TWI771856B - Adhesive composition and structure - Google Patents

Abstract

（式中，X表示有機基，R¹ 及R² 分別獨立地表示烷基，m表示0～2的整數，s表示6以上的整數）An adhesive composition containing a silane compound having a structure represented by the following general formula (I).

(in the formula, X represents an organic group, R ¹ and R ² each independently represent an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more)

Description

Adhesive composition and structure

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

In semiconductor elements and liquid crystal display elements (display elements), various adhesives have been conventionally used for the purpose of bonding various members in the elements. The properties required for adhesives include adhesiveness, and cover various aspects such as heat resistance and reliability under high temperature and high humidity conditions. Furthermore, as the adherend used in the bonding, metal (titanium, copper, aluminum, etc.), including ITO, IZO, IGZO, For substrates with various surface states such as SiN _x and SiO ₂ , molecular design of the adhesive is required for each adherend.

Conventionally, thermosetting resins (epoxy resins, acrylic resins, etc.) exhibiting high adhesiveness and high reliability have been used as adhesives for semiconductor elements or adhesives for liquid crystal display elements. As constituent components of an adhesive using an epoxy resin, an epoxy resin and a latent curing agent that generates a cationic species or an anionic species reactive with the epoxy resin by heat or light are generally used. The latent hardener is an important factor for determining the hardening temperature and the hardening rate, and various compounds can be used from the viewpoints of the storage stability at normal temperature and the hardening rate during heating. In an actual step, for example, desired adhesiveness is obtained by performing hardening under hardening conditions at a temperature of 170° C. to 250° C. for 10 seconds to 3 hours.

Furthermore, in recent years, along with the higher integration of semiconductor elements and the higher definition of liquid crystal display elements, there is a concern that the pitches between elements and wirings are narrowed, and surrounding members are adversely affected by heat during curing. Furthermore, in order to reduce the cost, it is necessary to increase the throughput, and a low temperature (90° C. to 170° C.) and a short time (within 1 hour, preferably within 10 seconds, and more preferably within 5 seconds) are required. In other words, a low-temperature short-time hardening (low-temperature rapid hardening) is required. It is known that in order to achieve this low-temperature and short-time hardening, it is necessary to use a thermally latent catalyst with a low activation energy, but it is very difficult to have storage stability near normal temperature.

Therefore, in recent years, attention has been paid to the combination of a (meth)acrylate derivative and a radical curing adhesive that uses a peroxide as a radical polymerization initiator, and an epoxy resin and an onium salt as a cationic polymerization initiator. Cationic hardening adhesive, etc. Radical curing systems can be cured in a short time because radicals as reactive species are very reactive, and peroxides exist stably when the decomposition temperature of the radical polymerization initiator is below the decomposition temperature, so It is a hardening system that combines low-temperature short-time hardening and storage stability (for example, storage stability near normal temperature). Since the onium salt as the reactive species is rich in reactivity, the cationic curing system can be cured in a short time, and when the decomposition temperature of the onium salt is lower than the decomposition temperature of the onium salt, the cationic species exist stably, so it is compatible with low-temperature and short-time curing and storage stability. Hardening system.

On the other hand, in order to achieve firm adhesion to the adherend, the adhesive agent exists to use a coupling agent or the like as a covalent bond, hydrogen bond, hydrophobic interaction due to Van der Waals force, etc. In the case of low molecular weight additives that interact with the body surface. As the coupling agent, for example, a silane coupling agent; a compound containing a phosphoric acid group, a carboxyl group, or the like can be used. In particular, organic functional groups (such as organic functional groups represented by epoxy groups, acryl groups, vinyl groups, etc.) incorporated into the resin matrix after hardening are used, and alkoxysilanes that interact with the surface of the adherend are used. Or in the case of a coupling agent (for example, a coupling agent having a functional group represented by a phosphoric acid group or the like), the adherend and the adhesive can be more firmly bonded (for example, refer to the following Patent Document 1). [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2013-191625 Patent Document 2: International Publication No. 2009/063827

[The problem to be solved by the invention] However, an adhesive composition containing a silane compound is required to have excellent adhesive strength after a reliability test held under high temperature and high humidity conditions such as 85°C 85%RH and 60°C 95%RH.

An object of the present invention is to provide an adhesive composition having excellent adhesive strength after a reliability test, and a structure using the same. [Means of Solving Problems]

（式中，X表示有機基，R¹ 及R² 分別獨立地表示烷基，m表示0～2的整數，s表示6以上的整數。）The adhesive composition of the present invention contains a silane compound having a structure represented by the following general formula (I). [hua 1]

(In the formula, X represents an organic group, R ¹ and R ² each independently represent an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more.)

However, there has been a case of using an adhesive containing a silane compound having an alkoxysilyl group and an organic group bonded to the alkoxysilyl group via an alkylene group. In this regard, the present inventors have found the following findings on such silane compounds. That is, in the conventional silane compound, the carbon number of the alkylene group existing between Si of the alkoxysilyl group and the organic group is small (for example, the number of methylene groups (CH ₂ ) is short and 3 or less). Therefore, when one of the first functional groups in the alkoxysilyl group and the organic group is reacted with one of the constituents of the adhesive (resin, etc.) and the adherend, the alkoxysilyl group and the organic group It is difficult to separate sufficiently, so that the steric freedom of the alkoxysilyl group and the other second functional group in the organic group is low, so the second functional group and the constituents of the adhesive (resin, etc.) and the adhesive in the adherend are low. On the other hand, the reaction does not proceed sufficiently, and the effect as a silane compound cannot be sufficiently exhibited. As a result, sufficient adhesive strength could not be obtained, and there were problems that the adhesive strength decreased after a reliability test left under high temperature and high humidity conditions such as 85° C. 85% RH and 60° C. 95% RH.

On the other hand, the adhesive composition of the present invention has excellent adhesive strength after the reliability test. In addition, for adherends composed of various materials (such as inorganic substances (oxides, metals, etc.), organic substances, and composites thereof), the adhesive composition of the present invention has excellent adhesion both before and after the reliability test. strength.

The organic group X preferably contains at least one selected from the group consisting of a (meth)acryloyl group, a vinyl group, an epoxy group, a nitrogen atom-containing group, and a sulfur atom-containing group.

The adhesive composition of the present invention may further contain an epoxy resin and a latent curing agent.

The adhesive composition of the present invention may further contain a radically polymerizable compound and a cured product that generates radicals by heat or light.

The adhesive composition of the present invention may further contain conductive particles.

The adhesive composition of the present invention can also be used for circuit connection (adhesive composition for circuit connection).

The structure of the present invention includes the adhesive composition or a cured product thereof.

