TWI786036B - Adhesive composition and structure for circuit connection - Google Patents

Abstract

An adhesive composition comprising: a first silane compound having a radical polymerizable functional group, a second silane compound reacting with the first silane compound, a radical polymerizable compound (equivalent to the first silane compound) Compounds except compounds), and peroxides whose 1-minute half-life temperature is below 120°C.

Description

Adhesive composition and structure for circuit connection

The invention relates to an adhesive composition and structure.

In semiconductor elements and liquid crystal display elements (display elements), various adhesives have been used for the purpose of joining various members in the element. The characteristics required for adhesives include adhesiveness, heat resistance, reliability under high temperature and high humidity conditions, and many other aspects. In addition, as the adherend used for bonding, printed wiring boards, organic substrates (polyimide substrates, etc.), metals (titanium, copper, aluminum, etc.), materials with ITO, IZO, IGZO, SiN _x , Substrates with surface states such as SiO ₂ require molecular design of the adhesive according to 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 liquid crystal display elements. As constituent components of an adhesive using an epoxy resin, an epoxy resin and a latent curing agent that generates cationic species or anionic species reactive with the epoxy resin by heat or light are generally used. The latent curing agent is an important factor for determining the curing temperature and curing rate, and various compounds can be used from the viewpoint of storage stability at room temperature and curing rate when heated. In the actual process, for example, the desired adhesiveness can be obtained by curing at a temperature of 170° C. to 250° C. for 10 seconds to 3 hours.

Furthermore, in recent years there has been a concern that with the high volume of semiconductor elements Due to the miniaturization and high-definition of liquid crystal display elements, the pitch between elements and wiring is narrowed, and the heat during curing will adversely affect peripheral components. Furthermore, in order to reduce the cost, it is necessary to increase the throughput, requiring low temperature (90 ° C ~ 170 ° C) and short time (within 1 hour, preferably within 10 seconds, more preferably within 5 seconds) followed by replacement In other words, low-temperature short-time hardening (low-temperature rapid hardening) is required. It is known that in order to achieve this low-temperature short-time curing, it is necessary to use a thermal latent catalyst with low activation energy, but it is very difficult to achieve storage stability near room temperature.

Therefore, in recent years, attention has been paid to radical-curing adhesives using a combination of a (meth)acrylate derivative and a peroxide as a radical polymerization initiator, and the like. Radical hardening system can be hardened in a short time because free radicals as active species are very reactive, and if the decomposition temperature of the radical polymerization initiator is lower than the decomposition temperature of the radical polymerization initiator, the peroxide exists stably, so It is a hardening system having both low-temperature short-time hardening and storage stability (for example, storage stability around normal temperature). For example, there are known radical-curing adhesive compositions containing silane compounds (silane coupling agents, etc.) having radically polymerizable functional groups ((meth)acryl, vinyl, etc.) Literature 1).

[Prior art literature]

[Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2013-191625

Patent Document 2: Japanese Patent Laid-Open No. 2006-22231

Patent Document 3: International Publication No. 2009/063827

However, when a conventional adhesive composition (mixture) containing a silane compound having a radically polymerizable functional group is preserved, the characteristics of the silane compound deteriorate significantly, and the adhesiveness of the adhesive composition decreases. Therefore, improvement in storage stability is required for conventional radical-curing adhesive compositions.

An object of the present invention is to provide an adhesive composition having excellent storage stability, and a structure using the same.

The inventors of the present invention presume the main cause of the deterioration of the properties of the silane compound in the conventional adhesive composition as follows. That is, when an initiator other than a silane compound starts a polymerization reaction during storage of the adhesive composition, the silane compound is incorporated into the polymerization reaction, and thus incorporated into the constituent materials (resin, etc.) of the adhesive composition )internal. From this, it is presumed that the number of molecules that can act on the interface between the adhesive composition and the adherend decreases, thereby deteriorating the properties.

Furthermore, the present inventors have found that when using a highly active peroxide having a half-life temperature of 120° C. or less in one minute in an adhesive composition of a radical polymerization system (for example, a (meth)acrylate radical system) (also known as That is, in the case of low-temperature short-time curing at 130° C. for 5 seconds, which has become increasingly demanded in recent years, the decrease in the properties is particularly remarkable.

The inventors of the present invention have conducted intensive studies to improve storage stability (pot life characteristics), and as a result, found that In the adhesive composition of a peroxide with a 1-minute half-life temperature of 120°C or less, a first silane compound having a functional group that can be radically polymerized and a second silane compound that reacts with the first silane compound are used In this case, the storage stability of the adhesive composition is remarkably improved.

The adhesive composition of the present invention contains: a first silane compound having a radical polymerizable functional group, a second silane compound reacting with the first silane compound, a radical polymerizable compound (corresponding to the first silane compound) compounds), and peroxides with a 1-minute half-life temperature below 120°C.

The adhesive composition of the present invention has more excellent storage stability than conventional ones. Such an adhesive composition can suppress the phenomenon that the adhesiveness of the adhesive composition decreases with time during storage.

The present inventors speculate as follows about the main reason for obtaining such an effect. That is, by making the first silane compound having a radically polymerizable functional group and the second silane compound reacting with the first silane compound exist in the adhesive composition, even during storage, the first silane compound When it is incorporated into the polymer by radical polymerization, the adhesive composition or its cured product can also be maintained by cross-linking the second silane compound with the first silane compound in the polymer and the adherend. The adhesiveness of the adherend.

However, in the aforementioned Patent Document 2, in the radical curing system, a silane coupling agent is used for the purpose of improving the initial adhesion of the connection and the adhesion after the reliability test. However, in Patent Document 2, a relatively high peroxide (in other words, a highly stable peroxide) having a one-minute half-life temperature of 125° C. is used. As a result of research conducted by the inventors, it was found that the effect of the silane coupling agent on storage stability may not be sufficiently confirmed. Furthermore, in Patent Document 2, it is found that the hardening reaction may not sufficiently occur under the connection conditions of 150° C. and 10 seconds, or the connection conditions of 130° C. and 5 seconds required in recent years. In this regard, the adhesive composition of the present invention can achieve low-temperature short-time curing (90°C~170°C, within 1 hour, preferably within 10 seconds, more preferably within 5 seconds), even at 130°C, 5 seconds It is also possible to fully achieve hardening under the connection conditions such as seconds.

Preferably, the functional group of the first silane compound includes at least one selected from the group consisting of (meth)acryl and vinyl. Preferably, the second silane compound has an epoxy group.

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 its cured product.

The structural body of the present invention may also be an embodiment that includes: a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and a circuit member disposed between the first circuit member and the circuit electrode. In the circuit connection member between the second circuit members, the first circuit electrode and the second circuit electrode are electrically connected, and the circuit connection member includes the adhesive composition or its cured product.

According to the present invention, it is possible to provide an adhesive composition and a structure using the adhesive composition having better storage stability than before.

