18的烷基或芳基，R⁴ 、R⁵ 及R⁶ 分別獨立地表示氫原子或特定的有機基。An adhesive composition comprising (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a radical polymerization initiator, and (d) a complex compound containing boron, and (d) containing boron The complex compound is a compound represented by the following general formula (A).

In formula (A), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbons or an aryl group, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or specific Organic base.

Description

Adhesive composition and connection structure

The present invention relates to an adhesive composition and a connecting structure.

In semiconductor elements and liquid crystal display elements, various adhesives have been used to combine various components in the element. The requirements for adhesives involve various aspects such as adhesiveness, heat resistance, and reliability in high temperature and high humidity conditions. The adhesive is used for the connection of liquid crystal display elements and Tape Carrier Package (TCP) (or Chip On Film (COF)), flexible printed circuit (FPC) and TCP (Or COF) connection, TCP (or COF) connection with printed wiring board, FPC and printed wiring board, etc. In addition, the adhesive is also used when mounting a semiconductor element on a substrate.

As a substrate for bonding, a printed wiring board, or polyimide resin, polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate can be used Organic substrates such as polyethylene naphthalate (PEN), metals such as copper and aluminum, or Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO) ), zinc and aluminum composite oxide (Aluminum Zinc Oxide, AZO), silicon nitride (SiN), silicon dioxide (SiO ₂ ) and other substrates with various surface conditions. Therefore, it is necessary to coordinate the molecular design of the adhesive composition of each adherend.

Recently, with the increase in the integration of semiconductor elements and the high definition of liquid crystal display elements, the pitch between elements and the pitch between wirings are becoming narrower. In addition, semiconductor elements, liquid crystal display elements, or touch panels using organic substrates with low heat resistance such as PET, PC, and PEN have begun to be used. If the heating temperature during curing of the adhesive composition applied to such semiconductor elements is high and the curing speed is slow, not only the desired connection part is overheated, but also the peripheral components are overheated to become peripheral components. The tendency of factors such as damage. Therefore, bonding by low-temperature curing is required for the adhesive composition.

Heretofore, as the adhesive for the semiconductor element or the liquid crystal display element, a thermosetting resin using an epoxy resin that exhibits high adhesiveness and high reliability has been used (for example, refer to Patent Document 1 below). As the constituent components of the resin, an epoxy resin, a curing agent (phenol resin, etc.) reactive with the epoxy resin, a thermal latent catalyst that promotes the reaction between the epoxy resin and the curing agent, and the like are generally used. Thermal latent catalyst is a substance that does not react at storage temperatures such as room temperature, and shows high reactivity when heated, and becomes an important factor in determining the curing temperature and curing speed. Self-adhesive storage at room temperature Various compounds are used from the viewpoint of stability and hardening speed during heating. In the actual process, the desired bonding is obtained by curing at a temperature of 170°C to 250°C for 1 hour to 3 hours. However, in order to harden the adhesive at low temperature, it is necessary to use a thermally latent catalyst with low activation energy, but it is very difficult to have storage stability at the same time.

In recent years, radical-curing adhesives that use radically polymerizable compounds such as acrylate derivatives and methacrylate derivatives in combination with peroxides as a radical polymerization initiator have attracted attention. Radical curing can be cured in a short time because radicals, which are reactive species, are highly reactive (for example, refer to Patent Document 2 below). Among such radical-curing adhesives, a method in which benzoyl peroxide (BPO), amine compounds, organoboron compounds, etc. are used in combination as a radical polymerization initiator has been proposed (for example, refer to the following patent Literature 3). Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 1-113480 Patent Document 2: International Publication No. 98/44067 Patent Document 3: Japanese Patent Laid-Open No. 2000-290121

[Problem to be solved by the invention] In order to make the free radical-curing adhesives harden at low temperature, a radical polymerization initiator must be used. However, the conventional free-radical-curing adhesives have both low-temperature curing properties and storage Stability is very difficult. For example, when the aforementioned benzoyl peroxide (BPO), amine-based compound, organoboron compound, etc. are used as a radical polymerization initiator for radically polymerizable compounds such as acrylate derivatives or methacrylate derivatives, The hardening reaction also progresses at room temperature (25°C, the same below), so the storage stability may decrease.

Therefore, the object of the present invention is to provide an adhesive composition having excellent low-temperature curability and storage stability. In addition, an object of the present invention is to provide a connection structure using such an adhesive composition. [Means to solve the problem]

The inventors of the present invention have studied diligently to solve the above-mentioned problems, and found that by using a specific complex containing boron as a constituent of the adhesive composition, excellent low-temperature curability and storage stability can be obtained. Thus completed the present invention.

[式（A）中，R¹ 、R² 及R³ 分別獨立地表示氫原子、碳數1～18的烷基或芳基，R⁴ 、R⁵ 及R⁶ 分別獨立地表示氫原子、碳數1～18的烷基、由下述通式（a1）所表示的有機基、或由下述通式（a2）所表示的有機基] [化2]

[式（a1）中，R^7a 表示氫原子或碳數1～6的烷基，R^7b 表示氫原子、胺基、烷氧基或碳數1～10的烷基。另外，s及t分別獨立地表示1～10的整數] [化3]

[式（a2）中，R⁸ 表示碳數1～10的烷基。另外，u表示1～10的整數]That is, the adhesive composition of the present invention includes (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a radical polymerization initiator, and (d) a boron-containing complex, and (d) The boron-containing complex is a compound represented by the following general formula (A). [化1]

[In formula (A), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbons or an aryl group, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, carbon An alkyl group of 1 to 18, an organic group represented by the following general formula (a1), or an organic group represented by the following general formula (a2)] [Chemical 2]

[In the formula (a1), R ^7a represents a hydrogen atom or an alkyl group having 1 to 6 carbons, and R ^7b represents a hydrogen atom, an amino group, an alkoxy group, or an alkyl group having 1 to 10 carbons. In addition, s and t each independently represent an integer of 1 to 10] [化3]

[In the formula (a2), R ⁸ represents an alkyl group having 1 to 10 carbon atoms. In addition, u represents an integer of 1-10]

In the present invention, since the adhesive composition includes (d) a complex containing boron, the decomposition of the (c) radical polymerization initiator at low temperatures (for example, 80°C to 120°C) can be promoted, so the adhesive The composition has excellent low-temperature curability. In addition, in the present invention, since the (d) boron-containing complex is a compound represented by the general formula (A), the storage stability of the adhesive composition (for example, near room temperature (for example, -20 ℃～25℃) excellent storage stability), even in the case of long-term storage of the adhesive composition, excellent adhesive strength and connection resistance can be obtained (for example, the connection structure of circuit members or the solar cell module Then strength and connection 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, regardless of whether the adhesive composition is stored for a long period of time, excellent adhesive strength and connection resistance can be obtained. In addition, in the present invention, regardless of whether the adhesive composition is stored for a long period of time, stable performance (adhesion strength and connection resistance) can be maintained after a long-term reliability test (high temperature and high humidity test).

In addition, in the adhesive composition of the present invention, the (b) radical polymerizable compound may include a vinyl compound having a phosphoric acid group and a radical polymerizable compound other than the vinyl compound. In this case, bonding by low-temperature hardening becomes easy, and the bonding strength with the substrate with the connection terminal can be further improved.

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

In addition, the adhesive composition of the present invention may further contain (e) conductive particles. In this case, good conductivity or anisotropic conductivity can be imparted to the adhesive composition, and therefore, it can be more suitably used for bonding applications of circuit members having connection terminals, solar cell modules, and the like. In addition, the connection resistance of the connection structure obtained by electrical connection via the adhesive composition can be more sufficiently reduced.

In addition, the inventors of the present invention found that the adhesive composition is useful for the connection of members having connection terminals. The adhesive composition of the present invention can be used to electrically connect the first connection terminal disposed on the main surface of the first substrate and the second connection terminal disposed on the main surface of the second substrate, or it can be used to The connection terminal of the solar battery cell of the connection terminal on the main surface of the substrate is electrically connected to the wiring member.

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

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

In one aspect of the connection structure of the present invention, at least one of the first substrate and the second substrate may include a material selected from polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. At least one substrate in the group. In this case, even in the case of using the first circuit member or the second circuit member having a substrate containing the specific material (material with low heat resistance), the adhesive of the present invention can be used The composition achieves low-temperature curing, and therefore can reduce thermal damage to the first circuit member or the second circuit member. In addition, the wettability of the substrate and the adhesive composition containing the specific material is improved, and the bonding strength can be improved in one step. Thereby, when a substrate containing the specific material is used, excellent connection reliability can be obtained.

The connection structure of one aspect of the present invention may be in the following aspect: the first substrate contains at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate A substrate, and the second substrate includes a substrate containing at least one selected from the group consisting of polyimide resin and polyethylene terephthalate. In this case, even when the first circuit member or the second circuit member having a substrate containing the specific material is used, low-temperature curing can be achieved by using the adhesive composition of the present invention. Therefore, the thermal damage to the first circuit member or the second circuit member can be reduced. In addition, the wettability of the substrate and the adhesive composition containing the specific material is improved, and the bonding strength can be improved in one step. Thereby, when a substrate containing the specific material is used, excellent connection reliability can be obtained.

A connection structure according to another aspect of the present invention includes: a solar battery unit having a substrate and connection terminals arranged on the main surface of the substrate; a wiring member; and a connection member arranged between the solar battery unit and the wiring member; and connection The member contains a cured product of the adhesive composition, and the connection terminal is electrically connected to the wiring member. In the connection structure of another aspect of the present invention, the connection member contains the cured product of the adhesive composition, so that the connection resistance and the bonding strength in the connection structure can be improved. [Effects of the invention]

According to the present invention, an adhesive composition having excellent low-temperature curability and storage stability can be provided. Such an adhesive composition can improve storage stability compared with the case of using an alkyl boron compound described in Patent Document 3. In addition, the adhesive composition of the present invention has an excellent balance between low-temperature curability and storage stability. Since the adhesive composition of the present invention has excellent 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 of the present invention, regardless of whether the adhesive composition is stored for a long time, excellent adhesive strength and connection resistance can be obtained. In addition, in the adhesive composition of the present invention, regardless of whether the adhesive composition is stored for a long time, stable performance (adhesion strength and connection resistance) can be maintained after a long-term reliability test (high temperature and high humidity test). The present invention can provide a connection structure using such an adhesive composition.