The structure of the present invention may be an embodiment including a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and a structure disposed between the first circuit member and the first circuit member. In a circuit connection member between two circuit members, the first circuit electrode and the second circuit electrode are electrically connected, and the circuit connection member includes the adhesive composition or a cured product thereof. [Effect of invention]

According to the present invention, an adhesive composition having excellent adhesive strength after a reliability test and a structure using the same can be provided. Furthermore, the present invention can provide an adhesive composition having an excellent adhesive strength before and after a reliability test, and a structure using the same for an adherend composed of various materials.

The present invention can provide the application of the adhesive composition or its cured product to a structure or its manufacture. The application of the adhesive composition or its cured product in circuit connection can be provided by the present invention. The present invention can provide the application of the adhesive composition or its cured product to a circuit connection structure or its manufacture.

Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited to these embodiments at all.

In this specification, "(meth)acrylate" means at least one of acrylate and its corresponding methacrylate. The same applies to other similar expressions such as "(meth)acryloyl" and "(meth)acrylic". The materials exemplified below may be used alone or in combination of two or more, unless particularly limited. As for the content of each component in the composition, when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the total amount of the plurality of substances present in the composition is indicated. The numerical range represented using "-" represents the range including the numerical values described before and after the "-" as the minimum value and the maximum value, respectively. The term "A or B" may include either one of A and B, and may include both. "Normal temperature" means 25°C.

In the numerical range described in stages in this specification, the upper limit or the lower limit of the numerical range in a certain stage may be replaced with the upper limit or the lower limit of the numerical range in another stage. In addition, in the numerical range described in this specification, the upper limit or the lower limit of this numerical range may be replaced with the value shown in an Example.

The adhesive composition of the present embodiment contains a silane compound having a structure represented by the following general formula (I) (hereinafter referred to as "silane compound A" in some cases). According to the adhesive composition of the present embodiment, the alkoxysilyl group and the organic group X are easily separated by substituting an alkylene group having a smaller carbon number with an alkylene group having 6 or more carbon atoms. After the reaction of one of the functional groups in the organic group and the organic group X, the steric freedom of the other functional group can also be ensured, thereby showing high adhesion strength to various adherends and sufficient adhesion strength after reliability tests. . Such an adhesive composition is suitably used as an adhesive composition for circuit connection.

（式中，X表示有機基，R¹ 及R² 分別獨立地表示烷基，m表示0～2的整數，s表示6以上的整數。在R¹ 多個存在的情況下，各R¹ 可相互相同亦可不同。在R² 多個存在的情況下，各R² 可相互相同亦可不同。R¹ 、R² 及C_s H_2s 的各個亦可分支）[hua 2]

(in the formula, X represents an organic group, R ¹ and R ² each independently represent an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more. When more than one R ¹ exists, each R ¹ may They may be the same or different from each other. When a plurality of R ² exists, each R ² may be the same or different from each other. Each of R ¹ , R ² and C _s H _2s may be branched)

The alkylene group of the silane compound A may be any of a straight-chain alkylene group and a branched-chain alkylene group. When the number of carbon atoms between the alkoxysilyl group and the organic group X in the straight-chain alkyl group and the branched-chain alkyl group is the same, from the viewpoint of making it easier to secure the steric freedom, straight chain is preferred. chain extension. In the case of using the silane compound A having a straight-chain alkyl group, since the number of methylene groups previously short is 6 or more, after the alkoxysilyl group and one of the functional groups in the organic group X are reacted, it is also possible to The steric degree of freedom of another functional group is ensured, thereby showing high adhesion strength to various adherends and sufficient adhesion strength after reliability test.

As the constituent components of the adhesive composition of the present embodiment, for example, (a) epoxy resin (hereinafter referred to as "(a) component)"), (b) latent curing agent (epoxy resin Latent hardener. Hereinafter referred to as "(b) component)"), (c) radically polymerizable compound (hereinafter referred to as "(c) component"), and (d) by heat (heating ) or light (light irradiation) to generate radicals (free radicals) hardeners (hereinafter referred to as "component (d)" in some cases). The first embodiment of the adhesive composition of the present embodiment contains (a) component and (b) component. The second embodiment of the adhesive composition of the present embodiment contains the (c) component and the (d) component. The third embodiment of the adhesive composition of the present embodiment contains (a) component, (b) component, (c) component, and (d) component.

Each component is demonstrated below.

(Silane compound) Examples of the organic group X of the silane compound A having the structure represented by the formula (I) include an ethylenically unsaturated bond-containing group (an ethylenically unsaturated bond-containing group) and a nitrogen atom-containing group (a nitrogen atom-containing group) , sulfur atom-containing groups (groups containing sulfur atoms), epoxy groups, etc. As an ethylenically unsaturated bond-containing group, a (meth)acryloyl group, a vinyl group, a styryl group, etc. are mentioned. As the nitrogen atom-containing group, an amino group, a monosubstituted amino group, a disubstituted amino group, an isocyanate group, an imidazolyl group, a urea group, a maleimide group, and the like can be mentioned. Examples of the monosubstituted amino group include alkylamino groups (methylamino groups, etc.), benzylamino groups, phenylamino groups, cycloalkylamino groups (cyclohexylamino groups, etc.), and the like. As a disubstituted amino group, an acyclic disubstituted amino group, a cyclic disubstituted amino group, etc. are mentioned. As an acyclic disubstituted amino group, a dialkylamino group (dimethylamino group etc.) etc. are mentioned. As a cyclic disubstituted amino group, a morpholino group, a piperazinyl group, etc. are mentioned. A mercapto group etc. are mentioned as a sulfur atom containing group. The epoxy group may be contained in an epoxy group-containing group (group containing an epoxy group) such as a glycidyl group and a glycidyloxy group. The (meth)acryloyloxy group may be contained in the (meth)acryloyloxy group.

The organic group X preferably has reactivity with the components of the adhesive composition other than the silane compound. From the viewpoint of further improving the reactivity of the components of the adhesive composition other than the silane compound, the organic group X preferably contains a group selected from the group consisting of a (meth)acryloyl group, a vinyl group, an epoxy group, a nitrogen atom-containing group, and The sulfur atom contains at least one of the group consisting of groups.

The number of carbon atoms in the alkyl group of R ¹ and R ² is, for example, 1 to 20. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc. As R ¹ and R ² , each structural isomer of the alkyl group can be used. The number of carbon atoms of the alkyl group of R ¹ is preferably 1 to 10, more preferably 1, from the viewpoint that the alkoxysilyl group is unlikely to become a steric hindrance when reacting with the adherend and further improves the adhesion to the adherend. ~5. From the viewpoint of further improving the adhesiveness with the adherend, the number of carbon atoms of the alkyl group of R ² is preferably 1-10, more preferably 1-5.

m is an integer of 0-2. From the viewpoint of further improving the adhesiveness with the adherend, m is preferably 0 to 1, more preferably 0. s is an integer of 6 or more. From the viewpoint of increasing the physical distance between the organic group X and the alkoxysilyl group and improving the reactivity of both functional groups, s is preferably an integer of 6-20, more preferably an integer of 6-10. From the same viewpoint, the number of carbon atoms in the carbon chain (linear part) between the organic group X and the alkoxysilyl group in the formula (I) is preferably 6-20, more preferably 6-10.

