JP2011038080A - Adhesive composition and connection structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition having excellent adhesive strength and stable performance, and a connection structure of a circuit member using the adhesive composition. <P>SOLUTION: This adhesive composition includes a thermoplastic resin (a), a radically polymerizable compound (b), a branched polymer (c) which is produced: by polymerizing a compound represented by formula (1) below; by polymerizing at least two compounds selected from among compounds represented by formulas (1), (2a) and (3b) below; or by polymerizing at least two compounds selected from among compounds represented by formulas (1), (2b) and (3a) below, and a radical polymerization initiator (d): A-R<SP>20</SP>-(B)<SB>x</SB>(1), R<SP>21</SP>-(A)<SB>2</SB>(2a), R<SP>21</SP>-(B)<SB>2</SB>(2b), R<SP>22</SP>-(A)<SB>3</SB>(3a), and R<SP>22</SP>-(B)<SB>3</SB>(3b) (wherein, R<SP>20</SP>is a (1+x) valent organic group, R<SP>21</SP>is a divalent organic group, R<SP>22</SP>is a trivalent organic group, x is an integer of 2 or more, A is a functional group reactive with B, and B is a functional group reactive with A). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

Various adhesives are used for bonding various members constituting elements such as semiconductor elements and liquid crystal display elements. The demand for such an adhesive is diverse, including adhesiveness, heat resistance, reliability in a high temperature and high humidity state, and the like. The adherend used for bonding, including organic substrate such as a printed wiring board or a polyimide, copper, (a composite oxide of indium and tin) metal or ITO, such as aluminum, SiN, SiO ₂ or the like, a wide variety A substrate having a surface state is used, and the adhesive is required to have a molecular design that matches the adherend.

  As an adhesive for a semiconductor element or a liquid crystal display element, a thermosetting resin using an epoxy resin having high adhesiveness and high reliability has been used (for example, see Patent Document 1). As a component of the thermosetting resin, a curing agent such as an epoxy resin, a phenol resin having reactivity with the epoxy resin, and a thermal latent catalyst that accelerates the reaction between the epoxy resin and the curing agent are generally used. A thermal latent catalyst is a substance that does not react at a storage temperature such as room temperature and exhibits high reactivity upon heating, and is an important factor that determines the curing temperature and the curing rate. Various compounds have been used as thermal latent catalysts from the viewpoint of storage stability of the adhesive at room temperature and curing rate during heating. In an actual process, desired adhesion is often obtained by curing at 170 to 250 ° C. for 1 to 3 hours. However, with recent high integration of semiconductor elements and high definition of liquid crystal elements, inter-element and The pitch between wirings has narrowed, and there has been a risk of adversely affecting peripheral members due to heating during curing. In order to reduce the cost, curing at a lower temperature and in a shorter time (low temperature rapid curing) is required. In order to achieve this low temperature rapid curing with an adhesive using an epoxy resin, it is necessary to use a thermal latent catalyst having a low activation energy. However, it is known that it is very difficult to combine storage stability near room temperature.

  Recently, a radical curable adhesive using a radical polymerizable compound such as an acrylate derivative or a methacrylate derivative in combination with a peroxide as a radical polymerization initiator has attracted attention. Radical curing can be cured for a short time because radicals that are reactive species are rich in reactivity (see, for example, Patent Document 2). However, since the radical curing adhesive has a large curing shrinkage when heated, it is inferior in adhesive strength as compared with the case of using an epoxy resin. As a method for solving such a problem, a method has been proposed in which liquid rubber is added to an adhesive to improve wettability and improve adhesive strength (for example, Patent Document 3).

Japanese Patent Laid-Open No. 1-113480 International Publication No. 98/44067 International Publication No. 2004/50779

  However, since organic substrates such as polyimide have a rigid and planar molecular structure and form a strong charge transfer complex between molecules, it is extremely difficult to form a covalent bond with the adhesive composition. It is. Furthermore, since the polyimide surface is usually smooth, the adhesion effect due to the physical anchoring effect (anchor effect) is small. Therefore, simply improving the wettability results in a decrease in adhesive strength after long-term exposure (for example, 85 ° C./85% RH) under high temperature and high humidity conditions. When these materials are used in adhesives for semiconductor elements and liquid crystal display elements that require stable performance even after prolonged exposure under high temperature and high humidity conditions, characteristics such as adhesive strength and connection resistance deteriorate after reliability testing. To do.

  Therefore, the present invention can provide excellent adhesive strength under low temperature and short time curing conditions, and stable performance (adhesive strength and connection resistance) even after a long-term reliability test (high temperature and high humidity test). It is an object of the present invention to provide an adhesive composition capable of maintaining the above and a circuit member connection structure using the same.

The present invention includes (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a branched polymer obtained by polymerizing a compound represented by the following general formula (1), the following general formula (1), ( Of the compounds represented by 2a) and (3b), a branched polymer obtained by polymerizing at least two compounds, or among the compounds represented by the following general formulas (1), (2b) and (3a) A branched polymer obtained by polymerizing at least two kinds of compounds,
A-R ^20- (B) _X (1)
_{^{R 21 - (A) 2 ...}} (2a), R 21 - (B) 2 ... (2b)
_{^{R 22 - (A) 3 ...}} (3a), R 22 - (B) 3 ... (3b)
[Wherein R ²⁰ is a (1 + x) valent organic group, R ²¹ is a divalent organic group, R ²² is a trivalent organic group, x is an integer of 2 or more, A is a functional group reactive with B, B represents a functional group reactive with A, respectively. And (d) a radical polymerization initiator. According to such a configuration, it is possible to perform adhesion by low-temperature rapid curing, and it is possible to maintain stable adhesive strength even after a long-term reliability test.