Hereinafter, a suitable embodiment of the present invention will be described in detail. Furthermore, in this specification, "(meth)acrylic acid" refers to acrylic acid and its corresponding methacrylic acid, and "(meth)acrylate" refers to acrylic acid ester and its corresponding methacrylic acid. Acrylate, the so-called "(meth)acrylic resin", refers to acrylic resin and its corresponding methacrylic resin, and the so-called "(meth)acryloyl" refers to acrylic resin and its corresponding methyl The acryloyl group, the so-called "(meth)acryloyloxy group", refers to the acryloyloxy group and the corresponding methacryloyloxy group.

In addition, in this specification, the "weight average molecular weight" refers to using a calibration curve using standard polystyrene under the conditions shown below, and using a gel permeation chromatography (Gel Permeation Chromatograph, GPC) The measured value. (Measurement conditions) Device: GPC-8020 manufactured by Tosoh Co., Ltd. Detector: RI-8020 manufactured by Tosoh Co., Ltd. Column: Gelpack GL-A-160- manufactured by Hitachi Chemical Co., Ltd. S+GL-A150 Sample concentration: 120 mg/3 ml solvent: tetrahydrofuran injection volume: 60 μl pressure: 30 kgf/cm ² flow rate: 1.00 ml/min

<Adhesive composition> The adhesive composition of this embodiment includes (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a radical polymerization initiator, and (d) a complex containing boron Things.

((A) Thermoplastic resin) (a) Thermoplastic resin refers to a resin (polymer) that has the following properties: it becomes a liquid state with high viscosity by heating and is freely deformed by external force. If it is cooled and the external force is removed , It becomes hard while maintaining its shape, and the process can be repeated. In addition, (a) the thermoplastic resin may be a resin (polymer) containing a reactive functional group having the above-mentioned properties. (A) The glass transition temperature (Tg) of the thermoplastic resin is preferably -30°C or higher, more preferably -25°C or higher, and still more preferably -20°C or higher. (A) The glass transition temperature (Tg) of the thermoplastic resin is preferably 190°C or lower, more preferably 170°C or lower, still more preferably 150°C or lower, particularly preferably 130°C or lower, and extremely preferably 110°C or lower.

(A) The thermoplastic resin may include, for example, a phenoxy resin, a polyurethane resin, a polyester urethane resin, a butyral resin (for example, a polyvinyl butyral resin), and a (meth)acrylic resin. , At least one of the group consisting of polyimide resins, polyimide resins, and copolymers having structural units derived from vinyl acetate (vinyl acetate copolymers, such as ethylene-vinyl acetate copolymers) . These thermoplastic resins can be used alone or in combination of two or more. Furthermore, these (a) thermoplastic resins may contain siloxane bonds or fluorine substituents. These thermoplastic resins are preferably in a state where the mixed resins are completely compatible with each other, or in a state where the mixed resins are microphase separated and become cloudy.

When the adhesive composition is used in the form of a film, (a) the larger the weight average molecular weight of the thermoplastic resin, the easier it is to obtain a good film formability. In addition, the composition of the film adhesive can be set in a wide range. The melt viscosity of the fluidity of the material. (A) The weight average molecular weight of the thermoplastic resin is preferably 5,000 or more, more preferably 7,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, and extremely preferably 25,000 or more. If (a) the weight average molecular weight of the thermoplastic resin is 5000 or more, there is a tendency that good film formability is easily obtained. (A) The weight average molecular weight of the thermoplastic resin is preferably 150,000 or less, more preferably 100,000 or less, still more preferably 80,000 or less, particularly preferably 70,000 or less, and extremely preferably 65,000 or less. If (a) the weight average molecular weight of the thermoplastic resin is 150,000 or less, there is a tendency that good compatibility with other components is easily obtained.

Based on the total mass of the adhesive components (components other than the conductive particles in the adhesive composition), the blending amount of (a) the thermoplastic resin in the adhesive composition is preferably 5% by mass or more, more preferably 15% by mass or more, more preferably 25% by mass or more, particularly preferably 35% by mass or more. If the blending amount of (a) the thermoplastic resin is 5% by mass or more, when the adhesive composition is used in a film form, there is a tendency that particularly good film formability is easily obtained. Based on the total mass of the adhesive components (components other than the conductive particles in the adhesive composition), (a) the blending amount of the thermoplastic resin is preferably 80% by mass or less, more preferably 70% by mass or less, and further It is more preferably 60% by mass or less, and particularly preferably 50% by mass or less. (A) If the blending amount of the thermoplastic resin is 80% by mass or less, there is a tendency that good fluidity of the adhesive composition is easily obtained.

((B) Radical polymerizable compound) (b) The radical polymerizable compound refers to a compound that undergoes radical polymerization by the action of a radical polymerization initiator. (B) The radically polymerizable compound may be a compound that itself generates free radicals by imparting activation energy such as light or heat. As the (b) radical polymerizable compound, for example, a functional group (vinyl group, (meth)acryloyl group, allyl group, maleimide) capable of polymerization by living radicals can be suitably used. Base, etc.).

(B) The radically polymerizable compound specifically includes epoxy (meth)acrylate oligomer, (meth)acrylate urethane oligomer, and polyether (meth)acrylic acid Oligomers such as ester oligomers and polyester (meth)acrylate oligomers; trimethylolpropane tri(meth)acrylate; polyethylene glycol di(meth)acrylate; polyalkylene Glycol di(meth)acrylate; Dicyclopentenyl (meth)acrylate; Dicyclopentenoxyethyl (meth)acrylate; Neopentyl glycol di(meth)acrylate; Dipentaerythritol hexa (Meth)acrylate; Isocyanuric acid modified difunctional (meth)acrylate; Isocyanuric acid modified trifunctional (meth)acrylate; Bisphenoxyethanol (meth)acrylic acid Ester; epoxy (meth)acrylate formed by addition of (meth)acrylic acid to the glycidyl group of bisphenol pyridyl diglycidyl ether; addition to the glycidyl group of bisphenol pyridyl diglycidyl ether A compound in which a (meth)acryloxy group is introduced into a compound made of ethylene glycol or propylene glycol; a compound represented by the following general formula (B) or general formula (C), and the like.

[式（B）中，R⁹ 及R¹⁰ 分別獨立地表示氫原子或甲基，a及b分別獨立地表示1～8的整數][化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]

[式（C）中，R¹¹ 及R¹² 分別獨立地表示氫原子或甲基，c及d分別獨立地表示0～8的整數][化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 the (b) radically polymerizable compound, even if it is waxy, crystalline, glassy, powdery, etc. when left alone at 30°C, it has no fluidity and shows a solid state. It can be used without particular restrictions. Specific examples of such (b) radically polymerizable compounds include N,N'-methylenebisacrylamide, diacetone acrylamide (alias: diacetone acrylamide), and N-hydroxyl Methacrylamide, N-phenylmethacrylamide, 2-acrylamide-2-methylpropanesulfonic acid, tris(2-acryloxyethyl) isocyanurate, N-benzene N-maleimide, N-(o-methylphenyl)maleimide, N-(m-methylphenyl)maleimide, N-(p-methylbenzene) Group) maleimide, N-(o-methoxyphenyl) maleimide, N-(m-methoxyphenyl) maleimide, N-(p-methoxyphenyl) maleimide Methoxyphenyl) maleimide, N-methyl maleimide, N-ethyl maleimide, N-octyl maleimide, 4, 4'-Diphenylmethane bismaleimide, meta-phenyl bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4 '-Diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, N-methacryloxy maleimide Amine, N-acryloyloxy maleimide, 1,6-bis-maleimide-(2,2,4-trimethyl)hexane, N-methacryloyloxy Divinyl succinimide, N-propylene oxy succinimide, 2-naphthyl methacrylate, 2-naphthyl acrylate, pentaerythritol tetraacrylate, divinyl ethylene urea, divinyl propylene urea, 2-polystyrylethyl methacrylate, N-phenyl-N'-(3-methacryloxy-2-hydroxypropyl)-p-phenylenediamine, N-phenyl-N'- (3-propenyloxy-2-hydroxypropyl)-p-phenylenediamine, tetramethylpiperidine methacrylate, tetramethylpiperidine acrylate, pentamethylpiperidine methacrylate, five acrylate Methyl piperidinate, stearyl acrylate, N-tert-butylacrylamide, N-(hydroxymethyl)acrylamide, compounds represented by the following formula (D) to formula (M), and the like.

[式（D）中，e表示1～10的整數][化6]

[In formula (D), e represents an integer of 1-10]

[化7]

[式（F）中，R¹³ 及R¹⁴ 分別獨立地表示氫原子或甲基，f表示15～30的整數][化8]

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

[式（G）中，R¹⁵ 及R¹⁶ 分別獨立地表示氫原子或甲基，g表示15～30的整數][化9]

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

[式（H）中，R¹⁷ 表示氫原子或甲基][化10]

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

[式（I）中，R¹⁸ 表示氫原子或甲基，h表示1～10的整數][化11]

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

[式（J）中，R¹⁹ 表示氫原子、或由下述式（i）或式（ii）所表示的有機基，i表示1～10的整數][化12]

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

[化14]

[化13]

[化14]

[式（K）中，R²⁰ 表示氫原子、或由下述式（iii）或（iv）所表示的有機基，j表示1～10的整數][化15]

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

[化17]

[化16]

[化17]

[式（L）中，R²¹ 表示氫原子或甲基][化18]

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

[式（M）中，R²² 表示氫原子或甲基][化19]

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

In addition, as the (b) radical polymerizable compound, (meth)acrylate urethane can be used. The (meth)acrylate urethane may be used alone or in combination with (b) radical polymerizable compounds other than (meth)acrylate urethane. By using (meth) urethane acrylate alone or in combination with (b) radical polymerizable compounds other than (meth) urethane acrylate, flexibility is improved and can be further improved Then intensity.