Examples of the silane compound A include glycidoxyalkyltrialkoxysilane, glycidoxyalkyldialkoxysilane, (meth)acryloyloxyalkyltrialkoxysilane, (methyl) ) acryloxydialkyldialkoxysilane, alkenyltrialkoxysilane, styrylalkyltrialkoxysilane, N-2-(aminoethyl)-8-aminooctyl Methyldimethoxysilane, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, 3-aminooctyltrimethoxysilane, 3-aminooctyltriethoxy Silane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)octylamine, N-phenyl-8-aminooctyltrimethoxysilane, 8-ureidooctyl Triethoxysilane, 8-mercaptooctylmethyldimethoxysilane, 8-mercaptooctyltrimethoxysilane, 8-isocyanatooctyltrimethoxysilane, 8-isocyanatooctyltriethoxy Silane etc.

As a glycidoxyalkyl trialkoxysilane, 8-glycidyloxyoctyltrimethoxysilane, 8-glycidoxyoctyltriethoxysilane, etc. are mentioned. As a glycidoxyalkyl dialkoxysilane, 8-glycidoxyoctylmethyldimethoxysilane, 8-glycidoxyoctylmethyldiethoxysilane, etc. are mentioned. Examples of (meth)acryloyloxyalkyltrimethoxysilane include 8-(meth)acryloyloxyoctyltrimethoxysilane, 8-(meth)acryloyloxyoctyltriethoxy Silane etc. Examples of (meth)acryloyloxydialkyldialkoxysilane include 8-(meth)acryloyloxyoctylmethyldimethoxysilane, 8-(meth)acryloyloxy Octylmethyldiethoxysilane, etc. As an alkenyltrialkoxysilane, an octenyltrialkoxysilane, an octenylalkyldialkoxysilane, etc. are mentioned. As octenyltrialkoxysilane, 7-octenyltrimethoxysilane, 7-octenyltriethoxysilane, etc. are mentioned. As an octenylalkyl dialkoxysilane, 7-octenylmethyldimethoxysilane, 7-octenylmethyldiethoxysilane, etc. are mentioned. Examples of the styrylalkyltrialkoxysilane include p-styryloctyltrimethoxysilane and the like.

The silane compound A can be synthesized, for example, by a method such as reacting an organochlorosilane with an alcohol. The silane compound A may be used alone or in combination of two or more. The adhesive composition of the present embodiment may further contain a silane compound in which s is 0 to 5 in formula (I).

From the viewpoint that the adhesive force at the interface between the adherend (circuit member, etc.) and the adhesive composition or its cured product (circuit connection member, etc.) tends to become stronger, the content of the silane compound A is preferably such that the adhesive The total mass of the adhesive component in the adhesive composition (solid content other than the conductive particles in the adhesive composition. The same applies hereinafter) is within the following range on the basis of the total mass. The content of the silane compound A is preferably 0.1% by mass or more, more preferably 0.25% by mass or more, and still more preferably 0.5% by mass or more. The content of the silane compound A is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less. From these viewpoints, the content of the silane compound A is preferably 0.1% by mass to 20% by mass, more preferably 0.25% by mass to 10% by mass, and still more preferably 0.5% by mass to 5% by mass.

((a) component: epoxy resin) As a component (a), a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a naphthalene type epoxy resin, a phenol novolak type epoxy resin, a cresol novolac type epoxy resin are mentioned. Novolak epoxy resin, bisphenol A novolak epoxy resin, bisphenol F novolak epoxy resin, alicyclic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, Hydantoin type epoxy resin, isocyanurate type epoxy resin, aliphatic chain epoxy resin, etc. The component (a) may be halogenated or hydrogenated. (a) A component may be used individually by 1 type, and may be used in combination of 2 or more types.

From the viewpoint of further improving the adhesiveness with the adherend, the content of the component (a) is preferably in the following range based on the total mass of the adhesive components of the adhesive composition. The content of the component (a) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. The content of the component (a) is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less. From these viewpoints, the content of the component (a) is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and still more preferably 15% by mass to 70% by mass.

((b) Ingredient: Latent Hardener) As (b) component, if epoxy resin can be hardened, it will not specifically limit. Examples of the component (b) include curing agents capable of generating anionic species by heat or light (anionic polymerizable catalyst-type curing agents, etc.), and curing agents capable of generating cationic species by heat or light (cationic polymerization Catalytic hardener, etc.), addition polymerization hardener, etc. (b) A component may be used individually by 1 type, and may be used in combination of 2 or more types. The (b) component is preferably a curing agent capable of generating anionic species or cationic species by heat or light, more preferably anionic polymerizable or cationic polymerizable, from the viewpoint of being excellent in rapid hardening properties without considering stoichiometry. Catalyst hardener.

Examples of anionic polymerizable catalyst-type hardeners include imidazole-based hardeners, hydrazide-based hardeners, boron trifluoride-amine complexes, amide imides, tertiary amines, and diamine maleic butenes. Dinitrile, melamine and its derivatives, salts of polyamines, dicyandiamide, etc., and conversion products of these can also be used. As a cationically polymerizable catalyst-type hardener, a diazonium salt, a pernium salt, etc. are mentioned, and the conversion product of these can also be used. As an addition polymerization type hardener, polyamines, polythiols, polyphenols, acid anhydrides, etc. are mentioned.

In the case of using tertiary amines, imidazole-based hardeners, etc. as an anionic polymerizable catalyst type hardener, it can be cured by heating at a moderate temperature of about 160°C to 200°C for about 10 seconds to several hours. Epoxy hardens. Therefore, usable life (pot life) can be made relatively long.

As a cationically polymerizable catalyst-type hardener, for example, photosensitive onium salts (aromatic diazonium salts, aromatic peronium salts, etc.) that can harden epoxy resins by irradiating energy rays are preferable. Moreover, as what activates and hardens an epoxy resin by heat other than irradiating an energy ray, aliphatic perylene salts etc. are mentioned. Such a hardening agent is preferable because it has rapid hardening properties.

Microencapsulated curing by coating the component (b) with a polymer substance (urethane-based, polyester-based, etc.), a metal (nickel, ketone, etc.) film, an inorganic substance (calcium silicate, etc.), etc. It can prolong the service life, so it is better.

From the viewpoint of further improving the adhesiveness with the adherend, the content of the component (b) is preferably within the following range with respect to 100 parts by mass of the component (a). The content of the component (b) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more. The content of the component (b) is preferably 500 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 70 parts by mass or less. From these viewpoints, the content of the component (b) is preferably 10 parts by mass to 500 parts by mass, more preferably 20 parts by mass to 100 parts by mass, and still more preferably 30 parts by mass to 70 parts by mass.