  (C) The branched polymer preferably has at least one urethane bond or imide bond. By having at least one or more such bonds in the branched polymer, heat resistance and adhesive strength with an organic substrate such as a printed wiring board or polyimide can be further improved, and excellent connection reliability can be obtained. .

  (C) The branched polymer preferably has an isocyanurate ring. By using a branched polymer having such a structure, it is possible to further improve the adhesive strength and heat resistance with an organic substrate such as a printed wiring board or polyimide, and to obtain excellent connection reliability. Become.

  (C) The weight average molecular weight of the branched polymer may be 1000 or more and less than 20000. By using a branched polymer having such a molecular weight, the heat resistance is further improved, and excellent connection reliability can be obtained.

  (C) The branched polymer may have a radical polymerizable functional group. When the branched polymer has a radical polymerizable functional group, the branched polymer reacts with other components to obtain a cross-linked structure, heat resistance is further improved, and excellent connection reliability can be obtained.

  In the above case, it is preferable that (c) the branched polymer has 3 or more radical polymerizable functional groups per molecule. When the number of radically polymerizable functional groups is equal to or more than the above numerical value, a high crosslinking density is obtained, heat resistance is further improved, and excellent connection reliability can be obtained.

  (B) The radical polymerizable compound preferably contains at least one vinyl compound having a phosphate group and one or more radical polymerizable compounds other than the compound. When the radically polymerizable compound contains such a compound, it becomes possible to obtain excellent adhesion strength to the substrate, particularly to the metal.

  (A) The thermoplastic resin preferably contains at least one resin selected from the group consisting of phenoxy resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin and polyimide resin. By using such a resin as a thermoplastic resin, heat resistance and adhesion are further improved, and these excellent characteristics can be maintained even after a long-term reliability test (high temperature and high humidity test). .

  It is preferable that the adhesive composition further contains (e) conductive particles. By containing conductive particles, it is possible to impart good conductivity or anisotropic conductivity to the adhesive composition, and the adhesive composition is particularly suitable for adhesive applications between circuit members having circuit electrodes. It can be preferably used. Moreover, the connection resistance between the circuits electrically connected via the adhesive composition can be more sufficiently reduced.

  The present invention relates to a circuit member connection structure comprising a first circuit member having a first connection terminal on the main surface, a second circuit member having a second connection terminal on the main surface, and a connection member. The first and second circuit members are disposed via the connection members so that the first and second connection terminals face each other, and the first and second connection terminals are electrically Provided is a circuit member connection structure in which the connection member is connected and the connection member is formed of a cured product of the adhesive composition of the present invention. In such a connection structure, since the cured product of the above-described adhesive composition is used to connect the pair of circuit members, the adhesive strength between the circuit members can be sufficiently increased, and further, for a long time. Stable performance can be maintained even after a reliability test (for example, at 85 ° C./85% RH). The adhesive composition of the present invention used as a connecting member does not need to be completely cured (the highest degree of curing that can be achieved under predetermined curing conditions), and is in a partially cured state as long as the above characteristics are produced. Also good.

  According to the present invention, excellent adhesive strength can be obtained even under low temperature and short curing conditions, and stable performance can be maintained even after a long-term reliability test (for example, 85 ° C / 85% RH). In addition, it is possible to provide an adhesive composition excellent in handleability and a circuit member connection structure using the same.

  Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, (meth) acrylic acid shows acrylic acid or methacrylic acid corresponding to it, (meth) acrylate means acrylate or a corresponding methacrylate, and (meth) acryloyl group corresponds to acryloyl group or it. Means a methacryloyl group;

  In addition, in this specification, (a) Glass transition temperature (Tg) of a thermoplastic resin means the main dispersion peak temperature defined below. That is, using a dynamic viscoelasticity measuring device (for example, a viscoelasticity analyzer “RSA-3” (trade name) manufactured by TA Instruments Inc.), (a) a temperature increase rate of a thermoplastic resin film Dynamic viscoelasticity is measured under the conditions of 5 ° C./min, frequency 10 Hz, measurement temperature −150 to 300 ° C., and the peak temperature of tan δ is defined as the main dispersion peak temperature.

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

  Hereinafter, embodiments of the adhesive composition of the present invention will be described in detail.

  The thermoplastic resin (a) used in the present invention is a solid at room temperature, becomes a liquid state by heating and can be freely deformed by external force, and when cooled and removed, it becomes hard while maintaining its shape. This is a resin (polymer) with the properties that can be repeated. Moreover, the resin (polymer | polymer) which has the above-mentioned property and has a reactive functional group is also included. (A) Tg of the thermoplastic resin is preferably 0 to 190 ° C, more preferably 20 to 170 ° C. Moreover, even if it corresponds to the definition of said thermoplastic resin, the compound which has the structure of (c) branched polymer mentioned later is classified into (c) branched polymer.