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

[式（N）中，R²³ 及R²⁴ 分別獨立地表示氫原子或甲基，R²⁵ 表示伸乙基或伸丙基，R²⁶ 表示飽和脂肪族基或飽和脂環式基，R²⁷ 表示含有酯基的飽和脂肪族基或飽和脂環式基、或者含有碳酸酯基的飽和脂肪族基或飽和脂環式基，k表示1～40的整數。再者，式（N）中，R²⁵ 彼此、R²⁶ 彼此分別可相同，亦可不同][化20]

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

The aliphatic diisocyanate or alicyclic diisocyanate constituting the (meth)acrylate urethane 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 xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated trimethyl Xylylene diisocyanate, etc.

In addition, the aliphatic ester-based diol or alicyclic ester-based diol constituting the (meth)acrylate urethane may be selected from ethylene glycol, propylene glycol (alias: 1,2-propylene glycol), 1, 3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2 ,4-pentanediol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2,2,4-trimethyl-1,3- Pentylene glycol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2 ,5-Dimethyl-2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,7-heptanediol, 1,9-nonanediol, 1,2 -Decanediol, 1,10-decanediol, dodecanediol (1,12-dodecanediol, etc.), pinacol, 1,4-butynediol, triethylene glycol, two Saturated or unsaturated low-molecular-weight glycols such as ethylene glycol, dipropylene glycol, cyclohexane dimethanol, 1,4-cyclohexane dimethanol, etc.; make adipic acid, 3-methyl adipic acid, 2,2 ,5,5-Tetramethyladipic acid, maleic acid, fumaric acid, succinic acid, 2,2-dimethylsuccinic acid, 2-ethyl-2-methylsuccinic acid Acid, 2,3-dimethylsuccinic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, butylmalonic acid, dimethylmalonic acid, glutaric acid, 2- Methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 2,4-dimethylglutaric acid, pimelic acid , Suberic acid, azelaic acid, sebacic acid and other dibasic acids or polyester diols obtained by dehydration and condensation of anhydrides corresponding to these acids; ring-opening of cyclic ester compounds such as ε-caprolactone Polyester diols obtained by polymerization. The aliphatic ester-based diol and the alicyclic ester-based diol may be used alone or in combination of two or more.

In addition, the aliphatic carbonate-based diol or alicyclic carbonate-based diol constituting the (meth)acrylate urethane may be selected from the group consisting of at least one of the diols and carbonyl dichloride. Polycarbonate diols obtained by the reaction. The polycarbonate-based diol obtained by the reaction of the diols and carbonyl dichloride may be used singly or in combination of two or more.

From the viewpoint of further improving the adhesive strength, the weight average molecular weight can be adjusted freely within the range of 5,000 or more and less than 30,000, and the (meth)acrylate urethane can be suitably used. If the weight average molecular weight of the (meth)acrylate urethane is within the above range, both flexibility and cohesiveness can be sufficiently obtained, and the bonding strength with organic substrates such as PET, PC, PEN, etc. is further improved , Can obtain more excellent connection reliability. In addition, from the viewpoint of obtaining this effect more fully, the weight average molecular weight of the (meth)acrylate urethane is more preferably 8,000 or more and less than 25,000, and still more preferably 10,000 or more and less than 25,000, particularly preferably above 10,000 but less than 20,000. Furthermore, if the weight average molecular weight is 5,000 or more, sufficient flexibility tends to be easily obtained, and if the weight average molecular weight is less than 30,000, the fluidity of the adhesive composition tends to be suppressed from decreasing.

In addition, based on the total mass of the adhesive components (components other than the conductive particles in the adhesive composition), the compounding amount of the (meth)acrylate urethane is preferably 5% by mass or more. It is more preferably 10% by mass or more, still more preferably 15% by mass or more, particularly preferably 25% by mass or more, and extremely preferably 35% by mass or more. If the blending amount is 5% by mass or more, there is a tendency that sufficient heat resistance is easily obtained after curing. In addition, based on the total mass of the adhesive components (components other than the conductive particles in the adhesive composition), the compounding amount of the (meth)acrylate urethane is preferably 95% by mass or less, It is more preferably 80% by mass or less, still more preferably 70% by mass or less, particularly preferably 60% by mass or less, and extremely preferably 50% by mass or less. If the compounding amount is 95% by mass or less, when the adhesive composition is used as a film-like adhesive, there is a tendency that good film formability is easily obtained.

(B) The radical polymerizable compound may each contain one or more phosphoric acid group-containing vinyl compounds (a vinyl compound having a phosphoric acid group) and radical polymerizable compounds other than the phosphoric acid group-containing vinyl compound. (B) The radically polymerizable compound may each include one or more N-vinyl compounds selected from the group consisting of N-vinyl compounds and N,N-dialkylvinyl compounds, and the N -Radical polymerizable compounds other than vinyl compounds. By using a vinyl compound containing a phosphoric acid group in combination, the adhesiveness of the adhesive composition to a substrate with connection terminals can be further improved. In addition, by using N-vinyl compounds in combination, the cross-linking ratio of the adhesive composition can be improved.

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 it is preferably a compound represented by the following general formula (O) to general formula (Q).

[式（O）中，R²⁸ 表示(甲基)丙烯醯氧基，R²⁹ 表示氫原子或甲基，l及m分別獨立地表示1～8的整數。再者，式（O）中，R²⁸ 彼此、R²⁹ 彼此、l彼此及m彼此分別可相同，亦可不同][化21]

[In formula (O), R ²⁸ represents a (meth)acryloyloxy group, R ²⁹ represents a hydrogen atom or a methyl group, and l and m each independently represent an integer of 1-8. Furthermore, in formula (O), R ²⁸ , R ²⁹ , l and m may be the same or different]

[式（P）中，R³⁰ 表示(甲基)丙烯醯氧基，n、o及p分別獨立地表示1～8的整數。再者，式（P）中，R³⁰ 彼此、n彼此、o彼此及p彼此分別可相同，亦可不同][化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. Furthermore, in formula (P), R ³⁰ , n, o, and p may be the same or different.]

[式（Q）中，R³¹ 表示(甲基)丙烯醯氧基，R³² 表示氫原子或甲基，q及r分別獨立地表示1～8的整數][化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 the vinyl compound containing a phosphoric acid group include: (meth)acrylic acid phosphooxyethyl, (meth)acrylic acid phosphooxypropyl, and acid phosphooxyethyl Polyoxyethylene glycol mono(meth)acrylate, acid phosphatidyloxy polyoxypropylene glycol mono(meth)acrylate, phosphoric acid 2,2'-bis(meth)acryloxydiethyl , Ethylene Oxide (EO) modified phosphoric acid di(meth)acrylate, phosphoric acid modified epoxy (meth)acrylate, 2-(meth)acryloxyethyl phosphate, vinyl phosphate Ester etc.

Specific examples of N-vinyl-based compounds include N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, and N-vinylcaprolactone Amine, 4,4'-vinylidene bis(N,N-dimethylaniline), N-vinylacetamide, N,N-dimethylacrylamide, N,N-diethylacrylamide Amine etc.

The compounding amounts of the phosphoric acid group-containing vinyl compound and the N-vinyl compound are respectively independent of the compounding amounts of the phosphoric acid group-containing vinyl compound and the free radical polymerizable compound other than the N-vinyl compound. Based on the total mass of the adhesive components (components other than the conductive particles in the adhesive composition), it is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more. It is preferably 1.0% by mass or more, and extremely preferably 1.5% by mass or more. If the blending amount is 0.2% by mass or more, there is a tendency that high adhesive strength is easily obtained. Based on the total mass of the adhesive components (components other than the conductive particles in the adhesive composition), the blending amounts of the phosphoric acid group-containing vinyl compound and the N-vinyl compound are preferably 15 masses each % Or less, more preferably 10 mass% or less, still more preferably 5 mass% or less, particularly preferably 3 mass% or less. If the blending 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, based on the total mass of the adhesive components (components other than the conductive particles in the adhesive composition), (b) other than the phosphate group-containing vinyl compound and N-vinyl compound The compounding amount of the base polymerizable compound is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, particularly preferably 25% by mass or more, and extremely preferably 35% by mass or more. If the blending amount is 5% by mass or more, there is a tendency that sufficient heat resistance is easily obtained after curing. Based on the total mass of the adhesive components (components other than conductive particles in the adhesive composition), (b) radical polymerization other than the phosphate group-containing vinyl compound and N-vinyl compound The compounding amount of the sexual compound is preferably 95% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, particularly preferably 60% by mass or less, and extremely preferably 50% by mass or less. If the compounding amount is 95% by mass or less, when the adhesive composition is used as a film-like adhesive, there is a tendency that good film formability is easily obtained.

((C) Radical polymerization initiator) As the (c) radical polymerization initiator, it is possible to use organic peroxides and azo compounds that are known from the past by using external energy A compound that produces free radicals. As the (c) radical polymerization initiator, from the viewpoints of stability, reactivity, and compatibility, an organic peroxide having a 1-minute half-life temperature of 90°C to 175°C and a weight average molecular weight of 180 to 1000 is preferred. Oxide. With the 1-minute half-life temperature in this range, the storage stability is more excellent, the radical polymerizability is also high enough, and it can be cured in a short time.