According to the present invention, the application of the adhesive composition or its cured product in the structure or its manufacture can be provided. According to the present invention, the application of the adhesive composition or its cured product in circuit connection can be provided. According to the present invention, application of an adhesive composition or its cured product to a circuit connection structure or its manufacture can be provided.

10: Circuit connection components

10a: insulating substance

10b: Conductive particles

20: Circuit components

21: Substrate

21a, 31a: main surface

22: Circuit electrode

30: circuit components

31: Substrate

32: 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.

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

Embodiments of the present invention will be described below, but the present invention is not limited by these embodiments.

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

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

<Adhesive composition>

The adhesive composition of the present embodiment contains a silane compound, a radical polymerizable compound (radical polymerizable substance), and a curing agent. The adhesive composition of this embodiment contains a first silane compound having a radically polymerizable functional group (a functional group that participates in a radical polymerization reaction of a curing system; a polymerizable functional group in a radical polymerization system), and the The second silane compound (excluding the compound corresponding to the first silane compound) reacted with the first silane compound is used as the silane compound. The adhesive composition of the present embodiment contains, as the curing agent, a peroxide having a one-minute half-life temperature of 120° C. or lower. The adhesive composition of this embodiment is a radical hardening type (radical polymerization type) adhesive composition. The adhesive composition of this embodiment can be used suitably as the adhesive composition for circuit connections. Hereinafter, each component is demonstrated.

(silane compound)

The adhesive composition of this embodiment contains the 1st silane compound which has a radically polymerizable functional group, and the 2nd silane compound which reacts with the said 1st silane compound. The second silane compound is not equivalent to the first silane compound, and does not have a radically polymerizable functional group. The silane compound can also be a silane coupling agent.

As a radically polymerizable functional group, for example, (meth)acryl Ethylenically unsaturated bond-containing groups such as vinyl groups, styryl groups, and maleimide groups. From the standpoint of obtaining more excellent storage stability and adhesiveness, the radically polymerizable functional group is preferably at least one selected from the group consisting of (meth)acryl and vinyl, more preferably ( Meth)acryl.

The second silane compound may have a functional group that does not participate in the radical polymerization reaction. Examples of functional groups that do not participate in radical polymerization include alkyl groups, phenyl groups, alkoxysilyl groups, amino groups, alkylamino groups (methylamino groups, etc.), benzylamino groups, and phenylamino groups. , cycloalkylamine group (cyclohexylamino group, etc.), morpholino group, piperazinyl group, isocyanate group, imidazolyl group, ureido group, dialkylamine group (dimethylamino group, etc.), epoxy group, etc. Epoxy groups may also be contained in epoxy group-containing groups (epoxy group-containing groups), such as glycidyl and glycidyloxy groups. From the viewpoint of obtaining more excellent storage stability, the second silane compound preferably has at least one selected from the group consisting of an alkyl group and an epoxy group, and more preferably has an epoxy group.

As the silane compound, a compound represented by the following general formula (I) can be used. The compound represented by the formula (I) can be synthesized by, for example, reacting an organochlorosilane with an alcohol.

[Chemical 1] XC _s H _2s -Si〔R ¹ 〕 _m 〔OR ² 〕 _3-m ． ． ． (I)

[wherein, X represents an organic group, R ¹ and R ² represent an alkyl group independently, m represents an integer of 0 to 2, and s represents an integer of 0 or more. When a plurality of R ¹ exists, each R ¹ may be the same as or different from each other. When a plurality of R ² exists, each R ² may be the same as or different from each other. Each of R ¹ , R ² and C _s H _2s may also be branched]

Examples of the organic group X include ethylenically unsaturated bond-containing groups (groups containing ethylenically unsaturated bonds), nitrogen atom-containing groups (groups containing nitrogen atoms), sulfur atom-containing groups (groups containing sulfur atoms), ring Oxygen etc. As an ethylenically unsaturated bond containing group, a (meth)acryl group, a vinyl group, a styryl group, etc. are mentioned. Examples of nitrogen atom-containing groups include amino groups, monosubstituted amino groups, disubstituted amino groups, isocyanate groups, imidazolyl groups, ureido groups, maleimide groups, and the like. Examples of the monosubstituted amino group include alkylamino groups (such as methylamino groups), benzylamino groups, phenylamino groups, cycloalkylamino groups (such as cyclohexylamino groups), 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 morpholinyl group, a piperazinyl group, etc. are mentioned. As a sulfur atom containing group, a mercapto group etc. are mentioned. Epoxy groups may also be contained in epoxy group-containing groups (epoxy group-containing groups), such as glycidyl and glycidyloxy groups. A (meth)acryloyl group may also be contained in a (meth)acryloyloxy group.

The carbon number of the alkyl group of R ¹ and R ² is, for example, 1-20. 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 above-mentioned alkyl group can be used. From the point of view that the alkoxysilyl moiety is difficult to become sterically hindered when reacting with the adherend and obtains better adhesion with the adherend, the carbon number of the alkyl group of R is preferably ¹ to 10, more preferably 1~5. From the viewpoint of obtaining better adhesion with the ^adherend , the carbon number of the alkyl group of R2 is preferably 1-10, more preferably 1-5.

m is an integer of 0-2. m is preferably from 0 to 1, more preferably 0, from the viewpoint that the alkoxysilyl moiety is less likely to become a steric hindrance when the adherend reacts with the adherend and more excellent adhesiveness with the adherend is obtained. s is an integer of 0 or more. From the viewpoint of obtaining more excellent storage stability, s is preferably an integer of 1-20, more preferably an integer of 1-10.

Examples of the first silane compound include (meth)acryloxyalkyltrialkoxysilane, (meth)acryloxydialkyldialkoxysilane, (meth)acryloxytrialkylsilane, and (meth)acryloxytrialkylsilane. Alkylalkoxysilane, alkenyltrialkoxysilane, styryltrialkoxysilane, styrylalkyltrialkoxysilane, etc. As the first silane compound, it is preferably selected from (meth)acryloxyalkyltrialkoxysilane and (meth)acryloxysilane from the viewpoint of obtaining more excellent storage stability and adhesiveness. At least one of the group consisting of dialkyldialkoxysilanes. Examples of (meth)acryloxyalkyltrialkoxysilane include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethyl Oxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 8-(meth)acryloxyoctyltriethoxysilane, etc. Examples of (meth)acryloxydialkyldialkoxysilane include 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxy Propylmethyldiethoxysilane, 8-(meth)acryloxyoctylmethyldimethoxysilane, 8-(meth)acryloxyoctylmethyldiethoxysilane, etc. . Examples of alkenyltrialkoxysilanes include vinyltrialkoxysilane, octenyltrialkoxysilane, octenylalkyldialkoxysilane, and the like. Vinyltrimethoxysilane, vinyltriethoxysilane, etc. are mentioned as vinyltrialkoxysilane. Examples of octenyltrialkoxysilanes include 7-octenyltrimethoxysilane, 7-octenyltriethoxysilane, etc. As octenylalkyldialkoxysilane, 7-octenylmethyldimethoxysilane, 7-octenylmethyldiethoxysilane, etc. are mentioned. As styryltrialkoxysilane, p-styryltrimethoxysilane etc. are mentioned. Examples of the styrylalkyltrialkoxysilane include p-styryloctyltrimethoxysilane and the like. The first silane compound may be used alone or in combination of two or more.