From the viewpoint of further improving the adhesiveness with the adherend, the content of the component (b) is preferably the following with respect to 100 parts by mass of the total of the component (a) and the film-forming material (component to be prepared as needed) range. The content of the component (b) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more. The content of the component (b) is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 70 parts by mass or less. From these viewpoints, the content of the component (b) is preferably 10 parts by mass to 90 parts by mass, more preferably 20 parts by mass to 80 parts by mass, and still more preferably 30 parts by mass to 90 parts by mass.

((c) Component: radically polymerizable compound) The component (c) is a compound having a radically polymerizable functional group. As (c) component, a (meth)acrylate compound, a maleimide compound, a citraconimide resin, a nadicimide resin, etc. are mentioned. The "(meth)acrylate compound" refers to a compound having a (meth)acryloyl group. The component (c) may be used in the form of a monomer or an oligomer, or a monomer and an oligomer may be used in combination. (c) A component may be used individually by 1 type, and may be used in combination of 2 or more types.

Specific examples of the (meth)acrylate compound include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, ethylene glycol Alcohol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, 2-hydroxyl -1,3-bis(meth)acryloyloxypropane, 2,2-bis[4-((meth)acrylooxymethoxy)phenyl]propane, 2,2-bis[4- ((meth)acrylooxypolyethoxy)phenyl]propane, dicyclopentenyl (meth)acrylate, tricyclodecyl (meth)acrylate, tris(() isocyanurate Meth)acryloyloxyethyl)ester, isocyanuric acid EO modified di(meth)acrylate, (meth)acrylate urethane, etc. As a radical polymerizable compound other than a (meth)acrylate compound, the compound described in patent document 2 (International Publication No. 2009/063827), for example, can be used suitably. (Meth)acrylate compound may be used individually by 1 type, and may be used in combination of 2 or more types.

From the viewpoint of being excellent in reactivity and stress relaxation properties, the component (c) is preferably a (meth)acrylate compound, and more preferably a (meth)acrylate urethane. From the viewpoint of improving heat resistance, the (meth)acrylate compound preferably has at least one substituent selected from the group consisting of a dicyclopentenyl group, a tricyclodecyl group, and a triazine ring.

Furthermore, as the component (c), it is preferable to use a radical polymerizable compound having a phosphoric acid ester structure represented by the following general formula (II), and it is more preferable to use the radical polymerizable compound such as a (meth)acrylate compound. The radically polymerizable compound having a phosphoric acid ester structure represented by formula (II) is used in combination. In these cases, since the bonding strength to the surface of an inorganic substance (metal etc.) improves, it is suitable for bonding of circuit electrodes, for example.

[式中，p表示1～3的整數，R表示氫原子或甲基][hua 3]

[In the formula, p represents an integer of 1 to 3, and R represents a hydrogen atom or a methyl group]

The radically polymerizable compound having the phosphoric acid ester structure can be obtained, for example, by reacting anhydrous phosphoric acid with 2-hydroxyethyl (meth)acrylate. Specific examples of the radically polymerizable compound having a phosphoric acid ester structure include mono(2-(meth)acryloyloxyethyl) phosphate and di(2-(meth)acryloyloxy phosphate) ethyl) ester, etc. The radically polymerizable compound having a phosphoric acid ester structure represented by formula (II) may be used alone or in combination of two or more.

From the viewpoint of further improving the adhesiveness with the adherend, the content of the radically polymerizable compound having a phosphoric acid ester structure represented by formula (II) is preferably based on the radically polymerizable compound (equivalent to the radically polymerizable compound) The total amount of the components of the compound) is 0.1 part by mass to 1000 parts by mass, more preferably 1 part by mass to 100 parts by mass per 100 parts by mass. From the viewpoint of further improving the adhesion with the adherend, the content of the radically polymerizable compound having a phosphoric acid ester structure represented by formula (II) is preferably relative to the radically polymerizable compound and the film-forming material (depending on It is 0.01 mass part - 50 mass parts with respect to a total of 100 mass parts of components to be used), More preferably, it is 0.5 mass part - 10 mass parts.

The radically polymerizable compound may contain allyl (meth)acrylate. In this case, the content of allyl (meth)acrylate is preferably 0.1 part by mass to 100 parts by mass in total of the radically polymerizable compound and the film-forming material (component used as needed). 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass.

From the viewpoint of further improving the adhesiveness with the adherend, the content of the component (c) is preferably in the following range based on the total mass of the adhesive components of the adhesive composition. The content of the component (c) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more. The content of the component (c) is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less. From these viewpoints, the content of the component (c) is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 30% by mass to 70% by mass.

(Component (d): hardener that generates radicals by light or heat) As the component (d), (d1) a curing agent that generates free radicals by heat (hereinafter referred to as "component (d1)" in some cases), or (d2) curing agent that generates free radicals by light can be used agent (hereinafter referred to as "(d2) ingredient" as the case may be). The component (d1) is a curing agent that decomposes by heat to generate free radicals. As the component (d1), peroxides (organic peroxides, etc.), azo-based compounds, and the like are exemplified. From the viewpoints of high reactivity and improvement in service life, the component (d1) is preferably an organic peroxide whose 10-hour half-life temperature is 40°C or higher and 1-minute half-life temperature is 180°C or lower, more preferably 10-hour half-life An organic peroxide whose temperature is 60°C or higher and whose 1-minute half-life temperature is 170°C or lower.

Specific examples of the component (d1) include dioxygenyl peroxide (benzyl peroxide, etc.), peroxydicarbonate, peroxyester, peroxyketal, peroxydialkyl, and hydrogen peroxide. , Silane peroxide, etc.

From the viewpoint of suppressing corrosion of electrodes (circuit electrodes, etc.), the component (d1) is preferably a curing agent containing chloride ions and organic acids with a concentration of 5,000 ppm or less, and more preferably organic compounds generated after thermal decomposition. Acid-less hardener. Specific examples of such a component (d1) include peroxyesters, dialkyl peroxides, hydrogen peroxide, silyl peroxides, and the like, and from the viewpoint of obtaining high reactivity, peroxyesters are more preferable.

Examples of the peroxyester include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, and 1-cyclohexyl-1-methyl peroxyneodecanoate Ethyl ethyl ester, 3-hexyl peroxyneodecanoate, 3-butyl peroxypivalate, 2-ethylhexanoic acid-1,1,3,3-tetramethylbutyl peroxide, 2,5 - Dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 2-ethylhexanoic acid-1-cyclohexyl-1-methylethyl peroxide, 2- 3-hexyl ethylhexanoate, 3-butyl 2-ethylhexanoate peroxide, 3-butyl peroxyisobutyrate, 1,1-bis(tert-butylperoxy)cyclohexane, 3,5,5-trimethylhexanoic acid, 3,5,5-trimethylhexanoate, 3,5,5-trimethylhexanoate - bis(m-toluyl peroxy) hexane, 3-butyl peroxyisopropyl monocarbonate, 3-butyl 2-ethylhexyl peroxymonocarbonate, 3-hexyl peroxybenzoate , tert-butyl peroxyacetate, etc. As the component (d1) other than the peroxyester, for example, the compounds described in Patent Document 2 (International Publication No. 2009/063827) can be suitably used. One type of peroxyester may be used alone, or two or more types may be used in combination.