  The thermoplastic resin preferably has a linear main chain. When the thermoplastic resin has a side chain, it is preferable that the side chain is not in a dendritic shape (refers to a shape in which branches increase toward the tip). As such a thermoplastic resin, polyimide resin, polyamide resin, phenoxy resin, (meth) acrylic resin, urethane resin, polyester urethane resin (urethane-modified polyester resin), polyvinyl butyral resin, or the like can be used. These can be used alone or in admixture of two or more. Furthermore, these thermoplastic resins may contain siloxane bonds or fluorine substituents. These can be suitably used as long as the resins to be mixed are completely compatible with each other or microphase separation occurs and becomes cloudy. When the adhesive composition is used in the form of a film, the larger the molecular weight of the thermoplastic resin, the easier it is to form the film, and the melt viscosity that affects the fluidity of the film-like adhesive composition is widened. Can be set. The weight average molecular weight is preferably 5,000 to 150,000, particularly preferably 10,000 to 80,000. When this value is 5,000 or more, good film formability is obtained, and when it is 150,000 or less, good compatibility with other components tends to be obtained.

  In the adhesive composition of the present invention, the content of the thermoplastic resin (a) is preferably 5 to 80% by mass, more preferably 15 to 70% by mass, based on the total amount of the adhesive composition. preferable. When the content is 5% by mass or more, particularly when the adhesive composition is used in the form of a film, good film formability tends to be obtained, and when it is 80% by mass or less, a good adhesive composition is obtained. It tends to be easy to obtain fluidity.

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

  Specifically, epoxy (meth) acrylate oligomer, urethane (meth) acrylate oligomer, polyether (meth) acrylate oligomer, oligomer such as polyester (meth) acrylate oligomer, trimethylolpropane tri (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, polyalkylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) acrylate, bisphenoxyethanol fluorene acrylate, bis Epoxy (meth) acrylate with (meth) acrylic acid added to glycidyl group of enolic fluorenediglycidyl ether, bisphenoxyethanol fluorene acrylate, epoxy with (meth) acrylic acid added to glycidyl group of bisphenol fluorenediglycidyl ether ) A compound obtained by adding a (meth) acryloyloxy group to a compound obtained by adding ethylene glycol or propylene glycol to a glycidyl group of acrylate or bisphenol fluorenediglycidyl ether; It is done.

（ここでＲ^１及びＲ^２は、各々独立に水素原子又はメチル基を示し、ａ及びｂは、各々独立に１〜８の整数を表す。）

(Here, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and a and b each independently represent an integer of 1 to 8.)

（ここでＲ^３及びＲ^４は、各々独立に水素原子又はメチル基を示し、ｃ及びｄは、各々独立に０〜８の整数を表す。）

(Here, R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and c and d each independently represents an integer of 0 to 8.)

  In addition, (b) as a radically polymerizable compound, when it is allowed to stand alone at 30 ° C., it does not have a fluidity such as wax, wax, crystal, glass or powder, and exhibits a solid state. Can be used without any particular limitation.

  Specifically, N, N′-methylenebisacrylamide, diacetone acrylamide, N-methylolacrylamide, N-phenylmethacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, tris (2-acryloyloxyethyl) isocyanurate N-phenylmaleimide, N- (o-methylphenyl) maleimide, N- (m-methylphenyl) maleimide, N- (p-methylphenyl) maleimide, N- (o-methoxyphenyl) maleimide, N- (m -Methoxyphenyl) maleimide, N- (p-methoxyphenyl) maleimide, N-methylmaleimide, N-ethylmaleimide, N-octylmaleimide, 4,4'-diphenylmethane bismaleimide, m-phenylenebismaleimide, 3,3 ' -Dimethyl-5 '-Diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, N-methacryloxymaleimide, N-acryloxymaleimide, 1,6-bismaleimide- (2,2,4 -Trimethyl) hexane, N-methacryloyloxysuccinimide, N-acryloyloxysuccinimide, 2-naphthyl methacrylate, 2-naphthyl acrylate, pentaerythritol tetraacrylate, divinylethylene urea, divinylpropylene urea, 2-polystyrylethyl methacrylate N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N-phenyl-N ′-(3-acryloyloxy-2-hydroxypropyl) -p-phenylenedia , Tetramethylpiperidyl methacrylate, tetramethylpiperidyl acrylate, pentamethylpiperidyl methacrylate, pentamethylpiperidyl acrylate, octadecyl acrylate, Nt-butylacrylamide, diacetone acrylamide, N- (hydroxymethyl) acrylamide, the following general formula (III ) To (XII).

（ｅは、１〜１０の整数を表す。）

(E represents an integer of 1 to 10)

（ここでＲ^５は、水素原子又はメチル基、Ｒ^６は、水素原子又はメチル基、ｆは、１５〜３０の整数を表す。）

(Here, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or a methyl group, and f represents an integer of 15 to 30.)

（ここでＲ^７は、水素原子又はメチル基、Ｒ^８は、水素原子又はメチル基、ｇは、１５〜３０の整数を表す。）

(Here, R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents a hydrogen atom or a methyl group, and g represents an integer of 15 to 30.)

（ここでＲ^９は、水素原子又はメチル基を表す。）

(Here, R ⁹ represents a hydrogen atom or a methyl group.)

（ここでＲ^１０は、水素原子又はメチル基、ｈは、１〜１０の整数を表す。）

(Here, R ¹⁰ represents a hydrogen atom or a methyl group, and h represents an integer of 1 to 10.)

（ここでＲ^１１は、水素原子又は下記一般式（ｉ）又は（ｉｉ）で示す有機基、ｉは、１〜１０の整数を表す。なお、一般式（ｉ）及び（ｉｉ）における＊は結合位置を示す。）

(Here, R ¹¹ represents a hydrogen atom or an organic group represented by the following general formula (i) or (ii), i represents an integer of 1 to 10. In the general formulas (i) and (ii), * represents Indicates the bonding position.)