As the second silane compound, glycidyloxyalkyltrialkoxysilane (3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 8-glycidoxypropyltriethoxysilane, Glyceryloxyoctyltrimethoxysilane, 8-glycidyloxyoctyltriethoxysilane, etc.), glycidyloxydialkyldialkoxysilane (3-glycidyloxypropylmethyldi Methoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 8-glycidyloxyoctylmethyldimethoxysilane, 8-glycidoxyoctylmethyldiethoxysilane silane, etc.), N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxy Silane, N-2-(aminoethyl)-8-aminooctylmethyldimethoxysilane, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, 3 -aminooctyltrimethoxysilane, 3-aminooctyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)octylamine, N- Phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 8-ureidooctyltriethyl Oxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 8-mercaptooctylmethyldimethoxysilane, 8-mercaptooctyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 8-isocyanatooctyl Trimethoxysilane, 8-isocyanatooctyltriethoxysilane, etc. From the viewpoint of obtaining better storage stability, the second silane compound is preferably selected from the group consisting of glycidyloxyalkyltrialkoxysilane and glycidoxydialkyldialkoxysilane At least one, more preferably at least one selected from the group consisting of 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane. The second silane compound may be used alone or in combination of two or more.

Examples of the second silane compound other than the compound represented by formula (I) include tetraalkoxysilane, alkyltrialkoxysilane, dialkyldialkoxysilane, and the like. Examples of such second silane compounds include methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and dimethyldimethoxysilane , Tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, etc. As the second silane compound other than the compound represented by formula (I), it is preferably selected from the group consisting of alkyltrialkoxysilane and tetraalkoxysilane from the viewpoint of obtaining more excellent storage stability. At least one of the group, more preferably at least one selected from the group consisting of methyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane and tetraethoxysilane. The second silane compound other than the compound represented by formula (I) may be used alone or in combination of two or more.

The content of the silane compound (including the first silane compound, the second silane compound, and other silane compounds) is not particularly limited, but it is easy to suppress the content of the adherend (circuit member, etc.) and the adhesive composition or its hardened product (circuit connection) components, etc.) From the viewpoint of generating peeling bubbles at the interface of the adhesive composition, the following range is preferable based on the total mass of the adhesive components of the adhesive composition (solid components other than the conductive particles in the adhesive composition. The same applies hereinafter). The content of the silane compound is preferably at least 0.1% by mass, more preferably at least 0.25% by mass, still more preferably at least 0.5% by mass, particularly preferably at least 1% by mass, most preferably at least 2% by mass, very preferably at least 3% by mass %above. The content of the silane compound is preferably at most 20 mass %, more preferably at most 15 mass %, further preferably at most 10 mass %, particularly preferably at most 5 mass %. From these viewpoints, the content of the silane compound is preferably 0.1% by mass to 20% by mass, more preferably 0.25% by mass to 15% by mass, still more preferably 0.5% by mass to 10% by mass, most preferably 1% by mass ~5% by mass, very preferably 2% by mass to 5% by mass, very preferably 3% by mass to 5% by mass.

From the viewpoint of easily suppressing the generation of peeling bubbles at the interface between the adherend (circuit member, etc.) and the adhesive composition or its cured product (circuit connection member, etc.), the content of the first silane compound is preferably the adhesive composition Based on the total mass of the adhesive components, it is within the following ranges. The content of the first silane compound is preferably at least 0.1 mass %, more preferably at least 0.25 mass %, further preferably at least 0.5 mass %, particularly preferably at least 1 mass %, most preferably at least 1.5 mass %. The content of the first silane compound is preferably at most 20 mass %, more preferably at most 15 mass %, further preferably at most 10 mass %, particularly preferably at most 5 mass %, most preferably at most 3 mass %. From these viewpoints, the content of the first silane compound is preferably 0.1% by mass to 20% by mass, more preferably 0.25% by mass to 15% by mass, still more preferably 0.5% by mass to 10% by mass, and most preferably 1% by mass. Mass%~5 mass%, excellent is 1.5 mass%~3 mass %.

From the viewpoint of easily suppressing the generation of peeling bubbles at the interface between the adherend (circuit member, etc.) and the adhesive composition or its cured product (circuit connection member, etc.), the content of the second silane compound is preferably the adhesive composition Based on the total mass of the adhesive components, it is within the following ranges. The content of the second silane compound is preferably at least 0.1 mass %, more preferably at least 0.25 mass %, further preferably at least 0.5 mass %, particularly preferably at least 1 mass %, most preferably at least 1.5 mass %. The content of the second silane compound is preferably at most 20 mass %, more preferably at most 15 mass %, further preferably at most 10 mass %, particularly preferably at most 5 mass %, most preferably at most 3 mass %. From these viewpoints, the content of the second silane compound is preferably 0.1% by mass to 20% by mass, more preferably 0.25% by mass to 15% by mass, still more preferably 0.5% by mass to 10% by mass, and most preferably 1% by mass. % by mass to 5% by mass, preferably 1.5% by mass to 3% by mass.

From the viewpoint of obtaining better storage stability and adhesiveness, the ratio (mass ratio: relative value of 1 to the content of the second silane compound) of the content of the first silane compound relative to the content of the second silane compound is preferable. It is 0.01 or more, more preferably 0.1 or more, still more preferably 0.2 or more, particularly preferably 0.5 or more, most preferably 1 or more. From the viewpoint of obtaining more excellent storage stability and adhesiveness, the ratio is preferably 100 or less, more preferably 10 or less, further preferably 5 or less, particularly preferably 3 or less, and most preferably 2 or less.

(radical polymerizable compound)

The radically polymerizable compound is a compound having a radically polymerizable functional group, and is not a compound corresponding to the first silane compound. as a free radical Examples of the polymerizable compound include (meth)acrylate compounds, maleimide compounds, citraconimide resins, nadicimide resins, and the like. The term "(meth)acrylate compound" means a compound having a (meth)acryl group. The radically polymerizable compound may be used in the form of a monomer or an oligomer, or may be used in combination of a monomer and an oligomer. A radical polymerizable compound may be used individually by 1 type, and may use it in combination of 2 or more types.

Specific examples of (meth)acrylate compounds 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-hydroxy -1,3-bis(meth)acryloxypropane, 2,2-bis[4-((meth)acryloxymethoxy)phenyl]propane, 2,2-bis[4- ((meth)acryloxypolyethoxy)phenyl]propane, dicyclopentenyl (meth)acrylate, tricyclodecanyl (meth)acrylate, isocyanuric acid tri(( Meth)acryloxyethyl) ester, urethane (meth)acrylate, isocyanuric acid EO modified di(meth)acrylate, 9,9-bis-[4-(2 -(meth)acryloyloxyethoxy)phenyl]oxene and the like. As the radically polymerizable compound other than the (meth)acrylate compound, for example, the compound described in Patent Document 3 (International Publication No. 2009/063827 ) can be suitably used. The (meth)acrylate compounds may be used alone or in combination of two or more.