(C) The radical polymerization initiator specifically includes 1,1,3,3-tetramethylbutyl peroxyneodecanoate, bis(4-tertiary butyl peroxydicarbonate) Hexyl) ester, bis(2-ethylhexyl) peroxydicarbonate, cumyl peroxide neodecanoate, dilaurin peroxide, 1-cyclohexyl-1-methyl ethyl peroxide, neodecanoate Trihexyl oxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate Ester, 2,5-Dimethyl-2,5-bis(2-ethylhexyl peroxide) hexane, tertiary hexyl peroxide-2-ethylhexanoate, 2-ethyl peroxide Tertiary butyl caproate, tertiary butyl peroxyneoheptanoate, tertiary pentyl peroxide-2-ethylhexanoate, di-tertiary butyl peroxide hexahydroterephthalate, peroxide-3 , 5,5-Trimethyl hexanoic acid tertiary amyl ester, peroxyneodecanoic acid 3-hydroxy-1,1-dimethylbutyl ester, peroxyneodecanoic acid tertiary amyl ester, bis(3-methyl Benzoyl) peroxide, dibenzyl peroxide, bis(4-methylbenzyl) peroxide, tertiary hexyl peroxide isopropyl monocarbonate, maleic acid peroxide Tertiary butyl ester, tertiary butyl peroxide-3,5,5-trimethylhexanoate, tertiary butyl peroxide laurate, 2,5-dimethyl-2,5-bis(peroxide 3 -Methylbenzyl)hexane, tert-butyl peroxy-2-ethylhexyl monocarbonate, tertiary hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(peroxy) Benzoyl oxide) hexane, tert-butyl peroxybenzoate, dibutyl peroxytrimethyladipate, tertiary amyl peroxide n-octanoate, tertiary amyl peroxide isononanoate, peroxy Organic peroxides such as tertiary amyl oxybenzoate; 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(1-acetoxy-1- Phenylethane), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyronitrile , 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(1-cyclohexanecarbonitrile) and other azo compounds. These compounds can be used alone or in combination of two or more.

In addition, as the (c) radical polymerization initiator, a compound that generates radicals by irradiation with light of 150 nm to 750 nm can be used. Examples of such compounds include "Photoinitiation, Photopolymerization, and Photocuring", J.-P. Fouassier, Hanser Publishers The reason for the α-aminoacetophenone derivatives and phosphine oxide derivatives described in (1995, p17 to p35) is that they have high sensitivity to light irradiation. These compounds can be used alone or in combination of two or more, and can also be used in combination with the organic peroxide or azo compound.

Based on the total mass of the adhesive components (components other than the conductive particles in the adhesive composition), the compounding amount of the (c) radical polymerization initiator is preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, particularly preferably 3% by mass or more, and extremely preferably 5% by mass or more. If the compounding amount is 0.5% by mass or more, the adhesive composition tends to be easily cured sufficiently. Based on the total mass of the adhesive components (components other than the conductive particles in the adhesive composition), the compounding amount of the (c) radical polymerization initiator is preferably 40% by mass or less, more preferably It is 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. If the blending amount is 40% by mass or less, the storage stability tends to be less likely to decrease.

[式（A）中，R¹ 、R² 及R³ 分別獨立地表示氫原子、碳數1～18的烷基或芳基，R⁴ 、R⁵ 及R⁶ 分別獨立地表示氫原子、碳數1～18的烷基、由下述通式（a1）所表示的有機基、或由下述通式（a2）所表示的有機基] [化25]

[式（a1）中，R^7a 表示氫原子或碳數1～6的烷基，R^7b 表示氫原子、胺基、烷氧基或碳數1～10的烷基。另外，s及t分別獨立地表示1～10的整數] [化26]

[式（a2）中，R⁸ 表示碳數1～10的烷基。另外，u表示1～10的整數]((D) Boron-containing complex compound) (d) Boron-containing complex compound (hereinafter referred to as "(d) component") is a compound represented by the following general formula (A). The component (d) contains a boron compound and ammonia or an amine compound as a basic substance relative to the boron compound. [化24]

[In formula (A), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbons or an aryl group, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, carbon An alkyl group having 1 to 18, an organic group represented by the following general formula (a1), or an organic group represented by the following general formula (a2)] [Chemical Formula 25]

[In the formula (a1), R ^7a represents a hydrogen atom or an alkyl group having 1 to 6 carbons, and R ^7b represents a hydrogen atom, an amino group, an alkoxy group, or an alkyl group having 1 to 10 carbons. In addition, s and t each independently represent an integer of 1 to 10] [化26]

[In the formula (a2), R ⁸ represents an alkyl group having 1 to 10 carbon atoms. In addition, u represents an integer of 1-10]

Examples of the boron compound contained in the component (d) include alkyl diaryl borane, dialkyl aryl borane, trialkyl borane, triaryl borane, and boron hydride. From the viewpoint of more excellent low-temperature curability, the boron compound is preferably a trialkylborane. The boron compound may also be a compound having a plurality of the structures of these compounds in the molecule, or a compound having the structure of the compound in the main chain and/or side chain of the polymer.

As the alkyl group bonded to the boron atom in the boron 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, n-butyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, and decyl. Octyl, propyl, isopropyl, isobutyl, second butyl, tertiary butyl, pentyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, isopentyl, heptyl, nonyl , Eleven base, third octyl, etc. Among these, the ethyl group, isopropyl group, and n-butyl group are preferable from the viewpoint of more excellent low-temperature curability. From the viewpoint of more excellent low-temperature curability, the carbon number of the alkyl group is preferably 1-12, more preferably 1-5. The alkyl groups bonded to the boron atom in the boron compound may be the same or different from each other.

Specific examples of the aryl group bonded to the boron atom in the boron compound include: phenyl, p-tolyl, m-tolyl, mesityl, xylyl, and p-tertiary butyl phenyl (4 -Tertiary butyl phenyl), p-methoxyphenyl, biphenyl, naphthyl, 4-methylnaphthyl, etc. Among these, from the viewpoint of more excellent low-temperature curability and storage stability, phenyl, p-tert-butylphenyl, and 4-methylnaphthyl are preferred, and phenyl is more preferred. The aryl groups bonded to the boron atom in the boron compound may be the same as or different from each other.

The amine compound used as the basic substance of the component (d) includes alkylamines, dialkylamines, trialkylamines, amines having an organic group represented by the general formula (a1), The amine etc. of the organic group represented by Formula (a2). Among these, from the viewpoint of more excellent low-temperature curability and storage stability, amines having an organic group represented by the general formula (a1), and amines having an organic group represented by the general formula (a2) are preferred. -Based amine. The amine compound may be a compound having a plurality of the structures of these compounds in the molecule, or a compound having the structure of the compound in the main chain and/or side chain of the polymer.

In particular, among the amine compounds, from the viewpoint of being more excellent in low-temperature curability and storage stability, an amine having an organic group represented by the general formula (a1) is preferred, and an amine having an organic group represented by the general formula (a1) is more preferred, a1) An amine having an organic group represented by two or more amine groups, and more preferably an amine having an organic group represented by general formula (a1) in which two or more R ^7a and R ^7b are hydrogen atoms. In this case, the solubility to the thermoplastic resin, the radical polymerizable compound, and the solvent is improved, and the low-temperature curability can be further improved.

As the alkyl group bonded to the nitrogen atom in the amine 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, n-butyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, and decyl. Octyl, propyl, isopropyl, isobutyl, second butyl, tertiary butyl, pentyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, isopentyl, heptyl, nonyl , Eleven base, third octyl, etc. Among these, from the viewpoint of more excellent low-temperature curability and storage stability, n-butyl is preferred. From the viewpoint of more excellent low-temperature hardenability and storage stability, the carbon number of the alkyl group is preferably 1-12, and more preferably 1-6.

In the general formula (a1), R ^{7a is} preferably a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. As R ^7b , a hydrogen atom and an alkyl group having 1 to 5 carbon atoms are preferred. The number of carbon atoms in the alkoxy group of R ^7b is preferably 1-3. As s, an integer of 1 to 5 is preferable. s may be an integer of 1-3, or an integer of 1-2. As t, the integer of 1-3 is preferable, and the integer of 1-2 is more preferable.

In the general formula (a2), R ^{8 is} preferably an alkyl group having 1 to 5 carbons, more preferably an alkyl group having 1 to 3 carbons, and still more preferably an alkyl group having 1 to 2 carbons. As u, the integer of 1-5 is preferable, and the integer of 1-3 is more preferable.

As a specific example of the compound represented by the general formula (A), it is preferably selected from the group consisting of triethylborane 1,3-diaminopropane, triethylborane, and triethylborane from the viewpoint of more excellent low-temperature curability and storage stability. Ethylborane N-(2-aminoethyl)ethane-1,2-diamine (alias; triethylborane N-(2-aminoethyl)-1,2-ethylenediamine) , Triethylborane 3-methoxy-1-amine propane (alias: triethylborane 3-methoxypropylamine), tri-n-butylborane 3-methoxy-1-amine Propane (alias: tri-n-butylborane 3-methoxypropylamine), and tri-n-butylborane 3-ethoxy-1-amine propane (alias: tri-n-butylborane 3 -At least one of the group consisting of ethoxypropylamine).

As the component (d), a combination of a trialkylborane and an amine having an organic group represented by the general formula (a1) or an organic group represented by the general formula (a2) is preferred. When the component (d) is a complex compound having such a configuration, the low-temperature curability and storage stability of the adhesive composition can be improved in a better balance.

Specifically, as the component (d), a complex obtained by the previous synthesis method described in Japanese Patent Publication No. 7-72264 etc. can be used. For example, when a trialkylborane-amine complex is to be obtained, a Tetrahydrofuran (THF) solution containing trialkylborane is added to the amine solution to obtain a trialkylborane-amine complex Things.

(D) A component can be used individually by 1 type, and it can also mix and use 2 or more types.

Based on the total mass of the adhesive components (components other than conductive particles in the adhesive composition), the blending amount of component (d) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more It is preferably 1.0% by mass or more, and particularly preferably 1.5% by mass or more. If the blending amount of the component (d) is 0.1% by mass or more, there is a tendency that the effect of promoting the reactivity of the radical polymerization initiator is easily obtained sufficiently. Based on the total mass of the adhesive components (components other than the conductive particles in the adhesive composition), the blending amount of component (d) is preferably 20% by mass or less, more preferably 15% by mass or less, and still more It is preferably 10% by mass or less, and particularly preferably 5% by mass or less. If the blending amount of the component (d) is 20% by mass or less, the storage stability of the adhesive composition tends to be less likely to decrease.