The component (d2) is a curing agent that decomposes by light to generate free radicals. As the component (d2), a compound that generates free radicals by irradiation with light having a wavelength of 150 nm to 750 nm can be used. As such a compound, for example, from the viewpoint of high sensitivity to light irradiation, preferably photoinitiation, photopolymerization, and photocuring (Photoinitiation, Photopolymerization, and Photocuring), J.-P. Fouassier, The α-acetamidophenone derivatives and phosphine oxide derivatives described in Hanser Publishers (1995), pages 17 to 35. The (d2) component may be used alone or in combination of two or more. (d2) component and (d1) component (the said peroxide, an azo compound, etc.) can also be used in combination. The component (d1) or the component (d2) may be used in combination with a curing agent that generates free radicals by ultrasonic waves, electromagnetic waves, or the like.

The component (d) can be appropriately selected according to the intended connection temperature, connection time, and use period. (d) A component may be used individually by 1 type, and may be used in combination of 2 or more types. The component (d) may be used in combination with a decomposition accelerator, a decomposition inhibitor, or the like. Further, the component (d) may be coated with a polyurethane-based or polyester-based polymer substance or the like to perform microencapsulation. Microencapsulated hardeners are preferred for extended service life.

When the connection time is 25 seconds or less, from the viewpoint of easily obtaining a sufficient reaction rate, the content of the component (d) is preferably within the following range. 0.1 mass part or more is preferable with respect to 100 mass parts of (c) components, and, as for content of (d) component, 1 mass part or more is more preferable. 40 mass parts or less are preferable with respect to 100 mass parts of (c) components, and, as for content of (d) component, 20 mass parts or less are more preferable. From these viewpoints, the content of the component (d) is preferably 0.1 to 40 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the (c) component.

When the connection time is 25 seconds or less, from the viewpoint of easily obtaining a sufficient reaction rate, the content of the component (d) is preferably within the following range. The content of the component (d) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the total of the component (c) and the film-forming material (component used as needed). The content of the component (d) is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, relative to 100 parts by mass of the total of the component (c) and the film-forming material (component used as needed). From these viewpoints, the content of the component (d) is preferably 0.1 parts by mass to 40 parts by mass, more preferably 100 parts by mass in total of the component (c) and the film-forming material (component used as needed). It is 1 mass part - 20 mass parts.

From the viewpoint of easily obtaining a sufficient reaction rate, when the connection time is not limited, the content of the component (d) is preferably within the following range. 0.01 mass part or more is preferable with respect to 100 mass parts of (c) components, and, as for content of (d) component, 0.1 mass part or more is more preferable. 30 mass parts or less are preferable with respect to 100 mass parts of (c) components, and, as for content of (d) component, 15 mass parts or less are more preferable. From these viewpoints, the content of the component (d) is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 15 parts by mass, relative to 100 parts by mass of the (c) component.

From the viewpoint of easily obtaining a sufficient reaction rate, when the connection time is not limited, the content of the component (d) is preferably within the following range. The content of the component (d) is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, relative to 100 parts by mass of the total of the component (c) and the film-forming material (component used as needed). The content of the component (d) is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, relative to 100 parts by mass of the total of the component (c) and the film-forming material (component used as needed). From these viewpoints, the content of the component (d) is preferably 0.01 parts by mass to 30 parts by mass, more preferably 100 parts by mass in total of the component (c) and the film-forming material (component to be used as needed). It is 0.1 mass part - 15 mass parts.

(film forming material) The adhesive composition of this embodiment may contain a film-forming material as needed. The film-forming material can improve the handleability of the film in a normal state (normal temperature and pressure) when the liquid adhesive composition is solidified into a film, and imparts resistance to cracking, breakage, and stickiness to the film. and other characteristics. As a film forming material, phenoxy resin, polyvinyl formaldehyde, polystyrene, polyvinyl butyral, polyester, polyamide, xylene resin, polyurethane, etc. are mentioned. From the viewpoint of being excellent in adhesiveness, compatibility, heat resistance, and mechanical strength, a phenoxy resin is preferable among these. The film-forming material may be used alone or in combination of two or more.

Examples of the phenoxy resin include resins obtained by addition-polymerizing bifunctional epoxy resins and bifunctional phenols, and those obtained by reacting bifunctional phenols with epihalohydrin until polymerized. of resin. Phenoxy resins can be prepared by, for example, 1 mole of bifunctional phenols and 0.985 moles to 1.015 moles of epihalohydrin in the presence of catalysts such as alkali metal hydroxides in a non-reactive solvent at 40°C to 120°C. obtained by reacting at the temperature. From the viewpoint of excellent mechanical properties and thermal properties of the resin, it is particularly preferable for the phenoxy resin to set the blending equivalent ratio of the bifunctional epoxy resin and the bifunctional phenol to epoxy group/phenolic hydroxyl group=1/0.9 ～1/1.1, in the presence of catalysts such as alkali metal compounds, organophosphorus compounds, cyclic amine compounds, etc., in organic solvents (amide, ether, ketone, lactone) with a boiling point of 120°C or higher , alcohol-based, etc.), it is obtained by heating to 50°C to 200°C under the condition that the solid content of the reaction is 50% by mass or less to carry out an addition polymerization reaction. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

Bifunctional epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, biphenyl diglycidyl ether, methyl methacrylate substituted biphenyl diglycidyl ether, etc. Bifunctional phenols are compounds having two phenolic hydroxyl groups. Examples of bifunctional phenols include hydroquinones, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, bisphenol fluoride (4,4'-(9-phenylene)diphenol, etc.) , bisphenols such as methyl-substituted bisphenol fluoride, dihydroxybiphenyl, methyl-substituted dihydroxybiphenyl, etc. Phenoxy resins can also be modified with radically polymerizable functional groups, or other reactive compounds (eg, epoxy modification).

The content of the film-forming material is preferably 10 to 90 parts by mass, more preferably 20 to 60 parts by mass, relative to 100 parts by mass of the adhesive component of the adhesive composition.

(conductive particles) The adhesive composition of the present embodiment may further contain conductive particles. Examples of the constituent material of the conductive particles include metals such as gold (Au), silver (Ag), nickel (Ni), copper (Cu), and solder, carbon, and the like. In addition, non-conductive resins, glass, ceramics, plastics, etc. are used as cores, and the cores may be coated with the above-mentioned metal (metal particles, etc.) or carbon-coated conductive particles. The coated conductive particles or the hot-melt metal particles have deformability due to heat and pressure, so that the height unevenness of the circuit electrodes is eliminated during connection, and the contact area with the electrodes during connection is increased, so that reliability is improved.