As the radical polymerizable compound, from the viewpoint of obtaining more excellent storage stability, a (meth)acrylate compound is preferable, and a (meth)acrylate urethane is more preferable. From the viewpoint of improving heat resistance, (meth)acrylic acid is preferable The ester compound has at least one substituent selected from the group consisting of dicyclopentenyl, tricyclodecanyl and triazine ring.

Furthermore, as the radical polymerizable compound, it is preferable to use a radical polymerizable compound having a phosphate 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 or the like. The polymerizable compound is used in combination with a radical polymerizable compound having a phosphate ester structure represented by formula (II). In these cases, since the adhesive strength to the surface of an inorganic substance (metal etc.) improves, it is suitable, for example for bonding of circuit electrodes.

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

The radical polymerizable compound which has the said phosphate ester structure can be obtained by making anhydrous phosphoric acid and 2-hydroxyethyl (meth)acrylate react, for example. Specific examples of the radically polymerizable compound having a phosphate ester structure include mono(2-(meth)acryloxyethyl)phosphate, di(2-(meth)acryloxyethyl)phosphate, and di(2-(meth)acryloxyethyl)phosphate. Ethyl) ester, etc. The radically polymerizable compound having a phosphate ester structure represented by formula (II) may be used alone or in combination of two or more.

From the viewpoint of obtaining better adhesion, the content of the radical polymerizable compound having a phosphate ester structure represented by the formula (II) is preferably 10% or less relative to the radical polymerizable compound (components corresponding to the radical polymerizable compound The total amount. With The same below) is 1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and more preferably 1 to 10 parts by mass for 100 parts by mass. From the viewpoint of obtaining more excellent adhesion, the content of the radically polymerizable compound having a phosphate ester structure represented by formula (II) is preferably relative to the radically polymerizable compound and the film-forming material (used as needed) Components) are 0.01 to 50 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass for 100 parts by mass in total.

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

From the viewpoint of obtaining more excellent adhesive properties, the content of the radically polymerizable compound is preferably in the following range on the basis of the total mass of the adhesive components of the adhesive composition. The content of the radically polymerizable compound is preferably at least 10% by mass, more preferably at least 20% by mass, further preferably at least 30% by mass, particularly preferably at least 40% by mass. The content of the radically polymerizable compound is preferably at most 90% by mass, more preferably at most 80% by mass, further preferably at most 70% by mass, particularly preferably at most 60% by mass, most preferably at most 50% by mass. From these viewpoints, the content of the radically polymerizable compound is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, further preferably 30% by mass to 70% by mass, particularly preferably 40% by mass to 60% by mass, preferably 40% by mass to 50% by mass.

(hardener)

As the curing agent, those that generate free radicals by heat (heating), those that generate free radicals by light, those that generate free radicals by ultrasonic waves, electromagnetic waves, and the like can be used.

The curing agent that generates free radicals by heat is a curing agent that decomposes by heat to generate free radicals. Examples of such curing agents include peroxides (organic peroxides, etc.), azo compounds, and the like. The hardener can be appropriately selected according to the target connection temperature, connection time, service life, and the like. The adhesive composition of the present embodiment contains a peroxide (hereinafter referred to as "peroxide A") having a half-life temperature of 120° C. or lower as the curing agent. From the viewpoint that low-temperature connection can be more easily achieved, the 1-minute half-life temperature in the peroxide A is preferably 40° C. or higher.

In addition, the so-called "half-life" is the time required for the concentration of peroxide to decrease to half of the initial value, and the 1-minute half-life temperature means the temperature at which the half-life becomes 1 minute. As the 1-minute half-life temperature, the value disclosed in the catalog (Organic Peroxides (10th Edition, February 2015)) published by NOF Corporation can be used.

Specific examples of curing agents that generate free radicals by heat include diacyl peroxides, peroxydicarbonates, peroxyesters, peroxyketals, dialkyl peroxides, hydrogen peroxide, and silanes. peroxides, etc.

From the viewpoint of suppressing corrosion of electrodes (circuit electrodes, etc.), the curing agent is preferably a curing agent that contains chloride ions and organic acids at a concentration of 5000 ppm or less, and is more preferably one that generates less organic acid after thermal decomposition. hardener. Specific examples of such hardening agents include ester peroxide, dialkyl peroxide, hydrogen peroxide, silicone Alkyl peroxides and the like are more preferably peroxyesters from the viewpoint of obtaining high reactivity.

Examples of peroxyesters include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, and 1-cyclohexyl-1-methyl peroxyneodecanoate. Ethyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxypivalate, 2-ethylhexanoate-1,1,3,3-tetramethylbutyl peroxide, 2,5 -Dimethyl-2,5-di(2-ethylhexylperoxy)hexane, 2-ethylhexanoic acid-1-cyclohexyl-1-methylethyl peroxide, 2- Tri-hexyl ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, 1,1-bis(tert-butylperoxy)cyclohexane, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, 2,5-dimethyl-2,5 - Di(m-cresylperoxy)hexane, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxide 2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate , tertiary butyl peroxyacetate, etc. As a curing agent that generates free radicals by heat other than the peroxyester, for example, compounds described in Patent Document 3 (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.

Examples of the peroxide A include di-n-propyl peroxydicarbonate (1-minute half-life temperature: 94.0° C.), diisopropyl peroxydicarbonate (1-minute half-life temperature: 88.3° C.), di-( 4-tert-butylcyclohexyl) ester (1-minute half-life temperature: 92.1°C), bis(2-ethylhexyl) peroxydicarbonate (1-minute half-life temperature: 90.6°C), peroxyneodecanoic acid third Hexyl ester (1-minute half-life temperature: 100.9°C), tert-butyl peroxyneheptanoate (1-minute half-life temperature: 104.6°C), tertiary hexyl peroxypivalate (1-minute half-life temperature: 109.1°C), Peroxide Tertiary butyl valerate (1-minute half-life temperature: 110.3°C), bis(3,5,5-trimethylhexyl) peroxide (1-minute half-life temperature: 112.6°C), dilauroyl peroxide (1 minute Half-life temperature: 116.4°C), 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane (1-minute half-life temperature: 118.8°C), etc. By using these peroxides A, high reactivity can be obtained. One type of peroxide A may be used alone, or two or more types may be used in combination.

The adhesive composition of the present embodiment may further contain a curing agent other than the peroxide A. That is, you may use combining peroxide A and the peroxide whose 1-minute half-life temperature exceeds 120 degreeC. In this case, there is a tendency that better low-temperature activity and storage stability are obtained. From the viewpoint of obtaining high reactivity and further improving the pot life, the curing agent other than peroxide A is preferably an organic peroxide having a half-life temperature of 40° C. or higher in 10 hours and a half-life temperature of 1 minute or less. The oxide is more preferably an organic peroxide having a 10-minute half-life temperature of 40° C. or higher and a 1-minute half-life temperature of 160° C. or lower.