((E) Conductive particles) (e) The conductive particles need only be particles whose whole or surface has conductivity, but when used for connection of a member having a connection terminal, the average particle size is preferably smaller than the connection terminal The distance between the particles.

(E) The conductive particles include metal particles containing metals such as Au, Ag, Ni, Cu, Pd, or solder, and particles containing carbon and the like. In addition, (e) the conductive particles may be particles obtained by using non-conductive glass, ceramic, or plastic as a core, and coating the core with the metal, metal particles, or carbon. As (e) conductive particles, particles formed by coating the metal, metal particles, or carbon on the core of the plastic, and hot-melt metal particles are deformable by heating and pressing, so they are connected to the electrode The contact area is increased and reliability is improved, so it is better. (E) The conductive particles may be particles obtained by coating metal particles containing copper with silver, for example. In addition, as the conductive particles (e), a metal powder as described in JP 2005-116291 A may be used, and the metal powder has a shape in which a plurality of fine metal particles are connected in a chain shape.

In addition, by using fine particles formed by further covering the surface of the (e) conductive particles with a polymer resin or the like, or using a method such as mixing, an insulating layer containing an insulating substance is provided on the surface of the (e) conductive particles In the resulting particles, when the blending amount of conductive particles is increased, the short circuit caused by the contact between the particles is suppressed, and the insulation between the electrode circuits is improved. Therefore, these particles can be used alone or in combination with (e) conductive particles.

From the viewpoint of excellent dispersibility and conductivity, (e) the average particle diameter of the conductive particles is preferably, for example, 1 μm to 18 μm. When such (e) conductive particles are contained, the adhesive composition can be suitably used as an anisotropic conductive adhesive. (E) The average particle size of the conductive particles can be measured with a laser diffraction particle size distribution measuring device (for example, a laser diffraction type SALD-2100 manufactured by Shimadzu Corporation).

(E) The compounding amount of conductive particles is not particularly limited, but based on the total volume of the adhesive components (components other than the conductive particles in the adhesive composition), it is preferably 0.1% by volume or more, more preferably 0.2% by volume or more, more preferably 0.5% by volume or more, particularly preferably 1% by volume or more. If the compounding amount is 0.1% by volume or more, there is a tendency to suppress the decrease in conductivity. Based on the total volume of the adhesive components (components other than the conductive particles in the adhesive composition), (e) the compounding amount of the conductive particles is preferably 30% by volume or less, more preferably 10% by volume or less, More preferably, it is 5 volume% or less. If the blending amount is 30% by volume or less, there is a tendency that a short circuit of the circuit will not easily occur. In addition, "volume %" is determined based on the volume of each component before curing at 23°C, but the volume of each component can be converted from weight to volume using specific gravity. In addition, it is also possible to put the component into a container in which a suitable solvent (water, alcohol, etc.) that does not dissolve or swell the component and sufficiently wet the component is put into a measuring cylinder, etc., and the increased volume is used as the component To find the volume.

(Other components) In order to control the curing speed and to further improve storage stability, the adhesive composition of the present embodiment may contain a stabilizer. As such stabilizers, known compounds can be used without particular limitations, but quinone derivatives such as quinone and hydroquinone; phenols such as 4-methoxyphenol and 4-tert-butylcatechol are preferred. Derivatives; 2,2,6,6-tetramethylpiperidine-1-oxyl radical and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical and other aminooxy radicals Derivatives; hindered amine derivatives such as tetramethylpiperidine methacrylate, etc. The stabilizer can be used alone or in combination of two or more.

Based on the total mass of the adhesive components (components other than the conductive particles in the adhesive composition), the blending amount of the stabilizer is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.02% by mass or more. If the blending amount is 0.005% by mass or more, the curing rate tends to be easily controlled and storage stability tends to be easily improved. Based on the total mass of the adhesive components (components other than the conductive particles in the adhesive composition), the blending amount of the stabilizer is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5 mass% or less. If the blending amount is 10% by mass or less, the compatibility with other components tends to be less likely to decrease.

In addition, the adhesive composition of the present embodiment may suitably contain coupling agents such as alkoxysilane derivatives and silazane derivatives, adhesion promoters, and leveling agents. As the coupling agent, specifically, a compound represented by the following general formula (R) is preferred. The coupling agent can be used alone or in combination of two or more.

[式（R）中，R³³ 、R³⁴ 及R³⁵ 分別獨立地表示氫原子、碳數1～5的烷基、碳數1～5的烷氧基、碳數1～5的烷氧基羰基或芳基，R³⁶ 表示(甲基)丙烯醯基、乙烯基、異氰酸基、咪唑基、巰基、胺基、甲基胺基、二甲基胺基、苄基胺基、苯基胺基、環己基胺基、嗎啉基、哌嗪基、脲基或縮水甘油基，v表示1～10的整數][化27]

[In formula (R), R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbons, an alkoxy group having 1 to 5 carbons, and an alkoxy group having 1 to 5 carbons Carbonyl or aryl group, R ³⁶ represents (meth)acryloyl, vinyl, isocyanate, imidazole, mercapto, amino, methylamino, dimethylamino, benzylamino, phenyl Amino, cyclohexylamino, morpholinyl, piperazinyl, ureido or glycidyl, v represents an integer of 1-10]

In order to relieve stress and improve adhesiveness, the adhesive composition of this embodiment may contain a rubber component. The rubber component refers to a component that exhibits rubber elasticity (JIS K6200) in its own state, or a component that exhibits rubber elasticity by reaction. The rubber component may be solid or liquid at room temperature (25°C), but from the viewpoint of improving fluidity, it is preferably liquid. As the rubber component, a compound having a polybutadiene skeleton is preferred. 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 terminal is preferable. Furthermore, even if it has a polybutadiene skeleton, it is classified as (a) a thermoplastic resin when it shows thermoplasticity, and it is classified as (b) a radical polymerizable compound when it shows radical polymerizability.

Specific examples of rubber components include: polyisoprene, polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1,2 -Polybutadiene, hydroxyl-terminated 1,2-polybutadiene, acrylic rubber, styrene-butadiene rubber, hydroxyl-terminated styrene-butadiene rubber, acrylonitrile-butadiene rubber, at the polymer end Acrylonitrile-butadiene rubber containing carboxyl, hydroxyl, (meth)acryloyl or morpholino, carboxylated nitrile rubber, hydroxyl-terminated poly(oxypropylene), alkoxysilyl-terminated poly(oxygen) Propylene glycol), poly(oxytetramethylene) glycol, polyolefin glycol, etc.

In addition, as the rubber component having a high polar group and being liquid at room temperature, specifically, a liquid acrylonitrile-butadiene rubber containing a carboxyl group, a hydroxyl group, (methyl) ) Liquid acrylonitrile-butadiene rubber based on acryloyl or morpholine, liquid carboxylated nitrile rubber, etc. The blending amount of acrylonitrile having a polar group is preferably 10% by mass to 60% by mass.

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

In addition, in order to relieve stress and improve adhesiveness, the adhesive composition of this embodiment may contain organic fine particles. The average particle diameter of the organic fine particles is preferably, for example, 0.05 μm to 1.0 μm. Furthermore, when the organic microparticles contain the rubber component, they are classified as rubber components instead of organic microparticles, and when the organic microparticles contain the (a) thermoplastic resin, they are classified as (a) thermoplastic resin instead of organic microparticles. .

Specific examples of organic fine particles include polyisoprene, polybutadiene, carboxy-terminal polybutadiene, hydroxyl-terminal polybutadiene, 1,2-polybutadiene, carboxy-terminal 1,2 -Polybutadiene, acrylic rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylonitrile-butadiene containing carboxyl, hydroxyl, (meth)acryloyl or morpholino at the end of the polymer Diene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly(oxypropylene), alkoxysilyl-terminated poly(oxypropylene), poly(oxytetramethylene) glycol, polyolefin glycol , Alkyl (meth)acrylate-butadiene-styrene copolymer, alkyl (meth)acrylate-silicone copolymer or silicone-(meth)acrylic acid copolymer, or a composite of these Of organic particles.

In addition, the connection structure described later (the substrate includes a base material containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate). The adhesive composition used may contain silicone fine particles.

By connecting the structure (in which the substrate includes a base material containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate and polyethylene naphthalate) used in The adhesive composition contains silicone microparticles, which can sufficiently alleviate internal stress. Therefore, the adhesive strength for polyethylene terephthalate, polycarbonate, and polyethylene naphthalate is further improved, and the Adhesion strength of the member connecting the terminal. In addition, more stable performance can be maintained after a long-term reliability test.

As the silicone fine particles, fine particles of polyorganosilsesquioxane resin having rubber elasticity are known, and spherical or amorphous silicone fine particles can be used. In addition, 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, the silicone microparticles preferably have a three-dimensional crosslinked structure. Such silicone microparticles have high dispersibility in resin, and have more excellent stress relaxation after curing. Silicone microparticles with a weight average molecular weight of 1 million or more, and/or silicone microparticles with a three-dimensional cross-linked structure have low solubility in polymers (thermoplastic resins, etc.), monomers, or solvents, so they can be obtained more significantly The effect. The term "having a three-dimensional crosslinked structure" here means that the polymer chain has a three-dimensional network structure. In addition, the glass transition temperature of the silicone particles is 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 alleviate the internal stress of the adhesive composition as a circuit connection material.