（ここでＲ^１２、は水素又は下記一般式（ｉｉｉ）又は（ｉｖ）で示す有機基、ｊは、１〜１０の整数を表す。なお、一般式（ｉｉｉ）及び（ｉｖ）における＊は結合位置を示す。）

(Here, R ¹² is hydrogen or an organic group represented by the following general formula (iii) or (iv), j represents an integer of 1 to 10. In the general formulas (iii) and (iv), * represents a bond) Indicates position.)

（ここでＲ^１３は、水素原子又はメチル基を表す。）

(Here, R ¹³ represents a hydrogen atom or a methyl group.)

（ここでＲ^１４は、水素原子又はメチル基を表す。）

(Here, R ¹⁴ represents a hydrogen atom or a methyl group.)

  (B) N-vinyl compounds selected from the group consisting of vinyl compounds having a phosphate group and N-vinyl compounds and N, N-dialkylvinyl compounds, which are compounds belonging to component (b) Can be used in combination with ingredients. By using in combination with a vinyl compound having a phosphate group, the adhesiveness of the adhesive composition to the metal substrate can be improved. Moreover, the crosslinking rate of an adhesive composition can be improved by using together with a N-vinyl type compound.

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

（ここでＲ^１５は、（メタ）アクリロイル基を示し、Ｒ^１６は、水素原子又はメチル基、ｋ及びｌは、各々独立に１〜８の整数を示す。なお、式中、Ｒ^１５同士、Ｒ^１６同士、ｋ同士及びｌ同士は、それぞれ同一でも異なってもよい。）

(Wherein ^{R 15} represents a (meth) acryloyl ^{group, R 16} is a hydrogen atom or a methyl group, k and l are each independently an integer of 1-8. In the ^{formulas, R 15} to each other, R ^{16 s} , k s, and l s may be the same or different.

（ここでＲ^１７は、（メタ）アクリロイル基を示し、ｍ及びｎは各々独立に１〜８の整数を示す。なお、式中、Ｒ^１７同士、ｍ同士及びｎ同士は、それぞれ同一でも異なってもよい。）

(Here, R ¹⁷ represents a (meth) acryloyl group, and m and n each independently represent an integer of 1 to 8. In the formula, R ^17s , ms and ns are the same or different. May be.)

（ここで、Ｒ^１８は、（メタ）アクリロイル基を示し、Ｒ^１９は、水素原子又はメチル基を示し、ｏ及びｐは各々独立に１〜８の整数を示す。）

(Here, R ¹⁸ represents a (meth) acryloyl group, R ¹⁹ represents a hydrogen atom or a methyl group, and o and p each independently represent an integer of 1 to 8)

  Specific examples of the compound include acid phosphooxyethyl methacrylate, acid phosphooxyethyl acrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol monomethacrylate, 2, 2'-di (meth) acryloyloxydiethyl phosphate, EO-modified phosphoric acid dimethacrylate, phosphoric acid-modified epoxy acrylate, vinyl phosphate, and the like.

  The addition amount of the vinyl compound having a phosphate group is 0 with respect to 100 parts by mass of (a) the thermoplastic resin, independently of the addition amount of the (b) radical polymerizable compound other than the vinyl compound having a phosphate group. It is preferable to set it as 2-300 mass parts, and it is more preferable to set it as 1-200 mass parts. By making the addition amount of the vinyl compound having a phosphoric acid group 0.2 parts by mass or more, high adhesive strength is easily obtained, and by making it 300 parts by mass or less, the adhesive composition after curing The physical properties are not easily lowered, and it becomes easy to ensure reliability.

  Specific examples of the N-vinyl compound include N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4′-vinylidenebis (N, N— Dimethylaniline), N-vinylacetamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and the like.

  The addition amount of the radically polymerizable compound (b) excluding the compound contained in the vinyl compound having a phosphoric acid group described above is 50 to 250 parts by mass with respect to 100 parts by mass of the (a) thermoplastic resin. Preferably, it is 60-150 mass parts. When the addition amount is 50 parts by mass or more, sufficient heat resistance is easily obtained after curing. Moreover, when it is 250 mass parts or less, when using as a film, favorable film formation property is easy to be obtained.

The branched polymer used in the present invention is, for example, self-polymerization of an AB _X- type monomer (x is an integer of 2 or more) having a total of 3 or more of two types of substituents in one molecule, and one type in one molecule. Polymerization of A ₂ type monomer having ₂ substituents of the above and B ₃ type monomer having 3 types of substituents other than A in one molecule, or AB _X type, A ₂ type and B _It can be obtained by polymerization of at least two monomers selected from the _three types. A branched polymer is also a polymerization of a B ₂ type monomer having two types of substituents in one molecule and an A ₃ type monomer having three types of substituents different from B in one molecule. Alternatively, it can be obtained by polymerization of at least two monomers selected from AB _X type, B ₂ type and A ₃ type.