From the viewpoint of being excellent in self-dispersibility and electrical conductivity, the average particle diameter of the conductive particles is preferably 1 μm to 30 μm. The average particle diameter of the conductive particles can be measured using, for example, machine analysis such as laser diffraction. From the viewpoint of excellent conductivity, the content of the conductive particles is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the adhesive component of the adhesive composition. The content of the conductive particles is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, relative to 100 parts by mass of the adhesive component of the adhesive composition, from the viewpoint of easily suppressing short circuits in electrodes (circuit electrodes, etc.).

(other ingredients) The adhesive composition of the present embodiment may suitably contain a polymerization inhibitor such as hydroquinone and hydroquinone methyl ethers as needed.

The adhesive composition of the present embodiment may further contain a homopolymer or a homopolymer obtained by polymerizing at least one monomer component selected from the group consisting of (meth)acrylic acid, (meth)acrylate, and acrylonitrile. copolymer. From the viewpoint of being excellent in stress relaxation, the adhesive composition of the present embodiment preferably contains an acrylic rubber or the like which is a copolymer obtained by polymerizing glycidyl (meth)acrylate having a glycidyl ether group. thing. From the viewpoint of improving the cohesive force of the adhesive composition, the weight average molecular weight of the acrylic rubber is preferably 200,000 or more.

The adhesive composition of the present embodiment may contain coated fine particles in which the surfaces of the conductive particles are coated with a polymer resin or the like. When such coated fine particles are used in combination with the conductive particles, even when the content of the conductive particles is increased, short-circuiting due to contact of the conductive particles with each other is easily suppressed, thereby insulating the adjacent circuit electrodes. Sexual improvement. The coated fine particles may be used alone without using the conductive particles, or the coated fine particles and the conductive particles may be used in combination.

The adhesive composition of this embodiment may contain rubber fine particles, fillers, softeners, accelerators, antiaging agents, colorants, flame retardants, thixotropic agents, coupling agents, phenol resins, melamine resins, isocyanates Wait. The adhesive composition of the present embodiment may suitably contain additives such as adhesion improvers (excluding coupling agents), tackifiers, levelers, colorants, and weather resistance improvers.

The rubber fine particles preferably have an average particle diameter that is not more than twice the average particle diameter of the conductive particles, and the storage elastic modulus at room temperature is 1/2 of the storage elastic modulus of the conductive particles and the adhesive composition at room temperature. the following particles. Especially when the rubber particles are made of silicone, acrylic emulsion, Styrene Butadiene Rubber (SBR), Nitrile-Butadiene Rubber (NBR) or polybutadiene In the case of rubber, the rubber fine particles are preferably used alone or in combination of two or more. The three-dimensionally crosslinked rubber fine particles are excellent in solvent resistance, and are easily dispersed in the adhesive composition.

The filler can improve electrical properties (connection reliability, etc.) between circuit electrodes. As the filler, for example, particles having an average particle diameter of 1/2 or less of the average particle diameter of the conductive particles can be suitably used. In the case of using non-conductive particles together with a filler, particles having an average particle diameter or less of the non-conductive particles can be used as the filler. The content of the filler is preferably 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the adhesive component of the adhesive composition. By making the said content 60 mass parts or less, there exists a tendency for the improvement effect of connection reliability to be acquired more fully. By making the said content into 5 mass parts or more, there exists a tendency for the addition effect of a filler to be fully acquired.

When the adhesive composition of the present embodiment is in a liquid state at normal temperature, it can be used in a paste state. When it is a solid at normal temperature, it may be gelatinized using a solvent other than heating and using. The usable solvent is not particularly limited as long as it has no reactivity with respect to the adhesive composition and additives and exhibits sufficient solubility, but the boiling point under normal pressure is preferably 50°C ~150°C solvent. If the boiling point is 50° C. or higher, the volatility of the solvent is poor at normal temperature, so it can be used even in an open system. When the boiling point is 150° C. or lower, since the solvent is easily volatilized, good reliability can be obtained after the bonding.

The adhesive composition of the present embodiment may be in the form of a film. If necessary, a solution obtained by adding a solvent, etc. to the adhesive composition is applied to a fluororesin film, a polyethylene terephthalate film, a releasable substrate (release paper, etc.), and then the solvent, etc. removed, thereby obtaining a film. Then, after impregnating a base material such as a nonwoven fabric with the solution and placing it on a releasable base material, a film can be obtained by removing the solvent or the like. When it is used in a film form, it is more convenient from the viewpoint of being excellent in workability and the like.

The adhesive composition of the present embodiment can be bonded by applying pressure together with heating or light irradiation. By using heating and light irradiation in combination, the bonding can be further performed at a low temperature for a short period of time. The light irradiation is preferably light in a wavelength region of 150 nm to 750 nm. Curing can be performed using low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps (ultra-high pressure mercury lamps, etc.), xenon lamps, metal halide lamps, etc., with an irradiation dose of 0.1 J/cm ² to 10 J/cm ² . The heating temperature is not particularly limited, but is preferably a temperature of 50°C to 170°C. The pressure is not particularly limited as long as it is in a range that does not damage the adherend, but is preferably 0.1 MPa to 10 MPa. It is preferable to heat and pressurize in the range of 0.5 second - 3 hours.

The adhesive composition of the present embodiment can be used as an adhesive for different types of adherends having different thermal expansion coefficients. Specifically, it can be used as a circuit connection material represented by anisotropic conductive adhesive, silver paste, silver film, etc.; elastomer for chip scale package (CSP), underfill material for CSP, lead on chip (Lead on chip) On Chip, LOC) tapes, etc. represented by the semiconductor element adhesive materials, etc. are used. For adherends composed of various materials (for example, inorganic substances (oxides, metals, etc.), organic substances, and composites thereof), the adhesive composition of this embodiment has excellent adhesive strength before and after the reliability test .

<Structure and method for manufacturing the same> The structure of this embodiment includes the adhesive composition of this embodiment or a cured product thereof. The structure of the present embodiment is, for example, a semiconductor device such as a circuit connection structure. As an embodiment of the structure of the present embodiment, the circuit connection structure includes a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and a circuit connection structure disposed between the first circuit member and the second circuit The circuit between the components connects the components. The first circuit member includes, for example, a first substrate and a first circuit electrode arranged on the first substrate. The second circuit member includes, for example, a second substrate and a second circuit electrode arranged on the second substrate. The first circuit electrode and the second circuit electrode are opposite to each other and are electrically connected. The circuit connection member contains the adhesive composition of the present embodiment or a cured product thereof. The structure of the present embodiment may be provided with the adhesive composition of the present embodiment or a cured product thereof, and a member (substrate or the like) not having a circuit electrode may be used instead of the circuit member of the circuit connection structure.