As the silicone microparticles having such a structure, specifically, an organopolysiloxane containing at least two vinyl groups, an organohydrogen polysilicon containing at least two hydrogen atoms bonded to silicon atoms can be used. Oxyane, silicone fine particles obtained by reaction with platinum-based catalysts (for example, Japanese Patent Laid-Open No. 62-257939); use of organopolysiloxane having alkenyl groups and organopolysiloxane having hydrosilyl groups Silicone fine particles obtained from oxane and platinum-based catalysts (for example, Japanese Patent Laid-Open No. 63-77942); using diorganosiloxane, 1-organossesquioxane, triorganosiloxane, and platinum series Silicone fine particles obtained by the catalyst (for example, Japanese Patent Laid-Open No. 62-270660); the water/alcohol solution of methyl silanetriol and/or its partial condensate is dropped into the alkaline aqueous solution and polycondensed Silicone fine particles obtained by the reaction (for example, Japanese Patent No. 3970453), etc. In addition, in order to improve the dispersibility and adhesion to the substrate, it is also possible to use silicone fine particles (for example, Japanese Patent Laid-Open Hei 3-167228) by adding an epoxy compound or copolymerizing an epoxy compound, adding an acrylate compound or Silicone microparticles etc. obtained by copolymerizing acrylate compounds.

In addition, in order to further improve the dispersibility, it is preferable to use silicone microparticles having a core-shell structure. As a core-shell structure, there are a structure including a surface layer (shell layer) having a glass transition temperature higher than the glass transition temperature of the core material (core layer) on the surface of the core material, and a structure outside the core material (core layer) With a grafted layer (shell layer) structure, silicone particles with different compositions in the core layer and shell layer can be used. Specifically, it is also possible to use a core-shell type silicone rubber obtained by adding an alkaline substance or an alkaline aqueous solution and an organic trialkoxysilane to an aqueous dispersion of silicone rubber spherical fine particles, followed by hydrolysis and condensation reactions. Particles (for example, Japanese Patent No. 2832143), such as the core-shell type silicone microparticles described in WO2009/051067. In addition, silicone microparticles containing functional groups such as a hydroxyl group, an epoxy group, a ketimine group, a carboxyl group, and a mercapto group on the molecular end or the inner chain of the molecule can be used. Such silicone fine particles have improved dispersibility with respect to film forming components and radical polymerizable substances, and are therefore preferable.

The average particle size of the silicone microparticles is preferably 0.05 μm-25 μm, more preferably 0.1 μm-20 μm. If the average particle diameter is 0.05 μm or more, the fluidity of the adhesive composition tends to be suppressed due to an increase in surface area. In addition, if the average particle size is 25 μm or less, there is a tendency that the relaxation of internal stress is likely to be fully exhibited.

Based on the total mass of the adhesive components (components other than the conductive particles in the adhesive composition), the blending amount of the silicone fine particles is preferably 3% by mass or more, more preferably 5% by mass or more. If the blending amount of the silicone fine particles is 3% by mass or more, it tends to be easy to sufficiently relax the internal stress. Based on the total mass of the adhesive components (components other than the conductive particles in the adhesive composition), the blending amount of the silicone fine particles is preferably 40% by mass or less, and more preferably 30% by mass or less. If the blending amount of silicone fine particles is 40% by mass or less, the decrease in flexibility (modulus of elasticity, elongation) of the adhesive composition is suppressed, and the adhesive strength tends to be less likely to decrease.

These silicone microparticles can be used alone or in combination of two or more.

The adhesive composition of this embodiment can be used in a paste form when the adhesive composition is liquid at room temperature. In the case where the adhesive composition is solid at room temperature, in addition to heating and using it, a solvent may be used for creaming. The usable solvent is preferably a solvent that is non-reactive with the adhesive composition and additives and exhibits sufficient solubility, and preferably has a boiling point of 50°C to 150°C under normal pressure. If the boiling point is 50°C or higher, there is a tendency that volatilization becomes less when left at room temperature, and the use in an open system becomes easier. In addition, if the boiling point is 150°C or less, the solvent tends to volatilize and the reliability after adhesion tends to be less likely to decrease.

In addition, the adhesive composition of the present embodiment may be formed into a film shape and used as a film adhesive. The film-like adhesive of this embodiment includes the adhesive composition. If necessary, a solution obtained by adding a solvent or the like to the adhesive composition can be applied to a release substrate such as a fluororesin film, a polyethylene terephthalate film, and a release paper, or the After the solution is impregnated in a substrate such as a nonwoven fabric and placed on a releasable substrate, the solvent and the like are removed and used as a film. If it is used in the shape of a film, it is more convenient in terms of handleability and the like. According to this embodiment, an adhesive sheet including a substrate and a film-like adhesive is provided. In the adhesive sheet, a film-like adhesive is arranged on a base material to form, for example, an adhesive layer.

The adhesive composition of the present embodiment can be used in combination with heating and pressure for bonding. The heating temperature is preferably a temperature of 100°C to 200°C. The pressure is preferably in a range that does not cause damage to the adherend, and is generally preferably 0.1 MPa to 10 MPa. The heating and pressurization are preferably performed in the range of 0.5 second to 120 seconds, and bonding can be performed even if heating is performed at 120°C to 190°C, 3 MPa, and 10 seconds.

The adhesive composition of the present 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. In addition, the adhesive composition of the present embodiment can be used to electrically connect the connection terminal of a solar battery cell having a connection terminal arranged on the main surface of the substrate and a wiring member.

The adhesive composition of this embodiment can be used as an adhesive for the same type of adherend, and can also be used as an adhesive for different types of adherends with different thermal expansion coefficients. Specifically, the adhesive composition of this embodiment can be used as a circuit connection material represented by anisotropic conductive adhesive, silver paste, silver film, etc., and elastic for chip size package (CSP) Adhesive materials for semiconductor devices represented by underfill materials for body, CSP, and lead on chip (LOC) tapes.

For example, by combining a first circuit member having a first circuit board and a first connection terminal arranged on the main surface of the first circuit board, and a first circuit member having a second circuit board and arranged on the main surface of the second circuit board The second circuit member of the second connection terminal on the upper side is arranged through the adhesive composition of this embodiment or its cured product in the following state to form a connection structure of the circuit member. The state is the first connection terminal and A state in which the second connection terminals are opposed to each other, and the first connection terminal and the second connection terminal are electrically connected. In this case, the adhesive composition of this embodiment is useful as an adhesive for circuit connection.

<Connected structure> Next, the connected structure using the said adhesive composition and its manufacturing method are demonstrated. According to this embodiment, there is provided a method of manufacturing a connection structure in which the adhesive composition is cured in a state in which the adhesive composition is interposed between the first circuit member and the second circuit member, thereby 1 The first circuit member and the second circuit member are connected in a state where the connection terminal is electrically connected to the second connection terminal. The first circuit member has a first substrate and a first substrate disposed on the main surface of the first substrate. A connection terminal, and the second circuit member has a second substrate and a second connection terminal arranged on the main surface of the second substrate. In addition, according to this embodiment, there is provided a method of manufacturing a connecting structure in which the adhesive composition is interposed between the solar battery cell and the wiring member, and the adhesive composition is cured, thereby connecting the terminal The solar battery cell and the wiring member are connected in a state of being electrically connected to the wiring member. The solar battery cell has a substrate and connection terminals arranged on the main surface of the substrate.

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

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

The connecting member 30 is arranged between the circuit member 10 and the circuit member 20. The connection member 30 connects the circuit member 10 and the circuit member 20 so that the main surface 12a and the main surface 22a face each other substantially in parallel. In the connection structure 100, the connection terminal 14 and the connection terminal 24 are arranged to face each other, and are electrically connected by contacting each other. The connecting member 30 includes a cured product of an adhesive composition 30a described later.

The connection structure 100 can be manufactured as follows, for example. First, as shown in FIG. 2, the circuit member 10, the circuit member 20, and the adhesive composition 30a containing the said adhesive composition are prepared. The adhesive composition 30a is formed by molding the adhesive composition into a film shape, for example. Next, the adhesive composition 30a is placed on the main surface 22a of the circuit member 20 on which the connection terminals 24 are formed. Then, the circuit member 10 is placed on the adhesive composition 30a so that the connection terminal 14 and the connection terminal 24 face each other. Then, while heating the adhesive composition 30a through the circuit member 10 and the circuit member 20, the adhesive composition 30a is hardened, and pressure is applied in the direction perpendicular to the main surface 12a and the main surface 22a, and the circuit A connecting member 30 is formed between the member 10 and the circuit member 20. Thereby, the connection structure 100 can be obtained.

When the adhesive composition contains conductive particles, the anisotropic conductive film produced by the adhesive composition is interposed between the facing connection terminals and heated and pressurized, so that the conductive particles will The connection terminals are electrically connected to each other and the circuit members are connected to each other, thereby obtaining a connection structure of the circuit member. Fig. 3 is a schematic cross-sectional view showing the connection structure of the second embodiment. Fig. 4 is a schematic cross-sectional view showing a method of manufacturing the connection structure shown in Fig. 3. The connection structure 200 of the circuit member shown in FIG. 3 is obtained using the adhesive composition containing (e) electroconductive particle.

The circuit member connection structure 200 shown in FIG. 3 includes the same circuit member 10 and circuit member 20 as the connection structure body 100, and the connection member 40. In the connection structure 200, the connection terminal 14 and the connection terminal 24 are opposed and arranged in a state of being isolated from each other.

The connecting member 40 is arranged between the circuit member 10 and the circuit member 20. The connecting member 40 includes 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 includes a cured product of the adhesive component 42a described later. In the connection structure 200, the conductive particles 44 contact the connection terminal 14 and the connection terminal 24 between the opposing connection terminal 14 and the connection terminal 24, and the connection terminal 14 and the connection terminal 24 are connected via the conductive particles 44. Electrically connected to each other.

The connection structure 200 can be manufactured as follows, for example. First, as shown in FIG. 4, the circuit member 10, the circuit member 20, and the adhesive composition 40a containing the said adhesive composition are prepared. The adhesive composition 40a is formed by molding the adhesive composition into a film shape, for example. The adhesive composition 40a has an adhesive component 42a and conductive particles 44 dispersed in the adhesive component 42a. Thereafter, the circuit member 10 and the circuit member 20 are connected via the adhesive composition 40a by the same method as the method of obtaining the circuit member connection structure 100. Thereby, the connection structure 200 can be obtained.