In the above monomers, AB _X type _{^{A-R 20 - (B)}} X, A 2 type are _{^{R 21 - (A) 2,}} B 3 type is ^R 22 - represented by _{(B) 3.} Further, _{B 2} type is _{^{R 21 - (B) 2,}} A 3 -inch is ^R 22 - represented by _{(A) 3.} Here, A and B are selected from a hydroxyl group (including a phenol hydroxyl group), a carboxylic acid group (including a carboxylic anhydride), an amino group, a thiol group, an isocyanate group, and the like, and A and B each represent a different functional group. It is preferable. When A and B are hydroxyl groups (including phenolic hydroxyl groups), carboxylic acid groups (including carboxylic anhydrides), amino groups, and isocyanate groups, A and B react to form ester bonds, amide bonds, urethane bonds, and imide bonds. Thus, the interaction and wettability with respect to an organic substrate such as a printed wiring board or polyimide is improved, and high adhesive strength is obtained. R ²⁰ , R ²¹ and R ²² are an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, a heteroatom-containing group, and groups represented by general formulas (XVI) to (XXVII). Etc. (in the formula, * indicates a bonding position). From the viewpoint of flexibility, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, a group derived from a compound having an aliphatic hydrocarbon skeleton and an aromatic hydrocarbon skeleton, an alicyclic hydrocarbon skeleton and an aromatic hydrocarbon A group derived from a compound having a skeleton, and a group derived from a compound having an aliphatic hydrocarbon skeleton, an alicyclic hydrocarbon skeleton, and an aromatic hydrocarbon skeleton are more preferable. Here, “derived group” means a group having a structure in which a hydrogen atom is removed. In addition, the group mentioned above may have an isocyanurate ring like group represented by a formula (XXVII). By adopting the above-described groups as R ²⁰ , R ²¹ , and R ²² , moderate flexibility is imparted to the cured product of the adhesive composition, adhesive strength is improved, and connection reliability is improved.

（式中、ｑは、１〜１０の整数を表す。）

(In the formula, q represents an integer of 1 to 10.)

（式中、ｒは、１〜１０の整数を表す。）

(In the formula, r represents an integer of 1 to 10.)

  The branched polymer obtained from these monomers may be used as a mixture of two or more, in addition to being used alone as the (c) branched polymer.

  In the adhesive composition of the present invention, the branched polymer preferably contains an isocyanurate ring from the viewpoint of improving the adhesive strength to the polyimide substrate. When the branched polymer contains an isocyanurate ring, heat resistance and adhesive strength with an organic base material such as a printed wiring board and polyimide can be improved, and excellent connection reliability can be obtained. Furthermore, it is more preferable that the bond produced | generated by reaction of the functional group shown by A and B contains a urethane bond and / or an imide bond. When the branched polymer contains an imide bond, heat resistance and adhesive strength with an organic base material such as a printed wiring board and polyimide can be improved, and excellent connection reliability can be obtained. Moreover, when the branched polymer contains a urethane bond, the adhesive strength with the base material is improved and the peeling tends to be suppressed.

  In addition, the degree of polymerization of the branched polymer used in the present invention can be freely adjusted and suitably used when the weight average molecular weight is 1000 or more and less than 20000. When the weight average molecular weight of the branched polymer is 1000 or more, there is a tendency that the film-forming properties and physical properties can be improved. When the weight average molecular weight is less than 20000, the solubility when the branched polymer is dissolved in a solvent and the adhesive composition are used. There is a tendency to improve the fluidity.

  In addition, the branched polymer (c) in the present invention preferably has radical polymerization at all or some of the terminal functional groups, and more preferably has at least three radical polymerizable functional groups from the viewpoint of heat resistance. Preferably, it has 3 or more and 15 or less radically polymerizable functional groups. When the number of radical polymerizable functional groups is 3 or more, a sufficient crosslinking density is easily obtained, and the heat resistance tends to be improved.

  Moreover, the addition amount of (c) branched polymer used for this invention is 0.2-100 mass parts with respect to 100 mass parts of (a) thermoplastic resin, Preferably it is 0.5-70 mass parts. It is. When the addition amount is 0.2 parts by mass or more, the heat resistance is improved, and when it is less than 100 parts by mass, the film formability tends to be improved when used as a film.

  As the radical polymerization initiator (d) used in the present invention, conventionally known compounds such as organic peroxides and azo compounds that generate radicals by applying external energy can be used. From the viewpoints of compatibility and compatibility, organic peroxides having a 1 minute half-life temperature of 90 to 175 ° C. and a molecular weight of 180 to 1,000 are preferred. When the 1-minute half-life temperature is within this range, the storage stability is excellent, the radical polymerizability is sufficiently high, and the composition can be cured in a short time.

(D) Specific examples of radical polymerization initiators include 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, and di (2 -Ethylhexyl) peroxydicarbonate, cumylperoxyneodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylper Oxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethyl) Hexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylpero Ci-2-ethylhexanoate, t-butylperoxyneoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy-3 , 5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, t-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, Di (3-methylbenzoyl) peroxide, dibenzoyl peroxide, di (4-methylbenzoyl) peroxide, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3, 5,5-trimethylhexanoate, t-butylperoxylaurate 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2, Organics such as 5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, dibutylperoxytrimethyladipate, t-amylperoxynormal octoate, t-amylperoxyisononanoate, t-amylperoxybenzoate Peroxides; 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobisisobutyronitrile, 2, , 2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyro Tolyl, 4,4'-azobis (4-cyanovaleric acid), azo compounds such as 1,1'-azobis (1-cyclohexanecarbonitrile); and the like.
These compounds may be used alone or as a mixture of two or more compounds.