The manufacturing method of the structure of this embodiment includes the step of hardening the adhesive composition of this embodiment. As an embodiment of the method of manufacturing a structure of the present embodiment, the method of manufacturing a circuit-connected structure includes an arranging step of placing between a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode The adhesive composition of the present embodiment is arranged between, and the heating and pressurizing step is performed to pressurize the first circuit member and the second circuit member to electrically connect the first circuit electrode and the second circuit electrode, and apply pressure to the adhesive composition. It is hardened by heating. In the arranging step, the first circuit electrode and the second circuit electrode may be arranged to face each other. In the heating and pressing step, pressure may be applied in a direction in which the first circuit member and the second circuit member face each other.

Hereinafter, the circuit connection structure and the manufacturing method thereof will be described as one embodiment of the present embodiment using the drawings. FIG. 1 is a schematic cross-sectional view showing an embodiment of a structure. The circuit connection structure 100 a shown in FIG. 1 includes a circuit member (first circuit member) 20 and a circuit member (second circuit member) 30 that face each other, and these are arranged and connected between the circuit member 20 and the circuit member 30 . The circuit of the component connects the component 10 . The circuit connection member 10 contains the hardened|cured material of the adhesive composition of this embodiment.

The circuit member 20 includes a substrate (first substrate) 21 and circuit electrodes (first circuit electrodes) 22 arranged on the main surface 21 a of the substrate 21 . On the main surface 21a of the board|substrate 21, an insulating layer (not shown) may be arrange|positioned according to the situation.

The circuit member 30 includes a substrate (second substrate) 31 and circuit electrodes (second circuit electrodes) 32 arranged on the main surface 31 a of the substrate 31 . On the main surface 31a of the board|substrate 31, an insulating layer (not shown) may be arrange|positioned in some cases.

The circuit connection member 10 contains an insulating substance (hardened product of components other than conductive particles) 10 a and conductive particles 10 b. The conductive particles 10b are arranged at least between the opposing circuit electrodes 22 and the circuit electrodes 32 . In the circuit connection structure 100a, the circuit electrode 22 and the circuit electrode 32 are electrically connected via the conductive particles 10b.

The circuit member 20 and the circuit member 30 have a single or a plurality of circuit electrodes (connection terminals). As the circuit member 20 and the circuit member 30, for example, a member including electrodes to be electrically connected can be used. As the circuit member, wafer parts such as semiconductor wafers (IC wafers), resistor wafers, and capacitor wafers, and substrates such as printed circuit boards and substrates for mounting semiconductors, and the like can be used. As the combination of the circuit member 20 and the circuit member 30 , for example, a semiconductor wafer and a substrate for mounting a semiconductor can be used. Examples of the material of the substrate include inorganic substances such as semiconductors, glass, and ceramics; organic substances such as polyimide, polyethylene terephthalate, polycarbonate, (meth)acrylic resin, and cyclic olefin resin; glass/ Compounds such as epoxy etc. The substrate can also be a plastic substrate.

FIG. 2 is a schematic cross-sectional view showing another embodiment of the structure. The circuit connection structure 100b shown in FIG. 2 has the same structure as the circuit connection structure 100a except that the circuit connection member 10 does not contain the conductive particle 10b. In the circuit connection structure 100b shown in FIG. 2, the circuit electrode 22 and the circuit electrode 32 are in direct contact with each other without the conductive particles, and are thus electrically connected.

The circuit connection structure 100a and the circuit connection structure 100b can be manufactured by the following method, for example. First, when the adhesive composition is in the form of a paste, the resin layer containing the adhesive composition is arranged on the circuit member 20 by applying the adhesive composition and drying. When the adhesive composition is in the form of a film, the resin layer containing the adhesive composition is disposed on the circuit member 20 by sticking the film-shaped adhesive composition on the circuit member 20 . Next, the circuit member 30 is placed on the resin layer arranged on the circuit member 20 so that the circuit electrode 22 and the circuit electrode 32 are arranged to face each other. Next, by subjecting the resin layer containing the adhesive composition to heat treatment or light irradiation, the adhesive composition is cured to obtain a cured product (circuit connecting member 10 ). By the above, the circuit connection structure 100a and the circuit connection structure 100b are obtained. [Example]

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

<Preparation of film-like adhesive composition> [Example 1] A phenoxy resin is synthesized from a bisphenol A epoxy resin and a phenol compound (4,4'-(9-perylene)-diphenol) having a perylene ring structure in the molecule. This phenoxy resin was melt|dissolved in the mixed solution of toluene/ethyl acetate=50/50 (mass ratio), and the solid content 40 mass % solution was prepared. Next, as a rubber component, an acrylic rubber (copolymer of 40 parts by mass of butyl acrylate-30 parts by mass of ethyl acrylate-30 parts by mass of acrylonitrile-3 parts by mass of glycidyl methacrylate, weight average molecular weight of 800,000) was prepared, This acrylic rubber was dissolved in a mixed solution of toluene/ethyl acetate=50/50 (mass ratio) to prepare a solution with a solid content of 15% by mass. Furthermore, a liquid containing latent curing agent (microencapsulated amine-based curing agent), bisphenol F-type epoxy resin, and naphthalene-type epoxy resin was prepared in a mass ratio of 34:49:17. Epoxy resin for hardener (epoxy equivalent weight: 202). Furthermore, 8-glycidyloxyoctyltrimethoxysilane (product name: KBM4803, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared as the silane compound.

The phenoxy resin, acrylic rubber, hardener-containing epoxy resin, and silane compound were mixed in a mass ratio (solid content) of 20:30:47:3 to prepare Varnish A1 (adhesive composition-containing liquid ). Furthermore, conductive particle A in which a nickel layer having a thickness of 0.2 μm was provided on the surface of the particle having polystyrene as a core was produced. The conductive particles had an average particle diameter of 5 μm and a specific gravity of 2.5. With respect to 100 parts by mass of the solid content of the varnish A1, 5 parts by mass of the conductive particles A were prepared to prepare a varnish B1 (a circuit-connecting material-containing liquid). On a polyethylene terephthalate (PET) film with a thickness of 50 μm that had been surface-treated on one side, the varnish B1 was applied using a coating tool, and then dried with hot air at 70° C. for 3 minutes to obtain A film-like adhesive composition with a thickness of 20 μm was formed on the PET film.

[Comparative Example 1] 3-glycidoxypropyltrimethoxysilane (product name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane compound instead of 8-glycidyloxyoctyltrimethoxysilane. 1 A film-like adhesive composition was produced in the same manner.

[Example 2] Prepared by dissolving 50 g of phenoxy resin (product name: PKHC, manufactured by Union Carbide Co., Ltd., weight average molecular weight 45,000) in a mixed solution of toluene/ethyl acetate=50/50 (mass ratio). A phenoxy resin solution with a solid content of 40% by mass. As the radical polymerizable compound, isocyanuric acid EO-modified diacrylate (product name: M-215, manufactured by Toagosei Co., Ltd.), 2-(meth)acryloyloxyethyl phosphate ( Product name: P-2M, manufactured by Kyoeisha Chemical Co., Ltd.) and urethane acrylate (product name: U-2PPA, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). As the silane compound, 7-octenyltrimethoxysilane (product name: KBM1083, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared. As a radical generator, benzyl peroxide (product name: NYPER-BMT-K40, manufactured by NOF Corporation) was prepared.