At least one of the circuit member connection structure 100 and the circuit board 12 and the circuit board 22 in the connection structure 200 may include a base material containing a thermoplastic resin having a glass transition temperature of 200° C. or less. For example, at least one of the circuit substrate 12 and the circuit substrate 22 may include an organic group containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. material. As a result, when organic substrates such as polyethylene terephthalate, polycarbonate, polyethylene naphthalate, etc. are used, the wettability with the adhesive composition in the circuit board is improved, thereby reducing the temperature Excellent bonding strength can also be obtained under the hardening conditions. Therefore, stable performance (adhesion strength and connection resistance) can be maintained after a long-term reliability test (high temperature and humidity test), and excellent connection reliability can be obtained.

In addition, when one of the circuit substrate 12 and the circuit substrate 22 includes a base containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate In the case of a material, the other circuit substrate of the circuit substrate 12 and the circuit substrate 22 may include a base material containing at least one selected from the group consisting of polyimide resin and polyethylene terephthalate. Thereby, the wettability and bonding strength with the adhesive composition in the circuit board are further improved, and more excellent connection reliability can be obtained.

Furthermore, the circuit board 12 and the circuit board 22 may also contain inorganic substances such as semiconductors, glass or ceramics; organic substances such as polyethylene terephthalate, polyethylene naphthalate, polyimide resin, or polycarbonate. ; Base material for composite materials such as glass/epoxy resin. In addition, the circuit board 12 and the circuit board 22 may be flexible boards.

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

The solar battery cell 310a and the solar battery cell 310b include a substrate 312, a surface electrode (connection terminal) 314 arranged on the surface (main surface) 312a of the substrate 312, and a back surface arranged on the back surface (main surface) 312b of the substrate 312 Electrode (connection terminal) 316. The substrate 312 includes, for example, inorganic materials such as semiconductors, glass or ceramics, and composite materials such as glass/epoxy resins. In addition, the substrate 312 may also be a flexible substrate. The surface 312a is a light receiving surface.

The wiring member 320 is a member used to electrically connect the solar battery unit 310a with other components, for example, to electrically connect one solar battery unit to another solar battery unit. In FIG. 5, the surface electrode 314 of the solar cell 310a and the back electrode 316 of the solar cell 310b are electrically connected by the wiring member 320.

The connecting members 330 are respectively arranged between the solar battery unit 310a and the wiring member 320 and between the solar battery unit 310b and the wiring member 320, and connect the solar battery unit 310a, the solar battery unit 310b and the wiring member 320. The connecting member 330 contains a cured product of the adhesive composition and contains 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 electrode 314 of the solar battery cell 310a and the wiring member 320 can be electrically connected via the conductive particles. In addition, the back electrode 316 of the solar battery cell 310b and the wiring member 320 may be electrically connected via conductive particles. When the connecting member 330 does not contain conductive particles, for example, the surface electrode 314 of the solar battery cell 310 a and/or the back electrode 316 of the solar battery cell 310 b may be in contact with the wiring member 320.

The solar cell module 300 uses the cured product of the adhesive composition to form the connecting member 330. Thereby, the bonding strength of the connecting member 330 between the solar battery unit 310a and the wiring member 320, and between the solar battery unit 310b and the wiring member 320 is sufficiently high, and the connection between the solar battery unit 310a, the solar battery unit 310b and the wiring member 320 The resistance becomes sufficiently small. In addition, even when it is left in a high-temperature and high-humidity environment for a long time, the decrease in bonding strength and the increase in connection resistance can be sufficiently suppressed. Furthermore, the connecting member 330 is a member that can be formed by heat treatment at a low temperature for a short time. Therefore, the solar battery module shown in FIG. 5 can be manufactured without deteriorating the solar battery unit 310a and the solar battery unit 310b during connection, and can have higher reliability than before.

The solar battery module 300 can use the solar battery unit 310a, the solar battery unit 310b, and the wiring member 320 instead of the circuit member 10 and the circuit member 20 in the manufacturing method of the connection structure 100 and the connection structure 200, and the same It is manufactured by the same method as the manufacturing method of the said connection structure.

Furthermore, in the connection structure 100, the connection structure 200, and the solar cell module 300, the adhesive composition used as the connection member does not need to be completely cured (the highest degree of curing that can be achieved under the specified curing conditions), As long as the characteristics are produced, it may be in a partially hardened state. Example

Hereinafter, the present invention will be specifically explained based on examples, but the present invention is not limited to these.

<Thermoplastic resin> (Preparation of polyester urethane resin) Polyester urethane resin (trade name: UR-4800, manufactured by Toyobo Co., Ltd., weight average molecular weight: 32,000, glass transition temperature: 106) °C) It is dissolved in a 1:1 mixed solvent of methyl ethyl ketone and toluene, and a mixed solvent dissolved material with a resin content of 30% by mass is prepared.

(Preparation of phenoxy resin) 40 parts by mass of phenoxy resin (trade name: YP-50, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., weight average molecular weight: 60,000, glass transition temperature: 80°C) In 60 parts by mass of ethyl ketone, a solution having a solid content of 40% by mass was prepared.

<radical polymerizable compound> (synthesis of acrylic urethane (UA1)) In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube with a calcium chloride drying tube, and a nitrogen inlet tube, it will be uniform in 3 hours Poly(1,6-hexanediol carbonate) with a number average molecular weight of 1000 (trade name: Duranol T5652, manufactured by Asahi Kasei Chemicals Co., Ltd.) 2500 mass parts (2.50) mol), and isophorone diisocyanate (manufactured by Sigma-Aldrich) 666 parts by mass (3.00 mol), after fully introducing nitrogen into the reaction vessel, heating to 70°C to 75°C 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) to the reaction vessel, 2-hydroxyethyl acrylate was added 238 parts by mass (2.05 mol) of ester (manufactured by Sigma-Aldrich), and then reacted at 70° C. for 6 hours in an air environment to obtain acrylic urethane (UA1). The weight average molecular weight of urethane acrylate is 15,000.

(Preparation of vinyl compound with phosphoric acid group (P-2M)) Prepare 2-(meth)acryloxyethyl phosphate (trade name: Light Ester) P-2M, Kyoeisha Chemical Co., Ltd. Company manufacture) as a vinyl compound with a phosphoric acid group.

<Complex containing boron> (Synthesis of triethylborane 3,3-diaminopropane (TEB-DAP)) Add 14.8 g to a three-necked flask containing a stirrer, a cooler, a thermometer, and a nitrogen introduction tube (0.20 mol) 1,3-propanediamine, while keeping it below about 40°C, add dropwise a solution of 13.1 g (0.13 mol) of triethylboron dissolved in 100 ml of tetrahydrofuran (THF). After completion of the dropwise addition, the mixture was stirred for about 0.5 hours to obtain triethylborane 1,3-diaminopropane (TEB-DAP).

(Synthesis of triethylborane N-(2-aminoethyl)ethane-1,2-diamine (TEB-DETA)) Into a three-necked flask containing a stirrer, a cooler, a thermometer and a nitrogen introduction tube Add 20.6 g (0.20 mol) of N-(2-aminoethyl)ethane-1,2-diamine, while keeping it below about 40°C, add 13.1 g (0.13 mol) of triethylboron. The solution is dissolved in 100 ml of tetrahydrofuran (THF). After the dropwise addition, the mixture was stirred for about 0.5 hours to obtain triethylborane N-(2-aminoethyl)ethane-1,2-diamine (TEB-DETA).

(Synthesis of tri-n-butylborane 3-methoxy-1-aminopropane (TnBB-MOPA)) Add 17.8 g (0.20 mol) to a three-necked flask containing a stirrer, cooler, thermometer, and nitrogen introduction tube While keeping the 3-methoxy-1-aminopropane below about 40℃, add dropwise a solution of 23.7 g (0.13 mol) of tri-n-butyl boron dissolved in 100 ml of tetrahydrofuran (THF) . After the dropwise addition was completed, the mixture was stirred for about 0.5 hours, thereby obtaining tri-n-butylborane 3-methoxy-1-aminopropane (TnBB-MOPA).

<Amine compound> N,N-dimethylaniline (abbreviation: DMA, manufactured by Sigma-Aldrich) was prepared as an amine compound.

<Free radical polymerization initiator> Dilaurel peroxide (trade name: Peroyl L, manufactured by NOF Corporation) was prepared.

<Conductive particles> (Preparation of conductive particles) A nickel layer with a thickness of 0.2 μm is provided on the surface of a particle with polystyrene as the core, and then a gold layer with a thickness of 0.02 μm is provided on the outside of the nickel layer. It becomes conductive particles with an average particle diameter of 10 μm and a specific gravity of 2.5.

<Example 1 to Example 6 and Comparative Example 1 to Comparative Example 4> (Production of Adhesive for Circuit Connection) Thermoplastic resin, radical polymerizable compound, and radical were blended as shown in Table 1 in terms of solid mass ratio A polymerization initiator, a complex compound or amine compound containing boron, and a conductivity of 1.5% by volume based on the total volume of the adhesive components (components other than conductive particles in the adhesive for circuit connection) The particles are dispersed to obtain an adhesive for circuit connection. Use a coating device to coat the obtained adhesive for circuit connection on a fluororesin film with a thickness of 80 μm, and dry it with hot air at 70°C for 10 minutes to obtain a film-like circuit with a thickness of the adhesive layer of 20 μm Adhesive for connection.