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

  The addition amount of the radical polymerization initiator (d) of the present invention is preferably 0.1 to 500 parts by mass, more preferably 1 to 300 parts by mass with respect to 100 parts by mass of the (a) thermoplastic resin. (D) When the addition amount of the radical polymerization initiator is 0.1 parts by mass or more, the adhesive composition is easily cured, and when it is 500 parts by mass or less, the storage stability tends to be good. is there.

(E) The conductive particles may be particles having conductivity on the whole or on the surface, but when used for connection of a circuit member having connection terminals, those having an average particle size smaller than the distance between the connection terminals. Use.
Examples of the conductive particles (e) used in the present invention include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon. Further, non-conductive glass, ceramic, plastic or the like may be used as a core, and the core may be coated with the metal, metal particles, or carbon. (E) In the case where the conductive particles are made of plastic as a core and the core is coated with the above metal, metal particles or carbon, or hot-melt metal particles, they are deformable by heating and pressurization, so that they are in contact with the electrode at the time of connection. This is preferable because the area is increased and the reliability is improved.

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

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

  (E) Although the amount of conductive particles used is not particularly limited, it is preferably 0.1 to 30% by volume, and preferably 0.1 to 10% by volume, based on the total volume of the adhesive composition. Is more preferable. If this value is 0.1% by volume or more, the conductivity tends to be high, and if it is less than 30% by volume, a short circuit tends to be difficult to occur. In addition, although volume% is determined based on the volume of each component before 23 degreeC hardening, the volume of each component can be converted into a volume from a weight using specific gravity. In addition, do not dissolve or swell the component in a graduated cylinder, etc., but put in a suitable solvent (water, alcohol, etc.) that wets the component well. You can ask for it.

  A stabilizer can be added to the adhesive composition of the present invention in order to control the curing rate and impart storage stability. As such a stabilizer, known compounds can be used without particular limitation, but quinone derivatives such as benzoquinone and hydroquinone; phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol; , 6,6-tetramethylpiperidine-1-oxyl, aminoxyl derivatives such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl; hindered amine derivatives such as tetramethylpiperidyl methacrylate;

  The addition amount of a stabilizer is 0.01-30 mass parts with respect to 100 mass parts of adhesive compositions, Preferably it is 0.05-10 mass parts. When the addition amount is 0.01 parts by mass or more, control of the curing rate and storage stability are easily imparted, and when it is less than 30 parts by mass, the compatibility with other components is hardly adversely affected.

  Adhesive aids such as coupling agents represented by alkoxysilane derivatives and silazane derivatives, adhesion improvers, and leveling agents may be appropriately added to the adhesive composition of the present invention. Specifically, a compound represented by the following general formula (XXVIII) is preferable, and in addition to using alone, two or more compounds may be mixed and used.

（ここでＲ^２３、Ｒ^２４、Ｒ^２５は独立に、水素原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、炭素数１〜５のアルコキシカルボニル基又はアリール基、Ｒ^２６は（メタ）アクリロイル基、ビニル基、イソシアナート基、イミダゾール基、メルカプト基、アミノ基、メチルアミノ基、ジメチルアミノ基、ベンジルアミノ基、フェニルアミノ基、シクロヘキシルアミノ基、モルホリノ基、ピペラジノ基、ウレイド基又はグリシジル基、ｓは１〜１０の整数を示す。）

(Wherein R ²³ , R ²⁴ and R ²⁵ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms or an aryl group, R ²⁶ is a (meth) acryloyl group, vinyl group, isocyanate group, imidazole group, mercapto group, amino group, methylamino group, dimethylamino group, benzylamino group, phenylamino group, cyclohexylamino group, morpholino group, piperazino group, (Ureido group or glycidyl group, s represents an integer of 1 to 10)

  The adhesive composition of the present invention may be used in combination with a rubber component for the purpose of stress relaxation and adhesion improvement. The rubber component refers to a component that exhibits rubber elasticity (for example, JIS K6200) as it is or a component that exhibits rubber elasticity by reaction. The rubber component may be solid or liquid at room temperature (25 ° C.), but is preferably liquid from the viewpoint of improving fluidity. As the rubber component, a compound having a polybutadiene skeleton is preferable. The rubber component may have a cyano group, a carboxyl group, a hydroxyl group, a (meth) acryloyl group, or a morpholine group. From the viewpoint of improving adhesiveness, a rubber component containing a cyano group or a carboxyl group, which is a highly polar group, in the side chain or terminal is preferable. In addition, even if it has a polybutadiene skeleton, if it exhibits thermoplasticity, it is classified as component (a), and if it exhibits radical polymerizability, it is classified as component (b).

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

The rubber component having a high polar group and being liquid at room temperature specifically includes a liquid acrylonitrile-butadiene rubber, a carboxyl group, a hydroxyl group, a (meth) acryloyl group or a morpholine group at the polymer end. Examples thereof include liquid acrylonitrile-butadiene rubber and liquid carboxylated nitrile rubber, and the content of acrylonitrile which is a polar group is preferably 10 to 60% by mass.
These compounds may be used alone or in admixture of two or more compounds.

  Further, the adhesive composition of the present invention may be used in combination with organic fine particles for the purpose of stress relaxation and adhesion improvement. The average particle diameter of the organic fine particles is 0.05 to 1.0 μm. When the organic fine particles are composed of the above rubber component, the organic fine particles are classified as a rubber component instead of the organic fine particles. When the organic fine particles are composed of the above-described (a) thermoplastic resin, the organic fine particles are classified as a thermoplastic resin instead of the organic fine particles. .