The curing agent that generates free radicals by light is a curing agent that is decomposed by light to generate free radicals. As such a curing agent, a compound that generates free radicals when irradiated with light having a wavelength of 150 nm to 750 nm can be used. As such a compound, for example, photoinitiation, photopolymerization, and photocuring (Photoinitiation, Photopolymerization, and Photocuring) are preferred from the viewpoint of high sensitivity to light irradiation, J.-P. Fouassier, α-Acetamidophenone derivatives and phosphine oxide derivatives described in Hanser Publishers (1995), pages 17 to 35.

A curing agent may be used alone or in combination of two or more. A hardening agent, a decomposition accelerator, a decomposition inhibitor, etc. can also be used together. Furthermore, microencapsulation may also be carried out by coating a curing agent with a polyurethane-based or polyester-based polymer, or the like. Microencapsulated hardeners are preferred because they prolong usable life.

When the connecting time is 25 seconds or less, the content of the peroxide A is preferably in the following range from the viewpoint of easily obtaining a sufficient reaction rate. The content of the peroxide A is preferably at least 0.1 parts by mass, more preferably at least 1 part by mass, further preferably at least 3 parts by mass, particularly preferably at least 5 parts by mass, relative to 100 parts by mass of the radically polymerizable compound. Above, very preferably 10 parts by mass or more. The content of the peroxide A is preferably at most 100 parts by mass, more preferably at most 50 parts by mass, further preferably at most 30 parts by mass, particularly preferably at most 20 parts by mass, relative to 100 parts by mass of the radically polymerizable compound. or less, preferably 15 parts by mass or less. From these viewpoints, the content of peroxide A is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and still more preferably 100 parts by mass of the radically polymerizable compound. It is 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass, and most preferably 10 to 15 parts by mass.

When the connecting time is 25 seconds or less, the content of the peroxide A is preferably in the following range from the viewpoint of easily obtaining a sufficient reaction rate. The content of the peroxide A is preferably at least 2 parts by mass, more preferably at least 3 parts by mass, and still more preferably at least 100 parts by mass of the total of the radically polymerizable compound and the film-forming material (components used if necessary). Preferably, it is 4 mass parts or more, and especially preferably, it is 5 mass parts or more. With respect to radically polymerizable compounds and film-forming materials (optionally used Components), the content of the peroxide A is preferably at most 10 parts by mass, more preferably at most 8 parts by mass, further preferably at most 7 parts by mass, particularly preferably at most 6 parts by mass, based on a total of 100 parts by mass. From these viewpoints, the content of the peroxide A is preferably 2 to 10 parts by mass relative to a total of 100 parts by mass of the radically polymerizable compound and the film-forming material (components used if necessary), and more preferably Preferably, it is 3-10 mass parts, More preferably, it is 4-8 mass parts, Most preferably, it is 5-7 mass parts, Most preferably, it is 5-6 mass parts.

From the viewpoint of easily obtaining a sufficient reaction rate, the content of the peroxide A in the case of not limiting the connection time is preferably in the following range. The content of peroxide A is preferably at least 0.01 parts by mass, more preferably at least 0.1 parts by mass, further preferably at least 1 part by mass, particularly preferably at least 3 parts by mass, relative to 100 parts by mass of the radically polymerizable compound. Above, preferably at least 5 parts by mass, very preferably at least 10 parts by mass. The content of the peroxide A is preferably at most 100 parts by mass, more preferably at most 50 parts by mass, further preferably at most 30 parts by mass, particularly preferably at most 20 parts by mass, relative to 100 parts by mass of the radically polymerizable compound. or less, preferably 15 parts by mass or less. From these viewpoints, the content of peroxide A is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, and still more preferably 100 parts by mass of the radically polymerizable compound. It is 1 to 30 parts by mass, particularly preferably 3 to 20 parts by mass, very preferably 5 to 15 parts by mass, and very preferably 10 to 15 parts by mass.

From the viewpoint of easily obtaining a sufficient reaction rate, the content of the peroxide A in the case of not limiting the connection time is preferably in the following range. relative to free radicals The content of the peroxide A is preferably at least 0.01 parts by mass, more preferably at least 0.1 parts by mass, and still more preferably 2 parts by mass based on 100 parts by mass of the total of the polymerizable compound and the film-forming material (components used if necessary). More than 3 parts by mass, particularly preferably 3 parts by mass or more, extremely preferably 4 parts by mass or more, very preferably 5 parts by mass or more. The content of the peroxide A is preferably at most 100 parts by mass, more preferably at most 50 parts by mass, and even more preferably at most 100 parts by mass relative to a total of 100 parts by mass of the radically polymerizable compound and the film-forming material (components used if necessary). It is preferably at most 10 parts by mass, particularly preferably at most 8 parts by mass, very preferably at most 7 parts by mass, and very preferably at most 6 parts by mass. From these viewpoints, the content of the peroxide A is preferably 0.01 parts by mass to 100 parts by mass relative to a total of 100 parts by mass of the radically polymerizable compound and the film-forming material (components used if necessary), and more preferably Preferably 0.1 to 50 parts by mass, more preferably 2 to 10 parts by mass, particularly preferably 3 to 8 parts by mass, most preferably 4 to 7 parts by mass, very preferably 5 parts by mass ~6 parts by mass.

(film forming material)

The adhesive composition of this embodiment may contain a film forming material as needed. When the film-forming material solidifies the liquid adhesive composition into a film, it can improve the operability of the film under normal conditions (at normal temperature and pressure), and provide the film with resistance to cracking, damage, and stickiness. and other characteristics. Examples of the film forming material include phenoxy resin, polyvinyl formaldehyde, polystyrene, polyvinyl butyral, polyester, polyamide, xylene resin, polyurethane and the like. Among them, phenoxy resin is preferable from the viewpoint of being excellent in adhesiveness, compatibility, heat resistance, and mechanical strength. 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 polymerization of bifunctional epoxy resins and bifunctional phenols, and resins obtained by reacting bifunctional phenols with epihalohydrins until they become polymerized. resin. Phenoxy resin, for example, can be prepared by 1 mole of 2-functional phenols and 0.985 moles to 1.015 moles of epihalohydrin in the presence of a catalyst such as alkali metal hydroxide in a non-reactive solvent at 40°C to 120°C obtained by reacting at a temperature. From the standpoint of excellent mechanical properties and thermal properties of the resin, it is particularly preferable that the compounding equivalent ratio of the bifunctional epoxy resin and the bifunctional phenol be epoxy group/phenolic hydroxyl group=1/0.9 for the phenoxy resin ~1/1.1, in the presence of catalysts such as alkali metal compounds, organophosphorus compounds, and cyclic amine compounds, organic solvents (amides, ethers, ketones, and lactones) with a boiling point above 120°C , alcohols, 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, and performing an addition polymerization reaction. The phenoxy resins may be used alone or in combination of two or more.