[Table 1]

(Measurement of Connection Resistance and Adhesion Strength) The adhesive for film circuit connection of Examples 1 to 6 and Comparative Examples 1 to 4 was interposed between a flexible circuit board (FPC) and glass (ITO, the surface resistance was 20 Ω/□), the flexible circuit board is a flexible circuit board with 500 copper circuits with a line width of 25 μm, a pitch of 50 μm, and a thickness of 8 μm on the polyimide film. The glass is a glass with a thickness of 1.1 mm in which a thin layer of ITO with a thickness of 0.2 μm is formed. Using a thermocompression bonding device (heating method: constant temperature heating type, manufactured by Toray Engineering Co., Ltd.), it is heated and pressurized at 120°C and 2 MPa for 10 seconds to connect over a width of 2 mm. The connection structure A (FPC/ITO) was produced. Immediately after the connection, and after keeping it in a constant temperature and humidity chamber at 85°C and 85% RH for 240 hours (after the 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 represented by the average of 37 resistances between adjacent circuits.

In addition, immediately after the connection and after the high-temperature and high-humidity test, the adhesive strength of the connected structure A was measured by the 90-degree peel method in accordance with JIS-Z0237. Here, as a measuring device of the adhesive strength, a Tensilon UTM-4 manufactured by Toyo Baldwin Co., Ltd. (peeling speed: 50 mm/min, 25° C.) was used.

The film-like circuit connection adhesives of Examples 1 to 6 and Comparative Examples 1 to 4 were interposed between a flexible circuit board (FPC) and a PET substrate (Ag). The flexible circuit board was Polyimide film (Tg: 350°C) is a flexible circuit board with 80 copper circuits with a line width of 150 μm, a pitch of 300 μm, and a thickness of 8 μm. The PET substrate (Ag) is formed with a thickness of It is a PET substrate (Ag) with a thickness of 0.1 μm in a thin layer of 5 μm Ag paste. Using a thermocompression bonding device (heating method: constant temperature heating type, manufactured by Toray Engineering Co., Ltd.), it is heated and pressurized at 120°C and 2 MPa for 20 seconds and connected over a width of 2 mm to form a connection structure Body B (FPC/Ag). Immediately after the connection, and after keeping in a constant temperature and humidity chamber at 85°C and 85% RH for 240 hours (after the high temperature and high humidity test), the resistance value between adjacent circuits of the connection structure B was measured with a multimeter. The resistance value is represented by the average of 37 resistances between adjacent circuits.

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

The measurement results of the connection resistance and adhesive strength (adhesive force) of the connection structure A and the connection structure B measured in the above manner are shown in Table 2 below.

[Table 2]

(Storage Stability Test) The film circuit connection adhesives of Examples 1 to 2 and Comparative Examples 1 to 2 were added to a gas barrier container (manufactured by Asahi Kasei Pax Co., Ltd., Trade name: Polyflex Bag (Polyflex Bag) flying dragon, model: N-9, material: nylon (thickness of 15 μm) / PE (thickness of 60 μm), size: 200 mm × 300 mm) inside, remove The air in the gas barrier container. Then, after sealing with a heat sealer, it was left in a 40°C environment for 48 hours. By placing it in the environment, it is the same as placing it at -10°C for 5 months. Thereafter, the film-like circuit connection adhesives of Examples 1 to 2 and Comparative Examples 1 to 2 were interposed between the same FPC as described above and the glass formed with a thin layer of ITO, and the FPC Between the PET substrate on which a thin layer of Ag paste is formed. This was heated and pressure-bonded under the same method and conditions as in the measurement of the connection resistance and the bonding strength to produce a connection structure. The connection resistance and bonding strength of this connection structure were measured by the same method as described above.

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

[table 3]

In addition, for the connection structure using the film-like circuit connection adhesive obtained in Example 3 to Example 6, the same test results as in Example 1 to Example 2 were also performed. 2 Similarly, low-temperature hardenability and storage stability are good.

The connection structure A of FPC/ITO using the circuit connection adhesive obtained in Examples 1 to 6, regardless of whether the storage stability test is performed, immediately after the connection at a heating temperature of 120°C, and at 85°C, After being kept in a constant temperature and humidity chamber of 85% RH for 240 hours (after the high temperature and high humidity test), both showed good connection resistance of 6.8 Ω or less and good adhesion strength of 600 N/m or more. In addition, in the FPC/Ag connection structure B, regardless of whether the storage stability test is performed, immediately after connection at a heating temperature of 120°C, and after being kept in a constant temperature and humidity bath at 85°C and 85%RH for 240 hours (After the high-temperature and high-humidity test), both exhibited a good connection resistance of 1.6 Ω or less and a good adhesive strength of 600 N/m or more. It was confirmed that the adhesives for circuit connection obtained in Examples 1 to 6 are excellent in low-temperature curability and storage stability.

In contrast, in the connection structure using the circuit connection adhesive obtained in Comparative Example 1 to Comparative Example 2, it was confirmed that a good connection can be obtained when the circuit connection adhesive before the storage stability test is used However, since the adhesive for circuit connection does not contain (d) complex compounds containing boron, when the adhesive for circuit connection after the storage stability test is used, it should be kept in a constant temperature and humidity bath for 240 hours (high temperature and high After the wet test), the connection resistance is increased compared to the examples. In addition, in the connection structure using the circuit connection adhesive obtained in Comparative Example 3 to Comparative Example 4, it was confirmed that the circuit connection adhesive did not contain (d) a complex compound containing boron. In the case of the storage stability test, the connection resistance after being kept in the constant temperature and humidity tank for 240 hours (after the high temperature and high humidity test) was also increased compared to the examples.

10‧‧‧Circuit component (first circuit component) 12‧‧‧Circuit board (first substrate) 12a‧‧‧Main surface 14‧‧‧Connecting terminal (first connecting terminal) 20‧‧‧Circuit component (second Circuit component) 22‧‧‧Circuit board (second substrate) 22a‧‧‧Main surface 24‧‧‧Connecting terminal (second connecting terminal) 30, 40‧‧‧Connecting member 30a, 40a‧‧‧ Adhesive composition 42, 42a‧‧‧Adhesive component 44‧‧‧Conductive particle 100,200‧‧‧Circuit member connection structure 300‧‧‧Solar cell module (connection structure) 310a, 310b‧‧‧Solar cell unit 312‧‧‧Substrate 312a‧‧‧Surface (main surface) 312b‧‧‧Back (main surface) 314‧‧‧Surface electrode 316‧‧‧Back electrode 320‧‧‧Wiring member 330‧‧‧Connecting member

Fig. 1 is a schematic cross-sectional view showing a connection structure according to a first embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing a method of manufacturing the connection structure shown in Fig. 1. Fig. 3 is a schematic cross-sectional view showing a connection structure according to a second embodiment of the present invention. Fig. 4 is a schematic cross-sectional view showing a method of manufacturing the connection structure shown in Fig. 3. Fig. 5 is a schematic cross-sectional view showing a connection structure according to a third embodiment of the present invention.

Claims (12)

An adhesive composition comprising (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a radical polymerization initiator, and (d) a complex compound containing boron, and the (d) The boron-containing complex is a compound represented by the following general formula (A), and the (d) boron-containing complex includes an amine having an organic group represented by the following general formula (a1) or The amine of an organic group represented by the following general formula (a2),

In formula (A), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbons or an aryl group, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, carbon number An alkyl group of 1 to 18, an organic group represented by the following general formula (a1), or an organic group represented by the following general formula (a2),

In formula (a1), R ^7a represents a hydrogen atom or an alkyl group having 1 to 6 carbons, and R ^7b represents a hydrogen atom, an amino group, an alkoxy group, or an alkyl group having 1 to 10 carbons; in addition, s and t are each independent Ground represents an integer from 1 to 10,

In the formula (a2), R ⁸ represents an alkyl group having 1 to 10 carbon atoms; and u represents an integer of 1 to 10. The adhesive composition according to claim 1, wherein the (b) radical polymerizable compound includes a vinyl compound having a phosphoric acid group and a radical polymerizable compound other than the vinyl compound. The adhesive composition according to item 1 of the scope of the patent application, wherein the (a) thermoplastic resin comprises selected from the group consisting of phenoxy resin, polyurethane resin, butyral resin, (meth)acrylic resin, At least one of a polyimide resin, a polyimide resin, and a copolymer having a structural unit derived from vinyl acetate. The adhesive composition according to claim 1, wherein the (a) thermoplastic resin includes a polyester urethane resin. The adhesive composition according to any one of items 1 to 4 in the scope of the patent application further includes (e) conductive particles. The adhesive composition described in any one of items 1 to 4 in the scope of the patent application is used to arrange the first connection terminal and the first connection terminal on the main surface of the first substrate. It is electrically connected to the second connection terminal arranged on the main surface of the second substrate. The adhesive composition described in any one of items 1 to 4 of the scope of the patent application is used to connect the connection terminal and wiring of a solar battery unit having a connection terminal arranged on the main surface of a substrate The components are electrically connected. A connection structure includes: a first circuit member having a first substrate and first connection terminals arranged on a main surface of the first substrate; a second circuit member having a second substrate and arranged on the first substrate 2 The second connecting terminal on the main surface of the substrate; and a connecting member arranged between the first circuit member and the second circuit member; the connecting member includes items 1 to 5 of the scope of patent application The cured product of any one of the adhesive composition, and the first connection terminal and the second connection terminal are electrically connected. The connection structure according to claim 8, wherein at least one of the first substrate and the second substrate includes a base material containing a thermoplastic resin having a glass transition temperature of 200°C or less. The connection structure according to item 8 of the scope of patent application, wherein at least one of the first substrate and the second substrate includes a material selected from polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. At least one substrate in the group consisting of ethylene formate. The connection structure described in item 8 of the scope of patent application, wherein the The first substrate includes a substrate containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate, and the second substrate includes a substrate containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. A base material of at least one of the group consisting of imide resin and polyethylene terephthalate. A connection structure including: a solar battery unit having a substrate and a connection terminal arranged on the main surface of the substrate; a wiring member; and a connection member arranged between the solar battery unit and the wiring member; The connecting member contains the cured product of the adhesive composition as described in any one of items 1 to 5 in the scope of patent application, and the connecting terminal is electrically connected to the wiring member.

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