Specific examples of the organic fine particles include polyisoprene, polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1,2-polybutadiene, acrylic rubber, styrene-butadiene rubber, and acrylonitrile-butadiene. Acrylonitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene), alkoxysilyl-terminated poly (oxypropylene), poly, which contains rubber, carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer end (Oxytetramethylene) glycol, polyolefin glycol (meth) alkyl acrylate-butadiene-styrene copolymer, alkyl (meth) acrylate-silicone copolymer or Recone - (meth) include organic fine particles of acrylic copolymer or complex.
These organic fine particles may be used alone or in combination of two or more compounds.

  The adhesive composition of the present invention can be used in the form of a paste when it is liquid at room temperature. In the case of a solid at room temperature, it may be used by heating, or may be pasted using a solvent. As the solvent that can be used, those that are not reactive with the adhesive composition and additives and that exhibit sufficient solubility are preferred, and those having a boiling point of 50 to 150 ° C. at normal pressure are preferred. When the boiling point is 50 ° C. or higher, there is little risk of volatilization even when left at room temperature, and use in an open system becomes easy. On the other hand, when the boiling point is less than 150 ° C., it is easy to volatilize the solvent, and adverse effects on reliability after bonding are reduced.

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

  The adhesive composition of the present invention can be bonded by using heating and pressurization together. The heating temperature is preferably 100 to 250 ° C. The pressure is preferably in a range that does not damage the adherend, and generally 0.1 to 10 MPa. These heating and pressurization are preferably performed in the range of 0.5 seconds to 120 seconds, and can be bonded even by heating at 140 to 200 ° C., 3 MPa, and 10 seconds.

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

  Below, an example of the connection of the adhesive composition of this invention containing electroconductive particle and the anisotropic conductive film produced using and an electrode is demonstrated. An anisotropic conductive film is present between opposing electrodes on the substrate, and is heated and pressed to obtain contact between both electrodes and adhesion between the substrates, thereby enabling connection with the electrodes. As a substrate for forming the electrode, an inorganic material such as a semiconductor, glass or ceramic, an organic material such as polyimide or polycarbonate, or a combination of these composites such as glass / epoxy can be applied.

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

(Preparation of thermoplastic resin (phenoxy resin))
Phenoxy resin (trade name: YP-50, manufactured by Toto Kasei Co., Ltd.) was prepared by dissolving 40 parts by mass of resin in 60 parts by mass of methyl ethyl ketone to obtain a solution having a solid content of 40% by mass.

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

(Synthesis of urethane resin)
450 parts by weight of polybutylene adipate diol having a weight average molecular weight of 2000 (manufactured by Aldrich), 450 parts by weight of polyoxytetramethylene glycol having a mean molecular weight of 2000 (manufactured by Aldrich), 1,4-butylene glycol (manufactured by Aldrich) ) 100 parts by mass is dissolved in 4000 parts by mass of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.), 390 parts by mass of diphenylmethane diisocyanate (manufactured by Aldrich) is added and reacted at 70 ° C. for 60 minutes to obtain a urethane resin. Got. It was 100000 when the weight average molecular weight of the obtained urethane resin was measured by GPC method.

(Preparation of rubber component)
Liquid rubber (trade name: Nipol DN601, manufactured by Nippon Zeon Co., Ltd.) was prepared.

(Preparation of branched polymer)
A hyperbranched polyimide polymer (trade name: V-8000 (Mw11500, acid value 40.3 mgKOH / g), manufactured by DIC Corporation) was prepared.

(Synthesis of branched polymer (HB-1))
In a reactor equipped with a reflux condenser, stirrer, thermometer, temperature controller and water separator, 100 g of V-8000, 150 ml of methyl ethyl ketone as a reaction solvent, 0.001 g of hydroquinone as a stabilizer, tetrabutyl as a base catalyst 0.053 g of ammonium chloride is charged, and 0.7 g (0.0049 mol) of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) is added dropwise with stirring. After the dropwise addition, the mixture was refluxed for 2 hours and allowed to cool, and then the reaction mixture was dropped into water for reprecipitation, and the obtained solid was dried to obtain 95 g of branched polymer (HB-1). The weight average molecular weight of the obtained branched polymer was 12500, and the acid value was 37.9 mgKOH / g.

(Synthesis of branched polymer (HB-2))
Branching was performed in the same manner as HB-1, except that the amount of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was 1.9 g (0.013 mol) and the amount of tetrabutylammonium chloride was 0.14 g. 95 g of polymer (HB-1) was obtained. The weight average molecular weight of the obtained branched polymer was 12500, and the acid value was 33.2 mgKOH / g.

(Preparation of branched polymer)
A branched polymer urethane acrylate (trade name: CN9013, manufactured by SARTOMER) was prepared.

(Preparation of radical polymerizable compound)
Isocyanuric acid EO-modified diacrylate (trade name: M-215, manufactured by Toa Gosei Co., Ltd.) was prepared.

(Synthesis of urethane acrylate (UA))
860 parts by mass of poly (hexamethylene carbonate) diol (manufactured by Aldrich Co., Ltd.) having a number average molecular weight of 860 in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube. 00 mol) and 5.53 parts by mass of dibutyltin dilaurate (manufactured by Aldrich). After sufficiently introducing nitrogen gas, the mixture was heated to 70 to 75 ° C., and 666 parts by mass (3.00 mol) of isophorone diisocyanate (manufactured by Aldrich Co., Ltd.) was uniformly added dropwise over 3 hours to be reacted. The reaction was continued for about 10 hours after the completion of the dropwise addition. To this, 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich) were further reacted for 10 hours. After confirming that the isocyanate had disappeared, the reaction was terminated to obtain urethane acrylate (UA). The number average molecular weight of the obtained urethane acrylate (UA) was 3,700.