Bifunctional epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AD epoxy resins, bisphenol S epoxy resins, biphenyl diglycidyl ether, methyl 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 stilbene, methyl-substituted bisphenol stilbene, dihydroxybiphenyl, Bisphenols such as substituted dihydroxybiphenyls, etc. The phenoxy resin can also be modified by free radical polymerizable functional groups or other reactive compounds (such as epoxy modification).

With respect to 100 parts by mass of the adhesive component of the adhesive composition, the film The content of the forming material is preferably from 10 parts by mass to 90 parts by mass, more preferably from 20 parts by mass to 60 parts by mass, further preferably from 30 parts by mass to 50 parts by mass.

(conductive particles)

The adhesive composition of the present embodiment may further contain conductive particles. Metals, such as gold (Au), silver (Ag), nickel (Ni), copper (Cu), solder, carbon, etc. are mentioned as a constituent material of an electroconductive particle. In addition, it may be a coated conductive particle in which a non-conductive resin, glass, ceramics, plastic, etc. is used as a core, and the metal (metal particles, etc.) or carbon is coated on the core. Coated conductive particles or hot-melt metal particles are deformable by heat and pressure, so that uneven height of circuit electrodes can be eliminated during connection, and the contact area with electrodes can be increased during connection, thereby improving reliability, which is preferable.

From the viewpoint of excellent self-dispersibility and electroconductivity, the average particle diameter of the conductive particles is preferably 1 μm to 30 μm. The average particle diameter of electroconductive particle can be measured using machine analysis, such as a laser diffraction method, for example. From the viewpoint of excellent electrical conductivity, the content of the conductive particles is preferably at least 0.1% by volume, more preferably at least 1% by volume, based on the total volume of the adhesive components of the adhesive composition. From the standpoint of preventing short-circuiting of electrodes (circuit electrodes, etc.), the content of conductive particles is preferably 50% by volume or less, more preferably 20% by volume or less, based on the total volume of the adhesive components of the adhesive composition. , and more preferably 10 volume % or less, particularly preferably 5 volume % or less, most preferably 3 volume % or less. From these points of view, the content of the conductive particles is preferably 0.1% by volume to 50% by volume, more preferably 0.1% by volume to 20% by volume, further preferably 1% by volume to 20% by volume, particularly preferably 1% by volume ~10% by volume, very preferably 1% to 5% by volume, very preferably 1% to 3% by volume. Furthermore, "Volume %" It is determined based on the volume of each component before hardening at 23° C., but the volume of each component may be converted from mass to volume using specific gravity. Furthermore, the volume of the target component can also be obtained by adding the volume increased by putting the target component into a container such as a graduated cylinder that does not dissolve or swell the target component and that is adequately wetted with the target component. Containers for solvents (water, alcohol, etc.).

(other ingredients)

The adhesive composition of this embodiment may contain polymerization inhibitors, such as hydroquinone and hydroquinone methyl ether, as needed.

The adhesive composition of this embodiment may further contain a homopolymer or copolymer obtained by polymerizing at least one monomer component selected from the group consisting of (meth)acrylic acid, (meth)acrylate, and acrylonitrile. things. From the viewpoint of excellent stress relaxation, it is preferable that the adhesive composition of the present embodiment contains acrylic rubber obtained by polymerizing glycidyl (meth)acrylate having a glycidyl ether group, etc. things. From the viewpoint of improving the cohesion 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 also contain coated fine particles in which the surfaces of the conductive particles are coated with a polymer resin or the like. In the case where such coated fine particles are used in combination with the conductive particles, even when the content of the conductive particles increases, it is easy to suppress the short circuit caused by the contact of the conductive particles with each other, thus making the insulation between adjacent circuit electrodes sexual enhancement. The coated fine particles may be used alone without using the conductive particles, or the coated fine particles may be used in combination with the conductive particles.

The adhesive composition of this embodiment may also contain gum particles, filler Agents (silicon dioxide particles, etc.), softeners, accelerators, anti-aging agents, colorants, flame retardants, thixotropic agents, etc. The adhesive composition of this embodiment may also suitably contain additives such as a tackifier, a leveling agent, a colorant, and a weather resistance improving agent.

The gum particles preferably have an average particle diameter twice or less than the average particle diameter of the conductive particles, and have a storage modulus of elasticity at room temperature that is 1/2 of the storage modulus of the conductive particles and the adhesive composition at room temperature. the following particles. Especially when the gum particles are made of silicone, acrylic emulsion, styrene-butadiene rubber (Styrene Butadiene Rubber, SBR), nitrile-butadiene rubber (Nitrile-Butadiene Rubber, NBR) or polybutadiene In the case of rubber, the gum fine particles are preferably used alone or in combination of two or more. The three-dimensionally crosslinked gum particles have excellent solvent resistance and are easily dispersed in the adhesive composition.

The filler improves electrical characteristics (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 conductive particles can be suitably used. When using the filler which does not have electroconductivity together, the particle which has an average particle diameter or less of the particle which does not have electroconductivity can be used as a filler. The content of the filler is preferably 0.1 to 60 parts by mass with respect to 100 parts by mass of the adhesive component of the adhesive composition. There exists a tendency for the improvement effect of connection reliability to be acquired more fully by making the said content into 60 mass parts or less. There exists a tendency for the addition effect of a filler to fully acquire by making the said content into 0.1 mass part or more.

When the adhesive composition of this embodiment is liquid at normal temperature, it can be used in paste form. When the adhesive composition is solid at normal temperature, In addition to heating and using, you may gelatinize using a solvent. The usable solvent is not particularly limited as long as it has no reactivity with the components in the adhesive composition and exhibits sufficient solubility. The solvent is preferably a solvent having a boiling point of 50° C. to 150° C. under normal pressure. If the boiling point is 50° C. or higher, the volatility of the solvent at room temperature is poor, so even an open system can be used. When the boiling point is 150° C. or lower, the solvent is easily volatilized, so good reliability can be obtained after bonding.

The adhesive composition of the present embodiment may also be in the form of a film. It is possible to apply an adhesive composition containing a solvent or the like as necessary on a fluororesin film, a polyethylene terephthalate film, or a release substrate (release paper, etc.), and then remove the solvent or the like to obtain Film-like adhesive composition. And after impregnating the said solution in base materials, such as a nonwoven fabric, and mounting on a peelable base material, a film-form adhesive agent composition can be obtained by removing a solvent etc.. When the adhesive composition is used in the form of a film, it is excellent in workability and the like. The thickness of the film-like adhesive composition may be 1 μm-100 μm, or 5 μm-50 μm.

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 together, bonding can be performed at a low temperature for a short time. Light irradiation is preferably irradiated with light in a wavelength region of 150 nm to 750 nm. As the light source, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps (ultrahigh-pressure mercury lamps, etc.), xenon lamps, metal halide lamps, and the like can be used. The irradiation dose can be 0.1J/cm ² ~10J/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 within 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 seconds to 3 hours.