The mass ratio of phenoxy resin, EO modified diacrylate of isocyanuric acid, 2-(meth)acryloyloxyethyl phosphate, urethane acrylate, silane compound and free radical generator ( These materials were blended so that the solid content) was 50:19:3:20:3:5 to prepare varnish B1 (adhesive composition-containing liquid). Further, 5 parts by mass of the conductive particles A were prepared with respect to 100 parts by mass of the solid content of the varnish B1 to prepare a varnish B2 (circuit-connecting material-containing liquid). On a polyethylene terephthalate (PET) film with a thickness of 50 μm that had been surface-treated on one side, the varnish B2 was applied using a coating tool, and then dried with hot air at 70° C. for 3 minutes. A film-like adhesive with a thickness of 20 μm was formed on the PET film.

[Comparative Example 2] A film-like adhesive was produced in the same manner as in Example 2, except that vinyltrimethoxysilane (product name: KBM103, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane compound instead of 7-octenyltrimethoxysilane. agent composition.

[Example 3] The same procedure as in Example 2 was performed except that 8-methacryloyloxyoctyltrimethoxysilane (product name: KBM5803, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane compound instead of 7-octenyltrimethoxysilane. In the same manner, a film-like adhesive composition was produced.

[Comparative Example 3] The same procedure as in Example 2 was performed except that 3-methacryloyloxypropyltrimethoxysilane (product name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane compound instead of 7-octenyltrimethoxysilane. In the same manner, a film-like adhesive composition was produced.

<Evaluation of Adhesion Strength> As the first circuit member, a flexible printed circuit (FPC) having 500 copper circuits with a line width of 75 μm, a pitch of 150 μm, and a thickness of 18 μm was prepared. As the second circuit member, glass (thickness 0.7 mm) on which a thin layer of silicon nitride (SiN _x ) of 0.5 μm was formed was prepared. A thermocompression bonding apparatus (heating method: constant temperature) was used in a state where the film adhesive compositions of Examples 1 to 3 or Comparative Examples 1 to 3 were interposed between the first circuit member and the second circuit member. type, manufactured by Toray Engineering Co., Ltd.), were heated and pressurized at 170° C. and 3 MPa for 20 seconds, and were connected with a width of 2 mm to produce a circuit connection structure (connector).

With regard to this circuit connection structure, in accordance with Japanese Industrial Standards (JIS) Z0237, the 90-degree peeling method was used to measure the adhesion immediately after (after heating and pressing at 170° C. and 3 MPa for 20 seconds). Strength and adhesion strength after standing in a constant temperature and humidity tank at 85°C and 85%RH for 100 hours. At this time, the measuring apparatus of the adhesive strength used Tensilon UTM-4 (peeling speed: 50 mm/min, 25° C.) manufactured by Toyo Baldwin Co., Ltd.

The results of the measurement as described above are shown in Table 1.

[Table 1] Evaluation item Linker processing conditions Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Next Strength (N/m) then shortly after 630 720 830 540 700 760 85℃85%RH 100 hours after treatment 590 700 850 400 500 550

From the above, it was confirmed that compared with Comparative Examples 1 to 3, each of Examples 1 to 3 had higher bonding strength immediately after the Adhesion to the surface of the substrate (inorganic substrate) can be maintained well.

10: Circuit connection components 10a: Insulating substances 10b: Conductive particles 20: First circuit component 21: The first substrate 21a, 31a: main surface 22: First circuit electrode 30: Second circuit component 31: Second substrate 32: Second circuit electrode 100a, 100b: circuit connection structure

FIG. 1 is a schematic cross-sectional view showing an embodiment of the structure of the present invention. 2 is a schematic cross-sectional view showing another embodiment of the structure of the present invention.

10: Circuit connection components

10a: Insulating substances

10b: Conductive particles

20: First circuit component

21: The first substrate

21a, 31a: main surface

22: First circuit electrode

30: Second circuit component

31: Second substrate

32: Second circuit electrode

100a: Circuit connection structure

Claims (11)

An adhesive composition comprising (A) an epoxy resin and a latent curing agent, and (B) at least one of a radically polymerizable compound and a curing agent that generates radicals by heat or light, and has the following When the silane compound of the structure represented by the general formula (I) is in the form of a film and contains the epoxy resin, the content of the epoxy resin is based on the total mass of the adhesive components of the adhesive composition. 5 mass % or more, XC _s H _2s -Si[R ¹ ] _m [OR ² ] _3-m . . . In the formula (I), X represents an organic group, R ¹ and R ² each independently represent an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more. The adhesive composition according to claim 1, which further contains conductive particles. An adhesive composition comprising a silane compound having a structure represented by the following general formula (I) and conductive particles, wherein the conductive particles are metal particles or metal-coated conductive particles, XC _s H _2s -Si[R ¹ ] _m [OR ² ] _3-m . . . In the formula (I), X represents an organic group, R ¹ and R ² each independently represent an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more. The adhesive composition according to claim 2 or claim 3, wherein the content of the conductive particles is 100 parts by mass or less with respect to 100 parts by mass of the adhesive component of the adhesive composition. The adhesive composition according to claim 1 or claim 3, wherein the organic group X contains a group selected from the group consisting of a (meth)acryloyl group, a vinyl group, an epoxy group, a nitrogen atom-containing group, and a sulfur atom-containing group At least one of the group consisting of, the nitrogen atom-containing group is an amine group, a monosubstituted amine group, a disubstituted amine group, an isocyanate group, an imidazole group, a urea group, or a maleimide group, the sulfur The atom-containing group is a mercapto group. The adhesive composition according to claim 1 or claim 3, comprising an epoxy resin and a latent curing agent. The adhesive composition according to claim 1 or claim 3, comprising a radically polymerizable compound and a curing agent that generates radicals by heat or light. The adhesive composition according to claim 1 or claim 3, which further contains a film-forming material. The adhesive composition according to claim 1 or claim 3, which further contains a rubber component. A structure comprising the adhesive composition according to any one of Claims 1 to 8 or a cured product thereof. A structure including a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, the first circuit electrode and the second circuit electrode being arranged to face the second circuit electrode, and a structure arranged on the A circuit connection member between the first circuit member and the second circuit member, the first circuit electrode and the second circuit electrode are electrically connected, and the circuit connection member includes an adhesive composition or a cured product thereof , the adhesive composition contains a silane compound having a structure represented by the following general formula (I), XC _s H _2s -Si[R ¹ ] _m [OR ² ] _3-m . . . In the formula (I), X represents an organic group, R ¹ and R ² each independently represent an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more.

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