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

(Preparation of radical polymerization initiator)
As a radical polymerization initiator, t-hexylperoxy-2-ethylhexanoate (trade name: perhexyl O, manufactured by NOF Corporation) was prepared.

(Preparation of conductive particles)
A nickel layer having a thickness of 0.2 μm is provided on the surface of particles having polystyrene as a core, and a gold layer having a thickness of 0.02 μm is provided outside the nickel layer, and conductive particles having an average particle diameter of 4 μm and a specific gravity of 2.5. Was made.

(Examples 1-7, Comparative Examples 1-4)
It mix | blends as shown in Table 2 by solid weight ratio, Furthermore, 1.5 volume% of electroconductive particles are mix-dispersed, this is apply | coated on an 80-micrometer-thick fluororesin film using a coating device, 70 degreeC, A film-like adhesive composition having an adhesive layer thickness of 20 μm was obtained by drying with hot air.

[Measurement of connection resistance and adhesive strength]
A flexible circuit board (FPC) having the film-like adhesive compositions of Examples 1 to 7 and Comparative Examples 1 to 4 having 500 copper circuits having a line width of 25 μm, a pitch of 50 μm, and a thickness of 18 μm on a polyimide film; It was interposed between the glass (thickness 1.1 mm, surface resistance 20Ω / □) on which a thin layer of 2 μm ITO was formed. Using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.), this was heated and pressurized at 160 ° C. and 3 MPa for 10 seconds to be connected over a width of 2 mm to produce a connected body. The resistance value between adjacent circuits of this connection body was measured with a multimeter immediately after bonding and after being held in a high-temperature and high-humidity bath at 85 ° C. and 85% RH for 240 hours (after the test). The resistance value was shown as an average of 37 resistances between adjacent circuits.

  Moreover, the adhesive strength of this connection body was measured by a 90-degree peeling method according to JIS-Z0237 and evaluated. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as a measuring device for adhesive strength. The results of measurement of the connection resistance and adhesive strength of the film adhesive composition performed as described above are shown in Table 3 below.

The adhesive compositions obtained in Examples 1 to 7 were about 3Ω at a heating temperature of 160 ° C. immediately after bonding and after being kept in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test). It was revealed that the following good connection resistance and good adhesive strength of 700 N / m or more were exhibited.
On the other hand, in Comparative Examples 1 and 2 that do not use the branched polymer (c) in the present invention, although it shows a good connection resistance immediately after bonding, it is in a high-temperature and high-humidity tank at 85 ° C. and 85% RH. After holding for 240 hours (after the test), it became clear that the connection resistance was high and the adhesive strength was low. Moreover, in Comparative Examples 3 and 4, it was revealed that the connection resistance was high immediately after bonding and after being held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after the test), and the adhesive strength was also low. .

Claims (10)

(A) a thermoplastic resin,
(B) a radically polymerizable compound,
(C) A branched polymer obtained by polymerizing a compound represented by the following general formula (1), and at least two compounds among the compounds represented by the following general formulas (1), (2a) and (3b) A branched polymer obtained by polymerization, or a branched polymer obtained by polymerizing at least two compounds among the compounds represented by the following general formulas (1), (2b) and (3a),
A-R ^20- (B) _X (1)
_{^{R 21 - (A) 2 ...}} (2a), R 21 - (B) 2 ... (2b)
_{^{R 22 - (A) 3 ...}} (3a), R 22 - (B) 3 ... (3b)
[Wherein R ²⁰ is a (1 + x) valent organic group, R ²¹ is a divalent organic group, R ²² is a trivalent organic group, x is an integer of 2 or more, A is a functional group reactive with B, B represents a functional group reactive with A, respectively. ]
And (d) an adhesive composition containing a radical polymerization initiator.   The adhesive composition according to claim 1, wherein the branched polymer has a urethane bond and / or an imide bond.   The adhesive composition according to claim 1, wherein the branched polymer has an isocyanurate ring.   The adhesive composition according to any one of claims 1 to 3, wherein the branched polymer has a weight average molecular weight of 1000 or more and less than 20000.   The adhesive composition according to any one of claims 1 to 4, wherein the branched polymer has a radical polymerizable functional group.   The adhesive composition according to any one of claims 1 to 4, wherein the branched polymer has three or more radically polymerizable functional groups per molecule.   (B) Adhesion as described in any one of Claims 1-6 in which a radically polymerizable compound contains 1 type or more of vinyl compounds which have a phosphate group, and radically polymerizable compounds other than this compound, respectively. Agent composition.   (A) The thermoplastic resin contains at least one selected from the group consisting of phenoxy resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin, and polyimide resin. The adhesive composition described in 1.   (E) Adhesive composition as described in any one of Claims 1-8 which further contains electroconductive particle. A circuit member connection structure comprising: a first circuit member having a first connection terminal on a main surface; a second circuit member having a second connection terminal on a main surface; and a connection member. And
The first and second circuit members are arranged via the connection member so that the first and second connection terminals face each other, and the first and second connection terminals are electrically connected. And the connection structure of the circuit member by which the said connection member is comprised with the hardened | cured material of the adhesive composition as described in any one of Claims 1-8.