The adhesive composition of the present embodiment may be used as an adhesive for the same adherend, or may 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.; elastomers for Chip Scale Package (CSP), underfill materials for CSP, lead wires on chips (Lead on Chip, LOC) tape, etc. are used as representative semiconductor element bonding materials.

<Structure and its manufacturing method>

The structure of this embodiment contains the adhesive composition of this embodiment or its cured product. The structure of the present embodiment is, for example, a semiconductor device such as a circuit-connected structure. As one embodiment of the structural body of this embodiment, the circuit connection structural body includes a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and Electrical connections between components. The first circuit component includes, for example, a first substrate and a first circuit electrode disposed on the first substrate. The second circuit component includes, for example, a second substrate and a second circuit electrode disposed on the second substrate. The first circuit electrode and the second circuit electrode face each other and are electrically connected. The circuit connection member contains the adhesive composition of this embodiment or its cured product. The structure of the present embodiment may include the adhesive composition of the present embodiment or its cured product, and a member (substrate, etc.) not having circuit electrodes may be used instead of the circuit member of the circuit connection structure.

The method of manufacturing the structure of the present embodiment includes the step of curing the adhesive composition of the present embodiment. As the manufacturing method of the structure of this embodiment In one embodiment, the method for manufacturing a circuit-connected structure includes: an arranging step of arranging the adhesive composition of this embodiment between a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode , the heating and pressing step, pressurizing the first circuit member and the second circuit member to electrically connect the first circuit electrode and the second circuit electrode, and heating and curing the adhesive composition. In the arranging step, the first circuit electrode and the second circuit electrode may be arranged so that they 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 its manufacturing method will be described using the drawings as one embodiment of the present embodiment. FIG. 1 is a schematic cross-sectional view showing an embodiment of a structure. The circuit connection structure 100a shown in FIG. 1 comprises a circuit member (first circuit member) 20 and a circuit member (second circuit member) 30 facing each other. The circuit of the component is connected to the component 10 . The circuit connection member 10 contains the cured product 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 21 a of the substrate 21 , an insulating layer (not shown) may also be arranged according to circumstances.

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 substrate 31, an insulating layer (not shown) may also be arranged depending on circumstances.

The circuit connection member 10 contains an insulating substance (other than conductive particles Component hardened product) 10a and conductive particles 10b. Conductive particle 10b is arrange|positioned at least between the circuit electrode 22 and the circuit electrode 32 which oppose. In the circuit connection structure 100a, the circuit electrode 22 and the circuit electrode 32 are electrically connected via the conductive particle 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, members including electrodes that require electrical connection can be used. As the circuit member, wafer components such as semiconductor wafers (IC wafers), resistor wafers, and capacitor wafers; substrates such as printed boards and semiconductor mounting substrates, and the like can be used. As a 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 substrate materials include inorganic substances such as semiconductors, glass, and ceramics; organic substances such as polyimide, polyethylene terephthalate, polycarbonate, (meth)acrylic resins, and cyclic olefin resins; glass and 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 structure similar to 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 electrodes 22 and the circuit electrodes 32 are in direct contact without conductive particles, and are 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 a paste form, the adhesive composition is applied and dried to arrange a resin layer containing the adhesive composition on the circuit member 20 . In the case where the adhesive composition is in the form of a film, the film-shaped adhesive composition is attached to the circuit member 20, thereby disposing the adhesive on the circuit member 20. A resin layer containing an adhesive composition is placed. 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, heat treatment or light irradiation is performed on the resin layer containing the adhesive composition, whereby the adhesive composition is cured to obtain a cured product (circuit connection member 10 ). The circuit-connected structure 100a and the circuit-connected structure 100b are obtained by the above.

[Example]

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.

(Synthesis of Polyurethane)

In a separable flask equipped with a reflux condenser, a thermometer, and a stirrer, 1000 parts by mass of polypropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., number average molecular weight Mn=2000) and 4000 parts by mass of glycols having ether bonds were added. After parting of methyl ethyl ketone (solvent), it stirred at 40 degreeC for 30 minutes, and prepared the reaction liquid. After raising the temperature of the reaction solution to 70° C., 0.0127 parts by mass of dimethyl tin laurate (catalyst) was added. Next, a solution prepared by dissolving 125 parts by mass of 4,4'-diphenylmethane diisocyanate in 125 parts by mass of methyl ethyl ketone was added dropwise over 1 hour to this reaction liquid. Thereafter, stirring was continued at the temperature until the absorption peak (2270 cm ⁻¹ ) derived from the isocyanate group could not be seen by an infrared spectrophotometer (manufactured by JASCO Co., Ltd.), and the formaldehyde of polyurethane was obtained. ethyl ethyl ketone solution. Next, the amount of the solvent was adjusted so that the solid content concentration (urethane concentration) of the solution became 30% by mass. The weight average molecular weight of the obtained polyurethane (urethane resin) was measured by gel permeation chromatography (Gel Permeation Chromatography, GPC), and it was 320000 (standard polystyrene converted value). Table 1 shows the measurement conditions of GPC.

(Synthesis of Acrylic Urethane)

In a 2L (liter) four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 4000 parts by mass of polycarbonate diol (manufactured by Aldrich (Aldrich) company, number average molecular weight: 2000), 238 parts by mass of 2-hydroxyethyl acrylate, 0.49 parts by mass of hydroquinone monomethyl ether, and 4.9 parts by mass of a tin-based catalyst to prepare a reaction solution. To the reaction liquid heated at 70 degreeC, 666 mass parts of isophorone diisocyanate (IPDI) was dripped uniformly over 3 hours, and it was made to react. After completion of the dropwise addition, the reaction was continued for 15 hours, and when NCO% (NCO content) became 0.2% by mass or less, the reaction was considered to be complete, and urethane acrylate was obtained. NCO% can be confirmed with a potentiometric automatic titration device (trade name: AT-510, manufactured by Kyoto Denshi Kogyo Co., Ltd.). As a result of GPC analysis, the weight average molecular weight of the urethane acrylate was 8500 (standard polystyrene conversion value). Furthermore, the analysis using GPC is based on the weight average molecular weight of the polyurethane The analysis was carried out under the same conditions.

(production of conductive particles)

A nickel layer with a thickness of 0.2 μm was formed on the surface of the polystyrene particles. Furthermore, a gold layer having a thickness of 0.04 μm was formed on the outer side of the nickel layer. In this way, conductive particles having an average particle diameter of 4 μm were produced.

(Production of film adhesive)

The components shown in Table 2 and Table 3 were mixed at the mass ratio (solid content) shown in Table 2 and Table 3 to obtain a mixture. The conductive particles were dispersed in the mixture at a ratio of 1.5% by volume (reference: the total volume of the adhesive components of the adhesive composition) to obtain a coating solution for forming a film-like adhesive. This coating liquid was coated on a polyethylene terephthalate (PET) film having a thickness of 50 μm using a coating tool. The coating film was dried with hot air at 70° C. for 10 minutes to form a film-like adhesive with a thickness of 18 μm.

The phenoxy resins shown in Table 2 and Table 3 were obtained by dissolving 40 g of PKHC (manufactured by Union Carbide Co., Ltd., trade name, weight average molecular weight: 45,000) in 60 g of methyl ethyl ketone to prepare a 40% by mass solution. Morphological use. As the polyurethane, the polyurethane synthesized as described above was used. As the radical polymerizable compound A, the urethane acrylate synthesized as above was used. As the radical polymerizable compound B, isocyanuric acid EO-modified diacrylate (trade name: M-215, manufactured by Toagosei Co., Ltd.) was used. As the radical polymerizable compound C (phosphate ester), 2-methacryloxyethyl phosphate (trade name: Light ester (Light ester) P-2M, manufactured by Kyoeisha Chemical Co., Ltd.) was used. use 9,9-double -[4-(2-acryloyloxyethoxy)phenyl] fennel (trade name: A-BPEF, manufactured by Shin-Nakamura Chemical Co., Ltd.) as the radical polymerizable compound D.

As the silane compound (first silane compound) having a radically polymerizable functional group (functional group participating in a curing system radical polymerization reaction), the following components were used. 3-Methacryloxypropylmethyldimethoxysilane (trade name: KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as silane compound A1, and 3-methacryloxypropyl Trimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) As the silane compound A2, 3-acryloxypropyltrimethoxysilane (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd. Co., Ltd.) as silane compound A3.

As a silane compound (second silane compound) having a functional group that does not participate in the radical polymerization reaction of the curing system and does not have a functional group capable of radical polymerization (a functional group participating in the radical polymerization reaction of the curing system), the following is used: ingredients. 3-glycidoxypropylmethyldimethoxysilane (trade name: KBM-402, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as silane compound B1, and 3-glycidoxypropyltrimethoxysilane was used (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) As the silane compound B2, methyltrimethoxysilane (trade name: KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane compound B3.

As a radical polymerization initiator, dilauroyl peroxide (Peroxide A1, trade name: PEROYL L, manufactured by NOF Co., Ltd., 1-minute half-life temperature: 116.4° C.), peroxide tertiary butyl pivalate (peroxide A2. Trade name: Perbutyl PV, manufactured by NOF Co., Ltd., 1-minute half-life temperature: 110.3°C), and 2-ethylhexanoic acid-1,1,3,3-tetramethyl peroxide butyl butyl ester (peroxide B, brand name: Perocta O, manufactured by NOF Co., Ltd., 1-minute half-life temperature: 124.3° C.).

Disperse 10 g of silica particles (trade name: R104, manufactured by AEROSIL Co., Ltd.) as inorganic particles in a mixed solvent of 45 g of toluene and 45 g of ethyl acetate to prepare a 10% by mass dispersion. It is prepared in the coating solution.

(Production of connectors)

A flexible circuit board (FPC) having 2,200 copper circuits with a line width of 75 μm, a pitch of 150 μm (a gap of 75 μm), and a thickness of 18 μm was prepared using the film adhesives shown in Table 2 and Table 3, and A SiN _x substrate (thickness 0.7 mm) including a glass substrate and a thin layer of silicon nitride (SiN _x ) formed on the glass substrate with a thickness of 0.2 μm is connected. The connection uses a thermocompression bonding device (heating method: constant temperature type, manufactured by Toray Engineering Co., Ltd.), and heats and presses at 130°C and 3MPa for 5 seconds or at 170°C and 3MPa for 5 seconds. pressure. In this way, a connected body in which the FPC and the SiN _x substrate were connected with a width of 1.5 mm by the hardened film-like adhesive was produced. The pressurized pressure was calculated with the crimp area set at 0.495 cm ² .

(Peel evaluation)

An optical microscope was used to observe the appearance of the connection shortly after the connection was made, and the appearance of the connection after the connection was placed in a constant temperature and humidity chamber at 85° C. and 85% RH for 250 hours (after the high-temperature and high-humidity test). The area where peeling occurred at the interface between the _SiNx substrate and the cured product in the gap portion (peeling area) was measured to evaluate the presence or absence of peeling. The case where the ratio of the peeled area to the entire gap was more than 30% was evaluated as "B" (peeling present), and the case where the ratio of the peeled area was 30% or less was evaluated as "A" (no peeling). The evaluation results are shown in Table 2 and Table 3. In addition, regarding the connection appearance immediately after preparation of the connection body, there was no peeling in any of the Examples and Comparative Examples.

(Evaluation of storage stability (lifetime characteristics))

The said film-form adhesive agent was processed in 40 degreeC thermostat for 1 day. Using this film-like adhesive, a connected body was produced by the same method as described above, and then a high-temperature and high-humidity test was performed. The evaluation results are shown in Table 2 and Table 3.

From Table 2 and Table 3, it was confirmed that the film-like adhesives of the examples were capable of low-temperature short-time connection (particularly, connection at 130° C. for 5 seconds) compared with the comparative examples. Furthermore, it was confirmed that the film-like adhesives of the Examples can maintain good adhesion to the surface of the substrate (inorganic substrate) even after high-temperature, high-humidity treatment, and are excellent in storage stability, compared with the Comparative Examples.

10: Circuit connection components

10a: insulating substance

10b: Conductive particles

20: Circuit components

21: Substrate

21a, 31a: main surface

22: Circuit electrode

30: circuit components

31: Substrate

32: Circuit electrode

100a: circuit connection structure

Claims (7)

An adhesive composition for circuit connection, which contains: a first silane compound having a radical polymerizable functional group, a second silane compound reacting with the first silane compound, a radical polymerizable compound (equivalent to excluding the first silane compound), and a peroxide having a half-life temperature of 120°C or less in 1 minute, wherein the first silane compound is 0.5 based on the total mass of the adhesive components of the adhesive composition Mass% or more. The adhesive composition for circuit connection as described in claim 1 of the patent application, wherein the mass ratio of the content of the first silane compound to the content of the second silane compound is 0.01-10. The adhesive composition for circuit connection as described in item 1 or item 2 of the scope of the patent application, wherein the functional group of the first silane compound is selected from the group consisting of (meth)acryl and vinyl At least one of the groups formed. The adhesive composition for circuit connection as described in claim 1 or claim 2, wherein the second silane compound has an epoxy group. The adhesive composition for circuit connection according to claim 1 or claim 2, which further contains conductive particles. A structure comprising the adhesive composition for circuit connection or its cured product as described in any one of the first to fifth claims of the patent application. A structure comprising: a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and a circuit connection arranged between the first circuit member and the second circuit member Component, the first circuit electrode and the second circuit electrode are electrically connected, and the circuit connection component includes the adhesive for circuit connection as described in any one of the 1st to 5th items in the scope of the patent application composition or its hardening.

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